174例男性不育症患者精浆微量元素检测与分析

检测了174例男性不育症患者精浆锌、铁、铅、钙、镁等五种微量元素,以探讨不育症患者精浆微量元素含量与精液质量的关系。结果显示：（1）粘稠性精液组精浆锌含量显著低于正常粘度精液组（P＜0．01）,精浆钙含量低于正常度精液组（P＜0．05）,铁、铅、镁含量无差异（P＜0．05）。（2）无精子及少精子症组精浆铁、钙含量高于精子密度正常组（P＜0．01）,铜含量低于精子密度正常组（P＜0．01）,锌、镁含量无差异（P＜0．05）。（3）精子活动率低下组与正常组浆微量元素含量无差异（P＜0．05）。提示精浆锌、铁、铅、钙等微量元素含量改变是影响精液质量的重要原因之一。精浆镁含量与精液质量似无明显关系。     

幼儿头发中微量元素含量与身高、体重关系研究

普查了４４９名１－６岁儿童头发中锌、铁、铜、钙、锰、铅含量,用分层聚类分析法对其身高、体重与各元素进行相关分析。幼儿身高与头发中锌含量呈相关关系,与头发中铅含量呈负相关关系。体重与头发中锌含量呈显著的正相关关系。与头发中铅含量呈负相关关系。说明锌有利于身体发育,而铅对身体发育不利。     

儿童反复呼吸道感染与发锌、铁、铜、钙关系分析

为了解反复呼吸道感染与头发微量元素的关系,测定了52例易感儿及41例健康儿童发锌,铁,铜,钙含量,结果显示,易感儿发锌含量极显著低于健康组（P＜0．01）,发钙偏低,0．05＞P＞0．01,发铁,铅含 量基本正常,两组无显著差异,本研究表明儿童反复呼吸道感染与缺锌,缺钙有关。     

淮安市1684名中小学生血清钙、铁、锌含量分析

为了解淮安地区中小学生血清中钙、铁、锌含量情况,应用改进的火焰原子吸收光谱法对1684名对象的血清中相关元素的含量进行了测定。结果表明,该地区3种元素总体水平在正常范围内,钙、铁、锌血清含量分别为（102．69±26．30）mg／L、（1．01±0．61）mg／L、（0．86±0．45）mg／L;性别、城乡差别无统计学意义（P〉0．05）;而年级的差别有统计学意义（P值均〈0．0001）,初中组各元素水平明显高于小学组。     

强直性脊柱炎患者全血微量元素测定分析

选取人类白细胞抗原（HLA－B27）呈阳性的强直性脊柱炎患者54例，采晨空腹血，用原子吸收光谱法测定了全血中锌，铜，铁，钙及锶五种必需元素的含量。与50名无关节炎者组成的正常对照组进行比较。结果表明，患者组全血锌，铁，钙含量显著低于对照组（P＜0．01），锶低于对照组（P＜0．05），铜无统计学意义。提示患者体内微量元素代谢失常，很可能与该病的发生与发展有一定的关系。     

中山市1387名青年学生头发微量元素检测与分析

为了探讨中山市青年学生头发中的微量元素含量,测定了该市来自三个学校的1387名青年学生头发中的锌、铁、铜、钙、阵、锰、铅含量。结果表明,女生与男生的头发锌含量有显著差异（P＜0．05）,女生与男生的头发中钙含量有高度显著差异（P＜0．001）;城区与乡镇的青年学生头发中钙、铜含量有高度显著性差异（P＜001）;父母文化程度高与父母文化低的青年学生头发中钙含量有高度显著性差异（P＜0．01）;在青年学生的年龄、性别、家庭、居住地区等不同的比较中,以发钙值含量差异显著性最高。提示青年学生应注意饮食营养均衡,补充必需的微量元素,加强体育锻炼,对提高体系有一定的意义。     

幼儿头发锌、铅含量与身高、体重关系的研究

测定了深圳市南山区486名3岁儿童的身高，体重及其发锌，铅的含量。并对儿童头发锌，铅含量与身高。体重之间的关系进行了分析。结果显示，儿童的身高，体重与发锌含量呈显著的正相关。而与发铅呈显著负相关。证实锌具有促进儿童体格发育的作用。而铅则对体格发育具有妨碍作用。     

肝豆状核变性病患者头发微量元素的含量分析

为了解肝豆状核变性患者头发微量元素的含量，以及微量元素与肝豆状核变性病的关系，用火焰原子吸收分光光度计分别测定了患者和健康者头发的铜、锌、钙、铁的含量。结果表明，患病组头发与健康头发铜、锌、铁含量均在正常范围，无显著性差异（P〉0．05），而患者头发钙含量明显低于健康组头发含量，有显著性差异（P〈0．05）。可见患者发铜、锌、铁含量测定对肝豆状核变性病临床诊断没有意义，而发钙与肝豆状核变性病有密切关系，能反映患者体内钙代谢情况，提示患者排铜治疗的同时应及时补钙。     

沈阳市学龄前儿童末梢血矿物质检测结果分析

为了解沈阳市学龄前儿童体内矿物质钙、铁、锌、铜、镁的含量与年龄和性别的关系,探讨防治其缺乏的综合措施,利用BH 5100型原子吸收光谱仪对3483例学龄前儿童末梢血中铜、锌、钙、镁和铁元素进行了检测,采用SPSS 17．0软件进行统计分析。结果表明,该地区学龄前4个不同年龄组儿童末梢血锌、钙、铁、铜元素缺乏严重,分别占总样本的66．90％、39．76％、32．5％和26．87％;3～岁组末梢血中钙、铁、锌、镁含量与其它年龄组比较差异有统计学意义（P〈0．05）,各元素在性别问差异无统计学意义（P〉0．05）。该地区学龄前儿童钙、铁、锌、铜失衡明显,应加强营养素的合理搭配及矿物质的补充,保证儿童的健康成长。     

广东省惠东县280例6个月婴儿血铁含量与血红蛋白相关分析

为了解惠东县280例6个月婴儿血铁含量分析及与血红蛋白含量之间的相关性,采用多通道原子吸收光谱分析仪对280例健康6个月婴儿的末梢血做了铁、锌、铜、钙、镁5种元素的测定,同时采用全血液分析仪做了血常规24项检测。结果表明,有201人铁含量低于7．52mmol／L．铁元素缺乏率为71．8％;血红蛋白低于110g／L 有105人,贫血发生率为37．5％;血铁含量与血红蛋白含量之间为正相关,r=0．997,P〈0．01。提示6个月婴儿贫血患病率较高,亚临床缺铁较为普遍,必须积极采取预防干预措施,降低贫血病率。     

Metal-Directed Formation of Tetra-, Hexa-, Octa-, and Nonanuclear Complexes of Magnesium,Calcium, Manganese,Copper, and Cadmium

Efficacious metal control of self-assembly of dialkylketipinate dianions leads to completely different supramolecular assemblies. The structures of grid 1 , double-decker 2 , triple-decker 3 , and metalla-spherand 4 were characterized by X-ray crystallographic analyses or by NMR spectroscopy.     

Structural, magnetic, and spectroscopic studies of YAgSn, TmAgSn, and LuAgSn

The rare earth-silver-stannides YAgSn, TmAgSn, and LuAgSn were synthesized from the elements by arc-melting and subsequent annealing. The three stannides were investigated by X-ray powder and single-crystal diffraction: NdPtSb type, P6₃mc, Z=2, a=468.3(1), pm, wR₂=0.0343, 353 F² values, 12 variables for YAgSn, and ZrNiAl type, P6¯2 m, a=726.4(2), , wR₂=0.0399, 659 F² values, 15 variables for TmAgSn, and a=723.8(2), , wR₂=0.0674, 364 F² values, 15 variables for LuAgSn. Besides conventional laboratory X-ray data with monochromatized Mo radiation, the structures were also refined on the basis of synchrotron data with , in order to clarify the silver-tin ordering more precisely. YAgSn has puckered, two-dimensional [AgSn] networks with Ag-Sn distances of 278 pm, while the [AgSn] networks of TmAgSn and LuAgSn are three-dimensional with Ag-Sn distances of 279 and 284 pm for LuAgSn. Susceptibility measurements indicate Pauli paramagnetism for YAgSn and LuAgSn. TmAgSn is a Curie-Weiss paramagnet with an experimental magnetic moment of 7.2 μ_B/Tm. No magnetic ordering is evident down to 2 K. The local environments of the tin sites in these compounds were characterized by ¹¹⁹Sn Mössbauer spectroscopy and solid-state NMR (in YAgSn and LuAgSn), confirming the tin site multiplicities proposed from the structure solutions and the absence of Sn/Ag site disordering. Mössbauer quadrupolar splittings were found in good agreement with calculated electric field gradients predicted quantum chemically by the WIEN2k code. Furthermore, an excellent correlation was found between experimental ¹¹⁹Sn nuclear magnetic shielding anisotropies (determined via MAS-NMR) and calculated electric field gradients. Electronic structure calculations predict metallic properties with strong Ag-Sn bonds and also significant Ag-Ag bonding in LuAgSn.     

Synthesis and characterization of metal-centered, six-membered, mixed-valent, heterometallic wheels of iron, manganese, and indium

Heptanuclear metal-centered, six-membered, mixed-valent, heterometallic wheels 1-3 of iron, manganese, and indium were prepared in a one-pot reaction from N-benzyldiethanolamine (H2L(1)), cesium carbonate, [PPh4]2[MnCl4], and FeCl3 or InCl3. All three complexes were characterized by the combination of elemental analysis, FAB mass spectroscopy, X-ray diffraction and cyclic voltammetry and in the case of 1 additionally by M?ssbauer spectroscopy. In 1, four Mn(II) ions in the periphery are arranged in pairs alternating with one Fe(III) ion each, with an Fe(III) ion located in the center. In 2, three Mn(II) ions alternate with three In(III) ions, whereas in 3, four In(III) ions are arranged in pairs and alternate with one Mn(II) ion each. In 2 and 3 an Mn(II) ion is encapsulated in the center.     

Theoretical Study of Molecular Structure,Reactivity, Lipophilicity,and Solubility of N-Hydroxyurea,N-Hydroxythiourea,and N-Hydroxysilaurea

Ab initio molecular orbital methods at the CBS-QB3 level of theory have been used to study the structure and gas-phase stability of various tautomers and rotamers of N-hydroxyurea, N-hydroxythiourea, and N-hydroxysilaurea, their anions and protonated forms. The geometries of N-hydroxyurea, N-hydroxythiourea, and N-hydroxysilaurea, their anions and cations were optimized at the Becke3LYP/CBSB7 level of theory. For all compounds studied, the amidic form is computed to be substantially more stable than the iminolic tautomer. N-Hydroxyurea and its thio and sila derivatives are computed to behave as Nacids in the gas phase. These compounds are in gas-phase weak acids with a calculated acidity of about 1425 to 1355 kJ-mol^–1. Basicities increase in the order: N-hydroxyurea < N-hydroxythiourea < N-hydroxysilaurea. The most stable protonated structures are represented by several isomers with almost equal stability. Thus, in the N-hydroxyurea, N-hydroxythiourea, and N-hydroxysilaurea, both protonation at the double bonded (C=O, C=S and Si=O) oxygen and sulfur atoms, as well as the protonation at the N(H)OH nitrogen basic center is equally probable. The experimental pK _a value (10.6) of N-hydroxyurea and the computed value (9.7) for its monohydrated complex with the specifically hydrogen-bonded water molecule to the ionizable OH group are in a good agreement. The experimental partition coefficient of N-hydroxyurea is best reproduced by the Alog P_s method. The formation of nitroxide radical in the reaction of N-hydroxyurea and its sulfur and silicon substituted derivatives with the phenol radical is an exothermic process. Thus, the \bondN(H)OH moiety of these compounds may quench the structurally related tyrosyl radicals in the active site of ribonucleotide reductase.     

Synthesis of yttrium,lanthanum, neodymium,praseodymium, and lutetium alkoxides and acetylacetonates

A convenient and practical method is proposed for the synthesis of lanthanide and yttrium alkoxides. The method involves dissolving the metals or their hydrides in a solution of dry HCl in the corresponding alcohol, with subsequent dehalogenation of the LnCl₃ solution by an equivalent amount of alkali metal (Na, Li), The rareearth alkoxides are easily converted into acetylacetonates Ln(acac)₃ by the action of acetylacetone.A. N. Nesmeyanov Institute of Elementoorganic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2490–2493, November, 1992.     

Transition-metal-free O-, S-, and N-arylation of alcohols, thiols, amides, amines, and related heterocycles

A new protocol for the Ullmann-type arylation process of different aromatic heterocycles without any transition-metal catalyst, implying the use of a combination of an excess of potassium hydroxide and dimethyl sulfoxide, is described. The reaction can be performed between a broad range of starting nucleophiles including phenol, alcohols, amines, nitrogen-containing five-membered systems such as pyrazoles, imidazoles, and indoles, and amides with haloarenes, iodide and bromide derivatives giving the best results, the possible pathway involving the in situ generation of the corresponding benzyne intermediate. When the reaction was performed with 2-iodoaniline and either carboxamides or isothiocyanato derivatives, the corresponding benzoazole derivatives were obtained.     

Structure and properties of HOO,HOS, HSO,HSS, FSO,FOS and FSS

High quality SCF-MO calculations are reported for the title molecules, including geometry optimization. One-electron properties are presented and discussed, and relative stabilities of (HOS, HSO) and (FOS, FSO) compared. Little experimental geometric data are available at present, but the calculated and experimental geometries of HO₂ agree well.     

Electronic structure, spectra, and magnetic circular dichroism of cyclohexa-, cyclohepta-, and cyclooctapyrrole

Three recently obtained expanded porphyrins represent nice examples of compounds for which the electronic and spectral properties can be predicted from symmetry considerations alone. Perimeter-model-based theoretical analysis of the electronic structure of doubly protonated cyclo[6], cyclo[7], and cyclo[8]pyrrole leads to the anticipation of qualitatively the same electronic absorption and magnetic circular dichroism patterns for all three compounds. These predictions are fully confirmed by experiments, as well as DFT and INDO/S calculations. Due to a characteristic pattern of frontier molecular orbitals, a degenerate HOMO and a strongly split LUMO pair, the three cyclopyrroles show comparable absorption intensity in the Q and Soret regions. Magnetic circular dichroism spectra reveal both A and B Faraday terms, of which the signs and magnitudes are in remarkably good agreement with theoretical expectations. The values of the magnetic moments of the two lowest degenerate excited states have also been obtained.     

Electronic structure,geometry, and stability of organic cations,dications, and donor-acceptor complexes

Geometric, electronic, and energy characteristics of the complexes formed in the CF₄ ·nAIF₃ (n = I or 2) and CBr₄ ·nAIBr₃ (n = 1, 2, or 4) systems have been determined by the semiempirical AM I method. Besides the donor-acceptor complexes, the CBr₃ ⁺...AIBr₄ ^–, CBr₃ ⁺...Al₂Br₇ ^–, CBr2²⁺...(AlBr₄ ^–)₂, and CBr₂ ²⁺...(Al₂Br₇ ^–)₂ ionic complexes can be formed in the CBr₄ ·nAlBr₃ systems. In the cations and dications of polyhalomethanes (when Hal = Cl, Br, or l) in both the free and bound (included in ionic complexes) states, carbon atoms carry negative charges, the C-Hal bonds are substantially shortened, and the positive charges are located on one-coordinate halogen atoms. These cations and dications can be considered as halenium ions that differ from halenium salts with dicoordinate halogen atoms. In the cationic and dicationic complexes of the CBr₄ ·nAlBr₃ systems, the maximum positive charges on the Br atoms are 0.39 and 0.94, respectively. Fluorine-containing cations and dications have structures similar to those of carbenium ions, whereas in the CF₄ ·nAIF₃ systems (n = l or 2), only donor-acceptor complexes are formed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya. No. 3, pp. 554–560, March, 1996.