Synthesis and Structure Investigations of Potential Sedative and Anticonvulsant Hydroxy- and Acetoxy-N-(3-oxobutyl)-pyrido[2,3-d]pyridazinonesa

Summary.  Novel N-(3-oxobutyl)-hydroxy- and acetoxypyrido[2,3-d]pyridazinones were synthesized and tested in vivo for their sedative and anticonvulsant activity. The Michael-type reaction of quinolinic acid hydrazide and methyl vinyl ketone afforded a mixture of two isomers, 5-hydroxy-N ⁷-(3-oxobutyl)-pyrido[2,3-d]pyridazin-8(7H)-one and 8-hydroxy-N ⁶-(3-oxobutyl)-pyrido[2,3,-d]pyridazin-5-(6H)-one, in a ratio of 2:1 which were separated by crystallization. Subsequent acetylation of both isomers yielded the corresponding 5- and 8-acetoxy compounds. The structures of the compounds were proven and completely assigned on the basis of ¹H, ¹³C, ¹⁵N NMR, and 1D NOE difference spectra as well as 2D C,H-correlation experiments. Preliminary pharmacological tests showed low acute toxicity with a LD ₅₀ > 1000 mg/kg in the mouse and sedative activity for the title compounds. 5-Acetoxy-N ⁷- (3-oxobutyl)-pyrido[2,3-d]pyridazin-8(7H)-one displayed a borderline anticonvulsant activity in the metrazole test model. Corresponding author. E-mail: edith.goessnitzer@uni-graz.at Received March 20, 2002; accepted April 3, 2002     

纤维素/甲壳素共混膜的结构表征与抗凝血性能

以 6wt %NaOH 4wt%尿素为纤维素的新溶剂 ,采用溶液共混法制备出纤维素 甲壳素共混膜 ,为甲壳素在碱性溶液中制膜提供了新的方法 .红外光谱、X 射线衍射、扫描电镜和力学性能、抗凝血性能测试结果表明 ,共混膜中甲壳素含量低于 4 0wt%时 ,纤维素与甲壳素分子间具有良好的相容性 ;在纤维素中引入适量甲壳素可提高共混膜的抗张强度 ,共混膜的干、湿态抗张强度在甲壳素含量 10wt%时最大 ,其值分别为 89 1MPa和 4 3 7MPa ,比纯态纤维素膜的干、湿态抗张强度分别提高了 6 7%和 11 5 % ;甲壳素的引入可明显降低血小板在共混膜表面的粘附、凝聚与变性 ,增大共混膜的抗凝血参数 ,甲壳素含量达到 5 0wt%时 ,该共混膜具有良好的抗凝血性能     

Optimizing Cs-exchange in titanosilicate with the mineral pharmacosiderite topology: framework substitution of Nb and Ge

Titanosilicates with complete or partial substitution of Ge or Nb in the framework and having the mineral pharmacosiderite topology were hydrothermally prepared and their ion-exchange properties towards Cs were studied for Ti/Ge/Si, Ti/Si, Nb/Ti/Si and pure Ge phases. The basis for the differences in the ion exchange properties measured as distribution coefficients (K_d) for these materials are detailed via structural characterization using the Rietveld refinement technique on the X-ray powder diffraction data. The differences in affinity towards Cs⁺ result either from the degree of hydration of the exchanger resulting in different coordination environments or the position of cesium ion in the eight-ring channel.     

固相氯化法合成氯化聚乙烯的红外光谱研究

本文研究在不同条件固相氯化聚乙烯(CPE)的红外光谱,探讨了一步和两步氯化合成的CPE的结构差别,着重讨论了两步氯化的CPE结构特点。从观察表征结晶结构和—(CH_2)_n—链段氯分布的特征频率变化表明,低温固相氯化主要发生在无定形区,并且在CPE中形成高氯化和低氯化链段(或未氯化)的嵌段结构。在两步固相氯化时,晶区受到较大程度的破坏,氯化作用已不局限在无定形区,其结晶结构的破坏主要同第二步氯化程度有关,即使CPE氯含量相同,若前后两步氯化程度不同,结构有很大差异。     

Pulse plating effect on microstructure and corrosion properties of Zn–Ni alloy coatings

The influence of pulse plating parameters on the surface morphology, grain size, lattice imperfection and corrosion properties of Zn–Ni alloy has been studied. The coatings were electrodeposited in an alkaline cyanide-free solution. AFM was applied for surface morphology examination, XRD measurements were carried out for phase composition and texture analysis, electron probe microanalysis was used for alloy chemical composition studies, while electrochemical techniques were applied for corrosion performance evaluation. The pulse plated Zn–Ni coatings appeared to consist of the γ-Zn₂₁Ni₅ phase and the composition of the alloy depended on the plating parameters. The grain size, lattice imperfection and homogeneity of grain distribution were established to be the main factors determining corrosion behaviour of the coating. Presented at the 4th Baltic Conference on Electrochemistry, Greifswald, March 13–16, 2005     

(XN)4R4簇合物的结构与化学键

用密度泛函理论,在B3LYP/6-311G水平上,对(XN)4R4 (X=C,Si,Ge;R=H,CH3,NH2,OH)及合成的先驱化合物(XN)2R2进行几何构型、电子结构、振动频率和化学反应焓变等进行了研究.结果表明,(RCN)4比(CNR)4更稳定.所有簇合物的零点能EZP值,R=H时最小,R=CH3时最大,R配位原子依次为C、N和O时,EZP值逐渐减小.     

第一性原理计算钛酸铅A位掺杂对其负热膨胀性的影响

近年来,实验发现钛酸铅基材料具有负热膨胀性,且其热膨胀程度会受到掺杂元素的影响. 目前所研究的A位掺杂体系中,仅Cd原子掺杂能使钛酸铅负热膨胀性增强. 所以研究A位掺杂钛酸铅,比较Cd原子与其他原子在掺杂钛酸铅时化学键的异同,有助于深刻理解钛酸铅负热膨胀的本质. 本文利用第一性原理,分别优化了Sr、Ba、Cd掺杂钛酸铅的晶格常数,计算了它们的态密度和电荷密度. 结果表明Cd―O键的共价性强于Pb―O键,而Ba―O键和Sr―O键几乎呈离子性,Ba/Sr对Pb的替代削弱了化合物的共价性,降低了自发极化强度. 与实验测量的热膨胀系数对比可以发现,A位原子与氧原子之间的共价性增强,化合物负热膨胀程度升高;若A位原子与氧原子之间的共价性削弱,负热膨胀程度降低. 可见A位原子与氧原子之间的共价性影响了钛酸铅基化合物负热膨胀性.     

Synthese,Struktur und einige Reaktionen [N-(N′,N′,N″,N″-tetramethyl)-guanidinyl]-substituierter Phosphorylverbindungen

Synthesis, Structure, and some Reactions of N-(N′,N′,N″,N″-tetramethyl)guanidinyl-substituted Phosphoryl Compounds The tetramethylguanidinyl-substituted phosphoryl compounds 1 – 10 were prepared in the reaction of the appropriate chlorophosphoryl compounds with either N′,N′,N″,N″-tetramethylguanidine (HTMG) or N-trimethylsilyl-(N′,N′,N″,N″-tetramethyl)guanidine (TMSTMG). With methyl iodide 1 reacted with N-alkylation to give the ammonium salt 11. 1 reacted with BF₃ · Et₂O at both imino nitrogen atoms with formation of the bis-BF₃-adduct 12 . The X-ray structure determination of phenylphosphonic acid-bis(N′,N′,N″,N″-tetramethylguanidinide) 3 shows shortened PN-bonds and widened PNC-angles, consistent with the partial double bond character of the PN-bond.     

原子结构参数的改进Xa法计算

六十年代后期,在Hartree－Fock-Slater法的基础上,提出了Xα法［1］．用于原子结构计算的Xα法与HF（Hartree－Fock）法的主要区别在于：用简单的统计平均交换势替代了HF法中计算最为困难的电子交换势,从而在保持较高理论严谨性和计算精确度的同时,大大减少了计算工作量,近年来获得了广泛的应用．我们尝试用经过适当修改的Xα方法,计算原子参数,解决分子结构中的某些问题．用原子参数解决分子问题,历来是化学和物理工作者常用的方法．本工作的意图是引入一个比HF法简单的容易在微机上实现的某种表现原子参数的计算方法,提供…