Exploitation of Catalytic Dyads by Short Peptide-Based Nanotubes for Enantioselective Covalent Catalysis

Extant enzymes with precisely arranged multiple residues in their three-dimensional binding pockets are capable of exhibiting remarkable stereoselectivity towards a racemic mixture of substrates. However, how early protein folds that possibly featured short peptide fragments facilitated enantioselective catalytic transformations important for the emergence of homochirality still remains an intriguing open question. Herein, enantioselective hydrolysis was shown by short peptide-based nanotubes that could exploit multiple solvent-exposed residues to create chiral binding grooves to covalently interact and subsequently hydrolyse one enantiomer preferentially from a racemic pool. Single or double-site chiral mutations led to opposite but diminished and even complete loss of enantioselectivities, suggesting the critical roles of the binding enthalpies from the precise localization of the active site residues, despite the short sequence lengths. This work underpins the enantioselective catalytic prowess of short peptide-based folds and argues their possible role in the emergence of homochiral chemical inventory.     

Enantioselective Synthesis of (−)‐Halenaquinone

The efficient, 12–14 step (LLS) total synthesis of (?)‐halenaquinone has been achieved. Key steps in the synthetic sequence include: (a) proline sulfonamide‐catalyzed, Yamada–Otani reaction to establish the C6 all‐carbon quaternary stereocenter, (b) multiple, novel palladium‐mediated oxidative cyclizations to introduce the furan moiety, and (c) oxidative Bergman cyclization to form the final quinone ring.     

ICP-MS multielement determination in fly ash after microwave-assisted digestion of samples

A microwave assisted digestion procedure has been developed for dissolution of fly ash samples prior to the inductively coupled plasma-mass spectrometric determination of their elemental composition. The developed methodology was validated by carrying out the analysis of two high-silicate containing reference materials (CRM 134R sewage amended soil and NIES JR 1 rock) and by means of the comparison between results found by microwave-assisted digestion and ICP-MS of fly ash samples with those found by neutron activation analysis (NAA) for Sb, Cs, Cr, Co, Fe, U and Zn determination. The method developed can be recommended for routine multielement analysis of fly ash.     

Isomeric complexes of ruthenium(II) with neutral heterocyclic schiff base ligands. High resolution proton resonance spectra of trans-cis isomeric pairs of RuX2L2 (L = 2-arylpyridinecarboxaldimine, X = Cl, Br) and comparison of their physical properties

The reaction of 2-arylpyridinecarboxaldimine [RH₄C₆NC(H)Py, L (1)] with hydrated RuX₃ (X = Cl, Br) in boiling C₂H₅OH affords dark crystals of RuX₂L₂. Two geometrical isomers of the compound have been isolated and characterized by analytical and spectroscopic data. The trans isomer of RuCl₂L₂ shows a single sharp band for ν(Ru---Cl), whereas two bands are observed for the corresponding cis isomer. The highresolution ¹H NMR spectra of the isolated complexes are reported and completely assigned. All the complexes have multiple t₂→π^*(L) transitions in the visible region. Each of the complexes display a quasi-reversible oxidative response due to an Ru^III/Ru^II couple in the range 0.25–0.40 V vs S.C.E. at a platinum working electrode. The formal potentials of this couple obey the Hammett relationship. The ligand-based irreversible oxidations are also briefly noted.     

Invariants for normal completely positive maps on the hyperfinite II1 factor

We investigate certain classes of normal completely positive (CP) maps on the hyperfinite II₁ factorA. Using the representation theory of a suitable irrational rotation algebra, we propose some computable invariants for such CP maps. Dedicated to Professor K B Sinha     

On approximately monotone and approximately Hölder functions

Periodica Mathematica Hungarica - A real valued function f defined on a real open interval I is called $$\Phi $$ -monotone if, for all $$x,y\in I$$ with $$x\le y$$ it satisfies $$\begin{aligned}...     

Effects of chemical reaction and radiation on an unsteady MHD flow past an accelerated infinite vertical plate with variable temperature and mass transfer

This paper deals with the study of the effects of first order chemical reaction and radiation on an unsteady MHD flow of an incompressible viscous electrically conducting fluid past an accelerated infinite vertical plate with variable temperature and mass transfer. The resulting approximate dimensionless system of governing partial differential equations are integrated in closed form by the Laplace transform technique A uniform magnetic field is assumed to be applied transversely to the direction of the flow. Rosseland model of radiation has been chosen in the investigation, the expressions for the velocity field, temperature field and concentration field and skin-friction in the direction of the flow, coefficient of heat transfer and mass flux at the plate have been obtained in non-dimensional form and these are illustrated graphically for various physical parameters involved in the study. Investigation reveals that the fluid velocity is decelerated in the region adjacent to the plate, due to the effect of first order chemical reaction and the rate of heat transfer (from plate to the fluid) decreases due to the absorption of thermal radiation. The results obtained in this work are consistent with physical situation of the problem.     

Risk Minimizing Option Pricing for a Class of Exotic Options in a Markov-Modulated Market

We address risk minimizing option pricing in a regime switching market where the floating interest rate depends on a finite state Markov process. The growth rate and the volatility of the stock also depend on the Markov process. Using the minimal martingale measure, we show that the locally risk minimizing prices for certain exotic options satisfy a system of Black-Scholes partial differential equations with appropriate boundary conditions. We find the corresponding hedging strategies and the residual risk. We develop suitable numerical methods to compute option prices.     

Transverse dynamics of space charge dominated beam during bunching

In this paper we present a technique to optimize the transport parameters for transverse matching of the space charge dominated beams in the presence of bunching. The increase in the current within the specified bunch width during the transport is obtained from the disc model and is included in the optimization method. A 2D particle in cell (PIC) code is then developed to study the details transverse dynamics of the bunch taking into account the effect of longitudinal compression by reweighting the charge and mass of macroparticles. The evolution of rms beam size obtained using PIC simulation agrees well with the results obtained by solving beam envelope equation. The PIC simulation shows emittance growth during bunching induced by the space charge effect for nonuniform distribution. The growth in the emittance increases with the nonlinearity of distribution and peaks near the time focus.