34 research outputs found

    Organic Super-Acceptors with Efficient Intramolecular Charge-Transfer Interactions by [2+2] Cycloadditions of TCNE, TCNQ, and F-4-TCNQ to Donor-Substituted Cyanoalkynes

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    Thermal [2+2] cycloadditions of tetracyanoethene (TCNE), 7,7,8,8-tetracyanoquinodimethane (TCNQ), and 2,3,4,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F-4-TCNQ) to N,N-dimethylanilino-substituted (DMA-substituted) alkynes bearing either nitrile, dicyanovinyl (DCV; -CH=C(CN)(2)), or tricyanovinyl (TCV; -C(CN)=C(CN)(2)) functionalities, followed by retro-electrocyclization, afforded a new class of stable organic super-acceptors. Despite the non-planarity of these acceptors, as revealed by X-ray crystallographic analysis and theoretical calculations, efficient intramolecular charge-transfer (CT) interactions between the DMA donors and the CN-containing acceptor moieties are established. The corresponding CT bands appear strongly bathochromically shifted with maxima up to 1120 nm (1.11 eV) accompanied by an end-absorption in the near infrared around 1600 nm (0.78 eV) for F-4-TCNQ adducts. Electronic absorption spectra of selected acceptors were nicely reproduced by applying the spectroscopy oriented configuration interaction (SORCI) procedure. The electrochemical investigations of these acceptors by cyclic voltammetry (CV) and rotating disc voltammetry (RDV) in CH2Cl2 identified their remarkable propensity for reversible electron Uptake rivaling the benchmark compounds TCNQ (E-red,E-1 = -0.25 V in CH2Cl2 vs. Fc(+)/Fc) and F-4-TCNQ (E-red,E-1 = +0.16 V in CH2Cl2 vs. Fc(+)/Fc). Furthermore, the electron-accepting power of these new compounds expressed as adiabatic electron affinity (EA) has been estimated by theoretical calculations and compared to the reference acceptor F-4-TCNQ. which is Used as a p-type dopant in the fabrication of organic light-emitting diodes (OLEDs) and solar cells. A good linear correlation exists between the calculated EAs and the first reduction potentials E-red,E-1 Despite the substitution with strong DMA donors, the predicted E-As reach the value calculated for F-4-TCNQ (4.96 eV) in many cases, which makes the new, acceptors interesting for potential applications as dopants in of-garlic optoelectronic devices. The first example of a charge-transfer salt between the DMA-substituted TCNQ adduct (E-red,E-1 = -0.27 V vs. Fc(+)/Fc) and the strong electron donor decamethyl-ferrocene ([FeCP*(2)]: W = pentamethylcylopentadienide; E-ox,E-1 = -0.59 V vs. Fc(+)/Fc) is described. Interestingly, the X-ray crystal structure showed that in the solid state the TCNQ moiety in the acceptor underwent reductive sigma-dimerization upon reaction with the donor

    Urban and rural comparison of vitamin D status in Pakistani pregnant women and neonates

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    We undertook a cross-sectional study in rural Jehlum and urban Karachi to evaluate the prevalence of vitamin D deficiency in Pakistani pregnant women and neonates and to assess any association of serum 25(OH) vitamin D [25(OH)D] concentration with vitamin D binding protein (Gc) genotypes. Altogether, 390 women and 266 neonates were recruited from urban and rural sites, respectively. Serum 25(OH)D was measured by an immunoassay, while Gc genotypes were identified using polymerase chain reaction followed by restriction fragment length polymorphism or PCR-RFLP. One-way analysis of variance or ANOVA and linear regression were used for statistical analysis. In urban Karachi, 99.5% of women and 97.3% of neonates were vitamin D deficient (\u3c 50 nmol/L), while 89% of women and 82% of neonates were deficient in rural Jehlum. Gc genotypes were not associated with serum 25(OH)D concentrations in both women and their neonates. We conclude that vitamin D deficiency is highly prevalent in Pakistani women and their neonates, and Gc genotypes are not associated with serum 25(OH)D concentrations

    Cardiac markers: profile in rats experimentally infected with Toxocara canis Marcadores cardíacos: perfil em ratos infectados experimentalmente com Toxocara canis

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    The aim of this study was to evaluate the profile of the enzymes creatine kinase (CK), creatine kinase MB (CK-MB) and lactate dehydrogenase (LDH) in Wistar rats infected with 250 (GI, n = 24) or 1000 (GII, n = 24) Toxocara canis eggs. Animals were evaluated on days 7, 15, 30, 60, 120 and 180 post-infection (DPI). Only the GI rats showed an increase in CK and CK-MB, at 15 and 30 DPI, respectively. Anti-Toxocara spp. antibodies were detected by ELISA in infected animals. Despite of the presence of eosinophilic infiltrate in the heart of three infected animals, none larva was recovered from the organ neither by acid digestion nor by Baermann procedure. Eosinophilia was observed in both groups but there was no significant difference in the eosinophil counts between GI and GII (p = 0.2239). It is possible to consider that cardiac lesion is an eventual finding in murine model for toxocariasis.<br>O objetivo do presente estudo foi avaliar o perfil das enzimas creatinoquinase (CK), creatinoquinase-MB (CK-MB) e lactato desidrogenase (LDH) em ratos Wistar infectados com 250 (GI, n = 24) ou 1000 (GII, n = 24) ovos de Toxocara canis. Os animais foram avaliados nos dias 7, 15, 30, 60, 120 e 180 pós-infecção (DPI). Observou-se que apenas os animais do GI apresentaram aumento da atividade de CK e CK-MB aos 15 e 30 DPI, respectivamente. Anticorpos anti-T. canis foram detectados por ELISA nos animais infectados. Apesar da presença de infiltrado eosinofílico em três animais infectados, nenhuma larva foi recuperada do coração pela digestão ácida ou pela técnica de Baermann. Eosinofilia foi observada em todos os momentos em GI e GII, sem diferença significativa entre os grupos (p = 0,2239). Pode-se considerar que as lesões cardíacas foram um achado eventual no modelo murino para toxocaríase
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