Metal-based anticancer agents: targeting androgen-dependent and androgen-independent prostate and COX-positive pancreatic cancer cells by phenanthrenequinone semicarbazone and its metal complexes

A planar, polycyclic and aromatic hydrocarbon ligand, namely 9,10-phenanthrenequinone semicarbazone, and its transition metal complexes have been synthesized and structurally characterized. The in vitro antiproliferative activity of these compounds against five human cancer cell lines revealed that they were effective against androgen receptor-positive/negative prostate cancer cells as well as COX-positive pancreatic BxPC-3 cancer cell line. The driving force behind such antiproliferative activity seems to be the up-regulated COX expression in these cells, which was amenable for targeting through metal complexation. These structural motifs can, therefore, serve as a starting point for developing novel cytotoxic agents against the growing number of prostate and pancreatic cancers.     

Characterisation of Polyurethane Coatings Using Thermoanalytical Techniques

A two-pack polyurethane coating was analyzed using thermoanalytical techniques. The curing reaction, monitored using pressure differential calorimetry (PDSC), rheometry and dynamic mechanical analysis (DMA) shows the temperature dependency of activation energy and hence rate of curing. In-situ ATR-FTIR shows the formation of urethane linkage over time. The decomposition behavior carried out under non-isothermal mode using thermogravimetric analysis (TGA) shows bimodal behavior. The activation energies of the initial step (10% decomposition) from both iso and non-isothermal experiments are in very good agreement with each other. The use of dynamic mechanical analysis (DMA) shows the difference in glass transition behavior (T_g) and elastic modulus (E') due to the different state of cure. Also the coating exhibits a very broad loss modulus peak (E') indicating higher energy dissipation with deformation.This revised version was published online in November 2005 with corrections to the Cover Date.     

Switch in Catalyst State: Single Bifunctional Bi-state Catalyst for Two Different Reactions

Disclosed here is a molecular switch which responds to acid-base stimuli and serves as a bi-state catalyst for two different reactions. The two states of the switch serve as a highly active and poorly active catalyst for two catalytic reactions (namely a hydrogenation and a dehydrogenative coupling) but in a complementary manner. The system was used in an assisted tandem catalysis set-up involving dehydrogenative coupling of an amine and then hydrogenation of the resulting imine product by switching between the respective states of the catalyst.     

Hydro­gen‐bonded adducts of ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol): monomeric and dimeric 1:1 adducts with 1,2‐bis(4‐pyridyl)­ethane and 1,2‐­diamino­ethane

In ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol)–4,4′‐ethyl­enedi­pyridine (1/1), [Fe(C₁₈H₁₅O)₂]·C₁₂H₁₂N₂, there is an intra­molecular O—H?O hydrogen bond in the ferrocenediol component and a single O—H?N hydrogen bond linking the two components into a finite monomeric adduct. Ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol)–ethyl­enedi­amine (1/1), [Fe(C₁₈H₁₅O)₂]·C₂H₈N₂, crystallizes with Z′ = 2 in space group P, and there are two independent four‐component aggregates in the structure, both of which are centrosymmetric. In the first type of aggregate, the molecular components are linked by O—H?N and N—H?O hydrogen bonds, in which both di­amine N atoms participate; in the second type of aggregate, the di­amine component is disordered over two sets of sites, but only one N atom is involved in the hydrogen bonding.     

Supramolecular self-assembly of water-soluble cavitands: investigated by molecular dynamics simulation

In this study, we have examined supramolecular self-assembly process of a hydrophobic guest with a water-soluble host known by the trivial name octa acid (OA). Two octa acids form a capsular assembly only in presence of a nonpolar guest(s). Size and shape of the guest control the stoichiometry of the capsular complex. Here, all atom molecular dynamics simulation has been utilized to investigate complex formation mechanisms of a nonpolar guest (nonylbenzene) with two OA cavitands. Nonylbenzene was encapsulated into the nonpolar cavity of OA capsule owing to solvophobic interactions. Upon encapsulation it was twisted and bent due to lack of free space within the capsule. These unusual forms obtained from the simulation study were in accord with experimental findings. The post-complexation attributes of the guest were regulated by the available free space within the OA and favorable non-covalent interactions between the guest and the walls of the OA capsule. In the identical simulation condition two OA cavitands did not form a capsule without a guest, thus indicating requirement of a guest during the self-assembly of OA cavitands.     

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.     

Solitary wave families of a generalized microstructure PDE

Wave propagation in a generalized microstructure PDE, under the Mindlin relations, is considered. Limited analytic results exist for the occurrence of one family of solitary wave solutions of these equations. Since solitary wave solutions often play a central role in the long-time evolution of an initial disturbance, we consider such solutions here (via normal form approach) within the framework of reversible systems theory. Besides confirming the existence of the known family of solitary waves, we find a continuum of delocalized solitary waves (or homoclinics to small-amplitude periodic orbits). On isolated curves in the relevant parameter region, the delocalized waves reduce to genuine embedded solitons. The new family of solutions occur in regions of parameter space distinct from the known solitary wave solutions and are thus entirely new. Directions for future work are also mentioned.     

On the Jacobi Last Multiplier, integrating factors and the Lagrangian formulation of differential equations of the Painlevé–Gambier classification

We use a formula derived almost seventy years ago by Madhav Rao connecting the Jacobi Last Multiplier of a second-order ordinary differential equation and its Lagrangian and determine the Lagrangians of the Painlevé equations. Indeed this method yields the Lagrangians of many of the equations of the Painlevé–Gambier classification. Using the standard Legendre transformation we deduce the corresponding Hamiltonian functions. While such Hamiltonians are generally of non-standard form, they are found to be constants of motion. On the other hand for second-order equations of the Liénard class we employ a novel transformation to deduce their corresponding Lagrangians. We illustrate some particular cases and determine the conserved quantity (first integral) resulting from the associated Noetherian symmetry. Finally we consider a few systems of second-order ordinary differential equations and deduce their Lagrangians by exploiting again the relation between the Jacobi Last Multiplier and the Lagrangian.     

Exponential type vector variational-like inequalities and vector optimization problems with exponential type invexities

A new class of exponential form of vector variational-like inequality problems is introduced, and then the equivalence among (weakly) efficient solutions, vector critical points of vector optimization problem and the solutions of vector variational-like inequalities under the framework of (p,r)-invexity is established. To the best our knowledge, the presented results are new and highly application oriented to other results based on generalized invexities to the context of optimization problems in the literature.     

Slope and curvature of Isgur-Wise function using variationally improved perturbation theory in a quantum chromodynamics inspired potential model

We used variationally improved perturbation theory (VIPT) in calculating the slope and curvature of Isgur-Wise (I-W) function with the Cornell potential −$ \frac{{4\alpha _s }} {{3r}} $ \frac{{4\alpha _s }} {{3r}} +br + c instead of the usual stationary state perturbation theory as done earlier. We used −(4α _s /3r), i.e. the Coulombic potential, as the parent and the linear one, i.e. br+c as the perturbed potential in the theory and calculated the slope and curvature of Isgur-Wise function including three states in the summation involved in the first-order correction to wave function in the method.