Novel Zn（Ⅱ） ladder-like coordination polymer constructed from designed ferrocenyl ligand

Reaction of Zn（NO3）2·6H2O with 3-（4-carboxylphenylamino）-l-ferrocenyl-2-butylen-l-one （HL） and 4,4′-bipyfidine （4,4′- bipy） in methanol solution resulted in a novel ladder-like coordination polymer {[Zn2L2（μ2-L）2（4,4′-bipy）2]·MeOH}n （1）. Its crystal structure, thermal and electrochemical properties are presented.     

Asymmetric Synthesis of (R)-and (S)-Moprolol

A simple and effective procedure for the enantioselective synthesis of (R)-and (S)-moprolol was described.The key step was the asymmetric synthesis of enantiopure (R)-and (S)-guaifenesin,which were synthesized from enantioenriched (R)-3-chloro-1,2-propanediol and (S)-epichlorohydrin via kinetics of hydrolysis resolution of racemic epichlorohydrin by chiral Salen-CoIIII complex.The e.e.values of both the optical compounds were above 98%,and the chemical structures of the target compounds were confirmed by 1H NMR,13C NMR,IR,and MS.     

On the Reactivity of (−)‐(R)‐Carvone and (−)‐4aα,7α,7aβ‐Nepetalactone: Synthesis of New Heterocycles

The 1,3‐dipolar cycloaddition of 4‐chlorobenzonitrile oxide to the unsaturated system of (?)‐(R)‐carvone occurred exclusively at C(8) to give a new isoxazoline derivative. This derivative reacts with NH₂OH to yield a new heterocycle, observed for the first time. On the other hand, the addition of 4‐chlorobenzonitrile oxide to the unsaturated lactone (?)‐4aα,7α,7aβ‐nepetalactone gave, in a good yield, also a new heterocycle, again obtained for the first time. The terpenoid (?)‐(R)‐carvone and iridoid (?)‐4aα,7α,7aβ‐nepetalactone were isolated from Moroccan species Mentha viridis (L.) and Nepeta tuberosa (L.), respectively. The new heterocycles obtained were identified by combination of chromatographic and spectroscopic methods.     

Vibrational spectra and reinvestigation of the crystal structure of a polymeric copper(II)-orotate complex, [Cu(μ-HOr)(H2O)2]n: The performance of new DFT methods, M06 and M05-2X, in theoretical studies

The crystal and molecular structure of a polymeric Cu(II)-orotate complex, [Cu(μ-HOr)(H₂O)₂]_n, has been reinvestigated by single crystal X-ray diffraction. It is shown that several synergistic interactions: two axial Cu-O interactions; intramolecular and intermolecular hydrogen bonds; and π-π stacking between the uracil rings contribute to the stability of the crystal structure. The Raman and FT-IR spectra of the title complex are reported for the first time. Comprehensive theoretical studies have been performed by using three unrestricted DFT methods: B3LYP; and the recently developed M06, and M05-2X density functionals. Clear-cut assignments of all the bands in the vibrational spectra have been made on the basis of the calculated potential energy distribution, PED. The very strong Raman band at 1219 cm⁻¹ is diagnostic for the N1-deprotonation of the uracil ring and formation of the copper-nitrogen bond, in this complex. The Cu-O (carboxylate) stretching vibration is observed at 287 cm⁻¹ in the IR spectrum, while the Cu-N (U ring) stretching vibration is assigned to the strong Raman band at 263 cm⁻¹. The molecular structure and vibrational spectra (frequencies and intensities) calculated by the M06 functional method are very similar to the results obtained by the B3LYP method, but M06 performs better than B3LYP in calculations of the geometrical parameters and vibrational frequencies of the interligand O-H?O hydrogen bonding. Unfortunately, the M05-2X method seriously overestimates the strength of interligand hydrogen bond.     

Automated flow-based anion-exchange method for high-throughput isolation and real-time monitoring of RuBisCO in plant extracts

In this work, a miniaturized, completely enclosed multisyringe-flow system is proposed for high-throughput purification of RuBisCO from Triticum aestivum extracts. The automated method capitalizes on the uptake of the target protein at 4 °C onto Q-Sepharose Fast Flow strong anion-exchanger packed in a cylindrical microcolumn (105 × 4 mm) followed by a stepwise ionic-strength gradient elution (0-0.8 mol/L NaCl) to eliminate concomitant extract components and retrieve highly purified RuBisCO. The manifold is furnished downstream with a flow-through diode-array UV/vis spectrophotometer for real-time monitoring of the column effluent at the protein-specific wavelength of 280 nm to detect the elution of RuBisCO. Quantitation of RuBisCO and total soluble proteins in the eluate fractions were undertaken using polyacrylamide gel electrophoresis (PAGE) and the spectrophotometric Bradford assay, respectively. A comprehensive investigation of the effect of distinct concentration gradients on the isolation of RuBisCO and experimental conditions (namely, type of resin, column dimensions and mobile-phase flow rate) upon column capacity and analyte breakthrough was effected. The assembled set-up was aimed to critically ascertain the efficiency of preliminary batchwise pre-treatments of crude plant extracts (viz., polyethylenglycol (PEG) precipitation, ammonium sulphate precipitation and sucrose gradient centrifugation) in terms of RuBisCO purification and absolute recovery prior to automated anion-exchange column separation. Under the optimum physical and chemical conditions, the flow-through column system is able to admit crude plant extracts and gives rise to RuBisCO purification yields better than 75%, which might be increased up to 96 ± 9% with a prior PEG fractionation followed by sucrose gradient step.     

Alkyne‐Mediated Approach to the Synthesis of (4R,5R)‐5‐Hydroxy‐4‐decanolide and (−)‐Muricatacin

The asymmetric synthesis of two naturally occurring 5‐hydroxy‐γ‐butyrolactones, (4R,5R)‐5‐hydroxy‐4‐decanolide ( 1a ) and (?)‐muricatacin ( 2 ), is described using a general alkyne‐mediated strategy. The key steps involved are Sonogashira coupling for the desired carbon‐chain extension followed by Sharpless asymmetric dihydroxylation to construct the hydroxy‐lactone framework.     

三有机锡(4R)-3-[[(2S)-5-氧-2-吡咯烷基]羰基]-4-噻唑烷甲酸酯的合成、结构和体外抗癌活性

利用三有机锡氢氧化物和手性配体(4R)-3-[[(2S)-5-氧-2-吡咯烷基]羰基]-4-噻唑烷甲酸(HL)反应合成了3个三有机锡(4R)-3-[[(2S)-5-氧-2-吡咯烷基]羰基]-4-噻唑烷甲酸酯R3SnL[1,R=c-C6H11(a),C6H5(b),C6H5C(CH3)2CH2(c)],通过元素分析、IR、1H NMR和X-射线单晶衍射表征了其结构。化合物1a属正交晶系,P212121空间群;化合物1b属单斜晶系,P21空间群。二者均为由羧基氧和内酰胺羰基氧桥联配位形成的右螺旋链状有机锡配位聚合物,锡原子具有五配位[SnC3O2]畸变三角双锥构型。化合物1a和1b对体外2种人癌细胞Colo205和Bcap37增殖均有强的抑制作用,其活性为1b1a。     

PW_(11)O_(39)Co(Ⅱ)(H_2O)~(5-)的均相及异相体系可见光催化性能研究

以模型污染物罗丹明B(RhB)的光降解为探针,评估了Keggin型钴取代杂多阴离子PW11O39Co髤(H2O)5-(PW11Co)及其异相体系PW11Co/D301R的可见光催化活性,提出了光催化反应的机理,同时考察了催化剂用量、溶液酸度以及溶液中PW11Co和RhB的相互作用对RhB可见光催化降解速率的影响。实验结果表明,PW11Co均相体系及其异相体系PW11Co/D301R对RhB的可见光降解均有较高的光催化活性,但PW11Co/D301R的光催化活性更高。导致RhB降解的主要是羟基自由基。与PW11Co均相体系相比,在PW11Co/D301R异相体系中由于PW11Co与RhB的配位作用大为减弱,同时D301R对RhB具有富集作用,因而大大提高了RhB的光催化降解速率。     

含氟体系中DDR型分子筛的合成

DDR (Deca-dodecasil 3R) zeolite was synthesized hydrothermally in fluoride medium. The effects of synthesis conditions including the amount of KF, different fluoride sources and seeds on crystallization of DDR zeolite were investigated. The as-synthesized DDR zeolite samples were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The results demonstrated that DDR crystallization was strongly affected by n_KF/n_SiO2, fluoride sources and seeds. Pure DDR zeolite could be successfully obtained in n_KF/n_SiO2 range of 0.5～1 after 9 days of hydrothermal synthesis. The synthesis time was reduced to 1 day by adding small amount of seeds with yield approaching 100%.     

[H3tren] templated iron fluorides; synthesis, crystal structures and Mössbauer studies

The hydrothermal synthesis, using tris-(2-ethylamino)amine (tren) as a template, and the crystal structures of three new hybrid iron fluorides, (H₃O)₂·[H₃tren]₂·(FeF₆)₂·(FeF₅(H₂O))·2H₂O (I), [H₃tren]₂·(FeF₆)₂·(FeF₂(H₂O)₄)·8H₂O (II) and [H₃tren]₂·(FeF₆)·(F)₃·H₂O (III), are reported. I, II, and III are triclinic (P-1), monoclinic (P2₁/c) and orthorhombic (I222), respectively. The structure of I is built up from isolated FeF₆ and FeF₅(H₂O) distorted octahedra separated by triprotonated [H₃tren]³⁺ cations, disordered H₃O⁺ cations and H₂O molecules. In II, Fe^IIIF₆ and neutral [Fe^IIF₂(H₂O)₄] octahedra form, together with [H₃tren]³⁺ cations, infinite (100) layers separated by extra water molecules. The structure of III consists of isolated and disordered FeF₆ octahedra, fluoride anions F⁻ connected to [H₃tren]³⁺ cations and extra fluoride anions F⁻ disordered with H₂O molecules. All [H₃tren]³⁺ cations have a “spider” type conformation. ⁵⁷Fe Mössbauer characterization shows that +III valence state can only be considered for iron cations in I and III and preliminary Mössbauer results are consistent with the presence of both +II and +III valences for iron cations in II, in agreement with the crystallographic results.