Strain induced strengthening of soft thermoplastic polyurethanes under cyclic deformation

We investigate the cyclic mechanical behavior in uniaxial tension of three different commercial thermoplastic polyurethane elastomers (TPU) often considered as a sustainable replacement for common filled elastomers. All TPU have similar hard segment contents and linear moduli but sensibly different large strain properties as shown by X-ray analysis. Despite these differences, we found a stiffening effect after conditioning in step cyclic loading which greatly differs from the common softening (also referred as Mullins effect) observed in chemically crosslinked filled rubbers. We propose that this self-reinforcement is related to the fragmentation of hard domains, naturally present in TPU, in smaller but more numerous sub-units that may act as new physical crosslinking points. The proposed stiffening mechanism is not dissimilar to the strain-induced crystallization observed in stretched natural rubber, but it presents a persistent nature. In particular, it may cause a local reinforcement where an inhomogeneous strain field is present, as is the case of a crack propagating in cyclic fatigue, providing a potential explanation for the well-known toughness and wear resistance of TPU.     

Graphical operations on projective spaces

Motivated by the work of Crapo and Rota [6] on the lifting of a projective complex, we introduce a class of invariant operations associated to integral-weighted graphs, which we call graphical operations. Such operations generalize the sixth harmonic of a quadranguler set on a projective line. We determine the expansion of the graphical operations in terms of multi-linear bracket polynomials in a Grassmann-Cayley algebra. Reducibility and compositions of such invariant operations are also investigated with a number of examples.Supported by Courant Instructorship, New York University.     

An alternative for moduli stabilisation

The one-loop vacuum energy is explicitly computed for a class of perturbative string vacua where supersymmetry is spontaneously broken by a T-duality invariant asymmetric Scherk–Schwarz deformation. The low-lying spectrum is tachyon-free for any value of the compactification radii and thus no Hagedorn-like phase-transition takes place. Indeed, the induced effective potential is free of divergence, and has a global anti-de Sitter minimum where geometric moduli are naturally stabilised.     

Thermal reactions of tributyltin hydride with alpha-azido esters: unexpected intervention of tin triazene adducts under both nonradical and radical conditions

Thermal reaction of various alpha-azido esters with Bu(3)SnH in refluxing benzene results in smooth production of 3-(tributylstannyl)-1-triazene adducts affording cyclized 1,2,3-triazol-4-ones in preference to reduced amines and thence provides a new useful method for the preparation of these triazole derivatives. In the presence of AIBN the occurrence of triazene products still remains important or even exclusive and, consequently, generation of the expected stannylaminyl radicals is seriously limited. With 2-azidomalonates and alpha-azido-beta-keto esters stannyltriazenes can similarly occur in the absence of the radical initiator, but in the latter cases the ensuing triazenes undergo preferential cyclization onto the ketone moiety to give reactive hydroxytriazolines. Contrary to alpha-azido esters, in the presence of AIBN alpha-azido-beta-keto esters as well as azidomalonates give rise only to the usual stannylaminyl radicals. A possible explanation for the different behavior of the mono- and dicarbonyl azides in the presence of AIBN is put forward.     

Models of pesticides inside cavities of molecular dimensions. A role of the guest inclusion in the dechlorination process

The reduction mechanism of the pesticide vinclozoline (3-(3,5-dichlorophenyl)-5-methyl-5-vinyl-1,3-oxazolidine-2,4-dione) was studied in nonaqueous solvents in the confined environment of a cyclodextrin (CD) cavity. The effect of the cavity dimensions on the mechanism of the redox process was evaluated using glucose as a reference and using three cyclodextrin molecules of different cavity sizes, namely, alphaCD, betaCD, and gammaCD. In the absence of CD the main reduction product of vinclozoline in the first reduction step is dichloroaniline. An addition of glucose leads to a quantitative change of mechanism with 10 products in total. Addition of CD, however, leads exclusively to dechlorination of the phenyl ring. The degree of dechlorination depends strongly on the choice of cyclodextrin molecule. The importance of the complex formation equilibria in the change of the mechanism is supported by a series of semiempirical AM1 quantum-mechanical calculations. Very good correlation (correlation coefficient 0.995) was obtained between the complex stabilization energy of the inclusion complex and the degree of pesticide dechlorination. Additionally, we were able to show that the complexes are stabilized by the formation of intermolecular hydrogen bonds between the host and guest species. CD molecules do not simply act as proton donors in a nonaqueous environment, but also protect parts of the molecule included within the cavity and steer the degradation process toward fewer products.     

Intramolecular cyclization of acyl radicals onto the azido group: a new radical approach to cyclized lactams

[reaction: see text] Aryl- and alkyl-derived azidoacyl radicals, generated from thiolesters by intramolecular homolytic substitution at the sulfur, can undergo five- and six-membered cyclization onto the azido moiety to give cyclized lactams.     

Traceless solid-phase synthesis of 2,4,6-chlorodiamino and triaminopyrimidines

An effective traceless solid-phase synthesis of chloro-diaminopyrimidines via an amino-de-chlorination reaction of polymer-bound 4-alkoxycarbonylamino-2,6-dichloropyrimidines has been developed. After release from the polymer the target molecules were obtained in good to excellent purity, although with modest regiocontrol. Further reaction of solid-supported N-alkoxycarbonyl-chloro-diaminopyrimidines with secondary amines afforded triaminopyrimidines in good purity under mild conditions, whereas less nucleophilic primary amines did not perform well under the conditions explored so far.     

Performance of a general-purpose electrochemical instrument aided by a stand-alone microcomputer system in trace analysis

The features of a microprocessor-based data acquisition and control unit, dedicated to electrochemical experiments, are described. The menu-selectable software allows smoothing, baseline drawing and subtraction as well as differentiation, even with signal amplitudes of some tenths of nA at signal/noise ratios lower than one, without forcing the data to follow theoretical models. Concentrations of cadmium ion as low as 2 × 10^?7, 5 × 10^?8 and 5 × 10^?9 M can be measured, within 10% accuracy and precision, by using sampled d.c. polarography, staircase voltammetry and fast-sweep differential pulse voltammetry, respectively; this is a consistent improvement on literature data. Depending on the electrochemical technique used, the most significant signal parameters, including derivatives, are measured automatically, listed and used in the decision-making process for chemical characterization.