Chemometric approach to the optimisation of LC-FL and GC-MS methods for the determination of nitrite and nitrate in some biological,food and environmental samples

Gas chromatography–mass spectrometry (GC-MS) method and a liquid chromatography–fluorescence (LC-FL) detection method using experimental design and optimisation approach were improved for the quantitative determination of nitrite and nitrate in biological, food and environmental samples. The obtained recoveries of nitrite and nitrate ions from samples based on both GC-MS and LC-FL results ranged from 98.5% to 98.9% for nitrite and 97.9% to 98.4% for nitrate. The precision of these methods, as indicated by the relative standard deviations (RSDs), was within the range from 2.4% to 3.6% for nitrite and 2.5% to 3.8% for nitrate, respectively. The limits of detection of nitrite and nitrate ions from samples based on GC-MS and LC-FL results ranged from 0.01 to 0.14 ng L^?1 for nitrite and 0.02 to 0.71 ng L^?1 for nitrate, respectively. The optimised isolation procedure by central composite design was successfully applied to real samples. The results revealed that the proposed procedure combined with GC-MS and LC-FL techniques is more sensitive, reliable and selective compared to the other methods available for the precise determination of trace levels of nitrite and nitrate in biological, food and environmental samples.     

Poly(allylamine hydrochloride) Functionalized Multiwalled Carbon Nanotube Modified Carbon Paste Electrode as Acetylcholinesterase Biosensor Transducer

In this work, a sensitive, practical and reliable acetylthiocholine (ATCh) biosensor based on poly(allylamine hydrochloride) functionalized multiwalled carbon nanotube (PAH/MWCNT) was fabricated and used for pesticide detection. As far as we know, this is the first work that constitutes the usage of PAH and MWCNT for ATCh biosensor. The developed system was characterized by using scanning electron microscopy, electrochemical impedance spectroscopy and cyclic voltammetry. The influence of parameters such as enzyme amount and pH were examined and a linearity between 5×10^?5 M?2.0×10^?3 M for ATCh was obtained. The proposed biosensor was applied for a model pesticide, monocrotophos, detection. The analytical curve showed an excellent linearity in the monocrotophos concentration range of 1–25 pg/mL with an incubation time of 5 min. Limit of detection and limit of quantification values were calculated as 0.88 and 2.9 pg/mL, respectively. The system was also applied for detection of monocrotophos in grape, tomatoe, tap and mineralized water samples and promising recovery values were obtained.     

Determination of low level nitrite and nitrate in biological, food and environmental samples by gas chromatography-mass spectrometry and liquid chromatography with fluorescence detection

Gas chromatography-mass spectrometry (GC-MS) and liquid chromatography with fluorescence detection (LC-FL) methods have been proposed for the determination of low level nitrite and nitrate in biological, food and environmental samples. The methods include derivatization of aqueous nitrite with 2,3-diaminonaphthalene (DAN), enzymatic reduction of nitrate to nitrite, extraction with toluene and chromatographic analyses of highly fluorescent 2,3-naphthotriazole (NAT) derivative of nitrite by using GC-MS in selected-ion-monitoring (SIM) mode and LC-FL. Nitrite and nitrate ions in solid samples were extracted with 0.5 M aqueous NaOH by sonication. The recoveries of nitrite and nitrate ions based on GC-MS and LC-FL results were 98.40% and 98.10% and the precision of these methods, as indicated by the relative standard deviations (RSDs) were 1.00% for nitrite and 1.20% for nitrate, respectively. The limits of detection of the GC-MS in SIM mode and LC-FL methods based on S/N = 3 were 0.02 and 0.29 pg/ml for nitrite and 0.03 and 0.30 pg/ml for nitrate, respectively.     

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     

Exergoeconomic analysis of a thermochemical copper–chlorine cycle for hydrogen production using specific exergy cost (SPECO) method

The manner is investigated in which exergy-related parameters can be used to minimize the cost of a copper–chlorine (Cu–Cl) thermochemical cycle for hydrogen production. The iterative optimization technique presented requires a minimum of available data and provides effective assistance in optimizing thermal systems, particularly in dealing with complex systems and/or cases where conventional optimization techniques cannot be applied. The principles of thermoeconomics, as embodied in the specific exergy cost (SPECO) method, are used here to determine changes in the design parameters of the cycle that improve the cost effectiveness of the overall system. The methodology provides a reasonable approach for improving the cost effectiveness of the Cu–Cl cycle, despite the fact that it is still in development. It is found that the cost rate of exergy destruction varies between $1 and $15 per kilogram of hydrogen and the exergoeconomic factor between 0.5 and 0.02 as the cost of hydrogen rises from $20 to $140 per GJ of hydrogen energy. The hydrogen cost is inversely related to the exergoeconomic factor, plant capacity and exergy efficiency. The results are expected to assist ongoing efforts to increase the economic viability and to reduce product costs of potential commercial versions of this process. The impact of the results are anticipated to be significant since thermochemical water splitting with a copper–chlorine cycle is a promising process that could be linked with nuclear reactors to produce hydrogen with no greenhouse gases emissions, and thereby help mitigate numerous energy and environment concerns.     

Characterization,slab-pair modeling and phase analysis of circular fishnet metamaterials

Planar metamaterials, which have incident to normal plane excitation unlike SRR-type structures and that are easily fabricated in multilayer form, have received great interest in recent years. In this paper, one-dimensional and polarization independent circular fishnet metamaterials and their equivalent discontinuous slab-pair modeling for tuning resonance frequencies are introduced. After the numerical and experimental demonstration of the inclusions, the standard retrieval characterization methods and the correspondent/related backward-wave propagation observation are realized in order to check the physical explanation mentioned in the paper. In addition, a detailed phase analysis is performed in order to demonstrate the application of the suggested structure as a phase compensator.     

Conjugation of linoleic acid over a hydrogen pre-activated heterogeneous catalyst

Development of a new heterogeneous catalytic pathway for isomerization of linoleic acid to conjugated linoleic acids at mild reaction conditions over Ni/H-MCM-41 in a soluted system.