Synergistic use of Knudsen effusion quadrupole mass spectrometry, solid-state galvanic cell and differential scanning calorimetry for thermodynamic studies on lithium aluminates

Three ternary oxides LiAl₅O₈(s), LiAlO₂(s) and Li₅AlO₄(s) in the system Li-Al-O were prepared by solid-state reaction route and characterized by X-ray powder diffraction method. Equilibrium partial pressure of CO₂(g) over the three-phase mixtures {LiAl₅O₈(s)+Li₂CO₃(s)+5Al₂O₃(s)}, {LiAl₅O₈(s)+5LiAlO₂(s)+2Li₂CO₃(s)} and {LiAlO₂(s)+Li₅AlO₄(s)+2Li₂CO₃(s)} were measured using Knudsen effusion quadrupole mass spectrometry (KEQMS). Solid-state galvanic cell technique based on calcium fluoride electrolyte was used to determine the standard molar Gibbs energies of formations of these aluminates. The standard molar Gibbs energies of formation of these three aluminates calculated from KEQMS and galvanic cell measurements were in good agreement. Heat capacities of individual ternary oxides were measured from 127 to 868 K using differential scanning calorimetry. Thermodynamic tables representing the values of Δ_fH⁰(298.15 K), S⁰(298.15 K) S⁰(T), C_p⁰(T), H⁰(T), {H⁰(T)-H⁰(298.15 K)}, G⁰(T), Δ_fH⁰(T), Δ_fG⁰(T) and free energy function (fef) were constructed using second law analysis and FACTSAGE thermo-chemical database software.     

Dielectric response of methyl isobutyl ketone (MIBK) in apolar solvents: solute-solvent interactions

Dielectric constants of binary mixtures of MIBK, an extractant used in nuclear energy industry, with six apolar solvents i.e. benzene, dioxane, cyclohexane, carbon tetrachloride, p-xylene and n-heptane have been measured at 455 kHz. The data are used to evaluate the Eyring’s structural parameter, G*, in these systems to assess the nature of non-specific solute-solvent interaction. The value of G* is found to be influenced by the nature of the solvent.     

Observation of a resonancelike structure in the pi +- psi' mass distribution in exclusive B-->Kpi +- psi' decays

A distinct peak is observed in the pi +/- psi' invariant mass distribution near 4.43 GeV in B-->K pi +/- psi' decays. A fit using a Breit-Wigner resonance shape yields a peak mass and width of M=4433+/-4(stat)+/-2(syst) MeV and Gamma=45-13+18(stat)-13+30(syst) MeV. The product branching fraction is determined to be B(B 0-->K -/+Z+/-(4430)) x B(Z+/-(4430)-->pi+/-psi')=(4.1+/-1.0(stat)+/-1.4(syst)) x 10(-5), where Z+/-(4430) is used to denote the observed structure. The statistical significance of the observed peak is 6.5 sigma. These results are obtained from a 605 fb(-1) data sample that contains 657 x 10(6) BB pairs collected near the Upsilon(4S) resonance with the Belle detector at the KEKB asymmetric energy e+ e- collider.     

Search for B+-->D*+pi0 decay

We report on a search for the doubly Cabibbo suppressed decay B+-->D*+pi0, based on a data sample of 657x10(6) BB pairs collected at the Upsilon(4S) resonance with the Belle detector at the KEKB asymmetric-energy e+e- collider. We find no significant signal and set an upper limit of B(B+-->D*+pi0)<3.6x10(-6) at the 90% confidence level. This limit can be used to constrain the ratio between suppressed and favored B-->D*pi decay amplitudes, r<0.051, at the 90% confidence level.     

Time-dependent CP-violating asymmetry in B0-->rho0gamma decays

We report the first measurement of CP-violation parameters in B0-->rho0gamma decays based on a data sample of 657x10(6)BB pairs collected with the Belle detector at the KEKB asymmetric-energy e+e- collider. We obtain the time-dependent and direct CP-violating parameters, Srho0gamma=-0.83+/-0.65(stat)+/-0.18(syst) and Arho0gamma=-0.44+/-0.49(stat)+/-0.14(syst), respectively.     

Measurement of time-dependent CP-violating parameters in B(0)-->K_(S)(0)K_(S)(0) decays

We report a measurement of the CP-violating parameters in B;{0}-->K_{S}{0}K_{S}{0} decays based on a data sample of 657x10{6} BB[over ] pairs collected at the Upsilon(4S) resonance with the Belle detector at the KEKB asymmetric-energy e;{+}e{-} collider. In this Letter, one neutral B meson is fully reconstructed in the B;{0}-->K_{S}{0}K_{S}{0} decay mode, and the flavor of the accompanying B meson is identified by its decay products. The CP-violating parameters are measured from the asymmetry in the distributions of the proper-time interval between the two B decays: S_K_{S}{0}K_{S}{0}}=-0.38_{-0.77}{+0.69}(stat)+/-0.09(syst) and A_{K_{S}{0}K_{S}{0}}=-0.38+/-0.38(stat)+/-0.05(syst).     

Thermal dynamics-based mechanism for intense laser-induced material surface vaporization

Laser material processing involving welding, ablation and cutting involves interaction of intense laser pulses of nanosecond duration with a condensed phase. Such interaction involving high brightness radiative flux causes multitude of non-linear events involving thermal phase transition at soild-liquid-gas interfaces. A theoretical perspective involving thermal dynamics of the vaporization process and consequent non-linear multiple thermal phase transitions under the action of laser plasma is the subject matter of the present work. The computational calculations were carried out where titanium (Ti) was treated as a condensed medium. The solution to the partial differential equations governing the thermal dynamics and the underlying phase transition event in the multiphase system is based on non-stationary Eulerian variables. The Mach number M depicts significant fluctuations due to thermal instabilities associated with the laser beam flux and intensity. A conclusive amalgamation has been established which relates material surface temperature profile to laser intensity, laser flux and the pressure in the plasma cloud.      

Chemical Regulation of DNA i‐Motifs for Nanobiotechnology and Therapeutics

DNA sequences rich in cytosine have the propensity, under acidic pH, to fold into four‐stranded intercalated DNA structures called i‐motifs. Recent studies have provided significant breakthroughs that demonstrate how chemists can manipulate these structures for nanobiotechnology and therapeutics. The first section of this Minireview discusses the development of advanced functional nanostructures by synthetic conjugation of i‐motifs with organic scaffolds and metal nanoparticles and their role in therapeutics. The second section highlights the therapeutic targeting of i‐motifs with chemical scaffolds and their significance in biology. For this, first we shed light on the long‐lasting debate regarding the stability of i‐motifs under physiological conditions. Next, we present a comparative analysis of recently reported small molecules for specifically targeting i‐motifs over other abundant DNA structures and modulating their function in cellular systems. These advances provide new insights into i‐motif‐targeted regulation of gene expression, telomere maintenance, and therapeutic applications.     

Concise synthesis of novel oxa-bridged compounds

[structures: see text] A stereoselective strategy for the replacement of the 1,2-dihaloalkene bridge of tetrahalonorbornyl derivatives by an oxygen bridge involving stepwise controlled oxidation, cleavage of the dione thus formed, and reiterative intramolecular S(N)2 displacement of two bridgehead halogens is devised. The synthesis of four highly strained pentacyclic bis-oxa-bridged derivatives 10, 27, 28, and 29 with interesting structural variations is presented. The two oxa bridges are syn to each other, separated by central cyclohexane and cycloheptane rings in 10 and 27, while they are anti to each other and are separated by central cyclopentane and furan rings in 28 and 29. In the case of the highly symmetric bis-oxa-bridged derivative 10 the two syn oxa bridges constrain the central cyclohexane ring into the boat form. The endo,anti,endo 2:1 bis adducts of 1,2,3,4-tetrahalo-5,5-dimethoxycyclopenta-1,3-diene with cyclopentadiene were prepared for the first time, while the reactivites of previously unexplored bis adducts derived from furan and cycloheptatriene were revealed.     

Effects of solvent on the reactions of coordination complexes: Part 17. Kinetics and mechanism of base hydrolysis of (αβS) (salicylato) (tetraethylenepentamine)cobalt (III) in methanol + water and dimethylsulphoxide + water media

The base hydrolysis of (αβS) (salicylato) (tetraethylenepentamine)cobalt(III) has been investigated in MeOH + water and DMSO + water media (0–70% (v/v) cosolvents) at 20.0 ? t°C ? 35.0 and I = 0.10 mol dm^?3 (ClO₄^?). The phenoxide species [(tetren)CoO₂CC₆H₄O]⁺ undergoes both OH^?-independent and OH^?-catalyzed hydrolysis via SN₁ICB and SN₁CB mechanism, respectively. The OH^?-independent hydrolysis of the phenoxide species is catalyzed by both DMSO + water and MeOH + water media, the former exerting a much stronger rate accelerating effect than the latter. The OH^?-catalyzed reaction is strongly accelerated by DMSO + water medium but insensitive to the composition of MeOH + water medium up to 40% (v/v) MeOH beyond which it was not detectable under the experimental conditions. Data analysis has been attempted on the basis of the solvent stabilizing and destabilizing effects on the initial state and transition state of the concerned reactions. The nonlinear variation of the activation parameters, ΔH^≠ and ΔS^≠, with solvent compositions presumably indicates that the solvent structural effects mediate the energetics of solvation of the initial state and transition state of the concerned reactions. The linearity in ΔH^≠ vs. ΔS^≠ plot accomodating all data for k₁ and k₂ paths in DMSO + water and MeOH + water further suggests that the solvent effects on these parameters are mutually compensatory.