The principle of microscopic reversibility in organic chemistry - a critique

The principle of microscopic reversibility is one of the few generalising principles used in organic chemistry which have their roots in the fundamental laws of thermodynamics. It has, therefore, been highly popular. However, although the principle has some important uses, its general application is not without pitfalls. The principle is easy to misunderstand and to misapply: indeed, some of its formulations are semantically dubious. The principle is most dangerous when used as a charm, for it is more subtle than some of its formulations suggest. But above all, the principle may not be used for deducing or disproving the mechanism of a reaction, except when the mechanism in the reverse direction is known independently. For, such use is, perhaps, the deadliest misapplication.

Phonons and fractons in sol-gel alumina: Raman study

We report Raman scattering from the boehmite, gamma-, delta- and alpha-phases of the alumina gel. Samples are characterized by transmission and scanning electron microscopy, X-ray diffraction and density measurements. The main Raman line in the boehmite phase is red-shifted as well as asymmetrically broadened with respect to that in the crystalline boehmite, signifying the nanocrystalline nature of the gel. Raman signatures are absent in the gamma- and delta-phases due to the disorder in cation vacancies. We also show that low frequency Raman scattering from the boehmite phase resembles that from a fractal network, characterized in terms of fraction dimension ($) over tilde d. Taking Hausdorff dimension D of the boehmite gel to be 2.5 (or 3.0), the value of ($) over tilde d is 1.33 +/- 0.02 (or 1.44 +/- 0.02), which is close to the theoretically predicted value of 4/3.

Role of surface tension driven convection in pulsed - laser melting and solidification

Surface melting by a stationary, pulsed laser has been modelled by the finite element method. The role of the surface tension driven convection is investigated in detail. Numerical results are presented for a triangular laser pulse of durations 10, 50 and 200 ms. Though the magnitude of the velocity is high due to the surface tension forces, the present results indicate that a finite time is required for convection to affect the temperature distribution within the melt pool. The effect of convection is very significant for pulse durations longer than 10 ms.

Mott insulator high T-c bipolaronic superconductor transition in cuprates - Discussion

All ‘undoped’ cuprates are antiferromagnetic Mott insulators. We argue that with doping they remain to be insulators including the ‘overdoped’ samples. Hence, there is no clear dividing line between non–metallic cuprates and high–temperature superconductors. Based on the generic Hamiltonian including the electron–phonon interaction and the direct Coulomb repulsion the ground state of doped cuprates is shown to be a charged 2e Bose liquid of small bipolarons. A theory of the normal state transport of copper oxides is developed. The temperature dependence of the resistivity and of the Hall effect agrees remarkably well with the experimental data in La2–xSrxCuO4 for the entire temperature regime including unusual ‘logarithmic’ low–temperature region. The violation of Kohler's rule in magnetoresistivity is explained. The resistive and thermodynamic superconducting transitions in a magnetic field are quantitatively described.

Oxidation of aqueous sulphur dioxide catalysed by poly-4-vinylpyridine-Cu(II) complex .2. Combined homogeneous and heterogeneous phase oxidation

Aqueous phase oxidation of sulphur dioxide at low concentrations catalysed by a PVP-Cu complex in the solid phase and dissolved Cu(II) in the liquid phase is studied in a rotating catalyst basket reactor (RCBR). The equilibrium adsorption of Cu(II) and S(VI) on PVP particles is found to be of the Langmuir-type. The diffusional effects of S(IV) species in PVP-Cu resin are found to be insignificant whereas that of product S(VI) are found to be significant. The intraparticle diffusivity of S(VI) is obtained from independent tracer experiments. In the oxidation reaction HSO3- is the reactive species. Both the S(IV) species in the solution, namely SO2(aq) and HSO3- get adsorbed onto the active PVP-Cu sites of the catalyst, but only HSO3- undergoes oxidation. A kinetic mechanism is proposed based on this feature which shows that SO2(aq) has a deactivating effect on the catalyst. A rate model is developed for the three-phase reaction system incorporating these factors along with the effect of concentration of H2SO4 on the solubility of SO2 in the dilute aqueous solutions of Cu(II). Transient oxidation experiments are conducted at different conditions of concentration of SO2 and O-2 in the gas phase and catalyst concentration, and the rate parameters are estimated from the data. The observed and calculated profiles are in very good agreement. This confirms the deactivating effect of nonreactive SO2(aq) on the heterogeneous catalysis.

Synthesis of two designed hairpin peptides on a newly developed 1,6-hexanediol diacrylate (HDODA)-crosslinked polystyrene resin

Synthesis of two designed hairpin peptides on 1,6-hexanediol diacrylate crosslinked polystyrene support using the standard solid phase methodology is described. Both the peptides are obtained in high yield and purity. The new polymeric system is an ideal support for the synthesis of hairpin peptides, which is a very difficult task by the solid phase method.

Constraints on the solar internal magnetic field from a buoyancy driven solar dynamo

We report here results from a dynamo model developed on the lines of the Babcock-Leighton idea that the poloidal field is generated at the surface of the Sun from the decay of active regions. In this model magnetic buoyancy is handled with a realistic recipe - wherein toroidal flux is made to erupt from the overshoot layer wherever it exceeds a specified critical field B-C (10(5) G). The erupted toroidal field is then acted upon by the alpha-effect near the surface to give rise to the poloidal field. In this paper we study the effect of buoyancy on the dynamo generated magnetic fields. Specifically, we show that the mechanism of buoyant eruption and the subsequent depletion of the toroidal field inside the overshoot layer, is capable of constraining the magnitude and distribution of the magnetic field there. We also believe that a critical study of this mechanism may give us new information regarding the solar interior and end with an example, where we propose a method for estimating an upper limit of the difusivity within the overshoot layer.

Risk-sensitive optimal control for Markov decision processes with monotone cost

The existence of an optimal feedback law is established for the risk-sensitive optimal control problem with denumerable state space. The main assumptions imposed are irreducibility and a near monotonicity condition on the one-step cost function. A solution can be found constructively using either value iteration or policy iteration under suitable conditions on initial feedback law.

A Passive Hopper With Lossless Collisions

A passive vertical hopping robot is here highly idealised as two vertically arranged masses acted on by gravity and coupled by a linear spring. The lower mass makes dead (e = 0) collisions with the rigid ground. The equations of motion can be reduced to a one dimensional map. Fixed points of the map are found in which case the robot hops incessantly. For these conservative solutions the lower mass collides with the ground with zero impact velocity. The interval of attraction for these conservative fixed points depends on system parameters.

Interfaces In Quasicrystalline Systems

Structural relations between quasicrystalline and related crystalline rational approximant phases have been of interest for some time now. Such relations are now being used to understand interface structures. Interfaces between structural motif - wise related, but dissimilarly periodic phases are expected to show a degree of lattice match in certain directions. Our earlier studies in the Al-Cu-Fe system using the HREM technique has shown this to be true. The structural difference leads to well defined structural ledges in the interface between the icosahedral Al-Cu-Fe phase and the monoclinic Al13Fe4 type phase. In the present paper we report our results on the HREM study of interfaces in Al-Cu-Fe and Al-Pd-Mn systems. The emphasis will be on heterophase interfaces between quasiperiodic and periodic phases, where the two are structurally related. An attempt will be made to correlate the results with calculated lattice projections of the two structures on the grain boundary plane.

Modeling the solubilities of fatty acids in supercritical carbon dioxide

A thermodynamic model was developed for modeling the solubilities of fatty acids in supercritical carbon dioxide. The model combines the Peng-Robinson equation of state (EOS) with the two parameter van der Waal's mixing rules. The model is applied to predict the solubilities of various fatty acids. The two adjustable interaction parameters in the model are found to vary linearly with the chain length of the fatty acids. Thus this model can be used to predict the solubilities of various fatty acids in supercritical carbon dioxide. (C) 2003 Elsevier Science B.V. All rights reserved.

Electrochemical determination of the Gibbs energy of formation of MgAl2O4

The standard Gibbs energy of formation of the spinel MgAl2O4 from component oxides, MgO and α-Al2O3, has been determined in the temperature range 900 to 1250 K using a solid-state cell incorporating single-crystal CaF2 as the solid electrolyte. The cell can be represented as—Pt,O2,MgO+MgF2|CaF2|MgF2+MgAl2O4+α-Al2O3,O2,Pt—The standard Gibbs energy of formation from binary oxides, computed from the reversible emf, can be represented by the expression—capdeltaG°f,ox=−23600 − 5.91T(±150) J/mol—The ‘second-law’ enthalpy of formation of MgAl2O4 obtained in this study is in good agreement with high-temperature solution calorimetric studies reported in the literature.

RAD51 as a potential biomarker and therapeutic target for pancreatic cancer

Chemotherapy is a very important therapeutic strategy for cancer treatment. The failure of conventional and molecularly targeted chemotherapeutic regimes for the treatment of pancreatic cancer highlights a desperate need for novel therapeutic interventions. Chemotherapy often fails to eliminate all tumor cells because of intrinsic or acquired drug resistance, which is the most common cause of tumor recurrence. Overexpression of RAD51 protein, a key player in DNA repair/recombination has been observed in many cancer cells and its hyperexpression is implicated in drug resistance. Recent studies suggest that RAD51 overexpression contributes to the development, progression and drug resistance of pancreatic cancer cells. Here we provide a brief overview of the available pieces of evidence in support of the role of RAD51 in pancreatic tumorigenesis and drug resistance, and hypothesize that RAD51 could serve as a potential biomarker for diagnosis of pancreatic cancer. We discuss the possible involvement of RAD51 in the drug resistance associated with epithelial to mesenchymal transition and with cancer stem cells. Finally, we speculate that targeting RAD51 in pancreatic cancer cells may be a novel approach for the treatment of pancreatic cancer. (C) 2011 Elsevier B.V. All rights reserved.

Laser‐Induced Turbulence

In a recent experiment on laser beam transmission through an absorbing gas, the critical Reynold's number for the flow, induced by the heating of the gas, to become turbulent was found to be less than 30, which is many orders of magnitude smaller than that for pure shear flow in pipes. It is shown here that a Rayleigh number is the more appropriate criterion to characterize the stability of flow in this situation, and its value estimated in two limiting cases is found to bracket the expected critical Rayleigh number for vertical concentric cylinders.