水热合成微孔纳米羟基磷灰石

以Ca(NO3)2·4H2O、P2O5为原料,水-乙醇为溶剂,在碱性介质中,采用水热法合成微孔纳米羟基磷灰石晶体(HAP),研究了水-乙醇的体积比对产物组成、晶体结构的影响. 利用X射线衍射(XRD)、红外光谱(FTIR)、热分析(TG/DTA)、透射电镜(TEM)等检测技术对HAP的晶相、化学组成和形貌进行了表征和分析. 结果表明,当V(水):V(乙醇)=1:1时,可得到晶体发育完整、晶体表面孔洞分布均匀(孔密度约为3×109个/cm2)和孔径约为1～2 nm的六方柱状纳米羟基磷灰石晶体(60 nm×100 nm).     

微孔纳米羟基磷灰石的水热合成与结构表征

以Ca(NO3)2.4H2O,P2O5为原料,水-乙醇体系为溶剂,在碱性介质中,采用水热法合成微孔羟基磷灰石,并考察了水热温度、时间对晶体结构的影响。通过X-射线衍射(XRD)、红外光谱(FTIR)、热分析(TG/DTA)、透射电镜(TEM)等检测手段对HAP的晶相、化学组成和形貌进行了表征和分析,结果表明:160℃下水热8小时,可得到粒径为70×167nm的六方柱状微孔纳米HAP晶体,晶体表面孔径大约为1~2nm,孔密度大约为3×109个/cm2。     

EDTA辅助水热法合成硫化铋晶体

以Bi(NO3)3·5H2O和Na2S2O3·5H2O为原料,用乙二胺四乙酸(EDTA)辅助水热法合成了纳米或微米级的Bi2S3晶体(1),其结构、形貌和光谱性能经XRD,FE-SEM和UV-Vis表征。结果表明:溶液的pH对1的形貌有显著的影响,随着pH的增大,1由纳米棒组成的微米球逐渐转变为微米级片状结构;1出现蓝移。     

乙二胺四乙酸辅助水热法合成NaYF_4纳米晶

用络合剂乙二胺四乙酸(EDTA)辅助水热法合成了NaYF4纳米球和微米棱柱,通过控制反应条件得到了立方相和六方相纳米晶体;采用X射线粉末衍射仪(XRD)、扫描电子显微镜(SEM)及荧光光谱仪(PL)分析了产物的结构、形貌及发光性能.结果表明,络合剂EDTA和氟化物的物质的量对NaYF4的形貌和粒度有很大影响,且产物的荧光性能呈现出尺寸依赖性.     

高度取向ZnO单晶亚微米棒阵列的制备与表征

通过低温压热的方法,在经过预先处理长满晶核的SnO2导电玻璃基底上制备出具有高度取向的ZnO亚微米棒阵列.用扫描电子显微镜(SEM)、选区电子衍射(SAED)及X射线粉末衍射(XRD),对制备出的ZnO亚微米棒的结构和形貌进行了表征.SEM测试结果表明,ZnO亚微米棒是六方型的,近乎垂直地长在基底上,棒的直径为400～500 nm,长度约为2 μm. SAED和XRD结果表明,ZnO亚微米棒为单晶,属于六方晶系,并且沿[001]方向择优取向生长.     

竹炭模板合成高度有序二氧化硅微米线组

通过扫描电子显微镜(SEM)系统地研究了竹炭的微观结构,并以竹炭孔道为模板,以正硅酸乙酯为硅源,采用溶胶-凝胶法合成出高度有序的二氧化硅微米线组,其形貌和组成分别通过SEM,EDX和XRD进行表征.结果表明,所得微米线为较纯的方石英晶型,直径约1～2μm,长达200μm以上,呈束状高度有序排列,其形貌高度复制了竹炭微孔孔道的结构,说明微孔在限域反应中起模板作用.     

离子液体中不同形貌ZnO纳米材料的合成及表征

在不同的咪唑基离子液体中通过微波加热合成出了ZnO的片状聚集体、棒状聚集体和塔棒聚集体等纳/微米结构, 考察了不同合成条件对ZnO形貌的影响, XRD表明产物为六方相纤锌矿ZnO结构, SEM和TEM表明产物形貌主要分为片的聚集体和棒的聚集体, 电子衍射表明ZnO棒具有单晶结构, 片的聚集体的PL谱表明在室温下这种形貌的ZnO具有很强的绿光发射和弱紫外光发射现象.     

熔盐分解制备氧化锌纳米晶

以新制的乙酰丙酮合锌为前驱体,添加NaCl助剂,在650℃熔盐分解制得了六棱柱形结构的ZnO纳米晶.用X-射线衍射分析(XRD)、能量色散X射线分析(EDX)和场发射扫描电子显微镜(FFSEM)对粉体进行了表征.结果表明,ZnO为六棱柱形纳米晶,属六方纤锌矿结构,结晶性好,平均长度约90nm,平均直径约60nm,长径比约为1.5:1.通过与不添加NaCl的对比试验,简单探讨了六棱柱形ZnO纳米晶的生长过程.     

以1,6-己二胺为模板剂的层状磷酸锆晶体的合成与表征

 采用水热法合成了以1,6-己二胺(HDA)为模板剂的层状磷酸锆晶体0.5·1.5H2O,并用单晶及粉末XRD,IR和TG-DTA等对其结构和性质进行了表征. 该晶体是由磷酸锆无机层、有机胺以及水分子三部分构成的层状结构,层间距约为1.77 nm,无机层结构为γ-型. 位于有机胺两端的氮与无机层表面部分羟基的氧以氢键连接,水分子占据磷酸锆层间的两种位置. 单晶结构模拟得到的XRD谱与从粉末样品采集的XRD谱基本吻合. 此晶体在180 ℃下脱去水分子,在220 ℃下加热3 h其结构未发生明显变化; 有机胺模板剂在250 ℃下开始分解.     

六棱柱状ＭｏＯ３的水热合成、表征及其形貌控制研究

以钼酸铵为原料,采用水热合成法制备出具有不同形貌的MoO3.考察了反应温度、反应时间以及硝酸加入量对合成产物的影响.同时比较了新鲜溶液和经过一定陈化时间后的溶液对产物形貌的影响.实验结果表明:用新鲜溶液在180℃反应40h后,可以得到形貌较好的六棱柱状MoO3,将反应溶液陈化一定的时间后再进行水热处理,得到的产物形貌为片状.同时还考察了无机盐的加入对MoO3形貌的影响.结果表明,加入FeCl3、Fe(NO3)3和Ce(NO3)3抑制了MoO3六棱柱的形成,加入KBr形成了规则的六棱柱状MoO3,同时产物的截面直径也变小.产物分别用场发射扫描电镜(FE-SEM)、X-射线粉末衍射仪(XRD)和傅立叶变换红外光谱仪(FT-IR)进行了表征.     

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.     

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.     

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.