A fluorescence toolbox: A review of investigation of electrophoretic separations,process, and interfaces

This review focuses on fluorescence spectroscopy techniques for the investigation of electrophoretic separations. Fluorescence has been used as a sensitive detector for capillary, gel, and microchip electrophoresis for decades. However, advanced fluorescence methods can be used to study transport, interfacial phenomena, intermolecular and affinity interactions, and other processes that occur during separation. This so‐called spectroscopic toolkit can be implemented to understand fundamental behavior in electrophoresis and electrokinetic chromatography. Techniques such as fluorescence recovery after photobleaching, fluorescence correlation spectroscopy, and fluorescence anisotropy are discussed in relation to electrophoretic separations. Newer methods such as super‐resolution microscope are also introduced.     

Intrinsic minimal atomic basis representation of molecular electronic wavefunctions

The problem of finding an effective minimal atomic basis that spans the exact occupied wavefunctions of a mean‐field theory at a given molecular geometry, which has a number of special properties, is studied and a new general procedure is developed that (1) solves for a raw minimal set of strongly atom‐centered functions—products of spherical harmonics and molecule‐optimized radial parts—that approximately span the occupied molecular wavefunctions and minimize the sum of their energies, (2) uses projection operators to get a new set of deformed atom‐centered functions that exactly span the occupied space and fall into core and valence subsets, (3) applies a new zero‐bond‐dipole orthogonalization scheme to the core‐orthogonalized valence subset so that for each two‐center product of these functions the projection of its dipole moment along the line going through the two centers is zero. The resulting effective minimal atomic basis is intrinsic to the molecular problem and does not need a free‐atoms input. Some interesting features of the zero‐bond‐dipole orthogonalization are showing up in the atomic population analysis of a diverse set of molecules. The new procedure may be useful for the interpretation of electronic structure, for the construction of model Hamiltonians in terms of transferable molecular integrals, and for the definition of active valence space in the treatment of electron correlation. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Electrochemical grafting by reduction of 4-aminoethylbenzenediazonium salt: Application to the immobilization of (bio)molecules

We propose in this study a simple and rapid way to produce stable amino-derivatized conductive surfaces for the subsequent immobilization of (bio)molecules. This was achieved through the use of (4-aminoethyl)benzenediazonium salt (AEBD), which was immobilized on glassy carbon and gold electrodes by its electrochemical reduction. The presence of terminal grafted amino functions was evidenced with XPS by analyzing N1s core level. Besides this conventional surface characterisation, an electrochemical strategy is proposed here to evidence the presence of immobilized amines, in which the chemical reactivity of amines towards 2,4,6-trinitrobenzenesulfonic acid (TNBS) is used. Surface-bound TNBS served as an electrochemical marker and was detected by cyclic voltammetry. Additionally, pre-modified gold electrodes with amino functions can be derivatized with biomolecules such as glutathione (GSH). Glutathione attachment was evidenced by studying the electrochemical behaviour of ferri/ferrocyanide redox before and after its immobilization. The functionalized electrodes were then used for the detection of copper ions in neutral aqueous solutions.     

Density functional and spectroscopic studies of nitrogen inversion in substituted dizocilpines

While developing a synthesis towards tagged dizocilpine (MK‐801) analogues, we observed highly restricted inversion of a nitrogen centre in a number hydroxylamines obtained as key intermediates. These compounds are shown to possess some of the structural elements which are expected to significantly hinder the nitrogen inversion, potentially leading to hydroxylamines with a chiral nitrogen centre. Free energy barriers (ΔG^≠) of the nitrogen inversion were estimated to be ca. 22 kcal mol^?1 at temperatures near 420 K using variable temperature NMR measurements in DMSO‐d₆. Further density functional studies of a number model systems were undertaken in order to better rationalize the measured inversion barriers and follow the role of various structural factors in raising the barrier height of the nitrogen inversion process. Copyright © 2008 John Wiley & Sons, Ltd.     

Fluidization of Nano-size Particles

Fluidization and collapsing bed experiments were performed with 'Tullanox', 10nm diameter fumed silica. The minimum fluidization velocity was determined to be 0.0115m/s at the unusually low volume fraction of solids of 0.0077. The solids volume fraction was measured using a -ray densitometer. Fluidization was without large bubbles, with a high bed expansion ratio. The highest granular temperature was of the order of that of Geldart B particles, as measured by Cody et al. (1996). The sedimentation process was simulated using a two-fluid hydrodynamic model. The input into the model was a measured solids stress modulus and an agglomerate size determined from the settling curves. With these two rheological parameters, there was good agreement between the sedimentation theory and the experiment. This study shows that the standard collapse bed experiment used in industry is a good test of rheological properties of particles.     

A Note on Error Bounds for Convex and Nonconvex Programs

Given a single feasible solution and a single infeasible solution of a mathematical program, we provide an upper bound to the optimal dual value. We assume that satisfies a weakened form of the Slater condition. We apply the bound to convex programs and we discuss its relation to Hoffman-like bounds. As a special case, we recover a bound due to Mangasarian [11] on the distance of a point to a convex set specified by inequalities.     

The string coupling accelerates the expansion of the universed

Generic cosmological models in non-critical string theory have a time-dependent dilaton background at a late epoch. The cosmological deceleration parameter q ₀ is given by the square of the string coupling, g _s ², up to a negative sign. Hence the expansion of the Universe must accelerate eventually, and the observed value of q ₀ corresponds to g _s ² ∼ 0.6. In this scenario, the string coupling is asymptotically free at large times, but its present rate of change is imperceptibly small. First Award in the 2005 Essay Competition of the Gravity Research Foundation. - Ed.     

Quotients of a universal locally projective polytope of type {5,3,5}

This article examines the universal polytope (of type {5,3,5}) whose facets are dodecahedra, and whose vertex figures are hemi-icosahedra. The polytope is proven to be finite, and the structure of its group is identified. This information is used to classifiy the quotients of the polytope. A total of 145 quotients are found, including 69 section regular polytopes with the same facets and vertex figures as . Mathematics Subject Classification (2000): 51M20, 20F65, 52B15 An erratum to this article is available at .     

Charge-transfer mechanism for cytochrome c adsorbed on nanometer thick films. Distinguishing frictional control from conformational gating

Using nanometer thick tunneling barriers with specifically attached cytochrome c, the electron-transfer rate constant was studied as a function of the SAM composition (alkane versus terthiophene), the omega-terminating group type (pyridine, imidazole, nitrile), and the solution viscosity. At large electrode-reactant separations, the pyridine terminated alkanethiols exhibit an exponential decline of the rate constant with increasing electron-transfer distance. At short separations, a plateau behavior, analogous to systems involving -COOH terminal groups to which cytochrome c can be attached electrostatically, is observed. The dependence of the rate constant in the plateau region on system properties is investigated. The rate constant is insensitive to the mode of attachment to the surface but displays a significant viscosity dependence, change with spacer composition (alkane versus terthiophene), and nature of the solvent (H(2)O versus D(2)O). Based on these findings and others, the conclusion is drawn that the charge-transfer rate constant at short distance is determined by polarization relaxation processes in the structure, rather than the electron tunneling probability or large-amplitude conformational rearrangement (gating). The transition in reaction mechanism with distance reflects a gradual transition between the tunneling and frictional mechanisms. This conclusion is consistent with data from a number of other sources as well.