白血病患儿体内铜锌代谢的动态观察

对白血病患儿体内血清锌、血清铜浓度以及血清铜/锌比值作了初步的观测.在41例白血病患儿和33例正常对照儿童中,观察到在明确诊断化疗前,41例白血病患儿中有20例患儿的血清锌浓度低于正常低限,他们的平均血清锌浓度为12.3±3.4 μmol/L,明显低于对照组18.3±4.0 μmol/L.白血病患儿的血清铜/锌比值为1.40±0.38,明显高于正常儿童1.19±0.25.经治疗后,有12例患儿获缓解并继续随访至发病后6～8周,平均血清锌浓度由11.4±2.2μmol/L,提高到13.7±2.1μmol/L,血清铜/锌比值由1.51±0.36,下降到1.29±0.23.说明白血病患儿体内存在着锌代谢的异常.     

基于有机溶剂原位制备的致密疏水铜金属层在保护锌负极中的应用

通过在 N-甲基吡咯烷酮(NMP)有机溶剂中锌电极与 CuI之间的置换反应,在锌电极上原位构建了一层致密且疏水的铜金属保护层(Cu@Zn)。铜金属保护层能有效地隔离锌电极与电解液的接触,减少锌电极-电解液界面的析氢和腐蚀等副反应。同时,铜金属保护层还具有较好的亲锌性,更小的界面电阻,更低的成核能垒,有利于锌离子均匀沉积,从而有效抑制了锌枝晶的生成。Cu@Zn对称电池实现了超过 1 700 h(1 mA·cm^-2)和 1 330 h(3 mA·cm^-2)的循环寿命。采用商用 MnO₂与之匹配得到的Cu@Zn||MnO₂全电池不仅在1 A·g^-1下具有168.5 mAh·g^-1的可逆比容量,还可稳定循环2 000次以上     

基于有机溶剂原位制备的致密疏水铜金属层在保护锌负极中的应用

通过在 N-甲基吡咯烷酮(NMP)有机溶剂中锌电极与 CuI之间的置换反应,在锌电极上原位构建了一层致密且疏水的铜金属保护层(Cu@Zn)。铜金属保护层能有效地隔离锌电极与电解液的接触,减少锌电极-电解液界面的析氢和腐蚀等副反应。同时,铜金属保护层还具有较好的亲锌性,更小的界面电阻,更低的成核能垒,有利于锌离子均匀沉积,从而有效抑制了锌枝晶的生成。Cu@Zn对称电池实现了超过 1 700 h(1 mA·cm^-2)和 1 330 h(3 mA·cm^-2)的循环寿命。采用商用 MnO₂与之匹配得到的Cu@Zn||MnO₂全电池不仅在1 A·g^-1下具有168.5 mAh·g^-1的可逆比容量,还可稳定循环2 000次以上。     

儿童发锌含量差异对血红蛋白及铜代谢的影响

分析测定了３４６名儿童的发锌（Ｚｎ）、发铜（Ｃｕ）含量，从中抽出发锌含量大于１００×１０－６和小于６０×１０－６的两组儿童进行比较，发现高锌儿童的血红蛋白（Ｈｂ）含量显著高于低锌儿童；身高、体重等代表体格发育的指标明显不同，高锌组儿童发育明显优于低锌组．说明发锌含量高低直接影响到儿童造血功能及发育水平．另外高锌组的发铜含量比低锌组低，两组μｕ／Ｚｎ比值有显著性差异，锌的高含量对铜的代谢有一定影响，锌对铜具有拮抗作用．     

电解液流速对锌镍单液流电池性能的影响简

通过电化学测试、扫描电子显微镜观察和X射线衍射分析研究了电解液流速、电流密度和锌沉积面容量三者关系及对锌镍单液流电池充放电性能和负极锌沉积形貌的影响. 结果表明,锌沉积面容量是影响锌镍单液流电池充放电效率和负极锌沉积形貌的最主要因素,电解液流速不宜过高或过低. 随着锌沉积面容量的增大,电池的充放电效率和循环稳定性对电流密度的变化更为敏感,适宜的电解液流速范围变窄. 锌沉积面容量在25 mA·h/cm2以上,锌沉积皆呈海绵状. 在较低锌沉积面容量下,电解液流速也较低时,海绵锌沉积较为均匀致密. 而在高的锌沉积面容量下,海绵状锌沉积的团簇和颗粒变大,不均匀性加重,仅在适中的电解液流速(7.1 L/min)下,锌沉积部分致密规整,电池具有较好的充放电性能.     

广州地区妊娠妇女锌、钙代谢状况调查

调查了31名早孕妇女的头发锌、钙含量,其中锌为(139.0±40.1)×10-6,钙为(1081±478)×10-6;中孕妇女37名,发锌为(142.4±25.2)×10-6,钙为(666.1±143.3)×10-6;而69名晚孕妇女头发锌含量为(140.9±25.0)×10-6,钙含量为(864.7±562.8)×10-6。对照组为非妊娠健康妇女,共41名,头发锌含量为(158.1±61.9)×10-6,钙含量为(1241±546)×10-6。结果显示,三期妊娠妇女的发锌、发钙含量均显著低于正常对照组。     

男性不育症患者头发、精液锌含量分析

测定了68例男性不育症患者精液中的锌含量及53例男性不育症患者头发中锌含量,与对照组相比两者显著偏低,分别为2.48±1.69 mmoL/L和(140.8±49.0)×10 -6.但头发锌和精液锌含量并不相关,r=-0.05,低精液锌患者的头发锌含量并不低于对照组.反映锌在男性生殖系统代谢中存在特异性.另精液不液化患者的精液锌水平较其它原因导致不育的患者要显著偏低.     

锌蒸气的氧化行为与氧化锌的结晶形貌

用热重法测定了不同气氛下锌蒸气的氧化动力学曲线,用扫描电镜跟踪观察分析了产物的结晶形貌,结果表明,氧化动力学遵守直线规律时,产物是无定形、颗粒状和单针状的ZnO;氧化动力学为抛物线规律时,产物是四针状或多针状的ZnO.动力学转变规律的原因是锌蒸气中气态锌原子与凝聚生成的锌液滴之间存在动态平衡,气态锌原子的氧化过程遵守直线规律;而锌液滴的氧化过程分为两个阶段,分别受收缩球状界面反应模型R₃和三维扩散模型D4动力学控制,表观活化能分别为106.3～108.2和114.2～117.3kJ/mol;扩散过程实际上是锌原子通过氧化膜层由里向外扩散,扩散系数D=2.46～9.70×10^-5cm²/s.     

电解液流速对锌镍单液流电池性能的影响

通过电化学测试、 扫描电子显微镜观察和X射线衍射分析研究了电解液流速、 电流密度和锌沉积面容量三者关系及对锌镍单液流电池充放电性能和负极锌沉积形貌的影响. 结果表明, 锌沉积面容量是影响锌镍单液流电池充放电效率和负极锌沉积形貌的最主要因素, 电解液流速不宜过高或过低. 随着锌沉积面容量的增大, 电池的充放电效率和循环稳定性对电流密度的变化更为敏感, 适宜的电解液流速范围变窄. 锌沉积面容量在25 mA·h/cm²以上, 锌沉积皆呈海绵状. 在较低锌沉积面容量下, 电解液流速也较低时, 海绵锌沉积较为均匀致密. 而在高的锌沉积面容量下, 海绵状锌沉积的团簇和颗粒变大, 不均匀性加重, 仅在适中的电解液流速(7.1 L/min)下, 锌沉积部分致密规整, 电池具有较好的充放电性能.     

Cyanex302在中空纤维膜器中萃取锌的传质动力学

锌;Cyanex302在中空纤维膜器中萃取锌的传质动力学     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.