化学•材料最新文献

The alarming increase in atmospheric CO2 levels, driven by fossil fuel combustion and industrial processes, is a major contributor to climate change. Effective technologies for selective CO2 removal are urgently needed, especially for industrial gas streams like flue gas and biogas, which contain impurities such as N2 and CH4. In this study, we designed and synthesized molecularly imprinted polymers (MIPs) using 4-vinylpyridine(4VP) and methacrylic acid(MAA) as functional monomers, and thiophene(Th) and formaldehyde(HC) as molecular templates. The MIPs were engineered to create selective molecular cavities within a nanoporous polymer matrix for efficient CO2 capture. By adjusting the molar ratios of the template to the functional monomers, we optimized the imprinting process to enhance CO2 selectivity over N2&CH4. The resulting MIPs exhibited excellent performance, achieving a maximum CO2/N2 selectivity of 153 at 25 bar and CO2/CH4 selectivity of 25.3 at 1 bar, significantly surpassing previously reported porous polymers and metal-organic frameworks(MOFs) under similar conditions. Heat of adsorption studies confirmed the strong and selective interaction of CO2 with the imprinted cavities, demonstrating the superior adsorption properties of the synthesized MIPs. This study highlights the potential of molecular imprinting for improving CO2 capture capacity and selectivity, offering a scalable solution for industrial CO2 separation.

Quantum-chemical fragmentation methods offer an attractive approach for the accurate calculation of protein-ligand interaction energies. While the molecular fractionation with conjugate caps (MFCC) scheme offers a rather straightforward approach for this purpose, its accuracy is often not sufficient. Here, we upgrade the MFCC scheme for the calculation of protein-ligand interactions by including many-body contributions. The resulting fragmentation scheme is an extension of our previously developed MFCC-MBE(2) scheme [J. Comput. Chem. 2023, 44, 1634-1644]. For a diverse test set of protein-ligand complexes, we demonstrate that by upgrading the MFCC scheme with many-body contributions, the error in protein-ligand interaction energies can be reduced significantly, and one generally achieves errors below 20 kJ/mol. Our scheme allows for systematically reducing these errors by including higher-order many-body contributions. As it combines the use of single amino acid fragments with high accuracy, our scheme provides an ideal starting point for the parametrization of accurate machine learning potentials for proteins and protein-ligand interactions.

The extensive application of plastic products in daily human life has led to the accumulation of microplastics (MPs) in agricultural soil. However, little is known about the cross-generational toxicity of MPs on terrestrial invertebrates. In this study, two-generational Eisenia fetida was exposed to low-density polyethylene (LDPE, 0-5%, w/w) for 98 days to reveal the cross-generational toxicity and the underlying mechanisms. Results showed that LDPE-MPs not only perpetrated deleterious effects on the development, hatchability, and fecundity of the F0 generation but also stimulated the antioxidant defense activity, inhibited lipid peroxidation, and disordered neurotransmission in F1 generation individuals. The susceptibility of the epidermal-intestinal barrier to LDPE-MPs was dose-dependent. According to the transcriptomic analysis, the cross-generational earthworms confirmed significant perturbances in the cell cycle, neural activity-related pathways, and amino acid metabolism pathways (p < 0.05). Nevertheless, the metabolomic profile of F1 generation individuals exhibited significant hyperactive responses in glutathione metabolism and alanine, aspartate, and glutamate metabolism (p < 0.05). This study provides a comprehensive knowledge of LDPE-MPs toxicity on cross-generational earthworms and highlights the hyperactive responses in the antioxidant defense performance of the offsprings. Our findings also underscore the necessity for long-term investigations in assessing the adverse impacts of emerging pollutants.

The di-π-methane (DPM) rearrangement is an important organic photorearrangement that converts 1,4-diene-containing compounds to vinyl cyclopropanes, often resulting in extensive, synthetically valuable restructuring of the substrate's carbon framework. We investigated the influence of Lewis and Brønsted acids on the DPM rearrangement of dibenzobarrelenes. These studies have culminated in the identification of a dual chiral Brønsted acid-iridium photosensitizer system that enables the first highly enantioselective catalytic all-carbon DPM rearrangement.

Environmental contaminants pose a significant selection pressure across taxa, potentiating evolved resistance to chemicals. However, rapid evolution may alter molecular and physiological homeostasis leading to trade-offs. To elucidate molecular underpinnings of evolved chemical resistance, we compared liver gene expression and methylation profiles in polycyclic aromatic hydrocarbon (PAH)-adapted Atlantic killifish (Fundulus heteroclitus) in the Republic site (RP), Elizabeth River, Virginia with PAH-sensitive Kings Creek (KC) fish. We found 1607 differentially expressed and 2252 alternatively spliced genes between RP and KC, with highly enriched genes involving lipid and amino acid metabolism, respectively. While 308 genes had differentially methylated regions, only 13 of these genes were differentially expressed. The aryl hydrocarbon receptor 2b gene (ahr2b) was differentially methylated and expressed, as well as alternatively spliced signifying its critical role in mediating PAH tolerance. Notably, the intrapopulation coefficient of variation (CoV) was lower in 82% of 17,566 expressed genes in RP fish compared to KC fish. Among other pathways, these genes with low CoV were highly enriched in bioenergetic processes inferring reduced metabolic physiological variation as a population in RP fish. Altered metabolic gene expression and overall reduced gene expression variance in RP fish warrant further studies on fitness trade-offs including altered susceptibility to other stressors associated with rapid adaptation to anthropogenic pressures.

Injectable hydrogels are a sub-type of hydrogels which can be delivered into the host in a minimally invasive manner. They can act as carriers to encapsulate and deliver cells, drugs or active biomolecules across several disease conditions. Polymers, either synthetic or natural, or even a combination of the two, can be used to create injectable hydrogels. Clinically approved injectable hydrogels are being used as dressings for burn wounds, bone and cartilage reconstruction. Injectable hydrogels have recently gained tremendous attention for their delivery into the liver in pre-clinical models. However, their efficacy in clinical studies remains yet to be established. In this article, we describe principles for the design of these injectable hydrogels, delivery strategies and their potential applications in facilitating liver regeneration and ameliorating injury. We also discuss the several constraints related to translation of these hydrogels into clinical settings for liver diseases and deliberate some potential solutions to combat these challenges.