Synthesis and Characterization of CdSe Nanocrystals Capped by CdS

CdSe semiconductor nanocrystals capped by CdS were synthesized in the aqueous solution with 2-mercaptoethanol as the stabilizer. The CdS capping with a higher band-gap than that of the core crystallite has successfully eliminated the surface traps. Optical absorption and fluorescence emission spectra were used to probe the effect of CdS passivation on the electronic structure of the nanocrystals. The composite CdSe/CdS nanocrystals exhibit strong, narrow(FWHM≤40 nm) and stable band-edge photoluminescence. X-ray powder diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy were used to analyze the composite nanocrystals and determine their average size, size distribution, shape, internal structure and elemental composition.     

基于柠檬酸盐修饰CdS量子点的高灵敏Ag~+传感器

以柠檬酸三钠作为表面修饰剂,利用简单的方法合成了水溶性柠檬酸三钠修饰的CdS量子点(Cit-CdS)。研究了反应前驱体中nCd/nS比、反应溶液pH值、反应温度等条件对产物的荧光性质的影响。在巯基乙酸存在下,Ag+能大大增强量子点的荧光。基于此,构建了基于Cit-CdS的高灵敏Ag+传感器。传感器在Ag+浓度为5.0×10-9~2.0×10-6mol·L-1内对银离子线性响应良好,检测限为1.0×10-9mol·L-1。其它常见金属离子对Ag+的测定并无明显干扰。     

Thermodynamic study of polyethylene-glycols in micellar solutions water+sodium dodecylsulfate

Interactions of a series of polyethyleneglycols (PEG) in aqueous micellar solutions of sodium dodecylsulfate (SDS) were investigated through thermodynamic properties. Volumes, heat capacities and enthalpies of dilution were measured at 25°C. The resulting transfer properties of PEG are reflecting hydrophobic interactions which increase with the polymer length and the hydrophilic interactions occurring in the aqueous polar layer of the micelles. Typically heat capacities clearly evidence various structural changes taking place in the micellar solutions.     

Mixing Behavior of Cationic Hydrotropes with Anionic Surfactant Sodium Dodecyl Sulfate

Mixing behavior of anionic surfactant sodium dodecyl sulfate (SDS) with cationic hydrotropes aniline hydrochloride (AH), o-toluidine hydrochloride (o-TH), and p-toluidine hydrochloride (p-TH) have been studied using conductivity at different temperatures. Critical micelle concentration for different mixing mole fractions, their ideal values, and different interaction parameters have been estimated. All the parameters show nonideal behavior with synergistic interactions. Thermodynamic parameters are also calculated for these systems.     

Application of Luminescent BSA‐Capped CdS Quantum Dots as a Fluorescence Probe for the Detection of Cu2+

CdS Quantum dots (QDs) are synthesized in aqueous solution with bovine serum albumin (BSA) as the stabilizing agents using a stepwise procedure at room temperature. They can be used as a new fluorescence probe in the determination of Cu²⁺, which is proved to be a simple, rapid and specific method. Approximate concentrations of other physiologically important cations, such as Zn²⁺, K⁺ etc, have no effect on the fluorescence. Under the optimum condition, the response is linear to the concentration of Cu²⁺ in the range of 0‐80.0 μol/L, and the detection limit is 50.0 nmol/L. This method is used to the determination of Cu²⁺ in human hair, the recovery is 98‐104%. And the possible detection mechanism is also discussed.     

Interaction of sodium dodecylsulfate (SDS) with homoionic montmorillonites: adsorption isotherms and metal-ion release

The interaction of dodecylsulfate anions (DS^–) with homoionic Ca-, Mg-, Ni-, Cu-, Cd-, Pb- and Fe-montmorillonites were investigated. Mg- and Cd-montmorillonite do not adsorb DS^–, and an anion exchange at the edges of the clay mineral does not take place. Three different adsorption processes are identified on the other montmorillonites: i) Fe-montmorillonite is covered with amorphous iron hydroxide, and DS^–-anions are bound at positively charged sites. ii) On Ca- and Pb-montmorillonite DS^– is precipitated as Me(DS)₂. iii) On Ni- and Cu-montmorillonite DS^– forms ion pairs with the cations on the surface. In all cases DS^– is not bound above the CMC but the metal ions are mobilized from the surface either by solubilization of the precipitates or by formation of mixed micelles.     

阴离子氨基酸表面活性剂调控下水热合成羟基磷灰石纳米片

利用水热合成方法, 在含有氨基酸结构的阴离子表面活性剂N-酰基十二烷基肌氨酸钠(Sar-Na)的控制下, 合成具有较大长径比(aspect ratio)的片状纳米羟基磷灰石晶体. 采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)和傅立叶变换红外(FTIR)光谱表征, 并分析了合成产物的形貌、结构和组成. 结果表明, 在Sar-Na的调控下合成了长度0.5-1.0 μm、宽约30 nm的片状羟基磷灰石晶体, 其长径比约为20:1. 考察了表面活性剂Sar-Na的用量对羟基磷灰石形貌的影响. 随着Sar-Na的添加及用量的增加, 羟基磷灰石由椭圆形变为长片状, 并且片的两端逐渐变尖. 结果显示了Sar-Na对羟基磷灰石形貌的控制作用, 为合成具有较大长径比的羟基磷灰石纳米片提供了一个新的途径.     

PAMAM树形分子与Cd2＋的配位作用研究及CdS/PAMAM纳米复合材料的制备与表征

CdS半导体纳米簇具有独特的光、电性能, 如何制备均匀分散的、能够稳定存在的CdS纳米簇是目前的研究热点之一. 以聚酰胺-胺(PAMAM)树形分子为模板, 原位合成了CdS纳米簇. 首先用UV-Vis分光光度法研究了与树形分子的配位机理, 得出G4.5和G5.0的平均饱和配位数分别为16和34, 并发现在G4.5PAMAM树形分子中Cd^2＋主要与最外层叔胺基配位, 在G5.0PAMAM树形分子中Cd^2＋主要与最外层伯胺基配位. 酯端基的G4.5的模板作用要明显优于胺端基的G5.0. 通过改变Cd^2＋与G4.5树形分子的摩尔比可以得到不同粒径的CdS纳米簇. 溶液的pH值对CdS纳米簇影响很大, pH在7.0左右制备的CdS纳米簇粒径小而均匀, 且溶液稳定性高. 用UV-Vis分光光度计和TEM对CdS纳米簇的大小和形貌进行了表征. 结果表明TEM观测CdS纳米簇的粒径要大于用Brus公式的估算值.     

毛细管电泳法测定针剂中亚硫酸氢钠甲萘醌的含量

建立了亚硫酸氢钠甲萘醌的高效毛细管电泳紫外测定方法。以未涂层融硅石英毛细管(55cm×75μm)为分离柱,40mmol/L磷酸盐+50mmol/LSDS(pH=7.5)为电泳介质,在分离电压为15kV,紫外检测波长为231nm的条件下对亚硫酸氢钠甲萘醌进行测定。讨论了缓冲溶液、pH值的选择,并着重研究了十二烷基硫酸钠对亚硫酸氢钠甲萘醌增溶作用机理。以磷酸吡哆醛为内标对亚硫酸氢钠甲萘醌注射液进行测定,方法简单可行且结果良好。     

富镉离子CdS量子点电化学发光法检测L-半脐氨酸

采用一锅法,通过控制镉硫比合成了表面富镉离子的硫化镉量子点,利用L-半胱氨酸可与量子点表面Cd2+结合,使量子点表面钝化,从而增强其电化学发光信号的性质,实现了对L-半胱氨酸的选择性检测.对合成的量子点进行了表征,优化了检测条件.在优化的条件下,L-半胱氨酸在5.0×10-9~1.0×10-5 mol/L浓度范围内与ECL信号呈良好的线性关系,检出限为1.2×10-9 mol/L(S/N=3).本方法对L-半胱氨酸具有良好的选择性,用于实际样品中L-半胱氨酸的测定,结果令人满意.     

手性模板合成CdS纳米棒

由于纳米材料具有量子尺寸效应及大的比表面积等性质而使其在电子学[1]、光学[2]、催化[3]和陶瓷[4]等领域显示出诱人的应用前景. 近年来纳米材料的制备及纳米技术发展迅速, 特别是具有特殊光电活性的新型无机纳米材料的制备已引起人们的普遍关注. 现在合成纳米材料的方法主要包括反相胶束法[5]、 LB膜法[6]、嵌段共聚物法[7]和模板合成法[8]. 其中模板合成技术不仅可以通过设计新型的模板分子, 还可通过模板分子的不同自组装行为来调控纳米材料的尺寸和形貌. Stupp等[9]曾利用溶致液晶的六方中间相作为模板, 在其纳米孔隙中成功地合成了具有六方排列超晶格纳米结构的材料. 本文以双亲性丙氨酸衍生物为模板, 在不同的化学微环境下合成了结构不同的CdS纳米棒.     

New elaboration of Na2O-B2O3-SiO2 glass doped with CdS nanocrystals from gel formed in aqueous solution

A new route for preparing a CdS doped sodium borosilicate glass from a gel formed in an aqueous solution is described. This elaboration process allows the preparation of a gel which starts densifying at 400°C just after the Cd sulphurizing process ensuring the protection of crystallites from oxidation. The densification of the matrix is completed at the fusion temperature (730°C), which is low enough to reduce the coalescence of the crystallites. Microstructural and optical characterization of the CdS doped glasses indicate that the crystallite size depends upon the Cd concentration. A model to calculate the crystallite size from optical absorption spectra is proposed. It indicates that the average sizes of crystallites range from 11 nm for a concentration of 0.03 mol% Cd to 3.7 nm for 0.016 mol% Cd.     

阴离子氨基酸表面活性剂调控碳酸钙的仿生合成

室温下, 在乙醇或乙醇-水混合体系中, 利用氨基酸表面活性剂N-酰基十二烷基肌氨酸钠(Sar)调控合成碳酸钙, 采用SEM, XRD和FTIR等技术表征了反应产物. 在乙醇体系中, 首先形成多面体形状的文石, 然后逐渐转变为圆球状的无定形碳酸钙. 在乙醇-水混合体系中, 合成了花簇状多级结构碳酸钙晶体. 增加N-酰基十二烷基肌氨酸钠的用量有助于形成球霰石结构, 当n(Ca2+)∶n(Sar)=1∶1 时, 得到的花状碳酸钙为球霰石和方解石的混合物, 当n(Ca2+)∶n(Sar)=1∶2 时, 得到纯净的球霰石, 其形貌为大小较均一的单分散的球, 直径约为7 μm; 另外, 当n(Ca2+)∶n(Sar)=1∶1时, 混合溶剂中水和乙醇的体积比由1.5∶1依次增加为7∶3和3∶1时, 碳酸钙晶体的形貌由花状逐渐向球形过渡, 晶体中球霰石和方解石的含量也随之变化, 其中, 当水和醇的体积比为7∶3时, 产物主要为球霰石型晶体.     

新型羧酸盐阴离子Gemini表面活性剂的合成及其表面活性

以丙二酸二乙酯为原料,与溴代正癸烷经单边取代反应制得2-癸基丙二酸二乙酯(1); 1与1,3-二溴丙烷发生双边取代反应制得四乙基二十五烷-11,11,15,15-四羧酸酯（2）; 2依次发生皂化、酸化及脱酸反应制得2,6-二癸基庚二酸（4）; 4和NaOH经酸碱中和反应合成了一种新型羧酸盐阴离子Gemini表面活性剂---2,6-二癸基庚二酸钠(5),总收率46.7%,其结构经¹H NMR,IR和MS表征。采用表面张力法研究了5的表面活性。结果表明：5具有较强的聚集能力和界面吸附能力,其cmc, γ_{c mc}, C₂₀, Γ_max和Amin分别为0.29 mmol·L^-1, 31.96 mN·m-¹, 5.640 μmol· m^-2和0.295 nm²。     

有机硫源溶剂热法合成CdS纳米晶体

以二硫化四甲基秋兰姆((TMTD)作为有机硫源,分别在苯、水-苯溶剂中于不同温度、不同时间溶剂热法合成了CdS纳米晶体。采用FE-SEM、XRD和FTIR对晶体的结构和成形机理进行了研究。结果表明,溶剂热温度比反应时间对晶体形貌的形成影响更大。CdS纳米晶体是立方与六角的混合晶型。此外,溶剂的种类也是影响CdS纳米晶体结构和成形的重要因素,并且对花形CdS纳米晶体进行了阴极发光(CL)光谱的研究。     

Synthesis of Nanosilica for the Removal of Multicomponent Cd2+ and Cu2+ from Synthetic Water: An Experimental and Theoretical Study

Copper and cadmium ions are among the top 120 hazardous chemicals listed by the Agency for Toxic Substances and Disease Registry (ATSDR) that can bind to organic and inorganic chemicals. Silica is one of the most abundant oxides that can limit the transport of these chemicals into water resources. Limited work has focused on assessing the applicability of nanosilica for the removal of multicomponent metal ions and studying their interaction on the surface of this adsorbent. Therefore, this study focuses on utilizing a nanosilica for the adsorption of Cd²⁺ and Cu²⁺ from water. Experimental work on the single- and multi-component adsorption of these ions was conducted and supported with theoretical interpretations. The nanosilica was characterized by its surface area, morphology, crystallinity, and functional groups. The BET surface area was 307.64 m²/g with a total pore volume of 4.95×10−3 cm³/g. The SEM showed an irregular amorphous shape with slits and cavities. Several Si–O–Si and hydroxyl groups were noticed on the surface of the silica. The single isotherm experiment showed that Cd²⁺ has a higher uptake (72.13 mg/g) than Cu²⁺ (29.28 mg/g). The multicomponent adsorption equilibrium shows an affinity for Cd²⁺ on the surface. This affinity decreases with increasing Cu²⁺ equilibrium concentration due to the higher isosteric heat from the interaction between Cd and the surface. The experimental data were modeled using isotherms for the single adsorption, with the Freundlich and the non-modified competitive Langmuir models showing the best fit. The molecular dynamics simulations support the experimental data where Cd²⁺ shows a multilayer surface coverage. This study provides insight into utilizing nanosilica for removing heavy metals from water.     

阴离子表面活性剂作为添加剂种子生长法制备尺寸可调的单分散金纳米棒

以不同阴离子表面活性剂作为添加剂种子生长法制备金纳米棒,并考察阴离子表面活性剂种类对金纳米棒形貌及光学性质的影响。在十二烷基苯基磺酸钠(SDBS)存在下,金纳米棒的产率明显高于使用十二烷基磺酸钠的反应体系。对添加SDBS的种子生长法制备金纳米棒的反应条件进行优化,得到十六烷基三甲基溴化铵、SDBS、抗坏血酸和硝酸银的最佳浓度分别为0.04 mol.L-1、2.4 mmol.L-1、1.2 mmol.L-1和0.08 mmol.L-1。在此条件下,金纳米棒的生长在30 min内完成,所制备的金纳米棒表面等离子共振吸收峰位于823 nm,其横纵比为(5±0.03)。当改变生长液中硝酸银浓度时,金纳米棒的尺寸也随之发生改变。此外,我们还探讨了SDBS的作用机理。相对于经典种子生长法,新方法制备纳米金棒在尺寸可调性、单分散性和生物毒性方面明显改善,可广泛应用于各种光学及生物分析。     

阴离子表面活性剂作为添加剂种子生长法制备尺寸可调的单分散金纳米棒

以不同阴离子表面活性剂作为添加剂种子生长法制备金纳米棒, 并考察阴离子表面活性剂种类对金纳米棒形貌及光学性质的影响。在十二烷基苯基磺酸钠(SDBS)存在下, 金纳米棒的产率明显高于使用十二烷基磺酸钠的反应体系。对添加SDBS的种子生长法制备金纳米棒的反应条件进行优化, 得到十六烷基三甲基溴化铵、SDBS、抗坏血酸和硝酸银的最佳浓度分别为0.04 mol·L^-1、2.4 mmol·L^-1、1.2 mmol·L^-1和0.08 mmol·L^-1。在此条件下, 金纳米棒的生长在30 min内完成, 所制备的金纳米棒表面等离子共振吸收峰位于823 nm, 其横纵比为(5±0.03)。当改变生长液中硝酸银浓度时, 金纳米棒的尺寸也随之发生改变。此外, 我们还探讨了SDBS的作用机理。相对于经典种子生长法, 新方法制备纳米金棒在尺寸可调性、单分散性和生物毒性方面明显改善, 可广泛应用于各种光学及生物分析。     

石墨烯/十二烷基硫酸钠复合物修饰碳糊电极测定氯霉素

以液体石蜡和硅油为混合粘合剂,与石墨粉混合制备了碳糊电极基底电极,将石墨烯/十二烷基硫酸钠复合物修饰在基底碳糊电极上,得到了基于石墨烯复合物的新型修饰碳糊电极。应用扫描电镜和循环伏安法分别研究了该电极的表面特性和电化学性质,结果表明,石墨烯和十二烷基硫酸钠修饰的碳糊电极增大了比表面积,有利于电子传递。在pH 3.0的HAc-NaAc缓冲溶液中,该修饰碳糊电极对氯霉素具有良好的电化学响应,氧化峰电位为0.194 V,氧化峰电流是基底碳糊电极的10倍。在最优实验条件下,该氧化峰电流与氯霉素的浓度在1.0×10~(-8)~5.0×10~(-4)mol/L范围内呈良好的线性关系,检出限为5.0×10~(-9)mol/L。该方法简便,重现性及选择性好,用于测定氯霉素滴眼液和虾中氯霉素残留,结果满意。     

壳聚糖吸附Cd2+的机理

壳聚糖分子中的大量氨基及部分酰胺基的存在 ,能够选择性地配位或吸附一些金属离子 ,尤其是对过渡金属离子具有较好的螯合能力。Ｐｉｒｏｎ等[2 ] 利用放射性85Ｓｒ研究了壳聚糖的氨基与碳酸锶离子对Ｓｒ2 +、ＣＯ2 -3 之间形成的三元络合物的结构。季君晖[3] 通过光电子能谱研究发现 :壳聚糖螯合Ｃｕ2 +,只与壳聚糖中的—ＮＨ2 配位。Ｔｓｅｚｏｓ[4] 利用ＩＲ、ＭＳ和ＥＰＲ说明铀与壳聚糖的络合点为氨基的氮原子。Ｇｕｉｂａｌ等[5] 用ＩＲ、ＣＰ ＭＡＳ1 3ＣＮＭＲ及反射光谱法证实吸附机理涉及氨基。含镉废水是危害较大的工业废水之一 …