A density functional theory study on the water aggregation behaviour of fatty acid-based anionic surface active ionic liquids

Structural Chemistry - The hydrogen bond interactions between methyl-imidazolium cation (MIM+) and fatty acid anions (CmHnCOO–, where m?=?1–6; n-3–13) of ionic liquids...     

High slew-rate CMOS operational amplifier

A 0.8 /spl mu/m CMOS operational amplifier configuration with a slew rate in excess of 2 V/ns and a unity gain bandwidth of 55 MHz with a load capacitance of 15 pF is proposed. This employs a dynamic technique that turns on a large current source when the rate of change of input is larger than a pre-decided value.     

Control of polishing of diamond films using microactuation and an atmospheric pressure plasma

In this work, the diamond deposited by hot filament chemical vapor deposition (CVD) is polished using an atmospheric pressure plasma. In order to position the film relative to the plasma, a microactuator system is designed using a stack of domed piezoelectric actuators. A dynamic model based on the physical system is developed and the model parameters are measured experimentally. A system based on laser triangulation is used to measure the position of the diamond film relative to the plasma. Control techniques are used to reduce the oscillations during actuation and to eliminate the steady state positioning error. With the application of feedback control, the overshoot is reduced to 2% and the settling time is reduced to 0.3 s. A preliminary set of experiments is performed to relate process parameters to the final surface roughness of the diamond film. The parameters studied include the film's time of exposure to the plasma, the height of the film relative to the plasma, and the distance from the film to the center of the plasma. It is found that the optimum exposure time is 15 min and the reduction of surface roughness is greatest when the distance between the film and the plasma is at a minimum. The best results are obtained when the top of the film is even in elevation with the tip of the top electrode. The diamond film is translated laterally along the plasma. When feedback control is not used, there is no change in the surface roughness. With feedback control implemented, the surface roughness of the diamond film is reduced by 33%.     

Non-protein amino acids in peptide design

An overview of the use of non-protein amino acids in the design of conformationally well-defined peptides, based on work from the author’s laboratory, is discussed. The crystal structures of several designed oligopeptides illustrate the useα-aminoisobutyric acid (Aib) in the construction of helices, D-amino acids in the design of helix termination segments and^DPro-Xxx segments for nucleating ofβ-hairpin structures.β- andγ-amino acid residues have been used to expand the range of designed polypeptide structures. Dedicated to Professor C N R Rao on his 70th birthday     

Comprehensive performance modeling and analysis of multicasting in optical networks

Multicasting is becoming increasingly important in today's networks. In optical networks, optical splitters facilitate the multicasting of optical signals. By eliminating the transmission of redundant traffic over certain links, multicasting can improve network performance. However, in a wavelength-division multiplexed (WDM) optical network, the lack of wavelength conversion necessitates the establishment of a single multicast circuit (light-tree) on a single wavelength. On the other hand, establishing several unicast connections (lightpaths) to satisfy a multicast request, while requiring more capacity, is less constrained in terms of wavelength assignment. The objective of the paper is to evaluate the tradeoff between capacity and wavelength continuity in the context of optical multicasting. To this end, we develop accurate analytical models with moderate complexity for computing the blocking probability of multicast requests realized using light-trees, lightpaths, and combinations of light-trees and lightpaths. Numerical results indicate that a suitable combination of light-trees and lightpaths performs best when no wavelength conversion is present.     

Aromatic-aromatic interactions in crystal structures of helical peptide scaffolds containing projecting phenylalanine residues

Aromatic-aromatic interactions between phenylalanine side chains in peptides have been probed by the structure determination in crystals of three peptides: Boc-Val-Ala-Phe-Aib-Val-Ala-Phe-Aib-OMe, I; Boc-Val-Ala-Phe-Aib-Val-Ala-Phe-Aib-Val-Ala-Phe-Aib-OMe, II; Boc-Aib-Ala-Phe-Aib-Phe-Ala-Val-Aib-OMe, III. X-ray diffraction studies reveal that all three peptides adopt helical conformations in the solid state with the Phe side chains projecting outward. Interhelix association in the crystals is promoted by Phe-Phe interactions. A total of 15 unique aromatic pairs have been characterized in the three independent crystal structures. In peptides I and II, the aromatic side chains lie on the same face of the helix at i/i + 4 positions resulting in both intrahelix and interhelix aromatic interactions. In peptide III, the Phe side chains are placed on the opposite faces of the helix, resulting in exclusive intermolecular aromatic interactions. The distances between the centroids of aromatic pair ranges from 5.11 to 6.86 A, while the distance of closest approach of ring carbon atoms ranges from 3.27 to 4.59 A. Examples of T-shaped and parallel-displaced arrangements of aromatic pairs are observed, in addition to several examples of inclined arrangements. The results support the view that the interaction potential for a pair of aromatic rings is relatively broad and rugged with several minima of similar energies, separated by small activation barriers.     

Rhodopsin reconstituted into a planar-supported lipid bilayer retains photoactivity after cross-linking polymerization of lipid monomers

Transmembrane proteins (TMPs), particularly ion channels and receptors, play key roles in transport and signal transduction. Many of these proteins are pharmacologically important and therefore targets for drug discovery. TMPs can be reconstituted in planar-supported lipid bilayers (PSLBs), which has led to development of TMP-based biosensors and biochips. However, PSLBs composed of natural lipids lack the high stability desired for many technological applications. One strategy is to use synthetic lipid monomers that can be polymerized to form robust bilayers. A key question is how lipid polymerization affects TMP structure and activity. In this study, we have examined the effects of UV polymerization of bis-Sorbylphosphatidylcholine (bis-SorbPC) on the photoactivation of reconstituted bovine rhodopsin (Rho), a model G-protein-coupled receptor. Plasmon-waveguide resonance spectroscopy (PWR) was used to compare the degree of Rho incorporation and activation in fluid and poly(lipid) PSLBs. The results show that reconstitution of Rho into a supported lipid bilayer composed only of bis-SorbPC, followed by photoinduced lipid cross-linking, does not measurably diminish protein function.     

A revised structure for hermonionic acid

Hermonionic acid and its decarboxylated product have been isolated from $\text{Garcinia}$$\text{quaesita}$. ¹³C NMR spectral and chemical evidence indicate that hermonionic acid is 2-0-[2-(3-methylbut-2-enyl)-3-methoxy- 4-hydroxy-5-(3,7-dimethylocta-2,6-dienyl]-4-methoxy-5-(3-methylbut-2-enyl-6-hydroxybenzoic acid. The previously assigned dienone structure for this acid is incorrect.     

CO(2)-expanded solvents: unique and versatile media for performing homogeneous catalytic oxidations

The work summarized here demonstrates a new concept for exploiting dense phase CO(2), media considered to be "green" solvents, for homogeneous catalytic oxidation reactions. According to this concept, the conventional organic solvent medium used in catalytic chemical reactions is replaced substantially (up to 80 vol %) by CO(2), at moderate pressures (tens of bars), to create a continuum of CO(2)-expanded solvent media. A particular benefit is found for oxidation catalysis; the presence of CO(2) in the mixed medium increases the O(2) solubility by ca. 100 times compared to that in the neat organic solvent while the retained organic solvent serves an essential role by solubilizing the transition metal catalyst. We show that CO(2)-expanded solvents provide optimal properties for maximizing oxidation rates that are typically 1-2 orders of magnitude greater than those obtained with either the neat organic solvent or supercritical CO(2) as the reaction medium. These advantages are demonstrated with examples of homogeneous oxidations of a substituted phenol and of cyclohexene by molecular O(2) using transition metal catalysts, cobalt Schiff-base and iron porphyrin complexes, respectively, in CO(2)-expanded CH(3)CN.