绿色单体二氧化碳参与的新型聚合反应

二氧化碳(CO₂)是一种丰富、廉价、无毒以及可再生的一碳资源,也是一种可用于聚合的绿色单体.基于CO₂的聚合是近年来的研究热点之一.目前广泛报道的是CO₂和环氧单体的聚合反应,经过几十年的发展已经成功实现工业化生产.最近几年,一些CO₂参与的新型聚合反应被陆续报道,这些工作大都通过两种途径实现从CO₂到高分子材料的转变.第一个途径是先将CO₂转化为可以聚合的单体,例如:内酯、环状碳酸酯和2,5-二呋喃甲酸等,再利用开环或者逐步聚合将单体转化为聚合物;另一个途径是直接以CO₂为单体和其他类型单体共聚得到聚合物.这两种途径对于发展CO₂参与的新型聚合反应,拓展CO₂基聚合物种类都具有重要意义.本综述按照CO₂直接还是间接参与聚合反应分类总结了近年来在CO₂制备高分子材料方面的进展,并对未来发展方向进行了简单阐述.     

Machine learning accelerated high-throughput screening of zeolites for the selective adsorption of xylene isomers

The production of widely used polymers such as polyester currently relies upon the chemical separation of and transformation of xylene isomers. The least valuable but most prevalent isomer is meta-xylene which can be selectively transformed into the more useful and expensive para-xylene isomer using a zeolite catalyst but at a high energy cost. In this work, high-throughput screening of existing and hypothetical zeolite databases containing more than two million structures was performed, using a combination of classical simulation and deep neural network methods to identify promising materials for selective adsorption of meta-xylene. Novel anomaly detection techniques were applied to the heavily biased classification task of identifying structures with a selectivity greater than that of the best performing existing zeolite, ZSM-5 (MFI topology). Eight hypothetical zeolite topologies are found to be several orders of magnitude more selective towards meta-xylene than ZSM-5 which may provide an impetus for synthetic efforts to realise these promising materials. Moreover, the leading hypothetical frameworks identified from the screening procedure require a markedly lower operating temperature to achieve the diffusion seen in existing materials, suggesting significant energetic savings if the frameworks can be realised.

A combination of machine learning and high throughput simulation has identified several potential zeolite structures that appear to outperform the leading commercially used material and explained the key factors for high selectivity.     

Pseudo-mono-axial ligand fields that support high energy barriers in triangular dodecahedral Dy(iii) single-ion magnets

The synthesis of air-stable, high-performance single-molecule magnets (SMMs) is of great significance for their practical applications. Indeed, Ln complexes with high coordination numbers are satisfactorily air stable. However, such geometries easily produce spherical ligand fields that minimize magnetic anisotropy. Herein, we report the preparation of three air-stable eight-coordinate mononuclear Dy(iii) complexes with triangular dodecahedral geometries, namely, [Dy(BPA-TPA)Cl](BPh₄)₂ (1) and [Dy(BPA-TPA)(X)](BPh₄)₂·nCH₂Cl₂ (X = CH₃O⁻ and n = 1 for 2; L = PhO⁻ and n = 2 for 3), using a novel design concept in which the bulky heptadentate [2,6-bis[bis(2-pyridylmethyl)amino]methyl]-pyridine (BPA-TPA) ligand enwraps the Dy(iii) ion through weak coordinate bonds leaving only a small vacancy for a negatively charged (Cl⁻), methoxy (CH₃O⁻) or phenoxy (PhO⁻) moiety to occupy. Magnetic measurements reveal that the single-molecule magnet (SMM) property of complex 1 is actually poor, as there is almost no energy barrier. However, complexes 2 and 3 exhibit fascinating SMM behavior with high energy barriers (U_eff = 686 K for 2; 469 K for 3) and magnetic hysteresis temperatures up to 8 K, which is attributed to the pseudolinear ligand field generated by one strong, highly electrostatic Dy–O bond. Ab initio calculations were used to show the apparent difference in the magnetic dynamics of the three complexes, confirming that the pseudo-mono-axial ligand field has an important effect on high-performance SMMs compared with the local symmetry. This study not only presents the highest energy barrier for a triangular dodecahedral SMM but also highlights the enormous potential of the pseudolinear Dy–L ligand field for constructing promising SMMs.

Air-stable triangular dodecahedral Dy(iii) single-ion magnets with pseudo-mono-axial linear ligand fields exhibit high energy barrier exceeding 600 K, which represent the highest energy barrier for mononuclear SMMs with triangular dodecahedron.     

Phytochemical Characterization,Antioxidant and Anti-Inflammatory Effects of Cleome arabica L. Fruits Extract against Formalin Induced Chronic Inflammation in Female Wistar Rat: Biochemical,Histological, and In Silico Studies

In recent decades, the use of herbs and plants has been of great interest, as they have been the sources of natural products, commonly named as bioactive compounds. In specific, the natural compounds from the Capparaceae family which has been proved to have antioxidant, anti-inflammatory, antimicrobial and anti-carcinogenic activities, by several studies. Cleome arabica L. (CA) specie is the most used medicinal plants in Tunisia and elsewhere in North African countries for treatment of various diseases including diabetes, rheumatism, inflammation, cancer, and digestive disorders. The current work was undertaken to estimate the total phenolic, flavonoid and condensed tannin contents, to identify and quantify the polyphenolic compounds, and to evaluate the antioxidant and the anti-inflammatory proprieties of CA fruits extract against formalin induced chronic inflammation in Female Wistar rats. In fact, the antioxidant activity was tested by Diphenyl-1-Picrylhydrazyl free radical scavenging (DPPH), Ferric reducing antioxidant power (FRAP) and Nitric Oxide radical (NO·). Anti-inflammatory effect of fruits extract was examined using formalin (2%) induced paw edema in rats. Molecular docking tools were used to investigate the interaction of some compounds from CA fruits extract with the cyclooxygenase-2 (COX-2) target protein. Our results showed that, the total phenolic, flavonoid and tannins contents, which were assessed by the Folin-Ciocalteu, Quercetin, and Catechin methods, respectively, were 230.22 mg gallic acid equivalent/g dry weight (mg GAE/g DW), 55.08 mg quercetin equivalent/g dry weight (QE/g DW) and 15.17 mg catechin equivalents/g dry weight (CatE/g DW), respectively. HPLC analysis revealed the presence of five polyphenolic compounds whose catechin was found to be the most abundant compounds. The antioxidant activity of extract was quantified by DPPH, FRAP and NO· tests and IC₅₀ reached the values of 3.346 mg/mL, 2.306 and 0.023 mg/mL, respectively. Cleome fruits ameliorated the histological integrity of the skin and alleviated the disruptions in hematological parameters (WBC, LYM, RBC, and HGB), inflammatory cytokines (IL-1β, IL-6, TNF-α), C-reactive protein, and some oxidative stress markers (TBARS (−49%) and AOPP (−42%) levels, SOD (+33%) and GPx (+75%) activities, and GSH (+49%) content) induced by formalin injection. Moreover, the in-silico investigation had shown that CA fruits extract compounds have a stronger interaction with COX-2 active site, more than the reference drug “indomethacin” (two H-bonds). Our research gives pharmacological backing to the healthcare utilization of Cleome plant in the treatment of inflammatory diseases and oxidative harm.     

Recent Progress in Type I Aggregation-Induced Emission Photosensitizers for Photodynamic Therapy

In modern medicine, precision diagnosis and treatment using optical materials, such as fluorescence/photoacoustic imaging-guided photodynamic therapy (PDT), are becoming increasingly popular. Photosensitizers (PSs) are the most important component of PDT. Different from conventional PSs with planar molecular structures, which are susceptible to quenching effects caused by aggregation, the distinct advantages of AIE fluorogens open up new avenues for the development of image-guided PDT with improved treatment accuracy and efficacy in practical applications. It is critical that as much of the energy absorbed by optical materials is dissipated into the pathways required to maximize biomedical applications as possible. Intersystem crossing (ISC) represents a key step during the energy conversion process that determines many fundamental optical properties, such as increasing the efficiency of reactive oxygen species (ROS) production from PSs, thus enhancing PDT efficacy. Although some review articles have summarized the accomplishments of various optical materials in imaging and therapeutics, few of them have focused on how to improve the phototherapeutic applications, especially PDT, by adjusting the ISC process of organic optics materials. In this review, we emphasize the latest advances in the reasonable design of AIE-active PSs with type I photochemical mechanism for anticancer or antibacterial applications based on ISC modulation, as well as discuss the future prospects and challenges of them. In order to maximize the anticancer or antibacterial effects of type I AIE PSs, it is the aim of this review to offer advice for their design with the best energy conversion.     

Rutin Inhibits Ox-LDL-Mediated Macrophage Inflammation and Foam Cell Formation by Inducing Autophagy and Modulating PI3K/ATK Signaling

Atherosclerosis (AS) is one of the leading causes of death among the elderly, and is primarily caused by foam cell generation and macrophage inflammation. Rutin is an anti-inflammatory, anti-oxidant, anti-allergic, and antiviral flavonoid molecule, known to have anti-atherosclerotic and autophagy-inducing properties, but its biological mechanism remains poorly understood. In this study, we uncovered that rutin could suppress the generation of inflammatory factors and reactive oxygen species (ROS) in ox-LDL-induced M2 macrophages and enhance their polarization. Moreover, rutin could decrease foam cell production, as shown by oil red O staining. In addition, rutin could increase the number of autophagosomes and the LC3II/I ratio, while lowering p62 expression. Furthermore, rutin could significantly inhibit the PI3K/ATK signaling pathway. In summary, rutin inhibits ox-LDL-mediated macrophage inflammation and foam cell formation by inducing autophagy and modulating PI3K/ATK signaling, showing potential in treating atherosclerosis.     

Montmorillonite KSF-Catalyzed Synthesis of 2,2′-(Arylmethylene)bis(3-hydroxy-5,5-dimethylcyclohex-2-en-1-ones) for the Functionalization of MCM-41 Silica Nanoparticles

Russian Journal of Organic Chemistry - A green protocol has been developed for the preparation of 2,2′-(arylmethylene)bis(3-hydroxy-5,5-dimethylcyclohex-2-en-1-ones) following the...     

Aggregation-Induced Generation of Reactive Oxygen Species: Mechanism and Photosensitizer Construction

Luminogens with aggregation-induced emission (AIEgens) have been widely applied in the field of photodynamic therapy. Among them, aggregation-induced emission photosensitizers (AIE–PSs) are demonstrated with high capability in fluorescence and photoacoustic bimodal imaging, as well as in fluorescence imaging-guided photodynamic therapy. They not only improve diagnosis accuracy but also provide an efficient theranostic platform to accelerate preclinical translation as well. In this short review, we divide AIE–PSs into three categories. Through the analysis of such classification and construction methods, it will be helpful for scientists to further develop various types of AIE–PSs with superior performance.     

Cu-Doped ZnO Nanoparticles for Non-Enzymatic Glucose Sensing

Copper-doped zinc oxide nanoparticles (NPs) Cu_xZn_1−xO (x = 0, 0.01, 0.02, 0.03, and 0.04) were synthesized via a sol-gel process and used as an active electrode material to fabricate a non-enzymatic electrochemical sensor for the detection of glucose. Their structure, composition, and chemical properties were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infrared (FTIR) and Raman spectroscopies, and zeta potential measurements. The electrochemical characterization of the sensors was studied using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and differential pulse voltammetry (DPV). Cu doping was shown to improve the electrocatalytic activity for the oxidation of glucose, which resulted from the accelerated electron transfer and greatly improved electrochemical conductivity. The experimental conditions for the detection of glucose were optimized: a linear dependence between the glucose concentration and current intensity was established in the range from 1 nM to 100 μM with a limit of detection of 0.7 nM. The proposed sensor exhibited high selectivity for glucose in the presence of various interfering species. The developed sensor was also successfully tested for the detection of glucose in human serum samples.     

Synthesis and Characterization of Some New Quinoxalin-2(1H)one and 2-Methyl-3H-quinazolin-4-one Derivatives Targeting the Onset and Progression of CRC with SAR,Molecular Docking,and ADMET Analyses

The pathogenesis of colorectal cancer is a multifactorial process. Dysbiosis and the overexpression of COX-2 and LDHA are important effectors in the initiation and development of the disease through chromosomal instability, PGE2 biosynthesis, and induction of the Warburg effect, respectively. Herein, we report the in vitro testing of some new quinoxalinone and quinazolinone Schiff’s bases as: antibacterial, COX-2 and LDHA inhibitors, and anticolorectal agents on HCT-116 and LoVo cells. Moreover, molecular docking and SAR analyses were performed to identify the structural features contributing to the biological activities. Among the synthesized molecules, the most active cytotoxic agent, (6d) was also a COX-2 inhibitor. In silico ADMET studies predicted that (6d) would have high Caco-2 permeability, and %HIA (99.58%), with low BBB permeability, zero hepatotoxicity, and zero risk of sudden cardiac arrest, or mutagenicity. Further, (6d) is not a potential P-gp substrate, instead, it is a possible P-gpI and II inhibitor, therefore, it can prevent or reverse the multidrug resistance of the anticancer drugs. Collectively, (6d) can be considered as a promising lead suitable for further optimization to develop anti-CRC agents or glycoproteins inhibitors.