Direct Synthesis of Titanium Complexes with Chelating cis‐9,10‐Dihydrophenanthrenediamide Ligands through Sequential C?C Bond‐Forming Reactions from o‐Metalated Arylimines

A series of new titanium(IV) complexes with o‐metalated arylimine and/or cis‐9,10‐dihydrophenanthrenediamide ligands, [o‐C₆H₄(CH?NR)TiCl₃] (R=2,6‐iPr₂C₆H₃ ( 3 a ), 2,6‐Me₂C₆H₃ ( 3 b ), tBu ( 3 c )), [cis‐9,10‐PhenH₂(NR)₂TiCl₂] (PhenH₂=9,10‐dihydrophenanthrene; R=2,6‐iPr₂C₆H₃ ( 4 a ), 2,6‐Me₂C₆H₃ ( 4 b ), tBu ( 4 c )), [{cis‐9,10‐PhenH₂(NR)₂}{o‐C₆H₄(HC?NR)}TiCl] (R=2,6‐iPr₂C₆H₃ ( 5 a ), 2,6‐Me₂C₆H₃ ( 5 b ), tBu ( 5 c )), have been synthesised from the reactions of TiCl₄ with o‐C₆H₄(CH?NR)Li (R=2,6‐iPr₂C₆H₃, 2,6‐Me₂C₆H₃, tBu). Complexes 4 and 5 were formed unexpectedly from the reactions of TiCl₄ with two or three equivalents of the corresponding o‐C₆H₄(CH?NR)Li followed by sequential intramolecular C? C bond‐forming reductive elimination and oxidative coupling reactions. Attempts to isolate the intermediates, [{o‐C₆H₄(CH?NR)}₂TiCl₂] ( 2 ), were unsuccessful. All complexes were characterised by ¹H and ¹³C NMR spectroscopy, and the molecular structures of 3 a , 4 a – c , 5 a , and 5 c were determined by X‐ray crystallography.     

螺二芴富勒烯吡咯烷衍生物的合成及电化学和光限幅性能

设计合成了3种新颖的螺二芴键联富勒烯(C₆₀/C₇₀)吡咯烷衍生物, 其结构通过IR, ¹H NMR, ¹³C NMR和MALDI-TOF进行确证, 其电化学性质用循环伏安法进行研究. 结果表明, C₇₀衍生物6的还原电位较C₆₀衍生物7分别向负电势移动0.1, 0.12和0.01 V. 同时, 使用纳秒和飞秒激光分别研究了化合物6, 7和8的光限幅性能, 其光限幅阈值分别为15.3, 23.3和13.7 J/cm², 表明材料具有优异的光限幅性能.     

聚对甲基苯胺的合成及其晶体结构

在水相中,FeCl3催化对甲基苯胺聚合合成了对甲基苯胺三分子聚合物——(N,N′E,N,N′E)-N,N′-(2-氨基-5-甲基-2,5-环己二烯-1,4-二亚基)二(4-甲基苯胺)(1),其结构经X-射线单晶衍射仪表征。1属六方晶系,R3空间群,晶胞参数:a=21.116(2),b=21.116(2),c=10.364(2),α=90°,β=90°,γ=120°,Mr=315.41,Z=9,V=4002.1(10)3,Dc=1.178 g.cm-3,μ=0.070 mm-1,λ=0.710 73,F(000)=1 512,R=0.067 8,wR=0.112 6。     

用电沉积法制备稀土填充热电材料Bi2Sb3Rex

分别以脉冲电沉积法和直流电沉积法制备了稀土填充热电材料Bi2Sb3Rex(Re=Ce,Nd)。结果表明,采用脉冲电沉积法,在通断脉宽为Ton=10ms(电流1A),Toff=40ms(电流0A),电流密度2000A.m-2,电沉积时间180s的条件下制得的电沉积膜Bi2Sb3Ce2,表面均匀、光滑、致密;在通断脉宽为Ton=0.4ms(电流1A),Toff=2.4ms(电流0A),电流密度2800A.m-2,电沉积时间120s,占空比为0.142的条件下制得的电沉积膜Bi2Sb3Nd0.1,表面均匀、光滑、致密。     

溶胶-凝胶法制备纳米氮化钒的研究

氮化钒(VN)具有十分高的热、化学稳定性和强的机械性能,广泛用于切削工具、磨具和结构材料;也是一种良好的催化剂,具有高催化活性、高选择性、良好的稳定性和抗中毒性能.细粒度的VN能有效提高催化活性,改善结构材料的韧性[1].传统上VN应用NH4VO3在NH3气氛中氨解,需要在1100℃下加热12h,冷却并研磨物料,再氨解12h,仅能获得90%的微米级VN粉体[2].     

BaCe_(0.8-x)Nb_xGd_(0.2)O_(3-δ)(0≤x≤0.45)的制备及性能研究

采用高温固相反应法制备了质子导体BaCe0.8-xNbxGd0.2O3-δ(0≤x≤0.45)。结合XRD、SEM、EIS等技术对其物相、微观形貌、稳定性及电导率进行了研究。结果表明,在1600℃烧结5h制备的质子导体BaCe0.8-xNbxGd0.2O3-δ(0≤x≤0.45)均能保持主相为斜方晶的钙钛矿结构。Nb的加入可明显提高烧结样品的致密性及在CO2和水蒸气气氛下的稳定性。在湿润H2/Ar(0.4%,V/V)气氛中800℃下,x=0.1样品的电导率为5.73mS·cm-1,电导活化能为0.35eV,与x=0的样品相当。     

Antigens synthesis and antibodies preparation for furazolidone and its metabolite 3-amino-2-oxazolidinone

<正>Two haptens of 3-[(5-amino-furan-2-ylmethylene)amino]oxazolidin-5-one(FZ-NH_2) and 3-{[(4-carboxyphenyl)methylene]-amino} -2-oxazolidinone(CPAOZ) were synthesized.For FZ-NH_2,immunogens were prepared by glutaraldehyde and diazo salt methods.For CPAOZ,immunogens were connected by the methods of the active ester and mixed acid anhydride.Compared with the combination,indirect competitive enzyme-linked immunosorbent assay(ic-ELISA) was developed with coating antigen of FZ-NH_2 -OVA via the glutaraldehyde method and immunogen of CPAOZ-KLH via active ester method.For furazolidone and its metabolite AOZ(NPAOZ as derivative),the sensitivities(IC_(50)) were 2.0μg/L and 2.5μg/L,limits of detection(IC_(15)) were 0.09μg/L and 0.25μg/L,respectively.A sensitive method was developed for the simultaneous determination of furazolidone in feed and its metabolite AOZ in tissue.