STRUCTURE OF 3-(N-METHYL- β-NAPHTHYLAMINO)-ACROLEIN,C_(14)H_(13)NO

<正> M=211.28, monoclinic, P21/c, a=10.268(2), b=11.581(2), c=9.605(2)A, β=100.40(2)°, V=1123.5(4)A3, 2=4, Dx=1.25 g/cm3, λ=0.71069A, u=0.73 cm-1, F(000)=448, room temperature, R=0.041. The planes of the formylvinyl groupand the naphthyl ring are tilted with respect to the plane of nitrogen frameN by 8.6 and 33.6 , respectively. The O atom and the methyl group are in Z position.     

STRUCTURE OF 5-(N-METHYL-β-NAPHTHYLAMINO)-PENTA-2,4-DIENAL,C_(16)H_(15)NO

<正> M=237.31, orthorhombic, Pbca, a=8.342(2), b=15.675(3), c=19.779 (4)A3, Z=8, Dx=1.21 g/cm3, λ(MoKα)=0.71069A, μ=0.71 cm-1, F(000)=1008, room temperture, R=0.046. The planes of the formyl butadienyl group and the naph-thyl ring are tilted with respect to the plane of the nitrogen frame N by 2.8° and 31.4° , respectively. The O atom and the methyl group are in Z position.     

4-(2-吡啶偶氮)-间苯二酚-SCN-体系吸光光度法测定微量NO2-

研究了PAR在酸性介质中质子化后与NO2-和SCN形成三元离子缔合物的最佳条件,提出了吸光光度法测定微量NO2-的新方法.在稀H2SO4介质中,三元离子缔合物的最大吸收峰位于370nm处,表观摩尔吸光系数为1.25×104L@mol-1@cm,NO2-含量在0～50μg/25ml范围内符合比耳定律.方法用于环境水样中微量NO2-的测定,结果满意.     

2-(2-羟基-5-氯苯基)-1H-苯并咪唑-铜(Ⅱ)配合物作为NO荧光探针的初探

常温下合成了2-(2-羟基-5-氯苯基)-1H-苯并咪唑荧光化合物和其二价铜离子的配合物,并对配合物的结构和稳定性进行了表征,用荧光光谱、质谱、红外光谱等研究了配合物与NO反应的机理.结果表明,该配合物与NO的反应具有高度的选择性,不受其他常见干扰分子的影响.配合物应用于脂多糖(LPS)激活的小鼠巨噬细胞中NO的测定,能够得到具有较好分辨率的荧光成像结果.     

Polymeric (NO)3(N2O) n , (NO)3(N2O) n + , and (NO)3(N2O) n − : an interpretation of experimental observations

Semi-empirical and ab initio calculations are reported which provide a possible explanation for reported experimental results on 2-photon ionization of NO containing a few percent of N₂O, which found (NO)₃(N₂O) _n ^+or? clusters to be significantly more abundant than other (NO) _m (N₂O) _n products. It is found that the observed abundances of (NO)₃(N₂O) _n ionic clusters may be accounted for by the existence of covalent cyclic trimers of nitric oxide attached to oligomers of nitrous oxide. The extra stability of NO trimers in the observed clusters appears to arise from (NO) ₃ ⁺ rather than (NO)₃. Attachment of an (N₂O) _n side chain to (NO) ₃ ⁺ occurs exothermically. It is suggested that the addition of N₂O to cyclic-(NO) ₃ ⁺ might provide a means of making a polymer of nitrous oxide, which could have useful properties.     

(S)-(-)-norlaudanosine和(S)-(-)-O,O-dimethylcoclaurine的合成

以高藜芦胺为起始原料,经N-磺酰化反应制得高藜芦磺酰胺(2);2分别与芳乙烯甲醚经对甲苯磺酸催化的Pictet-Spengler反应后用金属钠脱除Ts基团合成了(±)-norlaudanosine(5a)和(±)-O,O-dimethylcoclaurine(5b);使用半量拆分法,以N-乙酰-L-苯丙氨酸为拆分剂,制得(S)-(-)-5a和(S)-(-)-5b,其结构经1H NMR,13C NMR,IR,MS和HR-ESI-MS确证。     

La(NO3)3和Pr(NO3)3对高岭石脱羟基动力学的影响

采用热重和微商热重(TG/DTA)综合热分析技术在不同升温速率下研究了掺入La(NO₃)₃和Pr(NO₃)₃的高岭石的热分解过程, 利用Coats-Redfern积分法和Achar微分法对热分析实验数据进行动力学计算, 得到了高岭石脱羟基反应过程中的控制机理函数、 活化能和指前因子等动力学参数; 分析了2种稀土掺入对高岭石脱羟基过程动力学参数的影响, 并用Ozawa法对活化能进行了验证. 结果表明, 未掺稀土和掺入Pr(NO₃)₃的高岭石的脱羟基反应过程均受化学反应模型F₃控制, 反应的活化能分别为307.94和282.86 kJ/mol, 指前因子lnA的值分别为47.8980和44.1718; 掺入La(NO₃)₃的高岭石脱羟基反应过程控制机理函数发生改变, 受化学反应模型F₂控制, 反应活化能为196.02 kJ/mol, 指前因子lnA的值为29.5551. 与未掺稀土的高岭石对比, 掺入Pr(NO₃)₃后活化能和指前因子略有降低; 而掺入La(NO₃)₃后则显著降低, 分别降低了36.34%和38.30%. 采用Ozawa法验证得到的活化能与Coats-Redfern积分法和Achar微分法结果一致.     

镉还原法测定血清NO稳定代谢产物NO3-/NO2-

建立了血清NO的间接测定方法。采用正交设计法[L9(3^4)]观察不同还原剂及其用量,原时间和温度对NO3^-还原率的影响。最佳还原条件为400mg镀铜镉粒室温还原120min,还原率达97%以上。方法简便易行,不需昂贵设备,准确度较高,适合一般实验室用于各种生物医学实验中NO的间接测定。     

分馏萃取分离稀土的数学模拟—HEH(EHP)-煤油-HNO3-(Sm-Gd)(NO3)3体系

进行了HEH(EHP)-煤油-HNO₃-(Sm-Gd)(NO₃)₃体系的萃取平衡实验与分馏萃取实验。串级实验得到了水相出口Sm的纯度为96.7%,有机相出口Gd的纯度>99%的结果。应用萃取平衡实验数据建立了计算简便、精度较高的半经验两相分配模型: H_i3^aXj_i4^aYj_i5^a(i,j=1,2)。给出了由各级平衡分配模型和物料衡算式组成的非线性方程组—串级模型。介绍了模拟计算所用的矩阵解法及其FORTRAN程序,计算所得各级金属离子浓度、水相酸度、以及自由萃取剂浓度的分布与实验值符合程度较高。     

NO与Ag(110)表面的相互作用

采用Ｘ射线光电子能谱、紫外光电子能谱和原位Ｒａｍａｎ光谱研究了ＮＯ和Ｏ２在Ａｇ（１１０）表面的吸附和反应。结果表明，室温条件下，ＮＯ在银表面不发生明显的吸附和分解，氧的加入导致了ＮＯ在角表面的氧化反应生成吸附态的氮氧化物和原子态氧。     

Structural study of complex [Rh(NH3)5(NO2)](NO3)2·H2O, [Rh(NH3)5(NO2)][Pd(NO2)4], and K2[Rh(NH3)(NO2)5]·H2O salts

Compounds [Rh(NH₃)₅(NO₂)](NO₃)₂·H₂O (I) with a = 7.6230(3) Å, b = 7.6230(3) Å, c = 10.3584(4) Å, space group I-42m, Z = 2, d _calc = 2.026 g/cm³, V = 601.93(4) ų, Rh-NH_{3 eq} = 2.074 Å, Rh-NH_{3 ax} (NO₂) = 2.048 Å; [Rh(NH₃)₅(NO₂)][Pd(NO₂)₄] (II) with a = 8.095(3) Å, b = 22.422(8) Å, c = 7.887(3) Å, β = 98.559(17)°, space group Cc, Z = 4, d _calc = 2.461 g/cm³, V = 1415.6(9) ų, Rh-NH_{3 eq} = 2.069 Å, Rh-NH_{3 ax} = 2.090 Å, Rh-NO₂ = 2.002 Å; K₂[Rh(NH₃)(NO₂)₅]·H₂O (III) with a = 7.5177(5) Å, b = 20.9856(15) Å, c = 7.7017(5) Å, space group Cmc2₁, Z = 4, d _calc = 2.439 g/cm³, V = 1215.05(14) ų, Rh-NH_{3 ax} (NO₂) = 2.094 Å, Rh-NO_{2 eq} = 2.030 Å are synthesized and studied using single crystal X-ray diffraction.     

Structurally characterized ternary U-O-N compound, UN4O12: UO2(NO3)2.N2O4 or NO(+)UO2(NO3)3-?

The synthesis and characterization of the ternary U-O-N compound NO(+)UO2(NO3)3- (1) using IR and low-temperature and room-temperature Raman spectroscopy as well as 14N and 15N NMR spectroscopy are reported. In addition, solution Raman spectra of compound 1 recorded in various solvents are reported. The structure of compound 1 was determined using single-crystal X-ray diffraction techniques: monoclinic, C2/c, a = 13.3992(4) angstroms, b = 9.9781(4) angstroms, c = 7.6455(2) angstroms, beta = 115.452(2) degrees, V = 922.98(5) angstroms3, Z = 4. Compound 1 is highly moisture-sensitive and must be handled under an inert atmosphere. It reacts with water with the liberation of NO2. For the first time, this important precursor for the synthesis of anhydrous uranyl nitrate could be unambiguously identified and has been shown to be an ionic nitrosonium salt and not an adduct between uranyl nitrate and dinitrogen tetroxide, UO2(NO3)2.N2O4, as is incorrectly and predominantly cited in the literature.     

THE PHENOMENON OF KRYPTORACEMIC CRYSTALLIZATION. PART 1. COUNTERION CONTROL OF CRYSTALLIZATION PATHWAY SELECTION. PART 4. THE CRYSTALLIZATION BEHAVIOR OF (+/−)-[Co(tren)(NO2)2]Br(I), (+/−)-[Co(tren)(NO2)2]2Br(ClO4) · H2O(II), (+/(−)-[Co(tren)(NO2)2]ClO4(III) AND ATTEMPTS TO SOLVE THE STRUCTURE OF (+/−)-[Co(tren)(NO2)2]NO3(IV)

Abstract

Racemic aqueous solutions of (+/?)-[Co(tren)(NO₂)₂]Br (I), (+/?)-[Co(tren)(NO₂)₂]ClO₄ (III) and [Co(tren)(NO₂)₂]NO₃(IV) crystallize as racemates. By contrast, the double salt, (+/?)-[Co(tren)(NO₂)₂]₂Br(ClO₄) · H₂O(II), produces kryptoracemic crystals belonging to the enantiomorphic space group P2₁2₁2₁ (No. 19). The former three species crystallize with one molecule in the asymmetric unit; in the latter, a racemic pair is the asymmetric unit, a fact which is hidden by the enantiomorphic nature of its space group – thus the name of the crystallization phenomenon reported. In (II) pairs of cations are related by an approximate, non-crystallographic, inversion center. The crystal structure and polarity of (I) and the absolute configuration of (II) were determined by refinement. The crystalline contents of (I) to (III) consist of infinite strings of hydrogen bonded cations, the counter ions and (where relevant) waters of crystallization acting as a hydrogen-bonding glue linking the spiral strings

In (II), the N-CH₂-CH₂-NH₂-Co rings of Co(1) are (δδλ) and those of Co(2) are (λλδ) and adjacent strings are linked by the counter-anions and the water of crystallization. Pairs of Co(1) and of Co(2) cations are hydrogen bonded to one another by two N-O···H-N linkages. Finally, pairs of composition Co(1)-Co(1) as well as of Co(2)-Co(2) share another pseudo-inversion center which is approximately valid for the CoN₆ portion of each cation. Since the atoms of the cation are ordered, it is impossible for the pseudo-inversion center to be valid for the -CH₂-CH₂- fragment of the Co(1)-Co(1) or of Co(2)-Co(2) pairs. (I) and (III) crystallizes as racemates whose five-membered rings have chiroptical symbols (δδλ), or its enantiomer.     

由(S)-和( R )-天冬氨酸合成( R )-和(S)-(2-苄氧乙基)环氧乙烷的改良方法

苄氧乙基环氧乙烷;不对称合成;由(S)-和( R )-天冬氨酸合成( R )-和(S)-(2-苄氧乙基)环氧乙烷的改良方法     

Schiff碱配合物的研究(Ⅴ)——Fe(Salen)NO3与No2-的反应

Salen是最简单的Schiff碱之一。最近发现,其Fe(Ⅲ)的配合物Fe(Salen)NO_3能与仲胺作用,并很快生成致癌物质亚硝胺。另一方面,一些含Fe_4S_4簇的酶能将NO_2~-催化还原成氨。本文研究了Fe(Salen)NO_3与NO_2~-的作用及其产物的某些性质。 1 实验和结果     

AgmC60(OH)n(NO3)m的合成及其热稳定性

自从富勒烯被发现并克量级制备以来,富勒烯独特的结构和性质引起了人们极大兴趣和关注,对富勒烯及其衍生物的研究已迅速发展[1],由于C60具有光诱导剪切DNA、抑制艾滋病毒等特性,因而在生物化学及医学方面具有潜在应用前景,其中水溶性富勒烯衍生物的研究是富勒烯化学较为活跃的研究领域之一[2～5],尤其是羟基化富勒烯(或称富勒醇fullerenols)的合成方向的研究[5]。目前富勒烯羟基衍生物的合成方法已得以深入研究,但其化学反应性能的研究未见报道,本文合成了羟基C60银盐,并对其热稳定性能进行了研究。1　实验部分1 1　主要仪器及试剂C6…     

混合金属钴钌原子簇Co3Ru(CO)11(NO)2, (RC≡CR^1)Co3Ru(CO)9(NO)的合成与表征

本文报道Co-Ru簇的合成与表征的研究。由Et4N[RuCl4(CH3CN)2]和Co2(CO)8制备了Et4N[Co3Ru(CO)12]·1/3THF, 它与等摩尔的NOBF4反应得到Co3Ru(CO)11(NO)(1)和Co2Ru(CO)11(5)。簇合物1分别与乙炔、苯基乙炔和二苯基乙炔进一步反应得到(HC≡CH)Co3Ru(CO)9(NO)(2), (PhC≡CH)Co3Ru(CO)9(NO)(3)和(PhC≡CPh)Co3Ru(CO)9(NO)(4)。在上述反应中还分离得到(HC≡CH)Co2Ru(CO)9(6), (PhC≡CH)Co2Ru(CO)9(7)和(PhC≡CPh)Co2Ru(CO)9(8)。对所得族合物1,2,3,4进行了IR, UV,^1H NMR, m.p., 元素分析和单晶X射线衍射分析等性质表征, 簇合物3的晶体属单斜晶系, pα1/n空间群, 晶胞参数为: a=1.1438(9), b=.3033(6), c=1.4345(9)nm, β=100.72(4)°, 每个晶胞中有四个分子。     

混合金属钴钌原子簇Co3Ru(CO)11(NO)2, (RC≡CR^1)Co3Ru(CO)9(NO)的合成与表征

本文报道Co-Ru簇的合成与表征的研究。由Et4N[RuCl4(CH3CN)2]和Co2(CO)8制备了Et4N[Co3Ru(CO)12]·1/3THF, 它与等摩尔的NOBF4反应得到Co3Ru(CO)11(NO)(1)和Co2Ru(CO)11(5)。簇合物1分别与乙炔、苯基乙炔和二苯基乙炔进一步反应得到(HC≡CH)Co3Ru(CO)9(NO)(2), (PhC≡CH)Co3Ru(CO)9(NO)(3)和(PhC≡CPh)Co3Ru(CO)9(NO)(4)。在上述反应中还分离得到(HC≡CH)Co2Ru(CO)9(6), (PhC≡CH)Co2Ru(CO)9(7)和(PhC≡CPh)Co2Ru(CO)9(8)。对所得族合物1,2,3,4进行了IR, UV,^1H NMR, m.p., 元素分析和单晶X射线衍射分析等性质表征, 簇合物3的晶体属单斜晶系, pα1/n空间群, 晶胞参数为: a=1.1438(9), b=.3033(6), c=1.4345(9)nm, β=100.72(4)°, 每个晶胞中有四个分子。     

用于NO和C_(10)H_(22)氧化及C_(10)H_(22)选择性还原NO的(La_(0.8)A_(0.2))MnO_3(A=Sr,K)钙钛矿催化剂(英文)

In this work, we studied the catalytic activity of LaMnO3 and(La0.8A0.2)MnO3(A = Sr, K) perovskite catalysts for oxidation of NO and C10H22 and selective reduction of NO by C10H22. The catalytic per‐formances of these perovskites were compared with that of a 2 wt% Pt/SiO2 catalyst. The La site substitution increased the catalytic properties for NO or C10H22 oxidation compared with the non‐substituted LaMnO3 sample. For the most efficient perovskite catalyst,(La0.8Sr0.2)MnO3, the results showed the presence of two temperature domains for NO adsorption:(1) a domain corre‐sponding to weakly adsorbed NO, desorbing at temperatures lower than 270 °C and(2) a second domain corresponding to NO adsorbed on the surface as nitrate species, desorbing at temperatures higher than 330 °C. For the Sr‐substituted perovskite, the maximum NO2 yield of 80% was observed in the intermediate temperature domain (around 285 °C). In the reactant mixture of NO/C10H22/O2/H2O/He,(La0.8Sr0.2)MnO3 perovskite showed better performance than the 2 wt% Pt/SiO2 catalyst: NO2 yields reaching 50% and 36% at 290 and 370 °C, respectively. This activity improvement was found to be because of atomic scale interactions between the A and B active sites, Sr2+ cation and Mn4+/Mn3+ redox couple. Thus,(La0.8Sr0.2)MnO3 perovskite could be an alternative free noble metal catalyst for exhaust gas after treatment.     

Synthesis of (R)-(-)-γ-amino β-hydroxy Butyric Acid (GABOB)

An efficient enantiospecific synthesis of a neuromodulator, antiepileplic and hypotensive drug (R)-(-)-γ-amino-β-hydroxybutyric acid (1) starting from (+) tartaric acid is described.