0—3型PZT／P[VCF（77）—TrFE（23）]铁电复合物的非线性介电系数

用自建的非线性介电测试装置测得了０－３型ＰＺＴ／Ｐ「ＶＤＦ（７７）－ＴｒＦＥ（２３）」铁电复合物厚片在不同场强和温度下的线性和非线性介电系数。对于ＰＺＴ体积含量Φ〉０．３的复合物,介电系数ε１随测试场强的升高显著增大。在Φ〈０．１时,可用Ｍａｘｗｅｌｌ－Ｇａｒｎｅｔｔ方程拟合实验结果。     

钛酸铅/聚[偏氟乙烯(70)-三氟乙烯(30)]复合物的非线性介电性质

用自建的非线性介电测试装置研究了陶瓷相被极化 (B1 )以及陶瓷相和共聚物相都被极化 (B2 )的钛酸铅 /聚 [偏氟乙烯 ( 70 ) 三氟乙烯 ( 3 0 ) ](PT/P[VDF( 70 ) TrFE( 3 0 ) ]) 0 3型铁电复合物厚片在不同测试场强下的非线性介电系数 .对于PT含量 >0 3的复合物 ,介电系数ε1随场强的升高明显增大 .在 <0 1时 ,可用Maxwell Garnett方程拟合实验结果 .Bruggeman方程适合于低电场 ( <1MV/m)下复合物介电系数的预测 .通过Lz 的变化 ,用Yamada模型可拟合不同场强下复合物介电系数随的变化关系 .二阶非线性介电系数ε2 随的升高而增大 ,B2的ε2 大于B1 ,说明B2具有较高的剩余极化 .三阶非线性介电系数ε3 随场强的升高而减小 ,且高值的复合物具有较大的ε3 .两相都被极化试样的ε3 小于仅陶瓷相被极化的试样 .     

陶瓷/VDF-TrFE 0-3型铁电复合物的三阶非线性介电系数

在自建的非线性介电测试装置上测得了PT,BT、PZT和VDF-TrFE共聚物形成的0-3型铁电复合物厚片的三阶非线性介电系数ε3.研究发现,三种复合物的ε3都随陶瓷组分含量的上升而增大.测试场强升高,测得的ε3值减小,但对高陶瓷含量(φ＞0.4)的BT/VDF-TrFE和PZT/VDF-TrFE复合物则在6MV/m场强下出现极小值.二相都被预极化的复合物小于仅陶瓷相被预极化的ε3值.PZT/VDF-TrFE复合物的温度依赖关系显示了与(-阶)介电系数类似的表观热滞后现象.高PZT含量的复合物在相变区出现较大的ε3值.     

Ba1-xSrxMyTi1-yO3(M=Zr, Sn)纳米材料的软化学合成、结构与介电特性

用软化学方法,在１００℃以下合成了一系列Ｂａ_(１－ｘ)Ｓｒ_ｘＭ_ｙＴｉ_(１－ｙ)Ｏ_３固溶体纳米粉末（Ｍ＝Ｚｒ,Ｓｎ,０ ≤ｘ≤０．４,０≤ｙ≤０．３）,经ＸＲＤ物相分析和ｄ－间距－组成图证明,产品为立方晶系的完全互溶取代固溶体,结果符合Ｖｅｇａｒｄ定律．ＴＥＭ形貌观察,粒子为均匀球形,平均粒径７０ｎｍ．通过制陶实验,分别测定了该系列固溶体的室温介电常数以及介电常数随温度的变化．结果发现,用软化学方法在ＢａＴｉＯ_３中掺入适量锶和锆或锡,由于掺杂离子均匀进入母体晶格,引起Ｔｃ降低,介电性能改善显著．当ｘ＝０．２,ｙ＝０．１时,室温介电常数达 １１ ０００,比 ＢａＴｉＯ_３纯相提高 ８倍,而介电损失却下降 ３倍．     

显色剂N-间甲苯基-N''''-(氨基对苯磺酸钠)硫脲光度法测定微量铂(Ⅳ)

研究了新试剂－Ｎ间甲苯基－Ｎ’－（氨基对苯磺酸钠）硫脲（ＭＭＰＴ）与铂（Ⅳ）的显色反应，结果表明，在 ｐＨ ３．７～４．４的 ＨＡｃ－ＮａＡｃ缓冲体系中，Ｐｔ（Ⅳ）与 ＭＭＰＴ形成 １：３的绿色水溶性络合物，最大吸收波长位于 ７５４．４ ｎｍ，表观摩尔吸光系数ε７５４．４＝８．５８ × １０４·ｍｏｌ－１·ｃｍ－１，铂含量在０～１．２８ ｍｇ／Ｌ的范围内服从比尔定律。本法灵敏度高、选择性好、操作简便、测定结果准确可靠。将其用于矿石和催化剂中铂的测定，结果令人满意。     

Ni-Mo合金电沉积层织构及形成机理

在组成为：０．２２ｍｏｌ／Ｌ硫酸镍、０．０６ｍｏｌ／Ｌ钼酸钠和０．３ｍｏｌ／Ｌ柠檬酸钠的溶液,于纯铜片上采用恒电流沉积,所得Ｎｉ－Ｍｏ合金沉积层经Ｘ射线衍射测定,结果表明在温度为２５℃～５０℃,电流密度为１０ｍＡ·ｃｍ－２～３０ｍＡ·ｃｍ－２范围,Ｎｉ－Ｍｏ合金沉积层表现为（１１１）择优取向．循环伏安和电位阶跃实验表明镍钼合金电结晶过程按照连续成核和三维生长方式进行．Ｎｉ－Ｍｏ合金电沉积过程的电化学交流阻抗谱表明Ｎｉ－Ｍｏ共沉积过程经历了吸附中间产物步骤,由于吸附态物种氢氧化镍和钼的氧化物将阻化晶粒（１１１）晶面的生长,从而使镍钼沉积层表现为（１１１）择优取向．     

新试剂N-间甲苯基-N′-(氨基对苯磺酸钠)硫脲(MMPT)的合成及其在分析化学中的应用

本文合成新试剂Ｎ－间甲苯基－Ｎ′－（氨基对苯磺酸钠）硫脲（ＭＭＰＴ），经红外、紫外、核磁、元素分析等测试，确定其结构。研究测定了试剂与４０多种离子的反应及其配合物的表观摩尔吸光系数，它可作为Ｃｕ２＋（ｍ＝０．０１５μｇ，ｃ＝０．５μｇ／ｍＬ）、Ａｇ＋（ｍ＝０．１μｇ，ｃ＝３．３μｇ／ｍＬ）的新鉴定试剂和光度法测定Ｐｄ２＋（ε３０９．７＝６．３２×１０４Ｌ·ｍｏｌ－１·ｃｍ－１）、Ｐｔ（Ⅳ）（ε７５４．４＝８．５８×１０４Ｌ·ｍｏｌ－１·ｃｍ－１）等的显色剂，方法灵敏度高、选择性好，用于阳极泥、人发、矿石及催化剂中上述元素的鉴定或测定，均获满意结果。     

孔雀石绿增感聚苯乙炔的光导体

采用电位放电技术研究孔雀石绿（ＭＧ）增感顺式聚苯乙炔（ｃｔ－ＰＰＡ）光导体的光敏性，发现孔雀石绿是顺式聚苯乙炔新的有效增感剂。以Ａｌ／ｃｔ－ＰＰＡ：ＭＧ：ＰＣ（１００：５：１０）（１～１．５μｍ）／ＰＶＫ：ＴＰＡ：ＰＣ（１０：１０：１）（１５～２０μｍ）构成的光导体显示好的光敏性：表面接受电位，Ｖｍａｘ＞７００Ｖ；残余电位，Ｖｍｉｎ＜５０Ｖ；暗衰速率，ＲＤ＜１０Ｖ／ｓ；光衰放电量，△Ｖｔ＞５０％（１．０ｓ）；半衰时间，Ｔ１２＝０．８７Ｓ；感光灵敏度，Ｓ＝２．３×１０－３（１ｘ．ｓ）－１，较未增感ＰＰＡ光导体有较大的提高。ＭＧ对ＰＰＡ为光谱增感     

新试剂N—间甲苯基—N′—（氨基对苯磺酸钠）硫脲（MMPT）的合成及其在…

本文合成新试剂Ｎ－间甲苯基－Ｎ′－（氨基对苯磺酸钠）硫脲（ＭＭＰＴ）经红外，紫外，核磁，元素分析等测试，确定其结构，研究测定了试剂与４０多种种离子的反应及其配合物的表观洋吸光系数，它可作为Ｃｕ＾２＋（ｍ＝０．０１５μｇ，ｃ＝０．５μｇ／ｍＬ），Ａｇ＾＋（ｍ＝０．１μｇ，ｃ＝３．３μｇ／ｍＬ）的新鉴定试剂和光度法测定Ｐｄ＾２＋（ε３０９．７＝６．３２×１０＾４Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，Ｐｔ（Ⅳ）     

μ-氧桥联的双核铜(Ⅱ)配合物Cu2(Salen)2的合成、结构和光谱性质

报道了双核铜（Ⅱ）配合物Ｃｕ２（Ｓａｌｅｎ）２（Ｓａｌｅｎ为Ｎ,Ｎ′－二水杨醛乙二胺席夫碱）的合成、表征和晶体结构分析．该晶体属单斜晶系,具有Ｃ２／ｃ（Ｎｏ．１５）空间群,ａ＝２．６５８０（５）ｎｍ,ｂ＝０．６９８６（１）ｎｍ,ｃ＝１．４７１８（３）ｎｍ,β＝９７．６３（３）°,Ｖ＝２．７０８（１）ｎｍ３,Ｚ＝８,Ｄｃ＝１．６１８Ｍｇ／ｍ３,Ｆ（０００）＝１３５２,Ｒ＝０．０８８,ｗＲ＝０．０７３,ＧＯＦ（Ｆ）＝０．８９．该化合物是由两个氧桥桥联的双核铜（Ⅱ）配合物,铜（Ⅱ）离子处于五配位的畸变四方锥配位环境中报道了双核铜（Ⅱ）配合物Ｃｕ２（Ｓａｌｅｎ）２（Ｓａｌｅｎ为Ｎ,Ｎ′－二水杨醛乙二胺席夫碱）的合成、表征和晶体结构分析．该晶体属单斜晶系,具有Ｃ２／ｃ（Ｎｏ．１５）空间群,ａ＝２．６５８０（５）ｎｍ,ｂ＝０．６９８６（１）ｎｍ,ｃ＝１．４７１８（３）ｎｍ,β＝９７．６３（３）°,Ｖ＝２．７０８（１）ｎｍ３,Ｚ＝８,Ｄｃ＝１．６１８Ｍｇ／ｍ３,Ｆ（０００）＝１３５２,Ｒ＝０．０８８,ｗＲ＝０．０７３,ＧＯＦ（Ｆ）＝０．８９．该化合物是由两个氧桥桥联的双核铜（Ⅱ）配合物,铜（Ⅱ）离子处于五配位的畸变四方锥     

手性二噁唑啉吡啶铁和镍配合物的制备与表征

Tridentate bis(oxazolinylpyridine)(1) reacted with nickel chloride or ferrous chloride in anhydrous ethanol to form bis(oxazolinylpyridine) Nickel(Ⅱ) and Iron(Ⅱ) complexes. The stable solid complexes were characterized with IR， UV， MS， XPS and elemental analysis. No stable complexes were formed with bidentate bis(oxazoline)(2) ins- tead of bis(oxazolinylpyridine).     

Asymmetric Synthesis of (R)-and (S)-Moprolol

A simple and effective procedure for the enantioselective synthesis of (R)-and (S)-moprolol was described.The key step was the asymmetric synthesis of enantiopure (R)-and (S)-guaifenesin,which were synthesized from enantioenriched (R)-3-chloro-1,2-propanediol and (S)-epichlorohydrin via kinetics of hydrolysis resolution of racemic epichlorohydrin by chiral Salen-CoIIII complex.The e.e.values of both the optical compounds were above 98%,and the chemical structures of the target compounds were confirmed by 1H NMR,13C NMR,IR,and MS.     

Rhodium(III), palladium(II) and platinum(II) complexes of Bis(o-aminobenzenesulfonyl)ethylenediamine

New complexes of the formulae K₃[RhL ₃]·2 H₂O, [PdL]·H₂O and [M(LH₂)Cl₂] [whereM = Pd, Pt andLH₂ = bis(o-aminobenzenesulfonyl)ethylenediamine] have been prepared and characterized by conductivity measurements, thermogravimetric analysis, X-ray powder patterns and IR, Ligand Field and¹H-NMR spectroscopy.

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Rhodium(III), Palladium(II)- und Platin(II)-Komplexe mit Bis(o-aminobenzolosulfonyl)ethylendiamin (Kurze Mitteilung)

Zusammenfassung Neue Komplexe der allgemeinen Formeln K₃[RhL ₃]·2H₂O, [PdL]·H₂O und [M(LH₂)Cl₂] mitM = Pd, Pt undLH₂ = Bis(o-aminobenzolosulfonyl)ethylendiamin wurden dargestellt und mit Konduktionsmessungen, thermogravimetrischen Analysen, Röntgenstrukturanalysen, IR, Ligandfeld- und¹H-NMR-Spektroskopie charakterisiert.

     

(Phosphine)gold(I) Complexes of Benzenedithioles. Crystal structures of 1,2-benzenedithiolato-bis[triphenyl-phosphinegold(I)] and bis(triethylphosphine)gold(I) bis(1,2-benzenedithiolato)gold(III)

The reaction of 1,2- and 1,3-benzenedithiol C₆H₄(SH)₂ with chloro(phosphine)gold(I) complexes R₃PAuCl (R = Et, Ph) in the presence of triethylamine in tetrahydrofuran gives stable gold(I) complexes 1,2-C₆H₄(SAuPR₃)₂ [R = Et ( 1 ) and Ph ( 2 )] or 1,3-C₆H₄(SAuPPh₃)₂ ( 3 ), respectively, in high yield. The compounds have been characterized by analytical and NMR spectroscopic data. From the reaction of 1,2-C₆H(SH)₂ with Et₃P? AuCl a by-product [(Et₃P)₂Au]⁺ [Au(1,2? C₆H₄S₂)₂]^? ( 4 ) has also been isolated in low yield. The crystal structures of compounds 2 and 4 have been determined by single crystal X-ray diffraction. The gold(I) atoms in complex 2 are two-coordinate with bond angles S? Au? P of 175.2(1) and 159.5(1)°, Au? S bond distances of 2.304(1) and 2.321(1) å, and a short Au…?Au contact of 3.145(1) Å. The gold(I) atom in the cation of complex 4 is also linearly two-coordinate with a P? Au? P angle of 170.1(1) Å and Au? P distances of 2.296(3) and 2.298(3) Å. The geometry of the anion in 4 shows a square-planar coordination of gold(III) by two chelating 1,2-benzenedithiolate ligands with Au? S distances between 2.299(3) and 2.312(3) Å (for two crystallographically independent, centrosymmetrical anions in the unit cell).     

界面缩聚法合成双(烯基环戊二烯基)钛(锆)聚醚的研究

本文通过界面缩聚法利用双(烯基环戊二烯基)钛(锆)二氯化物与二酚反应,制成了16个新的高分子化合物,对它们进行了IR、TGA和分子量的测定。文中还对反应条件与分子量的关系进行了讨论。     

以氯醌酸二价阴离子为桥联配体的Fe(Ⅲ)-Fe(Ⅲ)和Mn(Ⅱ)-Mn(Ⅱ)双核配合物的合成与磁性

基于铁和锰的双核配合物在生物氧化还原过程中的重要作用及在化学的氧化还原过程中可能做为催化剂的应用前景,本文合成了两个新的以氯醌酸二价阴离子为桥联配体的Fe(Ⅲ)双核和Mn(Ⅱ)双核配合物:[Fe_2(phen)_4(μ-CA)](ClO_4)_4·2H_2O(1)和[Mn_2(phen)_4(μ-CA)](ClO_4)_2·3H_2O(2)(phen=1,10菲咯啉;CA=氯醌酸二价阴离子)。经元素分析、IR、电子光谱及磁性等测定,对两配合物进行了表征。     

新型温度敏感性自组装胶束P(NiPAAm-co-DMAA)-co-P(L-Ala)的合成和性能

通过原子转移自由基聚合(ATRP)合成了一种带有活性—NH2基团的温度敏感性亲水型共聚物P(NiPAAm-co-DMAA), 并将其作为引发剂, 合成了P(NiPAAm-co-DMAA)-co-P(L-Ala), 其分子量分布(PDI)在1.3左右. 聚合物通过自组装形成纳米胶束. 透射电镜(TEM)结果表明, 胶束大小200~300 nm, 具有明显的核壳结构. 共聚物的最低临界溶解温度(LCST)为45.5 ℃. 温度低于LCST时, 聚合物溶解形成胶束; 高于LCST时, 胶束解离, 聚合物不溶. 聚合物对温度的响应是快速而可逆的.     

N(B(NMe2)2)(Si(NMe2)3)(Ti(NMe2)3), [N(Si(NMe2)3)(Ti(NMe2)2)]2 und N(SiMe3)(Si(NMe2)3)(Ti(NMe2)3) — Synthese und Charakterisierung neuer molekularer Einkomponentenvorläufer für nitridische und carbonitridische Keramiken

N(B(NMe₂)₂)(Si(NMe₂)₃) (Ti(NMe₂)₃), [N(Si(NMe₂)₃)(Ti(NMe₂)₂)]₂ und N(SiMe₃)(Si(NMe₂)₃)(Ti(NMe₂)₃) — Synthesis and Characterization of New Molecular Single-source Precursors for Nitride and Carbonitride Ceramics Synthesis and spectroscopic data of the title compounds are reported. [N(Si(NMe₂)₃)(Ti(NMe₂)₂)]₂ crystallizes in the space group P1 , a = 8.406(7), b = 10.673(8), c = 10.872(6) Å, α = 68.45(4)°, β = 71.72(4)°, γ = 78.11(7)°, 2 877 diffractometer data (F_o ? 2σF_o), R = 0.051. The compound is characterized by a planar four-membered Ti₂N₂-ring with exocyclic tris(dimethylamino)silyl substituents attached to the nitrogen atoms of the ring.     

二(三苯基膦)乙基黄原酸金属配合物的晶体结构和谱学表征

0IntroductionTheincreasingcommercialvalueoftransitionmetalcomplexesofxanthateshasarousedconsiderableinterestingintheirchemistry.Whiletheiranalyticalapplicationsarewellknown犤1犦,theyarenowfindingextensiveuseinvulcanizationofrubber,frothfloatationprocessforconcentrationofsulphideores,asantioxi-dants,lubricants犤2,3犦,andhavebeenfoundtopossessfungicidalandinsecticidalactivity犤4犦.Inrecentyears,therehasbeengrowinginterestinthestudyofd10metalcomplexes,whichexhibitrichphotophysicalandpho-tochemica…     

U(IV)/LN(III) unexpected mixed site in polymetallic oxalato complexes. Part II. Substitution of U(IV) for Ln(III) in the new oxalates (N2H5)Ln(C2O4)2·nH2O (Ln=Nd, Gd)

Two new hydrazinium lanthanide(III) oxalates, (N₂H₅)[Nd(C₂O₄)₂(H₂O)]·4H₂O (1) and (N₂H₅)[Gd(C₂O₄)₂(H₂O)]·4.5H₂O (2) have been prepared and their crystal structures determined by single-crystal X-ray diffraction. The crystal structures were solved by the direct methods and Fourier difference techniques, and refined by a least-squares method on the basis of F² for all unique reflections. Crystallographic data: 1, triclinic, space group , , b=9.762(4), , α=62.378(5), β=76.681(5), γ=73.858(5), Z=2, R₁=0.0335 for 172 parameters with 3430 reflections with I?2σ(I); 2, triclinic, space group , , b=9.51(3), , α=62.11(4), β=76.15(5), γ=73.73(5), Z=2, R₁=0.0325 for 172 parameters with 1742 reflections with I?2σ(I). The two isotypic structures are built from a three-dimensional (3D) arrangement of lanthanide and oxalate ions. The lanthanide atom is coordinated by eight oxygen atoms from four tetradentate oxalate ions and one aqua oxygen. Alternating lanthanide and oxalate ions form six-membered rings that delimit tunnels running down three directions and occupied by hydrazinium and water molecules. Starting from these lanthanide(III) compounds two isotypic mixed Ln(III)/U(IV) oxalates, (N₂H₅)_0.75[Nd_0.75U_0.25(C₂O₄)₂(H₂O)]·4.5H₂O (3) and (N₂H₅)_0.75[Gd_0.75U_0.25(C₂O₄)₂(H₂O)]·4H₂O (4), are obtained by partial substitution of Ln(III) by U(IV) in the nine-coordinated site, the charge excess being compensated by removal of monovalent ions from the tunnels. Finally, using Na⁺ gel, two mixed Ln(III)/U(IV) sodium oxalates, Na_0.5[Nd_0.5U_0.5(C₂O₄)₂(H₂O)]·3H₂O (5) and Na_0.65[Gd_0.65U_0.35(C₂O₄)₂(H₂O)]·4.5H₂O (6) have been obtained without any change in the 3D framework.