Redox- and protonation-state driven substrate-protein dynamics in respiratory complex I

Respiratory complex I is a key enzyme in the electron transport chains of mitochondria and bacteria. It transfers two electrons to quinone and couples this redox reaction to proton pumping to electrically charge the membrane it is embedded in. The charge and pH gradient across the membrane drives the synthesis of ATP. The redox reaction and proton pumping in complex I are separated in space and time, which raises the question of how the two reactions are coupled so efficiently. Here, we focus on the unique ～35 Å long tunnel of complex I, which houses the binding site of quinone reduction. We discuss the redox and protonation reactions that occur in this tunnel and how they influence the dynamics of protein and substrate. On the basis of recent structural data and results from molecular simulations, we review how quinone reduction and dynamics may be coupled to proton pumping in complex I.     

Domino reactions in water for the stereoselective synthesis of novel spiro dihydro-2′H-[indene-2,3′-thiophen]-1(3H)-ones with three contiguous stereocenters

The domino reactions of (E)-2-(aryl)-2,3-dihydro-1H-inden-1-ones and 1,4-dithiane-2,5-diol in the presence of triethylamine in water stereoselectively afforded a library of 2′-(aryl)-4′-hydroxy-4′,5′-dihydro-2′H-spiro[indene-2,3′-thiophen]-1(3H)-ones. This transformation presumably proceeds via the generation of 2-mercaptoacetaldehyde from 1,4-dithiane-2,5-diol followed by Michael addition–intramolecular aldol sequence with C–C and C–S bond formations and creation of three contiguous stereocenters in a one-pot operation.     

A simple extrusion method for the synthesis of aligned silica nanowires using the template of a rigid surfactant mesophase

Long range alignment of silica nanowires has been accomplished by extrusion of a novel surfactant mesophase prior to silica synthesis.     

Vinylimidazole‐based asymmetric ion pair comonomers: Synthesis,polymerization studies and formation of ionically crosslinked PMMA

Vinylimidazole‐based asymmetric ion pair comonomers ( IPC s) which are free from nonpolymerizable counter ions have been synthesized, characterized and polymerized by free radical polymerization (FRP), atom transfer radical polymerization (ATRP), and reversible addition‐fragmentation chain transfer (RAFT) mediated polymerizations in solution and by dispersion polymerization in water. The asymmetric nature of IPC s is due to the fact that cationic component of these IPCs is derived from vinylimidazole (VIm) and anionic component is derived from either styrenesulfonate (SS) or 2‐acrylamido‐2‐methyl‐1‐propanesulfonate. Although under ATRP, conversions are either very low or negligible, FRP and RAFT produces polymers with high to moderate monomer conversions but with different solubility characteristics. This investigation provides insight to the polymerization behavior of each component of the asymmetric IPCs and also its effects on composition and solubility characteristics of the resulting polymers. The IPCs studied here are high temperature ionic liquid and thus the polymers synthesized from these IPCs are highly ionic in nature and possess very strong intermolecular interactions which makes some of these IPC based polymers completely insoluble in organic and aqueous solvents. This highly ionic interaction is exploited to synthesize ionically crosslinked PMMA. MMA on copolymerization with 5–6 mol % of IPC yielded copolymer which is insoluble in common organic solvents like THF, DMF, etc., unlike homo PMMA. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3260–3273     

Averaging of Singularly Perturbed Controlled Stochastic Differential Equations

An averaged system to approximate the slow dynamics of a two timescale nonlinear stochastic control system is introduced. Validity of the approximation is established. Special cases are considered to illustrate the general theory.     

Duality in disjunctive linear fractional programming

In this note a dual problem is formulated for a given class of disjunctive linear fractional programming problems. This result generalizes to fractional programming the duality theorem of disjunctive linear programming originated by Balas. Two examples are given to illustrate the result.     

A one-pot access to pyridine/benzo fused cyclododecanes via multi-component tandem reactions

A facile syntheses of novel poly-substituted pyridine/benzo fused cyclododecane hybrid heterocycles have been achieved through one-pot multi-component tandem strategy employing cyclododecanone, aromatic aldehydes and malononitrile.     

Broadening the Scope for Fluoride‐Free Synthesis of Siliceous Zeolites

Siliceous zeolites are ideally suited for emerging applications in gas separations, sensors, and the next generation of low‐k dielectric materials, but the use of fluoride in the synthesis significantly hinders their commercialization. Herein, we show that the dry gel conversion (DGC) technique can overcome this problem. Fluoride‐free synthesis of two siliceous zeolites—AMH‐4 (CHA‐type) and AMH‐5 (STT‐type), has been achieved for the first time using the method. Siliceous *BEA‐, MFI‐, and *MRE‐type zeolites have also been synthesized to obtain insights into the crystallization process. Charge‐balancing interactions between the inorganic cation, organic structure‐directing agent (OSDA), and Si?O^? defects are found to be an essential aspect. We quantify this factor in terms of the “OSDA charge/silica ratio” of the as‐made zeolites and demonstrate that the DGC technique is broadly applicable and opens up new avenues for fluoride‐free siliceous zeolite synthesis.     

Kinetic investigations on interaction of carbon monoxide with RuIICl2(PPh3)3 in mixed aqueous medium

Kinetics, equilibrium and thermodynamics of interaction of CO with RuCl₂(PPh₃)₃ (1) have been investigated in 1:1(v/v) water — 1,4-dioxan mixture in which 1 dissociates to RuCl₂(PPh₃)₂ (1a), by losing a coordinated PPh₃. The kinetics of complexation of (1a) with CO to form RuCl₂(CO)(PPh₃)₂ (2) indicated first order dependence in [1a] and [CO]. The thermodynamic parameters for the formation of 2 were determined.This revised version was published online in December 2005 with corrections to the Cover Date.