Microanalysis of Hydrogen, Boron and Fluorine in Vesuvianite by Means of SIMS, EPMA and FTIR

Vesuvianite, a complex sorosilicate, often contains variable (from trace-to-minor-element) amounts of H, B and F. We describe a microanalytical study of H, B and F in vesuvianite by means of Electron Probe Microanalysis (EPMA), Secondary Ion Mass Spectrometry (SIMS), and single-crystal Fourier-Transform InfraRed (FTIR) spectroscopy. Most crystals investigated are B- (up to 3.67 wt% B₂O₃) and F-rich (up to 2.38 wt%); H₂O ranges from 0.243 to 0.665 wt%. The H data obtained by SIMS allowed us to calibrate the quantitative analysis of H₂O by FTIR spectroscopy. The resulting molar absorption coefficient (ɛ _i = 100 000 ± 2000 L · mol⁻¹ · cm⁻²) is in excellent agreement with working curves available from the literature. Moreover, the SIMS data allowed us to obtain the calibration curve to estimate the B₂O₃ content on the basis on the FTIR absorbance: a _i = 34000 ± 1400 · B₂O₃ (wt%).     

Synthesis, Characterization, and Thermal Decomposition of Double Rare Earth Monomethylammonium Selenates

 Double rare earth monomethylammonium selenates of the general formula CH₃NH₃ Ln (SeO₄)₂·5H₂O (Ln = Sm, Eu, Gd, Tb, Ho, Y) were synthesized and characterized using X-ray powder diffraction and infrared spectroscopy. The thermal decomposition of the compounds were investigated using TG, DTG, and DTA techniques.     

Synthesis, Characterization, and Thermal Decomposition of Double Rare Earth Monomethylammonium Selenates

Summary.  Double rare earth monomethylammonium selenates of the general formula CH₃NH₃ Ln (SeO₄)₂·5H₂O (Ln = Sm, Eu, Gd, Tb, Ho, Y) were synthesized and characterized using X-ray powder diffraction and infrared spectroscopy. The thermal decomposition of the compounds were investigated using TG, DTG, and DTA techniques. Corresponding author. E-mail: vrajgaonkar@yahoo.com, vrajgaonkar@mail.mu.ac.in Received November 5, 2001. Accepted (revised) March 6, 2002     

Study of the reactions of cisplatin with ranitidine and nizatidine by means of 1H NMR spectroscopy in D2O

The reactions of cisplatin with nizatidine and ranitidine were studied in D₂O at pD 7.4 and 298 K by means of ¹H NMR spectroscopy. The second order rate constants, k ₂, for the reaction of cisplatin with nizatidine is (2.71 ± 0.11) × 10⁻⁴ M ⁻¹ s⁻¹, and for the reaction with ranitidine (6.72 ± 0.17) × 10⁻⁴ M ⁻¹ s⁻¹. The reactions of nizatidine and ranitidine were also studied with other Pd(II) and Pt(II) complexes. The set of the complexes was selected because of their difference in reactivity, steric hindrance, and binding properties. Correspondence: Prof. Dr. Živadin D. Bugarčić, Faculty of Science, University of Kragujevac, Radoja Domanovića 12, 34000 Kragujevac, Serbia.     

Physical and morphological characteristics and electrochemical behaviour in PEM fuel cells of PtRu /C catalysts

Platinum-ruthenium catalysts supported on carbon (PtRu/C) have been characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), specific surface area analysis (BET), X-ray photoelectron spectroscopy (XPS) and in proton exchange membrane (PEM) fuel cell tests. The results indicate the presence of strong metal-carbon interactions, which hinder the formation of a single-phase face-centered cubic (fcc) PtRu alloy. The particle size of the PtRu/C catalysts was smaller than both carbon-supported platinum (Pt/C) and ruthenium (Ru/C) catalysts. In the bimetallic electrocatalysts the intercrystallite distance decreased with respect to pure Pt and Ru metals. PEM fuel cell tests in H₂/air operation mode revealed a decrease of performance with increasing carbon content of the catalyst, at a fixed Pt loading. In H₂ + 100 ppm CO/air operation mode the maximum performance of the PEM fuel cell was attained at 0.63 atomic fraction Ru. Received: 2 December 1999 / Accepted: 27 January 2000     

Metal Oxoclusters as Molecular Building Blocks for the Development of Nanostructured Inorganic–Organic Hybrid Thin Films

Summary. Silica-based inorganic–organic hybrid thin films embedding the organically modified oxohafnium clusters (Hf₄O₂(OMc)₁₂, OMc=OC(O)–C(CH₃)=CH₂) were obtained by photo-activated free radical copolymerisation of the methacrylate groups of the cluster with those of the pre-hydrolysed (methacryloxypropyl)trimethoxysilane (MAPTMS, (CH₂=C(CH₃)C(O)O)(CH₂)₃Si(OCH₃)₃). By this route, a covalent anchoring of the cluster to the forming silica network was achieved. Samples characterized by two different Si/Hf compositions (18:1, 5:1) were prepared. The surface and in-depth composition of the thin films were investigated through Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). XPS depth profiles performed on the thin layers evidenced a homogenous in depth distribution of the hafnium guest species within the whole silica films and sharp film-substrate interfaces. Broad band dielectric spectroscopy (BDS) measurements permitted to investigate the electric response of the obtained films in the frequency and temperature range of 40 Hz – 1 MHz and 0–160°C.     

Impedance studies on the 5-V cathode material,LiCoPO<Subscript>4</Subscript>

Olivine-structured LiCoPO₄ is synthesized by a Pechini-type polymer precursor method. The structure and the morphology of the compounds are studied by the Rietveld-refined X-ray diffraction, scanning electron microscopy, Brunauer, Emmett, and Teller surface area technique, infrared spectroscopy, and Raman spectroscopy techniques, respectively. The ionic conductivity (σ ionic), dielectric, and electric modulus properties of LiCoPO₄ are investigated on sintered pellets by impedance spectroscopy in the temperature range, 27–50 °C. The σ (ionic) values at 27 and 50 °C are 8.8 × 10⁻⁸ and 49 × 10⁻⁸ S cm⁻¹, respectively with an energy of activation (E _a) = 0.43 eV. The electric modulus studies suggest the presence of non-Debye type of relaxation. Preliminary charge–discharge cycling data are presented.     

Metal Oxoclusters as Molecular Building Blocks for the Development of Nanostructured Inorganic–Organic Hybrid Thin Films

Silica-based inorganic–organic hybrid thin films embedding the organically modified oxohafnium clusters (Hf₄O₂(OMc)₁₂, OMc=OC(O)–C(CH₃)=CH₂) were obtained by photo-activated free radical copolymerisation of the methacrylate groups of the cluster with those of the pre-hydrolysed (methacryloxypropyl)trimethoxysilane (MAPTMS, (CH₂=C(CH₃)C(O)O)(CH₂)₃Si(OCH₃)₃). By this route, a covalent anchoring of the cluster to the forming silica network was achieved. Samples characterized by two different Si/Hf compositions (18:1, 5:1) were prepared. The surface and in-depth composition of the thin films were investigated through Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). XPS depth profiles performed on the thin layers evidenced a homogenous in depth distribution of the hafnium guest species within the whole silica films and sharp film-substrate interfaces. Broad band dielectric spectroscopy (BDS) measurements permitted to investigate the electric response of the obtained films in the frequency and temperature range of 40 Hz – 1 MHz and 0–160°C.     

Physicochemical characterization of self-assembled poly(∈-caprolactone) grafted dextran nanoparticles

Amphiphilic graft copolymer composed of poly(∈-caprolactone) and dextran was synthesized by ring opening polymerization of ∈-caprolactone initiated through the hydroxyl end of dextran in the presence of stannous 2-ethylhexanoate [Sn (oct)₂] as a catalyst. It has been widely characterized by Fourier transform infrared spectroscopy, ¹H NMR, and thermogravimetric analysis. Nanoparticles were prepared in aqueous medium by co-solvent evaporation technique at room temperature (25 °C). Hydrodynamic diameter and particle size were measured by dynamic light scattering spectroscopy and atomic force microscopy, respectively. Core-shell geometry of polymeric nanoparticle was characterized by fluorescence spectrophotometer using pyrene as a probe. Critical micelle concentration of polymer in triple distilled water decreased from 6.9 × 10⁻⁴ to 8.9 × 10⁻⁴ g/l with increasing hydrophobic moiety. Further, the physiological stability of the nanoparticles in phosphate buffer saline of pH 7.4 at 37 °C was evaluated, which showed promising in drug delivery system.     

Electrochemical kinetics of nanosized Ag and Ag2O thin films prepared by radio frequency magnetron sputtering

Ag and Ag₂O thin films have been prepared by radio frequency magnetron sputtering on Cu substrates and have been characterized by X-ray diffraction, scanning electron microscope and atomic force microscope. The electrochemical performance of the thin films has been studied by galvanostatic cycling and cyclic voltammetry. The potential dependence of Li-ion chemical diffusion coefficients, [(D)\tilde]_\textLi {\widetilde{D}_{\text{Li}}} , of the films has been determined by galvanostatic intermittent titration technique and electrochemical impedance spectroscopy. It is found that Li-ion chemical diffusion coefficients of the Ag film range from 10⁻¹⁶ to 3 × 10⁻¹⁴ cm² s⁻¹. The Ag/Li₂O composite that is formed from Ag₂O after the first cycle exhibits higher [(D)\tilde]_\textLi {\widetilde{D}_{\text{Li}}} values than the Ag film, especially at a low Li-intercalation content. The phase transitions in the two-phase region cause a significant decrease of chemical diffusion coefficients.     

In situ formation of polyethylene glycol–titanium complexes as solvent-free electrolytes for electrochromic device application

Transparent and ionic conductive polymeric electrolytes have been prepared through sol–gel method by adding titanium isopropoxide into an acidic polyethylene glycol (PEG) solution. After hydrolysis and condensation processes, new associations between titanium cations and ether oxygen atoms of PEG have been formed according to Fourier-transform infrared spectroscopy. Thermogravimetric analysis results of these hybrid materials indicate a better thermal stability with a less polydispersion of the molecular mass distribution in comparison with PEG. For the purpose of electrochromic or photoelectrochromic device applications, LiI was added into the hybrid materials to form solvent-free polymeric electrolytes. Optical transmittance spectra of these electrolytes show a red shift of the cutoff wavelength as a function of titanium isopropoxide percentage in the original sol–gel solutions. It is also observed that the amount of hydroxyl groups in the hybrid materials was reduced in comparison with the PEG one. This makes electrical conductivity of the hybrid electrolytes with LiI salt insensitive to humidity and solvents, which was about 2 × 10^-4 Ω⁻¹ cm⁻¹ at room temperature. A solid WO₃-based electrochromic device with the hybrid electrolyte keeps the same optical transmittance value after 1,000 cycles of switching polarization potentials between −1 and +1 V.     

Moisture uptake in native cellulose – the roles of different hydrogen bonds: a dynamic FT-IR study using Deuterium exchange

This paper aims at a better understanding of the interaction between cellulose and moisture. In particular, the role of different hydrogen bonds in moisture uptake is investigated. Dynamic Fourier transform infrared spectroscopy (FT-IR) has been used in combination with deuterium exchange, which permits the labelling of cellulose domains with different accessibilities. The static spectra indicate a marked exchange of deuterium for the O2–H⋯O6 bonds, but only a limited exchange for the O3–H⋯O5 bonds. In the dynamic FT-IR spectra, deuteration gives rise to the growth of a broad band at wavenumbers around 2500 cm⁻¹. The rather unstructured appearance of the band suggests that deuteration is occurring only on the surface of the cellulose crystallites, i.e. in more or less non-load-carrying parts. This is corroborated by the lack of split peaks related to OD bonds in this band. In agreement with these observations, the split peak related to O3–H⋯O5 bonds and assigned to the load carrying cellulose structure increases during both H₂O and D₂O moisture conditioning, indicating a shift of the load transfer towards the backbone of the cellulose structure.     

An electrochemical investigation on (MoO<Subscript>3</Subscript>+PVP+PVA) nanobelts for lithium batteries

Molybdenum trioxide (MoO₃) xerogel films modified with poly(vinyl alcohol)+poly(vinyl pyrrolidone) (PVP+PVA) polyblends were obtained by ion-exchange method with sol-gel technique. Investigations were conducted using X-ray “diffractometry”, Fourier transform infrared spectroscopy, and cyclic voltammetry. The results show that the H atoms in polyblend are H-bonded with the O atoms in the Mo=O bonds of MoO₃ xerogel, which effectively shield the electrostatic interaction between MoO₃ interlayer and Li⁺ ions when MoO₃ xerogel is modified by the intercalation of (PVP+PVA). The reversibility of the insertion/extraction of Li⁺ ions is greatly improved by the modification with polyblend of MoO₃ nanocomposite films. MoO₃ and (PVP+PVA) _x MoO₃ (x = 0, 0.5) nanobelts were obtained by a simple hydrothermal process from MoO₃ sol. The electrochemical cells with configuration Li/(LiPF₆+EC+DMC)/MoO₃ modified by (PVP+PVA) were fabricated and their discharge profiles studied.     

Disposable chemiluminometric sensor for rapid determination of EDTA

A new chemiluminescence-based disposable sensor for EDTA is described. The EDTA-sensitive element is a transparent bilayer membrane containing Ru(Bipy)₃ ²⁺ complex and Ce(IV), respectively, on a polyester support. The sample is injected by means of a syringe, acting pneumatically, into a 10 mm cell containing the CL membrane and placed in the external holder of a luminometer. The composition of the membrane and reaction conditions have been adjusted to obtain adequate sensitivity and selectivity. The disposable sensor responds to EDTA rapidly over a dynamic range from 6.6 × 10⁻⁶ M to 7.0 × 10⁻⁴ M, with sensor-to-sensor reproducibility around 6% as RSD (relative standard deviation) at the medium level of the range. The performance of the optical disposable sensor was tested for the analysis of EDTA in ophthalmic collyrium and different types of sauce samples, validating the results against a reference procedure. The sensing approach presented here demonstrates the feasibility of chemiluminescent disposable sensors for quantitative analysis with good features.     

Nature and importance of three-body interactions in the (H2O)2HCl trimer

 The nature and importance of nonadditive three-body interactions in the (H₂O)₂HCl cluster have been studied by the supermolecule coupled-cluster method and by symmetry-adapted perturbation theory (SAPT). The convergence of the SAPT expansion was tested by comparison with the results obtained from the supermolecule coupled-cluster calculations including single, double, and noniterative triple excitations [CCSD(T)]. It is shown that the SAPT results reproduce the converged CCSD(T) results within 3% at worst. The SAPT method has been used to analyze the three-body interactions for various geometries of the (H₂O)₂HCl cluster. It is shown that the induction nonadditivity is dominant, but it is partly quenched by the first-order Heitler–London-type exchange and higher-order exchange–induction/deformation terms. This implies that the classical induction term alone is not a reliable approximation to the nonadditive energy and that it will be difficult to approximate the three-body potential for (H₂O)₂HCl by a simple analytical expression. The three-body energy represents as much as 21–27% of the pair CCSD(T) intermolecular energy. Received: 15 September 1999 / Accepted: 3 February 2000 / Published online: 2 May 2000     

Oxygen excess nonstoichiometry and thermodynamic quantities of La2NiO4?+?δ

The oxygen excess nonstoichiometry of La₂NiO_4 + δ is measured as a function of temperature and oxygen partial pressure (pO₂) by coulometric titration method. A positive deviation from the ideal dilution solution behavior is exhibited, and the partial molar thermodynamic quantities of La₂NiO_4 + δ are calculated from the Gibbs–Helmholtz equation for regular solution by introducing the activity coefficient of the charge carriers. The activity coefficient of holes is successfully calculated by using the Joyce–Dixon approximation of the Fermi–Dirac integral. The effective mass of holes ( m_\texth^* m_{\text{h}}^{{*}} ) is 1.27–1.29 times the rest mass (m _h), which indicate the action of band-like conduction and allow the effect of the small degree of polaron hopping to be ignored. The activity coefficient of holes calculated against the oxygen nonstoichiometry clearly illustrates the early positive deviation of the activity coefficient of holes from unit, leading to g_{\texth ^·} \gamma_{{{\text{h}}^{ \bullet }}}  ≈ 14 at δ ≈ 0.08, which is quite close to the literature value of g_{\texth ^·} \gamma_{{{\text{h}}^{ \bullet }}}  ≈ 10 at δ ≈ 0.08. All the evaluated thermodynamic quantities are in good agreement with the experimental literature values.     

Fourier transform-IR and 1H NMR studies on the structure of water solubilized by reverse aggregates of calcium bis(2-ethylhexyl) sulfosuccinate in organic solvents

The structure of water solubilized by reverse aggregates of calcium bis(2-ethylhexyl) sulfosuccinate in deuterobenzene and toluene has been probed by Fourier transform-IR and ¹H NMR spectroscopies. The ν_OD band of solubilized HOD (4% D₂O in H₂O) has been recorded as a function of the [water]/[surfactant] molar ratio, W/S. Curve fitting of this band showed the presence of a main peak at 2550 ± 13 cm⁻¹ and a small one at 2405 ± 15 cm⁻¹. As a function of increasing W/S, the frequency of the main peak decreases, its full width at half-height increases, and its area increases linearly. The ¹H NMR chemical shift of solubilized H₂O–D₂O mixtures at W/S = 18.1 has been measured as a function of the deuterium content of the aqueous nanodroplet. These data were used to calculate the so-called “fractionation factor” of the aggregate-solubilized water, the value of which was found to be unity. The results of both techniques show that reverse aggregate-solubilized water, although different from bulk water, does not seem to coexist in “layers” of different degrees of structure, as suggested, for example by the two-state water-solubilization model. Received: 12 July 1999/Accepted: 30 August 1999     

Sensitive determination of fluphenazine at a dodecanethiol self-assembled monolayer-modified gold electrode, and its electrocatalysis to phenylephrine

Fluphenazine, an important tranquilizer, was found to undergo effective accumulation on dodecanethiol (DDT) self-assembled monolayer modified gold electrode (i.e. DDT/Au) and generated two anodic peaks at about 0.7 and 0.79 V (vs. SCE) in 0.05 M Na₂B₄O₇ (pH = 9.3) buffer solution. Sensitive and quantitative measurement of fluphenazine based on the former anodic peak was established under optimum conditions. The peak current was linear to fluphenazine concentration in the range from 5 × 10⁻⁷ to 5 × 10⁻⁵ M, with a detection limit of 5 × 10⁻⁹ M. This method was successfully applied to the determination of fluphenazine in drug tablets and proved to be reliable compared with UV spectrophotometry. In the presence of fluphenazine, the electrochemical oxidation of phenylephrine was catalyzed. The DDT self-assembled monolayer was characterized by Fourier transform infrared spectroscopy, surface Raman spectroscopy, X-ray photoelectron spectroscopy, electrochemical impedance spectroscopy, and electrochemical probing.     

The Thermal Dehydration of Magnesium Aluminum Pentafluoride Dihydrate: Crystal Structures of MgAlF5(H2O)2 and MgAlF5

Summary.  Small plate-like single crystals of MgAlF₅(H₂O)₂ have been obtained during hydrothermal treatment (270°C) of microcrystalline material prepared by precipitation of stoichiometric solutions of Al₂(SO₄)₃ ·  18H₂O and Mg(NO₃)₂ · 6H₂O with diluted hydrofluoric acid. The crystal structure of MgAlF₅(H₂O)₂ has been refined from single crystal data (Imma (# 74), Z = 4, a = 7.0637(7), b = 10.1308(10), c = 6.7745(7) ?, 398 structure factors, 33 parameters, R(F² > σ(F ²)) = 0.0245, wR(F² all) = 0.0525). Main features of the inverse weberite type structure are infinite chains of trans-bridged [AlF₆] octahedra which are connected via common fluorine atoms by isolated [MgF₄(H₂O)₂] octahedra. MgAlF₅(H₂O)₂ dehydrates at temperatures above 300°C to give MgAlF₅. XRPD analysis of this phase has revealed isotypism with FeAlF₅. The crystal structure of MgAlF₅ (Immm (# 71), Z = 2, a = 7.268(1), b = 6.123(2), c = 3.543(1) ?) is built of infinite chains of edge-sharing [MgF₆] octahedra and chains of corner-sharing [AlF₆] octahedra along [001]. Upon further heating to temperatures above 500°C, MgAlF₅ decomposes to MgF₂ and α − AlF₃. Received January 15, 2001. Accepted February 12, 2001     

Pathways for Water Loss from Doubly Protonated Peptides Containing Serine or Threonine

The doubly-protonated peptides Ala-Ala-Xaa-Ala-Ala-Ala-Arg show extensive loss of H₂O when Xaa = Ser or Thr. Using quasi-MS³ techniques the fragmentation reactions of the [M + 2H – H₂O]⁺² ions have been studied in detail. For both Ser and Thr, the [M + 2H – H₂O]⁺² ions show three primary fragmentation reactions, elimination of CH₃CH = NH, elimination of one Ala residue, and elimination of two Ala residues, in all cases forming doubly-charged products. From a study of the further fragmentation of these products, it is concluded that elimination of two Ala residues results in formation of a three-membered aziridine ring by interaction with the adjacent amide function as H₂O is lost. The elimination of one Ala residue results in formation of a five-membered oxazoline ring through interaction with the N-terminal adjacent carbonyl function as H₂O is lost. The elimination of CH₃CH = NH appears to involve formation of an eight-membered ring by interaction with the remote N-terminal carbonyl function as H₂O is lost. However, this initial structure undergoes rearrangement through interaction with the adjacent C-terminal carbonyl function prior to further fragmentation. The [MH – H₂O]⁺ ion of Ala-Ala-Ser-Ala-Ala-Ala also shows elimination of CH₃CH = NH, one Ala residue and two Ala residues.