Potential of electrophilic epoxide reactions for the monitoring of acid gases in the environment

Mineral and short-chain carboxylic acid vapours and NO(x) gases were reacted with cyclohexene oxide (1,2-epoxycyclohexane) to quantitatively produce specific, thermally stable cyclohexyl derivatives. Subsequent analysis of these derivatives by gas chromatography with mass spectroscopy and flame ionisation detection afforded a multi analyte method for the assay of these gaseous acidic atmospheric species. Derivatisation was found to be quantitative for the derivatives tested and the method highly sensitive (to 0.3 mg/m3 for a 30 l sample), accurate, precise and free from apparent interferences. The technique has been applied to "acid stack gases" and a number of other acid rich atmospheres and the results obtained show good agreement with the single analyte wet chemical determinations indicating that the approach has considerable potential as a routine analytical method for measuring such atmospheric pollutants. The high specificity of the reaction mechanism and its potential for the analysis of analyte mixtures is illustrated in the assay of nitric acid and its acid anhydride, dinitrogen pentoxide.     

Effects of Solar UVB Radiation on Growth, Flowering and Yield of Central and Southern European Maize Cultivars (Zea mays L.)

Abstract— Different cultivars of maize ( Zea mays L.) originating from Central and South Europe were grown from June to September 1994 for 16 weeks in two greenhouses covered with different UVB-absorbing (280–320 nm) plastic foils. Using the ambient UVB radiation level of a southern location (Portugal, 38.7°N) in one of the greenhouses as an enhanced radiation compared to the reduced radiation in the second greenhouse, an increase of about 12% of UVB was simulated. Six of the eight cultivars examined showed significant reductions in height of up to 18.9% at all developmental stages under increased UVB. In contrast to this, the fresh and dry weight as well as the leaf area was reduced under UVB only at early developmental stages, but with ongoing development the UVB stressed plants caught up. The total content of absorbing compounds of the maize cultivars was completely unaffected by UVB. A flowering delay up to a maximum of 5 days was observed under higher UVB in several cultivars. Probably due to this delay in the cob development the yield decreased to 27.7% under higher UVB at the first harvest after 12 and 14 weeks, whereas at the second harvest after 14 and 16 weeks yield reduction levelled off.     

1,2-Bis(2,5-diphenylphospholano)methane, a new ligand for asymmetric hydrogenation

1,2-Bis(2,5-diphenylphospholano)methane (Ph-BPM) has been prepared in good yield from 2,5-trans-diphenylphospholane-borane adduct. Rhodium and ruthenium complexes of this ligand have been prepared and their usefulness in asymmetric hydrogenation has been investigated. [Ph-BPM Rh(COD)]BF₄ showed high activity and selectivity for itaconate and dehydroamino acid hydrogenation. Ph-BPM RuCl₂(DPEN) was effective for imine hydrogenation.     

Scope and mechanism of palladium-catalyzed amination of five-membered heterocyclic halides

Detailed studies have been conducted to determine the activity of palladium catalysts for the amination of five-membered heterocyclic halides and to determine the factors that control the scope of this reaction. Palladium-catalyzed aminations of the electron-rich furanyl, thiophenyl, and indolyl halides and of the related 2-halogenated thiazoles, benzimidazole, and benzoxazole have been shown to occur with a subset of amines. Various combinations of palladium precursors and P(t)Bu(3) were tested as catalysts for reaction of 3-bromothiophene with N-methylaniline, and the fastest reactions occurred with the Pd(I) dimer, [PdBr(P(t)Bu(3))](2). The fastest aminations of thiazoles, benzimidazoles, and benzoxazoles occurred with the combination of palladium trifluoroacetate and P(t)Bu(3) as catalyst.     

Bridged peptide macrocycles as ligands for PDZ domain proteins

[reaction: see text] Conformationally constrained side chain-bridged cyclic peptides were prepared using bis-carboxylic acid ring spacers. These macrocyles were designed to inhibit protein-protein interactions mediated by the third PDZ domain (PDZ3) of a mammalian neuronal protein, PSD-95. Isothermal titration calorimetry (ITC) experiments measured dissociation constants in the low micromolar range. For each compound, the change in entropy (TdeltaS) of binding either is comparable in magnitude to the enthalpy change (deltaH) or is the predominant driving force for association.     

Silicone-modified starch/protein microparticles: protecting biopolymers with a hydrophobic coating

Silicone-coated starch/protein (human serum albumin, HSA) microparticles were prepared by precipitation of a starch/HSA/DMSO/water (water-in-oil) emulsion into acetone containing a silicone: the silicone polymer was either unfunctionalized (SiMe₃ terminated, PDMS) or functionalized at its termini with Si(OEt)₃ groups (TES-PDMS). The microparticles of approximate diameter 2–7 μm were highly hydrophobic with advancing contact angles 115°. Over several minutes, however, the contact angle decreased to ca. 40–70°. Soxhlet extraction with water led to degradation of the microparticles, irrespective of the nature of their silicone coating, as evidenced by release of the protein from them. Intraperitoneal (IP) or gastric administration of the two different particles to mice, however, showed a clear difference between the two silicones. The microparticles coated with either PDMS or TES-PDMS led to very different immune responses. Oral administration of the microparticles prepared with functionalized silicone elicited a significant production of antibodies, whereas the particles prepared with the unfunctionalized silicone (PDMS) were only weakly active. By contrast, the IP results demonstrated that particles coated with PDMS elicited an immune response that was established much more rapidly than with the particles modified with TES-PDMS. It is proposed that the TES-PDMS forms a physically adhering film or covalent bond to the protein molecules, which serves to protect the microparticle from biological degradation in the gut and/or facilitates the microparticle/protein interaction with the immune system.     

Fundamental role of the fostriecin unsaturated lactone and implications for selective protein phosphatase inhibition

Key derivatives and analogues of fostriecin were prepared and examined that revealed a fundamental role for the unsaturated lactone and confirmed the essential nature of the phosphate monoester. Thus, an identical 200-fold reduction in protein phosphatase 2A (PP2A) inhibition is observed with either the saturated lactone (7) or with an analogue that lacks the entire lactone (15). This 200-fold increase in PP2A inhibition attributable to the unsaturated lactone potentially may be due to reversible C269 alkylation within the PP beta12-beta13 active site loop accounting for PP2A/4 potency and selectivity.     

Structural transitions as determinants of the action of the calcium-dependent antibiotic daptomycin

Daptomycin is a cyclic anionic lipopeptide antibiotic recently approved for the treatment of complicated skin infections (Cubicin). Its function is dependent on calcium (as Ca2+). Circular dichroism spectroscopy indicated that daptomycin experienced two structural transitions: a transition upon interaction of daptomycin with Ca2+, and a further transition upon interaction with Ca2+ and the bacterial acidic phospholipid, phosphatidyl glycerol. The Ca2+-dependent insertion of daptomycin into model membranes promoted mild and more pronounced perturbations as assessed by the increase of lipid flip-flop and membrane leakage, respectively. The NMR structure of daptomycin indicated that Ca2+ induced a conformational change in daptomycin that increased its amphipathicity. These results are consistent with the hypothesis that the association of Ca2+ with daptomycin permits it to interact with bacterial membranes with effects that are similar to those of the cationic antimicrobial peptides.     

Synthesis and reactions of some dihydro and tetrahydro-4H-imidazo[5,4,1-ij]quinoline derivatives

Reaction of phenyl N-(8-quinolinyl)carbamate with sodium borohydride afforded 1,2-dihydro-4H-imidazo-[5,4,1-ij]quinolin-2-one, 2a . The 5,6-double bond of 2a was functionalized by reaction with nitrosyl chloride to give the nitroolefin 4 and by reaction with hypobromous acid to give the trans-bromohydrin 5 . Reaction of 5 with sodium azide led to the rearranged trans-6-azido-5-ol 7 , the structure of which was determined by ¹H nmr studies.     

Synthesis of the methanesulfonates of α-(4-chlorophenyl)-α-[1-(2-chlorophenyl)emenyl]-1H-1,2,4-triazole-1-ethanol and α-[1-(2-chlorophenyl)ethenyl]-α-(2,4-difluorophenyl)-1H-1,2,4-triazole-1-ethanol,alpha styryl carbinol antifungal agents

The methanesulfonates of (α-(4-chlorophenyl)-α-[1-(2-chlorophenyl)ethenyl]-1H-1,2,4-triazole-1-ethanol and α-[1-(2-chlorophenyl)ethenyl]-α-(2,4-difluorophenyl)-1H-1,2,4-triazole-1-ethanol ( 1a, b ) are orally effective α-styryl carbinol derivatives developed for the treatment and prevention of systemic fungal infections. Practical new processes amenable for the large-scale production of these compounds are described. Of note is the selection of dichlorostyrene as a convenient precursor of the styryl portion, modification of a sensitive Grignard addition into a realistic preparative reaction and the use of 1,2,4-triazole simultaneously as a base transfer agent and nucleophile.