Determination of intrinsic properties of immobilized enzymes

Staphylococcal nuclease has been insolubilized, directly through its amino groups, on CNBr-activated Sepharose 2B. For kinetic studies, a small substrate (thymidine 5′-(p-nitrophenyl phosphate) 3′-phosphate) has been used to measure the hydrolytic activity. With this system the absence of diffusional limitation has been proven. Eadie-Hofstee analysis of the data has been employed to determine the intrinsic kinetic constants of the insolubilized enzyme. Thek _cat-pH andK _M−pH profiles and the activation energies are similar for the soluble and for the insolubilized nuclease. At the same time conditions are established in which a stirred batch reactor containing particles of insolubilized nuclease behaves as an open system.     

Structural ordering and chemical stability of a complex perovskite oxide DyBa2ZrO5.5 with YBa2Cu3O7-δ superconductors

2 ZrO_5.5 has been synthesized by solid-state reaction. Structural ordering in this material has been studied by X-ray diffraction (XRD). The XRD spectra reveal that DyBa₂ZrO_5.5 has an ordered complex cubic perovskite structure. The presence of superstructure reflections in the XRD spectra is characteristic of A₂BB’O₆-type crystalline structure. The chemical stability of DyBa₂ZrO_5.5 with YBa₂CuO_7-δ (YBCO) superconductors has been studied by XRD and electrical resistivity measurements. These studies show that DyBa₂ZrO_5.5 is chemically stable with YBCO and there is no degradation in the superconducting transition temperature T_c of YBCO even when mixed up to 1:1 vol%, with DyBa₂ZrO_5.5 in YBCO. Detailed study of the superconducting transition region shows that T_c(onset) and T_c(0) values of pure YBCO and YBCO–DyBa₂ZrO_5.5 composites are similar in both cases. The implications are discussed. Accepted: 13 October 1997     

Buckling-driven morphological transformation of droplets of a mixed colloidal suspension during evaporation-induced self-assembly by spray drying

Morphological transformation during evaporation-induced self-assembly of a mixed colloidal suspension in micrometric droplets has been investigated. It has been demonstrated that a buckling-driven shape transition of drying droplets of mixed colloidal suspension takes place during evaporation-induced self-assembly. Further, it is also shown that the distortion modulations get significantly amplified with enhancement in volume fraction of anisotropic soft colloidal component of the mixed colloids. It has been argued that the reduction in elastic modulus of formed shell, at the boundary of a drying droplet, and the anisotropic nature of one of the colloidal components facilitate the deformation process. Hierarchical structures of these assembled colloidal grains have been probed using electron microscopy and scattering techniques.     

Photophysical studies of alpha,omega-dicyano-oligothiophenes NC(C4H2S)nCN (n = 1-6)

The photophysics of six oligothiophenes end-capped with cyano groups (CNalphan) was investigated in solution at room and low temperature. The study comprises singlet-singlet and triplet-triplet absorption and emission spectra together with lifetimes and quantum yields for all the radiative and nonradiative processes. From the lifetimes and quantum yields, it was possible to extract the rate constants for all the processes. Singlet oxygen yields were also determined, revealing an efficient sensitization (SDelta approximately 1) of its formation by the triplet state of the CNalphan. The introduction of the cyano groups is found to decrease the energetic separation between the highest occupied molecular orbital and the lowest unoccupied molecular orbital, leading to a red shift of the absorption and the emission when compared with the unsubstituted counterparts, the alpha-oligothiophenes. Phosphorescence is only observed for the first member of the series, CNalpha1.     

Evolution from BCS to BEC superfluidity in p-wave Fermi gases

We consider the evolution of superfluid properties of a three-dimensional p-wave Fermi gas from a weak coupling Bardeen-Cooper-Schrieffer (BCS) to strong coupling Bose-Einstein condensation (BEC) limit as a function of scattering volume. At zero temperature, we show that a quantum phase transition occurs for p-wave systems, unlike the s-wave case where the BCS to BEC evolution is just a crossover. Near the critical temperature, we derive a time-dependent Ginzburg-Landau (GL) theory and show that the GL coherence length is generally anisotropic due to the p-wave nature of the order parameter, and becomes isotropic only in the BEC limit.     

Methyl 3-methyl-2H-azirine-2-carboxylate photochemistry studied by matrix-isolation FTIR and DFT calculations

The aliphatic 2H-azirine, methyl 3-methyl-2H-azirine-2-carboxylate (MMAC), has been synthesized and its monomeric form investigated by IR spectroscopy in an argon matrix, at 10 K, as well as theoretically (DFT/B3LYP/6-311++G(d,p)). Two low-energy conformers of MMAC (Ct and Cc) were found in the matrix, both exhibiting the cis conformation around the C-O bond but differing in the arrangement around the C-C(alpha) bond. The two conformers were photoreactive upon in situ broadband UV excitation (lambda > 235 nm), yielding nitrile ylide (P1) and ketene imine (P2) type products, which resulted from cleavage of the C-C or C-N bond, respectively. The kinetics of the reactions leading to the formation of P1 and P2 are of first order, with the processes being favored when the reactant is in the Cc conformation. Very interestingly, the C-N bond photocleavage, which is unusual for aliphatic 2H-azirines, was found to be preferred over the generally favored in 2H-azirines C-C bond breakage. This behavior is attributed to the presence in the molecule of the electron-withdrawing methoxycarbonyl substituent, which accelerates the intersystem crossing toward the T(1) triplet state and, in this way, favors the C-N bond cleavage. In addition to the primary photoprocesses leading to formation of P1 and P2, secondary photoprocesses leading to the decarboxylation and decarbonylation of P2 have been also observed.     

Unusual photochemical C-N bond cleavage in the novel methyl 2-chloro-3-methyl-2H-azirine-2-carboxylate

The structure, preferred conformers, vibrational spectrum, and photochemical behavior of the novel azirine, methyl 2-chloro-3-methyl-2H-azirine-2-carboxylate (MCMAC) were investigated in low-temperature matrixes and in the neat solid amorphous state by infrared spectroscopy and quantum-chemical calculations. Two conformers of the compound were observed in argon, krypton, and xenon matrixes, in agreement with the DFT(B3LYP)/6-311++G(d,p) and MP2/6-311++G(d,p) theoretical calculations. Both conformers were found to exhibit the carboxylic ester group in the cis conformation, differing in the arrangement defined by the O=C-C-Cl dihedral angle (cis and trans, for Ct and Cc forms, respectively). The Ct conformer was found to be the most stable conformer in the gaseous phase as well as in both argon and krypton matrixes, whereas the more polar Cc conformer became the most stable form in the xenon matrix and in the neat solid amorphous phase. In situ broadband UV (lambda > 235 nm) excitation of matrix-isolated MCMAC led to azirine ring C-C and C-N bond cleavages, the latter process corresponding to the most efficient reaction channel. The photochemical cleavage of the C-N bond had never been previously observed in the case of aliphatic 2H-azirines. Two electron withdrawing substituents (methoxycarbonyl group and chlorine atom) are connected to the azirine ring in the novel MCMAC azirine. The simultaneous presence of these two groups accelerates intersystem crossing toward the triplet state where cleavage of the C-N bond takes place. The primary photoproducts resulting from the C-N and C-C ring-opening reactions were also found to undergo further photochemical decarbonylation or decarboxylation reactions.     

Softening induced instability of a stretched cohesive granular layer

We report on a cellular pattern which spontaneously forms at the surface of a thin layer of a cohesive granular material submitted to in-plane stretching. We present a simple model in which the mechanism responsible of the instability is the "strain softening" exhibited by humid granular materials above a typical strain. Our analysis indicates that such a type of instability should be observed in any system presenting a negative stress sensitivity to strain perturbations.     

Duality and Exact Penalization for General Augmented Lagrangians

We consider a problem of minimizing an extended real-valued function defined in a Hausdorff topological space. We study the dual problem induced by a general augmented Lagrangian function. Under a simple set of assumptions on this general augmented Lagrangian function, we obtain strong duality and existence of exact penalty parameter via an abstract convexity approach. We show that every cluster point of a sub-optimal path related to the dual problem is a primal solution. Our assumptions are more general than those recently considered in the related literature.     

Optimizing production and transportation in a commit-to-delivery business mode

In problems involving the simultaneous optimization of production and transportation, the requirement that an order can only be shipped once its production has been completed is a natural one. One example is a problem of optimizing shipping costs subject to a production capacity constraint studied recently by Stecke and Zhao. Here we present an integer programming formulation for the case in which only completed orders can be shipped that leads to very tight dual bounds and enables one to solve instances of significant size to optimality.