Microwave-assisted synthesis of hybrid colloids for design of conducting films

We report synthesis of colloids with polymer core and inorganic shell consisting of silver nanoparticles (AgNPs) which can be used as building blocks for the preparation of conducting composite films. Polymer colloids based on copolymer of styrene and butyl acrylate with variable film formation temperature and functional surface have been prepared by surfactant-free emulsion polymerization. Polymer particles with average size between 140 nm and 220 nm and narrow size distribution were used as templates for deposition of AgNPs by microwave-assisted reduction of silver precursors in aqueous medium. The loading of the AgNPs on the polymer particle surface has been increased up to 60 wt.-%. Obtained hybrid colloids were used for preparation of composite films. The electrical conductivity of the composite films starts to increase if the AgNPs loading on the polymer particle surface is above 20 wt.-%.     

A comprehensive review of the polymer-based hydrogels with electrochemically synthesized silver nanoparticles for wound dressing applications

Modernization and improvement of wound dressing materials is an important topic in biomaterials and biomedicine fields, as the traditional materials are inadequate and susceptible to bacterial infections. In recent times, polymer-based hydrogel materials have presented themselves as excellent candidates for new-generation wound dressings with improved properties, such as high sorption ability, good mechanical properties, and low adhesiveness. Additionally, cross linked hydrogel matrices serve as excellent carriers for controlled release of antibacterial agents, such as silver nanoparticles (AgNPs), which are preferred over conventional antibiotics due to multi-phase mechanism of action and low susceptibility to induce bacterial resistance. Their incorporation inside polymer matrices allows improvement of wound dressing properties and sustained protection against bacterial infection. Electrochemical methods for AgNPs synthesis are facile and green alternatives to chemical routes, allowing the formation of highly stable AgNPs with strong antibacterial effect. In this article, we aim to provide a comprehensive review of the existing research on the topic of electrochemically synthesized silver nanoparticles incorporated in polymer matrices with a special focus on the chitosan-based hydrogels as prospective materials for wound dressing applications.     

Tunable release of silver nanoparticles from temperature-responsive polymer blends

Polymer blends of thermoresponsive poly(N-isopropylacrylamide) and poly(methyl methacrylate) with in situ synthesized silver nanoparticles (AgNPs) are proposed as stimuli-responsive antimicrobial materials. AgNPs were prepared in the semi-dried polymer blends by N-methyl-2-pyrrolidone reduction. Temperature controlled kinetic of silver release was examined for different weight ratios of the polymers. Synthesized AgNPs were characterized by transmission electron microscopy and temperature-dependent releasing was analyzed by ultraviolet–visible and atomic absorption spectroscopies. Temperature-dependent changes of polymer matrices were observed by confocal microscopy and infrared spectroscopy. It was shown that the polymer weight ratio determines both, starting time and kinetic of nanoparticle release. Antibacterial activities of the prepared material were demonstrated on Gram-positive Staphylococcus aureus (S. aureus) and gram-negative Pseudomonas aeruginosa (P. aeruginosa). Quantitative evaluation of antimicrobial efficacy of prepared materials was performed on the base of inhibition zone size. It was shown that prepared materials could serve as effective antibacterial coating with quick antimicrobial response.     

Polymer Protected and Gel Immobilized Gold and Silver Nanoparticles in Catalysis

This mini-review is focused on preparation of polymer protected gold (AuNPs) and silver (AgNPs) nanoparticles that are immobilized on the surface of inorganic supporters and within hydrogel and/or cryogel matrices. A series of water soluble polymers such as poly(N-vinylpyrrolidone), poly(acrylic acid), branched polyethyleneimine, and amphoteric cryogel based on the copolymer of N,N-dimethylaminoethylmethacrylate and methacrylic acid poly(DMAEM-MAA) were used for reduction and stabilization of metal nanoparticles. The catalytic properties of polymer protected AuNPs and AgNPs were evaluated with respect to hydrogen peroxide decomposition, hydrogenation of 4-nitrophenol and oxidation of cyclohexane.     

In situ assembly of well-dispersed Ag nanoparticles (AgNPs) on electrospun carbon nanofibers (CNFs) for catalytic reduction of 4-nitrophenol

Carbon nanofibers/silver nanoparticles (CNFs/AgNPs) composite nanofibers were fabricated by two steps consisting of the preparation of the CNFs by electrospinning and the hydrothermal growth of the AgNPs on the CNFs. The as-prepared nanofibers were characterized by scanning electron microscopy, energy dispersive spectroscopy, transmission electron microscopy, X-ray diffraction, resonant Raman spectra, thermal gravimetric and differential thermal analysis, and X-ray photoelectron spectroscopy, respectively. The results indicated that not only were AgNPs (25-50 nm) successfully grown on the CNFs but also the AgNPs were distributed without aggregation on the CNFs. Further more, by adjusting the parameters in hydrothermal processing, the content of silver supported on the CNFs could be easily controlled. The catalytic activities of the CNFs/AgNPs composite nanofibers to the reduction of 4-nitrophenol (4-NP) with NaBH(4) were tracked by UV-visible spectroscopy. It was suggested that the CNFs/AgNPs composite nanofibers exhibited high catalytic activity in the reduction of 4-NP, which might be attributed to the high surface areas of AgNPs and synergistic effect on delivery of electrons between CNFs and AgNPs. And, the catalytic efficiency was enhanced with the increasing of the content of silver on the CNFs/AgNPs composite nanofibers. Notably, the CNFs/AgNPs composite nanofibers could be easily recycled due to their one-dimensional nanostructural property.     

Effect of plasma duty cycle on silver nanoparticles loading of cotton fabrics for durable antibacterial properties

A facile method for strongly anchoring silver nanoparticles (AgNPs) onto cotton fabrics was reported. It consists in loading AgNPs onto the cotton fiber preliminary coated with maleic anhydride plasma polymer layer. This results in hydrolyzis and ring opening of anhydride groups followed by electrovalent bonding of silver ions and reduction in NaBH₄. X‐ray photoelectron spectroscopy (XPS), infrared spectroscopy, and scanning electron microscope (SEM) were used to analyze changes in the surface chemical composition and morphology of the plasma modified fibers. The presence of AgNPs was confirmed by UV–Visible spectroscopy and atomic force microscopy (AFM) images. Remarkably, varying plasma duty cycle for plasma polymer deposition allowed tailoring the amount of loaded AgNPs. The highest amount of AgNPs was obtained with the lowest duty cycle values. Qualitative tests showed that silver containing plasma modified cotton displays significant antibacterial activity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41279.     

Effects of copper nanoparticle exposure on host defense in a murine pulmonary infection model

Background

The study investigated the distribution of silver after 28 days repeated oral administration of silver nanoparticles (AgNPs) and silver acetate (AgAc) to rats. Oral administration is a relevant route of exposure because of the use of silver nanoparticles in products related to food and food contact materials.

Results

AgNPs were synthesized with a size distribution of 14 ± 4 nm in diameter (90% of the nanoparticle volume) and stabilized in aqueous suspension by the polymer polyvinylpyrrolidone (PVP). The AgNPs remained stable throughout the duration of the 28-day oral toxicity study in rats. The organ distribution pattern of silver following administration of AgNPs and AgAc was similar. However the absolute silver concentrations in tissues were lower following oral exposure to AgNPs. This was in agreement with an indication of a higher fecal excretion following administration of AgNPs. Besides the intestinal system, the largest silver concentrations were detected in the liver and kidneys. Silver was also found in the lungs and brain. Autometallographic (AMG) staining revealed a similar cellular localization of silver in ileum, liver, and kidney tissue in rats exposed to AgNPs or AgAc. Using transmission electron microscopy (TEM), nanosized granules were detected in the ileum of animals exposed to AgNPs or AgAc and were mainly located in the basal lamina of the ileal epithelium and in lysosomes of macrophages within the lamina propria. Using energy dispersive x-ray spectroscopy it was shown that the granules in lysosomes consisted of silver, selenium, and sulfur for both AgNP and AgAc exposed rats. The diameter of the deposited granules was in the same size range as that of the administered AgNPs. No silver granules were detected by TEM in the liver.

Conclusions

The results of the present study demonstrate that the organ distribution of silver was similar when AgNPs or AgAc were administered orally to rats. The presence of silver granules containing selenium and sulfur in the intestinal wall of rats exposed to either of the silver forms suggests a common mechanism of their formation. Additional studies however, are needed to gain further insight into the underlying mechanisms of the granule formation, and to clarify whether AgNPs dissolve in the gastrointestinal system and/or become absorbed and translocate as intact nanoparticles to organs and tissues.     

Surface plasmon resonance study of (positive, neutral, negative) vesicles rupture by AgNPs’ attack for screening of cytotoxicity induced by nanoparticles

As the use of nanomaterials in industrial and commercial applications is growing, official reports concerning possible environmental and health effects of nanoparticles are also steadily increasing. Many toxicological studies on the adverse effects of silver nanoparticles (AgNPs) have used living organisms, which is a time consuming process. Therefore, we propose an alternative method to assess the in-vivo and in-vitro cytotoxicity of nanomaterials, involving a fast and simple screening procedure for vesicle rupture or fusion by the attack of AgNPs. With the assumption that particle interaction between AgNPs and vesicles is induced by electrostatic repulsion or attraction of surface charge, three vesicles with different charges (positive, neutral, and negative) were prepared and they were dispersed with AgNPs in different pH (3, 7, and 10) solutions to control the surface charge of AgNPs. Based on the results of vesicle rupture analyzed by SPR and TEM, screening of cell rupture through vesicles by AgNPs’ attack is determined to be most suitable at pH 7.     

Facile modification of thin-film composite nanofiltration membrane with silver nanoparticles for anti-biofouling

This study focuses on the modification of a commercial nanofiltration (NF) membrane by an in-situ reaction to load silver nanoparticles (AgNPs) for anti-biofouling. Poly (vinyl alcohol) (PVA) was coated onto the NF membrane firstly, and silver salt was then deposited on the surface of PVA layer. Through thermal reduction, AgNPs with 10–20 nm in diameter were formed and immobilized onto the membrane surface by the interaction between AgNPs and PVA, as confirmed by UV–vis absorption spectrum, SEM and XPS analysis. Compared to the pristine NF90 membrane, the PVA composite membranes (NF90-PVA) and AgNPs (NF90-PVA-AgNPs) modified membranes exhibit lower water flux and slightly higher salt rejection. Release of silver ion experiments were assessed via batch method, and the results indicate silver ion can be released from the AgNPs modified membrane continuously and steadily, which may be responsible for the improved and long-time antibacterial ability of the membrane. Due to the simplicity of the method, the ability to immobilize the AgNPs to avoid leaching out, and the strong antibacterial activity, this NF90-PVA-AgNPs composite membrane displays potential applications in industrial water-treatment.     

Laser ablation of polymers: a review

Laser ablation (LA), which employs a pulsed laser to remove materials from a substrate for generating micro‐/nanostructures, has tremendous applications in the fabrication of metals, ceramics, glasses and polymers. It has become a noteworthy approach for achieving various functional structures in engineering, chemistry, biology, medicine and other fields. Polymers are one such class of materials; they can be melted and vaporized at high temperature during the ablation process. A number of polymers have been researched as candidate substrates in LA, and many different structures and patterns have been realized by this method. The current states of research and progress are reviewed from basic concepts to optimal parameters, polymer types and applications. The significance of this paper is to provide a basis for follow‐up research that leads to the development of superior materials and high‐quality production through LA. In this review, we first introduce the basic concept of LA, including mechanism, laser types (millisecond, microsecond, nanosecond, picosecond and femtosecond) and influential parameters (wavelength, repetition rate, fluence and pulse duration). Then, we focus on several commonly used polymer materials and compare them in detail, including the effects of polymer properties, laser parameters and feature designs. Finally, we summarize the applications of various structures fabricated by LA in a variety of areas along with a perspective of the challenges in this research area. Overall, a thorough review of LA of several polymers is presented, which could pave the way for characterization of future novel materials. © 2019 Society of Chemical Industry     

Fabrication and characterization of chitosan/poly(vinyl alcohol) electrospun nanofibrous membranes containing silver nanoparticles for antibacterial water filtration

Electrospun nanofibrous membranes (ENMs) were fabricated based on chitosan/poly(vinyl alcohol) (CS/PVA) with a 70/30 mass ratio containing silver nanoparticles (AgNPs) via the electrospinning method. AgNPs were produced on the surface of CS/PVA nanofibers by adding AgNO₃ to a CS/PVA blend solution as a silver rendering component. The presence of AgNPs in the polymer blend solution was detected by UV spectrophotometry. The morphology of nanofibers before and after cross-linking with glutaraldehyde was investigated by the field emission scanning electron microscopy. The formation and size distribution of AgNPs onto the surface of nanofibers were observed by transmission electron microscopy and confirmed by energy dispersing X-ray spectroscopy. As-spun and cross-linked CS/PVA nanofibers revealed a smooth surface with diameters ranging from 58 to 73 nm and 95 to 109 nm, respectively. The effect of AgNP formation on the chemical structure of nanofibers was explored by Fourier transform infrared spectroscopy. Static and dynamic antibacterial filtration efficiencies of CS/PVA ENMs, containing differing amounts of AgNO₃, have been tested against Escherichia coli, a gram negative bacterium. The antibacterial assessment results exhibited a significant increase in both static and dynamic antibacterial filtration efficiencies of the prepared CS/PVA ENMs by addition of AgNO₃ as a bactericidal agent.     

Development of oral-fluid-impervious and fracture-resistant silver–poly(methyl methacrylate) nanoformulations for intra-oral/extra-oral rehabilitation

Poly(methyl methacrylate) (PMMA) based dental prosthetic materials have an inferior transverse resistance value and a high water-retention capacity. These drawbacks cause frequent prosthesis fractures both inside and outside the mouth, which require the remaking or repair of the prosthesis. The mechanical and physical durability of the polymer matrix can be improved by the incorporation of a multifunctional filler. In this study, we focused on the reinforcing effect of silver nanoparticles (AgNPs) on the flexural properties of PMMA. Apart from that, the transport behavior of water and saliva through this composite matrix was also studied extensively. Morphological analyses with scanning electron microscopy (SEM) and atomic force microscopy imaging techniques confirmed the uniform distribution of nanoparticles in the matrix with an increased surface roughness proportionate to the amount of AgNPs. The flexural strength and modulus were enhanced by the addition of up to 5 wt % AgNPs (p < 0.05); we also observed a significant increase in the fracture resistance. The SEM micrographs of the fractured ends of AgNP-reinforced groups had smaller cracks compared to the large multidirectional cracks in the unreinforced group. The diffusion of oral fluid through the composite was investigated in detail as a function of the AgNP content, the nature of the solvent (water or saliva), and the temperature (5, 28, 37, or 60°C). The water and saliva uptake, diffusion, sorption, and permeation constants were investigated and were found to decrease with increasing AgNP loading. The transport properties could have been related to the morphology of the nanocomposites and followed the Korsmeyer–Peppas model. At high concentrations, the AgNPs formed a local filler–filler network in the polymer matrix. This network hindered the transport of water and saliva through the polymer. The outcome deduced from this study confirmed that the reinforced nanocomposites improved the durability of the denture base and could be an effective replacement for the conventional denture base. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47669.     

含银高分子膜材料的应用及研究进展

随着高分子膜材料在水处理技术、医药、食品、农业和化工领域的广泛应用,利用不同方法改进高分子膜材料的抑菌性能、抗污染性能和水通量等,以延长高分子膜材料的使用寿命,已成为近几年研究的热点。介绍了含银高分子膜材料的主要应用。分别阐述了单质银和银离子对高分子膜材料改性的不同效果。主要讨论了相转化法、共混法、原位合成法、离子交换法和界面聚合法对含银高分子膜材料的改性方法,总结了不同改性方法对高分子膜材料改性后对其抑菌性能、抗污染性能及水通量的优化情况。通过引入银能够提高高分子膜材料的抑菌率,抑菌率最高可达100%。银的加入有效地提高了膜材料的抗污染性能,其对高分子膜材料的水通量也有一定的提高。     

非金属超疏水材料的制备方法及研究进展

介绍了构造超疏水材料的基本原理,综述了近年来超疏水材料的制备方法,重点介绍了构造表面微纳米粗糙结构的方法（刻蚀法、相分离法、模板法、化学液相沉积法、溶胶凝胶法）,并讨论了不同制备方法的优缺点和应用前景。用激光辐照、等离子体刻蚀等方法处理非金属材料都能得到理想的微纳米结构;用激光刻蚀低表面自由能的聚合物材料,可以不用修饰直接得到超疏水表面;相分离法适用于制备超疏水聚合物薄膜,其优点是设备简单,成本低,适合大规模制造;利用模板压印法制备聚合物超疏水材料简单易行,利用剥离力和反模板的作用,可以形成理想的二阶微纳米粗糙结构。     

Novel 3D scaffolds of chitosan-PLLA blends for tissue engineering applications: Preparation and characterization

This work addresses the preparation of 3D porous scaffolds of blends of chitosan and poly(l-lactic acid), CHT and PLLA, using supercritical fluid technology. Supercritical assisted phase-inversion was used to prepare scaffolds for tissue engineering purposes. The physicochemical and biological properties of chitosan make it an excellent material for the preparation of drug delivery systems and for the development of new biomedical applications in many fields from skin to bone or cartilage regeneration. On the other hand, PLLA is a synthetic biodegradable polymer widely used for biomedical applications. Supercritical assisted phase-inversion experiments were carried out in samples with different polymer ratios and different polymer solution concentrations. The effect of CHT:PLLA ratio and polymer concentration and on the morphology and topography of the scaffolds was assessed by SEM and Micro-CT. Infra-red spectroscopic imaging analysis of the scaffolds allowed a better understanding on the distribution of the two polymers within the matrix. This work demonstrates that supercritical fluid technology constitutes a new processing technology, clean and environmentally friendly for the preparation of scaffolds for tissue engineering using these materials.     

Novel 3D scaffolds of chitosan–PLLA blends for tissue engineering applications: Preparation and characterization

This work addresses the preparation of 3D porous scaffolds of blends of chitosan and poly(l-lactic acid), CHT and PLLA, using supercritical fluid technology. Supercritical assisted phase-inversion was used to prepare scaffolds for tissue engineering purposes. The physicochemical and biological properties of chitosan make it an excellent material for the preparation of drug delivery systems and for the development of new biomedical applications in many fields from skin to bone or cartilage regeneration. On the other hand, PLLA is a synthetic biodegradable polymer widely used for biomedical applications. Supercritical assisted phase-inversion experiments were carried out in samples with different polymer ratios and different polymer solution concentrations. The effect of CHT:PLLA ratio and polymer concentration and on the morphology and topography of the scaffolds was assessed by SEM and Micro-CT. Infra-red spectroscopic imaging analysis of the scaffolds allowed a better understanding on the distribution of the two polymers within the matrix. This work demonstrates that supercritical fluid technology constitutes a new processing technology, clean and environmentally friendly for the preparation of scaffolds for tissue engineering using these materials.     

Polyvinyl-Pyrrolidone-Coated Silver Nanoparticles—The Colloidal,Chemical, and Biological Consequences of Steric Stabilization under Biorelevant Conditions

(1) Background: Several properties of silver nanoparticles (AgNPs), such as cytotoxic, anticancer, and antimicrobial activities, have been subjects of intense research; however, important aspects such as nanoparticle aggregation are generally neglected, although a decline in colloidal stability leads to a loss of the desired biological activities. Colloidal stability is affected by pH, ionic strength, or a plethora of biomolecules that interact with AgNPs under biorelevant conditions. (2) Methods: As only a few studies have focused on the relationship between aggregation behavior and the biological properties of AgNPs, here, we have systematically evaluated this issue by completing a thorough analysis of sterically (via polyvinyl-pyrrolidone (PVP)) stabilized AgNPs that were subjected to different circumstances. We assessed ultraviolet–visible light absorption, dynamic light scattering, zeta potential measurements, in vitro cell viability, and microdilution assays to screen both colloidal stability as well as bioactivity. (3) Results: The results revealed that although PVP provided outstanding biorelevant colloidal stability, the chemical stability of AgNPs could not be maintained completely with this capping material. (4) Conclusion: These unexpected findings led to the realization that stabilizing materials have more profound importance in association with biorelevant applications of nanomaterials than just being simple colloidal stabilizers.     

Antifungal activity of denture soft lining material modified by silver nanoparticles-a pilot study

Soft liner materials in oral cavity environments are easily colonized both by fungi and dental plaque. These factors are the cause of mucosal infections. The microorganism that most frequently colonizes soft liner materials is Candida albicans. Colonization occurs on the surface of materials and within materials. A solution to this problem might involve modification of soft liner materials with silver nanoparticles (AgNPs). In this article, we present results showing the antifungal efficacy of silicone soft lining materials modified with AgNPs. The modification process was conducted by dissolving both material components (base and catalyst) in a colloidal solution of AgNPs and evaporating the solvent. Composites with various AgNP concentrations (10, 20, 40, 80, 120 and 200 ppm) were examined. The in vitro antifungal efficacy (AFE) of composite samples was 16.3% to 52.5%.     

Electrospinning of nanofibers

Nanotechnology is the study and development of materials at nano levels. It is one of the rapidly growing scientific disciplines due to its enormous potential in creating novel materials that have advanced applications. This technology has tremendously impacted many different science and engineering disciplines, such as electronics, materials science, and polymer engineering. Nanofibers, due to their high surface area and porosity, find applications as filter medium, adsorption layers in protective clothing, etc. Electrospinning has been found to be a viable technique to produce nanofibers. An in‐depth review of research activities on the development of nanofibers, fundamental understanding of the electrospinning process, and properties of nanostructured fibrous materials and their applications is provided in this article. A detailed account on the type of fibers that have been electrospun and their characteristics is also elaborated. It is hoped that the overview article will serve as a good reference tool for nanoscience researchers in fibers, textiles, and polymer fields. Furthermore, this article will help with the planning of future research activities and better understanding of nanofiber characteristics and their applications. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 557–569, 2005     

Phyto-synthesized silver nanoparticles for biological applications

Silver nanoparticles (AgNPs) are valuable metal nanoparticles that exhibit exceptional properties compared to their bulk materials. Pronounced surface area, quantum confinement effect complemented by small particle dimension, and many other extraordinary characteristics make AgNPs suitable in a variety of applications. Different methods have been adopted to synthesize AgNPs. Biological methods can formulate AgNPs in an environmentally friendly manner without producing toxic waste. Among the biological methods, plants are simple and attractive sources for AgNP synthesis. Compared to AgNPs produced via other modes of synthesis, phyto-synthesized AgNPs, due to their safety features, have been found to be advantageous for a variety of applications, especially biological applications. Strong research efforts have investigated the utility of phyto-synthesized AgNPs for different applications. Investigators are coming up with innovative applications of phyto-synthesized AgNPs for the development of science and technology and to benefit humankind. The present article focuses on phyto-synthesized AgNPs for biological applications, with a brief review of their synthesis, mechanism, and size/shape control.