银与碘化物和罗丹明B在水溶液中显色反应的研究

基于(AgIs)~2-络阴离子在聚乙烯醇存在下的水溶液中,与罗丹明 B 产生的离子缔合反应,提出了一个高灵敏度分光光度法测定银的方法.形成离子缔合物的适宜酸度范围是0～0.04N 硝酸(pH7～1.4).以连续变化法和平衡移动法确定离子缔合物的组成是[RB]_2[AgI_s].离子缔合物溶液的最大吸收位=j=600nm处,摩尔吸光系数为1.65×10~5·mol·~(-1)cm~(-1).方法有较好的选择性.在某些掩蔽剂存在下可用于钢中微量银的测定.     

催化过氧化氢氧化邻苯三酚红固体基质室温燐光猝灭法测定痕量钴

基于硼砂缓冲液中聚丙烯酰胺(PAM)存在下,邻苯三酚红(PGR)于滤纸固体基质上能发射强而稳定的室温燐光,PAM可活化钴离子催化H2O2氧化PGR反应,使PGR的室温燐光猝灭,从而建立了测定痕量钴的新方法。该方法的线性范围为4.8~960(×10-18g/斑)Co2+(浓度范围0.012~2.40×10-9g/L,0.4μL/斑),工作曲线的回归方程ΔIp=12.76+0.1248 mCo2+(×10-18g/斑),n=7,相关系数r=0.9993;检出限为1.2×10-18g/斑(对应浓度为3.0×10-12g/L)。对4.8和960(×10-18g/斑)Co2+重复测定11次(0.4μL点样量),RSD分别为3.6%和4.7%。用PAM比不加PAM时ΔIp增加4.6倍。本方法灵敏、准确、简便快速、重现性好,用于党参、当归、川芎、金银花和VB12中的痕量钴测定,结果满意。     

阻抑-褪色光度法测定痕量硅

基于NH3 NH4 Cl缓冲溶液介质中 ,Si 对H2 O2 氧化十六烷基三甲基溴化铵 姜黄素离子缔合物的褪色反应的抑制作用 ,提出了测定痕量硅新的高灵敏的褪色光度法。该方法的表观摩尔吸光系数ε50 0=5 .70× 10 5L·mol-1·cm-1;线性范围为 0 .4～ 3.6 μg/L ;线性回归方程ΔA =2 .2 3× 10 -4 + 0 .0 2 0 17CSi (μg/L) ;相关系数r =0 .9999;测定下限为 2 0× 10 -8g/L。本法用于人发样和水样中痕量硅的测定 ,结果满意。     

溶剂浮选缔合物光度法测定痕量硒

根据亚硒酸 ( H2 Se O3)氧化 I-生成 I2 ,I2 与 I-配阴离子 ,I-3 ,配阴离子I-3 与孔雀绿阳离子 ( MG+ )发生离子缔合反应 ,用 N2 气将此缔合物浮选的三元缔合物用光度法测定硒。方法的 ε为 2 .2× 1 0 6L· mol-1· cm-1,RSD为2 .7% ,检出限为 4.7× 1 0 -10 g· m L-1     

二氧化氯-碘化物-吖啶红高灵敏显色反应及其分析应用

在稀磷酸介质中 ,二氧化氯 ( Cl O2 )氧化 I- 形成 I3- ,I3- 进一步与吖啶红( ADR)阳离子形成离子缔合物 [ADR][I3]。在聚乙烯醇存在下 ,以试剂空白作参比 ,该离子缔合物的吸收波峰和波谷分别位于 5 82 nm和 5 2 6nm处 ,除波峰和波谷处吸光度与 Cl O2 的浓度有线性关系外 ,波峰和波谷的吸光度绝对值叠加也与 Cl O2 的吸光度呈直线关系。常规方法测定时 ,ε582 =1 .3× 1 0 5L· mol- 1· cm- 1;双波长法测定时 ,ε582 +52 6 =2 .9× 1 0 5L· mol- 1· cm- 1,对 Cl O2 的检出限分别为 0 .8μg/L和 0 .5μg/L。方法已成功地用于自来水中 Cl O2 的测定     

银碘络阴离子-丁基罗丹明B-吐温-80体系双波长分光光度法测定岩矿中痕量银

方法基于CAgI_3]~(2-)络阴离子与丁基罗丹明B形成离子缔合物,用非离子表面活性剂吐温-80实现增溶增稳。提出了一个高灵敏度的双波长分光光度测定银的方法。缔合物最大吸收波长为605nm,负峰波长为555nm,摩尔吸光系数为3.26×10~5L·mol~(-1)·cm~(-1),0～8μgAg/25ml符合比耳定律。用于岩矿中痕量银的测定,结果满意。     

氮气-苯浮选光度法测定痕量锰

提出了根据 Mn( )氧化 I-生成 I2 ,I2 与 I-反应生成 I-3 配阴离子 ,I-3 配阴离子与孔雀绿阳离子发生离子缔合反应 ,用苯和 N2 将此缔合物浮选 ,以光度法测定此缔合物间接测量锰新方法。表观摩尔吸光系数为(ε=5.0 4× 1 0 5 L· mol-1· cm-1) ,测定 5.0μg/2 0 0 m L的锰 ( n=6 ) RSD为 1 .8%。已用于水中锰的测定。     

硒钼杂多酸—罗丹明B离子缔合物显色反应的研究与应用

研究了在聚乙烯醇分散剂存在下 ,硒 钼酸铵 罗丹明B(RDB)三元缔合物的显色反应。建立了测定硒碘盐中微量硒的新方法。离子缔合物的最大吸收波长为 5 70nm ,表观摩尔吸光系数ε570 =5 .6× 10 5L·mol- 1·cm- 1。在测定条件下 ,硒含量在 0～ 6μg/ 2 5ml范围内符合比耳定律。对于硒碘盐样品的测定 ,RSD≤ 2 .5 % ,结果满意     

5-Br-PADAP-NO_2~--SCN~-三元离子缔合物分光光度法测定微量NO_2~-的研究

研究了在硫酸介质中 5 Br PADAP与NO-2 和SCN- 形成三元离子缔合物的最佳条件 ,其表观摩尔吸光系数ε550 =2 .4× 1 0 4 L/(mol·cm) ,缔合物组成比为n( 5 Br PADAP)∶n(NO-2 )∶n(SCN- ) =1∶1∶1 .提供了测定微量NO-2 离子的新方法 ,应用于环境水体中微量NO-2 离子的测定 ,结果较为满意。     

硼钼杂多酸-罗丹明B缔合显色反应的研究与应用

研究了在聚乙烯醇存在下 ,罗丹明 B( RDB)与硼钼杂多酸的离子缔合显色反应。在合适的硫酸介质环境下 ,形成硼钼杂多酸 ,再与 RDB形成离子缔合物 ,其 λmax=570 nm,ε570 =1 .0× 1 0 5L· mol-1· cm-1,硼浓度范围在 0～1 .2μg/2 5m L符合比尔定律。用等摩尔连续变化法 ,平衡移动法确定 B∶ Mo∶RDB=1∶ 7∶ 4。方法已用于添加硼烧结矿中微量全硼的测定     

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.     

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.     

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.     

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.