Publications by authors named "Neil Trout"

10 Publications

  • Page 1 of 1

Advanced Silicon Chemistry in Australia: Forming Strong Links with Asia.

Chem Asian J 2017 Jun 31;12(11):1123-1152. Epub 2017 May 31.

Associate (Research & Development: Polymer Chemistry), COOE Pty Ltd., 46/40 W Thebarton Rd, Thebarton, South Australia, 5031, Australia.

This paper details Australian commercial and academic silicon research. Areas of interest include silicon metal, polysiloxane polymers, copolymers, cyclics, emulsions, microemulsions, silanes, silane coupling agents, sol-gel chemistry and water-treatments, porous silicon, polysiloxane degradation, silicon hydrogel contact lenses, silanolate synthesis, siloxane interfacial polymerisation, hydrosilylation, polysiloxane electrolytes for lithium ion batteries, silanes for PBX materials, octafunctionalized polyhedral oligomeric silsesquioxanes (POSS), POSS hybrids, sol-gel hydrogenation catalysts, silane modification of silica, sol-gel energy storage, silicate grout stabilisation, GeoPolymer concretes, aerogel insulating foams, "Phaco-Ersatz" Accommodating Gel-Intraocular Lens technologies. Strong collaborative opportunities, in silicon, with Asia, exist with organisations such as: 1) The Asian Silicon Society and 2) The Agency for the Assessment and Application of Technology (BPPT) Indonesia.
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http://dx.doi.org/10.1002/asia.201700598DOI Listing
June 2017

Inhibition of atherosclerotic lesion development in the ApoE-/- mouse by a novel β-oxa polyunsaturated fatty acid.

J Cardiovasc Pharmacol 2010 Oct;56(4):431-9

Department of Immunopathology, SA Pathology at Women's and Children's Hospital, North Adelaide, South Australia.

Recent findings that a novel polyunsaturated fatty acid, β-oxa 23:4n-6, inhibits adhesion molecule expression on vascular endothelial cells and leukocyte adhesion led us to examine its ability to inhibit the development of atherosclerosis in the apoE-deficient (apoE) mouse. The mice were kept on normal chow or a high-fat/high-cholesterol diet for various periods and treated with either vehicle or β-oxa 23:4n-6 by the intraperitoneal route. The hearts and aortae were isolated and lesion development at the aortic root was determined. Morphometric assessment revealed that lesion development was a function of compensatory aortic enlargement, suggesting that measurement of plaque size per se is the appropriate assessment of lesion size. Using this criterion, we found that atherosclerosis development was reduced in response to β-oxa 23:4n-6, plaque size by 74% and aortic cross-sectional area by 62%, under an optimized regime. The number of foam cells per unit tissue area in the lesions of β-oxa 23:4n-6-treated mice was significantly reduced by 37.5%. The blood levels of β-oxa23:4n-6 in these mice exceeded the concentrations previously found to inhibit adhesion molecule expression in cultured endothelial cells. These data show that β-oxa23:4n-6 protects against experimental atherosclerosis, most likely by reducing the number of infiltrating monocytes.
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http://dx.doi.org/10.1097/FJC.0b013e3181f1d420DOI Listing
October 2010

Gas-phase facial diastereoselectivity of equatorial and axial 4-chloro-adamant-2-yl cations.

J Org Chem 2009 Aug;74(15):5135-44

Dipartimento di Chimica e Tecnologie del Farmaco, Università di Roma La Sapienza, P.le A. Moro, 5, Roma 00185, Italy.

The acid-catalyzed addition of CH3(18)OH to 2-methylene-adamantanes bearing a chlorine atom in the 4-equatorial (1e) or 4-axial (1a) position has been investigated in the gas phase, at 760 Torr, in the 40-120 degrees C temperature range. Two different experimental approaches were employed: (1) by adding neutral CH3(18)OH to the 2-methyl-4-Cl-adamant-2-yl cation, generated by protonation of the corresponding 2-methylene-4-Cl-adamantane (the extracomplex reaction) and (2) by reaction of 2-methylene-4-Cl-adamantane with CH3(18)OH2+, generated by methylation of H2(18)O (the intracomplex reaction). The crucial role of the nature of the noncovalent intermediates involved along the reaction coordinates emerges from the difference between the results obtained in the extracomplex and intracomplex reactions for both substrates investigated. The kinetic and stereochemical results indicate that the 4-Cl substituent plays a different role depending on its equatorial or axial orientation. Examination of the experimental results in the light of MP2/6-31G* theoretical calculations provides important information about the intrinsic factors governing the facial diastereoselectivity of trigonal carbocations. The effects due to differential face solvation phenomena emerge from the comparison of the present gas-phase results with those obtained from strictly related studies in solution.
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http://dx.doi.org/10.1021/jo9004298DOI Listing
August 2009

Gas-phase diastereoselectivity of secondary 5-substituted (X)-adamant-2-yl (X = F, Si(CH(3))(3)) cations.

J Org Chem 2007 May 28;72(11):4077-83. Epub 2007 Apr 28.

Dipartimento di Studi di Chimica e Tecnologia delle Sostanze Biologicamente Attive, Sapienza Università di Roma, 00185 Roma, Italy.

Secondary 5-X-adamant-2-yl cations IX (X = F, Si(CH3)3) have been generated in the gas phase (total pressure = 760 Torr) from protonation-induced defluorination of epimeric 2-F-5-X-adamantanes 1X and their kinetic diastereoselectivity toward CH318OH investigated in the 40-160 degrees C range. The experimental results indicate that the facial selectivity of IX is insensitive to the composition of the starting 1X epimers as well as to the presence and the concentration of a powerful base (N(C2H5)3). This kinetic picture, supported by B3LYP/6-31G* calculations, is consistent with a single stable pyramidalized structure for IX, that is, (Z)-5-F-adamant-2-yl (I(Z)F) and (E)-5-Si(CH3)3-adamant-2-yl cations (I(E)Si). The temperature dependence of the IX diastereoselectivity lends support to the intermediacy of noncovalent adducts [IX*CH318OH], characterized by a specific C2-H+...O18(H)CH3 hydrogen bonding interaction. Their conversion to the covalently bonded O-methylated (Z)- (II(Z)X) and (E)-5-X-adamantan-2-ols (II(E)X; X = F, Si(CH3)3) is governed by activation parameters, whose magnitude depends on the specific IX face accommodating CH318OH. The gas-phase diastereoselectivity of IX toward CH318OH is compared to that exhibited in related gas-phase and solution processes. The emerging picture indicates that the factors determining the diastereoselectivity of IX toward simple nucleophiles in the gaseous and condensed media are completely different.
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http://dx.doi.org/10.1021/jo0702140DOI Listing
May 2007

A novel beta-oxa polyunsaturated fatty acid downregulates the activation of the IkappaB kinase/nuclear factor kappaB pathway, inhibits expression of endothelial cell adhesion molecules, and depresses inflammation.

Circ Res 2006 Jul 8;99(1):34-41. Epub 2006 Jun 8.

Department of Immunopathology, Women's and Children's Hospital, University of Adelaide, South Australia, Australia.

Several novel polyunsaturated fatty acids (PUFAs) that contain either an oxygen or sulfur atom in the beta-position were found to exhibit more selective antiinflammatory properties than their natural PUFA counterparts. One of these, beta-oxa-23:4n-6, unlike natural PUFAs, lacked ability to stimulate oxygen radical production in neutrophils but caused marked inhibition of agonist-induced upregulation of leukocyte adhesion to cultured human umbilical vein endothelial cells (HUVEC) and E-selectin, intercellular adhesion molecule-1, and vascular cell adhesion molecule-1 expression. In addition, beta-oxa-23:4n-6 inhibited acute and chronic inflammatory responses in mice as well as the upregulation of adhesion molecule expression in arterial endothelium. This action of beta-oxa-23:4n-6 required a functional 12- but not 5-lipoxygenase or cyclooxygenases, consistent with its metabolism via the 12-lipoxygenase pathway. Whereas beta-oxa-23:4n-6 did not affect the activation of mitogen-activated protein kinases by tumor necrosis factor, activation of the IkappaB kinase/nuclear factor kappaB pathway was selectively inhibited. These novel PUFAs could form the basis for a potential new class of pharmaceuticals for treating inflammatory diseases, including atherosclerosis.
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http://dx.doi.org/10.1161/01.RES.0000231292.66084.cdDOI Listing
July 2006

Polar substituent effects in the bicyclo[1.1.1]pentane ring system: acidities of 3-substituted bicyclo[1.1.1]pentane-1-carboxylic acids.

J Org Chem 2005 Feb;70(3):1029-34

School of Chemistry, Physics, and Earth Sciences, The Flinders University of South Australia, Adelaide, Australia 5001.

Experimental gas-phase acidities are reported for a series of 3-substituted (X) bicyclo [1.1.1]pent-1-yl carboxylic acids (1, Y = COOH). A comparison with available calculated data (MP2/6-311++G**// B3LYP/6-311+G**) reveals good agreement. The relative substituent effects are shown to be adequately described by a much lower level of theory (B3LYP/6-31+G*). Various correlations are presented which clearly point to polar field effects as being the origin of the relative acidities.
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http://dx.doi.org/10.1021/jo040236bDOI Listing
February 2005

Importance of entropy in the diastereoselectivity of 5-substituted 2-methyladamant-2-yl cations.

J Org Chem 2004 Aug;69(17):5537-46

Dipartimento di Studi di Chimica e Tecnologia delle Sostanze Biologicamente Attive, Università di Roma "La Sapienza", 00185 Roma, Italy.

The diastereofacial selectivity of 2-methyl-5-X-adamant-2-yl cations IX (X = CN, Cl, Br, CH3O, COOCH3, C6H5, CH3, and (CH3)3Sn) toward methanol has been investigated in the gas phase at 750 Torr and in the 40-120 degrees C temperature range and compared with that of IF (X = F) and ISi (X = (CH3)3Si) measured previously under similar conditions. Detailed analysis of the energy surface of the IMe (X = CH3) ion reveals that the activation barrier of its syn addition to methanol is significantly lower than that of the anti attack. In the 40-100 degrees C range, such a difference is strongly reduced by adverse entropic factors which are large enough to invert the IMe diastereoselectivity from syn to anti at T > 69 degrees C. The behavior of IMe diverges markedly from that of IF and ISi. Large adverse entropic factors account for the predominant syn diastereoselectivity observed in the reaction with IF (X = F), notwithstanding the anti enthalpy barrier is lower than the syn one. Adverse entropy plays a minor role in the reaction with ISi (X = (CH3)3Si) which instead exhibits a preferred anti diastereoselectivity governed by the activation enthalpies. Depending on the electronic properties of X, the kinetic behavior of the other IX ions obeys one of the above models. The gas-phase diastereoselectivity of IX ions responds to a subtle interplay between the sigma-hyperconjugative/electrostatic effects of the X substituent and the activation entropy terms. sigma-Hyperconjugation/field effects determine the pyramidal structure and the relative stability of the syn and anti conformers of IX as well as the relative stability of their addition transition structures and their position along the reaction coordinate. The diastereoselectivity of IX in the gas phase is compared with that measured in solution and with theoretical predictions.
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http://dx.doi.org/10.1021/jo049481lDOI Listing
August 2004

Inhibition of neutrophil leukotriene B4 production by a novel synthetic N-3 polyunsaturated fatty acid analogue, beta-oxa 21:3n-3.

J Immunol 2003 Nov;171(9):4773-9

Department of Immunopathology, Women's and Children's Hospital, North Adelaide, South Australia, Australia.

We recently reported the synthesis and anti-inflammatory properties of a novel long chain polyunsaturated fatty acid (PUFA) with an oxygen atom in the beta-position, beta-oxa-21:3 n-3 (Z,Z,Z)-(octadeca-9,12,15-trienyloxy) acetic acid). Our data, from studies aimed at elucidating the mechanism of its action, show that pretreatment of human neutrophils with the beta-oxa-PUFA substantially depresses the production of leukotriene B(4) (LTB(4)) in response to calcium ionophore, A23187, comparable to standard leukotriene inhibitors such as zileuton and nordihydroguaiaretic acid. Interestingly, the n-6 equivalent, beta-oxa 21:3 n-6, is also a strong inhibitor of LTB(4) production. In contrast, naturally occurring PUFA only slightly reduce, for eicosapentaenoic (20:5n-3) and docosahexaenoic (22:6n-3) acids, or increase, for arachidonic acid (20:4n-6), the formation of LTB(4). The parent beta-oxa-21:3n-3 molecule, rather than its derivatives (methyl ester, saturated, monohydroperoxy, or monohydroxy forms), is exclusively responsible for attenuation of LTB(4) formation. beta-Oxa-21:3n-3 inhibits the conversion of [(3)H]20:4n-6 to [(3)H]5-hydroxyeicosatetraenoic acid and [(3)H]LTB(4) by neutrophils in the presence of calcium ionophore and also suppresses the activity of purified 5-lipoxygenase, but not cyclooxygenase 1 and 2. Beta-oxa-21:3n-3 is taken up by neutrophils and incorporated into phospholipids and neutral lipids. In the presence of calcium ionophore, the leukocytes convert a marginal amount of beta-oxa-21:3n-3 to a 16-monohydroxy-beta-oxa-21:3n-3 derivative. After administration to rodents by gavage or i.p. injection, beta-oxa-21:3n-3 is found to be incorporated into the lipids of various tissues. Thus, beta-oxa-21:3n-3 has the potential to be used in the treatment of inflammatory diseases, which are mediated by products of the lipoxygenase pathway.
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http://dx.doi.org/10.4049/jimmunol.171.9.4773DOI Listing
November 2003

Solvolysis of (Z)-5-trimethylstannyl 2-adamantyl p-bromobenzenesulfonate: mechanistic implications of a record-breaking secondary alpha-deuterium kinetic isotope effect for an SN1 substrate.

J Org Chem 2003 Jun;68(13):5399-402

School of Chemistry, Physics, and Earth Sciences, Flinders University of South Australia, Adelaide, SA 5001, Australia.

The secondary alpha-deuterium kinetic isotope effect (alpha-kie) for the solvolysis of (Z)-5-trimethylstannyl 2-adamantyl p-bromobenzenesulfonate in 97% w/w aqueous 2,2,2-trifluoroethanol (97T) at 25 degrees C has been measured (k(H)/k(D) = 1.33). The alpha-kie is abnormally high compared to the value of 1.23 for the corresponding limiting S(N)1 solvolysis of 2-adamantyl p-bromobenzenesulfonate, which proceeds via an extended ion-pair mechanism. A novel mechanism for the solvolysis of the tin compound is proposed that accommodates not only the high alpha-kie but also the absence of internal return.
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http://dx.doi.org/10.1021/jo0300892DOI Listing
June 2003

Diastereofacial Selectivity in Atom Transfer Reactions of 5-Substituted (X) Adamant-2-yl Radicals: Nature of the Electronic Factor.

J Org Chem 1998 Oct;63(21):7231-7235

Department of Chemistry, The Flinders University of South Australia, Adelaide, Australia 5001.

The diastereofacial selectivity in deuterium and halogen atom abstraction reactions of 5-fluoro- and 5-(trimethylstannyl)-2-adamantyl radicals has been investigated. Significant preferential syn (or zu) and anti (or en) face selectivity, respectively, is observed for these substituents of distinctly opposite electronic character. Although the observations are in accord with predictions from Cieplak's transition state hyperconjugation model, an alternative explanation can be advanced based on an early reactant-like TS model.
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http://dx.doi.org/10.1021/jo9805753DOI Listing
October 1998