Thermodynamics of alcohols and monosaccharides in aqueous solutions of biuret at 25°C

The excess enthalpies of ternary aqueous solutions of biuret with four aliphatic alcohols or four isomeric pentoses have been determined by flow microcalorimetry at 25°C. The coefficients of the virial expansion of the excess enthalpies have been evaluated and compared with those already reported for urea and thiourea with the same alcohols and pentoses used here. For biuret-alcohol systems, the cross coefficients are positive and depend on the length and branching of the alkyl chain of the alcohols. On the contrary, they are negative for biuret-pentose systems. Hence, biuret, as urea and thioura, is able to differentiate the behavior of families of solutes characterized by the same functional groups. The results are interpreted in terms of the relative stabilities of the hydration cospheres of predominantly hydrophobic or predominantly hydrophilic cosolutes. However, hypotheses about the hydration cospheres of the saccharides, which are more complex than those used previously, seem to be necessary to rationalize their complete behavior in water.     

Copper‐Catalyzed Propargylic Substitution of Dichloro Substrates: Enantioselective Synthesis of Trisubstituted Allenes and Formation of Propargylic Quaternary Stereogenic Centers

An easy and versatile Cu‐catalyzed propargylic substitution process is presented. Using easily prepared prochiral dichloro substrates, readily available Grignard reagents together with catalytic amount of copper salt and chiral ligand, we accessed a range of synthetically interesting trisubstituted chloroallenes. Substrate scope and nucleophile scope are broad, providing generally high enantioselectivity for the desired 1,3‐substitution products. The enantioenriched chloroallenes could be further transformed into the corresponding trisubstituted allenes or terminal alkynes bearing all‐carbon quaternary stereogenic centers, through the copper‐catalyzed enantiospecific 1,1/1,3‐substitutions. The two successive copper‐catalyzed reactions could be eventually combined into a one‐pot procedure and different desired allenes or alkynes were obtained respectively with high enantiomeric excesses.     

Hydrolytic and photoinduced degradation of tribenuron methyl studied by HPLC-DAD-MS/MS

The paper studies, with the help of HPLC-DAD-MS/MS technique, the hydrolytic and photoinduced degradation processes that take place in aqueous solutions of tribenuron methyl, both when preserved in the dark and when undergoing solar box irradiation under conditions that simulate sun light. The results indicate that the degradation products formed by hydrolysis alone and by photoirradiation are the same, but kinetics of the hydrolysis reaction is much slower. The degradation products are identified as 2-methoxy-4-methylamino-6-methyl-1,3,5-triazine (P1), methyl 2-aminosulfonylbenzoate (P2), and saccharin (P3) and quantified. Ecotoxicological biotests performed on 0.1 microg L(-1) photoirradiated solutions of the herbicide give a border line toxicity situation comparable to that of the precursor and indicate that the herbicide is characterized by low persistence in the environment, as required. Its degradation, however, does not lead to mineralization but to the formation of products of comparable toxicity. To evaluate the matrix effects, the photodegradation of the herbicide is also studied in the presence of rice paddy waters: the process is slower than in ultrapure water but leads to the same products. Experiments performed for comparison by irradiating ultrapure water solutions with UV lamp (254 nm) show that the degradation process is not only faster with respect to sunlight, but gives a different pathway, without in anyway leading to mineralization.     

Backward Stochastic Riccati Equations and Infinite Horizon L-Q Optimal Control with Infinite Dimensional State Space and Random Coefficients

We study the Riccati equation arising in a class of quadratic optimal control problems with infinite dimensional stochastic differential state equation and infinite horizon cost functional. We allow the coefficients, both in the state equation and in the cost, to be random. In such a context backward stochastic Riccati equations are backward stochastic differential equations in the whole positive real axis that involve quadratic non-linearities and take values in a non-Hilbertian space. We prove existence of a minimal non-negative solution and, under additional assumptions, its uniqueness. We show that such a solution allows to perform the synthesis of the optimal control and investigate its attractivity properties. Finally the case where the coefficients are stationary is addressed and an example concerning a controlled wave equation in random media is proposed.     

Studies of poly(vinylidene fluoride)/poly(vinyl pyrrolidone) blends. I. Thermal transitions by differential scanning calorimetry

Thermal measurements were carried out to investigate the macrostructure of as-cast poly(vinylidene fluoride) (PVDF)/poly(vinyl pyrrolidone) (PVP) blends. At high PVP content, above about 70 wt.%, the two components form a homogeneously mixed amorphous phase whose T_g varies with composition. Crystals are formed upon casting mixtures richer in PVDF; these systems exhibit complex thermal behavior that cannot be justified by a simple two-phase model. DSC measurements above room temperature on semicrystalline blends show, in addition to the melting of PVDF crystals at temperatures that decrease on increasing PVP content, a glass transition at about 80°C, independent of composition. Experimental results strongly support the hypothesis that an interphase, composed of essentially undiluted noncrystalline PVDF, is always associated with the lamellar crystals.     

High quantum yield photoluminescence of new polyamides containing oligo‐PPV amino derivatives and related oligomers

The synthesis and the chemical physical characterization of new photoluminescent (PL) chromophores and polymers are reported. Chromophores (oligo‐PPV symmetric derivatives ending with amino groups) are strong blue emitters with a PL quantum yield of ～70% in dioxane solution. They have been used to prepare polyamides by reaction with aliphatic acyl dichlorides in which emitting and non emitting units are alternated. PL properties of the synthesized polyamides have been evaluated in solution and reveal a strong blue emission (PL quantum yield ～60%), To increase the solubility of these systems, oligomers have been purposely prepared and then characterized. They show a peculiar white emission when excited in DMF solution; to get insight into this interesting behavior, asymmetric monoacetylated chromophores have been prepared as model compounds for the chromophoric end groups of the polyamide chains. The emission spectra of these compounds reveal a broad excimeric yellow emission which is responsible, along with the blue emission of the inner chromophoric units, of the overall white emission of the oligomers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2677–2689, 2009     

Relativistic dynamical reduction models: General framework and examples

The formulation of a relativistic theory of state-vector reduction is proposed and analyzed, and its conceptual consequences are elucidated. In particular, a detailed discussion of stochastic invariance and of local and nonlocal aspects at the level of individual systems is presented.     

Generating Multidirectional Variable Hidden Attractors via Newly Commensurate and Incommensurate Non-Equilibrium Fractional-Order Chaotic Systems

This article investigates a non-equilibrium chaotic system in view of commensurate and incommensurate fractional orders and with only one signum function. By varying some values of the fractional-order derivative together with some parameter values of the proposed system, different dynamical behaviors of the system are explored and discussed via several numerical simulations. This system displays complex hidden dynamics such as inversion property, chaotic bursting oscillation, multistabilty, and coexisting attractors. Besides, by means of adapting certain controlled constants, it is shown that this system possesses a three-variable offset boosting system. In conformity with the performed simulations, it also turns out that the resultant hidden attractors can be distributively ordered in a grid of three dimensions, a lattice of two dimensions, a line of one dimension, and even arbitrariness in the phase space. Through considering the Caputo fractional-order operator in all performed simulations, phase portraits in two- and three-dimensional projections, Lyapunov exponents, and the bifurcation diagrams are numerically reported in this work as beneficial exit results.     

Hyperinstantons,the Beltrami equation,and triholomorphic maps

We consider the Beltrami equation for hydrodynamics and we show that its solutions can be viewed as instanton solutions of a more general system of equations. The latter are the equations of motion for an sigma model on 4‐dimensional worldvolume (which is taken locally HyperKähler) with a 4‐dimensional HyperKähler target space. By means of the 4D twisting procedure originally introduced by Witten for gauge theories and later generalized to 4D sigma‐models by Anselmi and Fré, we show that the equations of motion describe triholomophic maps between the worldvolume and the target space. Therefore, the classification of the solutions to the 3‐dimensional Beltrami equation can be performed by counting the triholomorphic maps. The counting is easily obtained by using several discrete symmetries. Finally, the similarity with holomorphic maps for sigma on Calabi‐Yau space prompts us to reformulate the problem of the enumeration of triholomorphic maps in terms of a topological sigma model.