不同形貌PbS 纳米粒子形成机理的探讨

采用聚乙二醇辛基苯基醚(OP)/正戊醇/环己烷/水溶液所形成的W/O型微乳液中的水核作软模板,合成了不同形貌如球形、立方体形、纺锤形、梭形和棒形的PbS纳米粒子。运用透射电子显微镜(TEM)对产物的形貌进行了表征。考察了W/O型微乳液中水与表面活性剂的物质的量的比(ω0)、反应物浓度和陈化时间等条件对产物形貌的影响。对不同形貌PbS纳米粒子的形成机理进行了探讨。     

反相微乳液法制备纳米Al2O3颗粒及其形成反应机理的研究

通过聚乙二醇辛基苯基醚(曲拉通X-100)/正丁醇/环己烷/水溶液形成的体系, 采用反相微乳液法合成了Al₂O₃纳米粒子. 对前驱体进行热分析(TG-DTG-DTA), 确定了合适的煅烧温度为1150 ℃. 采用X射线衍射(XRD)、透射电镜(TEM)、紫外可见分光光度法(UV-vis)分别对产物的结构、粒度和形貌进行了表征, 考察了微乳液中水与表面活性剂的物质的量之比(ω_o)、煅烧温度和煅烧时升温速率等关键因素对产物形貌和晶相的影响, 并通过分析进一步揭示了Al₂O₃纳米粒子的形成机理. 结果表明, 控制ω_o为10、煅烧温度为1150 ℃可得到分散性好、粒径分布均匀的Al₂O₃纳米粒子, 且2 ℃/min的升温速率更有利于产物向稳定的α晶相转变.     

反相微乳液法制备纳米Al2O3颗粒及其形成反应机理的研究

通过聚乙二醇辛基苯基醚(曲拉通X-100)/正丁醇/环己烷/水溶液形成的体系, 采用反相微乳液法合成了Al₂O₃纳米粒子. 对前驱体进行热分析(TG-DTG-DTA), 确定了合适的煅烧温度为1150 ℃. 采用X射线衍射(XRD)、透射电镜(TEM)、紫外可见分光光度法(UV-vis)分别对产物的结构、粒度和形貌进行了表征, 考察了微乳液中水与表面活性剂的物质的量之比(ω_o)、煅烧温度和煅烧时升温速率等关键因素对产物形貌和晶相的影响, 并通过分析进一步揭示了Al₂O₃纳米粒子的形成机理. 结果表明, 控制ω_o为10、煅烧温度为1150 ℃可得到分散性好、粒径分布均匀的Al₂O₃纳米粒子, 且2 ℃/min的升温速率更有利于产物向稳定的α晶相转变.     

反相微乳液法制备纳米SiO2的研究

在壬基酚聚氧乙烯5醚(NP-5)/环己烷/氨水的反相微乳液体系中，进行正硅酸乙酯(TEOS)的水解、缩合反应，得到粒径在30～50 nm的单分散纳米SiO₂胶体。红外光谱法(FTIR)及透射电子显微镜(TEM)观察证明了纳米SiO₂粒子的生成。反相微乳液体系相图的研究表明，水相为氨水比纯水有较窄的W/O型微乳区。氨水微乳液是碱催化TEOS水解、缩合制备纳米SiO₂粒子的适宜体系。当体系中TEOS的浓度增大时，粒子的粒径随之增大。降低NP-5     

反相微乳液介质中纳米Sm2O3的制备

用十六烷基三甲基溴化铵(CTAB)/正丁醇/正辛烷/钐盐水溶液(氨水)所形成的反相微乳液体系, 控制合成Sm2O3球形纳米粒子. 绘制出25 ℃下CTAB/正丁醇/正辛烷/钐盐水溶液(氨水)体系的拟三元相图, 得到了反相微乳液区.在此反相微乳区内合成了Sm2O3的前驱体, 对前驱体进行热分析(TG-DSC), 确定了得到纳米Sm2O3产物的适宜焙烧温度为900 ℃, 并考察了微乳液中反应物浓度、反应时间等因素对合成产物的影响. 采用X射线衍射(XRD)、透射电镜(TEM)、激光粒度仪(NSA)、荧光光谱(FS)仪等分析方法对Sm2O3产物的形貌、晶形、粒径及荧光性质进行了表征. 结果表明, 25 益下利用反相微乳液法, 成功地制备了粒径分布较窄、分散性良好的球形纳米Sm2O3粒子, 粒径约20 nm左右, 且表现出较强的荧光性质.     

反相微乳液介质中纳米Sm2O3的制备

用十六烷基三甲基溴化铵(CTAB)/正丁醇/正辛烷/钐盐水溶液(氨水)所形成的反相微乳液体系,控制合成Sm2O3球形纳米粒子.绘制出25℃下CTAB/正丁醇/正辛烷/钐盐水溶液(氨水)体系的拟三元相图,得到了反相微乳液区.在此反相微乳区内合成了Sm2O3的前驱体,对前驱体进行热分析(TG-DSC),确定了得到纳米Sm2O3产物的适宜焙烧温度为900℃,并考察了微乳液中反应物浓度、反应时间等因素对合成产物的影响.采用X射线衍射(XRD)、透射电镜(TEM)、激光粒度仪(NSA)、荧光光谱(FS)仪等分析方法对Sm2O3产物的形貌、晶形、粒径及荧光性质进行了表征.结果表明,25℃下利用反相微乳液法,成功地制备了粒径分布较窄、分散性良好的球形纳米Sm2O3粒子,粒径约20 nm左右,且表现出较强的荧光性质.     

聚乙烯吡咯烷酮碱性水溶液中金纳米花的简易合成

以聚乙烯吡咯烷酮(PVP)兼作保护剂和还原剂在碱性水溶液中直接还原HAuCl₄制备出了60-80 nm的三维(3D)金纳米花. 产物的透射电子显微镜(TEM)和扫描电子显微镜(SEM)图像显示, 金纳米花表面布满10-15 nm左右的纳米触角, X射线衍射(XRD)表征揭示产物为金的面心立方晶体, 选区电子衍射(SAED)花样说明金纳米花为多晶结构. 金纳米花的生长经历了三个关键步骤, 即初级纳米晶聚集成多脚状纳米粒子, 随后在合适的PVP/HAuCl₄浓度比及NaOH浓度下, 多脚状纳米粒子进一步聚集形成疏松的花状粒子, 最终经过Ostwald熟化形成致密的花状产物. 一定HAuCl₄浓度下PVP/HAuCl₄浓度比和NaOH浓度对产物的形貌影响显著, 因此通过同时调控合适的PVP/HAuCl₄浓度比和NaOH浓度, 就能得到适应各种应用需求的尺度可控和纳米触角形貌可控的金纳米花.     

新型双链表面活性剂DDOBA的合成与高单分散性憎水纳米金的制备

自行设计合成了新颖的苄胺型双链表面活性剂3,4-双十二烷氧基苄胺(DDOBA). 利用DDOBA/正丁醇/正庚烷/甲酸/HAuCl₄·4H₂O自发形成的水/油(W/O)型微乳液作为微反应器, 通过微波辐射下的甲酸还原法成功制备了DDOBA保护的憎水性金纳米粒子, 并通过紫外-可见(UV-Vis)光谱、透射电镜(TEM)、高分辨透射电镜(HR-TEM)和X射线衍射(XRD)等方法进行了表征和分析. 结果显示, DDOBA既可参与形成稳定的W/O型(油包水型)微乳液, 又可作为金纳米粒子的良好保护剂. 在合适的微乳液体系组成范围内, 用本实验方法可以获得高单分散性的憎水性金纳米粒子, 并能在空气/水界面上自动形成大面积短程有序的纳米金二维自组装膜.     

粒径可控纳米CeO_2的微乳液法合成

以十六烷基三甲基溴化铵(CTAB)/正丁醇/正辛烷/硝酸铈(Ce(NO3)3)水溶液(氨水)所形成的反相微乳液体系合成CeO2前驱体,利用热重(TG)和X射线衍射(XRD)分析方法确定了得到纳米CeO2的适宜焙烧温度为550℃,CeO2前驱体经550℃焙烧后得到纳米CeO2.采用XRD、透射电镜(TEM)、紫外-可见(UV-Vis)分光光度计等表征手段分别对纳米CeO2的晶形、形貌、粒径及紫外吸收性质进行了表征,该纳米CeO2粒子具有立方晶型结构,分散性较好、粒径范围为5-18nm.考察了微乳液中正辛烷与正丁醇质量比、Ce(NO3)3浓度对纳米CeO2粒径的影响,结果表明:利用微乳液法,通过改变微乳液中正辛烷与正丁醇质量比、Ce(NO3)3浓度能够对纳米CeO2粒径进行有效控制;纳米CeO2的粒径均随着正辛烷与正丁醇质量比和Ce(NO3)3浓度的增大而减小.同时,对不同条件下制得的纳米CeO2的紫外吸收性质进行了考察.     

反相微乳液中憎水性纳米金的原位还原法合成

利用十八胺(C18NH2)/正丁醇/正庚烷/HAuCl4(aq)W/O型微乳液体系,在常温的碱促进条件下由正丁醇原位还原氯金酸合成了具有高度单分散的憎水性金纳米粒子。由C18NH2稳定的金纳米颗粒运用紫外可见光谱(UV-vis)、透射电镜(TEM)和X射线衍射(XRD)等分别进行了表征和分析,并探讨了微乳液体系各组分对形成金纳米粒子形貌、尺寸和单分散性的影响。结果显示,随十八胺/氯金酸摩尔比的增加,金粒子的尺寸逐渐减小而单分散性逐渐提高。在正丁醇原位慢还原氯金酸的过程中,实验所选W/O型微乳液模板和表面活性剂十八胺分子对憎水性金纳米粒子的形貌和尺寸仍具有良好的控制作用。     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.     

Catalyst free,visible-light promoted photoaddition reactions between C60 and N-trimethylsilylmethyl-substituted tertiary amines for synthesis of aminomethyl-1,2-dihydrofullerenes

An efficient and benign method for the preparation of aminomethyl-substituted fullerenes has been developed. The process, involving catalyst free, visible-light irradiation of 10% EtOH-toluene solutions containing fullerene C₆₀ and N-trimethylsilylmethyl-substituted amines by using a 20 W compact fluorescent lamp, leads to formation of aminomethyl-substituted fullerene adducts in a highly efficient manner. The photoaddition reaction takes place via a pathway initiated by visible light absorption by C₆₀, followed by SET from the amine to the triplet excited state of C₆₀. Ethanol-promoted desilylation of the resulting a minimum radical then generates the corresponding α-amino radical which couples with the C₆₀ radical anion to form the anion precursor of the fullerene adducts. The new approach using visible-light takes place under mild conditions and it does not require the use of photocatalysts. Thus, the method developed in this effort could broadens the range of functionalized fullerene derivatives that can be readily prepared.     

Highly efficient and stereoselective cycloaddition of nitrones to indolyl- and pyrrolylacrylates

The reactions of various nitrones with indolyl- and pyrrolylacrylates proceeds regioselectively with high diastereoselectivity in the case of aldonitrones, and represents an effective method for obtaining new indolyl- and pyrrolyl-substituted isoxazolidine carboxylates stabilized by weak (CH?O) and moderate (NH?N) strength intramolecular hydrogen bonding. The resulting cycloadducts exhibit promising in vitro anti-influenza activities.     

Transition metal-free direct amination of benzoxazoles using formamides as nitrogen sources

A transition metal-free method for the direct amination of benzoxazoles using formamides as nitrogen sources is reported, which was mediated by an inexpensive and environmentally friendly tetrabutylammonium iodide/tert-butyl hydroperoxide system and gave the 2-aminobenzoxazole derivatives with moderate to good yields.     

l-Proline-catalyzed five-component domino reaction leading to multifunctionalized 1,2,3,4-tetrahydropyridines

Multifunctionalized 1,2,3,4-tetrahydropyridines are concisely synthesized in good yields via l-proline-catalyzed or l-proline/FeCl₃-cocatalyzed one-pot multicomponent reactions (MCRs). The MCRs involve a domino hydroamination/prins reaction/Mannich-type reaction/intramolecular dehydration-cyclization process. The molecular structure of 5baa, one of multifunctionalized 1,2,3,4-tetrahydropyridines, was confirmed by single-crystal X-ray diffraction.     

Studies of Photoionization of CF3 I by Femtosecond Time-resolved Mass Spectrometry

The multi-photon dissociative photoionization dynamics of CF3I has been studied with femtosecond two-color pump-probe time of flight mass spectra at a pump pulse of 265 nm and a probe pulse of 398 nm. The life constants of CF3I+ and its fragment ions CF3+ and I+ are obtained as (96±7), (198±130) and (167±6)fs, respectively. The multi-photon dynamics leading to these ions differ. CF3I+ corresponds to a (1+2′) transition with one-photon pump excitation to the A band of CF3I. CF3+ are mainly formed by a tow-photon probe excitation to the CF3+ with subsequent dissociation of parent ions. I+ are produced in (2+2′) combined with (1+1′+2′) process. The results provide information on the multi-photon pathways involved.