A Comparison of Four Different Electrode Matrices on the Performance of Amperometric Hydrogen Peroxide (Bio)Sensors

A comparison of the analytical performances of four different (bio)sensor designs in H₂O₂ determination is discussed. The (bio)sensor designs developed were based on the use of (i) multiwalled carbon nanotubes (MWCNT), zinc oxide nanoparticles (ZnONP), prussian blue (PB); (ii) MWCNT, ZnONP, PB and ionic liquid (IL); (iii) MWCNT, ZnONP and horseradish peroxidase (HRP) and (iv) MWCNT, ZnONP, HRP and IL modified glassy carbon electrode (GCE). A performance comparison of (bio)sensors showed that the one based on HRP/IL-MWCNT-ZnONP/GCE showed the best analytical characteristics with a linear dynamic range of 9.99×10⁻⁸–7.55×10⁻⁴ M, detection limit of 1.37×10⁻⁸ M and sensitivity of 17.00 μA mM⁻¹.     

Mechanism of antioxidant capacity assays and the CUPRAC (cupric ion reducing antioxidant capacity) assay

We report on the application of a simple and versatile antioxidant capacity assay for dietary polyphenols, vitamin C and vitamin E utilizing the copper(II)-neocuproine (Cu(II)-Nc) reagent as the chromogenic oxidant, which we term the CUPRAC (cupric reducing antioxidant capacity) method. It involves mixing the antioxidant solution (directly or after acid hydrolysis) with solutions of CuCl₂, neocuproine, and ammonium acetate at pH 7, and measuring the absorbance at 450 nm after 30 min. Slowly reacting antioxidants required an incubation at 50 °C for 20 min for color development. The flavonoid glycosides were hydrolyzed to their corresponding aglycones by refluxing in 1.2 M HCl-containing 50% MeOH for fully exhibiting their antioxidant potencies. Certain compounds also needed incubation after acid hydrolysis for color development. The CUPRAC absorbances of mixture constituents were additive, indicating lack of chemical deviations from Beer’s law. The CUPRAC antioxidant capacities of a wide range of polyphenolics are reported in this work and compared to those found by ABTS/persulfate and Folin assays. The trolox-equivalent capacities of the antioxidants were linearly correlated (r = 0.8) to those found by ABTS but not to those of Folin. The highest antioxidant capacities in the CUPRAC method were observed for epicatechin gallate, epigallocatechin gallate, quercetin, fisetin, epigallocatechin, catechin, caffeic acid, epicatechin, gallic acid, rutin, and chlorogenic acid in this order, in accordance with theoretical expectations. The experiences of other CUPRAC users also are summarized. Correspondence: Reşat Apak, Department of Chemistry, Faculty of Engineering, Istanbul University, Avcilar, TR-34320 Istanbul, Turkey     

Cluster PID Control of Viaduct Road Vibration

Cluster control to suppress the structural vibrations of viaduct roads caused by the movement of vehicles is studied. A viaduct road is modeled using the finite-element method. The structural modes of a road element are obtained. The cluster-control method is used, which is based on a finite-element model of a flat road. The modes of a flat viaduct road are classified into four groups. Each group is controlled by a PID controller. It is verified that the cluster actuation and the sensing based on PID control suppress the structural modes under consideration, and no spillover effects are observed __________ Published in Prikladnaya Mekhanika, Vol. 41, No. 10, pp. 139–144, October 2005.     

Comparative evaluation of various total antioxidant capacity assays applied to phenolic compounds with the CUPRAC assay

It would be desirable to establish and standardize methods that can measure the total antioxidant capacity level directly from vegetable extracts containing phenolics. Antioxidant capacity assays may be broadly classified as electron transfer (ET)- and hydrogen atom transfer (HAT)-based assays. The majority of HAT assays are kinetics-based, and involve a competitive reaction scheme in which antioxidant and substrate compete for peroxyl radicals thermally generated through the decomposition of azo compounds. ET-based assays measure the capacity of an antioxidant in the reduction of an oxidant, which changes colour when reduced. ET assays include the ABTS/TEAC, CUPRAC, DPPH, Folin-Ciocalteu and FRAP methods, each using different chromogenic redox reagents with different standard potentials. This review intends to offer a critical evaluation of existing antioxidant assays applied to phenolics, and reports the development by our research group of a simple and low-cost antioxidant capacity assay for dietary polyphenols, vitamins C and E, and human serum antioxidants, utilizing the copper(II)-neocuproine reagent as the chromogenic oxidizing agent, which we haved named the CUPRAC (cupric ion reducing antioxidant capacity) method. This method offers distinct advantages over other ET-based assays, namely the selection of working pH at physiological pH (as opposed to the Folin and FRAP methods, which work at alkaline and acidic pHs, respectively), applicability to both hydrophilic and lipophilic antioxidants (unlike Folin and DPPH), completion of the redox reactions for most common flavonoids (unlike FRAP), selective oxidation of antioxidant compounds without affecting sugars and citric acid commonly contained in foodstuffs and the capability to assay -SH bearing antioxidants (unlike FRAP). Other similar ET-based antioxidant assays that we have developed or modified for phenolics are the Fe(III)- and Ce(IV)-reducing capacity methods.     

Self-tuning fuzzy logic control of a non-linear structural system with ATMD against earthquake

Self-tuning fuzzy logic controllers (STFLC) for the active control of Marmara Kocaeli earthquake excited building structures are studied in this paper. Vibration control using intelligent controllers, such as fuzzy logic has attracted the attention of structural control engineers during the last few years, because fuzzy logic can handle nonlinearities, uncertainties, and heuristic knowledge effectively and easily. The improved seismic control performance can be achieved by converting a simply designed static gain into a real time variable dynamic gain through a self-tuning mechanism. Self-tuning fuzzy logic controller is designed to reduce the story-drift of each floor. The simulated system has a nine-degree-of-freedom, which is modeled using nonlinear behavior of the base-structure interaction. Modeled system was simulated against the ground motion of the Marmara Kocaeli earthquake (M _w=7.4) in Turkey on 17 August, 1999. At the end of the study, the time history of the story displacements, accelerations, ATMD displacements, control voltage, and frequency responses of the both uncontrolled and controlled cases are presented. The robustness of the controller has been checked through the uncertainty in stiffness of the structure. Performance of the designed STFLC has been demonstrated for the different disturbance using ground motion of the Kobe earthquake. Simulations of an earthquake excited nine story structure are performed to prove the validity of proposed control strategy.     

Determination of the surface properties of untreated and chemically treated kaolinites by inverse gas chromatography

Inverse gas chromatography is used to study the surface properties of the untreated and chemically treated kaolinite samples. Changes in the enthalpy of adsorption for a variety of probes and in the surface energy of clays are measured and the effect of modification of the natural clay after chemical treatment with Na₂CO₃ is determined. The surface energy of the natural clay increased by the modification due to an increase in the surface area. It can be concluded that the dispersive component of surface free energy, γ _s ^d , decreases with temperature in the 200–275°C temperature range for both samples. Temperature coefficients of γ _s ^d for untreated and modified kaolinites are −0.1185 and −0.3966 mJ/(m² °C) with the correlation coefficients (R ²) of 0.8479 and 0.965, respectively. From the retention data for polar probes at infinite dilution, information on the accessibility of surface sites to the probes and on the acid-base character of the surface is obtained. The specific free energy of adsorption, the specific enthalpy of adsorption (ΔH ^sp), and the specific entropy of adsorption of polar probes on initial and modified kaolinites are determined. The ΔH ^sp values correlated with the donor numbers and modified acceptor numbers of the probes to quantify the acidity (K _A) and basicity (K _D) parameters of clay surfaces. The values of K _A and K _D for initial and modified kaolinites are determined to be 0.1202 and 0.2803; 0.0130 and 0.0408 with the correlation coefficients of −0.9805 and −0.9782, respectively. The unmodified clay sample indicated a more acidic character, while the modified clay sample conferred a largely basic character. Consequently, the predominant surface basicity of the modified kaolinite agrees with expectation, bearing in mind the treatment with Na₂CO₃, taking into consideration that such a modification contributes to a decrease in the hydrophilicity of the surface and also results in the surface showing only weak Lewis acidity. The text was submitted by the authors in English.     

Non-catalytic and catalytic hydrothermal liquefaction of biomass

Both the non-catalytic and catalytic hydrothermal liquefaction of biomass have been the objective of extensive research in recent years. An impressive amount of scientific studies related to non-catalytic and catalytic hydrothermal liquefaction of biomass has been reported in the literature. The experimental conditions such as temperature, residence time, pressure, the types of biomass, and the types of catalysts have an important effect on the product distributions. The details about the experimental conditions as well as the compositions of bio-oils are important for a better understanding of the biomass liquefaction pathways in hydrothermal media. This review is intended to summarize and discuss a survey of relevant research.     

Reactions of (1E)‐Buta‐1,3‐dien‐1‐yl Acetate with Diazocarbonyl Compounds

Carbene transfer to appropriate substrates is a highly versatile tool for the construction of carbon frameworks with increased functional and structural complexity. In this study, some novel cyclopropane derivatives were synthesized via carbenoid reactions and their further reactivities were investigated. (1E)‐Buta‐1,3‐dien‐1‐yl acetate was reacted with four different diazocarbonyl compounds, ethyl diazoacetate, dimethyl diazomalonate, 1‐diazo‐1‐phenylpropan‐2‐one, and methyl (3E)‐2‐diazo‐4‐phenylbut‐3‐enoate, in the presence of two catalysts. All synthesized substituted cyclopropanes were obtained chemoselectively with respect to less‐hindered C?C bonds. Under the applied conditions, while cyclopropanes 7a and 7d underwent further reactions, cyclopropanes 7b and 7c were stable enough. Cyclopropanes 7a and an additional equivalent of ethyl diazoacetate yielded polyfunctionalized cyclohexenes. Cyclopropanes from methyl (3E)‐2‐diazo‐4‐phenylbut‐3‐enoate yielded polyfunctionalyzed cycloheptadiene isomers by Cope rearrangement.     

Comparative evaluation of antioxidant capacities of thiol-based antioxidants measured by different in vitro methods

Thiol-type compounds are an important class of strong antioxidants and main determinants of total antioxidant capacity (TAC) of cellular homogenates. The TAC of thiol mixtures and the corresponding TEAC (trolox equivalent antioxidant capacity) values of individual thiols were determined by the CUPRAC (CUPric Reducing Antioxidant Capacity) method, and the results were compared with those found by reference assays for method validation. Synthetic mixtures of thiols were prepared, and the expected and found TAC values (in mM trolox (TR) equivalents) of these mixtures showed a good agreement. The technique of standard additions was performed for thiol mixtures and human serum, and the absorbance results confirmed that apparent chemical deviations from Beer's law were absent in the system. The CUPRAC results were compared with those of reference methods, namely 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS)/persulphate and Ferric Reducing Antioxidant Power (FRAP). As being a most important thiol (-SH) peptide at in vivo conditions, glutathione (GSH) showed a TEAC value of 0.57 in the CUPRAC method, as opposed to the corresponding value (1.51) in the ABTS/persulphate method. The ABTS/persulphate result was not in accordance with the reversible 1-e oxidation of GSH to the corresponding disulfide that is expected to occur under physiological conditions. FRAP did not give consistent results, and even at relatively high concentrations of GSH, the TEAC_FRAP value was only 0.07. The thiol-type antioxidant-bearing pharmaceuticals of Brunac eye drop, Trom and Mentopin effervescent tablets containing N-acetyl-l-cysteine (NAC) were assayed with HPLC for comparison, and the obtained results for NAC were in accordance with those found with CUPRAC.