Search Results (90)

A novel point-chiral six-membered cyclic phosphoric acid was synthesized starting from an enantiopure precursor via a concise three-step route. Its catalytic performance was evaluated in enantioselective three-component Mannich reactions. Under optimized conditions, the catalyst provided good yields and satisfactory enantiomeric excesses (up to 89%). The basic mechanism of the catalysis was also studied by the DFT method. Full article

Carbon materials, including graphene, carbon nanotubes, and fullerenes, serve as effective supports for catalysts and play a pivotal role in heterogeneous asymmetric catalysis due to their unique properties and ability to create defined environments for catalytic reactions. Recent research has focused on developing novel carbon-based catalysts that combine the advantages of heterogeneous catalysis with enhanced stability and reusability. This review highlights the synthesis and catalytic applications of graphene, carbon nanotubes, and fullerenes as heterogeneous support materials in asymmetric organocatalytic and organometallic reactions, covering their mechanisms, efficiency, and potential for advancing sustainable chemical processes. Full article

Bimetals—materials composed of two metal components with dissimilar standard reduction–oxidation (redox) potentials—offer unique electronic, optical, and catalytic properties, surpassing monometallic systems. These materials exhibit not only the combined attributes of their constituent metals but also new and novel properties arising from their synergy. Although many reviews have explored the synthesis, properties, and applications of bimetallic systems, none have focused exclusively on iron (Fe)- and aluminum (Al)-based bimetals. This systematic review addresses this gap by providing a comprehensive overview of conventional and emerging techniques for Fe-based and Al-based bimetal synthesis. Specifically, this work systematically reviewed recent studies from 2014 to 2023 using the Scopus, Web of Science (WoS), and Google Scholar databases, following the Preferred Reporting Items for Systematic Reviews and Meta-Analyses (PRISMA) guidelines, and was registered under INPLASY with the registration number INPLASY202540026. Articles were excluded if they were inaccessible, non-English, review articles, conference papers, book chapters, or not directly related to the synthesis of Fe- or Al-based bimetals. Additionally, a bibliometric analysis was performed to evaluate the research trends on the synthesis of Fe-based and Al-based bimetals. Based on the 122 articles analyzed, Fe-based and Al-based bimetal synthesis methods were classified into three types: (i) physical, (ii) chemical, and (iii) biological techniques. Physical methods include mechanical alloying, radiolysis, sonochemical methods, the electrical explosion of metal wires, and magnetic field-assisted laser ablation in liquid (MF-LAL). In comparison, chemical protocols covered reduction, dealloying, supported particle methods, thermogravimetric methods, seed-mediated growth, galvanic replacement, and electrochemical synthesis. Meanwhile, biological techniques utilized plant extracts, chitosan, alginate, and cellulose-based materials as reducing agents and stabilizers during bimetal synthesis. Research works on the synthesis of Fe-based and Al-based bimetals initially declined but increased in 2018, followed by a stable trend, with 50% of the total studies conducted in the last five years. China led in the number of publications (62.3%), followed by Russia, Australia, and India, while Saudi Arabia had the highest number of citations per document (95). RSC Advances was the most active journal, publishing eight papers from 2014 to 2023, while Applied Catalysis B: Environmental had the highest number of citations per document at 203. Among the three synthesis methods, chemical techniques dominated, particularly supported particles, galvanic replacement, and chemical reduction, while biological and physical methods have started gaining interest. Iron–copper (Fe/Cu), iron–aluminum (Fe/Al), and iron–nickel (Fe/Ni) were the most commonly synthesized bimetals in the last 10 years. Finally, this work was funded by DOST-PCIEERD and DOST-ERDT. Full article

To address the challenge of abatement of volatile organic compounds (VOCs) in environmental catalysis, this study developed a temperature-gradient hydrothermal strategy to fabricate SrSn(OH)₆ nanocatalysts and systematically investigatd their photocatalytic performance and mechanisms for gaseous toluene degradation. SrSn(OH)₆ (SSH) was synthesized via a simple hydrothermal method with optimal preparation conditions identified as a reaction temperature of 140 °C and duration of 12 h. The crystallinity of SrSn(OH)₆ was modulated by adjusting the pH of the precursor solution, yielding materials with distinct morphologies, specific surface areas, and band gaps. The narrowed band gap of SrSn(OH)₆ nanocatalysts facilitated electron excitation to generate additional photogenerated electron-hole pairs. The SSH-10.5 sample with ordered planar and hole-like structures promoted carrier migration, effectively suppressed electron-hole recombination, and enhanced the conversion of abundant surface hydroxyl groups into hydroxyl radicals. Under UV irradiation, SSH-10.5 achieved a toluene degradation efficiency of 69.56% and showed excellent stability after five reuse cycles. Electron spin resonance analysis confirmed the presence of •OH and •O₂⁻ radicals in the reaction system, with •OH identified as the dominant active species. In situ FT-IR spectroscopy revealed that •OH and •O₂⁻ radicals attacked the methyl group of toluene, converting it into intermediates including benzyl alcohol, benzaldehyde, and benzoic acid. This work provides a novel design of high-efficiency VOC-photocatalytic materials and shows significant implications for advancing industrial exhaust gas purification technologies. Full article

A new brazing process for thin-walled stainless steel was proposed by combining green and efficient Ni-Cr-P electrodeposition with brazing technology. Novel information was attained by analyzing the electrodeposited Ni-Cr-P interlayers and the brazed joints and characterizing them using a combination of advanced techniques. The incorporation mechanisms of impurities (i.e., oxygen and carbon) in the Ni-Cr-P interlayers electrodeposited from a Cr(III)–glycine solution were revealed. The oxygen mainly came from the Cr(III)–hydroxy complexes formed by the hydrolysis and olation between Cr(III) complexes and OH⁻ ions near the cathode. Glycine did not directly participate in the cathode reactions but decomposed on the anode surface. These byproducts (carbonyl compounds) were directly incorporated into the interlayers in a molecular pattern, forming a weak link to the metallic chromium. Brazing test results showed that a certain amount of Cr₂O₃ powder, formed by the decomposition of chromium hydroxides in the interlayers under high-temperature catalysis, would cause the degradation of the brazed joints. Using the step-wise brazing method, the brazing sheets were first annealed to eliminate the impurities by utilizing the strong reducing effect of hydrogen and the weak link characteristics between carbonyl compounds and metallic chromium atoms. An excellent joint with a shear strength of 63.0 MPa was obtained by subsequent brazing. The microstructural analysis showed that the brazed seam was mainly composed of a Ni-Fe-Cr solid solution, the Ni₃P eutectic phase, and small quantities of the Ni₅P₂ phase scattered in the Ni₃P eutectic phase. Fracture mode observations showed that the cracks extended along the interface between the brittle P-containing phase and the primary phase, resulting in fracture. Full article

UiO-66-NH₂ is a metal–organic framework (MOF) with open metal sites, making it a promising candidate for adsorption and catalysis. However, the powdery texture of MOFs and the use of toxic solvents during synthesis limit their application. A novel solution to this issue is to create a layered porous composite by encasing the MOF within a flexible and structurally robust aerogel substrate using safe, eco-friendly, and green solvents such as ethanol. The fibrous MOF aerogels, characterized by a desirable macroscopic shape of cylindrical block and hierarchical porosity, were synthesized by two approaches: in situ growth of amine-functionalized UiO-66-NH₂ crystals on a TEMPO-oxidized cellulose nanofiber (TOCNF) and ex situ crosslinking of UiO-66-NH₂ crystals onto a TOCNF network to form UiO-66-NH₂/TOCNF. The incorporation of MOF into the cellulose nanofibrils via the in situ method reduces their aggregation potential, alters the nucleation/growth balance to produce smaller MOF crystals, and enhances mechanical flexibility, as evidenced by SEM images. The three adsorbents, including UiO-66-NH₂, ex situ UiO-66-NH₂/TOCNF, and in situ UiO-66-NH₂/TOCNF, were synthesized and used in this study. The effects of pH, time, temperature, and initial concentration were studied. A maximum adsorption capacity (Qmax) of 549.45 mg/g for Congo Red (CR) and 171.23 mg/g for Orange II (ORII) was observed at pH 6, using 10 mg of in situ UiO-66-NH₂/TOCNF at 40 °C with a contact time of 75 min for CR and 2 h for ORII. The adsorption of both dyes primarily occurs through monolayer chemisorption on the in situ UiO-66-NH₂/TOCNF. The main removal mechanisms were hydrogen bonding and surface complexation. The noteworthy adsorption capacity of in situ UiO-66-NH₂/TOCNF coupled with environment-friendly fabrication techniques indicates its potential applications on a large scale in real wastewater systems. Full article

The Schrödinger equation, Heisenberg’s uncertainty principles, and the Boltzmann constant represent transformative scientific achievements, the impacts of which extend far beyond their original domain of physics. As we celebrate the centenary of these fundamental quantum mechanical formulations, this review examines their evolution from abstract mathematical concepts to essential tools in contemporary drug discovery and development. While these principles describe the behavior of subatomic particles and molecules at the quantum level, they have profound implications for understanding biological processes such as enzyme catalysis, receptor–ligand interactions, and drug–target binding. Quantum tunneling, a direct consequence of these principles, explains how some reactions occur despite classical energy barriers, enabling novel therapeutic approaches for previously untreatable diseases. This understanding of quantum mechanics from 100 years ago is now creating innovative approaches to drug discovery with diverse prospects, as explored in this review. However, the fact that the quantum phenomenon can be described but never understood places us in a conundrum with both philosophical and ethical implications; a prospective and inconclusive discussion of these aspects is added to ensure the incompleteness of the paradigm remains unshifted. Full article

Piezoelectric and photocatalytic technologies use mechanical and light energy to decompose environmental contaminants, demonstrating a beneficial synergistic impact. This investigation employs a two-step hydrothermal-calcination technique to synthesize N-doped MoS₂ photocatalytic materials. The ideal catalyst, N-MoS₂-3, utilizing the synergistic effect of piezoelectric–photocatalysis processes, attained a TC degradation rate of 90.8% in 60 min. The kinetic constant (0.0374 min⁻¹) is 1.75 times greater than the combined rates of single photocatalysis and piezoelectric catalysis, indicating a notable synergistic impact. The material has 80% degradation efficiency after five cycles, indicating its remarkable resilience. Mechanistic investigations reveal that nitrogen doping establishes an internal electric field by modulating the S-Mo-S charge distribution. Photogenerated electrons move to generate •O₂⁻, while holes accumulate internally. The ultrasound-induced piezoelectric polarization field interacts with the photogenerated electric field in reverse, thereby synergistically improving carrier separation efficiency and facilitating redox processes. This study emphasizes the viability of non-metal doping as a method for modifying the properties of two-dimensional materials, offering a novel approach to enhance the synergistic attributes of piezoelectric and photocatalytic processes. This technology possesses significant promise for environmental restoration through the utilization of solar and mechanical energy. Full article

High-entropy alloys (HEAs) are a novel class of metallic materials composed of five or more principal elements in near-equimolar ratios. This unconventional composition leads to high configurational entropy, which promotes the formation of solid solution phases with enhanced mechanical properties, thermal stability, and corrosion resistance. Phase stability plays a critical role in determining their structural integrity and performance. This study provides a focused review of HEA phase transitions, emphasizing the role of lattice gas models in predicting phase behavior. By integrating statistical mechanics with thermodynamic principles, lattice gas models enable accurate modeling of atomic interactions, phase segregation, and order-disorder transformations. The combination of computational simulations (e.g., Monte Carlo, molecular dynamics) with experimental validation (e.g., XRD, TEM, APT) improves predictive accuracy. Furthermore, advances in data-driven methodologies facilitate high-throughput exploration of HEA compositions, accelerating the discovery of alloys with optimized phase stability and superior mechanical performance. Beyond structural applications, HEAs demonstrate potential in functional domains, such as catalysis, hydrogen storage, and energy technologies. This review brings together theoretical modeling—particularly lattice gas approaches—and experimental validation to form a unified understanding of phase behavior in high-entropy alloys. By highlighting the mechanisms behind phase transitions and their implications for material performance, this work aims to support the design and optimization of HEAs for real-world applications in aerospace, energy systems, and structural materials engineering. Full article

In the food industry, food spoilage caused by spores is a pressing scientific challenge that needs to be addressed urgently, and spore germination is a key approach to solving this problem. Studies have shown that peptidoglycan-induced spore germination represents a novel mechanism of action, which can bind to the PASTA domain of the serine/threonine kinase PrkC. However, the signaling mechanism of peptidoglycan-induced spore germination remains unclear. This study focuses on Bacillus subtilis, using pull-down experiments to screen for proteins interacting with PrkC. There are 80 interaction proteins of PrkC that were identified in the spore. GO analysis reveals that PrkC-interacting proteins in the spore are mainly involved in metabolic processes, cell part and catalysis. KEGG results indicate that PrkC-interacting proteins in the spore are mainly involved in RNA degradation, quorum sensing, oxidative phosphorylation, etc. Additionally, proteins are categorized into six groups by function based on events that may be associated with post-germination triggered by peptidoglycan-induced activation of the PrkC signaling pathway, including “stimulate translation initiation” and “ATP synthesis and energy metabolism”. The experimental results provide a theoretical basis for further elucidating the signaling mechanism of PrkC, revealing the signaling pathway of peptidoglycan-induced spore germination, and identifying targeted inducers and repressors of spore germination. Full article

There is a growing demand for natural and potent α-glucosidase inhibitors due to the rising prevalence of diabetes. In this study, newly identified α-glucosidase inhibitory peptides were identified from the tryptic hydrolysate of hemp seed proteins based on peptidomics and in silico analysis. A total of 424 peptides, primarily derived from four cupin-type-1 domain-containing proteins, were identified, and 13 ultimately were selected for validation based on their higher PeptideRanker scores, solubility, non-toxicity, and favorable ADMET properties. Molecular docking revealed that these 13 peptides primarily interacted with α-glucosidase via hydrogen bonding and hydrophobic interactions. Among them, three novel peptides—NPVSLPGR (−8.7 kcal/mol), LSAERGFLY (−8.5 kcal/mol), and PDDVLANAF (−8.4 kcal/mol)—demonstrated potent α-glucosidase inhibitory activity due to their lower binding energies than acarbose (−8.1 kcal/mol), the first approved α-glucosidase inhibitor for type 2 diabetes treatment. The molecular mechanism analysis revealed that the peptides NPVSLPGR and LSAERGFLY inhibited α-glucosidase by simultaneously blocking substrate entry through occupying the entrance of the active site gorge and preventing catalysis by binding to active sites. In contrast, the peptide PDDVLANAF primarily exerted inhibitory effects by occupying the entrance of the active site gorge. Molecular dynamics simulation validated the stability of the complexes and provided additional insights into the molecular mechanism determined through docking. These findings contribute essential knowledge for the advancement of natural α-glucosidase inhibitors and offer a promising approach to effectively manage diabetes. Full article

Dihydroorotase (DHOase; EC 3.5.2.3) is a zinc-dependent metalloenzyme that plays a key role in the de novo pyrimidine biosynthesis pathway, catalyzing the reversible cyclization of N-carbamoyl aspartate to dihydroorotate. This reaction is essential for the production of uridine monophosphate, the precursor of all pyrimidine nucleotides required for DNA and RNA synthesis. Despite its conserved enzymatic function, DHOase exhibits significant structural diversity across species, particularly in its oligomeric states, gene fusion patterns, and active site architecture. A crucial structural feature of DHOase is its flexible active site loop, which undergoes dynamic conformational changes during catalysis. Previously, the loop-in conformation was associated with substrate binding, whereas the loop-out conformation was linked to product release and non-substrate ligand binding. However, recent crystallographic studies challenge this paradigm, revealing that certain non-substrate ligands and inhibitors, including malate, 5-fluoroorotate, plumbagin, 5-aminouracil, and 5-fluorouracil, interact with DHOase via a loop-in binding mechanism rather than the previously assumed loop-out mode. These findings necessitate a reassessment of the catalytic mechanism of DHOase and underscore the active site loop as a potential target for drug development. This review revisits the structural and biochemical mechanisms of DHOase, with a focus on recent crystallographic insights that redefine the loop-in binding mode for ligand interaction. By leveraging the unique conformational dynamics of the active site loop, novel inhibitors may be developed to selectively target pyrimidine biosynthesis in cancer cells and microbial pathogens. These insights emphasize the crucial role of structural biology in therapeutic design and highlight DHOase as a promising drug target. Full article

The current paradigm of low-T combustion and autoignition of hydrocarbons is based on the sequential two-step oxygenation of fuel radicals. The key chain-branching occurs when the second oxygenation adduct (OOQOOH) is isomerized releasing an OH radical and a key ketohydroperoxide (KHP) intermediate. The subsequent homolytic dissociation of relatively weak O–O bonds in KHP generates two more radicals in the oxidation chain leading to ignition. Based on the recently introduced intramolecular “catalytic hydrogen atom transfer” mechanism (J. Phys. Chem. 2024, 128, 2169), abbreviated here as I-CHAT, we have identified a novel unimolecular decomposition channel for KHPs to form their classical isomers—enol hydroperoxides (EHP). The uncertainty in the contribution of enols is typically due to the high computed barriers for conventional (“direct”) keto–enol tautomerization. Remarkably, the I-CHAT dramatically reduces such barriers. The novel mechanism can be regarded as an intramolecular version of the intermolecular relay transfer of H-atoms mediated by an external molecule following the general classification of such processes (Catal. Rev.-Sci. Eng. 2014, 56, 403). Here, we present a detailed mechanistic and kinetic analysis of the I-CHAT-facilitated pathways applied to n-hexane, n-heptane, and n-pentane models as prototype molecules for gasoline, diesel, and hybrid rocket fuels. We particularly examined the formation kinetics and subsequent dissociation of the γ-enol-hydroperoxide isomer of the most abundant pentane-derived isomer γ-C5-KHP observed experimentally. To gain molecular-level insight into the I-CHAT catalysis, we have also explored the role of the internal catalyst moieties using truncated models. All applied models demonstrated a significant reduction in the isomerization barriers, primarily due to the decreased ring strain in transition states. In addition, the longer-range and sequential H-migration processes were also identified and illustrated via a combined double keto–enol conversion of heptane-2,6-diketo-4-hydroperoxide as a potential chain-branching model. To assess the possible impact of the I-CHAT channels on global fuel combustion characteristics, we performed a detailed kinetic analysis of the isomerization and decomposition of γ-C5-KHP comparing I-CHAT with key alternative reactions—direct dissociation and Korcek channels. Calculated rate parameters were implemented into a modified version of the n-pentane kinetic model developed earlier using RMG automated model generation tools (ACS Omega, 2023, 8, 4908). Simulations of ignition delay times revealed the significant effect of the new pathways, suggesting an important role of the I-CHAT pathways in the low-T combustion of large alkanes. Full article

Metal–organic frameworks (MOFs) are hybrid inorganic–organic 3D coordination polymers with metal sites and organic linkers, which are a “hot” topic in the research of sorption, separations, catalysis, sensing, and environmental remediation. In this study, we explore the molecular mechanism and kinetics of interaction of the new copper porphyrin aluminum metal–organic framework (actAl-MOF-TCPPCu) compound 4 with a vapor of the volatile organic sulfur compound (VOSC) diethyl sulfide (DES). First, compound 4 was synthesized by post-synthetic modification (PSM) of Al-MOF-TCPPH₂ compound 2 by inserting Cu²⁺ ions into the porphyrin ring and characterized by complementary qualitative and quantitative chemical, structural, and spectroscopic analysis. Second, the interaction of compound 4 with DES vapor was analyzed dynamically by the novel method of in situ time-dependent attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy at controlled humidity levels. The sorbent–adsorbate interactions, as analyzed by the shifts in IR peaks, indicate that the bonding includes the hydroxy O-H, carboxylate COO⁻, and phenyl groups. The kinetics of sorption obeys the Langmuir pseudo-first-order rate law. The pre-adsorption of water vapor by compound 4 at the controlled relative humidity under static (equilibrium) conditions yields the binary stoichiometric adsorption complex (Al-MOF-TCPPCu)_1.0(H₂O)_8.0. The pre-adsorption of water vapor makes the subsequent sorption of DES slower, while the kinetics obey the same rate law. Then, static pre-adsorption of water vapor was followed by static sorption of DES vapor, and the ternary adsorption complex (Al-MOF-TCPPCu)_1.0(H₂O)_8.0(DES)₃.₈ was obtained. Despite the pre-adsorption of significant amounts of water, the binary complex adsorbs a large amount of DES: ca. 36.6 wt. % (per compound 4). Finally, the ternary complex is facilely regenerated by gentle heating under vacuum. Compound 4 and related MOFs are promising for adsorptive removal of vapor of DES and related VOSCs from dry and humid air. Full article

Cancer remains a formidable challenge, requiring the constant pursuit of novel therapeutic agents and strategies. Scorpionates, known for their unique coordination properties, have recently gained attention for their anticancer potential. Traditionally applied in catalysis, these compounds have demonstrated notable cytotoxicity across various cancer cell lines, often surpassing the efficacy of conventional chemotherapeutics. This review addresses recent findings on scorpionate complexes, emphasizing the impact of metal choice and ligand design on biological activity. Copper and ruthenium scorpionates show promise, leveraging redox activity and mitochondrial disruption mechanisms to selectively induce cancer cell death. Ligand modifications, including sulfur-containing heterocycles and unsubstituted pyrazoles, have proven effective in enhancing cytotoxicity and selectivity. Furthermore, dipodal ligands show unique potential, with selective binding sites that improve stability and facilitate specific cellular interactions, such as targeting metastatic pathways. These findings highlight the largely unexplored potential of scorpionate complexes, positioning them as candidates for next-generation anticancer therapies. Continued research into structure–activity relationships and precise mechanisms of action could pave the way for developing highly potent and selective anticancer agents based on scorpionate chemistry. Full article