铌(V)-1-苯基-3-甲基-4-苯甲酰基-吡唑啉酮-5络合物吸附波的研究

在pH=5.0的HAc-NaAc介质中,Nb(V)与1-苯基-3-甲基-4-苯甲酰基-吡唑啉酮-5(PMBP)生成络合物,于-0.96V(us.SCE)出现一尖锐的极谱波.在滴汞电极上用示波极谱仪或在悬汞电极上测吸附伏安曲线.峰电流与Nb(V)浓度分别在0.0075~0.80μg/mL及0.000075~0.0075μg/mL范围内呈线性关系.实验了30多种离子的干扰影响,经苯肿酸分离后用于钢中Nb(V)的测定.检出限为0.00003μg/mL.溶液可稳定96h以上.用多种电化学方法研究了电极反应机理.     

On the stereochemistry of the Horner—Emmons reaction between 3-functionally substituted 2-methyl-2-propenylphosphonates and aliphatic aldehydes

The reaction of diethyl 3-ethoxycarbonyl-2-methyl-2-propenylphosphonate (1) with 3-methylbutanal (2) in the system solid MOH (M=K, Na, Li)-benzene without phase transfer catalysts affords ethyl 3,7-dimethyl-2,4-octadienoate with the ratios of 2E,4E stereoisomer (3a) to 2Z,4E-stereoisomer (3b) of 4456, 4654, and 6040 for KOH, NaOH, and LiOH, respectively. The similar tendency is observed when DMSO is substituted for benzene, although the proportion of3a in this case is 65% with any MOH used. The reaction of1 with2 in the presence of a stoichiometric amount of a quaternary ammonium hydroxide QOH (Q=NMe₄, BnNMe₃, (n-Bu)₄N) in benzene gives higher3a3b ratios than those obtained with LiOH in the former reaction system. The increase in the content of 2E,4E-isomer3a is possibly due to the growth of the population of solvent-separated ion pairs or, generally, to the increase in the distance between the charge centers in the ionic intermediates on passing from KOH to LiOH and from [Me₄N]OH to [(n-Bu)₄N]OH. The position of the equilibrium betweenE- and Z-isomers of phosphonate1 under the reaction conditions (E-1Z-13565) is almost unaffected by the nature of the cation of the base.Part 5, see ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1089–1094, June, 1993.     

Reaktivität von Monophosphan-Platin(0)-Verbindungen gegenüber Schwefeldioxid

Reactivity of Monophosphine Platinum(0) Complexes with SO₂ . The addition reaction of (PPh₃)Pt(ViSi) (ViSi = {η²-H₂C?CHSiMe₂}₂O) ( 1 ) with SO₂ gives within 30 min the red SO₂ complex (PPh₃)Pt(η²-H₂C?CHSiMe₂- OSiMe₂CH?CH₂)(SO₂) ( 2 ). A reaction time of 24 h with SO₂ leads to the elimination of the ViSi ligand, and the unstable monomeric intermediate (PPh₃)Pt(SO₂) cyclo- trimerizes to the stable cluster [Pt(PPh₃)(SO₂)]₃ ( 3 ). 3 is also obtained within 30 min by the reaction of (PPh₃)Pt(C₂H₄)₂ ( 4 ) with SO₂. The crystal structure of 3 has been determined; space group P2₁/n, Z = 4, a = 1 606.1(3), b = 1 019.3(1), c = 3 624.6(5) pm, β = 93.67°, R/R_w = 0.102/0.121.     

Role of solvent in the compatibility of a vinylchloride–vinylacetate–maleic acid terpolymer and nitrocellulose blends

The compatibility of cast films of a vinylchloride–vinylacetate–maleic acid terpolymer (VMCH) and nitrocellulose (NC) blends is influenced by solvents. Transparent films of VMCH/NC blends are obtained when cast from solvents such as tetrahydrofuran or cyclohexanone, whereas hazy films are obtained when cast from solvents such as acetone or ethylacetate. Visible spectroscopy and phase morphology were used to analyse the compatibility–incompatibility of the blend. Differential scanning calorimetry (DSC) studies demonstrate that the transparent film is compatible, but the hazy film is incompatible. Fourier transform infra-red (FTIR) studies establish that a greater interaction is observed between the polymer pair in case of the compatible blend than in the case of the incompatible blend. A solvent dependency of blend compatibility is reflected in this study. The conformational state of the polymers in solution, which is responsible for the compatibility phenomena, may depend on the donor number and/or Taft-β value of the solvent. The greater the donor number and/or the Taft-β value, the higher may be the level of interaction between the solvent and the polymer molecules, which in turn may give a compatible blend after removal of the solvent.     

制备方法对WO_3/ZrO_2结构的影响

用XRD、比表面测定、LRS定性和定量的方法对用Zr（OH）4和已晶化的ZrO2作载体制得的两类WO3／ZrO2催化剂进行了表征．揭示了样品比表面、载体物相、活性组分的存在状态与制备方法、WO3含量、焙烧温度之间的关系．结果表明，WO3能单层分散在ZrO2上；单层覆盖在Zr（OH）4上的WO3使载体在焙烧时晶粒生长受阻，形成介稳的四方ZrO2，并阻止载体微粒间的烧结，使从Zr（OH）4出发制得的WO3／ZrO2比表面明显增大，在WO3含量达到单层分散容量时以上作用表现得最充分；WO3与Zr（OH）4（或四方ZrO2）在高温（～800℃）可能发生了某种化学结合，开创出超强酸位．用以上观点可对文献中已报导的主要实验事实作出较满意的解释.     

Temperature-sensitive luminescence of tris (β-diketone) europium chelates for monitoring high-speed cationic photopolymerizations

The temperature-dependent luminescence of tris (β-diketone) chelates of europium was used for in situ temperature measurements during cationic photopolymerizations of vinyl ethers. These molecular-level luminescent probes provided a real-time, noninvasive method for monitoring temperature during these high-speed polymerizations. Two specific probes, tris (benzoyl-1, 1, 1-trifluoroacetone) europium and tris (1,1,1,5,5,5,-hexafluoroacetylacetone) europium, met several stringent spectral and performance requirements for application in our system. The luminescence from these probes exhibits a reproducible temperature dependence over a wide temperature range and is not sensitive to changes in viscosity. In situ temperature profiles obtained using this novel technique verified the importance of thermal effects during these highly exothermic photopolymerizations. These studies have demonstrated the utility of the tris(β-diketone) europium chelates for characterizing the temperature during high-speed photopolymerizations that cannot be monitored using conventional techniques. © 1995 John Wiley & Sons, Inc.     

Intramolecular Diels-Alder Reactions of Thio-Substituted Dienes with Enones

Thio-substituted dienes bearing an enone moiety were readily prepared from 3-sulfolenes, and their intramolecular Diels-Alder (IMDA) reactions were studied. Octahydronaphthalenones were produced in good yield with high stereoselectivity. Hexahydroindenones were also obtained, but the stereoselectivity was lower.     

Theoretical study of intermolecular proton transfer reaction in isolated 5-hydroxyisoxazole–water complexes

A systematic investigation in isolated 5-hydroxyisoxazole–water complexes (5-HIO · (H₂O)_nn = 1–3) is performed at the DFT level, employing B3LYP/6-31G(d, p) basis set. Single-point energy calculations are also performed at the MP2 level using B3LYP/6-31G(d, p) optimized geometries and the 6-311++G(d, p) basis set. The computational results show that the keto tautomer K₂ is the most stable isomer in the gas phase, and the tautomer K₁ to be the next most stable tautomer. Hydrogen bonding between HIO and the water molecule(s) will dramatically lower the barrier by a concerted multiple proton transfer mechanism. The proton transfer process of 3WE_cis ↔ 3WK₁ and 2WE_trans ↔ 2WK₂ is found to be more efficient in two tautomerization, and the barrier heights are 7.03 and 14.15 kcal/mol at B3LYP/6-31G(d, p) level, respectively. However, the proton transfer reaction between E_cis and K₁ cannot happen without solvent-assisted.     

Graphs to chemical structures. 4: Combinatorial enumeration of planted three-dimensional trees as stereochemical models of monosubstituted alkanes

Planted three-dimensional (3D) trees, which are defined as a 3D version of planted trees, are enumerated by means of Fujita’s proligand method formulated in Parts 1–3 of this series [Fujita in Theor Chem Acc 113:73–79, 80–86, 2005; Fujita in Theor Chem Acc 115:37–53, 2006]. By starting from the concepts of proligand and promolecule introduced previously [Fujita in Tetrahedron 47:31–46, 1991], a planted promolecule is defined as a 3D object in which the substitution positions of a given 3D skeleton are occupied by a root and proligands. Then, such planted promolecules are introduced as models of planted 3D-trees. Because each of the proligands in a given planted promolecule is regarded as another intermediate planted promolecule in a nested fashion, the given planted promolecule is recursively constructed by a set of such intermediates planted promolecules. The recursive nature of such intermediate planted promolecules is used to derive generating functions for enumerating planted promolecules or planted 3D-trees. The generating functions are based on cycle indices with chirality fittingness (CI-CFs), which are composed of three kinds of sphericity indices (SIs), i.e., a _d for homospheric cycles, c _d for enantiospheric cycles, and b _d for hemispheric cycles. For the purpose of evaluating c _d recursively, the concept of diploid is proposed, where the nested nature of c _d is demonstrated clearly. The SIs are applied to derive functional equations for recursive calculations, i.e., a(x), c(x ²), and b(x). Thereby, planted 3D-trees or equivalently monosubstituted alkanes as stereoisomers are enumerated recursively by counting planted promolecules. The resulting values are collected up to 20 carbon content in a tabular form. Now, the enumeration problem initiated by mathematician Cayley [Philos Mag 47(4):444–446, 1874] has been solved in such a systematic and integrated manner as satisfying both mathematical and chemical requirements.     

Sr3Al2O6:Eu2+红色发光纳米晶的新型形貌与发光性能的研究

对于稀土发光纳米晶来讲,产品颗粒尺寸与形貌不仅对发光性能有影响,而且直接影响其应用[1,2].如颗粒尺寸在1～10 μm之间且形貌接近于球形的发光微米晶在涂屏时发光效率是最高的,而具有新型微观结构与形貌的稀土发光纳米晶,如纳米线、纳米棒及具有自组装特性的花晶等纳米结构材料由于在纳米发光器件方面有着潜在的应用价值,已成为当今纳米科学的研究焦点.