Micelles of poly(styrene-b-2-vinylpyridine-b-ethylene oxide) with blended polystyrene core and their application to the synthesis of hollow silica nanospheres

Core-shell-corona (CSC) micelles of asymmetric triblock copolymer, poly(styrene-b-2-vinylpyridine-b-ethylene oxide) (PS-PVP-PEO), containing polystyrene homopolymer (homo-PS) in the core were successfully prepared in aqueous media. The influence of homo-PS contents over the formation of the micelles was investigated thoroughly by various techniques such as dynamic light scattering (DLS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and fluorescence spectroscopy. It was found that the size of the PS core of the micelle was increased by the addition of homo-PS as observed by DLS and TEM techniques. The SEM and TEM measurements confirm the spherical morphology of the micelles and enlargement of PS core over the addition of homo-PS. The increase in the PS core volume of the PS-PVP-PEO micelles is attributed to the insertion of homo-PS in the PS core. The micelles have also been demonstrated as facile soft templates for synthesis of hollow silica nanospheres. The average diameter of the spherical hollow particles could be tuned between 30.6 and 38.8 nm with cavity sizes ranging from 20.7 to 28.5 nm using tetramethoxysilane as silica precursors under mild acidic conditions. The facile synthesis of hollow silica using the CSC micelles with different homo-PS contents indicates that the hollow void size can be controlled within a range of several nanometers.     

Polymerizable Molecular Silsesquioxane Cage Armored Hybrid Microcapsules with In Situ Shell Functionalization

We prepared core–shell polymer–silsesquioxane hybrid microcapsules from cage‐like methacryloxypropyl silsesquioxanes (CMSQs) and styrene (St). The presence of CMSQ can moderately reduce the interfacial tension between St and water and help to emulsify the monomer prior to polymerization. Dynamic light scattering (DLS) and TEM analysis demonstrated that uniform core–shell latex particles were achieved. The polymer latex particles were subsequently transformed into well‐defined hollow nanospheres by removing the polystyrene (PS) core with 1:1 ethanol/cyclohexane. High‐resolution TEM and nitrogen adsorption–desorption analysis showed that the final nanospheres possessed hollow cavities and had porous shells; the pore size was approximately 2–3 nm. The nanospheres exhibited large surface areas (up to 486 m² g^?1) and preferential adsorption, and they demonstrated the highest reported methylene blue adsorption capacity (95.1 mg g^?1). Moreover, the uniform distribution of the methacryloyl moiety on the hollow nanospheres endowed them with more potential properties. These results could provide a new benchmark for preparing hollow microspheres by a facile one‐step template‐free method for various applications.     

Fe3O4/Polypyrrole/Au nanocomposites with core/shell/shell structure: synthesis, characterization, and their electrochemical properties

Uniform Fe3O4 nanospheres with a diameter of 100 nm were rapidly prepared using a microwave solvothermal method. Then Fe304/polypyrrole (PPy) composite nanospheres with well-defined core/shell structures were obtained through chemical oxidative polymerization of pyrrole in the presence of Fe3O4; the average thickness of the coating shell was about 25 nm. Furthermore, by means of electrostatic interactions, plentiful gold nanoparticles with a diameter of 15 nm were assembled on the surface of Fe3O4/PPy to get Fe3O4/PPy/Au core/shell/shell structure. The morphology, structure, and composition of the products were characterized by transmission electronic microscopy (TEM), scanning electronic microscopy (SEM), X-ray powder diffraction (XRD), and Fourier transform infrared (FT-IR) spectroscopy. The resultant nanocomposites not only have the magnetism of Fe3O4 nanoparticles that make the nanocomposites easily controlled by an external magnetic field but also have the good conductivity and excellent electrochemical and catalytic properties of PPy and Au nanoparticles. Furthermore, the nanocomposites showed excellent electrocatalytic activities to biospecies such as ascorbic acid (AA).     

Fe3O4和Zn2+掺杂型Zn1-xFe2+xO4纳米晶的溶剂热合成和电磁性能

利用溶剂热法, 在醋酸钠静电保护剂的辅助下, 成功制备出Fe₃O₄和Zn²⁺掺杂型Zn_0.07Fe_2.93O₄纳米晶. 利用X射线衍射仪和扫描电子显微镜等对样品的晶体结构、粒径、形貌和化学组成进行了分析. 结果表明, 所得纳米晶的粒径均匀, 形貌为球形, 分散度好; Zn_0.07Fe_2.93O₄纳米晶的平均粒径(70 nm)明显小于Fe₃O₄(170 nm). 磁性能测量结果表明, 室温下Zn_0.07Fe_2.93O₄的饱和磁化强度(54.2 A·m²·kg^-1)小于Fe₃O₄ (81.6 A·m²·kg^-1). 利用矢量网络分析仪对样品的电磁性能和吸波性能进行了研究. 结果表明, Zn²⁺掺杂型Zn_0.07Fe_2.93O₄纳米晶的吸波性能优于Fe₃O₄, 前者的最大吸收峰(-19.3 dB)大于后者(-9.8 dB), 且吸收峰低于-10 dB的峰宽达2.5 GHz.     

Preparation of thermoresponsive and pH-sensitivity polymer magnetic hydrogel nanospheres as anticancer drug carriers

In this work, a novel thermo and pH responsive magnetic hydrogel nanosphere poly(N-isopropylacrylamide-co-acrylic acid)/Fe(3)O(4) (poly(NIPAAm-co-AA)/Fe(3)O(4)) has been successfully prepared. The magnetic hydrogel nanospheres with thermo and pH-sensitivity were characterized by transmission electron microscopy (TEM), dynamic light scattering (DLS), Fourier transform infrared-spectrometer (FT-IR), UV-vis absorption spectroscopy, and vibrating sample magnetometer (VSM). The magnetic hydrogel nanospheres exhibited uniform sphere structures and superparamagnetic property. Finally, the drug loading capacities and the releasing behavior of the magnetic hydrogel nanospheres were investigated with doxorubicin hydrochloride (DOX) as an anticancer drug model. The resulting magnetic hydrogel nanospheres exhibited high encapsulation efficiency (95%) to DOX under an appropriate condition. In vitro release experiments revealed that release was faster at pH 5.3 (37°C) than at pH 7.4 (25°C) or pH 7.4 (37°C). The DOX-loaded magnetic hydrogel nanospheres also showed enhanced anticancer effect compared with the free drug in vitro. These presented results suggested that the magnetic hydrogel nanospheres have a potential as tumor targeting drug carrier.     

W/O型微乳法制备淀粉基纳米粒

在正己烷、Span-60和NaOH水溶液的W／O型淀粉微乳液中,进行淀粉与环氧氯丙烷交联反应制备淀粉微球,用质量分数为1％的淀粉水浆液制备出微球的流体力学半径Rb为7．08—113nm,其中粒径不超过100nm的纳米粒在整个微粒体系中占69％,平均粒径为92．2nm。TEM和DLS结果表明,制得的微粒呈圆球形,且微粒的流体力学半径随淀粉水浆液浓度的增加而增大并分布变宽,淀粉水浆液的浓度低有利于淀粉基纳米粒的形成。     

Chirally Functionalized Hollow Nanospheres Containing L‐Prolinamide: Synthesis and Asymmetric Catalysis

Chirally functionalized hollow nanospheres with different surface properties were successfully synthesized by co‐condensation of (2S,1′R,2′R)‐N‐tert‐butyloxycarbonylpyrrolidine‐2‐carboxylic acid [2′‐(4‐trimethoxysilylbenzylamide)cyclohexyl] amide with 1,2‐bis(trimethoxysilyl)ethane or tetramethoxysilane using F127 (EO₁₀₆PO₇₀EO₁₀₆) as surfactant in water. The TEM and N₂ sorption characterizations show that the particle size of the hollow nanosphere is 15–21 nm with a core diameter of 10–16 nm. These L ‐prolinamide‐functionalized hollow nanospheres are highly efficient solid catalysts for the direct asymmetric aldol reaction between cyclohexanone and aromatic aldehydes. It was found that the addition of water in the reaction system not only enhanced the catalytic activity but also increased the enantioselectivity, which is probably due to the enhanced hydrogen bond between the amide oxygen atom and the hydroxyl group of water. Moreover, the catalytic activity increases sharply as the surface hydrophobicity of the hollow nanospheres increases. These hollow nanospheres are quite stable and can be reused with almost the same enantioselectivity and only a slight decrease in catalytic activity.     

Size-controlled syntheses and hydrophilic surface modification of Fe3O4, Ag, and Fe3O4/Ag heterodimer nanocrystals

High-quality, monodisperse, and size-controlled Fe(3)O(4), Ag, and bifunctional Fe(3)O(4)/Ag heterodimer nanocrystals (NCs) have been synthesized successfully. In the synthesis of Fe(3)O(4) NCs, dodecanol was chosen as the substitute of 1,2-hexadecanediol and "size control" was achieved by simply adjusting the proportion among the ligands instead of utilizing seed-mediated growth. In the synthesis of Ag NCs, organometallic silver acetylacetonate (Agacac) was used as precursors and tunable particle size could be easily obtained by adjusting the reaction temperatures. By using different sized Fe(3)O(4) NCs as seeds, Fe(3)O(4)/Ag heterodimer NCs with particle sizes tuned from 5 to 16 nm for Fe(3)O(4) and 4 to 8 nm for Ag were successfully synthesized and superparamagnetism were maintained. We found that the size of Ag attached on the Fe(3)O(4) NCs relied on the size of Fe(3)O(4) seed. UV-vis absorption spectra and TEM investigations revealed that the bigger the Fe(3)O(4) NCs seed used, the bigger the Ag NCs that were obtained from the heterodimer NCs. In addition, we demonstrated that all of these NCs were successfully transferred into water by surface modification with biocompatible carboxylic acid groups, which made them meet the basic requirement for biolabeling and biomedical applications.     

利用Kirkendall效应制备Ce1-xTixO2中空纳米球

利用Kirkendall效应, 在溶剂热条件下成功制备了复合氧化物Ce_1-xTi_xO₂的纳米空心球, 并通过XRD, TEM和XPS等测试手段进行了表征. 结果表明, Ce_1-xTi_xO₂纳米空心球的粒径为65 nm, 小于初始状态的CeO₂纳米球, 并且Ce_1-xTi_xO₂纳米空心球的结构与前驱体CeO₂晶体结构相同, 均为面心立方结构. Ti/Ce摩尔比和温度是影响产物形貌和结构的重要因素, 通过实验得出最佳反应条件为n(Ti)∶n(Ce)=8∶10, 于190 ℃反应8 h.     

Preparation of PdCo Bimetallic Hollow Nanospheres and its Electrocatalytic Activity for Oxidation of Formic Acid

The performance of the direct formic acid fuel cell (DFAFC) is considerably higher than the direct methanol fuel cell (DMFC) because of some characteristics of formic acid1. For example, formic acid is non-toxic. Formic acid has two orders of magnitude smaller crossover flux through a Nafion membrane than methanol2. In DFAFC, the concentration of formic acid can be as high as 20 mol/L, while the best concentration of methanol in DMFC is only about 2 mol/L3. Thus, the power density of …     

Fabrication of "tadpole"-like magnetite/multiwalled carbon nanotube heterojunctions and their self-assembly under external magnetic field

Novel "tadpole"-like Fe3O4/multiwalled carbon nanotube (MWCNT) heterojunctions were successfully synthesized by position-selectively attaching Fe3O4 sphere on the tips of MWCNTs through a straightforward and effective polyol-medium solvothermal method. Transmission and scanning electron microscopy (TEM and SEM) and X-ray diffraction (XRD) investigations show these Fe3O4 spheres are constructed with tiny nanocrystallites (approximately 5 nm in average diameter), which were preferentially aggregated in an oriented pattern on the open ends of the MWCNT template. Magnetic investigation indicates this novel Fe3O4/MWCNT hybrid presents superparamagnetic behavior. The size and corresponding magnetic performance of these magnetite/MWCNT hybrids can be adjustable to some extent for specific applications through altering the reaction parameters. Furthermore, these tadpolelike nanocomposites can orient and self-assemble into one-dimensional structure under external magnetic field, displaying great potential in precise manipulation and organization of carbon nanotube-based structures into integrated functional system.     

二吡啶甲基胺配合物修饰的肿瘤靶向性硅核壳纳米球(英文)

运用油包水微乳液方法制备了二吡啶甲基胺(dpa)及其锰(Ⅱ)和铁(Ⅲ)配合物修饰的Gd-DTPA配合物硅核壳纳米球,其中二吡啶甲基胺锰(Ⅱ)和铁(Ⅲ)配合物修饰的纳米球粒径分别为60和5nm。体外MRI成像研究表明3种纳米球能显著提高肿瘤细胞的磁共振成像效果,具备良好的肿瘤靶向性。生物活性数据显示三价铁配合物修饰的纳米球具备成像和抑制细胞生长的双重功能,而锰配合物修饰的纳米球不能抑制肿瘤细胞的生长,可作为低毒性的肿瘤成像剂。实验结果显示肿瘤靶向性配合物修饰的纳米球可发展成为新型多功能肿瘤靶向性纳米药物。     

One-step synthesis of hollow UO2 nanospheres via radiolytic reduction of ammonium uranyl tricarbonate

Black precipitates were successfully obtained by radiolytic reduction of ammonium uranyl tricarbonate in the aqueous solution of HCOONH_4 by one step.TEM,SAED,EDS,and XRD analysis indicated that the precipitates consist of hollow UO_2 nanospheres(φ:30-50 nm,wall thickness:8-15 nm,and cavity diameter:10-20 nm).The effect of HCOONH_4 concentration,irradiation time and dose rate on the morphology,and size of nanospheres was investigated.Then,a gas-bubble template mechanism was proposed.     

In vivo NIR imaging with CdTe/CdSe quantum dots entrapped in PLGA nanospheres

Luminescent near-infrared (NIR) CdTe/CdSe QDs were synthesized and encapsulated in poly(lactic-co-glycolic acid) (PLGA) nanospheres to prepare stable and biocompatible QDs-loaded nanospheres for in vivo imaging. QDs were encapsulated with PLGA nanospheres by a solid dispersion method and optimized to have high fluorescence intensity for in vivo imaging detection. The resultant QDs-loaded PLGA nanospheres were characterized by various analytical techniques such as UV-Vis measurement, dynamic light scattering (DLS), fluorescence spectroscopy, and transmission electron microscopy (TEM). Finally, we evaluated toxicity and body distribution of QDs loaded in PLGA nanospheres in vitro and in vivo, respectively. From the results, the QDs loaded in PLGA nanospheres were spherical and showed a diameter range of 135.0-162.3 nm in size. The QD nanospheres increased their stability against photooxidation and photobleaching, which have the high potential for applications in biomedical imaging. We have also attained non-invasive in vivo imaging with light photons, representing an intriguing avenue for obtaining biological information by the use of NIR light.     

La2O3 hollow nanospheres for high performance lithium-ion rechargeable batteries

An efficient and simple protocol for synthesis of novel La(2)O(3) hollow nanospheres of size about 30 ± 2 nm using polymeric micelles is reported. The La(2)O(3) hollow nanospheres exhibit high charge capacity and cycling performance in lithium-ion rechargeable batteries (LIBs), which was scrutinized for the first time among the rare-earth oxides.     

有机盐制备的Fe3O4-葡聚糖纳米粒子的磁性能及表征

By means of chemical co-deposition method in which added Ferric citrate and Ferrous Gluconate, Fe3O4-Dextran composite nano-particles having average diameter 26 nm, was obtained. The particles had a core of diameter 4.1 nm Fe3O4 with a shell of thickness 11 nm Dextran. In the experiment the critical structure of Fe3O4 inorganic particles abstained without N2 protection had no changes. From the result, it can be proven that organic salt has anti oxidation properties and the composite particles have superparamagnetic whose good magnetization is 52 emu/g at 300 K, and 63 emu/g at 5 K. The structure, pattern diameter and magnetic properties of the Fe3O4-Dextran composite particles were examined by means of TEM, XRD, DLS and VSM.     

Synthesis and self-assembly of side-chain azocomplex for preparation of solid and hollow nanosphere

A new strategy based on ionic self-assembly technology was provided for design of solid and hollow nanospheres. Solid azocomplex nanospheres were constructed by ionic self-assembly of statistical ionomer and metanil yellow. The structure of azocomplex and self-assembly behaviors were examined by a variety of techniques including ¹H-NMR, ¹³C-NMR, DSC, FTIR, UV–vis, TEM, and elemental analysis. The azocomplex was subjected to solvent-induced self-assembly to construct a variety of morphologies. Solid polymeric nanospheres with the sizes of 50~100?nm in diameter were formed in aqueous solution. High-resolution transmission electron microscopes and X-ray energy dispersion spectrometer were used to study the morphology and composition of the solid nanospheres. The spherical and ordered structure was destroyed in DMF, and converted into membrane structure. Polymeric hollow nanospheres with azobenzene chromophores were formed in DMF/H₂O mixed solvent, with 62.5% H₂O in mass. The size of these hollow nanospheres was 50~120?nm in diameter.     

Hydroxyapatite Hierarchically Nanostructured Porous Hollow Microspheres: Rapid,Sustainable Microwave‐Hydrothermal Synthesis by Using Creatine Phosphate as an Organic Phosphorus Source and Application in Drug Delivery and Protein Adsorption

Hierarchically nanostructured porous hollow microspheres of hydroxyapatite (HAP) are a promising biomaterial, owing to their excellent biocompatibility and porous hollow structure. Traditionally, synthetic hydroxyapatite is prepared by using an inorganic phosphorus source. Herein, we report a new strategy for the rapid, sustainable synthesis of HAP hierarchically nanostructured porous hollow microspheres by using creatine phosphate disodium salt as an organic phosphorus source in aqueous solution through a microwave‐assisted hydrothermal method. The as‐obtained products are characterized by powder X‐ray diffraction (XRD), Fourier‐transform IR (FTIR) spectroscopy, SEM, TEM, Brunauer–Emmett–Teller (BET) nitrogen sorptometry, dynamic light scattering (DLS), and thermogravimetric analysis (TGA). SEM and TEM micrographs show that HAP hierarchically nanostructured porous hollow microspheres consist of HAP nanosheets or nanorods as the building blocks and DLS measurements show that the diameters of HAP hollow microspheres are within the range 0.8–1.5 μm. The specific surface area and average pore size of the HAP porous hollow microspheres are 87.3 m²g^?1 and 20.6 nm, respectively. The important role of creatine phosphate disodium salt and the influence of the experimental conditions on the products were systematically investigated. This method is facile, rapid, surfactant‐free and environmentally friendly. The as‐prepared HAP porous hollow microspheres show a relatively high drug‐loading capacity and protein‐adsorption ability, as well as sustained drug and protein release, by using ibuprofen as a model drug and hemoglobin (Hb) as a model protein, respectively. These experiments indicate that the as‐prepared HAP porous hollow microspheres are promising for applications in biomedical fields, such as drug delivery and protein adsorption.     

支化侧链偶氮无规共聚物中空和类囊泡聚集体研究

研究了支化侧链型偶氮无规共聚物(PMAPB6P-AA)在THF/H2O混合溶液中的自组装行为.研究发现,通过缓慢增加体系的水含量,可以制备出具有中空结构的非球形聚集体.调节聚合物的初始浓度,可以得到不同粒径的聚集体.聚集体中偶氮生色团的光致异构化速率与异构化程度随聚合物初始浓度的增大而减小.在此基础上,采用更加缓慢的增加水含量的方法,使聚合物分子进行充分的疏水聚集与H-聚集,制备出类囊泡状聚集体.在紫外光照射条件下,观察到类囊泡聚集体发生了光致解聚集.     

Surfactant-assistant and facile synthesis of hollow ZnS nanospheres

Small and monodisperse ZnS hollow nanospheres with outer diameter ranging from 60 to 70 nm and wall thickness of 15-20 nm were fabricated in a large scale by a simple surfactant polyethylene glycol (PEG) assisted method. The diameter and the wall thickness of the hollow nanospheres could be controlled by manipulating the amount of PEG and the aging time, respectively. Moreover, the wall of these hollow nanospheres is very compact. The product was characterized by X-ray power diffraction (XRD), transmission electron microscopy (TEM), UV-vis spectrum and fluorescence spectroscopy. The photocatalytic activity of as-prepared ZnS hollow nanospheres was also evaluated by using methyl orange (MO) as a model organic compound and the result revealed that their photocatalytic activity is a little lower than that of Degussa P25 TiO(2) but better than that of ZnS nanocrystals prepared by literature method. Furthermore, a rational mechanism to the formation and evolution of the products is proposed.