Silver-protein (core-shell) nanoparticle production using spent mushroom substrate

A simple route for the synthesis of silver-protein (core-shell) nanoparticles using spent mushroom substrate (SMS) has been demonstrated in this work. SMS exhibits an organic surface that reduces silver ions and stabilizes the silver nanoparticles by a secreted protein. The silver nitrate solution incubated with SMS changed to a yellow color from 24 h onward, indicating the formation of silver nanoparticles. The purified solution yielded the maximum absorbance at 436 nm due to surface plasmon resonance of the silver nanoparticles. X-ray analysis of the freeze-dried powder of silver nanoparticles confirmed the formation of metallic silver. Transmission electron microscopic analysis of the samples showed a uniform distribution of nanoparticles, having an average size of 30.5 +/- 4.0 nm, and its corresponding electron diffraction pattern confirmed the face-centered cubic (fcc) crystalline structure of metallic silver. The characteristic fluorescence of the protein shell at 435 nm was observed for the silver nanoparticles in solution, when excited at 280 nm, while Fourier transform infrared (FTIR) spectroscopy confirmed the presence of a protein shell. The silver nanoparticles were found to be stable in solution for more than 6 months. It is observed that the reducing agents from the safflower stalks caused the reduction of silver ions while protein secreted by the fungus stabilized the silver nanoparticles. These silver nanoparticles showed excellent antibacterial activity against two representative bacteria, Staphylococcus aureus (Gram positive) and Klebsiella pneumoniae (Gram negative), in spite of the presence of an organic layer as a shell. Apart from ecofriendliness and easy availability, "SMS" as a biomanufacturing unit will give us an added advantage in ease of handling when compared to other classes of microorganisms.     

Preparation and surface characterization of polymer nanoparticles designed for incorporation into hybrid materials

We prepared water dispersions of poly(n-butyl methacrylate-st-butyl acrylate) crosslinked core-shell nanoparticles functionalized with different amounts of trimethoxisilane (TMS) groups in the outer shell. The purpose of the TMS groups is to chemically bind the rubbery particles to a nanostructured silica network, using sol-gel copolymerization. Here, we present nanoparticles containing 13 mol % and 30 mol % of TMS groups in the outer shell and compare their surface morphology with particles that do not contain TMS. The particles are prepared by a two-step seeded emulsion polymerization technique at neutral pH. In the first step, we obtained crosslinked seed particles (44 nm in diameter) by a batch process. In the second step, we used a semi-continuous emulsion polymerization technique under starved feed conditions to obtain monodispersed particles of controlled composition and size (ca. 100 nm in diameter). Fluorescence decay measurements were performed in situ on the dispersions, using a pair of cationic dyes adsorbed onto the surface of the nanoparticles: rhodamine 6G as the energy transfer donor and malachite green carbinol hydrochloride as the acceptor. The kinetics of F?rster resonance energy transfer (FRET) between the dyes is sensitive to the donor-acceptor distance, allowing us to obtain the binding distribution of the dyes at the nanoparticle surface. For the unmodified nanoparticles, we found a dye distribution that corresponds to an average interface thickness of delta = (5.2 +/- 0.2) nm. For the samples containing 13 mol % and 30 mol % of TMS groups in the outer shell we obtained broader interfaces, with widths of delta = (6.2 +/- 0.2) nm and delta = (6.5 +/- 0.1) nm respectively. This broadening of the distribution with the surface modification is interpreted in terms of the increase in free volume of the shell caused by the TMS groups. Finally, we studied the effect of temperature on the water-polymer interface fuzziness, in order to evaluate the accessibility of the TMS groups during the sol-gel synthesis of nanostructured hybrid materials.     

不同Pt壳厚度Au_(core)@Pt_(shell)纳米粒子SERS效应

以Au粒子(55nm)为核,抗坏血酸为还原剂,将不同量的Pt沉积在Au核上,制得可控壳层厚度(0.3～6nm)的Pt包Au纳米粒子(Aucore@Ptshell).用紫外-可见吸收光谱、扫描电镜(SEM)、透射电镜(TEM)和电化学循环伏安法等观测Aucore@Ptshell纳米粒子的表面形貌、结构和性能.另以SCN-为探针,考察了Pt壳厚度对Aucore@Ptshell纳米粒子SERS信号的影响.结果表明,SCN-离子的SERS信号强度随Pt壳厚度的增加呈指数衰减,当Pt壳厚度为1.4nm时,Aucore@Ptshel纳米粒子表现出铂良好的电化学性能,又具有较强的SERS活性.     

Thermosensitive pluronic micelles stabilized by shell cross-linking with gold nanoparticles

Gold nanoparticles were employed to prepare shell cross-linked Pluronic micelles that exhibit a reversibly thermosensitive swelling/shrinking behavior. Two terminal hydroxyl groups of Pluronic F127 were thiol-functionalized to form self-assembling Pluronic micelles in aqueous solution with exposed -SH groups in an outer shell layer. The thiol groups present in the outer shell were cross-linked by gold nanoparticles synthesized through NaBH4 reduction of gold precursor anions. The resultant shell cross-linked gold-Pluronic micelles exhibited a temperature-dependent volume transition: their hydrodynamic diameter was changed from 157.1 +/- 15.6 nm at 15 degrees C to 53.4 +/- 5.5 nm at 37 degrees C as determined by dynamic light scattering. The critical micelle temperature measured by a pyrene solubilization technique suggested that the reversible swelling/shrinking behavior of the micelles was caused by hydrophobic interactions of cross-linked or grafted Pluronic copolymer chains in the micelle structure with increasing temperature. Transmission electron microscopy directly revealed that the shell cross-linked micelles were indeed produced by gold nanoparticles covalently clustered on the surface. These novel self-assembled organic/inorganic hybrid micelles would hold great potential for diagnostic and therapeutic applications.     

A new kind of polyion complex nanoparticles and the covalent drug-loading pattern for doxorubicin and pH-controlled release

The one-pot synthesis method was developed for the preparation of complex nanoparticles with a narrow size distribution and stable morphology. The vinyl monomers of (2-dimethylamino)ethyl methacrylate (DEMA) and diacetone acrylamide (DAA) were copolymerized in the presence of alginic acid in an aqueous solution without any organic solvents or surfactants, yielding stable complex nanoparticles in one-pot synthesis. The nanoparticle was composed of the complex of poly(DEMA-co-DAA) and alginic acid. The complex was formed via electrostatic interaction between polycations of DEMA and polyanions of alginate. The residual alginate segment around the core formed the shell of the nanoparticles. The average diameter of the nanoparticles varied from 120 to 213 nm when the molar percentage of DAA changed from 0.5 to 0 with respect to DEMA. The anti-cancer drug doxorubicin could be loaded onto the nanoparticles with a high-loading efficiency through the formation of polymer–drug conjugate. The drug release could be controlled by adjusting the pH value of the medium.     

(Au)核(Ag)壳纳米微粒光度法快速检测过氧化氢

以粒径为10 nm的纳米金为晶种, 用柠檬酸钠还原硝酸银制备了平均粒径为30 nm的(Au)核(Ag)壳纳米微粒, 用高速离心纯化除去过量的柠檬酸三钠获得了较纯的(Au)核(Ag)壳纳米微粒, 其吸收峰位于393 nm处. 在pH 4.4的HAc-NaAc缓冲溶液中, Fenton反应产生的羟基自由基可以氧化(Au)核(Ag)壳纳米微粒银层生成银离子, 导致393 nm处的吸光度降低. H2O2的浓度(c)在6.58～421.1 μmol/L范围内与393 nm处的吸光度降低值ΔA 393 nm呈良好的线性关系, 回归方程为ΔA393 nm=0.00111c+0.0210, 相关系数为0.9908, 检出限为1.73 μmol/L. 本方法用于废水样品测定, 结果满意.     

Preparation of a new core-shell Ag@SiO2 nanocomposite and its application for fluorescence enhancement

Ag@SiO₂ nanoparticles with different shell thicknesses were synthesized via modified Stöber method. Rhodamine B isothiocyanate was covalently bound onto the surface of Ag@SiO₂ nanoparticles to form fluorescent core-shell Ag@SiO₂ nanocomposites. Effects of shell thickness on the fluorescence enhancement were examined using the corresponding nanobubbles prepared by cyanide etching as a control. The result showed that the fluorescence enhanced as the shell thickness increased till the distance between fluorophore and metal core reached about 75 nm with the optimal enhancement factor of ∼5-folds. Further increasing of fluorophore-metal distance caused a decrease in the enhancement factor.     

Separation distance dependent fluorescence enhancement of fluorescein isothiocyanate by silver nanoparticles

Nanocomposites consisting of a metal core, a silica-spacer shell with controlled thickness, and a dye-labelled shell were synthesized and separation distance dependent fluorescence enhancement of fluorescein isothiocyanate by silver nanoparticles was studied; the results indicated an optimum enhancement of 4.8 times with a spacer shell thickness of 21 nm.     

胶态磁组装光子晶体及其离子强度响应

采用细乳液聚合方法合成了聚合物包覆的磁性复合纳米粒子(MCNPs),通过磁场诱导组装制备得到胶态磁组装光子晶体(CMA-PCs).透射电子显微镜(TEM)和扫描电子显微镜(SEM)表征结果表明,MCNPs具有规整的球形形貌和明显的核壳结构,并且单分散性较好,平均粒径为112 nm,聚合物壳层厚约10 nm.MCNPs在外界磁场的作用下可以快速(1 s)组装形成光子晶体结构.当离子强度在0.03~0.75 mmol/L范围内变化时,CMA-PCs的衍射色呈现从橙红色到紫色的变化,反射波长从607 nm蓝移至434 nm,并且离子强度的响应在10 s内即可达到平衡,表明制得的CMA-PCs可以作为化学传感器应用于离子强度的半定量检测,并且具有简便、快速及裸眼可视化检测的优点.     

Synthesis of iron nanoparticles via chemical reduction with palladium ion seeds

We report on the synthesis of highly monodisperse iron nanoparticles, using a chemical reduction method. Iron nanoparticles with an average diameter of 6 nm and a geometric standard deviation of 1.3 were synthesized at a pH of 9.50 from ferric chloride precursor with sodium borohydride as the reducing agent, polyacrylic acid as the dispersing agent, and palladium ions as seeds for iron nanoparticle nucleation. The resulting nanoparticles were ferromagnetic at 5 K and superparamagnetic at 350 K. The dispersing agent polyacrylic acid (PAA) was shown to prevent iron nanoparticles and possibly palladium clusters from aggregating; in the absence of PAA, only aggregated iron nanoparticles were obtained. The addition of palladium ions decreased the diameter of iron nanoparticles presumably by providing sites for heterogeneous nucleation onto palladium clusters. In the absence of palladium ions, the mean diameter of iron nanoparticles was approximately 110 nm and the standard deviation increased to 2.0. The pH of the solution also was found to have a significant effect on the particle diameter, likely by affecting PAA ionization and altering the conformation of the polymer chains. At lower pH (8.75), the PAA is less ionized and its ability to disperse palladium clusters is reduced, so the number of palladium seeds decreases. Therefore, the resulting iron nanoparticles were larger, 59 nm in diameter, versus 6 nm for nanoparticles formed at a pH of 9.50.     

Efficient resonance energy transfer from dye to Au@SnO2 core–shell nanoparticles

The present study reports the shell thickness dependence fluorescence resonance energy transfer between Rhodamine 6G dye and Au@SnO₂ core–shell nanoparticles. There is a pronounced effect on the PL quenching and shortening of the lifetime of the dye in presence of Au@SnO₂ core–shell nanoparticles. The calculated energy transfer efficiencies from dye to Au@SnO₂ are 64.4% and 78.3% for 1.5 nm and 2.5 nm thickness of shell, respectively. Considering the interactions of single acceptor and multiple donors, the calculated average distances (r_n) are 75.8 and 71.5 Å for 1.5 nm and 2.5 nm thick core–shell Au@SnO₂ nanoparticles, respectively.     

pH-responsive luminescent properties of Ag@PPy nanoparticles

We measure the emission spectra and quantum yields of Ag@PPy nanoparticles with different volume ratios of Ag core and PPy shell, and ascribe the emission peaks around 460 and 520 nm, respectively, to the S(1) → S(0) transition of the PPy molecule, and to the charge transfer between Ag and PPy, as well as the Ag plasmon. The two peaks shift with the changed doping level of the PPy shell, which can be elucidated by consideration of the energy levels of Ag and PPy. According to these results, we investigate the fast and reversible pH-sensing function of Ag@PPy nanoparticles on the basis of the doping effect on the interaction between the Ag core and the PPy shell.     

pH‐responsive polymer core–shell nanospheres for drug delivery

Stimuli‐responsive polymer nanoparticles are playing an increasingly more important role in drug delivery applications. However, limited knowledge has been accumulated about processes which use stimuli‐responsive polymer nanospheres (matrix nanoparticles whose entire mass is solid) to carry and deliver hydrophobic therapeutics in aqueous solution. In this research, pyrene was selected as a model hydrophobic drug and a pyrene‐loaded core‐shell structured nanosphere named poly(DEAEMA)‐poly(PEGMA) was designed as a drug carrier where DEAEMA and PEGMA represent 2‐(diethylamino)ethyl methacrylate and poly(ethylene glycol) methacrylate, respectively. The pyrene‐loaded core‐shell nanospheres were prepared via an in situ two‐step semibatch emulsion polymerization method. The particle size of the core‐shell nanosphere can be well controlled through adjusting the level of surfactant used in the polymerization where an average particle diameter of below 100 nm was readily achieved. The surfactant was removed via a dialysis operation after polymerization. Egg lecithin vesicles (liposome) were prepared to mimic the membrane of a cell and to receive the released pyrene from the nanosphere carriers. The in vitro release profiles of pyrene toward different pH liposome vesicles were recorded as a function of time at 37 °C. It was found that release of pyrene from the core‐shell polymer matrix can be triggered by a change in the environmental pH. In particular the pyrene‐loaded nanospheres are capable of responding to a narrow window of pH change from pH = 5, 6, to 7 and can achieve a significant pyrene release of above 80% within 90 h. The rate of release increased with a decrease in pH. A first‐order kinetic model was proposed to describe the rate of release with respect to the concentration of pyrene in the polymer matrix. The first‐order rate constant of release k was thus determined as 0.049 h^?1 for pH = 5; 0.043 h^?1 for pH = 6; and 0.035 h^?1 for pH = 7 at 37 °C. The release of pyrene was considered to follow a diffusion‐controlled mechanism. The synthesis and encapsulation process developed herein provides a new approach to prepare smart nanoparticles for efficient delivery of hydrophobic drugs. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4440–4450     

Fe-containing nanocomposites based on a biocompatible copolymer 1-vinyl-1,2,4-triazole with <Emphasis Type="Italic">N</Emphasis>-vinylpyrrolidone

New polymer nanocomposites containing iron oxide nanoparticles stabilized with a biocompatible copolymer of 1-vinyl-1,2,4-triazole with N-vinylpyrrolidone were produced. The synthesis was conducted using the method of chemical reduction of iron ions with hydrazine hydrate in an aqueous medium in the presence of a polymer matrix. The ESR spectroscopy data showed that the core—shell type nanoparticles were obtained. The core generally consistsed of zero-valence iron coated with an oxide shell. According to the data of transmission electron microscopy, the obtained polymer nanocomposites consisted of nanoparticles of mainly spherical shape with a diameter from 1 to 14 nm. Aggregates formed from individual stabilized nanoparticles of up to 75 nm in size (in most cases) were also observed. These aggregated particles were found to self-organize and form branched chains. Nanocomposites were characterized by a different particle-size distribution, which was determined by the initial ratio of the copolymer and the precursor of iron nanoparticles.     

A facile synthesis of highly water-soluble, core–shell organo-silica nanoparticles with controllable size via sol–gel process

A series of highly water-soluble organo-silica nanoparticles, ranging from 2 to 10 nm in diameter, were synthesized by the cohydrolysis and copolycondensation reactions. ω-methoxy(polyethyleneoxy)propyltrimethoxysilane (PEG6-9) and hydroxymethyltriethoxysilane (HMTEOS) mixtures were catalyzed by sodium hydroxide in the presence of surfactant benzethonium chloride (BTC) with various ratios of PEG6-9/HMTEOS at room temperature. The synthesized organo-silica nanoparticles possess a core–shell structure with a core of organo-silica resulting from HMTEOS and a monolayer shell of PEG6-9. The chemo-physical characteristics of the particles were studied by gel permeation chromatography (GPC), Fourier transform infrared (FTIR) spectroscopy, ²⁹Si nuclear magnetic resonance (NMR), dynamic light scattering (DLS), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The molecular weight and particle size of the particles increased with increasing HMTEOS molar ratios. The richest HMTEOS composition for the water-soluble particles was found to be HMTEOS:PEG6-9 = 80:20, where the particles had a 6 nm diameter core and a 0.8 nm thick shell. We propose that these water-soluble organo-silica nanoparticles will be suitable for biomedical applications.     

反应介质pH值和前驱体用量对PSt/TiO_2复合微球结构形态及TiO_2空心微球形貌的影响

首先用聚乙烯亚胺(PEI)对粒径为360 nm的单分散无皂聚苯乙烯(PSt)乳胶粒进行修饰,得到表面荷正电的PSt种子乳液,然后将其滴加到溶有钛酸正丁酯(TBT)的乙醇与水的混合介质中,通过溶胶-凝胶(sol-gel)法制备出了核壳结构PSt/TiO2复合微球,系统研究了体系pH和TBT用量对复合微球结构形态的影响.研究表明,酸性条件不利于核壳结构PSt/TiO2复合微球的形成;当体系pH值为7.2时,可得到包覆完整、TiO2壳层厚度均一的PSt/TiO2复合微球,此后随着体系pH值的升高,包覆厚度逐渐提高;当pH值升高到11.0时,壳层厚度达到最大,但出现了包覆层不完整的复合微球.在固定聚合体系pH为8.5,EtOH/H2O质量比为100/6,表面修饰PSt种子乳液用量为0.5 g(固含量为4%)的条件下,随着TBT用量从0.01 g增加到0.16 g,复合微球壳层厚度从约0 nm逐渐增加到60 nm;当TBT用量增加到0.32 g时,壳层厚度迅速降至12nm,微球表面变得粗糙,并出现大量未包覆微粒;此后随着TBT用量的增加,包覆层厚度逐渐减少,未包覆微球逐渐增多.结果显示,当复合微球中TiO2包覆层达到一定厚度时,经煅烧后才能得到形貌完整的TiO2中空微球.     

Structural and optical investigations of SiO2-CdS core-shell particles

Cadmium sulfide nanoparticles (approximately 5 nm), chemically capped using thioglycerol molecules, have been anchored onto silica particles (approximately 80 nm) functionalized with 3-aminopropyltrimethoxysilane. Transmission electron microscopy clearly showed that at a low concentration of cadmium sulfide, nanoparticles were discretely and more or less uniformly attached onto the silica particles. At a high concentration of cadmium sulfide nanoparticles, an approximately 6-nm-thick compact shell of cadmium sulfide was formed on the silica particles. In both cases the nanocrystalline nature of cadmium sulfide particles was preserved, as is evident from X-ray diffraction and optical absorption spectra.     

壳核型磁性纳米纤维素微球的超声制备及表征

A kind of cellulose magnetic nanoparticle with a core / shell structure has been prepared by ultrasonic irradiation. Cellulose acts as the shell while Fe3O4 magnetic nanoparticles take the role as the core. Magnetic force microscopy（MFM）with atomic force microscopy（AFM）measurement showed that the size of the magnetic nanoparticles is about 30-50 nm in diameter,while the Fe3O4 core is about 20-30 nm. FT-IR,XRD and MFM was used to provide the chemical and magnetic information of the nanoparticles. The MFM image showed that the nanoparticles separate very well with each other,indicating the cellulose shell produces a good prevention from the aggregation of the Fe3O4 particles. MFM studies also showed two magnetic nanoparticles can form particle-pairs,indicating a weak magneto-dipole interaction between magnetic nanoparticles. It is also found that the average sizes of magnetic nanoparticles have relation to the power of ultrasonic irradiation,and the possible mechanism is discussed.     

Synthesis of cobalt ferrite core/metallic shell nanoparticles for the development of a specific PNA/DNA biosensor

Controlled synthesis of cobalt ferrite superparamagnetic nanoparticles covered with a gold shell has been achieved by an affinity and trap strategy. Magnetic nanoparticles are functionalized with a mixture of amino and thiol groups that facilitate the electrostatic attraction and further chemisorption of gold nanoparticles, respectively. Using these nanoparticles as seeds, a complete coating shell is achieved by gold salt-iterative reduction leading to monodisperse water-soluble gold-covered magnetic nanoparticles, with an average diameter ranging from 21 to 29 nm. These constitute a versatile platform for immobilization of biomolecules via thiol chemistry, which is exemplified by the immobilization of peptide nucleic acid (PNA) oligomers that specifically hybridize with complementary DNA molecules in solution. Hybridation with DNA probes has been measured using Rhodamine 6G fluorescence marker and the detection of a single nucleotide mutation has been achieved. These results suggest the PNA-nanoparticles application as a biosensor for DNA genotyping avoiding commonly time-consuming procedures employed.     

胶态磁组装分子印迹光子晶体及其对L-苯丙氨酸的响应性

将胶态磁组装光子晶体与分子印迹技术结合, 通过磁场诱导快速、 可逆地组装得到一种灵敏度高、 选择性强且响应速度快的胶态磁组装分子印迹光子晶体(CMA-MIPCs), 并将其用于L-苯丙氨酸(L-Phe)分子的响应性研究. 结果表明, 细乳液聚合法制得的L-Phe磁性分子印迹纳米粒子(MMIPs)具有规则的球形形貌和明显的核-壳结构, 平均粒径为104.3 nm. CMA-MIPCs对L-Phe分子的识别可直接通过光学信号进行表达, 当L-Phe的浓度从6.0×10^-7 mol/L增加至6.0×10^-4 mol/L时, CMA-MIPCs的衍射色发生从紫色到深黄色的明显变化, 最大衍射峰位置红移181 nm, 响应过程仅需1 min. CMA-MIPCs对L-Phe的结构类似物L-酪氨酸(L-Tyr)和L-色氨酸(L-Trp)均无响应性, 表明CMA-MIPCs具有良好的选择性.