Multilayer poly(vinyl alcohol)-adsorbed coating on poly(dimethylsiloxane) microfluidic chips for biopolymer separation

A poly(dimethylsiloxane) (PDMS) microfluidic chip surface was modified by multilayer-adsorbed and heat-immobilized poly(vinyl alcohol) (PVA) after oxygen plasma treatment. The reflection absorption infrared spectrum (RAIRS) showed that 88% hydrolyzed PVA adsorbed more strongly than 100% hydrolyzed one on the oxygen plasma-pretreated PDMS surface, and they all had little adsorption on original PDMS surface. Repeating the coating procedure three times was found to produce the most robust and effective coating. PVA coating converted the original PDMS surface from a hydrophobic one into a hydrophilic surface, and suppressed electroosmotic flow (EOF) in the range of pH 3-11. More than 1,000,000 plates/m and baseline resolution were obtained for separation of fluorescently labeled basic proteins (lysozyme, ribonuclease B). Fluorescently labeled acidic proteins (bovine serum albumin, beta-lactoglobulin) and fragments of dsDNA phiX174 RF/HaeIII were also separated satisfactorily in the three-layer 88% PVA-coated PDMS microchip. Good separation of basic proteins was obtained for about 70 consecutive runs.     

A Density Functional Theory Study on Electronic Structure and Second—order Nonlinear Optical Properties of Some Push—Pull Molecules

Time-dependent density-functional theory(TDDFT)has been applied to calculate the electronic structure and second-order nonlinear optical(NLO) properties of some organic molecules.The two-dimensional(2-D)charge transfer charateristics of calculated molecules were studied and compared with corresponding experimental results.All the theoretical results agree well with the measurement.For 2-D molecule with two-fold symmetry,the dominant charge transfer is off-diagonal,while for three-fold symmetry 2-D molecule,the dominant charge transfer is not only between branches and central group but also among branches.     

MCM-41分子筛负载钼钴系催化剂的噻吩HDS研究

通过氧吸附量、噻吩吸附热及反应速率常数的测定，研究了MoO3/MCM-41、MoO3-CoO(NiO)/MCM-41系列催化剂，发现，对于MoO3/MCM-41催化剂，当MoO3的质量分数（以MCM－41为底数，即MCM－41＝1g时，MoO3含量为0．15g，下同）从15％增加到20％时，其噻吩的加氢硫（HDS）活性增大，至25％时活性下降，所对应的氧吸附量（mL/g催化剂）也是先增大后减少，并且两者有很好的线性对应关系，而且噻吩吸附热则基本保持不变，采用不同的MoO3-CoO(NiO)浸渍顺序制备的MoO3-CoO(NiO)/MCM-41催化剂中，先浸渍CoO(NiO）再浸渍MoO3的催化剂，其噻吩HDS活性明显优于对其它浸渍顺序制备的催化剂，同时催化剂的氧吸附量和噻吩吸附热也最大。     

旋流煤粉燃烧的一维综合数值模拟

发展了综合考虑气－固两相旋流流动，气相燃烧，颗粒相变与燃烧及两相辐射传热的旋流煤粉燃烧－维数学模型，给出了气－固两相能量方程中颗粒相就源项的计算表达式，应用这一模型对涡旋燃烧炉环形通道内多组工况的旋流气体燃烧和煤粉燃烧进行了数值模拟，计算得到的炉内温度分布和燃烧效率与实验数据基本相符，表明本文建立的模型可用于旋流煤粉燃烧的一维综合数值模拟。     

负载型双噁唑啉催化剂上的不对称Diels-Alder反应

 分别以乙烷桥键磺酸官能化的有机-无机杂化介孔材料、十二钨磷酸铯、活化硅胶以及SBA-15为载体,通过非共价键作用制备了负载型双噁唑啉催化剂,并将该催化剂用于催化3-((E)-2-丁烯酰基)-1,3-噁唑啉-2-酮和环戊二烯的不对称Diels-Alder反应. 研究表明,催化剂的性能取决于载体本身以及载体表面阴离子的性质. 以SBA-15为载体时产物的对映体选择性较低,可归因于载体表面较低的羟基浓度.     

Construction of a Novel 2D Polymer [Co（dmpzm）（dca）2]∞ from Reaction of a Mononuclear Complex [Co（dmpzm）Cl2] with Sodium Dicyanamide （dca） [dmpzm=bis（3,5-dimethylpyrazolyl）methane]

Reaction of COC12.6H20 with equimolar bis（3,5-dimethylpyrazolyl）methane （dmpzm） produced a mononuclear adduct [Co（dmpzm）Cl2] （1）. Treatment of 1 with sodium dicyanamide （dca） afforded a polymeric complex [Co（dmpzm）（μ-dca）2]∞ （2）. 1 and 2 were characterized by elemental analysis, IR spectra, thermogravimetric analysis and single-crystal X-ray diffraction. The cobalt atom in 1 adopts a distorted tetrahedral coordination geometry, bound to two N atoms of one dmpzm and two Cl atoms. Complex 2 has a 2D brick-wall network （extended along the bc plane） in which the { [Co（dmpzm）（μ-dca）]2} n^2n＋ chains are interconnected by pairs of μ-dca anions along the c axis. The magnetic properties of 1 and 2 were also investigated.     

[{Cu(phen)2}(μ‐malato){Cu(phen)(NO3)}](NO3)·4H2O: malate acting as a tetra­dentate and dibridging ligand in a dinuclear copper complex

The crystal structure of the title compound, μ‐2‐hydroxy­butane­dioato‐1κ²O⁴,O^4′:2κ³O¹,O²,O⁴‐nitrato‐2κO‐tris­(1,10‐phen­anthroline)‐1κ⁴N,N′;2κ²N,N′‐dicopper(II) nitrate tetra­hydrate, [Cu₂(C₄H₃O₅)(NO₃)(C₁₂H₈N₂)₃](NO₃)·4H₂O, contains an unsymmetrical dinuclear copper complex with Cu(phen)₂ and Cu(phen)(NO₃) moieties (phen is 1,10‐phenanthroline) bridged by a malate (2‐hydroxy­butane­dioate) ligand, which acts as a double‐bridging and tetra­dentate ligand. As a result of this double‐bridging action, especially the direct coordination of the O atom of one carboxyl­ate group of malate to the two Cu atoms, the Cu⋯Cu distance is only 4.199 (1) Å and the two phen planes are roughly parallel [the shortest inter­planar distance is 3.28 (1) Å], exhibiting an obvious intra­molecular π–π stacking inter­action.     

超临界反应条件下Y型分子筛催化剂失活的研究

对苯烷基化过程中Ｙ型分子筛催化剂的失活进行了多方面的实验研究。结果表明，超临界条件下该催化剂的活性寿命比液相条件下长达四倍以上，借助色－质谱联用机分析两种操作的反应产物，发现含有多环物质，并且它们的种类和数量随条件而不同。根据热力学原理，建立了多环物在超蚧流体中的溶解模型，并以并四苯，并五苯和并六苯作为焦前物模拟物进行了计算。     

Direct Synthesis, Crystal Structure and Thermal Kinetics of Supramolecular Complex [Co（H2O）6]·（Hnip）2·（H2nip）2·（DMA）2·（H2O）8 （nip=5-nitroisophthalate, DMA=CH3NHCH3）

The crystal of [Co（H2O）6]·（Hnip）2·（H2nip）2·（OMA）2·（H2O）8 has been cultured using direct method and characterized by X-ray single crystal diffractometry, elemental analysis and FTIR spectroscopy. It crystallizes in triclinic system, P-1 space group with the cell parameters of a=0.7012（1） nm, b=1.1378（2） nm, c=1.6612（3） nm, α= 84.92（3）°, β=85.19（3）°, γ=85.91（3）°, V= 1.3128（5） nm^3, Z=1, Dc= 1.573 g·cm^-3. Final R indices [1〉2σ（I）] are： R1 =0.0279, wR2=0.0765 while R indices for all data are： R1 =0.0327, wR2=0.0806. The Co coordination octahadra are each surrounded by two Hnip, two H2nip, two DMA and eight water molecules that are linked by hydrogen bonds and π-π stacking interactions. Thermal analyses of DSC and TG-DTG have been performed on the complex to predict its thermal decomposition mechanism and determine the most probable kinetic model function using Kissinger, Ozawa, integral and differential methods.     

A novel three‐dimensional cadmium(II) coordination polymer incorporating 1,4‐bis­(1,2,4‐triazol‐1‐ylmethyl)­benzene and thio­cyanate

In the title complex, poly[cadmium(II)‐μ₂‐1,4‐bis­(1,2,4‐triazol‐1‐ylmeth­yl)benzene‐di‐μ₂‐thio­cyanato], [Cd(NCS)₂(C₁₂H₁₂N₆)]_n, the Cd^II atom lies on an inversion centre in a distorted octa­hedral environment. Four N atoms from the thio­cyanate and 1,4‐bis­(1,2,4‐triazol‐1‐ylmeth­yl)benzene (bbtz) ligands occupy the equatorial positions, and two S atoms from symmetry‐related thio­cyanate ligands occupy the axial positions. The benzene ring of the bbtz ligand lies about an inversion centre. Single thio­cyanate bridges link the Cd^II atoms into two‐dimensional sheets containing novel 16‐membered [Cd₄(μ‐NCS‐N:S)₄] rings. The bbtz ligands further link these two‐dimensional sheets into an unprecedented covalent three‐dimensional network for the cadmium–thio­cyanate system.