Influence of assembly pH on compression and Ag nanoparticle synthesis of polyelectrolyte multilayers

Influence of assembly pH on compression and Ag nanoparticle synthesis of polyelectrolyte multilayers was studied using poly(diallyldimethylammonium chloride) (PDADMAC) and poly(4-styrenesulfonic acid-co-maleic acid, 1:1SS:MA) sodium salt (PSSMA 1:1) as the building blocks. The thickest multilayers turned out at pH 4. A homogeneous compression by a silicone rubber stamp increased significantly the water contact angle to a same value which was independent on the original assembly pH anymore. The multilayers assembled at pH 4 could be maximumly compressed to a ratio of 70% by a silicone rubber stamp with linear patterns, which was considerably larger than those assembled at other pHs (the compression ratio ~50%). The Ag nanoparticles were then synthesized inside the multilayers either flat compressed or not. The results showed that the compression reduced significantly the amount of Ag nanoparticles for the multilayers assembled at pH 2 and pH 4. The particle amount was also decreased significantly when the multilayers were assembled at higher pH, pH 6, for example, regardless of the compression. Substantial alteration of the multilayers in terms of the surface morphology, thickness and refractive index was found during the reduction of Ag(+) containing multilayers by NaBH(4) solution.     

纳米银/高聚物复合材料的合成及其抑菌性研究进展

纳米银/高聚物复合材料以其优异的物理化学性质,在近几年得到快速发展。而其在高效抑菌灭菌方面的突出性更是引起科研人员的广泛关注。因此,纳米银/高聚物复合材料的合成方式和抑菌性能具有很大应用研究价值。本文综述了近年来纳米银/高聚物复合材料的制备方法和抑菌效果的比较,并展望了纳米银/高聚物的发展方向及应用前景。     

Fabrication and properties of pH-sensitive nanostructured polyelectrolyte microparticles loaded with insulin

Thorough investigation and comparative study were conducted for insulin-loaded microparticles fabricated by consecutive adsorption of polyanions (dextran sulfate and chitosan sulfate) and polycations (chitosan and protamine) onto protein microaggregates. The possible regulation of insulin release from the particles by variation in polyelectrolyte pairs, in the number of their adsorption cycles and in pH of media was demonstrated. For all studied cases the microparticles showed protective action towards insulin inactivation at acid pH values and protein release at pH > 5, corresponding to human gastro-intestinal conditions.     

Sucrose ester micellar-mediated synthesis of Ag nanoparticles and the antibacterial properties

Ag nanoparticles with diameter in the range of 10–25 nm had been synthesized using a simple sucrose ester micellar-mediated method. Ag nanoparticles were formed by adding AgNO₃ solution into the sucrose ester micellar solution containing sodium hydroxide at atmospheric condition after 24 h of aging time. Trace amount of dimethyl formamide (DMF) in the sucrose ester solution served as a reducing agent while NaOH acted as a catalyst. The produced Ag nanoparticles were highly stable in the sucrose ester micellar system as there was no precipitation after 6 months of storage. The as-synthesized Ag nanoparticles were characterized using transmission electron microscope (TEM), X-ray diffractometer (XRD), dynamic light scattering (DLS) and UV–vis spectroscopy (UV–vis). Formation mechanism of Ag nanoparticles in the micellar-mediated synthesis is postulated. The antibacterial properties of the Ag nanoparticles were tested against Methicillin-resistant Staphylococcus aureus (MRSA) (Gram-positive) and Aeromonas hydrophila (Gram-negative) bacteria. This work provides a simple and “green” method for the synthesis of highly stable Ag nanoparticles in aqueous solution with promising antibacterial property.     

Preparation and properties of textile materials modified with triclosan‐loaded polylactide microparticles

A convenient and simple method for preparation of commercial nonwovens with antimicrobial properties was elaborated. The process consists in preparation of poly(l ‐lactide) microspheres (from poly(l ‐lactide) with M _n  = 10,560 and M _w /M _n  = 1.39) containing triclosan (5‐chloro‐2‐(2,4‐dichlorophenoxy) phenol) and loading them onto the nonwovens. The microspheres were prepared by spray drying (D _n  = 3.91 μm, D _w /D _n  = 2.43) and oil‐in‐water emulsification‐solvent evaporation method (D _n  = 5.84 μm, D _w /D _n  = 1.25). Content of triclosan in microspheres ranged from 4.65 to 4.95 wt%. The antibacterial nonwovens were prepared by padding of the fibers with the microspheres using the microsphere suspension. The resulting antibacterial nonwovens were examined using inhibition zone measurement method. Inhibition zones from 4 to 9 mm indicated that the modified nonwovens had antibacterial properties against Gram (+)—Staphylococcus aureus and Gram (?)—Klebsiella pneumoniae . Nonwovens were conditioned up to 12 months at relative humidity <5%, 50%, and 100% in desiccators and up to 6 months air‐conditioning system at relative humidity = 65%. Antimicrobial activity of the modified nonwovens was examined as a function of time and air humidity. Time of conditioning has strong influence on antibacterial activity, whereas the impact of the air humidity was negligible. All nonwovens had antibacterial properties even after 12 months of conditioning. Copyright © 2017 John Wiley & Sons, Ltd.     

SERS in PAH-Os and gold nanoparticle self-assembled multilayers

We present a detailed structural and surface-enhanced Raman scattering (SERS) study of poly(allylamine) modified with Os(byp)2ClPyCHO (PAH-Os) and gold nanoparticles self-assembled multilayers [PAH-Os+(Au-nanoparticlesPAH-Os)n, n=1 and 5]. Atomic force microscopy and variable-angle spectroscopic ellipsometry measurements indicate that the first nanoparticle layer grows homogenously by partially covering the substrate without clustering. Analyzing the sample thickness and roughness we infer that the growth process advances thereafter by filling with nanoparticles the interstitial spaces between the previously adsorbed nanoparticles. After five immersion steps the multilayers reach a more compact structure. The interaction between plasmons of near-gold nanoparticles provides a new optical absorption around 650 nm which, in addition, allows a more effective SERS process in that spectral region than at the single-plasmon resonance (approximately 530 nm). We compare the electronic resonance Raman and SERS amplification mechanisms in these self-assembled multilayers analyzing Raman resonance scans and Raman intensity micromaps. As a function of nanoparticle coverage we observe large changes in the Raman intensity scans, with maxima that shift from the electronic transitions, to the plasmon resonance, and finally to the coupled-plasmon absorption. The Raman micromaps, on the other hand, evidence huge intensity inhomogeneities which we relate to "hot spots." Numerical discrete dipole approximation calculations including the interaction between gold nanoparticles are presented, providing a qualitative model for the coupled-plasmon absorption and redshifted Raman hot spots in these samples.     

Versatile scheme for the step-by-step assembly of nanoparticle multilayers

A versatile scheme for the preparation of nanoparticle (NP) multilayers is presented. The method is based on the step-by-step assembly of NPs and bishydroxamate disulfide ligand molecules by means of metal-organic coordination using easily synthesized tetraoctylammonium bromide (TOAB)-stabilized gold NPs. The assembly of NP multilayers was carried out via a Zr(IV)-coordinated sandwich arrangement of the hydroxamate ligands on Au and glass surfaces. The latter were precoated with electrolessly deposited Au clusters to enable binding of the first NP layer. The new method avoids the need to perform elaborate colloid reactions to prepare the NP building blocks. Au NP monolayer and multilayer films prepared in this manner were characterized by UV-vis spectroscopy, atomic force microscopy (AFM), and cross-sectional transmission electron microscopy (TEM), showing a regular growth of NP layers. The use of coordination chemistry as the binding motif between repeat layers allows for the convenient assembly of hybrid nanostructures comprising molecular and NP components. This was demonstrated by the construction of Au NP multilayers with controlled spacing from the surface or between two NP layers. Drying the samples during or after the construction process induces NP aggregation and changes in the film morphology and optical properties.     

Polyelectrolyte/magnetite nanoparticle multilayers: preparation and structure characterization

Polyelectrolyte composite planar films containing a different number of iron oxide (Fe3O4) nanoparticle layers have been prepared using the layer-by-layer adsorption technique. The nanocomposite assemblies were characterized by ellipsometry, UV-vis spectroscopy, and AFM. Linear growth of the multilayer thickness with the increase of the layer number, N, up to 12 reflects an extensive character of this parameter in this range. A more complicated behavior of the refractive index is caused by changes in the multilayer structure, especially for the thicker nanocomposites. A quantitative analysis of the nanocomposite structure is provided comparing a classical and a modified effective medium approach taking into account the influence of light absorption by the Fe3O4 nanoparticles on the complex refractive index of the nanocomposite and contributions of all components to film thickness. Dominant influence of co-adsorbed water on their properties was found to be another interesting peculiarity of the nanocomposite film. This effect, as well as possible film property modulation by light, is discussed.     

Electronic properties of Ag nanoparticle arrays. A Kelvin probe and high resolution XPS study

The electronic properties of citrate stabilised Ag nanoparticles with sizes ranging from 4 to 35 nm were investigated by the Kelvin probe method and high resolution XPS. Two and three dimensional assemblies of the particles were prepared by electrostatic adsorption from aqueous solution onto poly-l-lysine modified surfaces. The work function of the Ag particles increased from 5.29 +/- 0.05 to 5.53 +/- 0.05 eV as the particle size decreased. These values are approximately 0.8 eV higher than for clean polycrystalline Ag surfaces. The origin of these remarkable high work functions cannot be explained in terms of either citrate induced changes in the surface dipole or image forces in the confined metallic domains. High resolution XPS spectra of the Ag 3d(5/2) core level were characterised by broad bands and a 0.4 eV shift towards lower binding energies for the smallest particles. Comparisons with reported studies on extended Ag surfaces indicate that as-grown particles exhibit partially oxidised surfaces. The behaviour of the work function further suggests that the strength of the Ag-O bonding increases with decreasing particle sizes. These findings are highly relevant to the interpretation of the catalytic properties of Ag nanoparticles.     

The influence of nanoparticle architecture on latex film formation and healing properties

We present a study of chain interdiffusion in films formed by specially architectured PBMA nanoparticles by Förster Resonance Energy Transfer – FRET. Polymer nanoparticles contained linear chains with narrower molecular weight distributions than other previous reports, allowing a more detailed study. Apparent fractions of mixing and diffusion coefficients, determined from the quantum efficiency of energy transfer, were used to characterize the interdiffusion mechanism in the different films. The resistance of the films to dissolution by a good solvent was finally correlated with the interdiffusion results, in order to get information about film healing. We concluded that whenever interdiffusion occurs between nanoparticles containing linear chains and fully cross-linked nanoparticles, healing becomes more effective in spite of showing slower interdiffusion. We also observed that particles with longer chains are more effective for film healing. Finally, we concluded that interdiffusion occurs both ways across interfaces in blends formed by particles swollen with linear chains of different molecular weights.     

水溶性银纳米颗粒的制备及抗菌性能

采用液相还原法, 以单宁酸为还原剂, 聚乙烯吡咯烷酮(PVP)为修饰剂制备出了水溶性的表面修饰Ag纳米颗粒. 通过X 射线粉末衍射仪(XRD)、透射电子显微镜(TEM)、紫外-可见吸收分光光度计(UV-Vis)、傅里叶变换红外(FTIR)光谱仪等对所得样品的形貌和结构进行了表征. 采用肉汤稀释法测试了样品的抗菌性能, 考察了样品在水相中的分散稳定性, 提出了PVP修饰Ag纳米颗粒的形成机理. 结果表明所制备的样品具有Ag的面心立方晶体结构, 平均粒径为15-17 nm. 样品在水相中能长时间稳定分散; 对埃希氏大肠杆菌(E. coli)、金黄色葡萄球菌(S. aureus)具有明显的抗菌作用. 操作简便、条件温和的制备方法易于在工业规模上放大; 试剂无毒, 使得所制备的PVP修饰Ag纳米颗粒作为抗菌剂具有良好的应用前景.     

Biomagnetic nanoparticle formation and application

Magnetospirillum sp. AMB-1 is a bacterium that synthesizes intracellular particles of magnetite (Fe₃O₄). A magA gene required for the synthesis of bacterial magnetic particles (BMPs) was isolated from this strain and its gene product (MagA protein) was characterized as an iron transport protein. Intracellular localization analysis of the MagA protein using magA–Luc fusion proteins showed that MagA protein is localized on the surface of the lipid bilayer covering the BMPs. One particular BMP-associated protein, designated MpsA, was also purified from this strain and characterized. By the fusion-protein method using mpsA-luc genes, it was demonstrated that Mps-protein is preferentially partitioned onto the BMP membrane. Furthermore, application of BMPs to immunoassay is also described.     

Synthesis of quasi-hexagonal Ag/NiCo2O4 nanosheets and their photocatalytic and antibacterial properties

Journal of the Iranian Chemical Society - The precursors of NiCo2O4 and Ag/NiCo2O4 composite nanosheets with different Ag contents were prepared via a hydrothermal procedure. The final NiCo2O4 and...     

Formation and structure of polyelectrolyte and nanoparticle multilayers: effect of particle characteristics

The formation and structure of multilayer films containing a cationic polyelectrolyte and anionic silica nanoparticles were studied by means of ellipsometry and atomic force microscopy. Three types of silica particles of different sizes were examined. The density and thickness of the films as well as the adsorption kinetics appear to be strongly dependent on the choice of particle; smaller particles favor the formation of smooth and dense films with a higher content of the inorganic component.     

Cu2O/Ag纳米复合材料的绿色制备与抗菌性能研究

以乙酸铜为铜源、硝酸银为银源并利用天然蜂蜜为还原剂在无模板剂无需高压反应釜的条件下,环保地、简便地制备了Cu_2O/Ag复合材料。并采用X射线衍射、扫描电镜对材料的结构与形貌进行了表征。通过抑菌圈法证明Cu_2O/Ag复合材料相比Cu_2O对大肠杆菌有着更好的抑菌性能,通过分析Cu_2O/Ag对大肠杆菌生长过程的影响发现,当Cu_2O/Ag复合材料的浓度达到10μg/m L时,Cu_2O/Ag复合材料能够彻底抑制大肠杆菌的生长。通过SEM观察了Cu_2O/Ag复合材料对大肠杆菌作用过程中菌种形貌的变化表明,Cu_2O/Ag复合材料对大肠杆菌的抗菌作用过程是先破坏细胞膜结构使细菌断裂成小段,这些小段颗粒逐渐皱缩进而彻底被分解为大分子物质。本文制备的Cu_2O/Ag复合材料在抗菌剂领域具有潜在的应用价值。     

Interaction and adhesion properties of polyelectrolyte multilayers

The growth, morphology, and interaction/adhesion properties of supported poly(sodium 4-styrenesulfonate)/poly(allylamine hydrochloride) (PSS/PAH) and DNA/PAH multilayers were investigated by means of surface plasmon resonance spectroscopy, atomic force microscope (AFM) imaging, and AFM-related force measurements. Multilayers were assembled on a prelayer of poly(ethylenimine) (PEI) both with and without drying. SPR results showed a linear growth of the assembly in the case of PSS/PAH multilayers and nonlinear growth for DNA/PAH multilayers. Measurements of forces acting between a bare glass sphere and a multilayer-coated surface indicated repulsive or attractive forces, depending on surface charge, which suggests that, on approach, electrostatic forces dominate. On separation, we observed large pull-off forces in the case of positively charged multilayers and weak pull-off forces in the case negatively charged multilayers. Multiple adhesions and plateau regions observed on separation were interpreted in terms of a bridging of multiple polymer chains between the glass particle and the multilayer and a stretching of the polyelectrolyte loops. The dependence of the pull-off force on the number of deposited layers shows regular oscillations.     

Electrochemical characterization of polyelectrolyte/gold nanoparticle multilayers self-assembled on gold electrodes

Polyelectrolyte/gold nanoparticle multilayers composed of poly(l-lysine) (pLys) and mercaptosuccinic acid (MSA) stabilized gold nanoparticles (Au NPs) were built up using the electrostatic layer-by-layer self-assembly technique upon a gold electrode modified with a first layer of MSA. The assemblies were characterized using UV-vis absorption spectroscopy, cyclic and square-wave voltammetry, electrochemical impedance spectroscopy, and atomic force microscopy. Charge transport through the multilayer was studied experimentally as well as theoretically by using two different redox pairs [Fe(CN)(6)](3-/4-) and [Ru(NH(3))(6)](3+/2+). This paper reports a large sensitivity to the charge of the outermost layer for the permeability of these assemblies to the probe ions. With the former redox pair, dramatic changes in the impedance response were obtained for thin multilayers each time a new layer was deposited. In the latter case, the multilayer behaves as a conductor exhibiting a strikingly lower impedance response, the electric current being enhanced as more layers are added for Au NP terminated multilayers. These results are interpreted quite satisfactorily by means of a capillary membrane model that encompasses the wide variety of behaviors observed. It is concluded that nonlinear slow diffusion through defects (pinholes) in the multilayer is the governing mechanism for the [Fe(CN)(6)](3-/4-) species, whereas electron transfer through the Au NPs is the dominant mechanism in the case of the [Ru(NH(3))(6)](3+/2+) pair.     

Mechanical properties of magnetically oriented epoxy

The microstructure of an epoxy system oriented in high magnetic fields (15–25 T) has been observed to consist of highly oriented domains at the molecular level along the direction of the applied field. The changes in the microstructure have been characterized as a function of the magnetic‐field strength and have been investigated microscopically and with wide‐angle X‐ray diffraction. The mechanical properties of the epoxy have been examined in light of nanoindentation experiments at different load levels. The basic results of the experimental investigations for the effect of high magnetic fields on the structure and property of the epoxy are presented. Nanoindentation testing has revealed large differences in the nanomechanical behavior for thermomagnetically processed epoxy specimens. The differences can be ascribed to the microstructural changes (reorientation) of the polymer at the molecular level. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1586–1600, 2004     

Antibacterial and wound healing properties of cellulose acetate electrospun nanofibers loaded with bioactive glass nanoparticles; in-vivo study

Bioactive glasses (BGs) have gained great attention owing to their versatile biological properties. Combining BG nanoparticles (BGNPs) with polymeric nanofibers produced nanocomposites of great performance in various biomedical applications especially in regenerative medicine. In this study, a novel nanocomposite nanofibrous system was developed and optimized from cellulose acetate (CA) electrospun nanofibers containing different concentrations of BGNPs. Morphology, IR and elemental analysis of the prepared electrospun nanofibers were determined using SEM, FT-IR and EDX respectively. Electrical conductivity and viscosity were also studied. Antibacterial properties were then investigated using agar well diffusion method. Moreover, biological wound healing capabilities for the prepared nanofiber dressing were assessed using in-vivo diabetic rat model with induced wounds. The fully characterized CA electrospun uniform nanofiber (100–200 nm) with incorporated BGNPs exhibited broad range of antimicrobial activity against gram negative and positive bacteria. The BGNP loaded CA nanofiber accelerated wound closure efficiently by the 10th day. The remaining wound areas for treated rats were 95.7?±?1.8, 36.4?±?3.2, 6.3?±?1.5 and 0.8?±?0.9 on 1st, 5th, 10th and 15th days respectively. Therefore, the newly prepared BGNP CA nanocomposite nanofiber could be used as a promising antibacterial and wound healing dressing for rapid and efficient recovery.

     

Preparation of magnetically separable N-halamine nanocomposites for the improved antibacterial application

Magnetic N-halamine nanocomposites were synthesized through the encapsulation of the magnetic silica nanoparticles with antibacterial N-halamine polymer. The as-synthesized sample was characterized by transmission electron microscopy (TEM), dynamic light scattering (DLS), Fourier transform infrared (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), and thermogravimetric analysis (TGA). The fabricated magnetic N-halamine nanocomposites possessed enhanced antibacterial activity against both gram-positive and gram-negative bacteria compared with their bulk counterparts. The effect of chlorine content of the magnetic N-halamine nanocomposites on the antibacterial activity was investigated. The magnetic N-halamine nanocomposites also exhibited super-paramagnetic behavior and had a saturation magnetization of 4.728 emu g(-1) at room temperature, which made these nanocomposites separable magnetically after the antibacterial behavior. Performances derived from the synergism between magnetic core and antibacterial shell suggest that the magnetic N-halamine nanocomposites are qualified for antibacterial applications and separable by the aid of the external magnetic field.