Liquid chromatography–high-resolution mass spectrometry for identifying aqueous chlordecone hydrate dechlorinated transformation products formed by reaction with zero-valent iron

Chlordecone (CLD) is a persistent toxic chlorinated pesticide which contaminates different ecosystems in French West Indies. A soil remediation process including zero-valent iron (ZVI) has produced promising results but failed to completely degrade CLD, and the analytical procedures used yielded little information on the transformation products. To fill these gaps, dechlorination of aqueous CLD by micrometric particles of ZVI has been investigated. Aliquots of water with 25% (v/v) of acetone spiked with 100 ppm CLD were taken at different times during a 30-day ZVI treatment and directly analysed by ultra-high-performance liquid chromatography in negative electrospray ionisation mode. CLD has been totally transformed after 14 days into 14 dechlorinated degradation products, including 9 isomeric compounds. The maximum chloride concentrations appearing in the medium represent 44% of that which would result from total dechlorination of CLD. The CLD transformation products identified by accurate mass measurements on an ultra-high-resolution Q-TOF mass spectrometer (Q-TOF-MS) were C₁₀H₃Cl₉O₂, C₁₀H₄Cl₈O₂, C₁₀H₅Cl₇O₂, C₁₀H₆Cl₆O₂ and C₁₀H₇Cl₅O₂. The results show the interest of LC-Q-TOF-MS for identifying transformation products of organic contaminants, and the effectiveness of micrometric ZVI particles to totally transform CLD into less chlorinated products.     

温和条件下金属双氮杂环卡宾配合物催化CO2直接转化为炔酸的高效均相羧化反应

近年来,催化CO2合成精细化学品的研究备受关注。本研究在温和条件下利用金属双氮杂环卡宾催化剂实现CO2与末端炔烃的直接羧化反应,并提出合理的催化机理。首先,合成制备了铜基、银基两种金属双氮杂环卡宾催化剂,实验证明银双氮杂环卡宾配合物具有较好催化活性。通过改变环境条件和底物种类,对反应条件及催化剂底物适应性进行了探究,利用核磁共振谱仪表征产物分子结构并计算直接羧化反应的催化产率。结果表明,适宜催化条件为:1.2eq Cs2CO3作为添加剂、1大气压、室温、无水溶剂和1(mmol)%催化剂用量。银基金属催化剂活性较铜基催化剂高并具有广泛的底物适应性,对苯乙炔的催化产率高达93%;对乙炔气体同样具有良好的催化活性。此类催化剂具有优良的催化活性,能催化合成丙炔酸等重要医药中间体,在工业应用上具有极大潜力和广阔前景。     

Comb Poly(Oligo(2‐Ethyl‐2‐Oxazoline)Methacrylate)‐Peptide Conjugates Prepared by Aqueous Cu(0)‐Mediated Polymerization and Reductive Amination

The controlled synthesis of poly(oligo(2‐ethyl‐2‐oxazoline)methacrylate) (P(OEtOxMA)) polymers by Cu(0)‐mediated polymerization in water/methanol mixtures is reported. Utilizing an acetal protected aldehyde initiator for the polymerization, well‐defined polymers are synthesized (>99% conversion, Ð < 1.25) with subsequent postpolymerization deprotection resulting in α‐aldehyde end group containing comb polymers. These P(OEtOxMA) are subsequently site‐specifically conjugated, via reductive amination, to a dipeptide (NH₂‐Gly‐Tyr‐COOH) as a model peptide, prior to conjugation to the functional peptide oxytocin. The resulting oxytocin conjugates are evaluated in comparison to poly(oligo(ethylene glycol) methyl ether methacrylate) combs synthesized in the same manner for potential effects on thermal stability in comparison to the native peptide.

     

Regioselective para‐Carboxylation of Catechols with a Prenylated Flavin Dependent Decarboxylase

The utilization of CO₂ as a carbon source for organic synthesis meets the urgent demand for more sustainability in the production of chemicals. Herein, we report on the enzyme‐catalyzed para ‐carboxylation of catechols, employing 3,4‐dihydroxybenzoic acid decarboxylases (AroY) that belong to the UbiD enzyme family. Crystal structures and accompanying solution data confirmed that AroY utilizes the recently discovered prenylated FMN (prFMN) cofactor, and requires oxidative maturation to form the catalytically competent prFMN^iminium species. This study reports on the in vitro reconstitution and activation of a prFMN‐dependent enzyme that is capable of directly carboxylating aromatic catechol substrates under ambient conditions. A reaction mechanism for the reversible decarboxylation involving an intermediate with a single covalent bond between a quinoid adduct and cofactor is proposed, which is distinct from the mechanism of prFMN‐associated 1,3‐dipolar cycloadditions in related enzymes.     

On separating a fixed point from zero by invariants

Assume a fixed point v∈V^G can be separated from zero by a homogeneous invariant f∈𝕜[V]^G of degree p^rd, where p>0 is the characteristic of the ground field 𝕜 and p,d are coprime. We show that then v can also be separated from zero by an invariant of degree p^r, which we obtain explicitly from f. It follows that the minimal degree of a homogeneous invariant separating v from zero is a p-power.     

梁中非线性弯曲波传播特性的研究

研究了梁中的非线性弯曲波的传播特性，同时考虑了梁的大挠度引起的几何非线性效应和 梁的转动惯性导致的弥散效应，利用Hamilton变分法建立了梁中非线性弯曲波的波动方程. 对该方程进行了定性分析，在不同的条件下，该方程在相平面上存在同宿轨道或异宿轨道， 分别对应于方程的孤波解或冲击波解. 利用Jacobi椭圆函数展开法，对该非线性方程进行 求解，得到了非线性波动方程的准确周期解及相对应的孤波解和冲击波解，讨论了这些解存 在的必要条件，这与定性分析的结果完全相同. 利用约化摄动法从非线性弯曲波动方程中导 出了非线性Schr\"{o}dinger方程，从理论上证明了考虑梁的大挠度和转动惯性时梁中存在 包络孤立波.     

Moufang sets of mixed type F4

Moufang sets were introduced by Jacques Tits in order to understand isotropic linear algebraic groups of relative rank one, but the notion is more general. We describe a new class of Moufang sets, arising from so‐called mixed groups of type ${\mathsf{F}}_4$ in characteristic 2, obtained as the fixed point set under a suitable involution.     

新的滇桂艾纳香寡糖BROS结构分析

以滇桂艾纳香枝叶为原料,经陶瓷膜、有机膜分离,醇沉、Sevag法除蛋白,DEAE-纤维素柱层析和SephadexG- 10,SephadexG-50凝胶柱色谱纯化得到的BROS;经HPGPC检测分析表明,BROS为均一寡糖,MALDI-TOF-MS测定分子量为1314.用IR,HPLC,甲基化分析,GC-MS,NMR (1H NMR,13C NMR,1H)HCOSY,HMQC和HMBC)等方法对BROS结构进行表征,结果表明,该寡糖由1个葡萄糖(α-D-Glcp)和7个果糖(β-D-Fru组成,残基间以→2)Fruf-(1→链接,分子末端链接为a-Glcp-(1→,→2)-β-D-Fruf推出BROS的结构式为:β-D-Fruf1-(2→1)-β-D-Fruf2-(2→1)-β-D-Fruf3-(2→ 1)-β-D-Fruf4-(2→1)-β -D-Fruf5-(2→1)-β-D-Fruf6-(2→ 1)-β-D-Fruf7-(2→ 1)-a-D-Glcp.     

Observation and mechanistic study of facile C-O bond formation between a well-defined aryl-copper(III) complex and oxygen nucleophiles

A well-defined macrocyclic aryl–Cu(III) complex (2) reacts readily with a variety of oxygen nucleophiles, including carboxylic acids, phenols and alcohols, under mild conditions to form the corresponding aryl esters, biaryl ethers and alkyl aryl ethers. The relationship between these reactions and catalytic C-O coupling methods is demonstrated by the reaction of the macrocyclic aryl–Br species with acetic acid and p-fluorophenol in the presence of 10 mol% Cu(I). An aryl-Cu(III)-Br species 2(Br) was observed as an intermediate in the catalytic reaction. Investigation of the stoichiometric C-O bond-forming reactions revealed nucleophile-dependent changes in the mechanism. The reaction of 2 with carboxylic acids revealed a positive correlation between the log(k(obs)) and the pK(a) of the nucleophile (less-acidic nucleophiles react more rapidly), whereas a negative correlation was observed with most phenols (more-acidic phenols react more rapidly). The latter trend resembles previous observations with nitrogen nucleophiles. With carboxylic acids and acidic phenols, UV-visible spectroscopic data support the formation of a ground-state adduct between 2 and the oxygen nucleophile. Collectively, kinetic and spectroscopic data support a unified mechanism for aryl-O coupling from the Cu(III) complex, consisting of nucleophile coordination to the Cu(III) center, deprotonation of the coordinated nucleophile, and C-O (or C-N) reductive elimination from Cu(III).