Electroanalytical Exploitation of Nitroso Phenyl Modified Carbon‐Thiol Interactions: Application to the Low Voltage Determination of Thiols

The electrochemical generation of nitrosophenyl groups covalently attached to graphite powder (nitrosophenylcarbon) from carbon powder chemically modified with nitrophenyl groups and their subsequent reaction with thiols (glutathione, cysteine and homocysteine) has been investigated as a method by which the later can be quantified. The modified carbon powder was immobilized onto a basal plane pyrolytic graphite electrode and characterized by cyclic voltammetry by scanning between 1.0 V and ?1.0 V vs. SCE in phosphate buffer (pH 7). Square wave voltammetry (SWV) was used for the determination of thiols and the SWV parameters were optimized. The nitrosophenylcarbon is electrogenerated from nitrophenylcarbon and can chemically oxidize thiols to disulfides. Subsequent reduction of nitrosophenylcarbon to phenylhydroxylaminecarbon during the square wave voltammetric process leads to a decrease in the reductive current. This can be correlated to the concentration of thiol present within the medium. The cyclic voltammetric responses of basal plane pyrolytic graphite electrode, edge plane pyrolytic graphite electrode, glassy carbon electrode and boron‐doped diamond electrode in the direct oxidation of thiols were also investigated and all were found to have a significantly higher overpotential compared to the described method using nitrosophenylcarbon.     

Electrocatalytic detection of thiols using an edge plane pyrolytic graphite electrode

The first example of using an edge plane pyrolytic graphite electrode in electroanalysis is reported as the determination of homocysteine, N-acetylcysteine, cysteine and glutathione is studied. The response of the electrode in the direct oxidation of thiol moieties is explored and found to be electrocatalytic producing a reduction in the overpotential while having enhanced signal-to-noise characteristics compared to glassy carbon and basal plane pyrolytic graphite electrodes. The effectiveness of the methodology is examined in the determination of cysteine species in a growth tissue media that contains a high number of common biological interferences. The advantageous properties of this electrode for thiol determination lie in its excellent catalytic activity, sensitivity and simplicity.     

Thermal exfoliation of electrochemically synthesized graphite intercalation compound with perrhenic acid

In present work, we describe the synthesis of graphite intercalation compounds with perrhenic acid (HReO₄-GIC) through the anodic oxidation of graphite in aqueous perrhenic acid solution and their thermal exfoliation. Due to electrochemical treatment of graphite in perrhenic acid solution, ReO₄⁻ ions are intercalated into interlayer spaces of graphite. Anodic oxidation of graphite in HReO₄ solution leads to the formation of 3-stage GIC. Simultaneously, some amount of perrhenic acid becomes deposited on the graphite surface and edges. In the next step, thermal treatment of the previously synthesized GIC was performed, causing both the exfoliation of graphitic structure and transformation of perrhenic acid into rhenium oxides on the surface of graphene layers. The yielded product was exfoliated graphite-ReO₂/ReO₃ composite. The obtained composite was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and Raman spectroscopy. Additionally, specific surface area of the exfoliated materials was measured.

     

Photochemical instability of CdSe nanocrystals coated by hydrophilic thiols

The photochemical instability of CdSe nanocrystals coated by hydrophilic thiols was studied nondestructively and systematically in water. The results revealed that the photochemical instability of the nanocrystals actually included three distinguishable processes, namely the photocatalytic oxidation of the thiol ligands on the surface of nanocrystals, the photooxidation of the nanocrystals, and the precipitation of the nanocrystals. At first, the thiol ligands on the surface of a nanocrystal were gradually photocatalytically oxidized using the CdSe nanocrystal core as the photocatalyst. This photocatalytic oxidation process was observed as a zero-order reaction in terms of the concentration of the free thiols in the solution. The photogenerated holes in a nanocrystal were trapped onto the thiol ligands bound on the surface of the nanocrystal, which initiated the photooxidation of the ligands and protected the nanocrystal from any photooxidation. After nearly all of the thiol ligands on the surface of the nanocrystals were converted into disulfides, the system underwent several different pathways. If the disulfides were soluble in water, then all of the disulfides fell into the solution at the end of this initial process, and the nanocrystals precipitated out of the solution without much variation over their size and size distribution. When the disulfides were insoluble in water, they likely formed a micelle-like structure around the nanocrystal core and kept it soluble in the solution. In this case, the nanocrystals only precipitated after severe oxidation, which took a long period of time. If the system contained excess free thiol ligands, they replaced the photochemically generated disulfides and maintained the stability and solubility of the nanocrystals. The initiation stage of the photooxidation of CdSe nanocrystals themselves increased as the thickness and packing density of the ligand shell increased. This was explained by considering the ligand shell on the surface of a nanocrystal as the diffusion barrier of the oxygen species from the bulk solution into the interface between the nanocrystal and the surface ligands. Experimental results clearly indicated that the initiation stage of the photooxidation was not caused by the chemical oxidation of the system kept in air under dark conditions or the hydrolysis of the cadmium-thiol bonds on the surface of the nanocrystals, both of which were magnitudes slower than the photocatalytic oxidation of the surface ligands if they occurred at all. The results described in this contribution have already been applied for designing new types of thiol ligands which dramatically improved the photochemical stability of CdSe nanocrystals with a ligand shell that is as thin as approximately 1 nm.     

An efficient and convenient method for the preparation of disulfides from thiols using oxygen as oxidant catalyzed by tert-butyl nitrite

An efficient and convenient tert-butyl nitrite-catalyzed selective aerobic oxidation of thiols has been developed. Under the optimal reaction conditions, a number of thiol derivatives including aromatic thiols, heteroaromatic thiols and aliphatic thiols can be converted into their corresponding disulfides in good to excellent yields.     

Oxidation of thiol compounds by molecular oxygen in aqueous solutions

Side self-oxidation of thiols was studied. It was found that these reactions in neutral and alkaline solutions are induced by impurities of variable-valence metals. The ability of transition metals to catalyze oxidation of thiols changes in the order Cu > Mn > Fe > Ni Co. The plot of the self-oxidation rate vs. pH passes through a maximum whose position on the pH scale depends on both the nature of metal and the structure of the thiol oxidized. For thiols having different structures, the kinetic orders in reactions catalyzed by copper ions differently vary with pH, which is apparently associated with the formation of complexes possessing different catalytic activity.     

Solid-phase thiolsulfinates for the reversible immobilization of thiols

A new method for the reversible immobilization of thiol-containing substances on agarose beads is presented. It is based on the use of thiolsulfinate (disulfide monoxide) as a solid-phase reactive group. The thiolsulfinate groups are introduced by controlled oxidation of thiol agarose. The method comprises two steps: First, mild oxidation of the agarose thiol groups to disulfide structures with potassium ferricyanide. Second, the oxidation of the so-formed agarose disulfide groups to thiolsulfinate groups by use of a stoichiometric amount of the oxidizing agent magnesium monoperoxyphtalate. The solid-phase thiolsulfinate groups react very easily with thiols, which, as a result of the reaction, will be bound to the agarose beads by disulfide bonds. The adsorbent derivative is very suitable for the reversible immobilization of low as well as high-mol-wt thiols as demonstrated with reduced glutathione, penicillamine, mercaptoethanesulfonic acid, thiolated bovine serum albumin,β-galactosidase, and ±₁-antitrypsine. Since treatment of the agarose derivatives with an excess of low-mol-wt thiols (e.g., dithiothreitol) leads to release of the bound molecules and regeneration of the original thiol groups, the reactive thiolsulfinate groups can easily be regenerated by the mentioned two-step procedure. The cycle of oxidation, binding, reduction, and reoxidation can be performed several times while retaining thiol binding capacity.     

Catalytic oxidation of thiols at preheated glassy carbon electrode modified with abrasive immobilization of multiwall carbon nanotubes: applications to amperometric detection of thiocytosine, l-cysteine and glutathione

The performance of preheated glassy carbon electrode modified with carbon nanotubes is described. First glassy carbon electrode is heated for 5 min at 50 °C, then abrasive immobilization of multiwall carbon nanotubes on a preheated glassy carbon electrode was achieved by gentle rubbing of electrode surface on a filter paper supporting carbon nanotubes. Carbon nanotubes (CNTs)-modified glassy carbon electrodes exhibit strong and stable electrocatalytic response toward thiols oxidation in wide pH range. These properties permit an important decrease in over voltage for the oxidation of thiocytosine, glutathione and l-cysteine, as well as a dramatic increase in the peak currents in comparison with bare glassy carbon electrode. Furthermore, the thiols amperometric response of the coated electrodes is extremely stable, with more than 95% of the initial activity after 30 min stirring of 0.1 mM thiols. The electrocatalytic behavior is further exploited as a sensitive detection scheme for thiols detection by hydrodynamic amperometry. The substantial decrease in the overvoltage of the thiols oxidation associated with a stable amperometric response and antifouling properties of nanotubes films allow the development of highly sensitive thiols sensor without using any redox mediator. Such ability of carbon nanotubes to promote the thiols electron transfer reaction, short response time (5 s) and long-term stability, low detection limit, extended linear concentration range, high sensitivity suggest great promise for thiols amperometric sensors and detector for chromatographic analysis of thiol derivatives.     

Influence of ligand structure on the stability and oxidation of copper nanoparticles

The stability and oxidation of copper nanoparticles stabilized with various ligands have been studied. Lauric acid-capped copper nanoparticles were prepared by a modified Brust-Schiffrin method. Then, ligand exchange with an excess of different capping agents was performed. Oxidation and stability were studied by UV-vis, XRD, and TEM. Alkanethiols and oleic acid were found to improve air stability. The oxidation resistance of thiol-capped copper nanoparticles was found to increase with the chain length of the thiol. However, excess thiol caused etching of the particles under nitrogen. With oleic acid no etching was observed under nitrogen. After oxidation, no traces of the ligand-exchanged particles were found, suggesting their dissolution due to excess ligand. Oleic acid protected the particles against oxidation better than the tested thiols at large excess (ligand-copper ratio 20:1).     

石墨氧化过程的XRD/XPS研究

石墨用强氧化剂如硝酸、高氯酸、氯酸钾或高锰酸钾等处理后,在石墨层间形成一种没有化学计量的层间化合物,通常叫做氧化石墨,又称石墨酸犤1犦。氧化石墨的研究历史可追溯到1855年犤2犦,期间,有关氧化石墨的制备及表征的报导获得了广泛的重视。就目前的研究现状而言,普遍认为化学法制备的氧化石墨中存在羟基、环氧官能团和双键结构犤3犦,这一结果已经得到广泛的证实,如FTIR犤4犦结果表明氧化石墨中含有C-OH、-OH、C=O等基团,13CNMR犤5犦也检测到与醚或羟基相联的碳原子,并发现sp2杂化的碳原子,元素分析的结果表明犤6犦,氧化石墨中的C/…     

聚乙烯/石墨层间化合物热降解过程的TG-FTIR研究

将含磷化合物插层石墨层间化合物(GIC)用于聚乙烯(PE)的阻燃,采用氧指数(LOI)方法评价了PE/GIC的阻燃性能,并采用热分析-红外光谱联用技术(TG-FTIR)研究了PE/GIC的热降解过程,探讨了GIC的阻燃机理。研究表明,不同含磷化合物插层GIC阻燃聚乙烯的氧指数有显著差别,其中以多聚磷酸铵-GIC的阻燃效果较好,氧指数较高。TG-FTIR研究结果表明,GIC并未显著影响PE的热降解方式,但由于GIC体积膨胀所发生的氧化还原反应导致部分PE热降解提前并发生热氧化降解,促进了后期成炭的石墨化过程。     

Effects of aromatic thiols on thiol-disulfide interchange reactions that occur during protein folding

The folding of disulfide containing proteins from denatured protein to native protein involves numerous thiol-disulfide interchange reactions. Many of these reactions include a redox buffer, which is a mixture of a thiol (RSH) and the corresponding disulfide (RSSR). The relationship between the structure of RSH and its efficacy in folding proteins in vitro has been investigated only to a limited extent. Reported herein are the effects of aliphatic and especially aromatic thiols on reactions that occur during protein folding. Aromatic thiols may be particularly efficacious as their thiol pK(a) values and reactivities match those of the in vivo catalyst, protein disulfide isomerase (PDI). This investigation correlates the thiol pK(a) values of aromatic thiols with their reactivities toward small molecule disulfides and the protein insulin. The thiol pK(a) values of nine para-substituted aromatic thiols were measured; a Hammett plot constructed using sigma(p-) values yielded rho = -1.6 +/- 0.1. The reactivities of aromatic and aliphatic thiols with 2-pyridyldithioethanol (2-PDE), a small molecule disulfide, were determined. A plot of reactivity versus pK(a) of the aromatic thiols had a slope (beta) of 0.9. The ability of these thiols to reduce (unfold) the protein insulin correlates strongly with their ability to reduce 2-PDE. Since the reduction of protein disulfides occurs during protein folding to remove mismatched disulfides, aromatic thiols with high pK(a) values are expected to increase the rate not only of protein unfolding but protein folding as well.     

聚乙酰苯胺修饰碳纳米管载铂催化剂对甲醇电催化氧化

以原位化学聚合的聚乙酰苯胺/多壁碳纳米管(PAANI-MWCNTs)复合纳米材料作为载体,采用硼氢化钠还原法将Pt纳米粒子担载到PAANI-MWCNTs复合纳米材料表面,制备了Pt/PAANI-MWCNTs复合纳米催化剂.样品的结构和形貌用紫外-可见(UV-Vis)光谱、拉曼光谱、扫描电镜(SEM)、透射电镜(TEM)和X射线衍射(XRD)进行了表征.结果表明,聚乙酰苯胺与碳纳米管之间存在较强的π-π相互作用,使其能牢固地吸附于多壁碳纳米管表面,对碳纳米管的结构完整性和导电性有一定的改善作用.同时,金属Pt纳米颗粒较为均匀地分散在PAANI-MWCNTs表面,粒径分布范围较窄.采用循环伏安法和计时电流法在酸性溶液中研究了Pt/PAANI-MWCNTs催化剂对甲醇的电催化氧化活性,结果表明Pt/PAANI-MWCNTs复合纳米催化剂比用混酸处理的碳纳米管载铂催化剂对甲醇呈现出更高的电催化氧化活性和更好的抗中毒能力及稳定性.     

Application of thermal analysis to carbon black-elastomer systems

In this study a relationship between the surface and textural properties of carbon blacks and the gasification process induced thermally in air is noted. A temperature jump method was used to follow the gasification in air and to establish the relevant Arrhenius parameters. This can be associated with the activity of ‘basal’ plane carbon atoms as well as ‘edge’ carbon atoms at the surface. This is based on a model of carbon black structure consisting of the irregular packing of small graphite carbon structures. The carbon black surface was measured using a single measurement of adsorption based essentially on the BET volumetric method. The carbon black surface had a rate of oxidation per unit are which clearly indicated that the lower area carbon blacks had a predominately active area of ‘edge’ atoms at the surface while the surface of the higher area carbon blacks had a predominate amount of ‘basal’ plane graphite carbon atoms.     

Determination of sulphur functions with N-iodosuccinimide

Titrimetric determination of thioureas, thiols, xanthates and dithiocarbamates with N-iodosuccinimide (NIS) is described. The method for xanthate can be applied to carbon disulphide (converted into xanthate with potassium ethoxide). Acidic and non-aqueous solutions of the oxidizing agent are stable. The procedures are rapid and accurate to 0.1% with a precision of 0.2%. Hydrogen sulphide and thiocarbonyl compounds interfere. The behaviour of N-bromosuccinimide and NIS with thiols in aqueous medium is compared. It is shown that iodine is the oxidizing species in both cases. The limitations of iodine as a reagent for thiol determination are discussed. Cysteine, which cannot be determined with iodine, can be determined with NIS. The role of methanol in non-aqueous determination of thiols is discussed. Methanol accelerates the oxidation, which is otherwise slow in acetonitrile medium.     

Reaction Mechanism of Selenate(IV) Ions with Several Thiols in Aqueous Media

In several enzymatic systems, selenium (an essential element commonly incorporated as sodium selenite to the human diet) is bonded through a mercapto group of a cysteine residue. The reaction of Se^IV (as selenite) with different thiols in aqueous media was studied to increase the information about the mechanism of the enzyme reaction. The influence of the reagents' concentration on the reaction rate and temporal spectral changes was analyzed. A complex with a UV maximum between 270 and 290 nm was formed, which quickly decayed when the thiol concentration was increased. The proposed reaction mechanism includes a fast Se^IV–thiol association step followed by two parallel steps (one is first‐order in the complex and the other one is globally second‐order). Kinetics and equilibrium constants were obtained, and the rate dependence of the thiol oxidation on the Se^IV concentration was modelled for all thiols tested. Very good agreement between the experimental and calculated curves was observed.     

A study of the polymerization of styrene initiated by K-THF-GIC system

In this paper, the polymerization of styrene initiated by potassium (K)-tetrahydrofuran (THF)-graphite intercalation compound (GIC) (K-THF-GIC) was studied. The mechanism of the polymerization was determined to be anionic polymerization according to its characteristics. The effect of the concentration of the initiator and monomer was studied. It was found that the polymerization mainly occurred on the surface and edge of the intercalated graphite. It was also shown that the polarity of solvent has little effect on the polymerization yield in this system.     

Edge plane sites on highly ordered pyrolytic graphite as templates for making palladium nanowires via electrochemical decoration

An approach for the fabrication of metal nanowires is presented. Palladium wires with diameters less than 50 nm were produced by electrochemical decoration of step edge sites on the surface of highly ordered pyrolytic graphite via the following three steps. First an electrochemical activation step was used to oxidize the edge plane sites on highly ordered pyrolytic graphite surfaces in 0.5 M Na(2)SO(4). Second, a potential cycling step in a 1 mM PdCl(2) solution in 0.1 M H(2)SO(4) was used to form palladium oxide (s) and/or complexes of Pd on the step edges. Third, Pd nanowires were formed by electroreduction after transfer of the graphite to 0.1 M H(2)SO(4). The resulting wires showed a high degree of uniformity. A merit of this approach is that it allowed metal nanowires to be fabricated without the simultaneous formation of nanoparticles on the basal plane terraces, in contrast to other studies of this type. The mesoscopic palladium wires are shown to be useful for the electrochemical sensing of hydrazine.     

Modification of Ag nanoparticles with mixed thiols for improved SERS detection of poorly adsorbing target molecules: detection of MDMA

Here we report an example of a mixed thiol monolayer on the surface of Ag nanoparticles which promotes adsorption and quantitative SERS detection of 3,4-methylenedioxymethamphetamine (MDMA, "Ecstasy"); the thiols in the mixed monolayers act synergistically since MDMA does not adsorb onto colloids modified with either of the thiols separately.     

Biomimetic studies on selenoenzymes: modeling the role of proximal histidines in thioredoxin reductases

The roles of built-in thiol cofactors and the basic histidine (His) residues in the active site of mammalian thioredoxin reductases (TrxRs) are described with the help of experimental and density functional theory calculations on small-molecule model compounds. The reduction of selenenyl sulfides by thiols in selenoenzymes such as glutathione peroxidase (GPx) and TrxR is crucial for the regeneration of the active site. Experimental as well as theoretical studies were carried out with model selenenyl sulfides to probe their reactivity toward incoming thiols. We have shown that the nucleophilic attack of thiols takes place at the selenium center in the selenenyl sulfides. These thiol exchange reactions would hamper the regeneration of the active species selenol. Therefore, the basic His residues are expected to play crucial roles in the selenenyl sulfide state of TrxR. Our model study with internal amino groups in the selenenyl sulfide state reveals that the basic His residues may play important roles by deprotonating the thiol moiety in the selenenic acid state and by interacting with the sulfur atom in the selenenyl sulfide state to facilitate the nucleophilic attack of thiol at sulfur rather than at selenium, thereby generating the catalytically active species selenol. This model study also suggests that the enzyme may use the internal cysteines as cofactors to overcome the thiol exchange reactions.