磺化酞菁与人血清白蛋白复合物的光动力活性研究

通过光谱法研究了三种磺化酞菁(α位四磺化酞菁、β位四磺化酞菁和α位单取代磺化酞菁)与人血清白蛋白(HSA)的相互作用.结果 表明,HSA对α位四磺化酞菁的存在状态(单体、聚集体)影响显著,而对β位四磺化酞菁和α位单取代磺化酞菁的存在状态没有明显影响.磺化酞菁与HSA均存在明显的相互作用,且.四磺化酞菁与HSA的结合作用...     

磺化锌酞菁与胶束间的相互作用

用吸收光谱和荧光光谱研究了不同磺化程度酞菁与不同胶束间的相互作用并计算了结合常数。低磺化程度酞菁与三类胶束间均可发生相互作用,其标志是胶束的解聚作用;而高磺化程度酞菁与此显著不同,可结合在阳离子胶束表面,与非离子胶束无明显作用,而阴离子胶束对磺化酞菁只起促聚作用。用磺化程度变化导致酞菁分子体积、电荷及疏水性变化解释了实验结果。     

棒状薄层色谱/氢火焰法分析磺化酞菁钴的组成

研究建立了一种采用棒状薄层色谱／氢火焰离子检测（TLC／FID）对磺化酞菁钴组成进行定性、定量分析的方法。用薄层色谱并结合质谱分析 表明工业磺化酞菁钴中含有一磺化酞菁钴的两种同分异构体,二磺化酞菁钴的5种同分异构体及三磺化酞菁钴;用棒状薄层色谱／氢离子火焰检测方法可以对磺化酞菁钴中各组分进行定量分析。该方法操作简便,测定时间短,灵敏度高,可用于磺化酞菁钴工业合成的产品质量控制。     

磺化酞菁金属的聚集及对催化氧化硫醇性能影响

磺化酞菁金属主要用作液化气脱硫醇过程碱液氧化再生催化剂。为研究磺化酞菁金属易于失活的影响因素,对比探讨了5种磺化酞菁金属(Fe、Co、Ni、Cu、Zn )在相同溶剂以及不同溶剂中的聚集作用,并研究了聚集对催化氧化硫醇活性的影响。结果表明,磺化酞菁金属聚集受溶剂影响较大,溶剂极性越强,聚集越严重;磺化酞菁金属溶液放置时间越长,磺化酞菁金属聚集体粒径越大;金属种类不同,对磺化酞菁金属聚集也有影响。聚集导致CoSPc、CuSPc催化氧化硫醇活性显著降低20%左右。     

四磺化铁酞菁-阿尔新蓝8GX-对-羟基苯乙酸-H2O2催化荧光反应体系在核酸定量中的应用

阳离子荧光染料阿尔新蓝8GX与阴离子荧光染料四磺化铁酞菁发生缔合作用，使四磺化铁酞菁的荧光猝灭，当核酸存在时，削弱了离子缔合作用使四磺化铁酞菁的荧光恢复。荧光增强的程度与核酸的量成线性关系，据此实现了对核酸的定量测定。     

胶束中的磺化酞菁镓、磺化酞菁的二聚行为研究

本文研究了二磺化酞菁镓(S₂PcGa)、三磺化酞菁(S₃Pc)在胶束(TritonX-100)中的二聚行为。计算了S₃Pc、S₂PcGa在胶束中的二聚常数K_D及分配系数K。并对磺化酞菁在胶束中的增敏,解聚机理进行了探讨。     

磺化酞菁在甲醇-水溶液中的二聚作用研究

研究了不同磺化度的酞菁在甲醇－水混合溶剂中的聚集行为，通过紫外－可见光谱测定，发现磺化度在１．０以上的时染料在稀溶液中主要单体和二聚体的形式存在，并可用简单的方法计算出聚集平衡常数和平衡时单体所占的百分化，得到磺化越低越易聚集的结论，有关激发态的实验表明，增加酞菁磺化度有助于提高表观荧光量子产率，但对荧光寿命影响较小。     

酞菁与TiO2超微粒间的光诱导电子转移相互作用

带有负电荷取代基的四磺化酞菁化合物与 TiO2超微粒在溶液中通过静电相互吸引 ,能够形成基态复合物 .通过吸收光谱和荧光光谱 ,计算了磺化酞菁与 TiO2在溶液中的表观缔合平衡常数 K.与相应的烷氧基取代酞菁化合物作比较 ,并通过单光子计数技术测定染料荧光寿命 .结合荧光光谱 ,证明了磺化酞菁与 TiO2在溶液中的缔合作用 ,有利于激发态酞菁染料向半导体 TiO2的导带注入电子 ,从而发生分子间的电子转移反应 .将磺化酞菁吸附在 TiO2纳晶薄膜电极上 ,进行光电性能测试 .结果表明,染料敏化 TiO2纳晶薄膜电极光电响应的大小与染料在电极表面吸附的强弱有关 .     

酞菁与TiO2微粒间的光诱导电子转移相互作用

带有负电荷取代基的四磺化酞菁化合物与TiO2超微粒在溶液中通过静电相互吸引,能够形成基态复合物。通过吸收光谱和荧光光谱,计算了磺化酞菁与TiO2在溶液中的表现缔合平衡常数K.与相应的烷氧基取代酞菁化合物作比较,并通过单光子技术测定染料荧光寿命。结合荧光光谱,证明了磺化酞菁与TiO2在溶液中的缔合作用,有利于激发态酞菁染料向半导体TiO2的导带注入电子,从而发生分子间的电子转移反应,将磺化酞菁吸附在TiO2纳晶薄膜电极上,进行光电性能测试。结果表明,染料敏化TiO2纳晶薄膜电极光电响应的大小与染料在电极表面吸附的强弱有关。     

磺化酞菁镓的二聚现象研究

采用分光光度法研究了磺化酞菁镓的二聚现象;测定了二聚常数k_d,讨论了PH值、离子强度、水、温度等因素对k_d的影响,研究结果表明:磺化酞菁镓的二聚反应可表示成:2SPcGaOH⇔(SPcGa)₂O+H₂O 且磺化酞菁镓的二聚常数随着离子强度、磺酸基数目、水的浓度的增加而增加。     

层状苯膦酸-磷酸锆的合成与磺化研究

研究了制备苯膦酸-磷酸锆Zr(PO₄H)_2-n(PO₃Ph)_n的主要影响因素。在F^-/Zr⁴⁺=12和H₃PO₄/Zr⁴⁺=20条件下,通过改变苯膦酸用量获得了n=0～2的系列单一晶相层状苯膦酸-磷酸锆,其热稳定性达400℃以上。苯膦酸-磷酸锆的磺化试验表明层间苯环可被完全磺化,磺化产物Zr(PO₄H)_2-n(PO₃PhSO₃H)_n具有丰富的酸性位,其热稳定性亦可达到300℃以上。     

Heterogeneous ion-exchange membranes based on sulfonated poly(1,4-phenylene sulfide) and linear polyethylene: preparation, oxidation stability, methanol permeability and electrochemical properties

Poly(1,4-phenylene sulfide) was sulfonated with chlorosulfonic acid in 1,2-dichloroethane. The product (IEC = 2.38 mequiv./g) was ground and sieved (mesh size 63 μm) to obtain small particles. The particles and linear polyethylene were mixed in various ratios and the resulting blends were press-molded at 150 °C to obtain the membranes. Membranes containing up to 66 wt.% of sulfonated particles could be prepared without any problem in mechanical strength. The membranes were characterized by their stability in oxidative environment, ionic conductivity, and diffusive permeability to methanol. The membrane containing 66 wt.% of sulfonated particles was almost as conductive as Nafion 117; it exhibited, however, much lower diffusive permeability to methanol. In a strongly oxidative environment (3% aqueous H₂O₂ at 70 °C), the prepared membranes were less stable than Nafion 117, but much more stable than membranes with sulfonated poly(styrene-co-divinylbenzene) particles. In preliminary laboratory tests with H₂/O₂ and direct methanol fuel cells, the prepared membranes with high concentrations of sulfonated particles performed similarly to Nafion 117.     

Microwave spectroscopic and ab initio studies of pyrolysis products of 2-nitrosopropene (syn form) and its pyrolysis mechanism

The pyrolysis products of CH₂=C(CH₃)---NO (syn form) have been determined by microwave spectroscopy. The pyrolysis products of CH₂=C(CH₃)---NO (syn form) and its ¹⁵N isotopic species were found to be CH₂=O, CH₃CN, and CH₃C¹⁵N. The produce of formaldehyde and methyl cyanide suggests that the C=C and N=O double bonds of CH₂=C(CH₃)---N=O (syn form) were broken. To explain the generation of the two molecules, a four-membered ring molecule (9) as an intermediate, is proposed. The four-membered ring molecule as an intermediate is also supported by ab initio MO calculation. Applying the pyrolysis mechanism obtained for 2-nitrosopropene (syn form) to that of 1,1,2-trichloronitrosoethane, one of its complicated pyrolysis mechanisms was explained. The rotational constants and geometrical parameters of two intermediates, 9 and CH₂=CCl---NO (13), were obtained by ab initio MO calculation (MP2/6-31G**) to predict their microwave spectra.     

纳米晶钛镧酸盐的水热合成和表征

报道了在TiO₂-La₂O₃-M₂O-H₂O水热体系中,新型钛镧酸盐M_0.5La_0.5TiO₃(M=La,Ag_0.66Na_0.33,Li_0.6Na_0.4)的水热合成,用XRD、SEM、TEM、ICP、DTA-TG、IR和ac阻抗分析技术进行了结构表征.讨论了水热合成反应体系pH、反应混合物的组成比以及晶化温度等因素对合成的影响.XRD分析表明,Na_0.5La_0.5TiO₃和Ag_0.33Na_0.17La_0.5TiO₃具有立方结构,晶胞参数分别为a=0.3877nm和a=0.3890nm.Li_0.3Na_0.2La_0.5TiO₃具有正交结构,a=0.3894nm,b=0.3912nm,c=0.3890nm.TEM测定显示Na_0.5La_0.5TiO₃和Ag_0.33Na_0.17La_0.5TiO₃是纳米尺度晶体,平均粒度分别为50nm和70nm.Li_0.3Na_0.2La_0.5TiO₃的平均粒度分布为5Lm.Ag_0.33Na_0.17La_0.5TiO₃在440℃的电导率为1.9×10^-5S/cm,Li_0.3Na_0.2La_0.5TiO₃的电导率为1.5×10^-6S/cm.     

Pyrolysis and film growth studies of phosphinoborane compounds

Chemical vapor deposition experiments were conducted using phosphinoborane compounds of the type [R₂BPR′₂]_n, where R = CH₂CH₃ (1) or CH₃ (2), R′= C(CH₃)₃, and R = CH₂CH₃ (3) or CH₃ (4), R′ = Si(CH₃)₃. Thin films were deposited on Si substrates at 300–850°C under vacuum using 1–3, while no film formed using 4. All films contained considerable carbon (C/B = 0.67–7) and were deficient in phosphorus (P/B = 0-0.5) according to Auger electron spectroscopy. For 3, silicon was incorporated in the films (Si/B = 0.9–2). The preferential loss of phosphorus was nearly complete at higher pyrolysis temperatures that favor formation of carbon-rich films. Volatile products of the decompositions were observed by in situ mass spectroscopy and by ¹H nuclear magnetic resonance analysis of the condensate in a liquid nitrogen cooled trap. The products indicate that β-hydrogen elimination of alkene from boron is a preferred reaction pathway, while concerted elimination reactions appear to be inefficient. Although these phosphinoborane compounds do not appear to be suitable precursors for pure boron phosphide, the B-P-C films obtained are chemically inert and may be of interest as protective coatings.     

硅桥连双(三甲硅基环戊二烯基)钛化合物的合成及脱硅基反应

硅桥连双(三甲硅基环戊二烯基)双锂盐与TiCl₄·2THF反应,生成相应的钛化合物[E(C₅H₃SiMe₃)₂]TiCl₂[E=Me₂SiSiMe₂(3),Me₂SiOSiMe₂(5)],同时还分离到了脱一个三甲硅基的产物[E(C₅H₄)(C₅H₃SiMe₃)]TiCl₂[E=Me₂SiSiMe₂(4),Me₂SiOSiMe₂(6)].其中四甲基二硅氧桥连配体更容易发生这种脱硅基反应.通过元素分析、MS和¹HNMR谱表征了化合物3-6的分子结构.     

相转移催化下4-氯苯磺酰基乙酸异丙酯的烷基化反应

在有机合成中可用芳磺酰基作暂时性活化基团。芳磺酰基乙酸酯是具有活性亚甲基的弱酸性化合物。通常要在氢化钠、醇钠存在下才能起烷基化反应。Ono等曾报道4-甲苯磺酰基乙酸甲酯在DBu存在下进行烷基化反应,但反应时间长。近年来,相转移催化在有机反应中的应用受到重视,然而用固液相转移催化法使芳磺酰基乙酸酯起烷基化反应还未见报道。我们在K₂CO₃/DMF体系中,用TEBA作催化剂,研究了4-氯苯磺酰基乙酸异丙酯与不同类型卤代烃所起的烷基化反应。合成了尚未见报道的一或二烷基化产物。     

New heterometallic copper zinc alkoxides: synthesis, structure properties and pyrolysis to Cu/ZnO composites

The copper compound [(THF)KCu(O^tBu)₃]_∞ 1 was obtained by interaction of a 1:1 mixture of ZnCl₂/CuCl₂ with KO^tBu. Bi- and trifunctional aminoalcohols were used to synthesize the intramolecularly donor stabilized Cu(II) alkoxides Cu(OCH(R)CH₂NMe₂)₂ (3: R=Me, 4: =CH₂NMe₂) where 4 was structurally characterized. Lewis acid–base adduct formation with (Me₃Si)₃CZnCl gave the heterodinuclear compounds (Me₃Si)₃CZnCl · Cu(OCH(R)CH₂NMe₂)₂ (5: R=Me, 6: R=CH₂NMe₂), which were characterized by X-ray single-crystal structure analysis. The two metal centers Cu and Zn of 5 and 6 are bridged by two oxygen atoms to form a Cu–O–Zn core. Pyrolysis of compounds 5 and 6 in dry argon or a H₂/N₂ mixture at atmospheric pressure forms metallic copper and zinc oxide, whereas pyrolysis under O₂/Ar forms additionally oxidized copper species. Elemental analysis of the pyrolysis products showed carbon and nitrogen contamination. Scanning electron microscopy and energy dispersive X-ray analysis were performed to get information on the morphology and the chemical composition of the pyrolysis products.     

新型双四面体过渡金属簇合物的合成与表征

利用Co₂(CO)₈与[Cl₃CC(O)OCH₂]₂的反应合成了以C(O)OCH₂CH₂OC(O)桥联两个Co₃C四面体骨架为特征的新型双四面体簇合物[(CO)₉Co₃(μ₃-C)C(O)OCH₂]₂(1);1与不同物质的量比的Na[M(CO)₃C₅H₄R](M=Mo,W;R=H,C(O)Me)反应,得到一步交换的产物(CO)₉Co₃(μ₃-C)C(O)OCH₂CH₂OC(O)(μ₃-C)Co₂M(CO)₈(C₅H₄R)[M=Mo,R=H(2);M=Mo,R=C(O)Me(3);M=W,R=H(4);M=W,R=C(O)Me(5)]或两步交换的产物[(C₅H₄R)(CO)₈Co₂M(μ₃-C)C(O)OCH₂]₂[M=Mo,R=H(6);M=Mo,R=C(O)Me(7);M=W,R=H(8);M=W,R=C(O)Me(9)].5或9分别与Na[Mo(CO)₃C₅H₅]以12的物质的量比反应得到含一个手性四面体骨架(CoMoWC)的(C₅H₅)(CO)₈Co₂Mo(μ₃-C)C(O)OCH₂CH₂O·C(O)(μ₃-C)CoMoW(CO)₇(C₅H₄C(O)Me)(C₅H₅)(10)或含两个手性四面体骨架(CoMoWC)的[(C₅H₅)(C₅H₄C(O)Me)(CO)₇CoMoW(μ₃-C)C(O)OCH₂]₂(11);对化合物1_11进行了CH元素分析、IR和¹HNMR等表征.结果表明,在金属交换反应中处于不同簇环境下的Co(CO)₃基团反应活性不同.对化合物1进行了晶体X射线衍射分析.化合物1的晶体属单斜晶系,P2₁/n(#14)空间群,晶胞参数a=0.933 0(2)nm,b=1.519 7(4)nm,c=1.178 3(4)nm,=91.16(2)°,Z=2,F(000)=972.分子结构呈中心对称.     

CIDNP of Diecyl Peroxides Studies on the Kinetics of Decomposition of Diacyl Peiroxides Ⅷ in the Decomposition of Diacyl Peroxides

H CIDNP spectra recorded during the decomposition of aliphatic diacyl peroxides ((RCOO)2 R=n-C H (1),n-c5H11(2)) in ODCB in the presence of scavengers,such as I2C2H5I,(CH3)2CHI,and CH2=CHCH2 Br show multiplet effect for the scavenged products,RX(X=Br,I) and for disproportionation products,R-H.The reactionmechanism is discussed in terms of radical pair theory.