The increase in carbon dioxide emissions has a significant impact on human society and the global environment. As the most abundant and cheap C1 resource, the conversion and utilization of carbon dioxide has received extensive attention from researchers. In many methods of carbon dioxide conversion and utilization, the reverse water gas conversion reaction is considered to be one of the most effective ways. In this paper, the research progress of reverse water gas conversion reaction in recent years is introduced.

Water electrolysis is a compelling technology for the production of environmentally-friendly hydrogen, minimizing carbon emissions. The electrolysis process of water heavily relies on the effective and steady oxygen evolution reaction (OER) taking place at the anode. Herein, we in-troduce a highly promising catalyst for OER called CoSe2@NiFeOOH arrays, which are supported on a nickel foam. This catalyst, referred to as CoSe2@NiFeOOH/NF, is fabricated through a two-step process involving the selenidation of a Co-based porous metal organic framework and subsequent electrochemical deposition on a nickel foam. The CoSe2@NiFeOOH/NF catalyst demonstrates outstanding activity for the OER in an alkaline electrolyte. It exhibits a low over-potential (η) of 254 mV at 100 mA cm−2, a small Tafel slope of 73 mV dec−1, and excellent high stability. The high performance of CoSe2@NiFeOOH/NF can be attributed to the combination of the high conductivity of the inner layer and the synergistic effect between CoSe2 and NiFeOOH. This study offers an effective method for the fabrication of highly efficient catalysts for the OER.

To reduce environmental impacts from sodium silicate synthesis it was suggested the use of sugarcane bagasse ash (SCBA) as a source of silicon dioxide and sodium carbonate using the ceramic method. Although the production of sodium silicate is carried out on a large scale, it should be noted that its process requires temperatures above 1000 °C or the use of highly corrosive agents such as sodium hydroxide and chlorine gas used to neutralize the remaining sodium hydroxide. In the present work, the synthesis temperatures were reduced to 800 °C with a reaction time of 3 hours by pressing equimolar mixtures of previously purified SCBA and sodium carbonate, then heat treatment was carried out under the indicated conditions. The resulting materials were analyzed by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). Among the crystalline phases, calcium disodium silicate was identified, in addition to sodium silicate, so it was inferred that the other components of the ash can interfere with the synthesis of silicate. Therefore, to obtain the highest composition of sodium silicate, a leaching treatment of the SCBA is required.

With the evolution of toxic chemicals continuing to progress, developing methods for the destruction of chemical warfare agents (CWAs) has become an increasingly important research topic. Metal-organic frameworks (MOFs) are a class of porous crystalline solids that have sparked interest in this area. Due to their exceptional porosities and large surface areas, MOFs possess superior adsorption, reactivity, and catalytic abilities, making them structurally ideal candidates for the capture and decomposition of target species. Additionally, the tunable networks of MOFs allow their chemical functionalities to be customized for various applications and operating conditions, making them practicable in personal protective equipment and adjustable to dynamic environments. This paper reviews experimental and computational studies on CWA removal by MOFs, with a special emphasis on nerve agent (GB, GD, and VX) removal via hydrolysis and sulfur mustard (HD) removal via selective photooxidation. With extraordinary structural stability and reusability, zirconium-based MOFs are the most promising materials for hydrolytic and photooxidative degradation of CWAs and are thus the primary focus of this work. First-principles approximations of the intrinsic catalytic reaction mechanisms towards different agents in Zr-MOFs are summarized, and developments in the structure-property relationships governing Zr-MOF design rules for efficient degradation in the aqueous and solid phases are discussed. We also examine recent progress in tuning and functionalizing MOFs to promote practical CWA removal under realistic battlefield conditions.

The purpose of this study was to explore the association of cognition with hazardous drinking and alcohol related disorder in persons with bipolar disorder (BD). The study population included 1,268 persons from Finland with bipolar disorder. Alcohol use was assessed through hazardous drinking and alcohol related disorder including alcohol use disorder (AUD). Hazardous drinking was screened with the AUDIT-C (Alcohol Use Disorders Identification Test for Consumption) screening tool. Alcohol related disorder diagnoses were obtained from the national registrar data. Participants performed two computerized tasks from the Cambridge automated neuropsychological test battery (CANTAB) on tablet computer: the 5-choice serial reaction time task, or, reaction time (RT) test and the Paired Associative Learning (PAL) test. Association between RT-test and alcohol use was analyzed with log-linear regression, and eβ with 95% confidence intervals (CI) are reported. PAL first trial memory score was analyzed with linear regression, and β with 95% CI are reported. PAL total errors adjusted was analyzed with logistic regression and odds ratios (OR) with 95% CI are reported. After adjustment for age, education and housing status, hazardous drinking was associated with lower median and less variable RT in females while AUD was associated with a poorer PAL test performance in terms of the total errors adjusted scores in females. Our findings of positive associations between alcohol use and cognition in persons with bipolar disorder are unique.

Reverse water gas shift reaction (RWGS) is an important process which plays a vital role in many CO2 utilization related reactions. Noble metals are the most active catalysts in RWGS, but the high price and low reserve strangled their applications. In the present work, we reported a non-transition-metal MgAl2O4 catalyst which showed outstanding activity and stability at high temperatures in the RWGS reaction and improved performance after doping of single atomic Nin+. The catalyst can obtain 46% of CO2 conversion in durability test of 75 h at 800 °C under high weight hourly space velocities (225 000 ml g-1 h-1). The adsorption sites, possible reaction route, and effects of Nin+ single atoms on the (111) surface of MgAl2O4 for RWGS were investigated by in situ DRIFTS and DFT calculations. The results indicated that the rate determining reaction step of RWGS on MgAl2O4 and Ni (SA)/MgAl2O4 were both the reaction of OH* + H* → H2O* + *, but the energy barrier was significantly reduced after introducing single atomic Nin+. Nin+ atoms can increase the hydroxyl coverage on the surface of catalyst and Al3+ sites near the Nin+ ion are considered as the predominant active sites for RWGS reactions.

The prevalence of food allergy has increased in recent years, especially in children. Food allergen avoidance and symptomatic drugs in case of an allergic reaction remain the standard of care in food allergy. Nevertheless, increasing attention has been given to the possibility to treat food allergy, through immunotherapy, particularly oral immunotherapy (OIT). Several OIT protocols and clinical trials have been published. Most of them focus on children allergic to milk, egg, or peanuts, although recent studies developed protocols for other foods, such as wheat and different nuts. OIT efficacy in randomized controlled trials is usually evaluated as the possibility for patients to achieve desensitization, while the issue of a possible long-term sustained unresponsiveness has not been completely addressed. Here, we evaluated current OIT knowledge, focusing on the results of clinical trials and current guidelines. Specifically, we wanted to highlight what is known in terms of OIT efficacy and effectiveness, safety, and impact on quality of life. For each aspect, we reported the pros and the cons, inferable from published literature. In conclusion, even though many protocols, reviews and meta-analysis have been published on this topic, OIT remains a controversial therapy and no definitive generalized conclusion may be drawn so far. It should be an option provided by specialized teams, when both patients and their families are prone to adhere to the proposed protocol. Efficacy, long-term effectiveness, possible role of adjuvant therapies, risk of severe reactions including anaphylaxis or eosinophilic esophagitis, and impact on the quality of life of both children and caregivers are all aspects that should be discussed before starting OIT. Future studies are needed to provide firm clinical and scientific evidence, which should also consider patient reported outcomes.

The conversion of CO2 into more synthetically flexible CO is an effective and potential method for CO2 remediation, utilization and carbon emission reduction. In this paper, the reaction of carbon-carbon dioxide (Boudouard reaction) was performed in a microwave fixed bed reactor using semi-coke (SC) as both the microwave absorber and reactant and was systematically compared with that heated in a conventional thermal field. The effects of the heating source, SC particle size, CO2 flow rate and additives on CO2 conversion and CO output were investigated. By microwave heating (MWH), CO2 conversion reached more than 99 %, while by conventional heating (CH), the maximum conversion of CO2 was approximately 29% at 900 °C. Meanwhile, for the reaction with 5 wt% Barium Carbonate added as a promoter, the reaction temperature was significantly reduced to 750 °C with almost quantitative conversion of CO2. Further kinetic calculations showed that the apparent activation energy of the reaction under microwave heating was 46.3 kJ/mol, which was only one-third of that observed under conventional heating. The microwave-assisted Boudouard reaction with catalytic barium carbonate is a promising method for carbon dioxide utilization.

Polo is an equestrian team sport consisting of four players per team, with level of play determined by cumulative player handicap (-2 to + 10 goals), with a higher handicap denoting a better player. There is minimal literature investigating Polo players’ physical attributes, hence the understanding of the physical characteristics that may contribute to an improved handicap are unknown. This study sought to identify the relationship between pertinent strength measures (left and right hand grip strength; absolute and relative isometric mid-thigh pull) and reaction time in Polo handicap in 19 New Zealand Polo players, and ascertain whether handicap could be predicted by these measures. Correlation coefficients were expressed using R values, accompanying descriptors and 90% confidence intervals (C.I.). Variance explained was expressed via the R2 statistic, and statistical significance set at p < 0.05. Right hand grip strength, isometric mid-thigh pull values were found to significantly correlate to and explain variance within Polo player handicap (all moderate to large correlations; p< 0.05). Whereas left hand grip strength (R: 0.380; 90% C.I. -0.011 to 0.670) and reaction time (0.020; -0.372 to 0.406) were non-significant, moderate and trivial correlates and predictors of handicap respectively. Practically, these findings highlight the differing roles between rein and mallet hands of Polo players and emphasise the importance of a strong and stable platform when riding and striking the ball. Lack of association with reaction time may be explained in part by higher handicapped Polo players employing a more proactive approach to the game.

Sam Granick opened his seminal 1957 paper titled Speculations on the Origins and Evolution of Photosynthesis with the assertion that there is a constant urge in human beings to seek beginnings (I concur). This urge has led to an incessant stream of speculative ideas and debates on the evolution of photosynthesis that started in the first half of the twentieth century and shows no signs of abating. Some of these speculative ideas have become common place, are taken as fact, but find little support. Here I review and scrutinise three widely accepted ideas that underpin the current study of the evolution of photosynthesis: firstly, that the photochemical reaction centres used in anoxygenic photosynthesis are more primitive than those in oxygenic photosynthesis; secondly, that the probability of acquiring photosynthesis via horizontal gene transfer is greater than the loss of photosynthesis; and thirdly, and most importantly, that the origin of anoxygenic photosynthesis predates the origin of oxygenic photosynthesis. I shall attempt to demonstrate that these three ideas are often grounded on incorrect assumptions built on more assumptions with no experimental nor observational support. I hope that this brief review will not only serve as cautionary tale, but also that it will open new avenues of research aimed at disentangling the complex evolution of photosynthesis and its impact on the early history of life and the planet.

The development of novel porous composite materials for organic dye degradation and removal has received increasing attention due to water contamination problem. In this paper, hydrothermal synthesized nano zeolite A have been encapsulated with porous periodic mesoporous organosilica (PMO) through a simple modified StÖber method an organosilane-directed growth-induced etching strategy, the obtained yolk-shell structured sample was further functionalized by the impregnation of copper, realizing the composite material with hierarchical porous and catalytic properties. The morphology, porosity and metal content of the zeolite Cu/A and Cu/A@Et-PMO were fully characterized. As compared to the parent material, the composite Cu/A@Et-PMO have an efficient adsorption and catalytic degradation performance on methylene blue (MB), the removal efficiency reached as high as 95% of 60 mg/L MB with 10min. These novel structured porous composites may have great potential for adsorption and degradation application including waste effluents.

Membrane Inlet Mass Spectrometry (MIMS) was used to analyze monochloramine solutions (NH₂Cl) and ammonia solutions in a compact FTICR. Chemical ionization enables identification and quantification of the products present in the permeate. The responses of protonated monochloramine and ammonium increase linearly with the solution concentration. The enrichments were respectively 1.2 and 5.5. Pervaporation is dependent on pH and only the basic form of ammonia NH₃ pervaporates through the membrane. Unexpectedly, the small ammonia molecule permeated very slowly. It could be due to interactions with water molecules inside the membrane that create clusters. Moreover, NH₂Cl solutions, in addition to the NH₃Cl⁺ signal, presented a strong NH₄⁺ signal at m/z 18.034 . Ammonia presence in the low-pressure zone before ionization is probable as NH₄⁺ was detected with all the precursors used, particularly CF₃⁺ and trimethylbenzene that presents a proton affinity higher than monochloramine. Ammonia may be formed inside the membrane due to the fact that NH₂Cl is unstable and may react with the water present in the membrane. Those results highlight the need for caution when dealing with chloramines in MIMS and more generally with unstable molecules.

Some contaminants of emerging concern (CECs) are known to survive conventional wastewater treatment plants, which introduce them back to the environment and can potentially cycle up in drinking water supplies. This is especially concerning because of the inherent ability of some CECs to induce physiological effects in humans at very low doses. Advanced oxidation processes (AOPs) such as TiO2 based photocatalysis are of prominent interest for addressing CECs in aqueous environments. Natural water resources often contain dissolved metal cations concentrations in excess of targeted CEC concentrations. These cations may significantly, adversely impact degradation of CECs by scavenging TiO2 surface generated electrons. Consequently, simple pseudo first order or Langmuir-Hinshelwood kinetics are not sufficient for reactor design and process analysis in some scenarios. Rhodamine B dye and dissolved copper cations were studied as reaction surrogates to demonstrate that TiO₂ catalyzed degradation for very dilute solutions is very nearly completely due to homogeneous reaction with hydroxyl radicals and that in this scenario the hole trapping pathway has negligible impact. Chemical reaction kinetic studies were then carried out to develop a robust model for RB/metal reactions that is exact in the electron pathways for hydroxyl radical production and metal scavenging.

The purpose of our work was the search for safe and effective biologically active substances of cardiotropic action among 1,3- thiazole derivatives. New derivatives of 1-[(2Z)-2-[R-imin]-4-methyl-3-R¹-2,3-dihydro-1,3-thiazole-5-yl]ethan-1-one and ethyl-(2Z)-2-[R-imin]-4-methyl-3-R¹-2,3-dihydro-1,3-thiazole-5-carboxylate were synthesized by the Hantzsch reaction. The structure of the compounds obtained was confirmed by ¹H NMR spectroscopy and by the elemental analysis. The pharmacological screening showed that the obtained substances possess cardiotropic activity. The cardiotropic properties of the new 1,3-thiazole derivatives were studied on the isolated rings of the thoracic aorta of laboratory rats. A prospective substance 1-[(2Z)-2-[(4-methoxyphenyl)imin]-4-methyl-3-(4-methylpiperazin-1-yl) -2,3-dihydro-1,3-thiazol-5-yl]ethan-1-one hydrochloride, which exhibits cardiotropic activity exceeding the activity of L-carnitine and meldonia has been revealed during pharmacological researches of the substances obtained.

Valsartan (Val) is an important antihypertensive medication with side effects such as dizziness and angioedema. These constraints are due to the low oral bioavailability and relatively short half-life. The goal here is to incorporate Val into a mixed micelles system that can enhance transdermal delivery. Thin-film hydration and micro-phase separation were used to produce Val-loaded mixed micelle systems. A variety of factors, including surfactant type and drug-to-surfactant ratio, were optimized to produce micelles with low size and high Val entrapment efficiency (EE). The size, polydispersity index (PDI), zeta-potential, and drug entrapment efficiency of the prepared micelles were all measured. The drug release profiles in vitro were assessed using dialysis bags, and the permeation through abdominal rat skin was assessed using a Franz diffusion cell. All formulations had high EE levels exceeding 90% and low particle charges. The micellar sizes ranged from 107.6 to 191.7nm, with average PDI values of 0.3. The in vitro release demonstrated a uniform slow rate that lasted one week with varying extents. F7 demonstrated a significant (P < 0.01) transdermal efflux of 68.84 ± 3.96 µg/cm2/h through rat skin when compared to the control. As a result, the enhancement factor was 16.57. Val-loaded mixed micelles were successfully prepared using two simple methods with high reproducibility, and extensive transdermal delivery was demonstrated in the absence of any aggressive skin modifying enhancers.

Iapetus, a Saturn moon, shows the most differentiated albedo dichotomy of the Solar System. The dark leading side has a lower albedo than the bright trailing side. Spectral data on the visible light reveal the existence of two types of materials on the surface. The darkening in the leading side is thought to be originated by the presence of organic material and carbonaceous compounds on surface, while the trailing side is covered by water ice due to migration processes from the dark side. On airless bodies like Iapetus, the surface escape speed is greater than the speed of water molecules, resulting in the retention of a H2O atmosphere that allows some species to get diffused through it. Here, there were performed simulations of the evolution of the surface temperature for each of the two hemispheres of Iapetus. The results showed a slow yet steady increment of temperatures for both sides, with a steeper slope for the dark hemisphere. It was also simulated how much energy budget can be accumulated in both sides and its consequences. Finally, we calculated the diffusion coefficients for ammonia, methane, and water ice. The results let us infer how these compounds could evolve over time.

In this work, a novel silane coupled cationic precursor (SAGS) was synthesized by 3-glycidyloxypropyltrimethoxysilane and sodium 2-((2-aminorthyl)amino) ethanesulfonate. A series of cation exchange membranes were prepared with poly(vinyl alcohol) (PVA) and SAGS by sol-gel process. The structure of the prepared membranes were characterized by fourier transform infrared spectrum (FTIR) and scanning electron microscopy (SEM), and its properties were studied by water uptake (WR), cation exchange capacity (CEC), linear expansion ratio (LER), alkali stability, thermogravimetric analysis (TGA), mechanical properties and diffusion dialysis performance. FTIR and X-ray photoelectron spectroscopy (XPS）confirmed the successful preparation of SAGS membranes, and SEM images showed that the prepared membranes were dense and uniform. The WR values of the SAGS membranes were in the range of 91.49-122.39 %, and the LER values were 17.65-28.21 %. In addition, the SAGS membranes had suitable CEC value, good alkali resistance and thermal stability which ensured the application of membranes in the field of diffusion dialysis (DD) for alkali recovery. In DD test, the dialysis coefficients of NaOH (UOH) ranged from 0.012 mm/h to 0.023 mm/h, and the separation factors (S) was in the range of 30.77-16.43. In summary, the prepared membrane had good performance and simple preparation process, which had great application potential in textile industrial wastewater recovery.

An algorithm for the treatment of images affected by both blurring and salt&pepper noise is proposed with a cost only proportional to the number of pixels. The methodology uses a discretization scheme for the Laplace operator multiplied by a suitable nonlinear term depending on the gradient. Even if this approach resembles a diffusion type algorithm, only one step of the procedure is applied, leading to significant time savings. The procedure is successfully tested on some standard black&white natural images.

Voids in face-centered cubic (fcc) metals are commonly assumed to form by the aggregation of vacancies; however, the mechanisms of vacancy clustering and diffusion are not fully understood. In this study, we use computational modeling to provide a detailed insight into the structures and formation energies of primary vacancy clusters, mechanisms and barriers for their migration in bulk copper, and how these properties are affected at simple grain boundaries. The calculations were carried out using Embedded Atom Method (EAM) potentials and Density Functional Theory (DFT) and employed the Site-Occupation Disorder code (SOD), the Activation Relaxation Technique nouveau (ARTn) and the Knowledge Led Master Code (KLMC). We investigate stable structures and migration paths and barriers for clusters of up to six vacancies. Migration of vacancy clusters occurs via hops of individual constituent vacancies with di-vacancies having a significantly smaller migration barrier than mono-vacancies and other clusters. This barrier is further reduced when di-vacancies interact with grain boundaries. This interaction leads to the formation of self-interstitial atoms and introduces significant changes into the boundary structure. Tetra-, penta-, and hexa-vacancy clusters exhibit increasingly complex migration paths and higher barriers than smaller clusters. Finally, the direct comparison with the DFT results shows that EAM can accurately describe the vacancy-induced relaxation effects in the Cu bulk and in grain boundaries. Significant discrepancies between the two methods were found in structures with a higher number of low-coordinated atoms, such as penta-vacancies and di-vacancy absortion by grain boundary. These results will be useful for modeling the mechanisms of diffusion of complex defect structures and provide further insights into the structural evolution of metal films under thermal and mechanical stress.

Hydrogel microneedles are a promising technology for the delivery of different types of medicines locally and painlessly, as well as ISF extraction. As the hydrogel microneedles are inserted into the tissue, they swell and release drugs. To improve the effectiveness of this technology in delivering medicine at controlled and desirable doses and intervals, a deep understanding of the mechanism of drug delivery inside the microneedles is required. In this work, drug diffusion inside a tapered microneedle is investigated using numerical simulation. The microneedle is divided into many small elements, and the mass transfer equation of meloxicam is solved in each element over time. The skin is simulated as the sink in the microneedle surface for drug absorption. Simulations are performed for different sizes of microneedles. For a microneedle with a height of 500 µm and a base diameter of 250 µm, the drug completely penetrates the skin within 3.2 seconds. The rate of drug diffusion from the tip of the microneedle is higher than diffusion from the side area near the microneedle base. The obtained data demonstrate that in addition to the height and the base diameter, the microneedle’s aspect ratio, h/d, also affects the time of drug diffusion. We present a nonlinear equation to predict the time of complete drug diffusion as a function of the microneedle geometrical parameter, including the height and base diameter. The proposed equation calculates the total drug diffusion time with an error of less than 7% for all studied cases. Predicting drug diffusion patterns inside microneedles can be helpful in the biomedical field, especially in the drug-controlled release system for the optimization of drug delivery.

The conductor aluminum alloys Al-0.25wt.%Zr doped additionally with Х = Er, Si, Hf, and Nb were the objects of investigations. The fine-grained microstructure in the alloys was formed by Equal Channel Angular Pressing and Rotary Swaging. The thermal stability of the microstructure, specific electrical resistivity, and microhardness of the novel conductor aluminum alloys was investigated. The mechanisms of nucleation of the Al3(Zr,X) secondary particles during annealing the fine-grained aluminum alloys were determined using Jones-Mehl-Avrami-Kolmogorov equation. Using Zener equation, the dependencies of the mean secondary particle sizes on the annealing time were obtained on the base of analysis of the data on the grain growth in the aluminum alloys. The secondary particle nucleation during long-time low-temperature annealing (300 оC, 1000 hrs) was shown to go preferentially at the cores of the lattice dislocations. The Al-0.25%Zr-0.25%Er-0.20%Hf-0.15%Si alloy subjected to long-time annealing at 300 оC has the optimal combination of the microhardness and electrical conductivity (59.8%IACS, Hv = 480 ± 15 MPa).

The research was undertaken to study the way deformation behaves in ultrafine-grained (UFG) conducting Al-Zr alloys doped with Sc, Hf, and Yb. All in all, 8 alloys were studied with zirconium partially replaced by Sc, Hf, and/or Yb. Doping elements (X = Zr, Sc, Hf, Yb) in the alloys total 0.4 wt.%. The choice of doping elements is conditioned by possible precipitation of Al3X particles with L12 structure while annealing these alloys. Such particles provide higher thermal stability of a nonequilibrium UFG microstructure. Initial coarse-grained samples were obtained by induction casting. The UFG microstructure in the alloys was formed by Equal Channel Angular Pressing (ECAP) at 225°C. Superplasticity tests were carried out at temperatures ranging from 300 to 500 °C and strain rates varying between 3.310-4 and 3.310-1 s-1. The highest values of elongation to failure are observed in Sc-doped alloys. A UFG Al-0.2%Zr-0.1%Sc-0.1%Hf alloy has maximum ductility: at 450 °C and a strain rate of 3.310-3 s-1, relative elongation to failure reaches 765%. At the onset of superplasticity, stress–strain curves are characterized by a stage of homogeneous strain and a long stage of localized plastic flow. The dependence of homogeneous strain (eq) on test temperature in UFG Sc-doped alloys is increasing uniformly, which is not the case for other UFG alloys with eq(T) dependence peaking at 350-400 оС. Strain rate sensitivity coefficient of flow stress m is small and does not exceed 0.26-0.3 at 400-500 °C. In UFG alloys containing no scandium, m coefficient is observed to go down to 0.12-0.18 at 500 оС. It has been suggested that lower m values are driven by intensive grain growth and pore formation in large Al3X particles, which develop specifically at the ingot crystallization stage.

Nanomedicine holds great potential to devise better drug delivery systems (DDSs). However, many reported nanomedicines still fall short of commercial requirements including specific targetability, scale-up manufacturing and safety. Cell/tissue based carriers, including cell membrane vehicle and exosome, are biocompatible and targeting platforms but usually suffered from low yields and unstable reproducibility. Here in this study, we proposed the concept and preparation of reconstituted lipid nanoparticles (rLNPs) to develop highly reproducible cell/tissue based lipid nanoparticles (LNPs) for drug delivery, which holds the potential as a versatile drug delivery platform. The whole lipids of cell or tissue were firstly extracted and then prepared into rLNPs using solvent diffusion method. In this way, the preparation of ultra-small (~20 nm) rLNPs can be easily applied to both cell (mouse breast cancer cell line, 4T1) and tissue (mouse liver tissue). Our results demonstrated that mouse liver tissue derived rLNPs can be further labeled/modified with imaging, targeting or other functional moieties. Furthermore, rLNPs were highly biocompatible and capable of loading different drugs including doxorubicin hydrochloride (Dox) and curcumin (Cur). Most importantly, Dox loaded rLNPs (rLNPs/Dox) showed preferable in vitro and in vivo anticancer performance. Therefore, rLNPs might be a versatile drug delivery platform for future application in the treatment of a variety of diseases.

NMR Spectroscopy is used, in the temperature range 180-350K, to study local order and transport in liquid water (pure and confined) and its solutions with glicerol and methanol at different molar fractions. Being the liquid water thermodynamic dominated by polymorphism (two coexisting liquid phases: high- and low-density HDL and LDL) - with the LDL due to the hydrophilic HB interactions, originating in the supercooled regime the tetrahedral networking and the liquid-liquid transition – we focused our interest to hydrophobic effects (HE) on these. Nowadays, if compared to the hydrophilicity, little is known about hydrophobicity so that the main purpose of this study is to gain new information on it. We measured the relaxation times (T1 and T2) and the self-diffusion (DS). From the times we took advantage of the NMR property to follow the behaviors of each molecular component (the hydrophilic and hydrophobic groups) separately; they are studied directly and DS in terms of the Adam-Gibbs model: obtaining the configurational entropy (Sconf ) and the specific heat contributions (CP,conf ). Due to the HE all the studied quantities, behave differently. For water-glycerol the HB interaction is dominant for all the conditions, whereas for water-methanol are observable two different T-regions above and below 265 K, dominated respectively by the hydrophilicity and hydrophobicity. A situation linked to the water polymorphism. Below this temperature, where the LDL phase and the HB networking develops and grows, the times and CP,conf change behaviors leading to maxima and minima. Above it, where the HB becomes weak and less stable and the HDL dominates, the hydrophobicity determines the solution properties.

The diffusion process of water molecules within a polyetherimide (PEI) glassy matrix has been analyzed by combining the experimental analysis of water sorption kinetics performed by FTIR spectroscopy with theoretical information gathered from Molecular Dynamics simulations and with the expression of water chemical potential provided by a non-equilibrium lattice fluid model able to describe the thermodynamics of glassy polymers. This approach allowed to construct a convincing description of the diffusion mechanism of water in PEI providing molecular details of the process related to the effects of the cross- and self-hydrogen bondings established in the system on the dynamics of water mass transport.

An interesting anomaly of the diffusion process with an apparently negative diffusion coefficient defined through the mean-square displacement in a one-dimensional quantum molecular chain model is shown. Nevertheless, the system satisfies the H-theorem, so that the second law of thermodynamics is satisfied. The reason why the “diffusion constant” becomes negative is due to the effect of the phase mixing process, which is a characteristic result of the one-dimensionality of the system. We illustrate the situation where this negative “diffusion constant” appears.

The paper presents a model of moisture transport in wood taking into account diffusion and the accompanying adsorption of water vapour through the skeleton. A two-parameter form of the source term was proposed, depending on the distance of the current mass concentration of bound water from the equilibrium state. The tests on cubic samples with a side of 2 cm were carried out which allowed to determine the coefficients of the proposed model on the basis of the reverse method. The tests were performed for pine, larch, oak and ash in all directions of orthotropy. Also the tests on thin samples were performed to verify the source term.

FRAP technique have been used for decades to measure movements of molecules in 2D. Data obtained by FRAP experiments in cell plasma membranes are assumed to be described through means of two parameters, a diffusion coefficient D (as defined in a pure Brownian model) and a mobile fraction M. Nevertheless, it has also been shown that recoveries can be nicely fit using anomalous sub-diffusion. FRAP at variable radii has been developed using the Brownian diffusion model to access geometrical characteristics of the surrounding landscape of the molecule. Here we performed numerical simulations of continuous time random walk (CTRW) anomalous subdiffusion and interpreted them in the context of variable radii FRAP. These simulations were compared to experimental data obtained at variable radii on living cells using the PH domain of the membrane binding protein EFA6 (exchange factor for ARF6, a small G protein). This protein domain is an excellent candidate to explore the structure of the interface between cytosol and plasma membrane in cells. By direct comparison of our numerical simulations to the experiments, we show that this protein does not exhibit anomalous diffusion in BHK cells. The non Brownian PH-EFA6 dynamics observed here is more related to spatial heterogeneities such as cytoskeleton fences effects.

In this paper, the nanoscale dissipative mechanisms of a Cu pad in a Ball Grid Array (BGA) packaging structure during isothermal ageing and uniaxial tension were investigated by the molecular dynamics (MD) method and experiments. From the result of the isothermal ageing test, a nonuniform consumption of Cu and large amount of Kirkendall voids were observed at the interface of Cu and Cu₃Sn. To study the effect of pressure and orientation on this phenomenon, MD simulations were conducted on four types of Cu-Cu₃Sn interface structures with different orientations of Cu. By comparing the diffusion coefficients of atoms in those cases, it was found that the tensile stress would inhibit the diffusion of atoms, whereas compressive stress would accelerate it, and this would be more significant under a larger magnitude of stress and temperature. Note that, in the model with the (101) surface Cu at the interface, both Cu and Cu₃Sn have a higher diffusion coefficient compared with the model with (001) surface Cu. Thus, the orientation of Cu will also contribute to the uniform consumption of the pad. Uniaxial tension simulation combined with DXA and CSP analyses on those models also shows the model with (001) surface Cu has a greater mechanical reliability in our simulations and related experiments.

In this paper we report a new development on the numerical model for aluminum-steam combustion. This model is based on diffusion flame of continuum regime and the thermal equilibrium between the particle and the flow field, which can be used to calculate the aluminum particle combustion model for two phase calculation conditions. The model prediction is in good agreement with the experimental data. A new type of vortex combustor was proposed for the combustion of aluminum and steam, and the mathematical model of the two phase reacting flow with in this combustor was established. The turbulence effects are modeled using the Reynolds Stress Model (RSM) with Linear Pressure-Strain approach, and the Eddy-Dissipation model is used to simulate the gas phase combustion. Aluminum particles are injected into the vortex combustor and form a swirling flow around the chamber and their trajectories are traced using the Discrete Phase Model (DPM). The simulation results show that the vortex combustor can achieve high efficient combustion of aluminum and steam. The influencing factors, such as the eccentric distance of the inlet of aluminum particles, particle size and steam inlet diameter, etc., are studied. The work described in this paper represents an attempt to the design of a vortex combustor in order to increase aluminum combustion efficiency.

The effect of Localized Surface Plasmon (LSP) of 5 nm mean size Au particles deposited on TiO2 P25 was investigated during the photo-thermal water gas shift reaction (WGSR). The effects of CO concentration, excitation light flux and energy, and molecular oxygen addition during the reaction were investigated. The photocatalytic WGSR rate under light excitation with wavelengths extending from 320 to 1100 nm was found to be higher than the thermal reaction alone at the same temperature (85 oC). A ratio H2/CO2 of near unity was found at high concentrations of CO. Addition of molecular oxygen during the reaction resulted in a slight decrease of molecular hydrogen production while the rates of CO2 formation and that of CO consumption changed by one order of magnitude. More important, it was found that the WGSR rates were still high under only visible light excitation (600 - 700 nm). The results prove that Au LSP alone triggers this chemical reaction without the need to excite the semiconductor on which they are deposited.

In fuel-cell technological development, one of the most important objectives is to minimize the amount of Pt, the most employed material as oxygen reduction and methanol oxidation electro-catalyst. In this paper we report the synthesis and characterization of Te nanotubes (TeNTs) decorated with Pt nanoparticles, readily prepared from stirred aqueous solutions of PtCl2 containing a suspension of TeNTs and ethanol acting as a reducing agent, avoiding the use of any hydrophobic surfactants as capping stabilizing substance. The as obtained TeNTs decorated with Pt nanoparticles (TeNTs/PtNPs) have been fully characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area diffraction patterns (SAD), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). We demonstrate that the new material can be successfully employed in fuel cell either as anodic (for methanol oxidation reaction) and cathodic (for oxygen reduction reaction) electrode with high efficiency in terms of related mass activities and on-set improvement. Remarkably, the cell operates in aqueous electrolyte buffered at pH 7.0, thus avoiding acidic or alkaline conditions that may lead e. g. to Pt dissolution (at low pH) and paving the way for the development of biocompatible devices and on chip fuel cells.

In this paper, some new properties of the fundamental solution to the multi-dimensional space- and time-fractional diffusion-wave equation are deduced. We start with the Mellin-Barnes representation of the fundamental solution that was derived in the previous publications of the author. The Mellin-Barnes integral is used to get two new representations of the fundamental solution in form of the Mellin convolution of the special functions of the Wright type. Moreover, some new closed form formulas for particular cases of the fundamental solution are derived. In particular, we solve an open problem of representation of the fundamental solution to the two-dimensional neutral-fractional diffusion-wave equation in terms of the known special functions.

New furan, thiophene and triazole oximes were synthesized through several-step reaction paths to investigate their potential for development of central nervous systems (CNS)-active and cholinesterase-targeted therapeutics in organophosphorus compound (OP) poisonings. Acute OP poisoning is still a challenge in treating patients despite the development of a large number of oxime compounds that should have the capacity to reactivate acetylcholinesterase (AChE) and butyrylcholinesterase (BChE). The activity of these two enzymes, crucial for neurotransmission, are blocked by the OP, which has the consequence of disturbing normal cholinergic nerve signal transduction in the peripheral and CNS, leading to cholinergic crisis. Oximes in use have one or two pyridinium rings and cross the brain–blood barrier poorly due to the quaternary nitrogen. Following our recent study on 2-thienostilbene oximes, in this paper we described the synthesis of 63 heterostilbene derivatives out of which 26 oximes were tested as inhibitors and reactivators of AChE and BChE inhibited by OP nerve agents – sarin and cyclosarin. While the majority of oximes were potent inhibitors of both enzymes in micromolar range, we identified several oximes as BChE or AChE selective inhibitors with a potential for drug development. Moreover, even oximes were poor reactivators of AChE, four heterocyclic derivatives reactivated the cyclosarin-inhibited BChE up to 70%, and cis,trans-5 [2-((Z)-2-(5-((E)-(hydroxyimino)methyl)thiophen-2-yl)vinyl)benzonitrile] had comparable reactivation efficacy to the standard oxime HI-6. In silico analysis and molecular docking studies connected the kinetic data to the structural features of these oximes, and confirmed their productive interactions with the active site of the cyclosarin-inhibited BChE. Based on inhibition and reactivation and their ADMET properties regarding lipophilicity, CNS activity, and hepatotoxicity, these compounds could be considered for further development of CNS-active reactivators in OP poisoning as well as cholinesterase-targeted therapeutics in neurodegenerative diseases like Alzheimer’s and Parkinson’s.

Hydrogen is now recognized as the primary alternative to fossil fuels due to its renewable, safe, high energy density and environmentally friendly properties. Efficient hydrogen production through water splitting has laid the foundation for sustainable energy technologies. However, when hydrogen production is scaled up to industrial levels, operating at high current densities introduces unique challenges. It is necessary to design advanced electrocatalysts for hydrogen evolution reaction (HER) under high current densities. This review will briefly introduce chal-lenges posed by high current densities on electrocatalyst, including catalystic activity, mass dif-fusion and catalyst stability. In an attempt to address these issues, various electrocatalyst design strategies are summarized in detail. In the end, our insights into future challenges for efficient large-scale industrial hydrogen production from water splitting are presented. This review is expected to guide the rational design of efficient high current density water electrolysis electro-catalysts and promote the research progress of sustainable energy.

The quantification of human DNA extracts from forensic samples plays a key role in the forensic genetics process. Quantification guarantees maximum efficiency and avoids repeated analyses, over amplified samples, or unnecessary examinations. Here, we present our experience using an extremely sensitive real-time-based method with the Quantifiler® Trio DNA quantification kit, which we have explored in the ISO/IEC17025 accredited test validation process conducted in our laboratory. In this study, our focus was on establishing a minimum threshold beyond which DNA typing is unnecessary, by defining the correlation of negative quantification results with the absence of genetic profiles resulting from DNA typing. We investigated the results in the range in which the technique is used (50-0.005 ng/μl). In the validation process of the internally accredited method, we used data from the commercial quantification system, based on the average values of the standard curve using a wide range of samples, including artificially degraded samples. This method was extensively used continuously for nine years to quantify the DNA extract coming from a wide range of samples from criminal cases. The validation allowed us to verify the limits of the technique, especially in the use of the minimum quantities necessary to obtain genetic profiles acceptable for sending to the Italian DNA database. This optimization of the protocol for analysing forensic samples allows us to optimise the protocol for analysing forensic samples. However, the technique is used in our laboratory with a completely manual preparative phase, and we have decided to investigate the contribution of human error more accurately. Thus, in our experience, we have found that it is preferable to use quantification ranges rather than exact limits before deciding how to analyse the extracts via PCR. In addition, here we present some preliminary data related to the analysis of certain samples that initially appeared negative during quantification, applying a concentration method for maximum yield from forensic samples of judicial interest. Our aim is to ensure that no source of evidence is lost in the reconstruction of a criminal event.

In spite of prevalence gaps in several micronutrients supporting immune function, significance of their deficits/supplementation for efficacy of vaccines is underinvestigated. Thus, influence of supplementation combining vitamins C and D, zinc, selenium and manganese, and N-acetyl-cysteine on mouse IgG responses and underlying mechanisms to seasonal quadrivalent influenza vaccine (QIV) was investigated. QIV was given in two doses (28 days apart). The supplementation starting 5 days before the first injection increased the total serum IgG titre, through stimulation of germinal centre (GC) reaction in secondary lymphoid organs (SLOs), as indicated by increase in the frequency of GC B cells and follicular CD4+ T helper (Th) cells, and IL-21-producing Th cells. Additionally, the supplementation “optimized” IgG response following the second QIV injection by supporting more favorable (in respect to virus clearance) IgG2a response through favoring Th1 differentiation as indicating by Th1 (INF-γ) /Th2 (IL-4) signature cytokine level ratio upon QIV restimulation in SLO cell cultures. This most likely reflected partly their antioxidant action (as indicated by redox status analyses) on Th cell differentiation. Thus, the study forms solid base for further research aimed at repurposing use this safe and inexpensive micronutrient combination as an adjuvant for virus influenza vaccine.

Synthesis of natural products with complicated architecture often requires segments having the functional groups that can be structurally transformed with the desired stereogenic centers. Bicyclic ?-lactones have a great potential for a suitable segment for natural product synthesis. However, the stereoselective construction of such functionalized bicyclic ?-lactones is not as straightforward as one might expect. On the other hand, the Lewis acid template-mediated Diels-Alder reaction is one of the most powerful and versatile methods for providing bicyclic ?-lactones with high regioselectivity and stereoselectivity. In this reaction, the Lewis acid template activates the dienophile as well as linking the diene and dienophile by a temporary tether. Therefore, Diels-Alder reaction smoothly proceeds in a stereocontrolled manner, allowing a simple access to bicyclic ?-lactone as a valuable building block for the synthesis of complicated natural products. In this review, some highlights of the Lewis acid-mediated Diels-Alder reaction, along with its application to the synthesis of biologically active compounds are discussed.

Dimers and oligomers of alkenes represent a category of compounds that are in great demand for diverse industrial sectors. Among the developing synthetic methods, the catalysis of alkene dimerization and oligomerization using transition metal salts and complexes is of undoubted interest for practical application. This approach demonstrates substantial potential, offering not only elevated reaction rates but also precise control over the chemo-, regio-, and stereoselectivity of the reactions. In this review, we discuss the data on catalytic systems for alkene dimerization and oligomerization. Our focus lies in the analysis of how the activity and chemoselectivity of these catalytic systems are influenced by various factors, such as the nature of the transition metal, the ligand environment, the activator, and substrate structure. Notably, the review particularly discusses the reaction mechanisms, encompassing metal complex activation, structural and dynamic features, and the reactivity of hydride intermediates, which serve as potential catalytically active centers in alkene dimerization and oligomerization.

Sr4Al6O12SO4 samples were obtained from the compound mixture formed by a solid–state reaction of Al2O3, SrSO4, and SrCO3. Samples were compacted at 100MPa to form pellets of 1 and 4cm in diameter and were sintered at 1400°C for 4 hours. The compound was analyzed by X–ray diffraction. Static immersion and wettability tests were performed to evaluate corrosion resistance in contact with Al–Si. Corrosion tests were carried out by immersion at 800, 900, and 1000°C for 24, 50, and 100 hours, while wettability was carried out at 900, 1000, and 1100°C for 2 hours. Subsequently, the samples were prepared metallographically. Samples were analyzed by optical microscopy, scanning electron microscopy, and image analysis. In general, reaction products consisting of alumina, spinel, oxides, and sulfates were found. The contact angles obtained were 124° to 135°. It is concluded that ceramic substrate Sr4Al6O12SO4 is resistant to corrosion by Al–Si alloy, since the slight thickness of the reaction products found in the samples (100μm) considering the severe conditions of the experiment: 1000°C and 100 hours of isothermal temperature. Furthermore, it can be said that Sr4Al6O12SO4 is not wettable by Al–Si alloys.

The (Ti, Nb)(C, B)/IN625 composite coating with both homogeneous and defect-free microstructure were successfully prepared by in situ on the surface of 42CrMo steel using the coupling of the ultra-high-speed laser cladding (EHLA in German) technology with the direct reaction synthesis (DRS) technology, and were comparatively analyzed with the IN625 coating prepared by the EHLA. The microstructure of the fused cladding layer was investigated by selected scanning electron microscopy (SEM), energy dispersive spectrometer (EDS) and double spherical aberration transmission electron microscopy (DSA-TEM). The residual stress distribution on both sides of the fused cladding interface was characterised by nanoindentation stress test based on the modified O&P method and the G&S energy method. The results show that the interface of (Ti, Nb)(C, B)/IN625 composite coatings is affected by about 670 kJ Joule heat released from the in-situ reaction, and the interfacial width reaches 24 μm, so that it is 6 times higher than that of IN625 coating prepared by EHLA, which effectively reduces the stress gradient in the interfacial region and alleviates the stress mismatch on both sides of the interface. However, the surface hardness of (Ti, Nb)(C, B)/IN625 composite coating is lower than that of the IN625 coating, with a value of about 240 HV0.2, and the average wear weight loss was only 10% of that of the IN625 coating, which is on the one hand attributed to the in-situ authigenic TiCB, TiC, NbMo3B4, and NbMo2B2 phases supporting the (Ti, Nb)(C, B)/IN625 composite coating substrate to achieve the abrasion reduction and wear resistance. On the other hand, it is attributed to the formation of nano-equiaxial ultrafine grains in the depth range of 250 nm below the wear surface area by the coupling of the three fields of plastic rheology-heat-force, which dynamically strengthens the wear surface.

Partially automated driving functions (SAE Level 2) can control a vehicle's longitudinal and lateral movements. However, taking over the driving task involves automation risks that the driver must manage. In severe accidents, the driver's ability to avoid a collision must be assessed, considering their expected reaction behavior. The primary goal of this study is to generate essential data on driver reaction behavior in case of malfunctions in partially automated driving functions for use in legal affairs. A simulator study with two scenarios involving 32 subjects was conducted for this purpose. The first scenario investigated driver reactions to system limitations during cornering. The second scenario examined driver responses to phantom braking caused by the AEBS. As a result, the first scenario shows that none of the subjects could control the situation safely. Due to partial automation, we could also identify a new part of the reaction time, the hands-on time, which leads to increased steering reaction times of 1.18 to 1.74 seconds. In the second scenario, we found that 25 of the 32 subjects could not override the phantom braking by pressing the accelerator pedal, although 16 subjects were informed about the system analog to the actual vehicle manuals. Overall, the study suggests that the current legal perspective on vehicle control and the expected driver reaction behavior for accident avoidance should be reconsidered.

Electrocatalytic and photocatalytic hydrogen evolution reaction (HER) provides a promising approach to clean energy generation. Bimetallic single-atom catalysts raised and have been explored to be advanced catalysts for HER. It is urgent to review and summarize the recent advances in developing bimetallic single-atom HER catalysts. Firstly, the fundamentals of bimetallic single-atom catalysts are presented, highlighting their unique configuration of two isolated metal atoms on supports and resultant synergistic effects. Secondly, recent advances in bimetallic single-atom catalysts for electrocatalytic HER under acidic/alkaline conditions are then reviewed, including W-Mo, Ru-Bi, Ni-Fe, Co-Ag, and other dual-atom systems on graphene and transition metal dichalcogenides (TMDs) with enhanced HER activity versus monometallic analogs due to geometric and electronic synergies. Then, Photocatalytic bimetallic single-atom catalysts on semiconducting carbon nitrides for solar H2 production are also discussed. Finally, an outlook is provided on opportunities and challenges in precisely controlling bimetallic single-atom catalyst synthesis and gaining in-depth mechanistic insights into bimetallic interactions.

Information regarding physiological and molecular plant responses to the treatment with new biofertilizers is limited. In this study a fast-composting soil amendment (FCA), obtained from solid waste by means of a Fenton reaction, was tested to evaluate the effects on the growth of Lactuca sativa L. var. longifolia seedlings. Growth rate, leaves and roots biomass, chlorophyll concentration and total soluble proteins of seedlings treated with the 2% FCA soil amendment showed significant increase in comparison with control seedlings. Leaf proteomic analysis revealed that the FCA soil amendment induced the up-regulation of proteins belonging to photosynthesis machinery, carbohydrate metabolism and promoted the up-regulation of the water stress response. Root proteomics indicated that FCA strongly induced the organs morphogenesis and developments; root cap development, lateral root formation, post-embryonic root morphogenesis were the main biological processes enriched by the treatment. Overall, our data suggest that addition of FCA formulation to the base soils might ameliorate plant growth by inducing carbohydrates primary metabolism and the differentiation of a robust root system.

The synthesis 2-tert-butyl-4-methylphenol is of great significance because of its widely application in industry, and the development of highly efficient catalyst is necessary to the alkylation of p-cresol and tert-butyl alcohol. Here, an efficient and mild method was established, caprolactam was chosen as hydrogen-bonding acceptor, p-toluenesulfonic acid was employed as hydrogen-bonding donor, and deep eutectic solvent (DES) was prepared to catalyze the alkylation reaction. The structure of the DES catalyst was characterized by 1H NMR spectra, thermogravimetric analysis and fourier transform infrared spectra (FT-IR). In addition, response surface design based on Box-Behnken method was employed to optimize the alkylation reaction process parameters, the study of reaction kinetics was also carried out subsequently. The recycle performance of the catalyst was evaluated by recovery experiments, and a good result was obtained. Comparing with the literature reported, we here provide a mild method to the synthesis of 2-tert-butyl-4-methylphenol.

Biomimetic N-acetylcysteamine thioesters are essential for the study of polyketide synthases, non-ribosomal peptide synthetases and fatty acid synthases. The chemistry for their preparation is however limited by their specific functionalization and their susceptibility to undesired side reactions. This is especially detrimental to transition metal-catalyzed reactions. Here we report a method for the rapid preparation of N-acetylcysteamine (SNAC) 7-hydroxy-2-enethioates, which are suitable for the study of various enzymatic domains of megasynthase enzymes, particularly oxygen heterocycle-forming cyclase domains. The method is based on a one-pot sequence of hy-droboration and Suzuki-Miyaura reaction. Optimization of the reaction conditions made it possi-ble to suppress potential side reactions and to introduce the highly functionalized SNAC meth-acrylate unit in high yield. The versatility of the sequence was demonstrated on a dienal precur-sor, which was subjected to Brown crotylation followed by the hydroboration-Suzuki-Miyaura reaction sequence and deprotection, finally giving a complex polyketide SNAC thioester. Back-bone extension by six carbons and a terminal SNAC enethioate was achieved, introducing an E-configured double bond and two adjacent stereocenters in a highly selective manner. The pre-sented method allows for the synthesis of the target motif in significantly fewer steps and with higher overall yield than previously described approaches, while maintaining higher flexibility and control over the stereogenic elements. It is also the first reported example of a transition met-al-catalyzed cross-coupling reaction in the presence of an SNAC thioester.

Controlling and understanding Cu-catalyzed homocoupling reaction is crucial to prompt the development of efficient Cu-catalyzed cross-coupling reactions. The presence of a coordinating base (hydroxide, methoxide) enables the B-to-Cu(II) transmetalation from aryl boronic acid to CuIICl2 in methanol, through formation of a mixed Cu-(μ-OH)-B intermediates. A second B-to-Cu transmetalation to form bis-aryl Cu(II) complexes is disfavored. Instead, organocopper(II) dimers undergo a coupled transmetalation-electron-transfer (TET) allowing the formation of a bis-organocopper(III) complexes readily promoting reductive elimination. Based on this mechanism some guidelines are suggested to control the undesired formation of homocoupling product in Cu-catalyzed cross-coupling reactions.

There is a relationship between systemic sarcoidosis (SS) and malignancy. Sarcoidosis results from an exaggerated immune response in genetically susceptible individuals. In oncologic pa-tients with sarcoidosis, tumoral antigens and antineoplastic treatment are considered potential triggering factors. The observation of a patient with granulomas in a parotid carcinoma that later developed SS led us to review previous tumors of patients with SS. The aim of the study is to see if granulomas were already present in the tumors that preceded sarcoidosis. We identified 196 sarcoidosis patients, 47 of which had a previous tumor. We were able to review 29 cases 12 of which showed tumor associated granulomas (TAGs)(41.4%). This ratio is much higher than that of the normal population. We analyzed five control patients without sarcoidosis for each tumor. In conclusion, we have observed TAGs in patients who later develop SS. In our series, the ratio of TAGs in patients with SS was significantly greater than in the normal population. To prove our findings, we suggest reviewing the history of patients with SS in search of previous tumors. The histology of such tumors should be reviewed in an attempt to identify granulomas.

The steady-state multiplicity of the porous, non-isothermal, catalyst pellet when two parallel and consecutive chemical reactions take place was analysed in this work. The geometry selected for the catalyst pellet is finite hollow cylinder. A numerical multigrid continuation technique with the preconditioned conjugate gradient squared as coarse grid solver was used. The continuation parameter is the dimensionless adiabatic heat rise (Prater number) for the first chemical reaction. The effect of the other governing parameters was analysed and the results are compared to those provided by the single chemical reaction.

In this work, anchoring of cinchona derivatives to trifunctional cores (hub approach) was demonstrated to obtain size-enlarged organocatalysts. By modifying the cinchona skeleton in different positions, we prepared four C3-symmetric size-enlarged cinchona derivatives (hub-cinchonas), which were tested as organocatalysts and their catalytic activities were compared with the parent cinchona (hydroquinine) catalyst. We showed that in the hydroxyalkylation reaction of indole, hydroquinine provides good enantioselectivities (up to 73% ee), while the four new size-enlarged derivatives gave significantly lower values (up to 29% ee) in this reaction. Anchoring cinchonas to trifunctional cores was found to facilitate nanofiltration-supported catalyst recovery using PolarClean alternative solvent. The C3-symmetric size-enlarged organocatalysts were completely rejected by all the applied membranes, whereas the separation of hydroquinine was found to be insufficient using organic solvent nanofiltration. Furthermore, the asymmetric catalysis was successfully demonstrated in the case of Michael reaction of 1,3-diketones and trans-β-nitrostyrene using Hub3-cinchona (up to 96% ee) as a result of the positive effect of the C3-symmetric structure using a bulkier substrate. This means an increased selectivity of the catalyst in comparison to hydroquinine in the latter Michael reaction.

Background: drugs provide a significant benefit; however, their use implies an intrinsic potential danger, with the possibility to cause unwanted effects. These effects are known as adverse drug reactions (ADRs). Post-marketing drug safety surveillance detects unknown risks that have not been identified in clinical trials and it is necessary to monitor marketed medications under real-life practice. Due to the scarce information about fixed combination of ciprofloxacin 0.3% / dexamethasone 0.1% (SDO), we performed a drug safety surveillance study. (2) Methods: A prospective non-controlled drug safety surveillance study was conducted in Peruvian population. A total of 236 patients prescribed SDO were included derivates from 12 sites. Patients' standardized information was collected through two phone calls, including demographics, medical history, prescribing patterns of SDO, concomitant medication, and ADRs in detail. The ADRs were classified by causality and severity, followed by outcome measures to identify new risk. (3) Results: 236 patients prescribed with SDO participated in the study and 220 were included. A total of 82 ADRs/220 patients were reported after the use of SDO, presenting a ratio 0.37 ADR/patient. The most frequent ADR with SDO administration was eye irritation (30%). The totality of the ADR was classified as non-serious, and the 97.5% (n=80) was classified as mild and 2.5% as moderate (n=2). No cases under the severe category were identified. (4) Conclusion: No new risks were found in the population where this study was conducted.

Carbon dioxide has become a global challenge, where the emissions have become more than what could be handled. In this regard, conversion of CO2 to value added chemicals and thus recycling CO2 became a viable option. One of these options is the use of a process in strong development: oxycombustion. However, the gases resulting from this process contain some traces of impurities that can hinder the recovery of CO2 such as NO and CO. This work has therefore focused on the study of the reaction of NO reduction by CO in an oxidizing medium, using catalytic materials based on various supported noble metals. These materials were extensively characterized by a variety of methods including BET surface area measurements, hydrogen chemisorption, Transmission Electron Microscopy (TEM) and H2 temperature programmed reduction (H2-TPR). The obtained results show that the catalytic behaviour of M/Al2O3 catalysts in CO oxidation and NO reduction with CO in oxidative conditions depends mainly on the nature of the metal. The best result for these both reactions is obtained with Pt/Al2O3 catalyst. The Pt nanoparticles existing in the metallic form (Pt°) showed by TPR could explain the activity.

Hydrogen evolution reaction (HER) is one of the most important reaction in electrochemistry. This is not only because it is the simplest way to produce high purity hydrogen and the fact that it is the side reaction in many other technologies. HER actually shaped current electrochemistry because it was in focus of active research for so many years (and it still is). The number of catalysts investigated for HER is immense, and it is impossible to overview them all. In fact, it seems that the complexity of the field overcomes the complexity of HER. The aim of this review is to point out some of the latest developments in HER catalysis, current directions and some of the missing links between a single crystal, nanosized supported catalysts and, recently emerging, single atom catalysts for HER

This work demonstrates that a plasmid can function as an efficient biocatalyst in mediating the nitroaldol (Henry) reaction at high temperatures in ultrapure water. Compared with ssDNA, the plasmid displayed a remarkable catalytic efficiency (97% yield within 20 min). Aromatic aldehydes which bear strong or moderate electron-withdrawing groups reacted satisfactorily with nitromethane, which afforded the corresponding β-nitroalcohols in good yields within 2 h (up to 98%). By contrast, aliphatic and aromatic aldehydes with electron-donating groups did not react. Moreover, the yield significantly dropped when the size of the carbanion increased, and the yield was only 10% when nitropropane was used as the donor.

In this study, lithium reaction distributions, dependent on charge-discharge rate, were nondestructively visualized for a commercial lithium-ion battery, using the Compton scattering imaging technique. By comparing lithium reaction distributions obtained from two different charge-discharge speeds, residual lithium ions were detected at the center of the negative electrode on a fully discharged state, by relatively high-speed discharge rate. Moreover, we confirmed that inhomogeneous reactions were facilitated on a relatively high-speed charge-discharge rate, in both the negative and positive electrodes. A feature of our technique is that it can be applied to commercially used lithium-ion batteries, because it uses high-energy X-rays with a high penetration power. Our technique thus opens a novel analyzing pathway for developing advanced batteries.

Furfuryl alcohol (FA) is a biobased monomer derived from lignocellulosic biomass. The present work describes its polymerization in presence of protic polar solvents, i.e. water or isopropyl alcohol (IPA), using maleic anhydride (MA) as acidic initiator. The polymerization was followed from the liquid to the rubbery state by combining DSC and DMA data. In the liquid state, IPA disrupts the expected reactions during all the FA polymerization due to a stabilization of the furfuryl carbenium center. This causes the initiation of the polymerization at higher temperature, which is also reflected by higher activation energy. In water system, the MA opening allows to start the reaction at lower temperature. A higher pre-exponential factor value is obtained in that case. The DMA study of final branching reaction occurring in the rubbery state has highlighted continuous increase of elastic modulus until 290 °C. This increasing tendency of modulus was exploited to obtain activation energy dependences (Eα) of FA polymerization in the rubbery state.

Background: In rheumatoid arthritis (RA), anti-citrullinated protein/peptide antibodies (ACPAs) are responsible for disease onset and progression, however, our knowledge is limited on ligand binding affinities of autoantibodies with different citrulline-peptide specificity. Methods: Citrulline-peptide specific ACPA IgGs were affinity purified and tested by ELISA. Binding affinities of ACPA IgGs and serum antibodies were compared by surface plasmon resonance (SPR) analysis. Bifunctional nanoparticles harboring a multi-epitope citrulline-peptide and a complement activating peptide were used to induce selective depletion of ACPA producing B cells. Results: KD values of affinity purified ACPA IgGs varies between 10-6-10-8 M and inversely correlate with disease activity. Based on their cross-reaction with citrulline-peptides we designed a novel multi-epitope peptide, containing Cit-Gly and Ala-Cit motifs in two-two copies, separated with a short, neutral spacer. This peptide detects antibodies in RA sera with 66 % sensitivity and 98 % specificity in ELISA and is recognized by 90% of RA sera, while none of the healthy samples in SPR. When coupled to nanoparticles, the multi-epitope peptide specifically targets and depletes ACPA producing B cells ex vivo. Conclusions: The unique multi-epitope peptide designed on the basis of ACPA cross-reactivity might be suitable to develop better diagnostics and novel therapies for RA.

A new synthetic approach to polyfunctional hexahydropyrrolo[3,4-b]pyrroles was developed based on cyclization of N-arylbromomaleimides with aminocrotonic acid esters. A highly chemo- and stereoselective reaction is a Hantzsch-type domino process, involving the steps of initial nucleophilic C-addition or substitution and subsequent intramolecular nucleophilic addition without recyclyzation of imide cycle.

Cannabidiol (CBD) is a safe and non-psychotropic phytocannabinoid with a wide range of potential therapeutic antiinflamatory and antioxidant activity. Due to its lipophilicity, it is normally available dissolved in oily phases. The main aim of this work was to develop and characterize a new formulation of a microemulsion with a potential anti-inflammatory and antioxidant action for topical treatment of inflammatory skin disorders. The micro-emulsion system was obtained from a 20% CBD oil as hydrophobic phase, Labrasol/Plurol Oleique (1:1) as surfactant and cosurfactant (S/CoS) respectively and an aqueous vegetal extract obtained from S. ebulus L. ripe fruits, with a potential anti-oxidant and anti-inflammatory activity, as water phase. A pseudo-ternary phase diagram was elaborated, selecting an optimal proportion of 62% (S/CoS), 27% CBD oil and 11% water and, after testing its reproducibility, the aqueous phases were replaced by the vegetal hydrophilic extract. The defined systems were characterized in terms of conductivity, droplet size by laser scattering, compatibility of components by differential scanning calorimetry and rheological properties using a rotational rheometer. The designed microemulsion showed good stability and a slight pseudo-plastic behavior. The release properties of CBD from the oil phase and caffeic acid from the water phase of the microemulsion were studied by in vitro diffusion experiments using flow-through diffusion cells in comparison to a CBD oil and a microemulsion only with CBD as active substance. It was evidenced that the inclusion of the original oil in microemulsions did not provoke a significant modification of the release of CBD, incorporating the possibility of including hydrophilic active compounds in the formulation, stablishing an interesting strategy for the development of future formulations.

Being able to express broad families of equivariant or invariant attributed graph functions is a popular measuring stick of whether graph neural networks should be employed in practical applications. However, it is equally important to learn deep local minima of losses (i.e., with much smaller loss values than other minima), even when architectures cannot express global minima. In this work we introduce the architectural property of attracting GNN optimization trajectories to local minima as a means of achieving smaller losses. We take first steps in satisfying this property for losses defined over attributed undirected unweighted graphs with a novel architecture, called Universal Local Attractor (ULA). The latter refines each dimension of end-to-end trained node feature embeddings based on graph structure to track the optimization trajectories of losses satisfying some mild conditions. The refined dimensions are then linearly pooled to create predictions. We experiment on 10 tasks, from node classification to clique detection, on which ULA is comparable with or significantly outperforms popular alternatives of similar or greater theoretical expressive power.

For concrete structures exposed to offshore areas, chloride ion erosion is one of the main factors affecting the durability. It is crucial to evaluate chloride ion permeability resistance of concrete structures. In this article, a finite element simulation of the chloride ion diffusion process in concrete is conducted. A mass diffusion finite element model based on random aggregate approach is established to investigate the influence of aggregate, interface transition zone, and micro-cracks on chloride ion diffusion coefficients in concrete. The results show that the mass diffusion finite element analysis based on the exponential function model and power function model can effectively simulate the chloride ion diffusion process in concrete. In addition, the data reveal that coarse aggregate is the most important factor affecting chloride ion diffusivity in concrete. However, the interface transition zone significantly accelerates chloride ion diffusion in concrete. Moreover, this acceleration effect exceeds the barrier effect of aggregate.

To assess the impact of a deep learning (DL) denoising reconstruction algorithm applied to identical patient scans acquired with two different voxel dimensions, representing distinct spatial resolutions. This IRB approved prospective study was conducted at a tertiary pediatric center in compliance with the Health Insurance Portability and Accountability Act. We used a General Electric Signa Premier unit (GE Medical Systems, Milwaukee, WI) to acquire two DTI sequences of the left knee on each child at 3T: an in-plane 2.0 x 2.0 mm2 with section thickness of 3.0 mm and a 2 mm3 isovolumetric voxel, neither had an inter-section gap. We used a multi-band DTI acquisi-tion with fat-suppressed single-shot spin-echo echo-planar sequence (20 non-collinear directions; b-values of 0 and 600 sec/mm2). The MR vendor-provided a commercially available DL model applied with 75% noise reduction settings to same subject DTI sequences at different spatial res-olutions. We compared DTI tract metrics from both DL-reconstructed scans and non-denoised scans for femur and tibia, at each spatial resolution. Differences were evaluated using Wilcox-on-signed ranked test and Bland-Altman plots. When comparing DL versus non-denoised diffu-sion metrics in femur and tibia using the 2 mm x 2mm x 3 mm voxel dimension there were no significant differences between tract count (p = 0.1, p =0.14) tract volume (p = 0.14, p = 0.29), or tibial tract length (p=0.16); femur tract length exhibited a significant difference (p

Auger-emitting radionuclides exemplified by Pd-103, exhibit considerable therapeutic potential in cancer treatment due to their heightened cytotoxicity and localized biological impact. Despite these advantages, the separation of such radionuclides presents a complicated challenge, requiring intricate and time-intensive "wet chemistry" methods attributed to the exceptional chemical inertness of the associated metals. This study proposes an innovative solution to this separation challenge through the design and implementation of a radionuclide separation equipment (RSE). The equipment employs a dry distillation approach, capitalizing on differences in partial vapor pressures between irradiated and resulting radioactive metals, with a diffusion-driven extraction method applied to separate Pd-103 radionuclides generated via proton irradiation of Rh-103 at the ATOMKI MGC-20 cyclotron. Optimization endeavors focused on determining the optimal temperature for effective metal separation, adjusting diffusion, evaporation, and deposition rates, as well as addressing chemical impurities. Calculations indicate 17 % ± 2 % separation efficiency with our RSE. Approximately 77% ± 2% and 49% ± 2% of the deposited Pd-103 were isolated on substrates of Nb foil and ZnO-covered W disk, respectively. The proposed innovative dry distillation method that has been experimentally tested, offers a promising alternative to conventional separation techniques, enabling enhanced purity and cost-efficient cancer treatment strategies.

The presence of phase diffusion can lead to the loss of the advantages of quantum measurements. Squeezing is considered to be an effective method to reduce the detrimental effect of phase diffusion on the measurement. The Mach-Zehnder (MZ) interferometer has been exploited as a generic tool for precise phase measurement. Describing the reduction in quantum advantage caused by phase diffusion in an MZ interferometer that can be mitigated by squeezing is not easy to handle analytically, because the input state will change from a pure state to a mixed state after experiencing the diffusion noise in the MZ interferometer. We introduce a truncated MZ interferometer that can achieve the same potential phase sensitivity as the conventional MZ interferometer. This scheme can theoretically explain how phase diffusion reduces phase estimation and why squeezing counteracts in the presence of phase diffusion. Using the Gaussian property of the input state and the characteristic of Gaussian operation in the squeezing, the two orthogonal field quantities of the quantum state are squeezed and anti-squeezed to different degrees, and the analytic results are obtained. The truncated MZ interferometer is simpler to build and operate than the conventional MZ interferometer, and also mitigates the phase diffusion noise by the squeezing operation, thus making it useful for applications in precision metrology.

As part of a comprehensive research on eco-friendly processing techniques, the influence of heat treatment environment on the case-hardening of AISI 1018 steel using pulverized cassava leaf was studied. The process was carried out at two different temperatures (850˚C and 950˚C) and under three environmental conditions: (Process 1) the control experiment, was carried out in air only, (Process 2) the medium comprised of pulverized cassava leaves, and (Process 3) the combination of pulverized cassava leaves plus barium carbonate (BaCO3) as an energizer (CBC mixture). Vickers microhardness testing and scanning electron microscopy were used to evaluate the effect of processing environment on case hardening of the steel. As expected, regardless of the processing temperature, Process 1 resulted in little or no hardening of the steel surface. However, notable case hardening occurred when steel specimens were subjected to either Process 2 or Process 3. Furthermore, the inclusion of barium carbonate in Process 3 significantly enhanced the case hardening effectiveness of the cassava leaf as it pertains to rate and maximum hardness achieved. Maximum enhancement was observed at 950oC. After 1 hour, the increase in hardness were 160% and 280%, for Process 2 and Process 3, respectively. Upon increasing the processing time to 5 hours, the increase in hardness due to Process 2 was raised to 254%, while that of Process 3 remained at approximately 280%. Diffusivity of AISI 1018 was calculated using the microhardness data. Diffusivity was highest in Process 2 samples with values of 1.568 x 10-9 m2/s at 850°C and 1.893 x 10-9 m2/s at 950 °C.

The focus of this paper is on analyzing the role and the choice of parameters in sociophysics diffusion models, by leveraging the potentialities of sociophysics from a mathematical programming perspective. We first present a generalised version of Galam’s opinion diffusion model (see, e.g. , ). For a given selection of the coefficients in our model, this proposal yields the original Galam’s model. The generalised model suggests guidelines for possible alternative selection of its parameters that allow to foster diffusion. Examples of the parameters selection process as steered by numerical optimisation, taking into account various objectives, are provided.

This paper explores the relationships between marketing strategies, social media platforms, the adoption and diffusion of products and services, and organizational resilience to gain an understanding of the ability of organizations to cope with disruptive events (e.g., COVID-19). This can be achieved through effective marketing strategies and the efficient use of social media platforms. In fact, resilience thinking can help organizations maintain their operations by increasing the adoption and diffusion of their products and services through the use of effective marketing strategies. To achieve this article’s objectives, a literature review is conducted to help develop a conceptual framework that highlights a clear relationship between the previously discussed concepts. In addition, the novel nature of the relationship between marketing strategies and organizational resilience is dissected and its significance for organizations is demonstrated. In fact, the findings of this study suggest that effective marketing strategies that consider the "what," "who," and "how" dichotomies and the efficient use of social media to promote the adoption and diffusion of products and services can significantly enhance the resilience of organizations. These relationships can serve as a starting point for further studies examining and empirically analyzing marketing strategies and their positive effect on strengthening organizational resilience.

False positives on multiparametric (mp)-MRI result in a large number of unnecessary biopsies in men with clinically insignificant diseases. This study investigates whether quantitative diffusion MRI can improve differentiation between false positives, true positives and normal tis-sue. Twenty-three patients underwent mp-MRI and Vascular, Extracellular and Restricted Diffu-sion for Cytometry in Tumours (VERDICT)-MRI, followed by transperineal biopsy. The patients were categorised into two groups following biopsy: (1) significant cancer - true positive (2) atro-phy/inflammation/high-grade prostatic intraepithelial neoplasia (PIN) - false positive. The clinical apparent diffusion coefficient (ADC) values of the lesions were obtained, and the intravoxel inco-herent motion (IVIM), diffusion kurtosis imaging (DKI) and VERDICT models were fitted using a deep learning approach. Significant differences (p < 0.05) between true positive and false positive lesions were found in ADC, IVIM perfusion fraction (f) and diffusivity (D), DKI diffusivity (DK) and kurtosis (K) and VERDICT intracellular volume fraction (fIC), extracellular-extravascular vol-ume fraction (fEES) and diffusivity (dEES) values. Significant differences between false positives and normal tissue were only found for the VERDICT fIC. These results demonstrate that model-based diffusion MRI could reduce the number of unnecessary biopsies due to false positive prostate lesions and shows promising sensitivity to benign diseases that mimic cancer.

It is known that ammonium has a higher permeability through anion-exchange and bipolar membranes compared to K+ cation that has the same mobility in water. However, the mechanism of this high permeability is not clear enough. We develop a mathematical model based of the Nernst-Planck and Poisson equations for diffusion of ammonium chloride through an anion-exchange membrane; proton exchange reactions between ammonium, water and ammonia are taken into account. It is assumed that ammonium, chloride and OH− ions can only pass through membrane hydrophilic pores, while ammonia can also dissolve in membrane matrix fragments not containing water and diffuse through these fragments. It is found that due to the Donnan exclusion of H+ ions as coions, the pH in the membrane internal solution increases when approaching the membrane side facing distilled water. Consequently, there is a change in the principal nitrogen-atom carrier in the membrane: in the part close to the side facing the feed NH4Cl solution (pH&lt;8.8), it is the NH4+ cation, and in the part close to distilled water, NH3 molecules. The concentration of NH4+ reaches almost zero at a point close to the middle of the membrane cross-section, which approximately halves the effective thickness of the diffusion layer for the transport of this ion. When NH3 takes over the nitrogen transport, it only needs to pass through the other half of the membrane. Leaving the membrane, it captures an H+ ion from water, and the released OH− goes towards the membrane side facing the feed solution to meet the NH4+ ions. The comparison of the simulation with experiment shows a satisfactory agreement.

Sulphuric acid is a widely used raw material in the chemical industry. Its corrosive effect on materials varies considerably, depending on impurities, temperature and water content. Accordingly, good corrosion resistance under all conditions is very difficult to achieve. This is especially an issue for micro process apparatus with very thin walls. Furthermore, such devices are often joint by diffusion bonding what may alter materials properties due to high temperatures and long dwell times. In fact, for each new material, the diffusion bonding parameters must be optimized and the impact on mechanical as well as corrosion properties must be investigated. In this paper, two high molybdenum alloys, namely Hastelloy B3 and BC-1, were evaluated. Diffusion bonding tests were performed using ten layers of sheet material in between round stock. Corrosion tests were performed in 70 % sulphuric acid at 100°C for 1000 h. Tensile tests on both alloys were carried out for different material conditions, to determine the change in mechanical strength and elongation at fracture values. In general, independent of the condition of the materials, the fracture behavior of both alloys was found to be ductile and the specimens show the typical dimple structure, in the case of diffusion bonded samples, interrupted by weak spots or rather non-bonded areas. These areas are obviously causing the onset of material failure and thus, a degradation of mechanical properties. Tensile samples, that were aged in 70% sulphuric acid at 100°C for 1000 hours showed local corrosion attacks at the grain boundaries at the circumferential surfaces and especially at the joining planes – for Hastelloy B3 much more pronounced than for Hastelloy BC-1. Accordingly, a further decrease of both, the stress- and elongation at fracture values is observed. However, the typical material parameters like 0.2 % yield strength used for dimensioning components are found to be sufficient high, even when operating the materials under such harsh conditions. When concluding the results, at least Hastelloy BC-1 reveals both sufficient good mechanical properties and an excellent corrosion resistance, regardless of the heat treatment, and could be considered for manufacturing micro-process engineering apparatuses operated in a sulphuric acid environment. This is a significant advance compared to the results obtained within a AiF project, previously carried out on four different materials to investigate the corrosion resistance in sulphuric acid.

A novel drive current model covering the effects of source/drain voltage (VDS) and gate voltage (VGS) and incorporating drift and diffusion current on the surface channel at the nano-node level, especially beyond 28nm node is presented. The effect of the diffusion current added is more satisfactory to describe the behavior of the drive current in nano-node MOSFETs, fabricated with the atomic-layer-deposition (ALD) technology. This breakthrough in model establishment can expose the long and short channel devices together. Introducing the variables of VDS and VGS, the mixed current model more effectively and meaningfully demonstrates the drive current of MOSFETs under the operation of horizontal, vertical, or mixed electrical field. In comparison between the simulation and experimental consequences, the electrical performance is impressive. The error between both is less than 1%, better than the empirical adjustment to issue a set of drive current models.

Unsupervised metric learning has been generally studied as a byproduct of dimensionality reduction or manifold learning techniques. Manifold learning techniques like Diusion maps, Laplacian eigenmaps has a special property that embedded space is Euclidean. Although laplacian eigenmaps can provide us with some (dis)similarity information it does not provide with a metric which can further be used on out-of-sample data. On other hand supervised metric learning technique like ITML which can learn a metric needs labeled data for learning. In this work propose methods for incremental unsupervised metric learning. In rst approach Laplacian eigenmaps is used along with Information Theoretic Metric Learning(ITML) to form an unsupervised metric learning method. We rst project data into a low dimensional manifold using Laplacian eigenmaps, in embedded space we use euclidean distance to get an idea of similarity between points. If euclidean distance between points in embedded space is below a threshold t₁ value we consider them as similar points and if it is greater than a certain threshold t₂ we consider them as dissimilar points. Using this we collect a batch of similar and dissimilar points which are then used as a constraints for ITML algorithm and learn a metric. To prove this concept we have tested our approach on various UCI machine learning datasets. In second approach we propose Incremental Diusion Maps by updating SVD in a batch-wise manner.

Water electrolysis provides efficient and cost-effective production of hydrogen from renewable energy. Currently, the oxidation half-cell reaction relies on noble-metal catalysts, impeding widespread application. In order to adopt water electrolyzers as the main hydrogen production systems, it is critical to develop inexpensive and earth-abundant catalysts. This review discusses the proton exchange membrane (PEM) water electrolysis (WE) and the progress in replacing the noble-metal catalysts with earth-abundant ones. Researchers within this field are aiming to improve the efficiency and stability of earth-abundant catalysts (EACs), as well as to discover new ones. The latter is particularly important for the oxygen evolution reaction (OER) under acidic media, where the only stable and efficient catalysts are noble-metal oxides, such as IrO_x and RuO_x. On the other hand, there is significant progress on EACs for the hydrogen evolution reaction (HER) in acidic conditions, but how many of these EACs have been used in PEM WEs and tested under realistic conditions? What is the current status on the development of EACs for the OER? These are the two main questions this review addresses.

Innovations in drug delivery systems are crucial for enhancing therapeutic efficiency. Our research presents a novel approach based on Electro-fluid dynamic atomization (EFDA) to fabricate core-shell monophasic particles (CSMp) from sodium alginate blends of varying molecular weights. This study explores the morphological characteristics of these particles in relation to material properties and process conditions, highlighting their potential in drug delivery applications. A key aspect of our work is the development of a mathematical model that simulates the release kinetics of small molecules, specifically sodium diclofenac. By assessing the diffusion properties of different molecules and gel formulations through transport and rheological models, we have created a predictive tool for evaluating the efficiency of these particles in drug delivery. Our findings underscore two critical independent parameters for optimizing drug release: the external shell thickness and the diffusivity ratios within the dual layers. This allows for precise control over the timing and intensity of the release profile. The study advances our understanding of EFDA in the fabrication of CSMp and offers promising avenues for enhancing drug delivery systems by tailoring release profiles through particle characteristic manipulation.

Person Re-identification is the task of recognizing comparable subjects across a network of nonoverlapping cameras. This is typically achieved by extracting from the source image a vector of characteristic features of the specific person captured by the camera. Learning a good set of robust, invariant and discriminative features is a complex task, often leveraging contrastive learning. In this article, we explore a different approach, learning the representation of an individual as the conditioning information required to generate images of the specific person starting from random noise. In this way we decouple the identity of the individual from any other information relative to a specific instance (pose, background, etc.), allowing interesting transformations from one identity to another. As generative models, we use the recent diffusion models that have already proven their sensibility to conditioning in many different contexts. The results presented in this article serve as a proof-of-concept. While our current performance on common benchmarks is lower than state-of-the-art techniques, the approach is intriguing and rich of innovative insights, suggesting a wide range of potential improvements along various lines of investigation.

In this paper, we investigate a financial market in which asset prices evolve based on a multi-dimensional Brownian motion process and a multi-dimensional Poisson process with different credit and deposit rates We proceed to evaluate European options by establishing upper and lower hedging prices through a transition to a suitable auxiliary market. Additionally, we address the minimization of shortfall risk and no-arbitrage price bounds in incomplete markets within this framework.

Agriculture is pivotal in national economies, with pest detection significantly influencing food quality and quantity. Pest classification remains challenging in automated agriculture monitoring systems, exacerbated by the non-uniform pest scales and the scarcity of high-quality datasets. In this study, we constructed a pest dataset by acquiring domain-agnostic images from the Internet and resizing them to a standardized 299x299 pixel format. Additionally, we employed diffusion models to generate supplementary data. While Convolutional Neural Networks (CNNs) are prevalent for prediction and classification, they often lack effective global information integration and discriminative feature representation. To address these limitations, we propose the RS Transformer, an innovative model that combines elements like the Region Proposal Network, Swin Transformer, and ROI Align. Additionally, we introduce the Randomly Generated Stable Diffusion Dataset (RGSDD) to augment the availability of high-quality pest datasets. Extensive experimental evaluations demonstrate the superiority of our approach compared to both two-stage models (SSD and Faster R-CNN) and one-stage models (YOLOv3, YOLOv4, YOLOv5m, YOLOv8, and DETR). We rigorously assess performance using metrics such as mean Average Precision (mAP), F1Score, Recall, and mean Detection Time (mDT). Our research contributes to advancing pest detection methodologies in automated agriculture systems, promising improved food production and quality.

The current study primarily aimed to simulate detonation initiation via turbulent jet flame acceleration in partial-premixed H2-air mixtures. Different vertical concentration gradients were generated by varying the duration of hydrogen injection (referred to as diffusion time) within an enclosed channel filled with air. H2-air mixtures with average hydrogen concentrations of 22.5% (lean mixture) and 30% (near stoichiometric mixture) were investigated at diffusion times of 3, 5, and 60 seconds. Numerical results show that the vertical concentration gradient has a major influence on the early-stage of flame acceleration (FA). In the stratified lean mixture, detonation began in all the diffusion times, and comparing the flame-speed graphs showed that a decrease in the diffusion time and an increase in the mixture inhomogeneity speeded up the flame propagation and the jet flame to detonation transition occurrence in the channel. In the stratified H2-air mixture with an average hydrogen concentration of 30%, transition from a turbulent jet flame to detonation occurred in all the cases, and the mixture inhomogeneity weakened the FA and delayed the detonation initiation.

The introduction on Zinc oxide nanoparticles (ZnOn) in sunscreens solved the issue of poor spreadability of these formulations, which often left a white film on the skin. However, safety concerns have arisen regarding the topical application of ZnOn. Some studies employed commercial sunscreens to address the safety issues of the topical application of ZnOn; however, commercial formulations are often complex and contain a wide range of ingredients that could attenuate the potential damage caused by the ZnOn. Therefore, in this study we aimed to develop a simple stable formulation containing 20% of coated and uncoated ZnOn, characterize the formulations and the nanoparticles, and assess the skin penetration in Franz diffusion cell. The Feret's diameter for the uncoated and coated ZnOn was 137 nm and 134 nm, respectively. For the uncoated ZnOn the hydrodynamic size in water was 368 nm and for the coated ZnOn, the average hydrodynamic size in ethyl acetate was 135 nm. The incorporation of ZnOn led to formulations more consistent and easier to spread, as suggested by the lower work of shear and higher values of firmness, cohesiveness, consistency and index of viscosity compared with the vehicle. The stability assessment at 45ºC suggested that the formulations containing the ZnOn were stable for 30 days and the vehicle was stable for 90 days. The assessment off the skin penetration by reflectance confocal laser microscopy indicated that the formulations did not permeate into the deepest layers of the skin, but accumulated on the skin furrows, hair and hair follicle.

In this study, a new approach to pesticide permeation through the apple peel into the pulp is discussed. The tested compounds can be classified, based on mode of action, as systemic (boscalid, cyprodinil, pirimicarb, propiconazole and tebuconazole) or contact (captan, cypermethrin and fludioxonil) pesticides. The barrier effect was assessed using a Franz flow-type vertical diffusion cell system. Residue analysis was performed using a modified quick, easy, cheap, efficient, rugged and safe (QuEChERS) extraction method coupled to gas chromatography with tandem mass spectrometry (GC-MS/MS). The limits of detection (LODs) ranged between 2.6 µg kg-1 (pirimicarb) and 17 µg kg-1 (captan), with the coefficient of variability (CV) lower than 6%, while recoveries ranged from 85% (boscalid) to 112% (captan) at 0.1 and 1 mg kg-1 spiked levels. The highest peel penetration was observed for pirimicarb, captan and cyprodinil, with cumulative permeation of 90, 19 and 17 µg cm-2, respectively. The total absorption was in the range from 0.32% (tebuconazole) to 32% (pirimicarb). Only cypermethrin was not quantitatively detected in the pulp and its use can be recommended in crop protection techniques. The obtained results indicate that molecular weight, octanol-water partition coefficient and water solubility are important parameters determining the process of pesticide absorption.

The reference method for cefiderocol antimicrobial susceptibility testing is broth microdilution (BMD) with iron-depleted-Mueller-Hinton (ID-MH) medium, whereas breakpoints recommended for disk diffusion (DD) are based on MH-agar plates. We aimed to compare the performance of the commercial BMD tests ComASP (Liofilchem) and UMIC (Bruker), DD and E-test using MH- and ID-MH-agar plates with the reference BMD method using 100 carbapenem-resistant-A. baumannii isolates. Standard BMD was performed according to the EUCAST guidelines, DD and E-test were carried out using two commercial MH-agar plates (bioMérieux and Liofilchem) and an in-house ID-MH-agar plate, while ComASP and UMIC were performed according to the manufacturer’s guidelines. DD performed with the ID-MH-agar plates led to a higher categorical agreement (CA, 95.1%) with standard BMD and fewer categorization errors compared to the commercial MH-agar plates (CA bioMérieux 91.1%, Liofilchem 89.2%). E-test on ID-MH-agar plates exhibited a significantly higher essential agreement (EA, 75%) with standard BMD compared to the two MH-agar plates (EA bioMérieux 57%, Liofilchem 44%), and showed a higher performance in detecting high-level resistance than ComASP and UMIC (mean log2 difference with standard BMD for resistant isolates of 0.5, 2.83 and 2.08, respectively). In conclusion, DD and E-test on ID-MH-agar plates exhibit a higher diagnostic performance than on MH-agar plates and the commercial BMD methods. Therefore, we recommend using ID-MH-agar plates for cefiderocol susceptibility testing of A. baumannii.

The purpose of this paper is to study the influence of diffusion and thermal loading due to pulsed laser heating on a thermoelastic solid with voids in the context of the model of three-phase-lag. The non-dimensional governing equations are formulated and then the exact expressions for the temperature field, the displacement components, the stress components, the concentration field and the change in the volume fraction field are obtained using the normal mode technique. The material is an isotropic, homogeneous elastic half-space and heated by a non-Gaussian laser beam with pulse duration of ps. The magnesium crystal element is used as an application to compare the predictions induced by diffusion and laser pulse on poro-thermoelastic medium of the model of three-phase-lag with those for the theory of Green–Naghdi of type III. The results obtained for thermal changes are verified by comparison with two theories of thermoelasticity, namely the model of three-phase lag (3PHL) and the Green and Nagdi type III theory. Plot the expressions to examine the effect of the laser pulse at two different values of time and the effect void parameter. This study also yields some interesting special cases.

Recent advances in synthetic membranes allow their use in fields as diverse as food and agriculture, biotechnology, industrial wastewater treatment, and potable water production. Among the newly developed technologies, nanofiltration for liquids and more particularly for desalination of seawater or saline aquifers are actively pursued. However, current solid-state membranes performance is limited, which calls for the development of novel formulations for membranes offering both high permeability (ion and water flux) and ion differentiation (selectivity), usually considered antagonist features. We report the development of hybrid nanoporous membranes made of solid-state polymeric carbonate track-etched (PCTE) thin films in which biological ion channels such as Gramicidin A (GA), alpha-hemolysin (α-HL), and outer-membrane protein F (OmpF) aquaporin are confined and graphene oxide (GO) conjugated cobalt ion selective binding peptide motifs (Copep) are adsorbed, referring as bioinspired and biomimetic approaches, respectively. These solid-state nanoporous membranes are attracting widespread attention since they offer scalability, mechanical robustness, selectivity, controlled pore dimension and shape, for water sustainability. The ion permeability, ion diffusion coefficient and selective ion recognition are evaluated via nanofiltration, cell diffusion kinetics, and UV-Visible absorption spectroscopy to gain insights into the role of key performance parameters including effective ion confinement in track-etched pores, rich surface chemistry, and peptide-induced channel for selective ion transport. These findings provide new avenues for artificial ion channels by synergistic combination of eco-friendly material design such as GO enabled by bio-molecular recognition chemistry.

The durability of ecological concrete in a marine environment was studied. Specimens of a six-year-old submerged ecological concrete from a breakwater located in the East Mediterranean sea were analyzed for their biological carbonate deposition cover, chloride effective diffusion, carbonation, and mineralogy. About 57% of the surface was found to be covered by biogenic-deposited carbonates. The effective chloride diffusion coefficient and the carbonation rate were found to be reduced proportionally to the biogenic-carbonate cover. Most of the aluminates were found in non-crystalline minerals. No evidence of a sulfate attack was found.

Background: As coronavirus (COVID-19) continues to pose a threat to the entire world, it is critical to developing strategies for containing its spread. The purpose of this study was to assess the demographic characteristics, brain tomography characteristics, and diffusion magnetic resonance findings of COVID-19 positive individuals. Material and Method: Between January 1 and December 31, 2021, 317 patients over the age of 18 were admitted to the emergency department with symptoms consistent with COVID-19. Three groups were formed based on clinical findings in patients, divided into light, medium, and severe, and four groups were formed based on radiological imaging findings. Results: The mean age of the 317 patients included in the study was 67.28±12.06 years, with a range of 28-91 years. The clinical classification of the patients was based on laboratory parameters and radiological imaging, not on their age or gender. Mild cases were classified as CO-RADS 0-4; moderate and severe cases were classified as CO-RADS 5-6 (p=0.001). While 60 (18.9%) of patients were followed outpatient, 144 (45.4%) were admitted to the hospital, 73 (23%) were admitted to the intensive care unit, and 40 (12.7%) died (p=0.001). Direct radiographs revealed bilateral involvement in 224 (70.7%) cases, peripheral involvement in 259 (81.7%) cases, and mid-lower lobe lung involvement in 194 (61.2%) cases (p=0.001). Brain tomography revealed infarction in 42 (13.2%) of the patients who were followed and hospitalized and hemorrhage in 22 (6.9%) of the patients. Magnetic resonance imaging revealed diffusion involvement in 68 (21.5%) of the cases (p=0.001). Conclusion: A standardized reporting system for COVID-19 data is required, and it must be simple to use, quick to understand, and focused on determining the risk of pneumonia. Additionally, the diagnostic role of radiological imaging, prognosis prediction, and severity scoring of lung involvement should be included.

Nonlinear catastrophes caused by geological fluids are a fundamental issue in rock mechanics and the geoengineering hazard field. For the consideration of hydrodynamic force on red-bed mudstone softening damage, X-ray visualization test on the fissure flow in mudstone block failure under hydrodynamic force was performed in this study based on block scale and the physical phenomena of fissure seepage and nonlinear diffusion were further explored. A new method for evaluating the hydro-damage degrees of rocks using an X-ray image analysis was proposed, and the quantitative relation of diffusion coefficients of hydro-damage and seepage was established. The research results revealed that the hydrodynamic force promoted the fluid-filled fissure behavior in mudstone specimen failure. Also, the seepage and diffusion phenomena of fluid in rocks during failures were indicated using X-ray imaging. A dual mechanical behavior was presented in the nonlinear seepage and abnormal diffusion of a red mudstone geological body under hydrodynamic conditions. The damaged degree of mudstone was aggravated by the effect of hydrodynamic force, and the initial seepage–diffusion coefficient with respect to lower hydro-damage was larger than the final seepage–diffusion coefficient with respect to higher hydro-damage of rocks with a decreasing nonlinear trend.

Gradient-domain image processing is a technique where, instead of operating directly on the image pixel values, the gradient of the image is computed and processed. The resulting image is obtained by reintegrating the processed gradient. This is normally done by solving the Poisson equation, most oftenly by means of a finite difference implementation of the gradient descent method. However, this technique in some cases lead to severe haloing artefacts in the resulting image. To deal with this, local or anisotropic diffusion has been added as an ad-hoc modification of the Poisson equation. In this paper, we show that a version of anisotropic gradient-domain image processing can result from a more general variational formulation through the minimisation of a functional formulated in terms of the eigenvalues of the structure tensor of the differences between the processed gradient and the gradient of the original image. Example applications of linear and non-linear local contrast enhancement and colour image daltonisation illustrate the behaviour of the method.

For the past few decades, researchers have been intrigued with glassy polymers, which have applications ranging from gas separations to corrosion protection to drug delivery systems. The techniques employed to examine the sorption and diffusion of small molecules in glassy polymers are the subject of this review. Diffusion models in glassy polymers are regulated by Fickian and non-Fickian diffusion, with non-Fickian diffusion being more prevalent. The characteristics of glassy polymers are determined by sorption isotherms, and different models have been proposed in the literature to explain sorption in glassy polymers during the last few years. This review also includes the applications of glassy polymer. Despite having so many applications, current researchers still have difficulty in implementing coating challenges due to issues like as physical ageing, which is briefly discussed in the review.

Background: Glioblastoma is the deadliest, yet most common, brain tumor in adults, with poor survival and response to aggressive therapy. Therapeutic failure results from a number of causes inherent to these tumors. Imaging, computational, and drug delivery approaches can aid in the quest to access and kill each tumor cell in patients. One factor, interstitial fluid flow, is a driving force therapeutic delivery. However, convective and diffusive transport mechanisms are un-der-studied. In this study, we examine the application of a novel image analysis method to meas-ure fluid flow and diffusion in glioblastoma patients with MRI and compare to patient outcomes. Methods: Building on a prior imaging methodology tested and validated in vitro, in silico and in preclinical models of disease, here we apply our analysis method to archival patient data from the Ivy GAP dataset. Results: We characterize interstitial fluid flow and diffusion patterns in patients. We find strong correlations between flow rates measured within tumors and in the surrounding parenchymal space, where we hypothesized that velocities would be higher. Looking at overall magnitudes, there is significant correlation with both age and survival in this patient cohort. Additionally, we find that tumor size nor resection significantly alter the velocity magnitude. Last, we map the flow pathways in patient tumors and find variability in degree of directionality that we hypothesize in future studies may lead to information concerning treatment, invasive spread, and progression. Conclusions: Analysis of standard DCE-MRI in patients with glioblastoma offers more infor-mation regarding transport within and around tumor, can be measured post-resection and mag-nitudes correlate with patient prognosis.

The general coupling between particle transport and ionization-recombination processes in hot plasma is considered on the key concept of equilibrium charge state (CS) transport. A theoretical interpretation of particle and CS transport is gained in terms of a two-dimensional (2D) Markovian stochastic (random) processes, a discrete 2D Fokker-Plank-Kolmogorov equation (in charge and space variables) and generalized 2D coronal equilibrium between atomic processes and particle transport. The basic tool for analysis of CS equilibrium and transport is the equilibrium cell (EC) (two states on charge and two on space), which presents (i) a unit phase volume, (ii) the characteristic scale of local equilibrium, (iii) a comprehensive solution for the simplest nonlinear relations between transport and atomic processes. The approach opens up new perspectives on transport studies: (i) the direct modelling of equilibrium and transport of impurity using the atomic data base, (ii) recovery of the complete recombination rate profile based on knowledge of density profiles and ionization rate profiles, (iii) the local transport analysis, based on the reduction of the equilibrium set to the single EC (in particular, central or edge), (iv) analysis of the reduced transport coefficients (diffusion and convection) on the density profile measurements.

This study aimed to identify the utility of diffusion-weighted magnetic resonance (MR) imaging with an apparent diffusion coefficient (ADC) map as a predictor of the intrahepatic response of hepatocellular carcinoma (HCC) to cisplatin-based hepatic arterial infusion chemotherapy (HAIC). We retrospectively evaluated 113 consecutive patients with HCC who underwent gadoxetic acid-enhanced and diffusion-weighted MR imaging. The appropriate cutoff for the tumor-to-liver ADC ratio was determined to be 0.741. Of the 113 patients, 51 (45%) presented with a tumor-to-liver ADC ratio < 0.741. Evaluation of the intrahepatic treatment response after 2-3 cycles of HAIC in these 51 patients revealed that 20 patients (39%) experienced an objective response to HAIC. On the other hand, only 10 of the 62 patients with a tumor-to-liver ADC ratio ≥ 0.741 (16%) experienced an objective response. Thus, the objective response rate was significantly higher in patients with a tumor-to-liver ADC ratio < 0.741 than in those with a tumor-to-liver ADC ratio ≥ 0.741 (P = 0.006). Multivariate logistic regression analysis using parameters including perfusion alteration, percentage of a non-enhancing portion, and tumor-to-liver ADC ratio revealed that a tumor-to-liver ADC ratio < 0.741 (odds ratio 3.03; P = 0.015) is the sole predictor of an objective response to HAIC. Overall survival rates were significantly higher in patients with objective responses to HAIC than in those without objective responses (P = 0.001 by log-rank test). In conclusion, patients with unresectable HCC with a tumor-to-liver ADC ratio < 0.741 showed a favorable intrahepatic response to HAIC. Therefore, diffusion-weighted MR imaging can play a critical role as a predictor of response to cisplatin-based HAIC in unresectable HCC.

Medical institutions, where several patients are treated and medical workers engaged, are always exposed to secondary viral and bacterial infections. It is critical to prevent infection transmission by indirect as well as direct contact through air or splash. The infections of most diseases can be transmitted through the air. HEPA filters installed in air conditioning equipment are used to prevent infection transmission through air in medical institutions, but air circulation takes a long time in a large space. Virus and bacteria smaller than 0.3 μm cannot be removed by the HEPA filter; hence, those microbes remain alive throughout the air ventilation. A plasma sterilizer has the capability to provide environmental friendly sterilization by employing reactive oxide species and reactive nitrogen species at a low cost. We developed an excellent plasma sterilizer by using a non-thermal atmospheric-pressure biocompatible plasma (NBP). Ozone concentration in plasma sources has been derived by Kuhn et al. [1]. The diffusion coefficients inside (D₀) and outside (D₁) the plasma sterilizer have been calculated to be 0.0641 m² s^-1 and 0.717 m² s^-1, respectively. To sustain high O₃ concentrations over 121 ppm inside the plasma source and low O₃ concentrations below 0.05 ppm outside the sterilizer, it is necessary to keep O₃ concentrations at the exit of plasma sterilizer below 0.28 ppm. so that diffusion coefficient D₁ has been designed to be as large as 11 times of D₀.

The central limit theorem (CLT) and its generalization to stable distributions have been widely described in literature. However, many variations of the theorem have been defined and often their applicability in practical situations is not straightforward. In particular, the applicability of the CLT is essential for a derivation of heterogeneous ensemble of Brownian particles (HEBP). Here, we analyze the role of the CLT within the HEBP approach in more detail and derive the conditions under which the existing theorems are valid.

This work deals with the numerical investigation of the delivery of potential therapeutic agents through dentinal discs (i.e. a cylindrical segment of the dentinal tissue) towards the dentin-pulp junction. The aim is to assess the main key features (i.e. molecular size, initial concentration, consumption rate, disc porosity and thickness) that affect the delivery of therapeutic substances to the dental pulp and consequently to define the necessary quantitative and qualitative issues related to a specific agent before its potential application in clinical practice. The CFD code used for the computational study is validated with relevant experimental data obtained using micro Laser Induced Fluorescence (μ-LIF) a non-intrusive optical measuring technique. As the phenomenon is diffusion dominated and strongly dependent on the molecular size, the time needed for the concentration of released molecules to attain a required value can be controlled by their initial concentration. Finally, a model is proposed which, given the maximum acceptable time for the drug concentration to attain a required value at the pulpal side of the tissue along with the aforementioned key design parameters, is able to estimate the initial concentration to be imposed and vice versa.

The aim of this work is to present a design approach of a Shock-Induced Combustion Ramjet (Shcramjet) inlet, and present its optimization in terms of the flow and geometrical parameters. The flow properties of mixed compression type inlet of a Shcramjet are examined using analytical and numerical techniques. The geometries obtained with variations in the wedge angles, length, height and cowl lip positions are used to study the flow characteristics of inlet, identifying bow shock temperature ratio as the optimization parameter. The two-dimensional geometries of two-shock and three-shock inlet models designed analytically for shock-on-lip condition at Mach 12.5 and an altitude of 32.5 km are numerically simulated in OpenFOAM CFD Toolbox. A density based compressible CFD solver based on central upwind schemes of Kurganov and Tadmore is used to solve 2D inviscid Euler equations. The inlet total pressure recovery is expressed as a function of temperature ratios of compression shocks, and is found to have a maxima at a bow shock temperature ratio at the design condition when the bow and external shocks have equal strengths. The effect of considering the flow to be calorically imperfect is studied numerically, and the deviation from the analytical design is presented.

Drug hypersensitivity reactions (DHR) to platinum-based compounds (PC) are on the rise, and their personalized and safe management is essential to enable first-line treatment of these cancer patients. This study aimed to evaluate the usefulness of basophil activation test by flow cytometry (BAT-FC) and the newly developed sIgE-microarray and BAT-microarray in diagnosing IgE-mediated hypersensitivity reactions to PC. 24 patients with DHR to PC (20 oxaliplatin and four carboplatin) were evaluated: 13 patients diagnosed as allergic with positive skin tests (STs) or drug provocation tests (DPTs), six patients diagnosed as non-allergic with negative STs and DPTs, and five patients classified as suspected allergic because DPTs could not be performed. In addition, four carboplatin-tolerant patients were included as controls. BAT-FC was positive in 2 of 13 allergic patients, with a sensitivity of 15.4% and specificity of 100%. However, the sIgE- and BAT-microarrays were positive in 11 of 13 DHR patients, giving a sensitivity of over 84.6% and a specificity of 90%. Except for one patient, all samples from the non-allergic and control group were negative for the sIgE- and BAT-microarrays. Our experience indicates that sIgE- and BAT-microarray could be helpful in the endophenotyping of IgE-mediated hypersensitivity reactions to PC and may provide an advance in decision-making for drug provocation testing.

Silybin is a natural compound extensively studied for its hepatoprotective, neuroprotective and anti-cancer properties. Envisioning the enhancement of silybin potential by suitable modifications in its chemical structure, here, a series of new 7-O alkyl silybins derivatives were synthesized by Mitsunobu reaction starting from the silybins and tyrosol-based phenols, such as tyrosol (TYR, 3), 3-methoxytyrosol (MTYR, 4) and 3-hydroxytyrosol (HTYR, 5). This research sought to explore the antioxidant and anticancer properties of new eighteen derivatives and their mechanisms. In particular, the antioxidant properties of new derivatives outlined by DPPH assay, showed a very pronounced activity depending on the tyrosyl moiety (HTYR&gt;MTYR&gt;&gt;TYR). A significant contribution of the HTYR moiety was observed for silybins and 2,3-dehydro-silybin based derivatives. According to the very potent antioxidant activity, 2,3-dehydro-silybin derivatives 15ab, 15a and 15b exerted the most potent anticancer activity in human prostate cancer PC-3 cells. Furthermore, flow cytometric analysis for cell cycle and apoptosis revealed that 15ab, 15a and 15b induce strong G1 phase arrest and increase late apoptotic population in PC-3 cells. Additionally, western blotting for apoptotic marker cleaved caspase-3 confirmed apoptosis induction by these silybin derivatives in PC-3 cells. These findings hold significant importance in the investigation of anticancer properties of silybin derivatives and strongly encourage swift investigation in pre-clinical models and clinical trials.

There is currently much interest in avoiding precious metals in Catalysis. The devel-opment of nickel catalysts to replace palladium in the Mizoroki-Heck reaction is a relevant case in this line of research since both elements share many chemical features. This contri-bution focuses on -Phenyl elimination in alkylnickel complexes. This is the microscopic reverse of olefin insertion (or carbometallation), a fundamental step of the Heck cycle that is usually considered irreversible and selectivity-determining. However, the potential reversibil-ity of carbometallation is generally concealed by the facile beta-hydrogen elimination that follows. Where -hydrogen elimination is hindered, beta-aryl elimination may ensue. We have previously shown that cationic 2-methyl-2-phenylpropyl (neophyl) palladium com-plexes supported by bidentate ligands experience -Ph elimination, which can be seen as an example of olefin de-insertion. In this contribution, we report that -phenyl elimination can also occur in their nickel analogs, in which case fast hydrolyses of the resulting phenyl product can follow the reaction. We investigated the mechanism of these processes and compared their feasibility for nickel and palladium catalysts using DFT calculations. These results are relevant information for the design of nickel-based catalysts for the Heck reac-tion.

In order to study the feasibility of copper-nickel smelting slag（CNSS） and palygorskite for large-scale consumption and utilization in the field of mine filling, gellable composite materials were prepared from copper-nickel smelting slag ,cement and palygorskite. The effects of palygorskite addition and curing time on the mechanical properties and microstructure of copper-nickel smelting slag-based cementitious materials were studied in detail. The results showed that the addition of palygorskite had a positive effect on the curing of the cemented filler of the non-ferrous smelting slag by promoting the early hydration reaction. palygorskite also affected the mechanical properties of the cementitious materials with different maintenance times and the ability to cure heavy metals. The strength of gellable composite materials reaches 23.05MPa when 1% palygorskite, 50% of copper-nickel smelting slag and 48% cement were used, which meet the standards requirements of filling materials for mine goaf. The addition of 1% palygorskite can improve the ability of cementitious materials to solidify heavy metals to realize the economic utilization of solid waste in mining areas.

The performance analysis of the internal/external flows around a high speed vehicle in near-space is fundamental and critical to the configuration and structure design for high speed aircraft. In this paper, the two-dimensional coupled implicit Reynolds Average Navier-Stokes (RANS) solver and RNG k–ε turbulence model is employed to numerically simulate the flow field of an integrated high speed vehicle. The flow field are divided three parts to solve separately and compared with that solved by integrated simulation. The flow field are decomposed to save computer storage and simulation time. The first part is inlet/isolator, the second part is combustion chamber and the third is nozzle. In the computation process, the outlet condition of isolator is endowed to the inlet boundary of combustion chamber and the outlet boundary of combustion chamber is endowed to the inlet boundary of nozzle, then the whole flow field of integrated high speed vehicle is solved. Aerodynamic characteristic of fragment-computation and integration-computation is comparatively analyzed at different angles of attack, the results show that the maximum deviation of lift coefficient obtained by fragment-computation is less than 3% compared with that by integration, the maximum deviation of drag coefficient fragment-computation is less than 5% compared with that by integration, while pitching moment coefficient deviation less than 12%. However, for simulation time-consumption, the time used by fragment-computation reduces 45% compared with integration-computation. Meanwhile, by components force analysis, it can be concluded that the aerodynamic property of inlet/isolator can been obtained separately and hardly effected by other parts.