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PubMed2003

Comparative kinetic studies of the copolymerization of cyclohexene oxide and propylene oxide with carbon dioxide in the presence of chromium salen derivatives. In situ FTIR measurements of copolymer vs cyclic carbonate production.

The catalysis of the reaction of carbon dioxide with epoxides (cyclohexene oxide or propylene oxide) using the (salen)Cr(III)Cl complex as catalyst, where H(2)salen = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexenediimine (1), to provide copolymer and cyclic carbonate has been investigated by in situ infrared spectroscopy. As previously demonstrated for the cyclohexene oxide/CO(2) reaction in the presence of complex 1, coupling of propylene oxide and carbon dioxide was found to occur by way of a pathway first-order in catalyst concentration. Unlike the cyclohexene oxide/carbon dioxide reaction catalyzed by complex 1, which affords completely alternating copolymer and only small quantities of trans-cyclic cyclohexyl carbonate, under similar conditions propylene oxide/carbon dioxide produces mostly cyclic propylene carbonate. Comparative kinetic measurements were performed as a function of reaction temperature to assess the activation barrier for production of cyclic carbonates and polycarbonates for the two different classes of epoxides, i.e., alicyclic (cyclohexene oxide) and aliphatic (propylene oxide). As anticipated in both instances the unimolecular pathway for cyclic carbonate formation has a larger energy of activation than the bimolecular enchainment pathway. That is, the energies of activation determined for cyclic propylene carbonate and poly(propylene carbonate) formation were 100.5 and 67.6 kJ.mol(-1), respectively, compared to the corresponding values for cyclic cyclohexyl carbonate and poly(cyclohexylene carbonate) production of 133 and 46.9 kJ.mol(-1). The small energy difference in the two concurrent reactions for the propylene oxide/CO(2) process (33 kJ.mol(-1)) accounts for the large quantity of cyclic carbonate produced at elevated temperatures in this instance.

Journal Article↗
PubMed2005

The structure of a trimolecular liquid: tert-butyl alcohol:cyclohexene:water.

The structure of the trimolecular liquid mixture of 2:6:1 cyclohexene, tert-butyl alcohol, and water has been investigated using hydrogen/deuterium substitution neutron scattering techniques, and a three-dimensional structural model refined to be consistent with the experimental data has been built using the technique of Empirical Potential Structure Refinement. The model shows a well-mixed solution of the three molecular components where the competing interactions between the nonpolar cyclohexene and polar water molecules are balanced in the solution leading to largely pure-alcohol-like interactions between the tert-butyl alcohol molecules. Cyclohexene molecules favor direct solvation by alcohol methyl groups while water molecules are accommodated, dispersed throughout the solution, via hydrogen bonding interactions with the alcohol molecule hydroxyl groups. Rare occurrences of direct cyclohexene-water interactions are of the classic hydrophobic hydration type and no evidence is found for microscopic heterogeneity in the trimolecular mixture in contrast to the general findings for binary alcohol-water solutions.

Journal Article↗
PubMed1978

Breaks induced in the deoxyribonucleic acid of aerosolized Escherichia coli by ozonized cyclohexene.

The inactivation of aerosolized Escherichia coli by ozone, cyclohexene, and ozonized cyclohexene was studied. The parameters for damage were loss of reproduction and introduction of breaks in the deoxyribonucleic acid (DNA). Aerosolization of E. coli in clean air at 80 percent relative humidity or in air containing either ozone or cyclohexene hardly affected survival; however, some breaks per DNA molecule were induced, as shown by sucrose gradient sedimentation of the DNA. Aerosolization of E. coli in air containing ozonized cyclohexene at 80 percent relative humidity decreased the survival by a factor of 10(3) or more after 1 h of exposure and induced many breaks in the DNA.

Aerosols↗
PubMed2005

Fluorescent properties of pentamethine cyanine dyes with cyclopentene and cyclohexene group in presence of biological molecules.

A series of pentamethine cyanine dyes with cyclohexene or cyclopentene group in polymethyne chain, assumed as DNA groove-binders, were studied as fluorescent probes for nucleic acids as well as for native and denatured proteins. It was revealed that the presence of methyl or dimethyl substituent in 5 position of the cyclohexene group hinders the formation of dye-DNA fluorescent complex, while the methyl substituent in 2 position leads to the increasing of the dye-DNA complex fluorescence intensity. The dyes SL-251, SL-1041, and SL-1046 containing methyl group in the 2 position of the cyclic group, are reported as bright DNA-sensitive dyes. The study of the dyes DNA-binding specificity demonstrated significant AT-preference that points to the groove-binding interaction mode. At the same time, the dyes SL-251, SL-377, and SL-957 with the 2-methyl substituted cyclohexene group were shown to be sensitive fluorescent dyes both for nonspecific (in SDS presence) proteins detection and for native BSA.

Animals↗
PubMed2005

Oligonucleotides with cyclohexene-nucleoside building blocks: crystallization and preliminary X-ray studies of a left-handed sequence GTGTACAC.

Cyclohexene nucleic acids contain a cyclohexene ring instead of the normal beta-D-2'-deoxyribose. The cyclohexene oligonucleotide GTGTACAC was synthesized using phosphoramidite chemistry and standard protecting groups. Crystals of GTGTACAC were obtained at 289 K by the hanging-drop vapour-diffusion technique. The crystals diffract to 1.7 A resolution and belong to the trigonal space group R3, with unit-cell parameters a = 41.434, c = 66.735 A.

Base Sequence↗
PubMed1999

Purification and some properties of two enzymes from rat liver cytosol that catalyze carbonyl reduction of 6-tert-butyl-2, 3-epoxy-5-cyclohexene-1,4-dione, a metabolite of 3-tert-butyl-4-hydroxyanisole.

6-tert-Butyl-2,3-epoxy-5-cyclohexene-1,4-dione (TBE), a metabolite of 3-tert-butyl-4-hydroxyanisole, was converted to 6-tert-butyl-2, 3-epoxy-4(R)-hydroxy-5-cyclohexen-1-one ((4R)-TBEH) and 6-tert-butyl-2,3-epoxy-4(S)-hydroxy-5-cyclohexen-1-one ((4S)-TBEH) by TBE-reducing enzymes in rat liver cytosol. Two TBE-reducing enzymes (TBE-R1 and TBE-R2) were purified 18- and 117-fold, respectively, to apparent homogeneity from rat liver cytosol using DEAE-Sephacel, Blue Sepharose CL-6B, hydroxylapatite, and Sephadex G-100 column chromatography. Gel filtration and sodium dodecyl sulfate-polyacrylamide gel electrophoresis indicated that both enzymes were monomeric. The purified TBE-R1 and TBE-R2 had molecular weights of 37 and 35 kDa and isoelectric points of 6.5 and 5.8, respectively. Both enzymes had an optimum pH of about 5.5 with TBE as substrate. TBE-R1 utilized NADH or NADPH equally as cofactor, and the Km values of NADH and NADPH for TBE with TBE-R1 were estimated to be 15 and 29 microM, respectively. On the other hand, TBE-R2 specifically utilized NADPH and the Km value for TBE was estimated to be 92 microM in the presence of NADPH. Both enzymes reduced aromatic aldehydes, ketones, and quinones at higher rates. In addition, TBE-R2 reduced and oxidized 3-ketosteroids at a higher rate in the presence of NAD(H) and/or NADP(H). Both enzyme activities were inhibited by quercitrin or p-chloromercuribenzoic acid, but little inhibition was observed with phenobarbital or pyrazole. Dicoumarol inhibited significantly TBE-R1 activity but not TBE-R2 activity. In the conversion of TBE to TBEH, TBE-R1 preferentially reduced TBE to (4R)-TBEH, whereas TBE-R2 preferred the reduction of TBE to (4S)-TBEH.

Alcohol Oxidoreductases↗
PubMed1991

A bireactant, irreversible, active-site-directed inhibitor of beta-D-galactosidase (Escherichia coli). Synthesis and properties of (1/2,5,6)-2-(3-azibutylthio)-5,6-epoxy-3-cyclohexen-1-ol.

(1/2,5,6)-2-(3-Azibutylthio)-5,6-epoxy-3-cyclohexen-1-ol (1) was synthesized and was found to irreversibly inactivate beta-D-galactosidase (Escherichia coli). The inactivation was prevented by the presence of isopropyl 1-thio-beta-D-galactopyranoside (IPTG). The vinyloxirane group of 1 reacted with water and other nucleophiles, especially at higher pH values. Reaction of 1 with beta-D-galactosidase was slow enough so that a competitive-inhibition constant (Ki) of 29mM could be determined. The inhibition constant for (1,2/3,6)-6-(3-azibutylthio)-2-bromo-4-cyclohexene-1,3-diol (2), the precursor of the bireactant inhibitor 1, was 13 mM, while that of (1,3/2,4)-3-(3-azibutylthio)-5-cyclohexene-1,2,4-triol (3), the product formed when the reactant is allowed to react with water, was 23mM. After irradiation by light, beta-D-galactosidase that had initially been treated with the bireactant compound and then digested with trypsin, showed a new pattern of elution from h.p.l.c., indicating that there was reaction at two regions of the beta-D-galactosidase molecule.

Azo Compounds↗
PubMed1997

Effect of 2-cyclohexene-1-one-induced glutathione diminution on ischemia/reperfusion-induced alterations in the physical state of brain synaptosomal membrane proteins and lipids.

Glutathione is able to protect membrane proteins from oxidative stress. In ischemia/reperfusion injury, free radicals cause synaptosomal membrane protein and lipid oxidation that is prevented by the free radical scavenger N-tert-butyl-alpha-phenylnitrone (Hall N. C. et al. (1995) Neuroscience 64, 81-89; 69, 591-600). We wondered if diminution of glutathione would lead to further membrane alterations. Accordingly, the effects of glutathione depletion, by intraperitoneal administration of 2-cyclohexene-1-one, on the physical state of cortical synaptosomal membrane proteins and lipids, with and without global ischemia/reperfusion, were studied in vivo and in vitro in adult and aged gerbils utilizing electron paramagnetic resonance spectrometry. 2-Cyclohexene-1-one (100 mg/kg, i.p.) was administered 30 min prior to 10-min ischemia followed by 1 or 14 h reperfusion. This glutathione reduction agent was also administered to gerbils under the same temporal schedule in the absence of ischemia and compared to untreated controls. Synaptosomal membranes were labeled with a protein-specific spin label, 2,2,6,6-tetramethyl-4-maleimidopiperidine-1-oxyl, or a lipid-specific spin probe, 5-doxylstearic acid. There were no significant changes in the physical state of the lipid portion of synaptosomal membranes when comparing ischemia reperfusion and 2-cyclohexene-1-one-treated ischemia reperfusion in either the adult or aged gerbils. However, glutathione depletion without ischemia/reperfusion caused significant changes in the physical state of the protein portion of cortical synaptosomal membranes in both the adult and aged models. Glutathione depletion, without ischemia/reperfusion, in the adult model showed a maximum change at 3 h that returned to control values by 14 h. In contrast, the aged model showed significant changes at 1 h reperfusion, which did not return to control values by 14 h reperfusion. Glutathione depletion combined with ischemia/reperfusion caused initial protein change in both adult and aged models at 1 h reperfusion, which did not return toward control values by 14 h reperfusion. The results of this study suggest that glutathione depletion increases the severity of membrane protein damage associated with ischemia/reperfusion injury.

Animals↗
PubMed1992

Structure determination of the cyclohexene ring of retinal in bacteriorhodopsin by solid-state deuterium NMR.

The orientation and conformation of retinal within bacteriorhodopsin of the purple membrane of Halobacterium halobium was established by solid-state deuterium NMR spectroscopy, through the determination of individual chemical bond vectors. The chromophore ([2,4,4,16,16,17,17,17,18,18-2H11]retinal) was specifically deuterium-labeled on the cyclohexene ring and incorporated into the protein. A uniaxially oriented sample of purple membrane patches was prepared and measured at a series of inclinations relative to the spectrometer field. 31P NMR was used to characterize the mosaic spread of the oriented sample, and computer simulations were applied in the analysis of the 2H NMR and 31P NMR spectral line shapes. From the deuterium quadrupole splittings, the specific orientations of the three labeled methyl groups on the cyclohexene ring could be calculated. The two adjacent methyl groups (on C1) of the retinal were found to lie approximately horizontal in the membrane and make respective angles of 94 degrees +/- 2 degrees and 75 degrees +/- 2 degrees with the membrane normal. The third group (on C5) points toward the cytoplasmic side with an angle of 46 degrees +/- 3 degrees. These intramolecular constraints indicate that the cyclohexene ring lies approximately perpendicular to the membrane surface and that it has a (6S)-trans conformation. From the estimated angle of the tilt of the chomophore long axis, it is concluded that the polyene chain is slightly curved downward to the extracellular side of the membrane.

Bacteriorhodopsins↗
PubMed2005

Aluminum salen complexes and tetrabutylammonium salts: a binary catalytic system for production of polycarbonates from CO2 and cyclohexene oxide.

A series of complexes of the form (salen)AlZ, where H2salen = N,N'-bis(salicylidene)-1,2-phenylenediimine and various other salen derivatives and Z = Et or Cl, have been synthesized. Several of these complexes have been characterized by X-ray crystallography. An investigation of the utilization of these aluminum derivatives along with both ionic and neutral bases as cocatalysts for the copolymerization of carbon dioxide and cyclohexene oxide has been conducted. By studying the reactivity of these complexes for this process as substituents on the diimine backbone and phenolate rings are altered, we have observed that aluminum prefers electron-withdrawing groups on the salen ligands, thereby producing an electrophilic metal center to be most active toward production of polycarbonates from CO2 and cyclohexene oxide. For example, the complex derived from H2salen = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-ethylenediimine is essentially inactive when compared to the analogous derivative containing nitro substituents in the 3-positions of the phenolate groups. This is to be contrasted with the catalytic activity observed for the (salen)CrX systems, where electron-donating salen ligands greatly enhanced the reactivity of these complexes for the coupling of CO2 and epoxides. While (salen)AlZ complexes are capable of producing poly(cyclohexene oxide) carbonate with low amounts of polyether linkage along with small quantities of cyclic carbonate byproducts, their reactivities, covering a turnover frequency range of 5.2-35.4 mol of epoxide consumed/(mol of Al x h), are greatly reduced when compared to their (salen)CrX analogues under identical reaction conditions.

Journal Article↗
PubMed2006

Bimetallic fluorine-substituted anilido-aldimine zinc complexes for CO2/(cyclohexene oxide) copolymerization.

Regioselective nucleophilic aromatic substitution of an o-fluorine occurs to afford fluorine-substituted o-phenylene-bridged bis(anilido-aldimine) compounds o-C6H4[(C6H2R2)N=CH-C6F4-(H)N(C6H3R'2)]2 when Li(H)N-C6H3R'2 (R' = iPr, Et, Me) is reacted with o-C6H4[(C6H2R2)N=CH-C6F5]2 (R = iPr, Et, Me) in a nonpolar solvent such as diethyl ether or toluene. Successive additions of Me2Zn and SO2 gas to the bis(anilido-aldimine) compounds afford quantitatively dinuclear mu-methylsulfinato zinc complexes o-C6H4[[(C6H2R2)N=CH-C6F4-N(C6H3R'2)-kappa2N,N]Zn(mu-OS(O)Me)]2 (R = iPr, R' = iPr, 3a; R = iPr, R' = Me, 3c; R = Et, R' = (i)Pr, 3d; R = Et, R' = Et, 3e; R = Et, R' = Me, 3f; R = Me, R' = iPr, 3g; R = Me, R' = Et, 3h; R = Me, R' = Me, 3i). The molecular structure of 3c was confirmed by X-ray crystallography. Fluorine-substituted complexes 3a-i show significantly higher TOF (turnover frequencies) than the unfluorinated analogues for CO2/(cyclohexene oxide) copolymerization. The TOF is highly sensitive to the substituents R and R', and the highest TOF (2480 h(-1)) is obtained with 3g (R = Me, R' = iPr). Complex 3g is less sensitive to the residual protic impurities present in the monomers and shows activity at such a low catalyst concentration as [Zn]:[cyclohexene oxide] = 1:50,000, at which the unfluorinated analogue is completely inactive. By realizing the activity at such an extremely low [Zn]:[cyclohexene oxide] ratio, we achieve a high TON (turnover number) up to 10,100. High-molecular-weight polymers (M(n), 100,000-200,000) are obtained with a rather broad molecular-weight distribution (M(w)/M(n), 1.3-2.5). The obtained polymers are not perfectly alternating, and variable carbonate linkages (65-85%) are observed depending on the N-aryl ortho substituents R and R' and the polymerization conditions.

Journal Article↗
PubMed2000

Facial selectivity in epoxidation of 2-cyclohexen-1-ol with peroxy acids. A computational DFT study

We addressed the mechanism of epoxidation of 2-cyclohexen-1-ol by locating all the transition structures (TSs) for the reaction of peroxyformic acid (PFA) with both pseudoequatorial and pseudoaxial cyclohexenol conformers (five TSs for each conformer) and, for purpose of comparison, also those for the PFA epoxidation of cyclohexene. Geometry optimizations were performed at the B3LYP/6-31G level, energies refined with single point B3LYP/6-311+G// B3LYP/6-31G calculations and solvent effects introduced with the CPCM method. Our results can be summarized as follows: (i) all TSs exhibit a spiro-like structure, that is, the dihedral angle between the peroxy acid plane and the forming oxirane plane is closer to 90 degrees than to 0 degrees (or 180 degrees ); (ii) there is a stabilizing hydrogen bonding interaction in syn TSs that, however, is partly counteracted by unfavorable entropic effects; (iii) syn,exo TSs with hydrogen bonding at the PFA peroxy oxygens are definitely more stable than syn,endo TSs hydrogen bonded at the PFA carbonyl oxygen; (iv) facial selectivity of epoxidation of both cyclohexenol conformers is mostly the result of competition between only two TSs, namely, an anti,exo TS and its syn,exo counterpart. The latter TS is more stable than the former one, as stabilization by hydrogen bonding overrides the unfavorable entropic and solvent effects; (v) calculations correctly predict both the experimental dominance of attack leading to syn epoxide for both cyclohexenol conformers and the higher syn selectivity observed for the pseudoequatorial as compared to the pseudoaxial derivative. Moreover, also the experimental relative and absolute epoxidation rates for cyclohexene and cyclohexenol as well as for pseudoaxial and pseudoequatorial cyclohexenol derivatives are fairly well reproduced by computational data.

Journal Article↗
PubMed1981

Inhibition of human polymorphonuclear leukocyte function by 2-cyclohexene-1-one. A role for glutathione in cell activation.

2-cyclohexene-1-one and diethyl maleate specifically decrease reduced glutathione (GSH) levels in human polymorphonuclear leukocytes (PMN) by direct conjugation, and by interaction with the glutathione-s-transferase system. Using these two nontoxic reagents we have examined the effect of decreased GSH levels on five parameters of PMN activation: superoxide generation, release of the lysosomal enzymes lysozyme and beta-glucuronidase, and increases in the influx of Na+ and Ca2+. When PMN pretreated with 2-cyclohexene-1-one or diethyl maleate were incubated with formyl-methionyl-leucyl-phenylalanine (FMLP) or the proteolytic fragment of the fifth component membrane of complement, C5a, agents that interact with surface membrane receptors, increases in all five parameters were inhibited in a dose-dependent manner. For O-2 generation and lysosomal enzyme release the ID50 for 2-CHX-1 was 40--90 micrometers corresponding with a 30--50% decrease in intracellular GHS. In contrast stimulation of treated PMN by the divalent cation ionophore A23187 or 5-hydroxyeicosatetraenoic acid was much less sensitive to depressed GSH; the ID50 for 2-cyclohexene-1-one was 1 mM or greater, corresponding with an 80--90% decrease in GSH. The effect of lowered GSH was not the result of decreased binding of FMLP to surface receptors because [3H]-FMLP binding studies demonstrated a two- to three-fold increase in the number of available binding sites. These data indicate that normal GSH levels are necessary for the transduction of the activation signal from the exterior to the interior of the PMN, but once initiated the activation sequence proceeds normally despite markedly lowered intracellular GSH.

Calcium↗
PubMed2004

Comparative resistance of Anopheles albimanus and Aedes aegypti to N,N-diethyl-3-methylbenzamide (Deet) and 2-methylpiperidinyl-3-cyclohexen-1-carboxamide (AI3-37220) in laboratory human-volunteer repellent assays.

The insect repellents N,N-diethyl-3-methylbenzamide (Deet) and the racemate and 1S,2'S stereoisomer of 2-methylpiperidinyl-3-cyclohexene-1-carboxamide (AI3-37220) were tested against Anopheles albimanus Wiedemann and Aedes aegypti (L.) in laboratory human-volunteer assays. Estimated skin doses of Deet or racemic AI3-37220 required to reduce biting by 95% in Ae. aegypti were 2.3 and 3.5 x 10(-2) micromol/cm2 skin, respectively, whereas estimated doses for 95% bite reduction of An. albimanus in an approximately 40-yr-old laboratory colony established from El Salvador were 5 times higher at 12 x 10(-2) micromol Deet/cm2 skin and >20 x 10(-2) micromol/cm2 skin for AI3-37220. In tests with the 1S,2'S stereoisomer of AI3-37220, a newly established colony of An. albimanus from Belize bit less aggressively than El Salvador An. albimanus. However, the Belize-derived mosquitoes were as resistant as the old El Salvador colony to repellent effects of 1S,2'S stereoisomer of 2-methylpiperidinyl-3-cyclohexene-1-carboxamide. Earlier workers surmised that usual skin doses of Deet would offer only limited protection against An. albimanus in the field. Our findings support this speculation, but they also indicate that doses of Deet higher than those needed for protection against Ae. aegypti might offer reasonable protection against An. albimanus. Results indicate that neither racemate nor 1S,2'S stereoisomer of 2-methylpiperidinyl-3-cyclohexene-1-carboxamide offer as much protection as Deet against An. Albimanus, despite being highly effective against Ae. aegypti.

Aedes↗
PubMed1978

[Metabolic transformations of the trimethyl - 3,5,5, cyclohexene-2, one-1 (isophorone) (author's transl)].

In the rabbit, isophorone alpha is partly eliminated, unchanged in the expired air and in the urine and, for another part, metabolized in the organism and excreted in the urine. The metabolites which have been characterized are : dimethyl-5,5, cyclohexen-1, one-3, carboxylic-1 acid, deriving from isophorone by methyloxidation, isophorol (trimethyl-3,5,5 cyclohexen-2, ol-1) formed by the reduction of the ketonic group into a secondary alcohol and eliminated as a glucuronide, dihydroisophorone (trimethyl-3,5,5, cyclohexanone) proceeding from the hydrogenation of the cyclohexen cycle and cis and trans trimethyl-3,5,5, cyclohexanols-1. These latter compounds, found in small quantities, are very likely issued from dihydroisophorone which is transformed in the organism into isophorone alpha and cis and trans trimethyl-3,5,5, cyclohexanols-1, according to a process of dismutation.

Animals↗
PubMed1996

In vitro and in vivo (32)P-postlabeling analysis of 4-vinyl-1-cyclohexene (butadiene dimer) diepoxide-DNA adducts.

4-Vinyl-1-cyclohexene diepoxide (VCD), and industrial chemical, and its parent compound, 4-vinyl-1-cyclohexene (VCH), are potential health hazards, a they destroy oocytes in follicles in rodents. VCD is also a skin carcinogen at the site of application in both female and male mice and rats and after gavage, induces ovarian tumors in mice and forestomach tumors in rats. A (32)P-postlabeling assay was developed for the detection and measurement of VCD-DNA adducts. VCD, a direct-acting carcinogen, was reacted with DNA in vitro, as well as through mouse skin painting for 3 days with different doses of VCD. (32)P-Labeled adducts were separated by polyethyleneimine (PEI)-cellulose TLC and detected by screen-enhanced autoradiography. Comparable adduct profiles were obtained in vitro and in vivo. At higher doses (36-225 micro mol/mouse), adduct levels in vivo showed a linear dose response, while there was no difference between 14 and 36 micro mol/mouse. The limit of detection was estimated to be 1-3 adducts in 10(8) DNA nucleotides. The results show that VCD exposure gives rise to (presumably pre-mutagenic) DNA adducts in vivo and that (32)P-postlabeling can be applied to biomonitoring of VCD exposure.

Animals↗
PubMed2001

Modeling the formation of secondary organic aerosol (SOA). 2. The predicted effects of relative humidity on aerosol formation in the alpha-pinene-, beta-pinene-, sabinene-, delta 3-carene-, and cyclohexene-ozone systems.

Atmospheric oxidation of volatile organic compounds can lead to the formation of secondary organic aerosol (SOA) through the gas/particle (G/P) partitioning of the oxidation products. Since water is ubiquitous in the atmosphere, the extent of the partitioning for any individual organic product depends not only on the amounts and properties of the partitioning organic compounds, but also on the amount of water present. Predicting the effects of water on the atmospheric G/P distributions of organic compounds is, therefore, central to understanding SOA formation. The goals of the current work are to gain understanding of how increases in RH affect (1) overall SOA yields, (2) water uptake by SOA, (3) the behaviors of individual oxidation products, and (4) the fundamental physical properties of the SOA phase that govern the G/P distribution of each of the oxidation products. Part 1 of this series considered SOA formation from five parent hydrocarbons in the absence of water. This paper predicts how adding RH to those systems uniformly increases both the amount of condensed organic mass and the amount of liquid water in the SOA phase. The presence of inorganic components is not considered. The effect of increasing RH is predicted to be stronger for SOA produced from cyclohexene as compared to SOA produced from four monoterpenes. This is likely a result of the greater general degree of oxidation (and hydrophilicity) of the cyclohexene products. Good agreement was obtained between predicted SOA yields and laboratory SOA yield data actually obtained in the presence of water. As RH increases, the compounds that play the largest roles in changing both the organic and water masses in the SOA phase are those with vapor pressures that are intermediate between those of essentially nonvolatile and highly volatile species. RH-driven changes in the compound-dependent G/P partitioning coefficient Kp result from changes in both the average molecular weight MWom of the absorbing organic/water phase, and the compound-dependent activity coefficient zeta values. Adding water to the SOA phase by increasing the RH drives down MWom and thereby uniformly favors SOA condensation. The effect of RH on zeta values is compound specific and depends on the hydrophilicity of the specific compound of interest; the more hydrophilic a compound, the more increasing RH will favor its condensation into the SOA phase. The results also indicate that it may be a useful first approximation to assume that zeta = 1 for many compounds making up SOA mixtures.

Aerosols↗
PubMed2005

Role of the cocatalyst in the copolymerization of CO2 and cyclohexene oxide utilizing chromium salen complexes.

The mechanism of the copolymerization of cyclohexene oxide and carbon dioxide to afford poly(cyclohexylene)carbonate catalyzed by (salen)CrN3 (H2salen = N,N,'-bis(3,5-di-tert-butylsalicylidene)-1,2-ethylene-diimine) in the presence of a broad range of cocatalysts has been studied. We have previously established the rate of copolymer formation to be very sensitive to both the electron-donating ability of the salen ligand and the [cocatalyst], where N-heterocyclic amines, phosphines, and ionic salts were effective cocatalysts. Significant increases in the rate of copolymerization have been achieved with turnover frequencies of approximately 1200 h(-1), thereby making these catalyst systems some of the most active and robust thus far uncovered. Herein we offer a detailed explanation of the role of the cocatalyst in the copolymerization of CO2 and cyclohexene oxide catalyzed by chromium salen derivatives. A salient feature of the N-heterocyclic amine- or phosphine-cocatalyzed processes is the presence of an initiation period prior to reaching the maximum rate of copolymerization. Importantly, this is not observed for comparable processes involving ionic salts as cocatalysts, e.g., PPN+ X-. In these latter cases the copolymerization reaction exhibits ideal kinetic behavior and is proposed to proceed via a reaction pathway involving anionic six-coordinate (salen)Cr(N3)X- derivatives. By way of infrared and 31P NMR spectroscopic studies, coupled with in situ kinetic monitoring of the reactions, a mechanism of copolymerization is proposed where the neutral cocatalysts react with CO2 and/or epoxide to produce inner salts or zwitterions which behave in a manner similar to that of ionic salts.

Carbon Dioxide↗