Clinical pattern of ocular toxoplasmosis treated in a referral centre in Serbia

Purpose To analyze the clinical pattern of ocular toxoplasmosis (OT) in a referral centre in Serbia. Patients and methods The medical records of consecutive patients admitted for OT to the single referral centre for uveitis in Serbia between 2006 and 2010 were retrospectively analyzed. OT was diagnosed on the basis of typical fundus lesions and positive serology for Toxoplasma. Results In a total of 457 uveitis patients, OT was the third leading cause, with 59 patients (12.9%). Most OT cases (73%) were monocular. An active primary retinal lesion was observed in 36% and recurrent OT in 64% patients. Localization of lesions was central/paracentral (44%), juxtapapillar (27%), peripheral (19%), and multifocal (10%). Other ocular manifestations of inflammation included vitritis (44%), anterior uveitis (19%), and retinal vasculitis (10%). Complications included choroidal neovascularization in two and exudative retinal detachment with cataract, glaucoma, and cystoid macular oedema in one patient each. The detection of Toxoplasma-specific IgM antibodies in a single patient indicates a low rate of OT concomitant with acute infection. After treatment, the mean best-corrected visual acuity (BCVA) increased significantly. However, 14 (24%) patients ended up legally blind in the affected eye, of which 2 (3%) with bilateral blindness, all with a very poor BCVA (0.047 +/- 0.055) at presentation. Visual impairment and treatment outcome were both associated with central localization of lesions (P lt 0.0001 and P = 0.006, respectively). Conclusion OT is a significant cause of posterior uveitis in Serbia. Patients should be aware of the recurring nature of OT and react immediately if symptoms occur. Eye (2012) 26, 723-728; doi: 10.1038/eye.2012.20; published online 24 February 201

Decarboxylation versus Acetonitrile Loss in Silver Acetate and Silver Propiolate Complexes, [RCO2Ag2(CH3CN)(n)](+) (where R = CH3 and CH3C C; n=1 and 2)

Gas-phase experiments using collision-induced dissociation in an ion trap mass spectrometer have been used in combination with density functional theory (DFT) calculations (at the B3LYP/SDD6–31+G(d) level of theory) to examine the competition between decarboxylation and loss of a coordinated acetonitrile in the unimolecular fragmentation reactions of the silver acetate and silver propiolate complexes, [RCO2Ag2(CH3CN)n]+ (where R = CH3 and CH3C≡C; n = 1 and 2), introduced into the gas-phase via electrospray ionisation. When R = CH3, loss of acetonitrile is the sole reaction channel observed for both complexes (n = 1 and 2), consistent with DFT calculations, which highlight that the barriers for decarboxylation 2.18 eV (n = 2) and 1.96 eV (n = 1) are greater than the binding energies of the coordinated acetonitriles (1.60 eV for n = 2; 1.64 eV for n = 1). In contrast, when R = CH3C≡C, decarboxylation is the main fragmentation pathway observed for both complexes (n = 1 and 2), with loss of acetonitrile only being a minor product channel. This is consistent with DFT calculations, which reveal that the barriers for decarboxylation are 1.17 eV (n = 2) and 1.16 eV (n = 1), which are both below the binding energies of the coordinated acetonitriles (1.55 eV for n = 2; 1.56 eV for n = 1). The barrier for decarboxylation of [CH3C≡CCO2Ag2]+ is 1.22 eV, which is less than the 2.06 eV reported for decarboxylation of [CH3CO2Ag2]+ (Al Sharif et al. Organometallics, 2013, 32, 5416). The observed ease of decarboxylation of silver propiolate complexes in the gas-phase is consistent with the recently reported use of silver salts in metal catalysed decarboxylative C–C and C–X bond forming reactions of propiolic acids

Molecular Salt Effects in the Gas Phase: Tuning the Kinetic Basicity of [HCCLiCl](-) and [HCCMgCl2](-) by LiCl and MgCl2

A combination of gas-phase ion-molecule reaction experiments and theoretical kinetic modeling is used to examine how a salt can influence the kinetic basicity of organometallates reacting with water. [HC≡CLiCl](-) reacts with water more rapidly than [HC≡CMgCl2](-), consistent with the higher reactivity of organolithium versus organomagnesium reagents. Addition of LiCl to [HC≡CLiCl](-) or [HC≡CMgCl2](-) enhances their reactivity towards water by a factor of about 2, while addition of MgCl2 to [HC≡CMgCl2](-) enhances its reactivity by a factor of about 4. Ab initio calculations coupled with master equation/RRKM theory kinetic modeling show that these reactions proceed via a mechanism involving formation of a water adduct followed by rearrangement, proton transfer, and acetylene elimination as either discrete or concerted steps. Both the energy and entropy requirements for these elementary steps need to be considered in order to explain the observed kinetics

The role of peroxyl radicals in polyester degradation - a mass spectrometric product and kinetic study using the distonic radical ion approach

Mass spectrometric techniques were used to obtain detailed insight into the reactions of peroxyl radicals with model systems of (damaged) polyesters. Using a distonic radical ion approach, it was shown that N-methylpyridinium peroxyl radical cations, Pyr(+)OO˙, do not react with non-activated C-H bonds typically present in polyesters that resist degradation. Structural damage in the polymer, for example small amounts of alkene moieties formed during the manufacturing process, is required to enable reaction with Pyr(+)OO˙, which proceeds with high preference through addition to the π system rather than via allylic hydrogen atom abstraction (kadd/kHAT > 20 for internal alkenes). This is due to the very fast and strongly exothermic subsequent fragmentation of the peroxyl-alkene radical adduct to epoxides and highly reactive Pyr(+)O˙, which both could promote further degradation of the polymer through non-radical and radical pathways. This work provides essential experimental support that the basic autoxidation mechanism is a too simplistic model to rationalize radical mediated degradation of polymers under ambient conditions

Gas phase synthesis and reactivity of dimethylaurate

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)A combination of multistage mass spectrometry experiments and DFT calculations were used to examine the synthesis and reactivity of dimethylaurate. Collision induced dissociation (CID) of [(CH(3)CO(2))(4)Au](-) proceeded via reductive elimination of acetylperoxide to yield the diacetate [CH(3)CO(2)AuO(2)CCH(3)](-), which in turn underwent sequential CID decarboxylation reactions to yield the organoaurates [CH(3)CO(2)AuCH(3)](-) and [CH(3)AuCH(3)](-). The unimolecular chemistry of the dimethylaurate proceeds via a combination of bond homolysis to yield the methyl aurate radical anion [CH(3)Au](center dot-) as well as formation of the gold dihydride [HAuH](-). DFT calculations reveal that the latter anion is formed via a 1,2-dyotropic rearrangement to yield the isomer [CH(3)CH(2)AuH](-), followed by a beta-hydride elimination reaction. Ion-molecule reactions of [CH(3)AuCH(3)](-) with methyl iodide did not yield any products even at relatively high concentrations of the neutral substrate and longer reaction times, indicating a reaction efficiency of less than 1 in 20 000 collisions. DFT calculations were carried out on two different potential energy surfaces (PES) for the reaction of [CH(3)AuCH(3)](-) with CH(3)I: (i) an S(N)2 mechanism proceeding via a side-on transition state; and (ii) a stepwise mechanism proceeding via oxidative addition followed by reductive elimination. Both pathways have significant endothermic barriers, consistent with the lack of C-C bond coupling products being formed in the experiments. Finally, the reactivity of [CH(3)AuCH(3)](-) is compared to the previously studied [CH(3)AgCH(3)](-) and [CH(3)CuCH(3)](-), as well as condensed phase studies on dimethylaurate salts.o TEXTO COMPLETO DESTE ARTIGO, ESTARÁ DISPONÍVEL À PARTIR DE AGOSTO DE 2015.393786558662ARC [DP0558430]Faculty of Science for a Science Faculty ScholarshipUniversity of MelbourneFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)ARC [DP0558430

Gas-phase reactions of the rhenium oxide anions, [ReOx](-) (x=2-4) with the neutral organic substrates methane, ethene, methanol and acetic acid

The ion-molecule reactions of the rhenium oxide anions, [ReOx](-) (x = 2 - 4) with the organic substrates methane, ethene, methanol and acetic acid have been examined in a linear ion trap mass spectrometer. The only reactivity observed was between [ReO(2)](-) and acetic acid. Isotope labelled experiments and high-resolution mass spectrometry measurements were used to assign the formulas of the ionic products. Collision-induced dissociation and ion-molecule reactions with acetic acid were used to probe the structures of the mass-selected primary product ions. Density functional theory calculations [PBE0/LanL2DZ6-311+G(d)] were used to suggest possible structures. The three primary product channels observed are likely to arise from the formation of: the metallalactone [ReO(2)(CH(2)CO(2))](-) (m/z 277) and H(2); [CH(3)ReO(2)(OH)](-) (m/z 251) and CO; and [ReO(3)](-) (m/z 235), H(2) and CH(2)CO

Gas-Phase and Computational Study of Identical Nickel- and Palladium-Mediated Organic Transformations Where Mechanisms Proceeding via M-II or M-IV Oxidation States Are Determined by Ancillary Ligands

Gas-phase studies utilizing ion-molecule reactions, supported by computational chemistry, demonstrate that the reaction of the enolate complexes [(CH2CO2-C,O)M(CH3)](-) (M = Ni (5a), Pd (5b)) with allyl acetate proceed via oxidative addition to give M(IV) species [(CH2CO2-C,O)M(CH3)(η(1)-CH2-CH═CH2)(O2CCH3-O,O')](-) (6) that reductively eliminate 1-butene, to form [(CH2CO2-C,O)M(O2CCH3-O,O')](-) (4). The mechanism contrasts with the M(II)-mediated pathway for the analogous reaction of [(phen)M(CH3)](+) (1a,b) (phen = 1,10-phenanthroline). The different pathways demonstrate the marked effect of electron-rich metal centers in enabling higher oxidation state pathways. Due to the presence of two alkyl groups, the metal-occupied d orbitals (particularly dz(2)) in 5 are considerably destabilized, resulting in more facile oxidative addition; the electron transfer from dz(2) to the C═C π* orbital is the key interaction leading to oxidative addition of allyl acetate to M(II). Upon collision-induced dissociation, 4 undergoes decarboxylation to form 5. These results provide support for the current exploration of roles for Ni(IV) and Pd(IV) in organic synthesis