Bifunctional catalysts consisting of mono- or bimetallic nanoparticles (NPs) and zeolite supports received considerable attention due to excellent catalytic properties in numerous reactions including direct and indirect biomass processing. Here, we discuss major approaches to the preparation of NPs in zeolites, concentrating on methods allowing the best interplay (synergy) between metal and acid sites which is normally achieved for small NPs well-distributed through zeolite. We focus on modification of zeolites to provide structural integrity and controlled acidity which can be accomplished by incorporation of certain metal ions or elements. The other modification avenue is the adjustment of the zeolite morphology including creation of numerous defects for the NP entrapment and designed porosity. In this review we also provide examples of synergy between metal and acid sites and emphasize that without density functional theory calculations many assumptions about interactions between active sites stay unvalidated. Finally, we describe the most interesting examples of direct and indirect biomass (waste) processing for the last five years.

Glycerol is the main residue in the biodiesel production industry; therefore, their valorisation is crucial. Acetalization of glycerol towards fuel additives as solketal (2,2-dimethyl-1,3-dioxolan-4-methanol) is of high interest, promoting circular economy since it can be added to the biodiesel or even fossil-diesel to improve their quality and efficiency. Straightforward prepared metal-organic framework (MOF) materials of MOF-808 family were applied to the valorisation of glycerol for the first time. In particular, MOF-808(Hf) revealed to be an effective heterogeneous catalyst to produce solketal under moderate conditions: small amount of the MOF material (only 4wt% of glycerol), ratio 1:6 of glycerol/acetone and temperature of 60 ºC. The high efficiency of MOF-808(Hf) was associated with the high amount of acid centres present in its structure. Furthermore, its structural characteristics such as window opening cavities size and pore diameters showed to be ideal to reuse this material during at least ten consecutive reaction cycles without losing activity (conversion > 90% and selectivity > 98%). Remarkably, it was not necessary the washing or other activation treatment of the MOF-808(Hf) catalyst between cycles (no pore blockage occurred) and it maintained structural integrity after the ten cycles, confirming to be a sustainable heterogeneous catalyst to the glycerol valorisation.

Methane and carbon dioxide are the main contributors to global warming, being the methane effect twenty-five times more powerful than carbon dioxide. Although the sources of methane are diverse, it is a very volatile and explosive gas. One way to store the energy content of methane is its conversion to methanol. Methanol is liquid under ambient conditions, easy to transport and, apart from its use as an energy source, it is a chemical platform that can serve as a starting material for the production of various higher value-added products. Accordingly, the transformation of methane to methanol has been extensively treated in the literature, using traditional catalysts as different types of zeolites. However, in the last years, a new generation of catalysts have emerged to carry out this transformation with higher conversion and selectivity, and more importantly, under mild temperature and pressure conditions. These new catalysts typically involve the use of a highly porous supporting material such as zeolite, or more recently, metal-organic frameworks (MOFs) and graphene, and metallic nanoparticles or a combination of different types of nanoparticles that are the core of the catalytic process. In this review, the characteristics, the catalytic mechanisms, reactors, and the main results of these catalysts are presented as a way to overcome the challenges found in traditional catalysts.

When animals evolve sufficient intelligence and dexterity to be able to learn to fabricate utility products (UPs) like tools, the UP's they produce become part of an induced-reproduction system that intrinsically shares many life-like traits with biological organisms, including genome-like fabrication and operation information that is physically-encoded in the animal fabricator’s neural networks. When this set of life- like traits includes a sufficient capacity for system-improving cultural evolution (UP-evolvability), the UPs become ‘para-alive’, i.e., nearly alive, or a form of non-biological UP-paralife that is equivalent to the life- status of biological viruses, plasmids, and transposons. In the companion paper I focus on the evolution of UP-paralife in the context of modern, language-capable humans and its predicted evolution going forward in time (Rice 2022). Here I look backward in time and focus on the origin of UP-paralife and its subsequent coevolution with human intelligence. I begin by determining the pathways leading to the evolution of large brains in the rare lineages of biological life that have sufficient intelligence to learn to fabricate tools –a critical first step in the evolution of UP-paralife. The simplest forms of these learning- based UPs, made by species like chimpanzees and New Caledonian crows, represent only proto-UP- paralife because they lack sufficient UP-evolvability. Expanded UP-evolvability required a combination of three attributes that enabled continuous niche-expansion of the animal fabricator via a new and advanced form of UP-mediated teamwork (TW): i) self-domestication that facilitated TW among low-related individuals, ii) learned volitional words (protolanguage) that represent ephemeral UPs that coordinate TW, and iii) learned fabrication of simple flaked-stone tools with cutting and chopping capabilities (a UP to make other structural UPs) that expanded teammate phenotypes and TW capabilities. This specific triad of attributes is synergistic because each one acts as a TW-enhancer that can gradually erode different components of the three major constraints on TW operation and expansion: too much selfishness, insufficient coordination signals, and insufficient physical traits of teammates. The increase in UP- evolvability was transformative and marked the origin of UP-paralife and the initiation of coevolution between UP-paralife (cultural evolution) and the intelligence of its hominin/human symbiont (genetic evolution) that fostered 2.5 million years of: i) continuous brain size increase and niche-expansion within the genus Homo, and ii) parallel advances in the diversity, complexity and uses of UP-paralife. This coevolution also fostered evolutionary expansion of word-based communication, and eventually language, that acted in a catalyst-like manner to facilitate the evolution of increasingly complex forms of imagination, reasoning, mentalizing, and UP-generating technology. I next focus on the evolution of creativity in the human lineage –in the form of divergent thinking and creative imagination. I conclude that the evolution of this advanced cognitive feature required a preadaptation of sufficient intelligence and is the component of human cognition that was the major causal factor generating the greatly expanded diversity and complexity of UP-paralife currently associated with modern humans. Lastly, I apply my findings to the issue of the prevalence of extraterrestrial intelligent life. I conclude that any exoplanets with detected chemical life will very rarely (e.g., probability ~10-5 for a planet closely matching Earth’s characteristics) have evolved intelligence equalling or exceeding that of humans.

In recent years Pd-containing catalytic systems for tandem processes has drawn special attention due to the enhanced catalytic properties and possibility to perform several reactions without the necessity to separate the intermediates. In this review, recent progress in Pd-catalyzed tandem processes is considered. Three types of catalytic systems were described: homogeneous catalysts (including immobilized Pd complexes); heterogeneous catalysts supported on oxides, MOFs, COFs, etc. with particular attention to the supports containing acid/base sites; metal-enzyme catalysts for chemoenzymatic tandem processes applied in fine organic synthesis and biotechnology. For homogeneous Pd-catalyzed reactions different tandem reactions were considered, i.e. cross-coupling, cyclization, carbonylation, isomerization, alkylation, arylation, etc.

The hydrogen evolution reaction (HER) has garnered attention to access sustainable energy generation with a pollutant-free combustion product in the form of H2 gas. Despite the utility of this pathway in the context of growing climate concerns, stable HER electrocatalysts which avoid the use of rare-earth platinum while retaining high catalytic performance and efficiency remains a challenge. In this work, we present the application of a binuclear nickel (II/III) Schiff base complex [Ni]2[L]2 2 for HER electrocatalysis. The design of the electrocatalyst provides optimal HER activity as the presence of electronegative heteroatoms in proximity to the metal centers augments proton affinity. As a result, the catalyst displays excellent HER activity with 100% faradaic efficiency (FE) at an onset potential of 0.4 V vs. reverse hydrogen electrode (RHE), sustained catalytic activity during prolonged electrolysis for greater than 17 hours, and provided a turn over number (TON) of 0.0006 s-1.

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.

Deep eutectic solvents are a mixture of two or more components, that at a particular composition become liquids at room temperature. When the compounds that constitute the DES are primary metabolites, namely, amino acids, organic acids, sugars, or choline derivatives, the DES are so called natural deep eutectic solvents (NADES). NADES fully represent green chemistry principles. These solvents are highly welcome, as they are obtained from renewable resources, and gratifyingly biodegradable and biocompatible. They are an alternative to room temperature ionic liquids (RTILs). From the pharmaceutical industry point of view, they are highly desirable, but unfortunately have been rarely used despite their enormous potential. In this review, we will look at their impact on the asymmetric catalytic synthesis of key target molecules, via metal-based catalysis, biocatalysis and organocatalysis. In many cases the NADES that have been used are chiral and can even promote enantioselective reactions, this crucial and very exciting aspect will also be discussed and analysed.

A new approach to preparing a series of Co/Sm2O3 catalysts for hydrogen production by dry re-forming of methane (DRM) is developed. The catalysts precursors are synthesized by a simple method, including evaporation of aqueous solutions of cobalt and samarium nitrates, followed by a short-term calcination of the resulting material. The as-prepared and spent catalysts are characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), temperature-programmed reduction (H2-TPR), and thermogravimetric analysis (TGA). It is shown that the content of cobalt in the synthesized materials affects their phase composition and carbonization resistance in the DRM reaction. It is demonstrated that preheating under N2 affords catalysts providing stable hydrogen and CO yields of 94-98 % for at least 50 h at 900°C. These yields are among the highest ones currently available for DRM catalysts derived from Co-Sm complex oxides. It is found that reduction in the amount of cobalt in the catalyst and its preheating to an operating temperature of 900°C in a nitrogen flow con-tribute to preventing catalyst carbonization and metal particles sintering.

Conventional hydrogen production, as an alternative energy resource, has relied on fossil fuels to produce hydrogen, releasing CO2 into the atmosphere. Hydrogen production via the dry forming of methane (DRM) process is a lucrative solution to utilize greenhouse gases, such as carbon dioxide and methane, by using them as raw materials in the DRM process. However, there are a few DRM processing issues, with one being the need to operate at a high temperature to gain high conversion of hydrogen, which is energy intensive. In this study, bagasse ash, which contains a high percentage of silicon dioxide, was designed and modified for catalytic support. Modification of silicon dioxide from bagasse ash was utilized as a waste material and the performance was explored of bagasse ash-derived catalysts interacting with light irradiation and reducing the amount of energy used in the DRM process. The results showed that the performance of 3%Ni/SiO2 bagasse ash WI was higher than that of 3%Ni/SiO2 commercial SiO2 in terms of the hydrogen product yield, with hydrogen generation initiated in the reaction at 300 °C. Using the same synthesis method, the current results suggested that bagasse ash-derived catalysts had better performance than commercial SiO2-derived catalysts when exposed to an Hg-Xe lamp. This indicated that silicon dioxide from bagasse ash as a catalyst support could help improve the hydrogen yield while lowering the temperature in the DRM reaction, resulting in less energy consumption in hydrogen production.

The per capita availability of freshwater resources on a global scale is gradually decreasing due to population growth, rapid urbanization, industrialization, and modern lifestyles. In this situation, wastewater management becomes a major concern. Conventional treatment processes used to treat wastewater discharges are not adequate for the advanced removal of pollutants, especially refractory organic pollutants, which are mainly organic compounds that are not easily biodegradable in the environment. The use of photocatalytic membrane reactors (PMRs) for tertiary wastewater treatment has attracted much interest in recent periods, and various configurations have been investigated. The performance of a PMR using an iron doped titanium photo catalyst and Polysulfone-based polymeric membrane for municipal wastewater treatment was evaluated under natural and simulated solar light. Obtained results proved that solar driven PMRs can remove organic loading (COD) with high efficiencies and may represent a suitable alternative for the tertiary treatment step of municipal wastewater.

Fine chemicals are produced in small annual volume batch processes (often <10,000 tonnes per year), with a high associated price (usually > $10/kg). As a result of their usage in the production of speciality chemicals, in areas including agrochemicals, fragrances and pharmaceuticals, their necessity will remain high for the foreseeable future. This review article assesses current methods used to produce fine chemicals with heterogeneous catalysts, including both well-established methods as well as newer experimental methods. A wide range of methods utilising microporous and mesoporous catalysts has been explored, including their preparation and modification before use in industry. Their potential drawbacks, as well as benefits, have been analysed, with their feasibility compared to newer, recently emerging catalysts. The field of heterogeneous catalysis for fine chemical production is a dynamic and ever-changing area of research. This deeper insight into catalytic behaviour and material properties will produce more efficient, selective, and sustainable processes in the fine chemical industry. The findings from this article will provide an excellent foundation for further exploration and a critical review in this field of fine chemical production using micro- and mesoporous heterogeneous catalysts.

This short review is aimed at giving an overview of catalytic carbonylative double cyclization reactions, which are processes in which suitable organic substrates and carbon monoxide are sequentially activated by a promoting catalyst to afford the formation of two new cycles with concomitant incorporation of carbon monoxide as a carbonyl function into the final product. Paradigmatic examples of this powerful synthetic methodology, which allows the one-step synthesis of complex molecular architectures from simple building blocks using the simplest and readily available C-1 unit (CO) are illustrated and discussed. The review is divided into five sections: 1) Introduction; 2) Functionalized Olefinic Substrates; 3) Functionalized Acetylenic Substrates; 4) Functionalized Halides; 5) Conclusions and Future Perspectives.

Metal nanoframes have gained tremendous attention in the domain of modern research and development due to their distinctive 3D spatial structure, efficient physiochemical properties, and comparatively good activity. Different strategies have been implicated by the researchers to design nano frame of varying chemical nature and shapes. Most of the synthetic protocols being adopted to design a nano framee, mainly consist of two main steps, nucleation and growth of solid particles and secondly excavation of the interiors. In this context, many synthetic methods are overviewed. To show their unprecedented performance or activity, a few applications in catalytic, biomedical, theranostic, SERS, sensing of different materials, reduction of CO2, etc are also discussed.

The increading emission of carbon dioxide to the atmosphere has urged the scientific community to investigate alternatives to alleviate such emissions being the principal contributor to the greenhouse gas effect. One major alternative is carbon capture and utilisation (CCU) towards the production of value-added chemicals using diverse technologies. This work aims at the study of the catalytic potential of different cobalt-derived nanoparticels for methanol syntheis from carbon dioxide hydrogenation. Thanks to its abundance and cost-efficacy, cobalt can serve as an economical catalyst compared to noble-metal-based catalysts. In this work, we present a systematic comparison among different cobalt and cobalt oxide nanocomposites in terms of their efficiency as catalysts for carbon dioxide hydrogenation to methanol as well as how different supports can enhance their catalytic capacity. The oxygen vacancies in the cerium oxide act as carbon dioxide adsorption and activation sites, which facilitates a higher methanol production yield.

In this review, we focus on a small section of the extensive literature that deals with the materials containing pristine defective CNs and those incorporated in the hybrid materials. We will discuss only those topics that focus on structural defects related to the introduction of perturbation into the surface topology of a nanostructure. We focus mainly on the method using microwave (MW) irradiation, which is a powerful tool for synthesizing and modifying carbon-based solid materials. In addition, the simplicity of the technique, economy, and the possibility of conducting the reaction in solvents and solid phase, in the presence of components of different chemical nature, allows use in various combinations. In this review, we will emphasize the advantages of synthesis using MW-assisted heating and indicate the influence of the structure of the obtained materials on their physical and chemical properties. We will also highlight the role of the occurrence of defects in the carbon material and the implication in designing their properties and applications.

Hydrodechlorination reaction of 3-(benzo-1,3-dioxol-5-yl)-3-chloro-2-methylacrylaldehyde in the presence of different low metal content heterogeneous mono- or bi-metallic catalysts was tested for the synthesis of the fragrance Helional® (3-[3,4-methylendioxyphenyl]-2-methyl-propionaldehyde). In particular, mono Pd/Al2O3, Rh/Al2O3 or bi-metallic Pd-Cu/Al2O3, Rh-Cu/Al2O3 catalysts were tested in different reaction conditions from which it emerged that mono-Rh/Al2O3 was the best performing catalyst allowing to achieve 100% substrate conversion and 99% selectivity towards Helional® in 24h at 80°C, p(H2) 1.0 MPa in the presence of a base. To establish correlations between atomic structure and catalytic activity, catalysts were characterized by Cu, Rh and Pd K-edge XANES, EXAFS analysis. These characterizations allowed to verify that the formation of Pd-Cu alloys and the presence of Cu oxide/hydroxide species on the surface of the Al2O3 support, are responsible for the very low catalytic efficiency of bimetallic species tested.

This work shows the potential of a new way of co-treatment of domestic wastewater (DWW) and a liquid stream coming from the thermal hydrolysis of the organic fraction of municipal solid waste (OFMSW) mediated by a mixed culture of purple phototrophic bacteria (PPB) capable of assimilating carbon and nutrients from the medium. The biological system is an open single-step process operated under microaerophilic conditions at an oxidative reduction potential (ORP) < 0 mV with a photoperiod of 12/24 h and fed during the light Stage only, so the results can be extrapolated to outdoors open ponds operation by monitoring the ORP. The effluent mostly complies with the discharge values of the Spanish legislation in COD and P values (<125mg/L <2 mg/L), respectively, and punctually on values in N (<15mg/L). Applying an HRT of 3 d and a ratio of 100:7 (COD:N), the presence of PPB in the mixed culture surpassed 50% of 16S rRNA gene copies, removing 78% of COD, 53% of N and 66% of P. Furthermore, increasing the HRT to 5 d, removal efficiencies of 83% of COD, 65% of N and 91% of P were achieved. In addition, the reactors were further operated in a membrane bioreactor, thus separating the HRT from the SRT to increase the specific loading rate. Very satisfactory removal efficiencies were achieved by applying HRT and SRT of 2.3 and 3 d, respectively: 84% of COD, 49% of N and 93% of P despite low presence of PPB due to more oxidative conditions, which anyway step-by-step re-colonized the mixed culture until reaching >20% of 16S rRNA gene copies after 49 d of operation. These results open the door to scale up the process in open photobioreactors capable of treating urban wastewater and municipal solid waste in a single stage and under microaerophilic conditions by controlling the ORP of the system. This novel urban biorefinery allows reducing treatment costs of two urban wastes and embed them in the circular bioeconomy through water recycling and valorizing PPB biomass as a source of carbon, nitrogen and phosphorus.

Using the colloidal method, Au NP’s were deposited onto 6 different supports (TiO2,  and -Al2O3, HFeO2, CeO2, and C), and their catalytic activity and selectivity were compared in the alkylation of aniline by benzyl alcohol. Correlations were made between the nature of the support, the Au NP size and H-binding energy.

People wore clothes for warmth, survival and necessity in modern life as well but in modern era, eco-friendliness, shorten production time, design, and intelligence also matters. The seamless bonding technology strengthen the bond between fabrics in textiles, while Grey relational analysis (GRA) can be applied to fabrics to measure the relationship between data series and determine the closeness of each data series. In this study, polyurethane prepolymer, 2-Hydroxyethyl acrylate (2-HEA) as an end-capping agent, and n-octyl acrylate (ODA) as a photo-initiator were used to synthesize dual-curing polyurethane hot-melt adhesive. The Taguchi quality engineering and grey relational analysis used to discuss the influence of different mole ratio of NCO:OH, and the effect of the molar ratio of addition of octyl decyl acrylate on the mechanical strength. The Fourier transform infrared spectroscopy (FTIR) results showed the termination of prepolymer's polymerization reaction and the C=O peak intensity at 1730 cm-1 indicating the efficient bonding to main chain. The high molecular weight polymer (20,000-30,000) described by advanced polymer chromatography (APC) confirmed the polyurethane polymer bonded with octyl decyl acrylate to achieve the photo-thermosetting effect. The thermogravimetric analysis (TGA) results showed the thermal decomposition temperature of polyurethane hot melt adhesive also increased and highest pyrolysis temperature (349.89℃) for the polyhydric alcohols. The high value of shear strength (34.94 kg/cm2) as well as peel strength (1.68 kg/cm) were also observed in dual-cure photo-thermosetting polyurethane hot melt adhesive. The signal-to-noise ratio also used to generate the grey relational degree. It was observed that the best parameter ration of NCO: OH was 4:1 with 5 moles of monomer. The Taguchi quality engineering method was used to find the parameters of single quality optimization, and then the grey relation calculation was used to obtain the parameter combination of multi-quality optimization for thermosetting polyurethane hot melt adhesive. The study aims to meet the requirements of seamless bonding in textile factories and optimized experimental parameter design by setting target values can effectively increase production speed, reduce processing time and costs as well.

In the past few decades, N-heterocyclic carbenes (NHCs) open the new field of organocatalysis in synthetic organic chemistry. This review highlights the dramatic progress in the NHC-catalyzed C−O bond formation based on the activation of aldehyde C(sp2)−H bonds. The oxidative and redox transformations for the synthesis of various molecules with structural diversity and complexity are summarized. Furthermore, new methods and strategies for NHC catalysis are emerging continuously; thus, cooperative catalysis with Brønsted acid, hydrogen-bonding catalyst, transition-metal catalyst, and photocatalyst is also described.

By planting LEDs on the surfaces of orifice baffles, a novel batch oscillatory baffled photoreactor (OBPR) together with polymer-supported Rose Bengal (Ps-RB) beads are used to investigate reaction kinetics of a photo-oxidation reaction between α-terpinene and singlet oxygen (1O2). In the widely used NMR data analysis for this reaction, α-terpinene and ascaridole are treated as a reaction pair, assuming kinetically singlet oxygen is in excess or constant. We have, for the first time, examined the validity of the method, discovered that increasing α-terpinene initially leads to an increase of ascaridole, indicating that the supply of singlet oxygen is in excess. Applying kinetic analysis, a pseudo first order reaction kinetics is confirmed, supporting this assumption. We have subsequently initiated a methodology of estimating the 1O2 concentrations based on the proportionality of ascaridole concentrations with respect to its maximum under these conditions. With the help of the estimated singlet oxygen data, the efficiency of 1O2 utilization and the photo efficiency of converting molecular oxygen to 1O2 are further proposed and evaluated. We have also identified conditions where further increase of α-terpinene has caused decreases in ascaridole, implying kinetically that 1O2 has now become a limiting reagent, the method of treating α-terpinene and ascaridole as a reaction pair in the data analysis would no longer be valid under those conditions.

Layered double hydroxides (LDHs) have emerged as promising catalysts for various acid-base catalytic reactions. Due to their unique structure and regulatable dual acid-base properties, they offer more environmentally friendly and sustainable alternatives to traditional liquid acid and base catalysts. This study introduces the structural composition, preparation methods, and acid-base catalytic properties of LDHs-based catalysts. Recent application progress of LDHs and rehydrated LDHs, LDHs-based metal nanocatalysts, and LDHs-based mixed metal oxide catalysts used as solid acid-base catalysts in acid-base green catalytic conversion is reviewed. The challenges and prospects of LDHs-based catalysts as green and sustainable catalysts are summarized and proposed.

Using structured light to drive colloidal motors, due to its advantages of remote manipulation, energy tunability, programmability, and controllability of spatiotemporal distribution, has been attracting much attention in the fields of targeted drug delivery, environmental control, chemical agent detection, and smart device design. Here, we focus on studying the group control of colloidal made from a photo-responsive organic polymer molecule NO-COP (N,O-Covalent organic polymer). These colloidal motors mainly respond to the light intensity patterns. We chose a digital micromirror device (DMD) to modulate the structured light field shining on the sample, by considering its merit of fast refreshing speed, good programmability, and high-power threshold. It is found that under ultraviolet or green light modulation, such colloidal motors exhibit various group behaviors including group diffusion, group patterning, and group migration. The qualitative interpretation is also provided for these observations.

Biopolymers are of growing interest, but to improve some of their poor properties and performance, it is required the formulation of bio-based blends and/or adding of nanoparticles. For this purpose, in this work, two different metal oxides, such as zinc oxide (ZnO) and titanium dioxide (TiO2), at different concentrations (0.5, 1 and 2 %wt.) have been added in polylactic acid (PLA) and polylactic acid/polyamide 11 (PLA/PA11) blends to establish their effects on solid-state properties, morphology, melt behaviour, and photo-oxidation resistance. It seems that the addition of ZnO in PLA leads to a significant reduction of its rigidity probably due to an inefficient dispersion in the melt state, while the addition of TiO2 does not penalise PLA rigidity. Interestingly, the addition of both ZnO and TiO2 in PLA/PA11 blend has a positive effect on the rigidity because of blend morphology refinement and leads to a slight increase in film hydrophobicity. The photo-oxidation resistance of neat PLA and PLA/PA11 blend is significantly reduced due to the presence of both metal oxides, and this must be considered when designing the potential applications. The last results suggest that both metal oxides could be considered as photo-sensitive degradant agents for biopolymer and biopolymer blends.

Bioinformatics analysis of the sequences of orthologous zinc-containing peptidases of the M15_C subfamily revealed the presence of a conserved tryptophan residue near the active site, which is not involved in the formation of the protein core. Site-directed mutagenesis of this Trp114/109 residue using two representatives of the family, L-alanoyl-D-glutamate peptidases of bacteriophages T5 (Calcium-activated EndoT5) and RB49 (EndoRB49, without ion regulation) as an example, and further analysis of the 1H NMR spectra of the mutants showed that a decrease in the volume of the W → F → A residue leads to changes in the hydrophobic core and active center of the protein, and also decreased affinity for regulatory Ca2+ in the EndoT5 mutants. The inactive T5W114A mutant lacks the ability to bind the substrate. In general, the conserved Trp114/109 residue, due to the spatial restrictions of its side chain, significantly affects the formation of the catalytically active form of the enzyme and is critical for catalysis.

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.

The coombs (in Catalan comes) form an integral part of the landscape. These are small valleys, with the deepest and flattest part cultivated for agriculture. They are predominantly found in the most arid regions of Catalonia, particularly around the cities of Tarragona and Lleida. They are generally dry land areas. We propose that these coombs gained significance in the early centuries of the Middle Ages, a period marked by intense erosion. It is important to identify their locations and establish connections with medieval written documents, the settlements that thrived throughout the Middle Ages, archaeological sites such as necropolises, and the valuable data derived from to-ponymy studies. We think that understanding these coombs can greatly contribute to under-standing how the territory was organized in the Middle Ages, the extent of cultivated lands that were established, and the distribution of many settlements. Ultimately, this knowledge can aid in acquiring better understanding of the current landscape.

The removal of sulfur from fossil fuels is one of the most important processes in modern refineries. It is accomplished via hydrodesulfurization (HDS) of the sulfur organic compounds in presence of heterogeneous catalysts. In the current work, heterogeneous catalysts containing cobalt and mo-lybdenum supported on mesoporous materials type SBA-15 and AlSBA-15 were synthesized for application in the HDS reactions of thiophene in n-heptane stream. The mesoporous materials were synthesized by hydrothermal method starting from TEOS, pseudobohemite, hydrochloric ac-id and water. Pluronic P123 was used as template. The best calcination conditions for removal of the organic template were optimized by thermogravimetry analysis (TG/DTG). The calcined SBA-15 and AlSBA-15 supports were submitted to co-impregnation with solutions of cobalt nitrate and ammonium heptamolybdate, aiming the production of 15% in mass of metal loading with atomic ratio of [Co/(Co+Mo)]=0.45. The obtained materials were dried and calcined for obtaining the mesoporous catalysts in the form of CoMo/SBA-15 and CoMo/AlSBA-15. The catalysts were char-acterized by XRD, TG/DTG, SEM and nitrogen adsorption. From XRD analysis, it was verified that after decomposition of the cobalt and molybdenun salts, were formed MoO3, Co3O4 and Co-MoO4 oxides on the supports, being attributed to these chemical species the activity for the HDS reactions. The activity of the obtained catalysts was evaluated in a continuously flowing tubular fixed-bed microreactor coupled on-line to a gas chromatograph, using n-heptane stream contain-ing 12070 ppm of thiophene (ca. 5100 ppm of sulfur) as a model compound. From the catalytic tests it was verified that the synthesized catalysts presented good activity for the reaction, and the main obtained products were cis- and trans-2-butene, 1-butene, n-butane and low amounts of iso-butane. The presence of 1,3-butadiene and tetrahydrothiophene (THT) were not detected. A mechanism of the primary and secondary reactions and subsequent formation of the olefins and paraffins, in the CoMo/SBA-15 and CoMo/AlSBA-15 mesoporous catalysts were proposed, con-sidering steps of desulfurization, hydrogenation, dehydrogenation, THT decyclization and isomerization.

Electrochemical Promotion was used to modify the activity and selectivity of a Rh catalyst-electrode in the CO2 hydrogenation reaction. The experiments were carried out in a temperature range of 350-430οC at ambient pressure and at different CO2 to H2 gas feeding ratios (1:2 to 4:1). The only reaction products observed were CO and CH4, both under open and closed-circuit conditions. The CH4 formation rate was found to increase with both positive and negative potential or current application. The CO formation rate followed the opposite trend. The selectivity to CH4 increased under high values of hydrogen partial pressure and decreased at high pressures of CO2. The results demonstrate how Electrochemical Promotion can be used to finely tune activity and selectivity for a reaction of high technical and environmental importance.

(S)-Atenolol ((S)-2-(4-(2-Hydroxy-3-(isopropylamino)propoxy)phenyl)acetamide) has been synthesized in >99% ee with use of Candida antarctica lipase B from Syncozymes (Shanghai, China), in a kinetic resolution of the corresponding racemic chlorohydrin. Deprotonation of the starting phenol building block was base catalyzed. The enantiopurity of the chlorohydrin building block remained unchanged upon subsequent amination. All four steps in the synthesis protocol have been optimized compared to previously reported methods, which makes this new protocol more sustainable and in accordance with green chemistry principles compared to previously reported protocols.

How Nature discovered genetic coding is a largely ignored question, yet the answer is key to explaining the transition from biochemical building blocks to life. Other, related puzzles also fall inside the aegis enclosing the codes themselves. The peptide bond is unstable with respect to hydrolysis. So, it requires some form of chemical free energy to drive it. Amino acid activation and acyl-transfer are also slow and call for catalysis. All living things must thus also convert free energy and synchronize cellular chemistry. Most importantly, functional proteins occupy only small, isolated regions of sequence space. Nature evolved heritable symbolic data processing to seek out and use those sequences. That system has three parts: a memory of how amino acids behave in solution and inside proteins, a set of code-keys to access that memory, and a scoring function. The code-keys themselves are the genes for cognate pairs of tRNA and aminoacyl-tRNA synthetases, AARS. I outline the surprising links between all these questions and the structural duality of the base-pairing that holds genes together and how those links arise from the experiments.

The basic hydrolysis of Malachite Green in the presence of β-Cyclodextrin has been studied and a catalytic effect has been found. Indeed, this basic hydrolysis is catalyzed by the interaction of deprotonated cyclodextrin hydroxyl group with the carbocation in the host-guest complex. This behavior is like the hydrolysis of Cristal Violet in the same reaction media.

The enormous influence in terms of bioactivity, affinity, and selectivity represented by the replacement of (L)-2,6-dimethyl tyrosine (Dmt) instead of Phenylalanine (Phe) into Nociceptin/orphanin (N/OFQ) neuropeptide analogues, has been well documented in literature. More recently, the non-natural amino acid (L)-2-methyl tyrosine (Mmt), with steric hindrance among Tyr and Dmt, has been studied because of the modulation of steric effects in opioid peptide chains. Here we report a new synthetic strategy to obtain Mmt based on the well-known Pd-catalyzed ortho-C(sp2)–H activation approach, since there is a paucity of other synthetic routes in literature, to achieve it. The aim of this work was to force only the mono ortho-methylation process over the double ortho-methylation one. In this regard we are pleased to report that the introduction of the dibenzylamine moiety on Tyr aromatic nucleus is a convenient and traceless solution to achieve such a goal. Interestingly, our method provided the aimed Mmt either as N-Boc or N-Fmoc derivatives ready to be inserted into peptide chains through solid phase peptide synthesis (SPPS). Importantly, the introduction of Mmt in place of Phe1 in the sequence of N/OFQ(1-13)-NH2 was very well tolerated in terms of pharmacological profile and bioactivity.

Sequential reactions of aminoalkynes represent a powerful tool to easily assembly biologically important polyfunctionalized nitrogen heterocyclic scaffolds. Metal catalysis often plays a key role in terms of selectivity, efficiency, atom economy and green chemistry of these sequential approaches. This review examines the existing literature on the applications of reactions of aminoalkynes with carbonyls which are emerging for their synthetic potential. Aspect concerning the features of the starting reagents, the catalytic systems, alternative reaction conditions and the pathways as well as the possible intermediates are provided.

Bimetallic (or multimetallic) catalysis has emerged as a powerful tool in modern chemical synthesis, offering improved reaction control and versatility. This review focuses on the recent de-velopments in bimetallic sequential catalysis for the synthesis of nitrogen heterocycles, essential building blocks in pharmaceuticals and fine chemicals. The cooperative action of two (and sometimes more) different metal catalysts enables intricate control over reaction pathways, enhancing selectivity and efficiency of N-heterocyclic compounds synthesis. By activating less reactive substrates, this multimetal catalytic strategy opens new synthetic possibilities for challenging compounds. The use of catalytic materials in bimetallic systems reduces waste and improves atom efficiency, aligning with green chemistry principles. With a diverse range of metal combinations and reaction conditions, bimetallic catalysis provides access to a broad array of N-heterocyclic compounds with various functionalities. This paper highlights the significant progress made in the past decade in this topic, emphasizing the promising potential of bimetallic catalysis in drug discovery and the fine chemical industries.

The endo- and exo-N-heterocyclic carbene precursors based on camphor were prepared diastereoselectively in five synthetic steps starting from (1S)-(+)-ketopinic acid. The obtained N-heterocyclic carbene precursors were investigated in an asymmetric benzoin reaction. All new compounds were fully characterized and the absolute configurations were determined by X-ray diffraction and NOESY measurements.

Crystalline silver thin layers were obtained by high-energy pulsed laser ablation without heating of the deposition substrate. The fluid Plateau-Rayleigh (PRI), Rayleigh – Taylor (RTI) and Richtmyer – Meshkov (RMI) instabilities, as well as crown splash induced during pulsed laser deposition (PLD) in high energy regime, resulting in ring and pearl shaped structures, offer the benefit of increased sorption surface. These morphological structures obtained for the silver thin layers make them of interest for catalytic applications. The study presented with this work addresses both the fundamental and applied issues on the morphological structures obtained for the silver thin layer and their catalytic function in organic processes. In this sense, the catalytic action of the thin silver layer was highlighted by modifications of the Reactive Blue 21 dye (C.I.) in aqueous solution with sodium bicarbonate. Specific investigations and analyzes were carried out by electron microscopy and elemental analysis (SEM-EDX), atomic force microscopy (AFM) and profilometry, mass spectrometry, ablation plasma diagnosis, diffractograms (XRD), as well as IR spectroscopy (FTIR). In addition to the experimental investigation and analyzes, simulation of the ionization energy threshold was conducted in COMSOL for complementary evaluation on the involved processes and phenomena.

The quartz tuning fork used as an acoustic sensor in Quartz-Enhanced Photo-Acoustic Spectroscopy gas detection systems is usually read-out by means of a transimpedance preamplifier, based on a low-noise operational amplifier closed in a feedback loop. The gain-bandwidth product of the operational amplifier used in the circuit is a key parameter which must be properly chosen to guarantee that the circuit works as expected. Here we demonstrate that, if the value of this parameter is not sufficiently large, the response of the preamplifier exhibits a peak at a frequency which does not coincide with the series resonant frequency of the quartz tuning fork. If this peak frequency is selected for modulating the laser bias current and is also used as reference frequency of the lock-in amplifier, a penalty results in terms of signal to noise ratio at the output of the QEPAS sensor. This worsens the performance of the gas sensing system in terms of ultimate detection limits. We show that this happens when the front-end preamplifier of the quartz tuning fork is based on some amplifier models that are typically used for such application, both when the integration time of the lock-in amplifier filter is long, to boost noise rejection, and when it is short, in order to comply with a relevant measurement rate.

Laser-induced functionalisation using excimer laser irradiation has been widely applied to transparent conductive oxide films. However, exploring suitable irradiation conditions is time-consuming and cost-ineffective as there are numerous routine film fabrication and analytical processes. Thus, we herein explored a real-time technique to monitor the laser-induced functionalisation of transparent conductive oxide films. We developed two types of monitoring apparatus, electrical and optical, and applied them to magnetron-sputtered Sn-doped In2O3 films grown on glass substrates and hydrogen-doped In2O3 films on glass or plastic substrates using a picosecond Nd:YAG pulsed laser. Both techniques could monitor the functionalisation from a change in properties of the films on glass substrates by laser irradiation, but electrical measurement was unsuitable for plastic samples because of a laser-induced degradation of the underlying plastic substrate, which harmed proper electrical contact. Instead, we demonstrated that the optical properties in the near-infrared region were suitable for the monitoring and the changes in the optical properties were visually detected in real-time by using a near-infrared camera.

Since a large amount of sewage sludge (WSS) has been generated daily, it is necessary to explore effective methods for utilizing WSS. Although a photo-fermentation system sometimes alters the characteristics of microbial functions, there are no attempts to perform the photo-fermentation using WSS which is regularly treated under a dark-fermentation style. In this study, the effect of photo-fermentation (photo-irradiation) on anaerobic digestion using WSS was revealed. Photo-irradiation during the anaerobic digestion of WSS significantly reduced the amount of organic acids and hydrogen sulfide and methane production was also suppressed. However, it was shown that the activity of sulfate-reducing bacteria in WSS under the light treatment increased. Photo-irradiation also stimulated the growth of green-sulfur bacteria and induced anoxygenic photosynthesis, by which the fermented samples turned green linking with the consumption of hydrogen sulfide. Finally, a dark/light switching fermentation was able to reduce only hydrogen sulfide while methane production remained the same.

Photophysics properties such as fluorescence quenching, and photoexcitation dynamics of bimolecular non-covalent systems consisting of cationic poly[(9,9-di(3,3’-N,N’-trimethyl-ammonium) propyl fluorenyl-2,7-diyl)-alt-co-(9,9-dioctyl-fluorenyl-2,7-diyl)] diiodide salt (PFN) and anionic graphene carboxylate (GC) have been discovered for the first time by the steady state and time-resolved femtosecond transient absorption (TA) spectroscopy with broadband capabilities. The steady-state fluorescence of PFN is quenched with high efficiency by GC acceptor. Fluorescence lifetime measurements revealed that the quenching mechanism of PFN by GC is static. Here, the quenching mechanisms are well proven by TA spectra of PFN/GC systems. For PFN/GC systems, the photo electron transfer (PET) and charge recombination (CR) processes are ultrafast (within few tens of ps) related to static interactions whereas for PFN/DCB systems the PET takes place in few hundreds ps (217.50 ps)1 suggesting diffusion-controlled PET process. In the latter case, the PFN+•-DCB-• radical ion pairs as the result of PET from the PFN to DCB are clearly resolved and they are long-lived. The slow CR process (in 30 ns time scales)1 suggest PFN+• and DCB-• may already form separated radical ion pairs through charge separation (CS) process, which recombined back to the initial state with a characteristic time constant of 30 ns. The advantage of the present positively charged polyfluorene used in this work is the control over the electrostatic interactions and electron transfers in non-covalent polyfluorene/quencher systems in DMSO solution.

The broad emission bump in the electromagnetic spectra observed following the detection of gravitational waves created during the kilonova event of merger of two neutron stars in August 2017, GW170817, has been linked to the heavy elements of lanthanides (Z=57-71), and a new understanding of creation of heavy elements in the r-process. The initial spectral emission bump has a wavelength range of 3000 - 7000 \AA, thus covering the region of ultraviolet (UV) to optical (O) wavelengths, and is similar to those seen for lanthanides. Most lanthanides have large number of closely lying energy levels which introduce extensive sets of radiative transitions which often form broad region of lines of significant strength. The current study explores these broad features through photoabsorption spectroscopy of 25 lanthanides ions, Ho I-III, Er I-IV, Tm I-V, Yb I-VI and Lu I-VII. With excitations only to a few orbitals up beyond the ground configurations, we find most of these ions cover large number of bound levels with open $4f$ orbital and produce tens to about hundred thousands lines that may form one or multiple broad features in X-ray to UV, O, and infrared (IR) regions. Spectrum of each of 25 ions is presented indicating presence, shape and wavelength region of the features. Accuracy of atomic data to interpret the merger spectra has been a outstanding problem. The present study aims at providing improved atomic data for energies and transition parameters obtained using relativistic Breit-Pauli approximation implemented in the atomic structure code SUPERSTRUCTURE. The present data have been benchmarked with available experimental data for energies and transition parameters. The study finds that number of ions under the present study are possible contributors of the emission bump of GW170817. All atomic data will be made available online at NORAD-Atomic-Data database.

This study represents a significant stride in advancing furan chemistry, presenting the synthesis of high-molecular-weight polyfurfuryl alcohol (PFA) resin (Mw = 118,959 g/mol) from furfuryl alcohol (FA) using a co-catalytic system as against the conventional single-catalytic methods. The resulting PFA resin is fully characterised, and we conclude that it exhibits good shelf life and potential in diverse applications, serving as a standalone moulded material or contributing to composites, coatings, adhesives, and nanostructured carbons.

Photovoltaic materials convert light into electrical voltages. So far, most research in the field are focused on how to refine/improve the existing or standard photovoltaic cells to yield more efficient electricity, to reduce weight, to make more flexible shape, or to minimize costs under standard and uniform sunlight illuminations. In this project, we explore and demonstrate a hypothesis that non-uniform light illumination photovoltages can also be generated due to photo doping induced mobile charge carrier density gradient between light and dark areas in either p-type or n-type photo doping semiconductors. The term non-uniform light illumination was coined to refer to subjecting our photo sensing thin film devices to areas of high and low intensities of light illumination simultaneously, with an intention of creating a charge density gradient and therefore a voltage. Specifically, a polymeric composite thin film composed of P3HT (p-type photo doping semiconductor) and PCBM (photo doping electron acceptor and trap) at varying p-doping levels were studied. We observed that the fabricated photovoltaic cells with about 80% PCBM doped P3HT thin film devices exhibited 0.5-1.2 volts photovoltages under non-uniform light illuminations.

A series of polynuclear, dinuclear, and mononuclear Mo(VI) complexes were synthesized with the hydrazonato ligands derived from 5-methoxysalicylaldehyde and the corresponding hydrazides (isonicotinic hydrazide (H2L1), nicotinic hydrazide (H2L2), 2-aminobenzhydrazide (H2L3) or 4-aminobenzhydrazide (H2L4)). The metallosupramolecular compounds obtained from non-coordinating solvents, [MoO2(L1,2)]n (1 and 2) and [MoO2(L3,4)]2 (3 and 4), formed infinite structures and metallacycles, respectively. By blocking two coordination sites with cis-dioxo ligands, the molybdenum centers have three coordination sites occupied by the ONO donor atoms from the rigid hydrazone ligands and one by N atom of pyridyl or amine-functionalized ligand subcomponents from the neighbouring Mo building units. The reaction in methanol afforded the mononuclear analogues [MoO2(L1-4)(MeOH)] (1a-4a) with additional monodentate MeOH ligand. All isolated complexes were tested as catalysts for cyclooctene epoxidation using tBuOOH (TBHP) as an oxidant in water. The impact of the structure and ligand lability on the catalytic efficiency in homogeneous cyclooctene epoxidation was elucidated through theoretical considerations. Thus, dinuclear assemblies exhibited better catalytic activity than mononuclear or polynuclear complexes.

In this study, a new nitrogen-enriched multiwall carbon nanotube is prepared and utilized to stabilize palladium species. After the characterization of this new composite, it was applied as a catalyst in the reduction of nitroarenes and hydrodesulfurization of dibenzothiophene. Using this newly established catalyst, a wide range of aromatic compounds were reduced to the corresponding amines under a very low amount of Pd (0.005 mol%) in short reaction times. Also, dibenzothiophene (a major pollutant in fuel oil) was very efficiently transformed using this catalyst. Its robustness was studied in the recycling process where, after 20 runs in the reduction of 4-nitrotoluene and 5 times in the desulfurization of dibenzothiophene, the activity of the catalyst remained intact. According to the E-factor calculations, the present Pd catalyst meets the standards of green chemistry.

In this study, we demonstrate the direct preparation of dihalo-γ-lactams featuring two distinct halogens from dichloroamides using a novel Atom Exchange Radical Cyclization (AERC) procedure. This method integrates the established Atom Transfer Radical Cyclization with halogen exchange in solution. The technique operates under mild conditions and requires little amounts of metallic copper, serving as both a supplemental activator and reducing agent.

Proteases represent common targets in combating infectious diseases including COVID-19. The 3-chymotrypsin-like protease (3CLpro) is a validated molecular target for COVID-19 and it is key for developing potent and selective inhibitors for inhibiting viral replication of SARS-CoV-2. In this review, we discuss structural relationships and diverse subsites of 3CLpro, shedding light on the pivotal role of dimerization and active site architecture in substrate recognition and catalysis. Our analysis of bioinformatics and other published studies unveil a proposal of a novel catalytic mechanism for the SARS-CoV-2 polyprotein cleavage by 3CLpro, centering on the triad mechanism involving His41-Cys145-Asp187 and its indispensable role in viral replication. Recognizing Asp187 as a crucial component in the catalytic process underscores its significance as a fundamental pharmacophoric element in drug design. Next, we provide an overview of both covalent and non-covalent inhibitors, elucidating advancements in drug development observed in preclinical and clinical trials. By highlighting various chemical classes and their pharmacokinetic profiles, our review aims to guide future research directions toward the development of highly selective inhibitors, underscore the significance of 3CLpro as a validated therapeutic target, and propel the progression of drug candidates through preclinical and clinical phases.

Reducing CO2 emissions is urgently needed to slow down the impacts of climate change. CO2 capture using an amine solution has been developed and implemented on pilot and commercial scales. However, amine scrubbing, in particular, produces a lot of degraded solvent as waste and is energy intensive. Solid sorbents have been called to overcome those drawbacks. In this work, waste biomass-derived carbon materials were developed and tested for CO2 capture and conversion. Advanced thermal chemical processes i.e. hydrothermal and pyrolysis were applied to produce materials from agri-food waste such as soybean and okara. It was found that the number of functional groups (-C=O and -OH) in activated carbon appears in the synthesized materials, implying the generation of surface oxygenated groups. Preliminary results showed that the synthesized activated carbons are obtained with good yields, and a relatively high surface area, which may be applied as CO2 adsorption materials to solve the CO2 emission problems.