Nicotinamide complex of silver(III) with expanded coordination number

Abstract

In strongly alkaline media ([OH^?]?≥?0.12 M), nicotinamide (nica) forms a complex with square-planar Ag(OH)₄^? [nica]?≥?0.05 M. The complex decomposes in seconds to nicotinamide N-oxide. The correlation of maximum absorbance of the complex with concentrations of nicotinamide and hydroxide requires that the complex is either the five-coordinate Ag(OH)₄(H_-1nica)^2? or the six-coordinate Ag(OH)₅(nica)^2?. Comparison with the reactions of Ag(OH)₄^? with nicotinate ion (nic^?) and acetamide under similar conditions indicates that nicotinamide coordinates with Ag(OH)₄^? by the amido group rather than the nitrogen on the pyridine ring or the amido oxygen. Kinetics of the Ag(III)-nica redox reaction are consistent with direct reaction between nicotinamide and uncoordinated Ag(OH₄)^?. Oxidation takes place at the pyridine ring, yielding nicotinamide N-oxide. Silver(III) is reduced to monovalent silver.     

Preparation and Antibacterial Effect of Bamboo Charcoal/Ag on Staphylococcus Aureus and Pseudomonas Aeruginosa

Bamboo charcoal supporting silver (BC/Ag) was prepared by activation and chemical reduction. The BC/Ag composites were characterized by silver particle size and distribution, silver ion (Ag⁺) release and antibacterial properties. Scanning and transmission electron microscopy (SEM and TEM) showed that the Ag particles were distributed uniformly on the BC matrix. The Ag particle size was found to be less than 150 nm based on TEM. The Ag⁺ release increased initially which was followed by a marginal increase between the 8th and 24th hour. Composites contained higher amounts of silver exhibited a further rise in Ag⁺ release from the 24‐hours of storage in water. The antibacterial effects of the BC/Ag composite powders against Pseudomonas aeruginosa and Staphylococcus aureus were assessed from the minimum inhibitory concentrations (MICs) and minimum bactericidal concentrations (MBCs) method, and an excellent antibacterial performance was discovered.     

A disparate 3-D silver(I) coordination polymer of pyridine-3,5-dicarboxylate and pyrimidine with strong intermetallic interactions: X-ray crystallography,photoluminescence and antimicrobial activity

A polymeric silver(I) complex, [Ag₄(μ-pydc)₂(μ-pm)₂]_n (1) (pydc = pyridine-3,5-dicarboxylate and pm = pyrimidine), has been synthesized and characterized by elemental analysis, IR spectroscopy, thermal analysis, and single-crystal X-ray diffraction. X-ray crystallographic data of 1 revealed that pydc exhibits two different coordinaton modes that play a key role in the construction of the 3-D crystal network including Ag–carboxylate clusters in which close Ag–Ag distances exist. The magnitudes of close Ag–Ag interactions in second-order energy (E²) have been revealed by natural bond orbital analysis performed with single point energy calculation using the experimental geometry of 1. Furthermore, the luminescent properties of 1 show strong fluorescence with two emission maxima in the visible region. Also, 1 has antifungal activity on Candida albicans (MIC value, 4 μg mL^?1) and good antibacterial activity on micro-organisms (MIC value, 64–256 μg mL^?1).     

Ion Exchange Separation Ag(I) from Waste Waters

Abstract

In photographic industry and for preparing silver films, waste waters are rich with silver. Some of the silver is elecroanalytically regenerated, but low concentrations (0.5 gdm^?3) stay in waste waters. In our work, we separated and concentrated the silver by ion exchange resin.

Fixing baths and stop baths are polyvalent solutions, therefore we examine synthetic solutions. For exchange of silver, Amberlit IRA — 120 and Dowex 50 × 4 were used. The batch method was used to obtain a static equilibrium. The optimum medium concentrations and the time for sorption were determined: 1 × 10^?3 mol dm^?3 HNO₃ and 1 hour.

Silver elution from cation exchanger is based on silver transformation to a stable anion complex. Reference data determined the use of CN^? and S₂O₃ ^2- for forming stable complexes. By varying the ligands, pH and eluant concentrations, optimum elution has been in 1 hour, 2M KCN and 1M Na₂S₂O₃.     

Rapid determination of silver in cultivated Japanese and South Korean oysters and Japanese rock oysters using the 24.6-s neutron activation product 110Ag and estimation of its average daily intake

Soft tissues of cultivated Japanese (Miyagi Prefecture) and South Korean (Koje-do and Kosong) oysters and Japanese rock oysters (Honshu Island) were analyzed to measure silver levels. The soft tissues, namely hepatopancreas, gill, muscle, and mantle were separated, freeze-dried, pulverized, and analyzed by an instrumental neutron activation analysis method in conjunction with compton suppression spectrometry (INAA-CSS). The method consisted of the irradiation of samples in a neutron flux of 5 × 10¹¹ cm^?2 s^?1 using the rapid transfer system in an inner pneumatic irradiation site of the Dalhousie University SLOWPOKE-2 reactor (DUSR) facility for 12–15 s, decay for 20 s, and counting for 60 s. The 657.8-keV gamma-ray of the 24.6-s nuclide ¹¹⁰Ag was used for assaying silver. The method was validated using NIST, NRC and NIES certified reference materials. An absolute detection limit of 0.05 μg silver using NIST SRM 1566b Oyster Tissue was achieved. About 10–50 times higher levels of silver were found in cultivated Japanese oysters compared to the South Korean ones. The silver concentrations in cultivated oysters in Miyagi Prefecture showed the following trend: gill > mantle > hepatopancreas > muscle as well as on the age. Rock oysters generally had higher silver content compared to cultivated oysters. A very preliminary value of about 0.466 μg silver average intake per person per day was estimated from the consumption of oysters by the people living in the Sendai city of Miyagi Prefecture.     

KINETICS AND MECHANISM FOR INTRAMOLECULAR ISOMERIZATION OF HRu3 (μ3-η3-EtSCCMeCMe)(CO)9 TO Ru3(μ-SEt) (μ3-η3-CCMeCHMe)(CO)9

Abstract

The kinetics for isomerization of HRu₃ (μ₃-η³-EtSCCMeCMe)(CO)₉ TO Ru₃(μ-SEt) (μ₃-η³-CCMeCHMe)(CO)₉, were determined. The overall process involves C[sbnd]H elimination, C[sbnd]S and Ru[sbnd]Ru bond cleavage and Ru₂(μ-S) bond formation. Activation parameters were determined from the temperature dependence (ΔH^? = 127(3) kJ/mol, ΔS^?= 56(11) J/mol-K) and from the pressure dependence (0[sbnd]207 MPa, ΔV^? ₀ +12.7(1.1) cm³/mol, Δβ^? = +0.037(0.012) cm³/(mol-MPa)) of the rate constant. The data are consistent with an intramolecular reaction involving significant metal-metal or carbon-sulfur bond cleavage in the transition state. The activation volume is too large to be accommodated by C[sbnd]H elimination alone and CO dissociation is not involved.     

Characterization of a Silver Modified PVCAc Electrode and Its Application as a Ag(I)‐Selective Potentiometric Sensor

An all solid‐state Ag(I) ion‐selective electrode has been prepared by simply immersing a glassy carbon rod coated with PVCAc, which contained plasticizer and additive but no ionophore, into the AgNO₃ solution. The response of the electrode was linear with a Nernstian slope of 60.25 mV/decade within the concentration range from 1×10^?1 to 1×10^?5 M and with a detection limit of 4.25×10^?6 M. The stability as an effect of various cations was defined. The electrode is suitable for use in high acidic solutions (pH<1 to 7) and has successfully been applied for the determination of silver(I) concentrations in different samples.     

Determination of silver traces in air by neutron activation analysis

A non-destructive system for determination of silver traces in air particulates collected on cellulose filters is described, based on neutron activation followed by¹¹⁰Ag β⁻ counting instead of the 657.7 keV γ-ray. The determination limit (for 10% confidence limit) is estimated to be about 10⁻⁹ g. The method is easily applicable to the determination of silver in cloud seeding experiments, since the filters themselves provide a consistent and fairly uniform source and samples are collected in general far from industrial areas, where the concentration of possible interfering elements in air is reasonably low.     

A Simplified Neutron Activation Analysis Method for Copper and Manganese

Abstract

An activation analysis procedure has been developed to determine manganese and copper serum values in one milliliter of serum or less rapidly and with good precision. The sample is irradiated in a neutron flux of 10¹²cm^?2 sec^?1 for two hours followed by nitric acid digestion. The activity plus carrier is absorbed from saturated lithium chloride solution on Dowexl-8 contained in a syringe. After washing the resin with more lithium chloride, the syringe is counted in a five inch well crystal multichannel spectrometer. The carrier is washed off the syringe by dilute acid and analyzed. The sample concentration is determined by comparison to irradiated standards correcting the unknown for decay and chemical yield.     

Solid Microelectrodes for In Situ Voltammetric Measurements

Solid Au and Ag microelectrodes for both, model, and in situ voltammetric measurements, have been designed and tested. Amalgamation procedure and the parameters of measurement procedure are discussed. Differences between gold and silver electrodes were studied. Silver electrodes showed more stable behavior and were used prevalently for calibration and in situ measurements. Calibration of a 30‐μm diameter Ag electrode for Mn(II), Fe(II), I(?I) and S(?II) showed good linearity with reasonable confidence intervals, necessary for quantification of the signals obtained in situ, with average sensitivity of 0.05, 0.01, 0.16 and 1.10 nA/(μmol L^?1) and minimal detection limit of 3.5, 28, 0.3 and 0.05 μmol L^?1, respectively. Additional checking of the electrode sensitivity with the reduction peaks of oxygen is proposed.     

Synthesis and structural elucidation of 1-D silver(I) aliphatic carboxylate coordination polymers with 1,3,5-triaza-7-phosphaadamantane/N-methyl-1,3,5-triaza-7-phosphaadamantane

Reactions of silver(I) salts of acetate and trifluoroacetate with 1,3,5-triaza-7-phosphaadamantane (PTA) afforded 1-D coordination polymers [Ag(μ₂-PTA-κ²P?-:N)(μ₂-O₂CCH₃-κ²O:O′)]_n·2nH₂O (1) and [Ag(μ₂-PTA-κ²P:N)(μ₂-O₂CCF₃-κO)]_n·nH₂O (2), while a reaction of silver(I)trifluoroacetate with N-methyl-1,3,5-triaza-7-phosphaadamantane (PTAMe) afforded the coordination polymer [Ag(PTAMe)(μ₃-O₂CCF₃-κ³O:O:O’)(μ₂-O₂CCF₃-κ²O:O′)]_n (3). The coordination polymers were characterized using single-crystal X-ray diffraction. Nuclear magnetic resonance, infrared, and electron spray ionization mass spectrometries were used to initially establish complexation of Ag(I) to the PTA or PTAMe before recrystallization. In the crystal structures of 1 and 2, coordination of the PTA moieties to Ag(I) is via P and N forming chains that are linked through bridging carboxylates. The resulting structural motif can be described as ladder-like in which –[PTA–Ag–PTA]– chains are the strands while the bridging carboxylates comprising of –[Ag–O–C–O]₂– or –[Ag–O]₂– metallacycle rungs of the ladder. Compound 3 forms single-stranded coil-like coordination polymers with two non-equivalent Ag(I) centers, both tetrahedrally coordinated by four oxygens from four trifluoroacetates in one and by three oxygens from the trifluoroacetates and in each by the P of the PTAMe with alternating Ag?Ag interactions. The crystal structures of all three coordination polymers have a variety of fairly strong hydrogen bonds and intermolecular interactions which contribute stabilization of the crystal lattices.     

2-(2-Thiazolylazo)-p-cresol(TAC) as a Reagent for the Spectrophotometric Determination of Lead(II)

Abstract

The reaction between lead(II) and 2-(2-Thiazolylazo)-p-Cresol(TAC) in the presence of TERGITOL NPX (4 mg/ml) at an apparent pH 9.0–10.0 results in an intensely colored complex which is stable for at least 4 hr.

The composition of the complex is 1:2 cation: TAC and the log of the formation constant is 11.92 ± 0. 40. Beer's law is obeyed up to 6.0μg.ml^?1 of lead(II) at 650nm.

The apparent molar absorptivity at 650 nm is 2.07 × 10⁴ 1. mole^?1.cm^?1 and the detection limit was obtained as 10.0 ng.ml^?1 of lead(II).

The method is applied to determination of lead(II) in copper-base alloy.     

The Potential Response Of Copper(Ii) Sulfide Ion Selective Electrode To Hg(Ii) Ions In Aqueous Solution

Abstract

The application of a cupric ion-selective electrode with a membrane of mixed Ag₂S-CuS to measure the activity of Hg(II) is presented. The linear electrode response curve which covers near three decades, from 10^?5 to 10^?2 mol dm^?3, of mercuric concentration range was obtained, under background of acetate buffer.     

Novel Flow Injection/Potentiometric Measurement of Slightly Soluble Salts in Small Volumes: Determination of Solubility Product Constants of Some Silver Salts

Abstract

The flow injection technique is shown to provide fast, reliable and sensitive determination of solubility product constants of silver acetate, silver sulfate, silver oxide, silver bromate and silver chloride in microliter volume samples. Potentiometric detection using electrodes of the first kind and second kind was used for measuring silver ions and chloride ions, respectively. The solubilities were determined from measurement of the silver ion concentration in the saturated solutions. In the case of silver chloride, the solubility product constant was calculated from the concentrations corresponding to the intersection of the silver ion calibration curve and the chloride ion calibration curve, i.e., where the potentials of the two electrodes are equal. Tenth-molar sodium nitrate was used for all solutions to maintain constant ionic strength. At a concentration range of 1.00 × 10^?2 ? 1.00 × 10^?5 M silver, and 1.00 × 10^?2 ? 1.00 × 10^?4 M chloride, a Nernstian response of 60 m V per decade was obtained. At a sampling rate of 50–70 samples per hour, with 50 μl sample injections, high reproducibility of measurements was achieved, with a -pL 2% relative standard deviation in measured concentrations. The scope and applications of this system are discussed.     

Electrical Properties of Silver Photodoped Amorphous Red Phosphorus

Abstract

Effects of photodoping and thermal doping of silver into sputtered amorphous red phosphorus films (a-P_red) on the electrical properties are studied. The d. c. efectrical conductivity of the photodoped a-p_red at room temperature is about 1×10^?5 Scm^?1 which is a very high value comparing with that of the undoped a-p_red (1×10^?14 Scm^?1). The activation energy for the conduction of the photodoped a-P_red is lower than that of the a-p^red. In contrast, the activation energy of the thermally doped a-p_red is essentially the same as that of the undoped a-p_red. SEM-EDX analyses show that colloidal silver was deposited in the thermally doped a-p_red but not in the photodoped a-p_red. It seems that the photo-doping involves the ionization process of silver by illumination, i.e., Ag^o → Ag⁺ + e^?.     

A one-dimensional zigzag coordination polymer: {[Ag(2-amino-3-methylpyridine)](ClO4)}∞

The reaction of silver perchlorate with 2-amino-3-methylpyridine gives a one-dimensional zigzag coordination polymer {[Ag(2-amino-3-methylpyridine)](ClO₄)}_∞ (1) consisting of single chains. The geometry of all Ag(I) cations is linear: each ion links together two 2-pyridyl (Ag1) rings and two 2-amino (Ag2) groups, with the ligand exhibiting a ‘head-to-head’ orientation. Crystal data: monoclinic P2(1)/c, a?=?5.2296(8), b?=?20.668(3), c?=?8.8716(14)?Å, β?=?100.359(3)°, V?=?943.3(3)?ų, Z?=?2, D _c ?=?2.214?Mg/m³, μ?=?2.409?mm^?1, F(000)?=?612, R1?=?0.0426, wR1?=?0.0980 [I?>?2σ(I)], S?=?0.969.     

Environmental impact of radioactive silver released from nuclear power plant

Radioactive silver ^110mAg is not a fission product, but as a contaminant originating from Chernobyl, was registered in many European countries. The environmental impact of radioactive silver was specially expressed in the process of obtaining copper and noble metals from ores originating from opencast mines. Direct consequence was contaminated metal silver in the period of several years after the Chernobyl accident. It was shown that radioactive silver originating from nuclear plants, present in the environment in small concentrations due to the high concentration degrees (10⁴-10⁶) can cause high contamination in the process of the production of metal silver. Experts responsible for the functioning of nuclear power plants should have these facts in mind if they are using silver compounds in reactor core influence area.     

The Oxidation of Aliphatic Hydrocarbons in the Presence of Higher Oxidation States of Silver

Abstract

The compound silver “peroxide”? has been known for some time and its preparation is described in the literature.¹ The structure of this compound has been in dispute; however it appears to have been resolved using neutron diffraction techniques. Scatturin, Bellon and Salkind² have shown that silver “peroxide” is a rather complex material in which silver is present in two different oxidation states, namely Ag(I) and Ag(III). In the crystal, Ag(III) atoms are coordinated to oxygen in a square planar array and the Ag(I) atoms are linearly coordinated. There are no peroxide oxygens. Hence the formula for silver “peroxide” is more properly written Ag(I)Ag(III)02.     

DI-μ-CHLORO-BIS[l,2-BIS(DIPHENYLPHOSPHINO)-ETHANEPALLADIUM(II)]: SYNTHESIS AND CRYSTAL STRUCTURE

Abstract

On reacting 1,2-bis(diphenylphosphino)ethanedichloropalladium(II) with equimolar amount of silver perchlorate, a binuclear complex, di-μ-chloro-bis[1,2-bis(diphenylphosphino)ethane-palladium(II)] (1) is formed. The crystal structure of 1 has been solved. It crystallizes with two chloroform molecules. Chloro bridges are symmetrical and normal (Pd-Cl～2.414(3) Å). The immediate environment around palladium is slightly distorted square planar and the P-Pd-P angle is ～85°. IR bands at 290 and 270cm^?1 are observed for the chloro-bridged core of the complex.     

Non-destructive determination of silver in lead by neutron activation with a 227Ac-Be isotopic neutron source

A method has been developed for the determination of silver in lead by instrumental neutron activation analysis with the aid of a ²²⁷Ac-Be isotopic neutron source. The samples are irradiated for 60 s, allowed to decay for 10 s, and counted for 60 s. ¹¹⁰Ag can be measured free of interferences provided that copper and antimony do not occur in concentrations higher than ca. 1000 p.p.m. A calibration curve was established for silver concentrations between 0 and 4000 p.p.m. by means of standards prepared by melting together high-purity silver and lead under a hydrogen atmosphere. For 17.5-g lead samples, containing between 1000 and 2500 p.p.m. of silver, a mean relative precision of 0.8% was obtained after a 10-min analysis.