Titration of cyanide and hexacyanoferrate(II) with silver nitrate-I Calculation of titration curves for potentiometric and conductometric titration

Stepwise potentiometric titration of cyanide and hexacyanoferrate(II) with silver nitrate is possible in the absence of potassium ions. At an initial concentration below 5.00 x 10(-4)M, cyanide can be titrated with silver nitrate (Ag:CN = 1:2) and the end-point indicated by precipitation of silver hexacyanoferrate(II); hexacyanoferrate(II) can be titrated with silver nitrate (Ag: Fe(CN)(6) = 4:1) and the end-point indicated by precipitation of silver dicyanoargentate. The hexacyanoferrate(II) reacts with silver to form two poorly soluble salts, Ag(4)Fe(CN)(6), KAg(3)Fe(CN)(6). The formation of these salts has been confirmed by conductometric titration of hexacyanoferrate(II) with silver nitrate in solutions containing varying concentrations of potassium nitrate.     

Mechanisms of Diffusion-Reduction Interaction of Microcrystalline Cellulose and Silver Ions

The preparation of microcrystalline cellulose samples containing intercalated silver(0) particles includes two main stages: diffusion of silver ions from aqueous AgNO₃ into the microcrystalline cellulose matrix, followed by reduction of the silver ions bound to cellulose macromolecules to Ag(0) and growth of Ag(0) particles inside the cellulose matrix and on its surface. Mechanisms of interaction of silver ions with cellulose as reducer and with other reducers and ligands are considered.     

Antibacterial activity of silver bionanocomposites synthesized by chemical reduction route

ABSTRACT: BACKGROUND: The aim of this study is to investigate the functions of polymers and size of nanoparticles on the antibacterial activity of silver bionanocomposites (Ag BNCs). In this research, silver nanoparticles (Ag NPs) were incorporated into biodegradable polymers that are chitosan, gelatin and both polymers via chemical reduction method in solvent in order to produce Ag BNCs. Silver nitrate and sodium borohydride were employed as a metal precursor and reducing agent respectively. On the other hand, chitosan and gelatin were added as a polymeric matrix and stabilizer. The antibacterial activity of different sizes of silver nanoparticles was investigated against Gram-positive and Gram-negative bacteria by the disk diffusion method using Mueller-Hinton Agar. RESULTS: The properties of Ag BNCs were studied as a function of the polymer weight ratio in relation to the use of chitosan and gelatin. The morphology of the Ag BNCs films and the distribution of the Ag NPs were also characterized. The diameters of the Ag NPs were measured and their size is less than 20 nm. The antibacterial trait of silver/chitosan/gelatin bionanocomposites was investigated. The silver ions released from the Ag BNCs and their antibacterial activities were scrutinized. The antibacterial activities of the Ag BNC films were examined against Gram-negative bacteria (E. coli and P. aeruginosa) and Gram-positive (S. aureus and M. luteus) by diffusion method using Muller-Hinton agar. CONCLUSIONS: The antibacterial activity of Ag NPs with size less than 20 nm was demonstrated and showed positive results against Gram-negative and Gram-positive bacteria. The Ag NPs stabilized well in the polymers matrix.     

Production of chiral matrices with hybrid silver–thiocholesterol nanosystems and study of their properties

A new type of chiral matrix based on silver–thiocholesterol hybrid nanosystems adsorbed on silica gel has been proposed. The molar ratio of stabilized thiocholesterol (L) ligand and silver (Ag) was found to have little effect on the size of the resulting silver nanoparticles (SNPs). The average diameter of SNPs was 2.7 ± 0.4, 2.2 ± 0.4, and 2.1 ± 0.6 nm upon the ratios Ag: L = 1: 5, Ag: L = 1: 2, and Ag: L = 1: 0.5, respectively. The resulting chiral matrices possess enantioselectivity relative to the 1,1’-binaphthyl-2,2’-diamine (BNDA) and trifluoroanthranyl ethanol (TFAE) optical isomers. The TFAE optical isomers were successfully separated using thin layer chromatography (α = 1.56).     

Hyperstoichiometric interaction between silver and mercury at the nanoscale

Breaking through the stoichiometry barrier: as the diameter of silver particles is decreased below a critical size of 32 nm, the molar ratio of aqueous Hg(II) to Ag(0) drastically increases beyond the conventional Hg/Ag ratio of 0.5:1, leading to hyperstoichiometry with a maximum ratio of 1.125:1. Therein, around 99% of the initial silver is retained to rapidly form a solid amalgam with reduced mercury.     

Activation of the C-I and C-OH bonds of 2-iodoethanol by gas phase silver cluster cations yields subvalent silver-iodide and -hydroxide cluster cations

The gas phase ion-molecule reactions of silver cluster cations (Ag(n)(+)) and silver hydride cluster cations (Ag(m)H(+)) with 2-iodoethanol have been examined using multistage mass spectrometry experiments in a quadrupole ion trap mass spectrometer. These clusters exhibit size selective reactivity: Ag(2)H(+), Ag(3)(+), and Ag(4)H(+) undergo sequential ligand addition only, while Ag(5)(+) and Ag(6)H(+) also promote both C-I and C-OH bond activation of 2-iodoethanol. Collision induced dissociation (CID) of Ag(5)HIO(+), the product of C-I and C-OH bond activation by Ag(5)(+), yielded Ag(4)OH(+), Ag(4)I(+) and Ag(3)(+), consistent with a structure containing AgI and AgOH moieties. Ag(6)H(+) promotes both C-I and C-OH bond activation of 2-iodoethanol to yield the metathesis product Ag(6)I(+) as well as Ag(6)H(2)IO(+). The metathesis product Ag(6)I(+) also promotes C-I and C-OH bond activation.DFT calculations were carried out to gain insights into the reaction of Ag(5)(+) with ICH(2)CH(2)OH by calculating possible structures and their energies for the following species: (i) initial adducts of Ag(5)(+) and ICH(2)CH(2)OH, (ii) the subsequent Ag(5)HIO(+) product, (iii) CID products of Ag(5)HIO(+). Potential adducts were probed by allowing ICH(2)CH(2)OH to bind in different ways (monodentate through I, monodentate through OH, bidentate) at different sites for two isomers of Ag(5)(+): the global minimum "bowtie" structure, 1, and the higher energy trigonal bipyramidal isomer, 2. The following structural trends emerged: (i) ICH(2)CH(2)OH binds in a monodentate fashion to the silver core with little distortion, (ii) ICH(2)CH(2)OH binds to 1 in a bidentate fashion with some distortion to the silver core, and (iii) ICH(2)CH(2)OH binds to 2 and results in a significant distortion or rearrangement of the silver core. The DFT calculated minimum energy structure of Ag(5)HIO(+) consists of an OH ligated to the face of a distorted trigonal bipyramid with I located at a vertex, while those for both Ag(4)X(+) (X = OH, I) involve AgX bound to a Ag(3)(+) core. The calculations also predict the following: (i) the ion-molecule reaction of Ag(5)(+) and ICH(2)CH(2)OH to yield Ag(5)HIO(+) is exothermic by 34.3 kcal mol(-1), consistent with the fact that this reaction readily occurs under the near thermal experimental conditions, (ii) the lowest energy products for fragmentation of Ag(5)HIO(+) arise from loss of AgI, consistent with this being the major pathway in the CID experiments.     

Silver-109 NMR spectroscopy of inorganic solids

In this study the (109)Ag NMR spectra of the following solid inorganic silver-containing compounds were investigated: AgNO(3), AgNO(2), Ag(2)SO(4), Ag(2)SO(3), AgCO(3), Ag(3)PO(4), AgCl, AgBr, AgI, AgSO(3)CH(3), silver p-toluenesulfonate, NaAg(CN)(2), KAg(CN)(2), K(3)Ag(CN)(4), Me(4)NAgCl(2), silver diethylthiocarbamate, silver lactate, silver acetate, silver citrate, and bis[(N,N(1)-di-tert-butylformamidinato)silver(I)]. The magic angle spinning (MAS) spectra of all compounds were obtained. In some cases, when protons were available, the (1)H to (109)Ag cross-polarization (CP) technique was used to enhance the signal and shorten the experimental relaxation delay. It was possible to obtain slow MAS (or CP/MAS) or nonspinning spectra for 10 samples, allowing the determination of the principal components of the (109)Ag chemical shift (CS) tensors. The isotropic chemical shifts and the CS tensors are discussed in light of the available crystal structures. The need for an accepted standard for referencing (109)Ag chemical shifts and the use of AgSO(3)CH(3) as a CP setup sample are also discussed.     

Gas phase synthesis and reactivity of Agn+ and Ag(n-1)H+ cluster cations

Multi-stage mass spectrometry (MSn) on [(M + Ag - H)x + Ag]+ precursor ions (where M = an amino acid such as glycine or N,N-dimethylglycine) results in the formation of stable silver (Ag3+, Ag5+ and Ag7+) and silver hydride (Ag2H+, Ag4H+ and Ag6H+) cluster cations in the gas phase. Deuterium labelling studies reveal that the source of the hydride can be either from the alpha carbon or from one of the heteroatoms. When M = glycine, the silver cyanide clusters Ag4CN+ and Ag5(H,C,N)+ are also observed. Collision induced dissociation (CID) and DFT calculations were carried out on each of these clusters to shed some light on their possible structures. CID of the Agn+ and Ag(n-1)H+ clusters generally results in the formation of the same Ag(n-2)+ product ions via the loss of Ag2 and AgH respectively. DFT calculations also reveal that the Agn+ and Ag(n-1)H+ clusters have similar structural features and that the Ag(n-1)H+ clusters are only slightly less stable than their all silver counterparts. In addition, Agn+ and Ag(n-1)H+ clusters react with 2-propanol and 2-butylamine via similar pathways, with multiple ligand addition occurring and a coupled deamination-dehydration reaction occurring upon condensation of a third (for Ag2H+) or a fourth (for all other silver clusters) 2-butylamine molecule onto the clusters. Taken together, these results suggest that the Agn+ and Ag(n-1)H+ clusters are structurally related via the replacement of a silver atom with a hydrogen atom. This replacement does not dramatically alter the cluster stability or its unimolecular or bimolecular chemistry with the 2-propanol and 2-butylamine reagents.     

Fabrication of a Simple and Cheap Screen-printed Silver/Silver Chloride (Ag/AgCl) Quasi-reference Electrode

In this work, a silver/silver chloride ink is fabricated using two steps. First the silver ink is prepare using silver, nail polish and acetone. Then the silver ink is painted in a paper substrate and a silver chloride layer is deposited using a bleach solution. The result is the silver/silver chloride conductive ink. The silver ink is cheap ($2.49/g), well-dispersive and very easy to fabricate. The materials were characterized by SEM and XRD. The Ag ink showed the formation of a continuous network throughout the silver ink film with fewer agglomeration. The effective chlorination process was also observed in the Ag/AgCl characterization. Since the Ag/AgCl substrate will be used as a quasi-reference electrode, it is important to investigate the electrical properties. The Ag ink showed an average ohmic resistance of 2.27 Ω. The addition of the AgCl layer decreases the conductivity, as expected. In summary, the Ag/Ag/Cl ink developed is simple, well-dispersed, cheap and with good conductivity. Therefore, it can be used as a conductive ink in the fabrication of quasi-reference electrodes.     

Protection of Ag Clusters by Metal-Oxo Modules

Monodisperse and atomically precise Ag nanoclusters have attracted considerable recent research interest. A conventional silver cluster usually consists of a silver metallic kernel and an organic peripheral ligand shell. Nevertheless, the present inevitable problem is the unsatisfied stability of such nanoclusters. In this concept, we will give an introduction to Ag clusters protected by metal-oxo modules, which exhibit enhanced stability and unique properties. Accordingly, three different types of clusters are summarized: (1) Ag clusters protected by mononuclear oxometallates; (2) Ag clusters protected by block-like metal-oxo clusters; (3) Ag clusters protected by hollow-like metal-oxo clusters. The aim of this concept is to offer possible general guidance and insight into future rational design of more metal-oxo clusters protected silver clusters or even other coinage metal nanoclusters.     

Growth and reactivity of silver clusters in amino polycarboxylic acid solutions

Reduction and subsequent aggregation of silver ions in the presence of various chelating agents such as trans-1,2-diaminocyclohexanetetraacetic acid (DCTA) 1,2-propylenediaminetetraacetic acid (PDTA), diethylenetriaminepentaacetic acid (DTPA), and triethylenetetraaminehexaacetic acid (TTHA) have been studied by pulse radiolysis. Rate constants of formation and transient absorption spectra for the ligand-complexed Ag(0) and Ag(2)(+) have been determined. The redox potential of Ag(+)(L)/Ag(0)(L) becomes more negative than that of Ag(+)/Ag(0). Growth and reactivity of silver clusters were also studied in the presence of methyl viologen (MV(2+)). The kinetics of formation of the MV(+*) radical, produced by the same pulse as in the case of silver atoms, confirms the catalytic electron transfer toward super critical silver clusters in the presence of ligands. The results suggest that catalytic electron transfer activity of silver clusters depends on the ligand.     

Androgynous porphyrins. Silver(II) quinoxalinoporphyrins act as both good electron donors and acceptors

The metal-centered and macrocycle-centered electron-transfer oxidations and reductions of silver(II) porphyrins were characterized in nonaqueous media by electrochemistry, UV-vis spectroelectrochemistry, EPR spectroscopy, and DFT calculations. The investigated compounds are {5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)porphyrinato}silver(II), {5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)quinoxalino[2,3-b']porphyrinato}silver(II), {5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)bisquinoxalino[2,3-b':7,8-b']porphyrinato}silver(II), and {5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)bisquinoxalino[2,3-b':12,13-b']porphyrinato}silver(II). The first one-electron oxidation and first one-electron reduction both occur at the metal center to produce stable compounds with Ag(III) or Ag(I) metal oxidation states, irrespective of the type of porphyrin ligand. The electrochemical HOMO-LUMO gap, determined by the difference in the first oxidation and first reduction potentials, decreases by introduction of quinoxaline groups fused to the Ag(II) porphyrin macrocycle. This provides a unique androgynous character to Ag(II) quinoxalinoporphyrins that enables them to act as both good electron donors and good electron acceptors, something not previously observed in other metalloporphyrin complexes. The second one-electron oxidation and second one-electron reduction of the compounds both occur at the porphyrin macrocycle to produce Ag(III) porphyrin pi-radical cations and Ag(I) porphyrin pi-radical anions, respectively. The macrocycle-centered oxidation potentials of each quinoxalinoporphyrin are shifted in a negative direction, while the macrocycle-centered reduction potentials are shifted in a positive direction as compared to the same electrode reactions of the porphyrin without the fused quinoxaline ring(s). Both potential shifts are due to a stabilization of the radical cations and radical anions by pi-extension of the porphyrin macrocycle after fusion of one or two quinoxaline moieties at the beta-pyrrolic positions of the macrocycle. Introduction of quinoxaline groups fused to the Ag(II) porphyrin macrocycle provides a unique androgynous character to Ag(II) quinoxalinoporphyrins that enables them to act as both good electron donors and good electron acceptors.     

Ionic liquids of bis(alkylethylenediamine)silver(I) salts and the formation of silver(0) nanoparticles from the ionic liquid system

We have prepared novel ionic liquids of bis(N-2-ethylhexylethylenediamine)silver(I) nitrate ([Ag(eth-hex-en)(2)]NO(3) and bis(N-hexylethylenediamine)silver(I) hexafluorophosphate ([Ag(hex-en)(2)]PF(6)), which have transition points at -54 and -6 degrees C, respectively. Below these transition temperatures, both the silver complexes assume amorphous states, in which the extent of the vitrification is larger for the eth-hex-en complex than for the hex-en complex. The diffusion coefficients of both the complex cations, measured between 30 (or 35) and 70 degrees C, are largely dependent on temperature; the dependence is particularly large in the case of the eth-hex-en complex cation below 40 degrees C. Small-angle X-ray scattering studies showed that the bilayer structure of the metal complex is formed in the liquid state for both the silver complexes. A direct observation of the yellowish [Ag(eth-hex-en)(2)]NO(3) liquid by transmission electron microscopy (TEM) indicates the presence of nanostructures, as a microemulsion, of less than 5 nm. Such structures were not clearly observed in the [Ag(hex-en)(2)]PF(6) liquid. Although the [Ag(eth-hex-en)(2)]NO(3) liquid is sparingly soluble in bulk water, it readily incorporates a small amount of water up to [water]/[metal complex] = 7:1. Homogeneous and uniformly sized silver(0) nanoparticles in water were created by the reduction of the [Ag(eth-hex-en)(2)]NO(3) liquid with aqueous NaBH(4), whereas silver(0) nanoparticles were not formed from the [Ag(hex-en)(2)]PF(6) liquid in the same way.     

Preparation and characterization of activated carbon fibers supported with silver metal for antibacterial behavior

In this work, the effect of immersion in silver nitrate solution on activated carbon fibers (ACFs) was investigated in relation to adsorption behavior and antibacterial activity of ACFs supported with silver (ACF/Ag). The pore and surface properties were studied in terms of BET volumetric measurement with nitrogen adsorption, X-ray diffraction (XRD), and scanning electron microscopy (SEM). The antibacterial activities of ACF/Ag were studied in broth dilution tests against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) from a point of view of water purification. As an experimental result, the silver content of ACF/Ag increased with increasing concentration of silver nitrate. It was found that the micropore structure slightly decreased as the silver nitrate concentration increased. Otherwise, it was revealed that the ACF/Ag possessed a strong antibacterial activity and an inhibitory effect for the growing of E. coli and S. aureus, respectively. Silver content on ACF/Ag decreased rapidly because of rough morphology of silver particles in water erosion.     

Ag+及其配合物在活性炭上吸附行为研究

研究了配位体和氧化改性对活性炭吸附Ag^ 及其配合物的影响以及银在活性炭表面的分布特征。结果表明：(1)活性炭对Ag^ 的吸附非常快,且不受离子强度的影响．但当Ag^ 形成[Ag(NH3)2]^ 和[Ag(S2O3)2]^3-后在活性炭上吸附性能下降,氨水浓度增加对[Ag(NH3)2]^ 的吸附没有影响,而还原性的Na2S2O3浓度增加使[Ag(S2O3)2]^3-的吸附下降。(2)银主要分布在活性炭的外表面,Ag^ 浓度和吸附时间不同将导致银颗粒的分布及粒径也不同,合理控制Ag^ 浓度和吸附时间,就可以在活性炭表面负载纳米金属银．(3)活性炭氧化改性不利于Ag^ 和[Ag(S2O3)2]^3-的吸附,却有利于[Ag(NH3)2]^ 的吸附。     

Infrared spectra of the (AgCO)2 and AgnCO (n=2-4) molecules in rare-gas matrices

Reactions of laser-ablated silver atoms with carbon monoxide molecules in solid argon and neon have been investigated using matrix-isolation IR spectroscopy. Small silver cluster carbonyls, (AgCO)2 and AgnCO (n=2-4), as well as mononuclear silver carbonyls, Ag(CO)2 and Ag(CO)3, are generated upon sample annealing in the argon experiments and are characterized on the basis of the isotopic substitution, the CO concentration change, and the comparison with theoretical predictions. However, these polynuclear carbonyls are absent from the neon experiments. Density functional theory calculations have been performed on these silver carbonyls and the corresponding ligand-free silver clusters, which support the identification of these silver carbonyls from the matrix IRspectrum. A terminal CO has been found in the most stable structures of (AgCO)2, Ag2CO, Ag3CO, and Ag4CO. Furthermore, a plausible reaction mechanism has been proposed to account for the formation of the (AgCO)2 and AgnCO (n=2-4) molecules.     

Wolff rearrangement of alpha-diazoketones using in situ generated silver nanoclusters as electron mediators

[reaction: see text] We report Wolff rearrangement of alpha-diazoketones by in situ generated silver nanoclusters (Ag(n)(), 2-4 nm) from silver(I) oxide (Ag(2)O) involving a nonclassical electron-transfer process. Our results show that Ag(n)()(+)/Ag(n)()(0) redox couple allows the initial removal of an electron from alpha-diazoketone and its back-donation after chemical reaction(s). Controlled potential coulometry (CPC) of various alpha-diazoketones results in the realization of Wolff-rearranged carboxylic acids in excellent yields.     

氧化银纳米粒子的制备及其动态受激荧光

采用真空蒸发沉积法和辉光放电氧化法,制备了粒径在5～30 nm之间的可控、空间分布均匀、高纯度的氧化银纳米薄膜,使薄膜成岛状生长和避免光照是制备过程中的两个关键问题.用XPS分析了Ag 3d和O 1s轨道的结合能,计算了银和氧的原子比,证明其成分为Ag2O,用XRD确定了氧化银纳米薄膜最强的衍射峰分别对应Ag2O的（111）、（110）、（200）、（211）晶面族.研究了这种薄膜在可见光波段的光吸收,计算得氧化银的禁带宽度为2.8 eV.在蓝光持续照射几分钟激活后,观察到了其中纳米粒子在蓝光激发下发黄光和绿光,在绿光激发下发红光的现象,这种光致发光具有动态“闪烁”的特点.提出了氧化银光分解引入缺陷能级（如Ag3O, Ag2＋O和Ag3＋O）新的理论模型并对此现象进行定性的解释.     

Textile with silver silica spheres: its antimicrobial activity against <Emphasis Type="Italic">Escherichia coli and Staphylococcus aureus</Emphasis>

The aim of this study was to investigate antimicrobial activity of textiles doped with silver in different forms. Three types of textiles were prepared and examined: textiles doped with commercially available Ag nanoparticles, textiles doped with commercial colloidal silver and textiles doped with silver silica SiO₂/Ag spheres. The specimens of silica submicron spheres were synthesized by the sol–gel method as a matrix for biological active silver. The results of microbiological tests revealed that among three kinds of Ag doped textiles only these doped with SiO₂/Ag spheres are bacteriostatically active. During the experiments minimal inhibiting bacteria growth concentration of active SiO₂/Ag spheres added to textiles was determined.     

Gas phase synthesis, structure and unimolecular reactivity of silver iodide cluster cations, Ag(n)I(m)(+) (n = 2-5, 0 < m < n)

Multistage mass spectrometry (MS(n)) experiments reveal that gas phase silver iodide cluster cations, Ag(n)I(m)(+), are readily built up in a stepwise fashion via ion-molecule reactions between mass selected silver (Ag(3)(+) and Ag(5)(+)) or silver hydride (Ag(2)H(+) and Ag(4)H(+)) cluster cations and allyl iodide, in contrast to their reactions with methyl iodide, which solely result in ligation of the clusters. The stoichiometries of these clusters range from 1 < or = n < or = 5 and 1 < or = m < or = 4, indicating the formation of several new subvalent silver iodide clusters. Collision induced dissociation (CID) experiments were carried out on each of these clusters to shed some light on their possible structures. The products arising from CID of the Ag(n)I(m)(+) clusters are highly dependent on the stoichiometry of the cluster. Thus the odd-electron clusters Ag(4)I(2)(+) and Ag(5)I(+) fragment via loss of a silver atom. In contrast, the even-electron cluster ions all fragment via loss of AgI. In addition, Ag(2)I(2) loss is observed for the Ag(4)I(3)(+) and Ag(5)I(2)(+) clusters, while loss of Ag(3)I(3) occurs for the stoichiometric Ag(5)I(4)(+) cluster. DFT calculations were carried out on these Ag(n)I(m)(+) clusters as well as the neutrals associated with the ion-molecule and CID reactions. A range of different isomeric structures were calculated and their structures are described. A noteworthy aspect is that ligation of these silver clusters by I can have a profound effect on the geometry of the silver cluster. For example, D(3h) Ag(3)(+) becomes C(2v) Ag(3)I(+), which in turn becomes C(2h) Ag(3)I(2)(+). Finally, the DFT predicted thermochemistry supports the different types of reaction channels observed in the ion-molecule reactions and CID experiments.