Cu2O/Ag纳米复合物的表面增强拉曼光谱

用一种简单的化学还原方法制备了银纳米粒子包覆的氧化亚铜（Cu2O）纳米复合物。扫描电子显微镜显示Cu2O 为八面体型的纳米粒子,表面光滑,结构对称。包覆的Ag部分占据Cu2O粒子表面。通过比较Ag/Cu2O纳米复合物、Ag溶胶及Cu纳米粒子表面吸附的4-巯基吡啶（4-Mpy）分子表面增强拉曼光谱（SERS）发现,利用此方法得到了Cu2O粒子表面吸附分子的拉曼光谱。银纳米粒子所产生的电磁场增强又增强了吸附在Cu2O上的4-Mpy拉曼信号。这种方法为初步研究Cu2O表面吸附分子性质提供了依据,扩宽了SERS的使用范围,使SERS应用在纳米半导体材料上成为可能。     

由Keggin型簇和过渡金属配合物构筑的杂多钨酸盐锯齿链的合成和结构

采用水热法合成了一维锯齿链状的有机-无机杂化杂多钨酸盐[Cu（en）2（H2O）]{[Cu（en）2（H2O）][Cu（en）2]（α-SiW12O40）}（OH）2·H2O（记作1;en=1,2-乙二胺）;利用元素分析、红外光谱和X射线单晶衍射对其结构进行了表征.结果表明,化合物1属于三斜晶系,P-1空间群;其晶格参数为：a=1.297 6（6）nm,b=1.473 5（7）nm,c=1.909 9（9）nm,α=86.736（8）°,β=88.833（8）°,γ=74.840（8）°,V=3.519（3）nm3,Z=2.就分子结构而言,化合物1由一个常见的Keggin型多阴离子[α-SiW12O40]4-、两个不同的铜配位阳离子[Cu（en）2（H2O）]2＋和[Cu（en）2]2＋、一个游离的铜配位阳离子[Cu（en）2（H2O）]2＋、两个氢氧根离子和一个结晶水组成;相邻的[α-SiW12O40]4-多阴离子通过两个配位阳离子[Cu（en）2）]2＋相连,形成一维锯齿链状结构.     

旋光法测蔗糖水解反应速率常数实验的改进

蔗糖水解反应是物理化学实验之一,实验中所用的无机酸催化剂对旋光仪有强腐蚀性,会缩短仪器的正常使用时间;测试废液如果不进行处理就直接排放会对环境造成污染。针对实验中存在的这些不足,探讨了用强酸性阳离子树脂代替无机酸催化蔗糖水解,通过测定旋光度求得催化反应速率常数和活化能。实验结果表明:强酸性阳离子树脂催化蔗糖水解反应能达到与无机酸催化相同的实验效果,而且实验使用过的树脂经水洗涤后可循环使用。1　实验原理　　蔗糖水解反应为:　　　　C12H22O11 +H2O阳离子树脂C6H12O6 +C6H12O6蔗糖葡萄糖果糖　　在 323. 2~…     

D001树脂对酸性硫脲溶液中金银的交换性能研究

研究了D001型大孔强酸性阳离子交换树脂从H2SO4-Tu（硫脲）溶液中，富集回收Au（Ⅰ）、Ag（Ⅰ）的性能。结果表明在pH2．0左右，树脂对Au（Tu） 2、Ag（Tu）2 有良好的吸附性能，AU和Ag的交换容量分别为61，18mg／g-R和99．11mg／g-R。负载柱上的An、Ag可分别用NaCN－NaOH和H3BO3－NaOH－Na2S2O3洗脱液定量洗脱。     

氢氧化钙溶度积的测定

关于难溶电解质溶度积的测定,在无机化学教学实验中,目前有以Cu（OI3）2[1]、PbCl2[2]等作为实例来进行溶度积测定的。前者利用饱和溶液中的Cu2+离子与氨水形成兰色的Cu（NH3）42+,进行比色测定,从而算出Cu（IO3）2的溶度积,有人还对这一方法提出过改进意见[3];后者是采用离子交换法,将饱和溶液中的Pb2+交换到强酸型阳离子交换树脂上,再用NaOH标准溶液滴定被Pb2+交换出来的H+,算出[Pb2+],并进而求出PbCl2的溶度积。这些方法都是可行的。     

离子交换法处理曝气后氯化亚铜的废水研究

通过预曝气的方法,氯化亚铜废水溶液中Cu(Ⅰ)被氧化为Cu(Ⅱ),并能简化氯化亚铜废水溶液的粒子结构,分别采用201×7 OH-型强碱性阴离子树脂和732 Na型强酸性阳离子树脂处理曝气后的氯化亚铜废水,进行了曝气时间、pH值和温度等因素对废水处理效果的研究,得到最佳的处理废水条件。曝气180 min后,在温度60 ℃,V溶液/V树脂=2/1,阳离子交换反应15 min时,可使废水溶液中铜粒子浓度达到国家废水一级排放标准。     

Cu2+与硅酸、硅胶表面硅羟基的反应及其平衡常数

本文用铜电极法研究 Cu2 和硅酸、硅胶表面硅羟基的反应及其平衡常数 ,结果是 :Cu2 H3 Si O4-Cu H3 Si O 4 　　　　 K1 =5.0× 1 0 3Cu2 2 H3 Si O4-Cu(H3 Si O4) 2 　　 β2 =6.1× 1 0 8Cu2 Sis- OH Sis- OCu H 　 Ks1 =2 .0× 1 0 -6Cu2 2 Sis- OH ((Sis- O) 2 Cu 2 H 　βs2 =2 .5× 1 0 -1 2     

耐温阳离子树脂催化二壬基酚与苯酚合成壬基酚

用耐高温阳离子树脂催化二壬基酚与苯酚烷基转移为壬基酚．研究表明，经过耐温处理的强酸性阳离子交换树脂有较好的催化性能，当以CH2O2型树脂作为催化剂。在140℃，苯酚与二壬基酚摩尔比8：l的务件下反应2．5h，二壬基酚的转化率可以达到90％以上，适当延长反应时间。二壬基酚的转化率可以进一步提高，催化剂重复使用8次催化活性没有明显降低．     

化学发光法快速筛选纳米微粒模拟酶

本文提出了一种基于化学发光法快速筛选纳米微粒模拟酶的新方法,以H2O2-鲁米诺化学发光反应为模型体系,对CoFe2O4、CuFe2O4、γ-Fe2O3、MnFe2O4、NiFe2O4前驱体和MgFe2O4前驱体等6种铁氧体纳米微粒的过氧化物模拟酶活性进行快速筛选,并与辣根过氧化物酶（HRP）进行比较．结果表明：（1）与HRP类似,6种铁氧体纳米微粒均能够催化H2O2氧化鲁米诺产生增强化学发光,其催化活性依赖于pH、温度以及底物（H2O2）浓度;6种铁氧体纳米微粒均能够催化H2O2氧化TMB的显色反应,表明其具有过氧化物模拟酶特性;（2）以H2O2为底物的表观米氏常数（Km）从小到大依次为CoFe2O4〈y-Fe2O3〈NiFe2O4前驱体〈CuFe2O4〈MnFe2O4〈MgFe2O4前驱体;（3）铁氧体纳米微粒模拟酶比HRP具有更佳的pH及温度耐受能力．本法简单、快速,可用于大规模纳米微粒模拟酶的快速筛选．     

Au@Pt纳米粒子催化O2还原反应的电化学研究

以100 nm的Au粒子为核,抗坏血酸为还原剂,H2PtCl6·6H2O为前驱体,合成了Pt包Au核壳结构纳米粒子( Au@ Pt)及其修饰的玻碳(GC)电极(Au@ Pt/GC).采用旋转圆盘电极等常规电化学方法,比较了Au@ Pt/GC和商用碳载铂(Pt/C)修饰的玻碳电极(Pt/C/GC)催化O2还原反应活性及耐甲醇性能,发现Au@ Pt纳米粒子在铂用量很低的情况下,其催化O2还原反应活性仍与商用Pt/C相当,而且还具有优良的耐甲醇性能;其催化O2还原反应机理按O2直接还原成H2O的四电子历程进行.     

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.     

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.     

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.     

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.     

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.