新穴类大环配体——双环-N,N′,N″-三-(1,4-苯基)-二-氨三乙酰胺和双环-N,N′,N″-三-(1,2-苯基)-二-氨三乙酰胺的合成与表征

首次用二步合成法合成了大环螯合剂ＬＨ６,合环反应不需要高稀释技术,用这种方法合成六酰胺螯合剂达到了预期的目标。此法也可以用来进行对称和不对称大环分子的合成。     

Li-(Mg,Zn,Ni) Vanadates

Phase relations were determined in the systems of Li-(Mg,Zn,Ni) vanadates in the temperature range between 500° and 800°C. Each of the ternary systems Li₂O-(Mg, Zn, or Ni)O-V₂O₅ is characterized by an orthovanadate: olivine-type LiMgVO₄, phenakite-type LiZnVO₄, and spinel-type LiNiVO₄. Mutual solid solutions form between them. Two solid solutions, a large region of the NiV₂O₆ type and a complete series between MgV₂O₆ and ZnV₂O₆, exist in the system (Mg,Zn,Ni)V₂O₆. The system (Mg,Zn,Ni)₂V₂O₇ has an extensive solid-solution region based on Ni₂V₂O₇, whereas the system (Mg,Zn,Ni)₃V₂O₈ is characterized by a complete series.     

Synthesis,reactivity, and X-ray structural characterization of a vanadium(III) oxidation pre-catalyst, (CpPOEtCo)VCl2(DMF)

Vanadium complexes are extensively used in the chemical industry as oxidation catalysts. During the course of our investigations into vanadium oxidation catalysis, the rich reactivity of a vanadium(III) scorpionate analogue complex, (CpP^OEtCo)VCl₂(DMF) (1), was investigated. The octahedrally coordinated 1 was prepared by mixing vanadium(III) chloride with Na(CpP^OEtCo) in DMF. The crystal structure of 1 has been determined through X-ray diffraction. Complex 1, C₂₀H₄₂Cl₂CoNO₁₀P₃V, crystallizes in the monoclinic space group P2₁/c with a = 38.566(9) Å, b = 9.499(2) Å, c = 18.149(4) Å, and β = 100.485(4)° with Z = 8. Complex 1 was found to be an effective pre-catalyst for the oxidation of 3,5-di-tert-butylcatechol to 3,5-di-tert-butylquinone. The reactivity studies, oxidative catalytic ability, as well as X-ray structural characterization of (CpP^OEtCo)VCl₂(DMF) will be discussed. ((CpP^OEtCo) = [η⁵-cyclopentadienyltris(diethylphosphito-κ¹P) cobaltate(III)⁻; DMF = N,N-dimethylformamide).     

二二甲亚砜合硫氰酸镉（DSTC）晶体的合成、结构、表征与晶体生长

合成了金属有机配合物晶体二二甲亚砜合硫氰酸镉Cd(SCN) 2 (C2 H6 OS) 2 (简称DSTC)。用X射线四圆衍射方法确定了此化合物的晶体结构。用元素分析、红外光谱对其进行了化学表征。首次在DMSO/水的溶剂中 ,生长出尺寸为 3 5mm× 12mm× 11mm透明单晶。     

N，O，O′─三（对甲苯磺酰基）双（2─羟乙基）胺的合成

二乙醇胺和对甲苯磺酰氯在三乙胺存在下，反应生成Ｎ，０，Ｏ′－三（对甲苯磺酰基）双（２－羟乙基）胺，产率９３％。从反应混合物中分离得副产物Ｎ，Ｏ－二（对甲苯磺酰基）双（２－羟乙基）胺。     

(Ti,Mo,W,Ta,V,Nb)(C,N)多元陶瓷相的价电子结构

运用固体与分子经验电子理论(EET理论)计算了(Ti,Mo,W,Ta,V,Nb)(C,N)多元陶瓷相的价电子结构.结果表明,价电子结构参数(nA)随碳化物添加量的增加而增加.不同碳化物对价电子结构参数的影响不同,其中VC的影响最为显著.价电子结构参数(nA)可以用来评价金属陶瓷的力学性能,提出了相关的判据关系式.     

Properties of some polysilane polymers: (n-PrSiMe) n , (i-PrSiMe) n,and (sec-BuSiMe) n

Three polysilane polymers, (n-PrSiMe) _n , (i-PrSiMe) _n , and (sec-BuSiMe) _n , were synthesized and characterized by DSC. UV spectroscopy, wide-angle X-ray diffraction, and optical microscopy, all at variable temperatures. The known thermochromic transition of (n-PrSiMe) _n at ～48 C is associated with a change from an orthorhombic to an isotropic phase. (i-PrSiMe) _n was examned as an insoluble and soluble (lowM _w) fraction, both existing mainly in an orthohombic lattice at room temperature. (sec-BuSiMe) _n has a mesophase structure at 25 C, undergoes a weak endothermic transition to a second (nematic) mesophase near 65 C, and becomes isotropic at ～160 C.     

(K,Na) (Nb,Ta,Sb)O3粉体制备及陶瓷介电性能研究

Ta/Sb掺杂的K0.5Na0.5Nb0.7TaxSb0.3-xO3(KNNSTx,x＝0.06,0.09,0.12,0.15,0.18,0.21, 0.24)粉体经水热合成,Ta、Sb对粉体物相、微观结构的影响被系统研究,烧结后陶瓷的微观结构、介电性能表明:陶瓷物相均具有纯钙钛矿结构;随着Ta含量的增加陶瓷晶粒尺寸逐渐增大,x＝0.09、0.12时较小粒径颗粒均匀分布在大颗粒的空隙之间,陶瓷密度增加;样品的介电常数随着Ta含量的增加x＝0.06～0.12逐渐降低,x＝0.15～0.24逐渐增加,居里温度均在350 ℃左右,且x＝0.09、0.12时陶瓷介电损耗较小.     

N,N,N-三甲基-2,3-二(硬脂酰氧基)丙基氯化铵(CDESA)的生物降解性

采用活性环氧中间体失水甘油基三甲基氯化铵合成了一种阳离子双酯表面活性剂——N,N,N-三甲基-2,3-二(硬脂酰氧基)丙基氯化铵(CDESA),来代替传统的难降解的表面活性剂型柔软剂,如目前国内仍在大量使用的双十八烷基二甲基氯化铵(D1821)。对CDESA的好氧降解性能进行了研究:以天然环境中的生活沉降污泥作为微生物源,用河水稀释,经培养、驯化后用于测试降解时间和半衰期,并与D1821的好氧降解性能作了对比。结果表明,CDESA的半衰期为3 d,容易降解,而D1821半衰期为7 d,较难降解,CDESA生物降解性能优于D1821。     

Hybrid Metal (Gold)-Inorganic (Silica) Nanoparticles: Synthesis,Characterization, and Spin-Labeling

Water-soluble gold nanoparticles, capped with captopril, have been synthesized and characterized. Their average size is 2.3 nm, with a spherical shape. These gold nanoparticles can be easily labeled with stable free radicals (4-amino-tempo) by a coupling reaction performed in the presence of 2-ethoxy-1-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ). Both synthesized and spin-labeled gold nanoparticles can be incorporated into much bigger (100 nm) silica nanoparticles using the Stober method, thus forming hybrid metal (gold)-inorganic (silica) nanoparticles. These hybrid silica nanoparticles (containing or not spin-labeled gold nanoparticles) can be easily spin-labeled with another stable free radical (4-isocyanato-tempo), leading to the formation of a double spin-labeled material. In this way, some stable free radicals are attached on the gold surface while others are attached on the silica surface. Three types of EPR spectra were recorded and discussed for the hybrid gold-silica nanoparticles: (1) where the spin labels are attached to the embedded gold nanoparticles, (2) where the spin labels are attached to the silica nanoparticles, and (3) in the case of the double spin labeled material where both gold and silica nanoparticles are spin-labeled. Influence of different solvents on the EPR spectra is also discussed.     

Thortveitite-Type Manganese (Mg, Zn, Ni) Vanadates

By introducing manganese to (Mg,Zn,Ni) divanadates, a series of thortveitite-type phases, Mn(Mg _x Zn _y Ni _z )V₂O₇ with x + y + z = 1, has been synthesized. The limits of x , y , and z can be represented by four phases: Mn(Mg_0.2Zn_0.8)V₂O₇, Mn(Mg_0.5Zn_0.5)V₂O₇, Mn(Mg_0.1Zn_0.8Ni_0.1)V₂O₇, and Mn(Mg_0.4Zn_0.5Ni_0.1)V₂O₇. Their cell dimensions are, respectively, a = 0.6734, 0.6737, 0.6749, and 0.6749 nm, b = 0.8806, 0.8819, 0.8816, and 0.8787 nm, c = 0.4748, 0.4750, 0.4752, and 0.4753 nm, and β= 102.16°, 102.15°, 102.23°, and 102.41°.     

(Gd,Yb,Tb)PO(4) up-conversion nanocrystals for bimodal luminescence-MR imaging

Up-conversion (Gd,Yb,Tb)PO(4) materials and their potential for bimodal imaging have received little attention in the literature. Herein, we report the first study on the up-conversion emission of (Gd,Yb,Tb)PO(4) nanocrystals synthesized via a hydrothermal method at 150 °C. These materials exhibit ultraviolet, blue and green up-conversion emissions upon excitation with a 980 nm continuous wave laser diode. The intensity of the blue-emission band at 479 nm, ascribed to the cooperative up-conversion emission of a pair of excited Yb(3+) ions, depends on the Yb(3+)/Tb(3+) concentration ratio, calcination temperature and particle size. Strong green up-conversion emission of Tb(3+) is observed at 543 nm for the (5)D(4)→(7)F(5) transition. Relaxometry measurements reveal that the nanocrystals are efficient T(2)-weighted (negative) contrast agents which, combined with visible-light emission generated by infrared excitation, affords them considerable potential for being used in bimodal, photoluminescence-magnetic resonance, imaging.     

(S,S)-2,12-, (S,S)-2,13-, and (S,S)-2,14-diacetoxyheptadecanes: sex pheromone components of red cedar cone midge, Mayetiola thujae

We identified, synthesized, and field-tested the sex pheromone of female red cedar cone midge Mayetiola thujae (Hedlin) (Diptera: Cecidomyiidae), a pest insect in red cedar Thuja plicata seed orchards. Coupled gas chromatographic (GC)-electroantennographic detection analyses of pheromone extract revealed three components (A, B, C) that elicited responses from antennae of males, all of which occurred below the detection threshold of the mass spectrometer and thus had to be identified without spectroscopic data. Taking into account (1) their retention indices (RI) on three GC columns (DB-5, DB-23, and DB-210), (2) intercolumn RI differentials, and (3) the molecular structures of known cecidomyiid pheromones, we synthesized seven candidate pheromone components: 2,10-, 2,11-, 2,12-, 2,13-, 2,14-, 2,15- and 2,16-diacetoxyheptadecanes. Of these, 2,12-, 2,13-, and 2,14-diacetoxyheptadecane had RIs on all columns consistent with those of A, B, and C and elicited strong antennal responses when tested at picogram levels. In field experiments with the twelve stereoselectively synthesized stereoisomers, only the SS-stereoisomers of 2,12-, 2,13-, and 2,14-diacetoxyheptadecane attracted male M. thujae. The three-component SS-stereoisomer blend was more attractive than the 12-component blend of all stereoisomers, suggesting that one or several nonnatural stereoisomers are inhibitory. One-, two-, and three-component lures of the SS-stereoisomers were equally effective in attracting male M. thujae, indicating redundancy in the pheromone. Identification of the M. thujae sex pheromone will allow development of pheromone-based monitoring, and possibly control, of M. thujae populations in T. plicata seed orchards.     

Electrical properties of (Na2O)35.7(RE2O3)7.2(SiO2)57.1 (RE = Y,Sm, Gd,Dy, Ho,Er and Yb) glasses and ceramics

Fifteen kinds of sodium rare earth silicate glasses and ceramics with (Na₂O)_35.7(RE₂O₃)_7.2(SiO₂)_57.1 (RE = Y, Sm, Gd, Dy, Ho, Er and Yb) composition were synthesized from a mixture of Na₂CO₃, RE₂O₃ and SiO₂. The densities of the glasses were in fairly good agreement with the theoretical densities and were 0.2–0.41 g cm⁻³ larger than those of the polycrystalline ceramics. The conductivities of the glasses are 1–2 orders lower than those of the ceramics and the highest electrical conductivity was achieved for the Yb ceramic sample with the smallest ion radius of RE³⁺. The electromotive force, EMF, of the potentiometric CO₂ gas sensors using (Na₂O)_35.7(Y₂O₃)_7.2(SiO₂)_57.1 glass and ceramic increased linearly with an increase in the logarithm of CO₂ partial pressure, in accordance with Nernst's law. It was suggested from the slope of Nernst's equation that the two electron-transfer reaction associated with the carbon dioxide molecule takes place at the detection electrode above 450 °C.     

有经济效益地在桥梁上应用先进复合材料的设计方法和桥梁形式

分析了影响在桥梁上应用先进复合材料经济效益的因素,继之以考察正用于设计和建造先进复合材料结构物(包括桥梁)的设计方法和规范。介绍了不同的桥梁形式证明可采用先进复合材料(有时连同其它材料),并列举了对委托方和桥梁使用者的实惠。     

Dielectric Properties of (Sr1 - xPbx)TiO3, SPT Ceramics (= 0.05, 0.1, and 0.15) and Phase Transition of SPT (x = 0.05, 0.1, 0.15, 0.2, 0.25 and 0.3)

Dielectric properties of (Sr_{1 - x}Pb_x)TiO₃-SPT (x = 0.05, 0.10 and 0.15) and phase transitions of SPT (x = 0.05, 0.10, 0.15, 0.20, 0.25 and 0.30) ceramic samples are investigated. At 10 kHz relative permittivity of SPT(x = 0.05) has one maximum, SPT(x = 0.10) and SPT(x = 0.15) show the main relative permittivity peaks and the secondary peaks at lower temperatures. The primary dielectric constant peaks could be due to the phase transitions from the paraelectric to ferroelectric phases on cooling and the source of the secondary peaks is not clear. Lattice parameter vs. composition, x shows a linear relation and phase transition has also a linear relation to the composition.