CoVID-19 is a multi-symptomatic disease which has made a global impact due to its ability to spread rapidly, and its relatively high mortality rate. Beyond the heroic efforts to develop vaccines, which we will not discuss, the response of scientists and clinicians to this complex problem has reflected the need to detect CoVID-19 rapidly, to diagnose patients likely to show adverse symptoms, and to treat severe and critical CoVID-19. Here we aim to encapsulate these varied and sometimes conflicting approaches and the resulting data in terms of chemistry and biology. In the process we highlight emerging concepts, and potential future applications that may arise out of this immense effort.

Chemistry is the last natural science discipline to embrace prepublishing, namely the publication of non-peer reviewed scientific articles on the internet. After a brief insight into the origins and the purpose of prepublishing in science, we conduct a concrete analysis of the concrete situation, aiming at providing an answer to several questions. Why the chemistry community has been late in embracing prepublishing? Is this in relation with the slow acceptance of open access publishing by the same community? Will prepublishing become a common habit also for chemistry scholars?

Hydroxychloroquine, a known antiviral metabolite of chloroquine, is increasingly used along with antibiotic azithromycin for the treatment of COVID-19 infection. In about one month India, the world’s largest manufacturer, delivered hydroxychloroquine for treating COVID-19 to over 50 countries. The therapy is being used across the world both for patients staying at home at the early phase of symptoms, as well as for patients hospitalized. We summarize achievements as of late April 2020, review possible modes of action and suggest avenues for the quick scale-up of production of hydroxychloroquine.

After UV excitation, gas phase thymine returns to ground state in 5 to 7 ps, showing multiple time constants. There is no consensus on the assignment of these processes, with a dispute between models claiming that thymine is trapped either in the first (S1) or in the second (S2) excited states. In the present study, nonadiabatic dynamics simulation of thymine is performed on the basis of ADC(2) surfaces, to understand the role of dynamic electron correlation on the deactivation pathways. The results show that trapping in S2 is strongly reduced in comparison to previous simulations considering only non-dynamic electron correlation on CASSCF surfaces. The reason for the difference is traced back to the energetic cost for formation of a CO p bond in S2.

Due to metal leaching and poor catalyst stability, the chemical industry’s fine chemical and pharmaceutical sectors have been historically reluctant to use supported transition metal catalysts to manufacture fine chemicals and active pharmaceutical ingredients. With the advent of new generation supported metal catalysts and flow chemistry, we argue in this study, this situation is poised to quickly change. Alongside heterogenized metal nanoparticles, both single-site molecular and single-atom catalyst will become ubiquitous. This study offers a critical outlook taking into account both technical and economic aspects.

A basic problem in all postulated pathways of prebiotic chemistry is the low concentration which generally is expected for interesting reactants in fluid environments. Even though compounds like nucleobases, sugars or peptides principally may form spontaneously under environmental conditions, they will always be rapidly diluted in an aqueous environment. In addition, any such reaction leads to side products which often exceed the desired compound and generally hamper the first steps of a subsequent molecular evolution. Therefore, a mechanism of selection and accumulation of relevant prebiotic compounds seems to be crucial for molecular evolution. A very efficient environment for selection and accumulation can be found in the fluid continuum circulating in tectonic fault zones. Vesicles which form spontaneously at a depth of approximately 1 km present a selective trap for amphiphilic molecules, especially for peptides composed of hydrophilic and hydrophobic amino acids in a suitable sequence. The accumulation effect is shown in a numeric simulation on a simplified model. Further, possible mechanisms of a molecular evolution in vesicle membranes are discussed. Altogether, the proposed scenario can be seen as an ideal environment for constant, undisturbed molecular evolution in and on cell-like compartments, the latter offering preferential starting conditions for a subsequent RNA world.

Based on a new model of a possible origin of life, we establish an efficient and stable system undergoing structural reproduction, self-optimization and molecular evolution. This system is being formed under realistic conditions by the interaction of two cyclic processes, one of which offering vesicles as the structural environment, the other supplying peptides from a variety of amino acids as versatile building blocks. We demonstrate that structures growing in a combination of both cycles have the potential to support their own existence, to undergo chemical and structural evolution and to develop unpredicted functional properties. The key mechanism is the mutual stabilization of the peptides by the vesicles and of the vesicles by the peptides together with a constant production and selection of both. The development of the proposed system over time not only would represent one of the principles of life, but could also be a model for the formation of self-evolving structures ultimately leading to the first living cell. The experiment yields clear evidence on a vesicle-induced accumulation of membrane-interacting peptide which could be identified by liquid chromatography combined with high-resolution mass spectroscopy. We found that the selected peptide has an immediate effect on the vesicles, leading to i) reduced vesicle size, ii) increased vesicle membrane permeability, and iii) improved thermal vesicle stability.

Eddy-driven jets are of importance in the ocean and atmosphere, and to a first approximation are governed by Rossby wave dynamics. This study addresses the time-dependent flux of fluid and potential vorticity between such a jet and an adjacent eddy, with specific regard to determining zonal and meridional wavenumber dependence. The flux amplitude in wavenumber space is obtained, which is easily computable for a given jet geometry, speed and latitude, and which provides instant information on the wavenumbers of the Rossby waves which maximize the flux. This new tool enables the quick determination of which modes are most influential in imparting fluid exchange, which in the long term will homogenize the potential vorticity between the eddy and the jet. The results are validated by computing backward- and forward-time finite-time Lyapunov exponent fields, and also stable and unstable manifolds; the intermingling of these entities defines the region of chaotic transport between the eddy and the jet. The relationship of all of these to the time-varying transport flux between the eddy and the jet is carefully elucidated. The flux quantification presented here works for general time-dependence, whether or not lobes (intersection regions between stable and unstable manifolds) are present in the mixing region, and is therefore also easily computable for wave packets consisting of infinitely many wavenumbers.

ω-Transaminases have been immobilized on macrocellular silica monoliths and used as heterogeneous biocatalysts in a continuous flow mode enantioselective transamination reaction. The support was prepared by a sol-gel method based on emulsion templating. The enzyme was immobilized on the structured silica monoliths both by adsorption, and by covalent grafting using amino-functionalized silica monoliths and glutaraldehyde as a coupling agent. A simple reactor set-up based on the use of a heat-shrinkable Teflon tube is presented and successfully used for the continuous flow kinetic resolution of a chiral amine, 4-bromo-α-methylbenzylamine. The porous structure of the supports ensures effective mass transfer and the reactor works in the plug flow regime without preferential flow paths. When immobilized in the monolith and used in the flow reactor, transaminases retain their activity and their enantioselectivity. The solid biocatalyst is also shown to be stable both on stream and during storage. These essential features pave the way to the successful development of an environmentally friendly process for chiral amines production.

Emerging countries in Southeast Asia are facing considerable challenges in addressing rising motorisation and its negative impact on air quality, traffic, energy security, liveability, and greenhouse gas emissions. Indeed, even as initial policies to address these issues are being agreed and implemented, current trends are incompatible with sustainable development and long-term climate change targets. This paper presents a comparative analysis of the approach and status of sustainable, low-carbon transport policy in ASEAN countries and identifies differences and similarities, with the aim of helping assessment of feasibility of future policies and informing future studies on policy innovations and cross-country learning. The methodology is based on the taxonomy of policy components developed by Howlett and Cashore, and our data on comprehensive country studies for Indonesia, the Philippines, Thailand and Vietnam and interviews. We find that each country has a specific set of goals, objectives and targets that support sustainable transport, and, directly or indirectly, climate change mitigation. In terms of specific instruments and calibrations, which we analyse based on the Avoid-Shift-Improve approach, there are notable differences between the countries, for example in fuel economy policy.

Li₂TiO₃ nanopowders were synthesized by hydrothermal process using anatase TiO₂ and LiOH H₂O as raw materials. Li₂TiO₃ crystallizes in the layered monoclinic structure (space group C2/c) with average crystallite size of 34 nm. Morphology, elemental composition and local structure of products were carried out using HRTEM, FESEM, EDS, Raman and FTIR spectroscopy. Transport properties investigated by d.c. (4-probe measurements) and a.c. (complex impedance spectroscopy) show the activation energy of 0.71 and 0.65 eV, respectively. The ionic transport properties of Li⁺ ions in nanocrystalline Li₂TiO₃ characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) validate the good electrochemical properties of this anode material for lithium-ion batteries.

Technology has nearly reached to its climax but the basic understanding of science in many phenomena is still awaited. Scientific research reveals strong analogy between electron and photon. Atoms that execute suitable electronic transitions, on absorbing heat energy at shunt level, excite their electrons. De-excitation of an electron, where inertia is involved, results depicting energy in the shape-like Gaussian distribution. The wavelength of photon at point of generation remains in inter-state electron’s gap distance and atoms of all those suitable elements that glitter perform like magician, throwing one and catching other, where an electron excites at shunt level of energy and configure trajectory under inertia-levity-inertia and de-excites at free fall configuring trajectory under inertia-gravity-inertia and silicon atom is a model system. In such atoms, heat energy of merged photons is cultivated and that shunt energy perturb the balance of inherent energy between electron and nucleus while balancing it via another electronic transition in reverse mode of the same atom. Uninterrupted confined inter-state electron-dynamics results into wave that can travel immeasurable length and on breaking inter-state electron-dynamics results into fixed length discrete energy wave called a photon. Such photons increase wavelength on decreasing frequency, propagate to hard X-ray, to visible spectrum, and to beyond. Here, I discuss that heat energy is due to merged photons, photons characteristic current are due to photons having wavelength in inter-state electron’s gap distance and light is due to photons having wavelength in visible spectrum. Force of repulsion or attraction in certain materials engages the phenomenon of levitism or gravitism instead of magnetism where inertia is no longer prevailed. All structural motifs and dynamics are subjected to characteristic photons as long as bearing the neutral behavior of the external forces. A structural design delivers straight-forward application on coordinating different energy shaped photons. The various gadgets, devices and instruments only operate energy as per need of necessity. Here, materials science explores matter to sub-atomic level while coordinating and interacting energy and devises science to describe.

TaABCC13 is member of wheat ABCC subclass of transporters. The RNAi mediated silencing of this transporter in wheat results in lowering of seed phytic acid level and other developmental defects. In addition to that, wheat ABCC13 was involved in cadmium detoxification as evident by the complementation assays in yeast. The appearance of early lateral roots in these transgenic seedlings speculated the possibility for studying the role of localized auxin-mediated effects. In the current study, firstly, the expression of auxin related genes was studied in the transgenic roots. Enhanced expression of genes pertaining to either auxin biosynthesis or its transport was observed in transgenic wheat seedling roots suggesting the direct effect of the hormone. Further, the early emergence of lateral roots in transgenic wheat seedlings was affected due to the presence of auxin-transport inhibitor suggesting the direct effect of hormones in root development. In conclusion, herein we provide the novel evidence for the auxin mediated regulation of lateral root emergence in TaABCC13:RNAi seedlings.

A facilitative transport system exists on the blood brain barrier (BBB) that has been tacitly assumed to be a path for glutamate entry to brain. But glutamate is a non-essential amino acid whose brain content is much greater than plasma, and studies in vivo show that glutamate does not enter brain in material quantities except in those small regions with fenestrated capillaries (circumventricular organs). The situation became understandable when luminal (blood facing) and abluminal (brain facing) membranes were isolated and studied separately. Facilitative transport of glutamate and glutamine exist only on the luminal membranes whereas Na+-dependent transport systems for glutamate, glutamine and some other amino acids are present only on the abluminal membrane. The Na+-dependent cotransporters of the abluminal membrane are in a position to actively transport amino acids from the extracellular fluid (ECF) into the endothelial cells of the BBB. These powerful secondary active transporters couple the energy of the Na+-gradient to move glutamate and glutamine into the ECF whereupon glutamate can exit to blood on the luminal facilitative glutamate transporter. Glutamine may also exit brain on a separate facilitative transport system that exists on the luminal membranes or glutamine can be hydrolyzed to glutamate within the BBB thereby releasing ammonia that is freely diffusible. The γ-glutamyl participate cycle participates indirectly by producing oxoproline (pyroglutamate) that stimulates almost all secondary active transporters yet discovered in the abluminal membranes of the BBB.

Non-melanoma skin cancers (NMSCs) are the leading cause of skin cancer-related morbidity and mortality. Effective strategies are needed to control NMSC occurrence and progression. Non-toxic, plant-derived extracts have been shown to exert multiple anti-cancer effects. Graviola (Annona muricata), a tropical fruit-bearing plant, has been used in traditional medicine against multiple human diseases including cancer. The current study investigated the effects of graviola leaf and stem extract (GLSE) and its solvent-extracted fractions on two human NMSC cell lines, UW-BCC1 and A431. GLSE was found to: i) dose-dependently suppress UW-BCC1 and A431 cell growth, motility, wound closure, and clonogenicity; ii) induce G₀/G₁ cell cycle arrest by downregulating cyclin/cdk factors while upregulating cdk inhibitors, and (iv) induce apoptosis as evidenced by cleavage of caspases-3, -8 and PARP. Further, GLSE suppressed levels of activated hedgehog (Hh) pathway components Smo, Gli 1/2, and Shh while inducing SuFu. GLSE also decreased the expression of pro-apoptotic protein Bax while decreasing the expression of the anti-apoptotic protein Bcl-2. We determined that these activities were concentrated in an acetogenin/alkaloid-rich dichloromethane subfraction of GLSE. Our data identify graviola extracts and their constituents as promising sources for new chemopreventive and therapeutic agent(s) to be further developed for the control of NMSCs

How did life begin on Earth? And is there life elsewhere in the Cosmos? Challenging questions, indeed. The series of conferences established by NoR CEL in 2013, addresses these very same questions. The basis for this paper is the summary report of oral presentations that were delivered by NoR CEL’s network members during the 2018 Athens conference and, as such, disseminates the latest research which they have put forward. More in depth material can be found by consulting the contributors referenced papers. Overall, the outcome of this conspectus on the conference demonstrates a case for the existence of “probable chemistry” during the prebiotic epoch.

The chemical graph theory is a subfield of mathematical chemistry which applies classic graph theory to chemical entities and phenomena. Chemical graphs are main data structures to represent chemical structures in cheminformatics. Computable properties of graphs lay the foundation for (quantitative) structure activity and structure property predictions - a core discipline of cheminformatics. It has a historic relevance for natural sciences, such as chemistry, biochemistry and biology, and is in the heart of modern disciplines, such as cheminformatics and bioinformatics. This review first covers the history of chemical graph theory, then provides an overview of its various techniques and applications for CASE, and finally summarises modern tools using chemical graph theory for CASE.

The critical hypoxia in COVID-19 patients during this pandemic, has taken away many lives all around the globe. The mechanism has been poorly understood and initially, word got around that it was a SARS (Severe Acute Respiratory Syndrome) pneumonia. The atypical images in lung computerized axial tomography (CAT) scans were alarming. This immediately alerted everyone including poor countries to purchase lacking sophisticated ventilator equipment. However, in some countries, even 88% of the patients on ventilators lost their lives. New observations and pathological findings are gradually clarifying the disease. What seems evident is that it is not only one disease but several, with different responses in different countries and different altitudes. The critical hypoxia and «gasping» present in some patients are not totally understood. It was mentioned that it could be like a High-Altitude Pulmonary Edema (HAPE). Hereby, as high-altitude medicine and hypoxia physiology specialists, we compare the pathophysiology with that of high-altitude exposure in order to understand the mechanisms involved. Some differences in lung radiological images along with transmission and viral attack mechanisms are discussed. The oxygen transport triad used at high-altitude can be applied on this pathology in order to propose even the use of erythropoietin (EPO) early in the treatment. The immune system is the most important long-term survival tool, so we suggest a short-term strategy: the use of special Earth open-circuit astronaut-resembling suits with effective outside air filtering re-breathing mechanisms in order to return to work and daily activities, without contamination risk. Thereby, the curve can be flattened without quarantine and the economy could recover.

A numerical mechanism connecting ice algal ecodynamics with the buildup of organic macromolecules is tested within modeled pan-Arctic brine channels. The simulations take place offline in a reduced representation of sea ice geochemistry. Physical driver quantities derive from the global sea ice code CICE, including snow cover, thickness and internal temperature. The framework is averaged over ten boreal biogeographic zones. Computed nutrient-light-salt limited algal growth supports grazing, mortality and carbon flow. Vertical transport is diffusive but responds to pore structure. Simulated bottom layer chlorophyll maxima are reasonable, though delayed by about a month relative to observations due to uncertainties in snow variability. Upper level biota arise intermittently during flooding events. Macromolecular concentrations are tracked as proxy proteins, polysaccharides, lipids and refractory humics. The fresh biopolymers undergo succession and removal by bacteria. Baseline organics enter solely through cell disruption, so that the internal carbon content is initially biased low. By including exudation, agreement with dissolved organic or individual biopolymer data is achieved given strong release coupled to light intensity. Detrital carbon then reaches hundreds of micromolar, sufficient to support structural changes to the ice matrix.

Intensive application of synthetic pesticides was the routine practice of commercial agriculture during the Green Revolution to boost agricultural productivity to meet global food demand. Alongside this, the application of chemical pesticides caused adverse effects on the environment and its ecoreceptors including human health. Negative externalities arising from conventional farming instigated the call for sustainable development during the sixties to promote and balance the nexus between socially acceptable economic growth and environmental protection. Consequently, a blueprint of 17 Sustainable Development Goals (SDGs) and 169 targets including ecological stewardship and food security was drafted. Eight out of the 17 SDGs are directly linked to sustainable agriculture based on the direct impact of agriculture, judicious use of critical resources and conservation and the Principles of green chemistry. As a green chemical agent, biopesticides have been shown to have the potentials to substitute chemical pesticides with equal agricultural productivity. The adoption of bio-based pesticides via integrated pest management (IPM) has proven to be the most effective option to influence most dimensions of sustainable agriculture. Therefore, biopesticide-driven IPM if utilized with requisite education, skills and research would boost sustainable agriculture. This chapter reviews the prospects, importance, and limitations of biopesticides to sustainable agriculture and how sustainable agriculture is connected to sustainable development, Green Chemistry, and integrated pest management.

Given the persistence of microplastics in the environment and their potential toxicity to ecosystems, understanding of likely microplastic accumulation ‘hotspots’ in rivers is urgently needed. To contribute to this challenge, this paper reports results of a microplastic survey from a heavily urbanised catchment, the River Tame, which flows through the city of Birmingham, UK. All sediment sampled was found to contain microplastics with an average abundance of 165 particles kg-1. While urban areas generally have a greater abundance of microplastics as compared with rural, there is no simple relationship between microplastic numbers and population density or proximity to wastewater treatment sites. The greatest change in microplastic abundance was due to the presence of a lake along the course of the River Tame i.e. on entering the lake flow velocities are reduced which promotes the deposition of fine sediment and potentially microplastics. This suggests that the greatest concentrations of microplastics will not be found in-channel but rather on the floodplain and other low velocity environments such as meander cutoffs. We also identified a new mechanism of microplastic fixation in freshwater environments through ecological engineers, specifically caddisfly that incorporated microplastics into their casing. These results highlight the need to explore further hydrodynamic and ecological impacts on microplastics fate and transport in rivers.

Analytical channel design tools have not advanced appreciably in the last decades, and continue to produce designs based upon a single representative discharge that may not lead to overall sediment continuity. It is beneficial for designers to know when a simplified design may be problematic and to efficiently produce alternative designs that approximate sediment balance over the entire flow regime. The Capacity/Supply Ratio (CSR) approach, an extension of the Copeland method of analytical channel design for sand channels, balances the sediment transport capacity of a design reach with the sediment supply of a stable upstream reach over the entire flow duration curve (FDC) rather than just a single discharge. Although CSR has a stronger physical basis than previous analytical channel design approaches, it has not been adopted in practice because it can be a cumbersome and time-consuming iterative analysis without the use of software. We investigate eighteen sand-bed rivers in a comparison of designs based on the CSR approach and five single-discharge metrics: the effective discharge (Qeff), the 1.5-year recurrence interval discharge (Q1.5), the bankfull discharge (Qbf), and the discharges associated with 50th (Qs50) and 75th (Qs75) percentiles of the cumulative sediment yield curve. To facilitate this analysis we developed a novel design tool using the Visual Basic for Applications (VBA) programming language in Excel® to produce stable channel slope-width combinations based on the CSR methodology for both sand- and gravel-bed streams. The CSR Stable Channel Design Tool’s (CSR Tool) code structure was based on Copeland’s method in SAM and HEC-RAS (Hydrologic Engineering Center’s River Analysis System) and was tested with a single discharge to verify outputs. The Qs50 and Qs75 single-discharge designs match the CSR output most closely, followed by the Qbf, Qeff, and Q1.5. The Qeff proved to be the most inconsistent design metric because it can be highly dependent on the binning procedure used in the effectiveness analysis. Furthermore, we found that the more rigorous physical basis of the CSR analysis is potentially most important in designing ‘labile’ channels with highly erodible substrate, high perennial flow ‘flashiness,’ low width-to-depth ratio, and high incoming sediment load. The CSR Tool provides a resource for river restoration practitioners to efficiently utilize in-depth design techniques that can promote sediment balance in dynamic fluvial systems.

This paper addresses a wildlife monitoring problem using a team of UAVs for efficient monitoring of wildlife. The state-of-the-art technology using UAVs has been an increasingly popular tool to monitor wildlife compared to the traditional methods such as satellite imagery-based sensing or GPS trackers. However, there still exist unsolved problems as to how the UAVs need to cover a spacious domain to detect animals as many as possible. In this paper, we propose the optimal transport-based wildlife monitoring strategy for a multi-UAV system, to prioritize monitoring areas while incorporating complementary information such as GPS trackers and satellite-based sensing. Through the proposed scheme, the UAVs can explore the large-size domain effectively and collaboratively with a given priority. The time-varying nature of wildlife due to their movements is modeled as a stochastic process, which is included in the proposed work to reflect the spatio-temporal evolution of their position estimation. In this way, the proposed monitoring plan can lead to efficient wildlife monitoring with a high detection rate. Various simulation results including statistical data are provided to validate the proposed work.

Fostering fruitful collaboration between chemistry and physics scholars, the analysis of the differences in the practical approach to single atoms in chemistry and in physics affords a number of conceptual outcomes pointing to a more balanced relationship between chemistry and physics.

Electric mobility begins to enter East-African markets. This paper aims to investigate what policy level solutions and stakeholder constellations are established in the context of e-mobility in Dar es Salaam, Kigali, Kisumu and Nairobi and in which ways they attempt to tackle implementation of electric mobility solutions. The study employs two key methods including content analysis of policy and programmatic documents as well as interviews based on purposive sampling ap-proach with stakeholders involved in mobility transitions. The study findings point out that transport operators and their representative associations are less recognized as major players in the transition, far behind new e-mobility players (start-ups) and public authorities. The study further indicates that a set of financial and technical barriers persist such as high upfront invest-ment costs in vehicles and infrastructure, or anxieties regarding competitiveness with fossil fuel vehicles, that constrain the uptake of such private e-mobility initiatives. This study concludes by identifying current gaps that need to be tackled by policy makers and stakeholders in order to implement inclusive electric mobility in East-African cities, considering modalities that include transport providers and address their financial constraints.

Fabric phase sorptive extraction (FPSE) combines the advanced material properties of sol–gel derived microextraction sorbents and the flexible and permeable fabric support to create a robust, simple and green sample preparation device. It simultaneously improves the extraction sensitivity, and the speed of the extraction by incorporating high volume of sponge-like porous sol–gel hybrid inorganic–organic sorbents into permeable fabric substrates that is capable of extracting target analytes directly from simple to complex aqueous sample matrices. For the first time, this technique was applied to the trace level determination of selected polycyclic aromatic hydrocarbons (PAHs) in environmental water samples using a non-polar sol–gel C18 coated FPSE media. Several extraction parameters were optimized to improve extraction efficiency and to achieve high detection sensitivity. Validation tests of spiked samples showed good linearity for four selected PAHs (R² = 0.9983–0.9997) over a wide range of concentrations (0.010-10 ng/mL). Limits of detection (LODs) and quantification (LOQs) were measured at pg/mL levels, 0.1–1 pg/mL and 0.3–3 pg/mL, respectively. Inter- and intra-day precision tests showed variations of 1.1–4.1% for four selected PAHs. Average absolute recovery values were in the range of 88.1–90.5% surpassed the recovery prediction model, with relative standard deviations below 5%. The developed FPSE-HPLC-FLD protocol was finally applied to analyze 8 environmental water samples. Out of four selected PAHs, fluoranthene (Flu) and phenanthrene (Phen) were the most frequently detected in four samples, at concentration levels of 5.6–7.7 ng/mL and 4.1-11 ng/mL, respectively followed by anthracene (Anth) and pyrene (Pyr) in two samples. The newly developed FPSE-HPLC-FLD protocol is simple, green, fast and economical, with adequate sensitivity for trace levels of four selected PAHs and seems to be promising in routine monitoring of water quality and safety.

The theory and working principle of fabric phase sorptive extraction (FPSE) is presented that eloquently explains the mystery behind this new and powerful sample preparation technique. FPSE innovatively integrates the benefits of sol-gel coating technology and the rich surface chemistry of cellulose/polyester/fiberglass fabric, resulting in a microextraction device with very high sorbent loading in the form of an ultra-thin coating. This porous sorbent coating and the permeable substrate synergistically facilitate very fast extraction equilibrium. The flexibility of the FPSE device allows for direct insertion into original, unmodified samples of different origin. Strong chemical bonding between the sol-gel sorbent and the fabric substrate permits the exposure of FPSE devices to any organic solvent for analyte back-extraction/elution and to highly acidic or basic environments (pH 1-12) if required. A sol-gel derived sorbent, highly polar sol-gel poly(ethylene glycol) coating, was generated on cellulose substrates. Five cm2 segments of these coated fabrics were used as the FPSE devices for sample preparation using direct immersion. An important class of environmental pollutants, substituted phenols, was used as model compounds to evaluate the extraction performance of FPSE. The high primary contact surface area (PCSA) of the FPSE device and porous structure of the sol-gel coatings resulted in very high sample capacities and incredible extraction sensitivities for both the compound classes in a relatively short period of time. Different extraction parameters were evaluated and optimized. The new extraction devices demonstrated part per trillion level detection limits for substituted phenols, a wide range of detection linearity, and good performance reproducibility.

Glycerol is a subproduct of biodiesel production and represents an important problem when generated in large scale. Alternatives that can utilize this unrefined byproduct is of potential interest. It is herein described the synthesis of a series of 1,2,3-triazoles using glycerol as starting material. The key step involved in the preparation of triazolic derivatives corresponded to the Copper(I)-catalyzed Azide-Alkyne Cycloaddition (CuAAC), also known as click reaction, between 4-(azidomethyl)-2,2-dimethyl-1,3-dioxolane (3) and different terminal alkynes. The eight prepared derivatives were evaluated with regard to their fungicide, phytotoxic and cytotoxic activities. The fungicide activity was assessed in vitro against Colletotrichum gloeosporioides, the causing agent of papaya anthracnose. It was found that the compounds 1-(1-((2,2-dimethyl-1,3-dioxolan-4-yl)methyl)-1H-1,2,3-triazol-4-yl)cyclohexanol (4g) and 2-(1-((2,2-dimethyl-1,3-dioxolan-4-yl)methyl)-1H-1,2,3-triazol-4-yl)propan-2-ol (4h) demonstrated high efficiency on controlling C. gloeosporioides when compared to the commercial fungicide tebuconazole. The triazoles did not present any phytotoxic effect when evaluated against Lactuca sativa. However, five derivatives were mitodepressive, inducing cell death detected by the presence of condensed nuclei and acted as aneugenic agents in the cell cycle of L. sativa. It is believed that glycerol derivatives bearing 1,2,3-triazole functionalities may represent a scaffold to be explored toward the development of new agents to control C. gloeosporioides.

We present an exact expression for the upscaled dynamic dispersion coefficient (D) for one-dimensional transport by Hagen-Poiseuille flow which is the basis for modeling transport in porous media idealized as capillary tubes. The theoretical model is validated by comparing the breakthrough curves (BTCs) from a 1D advection-dispersion model with dynamic D to that from direct numerical solutions utilizing a 2D advection-diffusion model. Both Taylor dispersion theory and our new theory are good predictors of D at lower Peclet Number (Pe) regime, but gradually fail to capture most parts of BTCs as Pe increases. However, our model generally predicts the mixing and spreading of solutes better than Taylor’s theory since it covers all transport regimes from molecular diffusion, through anomalous transport, and to Taylor dispersion. The model accurately predicts D based on the early part of BTCs even at relatively high Pe regime (~62) where the Taylor’s theory fails. Furthermore, the model allows for calculation of the time scale that separates Fickian from non-Fickian transport. Therefore, our model can readily be used to calculate dispersion through short tubes of arbitrary radii such as the pore throats in a pore network model.

Urban areas are centres of business and innovation. Freight transport is indispensable for the proper functioning of any modern urban society. Urban areas can’t function without an appropriate freight transport system, due to the need to replenish stocks of food and other goods in retail shops. The complexity of the decisions concerning implementation of measures to improve the movement of goods in the city requires tools designed to support this process. The purpose of this article is to introduce the possibility of applying the Analytic Hierarchy Process (AHP) as well as the Decision Making Trial and Evaluation Laboratory Method (DEMATEL) in choosing a set of measures and in analysing in the field of distribution logistics, which will help to solve the delivery problems and streamline the cargo flows in Szczecin, in the context of sustainable development.

There is a large potential for cost-effective solutions to reduce greenhouse gas emissions and to improve the sustainability of the transport sector that is yet unexploited, in particular in the urban context. Considering the cost-effectiveness and the potential for co-benefits, it is hard to understand why energy gains and mitigation action in the transport sector is still lagging behind the potential. Particularly interesting is the fact that there is substantial difference among countries with relatively similar economic performances, such as the OECD countries in the development of their transport CO2 emission over the past thirty years despite the fact that these countries had relatively similar access to efficient technologies and vehicles. This study aims to apply some well established political science theories on the particular example of climate change mitigation in the transport sector in order to identify some of the factors that could help explain the variations in success of policies and strategies in this sector. The analysis suggests that institutional arrangements that contribute to consensus building in the political process provide a high level of political and policy stability which is vital to long-term changes in energy end-use sectors that rely on long-term investments. However, there is no direct correlation between institutional structures, e.g. corporatism and success in reducing greenhouse gas emissions in the transport sector. Environmental objectives need to be built into the consensus-based policy structure before actual policy progress can be observed. This usually takes longer in consensus democracies than in politically more agile majoritarian policy environments, but the policy stability that builds on corporatist institutional structures is likely to experience changes over a longer-term, in this case to a shift towards low-carbon transport that endures.

Heterocycles are unique precursors for the synthesis of various pharmaceuticals and agrochemicals particularly those possessing N- or O- moieties. The development of methods to prepare heterocycles is of great importance in synthesis of organic compounds, especially the heterocycles which can be found in natural products. The synthesis of nitrogen and oxygen containing heterocycles viz. coumarins, dihydropyrimidinones, imidazoles, isoxazoles and benzimidazoles represented an attractive and demanding work for chemists as these nucleus has found extensive applications in several fields such as material science, analytical chemistry and most importantly in medicinal chemistry. Organic synthesis has been attracted towards the development of new environmental friendly procedures to achieve the goals of green chemistry. The fundamental aspects of green chemistry are use of biocatalysts and environmental benign solvents under mild conditions. The present review article summarized the green synthetic methods and biological activities of nitrogen and oxygen containing heterocycles.

Observation of the ambient aerosol surface area concentrations is important to understand the aerosol toxicity because an increased surface area may be able to act as an enhanced reaction interface for certain reactions between aerosol particles and biological cells, as well as an augmented carrier surface for co-pollutants. In this study, the concentration of aerosol surface area was measured from April 2015 to March 2016 in Fukuoka, Japan. We investigated the monthly and diurnal variations in the correlations between the aerosol surface area and black carbon (BC) and sulfate concentrations. Throughout the year, aerosol surface area concentration was strongly correlated with the concentrations of BC, which has relatively large surface area since BC particles are usually submicron agglomerates consisting of much smaller (tens of nanometers) sized primary soot particles. The slopes of the regression between the aerosol surface area and BC concentrations was highest in August and September 2015. This appears to have been the results of an increase in the proportion of the airmass that originated on the main islands of Japan. This may enhance the introduction of the BC from the main islands of Japan that is relatively fresh (or “uncoated”), thereby maintaining its larger surface area.

A membrane can be represented by an energy landscape that solutes or colloids must cross. A model accounting for the momentum and the mass balances on the membrane energy landscape establishes a new way of writing for the Darcy law. The counter pressure in the Darcy law is no longer written as the result of an osmotic pressure difference but rather as a function of colloid-membrane interactions. The ability of the model to describe the physics of the filtration is discussed in detail. This model is solved on a simplified energy landscape to derive analytical relationships that describe the selectivity and the counter pressure from ab-initio operating conditions. The model shows that the stiffness of the energy landscape has an impact on the process efficiency: a gradual increase in interactions (like with hourglass pore shape) can reduce the separation energetic cost. It allows the introduction of a new paradigm to increase membrane efficiency: the accumulation that is inherent to the separation must be distributed across the membrane. Asymmetric interactions thus lead to direction-dependent transfer properties and the membrane exhibits diode behavior. These new transfer opportunities are discussed.

The link between ICTs, freight transport, and CO₂ emissions has not received much explicit examination by researchers, despite freight transportation being an egregious contributor to environmental degradation. This paper investigates how ICTs can affect environmental quality when interacting with freight transport activities in 43 countries over the period 2002-2014, using carbon emissions as a proxy for environmental damages. ICTs are measured in terms of internet, telephone, and mobile phone technologies. Using GMM methodology, the results show that ICTs contribute to dampening environmental degradation when interacting with freight transport activities. Specifically, a 10% increase in the interaction between ICTs and freight transportation will decrease carbon emissions by between 1.27% and 3.02%. The results further suggest that fixed and smartphone technologies are the main contributors to reducing emissions when adopted in some specific transport sectors (i.e. road, rail, and inland), while the internet is the most efficient technology when interacting with air transport activity. In addition, the interaction between ICTs and multimodality accelerates environmental quality. The policy implications of these findings are discussed.

Nanostructured materials have already become an integral part of our daily life. In many applications ion mobility decisively affects the performance of, e.g., batteries and sensors. Nanocrystalline ceramics often exhibit enhanced transport properties due to their heterogeneous structure showing crystalline (defect-rich) grains and disordered interfacial regions. In particular, anion conductivity in nonstructural binary fluorides easily exceeds that of their coarse-grained counterparts. To further increase ion dynamics aliovalent substitution is a practical method to influence the number of (i) defect sites and (ii) the charge carrier density. Here, we used high energy-ball milling to incorporate Y³⁺ ions into the cubic structure of SrF₂. As compared to pure nanocrystalline SrF2 the ionic conductivity of Sr_1-xYxF_2+x with x = 0.3 increased by 4 orders of magnitude reaching 0.8 x 10 ^-5 S/cm^-1 at 450 K. We discuss the effect of YF₃ incorporation on conductivities isotherms determined by both activation energies and Arrhenius pre-factors. The enhancement seen is explained by size mismatch of the cations involved, which are forced to form a cubic crystal structure with extra F anions if x is kept smaller than 0.5

Human-Computer Interaction, including technology-aided instruction, is beginning to focus on virtual reality (VR) technology due to its ability to support immersive learning, teaching through simulation, and gamification of learning. These systems can deliver high-level multisensory learning experiences that are important in the teaching of many subjects, especially those involving abstract concepts or requiring spatial skills, such as organic chemistry. Haptic experiences with VR, however, remain a challenge. In addition, development have focused on general entertainment/gaming; VR systems in chemistry implement simulations of the chemistry laboratory and other advanced systems whereas those that support safe, game-like, immersive and multisensory learning of organic chemistry with haptics at pre-university education levels are scarce. We developed the VR Multisensory Classroom (VRMC) as an immersive learning environment within a VR head-mounted display, where learners employ hand movements to build hydrocarbon molecules and experience haptic feedback through gloves with built-in sensors and hand-tracking with the Leap Motion system. We report here the evaluation of the first prototype by learners from diverse backgrounds who reported on the ability of the VRMC to support high engagement, motivation, interest and organic chemistry learning as well as diverse learning styles. The VRMC is a novel VR classroom that supports immersive learning in molecular organic chemistry with haptics for multisensory learning.

Experimental optimization of analytical methods based on solid-phase microextraction (SPME) is a complex and labor-intensive process associated with uncertainties. Using the theoretical basics of SPME and finite element analysis software for the optimization proved to be an efficient alternative. In this study, an improved finite element analysis-based model for SPME of volatile organic compounds (VOCs) by porous coatings was developed mainly focussing on the mass transport in coatings. Benzene and the Carboxen/polydimethylsiloxane (Car/PDMS) coating were used as the model VOC and a porous SPME coating, respectively. It has been established that in the coating, volumetric fractions of Carboxen, PDMS, and air are 33, 42 and 24%, respectively. Knudsen diffusion in micropores can slow down a mass transport of analytes in the coating. When PDMS was considered as the solid part of the coating, lower root-mean-square deviation of the modeling results from experimental data was observed. It has been shown that the developed model can be used to model the extraction of VOCs from air and water samples encountered in a typical SPME development method procedure. It was possible to determine system equilibration times and use them to optimize sample volume and Henry’s law constant. The developed model is relatively simple, fast, and can be recommended for optimization of extraction parameters for other analytes and SPME coatings. The diffusivity of analytes in a coating is an important property needed for improved characterization of existing and new SPME polymers and analytical method optimization.

Organic compounds that contain poly-triazole are very important intermediates in pharmaceutical and chemical industry. Click chemistry is one of essential reactions that can form C-N bond with high atom economy. The research progress in metals catalyzed Click chemistry of azides and alkynes from the perspective of reaction mechanism is categorized and summarized.

The enantioselective alpha-amination of 1,3-dicarbonyl compounds has been performed using a catalytic system based on deep eutectic solvents (DES) and chiral 2-amino benzimidazole-derived organocatalysts. This procedure avoids the use of toxic volatile organic compounds (VOCs) as a reaction medium, providing access to highly functionalized chiral molecules, which are important intermediates for the natural product synthesis, in a selective and efficient manner. Furthermore, the reaction can be performed on a large scale and recycling the catalytic system is possible for at least five times, leading to a clean, cheap, simple, and scalable procedure that meets most of the criteria required to be a green and sustainable process.

In recent years, marine, freshwater and terrestrial pollution with microplastics has been discussed extensively, whereas atmospheric microplastic transport has been largely overlooked. Here, we present the first global simulation of atmospheric transport of microplastic particles produced by road traffic (TWPs – tire wear particles and BWPs – brake wear particles), a major source that can be quantified relatively well. We find a high transport efficiency of these particles to remote regions, such as the Arctic Ocean (14%). About 34% of the emitted coarse TWPs and 30% of the emitted coarse BWPs (100 kt yr^-1 and 40 kt yr^-1 respectively) were deposited in the World Ocean. These amounts are of similar magnitude as the total estimated terrestrial and riverine transport of TWPs and fibres to the ocean (64 kt yr^-1). Atmospheric transport of microplastics is thus an underestimated threat to global terrestrial and marine ecosystems and affects air quality on a global scale, especially considering that other large but highly uncertain emissions of microplastics to the atmosphere exist. High latitudes and the Arctic are highlighted as an important receptor of mid-latitude emissions of road microplastics, which may imply a future climatic risk, considering their affinity to absorb solar radiation and accelerate melting.

Below T_CO=157 K the quasi-one-dimensional charge-transfer salt (TMTTF)_2SbF_6 undergoes a pronounced phase transition to a charge-ordered ground state. We have explored the non-linear and photoconductive behavior as a function of applied voltage, laser pulse energy and temperature. Besides a decay of the photoconductive signal in a double exponential fashion in the millisecond range, we discover current oscillations in the kHz range induced by the application of short laser pulses. While the resonance frequencies do not depend on voltage or laser intensity and vary only slightly with temperature, the amplitude changes linearly with the laser intensity and voltage. The findings are discussed and compared to comparable phenomena in other low-dimensional electron systems.

Mineral dust is one of the most important aerosol in mass over the world, affecting health and dynamics. This aerosol is mainly emitted over arid areas but may be long-range transported, impacting the local budget of air quality in many cities. While models were extensively used to study a single specific event, or making a global analysis at coarse resolution, the goal of our study is to simultaneously focus on several areas - Europe, North America, Central Asia, East China and the Caribbean area - for a one month period, March 2014, avoiding any parameter fitting to better simulate a given dust outbreak. The simulation is performed for the first time with the hemispheric version of the CHIMERE model, with a horizontal resolution of 10km. In this study, an overview of several simultaneous dust outbreaks over the north hemisphere is proposed to assess the capability of such modelling tools to predict dust pollution events. A quantitative and qualitative evaluation of the most striking episodes is presented with comparisons to satellite data, ground based Particulate Matter and calcium measurements. Despite some overestimation of dust concentrations far from emission areas, the model is able to simulate the timing of the arrival of dust outbreaks on observational sites. For instance, several spectacular dust storms in the US and China are perfectly captured by the models. The high resolution allows to better describe and understand the orographic effects and the long-range transport of dust plumes.

The procedures for the extraction and separation of lipids and nutraceutics from microalgae using classic solvents have been used many times. However, these production methods usually require expensive and toxic solvents. Based on our studies involving the use of eco-sustainable methodologies and alternative solvents, we select ethanol (EtOH) and cyclopentyl methyl ether (CPME) for extracting bio-oil and lipids from algae. Different percentage of EtOH in CPME favors the production of an oil rich of SFA useful to production biofuel or rich of compounds bioactive. The proposed method for obtain a rich extract of saturated or unsaturated fatty acids from dry algal biomass is disclosed is eco-friendly and allows a good extraction yield. The method is compared both in extracted oil percentage yield and in extracted fatty acids selectivity to extraction by supercritical carbon dioxide.

In the case of vascular plants the process of water loss by leafs and water absorption by the root is well known. There is agreement on the passive nature of long-distance moisture movement in the dead cells of the xylem; however, controversy exists focusing on the long-distance water transport principle. Hales (1726) founded a view of bulk flow based on water suction after experiments with cut twigs. The previous doctrine of long-distance water transport within vessel elements and tracheid of the xylem of intact plants – the relevant cohesion theory in text books – was developed mainly by Boehm (1893), Renner (1911) and Dixon (1914) with plant artefacts. Water movement according to this theory is based on an assumed hydrodynamic bulk fluid flow in xylem in continuous water columns (free of water vapour space), under tension, according to the law of Poiseuille (see e.g. Dixon 1914). Physically hydrodynamics is part of fluid mechanics, as a result Poiseuille’s law is usually valid only for hydrodynamic bulk flow in ideal capillaries (Sutera & Skalak, 1993). Besides the basic requirement for transport, according to cohesion theory, the existence of ideal capillaries is not compatible with either: “Because vessel elements and tracheid do not stand as ideal capillaries. …” (Bresinsky et al. 2008, translated from German). Unlike ideal capillaries, the walls of vessel elements and tracheid interact with the transported water. These walls are able to function as a source or as a sink for the transported water because of interaction with the cell walls. With the interaction, vessel elements and tracheid, part of the xylem, can shrink and swell, unlike ideal capillaries. Because the xylem (in woody plants part of the wood) is inconsistent with the basic law of fluid flow, the equation of mass balance (Zimmermann et al. 2004) and cohesion theory are not strictly followed.Many plant physiologists view the cohesion theory as appropriate, however, this theory remains controver­sial, i.e. by Eisenhut (1988), Laschimke (1990) and Hahn (1993). Nultsch (1996) gives doubts referring to the present doctrine of plant water transport. Zimmermann et al. (2004) reject the cohesion theory and conclude: “... that the arguments of the proponents of the Cohesion Theory are completely misleading” (Zimmermann et al. 2004). Hence cohesion theory can be treated as inapplicable and the question arises: how does water transport in fact function? In the following, it is gone into in more detail. A sorption hypothesis of actual water transport, based on empirical fact, shall be addressed in this paper.

Among extensive studies on click chemistry the inverse electron-demand Diels-Alder reaction between 1,2,4,5-tetrazine (Tz) and trans-cyclooct-2-en (TCO) has gained increasing attraction due to its exceptionally fast reaction kinetics and high selectivity for in vivo pretargeting applications including PET imaging. The facile two-step approach utilizing TCO-modified antibodies as targeting structures has not made it into clinic though as the increase in blood volume from mice to human seems to be the major limitation. This study aimed to show if the design of multimeric Tz-ligands by chelator scaffolding can improve the binding capacity and may lead to enhanced PET imaging with gallium-68. For this purpose we utilized the macrocyclic siderophore Fusarinine C (FSC) which allows to conjugate up to three Tz-residues due to three primary amines available for site specific modification. The resulting mono- di- and trimeric conjugates were radiolabelled with gallium-68 and characterized in vitro (logD, protein binding, stability, binding towards TCO modified rituximab (RTX)) and in vivo (biodistribution- and imaging studies in normal BALB/c mice using a simplified RTX-TCO tumour surrogate). The 68Ga-labelled FSC-based Tz-ligands showed suitable hydrophilicity, high stability, high targeting specificity and the binding capacity to RTX-TCO was increased by the grade of multimerization. Corresponding in vivo studies showed a multimerization typical profile but generally suitable pharmacokinetics with low accumulation in non-targeted tissue. Imaging studies in RTX-TCO tumour surrogate bearing BALB/c mice confirmed this trend and revealed improved targeting by multimerization as increased accumulation in RTX-TCO positive tissue was observed.

Crosslinking of proteins for their irreversible immobilization on surfaces is a proven and popular method. However, many protocols lead to random orientation and the formation of undefined or even inactive by-products. Most concepts to obtain a more targeted conjugation or immobilization requires the recombinant modification of at least one binding partner, which is often impractical or prohibitively expensive. Here a novel method is presented, which is based on the chemical preactivation of Protein A or G with selected conventional crosslinkers. In a second step, the antibody is added, which is subsequently crosslinked in the Fc part. This leads to an oriented and covalent immobilization of the immunoglobulin with a very high yield. Protocols for Protein A and Protein G with murine and human IgG are presented. This method may be useful for the preparation of columns for affinity chromatography, immunoprecipitation, antibodies conjugated to magnetic particles, permanent and oriented immobilization of antibodies in biosensor systems, microarrays, microtitration plates or any other system, where the loss of antibodies needs to be avoided, and maximum binding capacity is desired. This method is directly applicable even to antibodies in crude cell culture supernatants, raw sera or protein-stabilized antibody preparations without any purification nor enrichment of the IgG. This new method delivered much higher signals as a traditional method and, hence, seems to be preferable in many applications.

A new framework in quantum chemistry has been proposed recently ("An approach to first principles electronic structure calculation by symbolic-numeric computation'' by A. Kikuchi). It is based on the modern technique of computational algebraic geometry, viz. the symbolic computation of polynomial systems. Although this framework belongs to molecular orbital theory, it fully adopts the symbolic method. The analytic integrals in the secular equations are approximated by the polynomials. The indeterminate variables of polynomials represent the wave-functions and other parameters for the optimization, such as atomic positions and contraction coefficients of atomic orbitals. Then the symbolic computation digests and decomposes the polynomials into a tame form of the set of equations, to which numerical computations are easily applied. The key technique is Grröbner basis theory, by which one can investigate the electronic structure by unraveling the entangled relations of the involved variables. In this article, at first, we demonstrate the featured result of this new theory. Next, we expound the mathematical basics concerning computational algebraic geometry, which are necessitated in our study. We will see how highly abstract ideas of polynomial algebra would be applied to the solution of the definite problems in quantum mechanics. We solve simple problems in "quantum chemistry in algebraic variety'' by means of algebraic approach. Finally, we review several topics related to polynomial computation, whereby we shall have an outlook for the future direction of the research.

Tributyltin (TBT) is one of the most toxic anthropogenic compounds introduced into the marine environment. Despite its global ban in 2008, TBT is still a problem of great concern due to its high affinity for particulate matter, providing a direct and potentially persistent route of entry into benthic sediments. Bioremediation strategies may constitute an alternative approach to conventional physicochemical methods, benefiting from the microorganism’s potential to metabolize anthropogenic compounds. In this work, a simple, precise and accurate static headspace gas chromatography method was developed to investigate the ability of TBT degrading microbes in sedimentary microcosms over a period of 120 days. The proposed method was validated for linearity, repeatability, accuracy, specificity, limit of detection and limit of quantification. The method was subsequently successfully applied for the detection and quantification of TBT and degrading compounds in sediment samples on day 0, 30, 60, 90 and 120 of the experiment employing the principles of green chemistry. On day 120 the concentration of TBT remaining in the microcosms ranged between 91.91 ng/g wet wt for the least effective microbial inoculant to 52.73 ng/g wet wt for the most effective microbial inoculant from a stating concentration of 100 ng/g wet wt.

This paper describes the development of a two-dimensional water quality model that solves hydrodynamic equations tied to transport equations with reactions mechanisms inherent in the processes. This enable us to perform an accurate assessment of the pollution in a coastal ecosystem. The model was developed with data drawn from the ecosystem found in Mexico's southeast state of Tabasco. The coastal ecosystem consists of the interaction of El Yucateco lagoon with the Chicozapote and Tonalá rivers, that connect the lagoon with the Gulf of Mexico. We present the results of pollutants transport simulation in the coastal ecosystem, focusing on toxic parameters for two hydrodynamic scenarios: wet and dry seasons. As it of interest in the zone, we study the transport of four metals: Cadmium, Chromium, Nickel and Lead. In order to address our objectives we solved numerically a self-posed mathematical problem,which is based on the measured data. The performed simulations show to characterise metal transport within the acceptable range of accuracy and in accordance with the measured data. The performed simulations show to characterise metals transport with an acceptable accuracy, agreeing well with measured data in total concentrations in four control points along the water body. Although for the accurate implementation of the hydrodynamic-based water quality model herein presented, boundary (geometry, tides, wind, etc.) and initial (concentrations measurements) conditions are required, it poses as an excellent option when the distribution of solutes with high accuracy is required, easing environmental, economic and social management of coastal ecosystems.

Since fine powders tend strongly to adhesion and agglomeration, their processing with conventional methods is difficult or impossible. Typically, in order to enable the handling of fine powders, chemicals are added to increase the flowability and reduce adhesion. This contribution shows that instead of additives also vibrations can be used to increase the flowability, to reduce adhesion and cohesion, and thus to enable or improve processes such as precision dosing, mixing, and transport of very fine powders. The methods for manipulating powder properties are described in detail and prototypes for experimental studies are presented. It is shown that the handling of fine powders can be improved by using low-frequency, high-frequency or a combination of low- and high-frequency vibration.

In the last 20 years, a huge amount of experimental results about halogen bonding (XB) has been produced. Most of the systems have been characterized by solid state X-ray crystallography, whereas in solution the only routine technique is the titration (by using ¹H and ¹⁹F NMR, IR, UV-Vis or Raman spectroscopies, depending on the nature of the system), with the aim of characterizing the strength of the XB interaction. Unfortunately, the titration techniques have many intrinsic limitations and they should be coupled with other, more sophisticated techniques to have an accurate and detailed description of the geometry and stoichiometry of the XB adduct in solution. In this review, it will be shown how crucial information about XB adducts can be obtained by advanced NMR techniques, as Nuclear Overhauser Effect-based Spectroscopies (NOESY, ROESY, HOESY…) and diffusion NMR techniques (PGSE or DOSY).

Choice of the salts of therapeutic agents or active pharmaceutical ingredients (API) is based on the physicochemical properties of API and the dosage form considerations. The appropriate salt can have positive effect on overall therapeutic and pharmaceutical effects of API. However, the incorrect salt form can negatively affect the overall pharmaceutical outcomes of the API. This review addresses various criteria for choosing appropriate salt form along with the effect of salt forms on API’s pharmaceutical properties. In addition to comprehensive review of the criteria, this review also gives a brief historic perspective of the salt selection process.

The functionalization of polymeric substances is of great interest for the development of innovative materials for advanced applications. For many decades, the functionalization of chitosan has been a convenient way to improve its properties with the aim to prepare new materials with specialized characteristics. In the present article, we summarize the latest methods for the modification and derivatization of chitin and chitosan, trying to introduce specific functional groups under experimental conditions, which allow a control over the macromolecular architecture. This is motivated because an understanding of the interdependence between chemical structure and properties is an important condition for proposing innovative materials. New advances in methods and strategies of functionalization such as click chemistry approach, grafting onto copolymerization, coupling with cyclodextrins and reactions in ionic liquids are discussed.

The surface chemistry and the morphology of SnO2 nanowires, deposited by Vapour Phase Deposition (VPD) method on Au-covered silicon substrate, were studied before and after subsequent air exposure. For this purpose, surface-sensitive methods including X-ray Photoelectron Spectroscopy (XPS), Thermal Desorption Spectroscopy (TDS) and the Scanning Electron Microscopy (SEM) were applied. The studies presented within this paper allowed to determine the surface non-stoichiometry combined with the presence of carbon contaminations, in a good correlation with the surface morphology. The relative concentrations of the main components [O]/[Sn]; [C]/[Sn]; [Au]/[Sn] together with the O – Sn; O – Si bondings were analyzed. The results of TDS remained in a good agreement with the observations from XPS. Moreover, conclusions obtained for SnO2 nanostructures deposited with the use of Au catalyst were compared to the previous obtained for Ag-assisted tin dioxide nanowires. The information obtained within this studies are of great importance for the potential application of SnO2 nanowires deposited on Au covered Si substrate in the field of novel chemical nanosensor devices, since the results can provide an interpretation of how aging effects influence gas sensor dynamic characteristics.

We use a regional scale photochemical transport model to investigate the surface concentrations and column integrated amounts of ozone (O3) and nitrogen dioxide (NO2) during a pollution event that occurred in the St. Louis metropolitan region in 2012. These trace gases will be two of the primary constituents that will be measured by TEMPO (Tropospheric Emissions: Monitoring of Pollution), an instrument on a geostationary platform, which will result in a dataset that has hourly temporal resolution during the daytime and ~4 km spatial resolution. Although air quality managers are most concerned with surface concentrations, satellite measurements provide a quantity that reflects a column amount, which may or may not be directly relatable to what is measured at the surface. Our model results provide reasonably good agreement with observed surface O3 concentrations (correlation coefficients ranging from 0.69 to 0.87 at each of the nine monitoring stations in the St. Louis region), which is the only trace gas dataset that can be used for verification. The model shows that a plume of O3 extends downwind from St. Louis and contains an integrated amount of ozone of ~ 16 Dobson Units (DU; 1 DU = 2.69 x 1016 molecules cm-2), an amount lower than what was observed during two massive pollution episodes in the 1980s. Based on the smaller isolatable emissions coming from St. Louis, this quantity is not unreasonable, but may also reflect the reduction of photochemical ozone production due to the implementation of emission controls that have gone into effect since the 1980s.

Membrane-coupled RNA transport is an emerging theme in fungal biology. This review focuses on the RNA cargo and mechanistic details of transport via two inter-related sets of organelles: endosomes and extracellular vesicles for intra- and intercellular RNA transfer. Simultaneous transport and translation of messenger RNAs (mRNAs) on the surface of shuttling endosomes is a conserved process pertinent to highly polarised eukaryotic cells, such as hyphae or neurons. Here we detail the endosomal mRNA transport machinery components and mRNA targets of the core RNA-binding protein Rrm4. Extracellular vesicles (EVs) are newly garnering interest as mediators of intercellular communication, especially between pathogenic fungi and their hosts. Landmark studies in plant-fungus interactions indicate EVs as a means of delivering various cargos, most notably small RNAs (sRNAs), for cross-kingdom RNA interference. Recent advances and implications of the nascent field of fungal EVs are discussed and potential links between endosomal and EV-mediated RNA transport are proposed.

The exploitation and use of alternative synthetic methods, in the face of classical procedures that do not conform to the ethics of Green Chemistry, represent an ever present problem in pharmaceutical industry. The procedures for the synthesis of benzimidazoles have become a focus in synthetic organic chemistry, as they are building blocks of strong interest for the development of compounds with pharmacological activity. Various benzimidazole derivatives exhibit important activities such as antimicrobial, antiviral, anti-inflammatory and analgesic and some of the already synthesized compounds have found very strong application in medicine praxis. Here we report a selective and sustainable method for the synthesis of 1,2-disubstituted or 2-substituted benzimidazoles, starting from o-phenylenediamine in the presence of different aldehydes. The use of deep eutectic solvent (DES) both as reaction medium and reagent without any external solvent provides advantages in terms of yields as well as in the work up procedure of the reaction.

The spread of charging infrastructure (CIS) for battery electric vehicles is crucial for coping with the increasing number of electric vehicles. Therefore, the selection of ideal (fast-) charging locations determines acceptance, utilization and, thus, the economic viability of a single site or the whole charging network. The methodology of the Integrated Model Approach STELLA[1] for site identification of CIS uses proven methods of traffic modeling such as the classic four-step traffic modeling in a new context to enable statements regarding the positioning of CIS. Based on different spatial analyzes and characterizations of urban quarters, traffic generated by individuals is calculated using the FGSV approach of 2010. Because only (electric) motorized individual traffic is of importance for CIS, the share of trips is calculated by differentiating the modal split between various transport groups. One approach is to concretize the modal split share of public transport based on analyzes of different criteria and data sets, e.g. the accessibility of stops. The model approach STELLA, which also combines various extensive data (e.g. transport networks and traffic volumes, settlement structures, vehicle characteristics, power supply data and user requirements), is currently developed for a planning area covering the entire territory of the Federal Republic of Germany. [1] STELLA is the acronym for the German term "STandortfindungsmodell für ELektrische LAdeinfrastruktur”.

Roundabouts need capacity and safety improvements compatible with manual-driven, not only with autonomous vehicles. The signaling and control of roundabouts must evolve and incorporate current technologies. For that, we approach roundabouts as synchronous switches of vehicles. This paper describes Synchronous Roundabouts with Rotating Priorities, a roundabout control system based on vehicle platoons arriving at the roundabout at speed identical to the roundabout and within the time slot assigned to their entry, avoiding conflicts and stops, thus increasing roundabout capacity and safety. Signaling is visual for human drivers and also wireless for connected and autonomous vehicles. We evaluate analytically and with simulations roundabouts of different radius for several values of the average distance between vehicles. Average delays are 28,7 % lower, with negligible dispersion. The capacity improvements depend on design parameters: in our set is moderate for small roundabouts but goes up to 70-100 % for short distances and medium and large roundabouts.

Coupling the Maxwell tensor to the Riemann-Christoffel curvature tensor is shown to lead to a geometricized theory of electrodynamics. While this geometricized theory leads directly to the classical Maxwell equations, it also extends their interpretation by giving charge density and mass density, and the four-velocity that describes their motion geometric definitions. These geometric definitions are reminiscent of General Relativity’s interpretation of mass in terms of the scalar curvature R and hint at the emergence of gravity. The gravitational theory that does emerge is shown to be equivalent to Einstein’s General Relativity augmented by an energy-momentum tensor term that mimics the properties of dark matter and/or dark energy. In summary, the proposed geometrization of the Maxwell tensor puts both electromagnetic and gravitational phenomena on an equal footing with both being tied to the curvature of space-time. Using specific solutions to the proposed theory, the unification brought to electromagnetic and gravitational phenomena, as well as the relationship of those solutions to the corresponding solutions of the classical Maxwell and Einstein field equations are compared.

The origin of life was a cosmic event happened on primitive Earth. A critical problem to better understand the origins of life in Earth is to glimpse in which chemical scenarios the basic building blocks of biological molecules could be produced. Classic works in pre-biotic chemistry frequently considered early Earth as a homogeneous atmosphere constituted by chemical elements such as methane (CH₄), ammonia (NH₃), water (H₂O), hydrogen (H₂) and hydrogen sulfide (H₂S). Under that scenario, Stanley Miller was capable to produce amino acids and solved the question about the origin of proteins. Conversely, the origin of nucleic acids has tricked scientists for decades as nucleotides are complex though necessary molecules to allow the existence of life. Here we review possible chemical scenarios that allowed not only the formation of nucleotides but also other significant biomolecules. We aim to provide a theoretical solution for the origin of biomolecules at specific sites named “Prebiotic Chemical Refugia”. A prebiotic chemical refugium should therefore be understood as a geographic site in prebiotic Earth on which certain chemical elements were accumulated in higher proportion than expected, facilitating the production of basic biomolecules. Plus, this higher proportion should not be understood as static, but dynamic; once the physicochemical conditions of our planet changed periodically. This different concentration of elements, together with geochemical and astronomical changes along days, synodic months and years provided somewhat periodic changes in temperature, pressure, electromagnetic fields, and conditions of humidity; among other features. Recent and classic works suggesting most likely prebiotic refugia on which the main building blocks of biological molecules might be accumulated are reviewed and discussed.

: E-commerce sales surge represents a huge challenge for urban freight transport. Parcel lockers constitute a valid solution for addressing the challenges home deliveries imply. In fact, eliminating courier-consumer contact (also relevant for health-related issues, as made evident by COVID19 pandemic) and delivering in few predefined places might help coping with missed deliveries substantially. Furthermore, this option enables consolidated shipping and reducing delivery trip costs. This paper analyses and compares consumers’ preferences for alternative collection strategies. It investigates home delivery vs parcel locker use and forecasts their future market shares. This is performed based on both customers’ socio-economic variables and attributes characterising these alternative logistic fulfilment strategies. The case study considered rests upon a stated preference survey deployed in the city of Rome. The investigation specifically targets young people (i.e., population under 30 years) since they represent early adopters. Discrete choice models allow both quantifying the monetary value of parcel lockers attributes (i.e., willingness to pay measures) and estimating the potential demand for this innovative delivery scheme. Results show that distance and accessibility are the main choice determinants. Furthermore, there is an overall high propensity to adopt parcel lockers. This research can support policymakers when implementing such solutions.

This review presents an updated overview of research concerning Leishmania protein structures, primarily sourced from the Protein Data Bank (PDB), that play a role in the metabolic pathways of the Leishmania parasite. Furthermore, we assess the current progress in the identification and development of bioactive chemical agents aimed at addressing this substantially overlooked tropical disease. We have analyzed experimental data obtained from in vitro, in vivo and in silico sources. This data has been categorized into four main areas: a) vector taxonomy and geographic distribution; b) parasite taxonomy and geographic distribution; c) enzymatic functions of proteins engaged in parasite/host interactions throughout various developmental stages (such as oxidoreductases, transferases, hydrolases, lyases, isomerases, ligases, and cytokines); and d) established and experimental treatments employing bioactive chemical compounds. Our objective is to establish a foundational point of reference for research efforts concentrating on the elucidation of interaction mechanisms and the processes of ligand-protein activation/inactivation, specifically linked to Leishmania infections. Consequently, we emphasize enzymes recognized for their involvement in the biochemical pathways incited during Leishmania infection episodes. This review encapsulates the current understanding, offering insights to inform and direct future explorations aimed at targeting proteins and pathways to enhance the management of Leishmania-related diseases.

The impact of an unlicensed low-cost taxi in Bangladesh is very severe, especially in municipal cities. Day by day the numbers of unlicensed low-cost taxi are increasing by jumping up and creating pressure on traffic and transportation system. The aim of this study is to find out the causes of increasing illegal taxi and the extent of this vehicle in the municipalities of Bangladesh. Pabna municipality is used as a case study due to the more activeness of illegal taxi then the other municipalities. To achieve the objectives, the researcher used a qualitative approach to acquire more depth about the problems. Besides a direct observation of the study area, an open-ended questionnaire survey and HIS survey were conducted. The illegal low-cost taxi is very active it was analyzed through the field survey. A statistical model was developed to understand the actual causes of increasing illegal low-cost taxi, where ten predicted hypotheses (age, education level, marital status and family member support of illegal drivers, and the variable of commuter satisfaction e.g. safety, comfort, continuous service, affordability of service, reliability of service and driver behavior) were tested. The model was run through the multiple regression analyses technique in SPSS and the result proved that education level of illegal low-cost taxi drivers, and the commuter satisfaction variable (safety and comfort) had a positive and significant effect of increasing illegal low-cost taxi in the study area. However other variable had no significant effect in case of increasing illegal low-cost taxi. Besides the safety and comfort, steady job for the operators, provision of continuous, individual and door to door service system are the main reasons for increasing the illegal low-cost taxi in the study area. Finally, the researcher concludes with the requirement of some necessary action from the responsible authority on vehicular regulation for the improvement of the local public transport system in Bangladesh.

Legumes are important sources of nitrogen and, therefore, the nitrogen fixing ability of the legume-rhizobia symbiosis has great potential to improve crop yields or reduce nitrogen fertilizer use. Unfortunately, legumes face serious and increasing threats of both biotic and abiotic stresses among which Fe-deficiency has been increased from past years. Fe nutrient deficiency limits pulse production and nitrogen fixation by specifically affecting any one of the four phases of legume-rhizobium symbiosis. Although Fe in soil is often present in adequate quantities, it is mainly present in insoluble Fe-(III) precipitates, limiting its uptake and utilization. The present review has focused on the iron nutrition and deficiency and probable uptake, transport and metabolism in legumes.

In this paper is discussed sediment transport as a mechanical process that characterises a natural stream or channel flow regime. The objective of experimental work presented in this paper is to recall and to give another prospect of well-known Meyer-Peter and Müller approach for estimation of Shield’s number (θ_c,θ) in laboratory conditions, and calibration of dimensionless MPM number (A). For this purpose two different experiments are conducted, during the first experiment water amount flushed on the flume and bed slope was changed simultaneously until equilibrium state is achieved, meanwhile is estimated the critical Shield’s number (θ_c). While, during the second experiment, water amount was kept constant, only bed slope of flume was continuously tilted, meanwhile sediment, discharge and Shield’s number (θ) was determined for given hydraulic conditions. In addition calibration of dimensionless MPM number (A) was performed, where several iteration were considered until for (A=3.42), sediment discharge measured become almost equal with sediment discharge computed by using MPM formula. After these experiments, is concluded that MPM formula can be used also for other certain initial condition and similar procedure may be adopted to calibrate the dimensionless MPM number (A) .

In the smart city, information and communications technologies (ICTs) are proposed as solutions to urban challenges, including sustainability concerns. While sustainability commonly refers to economic and environmental dimensions, the concept also contains a social component. Our study asked how smartphone applications (apps) address social sustainability challenges in urban transport, if at all. We focused on transport disadvantages experienced due to low income, physical disability, and language barriers. A review of 60 apps showed that transport apps respond to these equity and inclusion issues in two ways: (a) by employing universal design in general-use apps; including cost-conscious features; and providing language options (b) by specifically developing smartphone apps for persons with disabilities. The article discusses the study by positioning it in the literature of smart cities as well as socially sustainable transport.

The field of Cooperative Intelligent Transport Systems and more specifically Pedestrians to Vehicles could be characterized as quite challenging, since there is a broad research area to be studied, with direct positive results to society. Pedestrians to Vehicles is a type of Cooperative Intelligent Transport System, within the group of Early Warning Collision/Safety System. In this article, we examine the research and applications carried out so far within the field of Pedestrians to Vehicles Cooperative Transport Systems by leveraging the information coming from Vulnerable Road Users’, smartphones. Moreover, an extensive literature review has been carried out in the fields of Vulnerable Road Users Outdoor Localisation via smartphones and Vulnerable Road Users Next Step/Movement Prediction, which are closely related to Pedestrian to Vehicle applications and research. We identify gaps that exist in these fields that could be improved/extended/enhanced or newly developed, while we address future research objectives and methodologies that could support the improvement/development of those identified gaps.

Mercury is a toxic pollutant emitted from both natural sources and through human activities. A global interest in atmospheric mercury has risen ever since the discovery of the Minamata disease in 1956. Properties of gaseous elemental mercury enable long range transport which can cause pollution even in pristine environments. Total gaseous mercury (TGM) was measured from winter 2016 to spring 2017 over the Baltic Sea. A Tekran 2357A mercury analyser was installed aboard the research and icebreaking vessel Oden for the purpose of continuous measurements of gaseous mercury in ambient air. Measurements were performed during a campaign along the Swedish east coast and in the Bothnian Bay near Lulea during the icebreaking season. Data was evaluated from Gothenburg using a plotting software and back trajectories for air masses were calculated. The TGM average of 1.365 ± 0.054 ng/m³ during winter and 1.288 ± 0.140 ng/m³ during spring was calculated as well as a total average of 1.362 ± 0.158 ng/m³. Back trajectories showed a possible correlation of anthropogenic sources elevating the mercury background level in some areas. There were also indications of depleted air, i.e., air with lower concentrations than average, being transported from the Arctic to northern Sweden resulting in a drop in TGM levels.

“Clickase” single-chain nanoparticles (Ck-SCNPs) are folded, enzyme-mimetic unimolecular polymeric nano-objects containing copper (Cu) ions able to catalyze the azide-alkyne Huisgen cycloaddition reaction in water and/or selected organic solvents, often in the presence of a reductant. Herein, we investigate the effect of morphology on catalytic activity of Ck-SCNPs synthesized by means of two different routes. An amphiphilic random copolymer composed of oligo(ethylene glycol) methyl ether methyl methacrylate (OEGMA) and 2-acetoacetoxy ethyl methacrylate (AEMA) units was used as precursor of these Ck-SCNPs. Folding was promoted through metal complexation between Cu(II) ions and beta-ketoester-containing AEMA moieties. The first route resulted in Ck-SCNPs1 containing Cu ions homogeneously distributed within each nanoparticle, whereas the second one promoted intra-chain clustering of Cu ions inside Ck-SCNPs2. A model fluorogenic “click” reaction between 9-(azidomethyl)anthracene and phenylacetylene, which was catalyzed either by Ck-SCNPs1 or Ck-SCNPs2, was used to unravel the effect of morphology on catalytic activity. This work paves the way to improve the catalytic activity of metallo-folded SCNPs through control of the intra-chain distribution of catalytic sites.

Hydrogenases are iron-sulfur enzymes that catalyze proton reduction and H₂ oxidation with outstanding efficiency. They are considered blueprints for the design of transition metal complexes, e.g. as heterogenous catalysts in the context of H₂ production from water. Moreover, hydrogenases are biological model systems for metal hydride chemistry and proton-coupled electron transfer. Depending on the composition of the active site cofactor, [NiFe]-hydrogenases are distinguished from [FeFe]-hydrogenases. The former binds a hetero bimetallic nickel/iron site, embedded in the protein by four cysteine ligands. The later, by contrast, carries a homo bimetallic iron/iron site attached to the protein by only a single cysteine. Carbon monoxide and cyanide ligands (CO/CN) at the active site facilitated detailed investigations of hydrogenase catalysis by infrared spectroscopy, owing to strong signals and redox-dependent frequency shifts. However, the details of proton transfer have not been addressed experimentally.We found that specific redox state transitions in [NiFe]- and [FeFe]-hydrogenase can be triggered by visible light to record extremely sensitive ‘light-minus-dark’ infrared difference spectra monitoring key amino acid residues as shown in the ToC figure. As these transitions are coupled to protonation changes, our data allowed investigating dynamic hydrogen-bonding changes that go well beyond the resolution of protein crystallography. In [NiFe]-hydrogenase, photolysis of the bridging hydride ligand in the ‘Ni-C’ state was followed by rapid accumulation of the ‘Ni-SI_a’ state and/or ‘Ni-L’ state. Infrared difference spectra in various isotopic media clearly indicated the formation of a protonated cysteine residue as well as hydrogen-bonding changes involving the COOH group of a glutamic acid residue and a ‘dangling water’ molecule. These findings are in excellent agreement with crystallographic analyses of [NiFe]-hydrogenase in the Ni-R state and allowed devising a molecular precise model of catalytic proton transfer. In [FeFe]-hydrogenase, an external redox dye was used to accumulate the ‘Hred’ state over the oxidized resting state ‘Hox’. Infrared difference spectra of wild-type enzyme and numerous amino acid variants indicated hydrogen-bonding changes involving the COOH groups of two glutamic acid residues. Moreover, we noted the deprotonation of an arginine residue. Crystallographic analyses of [FeFe]-hydrogenase in the Hox state failed to explain the rapid proton transfer due to a ‘breach’ in the succession of residues. To this end, our findings facilitated a molecular precise model of ‘discontinued’ proton transfer.The comparison of catalytic proton transfer in bimetallic hydrogenases emphasizes the role of the outer coordination sphere. We suggest that the stable protonation of a nickel-ligating cysteine in [NiFe]-hydrogenase has a crucial influence on the preferred direction of proton flow and catalysis (i.e., H₂ oxidation). On the contrary, proton transfer in [FeFe]-hydrogenase involves an adjacent cysteine as a relay group that promotes both proton release and proton uptake. We presume that this causes the notable bidirectionality of [FeFe]-hydrogenase. These observations must guide the design of biomimetic compounds for the production or consumption of H₂.

Fossils constitute the principal repository of data that allow for independent tests of hypotheses of biological evolution derived from observations of the extant biota. Traditionally, transformational series of structure, consisting of sequences of fossils of the same lineage through time, have been employed to reconstruct and interpret morphological evolution. More recently, a move toward an updated paradigm was fueled by the deliberate integration of developmental thinking in the inclusion of fossils in reconstruction of morphological evolution. The vehicle for this is provided by structural fingerprints – recognizable morphological and anatomical structures generated by (and reflective of) the deployment of specific genes and regulatory pathways during development. Furthermore, because the regulation of plant development is both modular and hierarchical in nature, combining structural fingerprints recognized in the fossil record with our understanding of the developmental regulation of those structures produces a powerful tool for understanding plant evolution. This is particularly true when the systematic distribution of specific developmental regulatory mechanisms and modules is viewed within an evolutionary (paleo-evo-devo) framework. Here, we discuss several advances in understanding the processes and patterns of evolution, achieved by tracking structural fingerprints with their underlying regulatory modules across lineages, living and fossil: the role of polar auxin regulation in the cellular patterning of secondary xylem and the parallel evolution of arborescence in lycophytes and seed plants; the morphology and life history of early polysporangiophytes and tracheophytes; the role of modularity in the parallel evolution of leaves in euphyllophytes; leaf meristematic activity and the parallel evolution of venation patterns among euphyllophytes; mosaic deployment of regulatory modules and the diverse modes of secondary growth of euphyllophytes; modularity and hierarchy in developmental regulation and the evolution of equisetophyte reproductive morphology. More generally, inclusion of plant fossils in the evo-devo paradigm has informed discussions on the evolution of growth patterns and growth responses, sporophyte body plans and their homology, sequences of character evolution, and the evolution of reproductive systems.

Prebiotic organic synthesis reactions catalyzed by Earth-abundant metal sulfides are key processes for understanding the evolution of biochemistry from inorganic molecules, yet the catalytic functions of sulfides have remained poorly explored in the context of the origins of life. Past studies on prebiotic chemistry have mostly focused on a few types of metal sulfide catalysts, such as FeS or NiS, which form limited types of products with inferior activity and selectivity. To explore the potential of metal sulfides on catalyzing prebiotic chemical reactions, here, the chemical diversity (variations in chemical composition and phase structure) of 304 natural metal sulfide minerals in a mineralogy database was surveyed and approaches to rationally predict the catalytic functions of metal sulfides are discussed based on advanced theories and analytical tools of electrocatalysis such as proton-coupled electron transfer, structural comparisons between enzymes and minerals, and in-situ spectroscopy. To this end, we introduce a model of geo-electrochemistry driven prebiotic synthesis for chemical evolution, as it helps us to predict kinetics and selectivity of targeted prebiotic chemistry under “chemically messy conditions”. We expect that combining the data-mining of mineral databases with experimental methods and theories developed in the field of electrocatalysis will facilitate the prediction and verification of catalytic performance under a wide range of pH and Eh conditions, and aid in the rational screening of mineral catalysts involved in the origins of life.

Shielding agents are commonly used to shield polyelectrolyte complexes, e.g. polyplexes, from agglomeration, precipitation in complex media, like blood, and thus enhance their circulation times in vivo. Since up to now primarily poly(ethylene glycol) (PEG) has been investigated to shield non-viral carriers for systemic delivery, we report on the use of polysarcosine (pSar) as a potential alternative for steric stabilization. A redox-sensitive, cationizable lipo-oligomer structure (containing two cholanic acids attached via a bioreducible disulfide linker to an oligoaminoamide backbone in T-shape configuration) was equipped with azide-functionality by solid phase supported synthesis. After mixing with small interfering RNA (siRNA), lipopolyplexes formed spontaneously and were further surface-functionalized with polysarcosines. Polysarcosine was synthesized by living controlled ring-opening polymerization using an azide-reactive dibenzo-aza-cyclooctyne-amine as an initiator. The shielding ability of the resulting formulations was investigated with biophysical assays and by near-infrared fluorescence bioimaging in mice. The modification of ~100 nm lipopolyplexes was only slightly increased upon functionalization. Cellular uptake into cells was strongly reduced by the pSar shielding. Moreover, polysarcosine-shielded polyplexes showed enhanced blood circulation times in bioimaging studies compared to unshielded polyplexes and similar to PEG-shielded polyplexes. Therefore, polysarcosine is a promising alternative for the shielding of non-viral, lipo-cationic polyplexes.

Public Transport has been seen since ages as the most environmentally sustainable mode of transport. The users of public transport are diverse and have different socio-economic character. Hence the public transport which is not only supposed to be environmentally sustainable but also envisaged to ensure equity amongst various stakeholders of society like the females, elderly and other vulnerable groups through its service. Gender in binary terms of being differentiated based on men and women is a social construct. Public transport systems in developing countries like India witness socio-cultural factors that shape the experience of women in public spaces by social norms extant in society. Along with this, gender-based issues related to public transport are social and behavioural shortcomings as a consequence of a lack of gender sensitivity. On similar lines, elderly have a negative experience involving safety threats, physical and psychological discomfort while accessing public transport systems. The literature published regarding such issues on the gender and elderly question in public transport systems have been studied and has been brought forth under a stand- alone narrative literature review. A literature review is a prerequisite to conducting either stand-alone reviews or as a preliminary study to be supported with quantitative or qualitative analysis. Here, a stand-alone literature review concerning issues in the public transport system in India has been performed. A narrative type of review is conducted to provide an overview of pre- existing published literature. Narrative overviews are useful educational articles as they help present a broad perspective on a topic and often define the development of a problem and/or ways to manage it. The semi-systematic or narrative-review approach is designed for topics that have been theorized differently and studied within diverse disciplines making it unfavourable to study under a full systematic-review process which majorly caters to reviewing quantitative researches. As narrative-styled literature reviews prefer a semi- systematic data collection method, utmost care has been taken to include perspectives from diverse disciplines. The scope of this review is restricted to summarizing the Indian policies, schemes of public transport in light of socio-equity consideration while narrowing the inherent discrepancies within the socio-cultural ethos of the Indian society which influences socio-equity consideration in public spaces in general and the modes of public transport in particular. Research articles from electronic databases were selected based on relevance to understand the issues this viewpoint, their essential findings and possible recommendations are formulated to provide a comprehensive summary of previous researches.

Today, transit control systems go beyond simple controllers located at the intersections of our streets, involving large companies in the field, which with the implementation and use of sophisticated equipment encompass endless new and advanced technologies that manage to give control to the massive automotive park, thus ensuring fluidity and road safety. Many of these systems are used in the big world capitals, which is why the model used in Santiago, Chile is a system applied and brought directly by the SIEMENS Company of England (specifically the system used in the City of London). It is capable of transmitting the different control signals in a similar and digital way from the different interconnected devices in and out of the road infrastructure.

According to the changed operative conditions due to lockdown and successive reopening a number of facts can be analysed. The main effects have been detected on: mobility, environment, social media and people flows. While in this first report only mobility, transport and environment are reported. The analysis performed identified a strong reduction of the mobility and transport activities, and in the pollutants. The mobility reduction has been assessed to be quite coherent with respect to what has been described by Google Global mobility report. On the other hand, in this paper a number of additional aspects have been put in evidence providing detailed aspects on mobility and parking that allowed us to better analyze the impact of the reopening on an eventual revamping of the infection. To this end, the collected data from the field have been compared from those of google and some considerations with respect to the Imperial college Report 20 have been derived. For the pollutant aspects, a relevant reduction on most of them has been measured and rationales are reported.

BTB domain and CNC homology 1 (BACH1) is a highly expressed transcription factor in tumors including breast and lung, relative to their non-tumor tissues. BACH1 is known to regulate multiple physiological processes including heme homeostasis, oxidative stress response, senescence, cell cycle, and mitosis. In a tumor, BACH1 promotes invasion and metastasis of cancer cells, and the expression of BACH1 presents a poor outcome for cancer patients including breast cancer patients. Recent studies identified novel functional roles of BACH1 in the regulation of metabolic pathways in cancer cells. BACH1 inhibits mitochondrial metabolism through transcriptional suppression of mitochondrial membrane genes. In addition, BACH1 suppresses activity of pyruvate dehydrogenase (PDH), a key enzyme that converts pyruvate to acetyl-CoA for the citric acid (TCA) cycle through transcriptional activation of pyruvate dehydrogenase kinase (PDK). Moreover, BACH1 increases glucose uptake and lactate secretion in aerobic glycolysis through the expression of metabolic enzymes involved such as hexokinase 2 (HK2) and glyceraldehyde 3- phosphate dehydrogenase (GAPDH). Pharmacological or genetic inhibition of BACH1 could reprogramme metabolic pathways, subsequently rendering metabolic vulnerability of cancer cells. Furthermore, inhibition of BACH1 decreased antioxidant-induced glycolysis rates as well as reduced migration and invasion of cancer cells, suggesting BACH1 as a potentially useful cancer therapeutic target.

Geochemists disagree whether or not prebiotic chemistry has existed already during the Hadean Eon and whether the then terrestrial atmosphere has been strongly or weakly reduced. Here I argue that cellular life has existed already just after the end of the Hadean Eon and that terrestrial life has survived a number of cataclysms during the Earth's history. I argue that although organic molecules have been detected in meteorites that most organic molecules required for the formation of macromolecules must have been formed on Earth. Finally, I argue that the primitive terrestrial atmosphere during the Hadean Eon has been weakly reduced, so that amino acids and small nucleic acids could have been formed. I suggest that the first self-replicable macromolecules have been similar to viroids.

The combination of eco-respectful epoxy compounds with the humins, a by-product of biomass chemical conversion technologies, allow the obtention of materials with high added value. In this work, we propose the chemical connection study of humins with two aliphatic diepoxides through the copolymerization reactions to synthesize sustainable bio-based thermosets. The mechanism insights for the crosslinking between the epoxides and humins was proposed considering the different functionalities of the humins structure. FT-IR spectroscopy, 1 D and 2 D NMR spectroscopy techniques were used to build the proposed mechanism. By these techniques, the principal chain connections and the reactivity of all the components were highlighted in the synthesized networks.

Novel 1,2,3-triazole compounds 3–4 were synthesised via the regioselective addition and cyclization reaction of 1,1-enediamines (EDAMs) 1 with p-methylbenzenesulfonyl azide (TsN₃) 2 in 1,4-dioxane at refluxing for 5 hours. As a result, 1,2,3-triazoles 3–4 can be easily and efficiently obtained via catalyst-free click chemistry. The reactions have some advantages such as metal-free catalyst, excellent yield, inexpensive raw materials, and convenient final treatment.

Surface passivation, which has been intensively studied recently, is essential for the perovskite solar cells (PSCs), due to the intrinsic defects in perovskite crystal. A series of chemical or physical methods have been published for passivating the defects of perovskite, which effectively suppressed the charge recombination and enhanced the photovoltaic performance. In this study, the n-type semiconductor of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) is dissolved in chlorobenzene (CB) for the surface passivation during the spin-coating process for depositing the two-dimensional (2D) perovskite film. This approach simplifies the fabrication process of 2D PSCs and benefits the film quality. As a result, the defects of perovskite film are effectively passivated by this method. A better perovskite/PCBM heterojunction is generated, exhibiting an increased film coverage and improved film morphology of PCBM. It is found that this technology results in an improved electron transporting performance as well as suppressed charge recombination for electron transport layer. As a result, PSCs based on the one-step formed perovskite/PCBM heterojunctions exhibit the optimized power conversion efficiency of 15.69% which is about 37% higher than that of regular perovskite devices. The device environmental stability is also enhanced due to the quality-improved electron transport layer.

The formal transfer of GNSS under water is not possible. It probably makes sense to talk only about the transformation of GPS into LPS, that is, in the Local Position System. However, the basic methods that are used to solve the problem of Spoofing Detection above water can be used under water. It should be understood that engineering problems are significantly different, since the nature of the propagation of acoustic waves in water and electromagnetic waves in the atmosphere are fundamentally different. In this article, we will limit the navigation with acoustically passive receiver. The receiver “listens” to the buoys and solves the problem of finding its own position based on the coordinates of the buoys (such systems are called GNSS-like Underwater Positioning Systems or GNSS-like UPS). Depending on the scale of system service areas, GNSS-like UPS are divided into global, regional, zonal and local system. In this article, we will limit ourselves to considering only local GNSS-like UPS. The acoustic signal generator transmits a signal simulation of several satellites. If the level of the simulated signal exceeds the signal strength of real satellites, the receiver of UPS will “capture” the fake signal and calculate the false position based on it.

Micromobility has gained attention from policymakers, industry stakeholders, and academia; however, a comprehensive conceptualization of micromobility is still missing. Existing definitions are largely vehicle-centric: either listing modes or detailing vehicle characteristics. This paper addresses this gap by developing a ‘beyond vehicles’, multi-dimensional conceptualization of micromobility, accompanied by a novel socio-technical definition. Through a review of related concepts, combined with an analysis of the use and definitions of the term micromobility in publications, this study establishes a new conceptualization of micromobility. It incorporates human, social, and cultural dimensions, considers environmental, economic, infrastructure, vehicle technology, regulatory and policy aspects, and considerations for public health. Our definition of micromobility encompasses a wide range of mobility options typically used for shorter trips and manoeuvrable by an individual without motor assistance, at least for short distances. These modes are characterized by their ‘micro’ attributes, including low energy demand, environmental impact, and road space use relative to automobility. The conceptualization incorporates a range of micromobility modes, including fully human-powered (including walking), partially motor-assisted, and fully powered options. These modes typically operate at speeds not exceeding 25 to 32 kilometres per hour (or 45 km/h for faster options), weigh (typically substantially) below 350 kilograms and often yield significant (public) health benefits. Trip length is generally less than 15 kilometres, and daily distances under 80 kilometres. Importantly, our definition includes the practices, policies, cultures, and infrastructures that emerge around the use of micromobility options and shape their uptake. This proposed conceptualization significantly broadens the prevailing vehicle-focus in micromobility debates towards a socio-technical perspective. Embracing a widely accepted conceptualisation of micromobility would offer several advantages, including robust design standards, legislation, and evaluation metrics and methods. Additionally, this paper highlights the pivotal role micromobilities can play in transcending the limitations of automobility, towards more sustainable and equitable mobility futures.

In this report we have discussed the important role of molecular modeling, especially the use of the molecular dynamics method, in investigating transport processes in nanoporous materials such as membranes. With the availability of high performance computers, molecular modeling can now be used to study rather complex systems at a fraction of the cost or time requirements of experimental studies. Molecular modeling techniques have the advantage of being able to access spatial and temporal resolution which are difficult to reach in experimental studies. For example, sub-Angstrom level spatial resolution is very accessible as is sub-femtosecond temporal resolution. Due to these advantages, simulation can play two important roles: Firstly because of the increased spatial and temporal resolution, it can help understand phenomena not well understood. As an example, we discuss the study of reverse osmosis processes. Before simulations were used it was thought the separation of water from salt was purely a coulombic phenomenon. However, by applying molecular simulation techniques, it was clearly demonstrated that the solvation of ions made the separation in effect a steric separation and it was the flux which was strongly affected by the coulombic interactions between water and the membrane surface. Additionally, because of their relatively low cost and quick turnaround (by using multiple processor systems now increasingly available) simulations can be a useful screening tool to identify membranes for a potential application. To this end, we have described our studies in determining the most suitable zeolite membrane for redox flow battery applications. As computing facilities become more widely available and new computational methods are developed, we believe molecular modeling will become a key tool in the study of transport processes in nanoporous materials.

Reemergence of deep Neural Networks (CNNs) has lead to high-performance supervised learning algorithms for the Electro-Optical (EO) domain classification and detection problems. This success is possible because generating huge labeled datasets has become possible using modern crowdsourcing labeling platforms such as Amazon Mechanical Turk that recruit ordinary people to label data. Unlike the EO domain, labeling the Synthetic Aperture Radar (SAR) domain data can be a lot more challenging and for various reasons using crowdsourcing platforms is not feasible for labeling the SAR domain data. As a result, training deep networks using supervised learning is more challenging in the SAR domain. In the paper,we present a new framework to train a deep neural network for classifying Synthetic Aperture Radar (SAR) images by eliminating the need for huge labeled dataset. Our idea is based on transferring knowledge from a related EO domain problem, where labeled data is easy to obtain. We transfer knowledge from the EO domain through learning a shared invariant cross-domain embedding space that is also discriminative for classification. To this end, we train two deep encoders that are coupled through their last year to map data points from the EO and the SAR domains to the shared embedding space such that the distance between the distributions of the two domains is minimized in the latent embedding space. We use the Sliced Wasserstein Distance (SWD) to measure and minimize the distance between these two distributions and use a limited number of SAR label data points to match the distributions class-conditionally. As a result of this training procedure, a classifier trained from the embedding space to the label space using mostly the EO data would generalize well on the SAR domain. We provide theoretical analysis to demonstrate why our approach is effective and validate our algorithm on the problem of ship classification in the SAR domain by comparing against several other learning competing approaches.

The aim of this study is to introduce a novel method which can separate sand or gravel dominated bed load transport in rivers with mixed-size bed material. In engineering practice, the Shields-Parker diagram could be used for such purposes, however, the method has certain applicability limits, due to the fact that it is based on uniform bed material and provides information rather on river-scale, instead of reach or local scale. When dealing with large rivers with complex hydrodynamics and morphodynamics the bed load transport modes can also indicate strong variation even locally, which requires a more suitable approach to estimate the locally unique behavior of the sediment transport. Here, we suggest that the decision criteria utilizes the shear Reynolds number (Re*). The method was verified against field and laboratory measurement data, both performed at non-uniform bed material compositions. The comparative assessment of the results show that the shear Reynolds number based method operates more reliably than the Shields-Parker diagram and it is expected to predict the sand or gravel transport domination with a < 5% uncertainty. The introduced results can greatly contribute to the improvement of numerical sediment transport modeling as well as to the field implementation of bed load transport measurements.

Sediment transport is highly sensitive to flow conditions, showing significant increase during flood events. Based on this principle, this study set out to rank flood events occurring along river Trotuș (Romania) based on the amount of transported sediment and event duration. The 77 flood events recorded from 2000 to 2017 were ranked into 4 classes: type A (4%); type B (16%), type C (14%) and type D (66%). The sediment transport specific for the 4 types of flood events was related to the flow discharge (sediment rating curve and hysteresis effect), the specific stream power and the energy expenditure of these events. More than 60% of the hysteresis loops typical for flood events were clockwise, thus singling out the channel as the main sediment source. Ca. 74% of the total sediment yield was transported at stream power values higher than the 300 Wm-2 threshold, which was exceeded in less than 1% of the investigated timeframe. The changes occurring in the sediment transport rates after major floods show that these events are significant thresholds in the hydrogeomorphic evolution of river channels.

The Simplified Spherical Harmonic (SPN) approximation was first introduced as a three-dimensional (3-D) extension of the plane-geometry Spherical Harmonic (PN) equations. A third order SPN (SP3) solver, recently implemented in the Nodal Expansion Method (NEM), has shown promising performance in the reactor core neutronics simulations. This work is focused on the development and implementation of the transport corrected interface and boundary conditions in NEM SP3 solver, following recent published work on the rigorous SPN theory for piecewise homogeneous regions. A streamlined procedure has been developed to generate the flux zero and second order/moment discontinuity factors (DFs) of the generalized equivalence theory to eliminate the error introduced by pin-wise homogenization. Moreover, several color set models with varying size and configuration are later explored for their capability of generating DFs that can produce results equivalent to that using the whole-core homogenization model for more practical implementations. The new developments are tested and demonstrated on the C5G7 benchmark. The results show that the transport corrected SP3 solver shows general improvements to power distribution prediction compared to the basic SP3 solver with no DFs or only zero order/moment DFs. The complete equivalent calculations using the DFs can almost reproduce transport solutions with high accuracy. The use of equivalent parameters from larger size color set models show better prediction in the whole-core calculations. By coupling different color set models DFs can offer the best accuracy at both eigenvalues and power distributions.

Daily thousands of people and goods move along Brazilian Federal highways. Traffic accidents are numerous on these highways and have a significant impact, whether on the economy or the health system. Identifying predictor variables, the probability of an event occurring and how to mitigate them are of paramount importance for the actions of the transit authorities that manage these roads. The main contribution of this study is the development of a predictive machine learning model which uses open data to shows graphically the critical points in the highways. This model is fully reproducible and can be applied to any region worldwide helping to minimize the number of accidents and to prevent deaths by automotive collisions. For this study, 43 variables were analyzed supporting the identification of the causes of accidents with fatal victims on the main highways in the south of Brazil. RoadLytics is proposed as a supervised machine learning model, using the Random Forest algorithm to analyze about 33 thousand occurrences between 2017 and 2020. An exploratory analysis of the data was carried out to support the modeling and to facilitate data visualization. In this sense, heat maps were developed to support the analysis and identification of potential risk areas. The results show that BR386 highway registers the highest number of fatal occurrences, regardless of the season. Additionally, concerning the weather conditions, the analysis shows that 52% of accidents occurred in favorable conditions, such as clear skies, victimizing 501 people. The driver’s lack of attention is the main reason for the accidents’ occurrences. Applying the developed model, an accuracy of 77% was achieved for the classification of fatal accidents.

Transport Layer Security (TLS) is a cryptographic protocol that provides communications security between two peers and it is widely used in many applications. To reduce the latency in TLS handshake session resumption using pre-shared key (PSK) had been used. But current methods in PSK mode handshake uses a fixed session key multiple times for the lifetime of session ticket. Reuse of fixed session key should be very careful in the point of communications security. It is vulnerable to replay attacks and there is a possibility of tracking users. Paired token (PT) is a new secondary credential scheme that provides pre-shared key in stateless way in client-server environment. Server issues paired token (public token and secret token) to authenticated client. Public token represents signed identity of client and secret token is a kind of shared secret between client and server. Once client is equipped with PT, it can be used for many symmetric key based cryptographic applications such as authentication, authorization, key establishment, etc. It was also shown that it can be used for one-time authenticated key establishment using the time-based one-time password (TOTP) approach. In this paper we apply the PT and TOTP approach to TLS to achieve stateless one-time authenticated session resumption. Server executes full handshake of TLS 1.3 and issues PT to authenticated client. Then client and server can execute one-time authenticated session resumption using PT in stateless way in server side. In every runs of session resumption distinct session keys are established that the same PT can be used safely for longer lifetime. If anonymous PT is used with renewal issuing, user privacy, untraceability and forward security can be achieved easily. It will provide a huge performance gain in large-scale distributed services.

Classical k-ratio models, e.g. ZAF and phi(rho z), used in electron probe microanalysis (EPMA) assume a homogeneous or multi-layered material structure, which essentially limits the spatial resolution of EPMA to the size of the interaction volume where characteristic x-rays are produced. We present a new model for characteristic x-ray emission that avoids assumptions on the material structure to not restrict the resolution of EPMA a-priori. Our model bases on the spherical harmonic (PN) approximation of the Boltzmann equation for electron transport in continuous slowing down approximation. PN models have a simple structure, are hierarchical in accuracy and well-suited for efficient adjoint-based gradient computation, which makes our model a promising alternative to classical models in terms of improving the resolution of EPMA in the future. We present results of various test cases including a comparison of the PN model to a minimum entropy moment model as well as Monte-Carlo (MC) trajectory sampling, a comparison of PN-based k-ratios to k-ratios obtained with MC, a comparison with experimental data of electron backscattering yields as well as a comparison of PN and Monte-Carlo based on characteristic X-ray generation in a three-dimensional material probe with fine structures.

A series of dinuclear copper(I) N,C,N- and P,C,P-carbodiphosphorane (CDP) complexes using multidentate ligands CDP(Py)2 (1) and (CDP(CH2PPh2)2 (13) have been isolated and characterized. Detailed structural information was gained by single crystal XRD analyses of nine representative examples. The common structural motive is the central double ylidic carbon atom with its characteristic two lone-pairs involved into binding of two geminal L-Cu(I) fragments at Cu-Cu distances in the range 2.55 – 2.67 Å. In order to enhance conformational rigidity within the characteristic Cu-C-Cu triangle, two types of chelating side arms were symmetrically attached to each phosphorus atom: two 2-pyridyl functions in ligand CDP(Py)2 (1) and its dinuclear copper complexes 2-9 and 11, as well as two diphenylphosphinomethylene functions in ligand CDP(CH2PPh2)2 (13) and its di- and mononuclear complexes 14-18. Neutral complexes were typically obtained via reaction of 1 with Cu(I) species CuCl, CuI, and CuSPh or via salt elimination reaction of [(CuCl)2(CDP(Py)2] (2) with sodium carbazolate. Cationic Cu(I) complexes were prepared upon treating 1 with two equivalents of [Cu(NCMe)4]PF6, followed by the addition of either two equivalent of an aryl phosphine (PPh3, P(C6H4OMe)3) or one equivalent of a bisphosphine ligands DPEPhos, XantPhos or dppf. For the first time carbodiphosphorane CDP(CH2PPh2)2 (13) could be isolated upon treating its precursor [CH(dppm)2]Cl (12) with NaNH2 in liquid NH3. A protonated and a deprotonated derivative of ligand 13 were prepared and their coordination was compared to neutral CDP ligand 13. NMR analysis and DFT calculations reveal, that the most stable tautomer of 13 does not show a CDP (or carbone) structure in its uncoordinated base form. For most of the prepared complexes, photoluminescence upon irradiation with UV light at room temperature was observed. Quantum yields (PL) were determined to 36% for dicationic [(CuPPh3)2(CDP(Py)2)](PF6)2 (4) and to 60% for neutral [(CuSPh)2(CDP(CH2PPh2)2] (16).

The cross-linkable PCL-PEG analogues block-graft copolymer was designed and synthesized, which with the copolymer of the MEO₂MA and OEGMA as graft chains to improve the mPEG-b-PCL-b-mPEG copolymer the aqueous solution properties. And successfully prepared two hydrogels via a copper-catalyzed 1, 3-dipolar azide-alkyne cycloaddition reaction of alkyne-terminated poly[glycidyl methacrylate-co-2-(2-methoxyethoxy) ethyl methacrylate-co-oligo (ethylene glycol) methacrylate] [P(GMA-co-MEO₂MA-co-OEGMA)] with azide end-functionalized PCL-PEG analogues block-graft copolymer, and tetrakis (2-propynyloxymethyl) -methane (TPOM) and with azide end-functionalized PCL-PEG analogues block-graft copolymer. The copolymer's chemical structure was characterized by proton nuclear magnetic resonance spectroscopy and fourier transform infrared spectroscopy. The molecular weights of the copolymers were decided with gel permeation chromatography. The water solubility and temperature sensitivity of the copolymers were studied by taking digital photos and transmittance change measured by UV spectrophotometer at different temperatures. Fluorescence probes, surface tension, dynamic light scattering and transmission electron microscopy were used to analyze the micelles that copolymers self-assembly in aqueous solution. The sol-gel behavior of copolymer solutions at high concentrations was explored by vial inversion experiments. Finally, the network structure of the gels was observed by scanning electron microscopy. These conclusions indicate that these hydrogels are expected to be used as a new material in the field of biomedicine.

Traffic source emissions inventories for the rapidly growing West African urban cities are necessary for better local characterization of vehicle emissions released into these cities atmosphere. This study based on local field campaign in a representative site of anthropogenic activities over West African cities such as Yopougon (Abidjan, Côte d'Ivoire) during 2016, provided useful information on vehicle type and age, traveling time, fuel type and amount for fuel consumption estimation. Also, high traffic flow of personal car were recorded on highway, boulevard and backstreet whereas high flows of intra-communal sedan taxi are recorded on main and secondary roads. In addition, the highest daily fuel consumption value of 56 L.day^-1 was recorded in heavy vehicle while the lowest value of 15 L.day^-1 is recorded for personal car using gasoline. This study will be useful for the improvement of uncertainties related to the different databases used to estimate inventories emissions either national or international reports. This work provides useful information for future studies on urban air quality, climate and health impacts assessment in African cities. It may also be useful for policy makers to support implementation of emission reduction policy in West African cities.

We report the electronic, magnetic and transport properties of a prototypical antiferromagnetic (AFM) spintronic device. We chose Cr as the active layer because it is the only room-temperature AFM elemental metal. We sandwiched Cr between two non-magnetic metals (Pt or Au) with large spin-orbit coupling. We also inserted a buffer layer of insulating MgO to mimic the structure and finite resistivity of a real device. We found that, while spin-orbit has a negligible effect on the current flowing through the device, the MgO layer plays a crucial role. Its effect is to decouple the Cr magnetic moment from Pt (or Au) and to develop an overall spin magnetization. We have also calculated the spin-polarized ballistic conductance of the device within the Büttiker-Landauer framework, and we have found that for small applied bias our Pt/Cr/MgO/Pt device presents a spin polarization of the current amounting to ~25%.

Leucokinins (LKs) constitute a family of neuropeptides identified in numerous insects and many other invertebrates. The LKs act on G-protein coupled receptors that display only distant relations to other known receptors. In adult Drosophila, 26 neurons/neurosecretory cells of three main types express LK. The four brain interneurons are of two types, and these are implicated in several important functions in the fly’s behavior and physiology, including feeding, sleep-metabolism interactions, state-dependent memory formation, as well as modulation of gustatory sensitivity and nociception. The 22 neurosecretory cells (ABLKs) of the abdominal neuromeres coexpress LK and a diuretic hormone (DH44), and together these regulate water and ion homeostasis and associated stress, as well as food intake. In Drosophila larvae, LK neurons modulate locomotion, escape responses, and aspects of ecdysis behavior. A set of lateral neurosecretory cells, ALKs, in the brain express LK in larvae, but inconsistently so in adults. These ALKs coexpress three other neuropeptides and regulate water and ion homeostasis, feeding and drinking, but the specific role of LK is not yet known. This review summarizes Drosophila data on embryonic lineages of LK neurons, functional roles of individual LK neuron types, interactions with other peptidergic systems, and orchestrating functions of LK.

Effective maintenance of railways requires a comprehensive assessment of the actual condition of the construction materials involved. In this regard, Ground-Penetrating Radar (GPR) stands as a viable alternative to the invasive and time-consuming traditional techniques for the inspection of these infrastructures. This work reports the experimental activities carried out on a test-site area within a railway depot in Rome, Italy. Specifically, a 30 m-long railway section was divided into 10 sub-sections reproducing different various physical and structural conditions of the track-bed. In more detail, combinations of varying scenarios of fragmentation and fouling of the ballast were reproduced. The set-up was then investigated using different multi-frequency GPR horn antenna systems. The effects of the different physical conditions of ballast on the electromagnetic response of the material were analysed for each scenario using time- and frequency-domain signal processing techniques. Parallel to this, modelling was provided to estimate fouling content. Interpretation of results has proven the viability of the GPR method in detecting signs of decay at the network level, thereby proving this technique to be worthy for implementation in asset management systems.

The main regulatory factors during the adaptation of cancer cells to hypoxic stress are the hypoxia-inducible factors (HIFs), which are being increasingly recognized as an interesting and challenging target for the design of new chemotherapeutic molecules. HIF2A was found to have an large internal hydrophilic cavity within its PAS-B domain, unique to this sub-unit and is suggested to be a possible ligand-binding site. Regulation of HIF2A by cellular molecules is still greatly unknown. In This paper we have employed in-silico techniques, such as molecular docking and dynamic simulation, to design new direct inhibitors against HIF-2A subunit via targeting one of its critical domains and the final top screened molecules have been tested on hypoxic cancer cells for further validation of their inhibitory potential. we targeted the hydrophilic cavity inside the PAS-B domain of the HIF2A to identify novel molecules with a high binding capacity. Virtual Screening methodology was used for molecular docking of NSC library against the target domain inside the HIF2A PAS-B domain with the top 5% compounds with significant MolDock and Re-rank scores were selected for further analysis. The NSC 106416, NSC 217021, NSC 217026, and NSC 215639 compounds were selected based on their docking scores. NSC 215639 had the minimum polar solvation energy and also had a relative strong binding energy. NSC 217026 had the strongest binding energy among other compounds.