Whole cell matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and in situ structure analysis of streptocidins, a family of tyrocidine-like cyclic peptides

Streptocidins, a family of tyrocidine-like cyclic decapeptides, are an ideal demonstration object for the detection and in situ structure analysis of natural compounds directly in microbial cells using whole cell matrix-assisted laser desorption/ionization time-of-flight-mass spectrometry (MALDI-TOFMS), an emerging technique that can be used for rapid sensitive metabolic profiling of microorganisms. Five main members of the streptocidin family (A-E) were detected in Brevibacillus cells picked from agar plates and identified by in situ structure analysis with post-source decay MALDI-TOFMS. This efficient modern method allows the precise detection of metabolites within minutes without the need to isolate and purify the target compounds. The generated mass spectra are of similar quality to those obtained for the purified peptides. In addition, surface extracts were prepared by treating Brevibacillus cells with 70% acetonitrile in the presence of 0.1% trifluoroacetic acid and fractionated by high-resolution reversed-phase high-performance liquid chromatography (HPLC). In this way ten minor streptocidins were detected demonstrating the full biosynthetic variety of streptocidin production on the cellular level. The streptocidins differ from the well-known tyrocidines essentially in position 3 of the decapeptide chain by replacement of the aromatic amino acid (F/W) found in tyrocidines by L-leucine or L-valine.     

The geometry of rational parameterized representations

We study the projective space of univariate rational parameterized equations of degree d or less in real projective space The parameterized equations of degree less than d form a special algebraic variety We investigate the subspaces on and their relation to rational curves in give a geometric characterization of the automorphism group of and outline applications of the theory to projective kinematics.     

Isolation and total synthesis of (E)-6, 10-dimethyl-9-methylidene-undec-5-en-2-one,a constituent of Costus root oil

(E)-6, 10-Dimethyl-9-methylidene-undec-5-en-2-one ( 1 ) has been isolated from Costus root oil. A total synthesis of this compound is reported.     

Interferons

Interferons are proteins which bring about a nonspecific and nonimmunological defence reaction against virus infections in vertebrates. Interferon formation is induced in vivo and in vitro by viruses and other agents, e.g. endotoxins, nucleic acids, synthetic anionic copolymers, and phytohemagglutinins. All attempts to produce pure interferons have so far been unsuccessful. Interferons can only exert an antiviral action when the cellular RNA and protein synthesis is intact.     

Hydrated Cs+-exchanged MFI zeolites: location and population of Cs+ cations and water molecules in hydrated Cs6.6MFI from in and ex situ powder X-ray diffraction data as a function of temperature and other experimental conditions

Extending our previous investigation of dehydrated, Cs-exchanged MFI zeolites (J. Phys. Chem. B 2006, 110, 97-106) to hydrated analogues, we have determined the crystal structures of members of the Cs(6.6)H(0.3)MFI.xH(2)O series, for 0 < x < 28, from synchrotron-radiation powder diffraction data. In the fully hydrated phase, three independent Cs(+) cations and six water molecules are identified in difference Fourier maps. The populations of the cations amount to 2.79/3.40/0.41 Cs/unit cell (uc) for the Cs1/Cs2/Cs3 sites, respectively, and those of the water molecules to 4/4/4/4/8/4 H(2)O/uc for the Ow1/Ow2/Ow3/Ow4/Ow5/Ow6 sites, respectively. Close to water saturation, the Cs3 and Ow6 sites are near each other (approximately 1.44 A) and are not occupied simultaneously. At saturation, Cs cations and water molecules form three interconnected Cs(H(2)O)(n) clusters and one (H(2)O)(4) cluster in the MFI channel system: Cs2(H(2)O)(5) centered at x/y/z approximately -0.018/0.146/0.546 (midway between the intersection and the straight channels), Cs1(H(2)O)(4) centered at approximately 0.056/0.240/0.889 (the zigzag channel openings), Cs3(H(2)O)(2) centered at approximately 0.228/0.25/0.899 (in the zigzag channel), and the (H(2)O)(4) cluster (in the zigzag channel) bonded to Cs1 and Ow1. (H(2)O)(4) and Cs3(H(2)O)(2) exclude each other. The Cs2(H(2)O)(5) clusters are connected through weak Ow5...Ow5' hydrogen bonds (2.88 A) and form polymeric chains in the straight channel direction (010). During progressive hydration this Cs2 cation enlarges its hydration shell, stepwise, from Cs2(H(2)O)(2) to Cs2(H(2)O)(3), to Cs2(H(2)O)(4), and finally to a Cs2(H(2)O)(5) cluster. During the dehydration process, these extraframework species migrate, and it is shown that for varying total H(2)O/uc loadings the individual populations of the Cs(+) cations and H(2)O molecules strongly depend on experimental and measurement (in situ vs ex situ) conditions. The shapes of the channels change also; except for T > 150 degrees C, in all the Cs(6.6)H(0.3)MFI.xH(2)O phases, the straight channel D10R (double 10-ring) pore openings (1.16 < epsilon < 1.23) become strongly elliptical. The framework structure of all the investigated phases conforms to orthorhombic Pnma space group symmetry. Hydration and dehydration in Cs(6.6)MFI are fully reversible processes. From a knowledge of the Cs(+) locations, we are able to estimate, by computer simulations, the positions of H(2)O molecules in Cs(6.6)H(0.3)MFI.28H(2)O. The maximum theoretically possible water loading in an hypothetical and idealized cationless [Cs(6.6)H(0.3)]MFI structure amounts to 48 H(2)O/uc (nine independent water species), which is in fair agreement with existing high-pressure data (47 H(2)O/uc). This value is to be compared with the water saturation capacity obtained in a structural refinement of sealed-tube diffraction data of a proton-exchanged H(6.9)MFI.38H(2)O (seven independent water molecules). In the crystal structure of this H-ZSM-5 phase, the straight channel openings are almost circular (epsilon = 1.08). From this we conclude that the main factor responsible for the flexibility of the MFI framework is the presence of the Cs(H(2)O)(n)() clusters residing in, or close to, the straight channel double 10-rings.     

Supermolecular structure and orientation of blown cellulosic films

N-Methylmorpholine-N-oxide (NMMO) technology provides new possibilities for shaping fibers and films from cellulose. We discuss a blow-extrusion technique can be applied to a cellulose-amine oxide dope, yielding blown cellulosie films. Process parameters, such as the draw down ratio and the blow ratio, can be used to control the mechanical film properties in both the machine and transverse directions. In this way, a wide range of properties is covered, and a completely balanced film can be manufactured. The film thickness can be made as small as 5 μm, and the membrane properties can be varied by the conditions of precipitation. The blown cellulosic films exhibit a partially crystalline supermolecular structure and, depending on the coagulation conditions, a symmetrical or asymmetrical homogeneous morphology and pore structure. Generally, a uniplanar orientation type was found, the chains being parallel to the film surface. Around the surface normal, the chain orientation can be varied from nearly random to strongly uniaxial, in this way determining the mechanical properties in the machine and transverse directions. As compared with the conventional viscose processing route of cellophane, the blown film's NMMO processing route is less complicated and friendlier to the environment. Blown films can be made much thinner, and the mechanical properties are superior to viscose films. Possible application fields of blown cellulose films are food casings, particularly small sausage casings, packaging, and membranes.     

Bonds and Options in Exponentially Affine Bond Models

Abstract

In this article we apply the Flesaker–Hughston approach to invert the yield curve and to price various options by letting the randomness in the economy be driven by a process closely related to the short rate, called the abstract short rate. This process is a pure deterministic translation of the short rate itself, and we use the deterministic shift to calibrate the models to the initial yield curve. We show that we can solve for the shift needed in closed form by transforming the problem to a new probability measure. Furthermore, when the abstract short rate follows a Cox–Ingersoll–Ross (CIR) process we compute bond option and swaption prices in closed form. We also propose a short-rate specification under the risk-neutral measure that allows the yield curve to be inverted and is consistent with the CIR dynamics for the abstract short rate, thus giving rise to closed form bond option and swaption prices.     

Potential Screening at Electrode/Ionic Liquid Interfaces from In Situ X-ray Photoelectron Spectroscopy

A new approach to investigate potential screening at the interface of ionic liquids (ILs) and charged electrodes in a two-electrode electrochemical cell by in situ X-ray photoelectron spectroscopy has been introduced. Using identical electrodes, we deduce the potential screening at the working and the counter electrodes as a function of applied voltage from the potential change of the bulk IL, as derived from corresponding core level binding energy shifts for different IL/electrode combinations. For imidazolium-based ILs and Pt electrodes, we find a significantly larger potential screening at the anode than at the cathode, which we attribute to strong attractive interactions between the imidazolium cation and Pt. In the absence of specific ion/electrode interactions, asymmetric potential screening only occurs for ILs with different cation and anion sizes as demonstrated for an imidazolium chloride IL and Au electrodes, which we assign to the different thicknesses of the electrical double layers. Our results imply that potential screening in ILs is mainly established by a single layer of counterions at the electrode.