Enzymatic kinetic of cellulose hydrolysis

The ethanol effect on the Trichoderma reesei cellulases was studied to quantify and clarify this inhibition type. To determine inhibition parameters of crude cellulase and purified exoglucanase Cel7A, integrated Michaelis-Menten equations were used assuming the presence of two inhibitors: cellobiose as the reaction product and ethanol as a possible bioproduct of cellulose fermentation. It was found that hydrolysis of cellulose by crude enzyme follows a model that considers noncompetitive inhibition by ethanol, whereas Cel7A is very slightly competitively inhibited. Crude cellulase is much more inhibited (K _iul=K _icl=151.9 mM) than exoglucanase Cel7A (K _icl=1.6 × 10¹⁵ mM). Also, calculated inhibition constants showed that cellobiose inhibition is more potent than ethanol inhibition both for the crude enzyme as well as exoglucanase Cel7A.     

Molecular orbital calculations on transition metal clusters

Transition metal clusters have been subject of experimental and theoretical interest due to their catalytic activity, as well as their unusual physical properties. Semi-empirical extended Hückel molecular orbital calculations are presented for a series of small metal clusters with nuclearity ranging from 3 to 6. Naked and carbonylated clusters of Fe, Ru, and Os are studied. The charge transfer between ligands shell and metal core is found to be a function of nuclearity, CO coordination and the chemical species forming the bare cluster. The observed magnetic properties of these systems are discussed in terms of their electronic structure and CO-metal charge transfer.     

Relation between structure and enthalpy for stacking interactions of aromatic molecules

An approximately linear correlation has been found between the enthalpy of complexation and the area of overlap of the chromophores using published structural and thermodynamical data on the self- and hetero-association of aromatic molecules measured under similar solution conditions. This finding is consistent with the assumption that short-range van-der-Waals forces dominate over other contributions to the enthalpy of stacking of aromatic molecules. It provides a ‘model-independent’ approach for a priori estimation of the enthalpy of aromatic–aromatic stacking interactions from knowledge of the structural properties or vice versa.     

Generalizing the Dokshitzer-Gribov-Lipatov-Altarelli-Parisi evolution of fragmentation functions to the smallest values

An approach valid to any order which unifies the fixed order Dokshitzer-Gribov-Lipatov-Altarelli-Parisi evolution of fragmentation functions at large x with soft gluon logarithmic resummation at small x is proposed. At lowest order, this approach, implemented with the double logarithmic approximation, reproduces exactly the modified leading logarithm approximation but is more complete due to the degrees of freedom given to the quark sector and the inclusion of the fixed order terms. We find that data from the largest x values to the peak region can be better fitted than with other approaches.     

Space distribution of harmonic mode vibration amplitudes in nonlinear finite piezoelectric transducer

Nonlinear elastic vibrations of cylindrical piezoelectric transducers are investigated both experimentally and theoretically. A particular behaviour, that relates the space distribution of the fundamental mode vibration to those of the second and third harmonic components, is observed. A simplified physical interpretation of the phenomenon is given.     

Discrimination among eight modified michaelis-menten kinetics models of cellulose hydrolysis with a large range of substrate/enzyme ratios

The kinetics of exoglucanase (Cel7A) from Trichoderma reesei was investigated in the presence of cellobiose and 24 different enzyme/Avicel ratios for 47 h, in order to establish which of the eight available kinetic models best explained the factors involved. The heterogeneous catalysis was studied and the kinetic parameters were estimated employing integrated forms of Michaelis-Menten equations through the use of nonlinear least squares. It was found that cellulose hydrolysis follows a model that takes into account competitive inhibition by cellobiose (final product) with the following parameters: Km = 3.8 mM, Kic = 0.041 mM, kcat = 2 h-1 (5.6 x 10-4 s-1). Other models, such as mixed type inhibition and those incorporating improvements concerning inhibition by substrate and parabolic inhibition, increased the modulation performance very slightly. The results support the hypothesis that nonproductive enzyme substrate complexes, parabolic inhibition, and enzyme inactivation (Selwyn test) are not the principal constraints in enzymatic cellulose hydrolysis. Under our conditions, the increment in hydrolysis was not significant for substrate/enzyme ratios <6.5.     

The influence of patterned nanofiber meshes on human mesenchymal stem cell osteogenesis

A specially designed electroconductive collector enables the electrospinning of P-NFM composed of areas of parallel/uniaxially aligned fibers and areas of random/orthogonal nanofiber distribution. The biological relevance of P-NFM is demonstrated using hBMSCs as an autologous cell source. The structures induce cell orientation along the uniaxially aligned fibers, mainly during earlier culturing periods under basal and osteogenic differentiation conditions. The microtopography of the P-NFM also controls the deposition of mineralized extracellular matrix along the pre-defined fiber direction. Genotypic characterization confirms the successful differentiation into the osteogenic lineage.     

Geometric nonlinear analyses of functionally graded beams using a tailored Lagrangian formulation

This paper presents a geometric nonlinear analysis formulation for beams of functionally graded cross-sections by means of a Total Lagrangian formulation. The influence of material gradation on the numerical response is investigated in detail. Two examples are given that illustrate the main features of the formulation, in which the behavior of beams of graded cross-sections is compared with homogeneous material beams. A motivation for this work is the potential development of functionally graded risers for the offshore oil exploration industry.     

EPR on the high-nuclearity palladium cluster Pd561Phen36O200

We present EPR measurements on the polynuclear metal-cluster compound Pd₅₆₁Phen₃₆O₂₀₀ for temperatures ranging from 300 K to 8 K. No temperature dependence was found in either the resonance field or the line-width. The signal intensity shows a Curie-like behavior. The effect of the ligand on this behavior is discussed. We also discuss the possibility that quantum size effects govern the observed temperature dependence of the line-width and resonance field.