A Markov model for relaxation and exchange in NMR spectroscopy

A two-state Markov noise process for lattice fluctuations and chemical exchange dynamics is used to derive a stochastic Liouville equation describing the evolution of the spin-density operator in nuclear magnetic resonance spectroscopy. Relaxation through lattice fluctuations and chemical exchange processes is incorporated into the theory at the same fundamental level, and the results are valid for all time scales provided that lattice fluctuations are much faster than chemical exchange kinetics. Time-scale separation emerges as an essential feature from the lowest-order perturbation expansion of the average resolvent in the Laplace domain.     

Structural properties of ultra-small thorium and uranium dioxide nanoparticles embedded in a covalent organic framework

We report the structural properties of ultra-small ThO₂ and UO₂ nanoparticles (NPs), which were synthesized without strong binding surface ligands by employing a covalent organic framework (COF-5) as an inert template. The resultant NPs were used to observe how structural properties are affected by decreasing grain size within bulk actinide oxides, which has implications for understanding the behavior of nuclear fuel materials. Through a comprehensive characterization strategy, we gain insight regarding how structure at the NP surface differs from the interior. Characterization using electron microscopy and small-angle X-ray scattering indicates that growth of the ThO₂ and UO₂ NPs was confined by the pores of the COF template, resulting in sub-3 nm particles. X-ray absorption fine structure spectroscopy results indicate that the NPs are best described as ThO₂ and UO₂ materials with unpassivated surfaces. The surface layers of these particles compensate for high surface energy by exhibiting a broader distribution of Th–O and U–O bond distances despite retaining average bond lengths that are characteristic of bulk ThO₂ and UO₂. The combined synthesis and physical characterization efforts provide a detailed picture of actinide oxide structure at the nanoscale, which remains highly underexplored compared to transition metal counterparts.

ThO₂ and UO₂ nanoparticles synthesized using a COF-5 template exhibit unpassivated surfaces and provide insight into nanoscale properties of actinides.     

In Ssarch of new anti-bacterial target genes: a comparative/structural genomics approach

We outline a joint academic/industrial (CNRS/AVENTIS) functional genomics project aiming at the discovery of new anti-bacterial gene targets. Starting from all publicly available bacterial genomes, a subset of the most evolutionary conserved protein-coding genes has been identified. We retained genes with clear homolog in E. coli and at least one gram-positive bacterium among B.subtilis, M. tuberculosis, L. lactis or S. pyogenes. This subset was further reduced to genes encoding non-membrane proteins of unknown or hypothetical functions. The 221 E. coli Open Reading Frames (ORFs) identified through this comprehensive bioinformatic analysis are now submitted to a systematic 3-D structure determination protocol including cloning, protein expression and purification, crystallisation and X-ray diffraction. Our strategy was designed to focus on promising wide-spectrum targets as well as original biochemical pathways. Bioinformatics is used throughout all phases of project, including the initial large-scale comparative genomics analyses, the purification/expression and crystallisation stages for the detection of helpful sequence-specific features (e.g. cofactor binding motifs, non-structured N- or C- term extremities, etc ), and finally for the interpretation of the structures in conjunction with multiple sequence alignments for the identification of key residues, interaction areas on molecular surfaces, and overall function predictions.     

Approximate solutions of the Bloch-McConnell equations for two-site chemical exchange.

Approximate formulas for the transverse-relaxation rate constant and resonance frequency have been derived for nuclear spins subject to two-site chemical exchange. The new results are more accurate than previous approximations when chemical exchange does not approach the fast-exchange limit or when site populations are not highly asymmetric. Results are derived from an effective average evolution operator that contains contributions from both exact eigenvalues of the Bloch-McConnell equations. These expressions are useful for interpretation of chemical exchange processes in NMR spectroscopy.     

Rational Design of a Uranyl Metal–Organic Framework for the Capture and Colorimetric Detection of Organic Dyes

A new uranyl containing metal–organic framework, RPL-1 : [(UO₂)₂(C₂₈H₁₈O₈)] ^. H₂O (RPL for Radiochemical Processing Laboratory), was prepared, structurally characterized, and the solid-state photoluminescence properties explored. Single crystal X-ray diffraction data reveals the structure of RPL - 1 consists of two crystallographically unique three dimensional, interpenetrating nets with a 4,3-connected tbo topology. Each net contains large pores with an average width of 22.8 Å and is formed from monomeric, hexagonal bipyramidal uranyl nodes that are linked via 1,2,4,5-tetrakis(4-carboxyphenyl)benzene (TCPB) ligands. The thermal and photophysical properties of RPL-1 were investigated using thermogravimetric analysis and absorbance, fluorescence, and lifetime spectroscopies. The material displays excellent thermal stability and temperature dependent uranyl and TCPB luminescence. The framework is stable in aqueous media and due to the large void space (constituting 76 % of the unit cell by volume) can sequester organic dyes, the uptake of which induces a visible change to the color of the material.     

A non-well-posed problem in convex optimal control

This article is devoted to the study of a non-well-set problem of optimal control for a system governed by an elliptic partial differential equation. By generalizing some classical methods in convex optimization, we state and prove the system of necessary and sufficient conditions for such a problem.     

Detection of the electron spin resonance of two-dimensional electrons at large wave vectors

We have investigated the electron spin resonance at nonzero wave vector in GaAs single quantum wells by combining the virtues of high frequency surface acoustic wave generation to produce excitations with large wave numbers with a sensitive optical scheme to detect resonant absorption. The observed large deviations from the single particle Zeeman energy are attributed to the exchange interaction. The enhancement of the electronic g* factor is, however, substantially smaller compared with theoretical predictions for spin waves when adopting a bare Coulomb interaction potential.     

Networks of coupled rotators: relationship between structures and internal dynamics in metal-binding proteins. Applications to apo- and holo-calbindin

This article presents an analysis of the internal dynamics of the Ca2+-binding protein calbindin, based on the Networks of Coupled Rotators (NCRs) introduced recently. Several fundamental and practical issues raised by this approach are investigated. The roles of various parameters of the model are examined. The NCR model is shown to account for the modifications of the internal dynamics upon Ca2+ binding by calbindin. Two alternative strategies to estimate local internal effective correlation times of the protein are proposed, which offer good agreement between predictions and experiment.     

Microbial evasion of the immune system: structural modifications of enterobactin impair siderocalin recognition

The mammalian protein siderocalin binds and inactivates the ferric complex of the bacterial siderophore enterobactin with a Kd value similar to that of the bacterial receptor FepA. However, microorganisms can evade this immune response by structural modifications of the siderophore. The binding of siderophores by siderocalin relies in part on electrostatic interactions and does not depend greatly on what metal is in the complex. It is also sterically limited by the rigid conformation of the protein calyx; methylation of the three catecholate rings of enterobactin hinders siderocalin recognition. The siderocalin binding has been probed for a series of enterobactin analogues in order to investigate in detail the specificity of siderocalin recognition.     

Evaluation of image quality of DWIBS versus DWI sequences in thoracic MRI at 3 T

Purpose

To compare diffusion weighted imaging with background suppression (DWIBS) sequence with classic spectral diffusion sequence (DWI) with and without respiratory gating in mediastinal lymph node analysis at 3 T.

Materials and methods

26 patients scheduled for mediastinoscopic lymph node analysis, prospectively undergone a thoracic 3 T MRI with DWIBS (FatSat = STIR; TR/TE = 6674.1/44.7 ms; IR = 260 ms) and DWI sequences (FatSat = SPIR; TR/TE = 1291/59.6 ms) (b = 0-400-800 s/mm2) with and without (free breathing) respiratory gating.Images at b = 800 were analyzed by two radiologists. They performed qualitative analysis of fat-sat homogeneity and motion artifacts, rated from 0 to 4, and quantitative evaluation by studying signal to background (STB) of lymph nodes.

Results

Quality of fat suppression was significantly higher for DWIBS than for DWI both for free-breathing (score 3.48 ± 0.65 vs. 1.76 ± 0.96, p < 0.0001) and respiratory-gated scans (3.17 ± 0.77 vs. 1.72 ± 0.73, p = 0.0001). Similarly, artifacts were reduced with DWIBS (3.16 ± 0.47 vs. 1.76 ± 0.59, p < 0.0001; 3.0 ± 0.73 vs. 2.04 ± 0.53, p = 0.0001). Quantitative analysis showed higher STB with DWIBS (3.26 ± 1.83 vs. 0.98 ± 0.44, p < 0.0001; 3.56 ±, 2.09 vs. 0.92 ± 0.59, p < 0.0001). Gating did not improve image quality and STB on DWIBS (p > 0.05).

Conclusion

In thoracic MRI, ungated DWIBS sequence improves fat-sat homogeneity, reduces motion artifacts and increases STB of lymph nodes. Respiratory gating does not improve DWIBS image quality.