环境监测现状

目前，全国已形成了国家、省、市、县四级环境监测网络，共有专业、行业监测站4800多个，其中环保系统监测站2200多个，行业监测站2600多个，国控的空气质量监测网站103个，酸雨监测网站113个，水质监测网站135个。同时，还建有噪声监测网、辐射监测网和区域监测网等。到2005年，国控环境监测网络调整为：环境空气监测网站226个，测点数793个；酸雨监测网站239个，测点数472个；水质监测网站197个；监测断面1074个；生态监测网站15个。目前，我国已制定各类国家环境标准410项，覆盖了大气、水质、土壤、噪声、辐射、农药等领域。开展了环境质量监测，     

meso-四(对烷氧苯基)卟啉金属配合物的合成和性能研究(II)

合成了Zn、Pb两个系列卟啉金属配合物12个,其中6个为未见文献报道的新化合物,用元素分析、IR、UV、^1HNMR、MS确证了其结构。总结了Zn、Pb与卟啉类配体配合的IR、UV、^1HNMR判据。研究了这两个系列化合物的液晶性能,发现9个化合物具有液晶性。     

基于药物数据报道数据库的虚拟组合片段库构建

对药物数据报道数据库中142553个药物分子进行统计分析, 提取得到了这些药物分子的共同结构特征. 根据药物分子的结构特征将其拆分为环结构、侧链和连接子, 共整理得到32017个片段结构, 其中环结构13642个、侧链10076个、连接子8299个. 为更好地指导全新药物设计, 利用拆分片段构建了三个虚拟组合片段数据库: 用环结构和侧链组合方式构建了药效基团库, 含有34244个片段; 用环结构的刚性特点构建了基本骨架库, 含有片段13574个; 直接利用连接子构建了连接片段库, 含有连接片段8051个. 库中所有片段都经过能量优化, 均具有合理的构型和构象, 可以用于虚拟组合库的构建和全新药物设计.     

卷烟内在质量的气相色谱－数学聚类法研究

采用吸附丝色谱方法采集和分析了红塔山牌卷烟的挥发性成分,对 10个真品进行 R型聚类分析和 R型因子分析,从 26个组分提取出对卷烟质量起主导作用的 7个特征变量（组分）,并对其丰度进行了讨论,进而建立了红塔山卷烟的质量数学模型,用 2个真品和 2 个假冒品对模型进行了检验,结果令人满意。     

新建本科院校化学师范专业人才培养模式的探索

韶关学院化学师范本科专业以培养应用型粤北山区中学化学教师为目标定位,通过优化重组相关的专业课程体系,创建基础与专业、综合与设计、科学探究与创新实验教学平台,构建了“1个核心、2个导向、3个凸显、4个结合、5个一体、6个共同、7个适应”的人才培养模式,完成了师范生培养与中学化学教学的无缝对接,实现了教师职前师范教育与职后教育培训一体化.     

meso-四(对烷氧苯基)卟啉金属配合物的合成和性能研究(Ⅱ)

合成了Zn、Pb两个系列卟啉金属配合物12个,其中6个为未见文献报道的新化合物,用元素分析、IR、UV、1HNMR、MS确证了其结构.总结了Zn、Pb与卟啉类配体配合的IR、UV、1H NMR判据.研究了这两个系列化合物的液晶性能,发现9个化合物具有液晶性.     

中学化学教师使用“课程标准”情况的调查研究

采用问卷调查法,科学取样,从“课标文本的4个部分”、“化学课程的8个模块”、“化学教学的4个环节”3个角度客观分析了化学教师使用《普通高中化学课程标准（实验）》的基本情况,并从主客观2个方面深入讨论了影响教师使用的各种因素。     

分子三维投影法在苯酚类化合物构效关系研究中的应用

对苯酚类化合物进行三维投影得到了5个形状参数,将其与3个Am指数及8个量子化学参数相结合.由最佳变量子集回归法对变量进行了压缩与选择,运用多元回归分析和人工神经网络法分别构造了预测数学模型,得到了满意的结果.     

meso-四(对烷氧苯基)卟啉及其金属配合物的合成、表征及液 晶性

合成了meso-四(对烷氧苯基)卟啉及其Cu,Co,Zn,Pb金属配合物38个,其中14个为未见文献报道的新化合物。用元素分析,IR,UV,^1HNMR,MS对其进行了表征,确证了其结构。研究了这五个系列化合物的液晶性能,发现16个化合物具有液晶性,探讨了烷氧基链长及配位金属离子对液晶性能的影响。     

meso-四(邻烷氧基苯基)卟啉及其铜配合物的合成、表征和性能研究

合成了meso-四(邻烷氧基苯基)卟啉及其铜配合物两个系列20个化合物, 其中未见文献报道的化合物16个, 研究了其合成、分离、纯化方法, 得到了这两个系列化合物的晶体或固体, 用¹H NMR, MS, IR, UV, 元素分析等方法确证了这些化合物的结构. 用差示扫描量热法(DSC)和偏光显微镜(PM)研究了这两个系列化合物的液晶性能, 发现19个化合物具有液晶性, 其液晶行为表现为升温单变液晶.     

Synthesis of acyclic quaternary ammonium compounds containing ω-alkoxyethyl and 2-hydroxyethyl substituents at the nitrogen atom

Russian Chemical Bulletin - A series of acyclic symmetric quaternary ammonium chlorides Me2(HOCH2CH2)N+(CH2CH2O)nR Cl– (n = 1, R = n-C9H19; n = 2, R = n-C6H13; n = 3, R = n-C3H7) was...     

Studies of gas-phase fragmentation reactions of [Pd(PPh3)2(OCOR)]+ by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Gas-phase fragmentation reactions of [Pd(PPh3)2(OCOR)]+ (R = H, CH3, CD3, C2H5, n-C3H7, n-C6H13 and C6H5) were studied by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS). In sustained off-resonance irradiation collision-activated dissociation (SORI-CAD) experiments, the complexes all dissociated to yield the same product ion at m/z 629.1. We propose that the fragmentation pathway occurs through the elimination of RCOOH and a palladium(IV) hydride intermediate. Semi-empirical (PM3) calculations shed light on the mechanism for the fragmentation reactions of these compounds. The results of deuterium-labeling experiments indicate that the protons of RCOOH lost from [Pd(PPh3)2(OCR)]+ originate from the phenyl in the triphenylphosphine ligand. [Pd(PPh3)2(OCOH)]+ undergoes two competitive pathways in SORI-CAD experiments, one of which is similar to that of [Pd(PPh3)2(OCOR)]+ (R = CH3, CD3, C2H5, n-C3H7, n-C6H13 and C6H5), and the other involves decarboxylation. The present study demonstrates that MS could play an important role in studying the gas-phase chemistry of palladium hydrides.     

Generation and reactivity of enantiomeric (BINOLato)Ni+ complexes with chiral secondary alcohols in the gas phase

In the presence of secondary alcohols, electrospray ionization of dilute methanolic solutions of nickel(II) salts and 1,1'-bis-2-naphthol (BINOL) leads to complexes of the formal composition [(BINOLato)Ni(CH3CH(OH)R)]+ (BINOLato refers to a singly deprotonated (R)- or (S)-1,1'-bis-2-naphthol ligand; R=CH3, C2H5, n-C3H7, n-C4H9, n-C5H11, n-C6H13, c-C6H11, and C6H5). Upon collision-induced dissociation, each mass-selected nickel complex either loses the entire secondary alcohol ligand or undergoes bond activation followed by elimination of the corresponding ketone, as revealed by deuterium labeling. When enantiomeric BINOLato ligands (R or S) are combined with chiral secondary alcohols (R or S), differences in the branching ratios between these channels for the two stereoisomers of the secondary alcohols provide insight into the chiral discrimination operative in the C--H- and O--H-bond activation processes. For saturated alkan-2-ols, the chiral discrimination is low, and if any preference is observed at all, ketone elimination from the homochiral complexes (R,R and S,S) is slightly favored. In contrast, the diastereomeric (BINOLato)Ni+ complexes of 1-phenylethanol exhibit preferential ketone losses for the heterochiral systems (S,R and R,S).     

Ferrimagnetic Mixed-Valency and Mixed-Metal Tris(oxalato)iron(III) Compounds: Synthesis, Structure, and Magnetism

The synthesis and structural and magnetic characterization of 16 compounds AM(II)Fe(III)(C(2)O(4))(3) (A = N(n-C(3)H(7))(4), N(n-C(4)H(9))(4), N(n-C(5)H(11))(4), P(n-C(4)H(9))(4), P(C(6)H(5))(4), N(n-C(4)H(9))(3)(C(6)H(5)CH(2)), (C(6)H(5))(3)PNP(C(6)H(5))(3), As(C(6)H(5))(4); M(II) = Mn, Fe) are reported. X-ray powder diffraction profiles are indexed in R3c or its subgroup P6(5)22 or P6/mmm to derive unit cell constants. The structures of all the compounds consist of two-dimensional honeycomb networks [M(II)Fe(III)(C(2)O(4))(3)(-)](infinity). The M(II) = Fe compounds behave as ferrimagnets with T(c) between 33 and 48 K, but five exhibit a crossover from positive to negative magnetization near 30 K when cooled in a field of 10 mT. The compounds exhibiting this unusual magnetic behavior are those that have the highest T(c). Within the set N(n-C(n)()H(2)(n)()(+1))(4)Fe(II)Fe(III)(C(2)O(4))(3) (n = 3-5), T(c) increases with interlayer separation and the low-temperature magnetization changes from positive (n = 3) to negative (n = 4, 5). In the M = Mn(II) compounds, the in-plane cell parameter a(0) is approximately 0.03 ? greater than in the corresponding M = Fe(II) ones while the interlayer separation (c(0)/6) is on average 0.08 ? smaller. All members of the M(II) = Mn series have magnetic susceptibilities showing broad maxima at 55 K characteristic of two-dimensional antiferromagnetism, but the magnetization of several of the salts increases sharply below 27 K due to the onset of spin canting, the magnitude of which varies significantly with A.     

Enantioselective self-assembly of bimetallic [Mn(II) (delta)-Cr(III)(C2O4)3]- and [Mn(II) (lambda)-Cr(III)(C2O4)3]- layered anionic networks templated by the optically active (Rp)- and (Sp)-[1-CH2N(n-C3H7)3-2-CH3-C5H3Fe-C5H5]+ ions

The ferrocenic ammonium (Rp)- and (Sp)-[1-CH2NR(3-)-2-CH3-C5H3Fe-C5H5] iodide salts with R=CH3, C2H5, n-C3H7, n-C4H9, were synthesized starting from the (Rp)- and (Sp)-[1-CH2N(CH3)2-2-CH3-C5H3Fe-C5H5] amines obtained in their optically active forms through asymmetric cyclopalladation of [C5H5Fe-C5H4CH2N(CH3)2]. 1H NMR studies of these planar chiral 1,2-disubstituted ferrocenic ammonium iodide salts in the presence of the (Delta)-(tris(tetrachlorobenzenediolato)phosphate(V) anion), [(Delta)-Trisphat] support the formation of specific diastereomeric ion pairs. Such intermolecular interactions can be related to the self-assembly of the two-dimensional optically active compounds [[(Sp)-1-CH2N(n-C3H7)3-2-CH3-C5H3Fe-C5H5][Mn (Delta)-Cr(C2O4)3]] and [[(Rp)-1-CH2N(n-C3H7)3-2-CH3-C5H3Fe-C5H5][Mn (Lambda)-Cr(C2O4)3]] starting from the resolved (Rp)- and (Sp)-[1-CH2N(n-C3H7)3-2-CH3-C5H3Fe-C5H5]+ ion associated to the racemic anionic building block rac-[Cr(C2O4)3]3- and Mn2+. Both enantiomeric forms of the networks behave as ferromagnets with a Curie temperature of 5.7 K.     

双酰胺双(3'-正十五烷基-苯并-15-冠-5)PVC膜钾离子选择电极的研究

本文合成了十个双酰胺型双(3'-正十五烷基-苯并-15-冠-5)化合物, 制成的PVC膜钾离子选择电极, 性能优良.     

(二乙基二茂铁基)二茂铁基甲醇及其胺衍生物的合成与 性质

1,1'-二乙基-2-(和3)-二茂铁酰基二茂铁经LiAlH4还原得到两种相应的双二茂铁基甲醇。它们对酸的敏感性很高，与BF3在二氯甲烷中作用可形成稳定的二茂铁基甲基碳正离子，无需从溶液中分离出来，便可与胺RNH2[R=C2H5,n-C3H7,n-C4H9,HOCH2CH2,HOCH(CH3)CH2,HOCH2CH(C2H5)]作用得到产率颇高的二茂铁基胺，这种由α-二茂铁基醇制备α-二茂铁基胺的方法具有简单、快速和原料廉价的特点。     

Palladium-Catalyzed Hydroalkoxylation of Methylenecyclopropanes

Hydroalkoxylations proceed by a different path than transition metal catalyzed hydrostannations and hydrosilylations. In the reaction of methylenecyclopropanes 1 with alcohols 2 in the presence of Pd(0), the distal bond in the cyclopropane ring is cleaved, and allyl ether 3 is formed selectively. R(1)=n-C(7)H(15), PhCH(2)CH(2); R(2)=H, PhCH(2)CH(2); R(3)=PhCH(2), CF(3)CH(2), Et(3)Si, n-C(4)H(9), etc.     

取代脲促进环氧树脂／双氰胺固化体系反应机理

双氰胺作为环氧树脂的固化剂，由于固化产物具有优良的机械和电性能，广泛应用在汽车、航天及电子等领域中．但由于其固化温度高达180C以上，使应用范围受到很大限制．专利文献曾报道晚衍生物作为环氧树脂／双氰胺固化体系的促进剂，可以使体系的固化温度降低到130～140oC，并且在室温下仍保持一定的潜伏性［‘，’］．在以往的研究中，认为取代脉的促进作用在于其与环氧发生反应生成环状化合物2一心竣烷酮和仲胺，仲胺与环氧基进一步反应生成的叔胺可以催化环氧发生阴离子聚合［’～’］．实验表明，环氧树脂／双氰胺／取代脉体系的固化温…     

Structures, electron affinities, and harmonic vibrational frequencies of the simplest alkyl peroxyl radicals and their anions

The molecular structures and electron affinities of the R-OO/R-OO(-) (R = CH3, C2H5, n-C3H7, n-C4H9, n-C5H11, i-C3H7, t-C4H9) species have been determined using seven different density functional or hybrid Hartree-Fock density functional methods. The basis set used in this work is of double-zeta plus polarization quality with additional diffuse s-type and p-type functions, denoted DZP++. The geometries are fully optimized with each density functional theory method. Harmonic vibrational frequencies were found to be within 3.1% of available experimental values for most functionals. Two different types of the neutral-anion energy separations reported in this work are the adiabatic electron affinity and the vertical detachment energy. The most reliable adiabatic electron affinities obtained at the DZP++ BP86 level of theory are 1.150 (CH3OO), 1.124 (C2H5OO), 1.146 (n-C3H7OO), 1.173 (n-C4H9OO), 1.184 (n-C5H11OO), 1.145 (i-C3H7OO), and 1.114 eV (t-C4H9OO). Compared with the experimental values, the average absolute error of the BPW91 method is 0.05 eV.