The Statistical Mechanics of Semiflexible Equilibrium Polymers

We give an overview of studies of models for semiflexible, equilibrium polymers with special emphasis on our work on both lattice and continuum models for such systems. We show, principally by Monte Carlo simulations, that, once monomers self assemble to form polymers, their semiflexibility leads to nematic phases at low temperatures. Attractive wall potentials encourage the adsorption of these equilibrium polymers on surfaces. Rapid cooling leads to the formation of glasses with entangled polymers. Shear promotes nematic ordering, but, at high shear rates, this tendency decreases since the equilibrium polymers are torn apart. A version of our model in which the polymers are directed shows the polymer analog of bosonic Mott-insulating, mass-density-wave, and supersolid phases. We give a brief comparison of our work with other studies and also explore the experimental implications of our study.     

Reaction of β-amino-α,β-unsaturated esters and amides with aryl diazonium salts : Synthesis of cinnoline derivatives

Conjugated esters and amides react with aryldiazonium salts at room temperature (MeCN) to form the corresponding iminium hydrazone derivatives, which can be thermally cyclized to cinnoline-3-esters and cinnoline-3-amides. In general the intermediate iminium salts derived from the enamine amides cyclize faster than those from the enamine esters. Furthermore, the ease of cyclization depends upon the structure of the base-component of the enamine ester or the amide and the substituent in the aryl moiety of the diazonium salt. The configurational structure of the iminium hydrazones, studied by NMR spectroscopy, has been shown to involve H-bonding of the hydrazonyl N-H with the ester or the amide CO group.     

Unconventional nucleotide analogues. 3. 4-(N1-pyrimidyl)-2-aminobutyric acids

Alkylation of 4-ethoxy-2-hydroxypyrimidines (10a, b), via their anions, provides a convenient procedure for preparing N₁-substituted derivatives. Reaction of 10a, b with t-butyl 4-bromo-2-benzyloxycarbamidobutyrate (17) gives good yields of the N₁-alkylated products 18a, b. The latter have been converted to uracil- (20a), thymine- (20b) and cytosine- (21) substituted -aminobutyric acids.     

Functionalized enamines—XXII : Annelation of enamines of polycyclic α,β-unsaturated ketones; a facile partial synthesis of furano- indolo- and benzsteroids. Total synthesis of 3-oxa-A-norsteroid

Reaction of dienamine 4a with substituted phenacyl bromides gave steroidal[3,4-b] furans 5a–g. The same principle reaction was utilized for the total synthesis of (±) 2 - (p - chlorophenyl) - 3 - oxa - A - nor - estra - 1,5(10), 9(11) - triene - 17 - acetate 12a. Treatment of 4a, b with benzenediazonium salts, in DMF, followed by a Fischer-indole cyclization yielded steroidal[6, 7-b] indoles 8a–k. Dienamine 4b could be annelated to benz[4, 5, 6] steroids 9a and 9b by reaction with methyl vinyl ketone and crotonaldehyde, respectively.     

In situ electro-oxidation and liquid-liquid extraction of cerium(IV) from nitric acid medium using tributyl phosphate and 2-ethylhexyl hydrogen 2-ethylhexyl phosphonate

The process of in situ electro-oxidation of Ce(III) to Ce(IV) followed by its extraction into the organic phase has been investigated for its applicability in the separation of Ce from nitrate medium. Solvent extraction of cerium from nitric acid after its electro-oxidation to fourth valency state was carried out using tributyl phosphate (TBP) and 2-ethylhexyl hydrogen 2-ethylhexyl phosphonate (KSM-17, equivalent to PC-88A). The efficiency of the extractants at different aqueous phase nitric acid concentrations and different electrode potentials were determined. Various reducing agents such as hydroxylamine hydrochloride, sodium nitrite, ferrous sulphate as well as complexing agents like EDTA, oxalic acid etc, were studied as strippants for the back extraction of cerium from the loaded organic phase. The method developed for the extraction of cerium was further extended to the partitioning of cerium from Ce-Am mixture obtained during the KSM-17 based extraction chromatographic elemental fractionation of PUREX High Activity Waste (HAW) solutions. Recovery of Ce obtained in the extraction experiments by batch as well as by continuous flow organic phase was >95% with good radiochemical purity.     

Cavitation--a novel technique for making stable nano-suspensions

The purpose of the present study was to obtain nano-scale particles of styrene butadiene rubber. As SBR particles are elastic in nature, conventional methods of size reductions such as impacting, grinding are unable to achieve the final size. So, attempts have been made here to make the nano-particles of the SBR using cavitation technique. Both acoustic and hydrodynamic cavitation techniques have been employed and studied. Hydrodynamic cavitation has been proved to be more energy efficient than the acoustic cavitation on the basis of various parameters. The maximum production rate equivalent to 2 kg/h (solid processing) has been achieved in the newly developed hydrodynamic cavitation set-up (made in house). Similar to transient cavitation, stable cavitation has also been shown to contribute for reduction in the size of the material with very low variation in size. This technique has been proved successful for the size-reduction of the elastic material to nano-scale, thus it may also be used for the size-reduction of the other brittle and hard material by adjusting various cavitational parameters.     

Dynamic multiscaling in two-dimensional fluid turbulence

We obtain, by extensive direct numerical simulations, time-dependent and equal-time structure functions for the vorticity, in both quasi-Lagrangian and Eulerian frames, for the direct-cascade regime in two-dimensional fluid turbulence with air-drag-induced friction. We show that different ways of extracting time scales from these time-dependent structure functions lead to different dynamic-multiscaling exponents, which are related to equal-time multiscaling exponents by different classes of bridge relations; for a representative value of the friction we verify that, given our error bars, these bridge relations hold.     

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.     

Synthesis of titanium dioxide by ultrasound assisted sol–gel technique: Effect of amplitude (power density) variation

Titanium dioxide was successfully synthesized by utilizing sol–gel technique modified by incorporation of ultrasound as a reaction aid. The effect of amplitude of irradiation (power input varied from 19.9 to 80.8 W) on % Rutile, % yield, % crystallinity, crystallite size and morphological (scanning electron microscopy) properties of the obtained nano-TiO₂ was studied. Calcination temperatures of all the samples were kept constant at 750 °C. With increasing ultrasonic irradiation amplitude it is observed that the values of % Rutile (after calcination) increased and reached a peak value after which further increase in amplitude resulted in a decrease in the % Rutile. A similar trend was observed in the case of % crystallinity and % yield of the reaction. On the basis of these results an optimum operating ultrasonic irradiation amplitude for the reaction has been suitably established.