Highly size- and shape-controlled synthesis of silver nanoparticles via a templated Tollens reaction.
ABSTRACT: A mild, facile one-step synthetic strategy for the preparation of size- and shape-controlled silver nanoparticles (AgNPs) is presented. The high degree of size- and shape-control of these AgNPs is achieved by the use of triazole sugar ligands scaffolded by a central resorcinol ether core. Both the triazoles and the resorcinol ether core mediate the nucleation, growth, and passivation phases of the preparation of AgNP in the presence of the Tollens reagent as the silver source. Kinetic and (1)H NMR titration data is presented describing the nature of the interactions between the Tollens reagent and these ligands.
Project description:Background:Silver nanoparticles (AgNPs) have attracted great attention due to their outstanding electrical, optical, magnetic, catalytic, and antimicrobial properties. However, there is a need for alternative production methods that use less toxic precursors and reduce their undesirable by-products. Phyto-extracts from the leaves of olive and rosemary plants can be used as reducing agents and (in conjunction with Tollens' reagent) can even enhance AgNP antimicrobial activity. Methods:Conditions for the proposed hybrid synthesis method were optimized for olive leaf extracts (OLEs) and rosemary leaf extracts (RLEs). The resultant AgNPs were characterized using UV-visible spectroscopy, an environmental scanning electron microscope, and Dynamic Light Scattering analysis. An atomic absorption spectrophotometer was used to measure AgNP concentration. Fourier transform infrared spectroscopy (FTIR) was used to determine the specific functional groups responsible for the reduction of both silver nitrate and capping agents in the leaf extract. Additionally, the antimicrobial properties of the synthesized AgNPs were assessed against Gram-negative bacteria (Escherichia coli and Salmonella enterica) and Gram-positive bacteria (Staphylococcus aureus), by using both the Kirby-Bauer and broth microdilution methods on Mueller-Hinton (MH) agar plates. Results and Discussion:A simple, feasible, and rapid method has been successfully developed for silver nanoparticle synthesis by reducing Tollens' reagent using leaf extracts from olive and rosemary plants (widely available in Jordan). Scanning electron microscopy images showed that the method produces AgNPs with a spherical shape and average core sizes of 45 ± 2 and 38 ± 3 nm for OLE and RLE, respectively. A negative zeta potential (?) of -43.15 ± 3.65 mV for OLE-AgNPs and -33.65 ± 2.88mV for RLE-AgNPs proved the stability of silver nanoparticles. FTIR spectra for AgNPs and leaf extracts indicated that the compounds present in the leaf extracts play an important role in the coating/capping of synthesized nanoparticles. The manufactured AgNPs exhibited an antibacterial effect against Escherichia coli and Staphylococcus aureus with minimum inhibitory concentrations (MIC) of 9.38 and 4.69 ?l/ml for OLE-AgNPs and RLE-AgNPs, respectively. The MIC for Salmonella enterica were 18.75 ?l/ml for both OLE-AgNPs and RLE-AgNPs. Furthermore, our results indicated that the RLE-AgNPs exhibited a stronger antibacterial effect than OLE-AgNPs against different bacteria species. These results contribute to the body of knowledge on nanoparticle production using plant-mediated synthesis and performance. They also offer insights into the potential for scaling up this production process for commercial implementation.
Project description:Nelson-Somogyi and 3,5-dinitrosalicylic acid (DNS) assays are the classical analytical methods for the determination of activity of starch-debranching enzymes, however, they have a narrow detection range and do not adapt to the quantitative measurement of linear polysaccharides. Herein, we developed a simple and accurate colorimetric assay for determining the activity of starch-debranching pullulanase through the modified Tollens' reaction in combination with UV irradiation. Silver nanoparticles (AgNPs) were formed by reducing aldehyde groups in short-chain glucans (SCGs) generated by debranching of waxy maize starch using pullulanase through the modified Tollens' reaction. In addition to providing a reducing moiety to the Tollens' reaction, the debranching product, SCGs, also enhanced the colloidal stability of synthesized AgNPs, of which the amplitude of its surface plasmon resonance (SPR) absorbance peak was proportional to the concentration of SCGs ranging from 0.01-10 mg/mL. The detection limit of this system was 0.01 mg/mL, which was found to be 100 times higher than that of the conventional DNS assay. The purification of SCGs by recrystallization and gelatinization improved the selectivity of this colorimetric assay for debranching products, which provides a simple and accurate means of monitoring the debranching process and characterizing the activity of starch-debranching enzymes.
Project description:The synthesis that is described in this study is for the preparation of silver nanoparticles of sizes ranging from 10 nm to 30 nm with a defined shape (globular), confirmed by UV-vis, SEM, STEM and DLS analysis. This simple and favorable one-step modified Tollens reaction does not require any special equipment or other stabilizing or reducing agent except for a solution of purified mesquite gum, and it produces aqueous colloidal dispersions of silver nanoparticles with a stability thatexceeds three months, a relatively narrow size distribution, a low tendency to aggregate and a yield of at least 95% for all cases. Reaction times are between 15 min and 60 min to obtain silver nanoparticles in concentrations ranging from 0.1 g to 3 g of Ag per 100 g of reaction mixture. The proposed synthetic method presents a high potential for scale-up, since its production capacity is rather high and the methodology is simple.The synthesis that is described in this study is for the preparation of silver nanoparticles of sizes ranging from 10 nm to 30 nm with a defined shape (globular), confirmed by UV-vis, SEM, STEM and DLS analysis. This simple and favorable one-step modified Tollens reaction does not require any special equipment or other stabilizing or reducing agent except for a solution of purified mesquite gum, and it produces aqueous colloidal dispersions of silver nanoparticles with a stability thatexceeds three months, a relatively narrow size distribution, a low tendency to aggregate and a yield of at least 95% for all cases. Reaction times are between 15 min and 60 min to obtain silver nanoparticles in concentrations ranging from 0.1 g to 3 g of Ag per 100 g of reaction mixture. The proposed synthetic method presents a high potential for scale-up, since its production capacity is rather high and the methodology is simple.
Project description:The potential for application of any nanoparticles, including silver nanoparticles (AgNPs), is strongly dependent on their stability against aggregation. Therefore, improvement of this parameter is a key task, especially in the case of AgNPs, because a correlation between size and biological activity has been demonstrated. In the present work, a natural stabilizer, gelatin, was investigated for the stabilization of AgNPs in an aqueous dispersion. The particles were prepared via a modified Tollens process, and the gelatin modifier was added prior to the reducing agent. The stability against aggregation of the AgNPs prepared by this method was more than one order of magnitude higher (on the basis of the critical coagulation concentration (CCC)) than that of AgNPs prepared via a similar method but without the assistance of gelatin. Their high stability against aggregation was confirmed over wide pH range (from 2 to 13) in which the particles did not exhibit rapid aggregation; such stability has not been previously reported for AgNPs. Additionally, gelatin not only fulfills the role of a unique stabilizer but also positively influences the modified Tollens process used to prepare the AgNPs. The diameter of the gelatin-modified AgNPs was substantially smaller in comparison to those prepared without gelatin. The polydispersity of the dispersion significantly narrowed. Moreover, the gelatin-stabilized AgNPs exhibited long-term stability against aggregation and maintained high antibacterial activity when stored for several months under ambient conditions.
Project description:A rapid synthesis of silver nanoparticles (AgNPs) using Agrimoniae herba extract as reducing agent and stabilizer (A. herba-conjugated AgNPs [AH-AgNPs]) were designed, characterized, and evaluated for antitumor therapy feasibility. In this study, critical factors in the preparation of silver nanoparticles, including extraction time, reaction temperature, the concentration of AgNO3, and A. herba extract amount, were investigated using ultraviolet-visible spectroscopy. AH-AgNPs with well-defined spherical shape, homogeneous distributional small size (30.34 nm), narrow polydispersity index (0.142), and high negative zeta potential (-36.8 mV) were observed by transmission electron microscopy and dynamic light scattering. Furthermore, the results of X-ray diffraction and Fourier-transform infrared spectroscopy further indicated successful preparation of AH-AgNPs. Acceptable long-term storage stability of AH-AgNPs was also confirmed. More importantly, AH-AgNPs displayed significantly higher antiproliferative effect against a human lung carcinoma cell line (A549 cells) compared with A. herba extract and bare AgNPs prepared by sodium citrate. The half-maximal inhibitory concentrations of AH-AgNPs, bare AgNPs, and A. herba extract were 38.13 ?g · mL(-1), 184.87 ?g · mL(-1), and 1.147 × 10(4) ?g · mL(-1), respectively. It is suggested that AH-AgNPs exhibit a strong antineoplastic effect on A549 cells, pointing to feasibility of antitumor treatment in the future.
Project description:Biosynthesis of plant-mediated silver nanoparticles is gaining significant importance due to environmentally safe 'green method' and it is an efficient alternative method. In the present study, silver nanoparticles were synthesized by using root extract of Glycyrrhiza glabra an important medicinal plant. The AgNPs are characterized by spectral analysis; the surface plasmon resonance (SPR) peak of AgNPs showed maximum absorption at 445 nm. Fourier-transform infrared spectroscopy (FT-IR) data show that the O-H hydroxyl groups, carboxylic acids, ester and ether groups and C-O stretching of alcohols have been utilized in the formation of AgNPs. The X-ray powder diffraction (XRD) data reveal that the AgNPs are face-centered cubic (fcc) in structure. The size was determined by particle size analyzer and atomic force microscope (AFM); the results reveal that AgNPs were spherical in shape and the average grain size is determined as 41.5-46.5 nm. Transmission electron microscopy (TEM) micrographs obtained show that AgNPs were roughly spherical and well dispersed with the sizes ranging from 10 to 45 nm ± 5 nm. The biofabricated AgNPs are extremely stable due to its high negative zeta potential -34.1 mV which indicates that the nanoparticles are polydispered in nature. The cytotoxic studies of AgNPs on human CD34 +ve stem cells in microcarrier culture reveal excellent growth at different concentrations of biosynthesized AgNPs. This is the first report of microcarrier culture of CD34 +ve stem cells on biosynthesized AgNPs.
Project description:The design of new materials with antimicrobial properties has emerged in response to the need for preventing and controlling the growth of pathogenic microorganisms without the use of antibiotics. In this study, partially reduced graphene oxide decorated with silver nanoparticles (GO-AgNPs) was incorporated as a reinforcing filler with antibacterial properties to poly(vinyl alcohol) (PVA) for preparation of poly(vinyl alcohol)/graphene oxide-silver nanoparticles nanocomposites (PVA/GO-AgNPs). AgNPs, spherical in shape and with an average size of 3.1 nm, were uniformly anchored on the partially reduced GO surface. PVA/GO-AgNPs nanocomposites showed exfoliated structures with improved thermal stability, tensile properties and water resistance compared to neat PVA. The glass transition and crystallization temperatures of the polymer matrix increased with the incorporation of the hybrid. The nanocomposites displayed antibacterial activity against <i>Staphylococcus aureus</i> and <i>Escherichia coli</i> in a filler content- and time-dependent manner. <i>S. aureus</i> showed higher susceptibility to PVA/GO-AgNPs films than <i>E. coli.</i> Inhibitory activity was higher when bacterial cells were in contact with nanocomposite films than when in contact with leachates coming out of the films. GO-AgNPs based PVA nanocomposites could find application as wound dressings for wound healing and infection prevention.
Project description:Porous hypercross-linked polymers based on perbenzylated monosugars (SugPOP-1-3) have been synthesized by Friedel-Crafts reaction using formaldehyde dimethyl acetal as an external cross-linker. Three perbenzylated monosugars with similar chemical structure were used as monomers in order to tune the porosity. These obtained polymers exhibit microporous and mesoporous features. The highest Brunauer-Emmett-Teller specific surface area for the resulting polymers was found to be 1220 m2 g-1, and the related carbon dioxide storage capacity was found to be 14.4 wt % at 1.0 bar and 273 K. As the prepared porous polymer SugPOP-1 is based on hemiacetal glucose, Ag nanoparticles (AgNPs) can be successfully incorporated into the polymer by an in situ chemical reduction of freshly prepared Tollens' reagent. The obtained AgNPs/SugPOP-1 composite demonstrates good catalytic activity in the reduction of 4-nitrophenol (4-NP) with an activity factor ka = 51.4 s-1 g-1, which is higher than some reported AgNP-containing composite materials.
Project description:Silver nanoparticles (AgNPs) are widely used as antibacterial products in various fields. Recent studies have suggested that AgNPs need an appropriate stabilizer to improve their stability. Some antibacterial traditional Chinese medicines (TCMs) contain various reductive components, which can not only stabilize AgNPs but also enhance their antimicrobial activity. In this study, we developed a series of novel AgNPs using a TCM extract as a stabilizer, reducing agent, and antimicrobial agent (TCM-AgNPs). A storage stability investigation of the TCM-AgNPs suggested a significant improvement when compared with bare AgNPs. Further, conjugation of TCMs onto the AgNP surface resulted in stronger antimicrobial potency on antibacterial evaluation using Pseudomonas aeruginosa, Staphylococcus epidermidis, and Staphylococcus aureus with minimum inhibitory concentration 50% (MIC50) ratios (and minimum bactericidal concentration 90% [MBC90] ratios) of AgNPs to respective TCM-AgNPs as assessment indices. Among these, P. cuspidatum Sieb. et-conjugated AgNPs (P.C.-AgNPs) had the advantage of a combination of TCMs and AgNPs and was studied in detail with regard to its synthesis and characterization. The extraction time, reaction temperature, and concentrations of AgNO3 and Polygonum cuspidatum Sieb. et extract were critical factors in the preparation of P.C.-AgNPs. Further, the results of X-ray diffraction and Fourier transform infrared spectroscopy indicated successful preparation of P.C.-AgNPs. In representative studies, P.C.-AgNPs showed a well-defined spherical shape, a homogeneous small particle size (36.78 nm), a narrow polydispersity index (0.105), and a highly negative zeta potential (-23.6 mV) on transmission electron microscopy and dynamic light scattering. These results indicate that TCM-AgNPs have a potential role as antibacterial agents in the clinic setting.
Project description:Hybrid nanoparticles involving 10-nm silver nanoparticles (AgNPs) nucleated on unmodified rod-like cellulose nanocrystals (CNCs) were prepared by chemical reduction. H2O2 used as a post-treatment induced a size-shape transition following a redox mechanism, passing from 10-nm spherical AgNPs to 300-nm triangular or prismatic NPs (AgNPrisms), where CNCs are the only stabilizers for AgNPs and AgNPrisms. We investigated the role of the H2O2/AgNP mass ratio (?) on AgNPs. At ? values above 0.20, the large amount of H2O2 led to extensive oxidation that produced numerous nucleation points for AgNPrisms on CNCs. On the contrary, for ? below 0.20, primary AgNPs are only partially oxidized, releasing a reduced amount of Ag+ ions and thus preventing the formation of AgNPrisms and reforming spherical AgNPs. While XRD and EXAFS reveal that the AgNP fcc crystal structure is unaffected by the H2O2 treatment, the XANES spectra proved that the AgNP-AgNPrism transition is always associated with an increase in the metallic Ag fraction (Ag0). In contrast, the formation of new 15-nm spherical AgNPs keeps the initial Ag0/Ag+ ratio unmodified. For the first time, we introduce a complete guide map for the fully-controlled preparation of aqueous dispersed AgNPs using CNC as a template.