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Selected AbstractsAmino-phosphanes in RhI -Catalyzed Hydroformylation: New Mechanistic Insights Using D2O as Deuterium-Labeling AgentEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 1 2006Jacques Andrieu Abstract In previous work, we have demonstrated that the dangling amino group in amino-phosphane ligands increases the rate of Rh-catalyzed styrene hydroformylation as a function of the amino group basicity and of the distance between the P and N functions. We now report additional stereochemical and mechanistic insights resulting from new catalytic experiments performed with Rh-,-P,N catalytic systems in the presence of D2O. In addition to the expected D0 product, the formation of the ,-D1 aldehyde, PhCH(CH2D)CHO was observed in all cases by 1H and 13C NMR spectroscopy, indicating that H/D exchange occurs for the rhodium-hydride complex. Minor amounts of a ,-D2 product, PhCH(CHD2)CHO, were also formed under certain conditions, demonstrating the reversibility of the olefin coordination step. The composition of the aldehyde mixture is slightly affected by the nature of the catalytic precursor or the P,N ligand used. In the specific case of the ,-P,N ligand [,-P,N = (SAr,SC)-Ph2PCH{o -C6H4Cl(Cr(CO)3)}NHPh], in combination with the [RhCl(COD)]2 precatalyst, products PhCD(CH3)CHO (,-D1) and PhCD(CH2D)CHO (,,,-D2) were also produced. This result suggests a reversible deprotonation assisted by an intramolecular H-bonding interaction between the dangling ammonium function and the carbonyl moiety. This isotopic exchange process decreases the asymmetric induction from 14 to 7,% ee when using the enantiopure version of this ligand. Aldehydes bearing a D atom on the formyl group, e.g. PhCH(CH3)CDO, were never observed. The latter observation excludes protonolysis of the rhodium-acyl intermediate as the aldehyde forming step. In addition, it also excludes a bimolecular reaction involving the rhodium-acyl and rhodium-hydride intermediates.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Compatibilization of PP/PAE blends by means of the addition of an ionomerPOLYMER ENGINEERING & SCIENCE, Issue 8 2010A. Granado Minor amounts of poly(ethylene- co -methacrylic acid) ionomer neutralized with Zn (PEMA-Zn) were added in the melt state to blends of polypropylene (PP) with up to 40% of poly(amino ether) (PAE) resin. Given the good barrier characteristics of PAE, it is a good candidate to improve the poor barrier properties of PP. However, PP/PAE blends were found to be almost fully immiscible, with a large dispersed phase size and a brittle mechanical behavior. Upon PEMA-Zn addition, the dispersed particle size clearly decreased from diameters of several microns to diameters mostly below 0.5 ,m, indicating that compatibilization occurred. This compatibilization was due to the presence of PEMA-Zn in the two phases of the blends and was additionally proven by the large decrease observed in the interfacial tension. Further, the fine morphology led to an enhancement in the unnotched impact strength of the ternary blends and of their ductile behavior (elongation at break 30- to 40-fold that of the corresponding binary blends). POLYM. ENG. SCI., 50:1512,1519, 2010. © 2010 Society of Plastics Engineers [source] Recent channel adjustments in alluvial rivers of Tuscany, central ItalyEARTH SURFACE PROCESSES AND LANDFORMS, Issue 6 2003Massimo RinaldiArticle first published online: 19 JUN 200 Abstract Drastic channel adjustments have affected the main alluvial rivers of Tuscany (central Italy) during the 20th century. Bed-level adjustments were identified both by comparing available topographic longitudinal profiles of different years and through field observations. Changes in channel width were investigated by comparing available aerial photographs (1954 and 1993,98). Bed incision represents the dominant type of vertical adjustment, and is generalized along all the fluvial systems investigated. The Arno River system is the most affected by bed-level lowering (up to 9 m), whereas lower incision (generally less than 2 m) is observed along the rivers of the southern part of the region. Human disturbances appear to be the dominant factors of adjustments: the main phase of vertical change occurred during the period 1945,80, in concomitance with the phase of maximum sediment mining activity at the regional scale. The second dominant type of adjustment that involved most of the rivers in the region consists of a narrowing of the active channel. Based on measurements of channel width conducted on aerial photographs, 38% of the reaches analysed experienced a narrowing greater than 50% of the initial channel width. The largest values of channel narrowing were observed along initially braided or sinuous with alternate bars morphologies in the southern portion of the region. A regional scheme of channel adjustments is derived, based on initial channel morphology and on the amounts of incision and narrowing. Different styles of channel adjustments are described. Rivers that were originally sinuous with alternate bars to braided generally became adjusted by a moderate incision and a moderate to intense narrowing; in contrast, sinuous-meandering channels mainly adjusted vertically, with a minor amount of narrowing. Copyright © 2003 John Wiley & Sons, Ltd. [source] Disposition and pharmacokinetics of L-N6-(1-iminoethyl)lysine-5-tetrazole-amide, a selective iNOS inhibitor, in ratsJOURNAL OF PHARMACEUTICAL SCIENCES, Issue 5 2004Ji Y. Zhang Abstract The metabolism, pharmacokinetics, tissue distribution, and excretion of L-N6-(1-iminoethyl)lysine-5-tetrazole-amide (L-NIL-TA), a selective inducible NO synthase (iNOS) inhibitor, were investigated in rats. [14C]L-NIL-TA is extensively metabolized after either oral or IV administration with a minor amount (<1%) excreted as the prodrug. L-NIL-TA is metabolized via a single hydrolysis pathway to form the active drug, L-N6-(1-iminoethyl)lysine (L-NIL). The oxidative deamination of 2-amino group of L-NIL forms a 2-keto metabolite (M5), which further loses carbon dioxide to yield a carboxylic acid metabolite (M6). Acetylation of L-NIL and M5 resulted in the formations of metabolites M7 and M4, respectively. Complete recovery of the radioactive dose was achieved after either oral (91.2% in urine and 4.66% in feces) and IV (99.3% in urine and 5.11% in feces) administration. L-NIL-TA-related material was extensively distributed to the tissues, with the highest concentration of radioactivity being found in muscle. Maximal concentration of radioactivity was reached between 0.5 and 1 h post-dose in the majority of tissues, with the exception of muscle and skin where the maximal concentrations were achieved at 8 h post-dose. © 2004 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 93:1229,1240, 2004 [source] Microstructure and Microwave Dielectric Properties of xCa(Al0.5Nb0.5)O3+(1,x)SrTiO3 Solid SolutionsJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 10 2010Mingzhe Hu The crystal structure evolution and microwave (MW) dielectric properties of xCa(Al0.5Nb0.5)O3+(1,x)SrTiO3 (xCAN+(1,x)ST, 0,x,1.0, ) dielectric ceramics were investigated. X-ray diffraction patterns illustrated that a single perovskite solid solution could be formed between the two end members; however, minor amount of pyrochlore phase was also detected in the composition range of 0.5,x,0.9. With the increase of x value, the crystal structure gradually evolved from a simple Pm3m cubic to a monoclinic P21/n space group with the octahedral tilting and the B-site ordering structure transition subsequently developed. The MW dielectric properties of xCAN+(1,x)ST solid solutions were elaborately investigated and correlated to their crystal structures. The microscopic structure-related thermal parameters in the xCAN+(1,x)ST solid solution were analyzed in terms of the Claussius,Mossotti equation to reveal the original contributors in temperature coefficients. Temperature coefficient-compensated ceramic could be obtained in the xCAN+(1,x)ST system in the range of 0.5 Effects of Ca/Ti Cosubstitution upon Microwave Dielectric Characteristics of CaSmAlO4 CeramicsJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 2 2009Xie Cheng Fan (Ca1+xSm1,x)(Al1,xTix)O4 (0,x,0.4) ceramics were synthesized by solid-state reaction method and their microstructures and microwave dielectric properties were investigated. X-ray diffraction analysis and energy-dispersive X-ray analysis indicated that the matrix phase was a solid solution with a composition represented by the chemical formula (Ca1+xSm1,x) (Al1,xTix)O4 and minor amount of (Ca,Sm)(Al,Ti)O3 secondary phase was detected. Ca/Ti cosubstitution could significantly improve the microwave dielectric characteristics of CaSmAlO4 ceramics, and the excellent microwave dielectric characteristics were obtained in the modified ceramics as ,r=19,23, Q×f=49 100,118 700 GHz, and ,f=,15,15 ppm/°C. [source] Studies on Molecular Composites of Polyamide 6/Polyamide 66MACROMOLECULAR RAPID COMMUNICATIONS, Issue 19 2004Yulin Li Abstract Summary: A series of molecular composites of PA 6/PA 66 was synthesized via in situ polymerization. The impact resistance of PA 6 was improved dramatically by incorporating a minor amount of PA 66 (2,10 wt.-%), without decreasing the tensile strength. Inserting PA 66 macromolecules at a molecular level into a PA 6 matrix may interfere with the arrangement of the hydrogen bonds of PA 6, in turn changing the crystalline structure and impeding the crystallization of PA 6. SEM micrograph of the fractured surface of a PA 6/PA 66 composite containing 10 wt.-% PA 66. [source] Polymerization of styrene with a simple rare earth metal initiatorPOLYMER INTERNATIONAL, Issue 11 2001Toshiyuki Hayakawa Abstract The catalytic activity in the polymerization of styrene has been examined using commercially available simple rare earth metal compounds such as Sm(OiPr)3, Sm(acac)3, Sm(OCOMe)3, SmI2(THF)2 or SmCl3 coupled with Et3Al or methylaluminoxane (MAO). Among these compounds, the Sm(OiPr)3/AlEt3 system shows the highest catalytic activity, especially in the presence of a minor amount of toluene at 60,°C. The random copolymerization of styrene with methyl methacrylate suggests that the present polymerization proceeds with a radical polymerization mechanism. (C5Me5)SmCl3Na(THF) and (C5Me5)SmCl3Li(THF) systems exhibit relatively low catalytic activity, even in the presence of AlEt3. © 2001 Society of Chemical Industry [source] Peptides of human gingival crevicular fluid determined by HPLC-ESI-MSEUROPEAN JOURNAL OF ORAL SCIENCES, Issue 6 2005Elisabetta Pisano The acidic-soluble protein content of human gingival crevicular fluid was analyzed by reverse-phase high-performance liquid chromatography (RP-HPLC), and the eluent deriving from the chromatography separation was directly introduced into an ion-trap mass spectrometer through electrospray ionization (ESI-IT MS). By this technique the molecular weight of peptides/proteins was determined with a precision of ,,1/10,000 amu. On the basis of the chromatographic behavior and the knowledge of the molecular mass value, some peptides and proteins soluble in acidic solution were unambiguously recognized. Besides high quantities of human serum albumin, , -defensins 1,4 and minor amounts of cystatin A, statherin, basic PB salivary peptide and other unidentified components were detected. The presence of , -defensins in gingival crevicular fluid is in agreement with their relevant contribution to protein composition deriving from granulocyte secretions. Other peptides and proteins abundant in human saliva, such as proline-rich proteins (PRPs) and histatins, were not detected in gingival crevicular fluid. Further investigations will be necessary to establish the origin of statherin and PB salivary peptide in gingival crevicular fluid. [source] ,- d -Mannopyranosyl-(1,2)-,- d -glucopyranosyl-(1,2)-glycerate in the thermophilic bacterium Petrotoga miotherma , structure, cellular content and functionFEBS JOURNAL, Issue 12 2007Carla D. Jorge The intracellular accumulation of low molecular mass organic compounds in response to stressful conditions was investigated in the thermophilic bacterium Petrotoga miotherma, a member of the order Thermotogales. This led to the discovery of a new solute, whose structure was established as ,- d -mannopyranosyl-(1,2)-,- d -glucopyranosyl-(1,2)-glycerate (MGG) by MMR spectroscopy and MS. Under optimum growth conditions (3% NaCl; 55 °C), MGG was the major solute [up to 0.6 µmol·(mg protein),1]; ,-glutamate and proline were also present but in minor amounts [below 0.08 µmol·(mg protein),1]. The level of MGG increased notably with the salinity of the growth medium up to the optimum NaCl concentration. At higher NaCl concentrations, however, the level of MGG decreased, whereas the levels of proline and ,-glutamate increased about five-fold and 10-fold, respectively. MGG plays a role during low-level osmotic adaptation of Petrotoga miotherma, whereas ,-glutamate and, to a lesser extent, proline are used for osmoprotection under salt stress. MGG is not part of the cell strategy for coping with heat or oxidative stress. Nevertheless, MGG was an efficient protector of pig heart malate dehydrogenase against heat inactivation and freeze-drying, although mannosylglycerate was better. This is the first report on the occurrence of MGG in living systems. [source] Asymmetric Abstraction and Allocation: The Israeli-Palestinian Water Pumping RecordGROUND WATER, Issue 1 2009Mark Zeitoun The increased attention given to international transboundary aquifers may be nowhere more pressing than on the western bank of the Jordan River. Hydropolitical analysis of six decades of Israeli and Palestinian pumping records reveals how ground water abstraction rates are as asymmetrical as are water allocations. The particular hydrogeology of the region, notably the variability in depth to ground water, variations in ground water quality, and the vulnerability of the aquifer, also affect the outcome. The records confirm previously drawn conclusions of the influence of the agricultural lobby in maintaining a supply-side water management paradigm. Comparison of water consumption rates divulges that water consumed by all sectors of the farming-based Palestinian economy is less than half of Israeli domestic consumption. The overwhelming majority of "reserve" flows from wet years are sold at subsidized rates to the Israeli agricultural sector, while very minor amounts are sold at normal rates to the Palestinian side for drinking water. An apparent coevolution of water resource variability and politics serves to explain increased Israeli pumping prior to negotiations in the early 1990s. The abstraction record from the Western Aquifer Basin discloses that the effective limit set by the terms of the 1995 Oslo II Agreement is regularly violated by the Israeli side, thereby putting the aquifer at risk. The picture that emerges is one of a transboundary water regime that is much more exploitative than cooperative and that risks spoiling the resource as it poisons international relations. [source] Oligonucleotide Analogues with Integrated Bases and Backbone.HELVETICA CHIMICA ACTA, Issue 5 2007Part 1 Abstract The self-complementary (Z)-configured U*[ce]A(*) dinucleotide analogues 6, 8, 10, 12, 14, and 16, and the A*[ce]U(*) dimers 19, 21, 23, 25, 27, and 29 were prepared by partial hydrogenation of the corresponding ethynylene linked dimers. Photolysis of 14 led to the (E)-alkene 17. These dinucleotide analogues associate in CDCl3 solution, as evidenced by NMR and CD spectroscopy. The thermodynamic parameters of the duplexation were determined by van't Hoff analysis. The (Z)-configured U*[ce]A(*) dimers 14 and 16 form cyclic duplexes connected by Watson,Crick H-bonds, the (E)-configured U*[ce]A dimer 17 forms linear duplexes, and the U*[ce]A(*) allyl alcohols 6, 8, 10, and 12 form mixtures of linear and cyclic duplexes. The C(6/I)-unsubstituted A*[ce]U allyl alcohols 19 and 23 form linear duplexes, whereas the C(6/I)-substituted A*[ce]U* allyl alcohols 21 and 25, and the C(5,/I)-deoxy A*[ce]U(*) dimers 27 and 29 also form minor amounts of cyclic duplexes. The influence of intra- and intermolecular H-bonding of the allyl alcohols and the influence of the base sequence upon the formation of cyclic duplexes are discussed. [source] Benzo[a]heptalenes from Heptaleno[1,2- c]furans.HELVETICA CHIMICA ACTA, Issue 4 2007Abstract It is shown in this ,Part 2' that heptaleno[1,2- c]furans 1 react thermally in a Diels,Alder -type [4+2] cycloaddition at the furan ring with vinylene carbonate (VC), phenylsulfonylallene (PSA), , -(acetyloxy)acrylonitrile (AAN), and (1Z)-1,2-bis(phenylsulfonyl)ethene (ZSE) to yield the corresponding 1,4-epoxybenzo[d]heptalenes (cf. Schemes,1, 5, 6, and 8). The thermal reaction of 1a and 1b with VC at 130° and 150°, respectively, leads mainly to the 2,3- endo -cyclocarbonates 2,3- endo - 2a and - 2b and in minor amounts to the 2,3- exo -cyclocarbonates 2,3- exo - 2a and - 2b. In some cases, the (P*)- and (M*)-configured epimers were isolated and characterized (Scheme,1). Base-catalyzed cleavage of 2,3- endo - 2 gave the corresponding 2,3-diols 3, which were further transformed via reductive cleavage of their dimesylates 4 into the benzo[a]heptalenes 5a and 5b, respectively (Scheme,2). In another reaction sequence, the 2,3-diols 3 were converted into their cyclic carbonothioates 6, which on treatment with (EtO)3P gave the deoxygenated 1,4-dihydro-1,4-epoxybenzo[d]heptalenes 7. These were rearranged by acid catalysis into the benzo[a]heptalen-4-ols 8a and 8b, respectively (Scheme,2). Cyclocarbonate 2,3- endo - 2b reacted with lithium diisopropylamide (LDA) at ,70° under regioselective ring opening to the 3-hydroxy-substituted benzo[d]heptalen-2-yl carbamate 2,3- endo - 9b (Scheme,3). The latter was O -methylated to 2,3- endo -(P*)- 10b. The further way, to get finally the benzo[a]heptalene 13b with MeO groups in 1,2,3-position, could not be realized due to the fact that we found no way to cleave the carbamate group of 2,3- endo -(P*)- 10b without touching its 1,4-epoxy bridge (Scheme,3). The reaction of 1a with PSA in toluene at 120° was successful, in a way that we found regioisomeric as well as epimeric cycloadducts (Scheme,5). Unfortunately, the attempts to rearrange the products under strong-base catalysis as it had been shown successfully with other furan,PSA adducts were unsuccessful (Scheme,4). The thermal cycloaddition reaction of 1a and 1b with AAN yielded again regioisomeric and epimeric adducts, which could easily be transformed into the corresponding 2- and 3-oxo products (Scheme,6). Only the latter ones could be rearranged with Ac2O/H2SO4 into the corresponding benzo[a]heptalene-3,4-diol diacetates 20a and 20b, respectively, or with trimethylsilyl trifluoromethanesulfonate (TfOSiMe3/Et3N), followed by treatment with NH4Cl/H2O, into the corresponding benzo[a]heptalen-3,4-diols 21a and 21b (Scheme,7). The thermal cycloaddition reaction of 1 with ZSE in toluene gave the cycloadducts 2,3- exo - 22a and - 22b as well as 2- exo,3- endo - 22c in high yields (Scheme,8). All three adducts eliminated, by treatment with base, benzenesulfinic acid and yielded the corresponding 3-(phenylsulfonyl)-1,4-epoxybenzo[d]heptalenes 25. The latter turned out to be excellent Michael acceptors for H2O2 in basic media (Scheme,9). The Michael adducts lost H2O on treatment with Ac2O in pyridine and gave the 3-(phenylsulfonyl)benzo[d]heptalen-2-ones 28a and 3- exo - 28b, respectively. Rearrangement of these compounds in the presence of Ac2O/AcONa lead to the formation of the corresponding 3-(phenylsulfonyl)benzo[a]heptalene-1,2-diol diacetates 30a and 30b, which on treatment with MeONa/MeI gave the corresponding MeO-substituted compounds 31a and 31b. The reductive elimination of the PhSO2 group led finally to the 1,2-dimethoxybenzo[a]heptalenes 32a and 32b. Deprotonation experiments of 32a with t -BuLi/N,N,N,,N,-tetramethylethane-1,2-diamine (tmeda) and quenching with D2O showed that the most acid CH bond is HC(3) (Scheme,9). Some of the new structures were established by X-ray crystal-diffraction analyses (cf. Figs.,1, 3, 4, and 5). Moreover, nine of the new benzo[a]heptalenes were resolved on an anal. Chiralcel OD-H column, and their CD spectra were measured (cf. Figs.,8 and 9). As a result, the 1,2-dimethoxybenzo[a]heptalenes 32a and 32b showed unexpectedly new Cotton -effect bands just below 300,nm, which were assigned to chiral exciton coupling between the heptalene and benzo part of the structurally highly twisted compounds. The PhSO2 -substituted benzo[a]heptalenes 30b and 31b showed, in addition, a further pair of Cotton -effect bands in the range of 275,245,nm, due to chiral exciton coupling of the benzo[a]heptalene chromophore and the phenylsulfonyl chromophore (cf. Fig.,10). [source] Diradical-Promoted Two-Carbon Ring-Expansion Reactions by Thermal Isomerization: Synthesis of Functionalized Macrocyclic KetonesHELVETICA CHIMICA ACTA, Issue 7 2004Georg Rüedi A new method for the smooth and highly efficient preparation of functionalized macrocyclic ketones has been developed. Pyrolysis of medium- and large-ring 3-vinylcycloalkanones by dynamic gas-phase thermo-isomerization (DGPTI) at 600,630° yielded, under insertion of a previously attached vinyl side chain by means of a 1,3-C shift, the corresponding ,,, -unsaturated cycloalkanones. The yield of the two-carbon ring-expanded ketones greatly depended on the relative ring strains of substrate and product (5,87%, cf. Table,5). The formation of minor amounts of one-carbon ring-expanded cycloalkenes (<10%) can be ascribed to a subsequent decarbonylation step. A reaction mechanism involving initial cleavage of the weakest single bond in the molecule has been established (cf. Scheme,6). Recombination within the generated diradical intermediate in terminal vinylogous position led to the observed products, while reclosure gave recovered starting material. Substituents on the vinyl moiety were transferred locospecifically into the ring-expanded products. An isopropenyl group did not significantly affect the isomerization process, whereas substrates bearing a prop-1-enyl group in , -position enabled competing intramolecular H-abstraction reactions, leading to acyclic dienones (cf. Schemes,9,11). DGPTI of the 13-membered analogue directly yielded 4-muscenone, which, upon hydrogenation, led to the valuable musk odorant (±)-muscone. Increasing the steric hindrance on the vinyl moiety gave rise to diminishing amounts of the desired ,,, -unsaturated cycloalkanones. This novel two-carbon ring-expansion protocol was also successfully applied to 3-ethynylcycloalkanones, giving rise to the corresponding ring-expanded cyclic allenes (cf. Scheme,13). [source] Reactions of 2-amino-3-cyano-4,5,6,7-tetrahydrobenzo[b]thiophene and 2-amino-3-cyano-4,7-diphenyl-5-methyl-4H -pyrano[2,3- c] pyrazole with phenylisocyanate, carbon disulfide, and thioureaHETEROATOM CHEMISTRY, Issue 1 2005Ahmed S. A. Youssef 2-Amino-3-cyano-4,5,6,7-tetrahydrobenzo[b]thiophene 1a or 2-amino-3-cyano-4,7-di- phenyl-5-methyl-4H -pyrano[2,3- c]pyrazole 2a reacted with phenylisocyanate in dry pyridine to give 2-(3-phenylureido)-3-cyanobenzo[b]thiophene 1b or 2-disubstituted amino-3-cyanopyranopyrazole 2b derivative. However, when 1a and 2a were refluxed with carbon disulfide in 10% ethanolic sodium hydroxide solution, they afforded the thieno[2,3- d]pyrimidin-2,4-dithione derivative 5 in the former case, 2,4-dicyano-1,3-bis(dithio carboxamino)cyclobuta-1,3- diene 6 and pyrazolopyranopyrido[2,3- d]pyrimidin- 2,4-dithione derivative 7 in the latter one. Treatment of 2a with thiourea in refluxing ethanol in the presence of potassium carbonate gave 2,2,-dithiobispyrimidine derivative 9 (major) in addition to pyranopyrazole derivative 10 and 2,2,-dithiobis ethoxypyrimidine derivative 11 in minor amounts. The structures of all products were evidenced by microanalytical and spectral data. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:6,11, 2005; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20070 [source] Simple Methodology for Heck Arylation at C-8 of Adenine NucleosidesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 4 2008Pallavi Lagisetty Abstract A simple method for the arylation of 8-vinyladenine nucleoside derivatives is reported. With a broad set of aryl iodides and bromides, the reaction is catalyzed by the simple combination palladium acetate/tris(o -tolyl)phosphine/triethylamine [Pd(OAc)2/(o -tol)3P/Et3N]. As expected, aryl chlorides are more difficult coupling partners but some undergo reactions with more exotic catalysts. Although trans -olefins are the major products, minor amounts of cis -isomers are detected in some cases, and a post -arylation mechanism for their formation is proposed. Finally, by subtle catalyst modulation chemoselective N -arylation of the nucleoside can be achieved in the presence of the vinyl moiety. [source] Holocene vegetation and climate change on the Colorado Great Plains, USA, and the invasion of Colorado piñon (Pinus edulis)JOURNAL OF BIOGEOGRAPHY, Issue 12 2009R. Scott Anderson Abstract Aim, To reconstruct the last c. 7000 years of vegetation and climate change in an unusual region of modern Great Plains grassland and scarp woodland in south-east Colorado (USA), and to determine the late Holocene biogeography of Colorado piñon (Pinus edulis) at its easternmost extent, using a series of radiocarbon-dated packrat (Neotoma sp.) middens. Location, The West Carrizo Canyon drains the Chaquaqua Plateau, a plateau that projects into the western extent of the southern Great Plains grasslands in south-eastern Colorado, USA. Elevations of the study sites are 1448 to 1525 m a.s.l. Today the plateau is mostly Juniperus scopulorum,P. edulis woodland. Methods, Plant macrofossils and pollen assemblages were analysed from 11 14C-dated packrat middens. Ages ranged from 5990 yr bp (6839 cal. yr bp) to 280 yr bp (485 cal. yr bp). Results, The results presented here provide information on the establishment and expansion of Juniperus,P. edulis woodland at its eastern limits. The analysis of both plant macrofossils and pollen from the 11 middens documents changes in plant communities over the last 7000 years, and the establishment of P. edulis at its easternmost limit. Though very minor amounts of P. edulis pollen occur as early as the middle Holocene, plant macrofossils were only recovered in middens dating after c. 480 cal. yr bp. Main conclusions, Originally, midden research suggested a late glacial refuge to the north-east of the Carrizo Canyon site, and a middle Holocene expansion of P. edulis. Results reported here are consistent with a late Holocene expansion, here at its eastern limits, but noted elsewhere at its northern and north-eastern limits. In general, this late Holocene expansion is consistent with pollen data from sediments in Colorado and New Mexico, and suggests that P. edulis is still expanding its range at its present extremes. This has implications for further extension of its range due to changing climatic conditions in the future. [source] Petrology of coesite-bearing eclogite from Habutengsu Valley, western Tianshan, NW China and its tectonometamorphic implicationJOURNAL OF METAMORPHIC GEOLOGY, Issue 9 2009Z. LÜ Abstract Coesite inclusions in garnet have been found in eclogite boudins enclosed in coesite-bearing garnet micaschist in the Habutengsu Valley, Chinese western Tianshan, which are distinguished from their retrograde quartz by means of optical characteristics, CL imaging and Raman spectrum. The coesite-bearing eclogite is mainly composed of porphyroblastic garnet, omphacite, paragonite, glaucophane and barroisite, minor amounts of rutile and dotted (or banded) graphite. In addition to coesite and quartz, the zoned porphyroblastic garnet contains inclusions of omphacite, Na-Ca amphibole, calcite, albite, chlorite, rutile, ilmenite and graphite. Multi-phase inclusions (e.g. Czo + Pg ± Qtz, Grt II + Qtz and Chl + Pg) can be interpreted as breakdown products of former lawsonite and possibly chloritoid. Coesite occurs scattered within a compositionally homogenous but narrow domain of garnet (outer core), indicative of equilibrium at the UHP stage. The estimate by garnet-clinopyroxene thermometry yields peak temperatures of 420,520 °C at 2.7 GPa. Phase equilibrium calculations further constrain the P,T conditions for the UHP mineral assemblage Grt + Omp + Lws + Gln + Coe to 2.4,2.7 GPa and 470,510 °C. Modelled modal abundances of major minerals along a 5 °C km,1 geothermal gradient suggests two critical dehydration processes at ,430 and ,510 °C respectively. Computed garnet composition patterns are in good agreement with measured core-rim profiles. The petrological study of coesite-bearing eclogite in this paper provides insight into the metamorphic evolution in a cold subduction zone. Together with other reported localities of UHP rocks from the entire orogen of Chinese western Tianshan, it is concluded that the regional extent of UHP-LT metamorphism in Chinese western Tianshan is extensive and considerably larger than previously thought, although intensive retrogression has erased UHP-LT assemblages at most localities. [source] Petrology and P,T path of the Fuping mafic granulites: implications for tectonic evolution of the central zone of the North China cratonJOURNAL OF METAMORPHIC GEOLOGY, Issue 4 2000G. C. Zhao The Fuping Complex and the adjoining Wutai and Hengshan Complexes are located in the central zone of the North China craton. The dominant rock types in the Fuping Complex are high-grade tonalitic,trondhjemitic,granodioritic (TTG) gneisses, with minor amounts of mafic granulites, syntectonic granitic rocks and supracrustal rocks. The petrological evidence from the mafic granulites indicates three stages of metamorphic evolution. The M1 stage is represented by garnet porphyroblasts and matrix plagioclase, quartz, orthopyroxene, clinopyroxene and hornblende. Orthopyroxene+plagioclase symplectites and clinopyroxene+plagioclase±orthopyroxene coronas formed in response to decompression during M2 following the peak metamorphism at M1. Hornblende+plagioclase symplectites formed as a result of further isobaric cooling and retrograde metamorphism during M3. The P,T estimates using TWQ thermobarometry are: 900,950 °C and 8.0,8.5 kbar for the peak assemblage (M1), based on the core compositions of garnet, matrix pyroxene and plagioclase; 700,800 °C and 6.0,7.0 kbar for the pyroxene+plagioclase symplectites or coronas (M2); and 550,650 °C and 5.3,6.3 kbar for the hornblende+plagioclase symplectites (M3), based on garnet rim and corresponding symplectic mineral compositions. These P,T estimates define a clockwise P,T path involving near-isothermal decompression for the Fuping Complex, similar to the P,T path estimated for the metapelitic gneisses. The inferred P,T path suggests that the Fuping Complex underwent initial crustal thickening, subsequent exhumation, and finally cooling and retrogression. This tectonothermal path is similar to P,T paths inferred for the Wutai and Hengshan Complexes and other tectonic units in the central zone of the North China craton, but different from anti-clockwise P,T paths estimated for the basement rocks in the eastern and western zones of the craton. Based on lithological, structural, metamorphic and geochronological data, the eastern and western zones of the craton are considered to represent two different Archean to Paleoproterozoic continental blocks that amalgamated along the central zone at the end of Paleoproterozoic. The P,T paths of the Fuping Complex and other tectonic units in the central zone record the collision between the eastern and western zones that led to the final assembly of the North China craton at c. 1800 Ma. [source] TEMPESTITE DEPOSITS ON A STORM-INFLUENCED CARBONATE RAMP: AN EXAMPLE FROM THE PABDEH FORMATION (PALEOGENE), ZAGROS BASIN, SW IRANJOURNAL OF PETROLEUM GEOLOGY, Issue 2 2004H. Mohseni The Pabdeh Formation is part of a thick carbonate-siliciclastic succession in the Zagros Basin of SW Iran which includes carbonate reservoirs of Cretaceous and Cenozoic ages. From field observations and petrographic and facies analysis of exposures in the type section of the Pabdeh Formation, four lithofacies were recognized. These are from oldest to youngest: (i) a mottled, bioturbated bioclastic wackestone/mudstone facies; (ii) a wackestone/packstone facies with horizontal burrows on bedding planes; (iii) a thin-bedded bioclastic wackestone/mudstone facies alternating with thin bioclastic-oolitic-intraclastic intervals; and (iv) a bioclastic foraminiferal / algal / peloidal packstone facies. These observations indicate that facies evolved upwards from deep outer-ramp deposits to inner-ramp deposits within a shoal complex, suggesting progradation of the ramp depositional system. Storm events significantly influenced the ramp system. Storm-generated surges transported sediments from nearshore to the deeper outer-ramp environment where they were deposited as shell-lags, composed mostly of bioclastic packstones, rich in pelagic microfauna with sharp, undulatory erosional basal contacts. The packstones rest on outer ramp mudstones deposited below storm base level. Sedimentary structures in the Pabdeh Formation are those typical of storm deposits, such as hummocky cross-stratification, ripple cross-lamination, ripple marks, escape burrows on the tops of the beds, couplets of fine- and coarse-grained laminae and mixed fauna, as well as intraclasts derived from underlying facies. These distinctive sequences are interpreted to have been generated by waning storm-generated currents. The dominance of fine-grained sediments (medium to fine sand); the lack of large- scale hummocky cross-stratification; the minor amounts of intraclasts derived from underlying facies; the paucity of amalgamated tempestite beds; and the finely-laminated (mm to cm scale) couplets of coarse and fine lamina all suggest a distal tempestite facies. Palaeogeographic reconstruction of the Zagros Basin during the Eocene indicates that the study area was situated in tropical, storm-dominated palaeolatitudes. [source] POST-DRILLING ANALYSIS OF THE NORTH FALKLAND BASIN, PART 1: TECTONO-STRATIGRAPHIC FRAMEWORKJOURNAL OF PETROLEUM GEOLOGY, Issue 3 2000P. C. Richards Six wells were drilled in the extensional North Falkland Basin in 1998. The wells encountered a Devonian to Cenozoic stratigraphy dominated by thick Mesozoic syn- and post-rift successions. Although most previously published models predicted that the succession would most likely be of marine origin, it is in fact predominantly terrestrial; marine conditions did not become established in the basin until the Late Cretaceous. The oldest rocks recorded are Devonian and these were penetrated in only one well. The overlying succession comprises: a fluvio-lacustrine, early syn-rft interval of ?mid-Jurassic to Tithonian age; a late syn-rift fluvio-lacustrine interval of Tithonian to Berriasian age; a rift-sag transitional unit of Berriasian to Valanginian age; an early post-rift lacustrine unit of Valanginian to early Aptian age; a middle post-rift, transgressive unit of Aptian to Albian age; a late post-rift, terrestrial to marine unit of Albian to early Palaeocene age; and a post-up lift thermal subsidence unit of Palaeocene to Recent age. Much of the sediment appears to have been derived from volcanic and/or metamorphic terranes, probably located to the north or NW of the basin. As well as the volcanic material which occurs in the ground mass and as lithoclasts in many of the units, some volcaniclastic rocks and minor amounts of ashfall tufls are observed, particularly within the late syn-rift succession. [source] Sintering of AlN Using CaO-Al2O3 as a Sintering Additive: Chemistry and Microstructural DevelopmentJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 12 2002Eirik Hagen The densification of aluminum nitride using Ca12Al14O33 as a sintering aid has been studied with emphasis on the effect of using coarse or fine powder, the amount of sintering aid, the sintering temperature, and embedding. Both crystalline and amorphous grain boundary phases were observed. Significant weight losses were observed for coarse-grained samples, and if suitable embedding was not used. Porous and coarse-grained ceramics with high contiguity and minor amounts of secondary phases were obtained by enhanced evaporation while dense ceramics were obtained limiting the evaporation. High weight losses in the graphite environment resulted in formation of a dense AlN surface layer. [source] Synthesis of Hard Materials by Field Activation: The Synthesis of Solid Solutions and Composites in the TiB2,WB2,CrB2 SystemJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 12 2001Hisashi Kaga The synthesis of solid solutions of (Ti,W,Cr)B2 from elemental reactants using the field-activated, pressure-assisted synthesis method and employing the SPS apparatus was investigated. The nature of the products depended on temperature; they were nearly pure solid solutions at 1900°C with minor amounts of ,-WB. The product density and microhardness depended on the temperature of synthesis for the same value of applied pressure (64 MPa). Samples with the highest density (94%) corresponded to a hardness of 22.7 GPa. When annealed at 1500°C, the solid solutions decomposed, precipitating a (W,Ti,Cr)B2 phase in a spinodal form. In addition, ,-WB precipitates in the form of thin (0.4,5.3 nm) layers were observed. They existed in a 60°/120° orientation to the (Ti,W,Cr)B2 matrix, in agreement with previous observations. Highly faceted, small (nanosized) pores associated with the ,-WB precipitates were also observed. [source] Synthesis and Characterization of Styrene/Butyl Acrylate Linear and Star Block Copolymers via Atom Transfer Radical PolymerizationMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 9 2006Jinyu Huang Abstract Summary: Well-defined styrene (S) and butyl acrylate (BA) linear and star-like block copolymers are synthesized via atom transfer radical polymerization (ATRP) using di- and trifunctional alkyl halide initiators employing the Cu/PMDETA (N,N,N,,N,,N,-pentamethyldiethylenetriamine) catalyst system. Initial addition of CuII deactivator and utilization of halogen exchange techniques suppresses the coupling of radicals and improves cross-propagation to a large extent, which results in better control over the polymerization. Two types of star-like PBA/PS block copolymers are prepared by using core-first techniques: a trifunctional PBA or PS macroinitiator extended with the other monomer. Block copolymers with a well-defined structure and low polydispersity (PDI,=,) are obtained in both cases. A trifunctional PBA3 macroinitiator with ,=,136,000 g,·,mol,1 and PDI,=,1.15 is extended to (PBA-PS)3 star-like block copolymer with ,=,171,100 g,·,mol,1 and PDI,=,1.15. A trifunctional PS3 macroinitiator with ,=,27,000 g,·,mol,1 and PDI,=,1.16 g,·,mol,1 is extended to (PS-PBA)3 with ,=,91,500 g,·,mol,1 and PDI,=,1.40. The individual star-like macromolecules as well as their aggregates are visualized by atomic force microscopy (AFM) where the PS and PBA adopt the globular and extended conformation, respectively. For the PBA core star block copolymers, PS segments tend to aggregate either intramolecularly or intermolecularly. PS core star block copolymers form aggregates with a PS core and emanating PBA chains. Most aggregates have ,n,×,3' arms but minor amounts of ,defective' stars with 4, 5, 8, or 11 arms are also observed. The AFM analysis shows that PS core star block copolymers contain about 92% three-arm block copolymers, and the efficiency of cross-propagation is 97.3%. Schematic representation of the synthesis of BA/S star-like block copolymers by ATRP, and their resultant AFM images. [source] Compatibilization of Polyamide-6/Polyarylate Blends by Means of an IonomerMACROMOLECULAR MATERIALS & ENGINEERING, Issue 8 2005Aritz Retolaza Abstract Summary: Polyamide-6 (PA6)/polyarylate of bisphenol A (PAr) blends rich in PA6 and modified with an additional 15% poly[ethylene- co -(methacrylic acid)] partially neutralized with zinc (PEMA-Zn) as a compatibilizer were obtained by melt mixing. Their phase structure, morphology, and mechanical performance were compared with those of the corresponding binary blends. The ternary blends were composed of a PA6 amorphous matrix and a dispersed PAr-rich phase in which reacted PA6 and PEMA-Zn were present. Additionally, minor amounts of a crystalline PA6 phase, and a PEMA-Zn phase were also present. The chemical reactions observed led to a clear decrease in the dispersed particle size when PEMA-Zn was added, indicating compatibilization. Consequently, the mechanical behavior of the blends with PEMA-Zn improved, leading, mainly in the case of the blend with 10% PAr, to significant increases in both ductility and impact strength with respect to those of the binary blends. These increases were more remarkable than the slight decrease in stiffness as a consequence of the rubbery nature of the compatibilizer. Cryogenically fractured surface of the PA6/PAr-PEMA-Zn 70/30-15 ternary blend. [source] Stress corrosion cracking susceptibility of stainless steels in pulp cooking processes,online capillary electrophoresis, potentiostatic and chromatographic studiesMATERIALS AND CORROSION/WERKSTOFFE UND KORROSION, Issue 8 2008H. Leinonen Abstract An online high temperature capillary electrophoresis instrument (HotUCE), a potentiometer and an ion chromatograph were used in studies on corrosive ions and changes in potential at normal pulping process temperatures in experimental liquors modelling pulp cooking processes at mills. The aim was to evaluate the stress corrosion cracking (SCC) susceptibility of stainless steels. The HotUCE instrument and the potentiometer were online coupled with an autoclave, where welded duplex stainless steel samples were immersed for 500 h in simulated high ionic strength hot black liquor (HBL), hot white liquor (HWL) or green liquor (GL) at 130, 150 or 170,°C, respectively. The results showed that only minor amounts of oxidized sulphur compounds were formed. The concentrations of corrosive sulphur anions were calculated against sulphur standards. Amounts of sulphur species in the liquor correlated with the changes in the potential of the duplex stainless steel specimens during the cooking experiments. The formation of sulphite during cooking was greater in HWL than in HBL. Changes in the potential showed that reduction processes occurred during the SCC tests. The results indicate that the SCC risk is enhanced at higher temperatures, probably, due to the increased formation of thiosulphate. [source] The determination of n -alkanes in the cuticular wax of leaves of Ludwigia adscendens L.PHYTOCHEMICAL ANALYSIS, Issue 2 2004A. Barik Abstract An n -hexane extract of fresh, mature leaves of Ludwigia adscendens, containing a thin layer of epicuticular waxes, has been analysed for the ,rst time by TLC, IR and GC using standard hydrocarbons. The leaves contained 22 identi,ed long chain (C15,C36) n -alkanes, accounting for 74.27% of the hydrocarbons present, and an unknown number of unidenti,ed branched chain alkanes. The predominant n -alkane was C25 (11.02%), whilst C18 (7.62%), C20 (6.14%), C29 (5.36%) and C27 (5.29%) n -alkanes were moderately abundant: the C35 homologue was present only in minor amounts (0.22%). Copyright © 2004 John Wiley & Sons, Ltd. [source] Effect of protein structure on deamidation rate in the Fc fragment of an IgG1 monoclonal antibody,PROTEIN SCIENCE, Issue 8 2009Sandipan Sinha Abstract The effects of secondary structure on asparagine (N) deamidation in a 22 amino acid sequence (369-GFYPSDIAVEWESNGQPENNYK-390) of the crystallizable (Fc) fragment of a human monoclonal antibody (Fc IgG1) were investigated using high-resolution ultra performance liquid chromatography with tandem mass spectrometry (UPLC/MS). Samples containing either the intact Fc IgG (,50 kD) ("intact protein"), or corresponding synthetic peptides ("peptide") were stored in Tris buffer at 37°C and pH 7.5 for up to forty days, then subjected to UPLC/MS analysis with high energy MS1 fragmentation. The peptide deamidated only at N382 to form the isoaspartate (isoD382) and aspartate (D382) products in the ratio of ,4:1, with a half-life of ,3.4 days. The succinimide intermediate (Su382) was also detected; deamidation was not observed for the other two sites (N387 and N388) in peptide samples. The intact protein showed a 30-fold slower overall deamidation half-life of ,108 days to produce the isoD382 and D387 products, together with minor amounts of D382. Surprisingly, the D382 and isoD387 products were not detected in intact protein samples and, as in the peptide samples, deamidation was not detected at N388. The results indicate that higher order structure influences both the rate of N-deamidation and the product distribution. [source] Ag-Cu-Pb-Bi-S Minerals Newly Discovered from the Ohori Base Metal Deposit, Yamagata Prefecture, NE Japan: Implications for Bi-metallogenesis in the Green-Tuff RegionRESOURCE GEOLOGY, Issue 1 2010Yu Yokoro Abstract The Ohori deposit, one of the base metal deposits in the Green-Tuff region, NE Japan, is composed of two types of mineralization; a skarn-type (Kaninomata orebody) made by the replacement of the Miocene calcareous layer, and a vein-type (Nakanomata orebody). While the ore mineral assemblage of the deposit (chalcopyrite, pyrite, sphalerite and galena) has been known for being rather simple, some Pb-Bi-S minerals have been discovered for the first time in the present study. The minerals mainly occur in the chalcopyrite-rich ores of both orebodies. They essentially belong to the Pb-Bi-S system and contain Cu and Ag in minor amounts, which correspond to the lillianite,gustavite solid solution series (phases Z and X), cosalite, neyite, felbertalite, krupkaite and Bi-bearing galena. The chalcopyrite-rich (Bi-bearing) ores from both orebodies are richer in chalcopyrite, pyrite and chlorite, and have higher homogenization temperatures (>300°C) of fluid inclusions, and higher FeS contents in sphalerite compared to the Bi-free ores. In the Green-Tuff region, Bi-minerals have been reported from many base metal deposits. Most of these Bi-bearing ore deposits are referred to as xenothermal-type deposits, and are characterized by the following common features; composite mineralization of high- and low-temperatures in the shallower environments, and close relationships with the Tertiary granitic rocks. The whole mineralization at the Ohori deposit also has a similar xenothermal character because of the coexistence of high-temperature chalcopyrite-rich ores with Pb-Bi-S minerals, which were formed by the influence of the Tertiary granitic rocks at a shallow depth. [source] Genesis of Tertiary Magnetite,Apatite Deposits, Southeast of Zanjan, IranRESOURCE GEOLOGY, Issue 4 2009Hossein Azizi Abstract Magnetite,apatite deposits in the Alborz volcano,plutonic belt, southeast Zanjan, in Iran, have blade, lenzoid, and vein forms, which extend in an E-W direction. There are many magnetite,apatite veins and veinlets in this region, and some of them are economically important, such as Zaker, Morvarid, Sorkheh,Dizaj, and Aliabad. The sizes of the vein orebodies vary between 2 and 16 m in width, 10,100 m in length, and 5,40 m in depth. Microscopic examination of thin sections and polishes indicate that they are composed of magnetite and apatite, with minor amounts of goethite, hematite, actinolite, quartz, muscovite,illite, talc, dolomite, and calcite. The geochemistry and mineralogy of the granitic host rock reveals that it is calc-alkaline and I-type. Field observations, mineral paragenesis, the composition of the orebodies, and the composition of the fluid inclusions in the apatite minerals with low salinity (less than 20 wt.% NaCl equivalent) indicate that these magnetite veins were hydrothermally generated at about 200,430°C and are not related to silica,iron oxide immiscibility, as are the major Precambrian magnetite deposits in central Iran. [source]
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