Adaptive coordination assemblies based on a flexible tetraazacyclododecane ligand for promoting carbon dioxide fixation

Coordination hosts based on flexible ligands have received increasing attention due to their inherent adaptive cavities that often show induced-fit guest binding and catalysis like enzymes. Herein, we report the controlled self-assembly of a series of homo/heterometallic coordination hosts (Me₄enPd)_2n(ML)_n [n = 2/3; M = Zn(ii)/Co(ii)/Ni(ii)/Cu(ii)/Pd(ii)/Ag(i); Me₄en: N,N,N′,N′-tetramethylethylenediamine] with different shapes (tube/cage) from a flexible tetraazacyclododecane-based pyridinyl ligand (L) and cis-blocking Me₄enPd(ii) units. While the Ag(i)-metalated ligand (AgL) gave rise to the formation of a (Me₄enPd)₄(ML)₂-type cage, all other M(ii) ions led to isostructural (Me₄enPd)₆(ML)₃-type tubular complexes. Structural transformations between cages and tubes could be realized through transmetalation of the ligand. The buffering effect on the ML panels endows the coordination tubes with remarkable acid–base resistance, which makes the (Me₄enPd)₆(ZnL)₃ host an effective catalyst for the CO₂ to CO₃²⁻ conversion. Control experiments suggested that the integration of multiple active Zn(ii) sites on the tubular host and the perfect geometry match between CO₃²⁻ and the cavity synergistically promoted such a conversion. Our results provide an important strategy for the design of adaptive coordination hosts to achieve efficient carbon fixation.

A series of coordination hosts were prepared and their applications in CO₂ fixation were studied.     

The Antioxidant and Hypolipidemic Effects of Mesona Chinensis Benth Extracts

In this study, the antioxidant and hypolipidemic effects of Mesona Chinensis Benth (MCB) extracts were evaluated. Seven fractions (F0, F10, F20, F30, F40, F50 and MTF) were obtained from the MCB ethanol extracts. Compared to the commercial antioxidants (vitamin C), MTF and F30 exhibited higher antioxidant activities in the antiradical activity test and the FRAP assay. The half-inhibition concentration (IC50) for MTF and F30 were 5.323 µg/mL and 5.278 µg/mL, respectively. MTF at 200 µg/mL significantly decreased the accumulation of TG in oleic acid (OA)-induced HepG2 cells and reversed the inhibitory effect of Compound C on AMPK (MTF and F30 significantly increased the glucose utilization of insulin-induced HepG2 cells). In addition, the components of MTF were identified by HPLC-MS, which were caffeic acid, quercetin 3-O-galactoside, isoquercetin, astragalin, rosmarinic acid, aromadendrin-3-O-rutinoside, rosmarinic acid-3-O-glucoside and kaempferol-7-O-glucoside. Through statistical correlations by Simca P software, it was found that the main antioxidant and hypolipidemic components of MCB might be caffeic acid, kaempferol-7-O-glucoside, rosmarinic acid-3-O-glucoside and aromadendrin-3-O-rutinoside, which may play important roles in the AMPK pathway. MTF and F30 in MCB could be potential health products for the treatment of hyperlipidemia.     

DMF体系中Cu2O球晶的制备及形貌分析

以N,N-二甲基甲酰胺(DMF)为溶剂,通过改变铜源和表面活性剂,调控反应参数,溶剂热条件下制备了三维十字形、空心及实心的Cu₂O球晶。利用XRD、SEM等表征手段,分析探讨了工艺条件变化对Cu₂O球晶形貌的影响。研究表明,随着DMF浓度的增大,体系的还原能力增强,Cu⁺增多,溶液的过饱和度增大,Cu₂O晶体集合体形态由晶体结构控制的各向异性与对称性的球晶逐渐向各向同性球晶演变。十二烷基硫酸钠(SDS)、十六烷基三甲基溴化铵(CTAB)、聚乙烯吡咯烷酮(PVP)等表面活性剂有助于降低溶液的过饱和度,增加结晶质的表面扩散能力,有利于规则形态Cu₂O晶粒的形成。反应体系中,Cu(Ac)₂·H₂O水解生成的羧基与DMF中的甲酰基在高温下发生脱羧反应产生CO₂气体以及SDS发泡作用产生的气体是形成空心Cu₂O球晶的重要原因。     

Dynamic Variation of Amino Acid Contents and Identification of Sterols in Xinyang Mao Jian Green Tea

As important biomolecules in Camellia sinensis L., amino acids (AAs) are considered to contribute to the overall green tea sensory quality and undergo dynamic changes during growth. However, limited by analytical capacity, detailed AAs composition in different growth stages remains unclear. To address this question, we analyzed the dynamic changes of 23 AAs during leaf growth in Xinyang Mao Jian (XYMJ) green tea. Using amino acid analyzer, we demonstrated that most AAs are abundant on Pure Brightness Day and Grain Rain Day. After Grain Rain, 23 AAs decreased significantly. Further analysis shows that theanine has a high level on the day before Spring Equinox and Grain Rain, accounting for 44–61% of the total free AAs content in tea leaves. Glu, Pro, and Asp are the second most abundant AAs. Additionally, spinasterol and 22,23-dihydrospinasterol are first purified and identified in ethanol extract of XYMJ by silica gel column chromatography method. This study reveals the relationship between plucking days and the dynamic changes of AAs during the growth stage and proves the rationality of the traditional plucking days of XYMJ green tea.     

EGFAFS: A Novel Feature Selection Algorithm Based on Explosion Gravitation Field Algorithm

Feature selection (FS) is a vital step in data mining and machine learning, especially for analyzing the data in high-dimensional feature space. Gene expression data usually consist of a few samples characterized by high-dimensional feature space. As a result, they are not suitable to be processed by simple methods, such as the filter-based method. In this study, we propose a novel feature selection algorithm based on the Explosion Gravitation Field Algorithm, called EGFAFS. To reduce the dimensions of the feature space to acceptable dimensions, we constructed a recommended feature pool by a series of Random Forests based on the Gini index. Furthermore, by paying more attention to the features in the recommended feature pool, we can find the best subset more efficiently. To verify the performance of EGFAFS for FS, we tested EGFAFS on eight gene expression datasets compared with four heuristic-based FS methods (GA, PSO, SA, and DE) and four other FS methods (Boruta, HSICLasso, DNN-FS, and EGSG). The results show that EGFAFS has better performance for FS on gene expression data in terms of evaluation metrics, having more than the other eight FS algorithms. The genes selected by EGFAGS play an essential role in the differential co-expression network and some biological functions further demonstrate the success of EGFAFS for solving FS problems on gene expression data.     

嵌段共聚物自组装的研究进展

嵌段共聚物自组装在光学、电子、信息、化学及生物领域有着广泛的应用前景.本文从实验观测、理论研究和计算机模拟三个方面概述了嵌段共聚物自组装领域的研究进展.在实验观测方面,着重介绍了嵌段共聚物在体相及膜中的自组装及外场调控作用方面的研究进展;理论方面则分别介绍了强分相理论、弱分相理论、自洽场理论、动态密度泛函方法和元胞动力学等在嵌段共聚物自组装领域的应用;计算机模拟方面就 Monte Carlo 模拟、耗散粒子动力学等方法在该领域的应用作了详细的阐述.     

Combining Metabolic Alkyne Labeling and Click Chemistry for Secretome Analysis of Serum-Containing Conditioned Medium

Main observation and conclusion Bioorthogonal click chemistry has emerged as a powerful tool for the specific modification of proteins in complex mixtures.Metab...     

Klein–Nishina Effect and the Cosmic Ray Electron Spectrum

Radiative energy losses are very important in regulating the cosmic ray electron and/or positron(CRE) spectrum during their propagation in the Milky Way. Particularly, the Klein–Nishina(KN) effect of the inverse Compton scattering(ICS) results in less efficient energy losses of high-energy electrons, which is expected to leave imprints on the propagated electron spectrum. It has been proposed that the hardening of CRE spectra around 50 GeV observed by Fermi-LAT, AMS-02, and DAMPE could be due to the KN effect. We show in this work that the transition from the Thomson regime to the KN regime of the ICS is actually quite smooth compared with the approximate treatment adopted in some previous works. As a result, the observed spectral hardening of CREs cannot be explained by the KN effect. It means that an additional hardening of the primary electrons spectrum is needed. We also provide a parameterized form for the accurate calculation of the ICS energy-loss rate in a wide energy range.     

Synthesis of a benzoxazine with precisely two phenolic OH linkages and the properties of its high‐performance copolymers

A phenolic OH‐containing benzoxazine ( F‐ap ), which cannot be directly synthesized from the condensation of bisphenol F, aminophenol, and formaldehyde by traditional procedures, has been successfully prepared in our alternative synthetic approach. F‐ap was prepared by three steps including (a) condensation of 4‐aminophenol and 5,5'‐methylenebis(2‐hydroxybenzaldehyde) (1) , (b) reduction of the resulting imine linkage by sodium borohydride, and (c) ring closure condensation by formaldehyde. The key starting material, (1) , was prepared from 2‐hydroxybenzaldehyde and s‐trioxane in the presence of sulfuric acid. F‐ap is structurally similar to bis(3,4‐dihydro‐2H‐3‐phenyl‐1,3‐benzoxazinyl)methane ( F‐a, a commercial benzoxazine based on bisphenol F/aniline/formaldehyde) except for two phenolic OHs. The phenolic OHs can provide reaction sites with epoxy and 1,1'‐(methylenedi‐p‐phenylene)bismaleimide (BMI). The structure–property relationships between the thermosets of F‐ap /epoxy, F‐a /epoxy, F‐ap /BMI, and F‐a /BMI were discussed. Experimental data showed that thermosets based on F‐ap /epoxy and F‐ap /BMI provided much better thermal properties than those based on F‐a /epoxy and F‐a /BMI. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2686–2694