Understanding and tuning the catalytic bias of hydrogenase

When enzymes are optimized for biotechnological purposes, the goal often is to increase stability or catalytic efficiency. However, many enzymes reversibly convert their substrate and product, and if one is interested in catalysis in only one direction, it may be necessary to prevent the reverse reaction. In other cases, reversibility may be advantageous because only an enzyme that can operate in both directions can turnover at a high rate even under conditions of low thermodynamic driving force. Therefore, understanding the basic mechanisms of reversibility in complex enzymes should help the rational engineering of these proteins. Here, we focus on NiFe hydrogenase, an enzyme that catalyzes H(2) oxidation and production, and we elucidate the mechanism that governs the catalytic bias (the ratio of maximal rates in the two directions). Unexpectedly, we found that this bias is not mainly determined by redox properties of the active site, but rather by steps which occur on sites of the proteins that are remote from the active site. We evidence a novel strategy for tuning the catalytic bias of an oxidoreductase, which consists in modulating the rate of a step that is limiting only in one direction of the reaction, without modifying the properties of the active site.     

Theoretical calculation of the low-lying sextet electronic states of CrF molecule

The potential energy curves have been investigated for the 12 lowest sextet electronic states in the ^2s+1Λ^(±)${}^{2s+1}{\mathrm{\Lambda }}^{(\pm )}$ representation below 53,000 cm⁻¹ of the molecule CrF via CASSCF and MRCI (single and double excitation with Davidson correction) calculations. Seven electronic states have been studied theoretically for the first time. The harmonic frequency ω_e, the internuclear distance R_e, the rotational constant B_e, the electronic energy with respect to the ground state T_e, and the permanent dipole moment μ have been calculated. By using the canonical functions approach, the eigenvalues E_v, the rotational constant B_v and the abscissas of the turning points R_min and R_max have been calculated for the considered electronic states up to the vibrational level v = 39. The comparison of these values to the theoretical and experimental results available in the literature shows a good agreement.     

Modeling and study of dynamic performance of a valveless micropump

This work presents an approximate nonlinear analytical model for the problem of fluid-structural interaction in a valveless micropump. The model is constructed using the lumped-mass approach and takes into account the inertial force and time variation of mass density of the working fluid within the micropump chamber, pressure viscous losses of the flow through the diffuser/nozzle elements and the structural geometric nonlinearity due to the membrane mid-plane stretching. It consists of a set of coupled partial integro-differential equations which is reduced to a third order nonlinear coupled fluid-plate vibration equation by using the assumed mode method to approximate the plate dynamic deflection. An approximate analytical solution for the nonlinear vibration model is carried out using the harmonic balance method and is used to investigate the effect of various system parameters on the performance of the micropump. The obtained model and approximate analytical results are compared with those available in the open literature. The approximate analytical results show that, depending on the micropump physical parameters and membrane driving frequency, the working fluid stiffness, which arise in the present model as a result of taking into account the variation of the fluid density with time, and the membrane geometric nonlinearity can have significant effects on the predicted micropump performance and can lead to a complex nonlinear dynamic behavior. The accuracy of these results is subject to a future numerical validation of the presented approximate theoretical model.     

Filling an area discretely and continuously

The literature dealing with student understanding of integration in general and the Fundamental Theorem of Calculus in particular suggests that although students can integrate properly, they understand little about the process that leads to the definite integral. The definite integral is naturally connected to the antiderivative, the area under the curve and the limit of Riemann sums; these three conceptualizations of the definite integral are useful in different contexts and provide students with what it takes to interpret the definite integrals. Research shows that students rarely invoke the multiplicatively-based summation conception of the definite integral although it is essential for evaluating line integrals, surface integrals and volumes. This paper describes a teaching module that promotes understanding as well as activating all three conceptualizations of the definite integral through motivating the accumulation area function and the results in the Fundamental Theorems of Calculus.     

Size‐resolved analysis of fine and ultrafine fractions of indoor particulate matter using energy dispersive X‐ray fluorescence and electron microscopy

We used a multistage PIXE inertial impactor with nine different aerodynamic diameter ranges (between 16 and 0.06 μm) to sample indoor particulate matter (PM). X‐ray fluorescence (XRF) measurements performed at cutoff diameters (CoDs) of 0.25, 0.5, 1, 2, 4, and 8 μm were used to identify elements in various size fractions. Anthropogenic sources were the dominant sources for fine and ultrafine particle sizes. The XRF results show that natural sources also contribute to the fine and ultrafine fractions of pollutants. Scanning electron microscopy and energy‐dispersive system analysis were performed on membranes having PM CoDs of 4, 2, 1, 0.5, and 0.25 μm. Elemental mappings show the membranes with PM of CoDs 0.25 and 0.5 μm having S as a dominant element, confirming the results obtained with XRF. Strong correlation among maps of S, N, and O show that ammonium sulfate is the major constituent at these size fractions. Other elements such as Si, Ca, Fe, Al, and Mg show up in smaller amounts at these size fractions but increase for membranes with larger particles. For size fractions larger than 0.5 μm, there is a good correlation between the elemental maps of these elements and oxygen, indicating that these elements exist mostly in oxide forms. The absence of clear N signals and the correlation between the Ca and S maps indicate that S in these size fractions is not due to ammonium sulfate. The presence of Mg, K, Cl, and Na at these CoDs shows that these elements are due to salts originating from sea breeze.     

Effects of Rice Husk Derived Amorphous Silica on the Thermal-Mechanical Properties of Unsaturated Polyester Composites

Rice husk is rich in amorphous silica which has found various applications as a filler in rubbers and plastics. In the research described here silica was extracted from rice husk ash in the form of sodium silicate which was used to produced amorphous precipitated silica (PS) and silica aerogel (SA) using a sol – gel process and supercritical drying. These materials were then physically mixed with unsaturated polyester (UP) resin and cured at room temperature to form polymer composites. The experimental results showed that the UP composites with 30% (volume percent) of SA filler had lower density and better thermal insulation than the composites with the same amount of PS. Thermogravimetric analysis (TGA) results showed that the T_onset of the PS and SA composites were slightly delayed by 15 and 10°C, respectively. The tensile stress-strain curves showed that addition of the fillers reduced the tensile strength, but increased the elastic moduli of the UP matrix. PS filled UP composites exhibit higher moduli (higher stiffness) than that of SA filled UP composites. This was due to agglomeration and poor adhesion of the SA particles to the UP matrix while better dispersion was observed for the PS filled composite.     

Quantitative proteomics: a review of different methodologies

The present review attempts to cover the vast array of methods which have appeared in the last few years for performing quantitative proteome analysis. These methods are divided into two classes: those applicable to conventional two-dimensional map analysis, coupling orthogonally a charge-based step (isoelectric focusing) to a size-based separation [sodium dodecylsulfate (SDS)-electrophoresis] and those applicable to two-dimensional chromatographic protocols. The first method, although being by and large the most popular approach, can offer differential display of paired samples with relatively few methods, the oldest one being based on statistical analysis performed on sets of gels via powerful software packages, such as the MELANIE, PDQuest, Z3 and Z4000, Phoretix and Progenesis. Recent developments comprise analysis performed on a single gel containing mixed samples differentially labeled, either with fluorophors (Cy3 and Cy5) or with d(0)/d(3) acrylamide. Conversely, chromatographic approaches, which mostly rely on analysis not of intact proteins but of their tryptic digests, offer a panoply of differential labeling protocols, most of which rely on stable isotope tagging. Essentially, all possible reactions have been described, such as those involving Lys, Asp, Glu, Cys residues, as well as a number of methods exploiting differential derivatization of amine and carboxyl groups generated during proteolysis. All such methods are described and evaluated.     

The Ã1A1-X̃1A1 two-photon fluorescence excitation spectrum of 1,2-difluorobenzene

The two-photon fluorescence excitation spectrum of 1,2-difluorobenzene was obtained with a tunable dye laser calibrated using a combination of the neon optogalvanic spectrum and etalon fringes. The spectrum consists only of A₁-A₁ bands but the use of linear and circular polarization divides the bands into two types. The 0⁰₀ type retains its intensity in circular polarization and, rotationally, shows little or no zero-rank contribution. The 5¹₀ (or 14¹₀) type loses much of its intensity in circular polarization and, rotationally, shows a large zero-rank contribution. These observations all accord with the trace of the two-photon transition tensor being close to zero for the 0⁰₀ type and large for the 5¹₀ type, the latter type being involved in vibronic interaction which mixes the $\text{A}\text{?}$ and $\text{X}\text{?}$ states. There is strong evidence for Fermi resonance between the 5¹ and 6¹10¹ levels. Parts of the one-photon absorption spectrum have been photographed to aid sequence identification and also to look for the 5¹₀, A₁-A₁ transition. This transition is not observed: nor is there any evidence for intensity stealing by b₂ vibrations.     

Wavelet and chaos analysis of irregularities of vortex shedding

This paper reports the potential of using two types of wavelets namely; the Mexican hat and the modulated Gaussian wavelets to analyze the frequency of vortex shedding from a single cylinder in a cross flow. Furthermore, the paper examines the chaotic behaviors of the vortex shedding signals of various positions along the cylinder span. It is found that the signals along the cylinder are characterized by high-energy contents in the low frequency range below the Strouhal frequency.