Total Thiols and MDA Levels in Patients with Acute Myocardial Infarction Before and After Reperfusion Therapy

Background: Reactive oxygen species have been implicated in the pathogenesis of ischemic and reperfusion injury. In the current work we have measured malondialdehyde (MDA), total thiols, total CK, CK-MB and AST in ECG proven acute myocardial infarction (AMI) patients immediately after admission and 24 hours after administration of thrombolytic agent streptokinase, and in healthy controls. Methods: Blood samples from 44 AMI patients and 25 age and sex matched healthy controls were obtained and analyzed for MDA, total thiols using spectrophotometric methods and cardiac enzymes CK, CK-MB and AST using automated analyzer. Results: We have found significant increase in MDA, CPK, CK-MB, AST (p< 0.001) and significant decrease in total thiols (p<0.001) in AMI patients after thrombolytic therapy compared to values at admission, and healthy controls. MDA correlated negatively with total thiols (r = - 0.333, p<0.05) and positively with CK-MB (r = 0.491, p<0.01) in AMI patients after thrombolytic therapy. Conclusions: Reperfusion following thrombolytic therapy increases reactive oxygen species with concomitant decrease in antioxidant total thiols

The nitrite anion: the key intermediate in alkyl nitrates degradative mechanism.

Alkyl nitrates, _in vivo_, are metabolized to yield nitric oxide, and thiol groups are considered necessary cofactors. This statement is based on studies that underline how these species potentiate hemodynamic responsiveness to nitrates in patients with ischemic heart disease. However, the role of thiols might be mediated by the formation of corresponding S-nitrosothiols, and a redox process is responsible for the nitrates&#x27; degradation: an enzyme, probably the cytochrome P450, is involved _in vivo_. Here, we report evidence that, in vitro, no reaction between thiols and alkyl nitrates takes place, but that stronger reducing agents, such as iron (II) derivatives, are necessary: alkoxy radicals and the nitrite anion are the reaction intermediates. The latter, in slightly acidic conditions, for instance mimicking ischemic conditions, is shown to nitrosilate thiols to the corresponding S-nitrosothiols: the real NO suppliers. Therefore, the direct release of NO from nitrates is excluded. Finally, the in vivo role of thiols on depletion and tolerance is also accounted for

The electrochemical stability of thiols on gold surfaces

In this paper we present a comparative analysis of the electrochemical stability of alkanethiols, aromatic and heterocyclic thiols on the Au(111) and Au(100) faces in relation to the theoretical energetic data. The peak potential and surface coverage are used as the key parameters to estimate the electrochemical stability while work function changes, adsorption energies and surface free energies calculated from periodic DFT, including van der Waals interactions, are used for the theoretical estimation. We find that the peak potentials do not correlate with work function changes and adsorption energies in particular for aromatic and heterocyclic thiols. In contrast, the reductive desorption potentials for the different thiols show a good correlation with the surface free energy of the SAMs estimated by density functional theory calculations. Surface coverage is a key factor that controls reductive desorption through van der Waals interactions.Fil: Salvarezza, Roberto Carlos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Carro, Pilar. Universidad de La Laguna; Españ

Transsulfuration pathway thiols and methylated arginines: the hunter community study

Background: Serum homocysteine, when studied singly, has been reported to be positively associated both with the endogenous nitric oxide synthase inhibitor asymmetric dimethylarginine [ADMA, via inhibition of dimethylarginine dimethylaminohydrolase (DDAH) activity] and with symmetric dimethylarginine (SDMA). We investigated combined associations between transsulfuration pathway thiols, including homocysteine, and serum ADMA and SDMA concentrations at population level. Methods: Data on clinical and demographic characteristics, medication exposure, C-reactive protein, serum ADMA and SDMA (LC-MS/MS), and thiols (homocysteine, cysteine, taurine, glutamylcysteine, total glutathione, and cysteinylglycine; capillary electrophoresis) were collected from a sample of the Hunter Community Study on human ageing [n = 498, median age (IQR) = 64 (60–70) years]. Results: Regression analysis showed that: a) age (P = 0.001), gender (P = 0.03), lower estimated glomerular filtration rate (eGFR, P = 0.08), body mass index (P = 0.008), treatment with beta-blockers (P = 0.03), homocysteine (P = 0.02), and glutamylcysteine (P = 0.003) were independently associated with higher ADMA concentrations; and b) age (P = 0.001), absence of diabetes (P = 0.001), lower body mass index (P = 0.01), lower eGFR (P&lt;0.001), cysteine (P = 0.007), and glutamylcysteine (P&lt;0.001) were independently associated with higher SDMA concentrations. No significant associations were observed between methylated arginines and either glutathione or taurine concentrations. Conclusions: After adjusting for clinical, demographic, biochemical, and pharmacological confounders the combined assessment of transsulfuration pathway thiols shows that glutamylcysteine has the strongest and positive independent associations with ADMA and SDMA. Whether this reflects a direct effect of glutamylcysteine on DDAH activity (for ADMA) and/or cationic amino acid transport requires further investigations.</br

Lattice Imaging of Self-Assembled Monolayers of Partially Fluorinated Disulfides and Thiols on Sputtered Gold by Atomic Force Microscopy

The structure of self-assembled monolayers (SAMs) of various fluorinated disulfides, perfluoroalkylamide thiols, and a mixed alkyl perfluoroalkylamide disulfide on sputtered gold was studied by atomic force microscopy (AFM). AFM, performed both in air and in ethanol, revealed the monolayer structure with molecular resolution on the polycrystalline gold substrates. For all partially fluorinated disulfides containing ester groups, a hexagonal lattice with a lattice constant of 5.8-5.9 Å was found. A mixed alkyl perfluoroalkylamide disulfide formed a hexagonal lattice of a slightly larger lattice constant (6.1 Å), whereas the lattice observed for fluorinated thiols containing an amide group was either hexagonal (5.7-5.8 Å) or distorted hexatic (5.6, 6.2, 5.6 Å), depending on the length of the perfluoroalkane segment and the imaging force. The observed deviation from hexagonal symmetry is attributed to the distorting effect of hydrogen bonding between neighboring amide groups within the monolayer. For short perfluoroalkane segments the distortion is observed at low imaging forces, whereas for long perfluoroalkane segments significantly higher imaging forces are necessary in order to observe the distortion. The force dependence of the measured lattice symmetries for different chain lengths suggests that the AFM tip penetrates into the SAM and probes at least partially the interior of the SAM

Effect of Thiols for Nitrogen Reduction to Ammonia

Ammonia is an important chemical used for fertilizers and also a potential carbon-free hydrogen storage medium. The Haber-Bosch process is the main production process, which requires large energy- and capital-input. Therefore, it is crucial to develop an alternate scalable synthesis that provides a less energy intensive and more economical route for synthetic ammonia production. In this paper, a 1Fe1Ni film was functionalized with C3OH and C6OH for the electrochemical synthesis of ammonia. This work will provide some insight into how thiol ligands can increase the selectivity of the catalyst for nitrogen reduction reaction and can be improved on to provide a new synthesis for ammonia

Acceleration of Range Points Migration-Based Microwave Imaging for Nondestructive Testing

We report on an experimental investigation of the properties of volume holographic recording in photopolymerizable nanoparticle?polymer composites (NPCs) doped with chain transferring multifunctional di- and tri-thiols as chain transfer agents. It is shown that the incorporation of the multifunctional thiols into NPCs more strongly influences on volume holographic recording than that doped with mono-thiol since more chemical reactions involve in the polymer network formation. It is found that, as similar to the case of mono-thiol doping, there exist optimum concentrations of di- and tri-thiols for maximizing the saturated refractive index modulation. It is also seen that recording sensitivity monotonically decreases with an increase in multifunctional thiol concentration due to the partial inhibition of the photopolymerization event by excessive thiols

Glutathione S-Transferase activity and total thiol status in chronic alcohol abusers before and 30 days after alcohol abstinence

Background: Glutathione S Transferase (GST) has been involved in detoxification process in the liver and its activity has been shown to be increased in alcohol abusers. In the current work we measured the GST activity, total thiol status, AST, ALT, and direct bilirubin in chronic alcohol abusers before and 30 days after alcohol abstinence and lifestyle modification. Methods: Serum and urine GST activity and total thiol status were determined using spectrophotometric methods and serum transaminases were determined using clinical chemistry analyzer. Results: We found,significant increase in serum and urine GST (p<0.001), AST (p<0.001), ALT (p<0.001), and decrease in total thiol status (p<0.001) in chronic alcohol abusers. GST activity significantly decreased (p<0.001) and total thiol status were improved significantly (p<0.001) 30 days after alcohol abstinence and lifestyle modification. Conclusion: This study provides preliminary data to suggest the role of GST as prognostic indicator of alcohol abstinence with possible trend towards an improvement in liver function

Volume holographic recording in nanoparticle–polymer composites doped with multifunctional chain transfer agents

We report on an experimental investigation of the properties of volume holographic recording in photopolymerizable nanoparticle–polymer composites (NPCs) doped with chain transferring multifunctional di- and tri-thiols as chain transfer agents. It is shown that the incorporation of the multifunctional thiols into NPCs more strongly influences on volume holographic recording than that doped with mono-thiol since more chemical reactions involve in the polymer network formation. It is found that, as similar to the case of mono-thiol doping, there exist optimum concentrations of di- and tri-thiols for maximizing the saturated refractive index modulation. It is also seen that recording sensitivity monotonically decreases with an increase in multifunctional thiol concentration due to the partial inhibition of the photopolymerization event by excessive thiols