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Full-Text Articles in Life Sciences
The Synthesis, Structures And Reactions Of Zinc And Cobalt Metal-Organic Frameworks Incorporating An Alkyne-Based Dicarboxylate Linker, Andrew D. Burrows, L C. Fisher, David M. Hodgson, Mary F. Mahon, Naomi Cessford, Tina Duren, Christopher Richardson, S P. Rigby
The Synthesis, Structures And Reactions Of Zinc And Cobalt Metal-Organic Frameworks Incorporating An Alkyne-Based Dicarboxylate Linker, Andrew D. Burrows, L C. Fisher, David M. Hodgson, Mary F. Mahon, Naomi Cessford, Tina Duren, Christopher Richardson, S P. Rigby
Faculty of Science - Papers (Archive)
The reaction of zinc(II) nitrate and 4,4′-ethynylenedibenzoic acid (H2edb) in DMF at 80 °C gave the metal–organic framework material [Zn4O(edb)3(H2O)2]·6DMF 1 in which edb ligands connect Zn4O centres into a doubly-interpenetrated cubic network with a similar topology to observed with other linear dicarboxylates in the IRMOF series. Analysis of the nitrogen isotherm revealed the material to have a BET surface area of 1088 m2 g−1, which is approximately one-third of the value calculated from GCMC simulations, suggesting incomplete activation or pore blocking in the activated …
Synthesis Of 3-Halo-2,5-Disubstituted Furans Via Cux Mediated Cyclization-Halogenation Reactions, Arife Yazici, Stephen G. Pyne
Synthesis Of 3-Halo-2,5-Disubstituted Furans Via Cux Mediated Cyclization-Halogenation Reactions, Arife Yazici, Stephen G. Pyne
Faculty of Science - Papers (Archive)
The Cu(I) halide (X = I, Br, Cl) mediated reactions of Cbz-protected cis-2-phenylethenyl-3-hydroxypyrrolidine gave novel 3-halo-2,5-trisubstituted furans in good yields, via a cyclization-halogenation, ring-opening reaction sequence. In contrast, the reactions with CuCN gave mainly the corresponding 3-cyanofuro[3,2-b]pyrrole formed from a cyclization-cyanation reaction.
Chemically Activated Reactions On The C7h5 Energy Surface: Propargyl + Diacetylene, I-C5h3 + Acetylene, And N-C5h3 + Acetylene, Gabriel Da Silva, Adam J. Trevitt
Chemically Activated Reactions On The C7h5 Energy Surface: Propargyl + Diacetylene, I-C5h3 + Acetylene, And N-C5h3 + Acetylene, Gabriel Da Silva, Adam J. Trevitt
Faculty of Science - Papers (Archive)
This study uses computational chemistry and statistical reaction rate theory to investigate the chemically activated reaction of diacetylene (butadiyne, C4H2) with the propargyl radical (C •H2CCH) and the reaction of acetylene (C 2H2) with the i-C5H3 (CH 2CCCC•H) and n-C5H3 (CHCC •HCCH) radicals. A detailed G3SX-level C7H 5 energy surface demonstrates that the C3H3 + C4H2 and C5H3 + C2H 2 addition reactions proceed with moderate barriers, on the order of 10 to 15 kcal mol-1, and form activated open-chain C 7H5 species that can isomerize to the fulvenallenyl radical with the highest barrier still significantly below the entrance channel …
Reactions Of Simple And Peptidic Alpha-Carboxylate Radical Anions With Dioxygen In The Gas Phase, Tony Ly, Benjamin B. Kirk, Pramesh I. Hettiarachchi, Berwyck L. Poad, Adam J. Trevitt, Gabriel Da Silva, Stephen J. Blanksby
Reactions Of Simple And Peptidic Alpha-Carboxylate Radical Anions With Dioxygen In The Gas Phase, Tony Ly, Benjamin B. Kirk, Pramesh I. Hettiarachchi, Berwyck L. Poad, Adam J. Trevitt, Gabriel Da Silva, Stephen J. Blanksby
Faculty of Science - Papers (Archive)
α-Carboxylate radical anions are potential reactive intermediates in the free radical oxidation of biological molecules (e.g., fatty acids, peptides and proteins). We have synthesised well-defined α-carboxylate radical anions in the gas phase by UV laser photolysis of halogenated precursors in an ion-trap mass spectrometer. Reactions of isolated acetate (CH2CO 2-) and 1-carboxylatobutyl (CH3CH 2CH2CHCO2-) radical anions with dioxygen yield carbonate (CO3-) radical anions and this chemistry is shown to be a hallmark of oxidation in simple and alkyl-substituted cross-conjugated species. Previous solution phase studies have shown that Cα-radicals in peptides, formed from free radical damage, combine with dioxygen to form …
Copper-Mediated Cyclization-Halogenation And Cyclization-Cyanation Reactions Of Β-Hydroxyalkynes And O-Alkynylphenols And Anilines, Nalivela K. Swamy, Arife Yazici, Stephen G. Pyne
Copper-Mediated Cyclization-Halogenation And Cyclization-Cyanation Reactions Of Β-Hydroxyalkynes And O-Alkynylphenols And Anilines, Nalivela K. Swamy, Arife Yazici, Stephen G. Pyne
Faculty of Science - Papers (Archive)
The CuX (X = I, Br, Cl, CN)-mediated cyclization-halogenation and cyclization-cyanation reactions of β-hydroxyalkynes and o-alkynylphenol and -aniline derivatives give rise to 3-halo- and 3-cyanofuro[3,2-b]pyrroles, 3-iodo-, 3-bromo-, and 3-cyanobenzofurans, and 3-cyanoindoles, respectively. © 2010 American Chemical Society.
Reactions Of The Cn Radical With Benzene And Toluene: Product Detection And Low-Temperature Kinetics, Adam J. Trevitt, Fabien Goulay, Craig A. Taatjes, David L. Osborn, Stephen R. Leone
Reactions Of The Cn Radical With Benzene And Toluene: Product Detection And Low-Temperature Kinetics, Adam J. Trevitt, Fabien Goulay, Craig A. Taatjes, David L. Osborn, Stephen R. Leone
Faculty of Science - Papers (Archive)
Low-temperature rate coefficients are measured for the CN + benzene and CN + toluene reactions using the pulsed Laval nozzle expansion technique coupled with laser-induced fluorescence detection. The CN + benzene reaction rate coefficient at 105, 165, and 295 K is found to be relatively constant over this temperature range, (3.9−4.9) × 10−10 cm3 molecule−1 s−1. These rapid kinetics, along with the observed negligible temperature dependence, are consistent with a barrierless reaction entrance channel and reaction efficiencies approaching unity. The CN + toluene reaction is measured to have a rate coefficient of 1.3 × 10−10 cm3 molecule−1 s−1 at 105 …
Ion-Molecule Reactions Of O,S-Dimethyl Methylphosphonothioate: Evidence For Intramolecular Sulfur Oxidation During Vx Perhydrolysis, Jilliarne Williams, Martin Paine, Stephen J. Blanksby, Michael L. Rogers, Andrew M. Mcanoy
Ion-Molecule Reactions Of O,S-Dimethyl Methylphosphonothioate: Evidence For Intramolecular Sulfur Oxidation During Vx Perhydrolysis, Jilliarne Williams, Martin Paine, Stephen J. Blanksby, Michael L. Rogers, Andrew M. Mcanoy
Faculty of Science - Papers (Archive)
The alkaline perhydrolysis of the nerve agent O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX) was investigated by studying the ion-molecule reactions of HOO- with O,S-dimethyl methylphosphonothioate in a modified linear ion-trap mass spectrometer. In addition to simple proton transfer, two other abundant product ions are observed at m/z 125 and 109 corresponding to the S-methyl methylphosphonothioate and methyl methylphosphonate anions, respectively. The structure of these product ions is demonstrated by a combination of collision-induced dissociation and isotope-labeling experiments that also provide evidence for their formation by nucleophilic reaction pathways, namely, (i) S(N)2 at carbon to yield the S-methyl methylphosphonothioate anion and (ii) nucleophilic …
Ion-Molecule Reactions Reveal Facile Radical Migration In Peptides, Stephen J. Blanksby, Benjamin N. Moore, Ryan R. Julian
Ion-Molecule Reactions Reveal Facile Radical Migration In Peptides, Stephen J. Blanksby, Benjamin N. Moore, Ryan R. Julian
Faculty of Science - Papers (Archive)
Ion-molecule reactions between molecular oxygen and peptide radicals in the gas phase demonstrate that radical migration occurs easily within large biomolecules without addition of collisional activation energy.
Intermolecular Addition Reactions Of N-Acyliminium Ions (Part Ii), Arife Yazici, Stephen G. Pyne
Intermolecular Addition Reactions Of N-Acyliminium Ions (Part Ii), Arife Yazici, Stephen G. Pyne
Faculty of Science - Papers (Archive)
This review highlights the advances in the literature up to July 2008 on the intermolecular reactions of acyclic and cyclic N-acyliminium ions. This is an update of an earlier review in 2000 oil this topic and does not include intramolecular addition reactions to N-acyliminium ions which was recently reviewed. This review is presented in two parts, with the first part having dealt with acyclic and pyrrolidinone-based N-acyliminium ions. Part II continues with other five-membered heterocyclic derivatives and higher systems.
Intermolecular Addition Reactions Of N-Acyliminium Ions (Part I), Arife Yazici, Stephen G. Pyne
Intermolecular Addition Reactions Of N-Acyliminium Ions (Part I), Arife Yazici, Stephen G. Pyne
Faculty of Science - Papers (Archive)
This review highlights the advances in the literature up to July 2008 on the intermolecular reactions of acyclic and cyclic N-acyliminium ions. This is an update of an earlier review in 2000 on this topic and does not include intramolecular addition reactions to N-acyliminium ions which was recently reviewed. This review is presented in two parts, with the first part dealing with acyclic and pyrrolidinone-based N-acyliminium ions. Part II continues with other five-membered heterocyclic derivatives and higher systems.
Diastereoselective Ritter Reactions Of Chiral Cyclic N-Acyliminium Ions: Synthesis Of Pyrido- And Pyrrolo [2,3-D] Oxazoles And 4-Hydroxy-5-N-Acylaminopyrrolidines And 5-Hydroxy-6-N-Acylaminopiperidines, Ian R. Morgan, Arife Yazici, Stephen G. Pyne, Brian W. Skelton
Diastereoselective Ritter Reactions Of Chiral Cyclic N-Acyliminium Ions: Synthesis Of Pyrido- And Pyrrolo [2,3-D] Oxazoles And 4-Hydroxy-5-N-Acylaminopyrrolidines And 5-Hydroxy-6-N-Acylaminopiperidines, Ian R. Morgan, Arife Yazici, Stephen G. Pyne, Brian W. Skelton
Faculty of Science - Papers (Archive)
Pyrido- and pyrrolo[2,3-d]oxazoles can be conveniently prepared in high yield from the Ritter reaction of nitriles and in situ generated chiral cyclic N-acyliminium ions. cis-4-Hydroxy-5-acylaminopyrrolidines and cis-5-hydroxy-6-acylaminopiperidines can be readily obtained by acid hydrolysis of these bicyclic heterocyclic compounds, respectively.
Reactions Of The Hydroperoxide Anion With Dimethyl Methylphosphonate In An Ion Trap Mass Spectrometer: Evidence For A Gas Phase A-Effect, Andrew M Mcanoy, Martin Paine, Stephen J. Blanksby
Reactions Of The Hydroperoxide Anion With Dimethyl Methylphosphonate In An Ion Trap Mass Spectrometer: Evidence For A Gas Phase A-Effect, Andrew M Mcanoy, Martin Paine, Stephen J. Blanksby
Faculty of Science - Papers (Archive)
The gas phase degradation reactions of the chemical warfare agent (CWA) simulant, dimethyl methylphosphonate (DMMP), with the hydroperoxide anion (HOO–) were investigated using a modified quadrupole ion trap mass spectrometer. The HOO– anion reacts readily with neutral DMMP forming two significant product ions at m/z 109 and m/z 123. The major reaction pathways correspond to (i) the nucleophilic substitution at carbon to form [CH3P(O)(OCH3)O]– (m/z 109) in a highly exothermic process and (ii) exothermic proton transfer. The branching ratios of the two reaction pathways, 89% and 11% respectively, indicate that the …
Base-Induced Decomposition Of Alkyl Hydroperoxides In The Gas Phase. Part 3. Kinetics And Dynamics In Ho + Ch3ooh, C2h5ooh, And Tert-C4h9ooh Reactions, Shuji Kato, G Barney Ellison, Veronica Bierbaum, Stephen J. Blanksby
Base-Induced Decomposition Of Alkyl Hydroperoxides In The Gas Phase. Part 3. Kinetics And Dynamics In Ho + Ch3ooh, C2h5ooh, And Tert-C4h9ooh Reactions, Shuji Kato, G Barney Ellison, Veronica Bierbaum, Stephen J. Blanksby
Faculty of Science - Papers (Archive)
The ECO2 elimination reactions of alkyl hydroperoxides proceed via abstraction of an α-hydrogen by a base: X− + R1R2HCOOH → HX + R1R2CO + HO−. Efficiencies and product distributions for the reactions of the hydroxide anion with methyl, ethyl, and tert-butyl hydroperoxides are studied in the gas phase. On the basis of experiments using three isotopic analogues, HO− + CH3OOH, HO− + CD3OOH, and H18O− + CH3OOH, the overall intrinsic reaction efficiency is determined to …
Reductive Ring Opening Reactions Of Diphenyldihydrofullerenylpyrroles, William Hawkins, Paul A. Keller, Stephen G. Pyne
Reductive Ring Opening Reactions Of Diphenyldihydrofullerenylpyrroles, William Hawkins, Paul A. Keller, Stephen G. Pyne
Faculty of Science - Papers (Archive)
The reductive ring opening reaction conditions for the simple [60]fullerenyldihydropyrrole 1 have been optimized to include acetic acid in the reaction mixture to rapidly protonate the anionic intermediate. Under these conditions, the ring opened dihydrofullerene 2 was obtained in 68% yield. Under slightly modified conditions and at −78 °C, the reductive bis-ring opening of the tethered trans-4 isomer 3 provided the novel racemic bis-dihydrofullerenyl derivative 7.
Structural Re-Assignment Of The Mono- And Bis-Addition Products From The Addition Reactions Of N-(Diphenylmethylene)Glycinate Esters To [60]Fullerene Under Bingel Conditions, Graham E Ball, Glenn Ashley Burley, Leila Chaker, William Hawkins, James Williams, Paul A. Keller, Stephen G. Pyne
Structural Re-Assignment Of The Mono- And Bis-Addition Products From The Addition Reactions Of N-(Diphenylmethylene)Glycinate Esters To [60]Fullerene Under Bingel Conditions, Graham E Ball, Glenn Ashley Burley, Leila Chaker, William Hawkins, James Williams, Paul A. Keller, Stephen G. Pyne
Faculty of Science - Papers (Archive)
The addition of N-(diphenylmethylene)glycinate esters (Ph2C=NCH2CO2R) to [60]fullerene under Bingel conditions gives [60]fullerenyldihydropyrroles and not methano[60]fullerenyl iminoesters [C60C(CO2R)(N=CPh2)] as previously reported. Unequivocal evidence for the structure of C60C(CO2Et)(N=CPh2) was provided by INADEQUATE NMR studies on 13C enriched material. New mechanistic details are proposed to account for the formation of [60]fullerenyldihydropyrroles and their reductive ring-opening reactions.