核壳结构三元含氟丙烯酸酯乳液的制备及表征

以甲基丙烯酸三氟乙酯(Actyflon-G03)、丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)为原料,采用质量比为 1/1 的 OP-10/SDS 复合乳化荆,利用种子乳液聚合法,合成了核壳结构共聚物乳液.研究了温度对聚合反应、氟单体含量对聚合物膜吸水性及硬度的影响,采用 DSC、SEM-EDX、TEM 表征了共聚物膜的性能及乳胶粒子特征.结果表明:当 Actyflon-G03 含量为 23.28%时,核壳型结构粒子呈球形分布,粒径约为 80～110 nm,膜吸水率最低,硬度最高,并有 75.85%的最大转化率和 0.58%的最低凝胶率.SEM-EDX 分析显示,氟原子在成膜过程中向膜表面迁移,降低了膜的表面能.     

蝎型钒氧配合物的合成、结构及量子化学研究

设计合成了两种新型的以聚类吡唑硼酸盐为配体的钒氧配合物VO(acac)[HB(pz)3](1)和VO(acac)[HB(3,5-Me2pz)3]·CH3CN(2). 运用元素分析、 红外光谱和紫外光谱对所合成的配合物进行了表征, 并用X射线衍射测定了它们的晶体结构. 同时, 采用量子化学的Hartree Fock方法和自然轨道分析方法(NBO), 使用3-21G*(6d, 7f)基组计算得到了两个分子体系的分子轨道、原子电荷以及键级, 并对其结构进行了分析.     

PbI4Cu2(PPh3)4: A heterometallic iodide with unusual cis-divacant octahedral coordination sphere for lead: Synthesis, structure, red-infrared fluorescence and theoretical studies

A new heterometallic iodide, PbI₄Cu₂(PPh₃)₄, was synthesized by reactions of PbI₂, CuI and triphenylphosphine (PPh₃) in DMF solution. The single-crystal X-ray diffraction analyses show that Pb(II) center adopts an unusual cis-divacant octahedral geometry. Crystal data: triclinic, space group , , , , α=106.623(4)°, β=103.478(6)°, γ=93.574(5)°, and Z=2. Density function theory (DFT) calculations and fragment orbital interaction analyses reveal the presence of a three-center four-electron (3c-4e) hypervalent bonding about lead; and the formation of the unusual cis-divacant [PbI₄]²⁻ octahedron is energetically favorable. The title yellow compound has an optical bandgap of 2.69 eV and shows remarkable red-infrared fluorescence emission at 732 nm with lifetime of 24 μs which is assigned as an iodine 5p-lead 6s to PPh₃-lead 6p charge transfer (XM-LM-CT).     

Syntheses, structures, and vibrational spectroscopy of the two-dimensional iodates Ln(IO3)3 and Ln(IO3)3(H2O) (LnYb, Lu)

The reaction of Lu³⁺ or Yb³⁺ and H₅IO₆ in aqueous media at 180 °C leads to the formation of Yb(IO₃)₃(H₂O) or Lu(IO₃)₃(H₂O), respectively, while the reaction of Yb metal with H₅IO₆ under similar reaction conditions gives rise to the anhydrous iodate, Yb(IO₃)₃. Under supercritical conditions Lu³⁺ reacts with HIO₃ and KIO₄ to yield the isostructural Lu(IO₃)₃. The structures have been determined by single-crystal X-ray diffraction. Crystallographic data are (MoKα, λ=0.71073 Å): Yb(IO₃)₃, monoclinic, space group P2₁/n, a=8.6664(9) Å, b=5.9904(6) Å, c=14.8826(15) Å, β=96.931(2)°, V=766.99(13), Z=4, R(F)=4.23% for 114 parameters with 1880 reflections with I>2σ(I); Lu(IO₃)₃, monoclinic, space group P2₁/n, a=8.6410(9), b=5.9961(6), c=14.8782(16) Å, β=97.028(2)°, V=765.08(14), Z=4, R(F)=2.65% for 119 parameters with 1756 reflections with I>2σ(I); Yb(IO₃)₃(H₂O), monoclinic, space group C2/c, a=27.2476(15), b=5.6296(3), c=12.0157(7) Å, β=98.636(1)°, V=1822.2(2), Z=8, R(F)=1.51% for 128 parameters with 2250 reflections with I>2σ(I); Lu(IO₃)₃(H₂O), monoclinic, space group C2/c, a=27.258(4), b=5.6251(7), c=12.0006(16) Å, β=98.704(2)°, V=1818.8(4), Z=8, R(F)=1.98% for 128 parameters with 2242 reflections with I>2σ(I). The f elements in all of the compounds are found in seven-coordinate environments and bridged with monodentate, bidentate, or tridentate iodate anions. Both Lu(IO₃)₃(H₂O) and Yb(IO₃)₃(H₂O) display distinctively different vibrational profiles from their respective anhydrous analogs. Hence, the Raman profile can be used as a complementary diagnostic tool to discern the different structural motifs of the compounds.     

Immunoassay of P-glycoprotein on single cell by capillary electrophoresis with laser induced fluorescence detection

The cellular mechanism based on P-glycoprotein (PGP) for its drug pump function has become very important in multidrug resistance (MDR) research. A method has been established to characterize PGP on single K562 cell by coupling capillary electrophoresis with laser induced fluorescence detection. A permeable intact cell after the immunoassay binding with fluorescence labeling antibody was injected into the capillary and directly separated without lysis. It was found that once 5-10 optional cells were detected in batch, the PGP amount on this cell line could be outlined and calculated clearly. The PGP amount on K562 MDR cell line is 3.88 times higher than that on K562 sensitive cell line. These two cell lines with immunoassay binding were also analyzed by injection of multi-cells in order to improve the throughput. A resistance factor so called multidrug resistance multiple (MRM) was introduced to evaluate the MDR difference between cell lines. The MRM values of the cell line K562 measured by single cell analysis are well correlated with those by flow cytometry, which also prove the validity of our method in single cell analysis for the possibility of cancer diagnosis, pharmacokinetics and drug screening in future.     

Homo- and copolymerizaton of norbornene and norbornene derivative with Ni- and Pd-based β-ketoiminato complexes and MAO

Neutral nickel(II) and palladium(II) complexes bearing β-ketoiminato ligand have been synthesized. The two complexes have been investigated as catalyst for the polymerization. Using methylaluminoxane (MAO) as a cocatalyst, both complexes produce vinyl-addition polynorbornenes, but palladium(II) complex displays much higher activity up to 8.0 × 10⁷ g/(molPd h). Furthermore, both Ni(II) and Pd(II)/MAO system can efficiently copolymerize norbornene and 5-norbornene-2-yl acetate (NB-OCOMe) in moderate yields and in relatively high molecular weights. The analyses of the product by FTIR, ¹H NMR and ¹³C NMR spectra give the verification of vinyl addition copolymer. The copolymers show narrow molecular weight distribution and good solubility in common organic solvents.     

Preparation and characterization of nitrogen-doped TiO2 photocatalyst in different acid environments

Nitrogen-doped TiO₂ powders were successfully prepared by a wet method, i.e., a micro-emulsion-hydrothermal method, in different acid environments. Several characterization techniques, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and UV-visible diffuse reflectance spectra, were combined to determine the crystal phase, concentration and chemical states of the nitrogen doped in TiO₂. The high photocatalytic activity of the nitrogen-doped TiO₂ was evaluated through the decomposition of rhodanmine B under visible light irradiation. It was suggested that the doped nitrogen formed oxynitride (NO) and produced impurity states at higher above the valence band of TiO₂. Therefore, the nitrogen doping could enhance the response of photocatalyst to the visible light and improve the photocatalytic activity because of the narrowing of band gap of TiO₂.     

Synthesis and Crystal Structure of a Coordination Polymer {[Co(phth)(phen)(H2O)]·(C2H5OH)}n

The coordination polymer {[Co(phth)(phen)(H2O)]·(C2H5OH)}n (phth = phthalate, phen = 1,10-phenanthroline) with formula C22H20CoN2O6 (Mr = 467.33) was synthesized by the solvothermal method under low temperature, and its crystal structure was determined by singlecrystal X-ray diffraction. The complex belongs to monoclinic system, space group P21/n with a =12.7352(16), b = 8.8125(11), c = 18.677(2) (A), β = 102.633(2)°, V = 2045.3(4) (A)3, Z = 4, Dc =1.518 g/cm3,μ = 0.882 mm-1, F(000) = 964, S = 1.053, the final R = 0.0401 and wR = 0.0984 for 3135 observed reflections (I ＞ 2σ(I)). Single-crystal X-ray analysis revealed that the Co(Ⅱ) ion is six-coordinated. The cobalt complex forms a one-dimensional chain structure via phthalate bridging ligand. In the cobalt complex, a 3D network structure is formed by π-π stacking interaction of 1,10-phenanthroline as well as intermolecular hydrogen bonding interactions.     

碳酸二甲酯法合成1，5-二氨基甲酸甲酯的反应机理

应用红外光谱技术研究了在乙酸锌催化作用下1，5-萘二胺与碳酸二甲酯甲氧基羰基化反应机理．结果表明，二水合乙酸锌只有失去两个结晶水变成无水乙酸锌后才能产生催化活性．无水乙酸锌与1，5-萘二胺形成一个新的配位络合物，该配位络合物是一个适宜的亲核试剂，能与碳酸二甲酯进行亲核反应，生成1，5-萘二胺的甲氧基羰基化产物．在无水乙酸锌与1，5-萘二胺形成配位络合物的过程中，无水乙酸锌的结构从双齿型转变成单齿型．