Deterministic schedules for robust and reproducible non-uniform sampling in multidimensional NMR

We show that a simple, general, and easily reproducible method for generating non-uniform sampling (NUS) schedules preserves the benefits of random sampling, including inherently reduced sampling artifacts, while removing the pitfalls associated with choosing an arbitrary seed. Sampling schedules are generated from a discrete cumulative distribution function (CDF) that closely fits the continuous CDF of the desired probability density function. We compare random and deterministic sampling using a Gaussian probability density function applied to 2D HSQC spectra. Data are processed using the previously published method of Spectroscopy by Integration of Frequency and Time domain data (SIFT). NUS spectra from deterministic sampling schedules were found to be at least as good as those from random schedules at the SIFT critical sampling density, and significantly better at half that sampling density. The method can be applied to any probability density function and generalized to greater than two dimensions.     

Equation of state of a model methane clathrate cage

We investigate the behavior of a model methane clathrate cage under high hydrostatic pressures. The methane clathrate cage consists of 20 water molecules forming 12 pentagonal faces, with a methane molecule positioned at the cage center. The clathrate compound is located inside a fullerene-type arrangement of 180 He atoms to simulate an isotropic pressure. Different pressures are simulated by decreasing the radius of the He array. The minimal energy of the total system for each configuration is calculated by using density functional theory. The variation of the energy with the volume of the imprisoned clathrate cage leads to the proposal of a (cold) equation of state in the pressure range [0,60] GPa. The elastic parameters of the state equation are found in agreement with equivalent quantities measured on clathrates in their sI conformation. Special attention is given to the distribution of the confined atoms and the eventual symmetry lost from the clathrate cage with the pressure, as the clathrate cage constitutes a basic structural unit of the crystal. Finally, the strengths and limitations of the model are discussed.     

Druggable exosites of the human kino-pocketome

Journal of Computer-Aided Molecular Design - Small molecules binding at any of the multiple regulatory sites on the molecular surface of a protein kinase may stabilize or disrupt the corresponding...     

Overview of DWDM/ODC Project

This article introduces the main achievements resulting from the DWDM/ODC project. The five areas of research activity within the DWDM/ODC project cover some of the main issues of design and development of dense wavelength division multiplexing systems for transparent optical networks. These issues are: performance assessment with arbitrary optical filtering; performance of signaling formats; dispersion compensation strategies for directly and externally modulated systems in presence of nonlinear transmission-induced degradation; and the impact of noise and crosstalk in the extent of transparent optical networks. All five areas of research activity have contributed significantly to a better understanding of the limitations present in dense wavelength division multiplexing systems.     

Charge‐induced modulation of magnetic interactions in a [2 × 2] metal‐organic grid complex

We investigate the magnetic state of a recently synthesized [2 × 2]‐metal‐organic grid complex as a function of its redox state. Our analysis of a phenomenological model for the relevant molecular orbitals reveals that additional electrons on the ligands can couple their spins via the bridging metal sites. We find that at certain stages of the reduction of the complex cation, a maximal total spin ground state of the complex (S = 3/2) can be stabilized by the Nagaoka mechanism. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Comparison between the dissolution of whey protein gels and of synthetic polymers

The dissolution behavior of heat‐induced whey protein gels in alkali is compared with the literature on the dissolution of (1) uncrosslinked synthetic polymers with chemical reaction, (2) uncrosslinked polymers in a good solvent, and (3) crosslinked hydrogels. Diffusion of hydroxide and acid–base reactions, which are key processes in the dissolution of phenolic resins in alkali (Case 1), are found not to be very important with protein gels. The strong dependency of the dissolution rate on the free volume observed in protein gels is described by a large scaling factor, as predicted for Case 2 theory, indicating that the disentanglement of long chains before they are released is important. The cleavage of intermolecular crosslinks, which is important in Case 3, is also identified as a key dissolution step, where the complexity of protein chemistry comes into play. Synthetic polymer mechanisms are therefore able to elucidate several aspects of protein gel dissolution, but are not yet sufficient to explain all aspects of the process. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1007–1021, 2008     

Applications of “Dry” Processing in the Microelectronics Industry Using Carbon Dioxide

Condensed carbon dioxide (CO₂) has emerged as a leading enabler of advanced semiconductor manufacturing processes. By exploiting the physical properties of CO₂, some of the current challenges encountered in microelectronics processing related to shrinking feature sizes and materials compatibility have been addressed. Furthermore, the potential for reduction of chemicals used in processing is realized. Applications of CO₂ in microelectronics operations such as wafer cleaning, spin-coating, development, and stripping of photoresists, drying, low-k film preparation and repair, etching, and metal deposition are discussed.     

A Bridged High-Spin Complex Bis-[Ni(II)( rac-5,5,7,12,12,14-hexamethyl- 1,4,8,11-tetraazacyclotetradecane)]-2,5-pyridinedicarboxylate Diperchlorate Monohydrate

A bridged high-spin complex,bis-[Ni(II)(rac-5,5,7,l2,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)]-2,5-pyridinedicarboxylate diperchlorate monohydrate has been obtained by reaction of [Ni(II)(rac-5,5,7, 12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)](ClO₄)₂ and 2,5-pyridinedicarboxylic acid in aqueousalkaline (NH₄OH) medium. C₃₉H₇₇Cl₂N₉Ni₂O₁₃, chemical formula weight 1068.42, orthorhombic, P2₁2₁2₁, a = 11 .423(3) Å,b = 14.770(6) Å, c = 31.608(7) Å, = = =90.00°, V = 5333(3) ų, Z = 4, D_calc = 1.331 g cm^-3, _calc = 0.869 mm^-1, F(000) = 2272, T = 293(2), R = 0.0870 for 2686 observed reflections [I > 2(I)]. The complexincludes two folded [Ni(rac- Me₆[14]aneN₄)]²⁺ units havingopposite diastereomeric configuration. They are bridged through a dianion of2,5-pyridinedicarboxylic acid, with one Ni-atom coordinated to the O-atom ofthe 2-carboxylic group and the pyridine N-atom (forming a 5-membered chelatering), and with the second Ni-atom coordinated to both O-atoms of the 5-carboxylic group (forming a 4-membered chelate ring). Hydrogen bonding involving macrocyclic NH groups, both 2- and 5-carboxylic groups, perchlorate anions and water molecules gives rise to the formation of an infinite supramolecular network in the title compound's crystals.     

Chemically patterned flat stamps for microcontact printing

Locally oxidized patterns on flat poly(dimethylsiloxane) stamps for microcontact printing were used as a platform for the transfer of a hydrophilic fluorescent ink to a glass substrate. The contrast was found to be limited. These locally oxidized patterns were conversely used as barriers for the transfer of hydrophobic n-octadecanethiol. In this case a good contrast was obtained, but the pattern was found to be susceptible to defects (cracks) in the barrier layer. Local stamp surface oxidation and subsequent modification with 1H,1H,2H,2H-perfluorodecyltrichlorosilane, for use as a barrier in the transfer of n-octadecanethiol, 16-mercaptohexadecanoic acid, and octanethiol, resulted in remarkably good contrast and stable patterns. The improved ink transfer control is ascribed to the reduction of undesired surface spreading and a superior mechanical stability of the stamp pattern. This new approach substantially expands the applicability of microcontact printing and provides a tool for the faithful reproduction of even extremely low filling ratio patterns.