Consecutive Reactions Research Articles

Integrated multi-omics unveil the impact of H-phosphinic analogs of glutamate and α-ketoglutarate on Escherichia coli metabolism

Desmethylphosphinothricin (L-Glu-γ-PH) is the H-phosphinic analogue of glutamate with carbon-phosphorus-hydrogen (C-P-H) bonds. In L-Glu-γ-PH the phosphinic group acts as a bioisostere of glutamate γ-carboxyl group allowing the molecule to be a substrate of Escherichia coli glutamate decarboxylase, a pyridoxal 5’-phosphate-dependent α-decarboxylase. In addition, the L-Glu-γ-PH decarboxylation product, GABA-PH, is further metabolized by bacterial GABA-transaminase, another pyridoxal 5’-phosphate-dependent enzyme, and succinic semialdehyde dehydrogenase, a NADP+-dependent enzyme. The product of these consecutive reactions, the so-called GABA shunt, is succinate-PH, the H-phosphinic analogue of succinate, a tricarboxylic acid cycle intermediate. Notably, L-Glu-γ-PH displays an antibacterial activity in the same concentration range of well-established antibiotics in E. coli. The dipeptide L-Leu-Glu-γ-PH was shown to display an even higher efficacy, likely as a consequence of an improved penetration into the bacteria.Herein, with the aim of further understanding the intracellular effects of L-Glu-γ-PH, 1H NMR-based metabolomics and LC-MS-based shotgun proteomics were used. This study included also the keto-derivative of L-Glu-γ-PH, α-ketoglutarate-γ-PH (α-KG-γ-PH), which also exhibits antimicrobial activity. L-Glu-γ-PH and α-KG-γ-PH are found to similarly impact the bacterial metabolism, though the overall effect of α-KG-γ-PH is more pervasive. Notably α-KG-γ-PH is converted intracellularly into L-Glu-γ-PH, but the opposite was not found. In general, both molecules impact the pathways where aspartate, glutamate and glutamine are used as precursors for the biosynthesis of related metabolites, activate the acid stress response and deprive cells of nitrogen.This work highlights the multi-target drug potential of L-Glu-γ-PH and α-KG-γ-PH and paves the way for their exploitation as antimicrobials.

Strategically engineered multifunctional graphene oxide hybrid nanomaterials for efficient catalytic degradation and emerging contaminants treatment

The use of functional textiles is growing in all fields of science and technology. Surface functionalization is mainly used to impart conventional textiles with new functionalities and improved performances. In the present study, a cobalt ferrite nanoparticle/graphene oxide (CoFe2O4/GO) coated polyethylene terephthalate (PET) fabric with excellent catalytic and antibacterial properties, has been successfully developed. The PET-coated CoFe2O4/GO samples, ranging from 1 % to 5 % wt. were obtained using a simple dip-coating method in CoFeO/GO solution (1 mg/mL), and were investigated through several physiochemical characterization techniques. CoFe2O4/GO and PET fabric have been shown to establish an interfacial connection by Fourier transform infrared spectroscopy (FTIR). X-ray diffraction (XRD) results showed that CoFe2O4/GO coating did not affect the PET crystallinity and that CoFe2O4/GO hybrid was incorporated in the PET samples, which was proved as well by the morphological study through Scanning electron microscopy (SEM). Furthermore, thermogravimetric characterisation (TGA) verified that the coating does not change or impair the quality of the fibre and that the PET@CoFe2O4/GO as made is thermally stable. Tensile strength tests demonstrated that coated fabrics exhibited outstanding mechanical properties in comparison with pristine PET. Moreover, the coated PET@CoFe2O4/GO fabric was used as a model catalytic system for peroxymonosulfate (PMS) activation in the rhodamine B (RhB) degradation reaction. Total Organic Carbon (TOC) measurements showed that TOC removal reached 89.82 % in only 12 min reaction. The results confirmed that the coated fabrics exhibited high catalytic performances, good stability and reusability in consecutive degradation experiments with a degradation rate over 60 % even after 7 degradation cycles; Moreover, it is easily and simply separated from the mixture, by removing the textile sample from the aqueous solution. It is worth mentioning that the PET@CoFe2O4/GO fabrics showed outstanding antibacterial activity against both Staphylococcus aureus (Gram-positive) and Escherichia coli (Gram-negative) bacteria with an inhibition diameter zone of up to 13 mm for PET@CoFe2O4/GO (5 %). Overall, these findings are of great importance as they permit the development of a novel multifunctional textile fabric, combining anti-bacterial activity, catalytic performance and mechanical properties. The study provides a textile-based catalyst with improved catalytic performance, re-usability in consecutive degradation reactions and easy catalyst separation compared to traditional supports. Thus, a huge potential application in several fields such as medicine, heterogeneous catalysis, and wastewater treatment.

Volatile Fatty Acids from Household Food Waste: Production and Kinetics

Household food waste (HFW), which is rich in organic matter, is a good candidate for producing added-value bio-based chemicals, such as volatile fatty acids (VFAs), by acidogenic fermentation processes. However, the lack of design tools, such as appropriate kinetic models, hinders the implementation of this technology because the results of these processes are affected by operational factors. In this work, VFA production by the acidogenic fermentation of HFW under uncontrolled pH levels (4–5) was studied at thermophilic (55 °C) and mesophilic (35 °C) temperature conditions. Batch reactors were used to digest HFW, and VFA production and the individual acid distributions were measured at different fermentation times from 0 to 624 h. The results showed higher individual and total VFA production at 35 °C and 120 h of fermentation time as a consequence of the competition between the VFA production and decomposition reactions. Acetic and valeric acids were VFAs mainly produced as a result of a high content of proteins in the initial substrate, and a small amount of propionic and butyric acids were present. A simplified kinetic model was successfully developed to represent the complex process of VFA formation from the acidogenic fermentation of HFW. A simple mechanism for the production–decomposition of VFAs, corresponding to a zero-order reaction for the first 48 h and a single consecutive reaction from that time on, was proposed. For both mesophilic and thermophilic conditions, the suggested kinetic model was able to predict the individual and total concentrations of VFAs along the fermentation time.

Insight into mechanisms behind complex reactions by high-dimensional vectorized dynamic analysis

Insight into the mechanisms governing complex reactions requires a thorough and reliable analysis integrating various detected signals. This paper presents a vectorized method for describing chemical reactions and comprehensively discusses the theory and framework of high-dimensional vectorized dynamic analysis for complex reactions. Experimental studies of typical reaction processes such as thermal decomposition of calcium carbonate, thermal oxidation of copper(II) sulfide (CuS), and thermal treatment of industrial waste of aluminum (Al) dross were conducted and analyzed within the high-dimensional vectorized framework. The study identified five sub-reactions of thermal oxidation of CuS, six sub-reactions of Al dross, particularly cross-reactions, competitive reactions, and consecutive reactions that emphasize the mechanisms governing complex reactions. Besides, the study discusses the feasibility, functionality, and application of high-dimensional vectorized dynamic analysis for complex reaction processes including dimension selection, sub-reaction identification, and determination of sub-reaction kinetic parameters. Overall, the high-dimensional vectorized dynamic analysis is confirmed as a scientifically sound method for gaining insight into the mechanisms behind complex reactions. A combination of artificial intelligence (AI) and the high-dimensional vectorized dynamic analysis will further improve significantly the capabilities of identification and analysis of the complex reaction processes.

Characterization of Cwc2, U6 snRNA, and Prp8 interactions destabilized by Prp16 ATPase at the transition between the first and second steps of splicing.

The spliceosome performs two consecutive transesterification reactions using one catalytic center, thus requiring its rearrangement between the two catalytic steps of splicing. The Prp16 ATPase facilitates exit from the first-step conformation of the catalytic center by destabilizing some interactions important for catalysis. To better understand rearrangements within the Saccharomyces cerevisiae catalytic center, we characterize factors that modulate the function of Prp16: Cwc2, N-terminal domain of Prp8, and U6-41AACAAU46 region. Alleles of these factors were identified through genetic screens for mutants that correct cs defects of prp16-302 alleles. Several of the identified U6, cwc2, and prp8 alleles are located in close proximity of each other in cryo-EM structures of the spliceosomal catalytic conformations. Cwc2 and U6 interact with the intron sequences in the first step, but they do not seem to contribute to the stability of the second-step catalytic center. On the other hand, the N-terminal segment of Prp8 not only affects intron positioning for the first step, but it also makes important contacts in the proximity of the active site for both the first and second steps of splicing. By identifying interactions important for the stability of catalytic conformations, our genetic analyses indirectly inform us about features of the transition-state conformation of the spliceosome.

Reducing Solvent Consumption in Reductive Catalytic Fractionation through Lignin Oil Recycling.

Reductive catalytic fractionation (RCF) enables the simultaneous valorization of lignin and carbohydrates in lignocellulosic biomass through solvent-based lignin extraction, followed by depolymerization and catalytic stabilization of the extracted lignin. Process modeling has shown that the use of exogenous organic solvent in RCF is a challenge for economic and environmental feasibility, and previous works proposed that lignin oil, a mixture of lignin-derived monomers and oligomers produced by RCF, can be used as a cosolvent in RCF. Here, we further explore the potential of RCF solvent recycling with lignin oil, extending the feasible lignin oil concentration in the solvent to 100 wt %, relative to the previously demonstrated 0-19 wt % range. Solvents containing up to 80 wt % lignin oil exhibited 83-93% delignification, comparable to 83% delignification with a methanol-water mixture, and notably, using lignin oil solely as a solvent achieved 67% delignification in the absence of water. In additional experiments, applying the RCF solvent recycling approach to ten consecutive RCF reactions resulted in a final lignin oil concentration of 11 wt %, without detrimental impacts on lignin extraction, lignin oil molar mass distribution, aromatic monomer selectivity, and cellulose retention. Overall, this work further demonstrates the potential for using lignin oil as an effective cosolvent in RCF, which can reduce the burden on downstream solvent recovery.

Hydrogen evolution from NaBH4 using novel Ni/Pt nanoparticles decorated on a niobium-based composite

The niobium-based nanocomposite (Nb-CP), inspired by MOF-based synthesis, was developed utilizing the ligands 4-benzenedicarboxylic acid (BDC) and 1,3,5-benzenetricarboxylic acid (BTC). This material was decorated with bimetallic nanoparticles (Ni2/Pt8 NPs-Nb-CP) and applied for the first time for hydrogen evolution from sodium borohydride (NaBH4). Characterization results indicated successful synthesis. The FT-IR analysis revealed the presence of functional groups such as -C-H, –CO, and -O-H from ligands in the composite. Thermogravimetric analysis confirmed the thermal stability of the niobium composite (Nb-CP). Through X-ray diffraction (XRD), peaks associated with sodium niobate were detected. Additionally, the material was functionalized with bimetallic Ni/Pt nanoparticles, whose presence was also identified by XRD. The cubic morphology of the material was observed, with the decoration of bimetallic nanoparticles (Ni2/Pt8 NPs-Nb-CP) with an average size of 7.80 ± 0.10 nm, uniformly distributed in Nb-CP. The catalytic performance of the material was evaluated in hydrogen evolution from NaBH4. Various reaction parameters were investigated, such as nanoparticle composition, variation in NaBH4 concentration, catalyst dose, NaOH concentration, and temperature. Remarkably, the material exhibited a hydrogen generation rate (HGR) of 1782 mL min−1 g−1cat and an activation energy of 23.1 kJ mol−1. Furthermore, it demonstrated efficiency close to 100% over 16 consecutive reaction cycles, indicating its promising stability and reusability. This study highlights the potential of Ni2/Pt8 NPs-Nb-CP as an efficient and durable catalyst for hydrogen production through borohydride hydrolysis, providing insights into the design and application of advanced heterogeneous catalytic materials.

Enhancing the Performance of BaxMnO3 (x = 1, 0.9, 0.8 and 0.7) Perovskites as Catalysts for CO Oxidation by Decreasing the Ba Content.

Mixed oxides featuring perovskite-type structures (ABO3) offer promising catalytic properties for applications focused on the control of atmospheric pollution. In this work, a series of BaxMnO3 (x = 1, 0.9, 0.8 and 0.7) samples have been synthesized, characterized and tested as catalysts for CO oxidation reaction in conditions close to that found in the exhausts of last-generation automotive internal combustion engines. All samples were observed to be active as catalysts for CO oxidation during CO-TPRe tests, with Ba0.7MnO3 (B0.7M) being the most active one, as it presents the highest amount of oxygen vacancies (which act as active sites for CO oxidation) and Mn (IV), which features the highest levels of reducibility and the best redox properties. B0.7M has also showcased a high stability during reactions at 300 °C, even though a slightly lower CO conversion is achieved during the second consecutive reaction cycle. This performance appears to be related to the decrease in the Mn (IV)/Mn (III) ratio.

Sulfonated Graphene‐Based Materials as Heterogeneous Acid Catalysts for Solketal Synthesis by Acetalization of Glycerol

AbstractAcid catalysis plays a pivotal role in the industrial landscape due to its multifaceted contributions to various chemical processes in numerous sectors, including petrochemicals, polymers, food processing, and biodiesel production, among others. Sulfonated graphenes hold notable relevance as heterogeneous acid catalysts due to their unique combination of graphene's structural properties and the introduction of sulfonic groups as catalytic acid sites. Herein, we report the preparation of three sulfonated graphene‐based materials – sulfonated reduced graphene oxide (rGO‐SO3H), chlorosulfonated reduced graphene oxide (rGO‐HSO3Cl) and sulfonated graphene oxide (GO‐SO3H) – by different synthetic approaches. Physicochemical, textural, morphological, and acidic properties of all materials were characterized in detail by different instrumental techniques. Innovatively, these materials have been evaluated as heterogeneous acid catalysts in the solketal synthesis by acetalization of glycerol, which is considered an interesting building block to produce added‐value products. The density of acidic active sites and hydrophobicity were found to be conditioning parameters of the resulting catalytic activity in terms of conversion and selectivity. The best catalytic performance was obtained by rGO‐SO3H, reaching the maximum conversion towards solketal in 15 minutes under mild reaction conditions. The reusability and stability of all materials were also examined after three consecutive acetalization reactions with only a slight loss of catalytic activity.

Reductive C−N Bond Formation of Nitroarenes Using Pd@rGO‐CuFe2O4 Magnetic Nanoparticles in Water towards the Synthesis of N‐Aryl Formamide and Azole Derivatives

Abstract.Reductive C−N bond generation strategies of nitroarenes to form N‐arylformamide and azole derivatives were developed under the influences of magnetically separable Pd@rGO‐CuFe2O4 nanoparticle‐catalyzed reaction conditions. These reactions proceed at a very low catalyst loading in H2O as the solvent, which leads to a higher percentage of yields (up to 96 %) of the products. The catalyst is recovered from the reaction medium by using an external magnet and recycled for four consecutive reaction cycles with a less amounts of leaching.

Roles of cytochrome P450 monooxygenases in triterpene biosynthesis and their potential impact on growth and development.

Pentacyclic triterpenoids, recognized for their natural bioactivity, display complex spatiotemporal accumulation patterns within the ecological model plant Nicotiana attenuata. Despite their ecological importance, the underlying biosynthetic enzymes and functional attributes of triterpenoid synthesis in N. attenuata remain unexplored. Here, we show that three cytochrome P450 monooxygenases (NaCYP716A419, NaCYP716C87, and NaCYP716E107) from N. attenuata oxidize the pentacyclic triterpene skeleton, as evidenced by heterologous expression in Nicotiana benthamiana. NaCYP716A419 catalyzed a consecutive three-step oxidation reaction at the C28 position of β-amyrin/lupeol/lupanediol, yielding the corresponding alcohol, aldehyde, and carboxylic acid. NaCYP716C87 hydroxylated the C2α position of β-amyrin/lupeol/lupanediol/erythrodiol/oleanolic acid/betulinic acid, while NaCYP716E107 hydroxylated the C6β position of β-amyrin/oleanolic acid. The genes encoding these three CYP716 enzymes are highly expressed in flowers and respond to induction by ABA, MeJA, SA, GA3, and abiotic stress treatments. Using VIGS technology, we revealed that silencing of NaCYP716A419 affects the growth and reproduction of N. attenuata, suggesting the ecological significance of these specialized metabolite biosynthetic steps.

Synthesis of pinolenic acid‐enriched triacylglycerol from pine nut oil via a two‐step consecutive enzyme reaction: Comparison of acyl donors

AbstractPinolenic acid (PLA) is a plant‐origin Δ5‐unsaturated polymethylene‐interrupted fatty acid that provides several beneficial health effects to the human body. A two‐step lipase‐catalyzed reaction was carried out to synthesize PLA‐enriched triacylglycerol (TAG) with pine nut oil (PNO) in the present study. In the first step, PLA was efficiently enriched from an initial value of 15–43 mol% in ethyl ester of the reaction mixture after Lipozyme 435‐catalyzed ethanolysis with PNO. In the second step, PLA‐enriched TAG was efficiently synthesized with the fatty acid form via Lipozyme 435‐catalyzed esterification at all temperatures when both ethyl ester form and fatty acid form were compared as acyl donors. The effect of vacuum on the synthesis of PLA‐enriched TAG with glycerol and PLA‐enriched fatty acid was studied. The optimum temperature and vacuum were 60°C, and 50 mmHg, respectively. A maximum TAG conversion of approximately 95% was achieved after 12 h under the optimum conditions.

Synthesis, spectroscopic and crystallographic characterization of various cymantrenyl thioethers [Mn{C5HxBry(SMe)z}(PPh3)(CO)2

Starting from [Mn(C5H4Br)(PPh3)(CO)2] (1a), the cymantrenyl thioethers [Mn(C5H4SMe)(PPh3)(CO)2] (1b) and [Mn{C5H4-nBr(SMe)n}(PPh3)(CO)2] (n= 1 for compound 2, n= 2 for 3 and n= 3 for 4) were obtained, using either n-butyllithium (n-BuLi), lithium diisopropylamide (LDA) or lithium tetramethylpiperidide (LiTMP) as base, followed by electrophilic quenching with MeSSMe. Stepwise consecutive reaction of [Mn(C5Br5)(PPh3)(CO)2] with n-BuLi and MeSSMe led finally to [Mn{C5(SMe)5}(PPh3)(CO)2] (11), only the fifth complex to be reported containing a perthiolated cyclopentadienyl ring. The molecular and crystal structures of 1b, 3, 4 and 11 were determined and were studied for the occurrence of S...S and S...Br interactions. It turned out that although some interactions of this type occurred, they were of minor importance for the arrangement of the molecules in the crystal.

Enhanced photocatalytic H2O2 production through synergistic double-vacancy engineering in Z-scheme TiO2-x/g-C3N4-x heterojunction

The photocatalytic synthesis of hydrogen peroxide (H2O2) is an environmentally benign and sustainable approach. In this study, we have synthesized a TiO2-x/g-C3N4-x(A-TxCNx) photocatalyst with a Z-scheme heterojunction by introducing oxygen and nitrogen double vacancies through a one-step reduction process. The optimized A-TxCNx catalyst exhibited a superior H2O2 yield of 1131.59 μmol L–1h−1 under visible light, which is 5.85 times greater than that of the A-TCN catalyst. This enhancement is ascribed to the synergistic effects of the oxygen vacancies (Ov) and nitrogen vacancies (Nv) defects, which amplify light absorption, facilitate electron-hole pair separation, and augment the number of active sites on the catalyst surface. Density functional theory (DFT) calculations and energy band analysis were employed to elucidate the photocatalytic mechanism of A-TxCNx, revealing that H2O2 synthesis predominantly occurs through two consecutive reactions, enabled by the catalyst’s unique electronic structure and defect configuration. This study not only validates the exceptional photocatalytic performance of A-TxCNx but also provides valuable insights for the design and optimization of future photocatalysts aimed at sustainable H2O2 production.

Artificial antibody-antigen-directed immobilization of α-amylase to hydrolyze starch for cascade reduction of 2-nitro-4-methylphenol to 2-amino-4-methylphenol

Nitrophenol is a hazardous substance that poses a threat to the environment and human health, and its treatment has attracted widespread attention. The purpose of this study is to establish an environmentally friendly α-amylase system for the hydrolysis of starch to reduce nitrophenol to aminophenol through cascade reactions. The α-amylase system was obtained through artificial antibody-antigen-directed immobilization, including the synthesis of artificial antibodies, synthesis of artificial antigens, and affinity assembly. In this process, catechol and protocatechuic aldehyde were used to prepare artificial antibodies and artificial antigens respectively through polymerization and Schiff base reactions. Then, artificial antibodies captured the catechol in the artificial antigen structure to form immobilized α-amylases. Compared with free α-amylase, the immobilized α-amylase showed a good reusability and excellent regenerative ability. Subsequently, the immobilized α-amylase were used in the reaction of catalyzing starch hydrolysis to synthesize 2-amino-4-methylphenol, and the yield of 2-amino-4-methylphenol was 58.88 ± 0.19 %. After 5 consecutive catalytic reactions, a yield of 47.61 ± 1.27 % can still be achieved.

Synthetic Modification and Insecticidal Activity of 4-epi-cis-Dihydroagarofuran Derivatives.

To synthesize the fundamental framework of dihydroagarofuran, a novel strategy was devised for constructing the C-ring through a dearomatization reaction using 6-methoxy-1-tetralone as the initial substrate. Subsequently, the dihydroagarofuran skeleton was assembled via two consecutive Michael addition reactions. The conjugated diene and trans-dihydroagarofuran skeleton were modified. The insecticidal activities of 33 compounds against Mythimna separata were evaluated. Compounds 11-5 exhibited an LC50 value of 0.378 mg/mL. The activity exhibited a remarkable 29-fold increase compared to positive control Celangulin V, which was widely recognized as the most renowned natural dihydroagarofuran polyol ester insecticidal active compound. Docking experiments between synthetic compounds and target proteins revealed the shared binding sites with Celangulin V. Structure-activity relationship studies indicated that methyl groups at positions C4 and C10 significantly improved insecticidal activity, while ether groups with linear chains displayed enhanced activity; in particular, the allyl ether group demonstrated optimal efficacy. Furthermore, a three-dimensional quantitative structure-activity relationship model was established to investigate the correlation between the skeletal structure and activity. These research findings provide valuable insights for discovering and developing dihydroagarofuran-like compounds.

Solar light driven degradation of piroxicam and paracetamol by heterogeneous photocatalytic fenton system: Process optimization, mechanistic studies and toxicity assessment

The widespread occurence of pharmaceutical pollutants seriously threatens the environment and human well-being. In the present study, zinc ferrite nanoparticles (ZnFe2O4 NPs) have been synthesized by co-precipitation method and used as photocatalyst for the degradation of two most commonly prescribed painkillers, piroxicam (PXM) and paracetamol (PCM), via heterogeneous Fenton process under the solar light. The synthesized ZnFe2O4 NPs showed a narrower band gap i.e. 1.87 eV, signifying the ability to efficiently work in visible light range. In context of photocatalytic applications, the operational conditions were optimized to achieve maximum degradation. PCM and PXM were completely degraded (100%) at the optimized photocatalytic dose (20 mg L−1), reaction time (180 min), initial drug concentration (10 mg L−1), and pH (6.0), which is close to the natural environment. The extent of mineralization as estimated by the reduction of total organic carbon (TOC) was observed to be ∼91 and 82% for PCM and PXM respectively. Kinetic studies revealed that photocatalytic degradation followed pseudo-first-order kinetics. Moreover, the ZnFe2O4 NPs retained ∼90 % of photocatalytic activity after five consecutive reaction cycles, showing remarkable reusability and stability of catalyst.

Optimizing carboxylated nanocellulose preparation: A kinetic and mechanistic study on the enhancement of TEMPO-mediated oxidation via swelling treatment

This study explored the application of swelling pretreatment as a solution to the high cost and contamination associated with the process of 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-mediated oxidation for nanocellulose preparation. The results demonstrated that swelling significantly expanded the fibers while preserving the degree of polymerization (DP) of cellulose (approximately 95 %). The native crystal structure and hydrogen bonding of cellulose were disrupted after swelling, leading to a reduction in crystallinity and crystallite size, and the decrease of bonding energy and content of intermolecular O6-H⋯O3′. The TEMPO-mediated oxidation processes of cellulose fibers with or without swelling were successfully fitted using a consecutive first-order reaction kinetic model. The fitting results indicated that swelling significantly reduced the activation energy of TEMPO-mediated oxidation and enhanced the reaction rate. Among three swelling systems, the NaOH/thiourea/water system exhibited the optimal promotion effect. Consequently, the swelling treatment enables a significant reduction of 30 % in the catalyst dose for the TEMPO-mediated oxidation while preserving a competitive reaction rate, yield, and product performance. Lower catalyst dosage helps to reduce cost and environmental impact, facilitating the industrial application of the TEMPO-mediated oxidation process.

Synthesis and Application of Robust Spiro [Fluorene-9] CAAC Ruthenium Alkylidene Complexes for the "One-Pot" Conversion of Allyl Acetate to Butane-1,4-diol.

A series of a novel CAAC ligands featuring a spiro-fluorene group have been synthesized and complexed with ruthenium alkylidenes, yielding the corresponding Hoveyda-type derivatives as a new family of olefin metathesis catalysts. The novel complexes have been characterized by XRD, HRMS and NMR measurements. The synthetised complexes were tested in catalysis and showed good activity in olefin metathesis, as demonstrated on diethyl diallylmalonate and allyl acetate substrates. The unique backbone in the ligand with the large, yet inflexible condensed system renders interesting properties to the catalyst, exemplified by the good catalytic performance and improved Z-selectivity. In addition, the complex can also serve as a hydrogenation catalyst in a consecutive (one-pot) reaction. The latter reaction can convert allyl acetate to butane-1,4-diol, a valuable chemical intermediate for biodegradable polybutylene succinate (PBS).

Loading Rh nanoparticles onto Bi2MoO6 hollow architectures: Unveiling heterojunction-driven photocatalytic enhancement towards organic dye degradation

A novel photocatalyst composed of bismuth molybdate (Bi2MoO6, BMO) coupled with rhodium (Rh) nanoparticles was synthesized and evaluated for its efficiency in degrading dye contaminant under visible light irradiation. The BMO/Rh composite demonstrated a significant enhancement in photocatalytic performance, achieving a 40 % higher degradation rate of Rhodamine B (RhB) compared to bare BMO. Enhanced charge separation and reduced electron-hole recombination were primarily attributed to the synergistic effects introduced by the Rh nanoparticles. Extensive characterization techniques provided insights into the structural and mechanistic aspects of the photocatalyst. Stability tests confirmed that BMO/Rh maintained over 95 % of its initial activity after five consecutive reaction cycles, highlighting its durability. Scavenger experiments identified superoxide radicals (•O2-) and hydroxyl radicals (•OH) as the primary active species, contributing to the high efficiency of dye degradation. This study underscores the potential of BMO/Rh hybrids as sustainable and effective photocatalysts for environmental remediation.