混合模式色谱分离材料的研究及其应用进展

近年来混合模式色谱以其独特的分离特性受到人们越来越多的关注。混合模式色谱的种类主要集中在反相/离子交换混合模式色谱(reversed-phase/ion-exchange mixed-mode chromatography, RPLC/IEX),亲水作用/离子交换混合模式色谱(hydrophilic interaction/ion-exchange mixed-mode chromatography, HILIC/IEX),反相/亲水作用混合模式色谱(reversed-phase/hydrophilic interaction mixed-mode chromatography, RPLC/HILIC)等混合模式。两种或多种机理混合使用,往往在分离选择性和色谱峰形等方面能得到不同于单一模式操作所得到的效果,分离选择性以及色谱峰形等都能得到极大的改善与提高,这使得混合模式色谱渐渐进入研究者们的视野。混合模式色谱的研究多数集中在色谱填料的设计。混合模式色谱填料的应用主要针对生物样品的分离分析。该文综述了近年来混合模式色谱的研究及其应用进展,并展望了混合模式色谱的发展。     

氨水介质和氟处理对铝柱层柱粘土性质的影响

 分别在氨介质和钠介质中制备了层柱蒙脱土和层柱累托石,并用氟化铵、氟硅酸铵和氟铝酸铵对层柱粘土进行处理,考察了处理条件对层柱粘土结构和酸性的影响. NH3-TPD和IR分析结果表明,氨介质中制备的层柱粘土比钠介质中制备的具有更强的酸性,经氟处理后层柱粘土的酸性有较大的提高. 氨介质中制备的层柱粘土的低钠含量是其酸性改善的主要原因,而氟处理对层柱粘土酸性的提高主要来自氟对铝柱的表面作用. 氟处理层柱粘土对异丙苯裂解具有很高的催化活性.     

钇铝石榴石对撞增强型相位共轭腔的研究

报道了一种新型的相位共轭腔——对撞型钇铝石榴石受激布里渊散射相位共轭激光腔,实验结果发现该腔具有较低的启动阈值和100mJ以上的输出能量,它能输出稳定的20ns左右的自调Q脉冲,发散角为1．3mrad。在一定范围内,抽运电压越高,输出脉宽越窄;相位共轭腔越长,输出脉宽越宽;聚焦透镜对输出脉宽也有影响,焦距越短,脉宽越窄;焦距与介质池相对长点,输出能量相对高,远场发散角相对小些。实验给出了不同条件下的输出能量、脉冲宽度和光束发散角的情况。     

多波长双向抽运光纤拉曼放大器的优化设计

通过合理分析提出了便于计算多波长双向抽运光纤拉曼放大器信号及噪声功率的实用数值模型,给出求解信号和噪声功率的快速算法。在定义抽运方向度为前向抽运功率与总抽运功率值的比值后,通过对计算结果的分析发现信道平均放大自发辐射噪声功率随着抽运方向度的提高而单调递减;而信道平均双重瑞利散射噪声功率相对抽运方向度的变化曲线始终成U字形。不同的增益下存在对应的最优抽运方向度,在此抽运方向度下放大器总噪声最低。进而考虑在信号非线性失真的条件下提出了抽运方向度优化的衡量指标。优化后的多波长双向抽运方式不仅能保证对所有信道的平坦放大,而且其综合性能明显高于后向抽运方式。     

Asymmetric Cyanation of Aldehydes,Ketones, Aldimines,and Ketimines Catalyzed by a Versatile Catalyst Generated from Cinchona Alkaloid,Achiral Substituted 2,2′‐Biphenol and Tetraisopropyl Titanate

Full investigation of cyanation of aldehydes, ketones, aldimines and ketimines with trimethylsilyl cyanide (TMSCN) or ethyl cyanoformate (CNCOOEt) as the cyanide source has been accomplished by employing an in situ generated catalyst from cinchona alkaloid, tetraisopropyl titanate [Ti(OiPr)₄] and an achiral modified biphenol. With TMSCN as the cyanide source, good to excellent results have been achieved for the Strecker reaction of N‐Ts (Ts=p‐toluenesulfonyl) aldimines and ketimines (up to >99 % yield and >99 % ee) as well as for the cyanation of ketones (up to 99 % yield and 98 % ee). By using CNCOOEt as the alternative cyanide source, cyanation of aldehyde was accomplished and various enantioenriched cyanohydrin carbonates were prepared in up to 99 % yield and 96 % ee. Noteworthy, CNCOOEt was successfully employed for the first time in the asymmetric Strecker reaction of aldimines and ketimines, affording various α‐amino nitriles with excellent yields and ee values (up to >99 % yield and >99 % ee). The merits of current protocol involved facile availability of ligand components, operational simplicity and mild reaction conditions, which made it convenient to prepare synthetically important chiral cyanohydrins and α‐amino nitriles. Furthermore, control experiments and NMR analyses were performed to shed light on the catalyst structure. It is indicated that all the hydroxyl groups in cinchona alkaloid and biphenol complex with Ti^IV, forming the catalyst with the structure of (biphenoxide)Ti(OR*)(OiPr). The absolute configuration adopted by biphenol 4 m in the catalyst was identified as S configuration according to the evidence from control experiments and NMR analyses. Moreover, the roles of the protonic additive (iPrOH) and the tertiary amine in the cinchona alkaloid were studied in detail, and the real cyanide reagent in the catalytic cycle was found to be hydrogen cyanide (HCN). Finally, two plausible catalytic cycles were proposed to elucidate the reaction mechanisms.     

含有NH2CH2CH2CH2NH2和o-C6H4(NH2)2配体的镍配合物的合成、结构和它们在乙烯聚合中的作用

两种镍的配合物[Ni(NH2CH2CH2CH2NH2)3]Cl2 (1)和[Ni(C6H4N2H4)2Cl2] (2)已经被合成并且通过红外和单晶X射线衍射分析对其进行了表征。在配合物1中,镍原子处于手性假八面体[NiN6]的几何构型中,它与三个1,3-丙二胺分子形成了三个六元环。在配合物2中,镍原子除了与两个o-苯二胺分子通过四个Ni-N键形成两个五元环外,它还与两个Cl原子配位形成了反式Ni-Cl2,这不同于以往报道过的镍的二胺配合物。这两个镍的配合物被MAO, MMAO或Et2AlCl活化后,对乙烯的二聚合或三聚合显示了很好的催化活性[对于配合物2,催化活性达到3.59×106 g mol-1 (Ni) h-1]。     

Pd-Mn/Stainless Steel Wire Mesh Catalyst for Catalytic Oxidation of Toluene,Acetone and Ethyl Acetate

A new 0.1%Pd‐6%Mn/stainless steel wire mesh catalyst was prepared and used for volatile organic compounds (VOC) elimination. The supported palladium and manganese catalyst over the stainless steel wire mesh was prepared by using an impregnation method. When an anodic oxidation technology was employed, an anodic oxidation membrane appeared on the stainless steel wire mesh. On the 0.1%Pd‐6%Mn/stainless steel wire mesh catalyst calcined at 500°C, the total oxidation of toluene, acetone and ethyl acetate was respectively at 260, 220 and 320°C. The activity could be stable for over 700 h for toluene oxidation. The scanning electron microscopy (SEM) investigation of the Pd‐Mn/stainless steel wire mesh catalyst shows that the presence of anodic oxidation membrane on the support surface is important for better dispersion of active phases.     

Removal of Naphthol Green B from Aqueous Solution by Calcined Layered Double Hydroxides:Adsorption Property and Mechanism Studies

The adsorption of naphthol green B (NGB) by Mg/Al‐LDO (layered double oxides) with a Mg/Al molar ratio of 3:1 was investigated in a batch mode. Our study indicates that the maximum capacity of NGB adsorption at equilibrium is 193.4 mg and the percentage of absorption is 96.7%, with an adsorbent dose of 1.0 g/L under the following condition: 200 mg/L NGB concentration, temperature 298 K, pH 10.0 and an equilibrium time of 80 min. Langmuir and Freundlich adsorption models were used for fitting the isotherms, and the thermodynamic parameters have been calculated, which showed that the adsorption process was spontaneous and exothermic in nature. In the light of so called "memory effect", the Mg/Al‐LDO was found to recover their original layered structure after adsorption, and part of NGB ions intercalated into the interlayer of LDH (layered double hydroxides), which has been supported by XRD and FTIR. In addition, the competitive anions for adsorption and the regeneration of Mg/Al‐LDO have also been investigated.     

A neutral polysaccharide from <Emphasis Type="Italic">Glycyrrhiza inflata</Emphasis>

A neutral polysaccharide Gi-A1 was isolated from the roots of Glycyrrhiza inflata Bat. It had a molecular mass of over 2000 kDa and showed [α]_D²⁰ + 81.4° (c 1.05, H₂O). Acid hydrolysis and methylation analysis indicated that Gi-A1 was mainly composed of α-D-glucose, α-L-arabinose, and α-D-galactose with a molar ratio of 8.0:1.8:1.0. It can significantly stimulate spleen cell proliferation in vitro (P < 0.01). Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 13–14, January–February, 2009.     

生物质热解油品位催化提升的思考和初步进展

生物质热解油是一种由几百种含氧有机物组成的混合物,需经过提质才能直接用作车用燃料.多数研究者以降低生物油的含氧量作为提质的目标,作者提出了一个完全不同的思路,以转化得到的稳定而易燃的含氧有机物为生物油提质的目标.实验表明,催化提质后生物粗油中不稳定的、腐蚀性的组分(如醛、酸、酚类等物质)大为减少,而相对稳定的、腐蚀性较低的组分(如酯、醇、酮类等物质)明显增加.本文小结了作者所在的研究团队在生物质热解油品位提升方面的近期研究进展.