碱土金属的极谱研究 I.钙一茜来红与配合吸附波及其应用

茜素红S在0.01M氢氧化钾介质中,于-0.67V处有一个导数波。加入钙离子后,在-0.77V出现一个尖锐的新的导数波。该波的峰高与钙离子浓度有良好的线性关系。在最佳条件下,钙的最低检测限为4x10[-3]M,浓度在7x10[-3]～7x10[-6]M内与峰高成正比。本文讨论了此极谱波的机理,确定了钙-茜素红S(ARS)配合物的组成为1:2。本法不需任何前处理,可直接应用于血清中微量钙的测定。     

L-苏糖酸锌的制备及其性质

L-苏糖酸作为金属离子的载体 ,可使金属离子易于与氨基酸或蛋白质结合而被动物吸收和利用[1] ,L -苏糖酸钙就是一种优秀的钙补充剂 ,其吸收率达 95%以上 ,是传统钙补充剂的 2～ 3倍 ,无任何毒副作用 ,1 %的 L -苏糖酸钙能使维生素 C的吸收增加 1 .8倍[2 ,3 ] .国外已有苏糖酸产品及专利[4 ] ,国内也有苏糖酸钙产品问世 .文献 [5]报道 0 .1 mol/ L苏糖酸钙在生理 p H下 ,将有 87%钙为分子状态 ,这一结果显然支持了“分子补钙”的理论 ,也是其成为优秀钙补充剂的原因 .锌是人体中必需的 1 4种微量元素之一 ,与人体中不下2 0 0种金属酶有关 …     

宏量元素及化合物对微量元素吸收的影响

钙：当饮水及食物中含钙量高时,可与植酸盐形成植酸钙,在pH为碱性的小肠内形成不溶性复合物而妨碍锌吸收。还有报导指出,高锌尿与高钙尿有关。推测,饮食中钙含量高导致的低锌,不仅系钙能妨碍锌吸收,也由于它能增加锌从尿中的排泄。钙不利于氟的吸收,主要与氟结合成牢固的化合物而减少氟化物的吸收利用。相反食物缺钙可增进氟吸收。应用大剂量的钙治疗氟中毒也是基于钙的这一特点。过量钙存在会阻碍锰和铁的吸收。此外,实验证明高钙饲料可抑制大鼠对铅的吸收。     

小型钙电极指示,血样加入法测定血清总钙

有关钙离子选择电极的研究和应用国外有报导。国内也有较快的发展。我们利用苏州计量管理局制备的,以二(2-异辛基苯基磷酸)钙为活性材料,用2-正辛基磷酸酯为溶剂的PVC膜制成有效面积1mm~2的小型钙离子选择电极。本文介绍以此电极为指示,用血样加入法测定血清中总钙。经与原子吸收法对比,结果较为满意,方法较为简单、快速。     

宏量元素及化合物对微量元素吸收的影响

一、钙：当饮水及食物中含钙量高时,可与植酸盐形成植酸钙,在pH为碱性的小肠内形成不溶性复合物而妨碍锌吸收。还有报导指出,高锌尿与高钙尿有关。推测,饮食中钙含量高导致的低锌,不仅系钙能妨碍锌吸收,也由于它能增加锌从尿中的排泄。钙不利于氟的吸收,主要与氟结合成牢固的化合物而减少氟化物的吸收利用。     

宏量元素及其化合物对微量元素吸收的影响

钙：当饮水及食物中含钙量高时，可与植酸盐形成植酸钙，在pH为碱性的小肠内形成不溶性复合物而妨碍锌吸收。还有报导指出，高锌尿与高钙尿有关。推测，饮食中钙含量高导致的低锌，不仅钙能妨碍锌吸收，也由于它能增加锌从尿中的排泄。钙不利于氟的吸收，主要与氟结合成牢固的化合物而减少氟化物的吸收利用。相反食物缺钙可增进氟吸收。应用大剂量的钙治疗氟中毒也是基于钙的这一特点。过量钙存在会阻碍锰和铁的吸收。此外，实验证明高钙饲料可抑制大鼠对铅的吸收。有人发现澳大利亚南部牧羊需铅量较大，与同时摄入大量的碳酸钙有关。     

原子吸收光谱法同时测定铅钙锡铝合金中钙和锡

铅钙锡铝合金广泛用于全密封免维护铅蓄电池极板的生产。合金中微量钙的测定有汞分离ＥＤＴＡ容量法[1] ,氯化铅 铜试剂分离ＥＤＴＡ容量法[2 ] ,原子吸收光谱法[3 ] 。锡的测定通常采用邻苯二酚紫 十六烷基三甲基溴化铵吸光光度法[4 ] 。而用原子吸收光谱法测定铅钙锡铝合金中钙和锡的方法还未见报道。科研所研制生产的铅钙锡铝合金中含钙0 0 75 %～ 0 .12 % ,含锡 0 .4 %～ 0 .6 % ,含铝 0 .0 2 %～ 0 .0 3% ,余量为铅。本文用原子吸收光谱法同时测定其中的钙和锡 ,吸收波长分别为 4 2 2 .7和2 86 3ｎｍ。为了防止铅钙锡铝合金中锡水…     

邻近非共振线背景校正-火焰原子吸收法测定酱油中的铅

利用火焰原子吸收光谱法测定高盐样品中的铅含量[1]时,由于分子吸收和光散射等背景吸收原因,测定结果会偏高,用氘灯无法理想地校正;塞曼效应虽然可以校正,但仪器成本较高,一般基层单位难以承受。邻近非共振线背景校正技术[2,3]虽然早在20世纪60年代就有文献报道,但具体操作方法     

氯化镧对缺钙黄瓜根系生理的影响

在缺钙营养条件下,5μmol/L的氯化镧促进了黄瓜的生长并使其根系活力增加。应用钙离子选择电极及ICP测定结果表明,在低浓度钙下,氯化镧处理抑制了黄瓜根系对钙的吸收并降低了植物组织中钙的含量;用两相法分离提纯了黄瓜根系的质膜组分,缺钙使质膜上K~ 、Mg~(2 )-ATPase活性降低,而氯化镧处理后则使其活性升高。这些研究表明,氯化镧对缺钙黄瓜生长的促进作用不是通过增加植物对外部溶液中钙离子的吸收,而是通过改变一些质膜上受缺钙影响的生理生化过程。     

鲁米诺-过氧化氢体系流动注射化学发光法测定维生素B4

维生素B4(VB4),又名磷酸腺嘌呤。它是核酸的组成成分,在体内参与RNA和DNA的合成。传统测定嘌呤类的方法是利用其在260 nm附近有最大吸收的性质,用紫外分光光度法定量[1],但此方法灵敏度不高。已报道的测定维生素B4的方法还有磷光法[2]、高效液相色谱法[3]、极谱法[4]、伏安法[5     

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%.     

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.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

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.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

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.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).