Chemistry - An Asian Journal最新文献

The introduction of phosphorous (P), and oxygen (O) heteroatoms in the natural honeydew chemical structure is one of the most effective, and practical approaches to synthesizing activated carbon for possible high-performance energy storage applications. The performance metrics of supercapacitors depend on surface functional groups and high-surface-area electrodes that can play a dominant role in areas that require high-power applications. Here, we report a phosphorous and oxygen co-doped honeydew peel-derived activated carbon (HDP-AC) electrode with low surface area for supercapacitor via H3PO4 activation. This activator form phosphorylation with cellulose fibers in the HDP. The formation of heteroatoms stabilizes the cellulose structure by preventing the formation of levoglucosan (C6H10O5), a cellulose combustion product, which would otherwise offer a pathway for a substantial degradation of cellulose into volatile products. Therefore, heteroatom doping has proved effective, in improving the electrochemical properties.  The improved performance is attributed to the high phosphorous doping with a hierarchical porous structure, which enables the transportation of ions at higher current rates. The high specific capacitance of 486, and 478 F/g at 0.6, and 1.3 A/g in 1M H2SO4 electrolyte with a prominent retention of 98% is observed for 2M H3PO4 having an impregnation ratio of 1:4.

Asymmetric synthesis of chiral chemicals in high enantiomeric excess (ee) is pivotal to the pharmaceutical industry, but classic chemistry usually requires multi-step reactions, harsh conditions, and expensive chiral ligands, and sometimes suffers from unsatisfactory enantioselectivity. Enzymatic catalysis is a much greener and more enantioselective alternative, and cascade biotransformations with multi-step reactions can be performed in one pot to avoid costly intermediate isolation and minimise waste generation. One of the most attractive applications of enzymatic cascade transformations is to convert easily available simple racemic substrates into valuable functionalised chiral chemicals in high yields and ee. Here, we review the three general strategies to build up such cascade biotransformations, including enantioconvergent reaction, dynamic kinetic resolution, and destruction-and-reinstallation of chirality. Examples of cascade transformations using racemic substrates such as racemic epoxides, alcohols, hydroxy acids, etc. to produce the chiral amino alcohols, hydroxy acids, amines and amino acids are given. The product concentration, ee, and yield, scalability, and substrate scope of these enzymatic cascades are critically reviewed. To further improve the efficiency and practical applicability of the cascades, enzyme engineering to enhance catalytic activities of the key enzymes using the latest microfluidics-based ultrahigh-throughput screening and artificial intelligence-guided directed evolution could be useful approaches.

Dicarboxylate metallosurfactants (AASM), synthesized by mixing N-dodecyl aminomalonate, -aspartate and -glutamate with CaCl2, MnCl2 and CdCl2, were characterized by XRD, FTIR, and NMR spectroscopy. Layered structures, formed by metallosurfactants, were evidenced from differential scanning calorimetry and thermogravimetric analyses. Solvent-spread monolayer of AASM in combination with soyphosphatidylcholine (SPC) and cholesterol (CHOL) were studied using Langmuir surface balance. With increasing mole fraction of AASM mean molecular area increased and passed through maxima at ~60 mol% of AASMs, indicating molecular packing reorganization. Systems with 20 and 60 mol% AASM exhibited positive deviations from ideal behavior signifying repulsive interaction between the AASM and SPC, while synergistic interactions were established from the negative deviation at other combinations. Dynamic surface elasticity increased with increasing surface pressure signifying formation of rigid monolayer. Transition of monolayer from gaseous to liquid expanded to liquid condensed state was established by Brewster angle microscopic studies. Stability of the hybrid vesicles, formed by AASM+SPC+CHOL, was established by monitoring their size, zeta potential and polydispersity index values over 100 days. Size and spherical morphology of hybrid vesicles were confirmed by transmission electron microscopic studies. Biocompatibility of the hybrid vesicles were established by cytotoxicity studies revealing their possible applications in drug delivery and imaging.

Iron-nitrogen functionalized graphene has emerged as a promising cathode host for rechargeable lithium-sulfur batteries (RLSBs) due to its affordability and enhanced battery performance. To optimize its catalytical efficiency, we propose a novel approach involving coordination engineering. Our investigation spans a plethora of catalysts with varied coordination environments, focusing on elements B, C, N and O. We revealed that Fe-C4 and Fe-B2C2-h are particularly effective for promoting Li2S oxidation, whereas Fe-N4 excels in catalyzing the sulfur reduction reaction (SRR). Importantly, our study identified specific descriptors - namely, the Integrated Crystal Orbital Hamilton Population (ICOHP) and the bond length between Fe and S in Li2S adsorbed state - as the most effective predictive descriptors for Li2S oxidation barriers. Meanwhile, Li2S adsorption energy emerges as a reliable descriptor for assessing the SRR barrier. These identified descriptors are expected to be instrumental in rapidly identifying promising cathode hosts across various metal-centered systems with diverse coordination environments. Our findings not only offer valuable insights into the role of coordination environment, but also present an effective path for rapidly identifying high performance catalysts for RLSBs, enabling the acceleration of advanced RLSBs development.

Photoswitchable lipids, particularly azobenzene-derivatized phosphatidylcholine (azoPC) lipids, offer a unique mechanism for reversible modification of membrane properties upon exposure to ultraviolet (UV) radiation. Through all-atom molecular dynamics simulations, we explore how UV irradiation-induced trans-to-cis photoisomerization(TCPI) of AzoPC lipid influences the structure and dynamics of a lipid membrane, composed of dipalmitoylphosphatidylcholine (DPPC) and cholesterol with similar composition to that of the DOXIL®.  Structural and dynamical analyses of two states of the membrane, 'dark' state (containing cis-azoPC lipid) and 'bright' state (containing 85% cis-azoPC and 15% trans-azoPC lipids) reveal that the TCPI reduces membrane packing density and increases diffusivity of lipids. We have demonstrated an enhanced intercalation of doxorubicine (DOX), an anticancer drug, in the 'bright' state of the membrane compared to that in 'dark' state. This study - elucidating the complex interplay between lipid composition, photoswitching, and lipid-drug interactions - contribute to the design of lipid-based systems for targeted drug delivery and biomedical applications.

Antimicrobial resistance (AMR) poses a serious threat to human health worldwide. It is now more challenging than ever to introduce a potent antibiotic to the market considering rapid emergence of antimicrobial resistance, surpassing the rate of antibiotic drug discovery. Hence, new approaches need to be developed to accelerate the rate of drug discovery process and meet the demands for new antibiotics, while reducing the cost of their development. Machine learning holds immense promise of becoming a useful tool, especially since in the last two decades, exponential growth has occurred in computational power and biological big data analytics. Recent advancements in machine learning algorithms for drug discovery have provided significant clues for potential antibiotic classes. Apart from discovery of new scaffolds, machine learning protocols will significantly impact prediction of AMR patterns and drug metabolism. In this review, we outline power of machine learning in antibiotic drug discovery, metabolic fate, and AMR prediction to support researchers engaged and interested in this field.

Uracil-DNA glycosylase (UDG) plays a crucial role in the removal of damaged uracil bases, thereby upholding genetic stability and integrity. An enzyme-powered, label-free DNA walker was devised for UDG activity detection. Initially, a label-free DNA track, incorporating a gold nanoparticle (AuNP), multiple hairpin structures, and various swing arms, was engineered for walking mechanism. The hairpin structure was meticulously crafted to include a G-quadruplex sequence, enabling the generation of a label-free fluorescence signal. The swing arm remained inert in the absence of UDG, but became activated upon the introduction of UDG, thereby initiating the enzyme-powered walking process and generating significant dissociative G-quadruplex sequences. By integrating a selective fluorescent dye into the design, an enhanced label-free fluorescence response was achieved. The proposed DNA walker presented a direct and label-free approach for UDG detection, demonstrating exceptional sensitivity with a detection limit of 0.00004 U/mL. Using the uracil glycosylase inhibitor (UGI) as an inhibitory model, inhibitor assay was conducted with satisfactory precision. Furthermore, successful analysis of cellular UDG at the single-cell level was accomplished. Consequently, the developed DNA walker serves as a label-free, selective, and sensitive tool for UDG activity assessment, showing great potential for applications in disease diagnosis, inhibitor screening, and biomedical investigations.

We report a systematic study on controlling the enzyme activity of a terminal uridylyl transferase (TUTase) called SpCID1, which provides methods to effect site-specific incorporation of a single modified nucleotide analog at the 3'-end of an RNA oligonucleotide (ON).  Responsive heterocycle-modified fluorescent UTP probes that are useful in analyzing non-canonical nucleic acid structures and azide- and alkyne-modified UTP analogs that are compatible for chemoenzymatic functionalization were used as study systems.  In the first strategy, we balanced the concentration of essential metal ion cofactors (Mg2+ and Mn2+ ions) to restrict the processivity of the enzyme, which gave a very good control on the incorporation of clickable nucleotide analogs.  In the second approach, borate that complexes with 2' and 3' oxygen atoms of a ribose sugar was used as a reversibly binding chelator to block repeated addition of nucleotide analogs.  Notably, in the presence of heterocycle-modified fluorescent UTPs, we obtained single-nucleotide incorporated RNA products in reasonable yields, while with clickable nucleotides yields were very good.  Further, 3'-end azide- and alkyne-labeled RNA ONs were post-enzymatically functionalized by CuAAC and SPAAC reactions with fluorescent probes.  These strategies broaden the scope of TUTase in site-specifically installing modifications of different types onto RNA for various applications.

Photoinduced 3D printing via photocontrolled reversible-deactivation radical polymerization (photoRDRP) techniques has emerged as a robust technique for creating polymeric materials. However, methods for precisely adjusting the mechanical properties of these materials remain limited. In this study, we present a facile approach for adjusting the mechanical properties of 3D-printed objects by adjusting the polymer dispersity within a Norrish type I photoinitiated reversible addition-fragmentation chain transfer (NTI-RAFT) polymerization-based 3D printing process. We investigated the effects of varying the concentrations and molar ratios of trithiocarbonate (BTPA) and xanthate (EXEP) on the mechanical properties of the printed materials. Our findings demonstrate that increased concentrations of RAFT agents or higher proportions of the more active BTPA lead to a decrease in Young's modulus and glass transition temperatures, along with an increase in elongation at break, which can be attributed to the enhanced homogeneity of the polymer network. Using a commercial LCD printer, the NTI-RAFT-based 3D printing system effectively produced materials with tailored mechanical properties, highlighting its potential for practical applications.

The reuse of waste biomass resources had become a hot topic in the sustainable development of human society. Biomass was an ideal precursor for preparing porous carbon. However, due to the complexity of biomass composition and microstructure, the quality reproducibility of biomass porous carbon was poor. Therefore, it was of great significance to develop a reliable method for preparing porous carbon from biomass. In this paper, The activated hydrothermal porous carbon was prepared by a combination of hydrothermal carbonization treatment and KHCO3 mild activation. The hydrothermal carbonization treatment could complete the morphology adjustment and iron doping of the carbon in one step, and the mild activation of KHCO3 could activate the porous carbon while maintaining the spherical morphology. Fe-modified porous carbon with carbon ball/nanosheet structure which facilitated ion/electrolyte diffusion and increased accessibility between surface area and electrolyte ions. Therefore, bagasse derived activated porous carbon had good specific capacitance (315.2 F/g at 1 A/g) and good cycle stability, with a capacitance loss of only 5.8% after 5000 charge-discharge cycles. This study showed that the combination of hydrothermal treatment and mild activation provided an effective way for the conversion of waste biomass into high-performance electrode materials.