氟阴离子在有机合成中的应用：Ⅱ.无水氟化钾催化乙酐与苯甲醛的Perkin反应

用无水醋酸盐催化苯甲醛与乙酐的Perkin反应,一般反应时间较长,产率最高为55—60％.用三乙胺、吡啶和无水碳酸钾等作催化剂,产率也无明显提高.近年来氟阴离子在有机合成中的应用迅速发展,我们曾用无水氟化钾催化成功地实施了丙二酸二乙酯与苯甲醛的Knoevenagel缩合,并研讨了该反应的微环境效应.本工作首次用无水氟     

The rate of convergence of q-Bernstein polynomials for

In the note, we obtain the estimates for the rate of convergence for a sequence of q-Bernstein polynomials {B_n,q(f)} for 0<q<1 by the modulus of continuity of f, and the estimates are sharp with respect to the order for Lipschitz continuous functions. We also get the exact orders of convergence for a family of functions , and the orders do not depend on α, unlike the classical case.     

捕捉和封存二氧化碳的化学原理及其应用前景

二氧化碳的捕捉与封存是实现温室气体减排的重要途径之一,也是未来实现低碳经济转型的重要环节,因此备受发达国家政府的重视和发展中国家的关注。介绍了“捕捉CO2”和“封存CO2”的化学反应原理和二氧化碳的捕捉和封存技术及其应用前景。     

Bioavailability Enhancement of Cepharanthine via Pulmonary Administration in Rats and Its Therapeutic Potential for Pulmonary Fibrosis Associated with COVID-19 Infection

Cepharanthine (CEP) has excellent anti-SARS-CoV-2 properties, indicating its favorable potential for COVID-19 treatment. However, its application is challenged by its poor dissolubility and oral bioavailability. The present study aimed to improve the bioavailability of CEP by optimizing its solubility and through a pulmonary delivery method, which improved its bioavailability by five times when compared to that through the oral delivery method (68.07% vs. 13.15%). An ultra-performance liquid chromatography tandem-mass spectrometry (UPLC-MS/MS) method for quantification of CEP in rat plasma was developed and validated to support the bioavailability and pharmacokinetic studies. In addition, pulmonary fibrosis was recognized as a sequela of COVID-19 infection, warranting further evaluation of the therapeutic potential of CEP on a rat lung fibrosis model. The antifibrotic effect was assessed by analysis of lung index and histopathological examination, detection of transforming growth factor (TGF)-β1, interleukin-6 (IL-6), α-smooth muscle actin (α-SMA), and hydroxyproline level in serum or lung tissues. Our data demonstrated that CEP could significantly alleviate bleomycin (BLM)-induced collagen accumulation and inflammation, thereby exerting protective effects against pulmonary fibrosis. Our results provide evidence supporting the hypothesis that pulmonary delivery CEP may be a promising therapy for pulmonary fibrosis associated with COVID-19 infection.     

Hydrogels formed by l-histidine derivatives with highly selective release for charged dyes

Hydrogels formed by UIPCA with CA could selectively release anionic dyes, chrome azurol S (A) and cationic dyes, methyl violet (B), showing excellent separating ability for differently charged dyes.     

Inhibition of [FeFe]-hydrogenase by formaldehyde: proposed mechanism and reactivity of FeFe alkyl complexes

The mechanism for inhibition of [FeFe]-hydrogenases by formaldehyde is examined with model complexes. Key findings: (i) CH₂ donated by formaldehyde covalently link Fe and the amine cofactor, blocking the active site and (ii) the resulting Fe-alkyl is a versatile electrophilic alkylating agent. Solutions of Fe₂[(μ-SCH₂)₂NH](CO)₄(PMe₃)₂ (1) react with a mixture of HBF₄ and CH₂O to give three isomers of [Fe₂[(μ-SCH₂)₂NCH₂](CO)₄(PMe₃)₂]⁺ ([2]⁺). X-ray crystallography verified the NCH₂Fe linkage to an octahedral Fe(ii) site. Although [2]⁺ is stereochemically rigid on the NMR timescale, spin-saturation transfer experiments implicate reversible dissociation of the Fe–CH₂ bond, allowing interchange of all three diastereoisomers. Using ¹³CH₂O, the methylenation begins with formation of [Fe₂[(μ-SCH₂)₂N¹³CH₂OH](CO)₄(PMe₃)₂]⁺. Protonation converts this hydroxymethyl derivative to [2]⁺, concomitant with ¹³C-labelling of all three methylene groups. The Fe–CH₂N bond in [2]⁺ is electrophilic: PPh₃, hydroxide, and hydride give, respectively, the phosphonium [Fe₂[(μ-SCH₂)₂NCH₂PPh₃](CO)₄(PMe₃)₂]⁺, 1, and the methylamine Fe₂[(μ-SCH₂)₂NCH₃](CO)₄(PMe₃)₂. The reaction of [Fe₂[(μ-SCH₂)₂NH](CN)₂(CO)₄]²⁻ with CH₂O/HBF₄ gave [Fe₂[(μ-SCH₂)₂NCH₂CN](CN)(CO)₅]⁻ ([4]⁻), the result of reductive elimination from [Fe₂[(μ-SCH₂)₂NCH₂](CN)₂(CO)₄]⁻. The phosphine derivative [Fe₂[(μ-SCH₂)₂NCH₂CN](CN)(CO)₄(PPh₃)]⁻ ([5]⁻) was characterized crystallographically.

The mechanism for inhibition of [FeFe]-hydrogenases by formaldehyde is examined with model complexes.     

Nonaqueous CE for Rapid and Sensitive Determination of Matrine and Oxymatrine in Sophora flavescens and Its Medicinal Preparations

A simple, rapid, and sensitive non-aqueous capillary electrophoresis procedure for the quantitative determination of matrine and oxymatrine is established. Optimum separation conditions were obtained when the sample was injected under pressure for 3 s at 50 mbar and separated with the buffer containing 70 mM ammonium acetate, 7.0% (v/v) acetic acid, and 10% (v/v) acetonitrile in methanol medium at 25 kV applied voltage. The analytes were detected at 205 nm. The two alkaloids can be separated within 12 min and quantified with high sensitivity. The method was validated in terms of reproducibility, linearity, and accuracy when applied to the analysis of matrine and oxymatrine in Sophora flavescens and its medicinal preparations.

     

New Class of Hydrido Iron(II) Compounds with cis‐Reactive Sites: Combination of Iron and Diphosphinodithio Ligand

The cationic complex [Fe(P₂S₂)(NCMe)₂]²⁺ (P₂S₂=(Ph₂PC₆H₄CH₂S)₂(C₂H₄) ([ 1 (NCMe)₂]²⁺)), with two MeCN ligands in a cis orientation, was synthesized and characterized. The MeCN ligand in [ 1 (NCMe)₂]²⁺ undergoes further substitution by a hydride ligand or CO to give iron(II) hydrides [H 1 (NCMe)]⁺, [H 1 H]⁰, and [H 1 (CO)]⁺. The order of reactivity of the hydrides was [H 1 H]⁰>[H 1 (NCMe)]⁺>[H 1 (CO)]⁺, and was illustrated by their reactions toward protic acids, the organic cation of 10‐methylacridinium (MeAcr⁺) as a hydride acceptor, and intermolecular hydride transfer reactions among these ferrous compounds. For example, MeAcr⁺ was reduced initially by a one‐electron transfer process from [H 1 H]⁰, resulting in competing reactions of MeAcr^. dimerization, hydrogen atom transfer from [H 1 H]⁺ to MeAcr^., and decomposition of [H 1 H]⁺. MeAcrH was produced in excellent yields through a single‐step H^? transfer from [H 1 (NCMe)]⁺ to MeAcr⁺, but [H 1 (CO)]⁺ was inactive toward MeAcr⁺.     

Multifunctional composite film based on biodegradable grape skin and polyvinyl alcohol

Cellulose - In winemaking, large amounts of grape skin (GS) are generated as by-products, which contain not only abundant degradable cellulose, hemicellulose, and pectin but various functional...