Raman spectroscopic and structural studies of indigo and its four 6,6'-dihalogeno analogues

The Raman and electron impact mass spectra of synthetic indigo and its four 6,6'-dihalogeno analogues are reported and discussed. The influence of varying the halogen on these Raman spectra is considered. Particular emphasis is laid on distinguishing indigo from 6,6'-dibromoindigo and differentiating between the dihalogenocompounds, so as to develop protocols for determining whether artefacts are coloured with dyes of marine or terrestrial origin and whether such artefacts are dyed with genuine "Tyrian Purple" or with dihalogenoindigo substitutes that do not contain bromine. The value of even low resolution electron impact mass spectrometry in a forensic context as a means of identifying authentic 6,6'-dibromoindigo and distinguishing it from its dihalogenoanalogues is emphasised     

Novel disposable bismuth-sputtered electrodes for the determination of trace metals by stripping voltammetry

This work describes a novel type of bismuth electrode for stripping voltammetry based on coating a silicon substrate with a thin bismuth film by means of sputtering. The bismuth-based sensors were characterized by optical methods (scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD)) and as well as by linear sweep voltammetry. Subsequently, the electrodes were tested for the detection of low concentrations of trace metals (Cd(II), Pb(II) and Ni(II)) by stripping voltammetry. Well-formed stripping peaks were observed for trace concentrations of the target analytes demonstrating “proof-of-principle” for these sensors. This type of electrochemical device, utilizing thin-film technology for the formation of the bismuth film, holds promise for future applications in trace metal analysis.     

Novel disposable microfabricated antimony-film electrodes for adsorptive stripping analysis of trace Ni(II)

This work describes a novel type of antimony electrode for adsorptive stripping voltammetry (AdSV). The electrode was microfabricated by coating a silicon chip with a thin antimony-film by means of sputtering and the active area of the electrode was defined by photolithography. The resulting antimony-film electrodes (SbFEs) were characterized by optical and electrochemical techniques. The sensors were tested for the detection of low concentrations of Ni(II) by AdSV in the presence of dimethylglyoxime. Well-formed stripping peaks and a linear dependence of the stripping peak current on the Ni(II) concentration were observed on the microfabricated SbFEs while comparative measurements attempted with electroplated SbFEs were unsuccessful. Utilizing thin-film technology for the formation of the antimony-film extends the scope of these devices as mercury-free sensors in AdSV.     

On special L-values attached to metaplectic modular forms

Mathematische Zeitschrift - In this paper we establish some algebraic properties of special L-values attached to Siegel modular forms of half-integral weight, often called metaplectic modular...     

Development of recombinant protein-based influenza vaccine. Expression and affinity purification of H1N1 influenza virus neuraminidase

The influenza virus surface glycoprotein antigen neuraminidase (NA) is a crucial viral enzyme with many potential medical applications; therefore, the development of efficient upstream and downstream processing strategy for the expression and purification of NA is of high importance. In the present work the NA gene from the H1N1 influenza virus strain A/Beijing/262/95 was cloned from viral RNA and expressed in expresSF+ insect cells using the baculovirus expression vector system (BVES). A limited affinity-ligand library was synthesized and evaluated for its ability to bind and purify the recombinant H1N1 neuraminidase. Affinity-ligand design was based on mimicking the interactions of the lock-and-key (LAK) motif (Phe-Gly-Gln), a common structural moiety found in the subunit interface of glutathione S-transferase I (GST I), and plays an important structural role in subunit-subunit recognition. Solid-phase combinatorial chemistry was used to synthesize 13 variants of the lock-and-key lead ligand (Phe-Trz-X, where X was selected alpha-amino acid) using the 1,3,5-triazine moiety (Trz) as the scaffold for assembly. One immobilized ligand, bearing phenylalanine and isoleucine linked on the chlorotriazine ring (Phe-Trz-Ile), displayed high affinity for NA. Absorption equilibrium and molecular modeling studies were carried out to provide a detailed picture of Phe-Trz-Ile interaction with NA. This LAK-mimetic affinity adsorbent was exploited in the development of a facile purification protocol for NA, which led to 335-fold purification in a single-step. The present purification procedure is the most efficient reported so far for recombinant NA.     

Chemical analyses of martian soil and rocks obtained by the Pathfinder Alpha Proton X-ray spectrometer

The US Mars Pathfinder spacecraft, which landed on the red planet on the 4th of July 1997, carried an Alpha Proton X-ray Spectrometer (APXS) that obtained the chemical composition of martian soil and rocks. The principles of the APXS operation are based on three interactions of alpha particles with matter: Rutherford alpha backscattering; (, p) nuclear reactions; and X-ray generation by charged particles and X-ray excitation. The APXS, as was implemented on the Pathfinder mission, uses for all three modes of operation a monoenergetic beam of alpha particles from about 40 mCi of ²⁴⁴Cm radioisotope. It employs Si charged particle detectors for alpha and proton modes and a specially designed silicon PIN detector for its X-ray mode that does not require cooling for its operation. The APXS can detect all of the elements (except H and He) present above a few tenths of a percent for all major elements and several hundred ppm for many minor and trace elements.

The APXS on Pathfinder was transported to various locations on the martian surface by the Sojourner rover which enabled it to analyze multiple soil and rock samples selected by the science team from the lander camera images. The APXS performed excellently under the adverse martian environment conditions and provided important information about the chemical composition of the martian soil and rocks. All of the analyzed rocks at the Pathfinder site were found to have high concentrations of silica, sulfur and iron, and low in magnesium, similar to those of the terrestrial basaltic andesites and definitely different from the SNC meteorites that are believed to have originated from Mars. All of the soil samples analyzed by the APXS have similar composition and are very close to the soil analyses obtained by the two Viking missions. The information derived from the Pathfinder APXS has significant implications about the origin and evolution of planet Mars.     

Synthesis,Kinetic and Conformational Studies of 2-Substituted-5-(β-d-glucopyranosyl)-pyrimidin-4-ones as Potential Inhibitors of Glycogen Phosphorylase

Dysregulation of glycogen phosphorylase, an enzyme involved in glucose homeostasis, may lead to a number of pathological states such as type 2 diabetes and cancer, making it an important molecular target for the development of new forms of pharmaceutical intervention. Based on our previous work on the design and synthesis of 4-arylamino-1-(β-d-glucopyranosyl)pyrimidin-2-ones, which inhibit the activity of glycogen phosphorylase by binding at its catalytic site, we report herein a general synthesis of 2-substituted-5-(β-d-glucopyranosyl)pyrimidin-4-ones, a related class of metabolically stable, C-glucosyl-based, analogues. The synthetic development consists of a metallated heterocycle, produced from 5-bromo-2-methylthiouracil, in addition to protected d-gluconolactone, followed by organosilane reduction. The methylthio handle allowed derivatization through hydrolysis, ammonolysis and arylamine substitution, and the new compounds were found to be potent (μM) inhibitors of rabbit muscle glycogen phosphorylase. The results were interpreted with the help of density functional theory calculations and conformational analysis and were compared with previous findings.     

Modification of Guanine with Photolabile N‐Hydroxypyridine‐2(1H)‐thione: Monomer Synthesis,Oligonucleotide Elaboration,and Photochemical Studies

The photochemistry of N‐hydroxypyridine‐2(1H)‐thione (NHPT), inserted as a photolabile modifier at the 6‐position of 2′‐deoxyguanosine or guanosine, has been evaluated. In particular, 6‐[(1‐oxidopyridin‐2‐yl)sulfanyl]‐ ( 1a ) and 6‐[(pyridin‐2‐yl)sulfanyl]‐2′,6‐dideoxyguanosine ( 2a ), novel photolabile derivatives of the natural nucleosides, were synthesized and characterized. The observed photolysis products of 1a in organic solvents could only be rationalized by assuming a rapid equilibrium with the corresponding 6‐[(2‐thioxopyridin‐1(2H)‐yl)oxy] analogue 3a (Scheme 5). Transient spectroscopy of 1a indicated a strong triplet‐excited state suitable for triplet → triplet energy transfer or singlet‐oxygen generation. The NHPT function was stable enough for (slightly modified) automated solid‐phase oligonucleotide synthesis. The utility of the above compounds is discussed, as well as their potential use in photosensitization of reactive oxygen species in DNA.     

Catalytic Ferrier rearrangement of unsaturated nucleosides

The attempted intermolecular addition of malonyl radicals to 1′,2′-unsaturated nucleosides has led to the unexpected formation of furanones. Thus, only catalytic amounts of ceric(IV) ammonium nitrate (CAN), induce a Ferrier rearrangement. The unsaturated lactone was isolated in good yield and can serve as a precursor for the synthesis of optically active products.     

Differentiation of ionised benzimidazole from its isomeric alpha-distonic ion by collision-induced dissociation and neutralisation-reionisation mass spectrometry

Ionised benzimidazole and its isomeric alpha-distonic ion (or ionised ylid) have been examined by recording their metastable ion, collision-induced dissociation and neutralisation-reionisation mass spectra. These tautomers may be distinguished by careful consideration of key features of the collision-induced dissociation spectra, with or without prior neutralisation and reionisation. Formation of doubly-charged ions by charge stripping occurs preferentially when the alpha-distonic ion is subjected to collision. This alpha-distonic ion survives neutralisation and reionisation, thus establishing that the corresponding ylid is stable on the microsecond time frame. The effects of benzannulation on the ease of differentiation of classical and distonic radical cations derived from biologically important heterocycles are considered.