Electronic structure and hydrogen bond in the crystal of paracetamol drugs

We study the density of state (DOS), band structure (BS), and atomic orbit projected density of state (PDOS) of paracetamol crystal adopting the density functional theory (DFT) technique in the local density approximation (LDA). The band structure around the Fermi level and the contributions from p-type orbit of C, N, O, and s-type orbit of H to the total density of state (TDOS) are addressed, and we find that the electronic characteristic is the key to form the hydrogen bond between O and H atoms. We show that the structure of paracetamol crystal consists of the –OH···O=C and –NH···OH hydrogen-bonding cycle by studying a single paracetamol molecule as well as the PDOS graph of O and H atoms in the crystal.     

Theoretical investigation of nitration and nitrosation of dimethylamine by N2O4

Reactive nitrogen oxygen species (RNOS) contribute to the deleterious effects attributed to reacting with biomolecules. The mechanisms of the nitration and nitrosation of dimethylamine (DMA), which is the simplest secondary amine by N2O4, a member of RNOS, have been investigated at the CBS-QB3 level of theory. The nitration and nitrosation proceed via different pathways. The nitration of DMA follows three pathways. The first is the abstraction of the hydrogen atom of the amino group of DMA by the NO2 radical followed by a recombination reaction of the resulting aminyl radical with another NO2 radical. The second is DMA directly reacting with symmetrical O2NNO2 leading to dimethylnitramine via a concerted and a stepwise mechanism. The third is the reaction of DMA with asymmetrical ONONO2. By computation, the main pathway for the formation of dimethylnitramine in the gas phase is by DMA directly reacting with asymmetrical ONONO2. As to the nitrosation, a concerted mechanism for the reaction of DMA with asymmetrical ONONO2 plays a major role in nitrosodimethylamine (NDMA) formation. In addition, the solvent effect on these nitration and nitrosation reactions has been also studied by using the implicit polarizable continuum model. Two major pathways of the formation of dimethylnitramine in water were found, and they are the radical process involving NO2 and the concerted mechanism starting from symmetrical O2NNO2. The result of the nitrosation of DMA in water is consistent with that in the gas phase. Comparison of the energy barriers of each mechanism leads to the conclusion that the nitrosation is more favorable than the nitration in the reaction of DMA with N2O4. This conclusion is in good agreement with the experimental results. The results obtained here will help elucidate the mechanism of the lesions of biomolecules by RNOS.     

Molar heat capacity and thermodynamic properties of 1,2-cyclohexane dicarboxylic anhydride [C8H10O3]

The molar heat capacity C _p,m of 1,2-cyclohexane dicarboxylic anhydride was measured in the temperature range from T=80 to 390 K with a small sample automated adiabatic calorimeter. The melting point T _m, the molar enthalpy Δ_fus H _m and the entropy Δ_fus S _m of fusion for the compound were determined to be 303.80 K, 14.71 kJ mol⁻¹ and 48.43 J K⁻¹ mol⁻¹, respectively. The thermodynamic functions [H _T-H _273.15] and [S _T-S _273.15] were derived in the temperature range from T=80 to 385 K with temperature interval of 5 K. The thermal stability of the compound was investigated by differential scanning calorimeter (DSC) and thermogravimetry (TG), when the process of the mass-loss was due to the evaporation, instead of its thermal decomposition.     

Methylene Blue/Carbon Dots Composite with Photothermal and Photodynamic Properties: Synthesis,Characterization, and Antibacterial Application

Photodynamic therapy and photothermal therapy provide new ways to combat antibiotic resistance. In this research, methylene blue (MB) as an effective photosensitizer was conjugated with carbon quantum dots (CQDs), the composite product not only possessed good antibacterial properties against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) due to excellent singlet oxygen (¹O₂) production rate and light heat transfer performance, but also showed good biocompatibility. Combined with 808 nm and 660 nm laser irradiation, the minimum bactericidal concentration of CQDs-MB towards S. aureus and E. coli was 5 μm . Therefore, this study provides a potential candidate material based on CQDs for clinical applications.     

Research progress on pesticide residue detection based on microfluidic technology

The problem of pesticide residue contamination has attracted widespread attention and poses a risk to human health. The current traditional pesticide residue detection methods have difficulty meeting rapid and diverse field screening requirements. Microfluidic technology integrates functions from sample preparation to detection, showing great potential for quick and accurate high-throughput detection of pesticide residues. This paper reviews the latest research progress on microfluidic technology for pesticide residue detection. First, the commonly used microfluidic materials are summarized, including silicon, glass, paper, polydimethylsiloxane, and polymethyl methacrylate. We evaluated their advantages and disadvantages in pesticide residue detection applications. Second, the current pesticide residue detection technology based on microfluidics and its application to real samples are summarized. Finally, we discuss this technology's present challenges and future research directions. This study is expected to provide a reference for the future development of microfluidic technology for pesticide residue detection.     

还原氧化石墨烯包覆MOF衍生In2Se3用于钠离子电池负极(英文)

MOF衍生金属硒化物由于其有序的碳骨架结构和高导电性,被认为是钠离子电池极具前景的负极材料。它们具有快速的电子/离子输运通道,有利于钠离子的嵌入和脱出。然而,循环过程中的大量体积膨胀会导致结构坍塌。为了解决这个问题,通过表面改性在MOF衍生金属硒化物表面引入了一个二维的还原氧化石墨烯网络,既可以缓解体积变化,又能加速电子转移。实验证实这种策略是有效的,在1 A·g^-1下500次循环后,包覆了还原氧化石墨烯的复合材料电极容量保持率提高到了95.2%。相比之下,不含还原氧化石墨烯的容量保留率仅为74.2%。此外,由于还原氧化石墨烯网络和MOF衍生In₂Se₃协同作用,在0.1 A·g^-1下显示出了468 m Ah·g^-1的优越容量。而在相同的电流密度下,未包覆还原氧化石墨烯的只产生393 m Ah·g^-1的比容量。采用循环伏安法(CV)研究了In₂Se₃@C/rGO电极的电化学过程,结果表明其具有良好的电化学反应活性...     

Observation of Asymmetric Oxidation Catalysis with B20 Chiral Crystals**

The study of heterogeneous reactions for enantiomeric processes based on inorganic crystals has been resurgent in recent years. However, the question remains how homochirality develops in nature and chemical reactions. Here, the successful growth of B20 group PdGa single crystals with different chiral lattices enabled us to achieve enantioselective recognition of 3,4-dihydroxyphenylalanine (DOPA) based on a new mechanism, namely orbital angular momentum (OAM) polarization. The orbital textures of PdGa crystals indicate large OAM polarization near the Fermi level and carrying opposite signs. A positive or negative magnetization in the [111] direction is expected depending on the chiral lattice of PdGa crystals. Due to this, the adsorption energies of PdGa crystals and DOPA molecules differ depending on how well the O-2p orbital of DOPA pairs with the Pd-4d orbital of PdGa. The results provide one possible explanation for how chirality arises in nature by providing an enantioselective route with pure inorganic crystals.     

Amplification of Dissymmetry for Circularly Polarized Photodetection by Cooperative Supramolecular Polymerization

Circularly polarized photodetectors require chiral light absorption materials with high sensing efficiency and low costs. Here readily accessible point chirality has been introduced to dicyanostilbenes as the chiral source, facilitating remote chirality transfer to the π-aromatic core by cooperative supramolecular polymerization. The single-handed supramolecular polymers display powerful circularly polarized photodetection capability with a dissymmetry factor value as high as 0.83, superior to those of π-conjugated small molecules and oligomers. Strong chiral amplification occurs between the enantiopure sergeants and the achiral soldiers. The resulting supramolecular copolymers exhibit comparable photodetection efficiency to those of the homopolymeric ones, with a 90 % decrease in the enantiopure compound consumption. Therefore, cooperative supramolecular polymerization provides an effective yet economical avenue toward circularly polarized photodetection applications.     

Selective CO2 Reduction to Ethylene Mediated by Adaptive Small-molecule Engineering of Copper-based Electrocatalysts

Electrochemical CO₂ reduction reaction (CO₂RR) over Cu catalysts exhibits enormous potential for efficiently converting CO₂ to ethylene (C₂H₄). However, achieving high C₂H₄ selectivity remains a considerable challenge due to the propensity of Cu catalysts to undergo structural reconstruction during CO₂RR. Herein, we report an in situ molecule modification strategy that involves tannic acid (TA) molecules adaptive regulating the reconstruction of a Cu-based material to a pathway that facilitates CO₂ reduction to C₂H₄ products. An excellent Faraday efficiency (FE) of 63.6 % on C₂H₄ with a current density of 497.2 mA cm⁻² in flow cell was achieved, about 6.5 times higher than the pristine Cu catalyst which mainly produce CH₄. The in situ X-ray absorption spectroscopy and Raman studies reveal that the hydroxyl group in TA stabilizes Cu^δ+ during the CO₂RR. Furthermore, theoretical calculations demonstrate that the Cu^δ+/Cu⁰ interfaces lower the activation energy barrier for *CO dimerization, and hydroxyl species stabilize the *COH intermediate via hydrogen bonding, thereby promoting C₂H₄ production. Such molecule engineering modulated electronic structure provides a promising strategy to achieve highly selective CO₂ reduction to value-added chemicals.