Bactericidal core-shell paramagnetic nanoparticles functionalized with poly(hexamethylene biguanide)

Bactericidal paramagnetic particles were obtained either through the attachment of a conjugate of poly(ethyleneimine) (PEI) and poly(hexamethylene biguanide) (PHMBG) to the surface of magnetite (Fe(3)O(4)) particles, or via the sol-gel encapsulation of magnetite particles with a functional silane (3-glycidoxypropyl trimethoxysilane) and subsequent binding of the polysiloxane shell by the amine/imine groups of PHMBG. The encapsulated core-shell particles possess a high saturation magnetization, which is preserved for more than 10 months while in contact with air in aqueous suspensions. The minimum inhibitory concentration (MIC) of the encapsulated particles for eight types of bacteria was size-dependent, with polydisperse submillimeter particles possessing a several-fold higher MIC than analogous particles sized below 250 nm. The encapsulated particles are biocompatible and nontoxic to mammalian cells such as mouse fibroblasts. The particles efficiently bind both glycopeptide components mimicking the gram-positive bacteria membranes and whole bacteria, and possess broad-range bactericidal activity. The cell-particle complexes can be captured, manipulated, and removed by means of a magnet.     

Stimuli-responsive hydrogel hollow capsules by material efficient and robust cross-linking-precipitation synthesis revisited

Monodisperse stimuli-responsive hydrogel capsules were synthesized in the 100-nm-diameter to 10-μm-diameter range from poly(4-vinylpyridine) (P4VP) and poly(ethyleneimine) (PEI) through a simple, efficient two-step cross-linking-precipitation template method under conditions of a good solvent. In this method, the core-shell particles were obtained by the deposition (heterocoagulation mechanism) of the cross-linked P4VP, PEI, or their mixtures on the surfaces of the template colloidal silica particles in nitromethane (for PEI) or a nitromethane-acetone mixture (for P4VP and P4VP-PEI mixtures) in the presence of cross-linker 1,4-diiodobutane. The cross-linked polymeric shell swollen in a good solvent stabilized the core-shell colloids. This mechanism provided the conditions for the synthesis of core-shell colloids in a submicrometer range of dimensions with an easily adjusted shell thickness (wall of the capsules) ranging from a few to hundreds of nanometers. The chemical composition of the shell was tuned by varying the ratio of co-cross-linked shell-forming polymers (P4VP and PEI). In the second step, the hollow capsules were obtained by etching the silica core in HF solutions. In this step, the colloidal stability of the hollow capsules was provided by ionized P4VP and PEI cross-linked shells. The hollow capsules demonstrate that the pH- and ionic-strength-triggered swelling and shrinking result in size-selective uptake and release properties. Cross-linked via quaternized functional groups, P4VP capsules undergo swelling and shrinking transitions at a physiologically relevant pH of around 6. The 200-nm-diameter hollow capsule with 25-nm-thick walls demonstrated a factor of 2 greater capacity to accommodate cargo molecules than the core-shell particles of the same dimensions because of an internal compartment and a combination of radial and a circumferential swelling modes in the capsules.     

AFM approach toward understanding morphologies in toughened thermosetting matrices

Atomic force microscopy, AFM, has been used for determining the microstructure of thermosetting matrices toughened by incorporation of core-shell particles and high-performance thermoplastics. A variety of systems has been considered in this work: one group is based on diglycidyl ether of bisphenol-A (DGEBA) epoxy matrix, and the other group is based on bisphenol-A dicyanate (DCBA) matrix. The studied epoxy systems were: DGEBA cured with an aromatic hardener, diamino diphenyl sulfone (DDS), and modified with polymethylmethacrylate (PMMA), or cured with a cycloaliphatic hardener, diamino dimethyl cyclohexylmethane (3DCM), and modified with core-shell particles of polystyrene-co-butylacrylate (PS-co-Bu). The DCBA-based matrices have been modified with polysulfone of bisphenol-A (PSU) or with polyetherimide (PEI). The influence of the modifiers and the curing conditions on the generated morphologies is reported as analysed by AFM in contact and tapping modes.     

种子乳胶粒表面修饰法制备核壳结构PSt/TiO_2复合微球

首先采用无皂乳液聚合法合成了表面带负电荷、粒径为360 nm的单分散聚苯乙烯(PSt)乳液,并利用聚乙烯亚胺(PEI)在25℃下对PSt乳胶粒表面进行修饰,得到了表面带有正电荷的PSt种子乳液;然后以乙醇和水的混合物为反应介质,采用种子乳液加入法,使钛酸正丁酯(TBT)在修饰后的乳胶粒表面进行水解与缩合,制备出了核壳结构PSt/TiO2复合微球,利用电镜对复合微球的结构形态进行了表征.结果表明,PSt乳液改性时体系的zeta电位随着PEI用量的增加而升高,当PEI用量为PSt聚合物重量的15%时,体系的zeta电位从原来的-40.3 mV升高到了38.3 mV,达到对PSt乳胶粒表面改性的最佳值;在制备PSt/TiO2复合微球时,TiO2包覆量随着反应时间的延长而增加,反应7 h时达到90.2%的最大值;随介质中水含量的增加,吸附到复合微球表面上的TiO2纳米颗粒逐渐减少,复合微球表面逐渐变得光滑,当EtOH/H2O质量比为100/6.0时,得到结构均一、壳层厚度为29 nm的核壳结构PSt/TiO2复合微球.     

Elaboration of fluorescent and highly magnetic submicronic polymer particles via a stepwise heterocoagulation process

Using the stepwise heterocoagulation concept, fluorescent and highly magnetic submicronic core-shell polymer particles were prepared. For this purpose a negatively charged oil-in-water magnetic emulsion was first modified by adsorbing the poly(ethyleneimine) (PEI). Secondly, low glass transition temperature (T _g=10°C) anionic film-forming nanoparticles were adsorbed onto the cationic magnetic droplets. Finally the encapsulation was induced by heating the heterocoagulates above the T _g of the film-forming nanoparticles. To produce labeled magnetic particles, fluorescent nanoparticles and film-forming nanoparticles were simultaneously adsorbed. PEI adsorption was investigated. Also investigated was the influence of the amount of film-forming nanoparticles and fluorescent nanoparticles on the encapsulation efficiency.     

Water-soluble pH-responsive dendritic core-shell nanocarriers for polar dyes based on poly(ethylene imine)

A simple general synthetic concept to build dendritic core-shell architectures with pH-labile linkers based on hyperbranched PEI cores and biocompatible PEG shells is presented. Using these dendritic core-shell architectures as nanocarriers, the encapsulation and transport of polar dyes of different sizes is studied. The results show that the acid-labile nanocarriers exhibit much higher transport capacities for dyes than unfunctionalized hyperbranched PEI. The cleavage of imine bonds and controlled release of the polar dyes revealed that weak acidic condition (pH approximately 5.0) could cleave the imine bonds linker and release the dyes up to five times faster than neutral conditions (pH = 7.4).     

氯丁胶乳-聚甲基丙烯酸甲酯复合乳胶粒结构形态

以氯丁胶乳（Pa）为种子乳液,甲基丙烯酸甲酯（Pb）为第二单体,采用种子乳液聚合法,制备了氯丁胶乳-聚甲基丙烯酸甲酯复合乳胶粒。 热力学分析表明,当Pb的体积分数Φb＜0.69时,可同时形成Pa-Pb型正核-壳和（Pa＋Pb）分离型乳胶粒,当Φb＞0.69时,形成Pb-Pa型翻转型核壳结构乳胶粒,并伴有Pa-Pb型正核-壳结构乳胶粒的形成。 动力学分析表明,引发剂类型、第二单体的加入方式、种子乳胶粒的交联、单体/聚合物质量比是影响乳胶粒形态的主要因素。 采用水溶性引发剂过二硫酸钾（KPS）,以饥饿态方式加入单体,氯丁胶乳 聚甲基丙烯酸甲酯(PCR-PMMA)复合乳胶粒呈现正核-壳结构,以充溢态方式加入单体则不能形成明显的核-壳结构;而以油溶性偶氮二异丁腈（AIBN）为引发剂时,单体无论以充溢态方式加入还是饥饿态加入均倾向于形成翻转核-壳型粒子。 在种子乳胶粒中加入一定量交联剂二缩三乙二醇二甲基丙烯酸酯,有利于形成明显的正核壳结构。 以饥饿态进料,KPS为引发剂时,随着单体用量增加,壳层变厚,仍呈正核-壳结构,与热力学分析结果相吻合;以AIBN为引发剂时,随着单体用量增加,PCR-PMMA复合乳胶粒逐渐由翻转核壳型结构变为互穿结构。     

Modification of gold nanoparticle composite nanostructures using thermosensitive core-shell particles as a template

We report the formation of novel thermosensitive hybrid core-shell particles via in situ synthesis of gold nanoparticles using thermosensitive core-shell particles as a template. The template core-shell particles, with cores composed mainly of poly(glycidyl methacrylate) (GMA) and shells composed mainly of poly(N-isopropylacrylamide) (PNIPAM), were synthesized in aqueous medium, and functional groups such as thiol groups were incorporated into each particle. We found that these particles containing thiol groups were effective for the in situ synthesis of gold nanoparticles in long-term storage. The obtained hybrid particles exhibited a reversible color change from red to purple, which originated from the surface plasmon resonance of gold nanoparticles and which was temperature-dependent in the range of 25-40 degrees C. In addition to their thermosensitive property, the hybrid particles exhibited the unique characteristic of uniform distribution on a solid substrate. The particles obtained by this approach have potential thermosensitive applications such as in sensors and photonic or electronic devices.     

High-resolution analysis of the influence of reactant concentration on nucleation time and growth of polyethyleneimine-trimethoxymethylsilane particles

High-resolution dynamic light scattering (DLS), scanning electron microscopy (SEM), time-lapse photography, and attenuated total reflectance Fourier transform infrared spectroscopy were used to analyze the growth kinetics of polyethyleneimine (PEI)-silica particles fabricated from the condensation of hydrolyzed trimethoxymethylsilane (TMOMS) and PEI/phosphate buffer (PEI/PB). Depending on the concentration of hydrolyzed TMOMS and PEI/PB, three stages were identified. We observed the existence of a nucleation time that has never been reported in the literature when TMOMS has been used. During this nucleation time, particles of less than 25 nm were detected using in situ DLS measurements taken every 15 s (high resolution), a DLS time-scale resolution not previously reported. In addition, the length of the nucleation time depended mainly on the PEI/PB concentration, but also TMOMS concentration. The growth stage was evident from the rapid increase of particle size with time. Due to the high resolution of the DLS measurements, a peak could be observed in the particle diameter during particle growth, which corresponds to a secondary population of particles required for the larger particles to further increase in size. Finally, during the equilibrium region, particles reached their maximum diameter that was independent of the concentration of PEI/PB and only changed with concentration of hydrolyzed TMOMS.     

均匀共沉淀法制备钛酸钡-钡铁氧体核-壳结构粒子

用均匀共沉淀法制备了钛酸钡-钡铁氧体核-壳粒子, 研究了沉淀反应温度、尿素/金属离子摩尔比值(R)和BaTiO₃浓度对核-壳粒子形貌和结构的影响, 探讨了钛酸钡-钡铁氧体核-壳粒子在焙烧时的形成过程及其磁性能. 采用透射电子显微镜(TEM)、X射线衍射(XRD)分析仪对钛酸钡-钡铁氧体前驱物核-壳粒子及钛酸钡-钡铁氧体核-壳粒子的形貌和结构进行了表征, 采用振动样品磁强计(VSM)研究了钛酸钡-钡铁氧体核-壳粒子的磁性能. 结果表明: 当沉淀反应温度为100 °C, R为180, BaTiO₃浓度为2.5 g·L^-1时, 金属离子沉淀完全, 得到的钛酸钡-钡铁氧体前驱物核-壳粒子包覆层均匀、完整、光滑, 厚度约为10 nm. 过高的温度和R值都会导致大量独立颗粒杂质的生成; 随着BaTiO₃浓度的增大, 包覆层厚度有减小的趋势. 当焙烧温度为900 °C时, 壳层中开始形成BaFe₁₂O₁₉相, 其形成过程为晶态的α-Fe₂O₃和BaCO₃首先生成中间相BaFe₂O₄, 然后由BaFe₂O₄和α-Fe₂O₃反应得到最终的BaFe₁₂O₁₉. 当焙烧温度为1000 °C时, 壳层完全转化为BaFe₁₂O₁₉相. 随着焙烧温度从900 °C升高到1000 °C, 所得BaTiO₃-BaFe₁₂O₁₉核-壳粒子的饱和磁化强度从16.5 A·m²·kg^-1增加到39.5 A·m²·kg^-1, 矫顽力从340 kA·m^-1略微降低到316 kA·m^-1.     

Preparation of multilayered gold-silica-polystyrene core-shell particles by seeded polymerization

A preparation method for multilayered gold-silica-polystyrene core-shell composite particles is proposed. The gold-silica core-shell particles of 192-nm-sized, synthesized by coating the 18-nm-sized gold particles with silica by a seeded growth technique, were used as cores for succeeding polystyrene coating. After surface modification of gold-silica composite particles by methacryloxypropyltrimethoxysilane (MPTMS), polymerizations of styrene (0.16-0.4 M) were conducted with 8 x 10(-3) M of potassium persulfate initiator in the presence of 1 x 10(-3) M of sodium p-styrenesulfonate anionic monomer. Multilayered core-shell gold-silica-polystyrene particles that contained a single core could be obtained. The coefficient of variation of size distribution (CV) of the composite particles was less than 7%, and polystyrene shell thickness was in a range of 193 to 281 nm.     

Antimicrobial silica particles loaded with quaternary ammonium polyethyleneimine network

Silica particles functionalized with quaternary ammonium groups were prepared by interpenetrating polyethylenimine (PEI) into silica particles and crosslinking with diiodopentane, followed by octyliodide alkylation and methyliodide quaternarization (S‐QA‐PEI). The synthesized S‐QA‐PEI particles were identified with a slight particle size increase of 2–3 µm. Different ratios of PEI:silica particles were prepared and analyzed. While silica particles are negatively charged, ?16.7 ± 5.11 mV, the prepared S‐QA‐PEI particles are positively charged, +50–60 mV. These particles were embedded in poly(ethylene vinyl acetate) and poly(ethylene methacrylic acid) coatings which exhibited strong antibacterial activity. Copyright © 2014 John Wiley & Sons, Ltd.     

原位制备PEI/SiO2复合材料及其改性环氧树脂的研究

在N,N-二甲基乙酰胺/四氢呋喃(DMAc/THF)混合溶剂中,在正硅酸乙酯(TEOS)存在条件下,通过溶胶-凝胶法原位制备了聚醚酰亚胺(PEI)/SiO2复合材料.在该复合材料中,当SiO2含量低于20 wt％时,透射电镜(TEM)和扫描电镜(SEM)的观察表明,SiO2纳米粒子可以均匀分散,粒径可在80～300 n...     

Polyamine-functional sterically stabilized latexes for covalently cross-linkable colloidosomes

Sterically stabilized polystyrene latexes were prepared by aqueous emulsion polymerization using a poly(ethylene imine) (PEI) stabilizer in the presence of 4-vinylbenzyl chloride (4-VBC; 1.0 wt % based on styrene). Partial quaternization of the amine groups on the PEI chains by 4-VBC occurs in situ, hence producing a chemically grafted steric stabilizer. Such 4-VBC-modified PEI chains were grafted more efficiently onto the polystyrene particles than unmodified PEI, as judged by aqueous electrophoresis, XPS, and nitrogen microanalysis. Moreover, partially quaternized PEI gave significantly smaller polystyrene particles than those synthesized in the absence of any PEI stabilizer or those synthesized using unmodified PEI. The partially quaternized PEI-stabilized polystyrene latex proved to be an effective emulsifier at pH 9, forming stable oil-in-water Pickering emulsions when homogenized (12,000 rpm, 2 min, 20 °C) with four model oils, namely, n-dodecane, methyl myristate, isononyl isononanoate, and sunflower oil. The primary and/or secondary amine groups on the PEI stabilizer chains were successfully cross-linked using three commercially available polymeric reagents, namely, tolylene 2,4-diisocyanate-terminated poly(propylene glycol) (PPG-TDI), poly(propylene glycol) diglycidyl ether (PPG-DGE), or poly(ethylene glycol) diglycidyl ether (PEG-DGE). Cross-linking with the former reagent led to robust colloidosomes that survived the removal of the internal oil phase on washing with excess alcohol, as judged by optical microscopy and SEM. PPG-TDI reacted very rapidly with the PEI stabilizer chains, with cross-linking being achieved during homogenization. Well-defined colloidosomes could be formed only by using sunflower oil and isononyl isononanoate with this cross-linker at 20 °C. However, cooling to 0 °C allowed colloidosomes to be formed using n-dodecane, presumably because of the slower rate of cross-linking at this reduced temperature. PPG-DGE proved to be a more generic cross-linker because it formed robust colloidosomes with all four model oils. However, cross-linking was much slower than that achieved using PPG-TDI, with intact colloidosomes being formed only after ～12 h at 20 °C. The PEG-DGE cross-linker allowed cross-linking to be conducted at 20 °C from the aqueous phase (rather from within the oil droplets for the oil-soluble PPG-TDI or PPG-DGE cross-linkers). In this case, well-defined colloidosomes were obtained at 50 vol % with surprisingly little intercolloidosome aggregation, as judged by laser diffraction studies.     

Synthesis of polyacrylate core-shell structure latex by radiation techniques

A series of poly(butyl acrylate-co-methyl methacrylate)/poly (ethyl acrylate-co-acrylic acid) interpenetrating polymer network (IPN) was synthesized in latex form by emulsion polymerization. The multiphase morphology of the latex particles was studied after two-stage polymerization by using transimission electron microscope (TEM), the result indicated that the morphology of the particles comprises gradient shell structure, cellular structure and core-shell structure. The change of morphology might stem from emulsion polymerization by radiation initiation or chemical initiation and the weight composition of poly(EA-co-MMA) seed latex which formed the core. By radiation techniques, we successfully synthesized poly( BA-co-MMA)/poly(EA-co-AA) latex of core-shell structure having (42-8)/(46-4) weight compositions. The PA core-shell structure latex applied to textile as a water proofing coating showed higher water-pressure and easier handling than that with PA homogeneous phase structure latex.     

Preparation of asymmetrically nanoparticle-supported, monodisperse composite dumbbells by protruding a smooth polymer bulge from rugged spheres

A novel method is proposed to create asymmetrically nanoparticle-supported, monodisperse composite dumbbells. The method consists of the three steps of double soap-free emulsion polymerizations before and after a heterocoagulation. In the first step, soap-free emulsion polymerization was conducted to cover silica cores with cross-linked poly(methyl methacrylate) (PMMA) shells. Then, positively or negatively charged silica nanoparticles were heterocoagulated with the silica-PMMA core-shell particles. In the heterocoagulations, the nanoparticles surface-modified with a cationic silane coupling agent, 3-aminopropyltriethoxysilane, were used as the positively charged ones, and silica nanoparticles without any treatment were used as the negatively charged ones. In the third step, soap-free polymerizations at different pH values were performed to protrude a polystyrene (PSt) bulge from the core-shell particles supporting the charged silica nanoparticles. In the polymerization, the core-shell particles heterocoagulated with the positively charged silica nanoparticles were aggregated in an acidic condition whereas the silica nanoparticles supported on the core-shell particles were dissolved in a basic condition. For the negatively charged silica nanoparticle, a PSt bulge was successfully protruded from the core-shell particle in acidic and neutral conditions without aggregation of the core-shell particles. The protrusion of the PSt bulge became distinctive when the number of heterocoagulated silica nanoparticles per core-shell particle was increased. Additional heterocoagulation experiments, in which positively or negatively charged magnetite nanoparticles were mixed with the asymmetrically nanoparticle-supported composite dumbbells, confirmed direct exposure of silica nanoparticles to the outer solvent phase.     

The influence of high dielectric constant core on the activity of core-shell structure electrorheological fluid

The core-shell structural dielectric particles are applied widely in the electrorheological (ER) fluids. The properties of the dielectric core are critical factors influencing their ER activity. In this paper, we successfully synthesized two kinds of core-shell hydroxyl titanium oxalate (TOC) particles with SiO(2) and TiO(2) as core, respectively. The obtained core-shell structural SiO(2)-TOC and TiO(2)-TOC particles were well-dispersed spherical nanoparticles with ideal morphology and a narrow size distribution. Under DC electric fields, the TiO(2)-TOC ER fluid showed notable ER activity with a yield stress of about 96 kPa (at 4 kV/mm), which is 3 times of that SiO(2)-TOC ER fluid and outclassed the yield stress of the TOC ER fluid. The dielectric spectra indicated that the higher dielectric constant of TiO(2) core induces the stronger interaction between the neighboring particles, which contribute to the enhancement of ER activity.     

Poly(ethylene imine)-controlled calcium phosphate mineralization

The current paper shows that poly(ethylene imine) (PEI) is an efficient template for the fabrication of spherical calcium phosphate (CaP)/polymer hybrid particles at pH values above 8. The polymer forms spherical entities, which contain one or a few CaP particles with diameters of ca. 6 nm. The samples contain up to 20 wt % polymer, which appears to be wrapped around the small CaP particles. The particles form via a mineralization-trapping pathway, where at the beginning of the precipitation small CaP particles form. Further particle growth is then prevented by precipitation of the PEI onto these particles at pH values of ca. 8. Stabilization of the particles is provided by the re-protonation of the PEI, which is adsorbed on the CaP particles, during the remainder of the mineralization process. At low pH, much larger particles form. They most likely grow via heterogeneous nucleation and growth on existing, polymer-modified CaP surfaces.     

Core-shell structured SiO2@YVO4:Dy3+/Sm3+ phosphor particles: sol-gel preparation and characterization

Spherical SiO(2) particles have been coated with YVO(4):Dy(3+)/Sm(3+) phosphor layers by a Pechini sol-gel process, leading to the formation of core-shell structured SiO(2)@YVO(4):Dy(3+)/Sm(3+) particles. X-ray diffraction (XRD), Fourier-transform IR spectroscopy, field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting SiO(2)@YVO(4):Dy(3+)/Sm(3+) core-shell phosphors. The obtained core-shell phosphors have perfect spherical shape with narrow size distribution (average size ca. 300 nm), smooth surface and non-agglomeration. The thickness of shells could be easily controlled by changing the number of deposition cycles (20 nm for one deposition cycle). The core-shell particles show strong characteristic emission from Dy(3+) for SiO(2)@YVO(4):Dy(3+) and from Sm(3+) for SiO(2)@YVO(4):Sm(3+) due to an efficient energy transfer from YVO(4) host to them. The PL intensity of Dy(3+) and Sm(3+) increases with raising the annealing temperature and the number of coating cycles.     

Electroactive core-shell nanocluster films of heme proteins, polyelectrolytes, and silica nanoparticles

Novel protein core-shell nanocluster films were assembled layer by layer on solid surfaces. In the first step, positively charged heme protein hemoglobin (Hb) or myoglobin (Mb) and negatively charged poly(styrenesulfonate) (PSS) were alternately adsorbed on the surface of SiO2 nanoparticles, forming core-shell SiO2-(protein/PSS)m nanoclusters. In the second step, the SiO2-(protein/PSS)m nanoclusters and polycationic poly(ethylenimine) (PEI) were assembled layer by layer on various solid substrates, forming [[SiO2-(protein/PSS)m]/PEI]n films. Various techniques were used to characterize the nanoclusters and monitor the film growth. [[SiO2-(protein/PSS)m]/PEI]n films at pyrolytic graphite (PG) electrodes exhibited well-defined, chemically reversible cyclic voltammetric reduction-oxidation peaks characteristic of the heme Fe(III)/Fe(II) redox couples. The proteins in the films retained near native conformations in the medium pH range, and the films catalyzed electrochemical reduction of oxygen and hydrogen peroxide. Advantages of the nanocluster films over the simple [SiO2/protein]n layer-by-layer films include a larger fraction of electroactive protein and higher specific biocatalytic activity. Using this approach, biocatalytic activity can be tailored and controlled by varying the number of bilayers deposited on the nanoparticle cores and the number of nanocluster layers on electrodes.