Pathways of liquefied petroleum gas pyrolysis in hydrogen plasma:A density functional theory study

A density functional theory(DFT) study has been conducted in this work to investigate the pyrolysis pathways of propane and n-butane,which are the main components of liquefied petroleum gas(LPG),for better understanding the pyrolysis behavior of LPG in hydrogen thermal plasma. Over 60 possible reactions are considered.The reaction enthalpies and activation energies of these reactions are calculated and analyzed with a Gaussian method of B3LYP and basic set of 6-31G(d,p).A most possible reaction pathway is brought up.According to this reaction pathway, the main products of LPG pyrolysis are acetylene,ethylene,methane,ethane and extra hydrogen.Acetylene mainly comes from the pyrolysis of propylene and ethylene,and hydrogen ion reactions are the main source of extra hydrogen gas.Active H·radicals are found to play a very important role in many reactions,and they can remarkably lower the energies needed for reactions.     

Hiv-1 Specific Reverse Transcriptase Inhibitors: why are Tsao-Nucleosides so Unique?

1. INTRODUCTION

AIDS will still be one of the most important challenges for the Scientific Community in the approaching new century. Since the identification, in 1983-84,^1,2 of human immunodeficiency virus (HIV) as the etiological agent of AIDS, significant progress has been made in the treatment of HIV-infected patients. This has been in part due to the discovery and clinical use of an increasing number of anti-HIV drugs. However, while highly active antiretroviral therapy (HAART)³ approaches have reduced the morbidity and mortality, the intertwined problems of drug induced viral resistance, poor compliance with complex regimens and therapy failure continue. Therefore, there remains a pressing need for the development of new antiviral agents that can be used not only as first line therapeutic candidates, but also in the antiretroviral-experienced patient population.     

Cytotoxic and NF-κB inhibitory sesquiterpene lactones from Piptocoma rufescens

Six new (1-6) and eight known germacranolide-type sesquiterpene lactones, along with several known phenylpropanol coumarates and methylated flavonoids, were isolated from the leaves of Piptocoma rufescens, collected in the Dominican Republic. The new compounds were identified by analysis of their spectroscopic data, with the molecular structure of 3 being established by single-crystal X-ray diffraction. The absolute configurations of the sesquiterpene lactones isolated were determined from their CD and NOESY NMR spectra, together with the analysis of Mosher ester reactions. Bioassay screening results showed the majority of the sesquiterpene lactones isolated (1-13) to be highly cytotoxic toward the HT-29 human colon cancer cell line, with the most potent compound being 15-deoxygoyazensolide (10, IC(50), 0.26 μM). In addition, several of the sesquiterpene lactones exhibited NF-κB (p65) inhibitory activity.     

Directed ortho-lithiation of unprotected diphenylphosphinic acids

Directed ortho lithiation of diphenylphosphinic acid and subsequent electrophilic trapping provides mono ortho-functionalized derivatives including enantiopure γ-aminophosphinic acids in moderate yields. Copper catalyzed coupling of the ortho anion leads to biphenyl-2,2′-diylbis(phenylphosphinic acid), a phosphorus analogue of biphenyl-2,2′-dicarboxylic acid. Preliminary studies of the metal-binding abilities of this O,O-chelating ligand towards a series of metal cations are included.     

Toward reactant encapsulation for substrate-selectivity

A synthetic tris-(bis-(aminomethyl)pyridine) receptor was prepared in excellent yields via reversible imine condensation strategy. Catalytic activity in Henry reactions of the corresponding copper(II) complex was studied. Capitalizing on previous works by Anslyn with related receptors, the dramatic increase in basicity induced by this type of complex on diketo-derivatives was used to perform a nucleophilic addition of a deprotonated substrate onto an electrophile within the cavity. Hence, a Lewis acid stabilized nitronate was reacted with various aldehydes. A notable preference for small reactants easily accommodated in the cavity over encumbered ones was observed, thus representing an example of substrate-selectivity.     

Influence of hydrogen bonds on the molecular structure and conformations of two (C30H48O2) pentacyclic triterpene isomers

The structural study of two (C₃₀H₄₈O₂) pentacyclic triterpene (PCTT) isomers is presented. These terpenes, known as 30-hydroxy-lup-20(29)-en-3-one (1) and (11α)-11-hydroxy-lup-20(29)-en-3-one (2), were isolated from Maytenus imbricata Mart. Ex Reissek (Celastraceae). The molecular structure of 1 and 2 differs in the position of the hydroxyl group. Both compounds crystallize in non-centrosymmetric space groups with two molecules in the asymmetric unit. The crystal structure of 1 shows a triclinic P1 space group (a = 9.5518(1) ?, b = 9.7083(1) ?, c = 14.4696(2) ?, α = 93.832(1)°, β = 102.833(1)°, and γ = 103.307(1)°), while compound 2 crystallizes in a monoclinic P2₁ one (a = 13.4439(16) ?, b = 14.4463(14) ?, c = 13.5224(9) ? and β = 99.703(8)°). The two molecules independent by symmetry of 1 differ slightly due to the presence of static disorder in oxygen atoms. In addition, the intermolecular geometries of 1 and 2 were analysed, and in each isomer the crystal packing is stabilized by O-H…O intermolecular hydrogen bonds and van der Waals forces.     

Biodegradable aromatic copolyesters made from bicyclic acetalized galactaric acid

Random poly(hexamethylene terephthalate‐co‐galactarate)s and poly(dodecamethylene terephthalate‐co‐galactarate)s copolyesters covering the whole range of compositions were obtained with weight‐average molecular weights of ～30,000–50,000 g mol^?1 by melt polycondensation. They were thermally stable above 300 °C, and displayed T_g in the +20 to ?20 °C range with values steadily decreasing with the content in galactarate units. All the copolyesters were semicrystalline with T_m between 50 and 150 °C and those made from dodecanediol were able to crystallize from the melt at a crystallization rate depending on composition. Copolyesters containing up to 50% of galactaric units retained the crystal structure of their respective polyterephthalate homopolyesters, whereas they adopted the structure of the respective polygalactarates when the content in Galx units reached 70%. Stress‐strain essays revealed decay in the mechanical parameters as the aromatic units were replaced by Galx. Incubation in aqueous buffer revealed that hydrolysis of the polyesters were largely enhanced by copolymerization and evidenced the capacity of the Galx unit for making aromatic polyesters susceptible to biodegradation. A detailed NMR analysis complemented by SEM observations indicated that hydrolysis took place by preferred splitting of galactarate ester bonds with releasing of alkanediol and Galx‐diacid. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012