High-resolution computer simulations of EKC

The electrophoresis simulation software, GENTRANS, has been modified to include the interaction of analytes with an electrolyte additive to allow the simulation of liquid-phase EKC separations. The modifications account for interaction of weak and strong acid and base analytes with a single weak or strong acid or base background electrolyte additive and can be used to simulate a range of EKC separations with both charged and neutral additives. Simulations of separations of alkylphenyl ketones under real experimental conditions were performed using mobility and interaction constant data obtained from the literature and agreed well with experimental separations. Migration times in fused-silica capillaries and linear polyacrylamide-coated capillaries were within 7% of the experimental values, while peak widths were always narrower than the experimental values, but were still within 50% of those obtained by experiment. Simulations of sweeping were also performed; although migration time agreement was not as good as for simple EKC separations, peak widths were in good agreement, being within 1-50% of the experimental values. All simulations for comparison with experimental data were performed under real experimental conditions using a 47 cm capillary and a voltage of 20 kV and represent the first quantitative attempt at simulating EKC separations with and without sweeping.

Aza-Michael addition of amines to activated alkenes catalyzed by Silica supported perchloric acid under a solvent-free condition

An efficient aza-Michael addition of amines to a series of ,-unsaturated ketones, carboxylic esters, nitriles and chalcones has been carried out using perchloric acid supported over silica gel (HClO4-SiO2) at room temperature in high yields under solvent-free reaction conditions.

Synthesis, spectral, and anti-microbial studies of thioiminium iodides and amine hydrochlorides

To avoid the undesired deprotonation during the addition of organolithium and organomagnesium reagents to ketones, the thioiminium salts, easily prepared from lactams and amides are converted into 2,2-disubstituted and 2-monosubstituted amines by reaction with simple nucleophiles such as organocerium and organocopper reagents. The reaction of thioiminium iodides with organocerium reagents derived by transmetalation of corresponding lithium reagents with anhydrous cerium(III) chloride has been investigated. These thioiminium iodides act as good electrophiles and accept alkylceriums towards bisaddition. The newly synthesized amines have been characterized by 1H and 13C NMR, IR and mass spectra. The amines have been converted into their hydrochlorides and characterized by COSY. These hydrochlorides have been subjected to antimicrobial screening with clinically isolated microorganisms, Staphylococcus aureus, Klebsiella pneumoniae, Pseudomonas aeruginosa, Salmonella typhi and Candida albicans. The hydrochlorides show quite good activity against these bacteria and fungus.

Optimization of a DNSH passive sampling method to measure airborne carbonyls

Various airborne aldehydes and ketones (i.e., airborne carbonyls) present in outdoor, indoor, and personal air pose a risk to human health at present environmental concentrations. To date, there is no adequate, simple-to-use sampler for monitoring carbonyls at parts per billion concentrations in personal air. The Passive Aldehydes and Ketones Sampler (PAKS) originally developed for this purpose has been found to be unreliable in a number of relatively recent field studies. The PAKS method uses dansylhydrazine, DNSH, as the derivatization agent to produce aldehyde derivatives that are analyzed by HPLC with fluorescence detection. The reasons for the poor performance of the PAKS are not known but it is hypothesized that the chemical derivatization conditions and reaction kinetics combined with a relatively low sampling rate may play a role. This study evaluated the effect of absorption and emission wavelengths, pH of the DNSH coating solution, extraction solvent, and time post-extraction for the yield and stability of formaldehyde, acetaldehyde, and acrolein DNSH derivatives. The results suggest that the optimum conditions for the analysis of DNSHydrazones are the following. The excitation and emission wavelengths for HPLC analysis should be at 250nm and 500nm, respectively. The optimal pH of the coating solution appears to be pH 2 because it improves the formation of di-derivatized acrolein DNSHydrazones without affecting the response of the derivatives of the formaldehyde and acetaldehyde derivatives. Acetonitrile is the preferable extraction solvent while the optimal time to analyze the aldehyde derivatives is 72 hours post-extraction. ^

Preliminary lipid analyses of two Quaternary sediments from DSDP Holes 66-487 and 66-491

We investigated the solvent-extractable hydrocarbons, ketones, alcohols, and carboxylic acids of two Quaternary sediments from the Middle America Trench (Sections 487-2-3 and 491-1-5). These lipids are derived from a mixed input of autochthonous and allochthonous materials, with minor contributions from thermally mature sources. Their compositions are typical of those of immature Quaternary marine sediments, and their lipid distributions show many similarities to those of Japan Trench sediments.

Petrography and geochemistry of organic matter in Triassic and Cretaceous sediments from the Wombat and Exmouth Plateau

Triassic (Carnian-Rhaetian) continental margin sediments from the Wombat Plateau off northwest Australia (Sites 759, 760, 761, and 764) contain mainly detrital organic matter of terrestrial higher plant origin. Although deposited in a nearshore deltaic environment, little liptinitic material was preserved. The dominant vitrinites and inertinites are hydrogen-lean, and the small quantities of extractable bitumen contain w-alkanes and bacterial hopanoid hydrocarbons as the most dominant single gas-chromatography-amenable compounds. Lower Cretaceous sediments on the central Exmouth Plateau (Sites 762 and 763) farther south in general have an organic matter composition similar to that in the Wombat Plateau sediments with the exception of a smaller particle size of vitrinites and inertinites, indicating more distal transport and probably deposition in deeper water. Nevertheless, organic matter preservation is slightly better than in the Triassic sediments. Long-chain fatty acids, as well as aliphatic ketones and alcohols, are common constituents in the Lower Cretaceous sediments in addition to n-alkanes and hopanoid hydrocarbons. Thin, black shale layers at the Cenomanian/Turonian boundary, although present at several sites (Sites 762 and 763 on the Exmouth Plateau, Site 765 in the Argo Abyssal Plain, and Site 766 on the continental margin of the Gascoyne Abyssal Plain), are particularly enriched in organic matter only at Site 763 (up to 26%). These organic-matter-rich layers contain mainly bituminite of probable fecal-pellet origin. Considering the high organic carbon content, the moderate hydrogen indices of 350-450 milligrams of hydrocarbon-type material per gram of Corg, the maceral composition, and the low sedimentation rates in the middle Cretaceous, we suggest that these black shales were accumulated in an area of oxygen-depleted bottom-water mass (oceanwide reduced circulation?) underlying an oxygen-rich water column (in which most of the primary biomass other than fecal pellets is destroyed) and a zone of relatively high bioproductivity. Differences in organic matter accumulation at the Cenomanian/Turonian boundary at different sites off northwest Australia are ascribed to regional variations in primary bioproductivity.

Organic carbon, age, lithology, and CPI-alkenes at DSDP Sites 57-440 and 56-436

"Bound" and "free" solvent-extractable lipids have been examined from Sections 440A-7-6, 440B-3-5, 440B-8-4, 440B-68-2, and 436-11-4. The compound classes studied include aliphatic and aromatic hydrocarbons, ketones, alcohols, and carboxylic acids. Carotenoids and humic acids have also been examined. The quantitative results are considered in terms of input indicators, diagenesis parameters, and structural classes. A difference in input is deduced across the Japan Trench, with a higher proportion of autochthonous components on the western inner trench slope compared with the more easterly, outer trench, wall and greater input in the early Pleistocene than in the Miocene. A variety of diagenetic transformations is observed at Site 440 as sample depth increases. Results are compared with those of samples from Atlantic Cretaceous sediments and from the Walvis Bay high productivity area.

Sea surface temperature variations in the western Mediterranean Sea

A high-resolution sea surface temperature (SST) reconstruction of the western Mediterranean was accomplished using two independent, algae-based molecular organic proxies, i.e. the UK'37 index based on long-chain unsaturated ketones and the novel long-chain diol index (LDI) based on the relative abundances of C28 and C30 1,13- and 1,15-diols. Two marine records, from the western and eastern Alboran Sea basin, spanning the last 14 and 20 kyr, respectively, were studied. Results from the surface sediments suggest that the two proxies presently reflect seasons with similar SST, or simply annual mean SST. Both proxy records reveal the transition from the Last Glacial Maximum to the Holocene in the eastern Alboran Sea with an SST increase of ca. 7 °C for UK'37 and 9 °C for LDI. Minimum SSTs (10-12 °C) are reached at the end of the Last Glacial Maximum and during the last Heinrich event with a subsequent rapid SST increase in LDI-SST towards the beginning of the Bölling period (20 °C), while UK'37-SST remains constantly low (~12 °C). The Bölling-Alleröd is characterized by a rapid increase and subsequent decrease in UK'37-SST, while the LDI-SST decrease continuously. Short-term fluctuations in UK'37-SST are probably related to availability of nutrients and seasonal changes. The Younger Dryas is recorded as a short cold interval followed by progressively warmer temperatures. During the Holocene, the general lower UK'37-derived temperature values in the eastern Alboran (by ca. 1.5-2 °C) suggest a southeastward cold water migration by the western Alboran gyre and divergence in the haptophyte blooming season between both basins.

Geochemistry and foraminiferal stable isotoe record of sediment core SCS90-36

Changes in the Southeast Asia monsoon winds and surface circulation patterns since the last glaciation are inferred using multiple paleoceanographic indicators including planktic foraminifer faunal abundances, fauna and alkenones sea-surface temperature (SST) estimates, oxygen and carbon isotopes of planktic and benthic foraminifers, and sedimentary fluxes of carbonates and organic carbon obtained from deep-sea core SCS90-36 from the South China Sea (SCS) (17°59.70'N, 111°29.64'E at water depth 2050 m). All these paleoceanographic evidences indicate marked changes in the SCS ocean system over the last glacial toward the Holocene. Planktic foraminiferal faunal SST estimates show stable warm-season SST of 28.6°C, close to the modern value, throughout the glacial-interglacial cycle. In contrast, cold-season SST increases gradually from 23.6°C in the last glacial to a mean value of 26.4°C in the Holocene with a fluctuation of about 3°C during 13-16 ka. SST estimates by UK'37 method reveal less variability and are in average 1-3°C lower than the fauna-derived winter-season SST. These patterns reveal that the seasonality of the SST is not only higher by about 3-4°C in the glacial, but also a function of the winter season SST. Sedimentation rates decrease from the last glacial-deglacial stage to the Holocene due to a reduction in supply of terrigenous components, which led to an increase of carbonate contents. Total organic carbon (TOC) contents of primarily marine sources decrease from the last glacial-deglacial to the Holocene. The last deglaciation is also characterized by high surface productivity as indicated by increased ketones abundances and high mass accumulation rates (MAR) of the TOC and carbonates. The gradient of planktic foraminifer ocygen and carbon isotopes of between surface dwellers and deep dwellers increases significantly toward Termination I and Holocene, and is indiscernibly small in the carbon isotope gradient of between 14 and 24 ka, revealing a deep-mixing condition in surface layers prior to 10 ka. The glacial-interglacial fluctuation of the carbon isotope value of a benthic foraminifer is 0.61%. which is significantly larger than a global mean value. The large carbon isotope fluctuation indicates an amplification of marginal-sea effects which is most likely resulted from an increase in surface productivity in the northern SCS during the last glacial-deglacial stage. The multiple proxies consistently indicate that the last glacial-deglacial stage winter monsoon in the Southeast Asia was probably strengthened in the northern SCS, leading to a development of deep-mixing surface layer conditions and a more efficient nutrient cycling which supports more marine organic carbon production.

Alkenone UK37 measured in the upper water column at pump stations CariacoTrench, Peru and Vertex

A series of long-chain (C37, C38, C39), primarily di and tri-unsaturated methyl and ethyl ketones, first identified in sediments from Walvis Ridge off West Africa and from Black Sea (de Leeuw et al., 1979), has been found in marine sediments throughout the world (Brassell et al., 1986 doi:10.1038/320129a0). The marine coccolithophorid Emiliania huxleyi and members of the class Prymnesiophyceae are now the recognized sources of these compounds (Volkman et al., 1979; Marlowe, et al., 1984). Experiments with laboratory cultures of algae showed the degree of unsaturation in the ketone seris biosynthesized depends on growth temperature (Brassell et al., 1986; Marlowe, 1984), a physiological respons observed for classical membrane lipids (vanDeenen et al., 1972). Brassell and co-workers (Brassell et al., 198; Brassell et al., 1986b) thus proposed that systematic fluctuations in the unsaturation of these alkenones noted down-core in sediments from the Kane Gap region of the north-east tropical Atlantic Ocean and correlated with glacial-interglacial cycles provide an organic geochemical measure of past sea-surface water temperatures. Using laboratory cultures of E. huxleyi, we have calibrated changes in the unsaturation pattern of the long-chain ketone series versus growth temperature. The calibration curve is linear and accurtely predicts unsuturation patterns observed in natural particulate materials collected from oceanic waters of known temperature. We present evidence supporting the proposed paleotemperature hypothesis (Brassell et al., 1986, Brassel et al., 1986b) and suggesting absolute 'sea-surface temperatures' for a given oceanic location can be estimated from an analysis of long-chain ketone compositions preserved in glacial and interglacial horizons of deep-sea sediment cores.

n-Alkan-2-ones in peat-forming plants from the Roñanzas ombrotrophic bog (Asturias, northern Spain)

We determined the distribution of lipids (n-alkanes and n-alkan-2-ones) in present-day peat-formingplants in the RoñanzasBog in northernSpain. Consistent with the observation of others, most Sphagnum (moss) species alkanes maximized at C23, whereas the other plants maximized at higher molecular weight (C27 to C31). We show for the first time that plants other than seagrass and Sphagnum moss contain n-alkan-2-ones. Almost all the species analysed showed an n-alkan-2-one distribution between C21 and C31 with an odd/even predominance, maximizing at C27 or C29, except ferns, which maximized at lower molecular weight (C21–C23). We also observed that microbial degradation can be a major contributor to the n-alkan-2-one distribution in sediments as opposed to a direct input of ketones from plants

Evolución paleoambiental de la Península Ibérica desde hace 1 Ma a partir de los biomarcadores del registro de la Turbera de Padul (Granada)

La Turbera de Padul, en la Provincia de Granada, ofrece unas posibilidades de estudio muy atractivas desde el punto de vista de la reconstrucción paleoambiental. Se trata de una fosa tectónica subsidente de naturaleza detrítica, a cuyo techo aparecen alternantes niveles de turba. El sondeo, de 107 metros, se realizó en un punto donde los estratos de turba aparecen a mayor profundidad, lo que permite obtener un registro geoquímico orgánico con mucho detalle con una antigüedad de hasta 1Ma. Se tomaron muestras cada 20 cm para el análisis de biomarcadores. Estos biomarcadores se obtuvieron mediante extracción Soxhlet, posterior separación de fracciones de diferente polaridad mediante Cromatografía en Columna, con Gel de Sílice y Alúmina, y posteriormente el análisis e identificación por Cromatografía de Gases - Espectrometría de masas, con confirmación de los compuestos químicos identificados por comparación con Bibliotecas de Espectros de Masas. La datación del sondeo se realizó utilizando distintos métodos como datación por 14C, U/Th, y datación por racemización de aminoácidos. Los resultados dataron el muro del sondeo con una antigüedad de 1 millón de años. El estudio de los biomarcadores ha permitido identificar episodios con distintas características en un escenario complejo, como es la Turbera de Padul, donde el aporte de agua por fusión nival complica la interpretación paleoambiental, y es la responsable de la existencia de la lámina de agua en la turbera en periodos secos con temperaturas elevadas. Se han identificado series de n-alcanos, de n-metilcetonas y series de nalcanoles, que han permitido identificar la aportación de materia orgánica de distintas fuentes al sedimento y por tanto la interpretación paleoambiental. La identificación de diterpenoides fenólicos (cis-Totatol, trans-Totarol y Ferruginol) han permitido identificar episodios de clima templado y húmedo con proliferación de cupresáceas, y precipitaciones abundantes. Por otro lado, se han identificado triterpenoides como el Friedelan-3-ona (Friedelin) y el A-norfriedel-8en-10-ona, cuya relación como precursor (Friedelin) y producto (A-norfriedel-8en-10-ona) ha permitido identificar episodios con fluctuaciones del espesor de la lámina de agua y aporte de material vegetal. ABSTRACT The Bog of Padul, in the province of Granada, offers very attractive possibilities for the study of paleoenvironmental reconstruction. It is a subsiding graben of detrital nature, whose upper part appear alternating peat levels. The core of 107 meters, obtained from a borehole drilled in a place where the layers of peat appear deeper, allowing to obtain organic geochemist information along the last 1 million years. Every 20 cm samples for biomarkers analysis were taken. These biomarkers were obtained by Soxhlet extraction, subsequent separation of fractions of different polarity by column chromatography with silica gel and alumina, and then analyzed and identified by gas chromatography - mass spectrometry, with confirmation of the chemicals identified by comparison to mass spectral libraries. The dating of the core was conducted using different methods such as 14C dating, U/Th, and amino acid racemization dating. The results dated the base of the core to be 1 million years old. The study has identified biomarkers episodes with different characteristics in a complex scenario, such as the Bog of Padul, where the contribution of snowmelt water complicates the paleoenvironmental interpretation, and is responsible for the existence of a sheet of water in dry periods with high temperatures. There have been identified series of n-alkanes, n-methyl ketones and series of n-alkanols that have shown the contribution of different organic matter sources to the sediment and therefore allowed to paleo interpretation. The identification of phenolic diterpenoids (cis-Totatol, trans-Totarol and Ferruginol) have identified episodes of mild and humid climate with proliferation of Cupressaceae, and abundant rainfall. In addition, triterpenoids have been identified, as the friedelan-3-one (friedelin) and the A-norfriedel-8en-10-one, whose relationship as precursor (friedelin) and product (A-norfriedel-8en-10-one) has identified episodes with fluctuations on the thickness of the sheet of water and supply of plant material debris.

Palaeoenvironmental reconstruction of Las Conchas Mire (Asturias, N. Spain) from the ketone and fatty acid record= reconstrucción paleoambiental de la Turbera de las Conchas (Asturias, N. España)a partir del registro de cetonas y ácidos grasos

Se han estudiado los biomarcadores, principalmente cetonas y ácidos, preservados en el registro de 3.2 m de la Turbera de Las Conchas. Las cetonas reflejan cierta actividad bacteriana desde 94 cm hasta la base del registro, Los ácidos grasos reflejan una buena preservación de la materia orgánica, salvo en los 20 cm superiores en los que hay indicios de oxidación microbiana de alcanos .The biomarkers, mainly ketones and fally aclds, preserved In 3.2 m deep Las Conchas Mire have been studied, Kelones reflect certain bacterial activity from 94 cm to the bottom of the record. Falty aclds indlcate a good preservation of the organlc matter, wlth the exception of the uppermost 20 cm In whlch mlcroblal oxldation of alkanes are likely to occur

Fractionation factors and activation energies for exchange of the low barrier hydrogen bonding proton in peptidyl trifluoromethyl ketone complexes of chymotrypsin

NMR investigations have been carried out of complexes between bovine chymotrypsin Aα and a series of four peptidyl trifluoromethyl ketones, listed here in order of increasing affinity for chymotrypsin: N-Acetyl-l-Phe-CF3, N-Acetyl-Gly-l-Phe-CF3, N-Acetyl-l-Val-l-Phe-CF3, and N-Acetyl-l-Leu-l-Phe-CF3. The D/H fractionation factors (φ) for the hydrogen in the H-bond between His 57 and Asp 102 (His 57-Hδ1) in these four complexes at 5°C were in the range φ = 0.32–0.43, expected for a low-barrier hydrogen bond. For this series of complexes, measurements also were made of the chemical shifts of His 57-Hɛ1 (δ2,2-dimethylsilapentane-5-sulfonic acid 8.97–9.18), the exchange rate of the His 57-Hδ1 proton with bulk water protons (284–12.4 s−1), and the activation enthalpies for this hydrogen exchange (14.7–19.4 kcal⋅mol−1). It was found that the previously noted correlations between the inhibition constants (Ki 170–1.2 μM) and the chemical shifts of His 57-Hδ1 (δ2,2-dimethylsilapentane-5-sulfonic acid 18.61–18.95) for this series of peptidyl trifluoromethyl ketones with chymotrypsin [Lin, J., Cassidy, C. S. & Frey, P. A. (1998) Biochemistry 37, 11940–11948] could be extended to include the fractionation factors, hydrogen exchange rates, and hydrogen exchange activation enthalpies. The results support the proposal of low barrier hydrogen bond-facilitated general base catalysis in the addition of Ser 195 to the peptidyl carbonyl group of substrates in the mechanism of chymotrypsin-catalyzed peptide hydrolysis. Trends in the enthalpies for hydrogen exchange and the fractionation factors are consistent with a strong, double-minimum or single-well potential hydrogen bond in the strongest complexes. The lifetimes of His 57-Hδ1, which is solvent shielded in these complexes, track the strength of the hydrogen bond. Because these lifetimes are orders of magnitude shorter than those of the complexes themselves, the enzyme must have a pathway for hydrogen exchange at this site that is independent of dissociation of the complexes.

Exceptionally potent inhibitors of fatty acid amide hydrolase: The enzyme responsible for degradation of endogenous oleamide and anandamide

The development of exceptionally potent inhibitors of fatty acid amide hydrolase (FAAH), the enzyme responsible for the degradation of oleamide (an endogenous sleep-inducing lipid), and anandamide (an endogenous ligand for cannabinoid receptors) is detailed. The inhibitors may serve as useful tools to clarify the role of endogenous oleamide and anandamide and may prove to be useful therapeutic agents for the treatment of sleep disorders or pain. The combination of several features—an optimal C12–C8 chain length, π-unsaturation introduction at the corresponding arachidonoyl Δ8,9/Δ11,12 and oleoyl Δ9,10 location, and an α-keto N4 oxazolopyridine with incorporation of a second weakly basic nitrogen provided FAAH inhibitors with Kis that drop below 200 pM and are 102–103 times more potent than the corresponding trifluoromethyl ketones.