Search

A proof-of-concept study is undertaken to demonstrate the utility of the machine learning combined with the thermodynamic perturbation theory (MLPT) to test the accuracy of electronic structure methods in finite-temperature thermodynamic calculations. As a test example, formic acid dimer is chosen, which is one of the systems included in the popular benchmark set S22 [Jurečka et al., Phys. Chem. Chem. Phys. 8, 1985–1993 (2006)]. Starting from the explicit molecular dynamics and thermodynamic integration performed at the PBE + D2 level, the MLPT is used to obtain fully anharmonic dimerization free and internal energies at the reference quality CCSD(T) level and 19 different density functional approximations, including GGA, meta-GGA, non-local, and hybrid functionals with and without dispersion corrections. Our finite-temperature results are shown to be both qualitatively and quantitatively different from those obtained using the conventional benchmarking strategy based on fixed structures. The hybrid functional HSE06 is identified as the best performing approximate method tested, with the errors in free and internal energies of dimerization being 36 and 41 meV, respectively. [ABSTRACT FROM AUTHOR]

This paper presents a detailed study of low energy positron scattering from formic acid, examining elastic scattering, electronic excitation and ionisation processes. Through detailed comparisons with previous experimental and theoretical data, it is clear that the picture for positron scattering from this target remains incomplete, with significant disagreement between experiment and theory in the comparisons of differential cross section data. Calculations of elastic electron scattering are unexpectedly in better agreement with the positron scattering experiments, and give some hints as to potential areas for improvement in the modelling of scattering for targets which tend to be dominated by dipole interactions. [ABSTRACT FROM AUTHOR]

The article focuses on recent advancements in chemistry, highlighting the development of new materials and chemical processes. Topics include the synthesis of insensitive energetic materials with enhanced detonation performance, the use of vanadium(V) complexes for syndiospecific ring-opening metathesis polymerization (ROMP) of cyclic olefins, and the exploration of metal-support interactions to enhance catalytic activity for hydrogen production.

The synthesis of noble metal/TiO2 composites without the use of additional reducing agents or surfactants is a notable achievement in catalyst preparation, as it simplifies the process and reduces potential impurities. A detailed analysis of catalysts using a range of methods like XRD, TEM, XPS, BET, and FT-IR offers a comprehensive insight into their structural and surface characteristics, essential for understanding their catalytic performance. The observation of enhanced catalytic activity with Pt-loaded composite catalysts compared to Pd and Au-loaded counterparts highlights the importance of noble metal selection in catalytic applications. Through BET and TEM characterization, it can be observed that there is no significant difference between the specific surface area of all noble metal/TiO2 composites and the size of the noble metal, which ranges from 2–7 nm. The correlation between the catalytic efficiency and the metal work function, along with the insights from XPS analysis, underscores the significance of the metal–titanium dioxide interaction in determining catalytic efficiency. This interaction may involve tuning the surface's electronic structure, the chemical bonding between the metal and the carrier, and the formation of surface active sites. These sites can adsorb reactants and facilitate the reaction, thus improving the catalytic activity and selectivity. This study provides an in-depth understanding and an important reference for the design and optimization of catalysts for hydrogen production from formic acid, which can help promote progress and applications in related fields. [ABSTRACT FROM AUTHOR]

Electrochemical carbon dioxide reduction reaction (ECO2RR) is an effective means to promote carbon cycling. Recently, Bi-based metal–organic frameworks (MOFs) have attracted significant attention due to their high efficiency for formic acid generation in ECO2RR, however, their composition and morphology transformation during electrocatalysis still lack a deep exploration. Herein, a Bi-MOF with 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine (H3TATB) ligand is used as the prototype to investigate its in situ transformation during ECO2RR. With various characterization methods, the detailed transformation processes are revealed. Firstly, the Bi-MOF was transformed into Bi2O2CO3 due to ligand substitution in KHCO3 electrolyte, resulting in changes in both shape and composition. Secondly, during ECO2RR, the Bi3+ ions can be reduced into metallic Bi0 nanoparticles and act as the real active component for ECO2RR. The resultant catalyst exhibits a high selectivity of up to 94.3% towards formate generation. At an optimal potential of −1.08 V vs. RHE, the catalyst can maintain a current density of −25 mA cm−2 and a faradaic efficiency of formate over 90% for 14.5 hours. This work not only develops an efficient electrocatalyst for ECO2RR but also provides a new insight into the in situ reconstruction of MOF precursor into the active catalyst, which is useful for the design and synthesis of other materials. [ABSTRACT FROM AUTHOR]

The interaction between Pt nanoparticles and their supports, and the Pt nanoparticle size influence the performance and stability of Pt catalysts. Polyaniline (PANI) serves as an effective support for Pt catalysts owing to its abundant functional groups and high electron conductivity. Strong chemical interactions exist between the Pt nanoparticles and the functional groups on PANI. In this study, through the use of different reducing agents, the sizes of Pt nanoparticles on PANI nanofibers are adjusted, resulting in the preparation of three Pt/PANI catalysts. Owing to the strong reducibility of sodium borohydride, its use as a reducing agent leads to rapid heterogeneous nucleation, and the obtained Pt/PANI catalyst exhibits the smallest Pt nanoparticle size among the three Pt/PANI catalysts. Consequently, many Pt nanoparticles are not deposited on the PANI nanofibers, which reduces the activity of the Pt/PANI catalyst. Conversely, when ethylene glycol is used as the reducing agent, the resulting catalyst exhibits the largest Pt nanoparticle size among the three Pt/PANI catalysts owing to the slow reduction rate of Pt4+. The Pt/PANI catalyst prepared using formic acid (Pt/PANI-FA) achieves an optimal reaction rate owing to the moderate reducibility of the reducing agent. Consequently, the Pt nanoparticles on PANI nanofibers in Pt/PANI-FA have a diameter of 3.32 nm, which is comparable to that of Pt nanoparticles in Pt/C catalysts. The half-wave potential of Pt/PANI-FA in the oxygen reduction reaction reaches 840 mV (vs. reversible hydrogen electrode), which surpasses the 801 mV achieved by Pt/C catalysts. [Display omitted] • Polyaniline nanofiber is used as Pt support to prepared three Pt/PANI catalysts. • The size of Pt nanoparticles is tuned by using three different reducing agents. • Compared to sodium borohydride and ethylene glycol, formic acid has optimized reducibility. • The half-wave potential of optimized Pt/PANI catalyst is 840 mV, higher than that of Pt/C. • Chemical interaction between Pt and PANI improves the Pt/PANI catalyst performance. [ABSTRACT FROM AUTHOR]

Formic acid (HCOOH) is a highly energy efficient product of the electrochemical CO2 reduction reaction (CO2RR). Bismuth‐based catalysts have shown promise in the conversion of CO2 to formic acid, but there is still a great need for further improvement in selectivity and activity. Herein, we report the preparation of Bi nanosheets decorated by cerium oxide nanoparticles (CeOx) with high Ce3+/Ce4+ ratio and rich oxygen vacancies. The CeOx nanoparticles affect the electronic structures of bismuth, enhance CO2 adsorption, and thus promote the CO2RR properties of Bi nanosheets. Compared with elemental Bi nanosheets, the hetero‐structured CeOx/Bi nanosheets exhibit much higher activity over a wide potential window, showing a current density of 16.1 mA cm−2 with a Faradaic efficiency of 91.1% at −0.9 V vs. reversible hydrogen electrode. [ABSTRACT FROM AUTHOR]

Electrochemical carbon dioxide (CO2) reduction reaction (CO2RR) to valuable liquid fuels, such as formic acid/formate (HCOOH/HCOO−) is a promising strategy for carbon neutrality. Enhancing CO2RR activity while retaining high selectivity is critical for commercialization. To address this, we developed metal‐doped bismuth (Bi) nanosheets via a facile hydrolysis method. These doped nanosheets efficiently generated high‐purity HCOOH using a porous solid electrolyte (PSE) layer. Among the evaluated metal‐doped Bi catalysts, Co‐doped Bi demonstrated improved CO2RR performance compared to pristine Bi, achieving ~90 % HCOO− selectivity and boosted activity with a low overpotential of ~1.0 V at a current density of 200 mA cm−2. In a solid electrolyte reactor, Co‐doped Bi maintained HCOOH Faradaic efficiency of ~72 % after a 100‐hour operation under a current density of 100 mA cm−2, generating 0.1 M HCOOH at 3.2 V. Density functional theory (DFT) results revealed that Co‐doped Bi required a lower applied potential for HCOOH generation from CO2, due to stronger binding energy to the key intermediates OCHO* compared to pure Bi. This study shows that metal doping in Bi nanosheets modifies the chemical composition, element distribution, and morphology, improving CO2RR catalytic activity performance by tuning surface adsorption affinity and reactivity. [ABSTRACT FROM AUTHOR]

The development of high‐performance catalysts for formic acid (FA) dehydrogenation is of extreme significance to the successful production of hydrogen under ambient conditions. Despite some encouraging progress, their activity is still unsatisfied than needed. In this work, it is presented that Lewis acidic VOx sites engineered ultrafine PdAu nanoclusters (PdAu‐VOx) perform perfectly for hydrogen production from FA dehydrogenation. Strikingly, the best catalyst — PdAu‐VOx embed in amino‐functionalized hollow mesoporous support (PdAu‐VOx/NHMS) discloses an impressive initial turnover frequency of 14155 h−1 and a low activation energy of 31.2 kJ mol−1 without additives at room temperature, and maintains 100% selectivity and conversion in the tenth cycle reaction. Mechanistic investigations illustrate that VOx species can serve as the Lewis acid sites, which not only regulate the adsorption strength of reactant and intermediate on PdAu, but also reinforce the C─H bond activation within FA molecule, thereby promoting the reaction kinetics for efficient hydrogen production. This work thus provides a strategy for the development of new‐style heterogeneous catalysts with Lewis acid‐base sites applied to a variety of energy‐related catalytic reactions. [ABSTRACT FROM AUTHOR]

In situ and operando investigation of photocatalysts plays a fundamental role in understanding the processes of active phase formation and the mechanisms of catalytic reactions, which is crucial for the rational design of more efficient materials. Using a custom‐made operando photocatalytic cell, an in situ procedure to follow the formation steps of Pd/TiO2 photocatalyst by synchrotron‐based X‐ray absorption spectroscopy (XAS) is proposed. The procedure resulted in the formation of ∼1 nm Pd particles with a much narrower size distribution and homogeneous spreading over TiO2 support compared with the samples generated in a conventional batch reactor. The combination of in situ XAS spectroscopy with high‐angle annular dark‐field scanning transmission electron microscopy demonstrated the formation of single‐atom Pd(0) sites on TiO2 as the initial step of the photodeposition process. Palladium hydride particles were observed for all investigated samples upon exposure to formic acid solutions. [ABSTRACT FROM AUTHOR]

This paper presents the results of the use of MFI zeolite as a catalyst modified with tin and iron. Sn‐MFI and Fe‐MFI catalysts were obtained by ion exchange under hydrothermal conditions with and without ammonium exchange. Catalytic materials were characterized with the use of analytical techniques such as X‐ray diffraction (XRD), Brunauer–Emmett–Teller method (BET), diffuse reflectance spectroscopy in the ultraviolet‐visible range (DRS UV–visible), hydrogen temperature programmed reduction (H2‐TPR), or Fourier transform infrared (FTIR) spectroscopy. The one‐pot catalytic conversion of fructose was performed at 220 °C for 1–5 h. Based on the results, the influence of time and material selection on the products obtained can be seen. Lactic acid (LAC) was obtained with a yield of 68.7% (after 2 h) and levulinic acid (LA) with a yield of 70.9% (after 5 h) with the participation of MFI. In turn, formic acid with a yield of 28.5% (after 5 h) was obtained with the participation of Fe‐MFI. [ABSTRACT FROM AUTHOR]

Additives are very important to enhance the performance of lead-acid batteries. In this paper, formic acid is used as an electrolyte additive to study its effect on battery performance. The results show formic acid has an opposite effect on the electrochemical properties of pure lead at positive and negative potentials. Besides, formic acid can make more active materials participate in the reaction, increase the rate of conversion of lead to lead sulfate, and reduce the internal resistance of the battery. Moreover, formic acid batteries exhibit better rate performance and higher specific discharge capacity than the blank. Especially, when the 0.5 wt% formic acid is used, the discharge capacity can reach 87.0 mAh g−1 when it is discharged at 400 mA g−1. After 1200 cycles of charge and discharge at a current density of 100 mA g−1, the specific discharge capacity is still 68.1 mAh g−1, which is 1.42 times higher than that of blank cells. [ABSTRACT FROM AUTHOR]

Dicarboxylic acids (DCAs) are major players in the formation of secondary organic aerosols (SOAs) and climate change. DCAs have potential impact on human health and environmental issues ranging from local scale to global scale participate mainly in the cloud condensation. In this context, oxalic acid (OA) and malonic acid (MA) are the most dominant DCAs in the atmosphere. A full atmospheric degradation mechanism of OA and MA with the most reactive tropospheric oxidants, namely, OH, Cl and NO3 radicals, were studied using M06‐2X, ωB97XD/cc‐pVTZ and 6‐311++G(2df,2p) level of theories. To evaluate the atmospheric influence, this study enables us to deep investigation of fate of OA and MA with respect to the mentioned radicals and their subsequent secondary reactions. The latter result in the formation of carbon dioxide (CO2), formic acid (HCOOH), which contributes to the formation of SOA and climate change. The reaction mechanism in this study was initiated through H‐abstraction reaction, followed by dehydrogenation and decarboxylation reaction of both DCAs. The rate coefficients of OA, MA with OH, Cl and NO3 radicals are determined theoretically using variational transition state theory (VTST) with Eckart tunnelling method in the temperature range of 278–1000 K. At 298 K, the rate coefficient of OA with OH, Cl and NO3 are 2.48 × 10−15, 2.37 × 10−20, 6.16 × 10−23 in cm3 molecule−1 s−1, whereas MA with OH, Cl and NO3 are 9.76 × 10−14, 1.01 × 10−12 and 5.89 × 10−18 in cm3 molecule−1 s−1, respectively. Our present results shed light on the atmospheric implications of two DCAs and provide the significant insight for the atmospheric pathways. [ABSTRACT FROM AUTHOR]

An ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method was developed for the determination of monocrotaline and usaramine in rat plasma, to study the plasma drug concentration and pharmacokinetics, and to calculate the absolute bioavailability. The plasma was treated with acetonitrile and methanol (9:1, v/v) protein precipitation method. The chromatographic column was UPLC HSS T3 (50 mm × 2.1 mm, 1.7 μm), the mobile phase was methanol-water (containing 0.1% formic acid with 10 mM ammonium acetate in water), and the elution time was 4 min at a flow rate of 0.4 mL min−1. Electrospray ionization (ESI) positive ion mode was used for detection and multiple reaction monitoring (MRM) mode was used for quantitative analysis. Monocrotaline and usaramine were administered sublingual intravenously (iv) 1 mg kg−1 and orally (po) 5 mg kg−1, respectively, with 6 rats in each group, for a total of 24 rats. Then the pharmacokinetic differences in rats were evaluated. For the UPLC-MS/MS method, the calibration curve showed good linearity in the range of 2–2,000 ng mL−1, where r was greater than 0.99. The precision, accuracy, recovery, matrix effect and stability results were all consistent with the requirements of biological sample detection methods. to provide scientific experimental basis for the basic research The bioavailability of monocrotaline and usaramine in rat plasma was calculated, which was 43.5 and 19.5%, respectively. [ABSTRACT FROM AUTHOR]

In situ and operando investigation of photocatalysts plays a fundamental role in understanding the processes of active phase formation and the mechanisms of catalytic reactions, which is crucial for the rational design of more efficient materials. Using a custom‐made operando photocatalytic cell, an in situ procedure to follow the formation steps of Pd/TiO2 photocatalyst by synchrotron‐based X‐ray absorption spectroscopy (XAS) is proposed. The procedure resulted in the formation of ∼1 nm Pd particles with a much narrower size distribution and homogeneous spreading over TiO2 support compared with the samples generated in a conventional batch reactor. The combination of in situ XAS spectroscopy with high‐angle annular dark‐field scanning transmission electron microscopy demonstrated the formation of single‐atom Pd(0) sites on TiO2 as the initial step of the photodeposition process. Palladium hydride particles were observed for all investigated samples upon exposure to formic acid solutions. [ABSTRACT FROM AUTHOR]

Copyright of Science & Technology of Food Industry is the property of Science & Technology of Food Industry Editorial Office and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

This article presents a new method for detecting oxytocin (OT) in nonhuman primate plasma using liquid chromatography-tandem mass spectrometry (LC/MS/MS). OT is a neuropeptide that affects social behavior, and current methods for measuring OT levels have limitations. The researchers developed a protocol for sample preparation and analysis using LC/MS/MS, which allowed for accurate measurement of OT concentrations in plasma. The study found that the method was accurate and precise, with a lower limit of quantification of 0.41 pg/mL. This is the first reported method with sufficient sensitivity to measure OT in nonhuman primate plasma. [Extracted from the article]

A leading cause of global warming is the increase of carbon dioxide (CO2) emissions due to anthropogenic activities which prompts an urgent need for substantial reduction. Recently, CO2 absorption in deep eutectic solvents (DESs) has attracted scientific attention, because of their adaptability compared to traditional ionic liquids and aqueous amine solutions. This study employs the heating method to synthesize DESs using tetrapropylammonium bromide (TPAB) and formic acid (Fa) with molar ratios of TPAB-Fa (1:1) and TPAB-Fa (1:2). Absorption experiments by static method quantified CO2 solubility in the DESs under varied pressures and temperatures. TPAB-Fa (1:2) at 25.0 °C was the most efficient with the CO2 solubility of 0.218. Thermodynamic modeling was performed by employing the nonrandom two liquids activity coefficient model and the Peng–Robinson equation of state for the liquid and gas phases, respectively. The Henry's law constant was determined from experimental data. CO2 physical absorption was confirmed via nuclear magnetic resonance (NMR) and Fourier-transform infrared (FT-IR) analyses. TPAB-Fa (1:2), as the superior DES, exhibited regeneration efficiency of 99% after five absorption/desorption cycles. [ABSTRACT FROM AUTHOR]

Development of efficient and stable non‐noble metal catalysts applied to the catalytic transfer hydrogenation of nitroarenes under mild conditions is still challenging. Herein, we report magnetically recyclable catalysts prepared via simple two‐stage pyrolysis of Co‐MOF‐74 and melamine composites. The optimized catalyst Co@C/CNTs‐10‐700 shows excellent conversion and selectivity towards transfer hydrogenation of nitroarenes with different hydrogen donors. Its excellent stability against formic acid corrosion makes it can be used in a wide range. The excellent catalytic performance can be ascribed to the synergistic effect between carbon nanotubes and Co nanoparticles. Furthermore, the catalyst was easily recycled owing to its magnetism and reused up to ten consecutive cycles without significant loss of activity, indicating that the excellent catalytic stability holds great promise in fields of industrial application. [ABSTRACT FROM AUTHOR]

Biomass valorisation over polyoxometalate‐based (POM) catalysts is a promising strategy for green and sustainable chemistry. In order to further improve such processes e. g. by using different additives, a better understanding of the chemical influence of various additives on the catalyst is paramount. The main objective of this study is to gain a deeper understanding of the effects caused by various additives on the catalytically active vanadium species in the selective aerobic oxidation of carbohydrates to formic acid (esters). After carefully choosing a suitable model system, the oxidation of glycolaldehyde using the heteropolyacid H5PV2Mo10O40 (HPA‐2) as a catalyst was studied in situ by Flow Nuclear magnetic resonance (FlowNMR) spectroscopy. These measurements allowed to identify the catalytically active isomer of the HPA‐2‐catalyst and to observe the influence of additives on the reaction kinetics in situ. These findings provide a good basis for further improving POM‐based catalytic aerobic oxidation of biomass. [ABSTRACT FROM AUTHOR]

Electrochemical CO2 reduction (ECR) to value‐added products such as formate/formic acid is a promising approach for CO2 mitigation. Practical ECR requires long‐term stability at industrially relevant reduction rates, which is challenging due to the rapid degradation of most catalysts at high current densities. Herein, we report the development of a bismuth (Bi) gas diffusion electrode on a polytetrafluoroethylene‐based electrically conductive silver (Ag) substrate (Ag@Bi), which exhibits high Faradaic efficiency (FE) for formate of over 90 % in 1 M KOH and 1 M KHCO3 electrolytes. The catalyst also shows high selectivity of formic acid above 85 % in 1 M NaCl catholyte, which has a bulk pH of 2–3 during ECR, at current densities up to 300 mA cm−2. In 1 M KHCO3 condition, Ag@Bi maintains formate FE above 90 % for at least 500 hours at the current density of 100 mA cm−2. We found that the Ag@Bi catalyst degrades over time due to the leaching of Bi in the NaCl catholyte. To overcome this challenge, we deposited a layer of Ag nanoparticles on the surface of Ag@Bi to form a multi‐layer Ag@Bi/Ag catalyst. This designed catalyst exhibits 300 hours of stability with FE for formic acid ≥70 % at 100 mA cm−2. Our work establishes a new strategy for achieving the operational longevity of ECR under wide pH conditions, which is critical for practical applications. [ABSTRACT FROM AUTHOR]

Hydrogen (H2) is being acknowledged as the future energy carrier due to its high energy density and potential to mitigate the intermittency of other renewable energy sources. H2 also ensures a clean, carbon‐neutral, and sustainable environment for current and forthcoming generations by contributing to the global missions of decarbonization in the transportation, industrial, and building sectors. Several H2 storage technologies are available and have been employed for its secure and economical transport. The existing H2 storage and transportation technologies like liquid‐state, cryogenic, or compressed hydrogen are in use but still suffer from significant challenges regarding successful realization at the commercial level. These factors affect the overall operational cost of technology. Therefore, H2 storage demands novel technologies that are safe for mobility, transportation, long‐term storage, and yet it is cost‐effective. This review article presents potential opportunities for H2 storage technologies, such as physical and chemical storage. The prime characteristics and requirements of H2 storage are briefly explained. A detailed discussion of chemical‐based hydrogen storage systems such as metal hydrides, chemical hydrides (CH3OH, NH3, and HCOOH), and liquid organic hydrogen carriers (LOHCs) is presented. Furthermore, the recent developments and challenges regarding hydrogen storage, their real‐world applications, and prospects have also been debated. [ABSTRACT FROM AUTHOR]

Reducing CO2 emissions is an urgent global priority. In this context, several mitigation strategies, including CO2 tax and stringent legislation, have been adopted to halt the deterioration of the natural environment. Also, carbon recycling procedures undoubtedly help reduce net emissions into the atmosphere, enhancing sustainability. Utilizing Earth's abundant CO2 to produce high‐potential green chemicals and light fuels opens new avenues for the chemical industry. In this context, many attempts have been devoted to converting CO2 as a feedstock into various value‐added chemicals, such as CH4, lower methanol, light olefins, gasoline, and higher hydrocarbons, for numerous applications involving various catalytic reactions. Although several CO2‐conversion methods have been used, including electrochemical, photochemical, and biological approaches, the hydrogenation method allows the reaction to be tuned to produce the targeted compound without significantly altering infrastructure. This review discusses the numerous hydrogenation routes and their challenges, such as catalyst design, operation, and the combined art of structure‐activity relationships for the various product formations. [ABSTRACT FROM AUTHOR]

Designing low-cost and efficient catalysts for formic acid dehydrogenation (FAD) is crucial to facilitate the practical applications of formic acid as a hydrogen carrier. Using density functional theory calculations, we designed nine graphdiyne-supported Pd/Cu single-, double-, and triple-atom catalysts, investigating their stability and formic acid dehydrogenation performance. The results indicate that as the number of active metal sites increases, the catalytic activity for formic acid dehydrogenation improves, i.e., M 3 @GDY > M 2 @GDY > M 1 @GDY (M = Pd/Cu). Moreover, a synergistic effect between Pd and Cu atoms is observed in Pd x Cu 3-x @GDY, where the activity sequence of triple-atom catalysts was Pd 1 Cu 2 @GDY > Pd 2 Cu 1 @GDY > Pd 3 @GDY > Cu 3 @GDY. Particularly, Pd 1 Cu 2 @GDY exhibits superior FAD catalytic activity and hydrogen selectivity, presenting a potential novel formic acid dehydrogenation catalyst. Electronic structure analysis indicates that the band center difference Δε (Δε = ε d - ε p) serves as an assessment descriptor for formic acid dehydrogenation activity. Microkinetic analysis further confirms the performance of TACs predicted by DFT results, and shows that all TACs have good H 2 selectivity even at a high temperature. [Display omitted] • A series of Pd x Cu y @GDY catalysts for formic acid dehydrogenation were designed. • Pd 1 Cu 2 @GDY shows best activity and H 2 selectivity among all catalysts. • Band center difference is a good descriptor of the catalytic activity. [ABSTRACT FROM AUTHOR]

Progress is made in the advancement of efficient and durable electrocatalysts for the ethylene glycol oxidation reaction (EGOR), which is a critical breakthrough in the conversion of waste plastic into high‐value‐added chemicals. Here, an organic ligand‐modified PdNi bimetallenes (PdNi O‐BMs) catalyst is designed and constructed through the one‐pot method. Benefiting from the frizzy and porous surface structure and inorganic–organic hybrid interface modification, PdNi O‐BMs undergo electrocatalytic reforming of ethylene glycol (EG) derived from polyethylene terephthalate (PET) to form formic acid. The unique structural advantages result in high EGOR performance. Meanwhile, the influence of Ni and organic ligand on the catalyst performance is confirmed through density functional theory calculations. This study reveals an advanced strategy for the synthesis of inorganic–organic hybrid bimetallenes, providing a green and sustainable new approach for PET value‐added transformation. [ABSTRACT FROM AUTHOR]

Industrial CO2 electrolysis via electrochemical CO2 reduction has achieved progress in alkaline solutions, while the same reaction in acidic solution remains challenging because of severe hydrogen evolution side reactions, acid corrosion, and low target product selectivity. Herein, an industrial acidic CO2 electrolysis to pure HCOOH system is realized in a proton-exchange-membrane electrolyzer using an acid-tolerant Bi-based metal-organic framework guided by a Pourbaix diagram. Significantly, the Faradaic efficiency of HCOOH synthesis reaches 95.10% at a large current density of 400 mA/cm2 with a high CO2 single-pass conversion efficiency of 64.91%. Moreover, the proton-exchange-membrane device also achieves an industrial-level current density of 250 mA/cm2 under a relatively low voltage of 3.5 V for up to 100 h with a Faradaic efficiency of 93.5% for HCOOH production, which corresponds to an energy consumption of 200.65 kWh/kmol, production rate of 12.1 mmol/m2/s, and an energy conversion efficiency of 38.2%. These results will greatly aid the contemporary research moving toward commercial implementation and success of CO2 electrolysis technology. This work develops an industrial-level CO2 electrolysis system for formic acid production by constructing a proton exchange membrane electrolyzer with an acid-tolerant Bismuth metal-organic framework. [ABSTRACT FROM AUTHOR]

Simple Summary: Stylo silage is widely used as a protein source for ruminants in tropical and subtropical regions. High levels of biogenic amines in stylo silage are harmful to the health of ruminant animals. The purpose of this work was to evaluate the effect of formic acid and sugar on biogenic amines and amino acids concentrations and bacterial composition and fermentation profile of stylo silage. The results showed that putrescine, cadaverine, and tyramine became predominant in the control silage, and applying formic acid and sugar significantly decreased putrescine, cadaverine, tyramine, and total biogenic amine concentrations. Clostridium pabulibutyricum, Weissella cibaria and W. paramesenteroides were the predominant bacteria in the control silage, and the application of both additives remarkably lowered their relative abundance. Correlation analysis showed that C. pabulibutyricum, W. cibaria and W. paramesenteroides were positively related to putrescine, cadaverine, and tyramine formation. The application of formic acid or sugar significantly reduced the undesirable bacterial population and improved the fermentation and hygienic quality of the stylo silage. Substantial proteolysis occurs and free amino acids can be degraded to biogenic amines by decarboxylation during stylo (Stylosanthes guianensis) ensiling. High biogenic amine concentrations in silage are harmful to the health of ruminant animals. The purposes of this work were to (1) analyze the biogenic amines and amino acids concentrations, bacterial composition, and fermentation profile of spontaneously fermented stylo silage, (2) explore the effect of formic acid or sugar additive on these silage parameters, and (3) further reveal the correlations between silage amines and fermentation parameters, amino acids, and bacteria. Freshly chopped stylo was treated with distilled water (control), formic acid (4 mL/kg), and sugar (20 g/kg) and fermented for 28 days. The results indicated that putrescine (321 mg/kg dry matter), cadaverine (384 mg/kg dry matter), and tyramine (127 mg/kg dry matter) rapidly increased in concentration and become predominant in the control silage after 28 days of fermentation. Applying formic acid and sugar at ensiling, especially the acidifier, significantly decreased putrescine, cadaverine, tyramine, and total biogenic amine concentrations compared with the control treatment (p < 0.0001). Clostridium pabulibutyricum, Weissella cibaria and W. paramesenteroides were the predominant bacteria in the control silage, and the application of both additives remarkably lowered their relative abundance in comparison with the control treatment (p < 0.001). Correlation analysis showed that putrescine, cadaverine, and tyramine were positively related to pH, butyric acid, non-protein nitrogen, and ammonia nitrogen (p < 0.01). These amines also had significant correlations with C. pabulibutyricum, W. cibaria and W. paramesenteroides (p < 0.001). Putrescine, cadaverine, and tyramine were the main biogenic amines and C. pabulibutyricum was the predominant undesirable bacterium in naturally fermented stylo silage. C. pabulibutyricum, W. cibaria and W. paramesenteroides were positively related to putrescine, cadaverine, and tyramine formation. The application of formic acid or sugar significantly reduced the undesirable bacterial population and improved the fermentation and hygienic quality of the stylo silage. These findings lay the foundation for further elucidating the microbial mechanism underlying the main biogenic amine formation during fermentation of stylo silage. [ABSTRACT FROM AUTHOR]

Simple Summary: Benzoic acid has been supplemented in feeds to improve intestinal health and the growth rate of nursery pigs. Benzoic acid, a colorless crystalline organic compound, consists of a benzene ring with a carboxyl substituent, representing the simplest form of aromatic carboxylic acid. In pig feeds, benzoic acid primarily influences the small intestine rather than the large intestine of pigs, as benzoic acid does not require degradation in the stomach or beyond the small intestine. Benzoic acid possesses acidic properties, making it an effective feed additive in pig production through its antimicrobial action by reducing pH in feed and digesta in the gastrointestinal tract, positively modulating intestinal microbiota and enhancing nutrient utilization and intestinal health in pigs. Benzoic acid supplementation also decreases urinary pH through the production of hippuric acid and reduces ammonia emissions, which can positively affect the conditions of barns considering the intense pig production systems. However, depending on the levels of benzoic acid, its impact on growth is not always consistent. Thus, this review investigated the functional roles of benzoic acid on the intestinal health, nutrient utilization, and growth performance of nursery pigs, determined the optimal dose level of benzoic acid on the growth rate in nursery pigs, and compared the efficacy of benzoic acid and other acids, aiming to clarify the potential benefits of benzoic acid in pig feeds. The objectives of this review are to investigate how benzoic acid can mitigate the negative effects of weaning stress, improve the intestinal microbiota, intestinal health, and growth of nursery pigs, determine the optimal dose level of benzoic acid for the growth rate in nursery pigs, and compare the efficacy of benzoic acid and other acids in pig feeds. After weaning, pigs are exposed to less lactose and solid feed with high acid-binding capacity at infrequent intervals, causing an increase in digesta pH, reducing protein digestion, and increasing ammonia-producing bacteria in the stomach. Benzoic acid supplementation has improved the intestinal health and growth of nursery pigs through its antimicrobial properties and pH reduction in the digesta. The positive modulation of luminal microbiota in the small intestine of pigs by benzoic acid improves intestinal morphology and enhances nutrient utilization, especially nitrogen, of nursery pigs. Benzoic acid supplementation of up to 1% in feeds also increases hippuric acid contents in the urine of nursery pigs, decreasing urinary pH, which is related to ammonia emission and barn conditions in intensive pig production. Supported by the beneficial impacts of benzoic acid, the growth performance of nursery pigs was also improved. However, excessive benzoic acid (over 2.5% up to 5%) in feeds reduces the growth performance of nursery pigs. Thus, this review conducted a meta-analysis of the results from 16 papers to determine the optimal dose level of benzoic acid for body weight gain of nursery pigs, which was found to be 0.60%. The efficacy of benzoic acid was similar to that of other organic acids, including citric acid, fumaric acid, formic acid, and formate salts. Collectively, benzoic acid supplementation can positively modulate the luminal and mucosal microbiota in the small intestine, increase nutrient utilization and intestinal health, decrease urinary pH, and improve the growth performance of nursery pigs. [ABSTRACT FROM AUTHOR]

In this study, we report the preparation and characterization of water-stable films with UV-shielding and good mechanical properties, exploiting the synergistic effect of regenerated silk fibroin and bamboo-derived cellulose. Silk fibroin (SF)/bamboo (B) hybrid films are achieved by solubilizing both silk and bamboo fibers in formic acid with added CaCl2. Infrared spectroscopy indicates that SF, when combined with bamboo, undergoes a conformational transition, providing evidence of an increase in SF crystallinity. Exploiting the intrinsic absorption of SF in the ultraviolet region, UV–Vis spectroscopy was used to assess the glass transition temperature (Tg) of SF/B films, showing a decrease in Tg by increasing the SF content. The addition of 10 wt% SF to the B matrix improved the elastic modulus by about 10% while conserving the strain at break with respect to the neat B films, increasing the UV shielding properties, while water absorption suggested the material's hydrophilic and swelling capacity even after one month. The hybrid films showed, under solar irradiation, a photoprotective behavior on keratinocyte human cells by increasing cellular viability. These findings may find potential applications in functional fabrics. [ABSTRACT FROM AUTHOR]

The skin of amphibians is a rich source of peptides with a wide range of biological activities. They are stored in secretory granules in an inactive form. Upon stimulation, they are secreted together with proteases into the skin. Once activated, they rapidly exert their biological effects, including fighting microorganisms and predators, while their excess is immediately destroyed by the released proteases. To keep bioactive peptides in their initial form, it is necessary to inhibit these enzymes. Several inhibitors for this purpose have previously been mentioned; however, there has not been any reliable comparison of their efficiency so far. Here, we studied the efficiency of methanol and hydrochloric and formic acids, as well as phenylmethylsulfonyl fluoride, in the inhibition of nine frog peptides with the known sequence, belonging to five families in the secretion of Pelophylax esculentus. The results demonstrated that methanol had the highest inhibitory efficiency, while phenylmethylsulfonyl fluoride was the least efficient, probably due to its instability in aqueous media. Possible cleavages between certain amino acid residues in the sequence were established for each of the inhibitors. These results may be helpful for future studies on the nature of proteases and on prediction of the possible cleavage sites in novel peptides. [ABSTRACT FROM AUTHOR]

In this work, highly efficient carbon‐supported Pd‐based catalysts for formic acid dehydrogenation were synthesized by a straightforward wet impregnation‐reduction method. The carbon support was obtained from a biomass residue (almond shell) prepared via H3PO4‐assisted hydrothermal carbonization (HTC) and thermal activation. This carbon support was doped with nitrogen groups to study the effect on the electronic properties and catalytic performance of the catalysts. Investigating the formation of PdAg alloys with varying Pd : Ag molar ratios resulted in catalysts exhibiting enhanced catalytic activity compared to monometallic Pd counterparts. Notably, the Pd1Ag0.5/NAS catalyst displayed outstanding catalytic performance, achieving an initial TOF of 1716 h−1 (calculated in the first 3 minutes of reaction and expressed per mole of Pd) and maintaining substantial activity over 6 consecutive reaction cycles. This work elucidates the successful synthesis of effective catalysts, emphasizing the influence of nitrogen doping and PdAg alloy composition on catalytic behavior and stability. [ABSTRACT FROM AUTHOR]

Pd-based anode catalysts with superior activity are urgent for formic acid oxidation to further boost the direct formic acid fuel cells (DFAFCs) technologies. Herein, a strategy of ethylenediamine (EDA) modified Pd/C catalyst was developed by two main steps of EDA adsorbed on Vulcan XC-72 carbon by impregnation and Pd nanoparticles loaded on the freeze-dried C-EDA supports by liquid reduction method. The effects of sweep rates and concentrations of EDA on the formic acid electrooxidation were systematically studied. Results showed that the above parameter was optimized as the concentration of EDA of 0.1 mol L−1. Pd nanoparticles with even distribution were fabricated and particle sizes were in the range of 3.5–4.2 nm. In addition, Pd particle size became smaller with the addition of EDA, suggesting that EDA could induce the generation of smaller Pd. Electrochemical measurements demonstrated that the electrocatalytic activity of Pd/C-0.22EDA (1021 mA mg−1) with optimized modification concentration was improved as a factor of 3.82 than that of Pd/C (267 mA mg−1). An enhanced stability (about 41 times higher than Pd/C) and faster charge-transfer kinetics of formic acid electrooxidation were observed for Pd/C-0.22EDA catalyst. CV and CA measurements showed that the most active catalyst was made of the smallest (3.5 nm) Pd nanoparticles for Pd/C-0.22EDA catalyst. The better electrocatalytic performances of Pd/C-0.22EDA might be ascribed to evenly dispersed Pd with relatively smaller particle size, electron regulation between Pd and amine group as well as stable Pd structure. • Ethylenediamine modified Pd/C was firstly prepared to enhance properties of formic acid oxidation. • The adding of EDA contributed to form fine and stable Pd with even distribution. • The modification of EDA greatly enhanced electrocatalytic activity and stability. • The mechanism of enhanced electrocatalytic performances for Pd/C-EDA was discussed. [ABSTRACT FROM AUTHOR]

Although phosphoric acid-doped PBI holds great promise for application in high-temperature proton exchange membrane fuel cells, the stabilities of phosphoric acid-doped membranes are compromised due to the low absorption capacity of phosphoric acid, poor solubility and difficulty in processing. In this study, by introducing poly (5-phenyl-1H-1,2,3-triazole) monomers into the polybenzimidazole main chains, a semi-flexible polybenzimidazole (PBI-QP) was prepared. The mechanical properties of PBI-QP membranes were better than that of PBI membrane. The tensile strength of PBI-QP-20 reached to 130.9 MPa. Compared with PBI, the solubility of PBI-QP has improved significantly. PBI-QP can be easily dissolved in the solvents of DMF, DMSO and formic acid separately at room temperature. All the membranes exhibited super thermal stability. At 800 °C there is still 72% quantity of residue and the thermal stability of PBI-QP can meet the thermal stability requirements of HT-PEMFCs. The membranes of PBI-QP demonstrated high phosphoric acid absorption (ADL 10.5) and enhanced antioxidant properties. The proton conductivity is 64.3 mS∙cm−1 at 170 °C and the peak power density attains an impressive level of 573.6 mW cm−2 at 180 °C. The results indicate that the synthesized HT-PEMs exhibit excellent solubility and impressive peak power density, underscoring their substantial promise for utilization in HT-PEMs. [Display omitted] • A novel semi-flexible polybenzimidazole proton exchange membrane material. • The QP was utilized for the modification of PBI membranes to enhance mechanical properties, ADL and proton conductivity. • The maximum power density can reach 573.6 mW cm−2 at 180 °C without humidity. [ABSTRACT FROM AUTHOR]

Copyright of Shipin Kexue/ Food Science is the property of Food Science Editorial Department and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

The conversion of biomass to chemicals/fuels has emerged as a valuable solution that offers both environmental and economic benefits, with the transformation of carbohydrate into formic acid garnering escalating scholar interest. However, the relative limited efficiency of catalyzed-oxidation or expensive cost of H2O2 and alkali in wet hydrothermal oxidation impose limitations on industrialization. This paper proposed a new idea for formic acid production by O2-H2O2 co-oxidation of carbohydrate. A two-step reaction method was developed, where the initial step is engineered to regulate the carbon chain cleavage of carbohydrates to augment the production of active intermediate. Oxygen was employed in the subsequent step as effective oxidant through free radical mechanism, resulting in a formic acid yield of 82.6%. Theoretical calculation, intermediates detection and real time EPR confirmed the reaction mechanism. Finally, the universality of the reaction was verified by using disaccharides and polysaccharides such as cellulose as substrates. [ABSTRACT FROM AUTHOR]

This document is a response to a critique of a scientific paper published in Nature Communications. The authors of the response address the criticisms made by Dr. Goldsmith and his colleagues regarding the enzyme activities described in their paper. They clarify that their results were measured using a different method than assumed by Dr. Goldsmith. The authors also present their own experiments that challenge the proposed substrate for one of the enzymes involved in the synthesis of β-ODAP, a compound found in grass peas that can cause a neurodegenerative disorder called lathyrism. They conclude that the synthesis of a key compound involved in β-ODAP synthesis is likely limited in the cytosol of grass pea plants. The article highlights the proposed mechanism for β-ODAP synthesis and provides experimental evidence to support it, while also addressing criticisms and emphasizing the importance of understanding this process for improving the crop. [Extracted from the article]

A number of phosphomolybdic acid dispersed on SBA-15 catalysts with structural defects and strong acidity were synthesized and applied for the production of ultralow sulfur diesel. The oxygen defect concentration in the catalysts was quantitatively determined by the Rietveld refinement method. These catalysts contained many Brønsted (B) and Lewis (L) acid sites (648 to 1479 μmol g−1) depending on the heteropolyacid content and the thermal treatment. The Mo5+/Mo6+ ratio calculated by XPS technique varied from 0.21 to 0.27%, indicating the creation of oxygen defects in the Keggin unit. The area under the IR absorption band at 980 cm−1 (characteristic of the Mo＝O bond) in the FTIR spectra of different catalysts was found to be inversely proportional to the variation of L acidity as a function of temperature, indicating that oxygen defects are the origin of the L acidity. In the oxidation reaction for removing dibenzothiophene, DBT, from a model diesel, the DBT conversion correlated well with the oxygen defect concentration and total surface acidity, confirming that the surface acidity and oxygen defects played key roles in DBT adsorption and oxidation. Almost 100% DBT conversion was achieved on the best 30 wt% H3PMo12O40/SBA-15 catalyst under the optimal reaction conditions (reaction time 60 min, reaction temperature 70 °C, H2O2/DBT molar ratio 6–8, catalyst concentration 2–2.5 mg ml−1, and hydrogen peroxide to formic acid molar ratio 1.5). A novel mechanism of the DBT oxidative removal in a biphasic system involving the participation of the neighboring L and B acid sites, oxygen defects, and the formation of peroxometallic and superoxometallic species was proposed. [ABSTRACT FROM AUTHOR]

The strategies for optimizing the morphology/structure and regulating the active sites of materials are effective ways to improve their electrocatalytic performance in the hydrogen evolution reaction (HER) and electrooxidation reaction. Herein, we demonstrate a facile strategy for constructing a NiO/NiCo2O4 porous nanowire catalyst on nickel foam (NiO/NiCo2O4/NF) as a bifunctional electrocatalyst to enhance the electrocatalytic performance for coupling the HER with the glucose oxidation reaction (GOR). Benefiting from the unique 1D porous nanowire structure and enhanced interfacial synergistic effect of the bicomponent catalyst, optimized NiO/NiCo2O4/NF-300 exhibited remarkable electrocatalytic activities for the GOR and HER with low potentials of 1.128 V and 0.212 V, respectively, at 100 mA cm−2. Moreover, the GOR exhibited a high yield of 72% for formic acid. This study provides a promising and simple strategy for the construction of 1D NiO/NiCo2O4 porous nanowire electrocatalysts with rich heterogeneous interfaces and paves a facile pathway for accelerating biomass electrochemical reaction-assisted hydrogen production. [ABSTRACT FROM AUTHOR]

The practical application of the electrocatalytic CO2 reduction reaction (CO2RR) to form formic acid fuel is hindered by the limited activation of CO2 molecules and the lack of universal feasibility across different pH levels. Herein, we report a doping‐engineered bismuth sulfide pre‐catalyst (BiS‐1) that S is partially retained after electrochemical reconstruction into metallic Bi for CO2RR to formate/formic acid with ultrahigh performance across a wide pH range. The best BiS‐1 maintains a Faraday efficiency (FE) of ~95 % at 2000 mA cm−2 in a flow cell under neutral and alkaline solutions. Furthermore, the BiS‐1 catalyst shows unprecedentedly high FE (~95 %) with current densities from 100 to 1300 mA cm−2 under acidic solutions. Notably, the current density can reach 700 mA cm−2 while maintaining a FE of above 90 % in a membrane electrode assembly electrolyzer and operate stably for 150 h at 200 mA cm−2. In situ spectra and density functional theory calculations reveals that the S doping modulates the electronic structure of Bi and effectively promotes the formation of the HCOO* intermediate for formate/formic acid generation. This work develops the efficient and stable electrocatalysts for sustainable formate/formic acid production. [ABSTRACT FROM AUTHOR]

Platinum-based catalysts that have long been used as the anodes for the formic acid electro-oxidation (FAO) in the direct formic acid fuel cells (DFAFCs) were susceptible to retrogradation in performance due to CO poisoning that impaired the technology transfer in industry. This work is designed to overcome this challenge by amending the Pt surface sequentially with nanosized cobalt (nano-CoOx, fibril texture of ca. 200 nm in particle size) and iron (nano-FeOx, nanorods of particle size and length of 80 and 253 nm, respectively) oxides. This enriched the Pt surface with oxygenated groups that boosted FAO and mitigated the CO poisoning. The unfilled d-orbitals of the transition metals and their tendency to vary their oxidations states presumed their participation in a faster mechanism of FAO. Engineering the Pt surface in this FeOx/CoOx/Pt hierarchy resulted in a remarkable activity toward FAO, that exceeded four times that of the Pt catalyst with up to ca. 2.5 times improvement in the catalytic tolerance against CO poisoning. This associated a ca. − 32 mV shift in the onset potential of FAO which increased to − 40 mV with a post-activation of the same catalyst at − 0.5 in 0.2 mol L–1 NaOH, displaying the catalyst's competitiveness in reducing overpotentials in DFAFCs. It also exhibited a favorable amelioration in the catalytic durability in long-termed chronoamperometric electrolysis. The electrochemical impedance spectroscopy and the CO stripping voltammetry were employed to elucidate the origin of enhancement. [ABSTRACT FROM AUTHOR]

Despite the great research interest in two‐dimensional metal nanowire networks (2D MNWNs) due to their large specific surface area and abundance of unsaturated coordination atoms, their controllable synthesis still remains a significant challenge. Herein, a microfluidics laminar flow‐based approach is developed, enabling the facile preparation of large‐scale 2D structures with diverse alloy compositions, such as PtBi, AuBi, PdBi, PtPdBi, and PtAuCu alloys. Remarkably, these 2D MNWNs can reach sizes up to submillimeter scale (~220 μm), which is significantly larger than the evolution from the 1D or 3D counterparts that typically measure only tens of nanometers. The PdBi 2D MNWNs affords the highest specific activity for formic acid (2669.1 mA mg−1) among current unsupported catalysts, which is 103.5 times higher than Pt‐black, respectively. Furthermore, in situ Fourier transform infrared (FTIR) experiments provide comprehensive evidence that PdBi 2D MNWNs catalysts can effectively prevent CO* poisoning, resulting in exceptional activity and stability for the oxidation of formic acid. [ABSTRACT FROM AUTHOR]

Formic acid (FA) has been increasingly favored by researchers as an ideal material for the chemical storage of hydrogen. However, the exploration of photocatalytic hydrogen evolution from FA is less extensive compared to conventional thermal catalytic FA decomposition. Therefore, constructing highly active photocatalysts for H 2 release from FA presents a challenging issue. Herein, we employed a strategy that involves Pd nanoparticles (NPs) immobilized on amine-functionalized mesoporous titanium dioxide (TiO 2 –NH 2) to promote hydrogen production from FA under full-spectrum light illumination. Impressively, the as-made 2 wt% Pd/TiO 2 –NH 2 catalyst showed remarkable activity under full-spectrum light (Turnover frequency (TOF) of 1380.5 h−1 at 308 K, H 2 selectivity: 100%). Characterization results indicated that the unique mesoporous structure of TiO 2 –NH 2 , the synergistic interaction of Pd NPs with –NH 2 , and the Mott-Schottky heterojunction are primarily responsible for the excellent photocatalytic performance of 2 wt% Pd/TiO 2 –NH 2. This study modulates the metal-support interactions through surface engineering and proposes a novel and effective method for the construction of high-performance photocatalysts for H 2 production from FA or other photoinduced reactions. • Ultrafine Pd nanoparticles was immobilized on amine-functionalized mesoporous TiO 2. • The 2 wt% Pd/TiO 2 –NH 2 catalyst showed remarkable activity in photocatalytic dehydrogenation of FA under full-spectrum light. • The superior photocatalytic activity is due to the synergistic interaction of Pd NPs with -NH 2 and the Mott-Schottky effect. [ABSTRACT FROM AUTHOR]

An accurate and precise reverse‐phase high‐performance liquid chromatographic technique for apremilast (APR) quantification in bulk, commercial tablets, and formulated APR‐loaded nanoformulations was developed and validated by the design of the experiment approach in accordance with the International Conference of Harmonization guidelines. APR was separated by using formic acid buffer (0.1%; pH 3.2):methanol (40:60, v/v) as a solvent system with a flow rate of 1 mL/min and was detected at a wavelength of 230 nm with a retention time of 7.1 min. The central composite design was employed to optimize the developed analytical method. The calibration curve for APR was linear (r2 = 0.999), with a limit of detection of 0.5 µg/mL and a limit of quantification of 1.52 µg/mL, respectively. A recovery of APR in tablet and nanoformulation was observed in the 98.56%–99.32% range. Forced degradation studies revealed the stability of the proposed analytical method, as the APR peak remained unchanged under stress‐induced degradation experiments. Hence, the proposed chromatographic technique with a cost‐effective solvent system could be employed in the pharmaceutical industry for estimating APR in various formulations. [ABSTRACT FROM AUTHOR]

To better apply solid acid catalysts for hydraulic cavitation technology, a ZrO2-ZSM-5 solid acid catalyst was prepared using impregnation and ion-exchange methods. The effects of the catalyst, hydrogen peroxide, and formic acid dosages, reaction temperature, and venturi tube type on the epoxidation of soybean oil were investigated. The appropriate reaction conditions were determined through a series of experiments: n(C = C):n(HCOOH) = 1:3.0, n(C = C):n(H2O2) = 1:2.2, reaction temperature 70 °C, catalyst dosage 1 wt%, and the reaction time 3 h. The epoxy value of the optimized product reached 6.19%. After the reaction, the catalyst was recovered, and catalyst-related mechanisms were hypothesized in conjunction with related analyses. A catalytic mechanism is proposed, and an explanation is provided on how the catalyst accelerates the reaction process. It was concluded that the catalyst can be effectively applied to the epoxidation reaction under the action of hydraulic cavitation, and the reaction rate can be effectively improved. [ABSTRACT FROM AUTHOR]

Formic acid is a promising candidate fuel that can be produced by reacting renewable hydrogen with carbon dioxide. However, the burning safety characteristics of formic acid–air mixtures have not been fully studied. This paper presents an extensive theoretical study of the adiabatic explosion pressure of formic acid–air premixed laminar flames at various initial conditions (composition of formic acid: 17–38% volume; initial pressure: 0.1–1.5 bar; initial temperature: 333–500 K), using the GASEQ software package. GASEQ software calculates chemical equilibria based on ideal gas behavior and is based on the hypothesis of adiabatic expansion inside a closed containment that allows ideal expansion. The influence of the initial conditions (pressure, temperature, and concentration) of formic acid–air mixtures on the adiabatic explosion pressures, maximum flame temperature, and peak concentrations of the main reaction intermediates is investigated and discussed. It is found that the adiabatic peak explosion pressure (calculated equilibrium pressure) of the studied concentrations decreases with increasing initial temperature and increases linearly with increasing initial pressure. [ABSTRACT FROM AUTHOR]

The present study details the strategic development of Co‐doped CuO nanostructures via sophisticated and expedited pulsed laser ablation in liquids (PLAL) technique. Subsequently, these structures are employed as potent electrocatalysts for the anodic methanol oxidation reaction (MOR), offering an alternative to the sluggish oxygen evolution reaction (OER). Electrochemical assessments indicate that the Co–CuO catalyst exhibits exceptional MOR activity, requiring a reduced potential of 1.42 V at 10 mA cm–2 compared to that of pure CuO catalyst (1.57 V at 10 mA cm–2). Impressively, the Co–CuO catalyst achieved a nearly 180 mV potential reduction in MOR compared to its OER performance (1.60 V at 10 mA cm−2). Furthermore, when pairing Co–CuO(+)ǀǀPt/C(−) in methanol electrolysis, the cell voltage required is only 1.51 V at 10 mA cm−2, maintaining remarkable stability over 12 h. This represents a substantial voltage reduction of ≈160 mV relative to conventional water electrolysis (1.67 V at 10 mA cm−2). Additionally, both in situ/operando Raman spectroscopy studies and theoretical calculations have confirmed that Co‐doping plays a crucial role in enhancing the activity of the Co–CuO catalyst. This research introduces a novel synthetic approach for fabricating high‐efficiency electrocatalysts for large‐scale hydrogen production while co‐synthesizing value‐added formic acid. [ABSTRACT FROM AUTHOR]

In this study, the density functional M06‐2X/6‐311++G(3df,3pd) method was employed to investigate the mutual isomerization reaction mechanism of 5‐chlorouracil from diketone to diol under the catalysis of water, methanol, formic acid, and an electric field. Parameters such as reaction enthalpy, activation energy, activation Gibbs free energy, and proton transfer reaction rate were obtained. The computational results show that under the same conditions, formic acid demonstrates the best catalytic effect, while the influence of electric field catalysis on the reaction barrier is minimal. [ABSTRACT FROM AUTHOR]

Limited or absent activity of the enzyme α-galactosidase A (α-Gal A), due to mutation in the related gene on the X chromosome, leads to the development of a rare hereditary and genetic disease known as Fabry disease (FD). This pathology involves a progressive accumulation in various organs of the substrates of the enzyme e.g., globotriaosylceramide (Gb3) and its deacylated form, globotriaosylsphingosine (Lyso-Gb3), suggesting these molecules as biomarkers of Fabry disease. The present paper describes the development of an analytical strategy for the identification and quantification of Gb3 and Lyso-Gb3, in serum and blood samples by using liquid chromatography (LC) coupled to mass spectrometry in multiple reaction monitoring (MRM/MS) ion mode. The best experimental conditions were obtained by extracting the glycolipids with chloroform/methanol/H2O (2/1/0.3) and by separating them on a C4 column with a linear gradient (A: H2O with 2 mM ammonium formate. B: methanol with 1 mM ammonium formate, both acidified with 0.2% formic acid). The best transitions (a combination of precursor and fragment ions—m/z) were 786.8 m/z > 268.3 m/z for Lyso-GB3, 1137.3 m/z > 264.3 m/z for Gb3, 1039.3 m/z > 264.4 m/z for N-heptadecanoyl-ceramide trihexoside, and 843.5 m/z > 264.3 m/z for N-glycinated lyso-ceramide trihexoside, the latter being used as an internal standard. The developed method provided a reliable, fast, and effective procedure for direct measurements of GB3 and Lyso-GB3 in serum and blood for diagnosis of Fabry disease, suggesting this method as a complementary assay to the current enzymatic test. Therefore, this approach could open new insights into the clinical diagnostics of lysosomal storage disorders. [ABSTRACT FROM AUTHOR]

The reduction of CO2 is an important method to produce chemicals such as methanol, formic acid, formaldehyde, etc. In general, the reduction of CO2 is carried out at high temperatures and pressures with precious metals as catalysts, which is not favorable for industrial procedures. Thus, it will be very useful if researchers can find cost-effective catalysts for industrial application in CO2 reduction. In this work, commercially available ethylenediaminetetraacetic acid (EDTA) was tested as a cheap, non-toxic, and recyclable catalyst to initiate the N-carbonylation reaction of CO2 with amines. After screening various reaction parameters, including temperature, pressure, time, solvent, and reducing agent, the optimal reaction conditions were obtained: 80 °C, 2 MPa, 6 h, 50 mmol% catalyst dosage, 1 mL DMSO, and 1:1 molar ratio of amine to reducing agent. Notably, further studies confirmed that EDTA could also be effective for N-formylation even under ambient conditions (0.1 MPa and room temperature). The suitability of the catalyst for 26 kinds of substrates (including aliphatic amines, aromatic amines, and alicyclic amines) and its reusability were also investigated, with satisfactory results. Scale-up research has been performed effectively with a high conversion of amine (83%) to obtain the mono-formylated product selectively. Finally, the mechanism of the reaction between amine and CO2 has been proposed via control experiments and compared with results in the literature. [ABSTRACT FROM AUTHOR]

The synthesis of carbocyclic-ddA, a potent antiviral agent against hepatitis B, relies significantly on (1 R ,3 R)-3-hydroxycyclopentanemethanol as a key intermediate. To effectively produce this intermediate, our study employed a chemoenzymatic approach. The selection of appropriate biocatalysts was based on substrate similarity, leading us to adopt the CrS enoate reductase derived from Thermus scotoductus SA-01. Additionally, we developed an enzymatic system for NADH regeneration, utilising formate dehydrogenase from Candida boidinii. This system facilitated the efficient catalysis of (S)-4-(hydroxymethyl)cyclopent-2-enone, resulting in the formation of (3 R)-3-(hydroxymethyl) cyclopentanone. Furthermore, we successfully cloned, expressed, purified, and characterized the CrS enzyme in Escherichia coli. Optimal reaction conditions were determined, revealing that the highest activity occurred at 45 °C and pH 8.0. By employing 5 mM (S)-4-(hydroxymethyl)cyclopent-2-enone, 0.05 mM FMN, 0.2 mM NADH, 10 μM CrS, 40 μM formic acid dehydrogenase, and 40 mM sodium formate, complete conversion was achieved within 45 min at 35 °C and pH 7.0. Subsequently, (1 R ,3 R)-3-hydroxycyclopentanemethanol was obtained through a simple three-step chemical conversion process. This study not only presents an effective method for synthesizing the crucial intermediate but also highlights the importance of biocatalysts and enzymatic systems in chemoenzymatic synthesis approaches. [Display omitted] • New chemoenzymatic route for the synthesis of anti-hepatitis B drug intermediates. • Novel application of CrS enoate reductase from Thermus scotoductus SA-01. • The further application of (S)-4-(hydroxymethyl)cyclopent-2-enone. [ABSTRACT FROM AUTHOR]