The application of different Stevia rebaudiana leaf extracts in the “green synthesis” of AgNPs

ABSTRACT

The present work reports a method for green synthesis of silver nanoparticles (AgNPs) by reducing Ag ions from silver nitrate solution using alcoholic, aqueous and alcoholic-aqueous Stevia rebaudiana extracts. Depending on a particular extract different sizes of AgNPs could be observed – 40?nm in aqueous and aqueous-alcoholic extracts and significantly bigger 170?nm in case of alcoholic extract. Synthesis of AgNPs was analyzed within spectra range of 300–700?nm. The performed research provided information that aqueous and aqueous-alcoholic extracts are excellent sources for synthesis of AgNPs; however AgNPs were unstable in the case of alcoholic extract. The aqueous-alcoholic extract showed the best properties during studies. Antioxidant potential, antimicrobial properties and cytotoxicity were determined. The 2,2-diphenyl-1-(2,4,6-triphenyl-hydrazyl) method showed that antioxidant activity of an extract containing AgNPs was higher compared to Stevia extract alone. Bacterial inhibition studies had shown substantial antibacterial properties of AgNPs, which was much higher than Stevia extract alone and silver nitrate.     

Uniformly Dispersed and Controllable Ligand‐Free Silver‐Nanoparticle‐Decorated TiO2 Nanotube Arrays with Enhanced Photoelectrochemical Behaviors

Homogeneously dispersed silver nanoparticles (AgNPs) were successfully decorated onto the surface of TiO₂ nanotube arrays (TNTA) by means of an in situ photoreduction method. TNTA films as supports exhibit excellent properties to prevent agglomeration of AgNPs, and they also avoid using polymer ligands, which is deleterious to enhancing the properties of the fabricated NPs. The silver particle size and its content could be controlled just by changing the immersion time. Detailed SEM and TEM analyses combined with energy‐dispersive X‐ray spectroscopy analyses with different immersion times (5, 10, 30, 60 min) have revealed the variation tendency. The prepared Ag/TNTA composite films were also characterized by XRD, X‐ray photoelectron spectroscopy, and high‐resolution TEM. The UV/Vis diffuse reflectance spectra displayed a redshift of the absorption peak with the growth of AgNPs. The photocurrent response and the photoelectrocatalytic degradation of methyl orange (MO) were used to evaluate the photoelectrochemical properties of the fabricated samples. The results showed that the photocurrent response and photoelectrocatalytic activity largely depended on the loaded Ag particle size and content. TNTA films with a diameter of 17.92 nm and silver content of 1.15 at % showed the highest photocurrent response and degradation rate of MO. The enhanced properties could be attributed to the synergistic effect between AgNPs and TiO₂. To make good use of this effect, particle size and silver content should be well controlled to develop the electron charge and discharge process during the photoelectrical process. Neither smaller nor larger AgNPs caused decreased photoelectrical properties.     

Biosynthesis optimization of silver nanoparticles (AgNPs) using Trichoderma longibranchiatum and biosafety assessment with silkworm (Bombyx mori)

Silver nanoparticles (AgNPs) have raised public concern due to their widespread application in the field of agriculture, medicine, and environment and their potential toxic effects on humans and the environments. In this study, biosynthesis of nanosilver particles mediated by Trichoderma longibranchiatum using orthogonal experimental design (OED) was optimized. Silkworm larvae were exposed via the mulberry leaves to AgNPs to evaluate their toxic effects. The results showed that 2 mmol/L silver nitrate and 55 °C of reaction temperature at pH 7.0 for 24 h were the optimum values for AgNPs biosynthesis with the synthesis amount and antifungal activity of AgNPs as the indices. The characterization of the biosynthesized AgNPs was conducted using electron microscopy, energy dispersive X-ray analysis (EDS), UV/visible spectrophotometry, Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD). The crystalline structured nanoparticles were spherical or polyhedral with a mean size ranging about 5–50 nm. FTIR showed that many functional group moieties (–OH, –CH₃, –C–O, etc.) involved as a capping and reducing agent in AgNPs biosynthesis. After the larvae were fed with 50 mg/mL AgNPs, there were no obvious adverse effects on the growth of larvae and cocoon quality. Further supplement of AgNPs-B could promote the weight of larvae and the cocoon shell ratio. The data presented herein provided valuable information on a reliable eco-friendly, simple, low-cost biosynthesis of AgNPs and its biosafety evaluation which may contribute to its increased application in the future.     

Differentiation and characterization of isotopically modified silver nanoparticles in aqueous media using asymmetric-flow field flow fractionation coupled to optical detection and mass spectrometry

The principal objective of this work was to develop and demonstrate a new methodology for silver nanoparticle (AgNP) detection and characterization based on asymmetric-flow field flow fractionation (A4F) coupled on-line to multiple detectors and using stable isotopes of Ag. This analytical approach opens the door to address many relevant scientific challenges concerning the transport and fate of nanomaterials in natural systems. We show that A4F must be optimized in order to effectively fractionate AgNPs and larger colloidal Ag particles. With the optimized method one can accurately determine the size, stability and optical properties of AgNPs and their agglomerates under variable conditions. In this investigation, we couple A4F to optical absorbance (UV–vis spectrometer) and scattering detectors (static and dynamic) and to an inductively coupled plasma mass spectrometer. With this combination of detection modes it is possible to determine the mass isotopic signature of AgNPs as a function of their size and optical properties, providing specificity necessary for tracing and differentiating labeled AgNPs from their naturally occurring or anthropogenic analogs. The methodology was then applied to standard estuarine sediment by doping the suspension with a known quantity of isotopically enriched ¹⁰⁹AgNPs stabilized by natural organic matter (standard humic and fulvic acids). The mass signature of the isotopically enriched AgNPs was recorded as a function of the measured particle size. We observed that AgNPs interact with different particulate components of the sediment, and also self-associate to form agglomerates in this model estuarine system. This work should have substantial ramifications for research concerning the environmental and biological fate of AgNPs.     

Measuring silver nanoparticle dissolution in complex biological and environmental matrices using UV-visible absorbance

Distinguishing the toxic effects of nanoparticles (NPs) themselves from the well-studied toxic effects of their ions is a critical but challenging measurement for nanotoxicity studies and regulation. This measurement is especially difficult for silver NPs (AgNPs) because in many relevant biological and environmental solutions, dissolved silver forms AgCl NPs or microparticles. Simulations predict that solid AgCl particles form at silver concentrations greater than 0.18 and 0.58 μg/mL in cell culture media and moderately hard reconstituted water (MHRW), respectively. The AgCl NPs are usually not easily separable from AgNPs. Therefore, common existing total silver techniques applied to measure AgNP dissolution, such as inductively coupled plasma mass spectrometry (ICP-MS) or atomic absorption, cannot accurately measure the amount of silver remaining in AgNP form, as they cannot distinguish Ag oxidation states. In this work, we introduce a simple localized surface plasmon resonance (LSPR) UV–visible absorbance measurement as a technique to measure the amount of silver remaining in AgNP form for AgNPs with constant agglomeration states. Unlike other existing methods, this absorbance method can be used to measure the amount of silver remaining in AgNP form even in biological and environmental solutions containing chloride because AgCl NPs do not have an associated LSPR absorbance. In addition, no separation step is required to measure the dissolution of the AgNPs. After using ICP-MS to show that the area under the absorbance curve is an accurate measure of silver in AgNP state for unagglomerating AgNPs in non-chloride-containing media, the absorbance is used to measure dissolution rates of AgNPs with different polymer coatings in biological and environmental solutions. We find that the dissolution rate decreases at high AgNP concentrations, 5 kDa polyethylene glycol thiol coatings increase the dissolution rate, and the rate is much higher in cell culture media than in MHRW.     

Silver nanoparticle-treated filter paper as a highly sensitive surface-enhanced Raman scattering (SERS) substrate for detection of tyrosine in aqueous solution

Highly sensitive SERS substrates based on deposition of silver nanoparticles on commercially available filter paper were prepared in this work, and used to overcome problems found in analyses of aqueous samples. To prepare silver nanoparticle- (AgNP) doped filter substrates, a silver mirror reaction was used. The procedures for substrate preparation were systematically optimized. Pretreatment of filter paper, reaction time, temperature, and concentration of reagents for silver mirror reactions were studied. The morphologies of the resulting substrates were characterized by field-emission scanning electron microscopy (FE-SEM) and correlated with the SERS signals by probing with p-nitrothiophenol (pNTP). Filter papers with different pretreatments were found to have different sizes and distributions of AgNPs. The best performance was found when filter paper was pre-treated with ammonia solution before growth of AgNPs. Based on the SEM images, the resulting AgNPs had roughly spherical shape with a high degree of uniformity. The silver-coated filter paper substrates provide much higher SERS signals compared to glass substrates and the reproducibility was improved significantly. Based on statistical analyses, the relative standard deviations for substrate-to-substrate and spot-to-spot were both were less than 8% and the enhancement factors for the substrates were, in general, higher than 107. The SERS substrates were used to selectively detect tyrosine in aqueous solution. Results indicate that filter-based SERS substrates are highly suited to detection of tyrosine. Compared to glass-based SERS substrates, 50 times more SERS signal was observed in detection of tyrosine. The linear range can be up to 100 μM with a detection limit of 625 nM (SN(-1)=3).     

Green synthesis and swelling behavior of Ag-nanocomposite semi-IPN hydrogels and their drug delivery using Dolichos biflorus Linn

Acrylic-based hydrogels with great potentials for usage in medical area were principally synthesized as per two strategies. The first involved reaction containing silver nitrate to yield silver nanoparticles (AgNPs) where Dolichos biflorus Linn acted as both reducing agent and stabilizing for green synthesized AgNPs was added to the reaction medium to establish reduction of Ag+ to AgNPs. The second strategy entailed preparation of nanosilver composite hydrogel that is carried out by free radical polymerization reaction in presence of Sodium Alginate and acrylamide (AAm) under the same conditions. In both strategies, factors affecting the characterization of AgNPs-loaded hydrogels were studied. Analysis and characterization of the so obtained hydrogels were performed through monitoring swelling behavior, FTIR spectroscopy, SEM, EDX, UV–Vis spectrophotometer, XRD, and TEM. Results indicate that modifying AAm and silver ion can improve swelling properties of the resultant nanocomposite hydrogel. pH response of this nanocomposite hydrogel in different pH made it suitable for drug delivery applications.     

A simple and sensitive assay of gallic acid based on localized surface plasmon resonance light scattering of silver nanoparticles through modified Tollens process

A simple, low toxic, sensitive strategy based on the localized surface plasmon resonance light scattering (LSPR-LS) properties of silver nanoparticles (AgNPs) is introduced for the detection of gallic acid (GA). It was found that the silver ammonium complex, [Ag(NH(3))(2)](+)(aq), could be reduced in the alkaline medium by GA at room temperature; this reaction formed dispersed AgNPs. Transmission electron microscopy analyses were performed to ascertain the formation of AgNPs. UV-visible spectra revealed the localized surface plasmon resonance (LSPR) absorption at 410 nm corresponding to the LSPR of AgNPs. On these basis, we could quantify the GA concentration in the range of 4 × 10(-7) - 5 × 10(-6) mol L(-1) in the optimized experimental conditions. This method was used for determining the concentration of GA in artificial samples with satisfactory results. The detailed mechanism underlying this special phenomenon was elucidated.     

Structure and Properties of Electrochemically Synthesized Silver Nanoparticles in Aqueous Solution by High-Resolution Techniques

The aim of this work was to deeply investigate the structure and properties of electrochemically synthesized silver nanoparticles (AgNPs) through high-resolution techniques such as transmission electron microscopy (TEM), scanning electron microscopy (SEM), Zeta Potential measurements, and matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF-MS). Strong brightness, tendency to generate nanoclusters containing an odd number of atoms, and absence of the free silver ions in solution were observed. The research also highlighted that the chemical and physical properties of the AgNPs seemed to be related to their peculiar oxidative state as suggested by X-ray photoelectron spectroscopy (XPS) and X-ray powder diffraction (XRPD) analyses. Finally, the MTT assay tested the low cytotoxicity of the investigated AgNPs.     

In situ generation of silver nanoparticles in cellulose matrix using Azadirachta indica leaf extract as a reducing agent

In the present work, silver nanoparticles (AgNPs) were in situ generated in cellulose matrix using leaf extract of Azadirachta indica as a reducing agent. The cellulose/AgNP composite films prepared were characterized by FTIR, X-ray diffraction (XRD), scanning electron microscope, and antibacterial tests. The infrared spectra indicated the association of organic materials with silver nanoparticles to serve as capping agents. Scanning electron micrographs showed that synthesized silver nanoparticles were nearly uniform and spherical in shape with diameter in the range of 61–110?nm. XRD confirmed the formation of AgNPs and Ag–O nanoparticles. The nanocomposite films showed good antibacterial activity against Escherichia coli bacteria.     

载银离子PLGA-PEG-PLGA温度敏感水凝胶的制备及体外抗菌性能

利用聚乙二醇(PEG 1000)引发乙交酯和 D,L-丙交酯开环共聚合, 制备了聚丙交酯乙交酯(PLGA)三嵌段共聚物(PLGA-PEG-PLGA)温敏水凝胶材料; 利用核磁共振氢谱( ¹H NMR)确定了产物的结构及组成. 通过还原硝酸银的方法制备银纳米粒子(AgNPs), 并将其与PLGA-PEG-PLGA三嵌段共聚物水凝胶混合, 制得新型AgNPs/PLGA-PEG-PLGA复合水凝胶; 对该复合水凝胶的相关性能进行了表征. AgNPs/PLGA-PEG-PLGA复合水凝胶仍然具有温敏性能, 随着温度升高可发生溶胶-凝胶的相转变; 还可以持续释放银纳米粒子, 从而发挥抗菌性能. 体外细胞实验结果表明, AgNPs/PLGA-PEG-PLGA复合水凝胶具有良好的生物相容性, 未见明显细胞毒性, 是具有应用前景的新型复合水凝胶.     

Structure and properties of biodegradable carboxymethyl cellulose films containing silver nanoparticles

Silver nanoparticles stabilized in a solution of sodium carboxymethyl cellulose with a degree of substitution of 0.85 and a degree of polymerization of 600 have been synthesized. The structuring; physical, chemical, and mechanical properties; and antimicrobial activities of films prepared from sodium carboxymethyl cellulose solutions containing silver nanoparticles have been studied. The shapes, quantities, and sizes of the silver nanoparticles occurring in the sodium carboxymethyl cellulose films were determined with the use of transmission electron microscopy, atomic force microscopy, and UV spectroscopy. It was found that an increase in the concentration of silver nitrate in sodium carboxymethyl cellulose solutions, as well as photoirradiation of the films, leads to the changes in the sizes and shapes of silver nanoparticles. The shapes, sizes, and quantities of silver nanoparticles determine their biological activity. An increase in the quantity of 5- to 25-nm silver nanoparticles was found to enhance the microbicidal activities of the carboxymethyl cellulose films.     

Ficus carica Latex-Mediated Synthesis of Silver Nanoparticles and Its Application as a Chemophotoprotective Agent

The present work provides scientific support on the use of latex of Ficus carica to synthesize stable silver nanoparticles (AgNPs). AgNPs synthesized immediately after the addition of latex to silver nitrate solution at room temperature. Synthesized nanoparticles were of spherical shape with average size of 163.7 nm. Fourier transform infrared spectroscopy analysis revealed capping of proteins and phenolic compound on AgNPs, while X-ray diffraction analysis confirmed the fcc nature of AgNPs. Particles formed were stable for a long time (6 months). It was found that incorporation of AgNPs with 2 and 4 % concentration exhibits synergistic increase in sun protection factor of commercial sunscreen and natural extracts ranging from 01 to 12,175 % than control. Further characterization of latex and AgNPs revealed total phenolic content of 98.75 and 94.88 μg/ml. The ferric ion reduction potentials of latex and AgNPs were 79.69 and 18.79 %. Reduction potential of ascorbic acid was synergistically increased after cumulative preparation of ascorbic acid with latex and AgNPs and found to be 106.76 and 101.50 % for ascorbic acid + latex and ascorbic acid + AgNPs, respectively.     

Antioxidant and antibacterial activity of silver nanoparticles biosynthesized using Chenopodium murale leaf extract

Silver is known for its antimicrobial effects and silver nanoparticles are gaining their importance due to their antimicrobial activities. The aims of the current study were to use plant extract for the biosynthesis of silver nanoparticles and to evaluate their antibacterial and antioxidant activity in vitro. The results indicated that silver nanoparticles (AgNPs) can be synthesized in a simple method using Chenopodium murale leaf extract. The TEM analysis showed that the sizes of the synthesized AgNps ranged from 30 to 50 nm. The essential oil of C. murale leaf extract was formed mainly of α-Terpinene, (Z)-Ascaridole and cis-Ascaridole. The total phenolic compounds and total flavonides were higher in AgNPs-containing plant extract compared to the plant extract. AgNPs-containing leaf extract showed a higher antioxidant and antimicrobial activity compared to C. murale leaf extract alone or silver nitrate. It could be concluded that C. murale leaf extract can be used effectively in the production of potential antioxidant and antimicrobial AgNPs for commercial application.     

可控纳米银胶体的稳定性研究

纳米银胶体(AgNPs)长期储存不稳定性问题是本研究的中心,着重考察了不同前驱体对纳米银胶体的稳定性影响.分别以银氨([Ag(NH₃)₂]OH)溶液和AgNO₃溶液为前驱体制备了多份纳米银胶体样品并通过UV-Vis、FE-SEM、EDS、ZETA电位仪等现代分析测试手段研究了纳米银胶的形貌、粒径大小以及稳定性.对比分析发现,以[Ag(NH₃)₂]OH溶液为前驱体,制备的纳米银胶体具有粒径可控,尺寸均一,分散性良好等特点;而且经过一个月的常温储存,表现出比用AgNO₃溶液为前驱体制备的纳米银胶体具有更高的储存稳定性.     

Silver nanoparticles formed in bio- and chemical syntheses with biosurfactant as the stabilizing agent

In this work, the comparison of the physical properties of silver nanoparticles (AgNPs) obtained via the reduction of silver nitrate (AgNO₃) in biological and chemical (model) syntheses supplemented with the biosurfactant surfactin is described. In the studies, two strains of Bacillus subtilis (denoted T’1 and I’1a) were used. The biological synthesis of AgNPs was performed using supernatants obtained from cultures of bacteria growing on brewery effluents, molasses, and Luria–Bretani (LB) medium. In model experiments, ascorbic acid served as the reductant; surfactin acted as the stabilizing agent. The surfactin concentrations were adjusted to 5 and 30?mg/L, which corresponded to minimum and maximum surfactin concentrations as measured in the supernatants obtained from the B. subtilis cultures. The chemical synthesis was carried out at acidic as well as alkaline pH. Dynamic light scattering (DLS) revealed that in model and biological samples, single AgNPs were accompanied by aggregated structures. Transmission electron microscopy showed that the contribution of the aggregates in bacterial supernatants and in chemical synthesis is negligible under acidic conditions. However, in the alkaline environment, this contribution predominates. In the model experiments, smaller nanoparticles were formed with higher concentrations of surfactant. The presence of surfactin significantly increased the stability of AgNPs in both bio- and chemical syntheses.     

Antibacterial and biocompatible surfaces based on dopamine autooxidized silver nanoparticles

A facile and green method is proposed to immobilize silver nanoparticles (AgNPs) showing antibacterial and biocompatible properties on surfaces of substrates. The adhesive and reductive polydopamine (Pdop) coating was applied on the substrates such as polyethylene, glass, poly(methyl methacrylate), and poly(lactic-co-glycolic acid) by simply dipping into dopamine solutions. AgNPs of 50–70 nm formed uniformly on the Pdop-coated surfaces after immersing in silver nitrate solution where the density of AgNPs was modulated by Pdop immobilization time. Antibacterial efficacy, lactate dehydrogenase assay, and cell morphology observed by microscopy indicated that the as-prepared AgNPs deposited on Pdop/substrates possessed effective biocidal properties and did not inhibit the growth of L-929 cells mouse fibroblasts. The proposed method can be easily applied on different substrates and revealed good biocompatibility, which could be further developed for applications in biomaterials. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Synthesis and spectroscopic studies of stable aqueous dispersion of silver nanoparticles

A facile approach for the synthesis of stable aqueous dispersion of silver nanoparticles (AgNPs) using glucose as the reducing agent in water/micelles system, in which cetyltrimethylammonium bromide (CTAB) was used as capping agent (stabilizer) is described. The evolution of plasmon band of AgNPs was monitored under different conditions such as (a) concentration of sodium hydroxide, (b) concentration of glucose, (c) concentration of silver nitrate (d) concentration of CTAB, and (e) reaction time. AgNPs were characterized by UV-visible spectroscopy, transmission electron microscopy (TEM), fluorescence spectroscopy and FT-IR spectroscopy. The results revealed an easy and viable strategy for obtaining stable aqueous dispersion of AgNPs with well controlled shape and size below 30 nm in diameter.     

Sodium 1‐Naphthalenesulfonate‐Functionalized Reduced Graphene Oxide Stabilizes Silver Nanoparticles with Lower Cytotoxicity and Long‐Term Antibacterial Activity

Silver nanoparticles (AgNPs) are increasingly used in daily life for their antibacterial properties, but their low stability and high cytotoxicity hamper practical applications. In this work, sodium 1‐naphthalenesulfonate‐functionalized reduced graphene oxide (NA‐rGO) was used as a substrate for AgNPs to produce a AgNP‐NA‐rGO hybrid. This hybrid showed substantially higher antibacterial activity than polyvinyl pyrrolidone(PVP)‐stabilized AgNPs, and the AgNPs on NA‐rGO were more stable than the AgNPs on PVP, resulting in long‐term antibacterial effects. More importantly, this hybrid showed excellent water solubility and low cytotoxicity, suggesting the great potential application as sprayable reduced graphene oxide based antibacterial solutions.     

Green synthesis of silver nanoparticles by using eugenol and evaluation of antimicrobial potential

The importance of green synthesis was revealed with advantages such as: eliminating the use of expensive chemicals; consume less energy; and generate environmentally benign products. With this aim, silver nanoparticles (AgNPs) were synthesized by using isolated eugenol from clove extract. Its antimicrobial potential was determined on three different microorganisms. Clove was extracted and eugenol was isolated from this extract. Green synthesis was performed and an anti‐microbial study was performed. All extraction and isolation analyses were performed by high‐performance liquid chromatography (HPLC); identification and confirmation were achieved using liquid chromatography–mass spectrometry (LC–MS); and scanning electron microscopy was used for characterization. Both HPLC and LC–MS analyses showed that eugenol obtained purely synthesized AgNPs and 20‐25‐nm‐sized and homogeneous shaped particles seen in images. The antimicrobial effects of AgNPs at eight concentrations were determinated against Staphylococcus aureus, Escherichia coli and Candida albicans, and maximum inhibition zone diameters were found as 2.6 cm, 2.4 cm and 1.5 cm, respectively. The results of the antimicrobial study showed that eugenol as a biological material brought higher antimicrobial effect to AgNPs in comparison to the other materials found in the literature.