Physicochemical study of the nanodiamond surface

Suspensions of five types of ultrafine diamond of a detonation synthesis in distilled water and 0.9 mol/l NaCl solution were found to have pHs in the range of 3–6, which results from the intrinsic acidity of their surfaces. The possibility of quantitatively determining the protogenic groups of a surface is found using the pH-potentiometric method. The data on the kinetics of the varying pH of suspensions in water and 0.9 mol/l NaCl solution and the data on the curves of the alkali titration of the suspensions of nanodiamond in the indicated systems make it possible to infer the presence of one or two types of acid groups on the surface of a diamond. The constants of dissociation (pK ₁) of these groups on the assumption of their single-base nature are estimated. From 1 × 10⁻³−5 × 10⁻² mol/l chloride solutions of H[AuCl₄] and RhCl₃ on the surface of diamond, gold(III) and rhodium(III) are found to be adsorbed; the adsorption of methylene blue from its 2.5 × 10⁻⁴−5 × 10⁻⁴ mol/l solutions reaches more than 90% (upon adsorption from 5 ml of the initial solution by a 0.05-g nanodiamond).     

Synthesis and antimicrobial activities of gold(I) sulfanylcarboxylates

Reaction of NaAuCl₄·H₂O and thiodiglycol (1:3 molar ratio) with 3-(aryl)-2-sulfanylpropenoic acids, H₂ xspa = [x:p = 3-phenyl-, f = 3-(2-furyl)-, t = 3-(2-thienyl)-, o-py = 3-(2-pyridyl)-, Clp = 3-(2-chlorophenyl)-, -o-mp = 3-(2-methoxyphenyl)-, -p-mp = 3-(4-methoxyphenyl)-, -o-hp = 3-(2-hydroxyphenyl)-, -p-hp = 3-(4-hydroxyphenyl)-, diBr-o-hp = 3-(3,5-dibromo-2-hydroxyphenyl)] and 2-cyclopentylidene-2-sulfanylacetic acid (H₂cpa) in a 1:1 metal/ligand molar ratio gave compounds of the type [Au(Hxspa)] or [Au(Hcpa)]. These compounds were reacted with diisopropylamine to afford [HQ][Au(xspa)] or [HQ][Au(cpa)] (HQ = diisopropylammonium) and with NaOH to afford Na[Au(xspa)]·H₂O and Na[Au(cpa)]·H₂O. All of the new compounds were isolated and characterised by IR and ¹H and ¹³C NMR spectroscopy. The antimicrobial activities of the complexes against Escherichia coli, Staphylococcus aureus, Bacillus subtilis, Candida albicans, Pseudomonas aeruginosa and carbapenem-resistant P. aeruginosa were evaluated and compared to those of the equivalent silver(I) complexes. The comparison shows that the gold compounds generally show better activity than the silver analogues against S. aureus and B. subtilis, but low sensitivity against E. coli, P. aeruginosa and C. albicans, suggesting a different mode of antimicrobial action for equivalent silver and gold compounds.     

Oxygen-free precursor for chemical vapor deposition of gold films: thermal properties and decomposition mechanism

Thermal properties of oxygen-, phosphorus-, and halogen-free dimethylgold(III) diethyldithiocarbamate complex (CH₃)₂AuS₂CN(C₂H₅)₂ (gold, dimethyl(diethylcarbamodithioato -S,S′)-) having excellent storage stability and the mechanism of its decomposition to elemental gold were studied. Saturated vapor pressure was found to be ~10⁻³–10⁻¹ Torr at 50–90°C. Decomposition of the vapor on the surface starts at T = 210°C. The temperature dependence of gas phase composition was studied using the original mass spectrometric technique, it was established that the decomposition of the compound on the surface in vacuum follows three main pathways. Two of them result in the formation of elemental gold, saturated C2–C4 alkanes and (1) protonated ligand or (2) methylated ligand. The third one results in elemental gold and gaseous products: C2–C3 alkylmercaptanes and CH₃SCN(C₂H₅)₂. The formation of gold as a sole solid product within the temperature range 210–240°C was confirmed by X-ray photoelectron spectroscopy analysis. It was shown that the compound exhibits the best combination of volatility, thermal, and storage stability among volatile organogold complexes and thus it may be a promising precursor for obtaining gold films by chemical vapor deposition.     

Gold complexes with

The reactions of methane with the gold complexes [Au(OH)]⁻, [Au(OCH₃)₄]⁻, [Au(O(CO)₂O₂]⁻ and [Au(O₂CH)₂]⁺, [Au^I(acac)], [Au^III(acac)₂]⁺ (acac-acetylacetonato) were studied using the DFT/PBE method with the SBK basis set. High activation barriers were obtained for the electrophilic substitution in [Au(OH)]⁻, [Au(OCH₃)⁴]⁻, [Au(O(CO)₂O)₂]-and [Au^III(acac)₂]⁺ complexes, which excludes the possibility that these reactions might proceed under mild conditions. The reactions of the [Au(HCO₂)₂]⁺ and [AuI(acac)] complexes with methane have rather low energy barriers and proceed through the formation of an intermediate complex. The alternative mechanism of methane oxidation with a gold complex in the presence of oxygen is simulated.     

Electroless synthesis of nano-structured gold particles using conducting polymer nanoparticles

In this study, gold nanoparticles were synthesized by electroless recovery of [AuCl₄]⁻ from an acidic aqueous solution using nano-structured conducting polymer, polypyrrole nanoparticles, as active surface. The formation of gold nanoparticles was confirmed by TEM, SEM and EDX measurements. The effects of the initial Au(III) concentration on the gold uptake was examined. The recovery capability and gold particle morphology prepared from polypyrrole nanoparticle were compared to that from cast PPy film counterpart.     

Di-(2-ethylhexyl) dithiophosphoric acid surface protected gold nanoparticles: micellar synthesis, stabilization, isolation, and properties

Gold nanoparticles (AuNPs) were synthesized in the organic solution by means of the reduction of HAuCl₄ by hydrazine in reverse micelles of oxyethylated surfactant Triton N-42, with decane as the dispersion medium. To isolate the powder of particles, the micelles were destroyed with chloroform in the presence of di-(2-ethylhexyl) dithiophosphoric acid as a surface protecting agent. According to the results of several experiments, the yield is within the limits of 90–98%, calculated for gold. The obtained preparations are dark blue hydrophobic powders containing aggregated but not agglomerated gold nanoparticles, as well as microcrystals (∼0.08–0.2 μm) of NaCl. The powders get re-dispersed in weakly polar organic solvents with the formation of colloidal solutions. The shape of the nanoparticles is spherical. Their nuclei are gold single crystals with a narrow size distribution; their diameter (d _Au) is about two times as large as the diameter of the aqueous nucleus (d _c) of initial micelles: d _Au = 7.7 ± 1.4 nm (d _c = 3.6 nm) and 8.8 ± 1.5 nm (4.6 nm). The preparations were studied by means of dynamic light scattering, atomic force microscopy, transmission electron microscopy, UV–vis spectroscopy, IR spectroscopy, X-ray powder diffraction, and thermogravimetric and elemental analyses. In the case of the particles with d _Au = 8.8 nm, the product is a mixture of AuNPs and the salt with the molar ratio Au/NaCl ≈ 1:4.54, while the gross composition of AuNPs per one gold atom is estimated as Au(C₁₆H₃₄O₂PS₂Na∙2N₂H₄)_0.16 with the number of gold atoms in one particle ∼21,000.     

Study on the boundary structures in a series of lanthanide hexacyanoferrate(III) n-hydrates

The properties of a series of lanthanide hexacyanoferrate(III) n-hydrates were studied by means of thermal analysis, IR spectroscopy, Raman spectroscopy and X-ray crystallography. Thermal analyses showed that there were two kinds of complexes in this series, Ln[Fe(CN)₆]·5H₂O (Ln=La–Nd) and Ln′[Fe(CN)₆]·4H₂O (Ln′=Sm–Lu). The boundary complex between them was Nd[Fe(CN)₆]·5H₂O. The IR spectra of the two kinds of complexes were obviously different. For the pentahydrates, there were two sharp CN stretching bands at 2050 and 2140 cm⁻¹, and one band at 1600 cm⁻¹ assigned to the HOH bending. On the other hand, for the tetrahydrates besides the two CN stretching bands at 2050 and 2140 cm⁻¹, a new band was observed at 1940 cm⁻¹, and the HOH bending band split into three bands around 1600 cm⁻¹. From the X-ray crystal analysis, the structure of the boundary complex Nd[Fe(CN)₆]·5H₂O was determined. It belonged to hexagonal, P6₃/m, with a=7.467(2) Å, c=13.793(3) Å and Z=2 (R=0.082, R_w=0.126). Neodymium was nine-coordinated in the form of the NdN₆(H₂O)₃ group. The three coordinated water molecules of the 5H₂O complex with Nd have a large value for the equivalent isotropic thermal parameter. One of the three water molecules was dissociated easily and the 5H₂O complex changed into the stable 4H₂O complex with Nd. The crystal of the 4H₂O complex is orthorhombic, and belongs to the space group Cmcm as well as the other Ln[Fe(CN)₆]·4H₂O (Ln=Sm–Lu). Therefore, the structure of Nd[Fe(CN)₆]·5H₂O is regarded as the boundary structure.     

Infrared brazing of Fe3Al intermetallic compound using gold-based braze alloy

Infrared-brazing Fe₃Al with Au–44Cu as filler metal has been investigated. The brazed joint consists mainly of a β-phase, Au_8 − x Cu_4 + x Al₄, caused by the dissolution of Al from Fe₃Al substrate into the braze alloy. The depletion of Al from Fe₃Al substrate results in the formation of a layer of β-phase particles dispersed in the Fe-rich phase. The highest shear strength for AuCu filler is 327 MPa for specimens infrared brazed at 880°C for 180 s. The brazed joint is mainly fractured along the central β-phase in which the fractograph exhibits quasi-cleavage with dimples. Increasing the brazing time or temperature will deteriorate the bonding strength of the joint, and the fracture mode is prone to cleavage of brittle fracture. Au–44Cu filler demonstrates a great potential for bonding Fe₃Al intermetallic compound.     

Kinetics of forward extraction of Ti（IV） from H_2SO_4 medium by P_（507） in kerosene using the single drop technique

The kinetics of forward extraction of Ti(IV) from H2SO4 medium by P507 in kerosene has been investigated using the single drop technique.In the low concentration region of Ti(IV),the rate of forward extraction at 298 K can be represented by F(kmol·m-2·s-1)=10-5.07 [TiO 2 + ][H+]-1 [NaHA 2 ](o)·Analysis of the rate expression reveals that the rate determining step is(TiO)(i)2+ +(HA 2)(i)-[TiO(HA2)](i)+.The values of Ea,H±,S±,and G±298 are calculated to be 22 kJ·mol-1,25 kJ·mol-1,-218 J·mol-1·K-1,and 25 kJ·mol-1,respectively.The experimental negative S± values indicate that the reaction step occurs via SN2 mechanism.     

Surface tension and thermodynamic properties of liquid Ag-Bi solutions

With the maximum bubble pressure method, the density and surface tension were measured for five Ag-Bi liquid alloys (X _Bi=0.05, 0.15, 0.25, 0.5, and 0.75), as well as for pure silver. The experiments were performed in the temperature range 544–1443 K. Linear dependences of both density and surface tension versus temperature were observed, and therefore the experimental data were described by linear equations. The density dependence on concentration and temperature was derived using the polynomial method. A similar dependence of surface tension on temperature and concentration is presented. Next, the Gibbs energy of formation of solid Bi₂O₃, as well as activities of Bi in liquid Ag-Bi alloys, were determined by a solid-state electromotive force (emf) technique using the following galvanic cells: Ni, NiO, Pt/O ⁻²/W, Ag _X Bi _(1−X), Bi ₂ O _3(s). The Gibbs energy of formation of solid Bi₂O₃ from pure elements was derived: =−598 148 + 309.27T [J · mol⁻¹] and =−548 008 + 258.94T [J · mol⁻¹]; the temperature and the heat of the α → δ transformation for this solid oxide were calculated as 996 K and 50.14 J · mol⁻¹. Activities of Bi in the liquid alloys were determined in the temperature range from 860–1075 K, for five Ag-Bi alloys (X _Ag=0.2, 0.35, 0.5, 0.65, 0.8), and a Redlich-Kister polynomial expansion was used to describe the thermodynamic properties of the liquid phase. Using Thermo-Calc software, the Ag-Bi phase diagram was calculated. Finally, thermodynamic data were used to predict surface tension behavior in the Ag-Bi binary system.     

Surface tension and thermodynamic properties of liquid Ag-Bi solutions

With the maximum bubble pressure method, the density and surface tension were measured for five Ag-Bi liquid alloys (X _Bi=0.05, 0.15, 0.25, 0.5, and 0.75), as well as for pure silver. The experiments were performed in the temperature range 544–1443 K. Linear dependences of both density and surface tension versus temperature were observed, and therefore the experimental data were described by linear equations. The density dependence on concentration and temperature was derived using the polynomial method. A similar dependence of surface tension on temperature and concentration is presented. Next, the Gibbs energy of formation of solid Bi₂O₃, as well as activities of Bi in liquid Ag-Bi alloys, were determined by a solid-state electromotive force (emf) technique using the following galvanic cells: Ni, NiO, Pt/O ⁻²/W, Ag _X Bi _(1−X), Bi ₂ O _3(s). The Gibbs energy of formation of solid Bi₂O₃ from pure elements was derived: =−598 148 + 309.27T [J · mol⁻¹] and =−548 008 + 258.94T [J · mol⁻¹]; the temperature and the heat of the α → δ transformation for this solid oxide were calculated as 996 K and 50.14 J · mol⁻¹. Activities of Bi in the liquid alloys were determined in the temperature range from 860–1075 K, for five Ag-Bi alloys (X _Ag=0.2, 0.35, 0.5, 0.65, 0.8), and a Redlich-Kister polynomial expansion was used to describe the thermodynamic properties of the liquid phase. Using Thermo-Calc software, the Ag-Bi phase diagram was calculated. Finally, thermodynamic data were used to predict surface tension behavior in the Ag-Bi binary system.     

Cyanide-bridged bimetallic multidimensional structures derived from organotin(IV) and dicyanoaurate building blocks: ion exchange, luminescence, and gas sorption properties

The recent success of using methyltin(IV) cations in constructing multidimensional structures containing the Au–CN–Sn link with interesting physical properties will be surveyed. The methyltin(IV)-dicyanoaurates, Me₃Sn[Au(CN)₂] (1) and Me₂Sn[Au(CN)₂]₂ (2) containing the Au–CN–Sn link can be easily prepared by aqueous reaction of Me₃SnCl or Me₂SnCl₂ with stoichiometric amounts of an aqueous solution of K[Au(CN)₂]. The room temperature solid-state emission spectrum of 1 excited at 254 nm shows two intense emission bands at 442 and 670 nm, and a shoulder at 390 nm. When excited at 320 nm, the crystalline sample shows two intense emission bands at 442 and 720 nm, and a shoulder at 380 nm. After 2 min of grinding, only the blue emission band at 442 nm is observed. In contrast, the emission spectrum of 2 shows only one emission maximum at 422 nm. The porosity of 1 and 2 was probed by gas sorption measurements performed at 77 K. 1 exhibited no detectable microporosity as revealed by the inspection of the N₂, H₂, as well as, O₂ isotherms. The gas adsorption studies reveal that only a small amount of N₂ and H₂ (3.82 and 4.66 cm³ g⁻¹, respectively) is adsorbed by the framework of 2 at 77 K. However, a CO uptake of 11.20 cm³ g⁻¹ can be reached at 1 atm. The framework of 2 can take up significant amounts of O₂ (23.27 cm³ g⁻¹). In addition to intriguing photoluminescence and gas sorption behavior, these complexes also exhibit ion exchange properties in the presence of bivalent transition metal cations, such as cobalt(II), nickel(II), copper(II), and zinc(II).     

Investigation on interface of NiFeCr/NiFe/Ta films with high magnetic field sensitivity

NiFeCr/NiFe/Ta films with excellent performance were prepared by magnetron sputtering system.The anisotropic magetoresistance (AMR) value (△R/R) and magnetic filed sensitivity (Sv,Sv=[d(△R/R)/dH]max.) for the 12 nm NiFe film deposited on NiFeCr buffer layer were 3.66％ and 1.42 × 10-4 ％T-1,respectively.The higher Sv of the film is close to that of a spin valve (SV).The microstructure analysis shows that the NiFeCr buffer layer has adopted the same structure with the same interplanar distance as the NiFe layer,inducing a strong NiFe (111) texture,and that the NiFeCr/NiFe interface is quite smooth,leading to a high degree of specular reflection of conduction electrons.Both increase the △R and reduce the R in the film,which lead to the high △R/R.Clean substrate surfaces are critical for preparation of high performance NiFeCr/NiFe/Ta films,and sputter cleaning or pre-deposition of 5 nm amorphous A12O3 layer in the deposition chamber can provide the required clean substrate surfaces for the growth of the buffer layer.     

Molybdate/Al(III) composite films on steel and zinc-plated steel by chemical conversion

A molybdate(VI)-Al(III) chemical conversion process was developed as an alternative to the chromate processes. Steel and zinc-plated steel specimens were treated in the solutions of 0.16 mol l⁻¹ ammonium alum (AlNH₄(SO₄)₂ · 12H₂O) with small amounts of ammonium molybdate(VI) (0.002-0.016 mol l⁻¹ (NH₄)₆Mo₇O₂₄ · 4H₂O) at 60 °C for 10-30 min in an ultrasonic rinsing apparatus. The formed films were composed of oxyhydroxides containing Mo(V,VI), Al(III), Fe(II,III), and sulfate ions (and Zn(II) ions in the case of zinc-plated steel), and showed good corrosion resistance in an aerated 0.5 mol l⁻¹ NaCl-0.15 mol l⁻¹ H₃BO₃ solution (pH=7). The films macerated during the corrosion test, but they did not detach and functioned as a protective layer. This process may be useful in forming undercoats for paints and polymer coatings on steel and zinc-plated steel.     

Novel cycloaurated gold(III) complexes and their effects on styrene polymerization

Novel cycloaurated gold(III) complexes were prepared by using Schiff bases with different substituents. Effects of the synthesized gold(III) complexes and substituent groups on styrene polymerization were investigated. As a result of these investigations, it was observed that gold(III) complexes could not catalyze polymerization reaction without addition of a co-catalyst like NaBAr′₄ (Ar′ = 3,5-bis(trifluoromethyl)phenyl). All ligands and complexes were characterized by using ¹H nuclear magnetic resonance (NMR), ¹³C-NMR, LC-MS, elemental analysis and FT-IR techniques. The architecture of the polymer was determined as an atactic or sydiotactic polymer by using ¹³C-NMR and DSC techniques. Molecular weights of the polymers were analyzed by using gel permeation chromatogram (GPC).     

Sensing behavior of silica-coated Au nanoparticles towards nitrobenzene

In the present work, we report silica-stabilized gold nanoparticles (SiO₂/Au NPs) as a wide-range sensitive sensing material towards nitrobenzene (NB). Surface hydroxyl groups of silica selectively form Meisenheimer complex with electron-deficient aromatic ring of NB and facilitate its immobilization and subsequent catalytic reduction by Au cores. Silica-coated Au NPs were synthesized and characterized for their chemical, morphological, structural, and optical properties. SiO₂/Au NPs-modified electrodes were characterized with impedometric and cyclic voltammetric electrochemical techniques. SiO₂/Au NPs are found to have a higher optical detection window of range, 0.1 M to 1 μM and a lower electrochemical detection window of range, 10⁻⁴ to 2.5 × 10⁻² mM with a detection limit of 12.3 ppb. A significant enhancement in cathodic peak current, C ₁, and sensitivity (102 μA/mM) was observed with modified electrode relative to bare and silica-modified electrodes. The I _P was found to be linearly co-related to NB concentration (R ² = 0.985). The interference of cationic and anionic species on sensor sensitivity was also studied. Selectivity in the present sensing system may be further improved by modifying silica with specific functional moieties.     

Coordination polymers with [Au(CN)4]- building blocks: a 1-d chain of molecular NiII2AuIII2 squares

A new coordination polymer utilizing the neglected cyanoaurate anion [Au(CN)₄]- building block is reported. Reaction of a Ni(II) salt, diethylenediamine (dien) and K[Au(CN)₄] yields Ni(dien)[Au(CN)4]₂, which consists of a unique bimetallic Ni(II)₂/Au(III)₂ supramolecular square through cis N(cyano) bridging of the [Au(CN)₄]- building block to [Ni(dien)]²⁺ cations. These squares further aggregate into a 1-D chain via Au-N(cyano) interactions; no Au(III)-Au(III) interactions are observed. Within the square, the magnetic coupling between the Ni(II) centres is very weak, indicating that the [Au(CN)₄]- unit is a poor mediator of magnetic exchange in this system.     

Die löslichkeitskonstanten der zinkhydroxidchloride-einbeitrag zur kenntnis der korrosionsprodukte des zinks

The solubilities of zinc hydroxychloride II and III have been studied at 25°C in solutionsof the constant ionic strength I = 0·2M. From experimental data the following values for equilibrium0842 constants are deduced: II:Zn(OH)_1,6 Cl_0,4: log[Zn²⁺] [Cl⁻]^10,4 [H⁺]^−1,6 = 8·22 ± 0,1 III: Zn(OH)_1,794 Cl_0,206: log[Zn²⁺] [Cl⁻]^0,206 [H⁺]^−1.794 = 9·84 ± 0,05. A value of K₁ = 6 ± 2 has been estimated for the equilibrium Zn²⁺ + Cl⁻ZnCl⁺. The relative stabilities of zinc hydroxychlorides and zinc hydroxides are represented with the aid of a predominance area diagram. Comparing recent data on the solubility of hydrozincite it is seen that zinc hydroxychlorides are not stable in natural waters.     

Multiphase magnetic state of Ca1 ? x La x MnO3 ? δ single crystals ( x = 0.03, 0.05, 0.07) containing oxygen vacancies

Magnetic properties (magnetization, dynamic and static susceptibility) and transport properties (resistance and magnetoresistance) have been studied in a temperature range of 2–600 K in magnetic fields to 90 kOe for single crystals of Ca_{1 − x} La _x MnO_{3 − δ} with a weak electron doping (x ≤ 0.07) grown in argon and oxygen atmospheres. The magnetic state of Ca_{1 − x} La _x MnO_{3 − δ} single crystals is multiphase. Below T = T _N(G) ∼ 110 K, in all the crystals there coexists an AFM G phase with an FM contribution and an AFM C phase. In crystals with x = 0.07, a transition from the paramagnetic phase into the AFM C phase occurs in part of their volume below T ∼ 130–150 K. In crystals with x = 0.05 annealed in oxygen, an anomaly of paramagnetic susceptibility is observed near T ^* ∼ 270 K, which is related to the formation of FM clusters near defects. At x = 0.05 and 0.07, AFM correlations are retained in the paramagnetic state (to 600 K). The differences in the magnetic and transport properties of single crystals grown in argon and oxygen are explained by the various content of oxygen vacancies and by their possible ordering. Original Russian Text ? N.N. Loshkareva, A.V. Korolev, T.I. Arbuzova, N.I. Solin, A.M. Balbashov, N.V. Kostromitina, 2007, published in Fizika Metallov i Metallovedenie, 2007, Vol. 103, No. 3, pp. 261–270.     

Synthesis and crystal structure of Ba3Si4C2

SiC powder prepared by the Na flux method at 1023 K for 24 h and Ba were used as starting materials for synthesis of tribarium tetrasilicide acetylenide, Ba₃Si₄C₂. Single crystals of the compound were obtained by heating the starting materials with Na at 1123 K for 1 h and by cooling to 573 K at a cooling rate of −5.5 K/h. The single crystal X-ray diffraction peaks were indexed with tetragonal cell dimensions of a = 8.7693(4) and c = 12.3885(6) Å, space group I4/mcm (No.140). Ba₃Si₄C₂ has the Ba₃Ge₄C₂ type structure which can be described as a cluster-replacement derivative of perovskite (CaTiO₃), and contains isolated anion groups of slightly compressed [Si₄]⁴⁻ tetrahedra and [C₂]²⁻ dumbbells. The electrical conductivity measured for a not well-sintered polycrystalline sample was 2.6 × 10⁻²–7 × 10⁻³ S cm⁻¹ in the temperature range of 370–600 K and slightly increased with increasing temperature. The Seebeck coefficient showed negative values of around −200 to −300 μV K⁻¹.