Hydrogel–silver nanoparticle composites: A new generation of antimicrobials

Design of consistant and eco‐friendly methods for the synthesis of silver nanoparticles (AgNPs) is a significant forward direction in the field of application of antibacterial bionanotechnology. One among the available options is hydrogel templates, which are highly useful to achieve this goal. This investigation involves the development of poly(acrylamide)/poly(vinyl alcohol) hydrogel–silver nanocomposites (HSNCs) to achieve AgNPs of ～2–3 nm size in gel networks. The nanocomposite synthesis process is quite convenient, direct, and very fast, and the obtained hydrogel AgNP composites can be used for antibacterial and wound dressing applications. All the nanocomposite aqueous solutions have shown absorption peaks at 420 nm in UV–visible absorption spectrum corresponding to the Plasmon absorbance of AgNPs. X‐ray diffraction spectrum of the HSNC exhibited 2θ values matching with silver nanocrystals. Transmission electron microscopy images of nanocomposites represent discrete AgNPs throughout the gel networks in the range of 2–3 nm. The developed nanocomposites were evaluated for antibacterial application on E. coli. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Development and Characterization of Highly Stable Silver NanoParticles as Novel Potential Antimicrobial Agents for Wound Healing Hydrogels

Recurrent microbial infections are a major cause of surgical failure and morbidity. Wound healing strategies based on hydrogels have been proposed to provide at once a barrier against pathogen microbial colonization, as well as a favorable environment for tissue repair. Nevertheless, most biocompatible hydrogel materials are more bacteriostatic than antimicrobial materials, and lack specific action against pathogens. Silver-loaded polymeric nanocomposites have efficient and selective activity against pathogenic organisms exploitable for wound healing. However, the loading of metallic nanostructures into hydrogels represents a major challenge due to the low stability of metal colloids in aqueous environments. In this context, the aim of the present study was the development of highly stable silver nanoparticles (AgNPs) as novel potential antimicrobial agents for hyaluronic acids hydrogels. Two candidate stabilizing agents obtained from natural and renewable sources, namely cellulose nanocrystals and ulvan polysaccharide, were exploited to ensure high stability of the silver colloid. Both stabilizing agents possess inherent bioactivity and biocompatibility, as well as the ability to stabilize metal nanostructures thanks to their supramolecular structures. Silver nitrate reduction through sodium borohydride in presence of the selected stabilizing agents was adopted as a model strategy to achieve AgNPs with narrow size distribution. Optimized AgNPs stabilized with the two investigated polysaccharides demonstrated high stability in phosphate buffer saline solution and strong antimicrobial activity. Loading of the developed AgNPs into photocrosslinked methacrylated hyaluronic acid hydrogels was also investigated for the first time as an effective strategy to develop novel antimicrobial wound dressing materials.     

Gamma irradiation synthesis and characterization of AgNP/gelatin/PVA hydrogels for antibacterial wound dressings

An antibacterial hydrogel wound dressing was successfully synthesized by the gamma irradiation method. A gelatin solution was mixed with a poly(vinyl alcohol) (PVA) solution of similar concentrations at different weight ratios of 100 : 0, 80 : 20, and 60 : 40 w/w, and irradiated at 30, 40, or 50 kGy. The testing of physical properties showed that the addition of PVA could improve both durability and mechanical integrity. The 60 : 40 hydrogels irradiated at 30 kGy were optimal, and chosen to add silver nitrate at 0.25, 0.50, 0.75, or 1.00 wt % (based on the solid content) to improve the antibacterial properties. After gamma irradiation, silver nanoparticles (AgNPs) were formed. The AgNP/gelatin/PVA hydrogels were characterized for physical properties, cytotoxicity, and antibacterial activity. The AgNP/gelatin/PVA hydrogels could be used as antibacterial wound dressings because they exhibited appropriate physical properties, noncytotoxicity, and could inhibit the growth of tested bacteria. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41138.     

Antibacterial poly(vinyl alcohol) film containing silver nanoparticles: Preparation and characterization

The importance of antibacterial materials for biomedical applications is growing nowadays. The presented article deals with the characterization of structural, mechanical and thermal properties and of antibacterial polymeric films based on polyvinyl alcohol (PVA) and silver nitrate, which can find their applicability in wound dressing components and protective coating. The methods of transmission electron microscopy, UV–vis and XRD spectroscopy, optical microscopy, differential scanning calorimetry, stress–strain analysis, and agar diffusion test were used to characterize the polymer films prepared. The results showed strong antibacterial activity against Escherichia coli and Staphylococcus aureus already at the lowest addition level of silver nitrate. An improvement of mechanical properties (Young's modulus) was also noticed due to a modification of PVA with silver nitrate up to 1 wt. % of silver content. Furthermore, the results show a strong effect of the thermal history of the sample preparation on the degree of silver‐ion reduction and formation of nanoparticles. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Physicochemical properties and antimicrobial activity of biocompatible carboxymethylcellulose‐silver nanoparticle hybrids for wound dressing and epidermal repair

Skin loss can be caused by accident, burn, trauma, chronic wounds, and diseases, which is severely aggravated by multidrug‐resistant bacterial infections. Soft hybrids based on biopolymers combined with silver nanoparticles (AgNPs) have potential applications as wound dressing supports and skin tissue repair. Thus, our study focused on the design, green synthesis, and comprehensive characterization of carboxymethyl cellulose (CMC–AgNP) nanocomposites for producing hydrogel membranes, with tunable physicochemical properties, cytocompatibility, and biocidal activity for potential application as wound dressing and skin repair. These nanocomposites were prepared using CMC with two degrees of carboxymethylation, distinct concentrations of citric acid (CA) crosslinker, and AgNPs by in situ chemical reduction, forming hybrid membranes by the solvent casting method. The results demonstrated that superabsorbent hydrogels were produced with swelling and degradation behaviors dependent on the concentration of CA crosslinker, degree of carboxymethylation of CMC, and content of AgNP in the matrices. Moreover, the Fourier transform infrared spectroscopy analysis evidenced that the CMC functional groups (e.g., ? COOH and ? OH) were directly involved in the chemical reactions for the formation of AgNPs and hydrogel crosslinking pathway. These nanocomposites were cytocompatible using in vitro 3‐(4,5‐dimethyl‐2‐thiazolyl)‐2,5‐diphenyltetrazolium bromide cell viability assay with of human embryonic kidney cells. Conclusively, the CMC–AgNP nanohybrids demonstrated to be simultaneously non‐toxic combined with highly effective antibacterial activity against gram‐positive multi‐resistant wound/skin pathogens (Staphylococcus aureus) and moderate effect towards gram‐negative strains (Escherichia coli and Pseudomonas aeruginosa). © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45812.     

Synthesis and characterization of hydrogel‐silver nanoparticle‐curcumin composites for wound dressing and antibacterial application

Hydrogel silver nanocomposites are found to be excellent materials for antibacterial applications. To enhance their applicability novel hydrogel‐silver nanoparticle‐curcumin composites have been developed. For developing, these composites, the hydrogel matrices are synthesized first by polymerizing acrylamide in the presence of poly(vinyl sulfonic acid sodium salt) and a trifunctional crosslinker (2,4,6‐triallyloxy 1,3,5‐triazine, TA) using redox initiating system (ammonium persulphate/TMEDA). Silver nanoparticles are generated throughout the hydrogel networks using in situ method by incorporating the silver ions and subsequent reduction with sodium borohydride. Curcumin loading into hydrogel‐silver nanoparticles composite is achieved by diffusion mechanism. A series of hydrogel‐silver nanoparticle‐curcumin composites are developed and are characterized by using Fourier transform infrared (FTIR) and UV–visible (UV–vis) spectroscopy, X‐ray diffraction, thermal analyses, as well as scanning and transmission electron microscopic (SEM/TEM) methods. An interesting arrangement of silver nanoparticles i.e., a shining sun shape (ball) (～ 5 nm) with apparent smaller grown nanoparticles (～ 1 nm) is observed by TEM. The curcumin loading and release characteristics are performed for various hydrogel composite systems. A comparative antimicrobial study is performed for hydrogel‐silver nanocomposites and hydrogel‐silver nanoparticle‐curcumin composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Facile Deposition of Silver Nanoparticles on Photonic Cellulose Nanocrystals Films: A Study on Solvent Stability and Post Antibacterial Activity

Cellulose nanocrystals (CNCs) incorporated with silver nanoparticles (AgNPs) photonic films have drawn considerable attention due to their plasmonic chiroptical activity. However, the exploitation of some fundamental properties for practical use such as the affinity analysis of metal nanoparticles attached to the surface of photonic films according to the solvent compatibility and antibacterial activity under physical conditions has yet not been studied. Hence, a facile process of in situ deposition of AgNPs into the chiral structure of CNC films is proposed. CNC photonic films, cross-linked by glutaraldehyde are prepared. This interaction generated the solvents-stable photonic film with a considerable amount of unreacted aldehyde functional groups that facilitates the reduction of Ag salt to AgNPs. The formed AgNPs in the photonic films show excellent stability over immersion in various polar and non-polar solvents. The post-solvent treated photonic films display excellent contact-based antibacterial behavior against gram-negative Escherichia coli.     

Optomechanical Processing of Silver Colloids: New Generation of Nanoparticle–Polymer Composites with Bactericidal Effect

The properties of materials at the nanoscale open up new methodologies for engineering prospective materials usable in high-end applications. The preparation of composite materials with a high content of an active component on their surface is one of the current challenges of materials engineering. This concept significantly increases the efficiency of heterogeneous processes moderated by the active component, typically in biological applications, catalysis, or drug delivery. Here we introduce a general approach, based on laser-induced optomechanical processing of silver colloids, for the preparation of polymer surfaces highly enriched with silver nanoparticles (AgNPs). As a result, the AgNPs are firmly immobilized in a thin surface layer without the use of any other chemical mediators. We have shown that our approach is applicable to a broad spectrum of polymer foils, regardless of whether they absorb laser light or not. However, if the laser radiation is absorbed, it is possible to transform smooth surface morphology of the polymer into a roughened one with a higher specific surface area. Analyses of the release of silver from the polymer surface together with antibacterial tests suggested that these materials could be suitable candidates in the fight against nosocomial infections and could inhibit the formation of biofilms with a long-term effect.     

In vitro and in vivo investigational studies of a nanocomposite‐hydrogel‐based dressing with a silver‐coated chitosan wafer for full‐thickness skin wounds

A nanocomposite reservoir‐type hydrogel dressing of poly vinyl alcohol (PVA) was fabricated by a freeze–thaw method and loaded with silver‐nanoparticle‐coated chitosan wafers (Ag–CHWs). The Ag–CHWs were synthesized by a sonication technique with silver nitrate (AgNO₃) and chitosan powder. Scanning electron microscopy images showed silver nanoparticles (AgNPs) with a size range of 10 ± 4 nm on the surface of the chitosan wafers, and the antibacterial efficacy (minimum inhibitory concentration) of the Ag–CHWs was measured against Pseudomonas aeruginosa (32 µg/mL), Staphylococcus aureus, (30 µg/mL) and Escherichia coli (32 µg/mL). The antimicrobial PVA hydrogel showed an improved tensile strength (～0.28 MPa) and gel content (～92%) in comparison with the blank hydrogels. Full‐thickness‐excision wound studies of the nanocomposite dressing on Wistar rats revealed enhanced wound contraction, improved inflammation response, re‐epithelization rate, neoangiogenesis, and granulation tissue formation in comparison to the control group. A flexible, biocompatible, nanocomposite reservoir dressing not only established the chitosan as a stabilizer but also proved the efficacious and safe utility of AgNPs toward chronic wound management. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43472.     

Rational Design of Ag/ZnO Hybrid Nanoparticles on Sericin/Agarose Composite Film for Enhanced Antimicrobial Applications

Silver-based hybrid nanomaterials are receiving increasing attention as potential alternatives for traditional antimicrobial agents. Here, we proposed a simple and eco-friendly strategy to efficiently assemble zinc oxide nanoparticles (ZnO) and silver nanoparticles (AgNPs) on sericin-agarose composite film to impart superior antimicrobial activity. Based on a layer-by-layer self-assembly strategy, AgNPs and ZnO were immobilized on sericin-agarose films using the adhesion property of polydopamine. Scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray powder diffraction spectroscopy were used to show the morphology of AgNPs and ZnO on the surface of the composite film and analyze the composition and structure of AgNPs and ZnO, respectively. Water contact angle, swelling ratio, and mechanical property were determined to characterize the hydrophilicity, water absorption ability, and mechanical properties of the composite films. In addition, the antibacterial activity of the composite film was evaluated against Gram-positive and Gram-negative bacteria. The results showed that the composite film not only has desirable hydrophilicity, high water absorption ability, and favorable mechanical properties but also exhibits excellent antimicrobial activity against both Gram-positive and Gram-negative bacteria. It has shown great potential as a novel antimicrobial biomaterial for wound dressing, artificial skin, and tissue engineering.     

利用二醛木聚糖一锅法制备纳米银抗菌水凝胶

利用二醛木聚糖(DAX)可与羧甲基壳聚糖(CMCS)以及银氨溶液同时反应的特性,即DAX的醛基与CMCS的氨基发生席夫碱反应形成亚胺键,同时,DAX含有的大量醛基与银氨溶液发生银镜反应,在室温条件下很快地还原出银纳米粒子(SNPs),一锅法制备出了具有优异抗菌性能的羧甲基壳聚糖-纳米银抗菌水凝胶。加入生物相容性良好的聚乙烯醇(PVA)并通过冻融法形成了与CMCS互穿的双网络结构,进一步提高了水凝胶的结构稳定性。采用FTIR、热重、TEM、XRD和SEM对DAX,SNPs和水凝胶的形貌、结构进行了表征。结果表明DAX在整个反应中起到了十分有效的双功能作用,成功的与CMCS和PVA发生反应,共同构成了双网络结构的水凝胶,从而提高了水凝胶的力学性能。同时,DAX将银氨溶液中的SNPs还原出来,且粒径在20-80 nm之间,具有较好的分散性,从而显著提高了水凝胶的抗菌性。本文中所制备的水凝胶具有伤口敷料方面的应用潜力。     

Hydrogels containing silver nanoparticles for burn wounds show antimicrobial activity without cytotoxicity

This research introduces a novel dressing for burn wounds, containing silver nanoparticles in hydrogels for infected burn care. The 2‐acrylamido‐2‐methylpropane sulfonic acid sodium salt hydrogels containing silver nanoparticles have been prepared via ultraviolet radiation. The formation of silver nanoparticles was monitored by surface plasmon bands and transmission electron microscopy. The concentration of silver nitrate loaded in the solutions slightly affected the physical properties and mechanical properties of the neat hydrogel. An indirect cytotoxicity study found that none of the hydrogels were toxic to tested cell lines. The measurement of cumulative release of silver indicated that 70%–82% of silver was released within 72 hr. The antibacterial activities of the hydrogels against common burn pathogens were studied and the results showed that 5 mM silver hydrogel had the greatest inhibitory activity. The results support its use as a potential burn wound dressing. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40215.     

Complexes of Silver(I) Ions and Silver Phosphate Nanoparticles with Hyaluronic Acid and/or Chitosan as Promising Antimicrobial Agents for Vascular Grafts

Polymers are currently widely used to replace a variety of natural materials with respect to their favourable physical and chemical properties, and due to their economic advantage. One of the most important branches of application of polymers is the production of different products for medical use. In this case, it is necessary to face a significant disadvantage of polymer products due to possible and very common colonization of the surface by various microorganisms that can pose a potential danger to the patient. One of the possible solutions is to prepare polymer with antibacterial/antimicrobial properties that is resistant to bacterial colonization. The aim of this study was to contribute to the development of antimicrobial polymeric material ideal for covering vascular implants with subsequent use in transplant surgery. Therefore, the complexes of polymeric substances (hyaluronic acid and chitosan) with silver nitrate or silver phosphate nanoparticles were created, and their effects on gram-positive bacterial culture of Staphylococcus aureus were monitored. Stages of formation of complexes of silver nitrate and silver phosphate nanoparticles with polymeric compounds were characterized using electrochemical and spectrophotometric methods. Furthermore, the antimicrobial activity of complexes was determined using the methods of determination of growth curves and zones of inhibition. The results of this study revealed that the complex of chitosan, with silver phosphate nanoparticles, was the most suitable in order to have an antibacterial effect on bacterial culture of Staphylococcus aureus. Formation of this complex was under way at low concentrations of chitosan. The results of electrochemical determination corresponded with the results of spectrophotometric methods and verified good interaction and formation of the complex. The complex has an outstanding antibacterial effect and this effect was of several orders higher compared to other investigated complexes.     

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.     

Radiation synthesis and characterization of poly(vinyl alcohol)/poly(N-vinyl-2-pyrrolidone) based hydrogels containing silver nanoparticles

A series of PVA/PVP based hydrogels at different compositions were prepared by gamma irradiation. The gel fraction degree of swelling were investigated. Highly stable and uniformly distributed silver nanoparticles have been obtained onto hydrogel networks. The morphology and structure of (PVA/PVP) hydrogel and dispersion of the silver nanoparticles in the polymeric matrix were examined by scanning electron microscopy (SEM) and infrared spectroscopy (FT-IR), respectively. The formation of silver nanoparticles has been confirmed by ultraviolet visible (UV–vis) spectroscopy. A strong characteristic absorption peak was found to be around 420 nm for the silver nanoparticles in the hydrogel nanocomposite. The X-ray diffraction pattern confirmed the formation of silver nanoparticles with average particle size of 12 nm. The diameter distribution of silver nanoparticles was determined by dynamic light scattering DLS. Transmission electron microscope (TEM) showed almost spherical and uniform distribution of silver nanoparticles through the hydrogel network and the mean size of silver nanoparticles ranging is 23 nm. The good swelling properties and antibacterial of PVA/PVP-Ag hydrogel suggest that it can be a good candidate as wound dressing.     

Construction of chitosan-carboxymethyl β-cyclodextrin silver nanocomposite hydrogel to improve antibacterial activity

Silver nanoparticles (AgNPs) are widely used in various fields but their physical and chemical instability have limited their applications. The present work demonstrates a novel approach for the synthesis and stabilising of AgNPs. Chitosan and carboxymethyl β-cyclodextrin were used to prepare a polymeric hydrogel with glutaraldehyde as cross-linker. As a result, AgNPs were formed with very high dispersion and stability in the hydrogel structure. It is possible to create nanoreactors to produce AgNPs by adding CM-βCD to the structure of the hydrogel. Fourier transform infrared (FTIR) analysis was employed to characterise the Cs-CM-βCD hydrogel. The morphologies of pure Cs-CM-βCD hydrogel and silver nanocomposite were observed by scanning electron microscopy. Moreover, UV–VIS spectroscopy and X-ray diffraction were used to characterise the prepared silver nanocomposite. In addition, the antibacterial properties of these silver nanocomposite hydrogels were investigated against Staphylococcus aureus (Gram positive) and Escherichia coli (Gram negative).     

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.     

Advances in Nanotechnology towards Development of Silver Nanoparticle-Based Wound-Healing Agents

Since antiquity, silver-based therapies have been used in wound healing, wound care and management of infections to provide adequate healing. These therapies are associated with certain limitations, such as toxicity, skin discolouration and bacterial resistance, which have limited their use. As a result, new and innovative wound therapies, or strategies to improve the existing therapies, are sought after. Silver nanoparticles (AgNPs) have shown the potential to circumvent the limitations associated with conventional silver-based therapies as described above. AgNPs are effective against a broad spectrum of microorganisms and are less toxic, effective at lower concentrations and produce no skin discolouration. Furthermore, AgNPs can be decorated or coupled with other healing-promoting materials to provide optimum healing. This review details the history and impact of silver-based therapies leading up to AgNPs and AgNP-based nanoformulations in wound healing. It also highlights the properties of AgNPs that aid in wound healing and that make them superior to conventional silver-based wound treatment therapies.     

海藻酸钙海绵及其载银后的性能研究

采用机械搅拌发泡,内源凝胶法,制备了多孔海藻酸钙海绵及负载纳米银海藻酸钙海绵。实验结果如下：乙醇处理湿凝胶可加速干燥过程,保留海绵孔道结构;乙醇-甘油水溶液后处理,可获得具有一定柔韧性的海藻酸钙海绵;海绵经AgNO₃溶液浸渍,乙醇-甘油水溶液处理,80 ℃干燥,可得到载纳米银海藻酸钙海绵;改变乙醇-甘油水溶液含量,可调节海绵的吸液率、保液率和力学性能;载纳米银海藻酸钙海绵对金黄色葡萄球菌和大肠杆菌均具有良好的抑菌性能。     

基于植物质还原的银纳米颗粒的制备及在织物抗菌整理上的应用

纳米银是以纳米技术为基础研制而成的新型抗菌产品,由于量子效应和尺寸效应具有普通银系抗菌剂无法比拟的抗菌效果。本研究以黄芩、丁香、洋浦桃、芳樟4种植物质提取液制备银纳米颗粒,并借助于UV-Vis、TEM以及XRD对产物进行表征,结果表明增加植物质提取液浓度或增大NaOH加入量,均有利于制得粒径较小的银纳米颗粒。SEM图片表明采用浸渍法可将所得纳米银颗粒负载于纯棉织物上,通过考察浸渍时间、温度、浴比对织物上载银量的影响,确定较优的浸渍条件为时间30 h,温度55℃,浴比为1:25。分别考察了银纳米颗粒粒径和植物质种类对所得载银织物抗菌性能的影响,发现负载到织物上的纳米银粒径越小,织物抑菌效果越好;利用本身具有抑菌效果的黄芩、丁香来制备银纳米颗粒,有利于增强所得载银织物的整体抗菌性能;4种植物质中以黄芩制得的载银织物抗菌效果最优,对金黄色葡萄球菌、大肠杆菌等实验菌株均有强烈的抑制作用。