Silver Species Research Articles

Recyclability‐by‐design of Printed Electronics by Low‐Temperature Sintering of Silver Microparticles

AbstractA low‐temperature sintering mechanism of silver microparticles is established and used to enable the design‐for‐recycling of printed electronics. The formation of necks during the initial phase sintering of precipitated and atomized silver microparticles is studied. Temperature‐ and time‐dependent in‐situ analyses indicate the existence of a mobile silver species that provides efficient mass transport. The activation energy of neck formation identifies silver ion formation as the rate‐limiting step of low‐temperature silver sintering. It is demonstrated that resistivities of 271 times that of bulk silver can be attained after 40 minutes at 150°C. Low‐temperature sintering not only reduces the energy required during thermal treatment but it yields layers that are suitable for recycling, too. The resulting layers have conductive necks that are mechanically weak enough to be broken during recycling. Printed layers are redispersed and the recycled silver powder is reused without loss of the electrical performance in new prints. Their conductivities are industrially relevant, which makes this recyclability‐by‐design approach promising for manufacturing more sustainable printed electronics.

Low toxicity of dissolved silver from silver-coated titanium dental implants to human primary osteoblast cells

Objectivesthe controlled release of silver as a biocide from Ag-coated medical implants is desirable. However, the biocompatibility of Ag leachates is poorly understood. This study investigated the toxicity of silver released from the silver plated titanium implants to human primary osteoblast cells; and the effect of cell culture medium on the silver speciation and bioavailability. Methods: Ti6Al4V discs were coated with Ag nanoparticles (NPs), silver plus hydroxyapatite (HA) nanoparticles (Ag+nHA), or Ag NPs plus microparticles (Ag+mHA). Primary human osteoblast cells were exposed to the leachates from the various discs for up to 7 days. Results: the total Ag concentrations released as leachate from the silver-plated titanium discs were 0.7–1.6 mg L−1, regardless of treatment. Cumulative silver release over 7 days was approximately 3 mg L−1 in all treatments. The concentration of total Ag in the cell homogenates from all the Ag-containing treatments was modest, ∼ 0.1 µg mg protein−1 or less at day 7. Cells showed normal healthy morphology with no appreciable leak of LDH or ALP activity into the external media compared to the reference control. Similarly, there was no significant differences (Kruskal Wallis, p > 0.05) in the LDH or ALP activity in the cell homogenate between treatments. Conclusions: overall, there was a controlled release of Ag into the external media, but this remained biocompatible with no deleterious effects on the osteoblast cells, which means that the released silver to the peri-implant environment is not toxic making the coating potential for clinical use

Enhanced Yield of Methyl Ethyl Ketone through Levulinic Acid Decarboxylation in the AgNO3/K2S2O8 System: Mechanistic Insights and Characterization of Metallic Species.

Methyl ethyl ketone (MEK) is among the most extensively utilized solvents in various industrial applications. In this study, we present a highly efficient synthesis route for MEK via the decarboxylation of biomass-derived levulinic acid, using potassium persulfate (K2S2O8) and silver nitrate (AgNO3) as key reagents. The specific roles of AgNO3 and K2S2O8 were thoroughly investigated. Additional silver species, such as Ag2O and AgO, were also detected during the reaction. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) analyses provided evidence of the evolution of solid phases throughout the reaction. Based on these findings, we propose a radical decarboxylation mechanism initiated by the generation of sulfate radicals (SO4•⁻) through the catalytic breakdown of K2S2O8 by AgNO3. This mechanistic understanding, combined with a parametric study, enabled us to achieve an unprecedented level of levulinic acid conversion (97.9%) and MEK yield (86.6%) with this system, surpassing all previously reported results in the literature.

Bactericidal activity of silver nanoparticles: An analytical approach based on single cell and single particle inductively coupled plasma mass spectrometry analysis to determine silver species involved

The bactericidal activity of silver nanoparticles is supported by a large number of studies, but their action mechanisms are still a controversial issue due to the role of the silver (I) released from the nanoparticles. In this study, direct analytical methods for detection and identification of dissolved and nanoparticulate silver based on single cell and single particle inductively coupled plasma mass spectrometry (ICP-MS) and hydrodynamic chromatography ICP-MS, in combination with alkaline digestions, have been used. Detection of silver species in Escherichia coli bacteria exposed to silver allowed to confirm the different bactericidal activity associated with silver nanoparticles of different sizes. In the case of 10 nm silver nanoparticles, a combined ion-particle action would be responsible for bactericidal effect, since ionic silver was not detected in the culture medium and both dissolved and particulate silver were detected in the exposed bacteria. On the other hand, bacteria did not internalize 60 nm silver nanoparticles and their bactericidal activity was related to the ionic silver released in the culture medium.

Silver Complex Bearing N-Heterocyclic Carbene Bidentate Chelating Ligand as an Efficient Catalyst in Solvent-Free KA2 Coupling.

We report a synthesis of silver complexes bearing chelating bidentate N-heterocyclic carbene, with various substitutions at the terminal positions of the imidazole moiety of the NHC units. The long aliphatic substituents proved to be beneficial in terms of the synthetic efficiency of the complexes, compared to previously reported methyl substitution. The complexes demonstrated excellent suitability for the KA2 coupling reaction, providing quaternary carbon-containing propargylic amines in yields up to 95 %, under solvent-free conditions. The method showed high tolerance for a wide range of substrates, including naturally occurring ketones, underscoring its practicality. To our knowledge, this represents the first use of a well-defined silver species in KA2 coupling, marking an advancement in the field.

Silver-Catalyzed Coupling of Unreactive Carboxylates: Synthesis of α-Fluorinated O-Aryl Esters.

α-Fluorinated aryl esters pose a challenge in synthesis via O-arylation of α-fluorinated carboxylates owing to their low reactivities. This limitation has been addressed by combining a silver catalyst with aryl(trimethoxyphenyl)iodonium tosylates to access α-fluorinated aryl esters. We envision that the catalytic system involves high-valent aryl silver species generated via the oxidation of silver(I) salt. The present method provided a synthetic protocol for various α-fluorinated aryl esters including fluorinated analogs of drug derivatives.

Atomically Precise Control of Silver Species Encaged in Zeolite Catalysts with Minimal Loading for Maximal Performance

Atomically Precise Control of Silver Species Encaged in Zeolite Catalysts with Minimal Loading for Maximal Performance

Temperature-driven dynamic evolution process of Ag species on silver-loaded Zr0.2Sn0.8O2 catalyst for selective catalytic oxidation of ammonia

Silver-based catalysts are extensively utilized in the selective catalytic oxidation of ammonia (NH3-SCO). However, enhancing low-temperature activity often causes a decline in N2 selectivity, presenting a substantial challenge in balancing activity and N2 selectivity. In this work, we introduced zirconium into the SnO2 support, resulting in a significant enhancement of low-temperature activity by 200 °C for the Ag/Zr0.2Sn0.8O2 catalyst; yet, this also led to the formation of N2O at low temperatures and NOx at high temperatures. Characterizations such as XPS and in situ DRIFTS revealed that the dynamic changes of silver species driven by temperature had a profound impact on the reaction mechanism and guided the formation of different products. Below 200 °C, the predominance of Ag+ directed the imide mechanism, with the –HNO species being the key intermediate leading to the production of N2O. Above 300 °C, Ag0 became dominant, favoring the internal selective catalytic reduction (i-SCR) mechanism and the production of NOx. This work provides novel insights into improving N2 selectivity of Ag-based catalysts and contributes to a deeper understanding of the reaction mechanisms.

Facile synthesis of Cu@Ag/SiO2 catalysts for the selective hydrogenation of dimethyl oxalate to methyl glycolate

A promising route for producing biodegradable polyglycolic acid material from syngas has garnered increasing attentions. In this route, one of the pivotal issues is developing favorable catalysts for semi-hydrogenation of dimethyl oxalate (DMO) to methyl glycolate (MG). Silver catalysts were reported to be effective but suffered from the high cost. Herein, we prepared small-sized Cu@Ag/SiO2 catalysts with appropriate Ag/Cu ratios by a facile wet impregnation method. This core–shell structure facilitated the intermetallic electronic transference from Cu to Ag. The surface exposure of electron-rich silver species could promote the catalytic activity and MG desorption in the DMO hydrogenation, which achieved high efficiency without compromising the MG selectivity. The optimal catalyst with Ag/Cu mass ratio of 3/2 displayed excellent space time yield towards MG of 47.3 g·gAg−1·h−1. These insights could offer a potential strategy to reduce the silver-based catalyst cost for the semi-hydrogenation of DMO to MG.

Silver Organometallics that are Highly Potent Thioredoxin and Glutathione Reductase Inhibitors: Exploring the Correlations of Solution Chemistry with the Strong Antibacterial Effects.

The antibacterial activity of silver species is well-established; however, their mechanism of action has not been adequately explored. Furthermore, issues of low-molecular silver compounds with cytotoxicity, stability, and solubility hamper their progress to drug leads. We have investigated silver N-heterocyclic carbene (NHC) halido complexes [(NHC)AgX, X = Cl, Br, and I] as a promising new type of antibacterial silver organometallics. Spectroscopic studies and conductometry established a higher stability for the complexes with iodide ligands, and nephelometry indicated that the complexes could be administered in solutions with physiological chloride levels. The complexes showed a broad spectrum of strong activity against pathogenic Gram-negative bacteria. However, there was no significant activity against Gram-positive strains. Further studies clarified that tryptone and yeast extract, as components of the culture media, were responsible for this lack of activity. The reduction of biofilm formation and a strong inhibition of both glutathione and thioredoxin reductases with IC50 values in the nanomolar range were confirmed for selected compounds. In addition to their improved physicochemical properties, the compounds with iodide ligands did not display cytotoxic effects, unlike the other silver complexes. In summary, silver NHC complexes with iodide secondary ligands represent a useful scaffold for nontoxic silver organometallics with improved physicochemical properties and a distinct mechanism of action that is based on inhibition of thioredoxin and glutathione reductases.

The Therapeutic Potential in Cancer of Terpyridine-Based Metal Complexes Featuring Group 11 Elements.

Terpyridine-based complexes with group 11 metals emerge as potent metallodrugs in cancer therapy. This comprehensive review focuses on the current landscape of anticancer examples, particularly highlighting the mechanisms of action. While Cu(II) complexes, featuring diverse ancillary ligands, dominate the field, exploration of silver and gold species remains limited. These complexes exhibit significant cytotoxicity against various cancer cell lines with a commendable selectivity for non-tumorigenic cells. DNA interactions, employing intercalation and groove binding, are pivotal and finely tuned through terpyridine ligand functionalization. In addition, copper complexes showcase nuclease activity, triggering apoptosis through ROS generation. Despite silver's high affinity for nitrogen donor atoms, its exploration is relatively sparse, with indications of acting as intercalating agents causing DNA hydrolytic cleavage. Gold(III) compounds, overshadowing gold(I) due to stability concerns, not only intercalate but also induce apoptosis and disrupt the mitochondrial membrane. Further investigations are needed to fully understand the mechanism of action of these compounds, highlighting the necessity of exploring additional biological targets for these promising metallodrugs.

Regioselective Arylation of Amidoaryne Precursors via Ag-Mediated Intramolecular Oxy-Argentation.

An unprecedented silver-mediated intramolecular oxy-argentation of 3-amidoaryne precursors that quickly generates a heteroarylsilver species is developed. AgF acts as both a stoichiometric fluoride source and a reagent for the formation of a benzoxazolylsilver intermediate via aryne generation. Pd-catalyzed coupling reactions of (hetero)aryl iodides with a silver species, generated in situ, allow for the synthesis of various C7-arylated benzoxazoles. As a result, an aryl group is selectively introduced into the meta-position of 3-amidobenzyne precursors. Mechanistic studies have indicated the presence of a benzoxazolylsilver intermediate and revealed that the reaction proceeds via an intramolecular oxy-argentation process, which is initiated by a direct fluoride attack on the silyl group.

Detailed Insight into Photocatalytic Inactivation of Pathogenic Bacteria in the Presence of Visible-Light-Active Multicomponent Photocatalysts.

The use of heterogeneous photocatalysis in biologically contaminated water purification processes still requires the development of materials active in visible light, preferably in the form of thin films. Herein, we report nanotube structures made of TiO2/Ag2O/Au0, TiO2/Ag2O/PtOx, TiO2/Cu2O/Au0, and TiO2/Cu2O/PtOx obtained via one-step anodic oxidation of the titanium-based alloys (Ti94Ag5Au1, Ti94Cu5Pt1, Ti94Cu5Au1, and Ti94Ag5Pt1) possessing high visible light activity in the inactivation process of methicillin-susceptible S. aureus and other pathogenic bacteria-E. coli, Clostridium sp., and K. oxytoca. In the samples made from Ti-based alloys, metal/metal oxide nanoparticles were formed, which were located on the surface and inside the walls of the NTs. The obtained results showed that oxygen species produced at the surface of irradiated photocatalysts and the presence of copper and silver species in the photoactive layers both contributed to the inactivation of bacteria. Photocatalytic inactivation of E. coli, S. aureus, and Clostridium sp. was confirmed via TEM imaging of bacterium cell destruction and the detection of CO2 as a result of bacteria cell mineralization for the most active sample. These results suggest that the membrane ruptures as a result of the attack of active oxygen species, and then, both the membrane and the contents are mineralized to CO2.

Ionic and nanoparticulate silver alleviate the toxicity of inorganic mercury in marine microalga Chaetoceros muelleri.

Toxicological effects of silver nanoparticles (SNPs) in different organisms have been studied; however, interactions of SNPs with other environmental pollutants such as mercury are poorly understood. Herein, bioassay tests were performed according to ΟECD 201 guideline to assess the toxic effects induced by mercury ions (mercury chloride, MCl) on the marine microalga Chaetoceros muelleri in the presence of SNPs or silver ions (silver nitrate, SN). Acute toxicity tests displayed that the presence of SNPs or SN (0.01mg L-1) significantly reduced the toxicity of MCl (0.001, 0.01, 0.1, 1, 10, and 100mg L-1) and increased the IC50 of MCl from 0.072 ± 0.014 to 0.381 ± 0.029 and 0.676 ± 0.034mg L-1, respectively. In the presence of SN or SNPs, the mercury-reducing effect on algal population growth significantly decreased. Considering the increase of IC50, the mercury toxicity decreased approximately 5.44 and 9.66 times in the presence of SNPs or SN, respectively. The chlorophyll a and c contents decreased at all exposures; however, the decrease by MCl-SNPs and MCl-SN was significantly less than MCl except at 1mg L-1. The lowering effect of MCl-SN on chlorophyll contents was less than MCl and MCl-SNPs. MCl exposure induced significant raises in total protein content (TPC) at concentrations < 0.01mg L-1, with a maximum of ~ 70.83% attained at 100mg L-1. The effects of MCl-SNPs and MCl-SN on TPC were significantly less than MCl. Total lipid content (TLC) at all MCl concentrations was higher than the control, while at coexposure to MCl-SN, TLC did not change until 0.01mg L-1 compared with the control. The effects of MCl-SN and MCL-SNPs on TPC and TLC were in line with toxicity results, and were significantly less than those of MCl individually, confirming their antagonistic effects on MCl. The morphological changes of algal cells and mercury content of the cell wall at MCl-SN and MCl-SNPs were mitigated compared with MCl exposure. These findings highlight the mitigatory impacts of silver species on mercury toxicity, emphasizing the need for better realizing the mixture toxicity effects of pollutants in the water ecosystem.

Photocatalytic oxidation of methane to methanol over zinc titanate supported silver catalysts

The direct activation of methane under mild condition to achieve highly selective of oxygenates is a challenging project. In this study, a well dispersed silver supported ZnTiO3 catalyst was prepared to achieve selective preparation of methanol from methane and water under mild condition. X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy characterizations demonstrate that silver species are uniformly dispersed on ZnTiO3 surface in the form of metallic silver nanoparticles. The photoelectric characterizations reveal that the addition of silver species enhances light absorption and promotes charge separation of the catalysts. Under the reaction conditions of 50 °C and 3 MPa, the methanol is obtained as the only liquid product over the designed Ag/ZnTiO3 catalyst under light irradiation. In this photocatalytic process, the holes generated by ZnTiO3 activate water to produce intermediate ·OH, which further reacts with methane to synthesize methanol. The silver species as co-catalysts extend the light absorption range of ZnTiO3 as well as promote charge separation.

Surface and bulk transformations of Ag2CuMnO4 delafossite during the interaction with CO+O2 mixture

Ternary oxide of silver, copper and manganese (Ag2CuMnO4) with delafossite-type structure demonstrates excellent catalytic activity in the reaction of CO oxidation at room temperature and even below. To prepare delafossite-based catalyst the hydrothermal approach using metal nitrates in alkaline solution with an excess of peroxodisulphate was applied. X-ray diffraction pattern of Ag2CuMnO4 particles was successfully simulated taking into an account crystallite shape anisotropy, particle size distribution, the presence of stacking faults, and the lattice expansion along c axis. As-prepared Ag2CuMnO4 sample was characterized by the presence of Ag1+-, Cu2+- and Mn4+-like surface species predominantly. In situ XRD data revealed the thermal stability of delafossite-type structure in catalytic CO+O2 mixture up to 500 °C, while ex situ XPS showed an evident reorganization of Ag2CuMnO4 surface at markedly lower temperatures (200–250 °C). Heating in CO+O2 medium at 150–400 °C also resulted in significant catalytic activation of Ag2CuMnO4 owing to the Mn enrichment and optimization of manganese and copper electronic exchange. The low-temperature activity of Ag2CuMnO4 catalyst in CO+O2 reaction was proposed to be mainly provided by redox transitions with the participation of Cu1+/Cu2+ and Mn3+/Mn4+ couples, while the catalytic role of silver species is considered as auxiliary only. The innovation point of this work is related to the investigation of the dynamics of surface and bulk structure transformations in connection with the catalytic activation of delafossite particles for the low-temperature oxidation.

Effect of pH on mussel shells-originated HAP supported Ag catalysts for catalytic combustion of VOCs

Volatile organic compounds (VOCs) triggered serious air pollution and mussel shell caused the marine environmental issues. Herein, hydroxyapatite (HAP) using mussel shells as calcium source was prepared by hydrothermal method with different pH (pH = 6, 8, 10, 11) controls to support Ag catalyst for removal of VOCs. It was found that the amount of skeletal hydroxyl species and textual properties of HAP were controlled by pH effectively, and the increase of hydroxyl groups in the framework resulted in forming smaller-sized Ag2O particles. When pH was 8, the Ag/HAP-BpH=8 catalyst exhibited 100 % conversion of ethyl acetate and toluene at 260 °C and 300 °C, respectively. Silver species were more likely existed on the surface of HAP-BpH=8 to form large-size Ag particles (6.4 nm) and more Ag2O species. The lower ratio of Ag0/Ag+ were crucial for improving the VOCs oxidation activity at lower temperatures. This work applied waste mussel shells to prepare high value-added Ag/hydroxyapatite catalysts and to promote VOCs catalytic oxidation.

Quantifying the probability of invasive carp introduction via freshwater diversions: Arrival Assessment

AbstractThe Mississippi River is host to multiple species of invasive carp, including bighead, silver, and black carp, which have been linked to negative ecological impacts upon introduction to a waterbody. Most of the rivers emptying into the Gulf of Mexico are hydrologically separated from the Mississippi River by seawater and have historically been considered safe from an invasion of carp attempting to traverse coastal waters due to their intolerance of seawater salinity levels. However, there is growing concern that freshwater diversions of the Mississippi River into brackish or saltwater systems could reduce salinity to a level that allows entrained carp to navigate freshwater plumes to uninvaded rivers. To help quantify this risk, we conducted an Arrival Assessment that estimates the number of invasive carp that will enter a receiving waterbody through a single freshwater diversion event. A case study using the Bonnet Carré Spillway is presented here to illustrate how water managers and spillway operators can derive predictions for a specific spillway and how mitigative steps can be taken to target the most influential parameters and help reduce the number of carp that pass. The findings of this case study suggest that, for an average spillway opening event, the number of invasive carp that pass through the Bonnet Carré Spillway is higher than many water managers may be willing to accept. This Arrival Assessment serves as the first of three components within a broader, forthcoming quantitative risk assessment that will also consider the number of carp that survive (Survival Assessment) to reach a suitable, uninvaded river for reproduction and population sustainment (Establishment Assessment) and determine the magnitude and uncertainty of the risk of introduction to uninvaded waters downstream from a freshwater diversion that forms a hydrological connection to a source waterbody inhabited by invasive carp.

Dual colorimetric detection and chemical reduction toward silver ions of imidazole-conjugated poly(diacetylenes)

In this article, we reported a new poly(diacetylenes)-based sensor (PDA-IBA) for silver ion detection and reduction through the chelation of imidazole moiety. The poly(diacetylenes) polymer functionalized with imidazole groups. As the concentration of silver ions in the solution increased, the PDA surface underwent oxidation concurrently with the reduction of silver ions was demonstrated through imidazole receptor. This chemical reaction resulted in a noticeable change in the color of the solution, shifting from blue to dark red. The limit of detection (LOD) was determined to be 0.034 mM. Zeta potential data analysis and electrochemical measurements further confirmed the PDA-IBA was capable to reduce Ag+ into Ag0. Moreover, the silver species produced were validated through inductively coupled plasma optical emission spectrometry (ICP-OES). Additionally, the color change observed in PDA-IBA as a response to silver ions was effectively demonstrated by integrating it into a paper-based sensor. This study introduces an innovative and promising approach for enhancing the capabilities of chemosensors in detecting and reducing Ag+.

Silver-Exchanged Zeolite Y Catalyzes a Selective Insertion of Carbenes into C–H and O–H Bonds

Silver-Exchanged Zeolite Y Catalyzes a Selective Insertion of Carbenes into C–H and O–H Bonds