Lamp‐based wavelength‐resolved fluorescence detection for protein capillary electrophoresis: Setup and detector performance

A lamp‐based fluorescence detection (Flu) system for CE was extended with a wavelength‐resolved (WR) detector to allow recording of full protein emission spectra. WRFlu was achieved using a fluorescence cell that employs optical fibres to lead excitation light from a Xe‐Hg lamp to the capillary window and protein fluorescence emission to a spectrograph equipped with a CCD. A 280 nm band pass filter etc. together with a 300 nm short pass cut‐off filter was used for excitation. A capillary cartridge was modified to hold the detection cell in a commercial CE instrument enabling WRFlu in routine CE. The performance of the WRFlu detection was evaluated and optimised using lysozyme as model protein. Based on reference spectral data, a signal‐intensity adjustment was introduced to correct for transmission losses in the detector optics that occurred for lower protein emission wavelengths. CE‐WRFlu of lysozyme was performed using BGEs of 50 mM sodium phosphate (pH 6.5 or 3.0) and a charged‐polymer coated capillary. Using the 3‐D data set, signal averaging over time and emission‐wavelength intervals was carried out to improve the S/N of emission spectra and electropherograms. The detection limit for lysozyme was 21 nM, providing sufficient sensitivity to obtain spectral information on protein impurities.     

Wavelet transform analysis of ab initio molecular dynamics simulation: application to core-excitation dynamics of BF3

We propose a novel analysis method of ab initio molecular dynamics (AIMD) simulation using a continuous wavelet transform (c-WT) technique. The c-WT technique, one of the time-frequency signal analysis methods, provides a clear view of the dynamical information in time developments. Combined with the auto-correlation function of velocity by AIMD simulation, c-WT analysis enables us to well understand dynamical distribution, such as the vibrational properties following a change of electronic structure in a molecular system. As a practical application, AIMD simulation of core-excited BF(3) (B1s --> 2a(2) (')) is illustrated. AIMD simulation leads to the change of vibrational motion as well as structural deformation by core-excitation. The c-WT analysis clarifies the relationship between structural deformation and the related significant vibrational modes in core-excitation within 50 fs.     

Analytical excited state forces for the time-dependent density-functional tight-binding method

An analytical formulation for the geometrical derivatives of excitation energies within the time-dependent density-functional tight-binding (TD-DFTB) method is presented. The derivation is based on the auxiliary functional approach proposed in [Furche and Ahlrichs, J Chem Phys 2002, 117, 7433]. To validate the quality of the potential energy surfaces provided by the method, adiabatic excitation energies, excited state geometries, and harmonic vibrational frequencies were calculated for a test set of molecules in excited states of different symmetry and multiplicity. According to the results, the TD-DFTB scheme surpasses the performance of configuration interaction singles and the random phase approximation but has a lower quality than ab initio time-dependent density-functional theory. As a consequence of the special form of the approximations made in TD-DFTB, the scaling exponent of the method can be reduced to three, similar to the ground state. The low scaling prefactor and the satisfactory accuracy of the method makes TD-DFTB especially suitable for molecular dynamics simulations of dozens of atoms as well as for the computation of luminescence spectra of systems containing hundreds of atoms.     

A meshless finite point method for three‐dimensional analysis of compressible flow problems involving moving boundaries and adaptivity

A finite point method for solving compressible flow problems involving moving boundaries and adaptivity is presented. The numerical methodology is based on an upwind‐biased discretization of the Euler equations, written in arbitrary Lagrangian–Eulerian form and integrated in time by means of a dual‐time steeping technique. In order to exploit the meshless potential of the method, a domain deformation approach based on the spring network analogy is implemented, and h‐adaptivity is also employed in the computations. Typical movable boundary problems in transonic flow regime are solved to assess the performance of the proposed technique. In addition, an application to a fluid–structure interaction problem involving static aeroelasticity illustrates the capability of the method to deal with practical engineering analyses. The computational cost and multi‐core performance of the proposed technique is also discussed through the examples provided. Copyright © 2013 John Wiley & Sons, Ltd.     

Electromechanical control of vibration on a plate submitted to a non-ideal excitation

This paper deals with the enhancement of electromechanical control of vibration on a thin plate submitted to non-ideal excitation. Modelling of the systems displays the non-ideal source used as external excitation above the structure on a particular surface and control force acting at specific points under the structure. The electromechanical device is composed by a RL circuit with a saturated inductance and stings connected to the plate is used as connection between the structure and the controller. Routh–Hurwitz criteria are used to obtain the stability condition of the controlled system and some dynamics exploration leads us to the condition for which the amplitude of vibration is reduced in the mechanical structure.     

Numerical modeling of chlorine concentration in water storage tanks

In this paper, we describe a numerical model to simulate the evolution in time of the hydrodynamics of water storage tanks, with particular emphasis on the time evolution of chlorine concentration. The mathematical model contains several ingredients particularly designed for this problem, namely, a boundary condition to model falling jets on free surfaces, an arbitrary Lagrangian–Eulerian formulation to account for the motion of the free surface because of demand and supply of water, and a coupling of the hydrodynamics with a convection–diffusion–reaction equation modeling the time evolution of chlorine. From the numerical point of view, the equations resulting from the mathematical model are approximated using a finite element formulation, with linear continuous interpolations on tetrahedra for all the unknowns. To make it possible, and also to be able to deal with convection‐dominated flows, a stabilized formulation is used. In order to capture the sharp gradients present in the chlorine concentration, particularly near the injection zone, a discontinuity capturing technique is employed. Copyright © 2015 John Wiley & Sons, Ltd.     

Explicit formulas for the reflection and transmission coefficients of one-component waves through a stack of an arbitrary number of layers

The transmission and reflection of one-component elastic, acoustic, optical waves on a stack of arbitrary number of different homogeneous layers have been intensively studied in the literature. However, all obtained formulas for the reflection and transmission coefficients are in implicit form. In this paper, we provide the explicit formulas for them. From these formulas we immediately arrive at the explicit formulas for the reflection and transmission coefficients of one-component waves through an FGM layer. Based on the obtained exact formulas, approximate formulas for the reflection and transmission coefficients are established for a stack of thin layers and for a thin FGM layer. It is numerically shown that they are good approximations. Since the obtained formulas are totally explicit, they are useful in evaluating, not only numerically but also analytically, the transmission and reflection coefficients of one-component waves.     

任意基数集上的拟阵的圈及连通性

通过研究任意基数集上的拟阵圈的性质,继而得出当此拟阵连通时,它可由含任一给定元素的圈集唯一确定的结论.     

Experimental dynamic analysis of elastic-plastic shear frames with secondary structures

Various experimental models are developed to study the influence of lightweight secondary structures on the dynamic response of elastic and elastic-plastic shear frames. Small-scale two-story model frames, with an elastic single-degree-of-freedom secondary structure attached, are considered for sinusoidal and random in-plane support excitation. Both elastic and elastic-plastic responses are recorded by varying the material properties of the columns of a distinguished floor. Parametric studies are performed by varying the secondary structure's fundamental frequency and damping. Experimental results are compared with those obtained by computational simulations. Experimental and numerical results are in excellent agreement, however they show that the material properties have to be determined very carefully. The statistic response of randomly excited elastic-plastic structures is not much affected by the motion of tuned secondary structures. However, this dynamic behavior is not true for elastic main structures. In this case, an optimally tuned secondary structure decreases the structural response up to 25%.     

Homonuclear decoupled 13C chemical shift anisotropy in 13C doubly labeled peptides by selective-pulse solid-state NMR

We describe a new experiment for measuring homonuclear-decoupled anisotropic chemical shift patterns in doubly 13C-labeled compounds under magic-angle spinning. The experiment combines a pair of selective and non-selective 180 degrees pulses to suppress the 13C-13C scalar and dipolar interactions. This is combined with the recently developed SUPER technique to recouple the chemical shift anisotropy. Demonstrations on 13Calpha and 13CO-labeled amino acids and peptides show that accurate chemical shift powder patterns can be obtained. This permits the use of chemical shift anisotropy for conformational studies of suitably extensively 13C-labeled peptides and proteins.