纳米银三角片的光诱导法可控制备及其抗菌活性

采用一种快速高效的光诱导法合成了纳米银三角片,系统地考察了光照时间、柠檬酸钠用量、OH-用量和合成方法对银纳米三角片的合成产率、尖端形貌及其稳定性的影响。研究结果表明,采用光诱导法合成纳米银三角片的最优条件为光照时间3.5 h,反应物物质的量之比n_(AgNO_3)∶n_(Na_3C_6H_5O_7)∶n_(NaBH_4)=1∶10∶0.8,OH-浓度0.125 mmol·L~(-1),合成出粒径70~80 nm的纳米银三角片,透射电镜和紫外可见分光光度的表征结果表明:光诱导法相对于直接化学还原法制得的纳米银三角片具有较好的微观形态、产率及稳定性。抗菌测试结果表明三角片形态的纳米银比球型颗粒形态的纳米银具有更优异的抗菌性能。     

CoSAPO-34分子筛的合成、表征及其光催化脱氮性能

利用水热合成法,以三乙烯四胺（TETA）为模板剂,正硅酸乙酯、磷酸、氢氧化铝及乙酸钴为原料,合成了CoSAPO-34分子筛。通过扫描电子显微镜（SEM）、粉末X射线衍射（XRD）、热重（TG）、N2吸附-脱附和紫外-可见漫反射光谱（UV-Vis DRS）等方法对合成的分子筛进行表征。以吡啶-正辛烷体系为模拟油品对分子筛催化剂的脱氮效果进行评价,考察了样品的用量、光催化时间及循环催化次数对其脱氮性能的影响。结果表明：当合成原料的物质的量之比为n_P2O5：n_AL2O3：n_SiO2：n_Co：n_TETA=1：0.26：0.82：0.81：2.05,在200 ℃晶化24 h,合成得到粒径约为50 μm、仍保持了SAPO-34分子筛的骨架结构、形貌为立方体的CoSAPO-34分子筛,而且该分子筛具有较好的热稳定性。在500 W氙灯光照条件下反应150 min,样品对质量分数为100 μg·g^-1模拟油品的脱除率达到70%,循环3次光催化脱氮活性基本保持不变。     

介孔硅铝酸盐的合成及其在傅克反应中的催化性能

采用溶胶凝胶法合成了一系列有序性好且酸性较强的介孔硅铝酸盐材料。利用X射线粉末衍射(XRD)、透射电镜(TEM)、²⁷Al核磁共振(²⁷Al NMR)、氨气程序升温脱附(HN₃-TPD)及吡啶吸附红外光谱(Py-FT-IR)对制备的介孔硅铝酸盐材料的结构和性能进行表征,并考察了材料在苯甲醚和苯甲醇的傅克烷基化反应中的催化活性。实验结果表明：合成过程中,表面活性剂的用量、硅铝物质的量的比会影响材料结构的有序性,醋酸用量对材料结构有序性影响很小;进一步研究结果表明,n_Si / n_Al比会影响材料的酸催化活性,当n_Si / n_Al=10时材料的酸催化活性最高。氨气程序升温脱附和吡啶吸附红外光谱表明n_Si / n_Al=10的材料含有最多的B酸酸量。     

碳酸盐共沉淀法可控制备超高倍率锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2

采用碳酸盐共沉淀法通过调节NH₃·H₂O用量来实现可控制备超高倍率纳米结构LiNi_1/3Co_1/3Mn_1/3O₂正极材料。NH₃·H₂O用量会对颗粒的形貌、粒径、晶体结构以及材料电化学性能产生较大的影响。X射线衍射（XRD）分析和扫描电镜（SEM）结果表明,随着NH₃·H₂O用量的降低,一次颗粒形貌由纳米片状逐渐过渡到纳米球状,且n_NH3·H2O：（n_Ni+n_Co+n_Mn）=1：2样品晶体层状结构最完善、Li⁺/Ni²⁺阳离子混排程度最低。电化学性能测试结果也证实了n_NH3·H2O：（n_Ni+n_Co+n_Mn）=1：2样品具有最优异的循环稳定性和超高倍率性能。具体而言,在2.7~4.3 V,1C下循环300次后的放电比容量为119 mAh·g^-1,容量保持率为81%,中值电压基本无衰减（保持率为97%）。在100C（18 Ah·g^-1）的超高倍率下,放电比容量还能达到56 mAh·g^-1,具有应用于高功率型锂离子电池的前景。此NH₃·H₂O比例值对于共沉淀法制备其他高倍率、高容量的正/负极氧化物材料具有一定的工艺参考价值。     

白光LED用铕掺杂硼铋钙玻璃的结构与光学性能

采用熔融冷却法制备了铕掺杂的硼铋钙玻璃。研究了不同硼铋比（n_B/n_Bi）和钙离子浓度条件下的密度、摩尔体积、折射率等物理性质,分析了玻璃的结构、光学性质和热稳定性。实验结果表明,Eu³⁺较好的熔融于玻璃中,形成发光中心,在465 nm蓝光激发下,613 nm处有较为强烈的发射,光谱强度值随n_B/n_Bi变化不明显,但随CaO浓度升高而逐渐递减。玻璃结构总体呈现非晶态,对称性相对较低,结构致密程度和对称性均随n_B/n_Bi的降低而降低,随CaO浓度的升高而升高。玻璃结构主要组成为[BO₃]三角体、[BiO3]三角体,[BO₄]四面体和[BiO₆]八面体,不存在[BO₃]组成的硼六元环。研究结果表明,此系列硼铋钙玻璃能有效匹配蓝光芯片发射红光,且具有熔点低、热稳定较好、折射率相对适宜的特点。     

松香基季铵盐为模板剂有序超微孔二氧化硅的合成

以松香基季铵盐(脱氢枞基三甲基溴化铵,标记为DTAB)为模板剂、正硅酸乙酯为硅源、氨水为碱性介质成功合成出具有纳米片状形貌的六方有序超微孔二氧化硅材料。采用X射线衍射、N₂吸附-脱附、透射电镜、扫描电镜等手段对样品进行表征,结果表明,体系中模板剂添加量、硅源添加量、碱性介质添加量、晶化温度、搅拌时间对前驱体的有序度有着较大的影响。当物质的量之比为n_Sio2:n_DTAB:n_NH3·H2O:n_H2O=1.0:0.1:11.3:924.0,晶化温度为373K,搅拌时间为24h,所得样品有序度最高。经煅烧后样品具有较大的比表面积(1024 m₂·g^-1)和孔容(0.56 cm³·g^-1),以及狭窄的孔径分布(集中于1.80 nm)。     

nFe3+/nSr2+和nOH-/nNO3-对锶铁氧体纳米片结构及磁性能的影响

采用改进的水热法成功合成了单分散的纯相锶铁氧体纳米片。借助DLS、XRD、FTIR、SEM、EDS和VSM等分析测试手段对SrFe₁₂O₁₉铁氧体粉体的粒度、结构、形貌和磁性能进行表征。研究结果表明,在240℃保温5 h,物质的量之比n_Fe³⁺/n_Sr²⁺(R_F/S)和n_OH^-/n_NO3^-(R_O/N)分别为5和2时,所得产物为单分散的纯相六角SrFe₁₂O₁₉铁氧体纳米片。随着R_F/S和R_O/N的变化,合成样品中有少量SrCO₃和Fe₂O₃杂相存在,这主要与反应条件和离子比例有关。磁性能测试结果显示,所得纯相的六角SrF₁₂O₁₉铁氧体纳米片具有优异的磁性能,其饱和磁化强度和矫顽力分别达到60.91 emu·g^-1和94.83 kA·m^-1,使其在医疗、催化和生物等高技术领域具有潜在的应用。     

"一步法"合成多级孔SAPO-34分子筛

以TPOAC和硅溶胶为硅源,合成了多级孔SAPO-34分子筛,总比表面积达到649 m²·g^-1。详细考察了TPOAC和硅溶胶的配比对多级孔SAPO-34外比表面的影响,通过XRD、BET、SEM、NH₃-TPD等对其结构进行表征,结果表明多级孔SAPO-34的外比表面积可调变,晶体外观有较多缺陷位置,弱酸量减少,强酸位有变弱的趋势。在TPOAC与硅溶胶的投料比为3:2,晶化时间为10 d,投料比为n_Al2O3:n_P2O5:n_Si:n_TEAOH:n_H2O=1:0.9:0.5:2:60时,合成的多级孔SAPO-34的外比表面积达到最大,为100 m²·g^-1。     

(GaP)n和(GaP)n－ (n＝10～16)团簇的结构与稳定性研究

采用密度泛函理论B3LYP/Lanl2dz方法对(GaP)_n和(GaP)_n^－ (n＝10～16)团簇的一系列异构体的结构和稳定性进行了研究. 讨论了中性团簇得到一个电子之后, 几何结构和电子性质的变化. 频率分析预测出最强吸收峰位于341～390 cm^－1区域. 从能隙、结合能和能量二次差分等方面综合考虑, 具有T_h对称性的(GaP)₁₂和(GaP)₁₂^－分别是中性(GaP)_n和阴离子(GaP)_n^－团簇中最稳定的, 而具有T_d点群结构的(GaP)₁₆也比较稳定, 究竟哪种结构易于合成还有待于实验的进一步证实. 在相同理论水平上计算了基态(GaP)_n (n＝10～16)的绝热电子亲合势(AEAs)及其基态阴离子的垂直电离能(VDEs), 这对以后的实验数据分析将有一定的参考价值.     

溶剂热法制备ATO纳米球及其性能研究

以五水四氯化锡和三氯化锑为主要原料,以乙二醇为溶剂,采用溶剂热法合成了锑掺杂氧化锡(ATO)纳米球。用X射线衍射仪和透射电子显微镜对合成的ATO纳米球进行结构表征,用紫外可见分光光度计和低阻抗表面阻抗仪研究其光电性能。结果表明：所合成的ATO均为四方晶型结构,由粒径为5~10 nm的ATO纳米晶聚集成直径为80~120 nm的纳米球,且分散性良好。Sb³⁺掺杂量对ATO纳米球的光、电性能有很大影响,随着Sb³⁺掺杂量的增加其可见光透过率和电导率都呈现先增大后减小的变化关系。在n_Sb/n_Sn比为9∶100时其光电性能达到最佳。     

Exploring the Interactions of Atomic Oxygen on Silver Clusters with Hydrogen

The interactions between Ag_nO^-(n=1-8) and H₂ (or D₂) were explored by combination of the mass spectroscopy experiments and density function theory (DFT) calculations. The experiments found that all oxygen atoms in Ag_nO^-(n=1-8) are inert in the interactions with H₂ or D₂ at the low temperature of 150 K, which is in contrast to their high reactivity with CO under the same condition. These observations are parallel with the preferential oxidation (PROX) of CO in excess hydrogen catalyzed by dispersed silver species in the condensed phase. Possible reaction paths between Ag_nO^-(n=1-8) and H₂ were explored using DFT calculations. The results indicated that adsorption of H₂ on any site of Ag_nO^-(n=1-8) is extremely weak, and oxidation of H₂ by any kind of oxygen in Ag_nO^-(n=1-8) has an apparent barrier strongly dependent on the adsorption style of the "O". These experiments and theoretical results about cluster reactions provided molecule-level insights into the activity of atomic oxygen on real silver catalysts.     

Colorimetric Determination Of Hydrogen Peroxide Based on Localized Surface Plasmon Resonance of Silver Nanoprisms Using a Microchannel Chip

Silver nanoprisms (AgNPrs) have unique optical phenomena due to their localized surface plasmon resonance that results in the extinction of light from the visible to the near-infrared spectral region. In this study, we propose the colorimetric determination of silver nanoprisms in microchannels using a smartphone camera. Image acquisition was performed by capturing an image of the colloidal solution of the silver nanoprisms in the microchannel using the transmitted light. Red, green, and blue chromaticity levels were extracted from the recorded images for further quantification of the silver nanoprisms. This technique was employed for the detection and colorimetric determination of hydrogen peroxide (H₂O₂). Good linearity between the change in the green chromaticity level and concentration of hydrogen peroxide was observed for values from 10 to 300?μM with an R² value of 0.9670. We anticipate that the developed methodology for the quantification of silver nanoprisms and hydrogen peroxide by monitoring the change in color in the images of transmitted light will enhance the development of simple, rapid, and reliable detection systems for quality control in the production of silver nanoprisms as well as in chemical sensor applications.     

Calculation of the Gibbs Energy of the Reaction OH-·(H2O)n-1 + H2O = OH-·(H2O)n by the Monte-Carlo Method

The energy, the Gibbs energy of the reaction OH^-·(H₂O) _{n- 1} + H₂O = OH^-·(H₂O) _n are calculated by the Monte-Carlo method with a large canonical ensemble for n = 1, ..., 20. The ion-waternonpair interaction potential was obtained by numerical fitting of calculated Gibbs energy and entropy of (H₂O)_n clusters (n = 1, ..., 5) to experimental ones. A good fit to experiment both of the internal energy and the Gibbs energy can be obtained in terms of a model allowing for nonpair interaction. It is shown that constructing an ion-water interaction potential without allowance for the entropy factor can lead to considerable errors in the Gibbs energy of cluster formation and in the nucleation rate.     

Synthesis,crystal structure,in vitro anticancer and in vivo acute oral toxicity studies of tetramethylene linked bis-benzimidazolium salts and their respective dinuclear Ag(I)–NHC complexes

The proligands of the series tetramethylenebis(N-n-alkylbenzimidazolium bromide) (where n = 3–10) (1–8) as N-heterocyclic carbene (NHC) precursors have been prepared by reacting the initially synthesized N-n-alkyl benzimidazole with 1,4-dibromobutane in 2 : 1 M ratio. A reaction of Ag₂O with 1–8 resulted in the formation of Ag(I) complexes tetramethylenebis{(N-n-alkylylbenzimidazol-2-ylidene)silver(I)hexafluorophosphate} (9–16), respectively. All the synthesized compounds were characterized by FT-IR, ¹H NMR, ¹³C NMR, atomic absorption and elemental analysis. Single-crystal X-ray diffraction study on tetramethylenebis{(N-n-octylbenzimidazol-2-ylidene)silver(I)hexafluorophosphate} (14) has revealed that the complex exists as a dinuclear compound. All compounds were assessed for their antiproliferation test on human colorectal cancer cell line (HCT 116). Interestingly, increasing the n-alkyl chain length from n = 3 to 10 of the proligands and their respective complexes showed trends in increased cytotoxicity against human colon cancer cell line. Cytotoxicity data showed that tetramethylene linked bis-benzimidazolium salts and their respective dinuclear Ag(I)–NHC complexes can be useful therapeutic agents against colon cancer.     

From mesogens to metallomesogens. Synthesis,characterisation, liquid crystal and luminescent properties

Continuation with our previous investigation which refers to the synthesis of a series of hydrophobic symmetrical azine compounds: 1,2-bis[4-(n-alkoxy)benzylidene]hydrazine (where, n-alkoxy: O(CH₂)_nH, n = 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 16 or 18), a series of hydrophobic asymmetrical azine compounds: [1-(4-propyloxy)-2-(4?-(n-alkoxy))benzylidene]hydrazine (where, n-alkoxy: O(CH₂)_nH, n = 1, 2, 4, 5, 6, 7, 8, 9, 10, 12, 16 or 18) was synthesised following an efficient and practical method. These compounds were synthesised by the condensation reaction of hydrazine hydrate with 4-propyloxybenzaldehyde and appropriately 4-(n-alkoxy)benzaldehydes in acidic medium and ambient conditions (very simple way with no need of any sophisticated techniques). Moreover, two new series of silver(I) complexes based on symmetrical or asymmetrical azines have been synthesised (linear-binuclear type complexes with the general formula [Ag₂(L)(NO₃)₂] were obtained). The organic compounds and their silver(I) complexes were characterised using different techniques: microelemental analysis and spectral data (FTIR, UV–Vis, ¹HNMR, ¹³C{¹H}NMR, 2D ¹H-¹H-COSY, 2D ¹H-¹³C-HSQC and mass spectra) as well as molar conductivity measurements for silver(I) complexes. Liquid crystal behaviour of the prepared compounds were studied using polarised light optical microscopy and confirmed with differential scanning calorimetry and X-ray powder diffraction techniques. The studies revealed that all azine compounds and some of silver(I) complexes are liquid crystal materials. The luminescent properties of all the prepared compounds were also investigated which confirmed that all of these compounds are photo-luminescent in the crystalline solid state and in the mesophase.     

Comparison of catalytic activity and efficiency of hydrogen peroxide utilization for di-iron-containing silicotungstate with those for iron containing complexes and the oxidation of methane and ethane

The Keggin-type di-iron-substituted γ-SiW₁₀{Fe(OH₂)}₂O₃₈ ^6- showed high efficiency of hydrogen peroxide utilization for the oxidation of cyclohexane. The efficiency and catalytic activity greatly depended on the structures of the iron centers. Such a structure dependency of the catalysis is significant and the remarkable catalytic performance of di-iron-substituted polyoxometalate may be related to the catalysis by methane monooxygenase. Not only cyclohexane but also cyclooctane, n-hexane, n-pentane, and adamantane were catalytically oxygenated with high efficiency of hydrogen peroxide utilization. Even methane and ethane were oxidized. It was also demonstrated that the potassium salt of γ-SiW₁₀{Fe(OH₂)}₂O₃₈ ^6- oxidized methane in water.     

银纳米棱镜的形成及其光学性能研究

以有机溶剂作为反应介质,聚合物为稳定剂,通过微波辅助溶液法成功地制备了具有特殊光学性能的银纳米棱镜.利用X射线衍射、透射电子显微镜和紫外-可见光谱等手段跟踪反应过程.结果显示,随着反应的进行,银纳米粒子由10nm左右的球形颗粒逐渐转变为具有规则三角形(或缺角的三角形)形貌的纳米棱镜;同时,紫外-可见吸收峰不但显示出明显的量子尺寸效应,而且吸收峰也由单一的等离子共振吸收峰变为多重的多极吸收峰共同存在,胶体溶液也随之显示出不同的颜色.改变反应物的配比、体系的浓度及无机前驱物都会得到位置和峰形各不相同的吸收曲线,从而得到多彩的纳米银胶体溶液.     

Unusual Rate Enhancement in the Hydroxide-Ion-Catalyzed Cleavage of Acetyl Salicylate Ion (Aspirin Anion) in the Presence of Anionic Micelles

The reaction rate studies on the hydrolytic cleavage of acetyl salicylate ion (AS^-) within the [^-OH] range 0.010-0.025 M reveal AS^- and ^-OH as the reactants. The effects of micelles of sodium dodecyl sulfate (SDS) on observed pseudo-first-order rate constants (k_obs) for the hydrolytic cleavage of AS^- have been studied at different [OH^-]. At a constant [OH^-], the rate constants (k_obs) follow an empirical relationship: k_obs = C + F [SDS]_T where [SDS]_T represents total SDS concentration. The magnitudes of C and F increase with an increase in [OH^-]. These data are explained in terms of the pseudophase model of the micelle.     

Synthesis and mesomorphism behaviour of chalcones and pyrazoles type compounds as photo-luminescent materials

The following organic and organic–inorganic hybrid compounds were prepared as photo-luminescent materials following efficient and practical synthetic methods: 1,3-bis[4-(n-alkoxy)phenyl]-2-propen-1-one (where, n-alkoxy: O(CH₂)_nH, n = 6,7,8,9 or 10); 3,5-bis[4-(n-alkoxy)phenyl]-1H-pyrazole (where, n-alkoxy: O(CH₂)_nH, n = 6,7,8,9 or 10) (in case of n = 7, a mixture of 3,5-bis(4-heptyloxyphenyl)-1H-pyrazole and 3,5-bis(4-heptyloxyphenyl)-4H-pyrazole was detected) and bis(3,5-bis [4-(n-alkoxy) phenyl]-1H-pyrazole) silver(I) nitrate (where, n-alkoxy: O(CH₂)_nH, n = 6,7,8,9 or 10). The prepared compounds have been characterised and their structures were elucidated depending upon (FTIR, UV-Vis, ¹HNMR, ¹³CNMR, 2D ¹H-¹H-COSY, 2D ¹H-¹³C-HSQC and mass spectra) in addition to molar conductivity measurements for silver(I) complexes. The mesomorphism behaviour of the prepared compounds was studied using polarised light optical microscopy and confirmed with differential scanning calorimetry and X-ray powder diffraction techniques. The studies showed that among all of these compounds only the pyrazole derivatives are liquid crystal materials. The luminescent properties of all the prepared compounds were also investigated which confirmed that all of these compounds are photo-luminescent in the crystalline solid state and in the mesophase.