75As, 63Cu NMR and NQR characterization of selected arsenic minerals

The direct measurement and identification of solid state arsenic phases using ⁷⁵As NMR is made difficult by the simultaneous conditions of large quadrupole moment and low coordination symmetry in many compounds. However, specific arsenic minerals can efficiently be detected and discriminated via nuclear quadrupolar resonance (NQR). We report on the first NMR and NQR measurements in the natural minerals enargite (Cu₃AsS₄), niccolite (NiAs), arsenopyrite (FeAsS) and loellingite (FeAs₂). The NQR frequencies have been determined from both high-field NMR powder patterns and via zero-field frequency sweeps. Density functional theory (DFT) based ab initio calculations support the experimental results. The compounds studied here are common in terms of the known set of As-containing minerals. They are sometimes encountered in the context of base metal or gold mining. The study represents a significant addition to the list of arsenic minerals that can now be detected with NQR techniques.     

Synthesis,spectroscopic, thermal and electrical conductivity studies of three charge transfer complexes formed between 1,3-di[(<Emphasis Type="Italic">E</Emphasis>)-1-(2-hydroxyphenyl)methylideneamino]-2-propanol Schiff base and different acceptors

Charge-transfer complexes (CTC) resulting from interactions of 1,3-di[(E)-1-(2-hydroxyphenyl) methylideneamino]-2-propanol Schiff base with some acceptors such as iodine (I₂), bromine (Br2), and picric acid (PiA) have been isolated in the solid state in a chloroform solvent at room temperature. Based on elemental analysis, UV-Vis, infrared, and ¹H NMR spectra, and thermogravimetric analysis (TG/DTG) of the solid CTC, [(Schiff)(I₂)] (1), [(Schiff)(Br₂)] complexes with a ratio of 1:1 and [(Schiff)(PiA)₃] complexes with 1:3 have been prepared. In the picric acid complex, infrared and ¹H NMR spectroscopic data indicate that the charge-transfer interaction is associated with a hydrogen bonding, whereas the iodine and bromine complexes were interpreted in terms of the formation of dative ion pairs [Schiff⁺, I₂^∙−] and [Schiff⁺, Br₂^∙−], respectively. Kinetic parameters were obtained for each stage of thermal degradation of the CT complexes using Coats–Redfern and Horowitz–Metzger methods. DC electrical properties as a function of temperature of these charge transfer complexes have been studied.     

Studies on the adsorption of arsenic on calix[6]arene

p‐tert‐butyl calix[6]arene (PTC6) was synthesized and characterized by solid‐ and liquid‐state NMR and LC‐MS techniques. The adsorption of arsenite and arsenate on calix[6]arene under different pH conditions and adsorbate doses was studied. The maximum adsorption of arsenic species on calix[6]arene was observed around neutral pH and the adsorption density of As (III) was higher than that of As (V). The adsorption of neutral H₃AsO₃ and negatively charged H₂AsO molecules on calix[6]arene was attributed to the condensation reaction between hydroxyl groups of PTC6 and arsenic species. The complexation of arsenite with phenolic oxygen was confirmed by solid‐state ¹³C NMR CP‐MAS. Exo attack mechanism was proposed to describe the interaction of arsenous and arsenic acid molecules with PTC6. The specific interaction between calix[6]arene and arsenic species was further substantiated by zeta‐potential (ζ‐potential) measurements and free energy of adsorption. The free energy of adsorption ( ) estimated from Stern–Grahame equation was found to be 25 kJ/mole for As (III) and 19 kJ/mole for As (V). Copyright © 2010 John Wiley & Sons, Ltd.     

Magnetic resonance study of arsenic bonding sites in ternary chalcogenide glasses

⁷⁵As NQR and high-field NMR experiments have been performed on Ge_xAs_ySe_1−x−y glasses. Evolution of As bonding structure from arsenic sites with axially symmetric distribution of the electric field gradient (EFG) to highly asymmetric As surroundings has been revealed. Arsenic atoms form pyramidal structural units in Ge₂As₂Se₇ with no evidence of significant concentration of homopolar bonds. In Ge₂As₂Se₅ most of arsenic atoms form structural units with two As-As bonds per atom and asymmetric EFG distribution. Arsenic bondings become more complicated in Ge_0.33As_0.12Se_0.55 where all arsenic sites are highly distorted. The combination of NQR and NMR data provide valuable information on arsenic bonding dynamics in these glasses.     

Efficient Sensitized Luminescence of Binuclear Ln(III) Complexes Based on a Chelating Bis-Carbacylamidophosphate

Binuclear rare earth complexes Ln₂L₃phen₂ (Ln^III?=?Nd^III, Sm^III, Eu^III, Tb^III, Dy^III, Yb^III and Y^III) with bis-CAPh type ligand - tetramethyl N,N′-(2,2,3,3,4,4-hexafluoro-1,5-dioxopentane-1,5-diyl)bis(phosphoramidate) (H₂L) and 1,10-phenanthroline (phen) were synthesized and characterized by elemental analysis, IR, NMR, absorption and luminescence spectroscopy. Luminescence measurements were performed for all the complexes in solid state and for the Eu^III, Tb^III and Y^III complexes - in solution in DMSO as well. The effective energy transfer from organic ligands to Ln^III ions strongly sensitizes the Ln^III ions emission and under excitation by UV light, the complexes exhibited bright characteristic emission of lanthanide metal centers. It was found that the energy level of the ligands lowest triplet state in the complexes matches better to resonance level of Eu^III rather than Tb^III ion. Depending on temperature the emission decay times of solid europium and terbium complexes were in the range of 1.5–2.0 ms. In solid state at room temperature the Eu^III complex possess intense luminescence with very high intrinsic quantum yield 91% and decay time equal 1.88 ms.

     

Synthesis and characterization of silver nanoparticles from (bis)alkylamine silver carboxylate precursors

A comparative study of amine and silver carboxylate adducts [R₁COOAg-2(R₂NH₂)] (R₁ = 1, 7, 11; R₂ = 8, 12) as a key intermediate in NPs synthesis is carried out via differential scanning calorimetry, solid-state FT-infrared spectroscopy, ¹³C CP MAS NMR, powder X-ray diffraction and X-ray photoelectron spectroscopy, and various solution NMR spectroscopies (¹H and ¹³C NMR, pulsed field gradient spin-echo NMR, and ROESY). It is proposed that carboxyl moieties in the presence of amine ligands are bound to silver ions via chelating bidentate type of coordination as opposed to bridging bidentate coordination of pure silver carboxylates resulting from the formation of dimeric units. All complexes are packed as lamellar bilayer structures. Silver carboxylate/amine complexes show one first-order melting transition. The evidence presented in this study shows that phase behavior of monovalent metal carboxylates are controlled, mainly, by head group bonding. In solution, insoluble silver salt is stabilized by amine molecules which exist in dynamic equilibrium. Using (bis)amine-silver carboxylate complex as precursor, silver nanoparticles were fabricated. During high-temperature thermolysis, the (bis)amine-carboxylate adduct decomposes to produce silver nanoparticles of small size. NPs are stabilized by strongly interacting carboxylate and trace amounts of amine derived from the silver precursor interacting with carboxylic acid. A corresponding aliphatic amide obtained from silver precursor at high-temperature reaction conditions is not taking part in the stabilization. Combining NMR techniques with FTIR, it was possible to follow an original stabilization mechanism.

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Graphical abstract The synthesis of a series (bis)alkylamine silver(I) carboxylate complexes in nonpolar solvents were carried out and fully characterized both in the solid and solution. Carboxyl moieties in the presence of amine ligands are bound to silver ions via chelating bidentate type of coordination. The complexes form layered structures which thermally decompose forming nanoparticles stabilized only by aliphatic carboxylates.

     

The near-ultraviolet spectrum of diacetylene trapped in solid argon at 9 K

The absorption spectra of normal and deuterated diacetylene trapped in solid argon at 9 K were investigated in the near-ultraviolet region between 2000 and 3000 Å. The vibrational structure observed at low temperature for the band system at 2448 Å, which was previously reported by Haink and Jungen in the gas phase, and identified as a ¹Δ_u ← X¹Σ_g⁺ transition, was analyzed. A comparison between the spectra for C₄H₂ and C₄D₂ suggests some revisions in the upper-state vibrational assignments. The possibility that the upper state assumes a C_2htrans configuration of ¹A_u symmetry is examined. The matrix spectra also appear to indicate that the absorption spectrum observed at 2576 Å in the gas phase and which has been assigned to a ¹Σ_u^? ← X¹Σ_g⁺ transition may not originate in the ground state of C₄H₂.     

EXAFS measurements of bond-stretching force constants in arsenic and arsenic compounds

The Einstein frequency ν_E obtained from temperature-dependent EXAFS measurements for the bond between an arsenic atom and a nearest neighbor in arsenic and certain arsenic halides and chalcogenides is considered. It is shown theoretically that in these materials ν_E should be approximately equal to the “natural” frequency of the bond, and hence that ν_E² is proportional to the bond-stretching force constant ⨍_r. Experimental EXAFS measurements on crystalline (c-) AsBr₃ and AsI₃, glassy (g-) As₂S₃ and As₂Se₃, and amorphous (a-) As yield force constants in reasonable agreement with those obtained from Raman and infrared studies.     

Optical and electrochemical characteristics of ethylenediamine complexes of Pt(II) and Ir(III) with metalated 2-phenyl- and 2-naphthylbenzothiazole

The cyclometalated complexes [Pt(С^N)En]PF₆ and [Ir(C^N)₂En]PF₆ ((C^N)^– are deprotonated forms of 2-phenylbenzothiazole or 2-naphthylbenzothiazole and En is ethylenediamine) are studied by ¹Н NMR, IR, electronic absorption, and emission spectroscopy, as well as by voltammetry. Metalation of heterocyclic ligands leads to the formation of five-membered {M(C^N)} cycles in the composition of squareplanar Pt(II) complexes and octahedral Ir(III) complexes of the cis-С,С structure. A bathochromic shift of the metal-to-cyclometalated ligand charge transfer bands and a decrease in the potential difference between the single-electron waves of metal-centered oxidation and ligand-centered reduction of complexes upon substitution of 2-phenylbenzothiazole by 2-naphthylbenzothiazole and of Pt(II) by Ir(II) are shown. The phosphorescence of complexes in the visible region is assigned to the radiative transition from the metal-modified intraligand electronic excited state.     

Synthesis and Fluorescence Properties of Lanthanide (III) Perchlorate Complexes with Bis(benzoylmethyl) Sulfoxide

A ligand with two carbonyl groups and one sulfinyl group has been synthesized by a new method and its several lanthanide (III) complexes were synthesized and characterized by element analysis, molar conductivity, coordination titration analysis, IR, TG-DSC, ¹H NMR and UV spectra. The results indicated that the composition of these complexes is REL₅(ClO₄)₃·3H₂O (RE = La(III), Pr(III), Eu(III), Tb(III), Yb(III), L = C₆H₅COCH₂SOCH₂COC₆H₅). The fluorescent spectra illustrate that both the Tb (III) and Eu (III) complexes display characteristic metal-centered fluorescence in solid state, indicating the ligand favors energy transfer to the excitation state energy level of them. However, the Tb (III) complex displays more effective luminescence than the Eu (III) complex, which is attributed to especial effectively in transferring energy from the average triplet energy level of the ligands (T) onto the excited state (⁵D₄) of Tb (III) than that (⁵D₀) of Eu (III), showing a good antenna effect for Tb(III) luminescence. The phosphorescence spectra and the relationship between fluorescence lifetimes and fluorescence intensities were also discussed.     

Spectroscopy of the ClCF radical in solid argon

Study of the ClCF emission and excitation spectra in solid Ar gives values of 392 and 712 cm^?1 for the upper state vibrations ν₂ and ν₃, respectively. The electronic transition has its origin at T₀ = 24 983 cm^?1 and a lifetime of 330 ± 20 nsec. The study of vibrationally unrelaxed emission shows, that intramolecular mode-to-mode energy transfer processes are slow compared to direct multiphonon vibrational relaxation.     

Ultrasound-assisted solid Lewis acid-catalyzed transesterification of Lesquerella fendleri oil for biodiesel synthesis

Biodiesel, a mixture of fatty acid methyl esters (FAME), is bio-renewable, non-toxic, biodegradable, and is an attractive alternative to petroleum diesel. This work studied the sonochemical transesterification of Lesquerella fendleri oil (LFO) using inexpensive solid Lewis acid (LA) catalysts with an aim to reduce environmental pollution and dependance on non-renewable fuel sources. Due to the presence of hydroxy fatty acid methyl esters (HFAME) in LFO (∼60%), in addition to producing biofuel it can also be used to generate chemically important estolides and cyclic lactones. AlCl₃, SnCl₂, and Sn(CH₃COO)₂ showed catalytic activity using direct immersion ultrasound (DI-US) among a list of LA catalysts investigated, with AlCl₃ being the best catalyst. Ultrasound increased the reaction rate by facilitating carbocation formation of glyceridic carbons. Experiments were carried out at room temperature in a solvent range from 3:1 to 18:1 methanol-to-oil molar ratio and catalyst loading from 1 wt% to 6 wt% over 10 to 60 min sonication time at 48% ultrasound amplitude (roughly 17 W/cm²). Complete conversion (>99%) was achieved in 40 min with 5 wt% AlCl₃ catalyst. A statistical regression analysis with STATA 14.0 software was performed to optimize process parameters. Chemical characterizations of the compounds were performed with nuclear magnetic resonance (NMR) spectroscopy (¹H NMR & ¹³C NMR), and % conversion of FAMEs was calculated from the ¹H NMR spectra. The fatty acid profile was determined by GC-FID and GC–MS analysis. FT-IR spectroscopic analysis and thermogravimetric analysis (TGA) were performed to investigate the infrared absorption pattern of the compound and the volatility difference between Lesquerella fendleri biodiesel and oil under nitrogen atmosphere. Results indicate that this is a fast, green, energy-efficient, sustainable, and industrially applicable method for biodiesel production from LFO.     

DNA Binding,Cleavage and Antibacterial Activity of Mononuclear Cu(II), Ni(II) and Co(II) Complexes Derived from Novel Benzothiazole Schiff Bases

A series of novel bivalent metal complexes M(L₁)₂ and M(L₂)₂ where M = Cu(II), Ni(II), Co(II) and L₁ = 2-((benzo [d] thiazol-6-ylimino)methyl)-4-bromophenol [BTEMBP], L₂ = 1-((benzo [d] thiazol-6-ylimino)methyl) naphthalen-2-ol [BTEMNAPP] were synthesized. All the compounds have been characterized by elemental analysis, SEM, Mass, ¹H NMR, ¹³C NMR, UV–Vis, IR, ESR, spectral data and magnetic susceptibility measurements. Based on the analytical and spectral data four-coordinated square planar geometry is assigned to all the complexes. DNA binding properties of these complexes have been investigated by electronic absorption spectroscopy, fluorescence and viscosity measurements. It is observed that these binary complexes strongly bind to calf thymus DNA by an intercalation mode. DNA cleavage efficacy of these complexes was tested in presence of H₂O₂ and UV light by gel electrophoresis and found that all the complexes showed better nuclease activity. Finally the compounds were screened for antibacterial activity against few pathogens and found that the complexes have potent biocidal activity than their free ligands.     

Studies of heterogeneous catalysis using high-resolution solid state NMR

Recent results obtained at the institute of Catalysis from studies of heterogeneous catalysis using high-resolution¹H,¹³C,¹⁵N,²⁷Al,²⁹Si,³¹P and⁵¹V solid state NMR have been summarized. Emphasis is made on: (1) structural studies of active in catalysis compounds and sites in supported oxides, hydrides and inorganic acids; (2) studies of structures and properties of surface OH groups active in Bronsted acid catalysis; (3) studies of Lewis acidity of heterogeneous catalysts using¹⁵N NMR of adsorbed N₂O and (4) studies of adsorption mechanisms for molecules of reactants over various catalysts.     

Feasibility of arsenic and antimony NMR spectroscopy in solids: An investigation of some group 15 compounds

The feasibility of obtaining ⁷⁵As and ^121/123Sb NMR spectra for solids at high and moderate magnetic field strengths is explored. Arsenic-75 nuclear quadrupolar coupling constants and chemical shifts have been measured for arsenobetaine bromide and tetraphenylarsonium bromide. Similarly, ^121/123Sb NMR parameters have been measured for tetraphenylstibonium bromide and potassium hexahydroxoantimonate. The predicted pseudo-tetrahedral symmetry at arsenic and the known trigonal bipyramidal symmetry at antimony in their respective tetraphenyl-bromide “salts” are reflected in the measured ⁷⁵As and ¹²¹Sb nuclear quadrupole coupling constants, C_Q(⁷⁵As)=7.8 MHz and C_Q(¹²¹Sb)=159 MHz, respectively. Results of density functional theory quantum chemistry calculations for isolated molecules using ADF and first-principles calculations using CASTEP, a gauge-including projector augmented wave method to deal with the periodic nature of solids, are compared with experiment. Although the experiments can be time consuming, measurements of ⁷⁵As and ¹²¹Sb NMR spectra (at 154 and 215 MHz, respectively, i.e., at B₀=21.14 T) with linewidths in excess of 1 MHz are feasible using uniform broadband excitation shaped pulse techniques (e.g., WURST and WURST-QCPMG).     

Scattering of slow neutrons by arsenic and selenium isotopes

Coherent neutron scattering lengths and free cross sections were measured for arsenic, for ordinary selenium and its isolated isotopes. By means of the Cristiansen filter technique the following scattering lengths for the bound atoms were obtained (in fm):b(As) =6.58(1) [b ₊=6.04(5) andb _?=7.47(8)],b(Se)=7.970(9),b(⁷⁶Se)=12.2(1),b(⁷⁷Se) =08.25(8),b(⁷⁸Se)=8.24(9),b(⁸⁰Se)=7.48(3) andb(⁸²Se)=6.34(8). Transmission measurements with neutrons of 1.26 eV and 5.19 eV resulted in an energy independent free scattering cross section for arsenic ofσ _{s, t}=5.40(3)b (in the eV-region). For ordinary selenium energy dependent free cross sections ofσ _{s, t}(1.26 eV)=7.9(1)b andσ _{s, t} (5.19 eV)=7.55(3)b were found. The results were compared with the resonance parameters of the nuclei and with different sets of potential scattering radii. Thus it could be concluded that there is no evidence for a bound state of the neutron-nucleus compound⁷⁵As+n but a clear evidence for strong bound levels of⁷⁶Se+n and⁷⁷Se+n.     

Emission and excitation spectra of the CCN free radical in solid argon

We demonstrate that 1216 Å photolysis of acetonitrile in rare gas solids leads to efficient production of the CCN free radicals. These radicals emit in solid Ar with a 170 ns lifetime. Study of the A²Δ_i → X²Π_i emission spectra provides values of 1066 and 1717 cm^?1, respectively, for the ground state stretching frequencies. Several weaker vibronic bands are interpreted in terms of the bending fundamentals ν′₂ and ν″₂.     

Structure of complexes in the H<Subscript>2</Subscript>SO<Subscript>4</Subscript>—2-pyrrolidone system as determined by IR-spectroscopy and quantum-chemical calculations

Specific features of complexation in solutions of a strong dibasic acid in the H₂SO₄–2-pyrrolidone (Pyr) system (in the range of compositions of 0–100% H₂SO₄) are studied using multiple frustrated total internal reflection IR spectroscopy. The conclusions drawn on the structure of the complexes formed in such solutions are confirmed by quantum-chemical calculations of the mPyr · nH₂SO₄ (m, n = 1, 2) heteroassociates and by comparison of their calculated and measured vibrational spectra. It is found that, in the investigated solutions, four types of acid–base complexes, with various degrees of proton transfer in the OHO bridge, are formed: (AHA)^– anions with quasi-symmetric H-bonds, solvated by acid molecules, or entering into the composition of PyrH⁺ · (AHA)^– ion pairs; quasi-ion pairs with incomplete proton transfer to the base molecule of 1: 1 and 2: 2 compositions; and 2Pyr · H₂SO₄ complexes with two O–H···O bridges of molecular type. The main differences in the mechanisms of the acid–base interactions in the H₂SO₄–Pyr system as compared to the CH₃SO₃H–Pyr system result from the participation of two OH-groups of H₂SO₄ molecule in these interactions. Therefore, two types of quasi-ion pairs and complexes of 2Pyr · H₂SO₄ composition are formed.     

Spectroscopic Characterization of Oxime Ligands and Their Complexes

New imine–oxime ligands H₃L¹–H₃L³ have been obtained from reactions of the Schiff base ligands H₂B¹–H₂B³ with monochloroglyoxime. Mononuclear copper(II), cobalt(II), nickel(II), vanadyl(IV) and zinc(II) complexes of the imine–oxime ligands H₃L¹–H₃L³ have been prepared and characterized by elemental analyses, infrared and electronic spectra, magnetic moment and molar conductance data. The molar conductance data show that the complexes are non‐electrolytes. When the imine–oxime ligands react with the metal salts in a 2:1 ratio, they behave as dibasic bidentate ligands towards one metal ion. The nickel(II) and zinc(II) complexes are diamagnetic. The ¹H(¹³C)‐nmr spectra of all ligands and nickel(II) and zinc(II) complexes of the ligands H₃L¹–H₃L³ have been recorded. Mass spectra of the imine–oxime ligands and their nickel(II) and zinc(II) complexes were recorded. Some of the ligands and metal complexes have antibacterial activity.     

Elastic constants of solid krypton at T = 77 K determined by inelastic neutron scattering

Long-wavelength acoustic phonons have been studied for each of the [ζ00]T, [ζ00]L, [ζζ0]L and [ζζ0]T₁ branches in solid Kr at T = 77 K by means of inelastic neutron scattering utilizing ‘cold neutrons’ as they are available in the long-wave length tail of the pile spectrum. The raw data have been corrected for resolution effects taking into account the curvature of the dispersion surface and variation of mode eigenvectors. It has turned out, that this yields appreciable shifts of the raw data. The results of our experiment give c₁₁ = 4·25 ± 0·10, c₄₄ = 2·04 ± 0·03, c₁₂ = 2·82 ± 0·12 and a value for B = (c₁₁ + 2c₁₂)/3 = 3·30 ± 0·09 × 10¹⁰ dyne/cm². Available thermodynamic data for Kr gives a derived value for B^ad = 2·58 ± 0·06 × 10¹⁰ dyne/cm² indicating a large difference between zero sound and first sound in solid Kr at high temperatures.