Design and synthesis of novel fluoropeptidomimetics as potential mimics of the transition state during peptide hydrolysis

alpha-Fluoroamino acids were targeted in our ongoing efforts to design novel fluoropeptidomimetics (1) as potential protease inhibitors. alpha-Fluoroglycine derivative (2) and alpha-fluoro-beta-aminoethanethiol derivatives (3-9) were synthesized for the first time en route to obtain the peptidomimetic moiety 1. The stability of 2-9 was investigated under organic as well as aqueous conditions. The stability of 3-9 under acidic and basic conditions, the effect of substitution at C-2 position, and potential biological activities are discussed.     

Expanding the repertoire of pyrrolidyl PNA analogues for DNA/RNA hybridization selectivity: aminoethylpyrrolidinone PNA (aepone-PNA)

New PNA analogues derived from aminoethylpyrrolidin-5-one backbone show stabilization of aepone-PNA:DNA hybrids and destabilization of the corresponding RNA hybrids compared to unmodified PNA.     

Pulsed remote Raman system for daytime measurements of mineral spectra

A remote Raman system has been developed utilizing a 532nm pulsed laser and gated intensified charged couple device (ICCD) detector in the oblique geometry. When the system is set for 50m sample distance it is capable of measuring Raman spectra of minerals located at distances in the range of 10-65m from the telescope. Both daytime and nighttime operations are feasible and the spectra of minerals can be measured in a short period of time, of the order of a few seconds. In oblique geometry, measured sampling depth is more than 30m, during which the system maintains very high performance without any adjustments. Much longer sampling depth (0.1-120m) has been observed when the system is configured in the coaxial geometry. Clear advantages of using a gated detection mode over the continuous (CW) mode of operation in reducing the background signal and eliminating long-lived fluorescence signals from the Raman spectra are presented. The performance of the pulsed Raman system is demonstrated by measuring spectra of Raman standards including benzene (C(6)H(6)) and naphthalene (C(10)H(8)), a low Raman cross section silicate mineral muscovite (KAl(2)(Si(3)Al)O(10)(OH)(2)), and a medium Raman cross section mineral calcite (CaCO(3)).     

Thermodynamics of molecular interactions in binary mixtures of non-electrolytes. Molar excess volumes

Molar excess volumes, V^E, for pyridine (A) + α-picoline (B), + β-picoline (B) and + γ-picoline (B) and benzene (A) + toluene (B), + o-xylene (B) and + p-xylene (B) and carbon tetrachloride (A) + n-heptane (B) have been measured dilatometrically as a function of temperature and composition and have been utilized to study B—B and B—B—B interactions in the presence of A via the Mayer—McMillan approach. A model has also been presented to account for these B—B and B—B—B interactions. The V^E data at 308.15 K have also been analysed in terms of the “graph theoretical” approach which describes the V^E data well for all these mixtures at 308.15 K. The “graph theoretical” approach has further been extended to successfully evaluate V^E data for a mixture at any temperature, T₂, when the V^E data at T₁ are known.     

Studies on the determination and degradation of pyrimethamine in mammals

Treatment of pyrimethamine with blood plasma in vitro yields a metabolite which is also produced when the drug is administered through intravenous injection in the rat. A thin layer liquid chromatographic method for quantitative and qualitative determination of pyrimethamine and its metabolite in plasma and biological tissues is described.     

Determination of 3-sulfolene in sulfolane by reaction gas chromatography

Summary A simple gas-liquid chromatographic method has been developed for determining 3-sulfolene in sulfolane. The method involves thermal decomposition of sulfolene and determination of the 1.3-butadiene evolved, by GLC. Influence of the operating parameters on quantitative decomposition of sulfolene has been studied. The accuracy of the method as studied in the concentration range from 0.05 to 4.0 % (w/v) of 3-sulfolene in sulfolane is found to be within ±3.0%. It is rapid and sensitive down to 10 ppm and has potentialities for on-line applications also.

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Bestimmung von 3-Sulfolen in Sulfolan durch Reaktions-Gas-Chromatographie

Zusammenfassung Eine einfache gas-chromatographische Methode wurde entwickelt, die auf der thermischen Zersetzung der Probe und der Bestimmung des dabei aus 3-Sulfolen gebildeten 1,3-Butadiens beruht. Der Einfluß der einzelnen Parameter wurde untersucht. Innerhalb eines Konzentrationsbereichs von 0,05–4,0% 3-Sulfolen ergaben sich Fehler von ±3%. Das Verfahren ermöglicht bis herab zu 10 ppm eine schnelle und empfindliche Bestimmung und eignet sich auch zum on-line Betrieb.

     

Colorimetric method for the determination of captafol (difolatan) in commercial formulations and residues on grains and apples.

A simple and rapid colorimetric method for the microdetermination of captafol (difolatan), based on its reaction with a dithiocarbamate, has been developed. The bright yellow colour which develops instantaneously on mixing the fungicide with the reagent is stable for at least 12 h. The method has been successfully adapted to the determination of captafol in its formulated products and residues on grains and apples.     

Synthesis,structural and biochemical aspects of titanocene and zirconocene chelates of acetylferrocenyl thiosemicarbazones

The reactions of bis(cyclopentadienyl)titanium(IV)/zirconium(IV) dichloride with a new class of organometallic thiosemicarbazones (LH), derived by condensing acetylferrocene with substituted thiosemicarbazides, have been studied and two types of bimetallic products, viz. [Cp₂M(L)Cl] (M = Ti or Zr) and [CpZr(L)₃], have been isolated. On the basis of various physicochemical and spectral studies, five- and seven-coordinate structures have been assigned to these derivatives, respectively. Attempts have been made to establish a correlation between biological activity and the structures of the products.     

Stereoselective synthesis of (−)-microcarpalide

A highly convergent and efficient synthesis of (−)-microcarpalide, a 10-membered lactone displaying remarkable microfilament disrupting activity is described. Ring-closing metathesis and Sharpless asymmetric dihydroxylations are the key steps. Our strategy highlights the application of novel hydroxy lactone precursors for the stereoselective synthesis of (−)-microcarpalide.