Quantum dynamics of relaxation of a pair of coupled Morse oscillators: Effects of mass and electrical asymmetries

A multiconfiguration time‐dependent Hartree method based recipe is used to study the role of mass and electrical asymmetry in controlling the quantum dynamics of relaxation of a locally excited O? H bond in a water molecule, modeled by a pair of interacting Morse oscillators. The fast periodic energy transfer between the two equivalent O? H bonds in H? O? H is replaced by a rather slow process when one of the H atom is replaced by a deuterium atom. Application of static electric field along the O? D bond in HOD molecule is seen to either enhance or damp the relaxation rate, depending on the strength of the applied field. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Kinetics of oxidation of hydrogen peroxide by [Mn3 IV(μ-O)4(phen)4(H2O)2]4+ (phen = 1,10-phenanthroline) in weakly acidic aqueous media

In the 3.33–4.95 pH range, buffered with an excess of phenanthroline (phen), [Mn ₃ ^IV (-O)₄(phen)₄(H₂O)₂]⁴⁺ (1) quantitatively oxidises H₂O₂ to O₂; the only manganese product is [Mn ₂ ^III,IV (-O)₂(phen)₄]³⁺ (2), provided a large excess of H₂O₂ is avoided; an excess of H₂O₂ [ > 7 × (1)] reduces (1) to Mn²⁺. When (1) and H₂O₂ were mixed in the stoichiometric molar proportion (1:0.75), the measured second-order rate constant for the reduction of (1) to (2) increased with increasing [H⁺], tending to saturate at lower pH. Added phenanthroline did not affect the rate constant. The results suggest an inner-sphere mechanism, ca. 10 times higher kinetic activity for (1) than for its hydroxo derivative [Mn ₃ ^IV (-O)₄(phen)₄(OH)(H₂O)]³⁺ (1h), and a hydrolysis constant K _a = (2.9 ± 1) × 10^–4 mol dm^–3 for (1) (1h) + H⁺.     

Excellent Suzuki–Miyaura catalytic activity of a new Pd(II) complex with sulfonamide–Schiff base ligand

A new air‐stable Pd(II) complex containing a sulfonamide–Schiff base ligand has been synthesized, characterized and investigated as a catalyst for the Suzuki–Miyaura reactions of aryl halides with arylboronic acids. Theoretical calculations (B3LYP) and spectroscopic evidence suggest that the sulfonamide–Schiff base coordinates to the Pd centre through sulfonamide nitrogen (? SO₂NH₂) rather than imine (? CH?N). The complex shows excellent cross‐coupling activity with aryl bromides in water at room temperature and aryl chlorides in isopropanol at 60°C. Copyright © 2016 John Wiley & Sons, Ltd.     

Study of a fractional-order model of chronic wasting disease

This paper studies a fractional-order modelling chronic wasting disease (CWD). The basic results on existence, uniqueness, non-negativity, and boundedness of the solutions are investigated for the considered model. The criterion for local as well as global stability of the equilibrium points is derived. A numerical analysis for Hopf-type bifurcation is presented. Finally, numerical simulations are provided to justify the results obtained.     

Computational Hardness of Collective Coin-Tossing Protocols

Ben-Or and Linial, in a seminal work, introduced the full information model to study collective coin-tossing protocols. Collective coin-tossing is an elegant functionality providing uncluttered access to the primary bottlenecks to achieve security in a specific adversarial model. Additionally, the research outcomes for this versatile functionality has direct consequences on diverse topics in mathematics and computer science. This survey summarizes the current state-of-the-art of coin-tossing protocols in the full information model and recent advances in this field. In particular, it elaborates on a new proof technique that identifies the minimum insecurity incurred by any coin-tossing protocol and, simultaneously, constructs the coin-tossing protocol achieving that insecurity bound. The combinatorial perspective into this new proof-technique yields new coin-tossing protocols that are more secure than well-known existing coin-tossing protocols, leading to new isoperimetric inequalities over product spaces. Furthermore, this proof-technique’s algebraic reimagination resolves several long-standing fundamental hardness-of-computation problems in cryptography. This survey presents one representative application of each of these two perspectives.     

A Brønsted Acid Catalyzed Cascade Reaction for the Conversion of Indoles to α-(3-Indolyl) Ketones by Using 2-Benzyloxy Aldehydes

A Brønsted acid catalyzed, operationally simple, scalable route to several functionalized α-(3-indolyl) ketones has been developed and the long-standing regioisomeric issue has been eliminated by choosing appropriate carbonyls. A readily available and cheap bottle reagent was used as the catalyst. This protocol was also applicable to the synthesis of densely functionalized α-(3-pyrrolyl) ketones. A detailed mechanistic study confirmed the involvement of enolether as a reaction intermediate. Several postsynthetic modifications along with easy access to β-carboline, tryptamines, tryptophols, and spiro-indolenine proclaim the synthetic utility of this powerful building block. On the basis of this concept, functionalized carbazoles were constructed by a cascade annulation strategy.     

Mechanistic aspects of ligand substitution on <Emphasis Type="Italic">cis</Emphasis>-diaqua(<Emphasis Type="Italic">cis</Emphasis>-1,2-diaminocyclohexane)platinum(II) by Glycine-<Emphasis Type="SmallCaps">l</Emphasis>-Leucine

The kinetics of the interaction of glycine-l-leucine (Glyleu) with cis-[Pt(cis-dach)(OH₂)₂]²⁺ (dach = 1,2-diaminocyclohexane) has been studied spectrophotometrically as a function of [cis-[Pt(cis-dach)(OH₂)₂]²⁺], [Glyleu] and temperature at pH 4.0, where the complex exists predominantly as the diaqua species and Glyleu as a zwitterion. The substitution reaction shows two consecutive steps: the first is the ligand-assisted anation and the second is the chelation step. The activation parameters for both the steps were evaluated using Eyring’s equation. The low ∆H₁^≠ (51.9 ± 2.8 kJmol⁻¹) and large negative value of ∆S₁^≠ (−152 ± 8 JK⁻¹mol⁻¹) as well as ∆H₂^≠ (54.4 ± 1.7 kJmol⁻¹) and ∆S₂^≠ (−162 ± 5 JK⁻¹mol⁻¹) indicate an associative mode of activation for both the aqua ligand substitution processes.