Synthesis,characterization, and properties of new sequenced poly(ether amide)s based on 2‐(4‐aminophenyl)‐5‐aminobenzimidazole and 2‐(3‐aminophenyl)‐5‐aminobenzimidazole

A set of new aromatic poly(ether amide)s containing benzimidazole groups and ethylene oxide sequences of different lengths were synthesized and characterized. The new polymers were prepared from two benzimidazole diamines, 2‐(4‐aminophenyl)‐5‐aminobenzimidazole and 2‐(3‐aminophenyl)‐5‐aminobenzimidazole, and various oligo(ethylene oxide)dibenzoyl chlorides. They exhibited good solubility in polar aprotic solvents and glass‐transition temperatures in the range of 125–300 °C (the longer the ethylene oxide spacer was, the lower the glass‐transition temperature was). The new polyamides were essentially amorphous, as observed by X‐ray diffraction measurements and confirmed by differential scanning calorimetry measurements, by means of which no melting endotherm was observed in any case. The decomposition temperatures, as revealed by thermogravimetric analysis in nitrogen, were about 400 °C for all of them, regardless of the length of the ethylene oxide content or the phenylene ring orientation (meta or para) of the diamine moiety. The number of ethylene oxide linkages per repeat unit also determined the water uptake. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1414–1423, 2006     

Effects of novel taxanes SB-T-1213 and IDN5109 on tubulin polymerization and mitosis

SB-T-1213 and IDN5109 are semisynthetic, orally available taxanes that are up to 400-fold more active than paclitaxel against drug-resistant cells. IDN5109 is in clinical trials. We investigated the primary target for SB-T-1213 and IDN5109 and whether the compounds interact with microtubules differently than paclitaxel. Unlike paclitaxel, at 1-10 microM both novel taxanes initiate microtubule polymerization in vitro with no lag. They enhance polymerization equally or more potently than paclitaxel. SB-T-1213 induces unusual microtubules with attached extra protofilaments or open sheets, and IDN5109 induces large protofilamentous sheets. Both inhibit HeLa cell proliferation, block mitosis at the metaphase/anaphase transition, bundle microtubules at high drug concentrations, and induce abnormal metaphase spindles and apoptosis. They target microtubules but alter their polymerization and structure differently than paclitaxel. These differences may play a role in their enhanced cytotoxicity and efficacy.     

New 1,2-disubstituted ferrocenyl stibines containing N-heterocyclic pendant arm: Sb-N hypervalent compounds

New 1,2-disubstituted ferrocenyl stibines viz. containing -CH₂NR or -CH₂NHR pendant arm at the ortho-position have been synthesized and characterized by various physicochemical methods. These new ferrocenylstibines were prepared by the nucleophilic substitution reaction of diphenyl[(N,N,N-trimethylaminomethylferrocenyl)iodide]stibine by different primary amines and secondary heterocyclic amines viz. furan-2-ylmethylamine, p-aminoacetophenone, 3-(1-hydroxyethyl)-aniline, 4-hydroxypiperidine, 1-ethylpiperazine and 4-(4-bromophenyl)-4-hydroxypiperidine. Molecular structure of stibine (2), (3), (5) and (7) have been determined by X-ray crystallography. Stibine (2), (5) and (7) show a weak hypervalent Sb-N interaction while stibine (3) does not show this interaction in solid state.     

Using ACCPM in a simplicial decomposition algorithm for the traffic assignment problem

The purpose of the traffic assignment problem is to obtain a traffic flow pattern given a set of origin-destination travel demands and flow dependent link performance functions of a road network. In the general case, the traffic assignment problem can be formulated as a variational inequality, and several algorithms have been devised for its efficient solution. In this work we propose a new approach that combines two existing procedures: the master problem of a simplicial decomposition algorithm is solved through the analytic center cutting plane method. Four variants are considered for solving the master problem. The third and fourth ones, which heuristically compute an appropriate initial point, provided the best results. The computational experience reported in the solution of real large-scale diagonal and difficult asymmetric problems—including a subset of the transportation networks of Madrid and Barcelona—show the effectiveness of the approach.     

Primal—dual methods for linear programming

Many interior-point methods for linear programming are based on the properties of the logarithmic barrier function. After a preliminary discussion of the convergence of the (primal) projected Newton barrier method, three types of barrier method are analyzed. These methods may be categorized as primal, dual and primal—dual, and may be derived from the application of Newton's method to different variants of the same system of nonlinear equations. A fourth variant of the same equations leads to a new primal—dual method.In each of the methods discussed, convergence is demonstrated without the need for a nondegeneracy assumption or a transformation that makes the provision of a feasible point trivial. In particular, convergence is established for a primal—dual algorithm that allows a different step in the primal and dual variables and does not require primal and dual feasibility.Finally, a new method for treating free variables is proposed.Presented at the Second Asilomar Workshop on Progress in Mathematical Programming, February 1990, Asilomar, CA, United StatesThe material contained in this paper is based upon research supported by the National Science Foundation Grant DDM-9204208 and the Office of Naval Research Grant N00014-90-J-1242.     

Deconjugation of dehydroamino acids: stereoselective synthesis of racemic (E)-vinylglycines

[reaction: see text] A practical and general two-step synthesis of carbamate-protected (E)-vinylglycines from aliphatic aldehydes is reported. The key step involves the kinetic alpha-protonation of dianionic dienolates derived from dehydroamino acids.     

Evolution of protein synthesis in a lattice model of replicators

The traditional chemical-kinetics approach to the study of prebiotic evolution cannot explain the evolution of protein synthesis in a homogeneous population of self-replicating molecules, because the invasion of a resident population of simpler, template-directed replicators by mutant protein-assisted replicators is deemed impossible. Approaching this problem in a spatial cellular automaton framework, we argue here that in such a setting evolution of protein synthesis is a likely event. In addition, we show that the onset of invasion may be viewed as a nonequilibrium phase transition, that can be characterized quantitatively by a set of critical exponents.     

Photoluminescence properties of BaMoO4 amorphous thin films

BaMoO₄ amorphous and crystalline thin films were prepared from polymeric precursors. The BaMoO₄ was deposited onto Si wafers by means of the spinning technique. The structure and optical properties of the resulting films were characterized by FTIR reflectance spectra, X-ray diffraction (XRD), atomic force microscopy (AFM) and optical reflectance. The bond Mo-O present in BaMoO₄ was confirmed by FTIR reflectance spectra. XRD characterization showed that thin films heat-treated at 600 and 200 °C presented the scheelite-type crystalline phase and amorphous, respectively. AFM analyses showed a considerable variation in surface morphology by comparing samples heat-treated at 200 and 600 °C. The reflectivity spectra showed two bands, positioned at 3.38 and 4.37 eV that were attributed to the excitonic state of Ba²⁺ and electronic transitions within MoO²⁻₄, respectively. The optical band gaps of BaMoO₄ were 3.38 and 2.19 eV, for crystalline (600 °C/2 h) and amorphous (200 °C/8 h) films, respectively. The room-temperature luminescence spectra revealed an intense single-emission band in the visible region. The PL intensity of these materials was increased upon heat-treatment. The excellent optical properties observed for BaMoO₄ amorphous thin films suggested that this material is a highly promising candidate for photoluminescent applications.