A computational study of SbnF5n (n = 1-4): Implications for the fluoride ion affinity of nSbF5

This contributions shows with a series of ab initio MP2 and DFT (BP86 and B3-LYP) computations with large basis sets up to cc-pVQZ quality that the literature value of the standard enthalpy of depolymerization of Sb₄F_20(g) to give SbF_5(g) (+18.5 kJ mol⁻¹) [J. Fawcett, J.H. Holloway, R.D. Peacock, D.R. Russell, J. Fluorine Chem. 20 (1982) 9] is by about 50 kJ mol⁻¹ in error and that the correct value of (Sb₄F_20(g)) is +68 ± 10 kJ mol⁻¹. We assign , , and values for Sb_nF_5n with n = 2-4 and compare the results to available experimental gas phase data. Especially the MP2/TZVPP values obtained in an indirect procedure that rely on isodesmic reactions or the highly accurate compound methods G2 and CBS-Q are in excellent agreement with the experimental data, and reproduce also the fine experimental details at temperatures of 423 and 498 K. With these data and the additional calculation of [Sb_nF_5n+1]⁻ (n = 1-4), we then assessed the fluoride ion affinities (FIAs) of Sb_nF_5n(g), nSbF_5(g), nSbF_5(l) and the standard enthalpies of formation of Sb_nF_5n(g) and [Sb_nF_5n+1]⁻_(g): FIA(Sb_nF_5n(g)) = 514 (n = 1), 559 (n = 2), 572 (n = 3) and 580 (n = 4) kJ mol⁻¹; FIA(nSbF_5(g)) = 667 (n = 2), 767 (n = 3) and 855 (n = 4) kJ mol⁻¹; FIA(nSbF_5(l)) = 434 (n = 1), 506 (n = 2), 528 (n = 3) and 534 (n = 4) kJ mol⁻¹. Error bars are approximately ±10 kJ mol⁻¹. Also the related Gibbs energies were derived. Δ_fH°([Sb_nF_5n+1]⁻_(g)) = −2064 ± 18 (n = 1), −3516 ± 25 (n = 2), −4919 ± 31 (n = 3) and −6305 ± 36 (n = 4) kJ mol⁻¹.     

Electroanalysis of dopamine at a gold electrode modified with N-acetylcysteine self-assembled monolayer

Voltammetric behavior of dopamine (DA) on a gold electrode modified with the self-assembled monolayer (SAM) of N-acetylcysteine has been investigated, and one pair of well-defined redox peaks of dopamine is obtained at the SAM modified gold electrode. The oxidation peak current increases linearly with the concentration of dopamine in the range of  mol l⁻¹. The detection limit is 8.0×10⁻⁷ mol l⁻¹. This method will be applicable to the determination of dopamine in injection of dopamine hydrochloride, and the good recovery of dopamine is obtained. Furthermore, The SAM modified gold electrode can resolve well the voltammetric responses of dopamine and ascorbic acid (AA), so it can also be applied to the determination of dopamine in the presence of ascorbic acid.     

Preliminary study of a microbeads based histamine detection for food analysis using thermostable recombinant histamine oxidase from Arthrobacter crystallopoietes KAIT-B-007

We designed and prepared a micro biosensing system consisting of a flow through system with a sub-micro liter injection valve and a sub-micro liter volume bioreactor. An electrochemical detector was combined with the reactor for immediate detections. The volumes of the reactor and the sample loop for the injection were 850 nl and 320 nl, respectively. This paper described about the characteristics of the sensing system in the case of histamine detection for food analysis. Histamine oxidase from KAIT-B-007 was prepared by using a gene recombination technique and they were immobilized with chitosan beads (? = 70-105 μm). The detection less than one minute after injection made possible fast analysis for histamine. The biosensing system also showed a high performance for histamine detection in wide range of 1 μM-1 mM. In addition, we practically measured histamine content in raw tuna stored at room temperature and 35 °C up to 96 h. As a result of the comparison between our sensing system and HPLC method, there was good agreement. These results show that our microfluidic biosensing system has the potential to assist miniaturization with small sample volume and short determination time for a sequential food analysis.     

Determination of sulfur-containing amino acids by capillary electrophoresis dynamic reaction cell inductively coupled plasma mass spectrometry

Capillary electrophoresis dynamic reaction cell™ inductively coupled plasma mass spectrometry (CE-DRC-ICP-MS) for the determination of sulfur-containing amino acids is described. The sulfur-containing amino acids studied include l-cysteine, l-cystine, dl-homocystine and l-methionine. The species studied were well separated using a 70 cm length×75 μm i.d. fused silica capillary while the applied voltage was set at +22 kV and a 10 mmol l⁻¹ disodium tetraborate buffer (pH 9.8) containing 0.1 mmol l⁻¹ EDTA and 0.5 mmol l⁻¹ Triton X-100 was used as the electrophoretic buffer. The sulfur-selective electropherogram was determined at m/z 48 as by using its reaction with O₂ in the reaction cell. The method avoided the effect of polyatomic isobaric interferences at m/z 32 caused by and on by detecting as the oxide ion at m/z 48, which is less interfered. The detection limit of various species studied was in the range of 0.047-0.058 μg S ml⁻¹, which corresponded to the absolute detection limit of 1.3-1.6 pg S based on the injection volume of 27 nl. We determined the concentrations of selected sulfur-containing amino acids in urine and nutritive complement samples. The recovery was in the range of 92-128% for various species.     

Voltammetric study on the complex of thiram-copper(II) and its application

Based on the formation of tetramethylthiuram disulfide (thiram)-copper(II) complex by square-wave voltammetry on a glassy carbon electrode, a new method is proposed for determination of thiram. There is a good linear relationship between peak current and concentration of thiram in the range of  mol l⁻¹ (r=0.999). The method is applied to the determination of thiram residue in plant with satisfactory results, compared with results achieved by using HPLC. Two oxidation peaks and two reduction peaks are obtained by cyclic voltammetry on a glassy carbon electrode in 0.2 mol l⁻¹ HAc-NaAc (pH 4.0) solution containing thiram-copper(II) complex. The electrode reaction process is quasi-reversible with adsorptive characteristics. The mechanism of electrode reaction is discussed.     

Determination of arsenic, iron and selenium in moss samples using hexapole collision cell, inductively coupled plasma-mass spectrometry

Different collision gases (H₂, He and premixed 7% H₂ in He) used in the hexapole collision cell of an inductively coupled plasma-mass spectrometer (ICP-MS) were compared, and the gas-flow rates were optimized for the determination of arsenic (), iron () and selenium (). The study showed that the argon-based interferences at mass-to-charge ratios (m/z) of 56, 75 and 80 can be overcome by the optimized gas flows (7.5 ml min⁻¹ premixed 7% H₂ in He and 2 ml min⁻¹ H₂) in the hexapole collision cell. Detection limits of 15.5 ng l⁻¹ for iron () and 29 ng l⁻¹ for selenium () in 2% (v/v) HNO₃ were obtained under optimized collision cell conditions. The detection limit for arsenic () obtained in difficult hydrochloride acid matrix (5% HCl (v/v)) was 153 ng l⁻¹. The accuracy of the optimized method was confirmed by analyzing two moss reference materials. The results obtained by ICP-MS for arsenic, selenium and iron from both moss reference samples were, in most cases, in good agreement with the certified values.     

Phase polymorphism of [Zn(DMSO)6](ClO4)2 studied by differential scanning calorimetry

Four solid phases of [Zn(DMSO)₆](ClO₄)₂ have been detected by differential scanning calorimetry (DSC). Specifically, the phase transitions were detected between: metastable phase KII ↔ supercooled phase K0 at , stable phase KIb ↔ stable phase KIa at , stable phase KIa ↔ stable phase K0 at . At T_m2 = 389 K crystals partially and at T_m1 = 465 K completely melts. From the entropy change values it was concluded that the phases: K0 and K0′ are the orientationally dynamically disordered phases, so called ODDIC crystals, and phases KIa, KIb and metastable KII are dynamically ordered but with some degree of positional disorder.     

Reactions of pyridyl donors with halogens and interhalogens: an X-ray diffraction and FT-Raman investigation

Three different N-donors L, namely N-ethyl-N′-3-pyridyl-imidazolidine-4,5-dione-2-thione (1), N,N′-bis(3-pyridylmethyl)-imidazolidine-4,5-dione-2-thione (2), and tetra-2-pyridyl-pyrazine (3), bearing one, two and four pyridyl substituents, respectively, have been reacted with halogens X₂ (X = Br, I) or interhalogens XY (X = I; Y = Cl, Br). CT σ-adducts L · nXY, bearing linear N?XY moieties (L = 3; X = I; Y = Br, I; n = 2), and salts containing the protonated cationic donors H_nLⁿ⁺ (L = 1 − 3; n = 1, 2, 4), counterbalanced by Cl⁻, Br⁻, , , , , I₂Br⁻, , or anions, have been isolated. Among the reactions products, (H1⁺)Cl⁻, (H1⁺)Br⁻, , , and 3 · 2IBr have been characterised by single-crystal X-ray diffraction. The nature of the products has been elucidated based on elemental analysis and FT-Raman spectroscopy supported by MP2 and DFT calculations.     

Thermodynamic properties of lithium mica: Lepidolite

Calorimetric measurements were made on natural sample of lepidolite having the composition (K_0.80Na_0.05Ca_0.07Rb_0.16Cs_0.03)(Li_1.34Al_1.40Fe³⁺_0.01)[Si_3.25Al_0.75O₁₀]F_1.80(OH)_0.20 from Na-Li-type rare-element-rich pegmatites of East Sayany, Russia. High-temperature enthalpy increments were measured with a Tian-Calvet calorimeter at 444-972 K using the drop method. The resultant (T) equation in the interval T = 298.15-972 K was calculated:  = 316.10 + 228.12 × 10⁻³ T − 50.10 × 10⁵ T⁻² (J K⁻¹ mol⁻¹) [± 0.4%] and the value of (298.15 K) = 327.8 J K⁻¹ mol⁻¹ was obtained. The standard molar enthalpy of formation from the elements was determined by high-temperature drop solution calorimetry in molten lead borate at T = 973 K. The value of Δ_f(298.15 K) for lepidolite was found to be −6201 ± 18 kJ mol⁻¹. The thermodynamic properties of lepidolite of idealized composition KLi_1.5Al_1.5[Si₃AlO₁₀]F₂ were estimated based on the experimental data obtained.     

Enthalpies of solution of 1,1,3,3-tetramethylurea in normal and branched alkanols (C2-C4) at 298.15 K

The enthalpies of solution were determined for 1,1,3,3-tetramethylurea in ethanol, 1-propanol, 2-propanol, 1-butanol, and t-butanol (2-methyl-2-propanol). Measurements were made at 298.15 K and molalities m ≅ (0.007 to 0.036) mol · kg⁻¹ with a precise isoperibol ampoule-type calorimeter. Standard enthalpies of solution and transfer from one alkanol to the other (including methanol) were calculated. The obvious relationship between the enthalpic and volumetric effects of solution of tetramethylurea in the n-alkanols (C₁-C₄) was discovered. The enthalpic effects of transfer caused by branching of the alkanol molecules, 1-propanol → 2-propanol, and 1-butanol → t-butanol, are opposite in sign and dominated by the configurational changes in the solvation environment of tetramethylurea.     

Heat capacity and standard molar enthalpy of formation of crystalline 2,6-dicarboxypyridine (C7H5NO4)

Low-temperature heat capacity C_p,m of 2,6-dicarboxypyridine (C₇H₅NO₄; CAS 499-83-2) was precisely measured in the temperature range from (80 to 378) K with a high precision automated adiabatic calorimeter. No phase transition or thermal anomaly was observed in this range. The thermodynamic functions [H_T − H_298.15] and [S_T − S_298.15] were calculated in the range from (80 to 378) K. The standard molar enthalpy of combustion and the standard molar enthalpy of formation of the compound have been determined, and , by means of a precision oxygen-bomb combustion calorimeter at T = 298.15 K. The thermodynamic properties of the compound were further investigated through differential scanning calorimeter (DSC) and the thermogravimetric (TG) analysis.     

The thermodynamic dissociation constants of ambroxol, antazoline, naphazoline, oxymetazoline and ranitidine by the regression analysis of spectrophotometric data

The mixed dissociation constants of five drug acids—ambroxol, antazoline, naphazoline, oxymetazoline and ranitidine—at various ionic strengths I of range 0.01 and 1.0 and at temperatures of 25 and 37 °C were determined using SQUAD(84) regression analysis of the pH-spectrophotometric titration data. A proposed strategy of efficient experimentation in a protonation constants determination, followed by a computational strategy for the chemical model with a protonation constants determination, is presented on the protonation equilibria of ambroxol. The thermodynamic dissociation constant pK_a^T was estimated by non-linear regression of {pK_a, I} data at 25 and 37 °C: for ambroxol and 8.25 (4), log  and 11.83 (8), for antazoline and 7.83 (6), and 9.55 (2), for naphazoline and 10.63 (1), for oxymethazoline and 10.77 (7), pK_a,2^T=12.03(3) and 11.82 (4) and for ranitidine and 1.77 (1). Goodness-of-fit tests for various regression diagnostics enabled the reliability of the parameter estimates to be found.     

Organic tin compounds combined with anionic additives-an ionophore system leading to a phosphate ion-selective electrode?

The potentiometric response characteristics of electrodes based on organic trialkyl/aryl-tin compounds combined with various amounts of anionic additive (NaTFPB) were investigated in 0.1 M bis-Tris-H₂SO₄ buffer solution at pH 7.0. The best result for phosphate sensing was obtained for the electrode membrane containing tributyltin chloride and 25 mol% NaTFPB, where the electrode exhibits high selectivity towards phosphate anions with a slope of −60 mV per decade. It was demonstrated that the interference from more lipophilic anions is drastically suppressed (, i=H₂PO₄⁻: salicylate, 0.5; SCN⁻, −0.8; ClO₄⁻, −2.3) under this optimized measurement conditions.     

Evaluation of C18 adsorbent cartridges for sampling and derivatization of primary amines in air

The sampling efficiency of C₁₈ solid-phase extraction cartridges was investigated for methylamine, ethylamine, propylamine, butylamine and pentylamine, in air. Determination of these analytes was based on derivatization with o-phthaldialdehyde-N-acetylcysteine (OPA-NAC) on the solid support and fluorescence detection at λ_excitation=330 nm and λ_emission=440 nm of the eluted derivatives. The calibration model derived from aqueous standards was statistically comparable with the calibration model for air standards. Aqueous amines can be used as standards. The method was useful for calculating short-term exposure limits (STEL). A sampling time of 15 min at 30 ml min⁻¹ was employed. Good recoveries for amines alone and their mixtures were obtained from air and water samples, 98±14 and 97±12% (mean ), respectively. Recovery values were independent of amine concentration. The detection limits varied between 0.16 and 0.52 μg per sample (0.35 and 1.18 mg m⁻³, respectively) and the calibration graphs were linear in the range 0.5-2 μg per sample except for pentylamine, which was 1.5-5 μg per sample. The utility of the method was demonstrated for the estimation of methylamine in two generated air samples.     

Synthesis and single crystal structures of ternary phosphides Li4SrP2 and AAeP (A=Li, Na; Ae=Sr, Ba)

Two new (NaSrP, Li₄SrP₂) and two known (LiSrP, LiBaP) ternary phosphides have been synthesized and characterized using single crystal X-ray diffraction studies. NaSrP crystallizes in the non-centrosymmetric hexagonal space group (#189, a=7.6357(3) Å, c=4.4698(3) Å, V=225.69(2) Å³, Z=3, and R/wR=0.0173/0.0268). NaSrP adopts an ordered Fe₂P structure type. PSr₆ trigonal prisms share trigonal (pinacoid) faces to form 1D chains. Those chains define large channels along the [001] direction through edge-sharing. The channels are filled by chains of PNa₆ face-sharing trigonal prisms. Li₄SrP₂ crystallizes in the rhombohedral space group (#166, a=4.2813(2) Å, c=23.437(2) Å, V=372.04(4) Å³, Z=3, and R/wR=0.0142/0.0222). In contrast to previous reports, LiSrP and LiBaP crystallize in the centrosymmetric hexagonal space group P6₃/mmc (#194, a=4.3674(3) Å, c=7.9802(11) Å, V=131.82(2) Å³, Z=2, and R/wR=0.0099/0.0217 for LiSrP; a=4.5003(2) Å, c=8.6049(7) Å, V=150.92(2) Å³, Z=2, and R/wR=0.0098/0.0210 for LiBaP). Li₄SrP₂, LiSrP, and LiBaP can be described as Li₃P derivatives. Li atoms and P atoms make a graphite-like hexagonal layer, . In LiSrP and LiBaP, Sr or Ba atoms reside between layers to substitute for two Li atoms of Li₃P, while in Li₄SrP₂, Sr substitutes only between every other layer.     

Thermodynamic studies on the interactions of diglycine with magnesium chloride in aqueous medium at different temperatures

Apparent molar heat capacities (C_P2,?), apparent molar volumes (V_2,?), and viscosities (η) of diglycine in water and in aqueous magnesium chloride (MgCl₂) solutions of molality m_S ≈ (0.05 to 0.70) mol · kg⁻¹ over the temperature range T = (288.15 to 328.15) K have been determined using high sensitivity micro-differential scanning calorimeter, vibrating-tube digital density meter, and automatic viscosity measuring unit (AVS 350), respectively. The data have been used to calculate the partial molar heat capacities and partial molar volumes at infinite dilution. The viscosity B-coefficients have also been obtained from viscosity data using Jones-Dole equation. The and values of diglycine in aqueous MgCl₂ solutions are higher than those in water and thus exhibit positive transfer functions ( and ), which are indicative of strong interactions between diglycine and MgCl₂. Corresponding viscosity B-coefficients of transfer are also generally positive. The transfer functions decrease with increase in temperature and increase with the concentration of MgCl₂. The free energies, enthalpies and entropies of activation for viscous flow of diglycine in aqueous MgCl₂ solutions have been obtained by using the Feakins transition-state theory. Partial molar expansibilities and at infinite dilution along with their temperature dependence, the interaction coefficients from the volume, heat capacity, and viscosity B-coefficients have been used to divulge the various kinds of plausible interactions between solute (diglycine) and cosolute (MgCl₂) in solutions.     

Syntheses, crystal and electronic structure, and some optical and transport properties of LnCuOTe (Ln=La, Ce, Nd)

Three new compounds, LaCuOTe, CeCuOTe, and NdCuOTe, have been synthesized from the respective rare-earth elements, CuO, and a KI flux at 1023 K. The compounds, which have the ZrSiCuAs structure type, are isostructural to LaCuOS, and crystallize in space group P4/nmm of the tetragonal system with two formula units in cells of dimensions at 153 K of , , for LaCuOTe; , , for CeCuOTe; and , , for NdCuOTe. The structure of LnCuOTe (Ln=La, Ce, Nd) is composed of alternating PbO-like [Ln₂O₂] and anti-PbO-like [Cu₂Te₂] layers stacked perpendicular to [0 0 1]. The experimental optical band gaps of LaCuOTe and NdCuOTe are 2.31 and 2.26 eV, respectively. At 298 K the electrical conductivity of LaCuOTe is 1.65 S/cm and the Hall mobility is +80.6 cm² V⁻¹ s⁻¹. The positive values of the Seebeck and Hall coefficients indicate p-type electrical conduction. First-principles theoretical calculations were performed on LaCuOQ (Q=S, Se, Te). In LaCuOTe, Cu 3d and Te 5p orbitals dominate the states near the valence band maximum; the states near the conduction band minimum are composed of Cu 4s, Te 5p, and La 5d orbitals. The larger dispersion of Cu 3d orbitals and the presence of Te 5p orbitals near the valence band maximum are responsible for the larger hole mobility of LaCuOTe compared to LaCuOS and LaCuOSe.