A CIDEP study of photolysis of duroquinone/hydrogen-donor homogeneous and triton micelle solutions

The CIDEP spectra of transient radicals during photolysis of the duroquinone (DQ)/ethylene glycol (EG) system in acid, basic, and micellar environments were measured with a home-made highly time-resolved ESR spectrometer. In the DQ/EG homogeneous solution, the enhanced emissive CIDEP signal of the neutral durosemiquinone radical DQH^• was observed. When the DQ/EG solution at pH 9 or the DQ/EG/TX-100/H₂O micelle system was photolyzed, the CIDEP signal of the duroquinone anion radical (DQ^•−) was obtained. When the DQ/EG solution at pH 2.5 was irradiated, the CIDEP signal of DQH^• appeared. These experimental results indicate that the neutral radical DQH^• was formed by proton transfer from EG to ³DQ*, and that DQ^•− was formed by dissociation of DQH^• accompanying polarization transfer.     

Catenated Gallium Compounds Supported by a<Emphasis Type="Italic"> Tris</Emphasis>(pyrazolyl)hydroborato Ligand

[ \textTp^\textMe₂ {\text{Tp}}^{{{\text{Me}}_{2} }} ]M (M = K, Tl) reacts with “GaI” to give a series of compounds that feature Ga–Ga bonds, namely [ \textTp^\textMe₂ {\text{Tp}}^{{{\text{Me}}_{2} }} ]Ga→GaI₃, [ \textTp^\textMe₂ {\text{Tp}}^{{{\text{Me}}_{2} }} ]GaGaI₂GaI₂( \textHpz^\textMe₂ {\text{Hpz}}^{{{\text{Me}}_{2} }} ) and [ \textTp^\textMe₂ {\text{Tp}}^{{{\text{Me}}_{2} }} ]Ga(GaI₂)₂Ga[ \textTp^\textMe₂ {\text{Tp}}^{{{\text{Me}}_{2} }} ], in addition to the cationic, mononuclear Ga(III) complex {[ \textTp^\textMe₂ {\text{Tp}}^{{{\text{Me}}_{2} }} ]₂Ga}⁺. Likewise, [ \textTp^\textMe₂ {\text{Tp}}^{{{\text{Me}}_{2} }} ]M (M = K, Tl) reacts with (HGaCl₂) ₂ and Ga[GaCl₄] to give [ \textTp^\textMe₂ {\text{Tp}}^{{{\text{Me}}_{2} }} ]Ga→GaCl₃, {[ \textTp^\textMe₂ {\text{Tp}}^{{{\text{Me}}_{2} }} ]₂Ga}[GaCl₄], and {[ \textTp^\textMe₂ {\text{Tp}}^{{{\text{Me}}_{2} }} ]GaGa[ \textTp^\textMe₂ {\text{Tp}}^{{{\text{Me}}_{2} }} ]}[GaCl₄]₂. The adduct [ \textTp^\textMe₂ {\text{Tp}}^{{{\text{Me}}_{2} }} ]Ga→B(C₆F₅)₃ may be obtained via treatment of [ \textTp^\textMe₂ {\text{Tp}}^{{{\text{Me}}_{2} }} ]K with “GaI” followed by addition of B(C₆F₅)₃. Comparison of the deviation from planarity of the GaY₃ ligands in [ \textTp^\textMe₂ {\text{Tp}}^{{{\text{Me}}_{2} }} ]Ga→GaY₃ (Y = Cl, I) and [ \textTm^{\textBu\textt} {\text{Tm}}^{{{\text{Bu}}^{\text{t}} }} ]Ga→GaY₃, as evaluated by the sum of the Y–Ga–Y bond angles, Σ(Y–Ga–Y), indicates that the [ \textTm^{\textBu\textt} {\text{Tm}}^{{{\text{Bu}}^{\text{t}} }} ]Ga moiety is a marginally better donor than [ \textTp^\textMe₂ {\text{Tp}}^{{{\text{Me}}_{2} }} ]Ga. In contrast, the displacement from planarity for the B(C₆F₅)₃ ligand of [ \textTp^\textMe₂ {\text{Tp}}^{{{\text{Me}}_{2} }} ]Ga→B(C₆F₅)₃ is greater than that of [ \textTm^{\textBu\textt} {\text{Tm}}^{{{\text{Bu}}^{\text{t}} }} ]Ga→B(C₆F₅)₃, an observation that is interpreted in terms of interligand steric interactions in the former complex compressing the C–B–C bond angles.     

Standard enthalpies of formation of Li,Na, K,and Cs thiolates

The standard enthalpies of formation of alkaline metals thiolates in the crystalline state were determined by reaction-solution calorimetry. The obtained results at 298.15 K were as follows: \Updelta_\textf H_\textm^\texto (\textMSR,  \textcr) \Updelta_{\text{f}} H_{\text{m}}^{\text{o}} ({\text{MSR,}}\;{\text{cr}}) /kJ mol⁻¹ = −259.0 ± 1.6 (LiSC₂H₅), −199.9 ± 1.8 (NaSC₂H₅), −254.9 ± 2.4 (NaSC₄H₉), −240.6 ± 1.9 (KSC₂H₅), −235.8 ± 2.0 (CsSC₂H₅). These results where compared with the literature values for the corresponding alkoxides and together with values for \Updelta_\textf H_\textm^\texto ( \textMSH,  \textcr) \Updelta_{\text{f}} H_{\text{m}}^{\text{o}} \left( {{\text{MSH}},\;{\text{cr}}}\right) were used to derive a consistent set of lattice energies for MSR compounds based on the Kapustinskii equation. This allows the estimation of the enthalpy of formation for some non-measured thiolates.     

Solvent extraction of microamounts of cesium into nitrobenzene using ammonium and thallium dicarbollylcobaltates in the presence of 2,3-naphtho-15-crown-5

Extraction of microamounts of cesium by a nitrobenzene solution of ammonium dicarbollylcobaltate ( \textNH ₄ ⁺ \textB ^- ) ( {{\text{NH}}_{ 4}^{ + } {\text{B}}^{ - } }) and thallium dicarbollylcobaltate ( \textTl ⁺ \textB ^- ) ( {{\text{Tl}}^{ + } {\text{B}}^{ - } }) in the presence of 2,3-naphtho-15-crown-5 (N15C5, L) has been investigated. The equilibrium data have been explained assuming that the complexes \textML ⁺ {\text{ML}}^{ + } and \textML ₂ ⁺ {\text{ML}}_{ 2}^{ + } ( \textM ⁺ = \textNH₄ ⁺ ,\textTl ⁺ ,\textCs ⁺ ) ( {{\text{M}}^{ + } = {\text{NH}}_{4}^{ + } ,{\text{Tl}}^{ + } ,{\text{Cs}}^{ + } } ) are present in the organic phase. The stability constants of the \textML ⁺ {\text{ML}}^{ + } and \textML₂ ⁺ {\text{ML}}_{2}^{ + } species ( \textM ⁺ = \textNH₄ ⁺ ,\textTl ⁺ ) ( {{\text{M}}^{ + } = {\text{NH}}_{4}^{ + } ,{\text{Tl}}^{ + } }) in nitrobenzene saturated with water have been determined. It was found that the stability of the complex cations \textML ⁺ {\text{ML}}^{ + } and \textML₂ ⁺ {\text{ML}}_{2}^{ + } (\textM ⁺ = \textNH₄ ⁺ ,\textTl ⁺ ,\textCs ⁺ ;  \textL = \textN15\textC5) ({{\text{M}}^{ + } = {\text{NH}}_{4}^{ + } ,{\text{Tl}}^{ + } ,{\text{Cs}}^{ + } ;\;{\text{L}} = {\text{N}}15{\text{C}}5}) in the mentioned medium increases in the \textCs ⁺   <  \textNH₄ ⁺   <  \textTl ⁺ {\text{Cs}}^{ + }\,<\, {\text{NH}}_{4}^{ + }\,<\,{\text{Tl}}^{ + } order.     

Kinetics and mechanism of oxidation of aquaethylenediaminetetraacetatocobaltate(II) by <Emphasis Type="Italic">N</Emphasis>-bromosuccinimide in aqueous acidic solution

The oxidation of aquaethylenediaminetetraacetatocobaltate(II) [Co(EDTA)(H₂O)]⁻² by N-bromosuccinimide (NBS) in aqueous solution has been studied spectrophotometrically over the pH 6.10–7.02 range at 25 °C. The reaction is first-order with respect to complex and the oxidant, and it obeys the following rate law:

Vanadium(V)-substituted Keggin-type heteropolyoxotungstophosphates as electron transfer and antimicrobial agents: oxidation of glutathione and sensitization of MRSA towards β-lactam antibiotics

Glutathione (GSH) undergoes facile electron transfer with vanadium(V)-substituted Keggin-type heteropolyoxometalates, [ \textPV^\textV \textW _{1 1} \textO _{4 0} ] ^{4 -} [ {\text{PV}}^{\text{V}} {\text{W}}_{ 1 1} {\text{O}}_{ 4 0} ]^{{ 4 { - }}} (HPA1) and [ \textPV^\textV \textV^\textV \textW _{1 0} \textO _{4 0} ] ^{5 -} [ {\text{PV}}^{\text{V}} {\text{V}}^{\text{V}} {\text{W}}_{ 1 0} {\text{O}}_{ 4 0} ]^{{ 5 { - }}} (HPA2). The kinetics of these reactions have been investigated in phthalate buffers spectrophotometrically at 25 °C in aqueous medium. One mole of HPA1 consumes one mole of GSH and the product is the one-electron reduced heteropoly blue, [ \textPV^\textIV \textW _{1 1} \textO ₄₀ ] ^5- [ {\text{PV}}^{\text{IV}} {\text{W}}_{ 1 1} {\text{O}}_{ 40} ]^{ 5- } . But in the GSH-HPA2 reaction, one mole of HPA2 consumes two moles of GSH and gives the two-electron reduced heteropoly blue [ \textPV^\textIV \textV^\textIV \textW ₁₀ \textO ₄₀ ] ^7- [ {\text{PV}}^{\text{IV}} {\text{V}}^{\text{IV}} {\text{W}}_{ 10} {\text{O}}_{ 40} ]^{ 7- } . Both reactions show overall third-order kinetics. At constant pH, the order with respect to both [HPA] species is one and order with respect to [GSH] is two. At constant [GSH], the rate shows inverse dependence on [H⁺], suggesting participation of the deprotonated thiol group of GSH in the reaction. A suitable mechanism has been proposed and a rate law for the title reaction is derived. The antimicrobial activities of HPA1, HPA2 and [ \textPV^\textV \textV^\textV \textV^\textV \textW ₉ \textO _{4 0} ] ^{6 -} [ {\text{PV}}^{\text{V}} {\text{V}}^{\text{V}} {\text{V}}^{\text{V}} {\text{W}}_{ 9} {\text{O}}_{ 4 0} ]^{{ 6 { - }}} (HPA3) against MRSA were tested in vitro in combination with vancomycin and penicillin G. The HPAs sensitize MRSA towards penicillin G.     

Thermodynamic properties of rubidium niobium tungsten oxide

In the present work temperature dependence of heat capacity of rubidium niobium tungsten oxide has been measured first in the range from 7 to 395 K and then between 390 and 650 K, respectively, by precision adiabatic vacuum and dynamic calorimetry. The experimental data were used to calculate standard thermodynamic functions, namely the heat capacity ^ (T), C_{\text{p}}^{\text{o}} (T), enthalpy H^\texto (T) - H^\texto (0) H^{\text{o}} ({\rm T}) - H^{\text{o}} (0) , entropy S^\texto (T) - S^\texto ( 0 ) S^{\text{o}} (T) - S^{\text{o}} \left( 0 \right) , and Gibbs function G^\texto (T) - H^\texto (0) G^{{^{\text{o}} }} ({\rm T}) - H^{{^{\text{o}} }} (0) , for the range from T→0 to 650 K. The high-temperature X-ray diffraction and the differential scanning calorimetry were used for the determination of temperature and decomposition products of RbNbWO₆.     

A thermodynamic study on the binding of mercury and silver ions to urease

In this article, a thermodynamic study on the interaction of Jack bean urease, JBU, with \textHg ²⁺ {\text{Hg}}^{ 2+ } and \textAg ⁺ {\text{Ag}}^{ + } ions were studied by isothermal titration calorimetry (ITC) at 300 and 310 K in 30 mM Tris buffer solution, pH 7.0. The heats of \textJBU + \textHg ²⁺ {\text{JBU}} + {\text{Hg}}^{ 2+ } and \textJBU + \textAg ⁺ {\text{JBU}} + {\text{Ag}}^{ + } interactions are reported and analyzed in terms of the extended solvation model. It was indicated that there are a set of 12 identical and non-cooperative sites for \textHg ²⁺ {\text{Hg}}^{ 2+ } and \textAg ⁺ {\text{Ag}}^{ + } ions. The binding of \textHg ²⁺ {\text{Hg}}^{ 2+ } and \textAg ⁺ {\text{Ag}}^{ + } ions with JBU are exothermic with association equilibrium constants of 5415.65 and 4368.15 for \textAg ⁺ {\text{Ag}}^{ + } and 2389 and 2087 M ^{- 1} M^{ - 1} for \textHg ²⁺ {\text{Hg}}^{ 2+ } at 300 and 310 K, respectively.     

Standard molar enthalpies of formation of some methylfuran derivatives

The standard (p ^o = 0.1 MPa) molar enthalpies of formation \Updelta_\textf H_\textm^\texto ( \textl), {{\Updelta}}_{\text{f}} H_{\text{m}}^{\text{o}} ( {\text{l),}} of the liquid 2-methylfuran, 5-methyl-2-acetylfuran and 5-methyl-2-furaldehyde were derived from the standard molar energies of combustion, in oxygen, at T = 298.15 K, measured by static bomb combustion calorimetry. The Calvet high temperature vacuum sublimation technique was used to measure the enthalpies of vaporization of the three compounds. The standard (p ^o = 0.1 MPa) molar enthalpies of formation of the compounds, in the gaseous phase, at T = 298.15 K have been derived from the corresponding standard molar enthalpies of formation in the liquid phase and the standard molar enthalpies of vaporization. The results obtained were −(76.4 ± 1.2), −(253.9 ± 1.9), and −(196.8 ± 1.8) kJ mol⁻¹, for 2-methylfuran, 5-methyl-2-acetylfuran, and 5-methyl-2-furaldehyde, respectively.     

Thermochemistry of paracetamol

Combustion calorimetry, Calvet-drop sublimation calorimetry, and the Knudsen effusion method were used to determine the standard (p ^o = 0.1 MPa) molar enthalpies of formation of monoclinic (form I) and gaseous paracetamol, at T = 298.15 K: \Updelta_\textf H_\textm^\texto ( \textC ₈ \textH ₉ \textO ₂ \textN,\text cr I ) = - ( 4 10.4 ±1. 3)\text kJ  \textmol ^{- 1} \Updelta_{\text{f}} H_{\text{m}}^{\text{o}} \left( {{\text{C}}_{ 8} {\text{H}}_{ 9} {\text{O}}_{ 2} {\text{N}},{\text{ cr I}}} \right) = - ( 4 10.4 \pm 1. 3){\text{ kJ}}\;{\text{mol}}^{ - 1} and \Updelta_\textf H_\textm^\texto ( \textC ₈ \textH ₉ \textO ₂ \textN,\text g ) = - ( 2 80.5 ±1. 9)\text kJ  \textmol ^{- 1} . \Updelta_{\text{f}} H_{\text{m}}^{\text{o}} \left( {{\text{C}}_{ 8} {\text{H}}_{ 9} {\text{O}}_{ 2} {\text{N}},{\text{ g}}} \right) = - ( 2 80.5 \pm 1. 9){\text{ kJ}}\;{\text{mol}}^{ - 1} . From the obtained \Updelta_\textf H_\textm^\texto ( \textC ₈ \textH ₉ \textO ₂ \textN,\text cr I ) \Updelta_{\text{f}} H_{\text{m}}^{\text{o}} \left( {{\text{C}}_{ 8} {\text{H}}_{ 9} {\text{O}}_{ 2} {\text{N}},{\text{ cr I}}} \right) value and published data, it was also possible to derive the standard molar enthalpies of formation of the two other known polymorphs of paracetamol (forms II and III), at 298.15 K: \Updelta_\textf H_\textm^\texto ( \textC ₈ \textH ₉ \textO ₂ \textN,\text crII ) = - ( 40 8.4 ±1. 3)\text kJ  \textmol ^{- 1} \Updelta_{\text{f}} H_{\text{m}}^{\text{o}} \left( {{\text{C}}_{ 8} {\text{H}}_{ 9} {\text{O}}_{ 2} {\text{N}},{\text{ crII}}} \right) = - ( 40 8.4 \pm 1. 3){\text{ kJ}}\;{\text{mol}}^{ - 1} and \Updelta_\textf H_\textm^\texto ( \textC ₈ \textH ₉ \textO ₂ \textN,\text crIII ) = - ( 40 7.4 ±1. 3)\text kJ  \textmol ^{- 1} . \Updelta_{\text{f}} H_{\text{m}}^{\text{o}} \left( {{\text{C}}_{ 8} {\text{H}}_{ 9} {\text{O}}_{ 2} {\text{N}},{\text{ crIII}}} \right) = - ( 40 7.4 \pm 1. 3){\text{ kJ}}\;{\text{mol}}^{ - 1} . The proposed \Updelta_\textf H_\textm^\texto ( \textC ₈ \textH ₉ \textO ₂ \textN,\text g ) \Updelta_{\text{f}} H_{\text{m}}^{\text{o}} \left( {{\text{C}}_{ 8} {\text{H}}_{ 9} {\text{O}}_{ 2} {\text{N}},{\text{ g}}} \right) value, together with the experimental enthalpies of formation of acetophenone and 4′-hydroxyacetophenone, taken from the literature, and a re-evaluated enthalpy of formation of acetanilide, \Updelta_\textf H_\textm^\texto ( \textC ₈ \textH ₉ \textON,\text g ) = - ( 10 9. 2 ± 2. 2)\text kJ  \textmol ^{- 1} , \Updelta_{\text{f}} H_{\text{m}}^{\text{o}} \left( {{\text{C}}_{ 8} {\text{H}}_{ 9} {\text{ON}},{\text{ g}}} \right) = - ( 10 9. 2\,\pm\,2. 2){\text{ kJ}}\;{\text{mol}}^{ - 1} , were used to assess the predictions of the B3LYP/cc-pVTZ and CBS-QB3 methods for the enthalpy of a isodesmic and isogyric reaction involving those species. This test supported the reliability of the theoretical methods, and indicated a good thermodynamic consistency between the \Updelta_\textf H_\textm^\texto \Updelta_{\text{f}} H_{\text{m}}^{\text{o}} (C₈H₉O₂N, g) value obtained in this study and the remaining experimental data used in the \Updelta_\textr H_\textm^\texto \Updelta_{\text{r}} H_{\text{m}}^{\text{o}} calculation. It also led to the conclusion that the presently recommended enthalpy of formation of gaseous acetanilide in Cox and Pilcher and Pedley’s compilations should be corrected by ~20 kJ mol⁻¹.     

Sorption of Th(IV) on MX-80 bentonite: effect of pH and modeling

MX-80 bentonite was characterized by XRD and FTIR in detail. The sorption of Th(IV) on MX-80 bentonite was studied as a function of pH and ionic strength in the presence and absence of humic acid/fulvic acid. The results indicate that the sorption of Th(IV) on MX-80 bentonite increases from 0 to 95% at pH range of 0–4, and then maintains high level with increasing pH values. The sorption of Th(IV) on bentonite decreases with increasing ionic strength. The diffusion layer model (DLM) is applied to simulate the sorption of Th(IV) with the aid of FITEQL 3.1 mode. The species of Th(IV) adsorbed on bare MX-80 bentonite are consisted of “strong” species o \textYOHTh^{4 +} \equiv {\text{YOHTh}}^{4 + } at low pH and “weak” species o \textXOTh(OH)₃ \equiv {\text{XOTh(OH)}}_{3} at pH > 4. On HA bound MX-80 bentonite, the species of Th(IV) adsorbed on HA-bentonite hybrids are mainly consisted of o \textYOThL₃ \equiv {\text{YOThL}}_{3} and o \textXOThL₁ \equiv {\text{XOThL}}_{1} at pH < 4, and o \textXOTh(OH)₃ \equiv {\text{XOTh(OH)}}_{3} at pH > 4. Similar species of Th(IV) adsorbed on FA bound MX-80 bentonite are observed as on FA bound MX-80 bentonite. The sorption isotherm is simulated by Langmuir, Freundlich and Dubinin–Radushkevich (D–R) models, respectively. The sorption mechanism of Th(IV) on MX-80 bentonite is discussed in detail.     

Studies on electron transfer reactions: reduction of heteropoly 10-tungstodivanadophosphate by <Emphasis Type="SmallCaps">l</Emphasis>-cysteine in aqueous acid medium

l-cysteine undergoes facile electron transfer with heteropoly 10-tungstodivanadophosphate, [ \textPV^\textV \textV^\textV \textW _{1 0} \textO _{4 0} ]^{5 -} , \left[ {{\text{PV}}^{\text{V}} {\text{V}}^{\text{V}} {\text{W}}_{ 1 0} {\text{O}}_{ 4 0} } \right]^{5 - } , at ambient temperature in aqueous acid medium. The stoichiometric ratio of [cysteine]/[oxidant] is 2.0. The products of the reaction are cystine and two electron-reduced heteropoly blue, [PV^IVV^IVW₁₀O₄₀]⁷⁻. The rates of the electron transfer reaction were measured spectrophotometrically in acetate–acetic acid buffers at 25 °C. The orders of the reaction with respect to both [cysteine] and [oxidant] are unity, and the reaction exhibits simple second-order kinetics at constant pH. The pH-rate profile indicates the participation of deprotonated cysteine in the reaction. The reaction proceeds through an outer-sphere mechanism. For the dianion ⁻SCH₂CH(NH₃ ⁺)COO⁻, the rate constant for the cross electron transfer reaction is 96 M⁻¹s⁻¹ at 25 °C. The self-exchange rate constant for the ^- \textSCH₂ \textCH( \textNH₃ ⁺ )\textCOO ^- \mathord

Thermochemical properties of two nitrothiophene derivatives

This article reports the values of the standard (p ^o = 0.1 MPa) molar enthalpies of formation, in the gaseous phase, \Updelta_\textf H_\textm^\texto ( \textg ), {{\Updelta}}_{\text{f}} H_{\text{m}}^{\text{o}} \left( {\text{g}} \right), at T = 298.15 K, of 2-acetyl-5-nitrothiophene and 5-nitro-2-thiophenecarboxaldehyde as −(48.8 ± 1.6) and (4.4 ± 1.3) kJ mol⁻¹, respectively. These values were derived from experimental thermodynamic parameters, namely, the standard (p ^o = 0.1 MPa) molar enthalpies of formation, in the crystalline phase, \Updelta_\textf H_\textm^\texto ( \textcr ) , {{\Updelta}}_{\text{f}} H_{\text{m}}^{\text{o}} \left( {\text{cr}} \right) , at T = 298.15 K, obtained from the standard molar enthalpies of combustion, \Updelta_\textc H_\textm^\texto , {{\Updelta}}_{\text{c}} H_{\text{m}}^{\text{o}} , measured by rotating bomb combustion calorimetry, and from the standard molar enthalpies of sublimation, at T = 298.15 K, determined from the temperature–vapour pressure dependence, obtained by the Knudsen mass loss effusion method. The results are interpreted in terms of enthalpic increments and the enthalpic contribution of the nitro group in the substituted thiophene ring is compared with the same contribution in other structurally similar compounds.     

Large Carbon Cluster Anions Generated by Laser Ablation of Graphene

The formation of large even-numbered carbon cluster anions, \textC_\textn ^- {\text{C}}_{\text{n}}^{ - } , with n up to 500 were observed in the mass spectra generated by laser ablation of graphene and graphene oxide, and the signal intensity of the latter is much weaker than that of the former. The cluster distributions generated from graphene can be readily altered by changing the laser energy and the accumulation period in the FT - ICR cell. By choosing suitable experimental conditions, weak signals of odd-numbered anions from \textC₁₂₅ ^- {\text{C}}_{{125}}^{ - } to \textC₂₁₁ ^- {\text{C}}_{{211}}^{ - } , doubly charged anions from \textC₇₀^{2 -} {\text{C}}_{{70}}^{{2 - }} to \textC₂₃₀^{2 -} {\text{C}}_{{230}}^{{2 - }} and triply charged cluster anions from \textC₈₀^{3 -} {\text{C}}_{{80}}^{{3 - }} to \textC₂₂₄^{3 -} {\text{C}}_{{224}}^{{3 - }} can be observed. Tandem MS was applied to some selected cluster anions. Though no fragment anions larger than \textC₂₀ ^- {\text{C}}_{{20}}^{ - } can be observed by the process of collisional activation with N₂ gas for most cluster ions, several cluster anions can lose units of C₂, C₄, C₆ or C₈ in their collision process. The differences in their dissociation kinetics and structures require further calculations and experimental studies.     

$$ {{\text{C}}_{\alpha }} - {\text{C}} $$ Bond Cleavage of the Peptide Backbone in MALDI In-Source Decay Using Salicylic Acid Derivative Matrices

The use of 5-formylsalicylic acid (5-FSA) and 5-nitrosalicylic acid (5-NSA) as novel matrices for in-source decay (ISD) of peptides in matrix-assisted laser desorption/ionization (MALDI) is described. The use of 5-FSA and 5-NSA generated a- and x-series ions accompanied by oxidized peptides [M – 2 H + H]⁺. The preferential formation of a- and x-series ions was found to be dependent on the hydrogen-accepting ability of matrix. The hydrogen-accepting ability estimated from the ratio of signal intensity of oxidized product [M – 2 H + H]⁺ to that of non-oxidized protonated molecule [M + H]⁺ of peptide was of the order 5-NSA > 5-FSA > 5-aminosalicylic acid (5-ASA) ≒ 2,5-dihydroxyl benzoic acid (2,5-DHB) ≒ 0. The results suggest that the hydrogen transfer reaction from peptide to 5-FSA and 5-NSA occurs during the MALDI-ISD processes. The hydrogen abstraction from peptides results in the formation of oxidized peptides containing a radical site on the amide nitrogen with subsequent radical-induced cleavage at the \textC_a - \textC {{\text{C}}_{\alpha }} - {\text{C}} bond, leading to the formation of a- and x-series ions. The most significant feature of MALDI-ISD with 5-FSA and 5-NSA is the specific cleavage of the \textC_a - \textC {{\text{C}}_{\alpha }} - {\text{C}} bond of the peptide backbone without degradation of side-chain and post-translational modifications (PTM). The matrix provides a useful complementary method to conventional MALDI-ISD for amino acid sequencing and site localization of PTMs in peptides.     

Study into melting-crystallization of silver thiogallate by the statistical thermal analysis method

The influence of heat treatment of a liquid phase on “melting-crystallization” processes of silver thiogallate (AgGaS₂) having chalcopyrite structure I [`4]2\textd \bar{4}2{\text{d}} , has been studied by the method of statistical thermal analysis (STA). It is shown that the melting temperature of solid phase (T _m) increases non-monotonic from 970 °C due to rise in the preliminary melt overheating, and T _m reaches asymptotically 1010 °C. The equilibrium melting-crystallization temperature ( T_\textm^\texto T_{\text{m}}^{\text{o}} ) has been defined as 989.2 °C. It is also found an extreme dependence of the melt supercooling on its overheating. The two curves of irregular dependence of nucleation rate on melt supercooling have been plotted at different melt overheating.     

Thermochemical study on ternary complex of dysprosium <Emphasis Type="Italic">m</Emphasis>-nitrobenzoic acid with <Emphasis Type="Italic">o</Emphasis>-phenanthroline

A ternary binuclear complex of dysprosium chloride hexahydrate with m-nitrobenzoic acid and 1,10-phenanthroline, [Dy(m-NBA)₃phen]₂·4H₂O (m-NBA: m-nitrobenzoate; phen: 1,10-phenanthroline) was synthesized. The dissolution enthalpies of [2phen·H₂O(s)], [6m-HNBA(s)], [2DyCl₃·6H₂O(s)], and [Dy(m-NBA)₃phen]₂·4H₂O(s) in the calorimetric solvent (V_DMSO:V_MeOH = 3:2) were determined by the solution–reaction isoperibol calorimeter at 298.15 K to be \Updelta_\texts H_\textm^q \Updelta_{\text{s}} H_{\text{m}}^{\theta } [2phen·H₂O(s), 298.15 K] = 21.7367 ± 0.3150 kJ·mol⁻¹, \Updelta_\texts H_\textm^q \Updelta_{\text{s}} H_{\text{m}}^{\theta } [6m-HNBA(s), 298.15 K] = 15.3635 ± 0.2235 kJ·mol⁻¹, \Updelta_\texts H_\textm^q \Updelta_{\text{s}} H_{\text{m}}^{\theta } [2DyCl₃·6H₂O(s), 298.15 K] = −203.5331 ± 0.2200 kJ·mol⁻¹, and \Updelta_\texts H_\textm^q \Updelta_{\text{s}} H_{\text{m}}^{\theta } [[Dy(m-NBA)₃phen]₂·4H₂O(s), 298.15 K] = 53.5965 ± 0.2367 kJ·mol⁻¹, respectively. The enthalpy change of the reaction was determined to be \Updelta_\textr H_\textm^q = 3 6 9. 4 9 ±0. 5 6   \textkJ·\textmol ^{- 1} . \Updelta_{\text{r}} H_{\text{m}}^{\theta } = 3 6 9. 4 9 \pm 0. 5 6 \;{\text{kJ}}\cdot {\text{mol}}^{ - 1} . According to the above results and the relevant data in the literature, through Hess’ law, the standard molar enthalpy of formation of [Dy(m-NBA)₃phen]₂·4H₂O(s) was estimated to be \Updelta_\textf H_\textm^q \Updelta_{\text{f}} H_{\text{m}}^{\theta } [[Dy(m-NBA)₃phen]₂·4H₂O(s), 298.15 K] = −5525 ± 6 kJ·mol⁻¹.     

Effect of the cathode structure on the electrochemical performance of anode-supported solid oxide fuel cells

The study elementarily investigated the effect of the cathode structure on the electrochemical performance of anode-supported solid oxide fuel cells. Four single cells were fabricated with different cathode structures, and the total cathode thickness was 15, 55, 85, and 85 μm for cell-A, cell-B, cell-C, and cell-D, respectively. The cell-A, cell-B, and cell-D included only one cathode layer, which was fabricated by ( \textLa_0.74 \textBi_0.10 \textSr_0.16 )\textMnO_{3 - d} \left( {{\text{La}}_{0.74} {\text{Bi}}_{0.10} {\text{Sr}}_{0.16} } \right){\text{MnO}}_{{3 - \delta }} (LBSM) electrode material. The cathode of the cell-C was composed of a ( \textLa_0.74 \textBi_0.10 \textSr_0.16 )\textMnO_{3 - d} - ( \textBi_0.7 \textEr_0.3 \textO_1.5 ) \left( {{\text{La}}_{0.74} {\text{Bi}}_{0.10} {\text{Sr}}_{0.16} } \right){\text{MnO}}_{{3 - \delta }} - \left( {{\text{Bi}}_{0.7} {\text{Er}}_{0.3} {\text{O}}_{1.5} } \right) (LBSM–ESB) cathode functional layer and a LBSM cathode layer. Different cathode structures leaded to dissimilar polarization character for the four cells. At 750°C, the total polarization resistance (R _p) of the cell-A was 1.11, 0.41 and 0.53 Ω cm² at the current of 0, 400, and 800 mA, respectively, and that of the cell-B was 1.10, 0.39, and 0.23 Ω cm² at the current of 0, 400, and 800 mA, respectively. For cell-C and cell-D, their polarization character was similar to that of the cell-B and R _p also decreased with the increase of the current. The maximum power density was 0.81, 1.01, 0.79, and 0.43 W cm⁻² at 750°C for cell-D, cell-C, cell-B, and cell-A, respectively. The results demonstrated that cathode structures evidently influenced the electrochemical performance of anode-supported solid oxide fuel cells.     

Synergistic extraction of some univalent cations into nitrobenzene by using sodium dicarbollylcobaltate and hexaethyl <Emphasis Type="Italic">p</Emphasis>-<Emphasis Type="Italic">tert</Emphasis>-butylcalix[6]arene hexaacetate

From extraction experiments and γ-activity measurements, the exchange extraction constants corresponding to the general equilibrium M⁺ (aq) + NaL⁺ (nb) ⇔ ML⁺ (nb) + Na⁺ (aq) taking place in the two-phase water–nitrobenzene system (M⁺ = H₃O⁺, \textNH₄⁺ {\text{NH}}_{4}{}^{+} , Ag⁺, Tl⁺; L = hexaethyl p-tert-butylcalix[6]arene hexaacetate; aq = aqueous phase, nb = nitrobenzene phase) were evaluated. Furthermore, the stability constants of the ML⁺ complexes in nitrobenzene saturated with water were calculated; they were found to increase in the following order: \textAg ⁺   <  NH₄ ⁺   <  \textH ₃ \textO ⁺   <  \textNa ⁺   <  \textTl ⁺ . {\text{Ag}}^{ + } \, < \,\hbox{NH}_{4}{}^{ + } \, < \,{\text{H}}_{ 3} {\text{O}}^{ + } \, < \,{\text{Na}}^{ + } \, < \,{\text{Tl}}^{ + }.     

Iron release from ferritin induced by light and ionizing radiation

The reductive release of iron from ferritin by UV light or ionizing radiation has been investigated in separate experiments. When ferritin is exposed to light, the mineral core is the main photoreceptor for the Fe(III) reduction. In radiolytic studies, we determined that, in the absence of oxygen, the hydrated electron (e_aq⁻) is the reducing agent triggering redox reactions associated with iron mobilization from ferritin. In an aerobic system, the superoxide radical anion (O₂^•−) is also involved in the iron release process. We found that, in photochemical and radiolytical studies, Fe(II) mobilization from ferritin required an iron chelator. Without a chelator, ferritin is an electron-storage molecule for a long period, on the order of at least several hours. The reductant or chelator entry into the ferritin core is not necessary for iron release. The ferrozine is a convenient chelating agent to monitor Fe(II) mobilization, due to a high extinction coefficient of \textFe ( \textferrozine )₃^{4 -} {\text{Fe}}\,\left( {\text{ferrozine}} \right)_{3}^{4 - } and a high rate constant of complexation process (2.65 × 10⁴ dm³ mol⁻¹ s⁻¹).