A novel method for quantification of ethanol and methanol in distilled alcoholic beverages using Raman spectroscopy

In this study, direct quantification of ethanol and methanol in distilled alcoholic beverages using Raman spectroscopy was performed. Raman spectra of varying ethanol–methanol mixtures were obtained, baseline corrections were made, and the data were normalized using Raman scattering intensity of an internal standard (acetonitrile, 921 cm^–1). Then, calibration graphs were produced for ethanol and methanol concentrations in the ranges of 0–7 M and 0–10 M, respectively. Accurate R² values of the calibration graphs proved the notable linear correlations (0.998 for ethanol and 0.998 for methanol). The method was validated based on linearity, sensitivity, intraday and interday repeatability, and recovery tests. The limit of detection and limit of quantification values of the validated method were determined for ethanol concentration as 1.2 and 3.7 mM, and for methanol concentration as 3.4 and 10.3 mM, respectively. The ability of the developed method to detect ethanol and methanol concentrations in real samples was also investigated. The results of the developed method were compared with the experimental results from traditional method and high correlation value (R² = 0.926) was obtained. Besides being sensitive and cheap, the developed method is rapid with the analysis time of less than 30 s. Furthermore, it eliminates labor‐consuming operations, chromatographic separation, and measurement error due to the high number of experiment steps in the standard method. Copyright © 2012 John Wiley & Sons, Ltd.     

(137)Cs and (40)K activity concentration measurements and elemental analysis in lichen samples collected from the Giresun province of northeastern Turkey

About 21 years after the Chernobyl accident, (137)Cs and (40)K activity concentration measurements using gamma-ray spectroscopy and elemental analysis using energy dispersive X-ray spectroscopy were performed in five different lichen species collected from the Giresun province of northeastern Turkey. Being a symbiosis of algae and fungi, lichens are mostly used for environmental measurements since the fungal partner is responsible for the uptake of necessary nutrients or harmful substances, such as heavy metals of radionuclides. The gamma activity results showed that (137)Cs, an artificial radionuclide released from the Chernobyl power plant accident, is still eminent in the environment of the province. The mean activity concentrations of (137)Cs and (40)K ranged from 24 to 254 with the mean value of 102 Bq kg(-1) and from 345 to 2103 with the mean value of 1143 Bq kg(-1) in dry weight. The results of the elemental analyses showed potassium, calcium, titanium, iron, tin, and barium in different concentrations.     

Characterization of self-assembled films of NiGa layered double hydroxide nanosheets and their electrochemical properties

In this study, we have demonstrated the synthesis and delamination of a rarely studied NiGa layered double hydroxide (LDH) system. Hydrothermal treatment under agitation conditions at 200 °C for 4 h resulted in the formation of highly crystalline NiGa LDHs in a shorter time than those synthesized without agitation. The LDH was delaminated into the individual nanosheets in formamide. The most significant finding in this study is the electrochemical behavior of interlayer ferricyanide anions intercalated with the layer-by-layer (LBL) assembly method. The morphology of LBL film with one layer is also monitored with atomic force microscopy. The cyclic voltammogram is similar to potassium metal hexacyanoferrate systems with its unique two-peak wave. Raman spectrum of the film revealed that the metal center of the interlayer cyano complex is in interaction with the Ni²⁺ of the host layer. It was concluded that the two-peak cyclic voltammogram of the film is a result of two different forms of the hexacyanoferrate in the interlayer.     

Performance of different crystal structures of PbO2 on electrochemical degradation of phenol in aqueous solution

Phenol degradation was carried out in acidic aqueous solution on different crystal structures of PbO₂ surfaces at room temperature. Phenol, benzoquinone and maleic acid concentrations were monitored during the electrolysis process. It was determined that β surfaces have higher performance than surfaces on phenol degradation. Then, the effect of crystallinities of pure β-PbO₂ surfaces was investigated and found that higher crystallinity increased the efficiency of the phenol degradation process.     

Association of the XRCC1 gene polymorphisms with cancer risk in Turkish breast cancer patients

The X-ray repair cross-complementing group 1 (XRCC1) gene is believed to play an important role in base excision repair and displays genetic polymorphisms. Data on the role of XRCC1 polymorphisms in cancer susceptibility is inconsistent. In the present study, we investigated the effect of two XRCC1 polymorphisms, Arg194Trp and Arg399Gln, on breast cancer risk in a case- control study involving Turkish breast cancer patients and healthy women. Both alleles exhibited a similar distribution among cases and controls leading to lack of any significant association between the XRCC1 polymorphisms and breast cancer risk, either in homozygotes and heterozygotes or combined. The allele frequency of the codon 194 variant was very low in cases and healthy individuals (5.3 and 3.9%, respectively) compared to that of the variant 399Gln allele (39.7 and 37.4%). Our results do not support evidence for a role of the XRCC1 polymorphism in developing breast cancer.     

EPR study of gamma-irradiated 2-Bromo-4′-methoxyacetophenone single crystals

The gamma-irradiated single crystals of 2-Bromo-4′-methoxyaceto-phenone (2B4MA) were investigated using electron paramagnetic resonance (EPR) technique. Density-functional theory calculations were employed to investigate and identify the radicals that have been assumed to be formed upon irradiation of 2B4MA single crystals. The EPR spectra of 2B4MA were recorded at different orientations in the magnetic field at room temperature. Taking into account the chemical structure and experimental spectra of irradiated single crystal of 2B4MA, it was assumed that at least two different radicals were produced in the sample. Following this assumption, six possible radicals were modeled and EPR parameters were calculated by using the DFT, B3LYP/6-311+G(d), for the modeled radicals individually. The calculated hyperfine coupling constants and g-tensors were used as initial values for simulation studies. The three crystallographic axes on the simulated spectra were well matched with experimental spectra for the two modeled radicals. Thus, we identified the R1 type radical and R4 type radical as paramagnetic species produced in gamma-irradiated 2B4MA.     

A new approach for the synthesis of layered niobium sulfide and restacking route of NbS2 nanosheet

We have developed a new process for the synthesis of a layered niobium sulfide that involves heating K₄Nb₆O₁₇·3H₂O with a H₂S/N₂ gas mixture. It was confirmed that heating the starting layered oxide at 750 °C for 10 h under the gas flow yielded a highly crystalline, single-phase K_0.34(H₂O)_0.7NbS₂. The layered sulfide slabs had a large plate-like shape. Potassium ions in the interlayer of K_0.34(H₂O)_0.7NbS₂ could be exchanged with protons by stirring in 2 M H₂SO₄. It was found that the proton in the proton-exchanged form can be easily exchanged with other cations. The proton-exchanged form was exfoliated into NbS₂ nanosheets by ultrasonication in water. According to the atomic force microscopy (AFM) images, NbS₂ nanosheets had a thickness of around 4 Å, which roughly corresponded to the thickness of a single NbS₂ host layer. NbS₂ nanosheets could be restacked with the intercalation of Eu³⁺ or tetrabutylammonium ions by an electrostatic self-assembly deposition (ESD) technique.     

Well-posedness of the Dirichlet problem for the non-linear diffusion equation in non-smooth domains

We investigate the Dirichlet problem for the parablic equation

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in a non-smooth domain . In a recent paper [U.G. Abdulla, J. Math. Anal. Appl., 260, 2 (2001), 384-403] existence and boundary regularity results were established. In this paper we present uniqueness and comparison theorems and results on the continuous dependence of the solution on the initial-boundary data. In particular, we prove -contraction estimation in general non-smooth domains.

     

Selective syntheses of vinylenedithiathiophenes (VDTTs) and dithieno[2,3-b;2′,3′-d]thiophenes (DTTs); building blocks for π-conjugated systems

Selective syntheses of 3,4-vinylenedithiathiophenes (VDTTs) and dithieno[2,3-b;2′,3′-d]thiophenes (DTTs), having Ph, 4-CH₃OC₆H₄, 4-BrC₆H₄, 4-NO₂C₆H₄ and 4-(CH₃)₂NC₆H₄ groups, were achieved through the reaction of 1,8-diketone with phosphorus decasulfide (P₄S₁₀). The reaction could be shifted between VDTT and DTT by adding base (sodium bicarbonate) or acid (para-toluenesulfonic acid), respectively, to the reaction mixture. While the VDTTs were obtained in moderate yields, an important achievement has been made with the syntheses of the DTTs, obtaining them in higher yields compared with the previous report. Polymers of the VDTTs, which are the analogues of ethylenedioxythiophene, EDOT, were prepared using FeCl₃. Unfortunately, all attempts for their electropolymerization failed. Spin density calculations revealed that none of the VDTTs had a significant positive spin density at the ‘α’ carbon atoms of the thiophene ring. Considering their solubility and functional groups, which could be further derivatized, they are useful building blocks for the preparation of new organic materials.