W/O型微乳液中不同形貌PbS纳米粒子的制备及其形成机理的探讨

用聚乙二醇辛基苯基醚(OP)/异辛醇/环己烷/水溶液所形成的微乳液体系控制合成出了PbS纳米粒子，考察了微乳液中水与表面活性剂的物质的量的比(ω₀)、反应物浓度及浓度比、陈化时间等条件对产物形貌的影响。采用透射电子显微镜(TEM)、X-射线衍射(XRD)分别对产物的结构、粒度和形貌进行了表征。结果表明，在微乳液体系中，控制不同的实验条件，可以成功地合成球形、梭形、针状和棒状的PbS纳米粒子，并且粒径分布集中，无团聚现象。论文还对不同形貌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.     

硫纳米粒子的液相合成与表征

以硫粉为起始原料, 采用甲酸做沉淀剂、聚乙二醇-400为分散剂, 在常温、常压、液相条件下合成了硫纳米粒子. 对影响硫纳米粒子合成的条件进行了优化和分析, 考察了其在有机溶剂中的分散性. 用激光粒度分析仪测定产物的粒径分布, 透射电镜观察产物的形貌, X射线衍射仪分析产物的晶相. 结果表明, 用液相沉淀法成功地合成了颗粒均匀、粒径50～80 nm 的球形单斜相硫纳米粒子. 本方法条件温和、操作简单、成本低廉, 适用于工业化生产.     

微乳液和均匀沉淀耦合法制备CeO2纳米粒子

用W/O微乳液和草酸二甲酯均匀沉淀耦合法制备出单分散性好并具有较窄粒度分布的CeO2纳米粒子,测试了其形貌、粒径及粒径分布和晶体结构等特征.实验结果表明,表面活性剂的种类和反应物的相对初始浓度对产物平均粒径具有规律性的影响;随着焙烧温度升高,产物的平均粒径明显增大.     

复配乳液体系中聚氯甲基苯乙烯纳米颗粒的制备

以初始质量分数为21.4%的氯甲基苯乙烯,在十二烷基苯磺酸钠(LAS)/聚醚复配乳液体系中制备了粒径为65.0nm,单分散性良好的聚氯甲基苯乙烯纳米微球.用红外光谱仪、透射电子显微镜、Zeta电位粒度仪测试技术对产物的化学结构、粒径大小、形貌、单分散性进行了表征.结果表明,在复配乳液体系中可以在提高单体含量的同时,保持产物的粒径在纳米级,同时体系的稳定性良好.透射电子显微照片显示,制得的纳米微球之间存在黏连.并提出了氯甲基的存在可能是产生这种现象的原因.     

聚异戊二烯-丝胶接枝共聚物的合成与性能研究

以异丙苯过氧化氢和四乙烯五胺为氧化还原对引发剂,通过乳液聚合合成了聚异戊二烯接枝丝胶乳液(PL-g-SS),其结构和性能经NMR,TEM及激光粒度分析表征.结果表明:丝胶成功地接枝到聚异戊二烯上;PL-g-SS双亲纳米微球具有明显的PL为核,SS为壳的核壳结构,平均粒径48nm,且粒径分布较为均匀.采用杂凝聚法将PL-...     

微乳液法制备固体催化剂在多相催化领域中的应用

采用微乳液法制备纳米粒子具有粒径可控、粒度分布均匀、粒子不易团聚等优点,在一些反应中表现出优良的催化性能.本文介绍了微乳液的概念,阐述了反相微乳体系(W/O)作为纳米反应器的原理以及用于制备固体催化剂的方法.综述了反相微乳液法制备固体催化剂在多相催化领域中的应用,并指出该技术存在的问题和发展趋势.     

La（Oxin）3·3H2O纳米晶的一步固相化学合成及表征

在近室温条件和超声波作用下,通过固相化学反应一步合成了La（Oxin）3·3H2O（8-羟基喹啉镧）纳米晶。用X射线衍射及电子衍射法分析了固相产物的物相,用透射电子显微镜观测粒子的大小、形貌、粒径及粒径分布。结果表明,产物为颗粒大小均匀、平均粒径约为40nm的纳米晶,产率为95．9％。改变反应物、反应物配比、掺人惰性物质、加入微量溶剂或表面活性剂、研磨不同时间等固相反应条件对合成纳米晶的晶粒形貌、粒度和粒径分布有一定影响。合成的纳米晶材料具有操作方便、合成工艺简单、产率高、选择性好、粒径均匀、且粒度可控、污染少,同时又可以避免或减少液相中易出现的硬团聚现象等突出优点。     

有机硅-丙烯酸酯微乳液的合成与表征

采用高温乳化种子单体滴加法制备了有机硅-丙烯酸酯共聚微乳液。对合成条件及微乳液的性能进行了研究。用红外光谱(FT-IR)、透射电镜(TEM)、动态激光粒度仪(PCS)对微乳液的结构和粒子形态进行了表征。结果表明:有机硅氧烷与丙烯酸酯发生了共聚反应,生成的微乳液粒子大致为球形结构,粒子大小比较均一,粒径较小。     

Crosslinked Polymeric Nanocapsules Via Surface-initiated Atom Transfer Radical Polymerization from SiO2 Nano-templates

The aim of the present work was to develop the crosslinked polymeric nanocapsules for drug delivery from the SiO₂ nano-templates via surface-initiated atom transfer radical polymerization (SI-ATRP) technique. The crosslinked polymeric nanocapsules were fabricated via the SI-ATRP of 2-hydroxyethyl acrylate (HEA) from initiator modified silica nano-templates. After the hydroxyl side-groups of the polymer grafted silica nanoparticles (SN@PHEA) were crosslinked with hexamethylene diisocyanate (HDI), the silica templates encapsulated in the crosslinked polymer shells were removed by being etched with HF to produce the crosslinked polymeric nanocapsules. The diameter of the polymeric nanocapsules is in the range of 20–40 nm, characterized by transmission electron microscopy (TEM).     

Synthesis and Properties Research on the Nanocapsulated Capsaicin by Simple Coacervation Method

A new nanoencapsulation was established in which small nanocapsules with a natural polymeric wall could be fabricated, capsulizing the capsaicin having pungent odor. The new nanoencapsulation is based on a simple coacervation process. In this technique, gelatin was used as the wall material of the nanocapsules, and an insoluble polymer film was formed after cross‐linking reaction. The shell formation mechanism and the effects of the process conditions such as shearing force, the gelatin viscosity, cross‐linking time, and so on, on the particle size of the nanocapsulated capsaicin (NC) agents were discussed. Meanwhile, the morphology and size distribution of the nanocapsules prepared by the most suitable conditions, were analyzed by Fourier transform infrared (FTIR) spectroscopy, laser particle size analyzer, transmission electron microscopy (TEM), and atomic force microscopy (AFM). The NC agents had a mean particle size of about 100 nm. Moreover, the thermal properties of the NC agents were measured by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). It was demonstrated that the melting point and thermal pyrolysis temperature of the NC agents were improved from 75 to 100°C, 230 to 240°C, 310 to 320°C, and from 450 to 540°C compared with that of the uncovered capsaicin, which were caused by the encapsulation of the cross‐linked gelatin over the surface of the capsaicin.     

Preparation and characteristics of hydroxypropyl-β-cyclodextrin polymeric nanocapsules loading nimodipine

Nimodipine loaded hydroxypropyl-β-cyclodextrin polymeric nanocapsules were prepared by interfacial polyaddition of hydroxypropyl-β-cyclodextrin and isophorone diisocyante in a miniemulsion system. The effects of ultrasonicate times on the preparation of miniemulsion, the total amount of hydroxypropyl-β-cyclodextrin and isophorone diisocyante, and the molar ratio of isophorone diisocyante to hydroxypropyl-β-cyclodextrin on the capsule size and drug release behavior from capsule were investigated. The chitosan based polymeric nanocapsules were prepared as a control to study the effect of hydroxypropyl-β-cyclodextrin molecules in capsule matrix on the drug release. The results indicated that the droplet size of miniemulsion and capsule size decreased with increasing sonicate times. When the total amount of hydroxypropyl-β-cyclodextrin and isophorone diisocyante, and the molar ratio of isophorone diisocyante to hydroxypropyl-β-cyclodextrin were increased, the capsule as well, but the drug release rates from capsules became slower. The drug release behaviors from hydroxypropyl-β-cyclodextrin polymeric nanocapsules were affected by the drug diffusion through the polymer matrix and the formation of inclusion complex between drug and hydroxypropyl-β-cyclodextrin.     

An improved interfacial coacervation technique to fabricate biodegradable nanocapsules of an aqueous peptide solution from polylactide and its block copolymers with poly(ethylene glycol)

ABA block copolymers of polylactide and poly(ethylene glycol) as amphiphilic bioabsorbable polymers were synthesized by the ring-opening polymerization of dl- lactide onto poly(ethylene glycol) (PEG 2000 or PEG 6000) and their structures were characterized on the basis of proton NMR. Biodegradable nanocapsules of an aqueous insulin solution were prepared from the block copolymers and polylactide by an improved interfacial coacervation technique. The results showed that the diameters of the nanocapsules were mainly dependent on the ratio of the two chains in the block polymers. The size of the nanocapsules decreased with an increase in the amount of surfactant used. More insulin solution resulted in an enlargement of the nanocapsules in diameter. In an optimum condition, biodegradable nanocapsules could be achieved with a size around 250 nm with a narrow distribution. The encapsulation percentages of insulin were larger in the nanocapsules from the PEG 2000 copolymers than in those from the PEG 6000 analogs and changed with the ratios of the blocks in the block copolymers. Received: 17 July 2000 Accepted: 24 November 2000     

Facile fabrication of hollow polystyrene nanocapsules by microemulsion polymerization

The fabrication of polymer nanocapsules with tailored dimensions has been accomplished by microemulsion polymerization using different surfactants.     

A polymer—microemulsion interaction: The coacervation model

A model which successfully predicts many of the qualitative features of the phase separation can be based upon the assumption that the microemulsion particle retains its integrity when diluted with external phase or when mixed with a polymer (which does not complex with the surfactants). In this case, the microemulsion particle behaves thermodynamically in a manner similar to a macromolecule so that one can predict that the polymer—microemulsion phase diagram will have qualitative similarities to that exhibited by the polymer—polymer₂-solvent case. Most of the experiments were conducted by following the phase boundaries by measurements of the cloud points of the polymermicroemulsion mixtures. The cloud points of the mixtures were found to be (usually) linear functions of the weight fraction of the added polymer and decreased with increasing molecular weight. Plots of the logarithm of the slopes of these curves against the logarithm of the polymer molecular weight were linear, with a slope designated as β. The values for β for twenty-five systems studied fell within the narrow range of 0.55 ± 0.15. These values were seen to be the same as the Mark—Houwink exponents in the relationship between the intrinsic viscosity and the polymer molecular weight. The reason for this correspondence appears to be that the coacervation occurs at a polymer concentration about equal to the threshold overlap concentration. Ternary phase diagrams with microemulsion particles, brine, and polymer selected as pseudocomponents also exhibit many of the features predicted by the model. The phase boundary asymmetry is in the direction expected and asymptotes with the expected independence upon microemulsion and polymer molecular weights are also demonstrated. In agreement with the model, it is shown that the controlling variable is polymer weight average, rather than z or number average molecular weight.     

Selective Fabrication of Polymer Nanocapsules and Nanotubes Using Cyclodextrin as a Nanoporogen

Summary: Polyacrylonitrile (PAN) nanocapsules and nanotubes were selectively synthesized by microemulsion polymerisation using β‐cyclodextrin (β‐CD) as a nanoporogen. Iron(III ) chloride (FeCl₃) was used as a structure‐directing agent to fabricate polymer nanotubes. In addition, the average pore size of the PAN nanocapsules and nanotubes could be controlled with the concentration of β‐CD.

(a) TEM image of PAN nanocapsules; (b) SEM image of PAN nanotubes.     

"Two-in-one" fabrication of Fe3O4/MePEG-PLA composite nanocapsules as a potential ultrasonic/MRI dual contrast agent

A new method for the fabrication of Fe(3)O(4) nanoparticles enveloped by polymeric nanocapsules is proposed. This method is characterized by combining a double emulsification with the interfacial coprecipitation of iron salts to form Fe(3)O(4)/polymer composite nanocapsules in a single step. To demonstrate the viability of this approach, methoxy poly(ethylene glycol)-poly(lactide) (MePLEG) was chosen as the shell material for Fe(3)O(4)/MePLEG nanocapsules. In addition to the versatility offered for fabricating nanocapsules with different shell materials, the method was found to be convenient for adjusting the magnetite content of the nanocapsules from 0 to 43%. In addition to their confirmed T(2)-weighted magnetic resonance imaging (MRI) enhancement, the resultant composite nanocapsules display much more obvious acoustic responses than MePLEG nanocapsules in an acoustic investigation. Furthermore, the low toxicity of these composite nanocapsules, as confirmed by our study, combined with their magnetic and acoustic properties ensure that these composite nanocapsules have great potential in acting as ultrasonic/MRI dual contrast agents.     

Preparation of protected photoinitiator nanodepots by the miniemulsion process

The solid photoinitiator Lucirin TPO was encapsulated within a polymer shell by using the miniemulsion process. A solution of Lucirin TPO in methyl methacrylate (MMA) or butyl acrylate (BA)/MMA mixture was miniemulsified in water followed by a polymerization process in which phase separation of the Lucirin TPO and the formed polymer led to amorphously solidified Lucirin TPO nanoparticles encapsulated by polymer. These nanocapsules were freeze-dried and could be redispersed in acidic monomers, which are applied in polymeric dental adhesives. It is shown by ¹H nuclear magnetic resonance spectroscopy that the shell separates the Lucirin TPO, which is sensitive to degradation in acidic media, from an ambient acidic monomer phase and protects it from fast decomposition. Investigations of the release kinetics of Lucirin TPO from the nanocapsules reveal that the kinetics are strongly dependent on the composition of the surrounding continuous phase.     

Polymer nanodisks by collapse of nanocapsules

It is an important challenge to make disk-like polymeric nanostructures. Herein we report a facile method for preparing polymer nanodisks by self-collapse of nanocapsules self-assembled from a statistical copolymer after partial hydrolysis. We find that partial hydrolysis of the statistical copolymer is crucial for the formation of nanodisks as it affords a suitable rigidity for the membrane of nanocapsules. The nanodisk structure has been confirmed by transmission electron microscopy(TEM), scanning electron microscopy(SEM) and atomic force microscopy(AFM) studies with a thickness of 6.3±0.2 nm. Overall, our results demonstrated a new method for making disk-like nano-objects.