Bioelectronics and biometallocatalysis for production of fuels and chemicals by photosynthetic water splitting

Applied Biochemistry and Biotechnology - By inserting metallocatalysts (such as platinum, osmium, or ruthenium) at the reducing site of photosystem I (PSI), electrons that emerge from PSI can be...     

Measurement of storage time, estimation of ion number and study of absorption line profile in a Paul trap

Europium (Eu⁺) ions were confined in a Paul trap and detected by non-destructive method. Storage time of Eu⁺ ions achieved in vacuum was improved by orders of magnitude employing buffer gas cooling. The experimentally detected signal was fitted to the ion response signal and the total number of ions trapped was estimated. It is found that the peak signal amplitude as well as the product of FWHM and the peak signal amplitude is proportional to the total number of trapped ions. The trapped ion secular frequency was swept at different rates and its effect on the absorption line profile was studied both experimentally and theoretically.     

The semiclassical regime of the chaotic quantum-classical transition

An analysis of the semiclassical regime of the quantum-classical transition is given for open, bounded, one-dimensional chaotic dynamical systems. Environmental fluctuations-characteristic of all realistic dynamical systems-suppress the development of a fine structure in classical phase space and damp nonlocal contributions to the semiclassical Wigner function, which would otherwise invalidate the approximation. This dual regularization of the singular nature of the semiclassical limit is demonstrated by a numerical investigation of the chaotic Duffing oscillator.     

The dielectric response of interfacial water—from the ordered structures to the single hydrated shell

Water is the universal solvent in nature. Does this imply, however, that its interaction with its environment is also a universal feature? While this question maybe too fundamental to be answered by one method only, we present evidence that the broadening of the dielectric spectra of water presents universal features of dipolar interactions with different types of matrixes. If in aqueous solutions the starting point of water’s state can be considered as bulk, with only partial interactions with the solute, then the state of water adsorbed in heterogeneous materials is determined by various hydration centers of the inhomogeneous material (the matrix) and it is significantly different from the bulk. In both cases, the dielectric spectrum of water is symmetrical and can be described by the Cole–Cole (CC) function. The phenomenological model that describes a physical mechanism of the dipole–matrix interaction in complex systems underlying the CC behavior has been applied to water adsorbed in porous glasses. It was then extended to analyses of the dynamic and structural behavior of water in nonionic and ionic aqueous solutions. The same model is then used to analyze the CC relaxation processes observed in clays, aqueous solutions of nucleotides, and amino acids.     

Sequestering of Eu(III) by a GAAA RNA tetraloop

The site-specific binding of metal ions maintains an important role in the structure, thermal stability, and function of folded RNA structures. RNA tetraloops of the "GNRA" family (where N = any base and R = any purine), which owe their unusual stability to base stacking and an extensive hydrogen bonding network, have been observed to bind metal ions having different chemical and geometric properties. We have used laser-induced lanthanide luminescence and isothermal titration calorimetry (ITC) to examine the metal-binding properties of an RNA stem loop of the GNRA family. Previous research has shown that a single Eu(III) ion binds the stem loop fragment in a highly dehydrated site with a K(d) of approximately 12 microM. Curve-fitting analysis of the broad luminescence excitation spectrum of Eu(III) upon complexation with the tetraloop fragment indicates the possibility of two microenvironments that do not differ in hydration number. Binding of Eu(III) to the loop was accompanied by positive enthalpic changes, consistent with energetic cost of removal of water molecules and suggesting that the binding is entropically driven. By comparison, binding of Mg(II) or Mn(II) to the RNA loop, or Eu(III) to the DNA analogue of the loop, was associated with exothermic changes, consistent with predominantly outer-sphere coordination. These results suggest specific binding, most probably involving ligands on the 5' side of the loop.     

Field-portable wide-field microscopy of dense samples using multi-height pixel super-resolution based lensfree imaging

We report a field-portable lensfree microscope that can image dense and connected specimens with sub-micron resolution over a large field-of-view of ~30 mm(2) (i.e., ~6.4 mm × ~4.6 mm) using pixel super-resolution and iterative phase recovery techniques. Weighing ~122 grams with dimensions of 4 cm × 4 cm × 15 cm, this microscope records lensfree in-line holograms of specimens onto an opto-electronic sensor-array using partially coherent illumination. To reconstruct the phase and amplitude images of dense samples (with >0.3 billion pixels in each image, i.e., >0.6 billion pixels total), we employ a multi-height imaging approach, where by using a mechanical interface the sensor-to-sample distance is dynamically changed by random discrete steps of e.g., ~10 to 80 μm. By digitally propagating back and forth between these multi-height super-resolved holograms (corresponding to typically 2-5 planes), phase and amplitude images of dense samples can be recovered without the need for any spatial masks or filtering. We demonstrate the performance of this field-portable multi-height lensfree microscope by imaging Papanicolaou smears (also known as Pap tests). Our results reveal the promising potential of this multi-height lensfree computational microscopy platform for e.g., pathology needs in resource limited settings.     

Broadband NMR Relaxometry as a Powerful Technique to Study Molecular Dynamics of Ionic Liquids

Fast field cycling nuclear magnetic resonance (FFC NMR) relaxometry technique has been demonstrated to be a useful analytical tool to investigate molecular dynamics in very diverse systems during the last decades. Of particular importance has been its application in studying ionic liquids, upon which this review article is based. Some of the research carried out on ionic liquids during the last ten years using this technique is highlighted in this article with the aim of promoting the favorable features of FFC NMR applied toward understanding dynamics of complex systems.     

Chemical interaction of flue gas components with the growth ofcyanidium caldarium

Applied Biochemistry and Biotechnology - Normal photosynthesis byCyanidium results in O2 evolution, suggesting that the uptake and subsequent reduction of CO2 also occur. This process, therefore,...     

Optimal preconditioners of a given sparsity pattern

We consider the problem of finding the symmetric positive definite preconditionerM of a given form- e.g., having nonzero elements only in specified positions — which minimizes the ratio of the largest to smallest eigenvalue ofM ^–1 A, for a given symmetric positive definitive matrixA. We show how this problem can be expressed as one of minimizing a convex function and how an optimization code can be used to solve the problem numerically. Results are presented showing optimal preconditioners of various sparsity patterns and comparing these to preconditioners that have been proposed in the literature. Several conjectures are made, based on results from the optimization code.This work was supported by the Advanced Research Projects Agency of the Department of Defense under contract F49620-87-C-0065 and by the Applied Mathematical Sciences Program of the U.S. Department of Energy under contract DE-AC02-76ER03077.