Formation of Silver Nanoparticles by Electron Transfer in Peptides and c-Cytochromes

The reduction of Ag⁺ ions to Ag⁰ atoms is a highly endergonic reaction step, only the aggregation to Ag_n clusters leads to an exergonic process. These elementary chemical reactions play a decisive role if Ag nanoparticles (AgNPs) are generated by electron transfer (ET) reactions to Ag⁺ ions. We studied the formation of AgNPs in peptides by photoinduced ET, and in c-cytochromes by ET from their Fe²⁺/hemes. Our earlier photoinduced experiments in peptides had demonstrated that histidine prevents AgNP formation. We have now observed that AgNPs can be easily synthesized with less-efficient Ag⁺-binding amino acids, and the rate increases in the order lysine<asparagine<aspartate<serine. The ability of Fe²⁺/hemes of c-cytochromes to reduce Ag⁺ to AgNPs was studied in an enzymatic experiment and with living bacteria Geobacter sulfurreducens (Gs).     

Ultrafine Au and Ag Nanoparticles Synthesized from Self‐Assembled Peptide Fibers and Their Excellent Catalytic Activity

The self‐assembly of an amphiphilic peptide molecule to form nanofibers facilitated by Ag⁺ ions was investigated. Ultrafine AgNPs (NPs=nanoparticles) with an average size of 1.67 nm were synthesized in situ along the fibers due to the weak reducibility of the ‐SH group on the peptide molecule. By adding NaBH₄ to the peptide solution, ultrafine AgNPs and AuNPs were synthesized with an average size of 1.35 and 1.18 nm, respectively. The AuNPs, AgNPs, and AgNPs/nanofibers all exhibited excellent catalytic activity toward the reduction of 4‐nitrophenol, with turnover frequency (TOF) values of 720, 188, and 96 h^?1, respectively. Three dyes were selected for catalytic degradation by the prepared nanoparticles and the nanoparticles showed selective catalysis activity toward the different dyes. It was a surprising discovery that the ultrafine AuNPs in this work had an extremely high catalytic activity toward methylene blue, with a reaction rate constant of 0.21 s^?1 and a TOF value of 1899 h^?1.     

Galvanic Replacement Reactions of Active‐Metal Nanoparticles

We present a systemic investigation of a galvanic replacement technique in which active‐metal nanoparticles are used as sacrificial seeds. We found that different nanostructures can be controllably synthesized by varying the type of more noble‐metal ions and liquid medium. Specifically, nano‐heterostructures of noble metal (Ag, Au) or Cu nanocrystals on active‐metal (Mg, Zn) cores were obtained by the reaction of active‐metal nanoparticles with more noble‐metal ions in ethanol; Ag nanocrystal arrays were produced by the reaction of active‐metal nanoparticles with Ag⁺ ions in water; spongy Au nanospheres were generated by the reaction of active‐metal nanoparticles with AuCl₄^? ions in water; and SnO₂ nanoparticles were prepared when Sn²⁺ were used as the oxidant ions. The key factors determining the product morphology are shown to be the reactivity of the liquid medium and the nature of the oxidant–reductant couple, whereas Mg and Zn nanoparticles played similar roles in achieving various nanostructures. When microsized Mg and Zn particles were used as seeds in similar reactions, the products were mainly noble‐metal dendrites. The new approach proposed in this study expands the capability of the conventional nanoscale galvanic replacement method and provides new avenues to various structures, which are expected to have many potential applications in catalysis, optoelectronics, and biomedicine.     

Green Synthesis of Silver Nanoparticles Using Acacia farnesiana (Sweet Acacia) Seed Extract Under Microwave Irradiation and Their Biological Assessment

In the present study, Acacia farnesiana (Sweet acacia) seed extract is used to reduce Ag⁺ → Ag⁰ under microwave irradiation. The formation of silver nanoparticles (AgNPs) is monitored by recording the UV–Vis absorption spectra for surface plasmon resonance (SPR) peak at ~450 nm. The absorbance of SPR increases linearly with increasing temperature of the reaction mixture. Rapid reduction of silver ions occurred to form AgNPs, 80–90 % yield in about 150 s. A marginal decrease in pH and increase in solution potential (E) of the reaction mixture during the formation of AgNPs are in agreement with the proposed mechanism. XRD pattern of the AgNPs agree with the fcc structure of Ag metal, and the calculated crystallite size is ~17 nm. FT-IR and solid-state ¹³C NMR spectra indicate the functional groups of flavonones and terpenoids (biomolecules from plant extract) which are adsorbed on AgNPs, thereby the present method led to in situ biofunctionalization/bio-capping of AgNPs. TG analysis shows the thermal decomposition of these plant residues present on AgNPs at about 250 °C. The spherical shape of the particles with a diameter (?) in the range of ~15–20 nm is evident from FE-SEM image. Elemental analysis by EDX analysis confirms the presence of Ag as the only major element. The in vitro antibacterial screening of AgNPs shows that these bio-capped AgNPs have higher inhibitory action for E. coli and S. aureus followed by B. subtilis and P. aeruginosa. In addition, AgNPs show very good antioxidant property.     

Inhibition and enhancement of glucose oxidase activity in a chitosan-based electrode filled with silver nanoparticles

A chitosan-based electrode filled with silver nanoparticles (AgNPs) and glucose oxidase (GOD) was used as an enzyme electrode to investigate the effect of aging process of AgNPs on the GOD activity. Freshly prepared AgNPs inhibit the GOD activity, however, the inhibitory effect decreased with the increase of aging time. After aged for a period of time, AgNPs showed enhancement effect on the GOD activity. The effect of aging was studied by the measurements of Ag⁺ ions concentration, zeta (ζ) potential and X-ray photoelectron spectroscopy (XPS). And the results indicated that the concentration of Ag⁺ ions in the silver sol decreased during the aging period (i.e. Ag⁺ ions converted to more inert silver metal Ag⁰). The effect of AgNPs on the GOD activity can be changed by controlling the aging time of AgNPs. This research provides a new and simple approach to mediate AgNPs property, which is of great value in potential application of AgNPs in biosensors and nanoscale devices.     

Supported Ag nanoparticles as trace iodide adsorbent from acetic acid

Ag nanoparticles (AgNPs) were used as adsorbent to remove trace iodide from acetic acid. Under identical conditions, AgNPs adsorbent with 0.5 wt % Ag has the same performance as commercial adsorbent with 10 wt % Ag⁺. In addition, Ag loss of AgNPs adsorbent is remarkably lower than that of commercial adsorbent. The Ag content in AgNPs adsorbent affects its adsorption performance, and the optimal content is 1.0 wt %. Saturated AgNPs adsorbent can be regenerated by hydrogen reduction and reused with satisfying performance. The properties of AgNPs adsorbent are based on surface effect of nanoparticles, differing from commercial Ag⁺ type adsorbents. In a word, AgNPs adsorbent is of high efficiency, low Ag loss and easy recycling, thus making it ??green adsorbent?? for removing iodide from acetic acid.     

Sol–gel synthesis of nanosilver embedded hybrid materials using combined organosilica precursors

A facile sol–gel route to the fabrication of size-controllable nanosilver embedded hybrid materials at room-temperature is presented. The preparation process involves using three kind of organosilica precursors, i.e. tetraethoxysilane, 3-mercaptopropyltrimethoxysilane and polymethylhydrosiloxane, which behaved as framework constructor, complexing agent toward metal ions and in situ reducing agent for Ag⁺ ions, respectively, under alcohol-rich synthesis conditions. The prepared hybrid materials were characterized by Ultraviolet–visible diffuse reflectance spectra, Fourier transform infrared, transmission electron microscopy, X-ray diffraction, nitrogen adsorption–desorption measurements. It was shown that well-dispersed silver nanoparticles (AgNPs) with small particle size were successfully embedded in the hybrid skeleton, and the mean particle size of AgNPs could be controlled at ca. 2–5 nm.     

Formation mechanism of nanostructured Ag films from Ag2O particles using a sonoprocess

Nanostructured Ag films composed of nanoparticles and nanorods can be formed by the ultrasonication of ethanol solutions containing Ag₂O particles. The present work examined the formation process of these films from ethanol solutions by two different agitation methods, including ultrasonication and mechanical stirring. The mass-transfer process from Ag₂O particles to ethanol solvent is accelerated by the mechanical effects of ultrasound. Ag⁺ ions and intermediately reduced Ag clusters were released into the ethanol. These Ag⁺ ions and Ag clusters provide absorption bands at 210, 275 and 300 nm in UV-vis spectra. These bands were assigned to the absorption of Ag⁺, Ag ₄ ²⁺ and Ag_n (n?≈?3). The Ag_n clusters that readily grow to become Ag nanoparticles were formed due to the surface reaction of Ag₂O particles with ethanol under ultrasonication. The reactions of Ag⁺ ions in ethanol to form Ag nanomaterials (through the formation of Ag ₄ ²⁺ clusters) were also accelerated by ultrasonication.     

Synthesis and Study of Plasmon‐Induced Carrier Behavior at Ag/TiO2 Nanowires

Nanocomposites of Ag/TiO₂ nanowires with enhanced photoelectrochemical performance have been prepared by a facile solvothermal synthesis of TiO₂ nanowires and subsequent photoreduction of Ag⁺ ions to Ag nanoparticles (AgNPs) on the TiO₂ nanowires. The as‐prepared nanocomposites exhibited significantly improved cathodic photocurrent responses under visible‐light illumination, which is attributed to the local electric field enhancement of plasmon resonance effect near the TiO₂ surface rather than by the direct transfer of charge between the two materials. The visible‐light‐driven photocatalytic performance of these nanocomposites in the degradation of methylene blue dye was also studied, and the observed improvement in photocatalytic activity is associated with the extended light absorption range and efficient charge separation due to surface plasmon resonance effect of AgNPs.     

Oxidative Dissolution of Silver Nanoparticles by Dioxygen: A Kinetic and Mechanistic Study

We have recently reported a kinetic and mechanistic study on oxidative dissolution of silver nanoparticles (AgNPs) by H₂O₂. In the present study, the parameters that govern the dissolution of AgNPs by O₂ were revealed by using UV/Vis spectrophotometry. Under the same reaction conditions (Tris‐HOAc, pH 8.5, I=0.1 M at 25 °C) the apparent dissolution rate (k_app) of AgNPs (10±2.8 nm) by O₂ is about 100‐fold slower than that of H₂O₂. The reaction rate is first‐order with respect to [Ag⁰], [O₂], and [Tris]_T, and inverse first‐order with respect to [Ag⁺] (where [Ag⁰]=total concentration of Ag metal and [Tris]_T=total concentration of Tris). The rate constant is dependent on the size of AgNPs. No free superoxide (O₂⁻) and hydroxyl radical (⋅OH) were detected by trapping experiments. On the basis of kinetic and trapping experiments, an amine‐activated pathway for the oxidation of AgNPs by O₂ is proposed.     

Characterization of [peptide+(Ag)n]+ complexes using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Silver ion complexes of peptides [M + (Ag)_n]⁺, M = angiotensin I or substance P where n = 1–8 and 17–23 for angiotensin I and n = 1–5 for substance P, are identified and characterized using matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOFMS). The Ag⁺ coordination number exceeds the number of available amino acid residues in angiotensin I whereas the number of observed complexes in substance P is less than the number of amino acid residues in it. The larger coordination number of angiotensin I with Ag⁺ indicates the simultaneous binding of several Ag⁺ ions to the amino acid residue present in it. The lower number of observed complexes in substance P suggests the binding of two or more residues to one Ag⁺ ion. The presence of trifluoroacetic acid in the peptide samples reduces the Ag⁺ coordination ability in both the peptides which indicates that the basic residues in it are already protonated and do not participate in the Ag⁺‐binding process. The Ag⁺ ion also forms a complex with the α‐cyano‐4‐hydroxycinnamic acid (CHCA) matrix and is observed in the MALDI mass spectra and the formation of [CHCA + Ag]⁺, [CHCA + AgNO₃]⁺ and [(CHCA)₂ + Ag]⁺ ions is due to the high binding affinity of Ag⁺ to the CN group of CHCA. Copyright © 2010 John Wiley & Sons, Ltd.     

A surfactant‐free synthesis of the silica nanosphere‐supported ultrafine silver nanoparticles and their antibacterial effects

In this study, a facile, efficient, and surfactant‐free method to synthesize silica nanosphere‐supported ultrafine silver nanoparticles (AgNPs) (~2.5 nm) was developed, and their antibacterial effects were investigated. In the synthesis process, the hydrolysis of 3‐mercaptopropyltrimethoxysilane was adopted to provide thiol groups and in situ reduce Ag⁺ to Ag⁰ for ultrafine AgNPs formation on the surface of the silica nanosphere. Electron microscopy characterization of the complex formed revealed that the ultrafine AgNPs were not agglomerated and grow without any surfactants because there were no excess electrons transported from the shell to reduce the silver ions to silver atoms. The antibacterial effects of the supported ultrafine AgNPs with the surfactant‐free surface were evaluated against the Escherichia coli even at very low dosage. After incubation with 20 μg/mL silica‐supported AgNPs up to 120 min, 99.7% of the E. coli were inactivated, according to the bacterial viability measured by flow cytometry.     

Highly Efficient Visible Light Plasmonic Photocatalyst Ag@Ag(Br,I)

The new plasmonic photocatalyst Ag@Ag(Br,I) was synthesized by the ion‐exchange process between the silver bromide and potassium iodide, then by reducing some Ag⁺ ions in the surface region of Ag(Br,I) particles to Ag⁰ species. Ag nanoparticles are formed from Ag(Br,I) by the light‐induced chemical reduction reaction. The Ag@Ag(Br,I) particles have irregular shapes with their sizes varying from 83 nm to 1 μm. The as‐grown plasmonic photocatalyst shows strong absorption in the visible light region because of the plasmon resonance of Ag nanoparticles. The ability of this compound to reduce Cr^VI under visible light was compared with those of other reference photocatalyst. The plasmonic photocatalyst is shown to be highly efficient under visible light. The stability of the photocatalyst was examined by X‐ray diffraction and X‐ray photoelectron spectroscopy. The XRD pattern and XPS spectra prove the stability of the plasmonic photocatalyst Ag@Ag(Br,I).     

Green synthesis and antibacterial effects of aqueous colloidal solutions of silver nanoparticles using clove eugenol

Silver nanoparticles were synthesized using clove extract (CE). Scanning transmission electron microscopy (STEM) revealed the morphology of the metallic Ag nanoparticles obtained via the clove extract synthesis (Ag NPs‐CE), which had a uniform distribution and average sizes varying from 10 nm to 100 nm. Fourier transform infra‐red (FTIR) spectroscopy showed that clove eugenol acts as a capping and reducing agent being adsorbed on the surface of Ag NPs‐CE, enabling their reduction from Ag⁺ and preventing their agglomeration. Formation of the Ag⁰ structure is also confirmed in the FTIR spectrum by the presence in the Ag NPs‐CE sample of the –C=O and –C=C vibrations at wavenumbers 1600 and 2915 cm^‐1, respectively. Antibacterial and antifungal tests using three strains of bacteria and one fungi strain showed that the Ag NPs‐CE performed better compared to pure clove extract (CE) sample.     

Nucleation of Tiny Silver Nanoparticles by Using a Tetrafacial Organic Molecular Barrel: Potential Use in Visible-Light-Triggered Photocatalysis

Coordination-driven self-assembly of discrete molecular architectures of diverse shapes and sizes has been well studied in the last three decades. Use of dynamic imine bonds for designing analogous metal-free architectures has become a growing challenge recently. This article reports an organic molecular barrel ( OB4^R ) as a potential template for nucleation and stabilization of very tiny (<1.5 nm) Ag nanoparticles (AgNPs). Imine bond condensation of a rigid tetra-aldehyde with a flexible diamine followed by imine-bond reduction yielded the discrete tetragonal organic barrel ( OB4^R ). The presence of a molecular pocket ornamented with eight diamine moieties gives the potential for encapsulation of silver(I). The organic barrel was finally used as a molecular vessel for the controlled nucleation of silver nanoparticles (AgNPs) with fine size tuning through binding of Ag^I ions in the confined space of the barrel followed by reduction. Transmission electron microscopy (TEM) analysis of the Ag⁰@OB4^R composite revealed that the mean particle size is 1.44±0.16 nm. The composite material has approximately 52 wt % silver loading. The barrel-supported ultrafine AgNPs [ Ag⁰@OB4^R ] are found to be an efficient photocatalyst for facile Ullmann-type aryl-amination coupling of haloarenes at ambient temperature without using any additives. The catalyst was stable for several cycles of reuse without any agglomeration. The new composite Ag⁰@OB4^R represents the first example of discrete organic barrel-supported AgNPs employed as a photocatalyst in Ullmann-type coupling reactions at room temperature.     

Contiguous metal-mediated base pairs comprising two Ag(I) ions

The incorporation of transition‐metal ions into nucleic acids by using metal‐mediated base pairs has proved to be a promising strategy for the site‐specific functionalization of these biomolecules. We report herein the formation of Ag⁺‐mediated Hoogsteen‐type base pairs comprising 1,3‐dideaza‐2′‐deoxyadenosine and thymidine. By defunctionalizing the Watson–Crick edge of adenine, the formation of regular base pairs is prohibited. The additional substitution of the N3 nitrogen atom of adenine by a methine moiety increases the basicity of the exocyclic amino group. Hence, 1,3‐dideazaadenine and thymine are able to incorporate two Ag⁺ ions into their Hoogsteen‐type base pair (as compared with one Ag⁺ ion in base pairs with 1‐deazaadenine and thymine). We show by using a combination of experimental techniques (UV and circular dichroism (CD) spectroscopies, dynamic light scattering, and mass spectrometry) that this type of base pair is compatible with different sequence contexts and can be used contiguously in DNA double helices. The most stable duplexes were observed when using a sequence containing alternating purine and pyrimidine nucleosides. Dispersion‐corrected density functional theory calculations have been performed to provide insight into the structure, formation and stabilization of the twofold metalated base pair. They revealed that the metal ions within a base pair are separated by an Ag???Ag distance of about 2.88 Å. The Ag–Ag interaction contributes some 16 kcal mol^?1 to the overall stability of the doubly metal‐mediated base pair, with the dominant contribution to the Ag–Ag bonding resulting from a donor–acceptor interaction between silver 4d‐type and 4s orbitals. These Hoogsteen‐type base pairs enable a higher functionalization of nucleic acids with metal ions than previously reported metal‐mediated base pairs, thereby increasing the potential of DNA‐based nanotechnology.     

Three-dimensional printed knotted reactors enabling highly sensitive differentiation of silver nanoparticles and ions in aqueous environmental samples

Whether silver nanoparticles (AgNPs) persist or release silver ions (Ag⁺) when discharged into a natural environment has remained an unresolved issue. In this study, we employed a low-cost stereolithographic three-dimensional printing (3DP) technology to fabricate the angle-defined knotted reactors (KRs) to construct a simple differentiation scheme for quantitative assessment of Ag⁺ ions and AgNPs in municipal wastewater samples. We chose xanthan/phosphate-buffered saline as a dispersion medium for in situ stabilization of the two silver species, while also facilitating their extraction from complicated wastewater matrices. After method optimization, we measured extraction efficiencies of 54.5 and 32.3% for retaining Ag⁺ ions and AgNPs, respectively, in the printed KR (768-turn), with detection limits (DLs) of 0.86 and 0.52 ng L⁻¹ when determining Ag⁺ ions and AgNPs, respectively (sample run at pH 11 without a rinse solution), and 0.86 ng L⁻¹ when determining Ag⁺ ions alone (sample run at pH 12 with a 1.5-mL rinse solution). The proposed scheme is tolerant of the wastewater matrix and provides more reliable differentiation between Ag⁺/AgNPs than does a conventional filtration method. The concept and applicability of adopting 3DP technology to renew traditional KR devices were evidently proven by means of these significantly improved analytical performance. Our analytical data suggested that the concentrations of Ag⁺ ions and AgNPs in the tested industrial wastewater sample were both higher than those in domestic wastewater, implying that industrial activity might be a main source of environmental silver species, rather than domestic discharge from AgNP-containing products.     

Preparation of antimicrobial poly(vinyl alcohol) nanofibers containing silver nanoparticles

Polyvinyl alcohol (PVA) nanofibers containing Ag nanoparticles were prepared by electrospinning PVA/silver nitrate (AgNO₃) aqueous solutions, followed by short heat treatment, and their antimicrobial activity was investigated for wound dressing applications. Since PVA is a water soluble and biocompatible polymer, it is one of the best materials for the preparation of wound dressing nanofibers. After heat treatment at 155 °C for 3 min, the PVA/AgNO₃ nanofibers became insoluble, while the Ag⁺ ions therein were reduced so as to produce a large number of Ag nanoparticles situated preferentially on their surface. The residual Ag⁺ ions were reduced by subsequent UV irradiation for 3 h. The average diameter of the Ag nanoparticles after the heat treatment was 5.9 nm and this value increased slightly to 6.3 nm after UV irradiation. It was found that most of the Ag⁺ ions were reduced by the simple heat treatment. The PVA nanofibers containing Ag nanoparticles showed very strong antimicrobial activity. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2468–2474, 2006     

Tandem synthesis of silver nanoparticles and nanorods in the presence of poly(oxyethylene)-amidoacid template

Sequential formation of silver nanoparticles (AgNPs) and nanorods from the reduction of AgNO₃ was affected by a poly(oxyethylene)-amidoacid (POE-amidoacid) in aqueous solution. The requisite POE-amidoacid, consisting of –(CH₂CH₂O)_n– segments with amide and carboxyl groups, was simply prepared via amidation with trimellitic anhydride of a poly(oxyethylene)-monoamine (POE-amine) of molecular weight (M_w) ∼2000 g/mol. The POE-amidoacid afforded AgNPs as small as 5 nm in diameter, which gradually (over a period of months) self-assembled into nanorods that were 10–15 nm in width and 30–50 nm in length. The hierarchical formation of Ag species occurred only at ambient temperature, but Ag aggregates formed above 50 °C. The process could be monitored by UV absorption at 420 and 380 nm for AgNPs and nanorods, respectively, and by transmission electron microscopy (TEM) for the nanorods. Fourier transform infrared (FTIR) and tapping-mode atomic force microscopy (TM-AFM) analyses revealed that the structurally tailored POE-amidoacid was indeed multifunctional: it reduced Ag⁺, stabilized the obtained Ag⁰ species, and served as a template for the tandem formation of AgNPs and nanorods.     

Biological Evaluation of Silver Nanoparticles Obtained from T. arjuna Bark Extract as Both Reducing and Capping Agent

A simple, environmentally benign and cost effective method is reported to obtain silver nanoparticles (AgNPs) using aqueous solution of AgNO₃ and T. Arjuna (Terminalia Arjuna) bark extract, which act as both reducing and capping agent, under microwave irradiation. The formation of AgNPs was monitored by recording optical absorption spectra for surface plasmon resonance observed at ~425 nm. The bioactive polyphenols extracted from the plant extract are responsible for reduction of Ag⁺ → Ag⁰. During the formation of AgNPs, the reaction mixture showed gradual decrease in pH and an increase in reduction potential. The powder XRD pattern of AgNPs confirmed their fcc structure. An FTIR spectrum showed the presence of plant-residues adsorbed on the surface of AgNPs, which indicates the in situ bio-capping. The TG curve of AgNPs showed ~30 % weight loss due to thermal degradation of these plant-residues. The FE-SEM images showed spherical shape of AgNPs with an average particle size of 10–15 nm. The EDX analysis confirmed the presence of Ag as a major element. The biological evaluation of AgNPs showed higher inhibitory action for both bacteria and yeast when compared to that of fungus. A very good antioxidant property was also observed for these bio-capped AgNPs.