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Isoprene
Terms modified by Isoprene Selected AbstractsCharacterization of marine isoprene-degrading communitiesENVIRONMENTAL MICROBIOLOGY, Issue 12 2009Laura Acuña Alvarez Summary Isoprene is a volatile and climate-altering hydrocarbon with an atmospheric concentration similar to that of methane. It is well established that marine algae produce isoprene; however, until now there was no specific information about marine isoprene sinks. Here we demonstrate isoprene consumption in samples from temperate and tropical marine and coastal environments, and furthermore show that the most rapid degradation of isoprene coincides with the highest rates of isoprene production in estuarine sediments. Isoprene-degrading enrichment cultures, analysed by denaturing gradient gel electrophoresis and 454 pyrosequencing of the 16S rRNA gene and by culturing, were generally dominated by Actinobacteria, but included other groups such as Alphaproteobacteria and Bacteroidetes, previously not known to degrade isoprene. In contrast to specialist methane-oxidizing bacteria, cultivated isoprene degraders were nutritionally versatile, and nearly all of them were able to use n -alkanes as a source of carbon and energy. We therefore tested and showed that the ubiquitous marine hydrocarbon-degrader, Alcanivorax borkumensis, could also degrade isoprene. A mixture of the isolates consumed isoprene emitted from algal cultures, confirming that isoprene can be metabolized at low, environmentally relevant concentrations, and suggesting that, in the absence of spilled petroleum hydrocarbons, algal production of isoprene could maintain viable populations of hydrocarbon-degrading microbes. This discovery of a missing marine sink for isoprene is the first step in obtaining more robust predictions of its flux, and suggests that algal-derived isoprene provides an additional source of carbon for diverse microbes in the oceans. [source] Aminopyridinate-Stabilized Lanthanoid Complexes: Synthesis, Structure and Polymerization of Ethylene and IsopreneEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 18 2010Christian Döring Abstract A series of aminopyridinate-stabilized dialkyl-lanthanoid complexes has been synthesized and characterized. The complexes were prepared by alkane elimination reacting [Ln(CH2SiMe3)3(thf)2] (Ln = Er, Yb, Lu) or [Ln(CH2Ph)3(thf)3] (Ln = Y, Er, Lu) with one equivalent of the bulky aminopyridine (2,6-diisopropylphenyl)-[6-(2,4,6-triisopropylphenyl)pyridin-2-yl]amine. Single-crystal X-ray analyses were carried out for all of the benzyl derivatives. The reaction of these compounds with ammonium borate leads to the elimination of one of the two alkyl functions and affords organolanthanoid cations. The aminopyridinate-stabilized dialkyl-lanthanoid compounds can initiate the polymerization of isoprene after activation with perfluorinated tetraphenyl borates. The obtained polymers have a 3,4-content of 60,95,%. The metal ion size as well as the addition of alkylaluminium compounds influences the microstructure of the obtained polymer. Aminopyridinate-stabilized organolanthanoid cations of Sc, Lu, Er and Y can polymerize ethylene in the presence of alkylaluminium compounds. The Lu, Er and Y complexes act as a CCTP catalyst and the erbium compound exhibits the highest activity. [source] Palladium-Catalysed Telomerisation of Isoprene with Glycerol and Polyethylene Glycol: A Facile Route to New Terpene DerivativesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 3 2009Alvaro Gordillo Abstract We present here the first example of the telomerisation of isoprene with glycerol and polyethylene glycol (PEG-200), opening a facile route to new terpene structures, based on a combination of renewable and petroleum-based feedstocks. The reaction is catalysed by a palladium-carbene complex. Significantly, this system gives >99% of linear monotelomer products. The factors that govern substrate conversion, dimerisation/telomerisation selectivity, and catalyst activity are studied and discussed. [source] Lanthanide Metal-Organic Frameworks as Ziegler,Natta Catalysts for the Selective Polymerization of IsopreneMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 22 2009Marta J. Vitorino Abstract The unprecedented ability of neodymium-based metal organic frameworks (MOFs) as polymerisation pre-catalysts towards isoprene is reported. Combined with methylaluminoxane (MAO) or modified MAO (MMAO), they afford mainly cis -selective polyisoprene, up to 90.7%. Both the activity and the selectivity are tentatively ascribed to the intrinsic microstructure of the starting materials. Compared to conventional carboxylates, MOFs associated to an Al co-catalyst are less active but the selectivity is found to be higher, and it may be modified by controlling the access to the pores, which would be favored at higher temperatures. Some residual crystalline MOF remains disseminated within the polymer matrix, as shown by X-ray diffraction and X-ray absorption spectroscopy studies. [source] Determination of the stable carbon isotopic compositions of 2-methyltetrols in ambient aerosols from the Changbai MountainsRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 11 2010Li Li Isoprene is one of the most important non-methane hydrocarbons (NMHCs) in the troposphere: it is a significant precursor of O3 and it affects the oxidative state of the atmosphere. The diastereoisomeric 2-methyltetrols, 2-methylthreitol and 2-methylerythritol, are marker compounds of the photooxidation products of atmospheric isoprene. In order to obtain valuable information on the ,13C value of isoprene in the atmosphere, the stable carbon isotopic compositions of the 2-methyltetrols in ambient aerosols were investigated. The 2-methyltetrols were extracted from filter samples and derivatized with methylboronic acid, and the ,13C values of the methylboronate derivatives were determined by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). The ,13C values of the 2-methyltetrols were then calculated through a simple mass balance equation between the 2-methyltetrols, methylboronic acid and the methylboronates. The ,13C values of the 2-methyltetrols in aerosol samples collected at the Changbai Mountain Nature Reserves in eastern China were found to be ,24.66,±,0.90, and ,24.53,±,1.08, for 2-methylerythritol and 2-methylthreitol, respectively. Based on the measured isotopic composition of the 2-methyltetrols, the average ,13C value of atmospheric isoprene is inferred to be close to or slightly heavier than ,24.66, at the collection site during the sampling period. Copyright © 2010 John Wiley & Sons, Ltd. [source] Isoprene Formation in Bacillus subtilis: A Barometer of Central Carbon Assimilation in a Bioreactor?BIOTECHNOLOGY PROGRESS, Issue 5 2002Megan C. Shirk Isoprene (2-methyl-1,3-butadiene) is a volatile hydrocarbon of uncertain function in Bacillus subtilis, and we hypothesized that it is an overflow metabolite produced during excess carbon utilization. Here we tested this idea for phase 2 of isoprene release, a phase that occurs during extracellular acetoin accumulation and its reassimilation. Phase 2 isoprene formation could be disrupted in three different ways, all related to acetoin metabolism. Disruption of a gene essential for acetoin biosynthesis (acetolactic acid synthase, alsS) blocked acetoin formation and led to cessation of phase 2 isoprene formation as well as a variety of pleiotropic effects related to loss of pH control. Growth of the alsS mutant with external pH control reversed most of these effects. Disruption of acetoin catabolism (acetoin dehydrogenase, acoA), also eliminated phase 2 isoprene formation and caused cells to transition directly from phase 1 to phase 3; the latter is attributed to amino acid catabolism. A third alteration of acetoin metabolism was detected in the widely used strain 168 ( trpC2) but not in strain MS175, a trpC mutant constructed in the Marburg strain genetic background. Strain 168 exhibited slow acetoin assimilation compared to that of MS175 or the parental strain, with little or no isoprene formation during this growth phase. These findings support the idea that isoprene release occurs primarily when the rate of carbon catabolism exceeds anabolism and that this volatile hydrocarbon is a product of overflow metabolism when precursors are not required for higher isoprenoid biosynthesis. It is suggested that isoprene release might serve as a useful barometer of the rise and fall of central carbon fluxes during the growth of Bacillus strains in industrial bioreactors. [source] Tobacco smoke carcinogens and breast cancerENVIRONMENTAL AND MOLECULAR MUTAGENESIS, Issue 2-3 2002Stephen S. Hecht Abstract Cigarette smoking is an established cause of a variety of cancer types, but its role in breast cancer etiology is not clear. In this report, the potential role of cigarette smoke carcinogens as causes of human breast cancer is evaluated. Of over 60 known carcinogens in tobacco smoke, several are known to induce mammary tumors in laboratory animals: benzo[a]pyrene (B[a]P), dibenzo[a,l]pyrene (DB[a,l]P), 2-toluidine, 4-aminobiphenyl, 2-amino-3-methylimidazo[4,5- f]quinoline (IQ), 2-amino-1-methyl-6-phenylimidazo[4,5- b]pyridine (PhIP), 1,3-butadiene, isoprene, nitromethane, ethylene oxide, and benzene. Studies in humans demonstrate that tobacco constituents can reach breast tissue. The uptake and metabolic activation of mammary carcinogens such as polycyclic aromatic hydrocarbons (PAHs) and 4-aminobiphenyl are frequently higher in smokers than in nonsmokers. Although it is likely that specific mammary carcinogens in tobacco smoke can reach breast tissue, evidence is lacking at the present time. Some PAHs present in cigarette smoke can be metabolized to sterically hindered diol epoxides, which are potent mammary carcinogens. Thus, compounds such as benzo[c]phenanthrene (B[c]P), not classically considered to be a strong carcinogen in rodents, could nevertheless be metabolized in humans to diol epoxides carcinogenic to the breast. Collectively, the link between smoking and breast cancer is plausible but has been difficult to establish, probably because of the low carcinogen dose. Environ. Mol. Mutagen. 39:119,126, 2002. © 2002 Wiley-Liss, Inc. [source] Characterization of marine isoprene-degrading communitiesENVIRONMENTAL MICROBIOLOGY, Issue 12 2009Laura Acuña Alvarez Summary Isoprene is a volatile and climate-altering hydrocarbon with an atmospheric concentration similar to that of methane. It is well established that marine algae produce isoprene; however, until now there was no specific information about marine isoprene sinks. Here we demonstrate isoprene consumption in samples from temperate and tropical marine and coastal environments, and furthermore show that the most rapid degradation of isoprene coincides with the highest rates of isoprene production in estuarine sediments. Isoprene-degrading enrichment cultures, analysed by denaturing gradient gel electrophoresis and 454 pyrosequencing of the 16S rRNA gene and by culturing, were generally dominated by Actinobacteria, but included other groups such as Alphaproteobacteria and Bacteroidetes, previously not known to degrade isoprene. In contrast to specialist methane-oxidizing bacteria, cultivated isoprene degraders were nutritionally versatile, and nearly all of them were able to use n -alkanes as a source of carbon and energy. We therefore tested and showed that the ubiquitous marine hydrocarbon-degrader, Alcanivorax borkumensis, could also degrade isoprene. A mixture of the isolates consumed isoprene emitted from algal cultures, confirming that isoprene can be metabolized at low, environmentally relevant concentrations, and suggesting that, in the absence of spilled petroleum hydrocarbons, algal production of isoprene could maintain viable populations of hydrocarbon-degrading microbes. This discovery of a missing marine sink for isoprene is the first step in obtaining more robust predictions of its flux, and suggests that algal-derived isoprene provides an additional source of carbon for diverse microbes in the oceans. [source] Aminopyridinate-Stabilized Lanthanoid Complexes: Synthesis, Structure and Polymerization of Ethylene and IsopreneEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 18 2010Christian Döring Abstract A series of aminopyridinate-stabilized dialkyl-lanthanoid complexes has been synthesized and characterized. The complexes were prepared by alkane elimination reacting [Ln(CH2SiMe3)3(thf)2] (Ln = Er, Yb, Lu) or [Ln(CH2Ph)3(thf)3] (Ln = Y, Er, Lu) with one equivalent of the bulky aminopyridine (2,6-diisopropylphenyl)-[6-(2,4,6-triisopropylphenyl)pyridin-2-yl]amine. Single-crystal X-ray analyses were carried out for all of the benzyl derivatives. The reaction of these compounds with ammonium borate leads to the elimination of one of the two alkyl functions and affords organolanthanoid cations. The aminopyridinate-stabilized dialkyl-lanthanoid compounds can initiate the polymerization of isoprene after activation with perfluorinated tetraphenyl borates. The obtained polymers have a 3,4-content of 60,95,%. The metal ion size as well as the addition of alkylaluminium compounds influences the microstructure of the obtained polymer. Aminopyridinate-stabilized organolanthanoid cations of Sc, Lu, Er and Y can polymerize ethylene in the presence of alkylaluminium compounds. The Lu, Er and Y complexes act as a CCTP catalyst and the erbium compound exhibits the highest activity. [source] Toward Diels,Alder Reactions on a Solid Support Using Polymer Bound N -Substituted 3-Hydroxy-4,4-dimethyl-2-pyrrolidinone Acrylate DerivativesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 11 2004Rhalid Akkari Abstract Several N -substituted 3-hydroxy-4,4-dimethyl-2-pyrrolidinone acrylate derivatives, selected to allow their attachment to a polymer, have been prepared and tested as dienophiles in the Diels,Alder reaction. The experiments, performed under TiCl4 catalysis in solution or the solid phase with isoprene and cyclopentadiene as dienes, pointed out the difficulties associated with some of these compounds that failed to give the corresponding cycloadduct. 13C NMR studies provided some evidence regarding the nature of the interactions between the acrylate compounds and TiCl4. It appears that the outcome of the reaction is dependent on the acrylate structure and that the 4-(3-hydroxy-4,4-dimethyl-2-oxopyrrolidin-1-yl)benzoic acid acrylate derivatives are highly efficient to give the cycloadduct in good yield and with high regio- or endoselectivity in both solution and solid-phase reaction conditions. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Control of Solid-State Dye-Sensitized Solar Cell Performance by Block-Copolymer-Directed TiO2 SynthesisADVANCED FUNCTIONAL MATERIALS, Issue 11 2010Pablo Docampo Abstract Hybrid dye-sensitized solar cells are typically composed of mesoporous titania (TiO2), light-harvesting dyes, and organic molecular hole-transporters. Correctly matching the electronic properties of the materials is critical to ensure efficient device operation. In this study, TiO2 is synthesized in a well-defined morphological confinement that arises from the self-assembly of a diblock copolymer,poly(isoprene- b -ethylene oxide) (PI- b -PEO). The crystallization environment, tuned by the inorganic (TiO2 mass) to organic (polymer) ratio, is shown to be a decisive factor in determining the distribution of sub-bandgap electronic states and the associated electronic function in solid-state dye-sensitized solar cells. Interestingly, the tuning of the sub-bandgap states does not appear to strongly influence the charge transport and recombination in the devices. However, increasing the depth and breadth of the density of sub-bandgap states correlates well with an increase in photocurrent generation, suggesting that a high density of these sub-bandgap states is critical for efficient photo-induced electron transfer and charge separation. [source] Interactive effects of elevated CO2 and soil fertility on isoprene emissions from Quercus roburGLOBAL CHANGE BIOLOGY, Issue 11 2004Malcolm Possell Abstract The effects of global change on the emission rates of isoprene from plants are not clear. A factor that can influence the response of isoprene emission to elevated CO2 concentrations is the availability of nutrients. Isoprene emission rate under standard conditions (leaf temperature: 30°C, photosynthetically active radiation (PAR): 1000 ,mol photons m,2 s,1), photosynthesis, photosynthetic capacity, and leaf nitrogen (N) content were measured in Quercus robur grown in well-ventilated greenhouses at ambient and elevated CO2 (ambient plus 300 ppm) and two different soil fertilities. The results show that elevated CO2 enhanced photosynthesis but leaf respiration rates were not affected by either the CO2 or nutrient treatments. Isoprene emission rates and photosynthetic capacity were found to decrease with elevated CO2, but an increase in nutrient availability had the converse effect. Leaf N content was significantly greater with increased nutrient availability, but unaffected by CO2. Isoprene emission rates measured under these conditions were strongly correlated with photosynthetic capacity across the range of different treatments. This suggests that the effects of CO2 and nutrient levels on allocation of carbon to isoprene production and emission under near-saturating light largely depend on the effects on photosynthetic electron transport capacity. [source] Kinetic and product study of the gas-phase reaction of sabinaketone with OH radicalINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 7 2007Nathalie Carrasco Sabinaketone is one major photooxidation product of sabinene, an important biogenic volatile organic compound. This article provides the first product study and the second rate constant determination of its reaction with OH radicals. Experiments were investigated under controlled conditions for pressure and temperature in the LISA indoor simulation chamber using FTIR spectrometry. Kinetic study was carried out at 295 ± 2 K and atmospheric pressure using the relative rate technique with isoprene as the reference compound. The rate constant was found to be ksabinaketone + OH = (7.1 ± 1.0) × 10,12 molecule,1 cm3 s,1. Acetone and formaldehyde were detected as products of the reaction with the respective yields of Racetone = 0.9 ± 0.2 and RHCHO = 1.2 ± 0.3. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 415,421, 2007 [source] Absolute rate constants for the gas-phase ozonolysis of isoprene and methylbutenolINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 3 2004N. Klawatsch-Carrasco The reactions of the biogenic organic compounds isoprene and 2-methyl-3-buten-2-ol (MBO) with ozone have been investigated under controlled conditions for pressure (atmospheric pressure) and temperature (293 ± 2 K), using FTIR spectrometry. CO was added to scavenge hydroxyl radical formation during the ozonolysis experiments. Reaction rate constants were determined by absolute rate technique, by measuring both ozone and the organic compound concentrations. The measured values were k1 = (1.19 ± 0.09) × 10,17 cm3 molecule,1 s,1 for the reaction between ozone and isoprene and k2 = (8.3 ± 1.0) × 10,18 cm3 molecule,1 s,1 for the reaction between ozone and MBO. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 152,156 2004 [source] Rate coefficients and mechanisms of the reaction of cl-atoms with a series of unsaturated hydrocarbons under atmospheric conditionsINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 8 2003John J. Orlando Rate coefficients and/or mechanistic information are provided for the reaction of Cl-atoms with a number of unsaturated species, including isoprene, methacrolein (MACR), methyl vinyl ketone (MVK), 1,3-butadiene, trans -2-butene, and 1-butene. The following Cl-atom rate coefficients were obtained at 298 K near 1 atm total pressure: k(isoprene) = (4.3 ± 0.6) × 10,10cm3 molecule,1 s,1 (independent of pressure from 6.2 to 760 Torr); k(MVK) = (2.2 ± 0.3) × 10,10 cm3 molecule,1 s,1; k(MACR) = (2.4 ± 0.3) × 10,10 cm3 molecule,1 s,1; k(trans -2-butene) = (4.0 ± 0.5) × 10,10 cm3 molecule,1 s,1; k(1-butene) = (3.0 ± 0.4) × 10,10 cm3 molecule,1 s,1. Products observed in the Cl-atom-initiated oxidation of the unsaturated species at 298 K in 1 atm air are as follows (with % molar yields in parentheses): CH2O (9.5 ± 1.0%), HCOCl (5.1 ± 0.7%), and 1-chloro-3-methyl-3-buten-2-one (CMBO, not quantified) from isoprene; chloroacetaldehyde (75 ± 8%), CO2 (58 ± 5%), CH2O (47 ± 7%), CH3OH (8%), HCOCl (7 ± 1%), and peracetic acid (6%) from MVK; CO (52 ± 4%), chloroacetone (42 ± 5%), CO2 (23 ± 2%), CH2O (18 ± 2%), and HCOCl (5%) from MACR; CH2O (7 ± 1%), HCOCl (3%), acrolein (,3%), and 4-chlorocrotonaldehyde (CCA, not quantified) from 1,3-butadiene; CH3CHO (22 ± 3%), CO2 (13 ± 2%), 3-chloro-2-butanone (13 ± 4%), CH2O (7.6 ± 1.1%), and CH3OH (1.8 ± 0.6%) from trans -2-butene; and chloroacetaldehyde (20 ± 3%), CH2O (7 ± 1%), CO2 (4 ± 1%), and HCOCl (4 ± 1%) from 1-butene. Product yields from both trans -2-butene and 1-butene were found to be O2 -dependent. In the case of trans -2-butene, the observed O2 -dependence is the result of a competition between unimolecular decomposition of the CH3CH(Cl)CH(O,)CH3 radical and its reaction with O2, with kdecomp/kO2 = (1.6 ± 0.4) × 1019 molecule cm,3. The activation energy for decomposition is estimated at 11.5 ± 1.5 kcal mol,1. The variation of the product yields with O2 in the case of 1-butene results from similar competitive reaction pathways for the two ,-chlorobutoxy radicals involved in the oxidation, ClCH2CH(O,)CH2CH3 and ,OCH2CHClCH2CH3. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 334,353, 2003 [source] Temperature-dependent kinetic study for ozonolysis of selected tropospheric alkenesINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 12 2002Elena V. Avzianova Ozonolysis reactions of alkenes are suggested to play major roles in the chemistry of the troposphere. Rate constants for the gas-phase reactions of O3 with a series of alkenes were determined using relative rate technique based on GC/FID measurements of alkene decays. Experiments were carried out in air over the temperature range of 278,353 K at an atmospheric pressure of 760 Torr. An excess of 1,3,5-trimethylbenzene was used as a HO radical scavenger in all experiments. Arrhenius parameters were calculated for ozonolysis of 1-butene, 1-pentene, 1-hexene, 1-heptene, 2-methyl-1-butene, isobutene, trans -2-butene, trans -2-pentene, cis -2-pentene, trans -2-hexene, cis -2-hexene, 3-chloropropene, 1,1-dichloroethene, and isoprene from temperature-dependent studies of the rate constants. The rate constants obtained in this study are compared with previous literature data. A good linear correlation between the logarithms of the rate constants and calculated HOMO energies of selected alkenes is observed. However, no clear correlation could have been drawn for chlorinated substituted alkenes. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 678,684, 2002 [source] The fate of the hydroxyalkoxy radical in the OH-initiated oxidation of isopreneINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 4 2002June E. Reitz Rate constants for several intermediate steps in the OH-initiated oxidation of isoprene were determined using laser-photolysis/laser-induced fluorescence of OH radicals at total pressures between 3 and 4 Torr at 295 K. The rate constant for decomposition of the hydroxyalkoxy radical was determined to be (3.0 ± 0.5) × 104 s,1 in this pressure range, which is in fair agreement with previous work. The presence of a prompt alkoxy decomposition pathway was also investigated and found to contribute less than 10% to the total hydroxyalkoxy radical decomposition. The rate constant for the reaction of the hydroxyperoxy radical with NO was determined to be (2.5 ± 0.5) × 10,11 cm3 molecule,1 s,1, which is moderately higher than previously reported. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 255,261, 2002 [source] Kinetics of the reactions of OH with 3-methyl-2-cyclohexen-1-one and 3,5,5-trimethyl-2-cyclohexen-1-one under simulated atmospheric conditionsINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 1 2002James B. McQuaid Relative rate coefficients for the reactions of OH with 3-methyl-2-cyclohexen-1-one and 3,5,5-trimethyl-2-cyclohexen-1-one have been determined at 298 K and atmospheric pressure by the relative rate technique. OH radicals were generated by the photolysis of methyl nitrite in synthetic air mixtures containing ppm levels of nitric oxide together with the test and reference substrates. The concentrations of the test and reference substrates were followed by gas chromatography. Based on the value k(OH + cyclohexene) = (6.77 ± 1.35) × 10,11 cm3 molecule,1 s,1, rate coefficients for k(OH + 3-methyl-2-cyclohexen-1-one) = (3.1 ± 1.0) × 10,11 and k(OH + 3,5,5-trimethyl-2-cyclohexen-1-one) = (2.4 ± 0.7) × 10,11 cm3 molecule,1 s,1 were determined. To test the system we also measured k(OH + isoprene) = (1.11 ± 0.23) × 10,10 cm3 molecule,1 s,1, relative to the value k(OH + (E)-2-butene) = (6.4 ± 1.28) × 10,11 cm3 molecule,1 s,1. The results are discussed in terms of structure,activity relationships, and the reactivities of cyclic ketones formed in the photo-oxidation of monoterpene are estimated. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 34: 7,11, 2002 [source] Structure of charge-transfer reaction complexes in anionic polymerization of isoprene: Quantum chemical calculationsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 2 2005K. K. Kalninsh Abstract A new mechanism of isoprene anionic polymerization is proposed. Its central moment is thermal electronic excitation of a living polyisoprene,isoprene complex into the quasi-degenerate electronically excited state (S · T)1, which is of the charge (electron) transfer character. It is asserted that the probability of chemical bond formation is determined by the free valence index on carbon atoms and by the geometry of reacting complex in the excited state (S · T)1. Semi-empirical AM1 and ab initio 6-31G* quantum chemical calculations revealed low energies of triplet excited levels (<10 kcal/mole). Comparison of isoprene polymerization on free anions and on solvated ion pairs shows that both types of active centers produce vinyl 1,2 (4,3)-units. Free anions generate predominantly 1,2-units, whereas solvated ion pairs tend to form units with the 4,3-structure. Analysis of energies of excited isoprenyl lithium + isoprene complexes shows that the formation of 1,4 (4,1)- cis -polyisoprene in an inert media is most preferable. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 [source] Palladium-Catalysed Telomerisation of Isoprene with Glycerol and Polyethylene Glycol: A Facile Route to New Terpene DerivativesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 3 2009Alvaro Gordillo Abstract We present here the first example of the telomerisation of isoprene with glycerol and polyethylene glycol (PEG-200), opening a facile route to new terpene structures, based on a combination of renewable and petroleum-based feedstocks. The reaction is catalysed by a palladium-carbene complex. Significantly, this system gives >99% of linear monotelomer products. The factors that govern substrate conversion, dimerisation/telomerisation selectivity, and catalyst activity are studied and discussed. [source] Synthesis and characterization of low relative molecular weight trans -1,4-poly(isoprene)JOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2008Huafeng Shao Abstract Low relative molecular weight trans-1,4-polyisoprene oligomers were synthesized successfully by bulk precipitation and solution polymerization with supported titanium catalyst using hydrogen as relative molecular weight modifier. The effects of polymerization conditions on intrinsic viscosity ([,]), catalyst efficiency (CE) and structure of polymer were studied. Increasing the hydrogen pressure resulted in the decrease of [,] of the polymer. With the increasing of hydrogen pressure and reaction temperature, CE decreased but still maintained above 2500 g polymer/g Ti. The percentage composition of (trans-1, 4-unit) in the polymer was over 90% in all results. The crystallinity of polymer was about 50,60% with Tm being about 60°C. The relative molecular weight distribution index (MWD) was quite difference according to the polymerization method. While number average molecular weight (Mn) exceeded 860, polymer turned from viscous materials to fragile wax materials, and then to toughness materials at 1800. Dynamic property testing showed that the additional of this oligomer could increase the wet-skid resistance of the rubber. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Utilisation of C2,C4 gaseous hydrocarbons and isoprene by microorganismsJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 3 2006Jean L Shennan Abstract Microorganisms able to grow on low molecular weight aliphatic hydrocarbon gases, i.e. the n -alkanes, ethane, propane and butane, and the terminal alkenes, ethylene, propylene and butylene, are not uncommon but mainly belong to certain taxonomic groups. These microbes are described in this review together with the pathways by which the hydrocarbons are assimilated. Microbial oxidation of the volatile alkadiene, isoprene, is also discussed. Avenues for possible commercial exploitation of these metabolic activities are also reviewed. Short-chain n -alkane-utilising organisms have been investigated as tools in petroleum exploration and for production of single cell protein. More recently microbes grown on gaseous hydrocarbons other than methane have been evaluated for use in biotechnological production of epoxides, synthesis of chiral epoxyalkanes and as catalysts in bioremediation systems. Copyright © 2005 Society of Chemical Industry [source] Dissociative photoionization of isoprene: experiments and calculationsJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 3 2009Xianyun Liu Abstract Vacuum ultraviolet (VUV) dissociative photoionization of isoprene in the energy region 8.5,18 eV was investigated with photoionization mass spectroscopy (PIMS) using synchrotron radiation (SR). The ionization energy (IE) of isoprene as well as the appearance energies (AEs) of its fragment ions C5H7+, C5H5+, C4H5+, C3H6+, C3H5+, C3H4+, C3H3+ and C2H3+ were determined with photoionization efficiency (PIE) curves. The dissociation energies of some possible dissociation channels to produce those fragment ions were also determined experimentally. The total energies of C5H8 and its main fragments were calculated using the Gaussian 03 program and the Gaussian-2 method. The IE of C5H8, the AEs for its fragment ions, and the dissociation energies to produce them were predicted using the high-accuracy energy model. According to our results, the experimental dissociation energies were in reasonable agreement with the calculated values of the proposed photodissociation channels of C5H8. Copyright © 2009 John Wiley & Sons, Ltd. [source] Investigation of thiol-ene addition reaction on poly(isoprene) under UV irradiation: Synthesis of graft copolymers with "V"-shaped side chainsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 17 2010Guowei Wang Abstract Poly(isoprene) (PI) with pendant functional groups was successfully synthesized by thiol-ene addition reaction under 365 nm UV irradiation, and the functionalized PI was further modified and used to prepare graft copolymers with "V"-shaped side chains. First, the pendant SCH2CH(OH)CH2OH groups were introduced to PI by thiol-ene addition reaction between 1-thioglycerol and double bonds, and the results showed that the addition reaction carried out only on double bonds of 1,2-addition isoprene units. After the esterification of hydroxyl groups by 2-bromoisobutyryl bromide, the forming macroinitiator was used to initiate the atom transfer radical polymerization (ATRP) of styrene (St) and tert -butyl acrylate (tBA), and the graft copolymers PI- g -PS2 and PI- g -PtBA2 or PI- g -PAA2 (by hydrolysis of PI- g -PtBA2) were obtained, respectively. It was confirmed that the graft density of side chains on PI main chains could be easily controlled by variation of the contents of modified 1,2-addition isoprene units on PI. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3797,3806, 2010 [source] Ferrocenyl-functionalized long chain branched polydienesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 10 2009Frederik Wurm Abstract A convenient two-step approach for the synthesis of ferrocenyl-functionalized long chain branched polydienes, based on both butadiene and isoprene, respectively, is presented. Classical living anionic polymerization was used to synthesize different ABn type poly(diene) macromonomers with moderate molecular weights between 1700 and 3200 g/mol and narrow polydispersity. Quantitative end-capping with chlorodimethylsilane resulted in the desired ABn macromonomer structures. In the ensuing Pt-catalyzed hydrosilylation polyaddition, branched, functionalized polydienes were obtained by a concurrent ABn + AR type of copolymerization with mono- and difunctional ferrocenyl silanes (fcSiMe2H or fc2SiMeH). Molecular weights of the branched polymers were in the range of 10,000 to 44,000 g/mol (SEC/MALLS). Because of the large number of functional end groups, high loading with ferrocene units up to 63 wt % of ferrocene was achieved. Detailed studies showed full conversion of the functional silanes and incorporation into the branched polymer. Further studies using DSC, TGA, and cyclovoltammetry (CV) measurements have been performed. Electrochemical studies demonstrated different electrochemical properties for fcSiMe2 - and fc2SiMe-units. The CVs of polymers modified with diferrocenylsilane units exhibit the pattern of communicating ferrocenyl sites with two distinct, separate oxidation waves. The polymers were also deposited on an electrode surface and the electrodes investigated via CV, showing formation of electroactive films with promising results for the use of the materials in biosensors. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2518,2529, 2009 [source] Synthesis and characterization of ether derivatives of brominated poly(isobutylene- co -isoprene)JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 2 2006Sergio A. Guillén-Castellanos Abstract Variations of the Williamson ether synthesis were employed to prepare a range of new derivatives of brominated poly(isobutylene- co -isoprene) (BIIR). Unambiguous characterization of the polymeric products was accomplished by spectroscopic comparisons to low-molecular-weight analogues derived from brominated 2,2,4,8,8-pentamethyl-4-nonene, which served as a model for the reactive functionality found within BIIR. The substitution of bromide from BIIR occurred at moderate temperatures with stoichiometric amounts of quaternary ammonium phenoxide to yield O-alkylation products in high yields. Simple mixtures of BIIR, KOH, and aliphatic alcohols generated the desired allylic ethers when heated above 110 °C in the absence of quaternary ammonium salts. Knowledge gained from these small-molecule alkylations was used to prepare graft copolymers from BIIR and poly(ethylene oxide) through the exploitation of the apparent ability of polyethers to activate potassium alkoxides in nucleophilic substitutions. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 983,992, 2006 [source] Double hydrophilic block copolymers of sodium(2-sulfamate-3-carboxylate)isoprene and ethylene oxideJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 1 2006Stergios Pispas Abstract Poly(sodium(2-sulfamate-3-carboxylate)isoprene)- b -poly(ethylene oxide) and poly(ethylene oxide)- b -poly(sodium(2-sulfamate-1-carboxylate)isoprene)- b -poly(ethylene oxide) double hydrophilic block copolymers were prepared by selective post polymerization reaction of the polyisoprene block, of poly(isoprene- b -ethylene oxide) diblocks or poly(ethylene oxide- b -isoprene- b -ethylene oxide) triblock precursors, with N -chlorosulfonyl isocyanate. The precursors were synthesized by anionic polymerization high vacuum techniques and had narrow molecular weight distributions and predictable molecular weights and compositions. The resulting double hydrophilic block copolymers were characterized by FTIR and potentiometric titrations in terms of the incorporated functional groups. Their properties in aqueous solutions were studied by viscometry and dynamic light scattering. The latter techniques revealed a complex dilute solution behavior of the novel block copolymers, resulting from the polyelectrolyte character of the functionalized PI block and showing a dependence on solution ionic strength and pH. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 606,613, 2006 [source] Synthesis and spectroscopic characterization of symmetrical isoprene,methyl methacrylate diblock copolymers bearing different anthracene derivatives at the junctionsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 9 2003Jian Yang Abstract We describe the synthesis and characterization of 1-(1-anthryl)-1-phenylethylene (1-An-E) and 1-(2-anthryl)-1-phenylethylene (2-An-E). These species were used to end cap the living end group of polyisoprene (PI) obtained by anionic polymerization in tetrahydrofuran. The anions generated were used to initiate methyl methacrylate polymerization. In this way, we synthesized two symmetrical PI-poly(methyl methacrylate) (PMMA) block copolymers each with a single dye at the junction. PI-An1-PMMA has an anthracene linked via its 1-position. PI-An2-PMMA has the anthracene linked via its 2-position. We compare the UV and fluorescence properties of the polymers to model compounds with similar chromophores. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1225,1236, 2003 [source] Synthesis of a model cyclic triblock terpolymer of styrene, isoprene, and methyl methacrylateJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 10 2002Dimitris Pantazis Abstract The synthesis of a model cyclic triblock terpolymer [cyclic(S- b -I- b -MMA] of styrene (S), isoprene (I), and methyl methacrylate (MMA) was achieved by the end-to-end intramolecular amidation reaction of the corresponding linear ,,,-amino acid precursor [S- b -I- b -MMA] under high-dilution conditions. The linear precursor was synthesized by the sequential anionic polymerization of S, I, and MMA with 2,2,5,5-tetramethyl-1-(3-lithiopropyl)-1-aza-2,5-disilacyclopentane as an initiator and amine generator and 4-bromo-1,1,1-trimethoxybutane as a terminator and carboxylic acid generator. The separation of the unreacted linear polymer from the cyclic terpolymer was facilitated by the transformation of the unreacted species into high molecular weight polymers by the evaporation of the reaction solvent and the continuation of the reaction under high-concentration conditions. The intermediate materials and the final cyclic terpolymer, characterized by size exclusion chromatography, vapor pressure osmometry, thin-layer chromatography, IR and NMR spectroscopy, exhibited high molecular weight and compositional homogeneity. Dilute-solution viscosity measurements were used as an additional proof of the cyclic structure. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1476,1483, 2002 [source] Lanthanide Metal-Organic Frameworks as Ziegler,Natta Catalysts for the Selective Polymerization of IsopreneMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 22 2009Marta J. Vitorino Abstract The unprecedented ability of neodymium-based metal organic frameworks (MOFs) as polymerisation pre-catalysts towards isoprene is reported. Combined with methylaluminoxane (MAO) or modified MAO (MMAO), they afford mainly cis -selective polyisoprene, up to 90.7%. Both the activity and the selectivity are tentatively ascribed to the intrinsic microstructure of the starting materials. Compared to conventional carboxylates, MOFs associated to an Al co-catalyst are less active but the selectivity is found to be higher, and it may be modified by controlling the access to the pores, which would be favored at higher temperatures. Some residual crystalline MOF remains disseminated within the polymer matrix, as shown by X-ray diffraction and X-ray absorption spectroscopy studies. [source] | |||||||||||||||||||||||||||||||