Abstract  One-dimensional and comprehensive two-dimensional flow modulated gas chromatography with simultaneous flame ionization and mass spectrometric detection were applied for the identification and quantification of benzene, toluene, ethyl benzene and xylenes (BTEX) as well as of all C9-C11 aromatic hydrocarbons in the low-boiling petroleum products gasoline, reformate and fluid catalytic cracking (FCC) samples. GC x GC experiments were performed on two reversed phase polarity column sets namely SLB-IL100 (25 m x 250 mu m i.d. x 0.2 mu m d(f)) + HP-5MS (5 m x 250 mu m i.d. x 0.25 mu m d(f)) and SLB-IL111 (30 m x 250 mu m i.d. x 0.2 mu m d(f))+ HP-5MS (5 m x 250 mu m id. x 0.25 pm d(f)). The one-dimensional GC experiments were carried out on the same ionic liquid columns. The most powerful method is GC x GC on the SLB-111+ HP-5MS column combination. Quantitative analysis of individual aromatic hydrocarbons (C6-C11) present in gasoline, reformate and fluid catalytic cracking (FCC) samples was performed by GC x GC-FID using the internal normalization method. Mass spectra obtained by GC x GC-qMSD were used for identification of the aromatic hydrocarbons in these samples. (C) 2013 Elsevier B.V. All rights reserved.

Abstract  A transition-metal-free synthetic method has been developed for the synthesis of unsymmetrical diaryl chalcogenides (S, Se, and Te) from diaryl dichalcogenides and arenes under oxidative conditions by using potassium persulfate at room temperature. Variously substituted arenes such as anisole, thioanisole, diphenyl ether, phenol, naphthol, di- and trimethoxy benzenes, xylene, mesitylene, N,N-dimethylaniline, bromine-substituted arenes, naphthalene, and diaryl dichalcogenides underwent carbon-chalcogen bond-forming reaction to give unsymmetrical diaryl chalcogenides in trifluoroacetic acid. To understand the mechanistic part of the reaction, a detailed in situ characterization of the intermediates has been carried out by (77)Se NMR spectroscopy by using diphenyl diselenide as the substrate. (77)Se NMR study suggests that electrophilic species ArE(+) is generated by the reaction of diaryl dichalcogenide with persulfate in trifluoroacetic acid. The electrophilic attack of arylchalcogenium ion on the arene may be responsible for the formation of the aryl-chalcogen bond.

Abstract  Certain coral reef systems north of the Arabian Gulf are characterized by corals with a unique ability to thrive and flourish despite the presence of crude oil continuously seeping from natural cracks in the seabed. Harboring oil-degrading bacteria as a part of the holobiont has been investigated as a potential mechanism of adaptation and survival for corals in such systems. The use of conventional and molecular techniques verified a predominance of bacteria affiliated with Gammaproteobacteria, Actinobacteria and Firmicutes in the mucus and tissues of Acropora clathrata and Porites compressa. These bacteria were capable of degrading a wide range of aliphatic (C9-C28) aromatic hydrocarbons (Phenanthrene, Biphenyl, Naphthalene) and crude oil. In addition, microcosms supplied with coral samples and various concentrations of crude oil shifted their bacterial population toward the more advantageous types of oil degraders as oil concentrations increased.

Abstract  Naphthalene diimides (NDIs) form emissive ground-state charge-transfer (CT) complexes with various electron rich aromatic solvents like benzene, o-xylene and mesitylene. TD-DFT calculation of the complexes suggests CT interaction and accounts for the observed ground-state changes.

Abstract  Lithiated mesitylene was investigated as a multifunctional initiator for the living anionic polymerization of isoprene. All three methyl groups of mesitylene could be successfully lithiated by using n-BuLi in the presence of tetramethylethylenediamine (TMEDA) in cyclohexane. The average number of lithiated positions in mesitylene increased with reaction time. The solubility of the lithiated products in cyclohexane decreased with the number of lithiated groups, so that the trilithiated product was almost exclusively collected by the filtration of the precipitate. Isoprene could effectively be polymerized by living anionic polymerization by using the lithiated product and a three-arm polyisoprene with a relatively narrow molecular weight distribution was successfully obtained through the "core-first" approach.

Abstract  Prompted by the continued prevalence of hearing related disabilities accepted as eligible for compensation and treatment under Australian Department of Veterans' Affairs legislation, a review of recent literature regarding possible causation mechanisms and thus, possible prevention strategies, is timely. The emerging thoughts on the effects of a combination of jet fuel and noise exposure on the central auditory nervous system (CANS) have relevance in the military aviation context because of the high exposures to solvents (including fuels) and unique noise hazards related to weapons systems and military aircraft. This literature review aimed to identify and analyze the current knowledge base of the effects of combined exposure to JP-8 jet fuel (or its aromatic solvent components) and noise on the CANS in human populations. We reviewed articles examining electrophysiological and behavioral measurement of the CANS following combined exposures to jet fuel (or its aromatic constituents) and noise. A total of 6 articles met the inclusion criteria for the review and their results are summarized. The articles considered in this review indicate that assessment of the CANS should be undertaken as part of a comprehensive test battery for military members exposed to both noise and solvents in the workplace.

Abstract  A 9-Point Lean Direct low emissions combustor concept was utilized to evaluate gaseous emissions performance of two bio-derived alternative jet fuels and a JP-8 fuel for comparison. Gaseous emissions were measured in a flame tube operating at inlet temperatures from 650 up to 1030 F, pressures of 150, 250, and 350 psia, and a range of fuel/air ratios. The alternative fuels consisted of a Hydroprocessed Esters and Fatty Acids Fuel made from tallow and a second bio derived fuel produced from direct fermentation of sugar.

Abstract  The syntheses of silicas with highly ordered cubic Ia3d structure templated by Pluronic P123 (EO20PO70EO20) block copolymer surfactant and sodium dodecyl sulfate (SDS) additive in the presence of swelling agents are demonstrated. It was found that the cubic Ia3d silica forms at 25 °C when a moderate amount of a swelling agent, such as 1,3,5-triisopropylbenzene (TIPB), 1,4-diisopropylbenzene (DIPB), or 1,3,5-triethylbenzene (TEB), is added. However, 1,3,5-trimethylbenzene was not found suitable, suggesting that the success of the synthesis requires a careful selection of a swelling agent. An increase in the relative amount of the swelling agent in a limited range tends to cause an increase in the unit-cell size, while a further unit cell parameter increase can be accomplished with TIPB through a concomitant decrease in the synthesis temperature and increase in the relative amount of the swelling agent. Many of the cubic Ia3d products, including those with the largest attained unit-cell sizes, were highly ordered. When TIPB was used as a swelling agent, the products typically had unusually high mesopore volumes. The latter was largely independent of the ratio of the silica precursor to the Pluronic P123 surfactant for high quality products obtained under particular conditions, which suggests that the cubic Ia3d structure forms at a nearly constant silica-to-surfactant ratio.

Abstract  Enhancing the quality of beef meat is an important goal in terms of improving both the nutritional value for the consumer and the commercial value for producers. The aim of this work was to study the effects of different vegetable oil supplements on growth performance, carcass quality and meat quality in beef steers reared under intensive conditions. A total of 240 Blonde D' Aquitaine steers (average BW=293.7±38.88 kg) were grouped into 24 batches (10 steers/batch) and were randomly assigned to one of the three dietary treatments (eight batches per treatment), each supplemented with either 4% hydrogenated palm oil (PALM) or fatty acids (FAs) from olive oil (OLI) or soybean oil (SOY). No differences in growth performance or carcass quality were observed. For the meat quality analysis, a steer was randomly selected from each batch and the 6th rib on the left half of the carcass was dissected. PALM meat had the highest percentage of 16:0 (P<0.05) and the lowest n-6/n-3 polyunsaturated fatty acids (PUFA) ratio (P<0.05), OLI had the highest content of t11-18:1 (P<0.01) and c9,t11-18:2 (P<0.05) and SOY showed the lowest value of monounsaturated fatty acids (MUFA) (P<0.001), the highest percentage of PUFA (P<0.01) and a lower index of atherogenicity (P=0.07) than PALM. No significant differences in the sensory characteristics of the meat were noted. However, the results of the principal component analysis of meat characteristics enabled meat from those steers that consumed fatty acids from olive oil to be differentiated from that of steers that consumed soybean oil.

Abstract  BACKGROUND: The transcription factor homeobox C9 (HOXC9) plays a crucial role in developmental regulatory systems, where it determines the specific positional identities of cells along the anteroposterior axis. The expression of HOXC9 has been found to be dysregulated in some cancers such as lung cancer, breast cancer, and neuroblastoma. Here, we report for the first time that HOXC9 is a novel autophagy regulator and reveal its oncogenic role in cell survival and its usefulness as a prognostic marker in glioblastoma patients.

METHODS: Kaplan-Meier analysis was performed to evaluate the possible prognostic value of HOXC9 in glioblastoma. Growth curve assays, subcutaneous, and orthotopic implantations were used to analyze cell viability and tumor formation, respectively. Luciferase and chromatin immunoprecipitation assays were employed to explore the mechanisms involved in the association between HOXC9 and its downstream effector, death-associated protein kinase 1 (DAPK1).

RESULTS: High expression of HOXC9 was found to be an indicator of a poor prognosis in glioblastoma. HOXC9 knockdown resulted in a significant reduction of cell viability, migration, invasion, and tumorigenicity and a marked increase in autophagy. During the autophagy process, HOXC9 inhibited DAPK1 transcription by directly binding to its promoter. The downregulation of HOXC9 releases its transcriptional inhibition of DAPK1, resulting in the activation of the DAPK1-Beclin1 pathway, which induces autophagy in glioblastoma cells.

CONCLUSIONS: Collectively, our data indicate that HOXC9 is an oncogene in glioblastoma. We have revealed its role in the control of autophagy, and we suggest that HOXC9 is a novel and promising therapeutic target.

Abstract  The search for functional supramolecular aggregations with different structure has attracted interest of chemists because they have the potential in industrial and technological application. Hydrophobic interaction has great influence on the formation of these aggregations, such as hexagonal liquid crystals, wormlike micelles, hydrogels, etc. So a systematical investigation was done to investigate the influence of alkyl chain length of surfactants on the aggregation behavior in water. The aggregation behavior of 1-hexadecyl-3-alkyl imidazolium bromide and water has been systematically investigated. These ionic liquid surfactants are denoted as C16-Cn (n = 2, 3, 4, 6, 8, 9, 10, 12, 14, 16). The rheological behavior and microstructure were characterized via a combination of rheology, cryo-etch scanning electron microscopy, polarization optical microscopy, and X-ray crystallography. The alkyl chain has great influence on the formation of surfactant aggregates in water at the molecular level. With increasing alkyl chain length, different aggregates, such as hexagonal liquid crystals, wormlike micelles, and hydrogels can be fabricated: C16-C2 aqueous solution only forms hexagonal liquid crystal; C16-C3 aqueous solution forms wormlike micelle and hexagonal liquid crystal; C16-C4, C16-C6 and C16-C8 aqueous solutions only form wormlike micelle; C16-C9 aqueous solution experiences a transition between wormlike micelle and hydrogel; C16-C10, C16-C12, C16-C14 and C16-C16 only form hydrogel. The mechanism of the transition of different aggregation with increasing alkyl chain length was also proposed.

Abstract  Number of seeds per silique (NSS) is an important determinant of seed yield potential in Brassicaceae crops and is controlled by naturally occurring quantitative trait loci (QTLs). We previously mapped a major QTL, qSS.C9, on the C9 chromosome that controls NSS in rapeseed (Brassica napus L.). To gain a better understanding of how qSS.C9 controls NSS in rapeseed, we isolated this locus through a map-based cloning strategy. qSS.C9 encodes a predicted small protein with 119 amino acids, designated as BnaC9.SMG7b, that shows homology with the Ever Shorter Telomere 1-tertratricopeptide repeats (EST-TPR) and EST-central domains (CD) of Arabidopsis SUPPRESSOR WITH MORPHOGENETIC EFFECTS ON GENITALIA7 (SMG7). BnaC9.SMG7b plays a role in regulating the formation of functional female gametophyte, thus determining the formation of functional megaspores and then mature ovules. Natural loss or artificial knockdown of BnaC9.SMG7b significantly reduces the number of functional ovules per silique and thus results in decreased seed number, indicating that qSS.C9 is a positive regulator of NSS in B. napus. Sequence and function analyses show that BnaC9.SMG7b experiences a subfunctionalization process that causes loss of function in nonsense-mediated mRNA decay (NMD), as in Arabidopsis SMG7. Haplotype analysis in 84 accessions showed that the favorable BnaC9.SMG7b alleles are prevalent in modern B. napus germplasms, suggesting that this locus has been a major selection target of B. napus improvement. Our results represent the first step toward unraveling the molecular mechanism that controls the natural variation of NSS in rapeseed.

Abstract  Some of NOD-like receptors (NLRs), the cytosolic pattern recognition receptors form a multi-protein complex, inflammasome consisting of one or more NLRs, the adaptor protein ASC and inflammatory caspase to generate mature inflammatory cytokines, interleukin (IL)-1β and IL-18. However, inflammasome-mediated inflammatory cascade involving any NLR member is unknown in a lower vertebrate like fish. Also, inflammatory cytokine induction pathway in response to a specific ligand, namely bacterial lipopolysaccharide (LPS) has not yet been clarified. Therefore, 13 predicted NLR sequences of the Japanese pufferfish, Fugu (Takifugu rubripes) were retrieved in silico and categorized as NLR-C1∼13. Expression analysis of these genes in Fugu head kidney (HK) cells stimulated with a heat-killed Lactobacillus paracasei spp. paracasei (Lpp), LPS, nigericin and a combination of nigericin + LPS showed consistent up-regulations of NLR-C1, 5, 7, 10 and 12 genes in both Lpp and LPS stimulations and NLR-C9 gene in LPS stimulation only. However, nigericin and nigericin + LPS caused an increased expression of NLR-C10 and 12 in HK cells and leukocytes. Fugu treated with Lpp and LPS (in vivo), and infected with Vibrio harveyi had an elevated expression of NLR-C10 and 12. Increased transcription of caspase-1, ASC, IL-1β and IL-18 was recorded in nigericin-stimulated HK cells and leukocytes. Results suggested activation of probable inflammasome-mediated inflammatory cytokine response in Fugu. Moreover, LPS may be a key ligand that induces some of the Fugu NLR-Cs (NLR-C9, 10 and 12). Further characterization and functional analysis of Fugu NLR-C10 and 12 for ligand sensing, and processing of pro-inflammatory cytokine, IL-1β would elucidate the inflammasome evolution in fish.

Abstract  Dynamic kinetic resolution of phthalides through asymmetric transfer hydrogenation for the construction of 3-(2-hydroxy-2-arylethyl)isobenzofuran-1(3H)-one with 1,3-distereocenters has been developed. This procedure is carried out under a mild condition at 40 °C catalyzed with RuCl[(S,S)-TsDPEN](mesitylene) using HCOOH/Et3N (5:2) as a hydrogen source. A variety of phthalides are smoothly transferred to provide optically pure phthalides with high yields, excellent enantioselectivities, and acceptable diastereomeric ratios.

Abstract  Systemic acquired resistance (SAR) is a form of broad-spectrum disease resistance that is induced in response to primary infection and that protects uninfected portions of the plant against secondary infections by related or unrelated pathogens. SAR is associated with an increase in chemical signals that operate in a collective manner to confer protection against secondary infections. These include, the phytohormone salicylic acid (SA), glycerol-3-phosphate (G3P), azelaic acid (AzA) and more recently identified signals nitric oxide (NO) and reactive oxygen species (ROS). NO, ROS, AzA and G3P function in the same branch of the SAR pathway, and in parallel to the SA-regulated branch. NO and ROS function upstream of AzA/G3P and different reactive oxygen species functions in an additive manner to mediate chemical cleavage of the C9 double bond on C18 unsaturated fatty acids to generate AzA. The parallel and additive functioning of various chemical signals provides important new insights in the overlapping pathways leading to SAR.

Abstract  Density functional theory (DFT) calculations are performed on the active site of biotin synthase (BS) to investigate the sulfur transfer from the Fe2S2 cluster to dethiobiotin (DTB). The active site is modeled to include both the 1st and 2nd sphere residues. Molecular orbital theory considerations and calculation on smaller models indicate that only an S atom (not S(2-)) transfer from an oxidized Fe2S2 cluster leads to the formation of biotin from the DTB using two adenosyl radicals generated from S-adenosyl-L-methionine. The calculations on larger protein active site model indicate that a 9-monothiobiotin bound reduced cluster should be an intermediate during the S atom insertion from the Fe2S2 cluster consistent with experimental data. The Arg260 bound to Fe1, being a weaker donor than cysteine bound to Fe2, determines the geometry and the electronic structure of this intermediate. The formation of this intermediate containing the C9-S bond is estimated to have a ΔG(≠) of 17.1 kcal/mol while its decay by the formation of the 2nd C6-S bond is calculated to have a ΔG(≠) of 29.8 kcal/mol, i.e. the 2nd C-S bond formation is calculated to be the rate determining step in the cycle and it leads to the decay of the Fe2S2 cluster. Significant configuration interaction (CI), present in these transition states, helps lower the barrier of these reactions by ~30-25 kcal/mol relative to a hypothetical outer-sphere reaction. The conserved Phe285 residue near the Fe2S2 active site determines the stereo selectivity at the C6 center of this radical coupling reaction. Reaction mechanism of BS investigated using DFT calculations. Strong CI and the Phe285 residue control the kinetic rate and stereochemistry of the product.

Abstract  PURPOSE: The pathogenesis of age-related macular degeneration (AMD) is associated with systemic and local inflammation. Various studies suggested that viral or bacterial infection may aggravate retinal inflammation in the aged retina. We compared the effects of synthetic viral RNA (poly(I:C)) and viral/bacterial DNA (CpG-ODN) on the expression of genes known to be involved in the development of AMD in retinal pigment epithelial (RPE) cells.

METHODS: Cultured human RPE cells were stimulated with poly(I:C; 500 µg/ml) or CpG-ODN (500 nM). Alterations in gene expression and protein secretion were determined with real-time RT-PCR and ELISA, respectively. Phosphorylation of signal transduction molecules was revealed by western blotting.

RESULTS: Poly(I:C) induced gene expression of the pattern recognition receptor TLR3, transcription factors (HIF-1α, p65/NF-κB), the angiogenic factor bFGF, inflammatory factors (IL-1β, IL-6, TNFα, MCP-1, MIP-2), and complement factors (C5, C9, CFB). Poly(I:C) also induced phosphorylation of ERK1/2 and p38 MAPK proteins, and the secretion of bFGF and TNFα from the cells. CpG-ODN induced moderate gene expression of transcription factors (p65/NF-κB, NFAT5) and complement factors (C5, C9), while it had no effect on the expression of various TLR, angiogenic factor, and inflammatory factor genes. The activities of various signal transduction pathways and transcription factors were differentially involved in mediating the poly(I:C)-induced transcriptional activation of distinct genes.

CONCLUSIONS: The widespread effects of viral RNA, and the restricted effects of viral/bacterial DNA, on the gene expression pattern of RPE cells may suggest that viral RNA rather than viral/bacterial DNA induces physiologic alterations of RPE cells, which may aggravate inflammation in the aged retina. The data also suggest that selective inhibition of distinct signal transduction pathways or individual transcription factors may not be effective to inhibit viral retinal inflammation.

Abstract  Alternative jet fuels (Fischer-Tropsch fuels and Biomass derived fuels) lack aromatic compounds and does not provide the desired seal-swell characteristics and other needed "fit-for-purpose" (FFP) properties. The research need is to investigate the effect of alternative fuels and fuel blends on elastomer seals in a simulated turbojet engine environment. In light of this research need, this paper describes the laboratory bench top apparatus that evaluates the engineering performance of elastomer o-rings exposed to alternative fuels and fuel blends under dynamic conditions. The three elastomer materials selected for dynamic tests were Fluorosilicone, Viton, and Buna-N o-rings. The performance of the elastomer o-rings was determined in terms of failure time that was based on fuel leakage past the o-ring seals. Pre-test and post-test elastomer properties were measured. Performance-property envelopes were used as a metric to compare different elastomer materials exposed to the same fuel and further investigate the effect of different alternative fuels on elastomers under dynamic conditions. This paper presents and compares the results from the alternative fuel (R8) and a 50/50 blend containing R-8-JP-8 on all three elastomer materials in terms of performance-property envelope charts.

Abstract  In a 2×2 factorial design, 12 Thai Native and 12 Holstein bulls were fed ad libitum a total mixed ration (20 : 80; roughage : concentrate) with whole cottonseed (WCS) or sunflower seed (SFS) as oilseed sources. The rations contained 7% crude fat and were fed for 90 days. Plasma was taken at three times during the experiment, and at slaughter the longissimus dorsi and subcutaneous fat were sampled for fatty acid analysis. Ration did not affect rumen fermentation parameters. The plasma fatty acid profile was not affected by ration. In subcutaneous fat, a ration×breed interaction for the saturated fatty acid (SFA) and c9t11 CLA proportions was observed, resulting from larger differences between the rations in Thai Native compared with Holstein bulls. The WCS ration resulted in higher proportions of SFA and lower proportions of monounsaturated fatty acids and c9,t11 CLA compared with the SFS ration (P<0.01). In the intramuscular fat, the WCS ration was also associated with a lower c9t11 CLA proportion (P<0.01) and higher SFA proportion (P<0.05). The intramuscular proportion of polyunsaturated acids was higher and the proportion of SFA was lower in Thai Native compared with Holstein bulls (P<0.05), irrespective of ration.

Abstract  Senegalese sole (Solea senegalensis) has been considered since the 1990's to be a promising flatfish species for diversifying European marine aquaculture. However, pathogen outbreaks leading to high mortality rates can impair Senegalese sole commercial production at the weaning phase. Different approaches have been shown to improve fish immunocompetence; with this in mind the objective of the work described herein was to determine whether increased levels of dietary vitamin A (VA) improve the immune response in early juveniles of Senegalese sole. For this purpose, Senegalese sole were reared and fed with Artemia metanauplii containing increased levels of VA (37,000; 44,666; 82,666 and 203,000 total VA IU Kg(-1)) from 6 to 60 days post-hatch (early juvenile stage). After an induced bacterial infection with a 50% lethal dose of Photobacterium damselae subsp. damselae, survival rate, as well as underlying gene expression of specific immune markers (C1inh, C3, C9, Lgals1, Hamp, LysC, Prdx1, Steap4 and Transf) were evaluated. Results showed that fish fed higher doses of dietary VA were more resistant to the bacterial challenge. The lower mortality was found to be related with differential expression of genes involved in the complement system and iron availability. We suggest that feeding metamorphosed Senegalese sole with 203,000 total VA IU Kg(-1) might be an effective, inexpensive and environmentally friendly method to improve Senegalese sole immunocompetence, thereby improving survival of juveniles and reducing economic losses.

Abstract  Kidney urea transporters are targets for development of small-molecule inhibitors with action as salt-sparing diuretics. A cell-based, functional high-throughput screen identified 2,7-bisacetamido fluorenone 3 as a novel inhibitor of urea transporters UT-A1 and UT-B. Here, we synthesized twenty-two 2,7-disubstituted fluorenone analogs by acylation. Structure-activity relationship analysis revealed: (a) the carbonyl moiety at C9 is required for UT inhibition; (b) steric limitation on C2, 7-substituents; and (c) the importance of a crescent-shape structure. The most potent fluorenones inhibited UT-A1 and UT-B urea transport with IC50 ~ 1 μM. Analysis of in vitro metabolic stability in hepatic microsomes indicated metabolism of 2,7-disubstituted fluorenones by reductase and subsequent elimination. Computational docking to a homology model of UT-A1 suggested UT inhibitor binding to the UT cytoplasmic domain at a site that does not overlap with the putative urea binding site.

Abstract  Effects of pore structures of ZSM-5, MOR, Beta and USY on their catalytic properties in the transalkylation of toluene with 1,2,4-trimethylbenzene (1,2,4-TMB) were investigated by studying the catalytic mechanism and the diffusion behavior of reactants and products. The medium-pore ZSM-5 shows low catalytic activity as a result of slow decomposition of diphenylmethane (DPM) intermediates and occurrence of severe cracking of 1,2,4-TMB via the monomolecular reaction pathway. In contrast, the large-pore MOR, Beta and USY zeolites allow rapid formation and transformation of bulky DPM species, consequently exhibiting higher catalytic activity. The diffusion experiments show that 1,2,4-TMB and 1,2,4,5-tetramethylbezene (1,2,4,5-TeMB) more easily diffuse into/out of the pores of MOR zeolite than of Beta and USY. Thus, the disproportionation of 1,2,4-TMB and coking were inhibited in MOR, which makes it exhibit higher catalytic stability and xylene selectivity. A detailed analysis of the deposited coke species with GC-MS indicates that the transalkylation of toluene with 1,2,4-TMB occurs via the bimolecular intermediate mechanism.

Abstract  The polymerization of 3-hexylthiophene with FeCl3 was carried out in aromatic solvents. The incorporation of aromatic solvent molecules such as benzene, toluene, xylene, and mesitylene into the resultant polymer main chain was clarified by H-1 NMR and matrix-assisted laser desorption/ionization mass spectrometry for the first time. More amount of benzene (12 mol%) was incorporated into the resultant polymer, compared with toluene, xylene, and mesitylene. The polymeric product prepared in benzene at 23 degrees C afforded an electrical conductivity (0.3 S cm(-1)) much better than that of the polymer prepared in toluene (0.05 S cm(-1)).

Abstract  An array of new MCM-41 with substantially larger average pore diameters was synthesized through adding 1,3,5-trimethylbenzene (TMB) as the swelling agent to explore the effect of pore size on final adsorbent properties. The pore expanded MCM-41 was also grafted with (3-Aminopropyl)triethoxysilane (APTES) to determine the optimal pore size for CO2 adsorption. The pore-expanded mesoporous MCM-41s showed relatively less structural regularity but significant increments of pore diameter (4.64 to 7.50 nm); the fraction of mesopore volume also illustrated an increase. The adsorption heat values were correlated with the order of the adsorption capacities for pore expanded MCM-41s. After amine functionalization, the adsorption capacities and heat values showed a significant increase. APTES-grafted pore-expanded MCM-41s depicted a high potential for CO2 capture regardless of the major drawback of the high energy required for regeneration.

Abstract  Exposure of complex [(eta-C4Me4)Co(eta-C6H6)](+) (2a) to visible light in the presence of benzene or cycloheptatriene derivatives in CH2Cl2 led to the cations [(eta-C4Me4)Co(arene)](+) (2b-h; arene is toluene (b), m-xylene (c), p-xylene (d), mesitylene (e), durene (f), phenol (g), anisole (h)) and [(eta-C4Me4)Co(eta(6)-C7H8)](+) (4) as a result of the arene exchange. Cation 2e was also obtained upon reflux of compound 2a and mesitylene in the presence of a catalytic amount of acetonitrile. The process of the thermal exchange of arene in complex 2a was analyzed using the DFT calculations. The reaction of acetonitrile derivative [(eta-C4Me4)Co(MeCN)(3)](+) (3) with sterically hindered hexamethylbenzene, as well as indene and indole allowed us to synthesize cations [(eta-C4Me4)Co(eta-C6Me6)](+) (2i), [(eta-C4Me4)Co(eta(6)-indene)](+) (5), and [(eta-C4Me4)Co(eta(6)-indene)](+) (6). Complexes [(eta-C4Me4)Co(eta-C6H5C(O)Me)](+) (2k) and [(eta-C4Me4)Co(eta-1,4-C6H4Cl2)](+) (2l) were obtained by the reaction of [Cb*CoI](2) with acetophenone or dichlorobenzene in the presence of thallium salts. The structures of complexes [2a]PF6 and [4]PF6 were determined by X-ray diffraction.