YSi_2纳米颗粒的制备及光学、电学性能研究

采用脉冲激光烧蚀高纯YSi2靶,在n型Si(100)单晶衬底上制备YSi2纳米颗粒。原子力显微镜(AFM)观察样品表面颗粒尺寸约40~50 nm。X射线光电子能谱(XPS)测试结果表明,YSi2纳米颗粒成分为Y-O-Si。室温下对样品的光致发光(PL)性能进行测试,在500 nm处有一个较大的宽峰,409 nm附近出现强度较弱的发光峰。前者与样品中Y-O-Si电荷迁移带有关,后者为衬底表面纳米尺寸SiOx复合中心离子发光。室温下,对原位制备的薄膜电学(I-V/C-V)性能进行测试,结果表明薄膜的介电常数约为13.6。     

简单低温水浴法合成鳞片状氧化铜/四针状氧化锌晶须复合光催化剂(英文)

以硝酸铜为原料,聚乙二醇(PEG,Mw=400)为稳定剂和模板剂,采用简单的低温水浴合成法成功合成了四针状氧化锌晶须(T-ZnOw)表面负载鳞片状CuO的纳米复合光催化剂,系统研究了复合催化剂样品的晶体结构和形貌,通过荧光发光光谱(PL)和紫外光照射的条件下样品对阳离子污染物(亚甲蓝,MB)和阴离子污染物(甲基橙,MO)的光催化降解效率表征了样品的光催化性能,同时采用ICP-AES详细分析了PEG 400浓度对T-ZnOw表面负载CuO纳米颗粒数量的影响.结果表明,T-ZnOw表面有序地沉积了大量鳞片状CuO纳米颗粒,随着PEG 400浓度增加,T-ZnOw表面沉积的CuO纳米片数量逐渐增多,且CuO纳米片在T-ZnOw表面的排列更加有序.同时,PEG 400浓度的变化对合成样品特征发光峰的强度也有一定影响,当PEG 400浓度小于0.60 mol/L时,合成样品特征发光峰强度随着PEG 400浓度增大而减小;当PEG 400浓度大于0.60 mol/L时,样品的特征发光峰强度随之有所增加.在紫外光照射条件下,CuO/T-ZnOw纳米复合催化剂样品对MB和MO水溶液的降解均表现出优异的光催化活性,当PEG 400浓度≤0.60 mol/L时,样品的光催化活性随着PEG 400浓度的增大而增加;而当PEG 400浓度大于0.60 mol/L时,样品的光催化活性反而有所降低.此外,在相同条件下,所有样品对MB水溶液的降解效率明显高于对MO水溶液的降解效率.     

超细YF_3与GdF_3纳米晶的合成及其上转换发光

当使用液固溶法(LSS法)制备分散性纳米晶时,将传统油酸/油酸钠/酒精反应体系中的NaOH用氨水取代时,氨水将会与油酸形成新的表面活性剂油酸铵,这样就可以合成各种超细分散性的REF3纳米晶(RE代表稀土元素)。在这种新的反应体系中,合成了平均直径小于10 nm的YF3和GdF3超细颗粒,X射线与透射电镜测试表明YF3是正交相,而GdF3是面心立方结构,空间群为Fm3m,晶格常数为0.582 9 nm。在980 nm半导体激光器激发下,可检测到YF3∶Yb/Er在515~570 nm处有较强的绿色发光峰、645~675 nm处有较强的红色发光峰,呈橙色发光。YF3∶Yb/Tm和GdF3∶Yb/Tm样品在460~490 nm处有较强的蓝色发光峰,而在800 nm附近有更强的近红外发光峰。由于其超细的尺寸及红外上转换发光特性,合成的样品在生物成像、生物标签等方面有潜在的应用价值。     

Mn掺杂SnO_2一维纳米结构的制备、形貌及光学性质

用化学气相沉积(CVD)法制备了Mn掺杂的SnO2一维纳米结构(纳米线及纳米带),X射线衍射(XRD)显示样品为金红石型SnO2晶体,其生长机理可分别归结为气-液-固(VLS)和气-固(VS)机理,生长温度和气态原料浓度的差别是造成样品形貌及生长机理不同的主要原因.样品的拉曼谱出现了500、543、694和720cm-1四个新拉曼谱峰,分别是由活性的红外模和表面模引起的.纳米线及纳米带发光峰位于520nm处,发光强度随样品中氧空位的增减出现由强到弱的变化.     

水热合成GdVO4:Eu3+晶体随pH值的形貌和性能演变

使用氧化钆、氧化铕和偏钒酸铵为原料,以DTAB为表面活性剂,在不同的反应溶液pH值条件下,采用水热合成法得到了从微米尺度到纳米尺度的一系列钒酸钆荧光粉。通过X射线衍射(XRD),场发射扫描电子显微镜(FESEM)、透射电子显微镜(TEM)和荧光光谱(PL)等测试手段对不同形貌的样品的物相及微观形貌和发光性能进行表征。结果表明,在强酸环境下,晶体颗粒较大,为微米级,随着pH值的提升,晶体颗粒尺寸变小,进入纳米级,在pH为7,10时,分别得到50 nm以下的纳米晶片,且分散性良好。另外pH=7时观察到更为微小的小晶粒团,相比之下碱性环境下纳米晶片的结晶度较高。发光性能测试表明,样品发光性能随晶粒尺寸和结晶度变化显著。纳米尺度结晶良好的产品发光性能优异。     

银纳米颗粒的合成及其与曙红Y的相互作用

分别制备了以L-半胱氨酸(L-cyst.)或以巯基乙酸(TGA)保护的银纳米颗粒,并用紫外-可见分光光度法和透射电子显微技术(TEM)对两种不同状态的银纳米颗粒的结构作了表征。由其吸收光谱图显示,L-cyst.和TGA保护的银纳米颗粒的吸收峰依次位于384 nm和392 nm波长处;由TEM的检测结果表明:上述2种形态银纳米颗粒的粒度大小依次在10~40 nm和20~30 nm范围内。试验中发现,以L-cyst.保护的银纳米颗粒与曙红Y之间有明显的相互作用,导致其吸收峰从384 nm红移至395 nm;以TGA保护的银纳米颗粒与曙红Y之间未见有相互反应。初步探讨了其作用机理,认为系由于结合于银纳米颗粒表面的L-半胱氨酸分子所带的正电荷与曙红Y分子上的负电荷之间的静电作用的结果。     

ZnS纳米球的水热法制备及其光催化性能研究

在表面活性剂十六烷基三甲基溴化铵(CTAB)的辅助下,以乙酸锌为锌源,硫脲(NH2)2CS为硫源,使用水热法通过改变反应时间,成功制备了不同粒径的ZnS球状颗粒。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、X-射线能谱,高分辨透射电子显微镜(HRTEM))、紫外可见分光光谱和光致发光谱(PL)等测试手段对样品的晶体结构、形貌、光学性质进行了分析。通过对不同粒径的ZnS纳米颗粒对亚甲基蓝的光催化降解的催化活性进行了评估。实验结果表明:在表面活性剂CTAB的作用下,随着反应时间的增加,生成的ZnS晶核生长成纳米颗粒,然后ZnS纳米颗粒将进一步发生团聚从而形成平均粒径超过500nm的ZnS纳米球,但制备的ZnS产物的晶体结构均为立方纤锌矿结构。随着ZnS粒径的增加,样品的紫外吸收峰从418nm逐渐蓝移到362nm,而PL发射峰位的峰强随着粒径的增大而增强。光催化结果显示,反应12h制备的ZnS纳米球的光催化性能最佳。     

Zn_2GeO_4纳米棒的制备及发光性质

采用水热合成法制备了纯菱形相的Zn_2GeO_4纳米棒,研究了水热制备前驱体溶液的pH值对材料尺寸及形貌的影响以及Zn_2GeO_4纳米棒的光学性质。扫描电子显微镜(SEM)测试结果表明,随着前驱体溶液pH值的变化样品逐渐由微米级块状结构生长成为纳米颗粒,并且进一步形成纳米棒结构。纳米棒的尺寸由长200 nm变化到500 nm。室温光致发光(PL)光谱中观察到位于450和530 nm两个不同的发光峰,其分别源于Zn_2GeO_4的不同缺陷能级。     

银纳米颗粒对CaSrSiO_4:Tb~(3+)光致发光性能的影响

采用高温固相反应法制备了系列的Ag, Tb~(3+)单掺和共掺CaSrSiO_4纳米荧光粉。XRD和SEM分析结果表明, Tb~(3+)和Ag颗粒的掺入对纳米粉末晶体结构的影响较弱,但CaSrSiO_4:0.7Tb~(3+),0.1Ag样品呈现了立方体结构,且颗粒尺寸明显增大。XPS结果显示Ag单质和Ag~+共存于荧光粉中。在243 nm激发下,同时观测到强的545, 415和381 nm的光致发光谱,以及较弱的437, 586和624 nm发光峰。掺入0.1%(摩尔分数)Ag纳米颗粒时,能够使CaSrSiO_4:0.7Tb~(3+)纳米荧光粉的光致发光强度增强25%。最后讨论了掺Ag颗粒浓度对Tb~(3+)的545和381 nm特征峰衰减曲线的影响。     

纳米二苯甲酰甲烷铕配合物的制备和表征

以聚乙烯吡咯烷酮为表面活性剂,在无水乙醇中制备了纳米二苯甲酰甲烷铕配合物Eu(DBM)3,对其进行了红外光谱(IR)、透射电镜(TEM)、X-射线衍射(XRD)、荧光光谱(FS)等表征。结果表明,配合物在聚乙烯吡咯烷酮中呈纳米颗粒分散,分散尺度在5～30Nm之间,与普通二苯甲酰甲烷铕配合物相比,其主要荧光发射峰强度较高;后者在675．6、702．6、719．3、740．5nm处的小峰消失,612．9nm峰红移至611．8nm。     

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.