Structures of uranyl peroxide hydrates: a first-principles study of studtite and metastudtite

The structures of the only known minerals containing peroxide, namely studtite [(UO(2))O(2)(H(2)O)(4)] and metastudtite [(UO(2))O(2)(H(2)O)(2)], have been investigated using density functional theory. The structure of metastudtite crystallizing in the orthorhombic space group Pnma (Z = 4) is reported for the first time at the atomic level and the computed lattice parameters, a = 8.45, b = 8.72, c = 6.75 ?, demonstrate that the unit cell of metastudtite is larger than previously reported dimensions (Z = 2) derived from experimental X-ray powder diffraction data.     

Chemical details on nucleolipid supramolecular architecture: molecular modeling and physicochemical studies

Nucleolipids are currently under investigation as vectors for oligonucleotides (ON) delivery thanks to their supramolecular organization properties and their ability to develop specific interactions (i.e., stacking and potential Watson and Crick hydrogen bonds) for lipoplexes formation. To investigate the factors that govern the interaction events at a molecular level and optimize nucleolipid chemical structures, physicochemical experiments (tensiometry, AFM, BAM, and ellipsometry) combined with molecular dynamics simulation were performed on a series of zwitterionic nucleolipids (PUPC, DPUPC, PAPC) featuring a phosphocholine chain (PC). After construction and initial equilibration, simulations of pure nucleolipid bilayers were run for 100 ns at constant temperature and pressure, and their properties were compared to experimental data and to natural dipalmitoylphosphatidylcholine (DPPC) bilayers. Nucleolipid-based membranes are significantly more ordered and compact than DPPC bilayers mainly due to the presence of many intermolecular interactions between nucleoside polar heads. The hydrophilic phosphocholine moieties connected to the 5' hydroxyls are located above the bilayers, penalizing nucleic bases accessibility for further interactions with ON. Hence, a neutral nucleolipid (PUOH) without hydrophilic phosphocholine was inserted in the membranes. Simulations and experimental analysis of nucleolipid membranes in interaction with a single strand RNA structure indicate that PUOH interacts with ON in the subphase. This study demonstrates that molecular modeling can be used to determine the interactions between oligonucleotide and nucleolipids.     

Improving the Selectivity of the Phosphoric Acid β-Elimination on a Biotinylated Phosphopeptide

This study aims at improving the MALDI-TOF detection of a phosphorylated peptide containing a cysteine residue by ??-elimination of H₃PO₄ hardly enriched by classical methods. The experimental conditions were optimized on this phosphopeptide (biot-pAdd) and its nonphosphorylated counterpart (biot-Add). The major side-reactions were H₂S elimination on the cysteine residues and H₂O elimination on the non phosphorylated serine residue of biot-Add. The former dilutes the MALDI-TOF signal for the desired species. The latter gives a product similar to what is obtained by H₃PO₄ elimination and should prompt to caution when working with a mixture between phosphorylated and non phosphorylated peptides. Modifications on the solvent, the reaction temperature and time, the nature, and concentration of the base were made. Major improvement of the selectivity of the reaction was observed in 30?% ACN, at room temperature for 4?h. However, these optimizations are specific to these sequences and should be performed anew for different peptides. The selectivity of the reaction towards H₃PO₄ elimination is improved, but the persistence of side-reactions renders a previous sample fractionation necessary. In these optimized conditions, the ionization enhancement is 3-fold and the detection limits for biot-pAdd are similar to biot-Add (100?fmol).     

A Rigorous Proof of the Landau-Peierls Formula and much more

We present a rigorous mathematical treatment of the zero-field orbital magnetic susceptibility of a non-interacting Bloch electron gas, at fixed temperature and density, for both metals and semiconductors/insulators. In particular, we obtain the Landau-Peierls formula in the low temperature and density limit as conjectured by Kjeldaas and Kohn (Phys Rev 105:806–813, 1957).     

Flow-induced polymer degradation probed by a high throughput microfluidic set-up

A complex fluid submitted to strong flows can endure irreversible changes in its structure. This is the case for long chain polymer additives that are commonly used as viscosity enhancers in industry, notably for oil recovery. These polymers break in solution when submitted to high deformation rates, eventually causing a serious viscosity loss. This problem of practical importance is though difficult to handle from a fundamental point of view given its complexity. We introduce here a new tool, based on microfluidic technology, for the screening of the degradation of solutions in the model situation of the flow through a constriction. We integrate two functions in a single set-up, a micro-fabricated constriction and an on-chip viscosimeter. This tool enables us to probe rapidly the viscosity loss imparted by flowing through the constriction at a given flow rate. Thanks to microfluidics, the sample preparation and measurement time are significantly lower than those implied by classical measurement protocols (reduction by up to two orders of magnitude). In addition, confinement provides control of the flow in terms of inertia. To illustrate the potential of this approach in a screening perspective, we use this tool to study the degradation of a series of semi-dilute aqueous solutions of PEO of varying molecular weights and concentrations. For each solution we identify a threshold flow rate for polymer degradation. The corresponding critical deformation rate decreases with molecular weight and concentration, as expected (the mass dependence is in line with previous reports and theories for dilute solutions). In addition we characterize the viscosity loss for larger deformation rates and find that, despite the polydispersity of our solutions, the observations for the various solutions can be roughly recast on a master curve by renormalization of the imposed deformation rates according to a law $M_w^{?1.7\pm 03}{c}^{?0.7\pm 03}$.     

A Sobolev mapping property of the Bergman kernel

We prove that if D is a pseudoconvex domain with Lipschitz boundary having an exhaustion function such that is plurisubharmonic, then the Bergman projection maps the Sobolev space boundedly to itself for any . Received March 10, 1999 / Published online May 8, 2000     

The Euclidean Steiner tree problem in Rn: A mathematical programming formulation

A nonconvex mixed-integer programming formulation for the Euclidean Steiner Tree Problem (ESTP) in Rⁿ is presented. After obtaining separability between integer and continuous variables in the objective function, a Lagrange dual program is proposed. To solve this dual problem (and obtaining a lower bound for ESTP) we use subgradient techniques. In order to evaluate a subgradient at each iteration we have to solve three optimization problems, two in polynomial time, and one is a special convex nondifferentiable programming problem. This revised version was published online in June 2006 with corrections to the Cover Date.     

Fast algorithm for solving the Hankel/Toeplitz Structured Total Least Squares problem

The Structured Total Least Squares (STLS) problem is a natural extension of the Total Least Squares (TLS) problem when constraints on the matrix structure need to be imposed. Similar to the ordinary TLS approach, the STLS approach can be used to determine the parameter vector of a linear model, given some noisy measurements. In many signal processing applications, the imposition of this matrix structure constraint is necessary for obtaining Maximum Likelihood (ML) estimates of the parameter vector. In this paper we consider the Toeplitz (Hankel) STLS problem (i.e., an STLS problem in which the Toeplitz (Hankel) structure needs to be preserved). A fast implementation of an algorithm for solving this frequently occurring STLS problem is proposed. The increased efficiency is obtained by exploiting the low displacement rank of the involved matrices and the sparsity of the associated generators. The fast implementation is compared to two other implementations of algorithms for solving the Toeplitz (Hankel) STLS problem. The comparison is carried out on a recently proposed speech compression scheme. The numerical results confirm the high efficiency of the newly proposed fast implementation: the straightforward implementations have a complexity of O((m+n)³) and O(m³) whereas the proposed implementation has a complexity of O(mn+n²). This revised version was published online in June 2006 with corrections to the Cover Date.