Synthetic and physicochemical studies of uranium complexes with semicarbazone and hydrazone

Uranyl complexes of two Schiff bases, semicarbazone and hydrazone containing OON donor atoms have been synthesized and characterized on the basis of NMR, IR and electronic spectral studies, conductance, magnetic susceptibility and thermogravimetric data. The 1H NMR spectrum of the semicarbazone complex shows low field signals due to OH, NH and ---CH=N groups at 10.23, 9.31 and 8.17 ppm, respectively. The aromatic protons appear in the range 7.74–7.40 ppm. On complexation with U(VI) the signals due to OH and NH disappear evidently due to their participation in coordination. The coordination number of the o-vanillin semicarbazone (oVSC) complex is 6 whereas, that of the o-vanillin isonicotinic acid hydrazone (oVINAH) complex is 8, in addition to the two oxygen atoms already bonded to U(VI) in each species. The thermograms show the presence of 3 and 2 water molecules in these complexes, respectively and the IR spectral data also support the above conclusion. Suitable structures have been assigned.

Structural effects on the vaporization of high molecular weight esters

To understand the effect of molecular weight and branching on the heats of vaporization (AH,) and their flow behavior, AH, and viscosity (7) were measured at different temperatures in the high molecular weight ester series: linear flexible di-n-alkyl sebacates and compact branched triglycerides with molecular weight ranging from 300 to 900. AHv" values (AHv corrected to 298 K) have been obtained with experimental AH, and also computed according to the group additivity method; a smaller-CH,- group value of 3.8 kJ mol-' compared to the normal value of 5.0 kJ mol-' is found to give good agreement with the experimental data (within 2-5% error). Both ester series have the same AH," irrespective of their molecular features, namely,shape, flexibility, and polarity, suggesting the coiling of the molecules during vaporization. The segmental motion of these ester series during their flow and its dependence on their molecular features unlike AH,' are demonstrated by the correlation of the enthalpy of activation for viscous flow (AH*) and the ratio AE,/AH* = n (AE, is the energy of vaporization) with molecular weight.

Novel photocrosslinkable liquid-crystalline polymers: poly[bis(benzylidene)] esters

A new class of photo-cross-linkable main-chain liquid crystalline polymers (PMCLCPs) containing bis(benzylidene)cycloallranone groups have been synthesized and studied for their liquid crystalline and photochemical properties. The bis(benzylidene)cycloalkanone group in the chain functions both as a mesogen and as a photoreactive center. All of the polymers exhibit a nematic mesophase. Two kinds of photoreactions, namely, photoisomerization and photo-cross-linking, operate in these polymers. Above Tu at the initial stages of irradiation, photoisomerization predominates the cross-linking, which resulta in the disruption of the chromophore aggregates. Below T8, because of the restricted mobility of the chains, only cross-linking takes place. Studies on the model compound, bis(benzylidene)cyclopentanone, confii the above observations and demonstrate further that the cross-linking proceeds by the 2r + 2r cycloaddition reaction of the bis(benzylidene)cycloallranone moieties. The cross-linking rate decreases with increase in the size of the cycloalkanone ring. Heating the solution cast polymer fii results in the ordered aggregation of the chromophores just above TI and also at the crystal to crystal transition temperature, which facilitates the phobcross-linking reactions. In the isotropic phase, the random orientation of the chromophores drastically curtails the cross-linking rata

The Design and Construction of Synthetic Protein Mimics

A strategy for the modular construction of synthetic protein mimics based on the ability non-protein amino acids to act as stereochemical directors of polypeptide chain folding, is described. The use of alpha-aminoisobutyric acid (Aib) to construct stereochemically rigid helices has been exemplified by crystallographic and spectroscopic studies of several apolar peptides, ranging in length from seven to sixteen residues. The problem of linker design in elaborating alpha,alpha motifs has been considered. Analysis of protein crystal structure data provides a guide to choosing linking sequences. Attempts at constructing linked helical motifs using linking Gly-Pro segments have been described. The use of flexible linkers, like epsilon-aminocaproic acid has been examined and the crystallographic and solution state analysis of a linked helix motif has been presented. The use of bulky sidechain modifications on a helical scaffold, as a means of generating putative binding sites has been exemplified by a crystal structure of a peptide packed in a parallel zipper arrangement.

A study of the synthetic methods and properties of graphenes

Graphenes with varying number of layers can be synthesized by using different strategies. Thus, single-layer graphene is prepared by micromechanical cleavage, reduction of single-layer graphene oxide, chemical vapor deposition and other methods. Few-layer graphenes are synthesized by conversion of nanodiamond, arc discharge of graphite and other methods. In this article, we briefly overview the various synthetic methods and the surface, magnetic and electrical properties of the produced graphenes. Few-layer graphenes exhibit ferromagnetic features along with antiferromagnetic properties, independent of the method of preparation. Aside from the data on electrical conductivity of graphenes and graphene-polymer composites, we also present the field-effect transistor characteristics of graphenes. Only single-layer reduced graphene oxide exhibits ambipolar properties. The interaction of electron donor and acceptor molecules with few-layer graphene samples is examined in detail.

Bound states of two spin-1/2 fermions in a synthetic non-Abelian gauge field

We study the bound states of two spin-1/2 fermions interacting via a contact attraction (characterized by a scattering length) in the singlet channel in three-dimensional space in presence of a uniform non-Abelian gauge field. The configuration of the gauge field that generates a Rashba-type spin-orbit interaction is described by three coupling parameters (lambda(x),lambda(y),lambda(z)). For a generic gauge field configuration, the critical scattering length required for the formation of a bound state is negative, i.e., shifts to the ``BCS side'' of the resonance. Interestingly, we find that there are special high-symmetry configurations (e.g., lambda(x) = lambda(y) = lambda(z)) for which there is a two-body bound state for any scattering length however small and negative. Remarkably, the bound-state wave functions obtained for such configurations have nematic spin structure similar to those found in liquid He-3. Our results show that the BCS-BEC (Bose-Einstein condensation) crossover is drastically affected by the presence of a non-Abelian gauge field. We discuss possible experimental signatures of our findings both at high and low temperatures.

Diastereoselective reduction of α-keto esters derived from functionalised cholic acid

The reduction of phenylglyoxalate 2a and pyruvate 2b with LiBH4 in THF at -80 degrees C yield the corresponding alpha-hydroxy esters with ca. 70% diastereoselectivity.

Application of microwave heating technique for rapid synthesis of ?,?-unsaturated esters

The use of microwave heating technique for the acceleration of ortho ester Claisen rearrangement (a three step transformation) is described. Irradiation of a DMF solution of the allyl alcohol 5, triethyl orthoacetate and propionic acid (catalytic) in an Erlenmeyer flask for 10 minutes in a microwave oven generated the ester 8 in 83% yield. Analogously, ortho ester Claisen rearrangement of a variety of allyl and propargyl alcohols (9, 12-22) were achieved. The formation of the diester 10 from 2-butyne-1,4-diol (9) via the ortho ester Claisen rearrangement of two allyl alcohol moieties (involving sh steps) in 15 minutes, demonstrates the versatility of the microwave heating technique.

1,3-Dipolar cycloaddition reaction of ?,?-unsaturated esters and lactones with diazomethane

1,3-Dipolar cycloaddition of diazomethane to the alpha,beta-unsaturated esters and lactones such as 2-4, 6-8, 10 and 13 occurs in a stereoselective manner affording conjugated Delta(2)-pyrazolines. E and Z isomers of D-mannitol lead to identical product which was cyclised to investigate the absolute stereochemistry of the product. The regiospecificities of all the reactions are consistent with FMO coefficients obtained through AM1 calculations.

Novel reduction (Zn-AcOH) of DDHQ esters - A new route to tropone synthesis

Zn/acetic acid reaction of DDHQ esters 1 a-d gave the saturated acids 3 a-d and the hydrocarbons 7 a-d. The intermediacy of the aldehydes 10 and 11 in the formation of the products has been established. Oxidation of hydrocarbons 7a and 7b gave the corresponding tropones (5a and 5b).

Reduction of DDHQ and TCC esters by NaBH4-its specificity in the presence of Alkyl/Aryl esters

DDHQ/TCC esters 3a–f, 7a–g were prepared either by oxidation of spiroketones 1 with DDQ/Image -chloranil or by condensation of acid chloride with DDHQ/TCC. NaBH4 reduction of unsaturated DDHQ 3a–b and TCC 7a–c esters gave the corresponding allylic alcohols in good yield without any observable 1,4-addition products. Reduction of saturated esters 3e, 7d, gave the corresponding alcohols. Alkyl esters 5 and 6, methyl benzoate and phenyl benzoate remained unaffected under these reduction conditions. In the reduction of compound 7e containing both alkyl and TCC esters, TCC ester is selectively reduced. Reduction of TCC mono esters 7f–g gave the lactones. The observed facile reduction has been rationalised.

Synthetic approaches to homogynolides A and B

A four step, efficient and general methodology for the conversion of a cyclic ketone into the corresponding alpha-spiro-beta-methylene-gamma-butyrolactone, the key structural feature present in tricyclic sesquiterpenes bakkanes, has been developed employing a regiospecific 5-exo dig radical cyclisation reaction as the key step. The methodology has been extended to the total synthesis of bakkanes including homogynolide-B and chiral homogynolide-A.