Bio-devices are designed to allow biological matter to perform in vitro almost the same functions it performs in vivo. Therefore, they can benefit from the specificities of such materials and are expected to perform better than traditional devices. On the other hand, the integration of biological material with electronic/electrochemical instrumentation requires careful attention and can produce unconventional results. In this paper, we describe the impedance response of an electrochemical cell that converts sunlight into electrical power. It uses the photosynthetic system known as Reaction Center, which is the core of photosynthesis in several living beings. Under illumination, an abrupt transformation drives the cell electrical response from insulator to conductor and a photocurrent is observed. The impedance spectrum shows a peculiar shape which significantly modifies with the protein activation. It has been analyzed by means of a graphical/analytical/ numerical procedure. The modelling identifies an analogue electrical circuit, whose parameters give quantitative information about the underlying process. Finally, an appropriate normalization of data is proposed which validates data in dark and light and can be useful as a fast screening of measurements.

This review describes major advances in the use of functionalized molecular metal oxides (polyoxometalates, POMs) as water oxidation catalysts under electrochemical conditions. The fundamentals of POM-based water oxidation are described together with a brief overview of general approaches to designing POM water oxidation catalysts. Next, the use of POMs for homogeneous, solution-phase water oxidation is described together with a summary of theoretical studies shedding light on the POM-WOC mechanism. This is followed by a discussion of heterogenization of POMs on electrically conductive substrates for technologically more relevant application studies. Stability of POM water oxidation catalysts are discussed on selected examples where detailed data is already available. The review finishes with an outlook on future perspective and emerging themes in electrocatalytic polyoxometalate-based water oxidation research.

Copper-based nanoparticles were synthesized using the glycine–nitrate process (GNP) by using copper nitrate trihydrate [Cu(NO₃)₂‧3H₂O] as the main starting material and glycine [C₂H₅NO₂] as the complexing and incendiary agent. The as-prepared powders were characterized through X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) analysis, X-ray photoelectron spectroscopy, and scanning electron microscopy. Using Cu(NO₃)₂.3H₂O as the oxidizer (N) and glycine as fuel (G), we obtained CuO, mixed-valence copper oxides (CuO + Cu₂O, G/N = 0.3–0.5), and metallic Cu (G/N = 0.7). The XRD and BET results indicated that increasing the glycine concentration (G/N = 0.7) and reducing particle surface area increased the yield of metallic Cu. The effects of varying reaction parameters such as catalyst activity, catalyst dose, and H₂O₂ concentration on nonylphenol-9-polyethoxylate (NP9EO) degradation were assessed. With a copper‐based catalyst in a heterogeneous system, the NP9EO and total organic carbon removal efficiencies were 83.1% and 70.6%, respectively, under optimum operating conditions (pH, 6.0; catalyst dose, 0.3 g/L; H₂O₂ concentration, 0.05 mM). The results suggested that removal efficiency increased with an increase in H₂O₂ concentration but decreased when the H₂O₂ concentration exceeded 0.0.5 mM. Furthermore, the trend of photocatalytic activity was as follows: G/N = 0.5 > G/N = 0.7 > G/N = 0.3. The G/N = 0.5 catalysts showed the highest photocatalytic activity and resulted in 94.6% NP9EO degradation in 600 min.

Developing sustainable and renewable energy sources is critical as higher and higher global energy and environmental challenges arise. Hydrogen has the highest mass/energy density of any fuel and is considered one of the best sources of clean energy. Water splitting is regarded as one of the most promising solutions for hydrogen production on a large scale. Highly efficient, durable and cost-effective catalysts for hydrogen evolution reaction (HER) are critical in the realization of this goal. Among many materials proposed, graphene-based materials offer some unique properties for HER catalysis. In this review, we present recent progress on development of graphene-based electrocatalysts toward HER throughout the past few years.

The diffusion coefficients of ions are measured in a microchip filled with a cationic charged 3D hydrogel in order to study the effect of cationic charged 3D hydrogel on the diffusivity of ions. In this study, poly-diallyl-dimethyl-ammoniumchloride (poly-DADMAC) is used to produce a 3D hydrogel. Four different fluorophores are used in the 3D hydrogel rhodamine 6G, rhodamine-BSA, fluorescein isothio-cyanate (FITC) and FITC-BSA. The rhodamine 6G and rhodamine-BSA are positively charged (cations), while fluorescein isothio-cyanate (FITC) and FITC-BSA are negatively charged (anions). Two widely used techniques which are short time diffusivity measurement technique and long time diffusivity measurement techniques are used to measure the diffusion coefficients. For the short time measurement, Fluorescence recovery after photo-bleaching (FRAP) is used by a 3D confocal microscope. For the long time measurement, fluorescence images are taken for 11 days to observe a pure diffusivity without any convective movement. As a result, the diffusivity of the cations was found to be lower than that of the anions in the cationic charged hydrogel.

The chlorophyll is one of the most important natural pigments used extensively in the food industry. Two important factors for the production of chlorophyll are the use of plants rich in chlorophyll and efficiency of extraction method. Present investigation was performed to compare the extraction of photosynthetic pigments by using solvents of different chemical nature. The purslane plants with different growth behavior viz. Scrollable and standing were grown under shade and sunshine stress condition. Different solvents including diethyl ether, 5% ethanol, pure acetone, 20% acetone, pure methanol and 10% methanol were used to extract chlorophyll and carotenoids from the purslane plant. The results indicated that stress, growth type and different solvents had a significant effect on the extraction of chlorophyll and carotenoids. Different trend was observed in extraction rate for chlorophylls and carotenoids. Among the solvents, pure methanol was the best for extraction of chl a. Methanol and acetone were appropriate solvents to achieve the highest amount of chlorophyll from plant tissues. Among different solvents, pure methanol for chl a, pure acetone and methanol for carotenoids were best solvent for purslane plant with a growing type scrollable of under shade.

Due to an increase of the monocrystalline PV systems installations, for a drive towards the sustainable smart cities in the hot arid developing country such as Pakistan, pose challenges of the performance and degradation issues. Monocrystalline PV module efficiencies are declining and damaging under the continuous exposure to higher surface day-time temperatures in the different parts of the country. A MATLAB simulations were performed based on the validated mathematical approach. This paper investigates the hot arid surface temperature impacts on the performance of PV modules during the summer and winter seasons in Pakistan. The investigations are performed examining the power generating efficiency of the PV system. This paper also investigates the influence of installations of PV-system in the North, South, East and West regions of Pakistan. It was examined that the northern areas of Pakistan are more suitable for maintaining the long-term durability of the PV system. Investigations are performed for the peak summer and peak winter days. During summer months, cooling strategies have to be implemented to overcome the heating effects whilst reducing degradation effect on installed PV-system.

In this paper, first the Self-Written Waveguide (SWW) process in wet photopolymer media (liquid solutions), are examined for three examples: single-, counter-, and co-fibers exposure. Then the SWWs formed inside solid material are examined including the effects of manipulating the alignment of the fibers. In all cases high precision measurements are used to position the fiber optic cables (FOCs) before exposure using a microscope. The self-writing process is indirectly monitored by observing (imaging) the light emerging from the side of the material sample during SWW formation. In this way the optical waveguide trajectories formed in an Acrylamide/Polyvinyl Alcohol (AA/PVA) a photopolymer material (sensitized at 532 nm) are examined. First the transmission of light by this material is characterized. Then the bending and merging of the waveguides which occur are investigated. The predictions of our model are shown to qualitatively agree with the observed trajectories. The largest index changes taking place at any time during the exposure, i.e. during SWW formation, are shown to take place at the positions where the largest exposure light intensity is present. Typically, such maxima exist close to the input face and the first maximum is referred to as the location of the Primary Eye. Other local maxima also appear further along the SWW and are referred to as Secondary Eyes, i.e. deeper within the material.

This study investigates the role of oxygen vacancy on Fe-doped CeO₂ catalyst activity for soot oxidation. The oxygen vacancy was assessed through Ce³⁺ content. The Fe content was varied between 0 and 30% for two catalyst preparation methods, co-precipitation (CP) and solution combustion synthesis (SCS). X-ray photoelectron spectroscopy indicates that ceria exists as both Ce₄₊ and Ce₃₊, while iron is present only as Fe₃₊. The catalyst’s activity was evaluated by ignition (T10) and combustion (T50) temperatures using thermogravimetric analysis. Optimum Fe contents yielding the highest activity were found to be 10% and 5% for CP and SCS catalysts, respectively. The surface area and morphology have shown moderate effect on catalyst activity, because catalytic soot oxidation involves solid-solid contact. More importantly, regardless of the fabrication method, it was found that Ce₃₊ content, which is closely related to oxygen vacancies, plays the most important role in affecting the catalyst activity.

The noble metals palladium and silver find use in many high performance applications, and their alloys (PdAg), known for more than sixty years, are industrially important, finding use in many fields including hydrogen purification and separation, numerous facets of catalysis, and in fuel cells. In recent years, interest in these materials has grown significantly, particularly in energy generating applications and due to their performance as solid-state chemical sensors for a range of small molecules. PdAg thin films can be prepared using traditional physical methods such as cold rolling, or more modern and controllable chemical or physical deposition techniques such as electrodeposition or chemical vapour deposition. Despite the wide-reaching uses of PdAg, several recent advancements in materials preparation, such as additive manufacturing, better known as 3-D printing, remain unexplored for this material due to the differing chemistries of the two elements. In this review, we explore the manufacturing methods commonly employed for the preparation of PdAg thin films, the common and niche applications of these materials, and opportunities for the future development of these two aspects, with an emphasis on how preparation of thin films can utilise additive manufacturing approaches.

This data descriptor summarizes the process applied and data gathered from 50 publications/papers reporting on the use of photography generated by tourists, tour operators and members of the public, with a particular focus on the crowdsourcing of photographs through online platforms and social networking sites (SNSs) as a method of research for wildlife conservation and ecotourism. The papers were collected in a systematic literature review to inform a pilot study of the feasibility of using SNSs to crowdsource georeferenced photographs of endangered Bornean Pygmy Elephants (Elephas maximus borneensis) taken by ecotourists along the Lower Kinabatangan River region of Sabah, Malaysia. Papers were sourced using the Murdoch University Findit online-search tool to search over 100 databases, including Proquest, Scopus and Web of Science. The criteria for a paper to be included in the review (and shared via the dataset attached to this this data descriptor) were that it was peer-reviewed, published in English, between 1997 and the 31 December 2017, had the full text accessible online and reported on a study or studies that utilized photographs that tourists, tour operators and/or members of the public generated and shared via SNSs or online platforms.

The first two decades of the 21st-century have seen the emergence of the modern citizen science movement, increased demand for niche eco and wildlife tourism experiences, and the willingness of people to voluntarily share information and photographs online. To varying extents, the rapid growth of these three phenomena has been driven by the availability of portable smart devices, access to the Web 2.0 internet from almost anywhere on the planet, and the development of applications and services, including social media/networking sites (SNSs). In addition, the number of peer-reviewed publications that explore how text and images shared on SNSs can be data-mined for academic research has surged in recent years. This systematic quantitative review has two goals. The first goal is to provide an oversight of how the photographs that ecotourists share online are contributing to wildlife tourism research. The second goal is to promote the emerging photovoice technique as a theoretical context for social research based on the photographs and comments that ecotourists share on SNSs. From the perspectives of community benefits, conservation behaviours, and environmental education, there are many similarities between authentic ecotourism experiences and quality ecological citizen science programs. Much of the literature regarding the theory and practice of citizen science reports on the difficulties of attracting, training, motivating and retaining community members. The synthesis of this review is that crowdsourcing wildlife and tourism data from comments and photographs that ecotourists share on SNSs is a credible method of research that provides a self-replenishing pool of citizen scientists.

Clean production of renewable fuels is a great challenge of our scientific community. Iridium complexes have demonstrated a superior catalytic activity in the water oxidation (WO) reaction, which is a crucial step in water splitting process. Herein we have used a defective zirconium MOF with UiO-66 structure as support of a highly active Ir complex based on EDTA with formula [Ir(HEDTA)Cl]Na. The defects are induced by the partial substitution of tereftalic acid with smaller formiate groups. Anchoring of the complex occurs through a post-synthetic exchange of formiate anions, coordinated at the zirconium clusters of the MOF, with the free carboxylate group of the [Ir(HEDTA)Cl]-complex. The modified material was tested as heterogenous catalyst for the WO reaction by using Cerium Ammonium Nitrate as sacrificial agent. Although TOF and TON values are comparable to those of other iridium heterogenized catalysts, the MOF exhibits iridium leaching not limited at the first catalytic run, as usually observed, suggesting a lack of stability of the hybrid system under strong oxidative conditions.

Redox reactions are of great importance in environmental catalysis. Gold nanoparticles (NPs) have attracted much attention because of their catalytic activity and their localized surface plasmon resonance (LSPR). In the present study, we investigated in details the reduction of ferricyanide (III) ion into ferrocyanide (II) ion catalyzed by spherical gold nanoparticles of two different sizes 15 nm and 30 nm and excited at their LSPR band. Experiments were conducted in the presence (or not) of sodium thiosulfate. This catalysis is enhanced in the presence of Au-NPs under visible light excitation. This reduction takes also place even without sodium thiosulfate. Our results demonstrate the implication of hot electrons in this reduction.

Traditional phase change composites usually suffer poor mechanical property and easy collapsing in the phase changing process. Herein, a highly flexible phase change composite is fabricated using thermoplastic elastomer as the basic gel and the expanded graphite/paraffin as the filler. This new phase change composite shows a tensile strength of 2.1 MPa and a breaking elongation of 220%. It has a melting enthalpy of 145.4 J•g^-1 and a thermal conductivity of 2.2 W•m^-1•K^-1 with 70% of expanded graphite/paraffin. The thermoplastic elastomer based phase change composite exhibits great reversible property after 200 heating/cooling cycles. This flexible phase change composite demonstrates good photo-thermal energy charging/discharging property and shows great potential to be applied in the solar thermal energy systems.

The organo-catalyzed enantioselective benzylation reaction of α-trifluoromethoxy indanones afforded α-benzyl-α-trifluoromethoxy indanones with a tetrasubstituted stereogenic carbon center in excellent yield with moderate enantioselectivity (up to 57% ee). Cinchona alkaloid-based chiral phase transfer catalysts were found to be effective for this transformation, and both enantiomers of α-benzyl-α-trifluoromethoxy indanones were accessed, depended on the use of cinchonidine and cinchonine-derived catalyst. The method was extended to the enantioselective allylation reaction of α-trifluoromethoxy indanones to give the allylation products in moderate yield with good enantioselectivity (up to 76% ee).

Structural perturbations in the Mn4CaO5 cluster site, an oxygen-evolving complex of photosystem II, such as those induced by Ca2+/Sr2+ exchanges or Ca/Mn-removal have been known to induce long-range positive shifts (+30 mV to +150 mV) in the redox potential of the primary quinone electron acceptor plastoquinone A (QA) located 40 Å distant from the OEC. Here, we reanalyzed the crystal structure of Sr-PSII solved at 2.1 Å and compare it with the native Ca-PSII of 1.9 Å with focus on the acceptor site and report on the possible long-range interactions between the donor, Mn4Ca(Sr)O5 cluster, and acceptor sites.

Applied electrostatic engineering can be used to construct greenhouses that prevent entry of insect pests. Two types of electric field screen were used to exclude pests from the greenhouse: single- and double-charged dipolar electric field screens (S- and D-screen, respectively). The S-screen consisted of iron insulated conductor wires (ICWs) arrayed in parallel (ICW-layer), a grounded metal net on either side of the ICW-layer, and a direct current voltage generator. S-screens were attached to the side windows of the greenhouse to repel whiteflies (Bemisia tabaci) that approached the nets. The D-screen was installed in a small anteroom at the greenhouse entrance to capture whiteflies entering through it. The ICW-layers of the D-screen were oppositely charged with equal voltages and arrayed alternately, and an insulator board or grounded metal net was placed on one side of the ICW-layer. The ICW-layers captured whiteflies entering the electric field of the double-charged dipolar electric field. Three screens equipped with yellow or gray boards or a grounded metal net were installed in the anteroom based on the airflow inside the room, as most whiteflies were brought in by air when the door was opened. Two D-screens with boards were useful for directing the airflow toward the wall with the netted D-screen. This screen eliminated the insects and the pest-free air was circulated inside the greenhouse. The D-screen with the yellow board attracted the whiteflies and was effective for trapping them when there was no wind. Our method kept the greenhouse pest-free throughout the entire period of tomato (Solanum lycopersicum) cultivation.

Land degradation monitoring and assessment in the Sahel zone has relied substantially on temporal trends of remote sensing-based vegetation indices, which are proxies for the bioproductivity of the land. However, prior studies have shown that negative or positive trends in bioproductivity are not necessarily associated with degradation or improvement of land condition. In this short communication, while acknowledging the contributions of remote sensing-based indices and global-scale datasets to dismantling an outdated desertification narrative, we argue that local land users have much to contribute to our understanding of land degradation, and particularly to ensuring that scientific assessments of degradation capture variables relevant to them. We used the participatory photo elicitation method in three sites in the Senegalese Ferlo in order to elicit local pastoralists’ perspectives on land degradation and identify the indicators that they use to characterize pasture quality, while empowering them to lead the discussion. The discussion revealed indicators far beyond bioproductivity, including livestock performance as well as composition and quality of the herbaceous and woody vegetative cover, invasive species, soil quality and water availability. We found that the pastoralists’ knowledge and interest in the issue could potentially be harnessed more systematically, and at larger scales, in order to build a spatially explicit field-based knowledge base of land degradation complementary to remote sensing-based maps of trends in bioproductivity. Such a dataset could serve as a standalone product or as a reference dataset for development and validation of remote sensing-based indicators.

A simple and eco-friendly Montmorillonite K10 (MK10) catalyzed method for the synthesis of cyclopentenone derivatives from biomass-produced furfural has been developed. The versatility of this protocol is that the reactions were carried out in solvent free condition and in short reaction time under heterogeneous catalysis. Montmorillonite K10 is a material most explored as heterogeneous catalyst since it is inexpensive and environmentally friendly.

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

A simple solid acid catalyst γ-AlOOH was employed to synthesize 5-hydroxymethylfurfural (HMF) from glucose in the dimethyl sulfoxide. Various reaction parameters, such as catalyst loading, temperature, reaction duration and solvent, were investigated. A high HMF yield of 61.24 % was obtained at the mild reaction condition of 130 °C for 3 h. More importantly, the catalyst γ-AlOOH could be reused for several times without the loss of its significant catalytic activities. After five reaction runs, a HMF yield about 57.23 % was obtained. In addition, the results demonstrated that the γ-AlOOH also had high catalytic activities on the degradation of other polysaccharides, like Maltose, Sucrose and Cellulose, into HMF using ionic liquid 1-butyl-3-methylimidazolium chloride, DMSO and a small amount of water as the reaction solvents. For instance, a high HMF yield of 50.26 % was obtained at 170 °C for 2.5 h on the decomposition of Cellulose.

Nanoparticles of platinum-group metals (PGM) on carbon supports are widely used as catalysts for a number of chemical and electrochemical conversions on laboratory and industrial scale. The newly emerging field of single atom catalysis focuses on the ultimate level of metal dispersion, i.e. atomically dispersed metal species anchored on the substrate surface. However, the presence of single atoms in traditional nanoparticle-based catalysts remains largely overlooked. In this work we use aberration-corrected scanning transmission electron microscope to investigate four commercially available nanoparticle-based PGM/C catalysts (PGM = Ru, Rh, Pd, Pt). We show that in addition to nanoparticles, single atoms are also present on the surface of carbon substrates. These observations raise questions about the role that single atoms play in conventional nanoparticle PGM/C catalysts. We critically discuss the observations with regard to the quickly developing field of single atom catalysis.

A visible-light photoredox functionalization of 3,4-dihydro-1,4-benzoxazin-2-ones through a Friedel-Crafts reaction with indoles using an inexpensive organophotoredox catalyst is described. The reaction uses a dual catalytic system formed by a photocatalyst simple and cheap, 9,10-phenanthrenedione, and a Lewis acid, Zn(OTf)₂. 5W white LEDs are used as visible-light source and oxygen from air as a terminal oxidant, obtaining the corresponding products with good yields. The reaction can be extended to other electron-rich arenes.

Carbon nanotubes have been attracting considerable interest among material scientists, physicists, chemists and engineers for almost 30 years. Owing to their high aspect ratio, coupled with remarkable mechanical, electronic and thermal properties, carbon nanotubes have found application in diverse fields. In this review, we will cover the work on carbon nanotubes used for sensing applications. In particular, we will see examples where carbon nanotubes act as main players in devices sensing biomolecules, gas, light or pressure changes. Furthermore, we will discuss how to improve the performance of carbon nanotube-based sensors after proper modification.

To circumvent the thermodynamic limitation of the synthesis of oxazolidinones starting from 2-aminoethanols and CO2 and realize incorporation CO2 under atmospheric pressure, a protic ionic liquid-facilitated three-component reaction of propargyl alcohols, CO2 and 2-aminoethanols was developed to produce 2-oxazolidinones along with equal amount of α-hydroxyl ketones. The ionic liquid structure, reaction temperature and reaction time were in detail investigated. And 15 mol% [TBDH][TFE] (1,5,7-triazabicylo[4.4.0]dec-5-ene trifluoroethanol) was found to be able to synergistically activate the substrate and CO2, thus catalyzing this cascade reaction under atmospheric CO2 pressure. By employing this task-specific ionic liquid as sustainable catalyst, 2-aminoethanols with different substituents were successfully transformed to 2-oxazolidinones with moderate to excellent yield after 12 h at 80 oC. This three-component reaction running under atmospheric pressure proves to be a clever detour to avoid the thermodynamic issue in the synthesis of 2-oxazolidinones starting from 2-aminoethanols and CO2.

Minerals might have played critical roles for the origin and evolution of possible life forms on Mars. The study of the interactions between “building blocks of life” and minerals relevant to Mars mineralogy under conditions mimicking the harsh Martian environment may provide key insight into possible prebiotic processes. Therefore, this contribution aims at reviewing the most important investigations carried out so far about the catalytic/protective properties of Martian minerals toward molecular biosignatures under Martian-like conditions. Overall, it turns out that the fate of molecular biosignatures on Mars depends on a delicate balance between multiple preservation and degradation mechanisms often regulated by minerals, which may take place simultaneously. Such a complexity requires more efforts in simulating realistically the Martian environment in order to better inspect plausible prebiotic pathways and shed light on the nature of the organic compounds detected both in meteorites and on the surface of Mars through in situ analysis.

In this work, the solar light-induced redox photoactivity of the ZnO semiconductor material was used to prepare at room temperature CuxO-ZnO composite catalysts with a control of the chemical state of the copper oxide phase. The preparation of Cu2(I)O-ZnO and Cu(II)O-ZnO composite catalysts was achieved by using Cu(acac)2 in THF-water and Cu(NO3)2 in water as metallic precursor, respectively. Prior to the implementation of the photo-assisted synthesis method, the most efficient photoactive ZnO material was selected among different ZnO materials prepared by the low temperature polyol method and through the precipitation method with carbonates and carbamates as precipitation agent, by taking the photocatalytic degradation of the 4-chlorophenol compound in water under simulated solar light as model reaction. The ZnO support materials were characterized by XRD, BET, TGA, SEM and TEM, and the synthesis method was strongly influencing their photoactivity in terms of 4-chlorophenol degradation and of total organic carbon removal. The most photoactive ZnO material was prepared by precipitation with carbonates and calcined at 300°C, and was taking advantage of a high specific surface area and a small mean crystallite size for achieving a complete 4-chlorophenol mineralization within 70 min of reaction, with a minimum Zn2+ released to the solution due to surface photocorrosion. Beside thermal catalysis applications, this work opened a new route for the facile synthesis of Cu2O-ZnO heterojunction photocatalysts, that could take advantage under solar light of the heterojunction built between the p-type semi-conductor Cu2O with direct visible light band gap and the ZnO semiconductor phase.

The development of a method to produce coumarins unsubstituted on the pyranic nucleus catalyzed from Wells–Dawson heteropolyacid (H₆P₂W₁₈O₆₂), phenol derivatives and ethyl 3,3-diethoxypropionate using Pechmann condensation under solvent-free conditions is described. This catalytic method was also applied successfully to synthesize various substituted coumarins, including the corresponding phenols and ethyl 3,3-diethoxypropionate. This work provides a novel, cheaper and safer way to syhthesize coumarins unsubstituted on the pyranic nucleus.

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

As a photo-catalytic titanium oxide film deposition process, thermal spray is hoped to be utilized practically on the condition that it is relatively easy to deposit anatase rich films. However, because of its high equipment and feedstock powder costs, it is very difficult to introduce thermal spray equipment into small companies. In this study, to develop a low cost thermal spray system, low power atmospheric suspension plasma spray equipment with titanium hydroxide suspension created by hydrolysis of titanium tetra iso butoxide using Ar, N2 as working gases. For avoiding sedimentation of the hydroxide particles in the suspension, mechanical milling of the suspension was conducted to create colloidal suspension before using it as feedstock. Moreover, an Ultrasonic wave container was used to keep the suspension particles moving while the spray process was conducted. After the film deposition, with As for the coating, anatase rich TiO2 film could be obtained. For characterization of the film, microstructure observation by optical microscope and X-ray diffraction was carried out. Consequently, by creation of colloidal suspension, deposition could be conducted without sedimentation of the hydroxide particle in the suspension during operation. Besides, it was proved the film had enough photo-catalytic property to decolor methylene-blue droplet

Recent advances in single-atom catalysis resulted in readily accessible materials whose application in most catalytic reactions mediated by conventional nanoparticle-based catalysts often results in higher activity and selectivity. Can we expect catalysis by atomically dispersed atoms to find practical applications? Which are the hurdles to be overcome prior to widespread uptake of atomically dispersed metals in industrial synthetic processes and in hydrogen fuel cells?

Groundwater contamination by nitrate and organic chemicals (e.g. 1,4-dioxane) is a growing worldwide concern. This work presents a new approach for simultaneously treating nitrate and 1,4-dioxane, which is based on UV sensitization of nitrate and sulfite, and the production of reactive species. Specifically, water contaminated with nitrate and 1,4-dioxane is irradiated by a UV source (< 250 nm) at relatively high doses, to sensitize in-situ nitrate and generate HO•. This leads to the oxidation of 1,4-dioxane (and other organics), and the (undesired) production of nitrite as an intermediate. Subsequently, sulfite is added at an optimized time-point, and its UV sensitization produces hydrated electrons which reacts and reduces nitrite. Our results confirmed the effectivity of the proposed treatment: UV irradiation of nitrate (at > 5 mg N/L) efficiently degraded 1,4-dioxane, while producing nitrite at levels higher than 1 mg N/L (its MCL in drinking water). Adding sulfite to the process after 10 minutes of irradiation reduced the concentration of nitrite, without affecting the degradation rate of 1,4-dioxane. The treated water contained elevated levels of sulfate; albeit at much lower concentration than its MCL. Treating water contaminated with nitrate and organic chemicals (often detected concomitantly) typically requires several (expensive) treatment processes. The proposed approach may present a cost-effective alternative, employing a single system for the treatment of nitrate and organic contaminants

Transition-metal-catalyzed amide bond formation from alcohols and amines is an atom-economic and eco-friendly route. Herein, we identified a highly active in situ N-heterocyclic carbene (NHC)/ruthenium (Ru) catalytic system for this amide synthesis. Various substrates, including sterically hindered ones, could be directly transformed into the corresponding amides with the catalyst loading as low as 0.25 mol%. In this system, we replaced the p-cymene ligand of the Ru source with a relatively labile cyclooctadiene (cod) ligand so as to more efficiently obtain the corresponding poly-carbene Ru species. Expectedly, the weaker cod ligand could be more easily substituted with multiple mono-NHC ligands. Further HR-MS analyses revealed that two tetra-carbene complexes were probably generated from the in situ catalytic system.

Herein, we report about the monometallic Ni and bimetallic Pd-Ni catalysts supported on CeO2-Al2O3 binary oxide, which were investigated in oxy-steam reforming of methanol (OSRM). Monometallic and bimetallic supported catalysts were prepared by wet aqueous impregnation and subsequent impregnation method, respectively. The physicochemical properties of the catalytic systems were investigated using various methods such as: BET, XRD, TPR-H2, TPD-NH3, XPS and SEM-EDS techniques. It has been proven that the addition of palladium to the nickel catalyst facilitates its reduction. The activity tests performed for all catalysts confirmed the promotion effect of palladium on catalytic activity of nickel catalyst and selectivity towards hydrogen production. Both nickel and bimetallic palladium-nickel supported catalysts showed excellent stability during the reaction. Such catalytic systems are valuable for the advance of the field of fuel cell technology.

Carbon nanotubes (CNTs) are effective supports for nano metals and together they represent hybrids that combine unique properties of both. A microwave induced reaction was used to deposit nano palladium on carboxylated and octadecylamine functionalized multiwall CNTs, which were used to carry out C-C coupling reactions in DMF and toluene. These hybrids showed excellent catalytic activity with yield as high as 99.8% while its enhancement with respect to commercially available Pd/C catalyst reached as high as 109%, and the reactions times were significantly lower. Polarity of the functionalized form was found to be a significant factor with the polar carboxylated CNT showing better activity in DMF while the relatively nonpolar octadecyl amine was better in toluene. The results suggest the possibility of tailor making functionalized CNT when used as catalyst supports

The tetracyclic pyrido[4,3-b]carbazole olivacine and four of its oxygenated derivatives have been synthesized by a late-stage palladium-catalyzed Heck-type cyclization of the pyrrole ring as key step. In a test for inhibition of the growth of Mycobacterium tuberculosis 9-methoxyolivacine showed the most significant inhibiting activity against Mycobacterium tuberculosis with an MIC₉₀ value of 1.5 μM.

The kinetics and optimal efficacy conditions of photoinitiated polymerization are theoretically presented. Analytic formulas are derived for the crosslink time, crosslink depth and efficacy function. The roles of photosensitizer (PS) concentration, diffusion depth and light intensity on the polymerization spatial and temporal profiles, for both uniform and non-uniform cases, are presented . For optimal efficacy, a strategy via controlled PS concentration is proposed, where re-supply of PS in high light intensity may achieve a combined-efficacy similar to low light intensity, but has a much faster procedure. A new criterion of efficacy based on the polymerization (crosslink) [strength] and [depth] is introduced.

Stimuli-responsive polymeric materials have attracted significant attentions in a variety of high-value-added and industrial applications during the past decade. Among various stimuli, light is of particular interest as a stimulus due to its unique advantages such as precisely spatiotemporal control, mild conditions, ease of use, and tunability. In recent years, a lot of effort toward synthesis of biocompatible and biodegradable polypeptide has resulted in many examples of photo-responsive nanoparticles. Depending on the specific photochemistry, those polypeptide derived nano-assemblies are capable of crosslinking, disassembling, or morphing into other shapes upon light irradiation. In this mini-review, we aim to assess the current state of photo-responsive polypeptide based nanomaterials. First, those “smart” nanomaterials will be categorized by their photo-triggered events (i.e., crosslinking, degradation, and isomerization) which are inherently governed by photo-sensitive functionalities including o-nitrobenzyl, coumarin, azobenzene, cinnamyl, and spiropyran. In addition, the properties and applications of those polypeptide nanomaterials will be highlighted as well. Finally, the current challenges and future directions of this subject will be evaluated.

Catalytic upgrading of bio-based platform molecules is one of promising approaches for biomass valorization. However, most solid catalysts are thermally and/or chemically unstable and difficult to prepare. In this study, a stable organic phosphonate-hafnium solid catalyst (PPOA-Hf) was synthesized, and acid-base bifunctional sites were found to play a cooperative role in the cascade transfer hydrogenation and cyclization of ethyl levulinate (EL) to γ-valerolactone (GVL). Under relatively mild reaction conditions of 160 ºC for 6 h, EL was completely converted to GVL in a good yield of 85%. The apparent activation energy was calculated to be 53 kJ/mol, which was lower than other solid catalysts for the same reaction. In addition, the PPOA-Hf solid catalyst did not significantly decrease its activity after five recycles, and no evident leaching of Hf was observed, indicating its high stability and potential practical application.

The current report contributes to the understanding of the stereoselectivity of the chiral dirhodium(II) carboxylate catalysts derived from N-protected amino acid ligands. Investigating the possible effect of ligand stereo-purity on catalyst structure and enantioselectivity was carried out. This was justified through a new X-ray crystal structure for Rh2(S,S,S,R-PTTL)4 diastereomer.

In a world where conventional sources of energy are fast depleting, the quest for alternative energy sources may hold the key for the survival of humanity. In the present work, emphasis has been given to the idea of producing energy from perovskite based solar cells. In order to bring this idea into fruition, a unique and novel nano structured perovskite material n-propyl ammonium lead chloride (C₃H₇NH₃⁺PbCl₃⁻) was prepared through a unique co-precipitation route using n-propyl amine (n-C₃H₇NH₂) and hydrochloric acid as the starting precursors with aqueous solution of Pb(CH₃COO)₂3H₂O. Finally acetic acid was added to the solution and this solution was allowed to concentrate and then gradually cooled down to room temperature. After math, the synthesized material was spin-coated on TiO₂ film to fabricate the solar cell. The device was then undergone systematic analysis using XRD, SEM, UV and Photo Conversion to get a transparent idea regarding its structural, electrical and optical properties. When experimentally applied, this perovskite-based solar cell has shown energy conversion efficiency (η) of around 6.01 % which is noticeably good. Thus it can be concluded that this material is promising for fabrication of vastly efficient solar cells. This technology can be tried in large scale as an alternative of conventional energy in the near future.

Nickel molybdate, NiMoO₄, nanoparticles were synthesized via calcination of an oxalate complex in static air at 500 °C. The oxalate complex was analyzed by thermal gravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR). The as-synthesized nickel molybdate was characterized by Brunauer–Emmett–Teller technique (BET), X-ray diffraction (XRD), and transmission electron microscopy (TEM) and its catalytic efficiency was tested in the reduction reaction of the three-nitrophenol isomers. The nickel molybdate displays a very high activity in the catalytic reduction of the nitro functional group to an amino. The reduction progress was controlled using UV-Vis absorption.

Starting from the environmental issues related to global warming, climate change and reduction of greenhouse gas emissions, this review paper describes how CO₂ recycling can represent a challenging strategy suitable to explore new concepts and opportunities for catalytic and industrial development. In this view, the production of dimethyl ether (DME) from catalytic hydrogenation of CO₂ appears as a viable technology, able to meet also the ever-increasing need for alternative environmentally-friendly fuels and energy carriers. Basic considerations on thermodynamic aspects controlling DME production from CO₂ are presented, then summarizing the main catalytic systems developed in such a field. Special attention is paid on the role assumed during last years by zeolite-based systems, either in the methanol-to-DME dehydration step or in the one-pot CO₂-to-DME hydrogenation. On the whole, the productivity of DME results significantly to be dependent on several catalyst features, linked not only to the metal-oxide phase responsible for CO₂ activation/hydrogenation, but also to specific properties of the zeolites (i.e., topology, porosity, surface area, acidity, interaction with active metals, distributions of metal particles, …) influencing activity and stability of hybridized bifunctional heterogeneous catalysts.

It is of great significance to develop sustainable processes of catalytic reaction. We report an efficient and selective procedure for the synthesis of acetylated bioactive compounds in water. The use of 1-acetylimidazole combined with Er(OTf)₃ as Lewis acid catalyst gives high regioselectivity and good to excellent yields for the acetylation of primary hydroxyl groups as well as amino groups. The protection is achieved in short reaction times under microwave irradiation and is successful even in the case of base-sensitive substrates.

On June 8 and June 9, 2017, we gave two invited lectures at the Zelinsky Institute of Organic Chemistry (ZIOC) of the Russian Academy of Sciences, Moscow. The first lecture, “Sol-Gel Catalysts: Making Green Chemistry Possible”, focused on the practical outcomes of 25 years of research on sol-gel entrapped catalysts. The second, “Chemistry for the Bioeconomy: From Discussion to Action”, offered a critical insight to the forthcoming bioeconomy. Both lectures aroused much interest in the audience and ended with a vigorous discussion lasting about one hour. An outlook is provided herein.

Phosphorylation reactions of glycerol were studied using different inorganic phosphates such as sodium phosphate, trimetaphosphate (a condensed phosphate), and struvite. The reactions were carried out in two non-aqueous solvents: formamide and a eutectic solvent consisting of choline chloride and glycerol in a ratio of 1:2.5. The glycerol reacted in formamide and in the eutectic solvent with phosphate to yield its phosphorylated derivatives in the presence of silicates such as quartz sand and kaolinite clay. The reactions were carried out by heating glycerol with a phosphate source at 85 °C for one week and were analyzed by 31P nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry (MS). The yield of the phosphorylated glycerol was improved by the presence of silicates, and reached 90% in some experiments. Our findings further support the proposal that non-aqueous solvents are advantageous for the prebiotic synthesis of biomolecules, and suggest that silicates may have aided in the formation of organophosphates on the prebiotic earth.

Synergistic effects between reactions, reagents and catalysts can lead to minor heats of reaction and occur as an inherent result of multi-component reactions (MCRs) and their extensions. They enable syntheses to be performed at a low energy level and the number of synthesis steps to be drastically reduced in comparison with ‘classical’ two-component reactions. The very high potential for variability, diversity and complexity of MCRs additionally generates an extremely diverse range of products, thus bringing us closer to the aim of being able to produce tailor-made and extremely low-priced materials, drugs and libraries.

Surface initiated atom transfer radical polymerization (SI-ATRP) is one of the most versatile technique to modify the surface properties of material. Recent developed metal free SI-ATRP makes such technique more widely applicable. Herein photo-induced metal-free SI-ATRP of methacrylates, such as methyl methacrylate, N-isopropanyl acrylamide, and N,N- dimethylaminoethyl methacrylate, on the surface of SBA-15 was reported to fabricate organic-inorganic hybrid materials. SBA-15 based polymeric composite with adjustable graft ratio was obtained. The structure evolution during the SI-ATRP modification of SBA-15 was monitored and verified by FT-IR, XPS, TGA, BET, and TEM. The obtained polymeric composite showed enhanced adsorption ability for the model compound toluene in aqueous. This procedure provides a low cost, ready availability, and facile modification way to synthesize the polymeric composites without the contamination of metal.

In this research paper a novel Ultra Violet Photo Catalyst Oxidation (UVPCO) sensor for air and surface sanitization using Common Source (CS) amplifier is presented. The ultra violet photo catalysis is the process in which the highly reactive radicals like H+, OH-and peroxides ions are produced from air in the presence of the ultra violet radiation and photo catalyst. In this process, the free radicals outbreaks the bio aerosols like bacteria, fungus and volatile organic compounds (VOCs) and destroy them. The proposed system is relies on the fast operation of PCS which operates under sub-threshold conditions and reduced computation time. The properties of common source amplifier like very high voltage gain and input output resistance increased the sensitivity as well as stability of the circuit. The system is more user friendly and the outcomes of simulation are fairly in agreement with the theoretical estimation. Keywords: bio aerosol, Photo Catalytic Oxidation (PCO), hydroxyl, hydrogen peroxide, SPICE, surface sanitizer.