International Journal of Analytical Chemistry The latest articles from Hindawi Publishing Corporation © 2017 , Hindawi Publishing Corporation . All rights reserved. Trace Detection of Metalloporphyrin-Based Coordination Polymer Particles via Modified Surface-Enhanced Raman Scattering Assisted by Surface Metallization Mon, 26 Dec 2016 13:43:56 +0000 This study proposed a facile method to detect metalloporphyrin-based coordination polymer particles (Z-CPPs) in aqueous solution by modified surface-enhanced Raman scattering (SERS). The SERS-active particles are photodeposited on the surface of Z-CPPs, offering an enhanced Raman signal for the trace detection of Z-CPPs. Yu Sun and Alessio Caravella Copyright © 2016 Yu Sun and Alessio Caravella. All rights reserved. Simultaneous Determination of Bergapten, Imperatorin, Notopterol, and Isoimperatorin in Rat Plasma by High Performance Liquid Chromatography with Fluorescence Detection and Its Application to Pharmacokinetic and Excretion Study after Oral Administration of Notopterygium incisum Extract Mon, 26 Dec 2016 12:02:58 +0000 A specific, sensitive, and reliable high performance liquid chromatography with fluorescence detection (HPLC-FLD) was first optimized and then used in the simultaneous quantification of bergapten, imperatorin, notopterol, and isoimperatorin in rat plasma using osthole as the internal standard. Liquid-liquid extraction with ethyl acetate was employed in treating the rat plasma samples obtained. Separation was carried out with a Hedera™ ODS column (4.6 × 250 mm, 5 μm) by gradient elution at a temperature of 40°C. Excitation and emission of the fluorescence detector were set to 300 and 490 nm, respectively. The lower limits of quantification for bergapten, imperatorin, notopterol, and isoimperatorin in rat plasma were 4, 40, 4, and 2 ng mL−1, respectively. The intraday and interday precision and accuracy for the four coumarins were within acceptable criteria. The recovery of the method was satisfactory with a range of 80.3–114%. The validated method was successfully used for the simultaneous determination of the four coumarins in Notopterygium incisum extracts and also for the pharmacokinetic and excretion study of bergapten, imperatorin, notopterol, and isoimperatorin in rats. John Teye Azietaku, Xie-an Yu, Jin Li, Jia Hao, Jun Cao, Mingrui An, Zhijing Tan, and Yan-xu Chang Copyright © 2016 John Teye Azietaku et al. All rights reserved. Application of Long-Range Surface Plasmon Resonance for ABO Blood Typing Thu, 22 Dec 2016 07:38:56 +0000 In this study, we demonstrate a long-range surface plasmon resonance (LR-SPR) biosensor for the detection of whole cell by captured antigens A and B on the surface of red blood cells (RBCs) as a model. The LR-SPR sensor chip consists of high-refractive index glass, a Cytop film layer, and a thin gold (Au) film, which makes the evanescent field intensity and the penetration depth longer than conventional SPR. Therefore, the LR-SPR biosensor has improved capability for detecting large analytes, such as RBCs. The antibodies specific to blood group A and group B (Anti-A and Anti-B) are covalently immobilized on a grafting self-assembled monolayer (SAM)/Au surface on the biosensor. For blood typing, RBC samples can be detected by the LR-SPR biosensor through a change in the refractive index. We determined that the results of blood typing using the LR-SPR biosensor are consistent with the results obtained from the agglutination test. We obtained the lowest detection limits of 1.58 × 105 cells/ml for RBC-A and 3.83 × 105 cells/ml for RBC-B, indicating that the LR-SPR chip has a higher sensitivity than conventional SPR biosensors (3.3 × 108 cells/ml). The surface of the biosensor can be efficiently regenerated using 20 mM NaOH. In summary, as the LR-SPR technique is sensitive and has a simple experimental setup, it can easily be applied for ABO blood group typing. Wanida Tangkawsakul, Toemsak Srikhirin, Kazunari Shinbo, Keizo Kato, Futao Kaneko, and Akira Baba Copyright © 2016 Wanida Tangkawsakul et al. All rights reserved. Determination of Spatial Chromium Contamination of the Environment around Industrial Zones Thu, 01 Dec 2016 14:06:31 +0000 This study was conducted to determine the spatial levels of chromium contamination of water, agricultural soil, and vegetables in the leather tanning industrial areas using spectrophotometric methods. The results showed elevated accumulation of total Cr ranging from  mg/L to  mg/L,  mg/Kg to  mg/Kg, and  mg/Kg to  mg/Kg in water, agricultural soil, and vegetable samples, respectively. The highest levels of chromium (VI) found from the speciation study were  mg/Kg and  mg/L in soil and water samples, respectively, which decreased with distance from the tannery. Among the vegetables, the highest load of Cr(VI) was detected in onion root ( mg/Kg) and the lowest ( mg/Kg) in fruit of green pepper. The detected levels of Cr in all of the suggested samples were above the WHO permissible limits. The variations of the levels Cr(III) and Cr(VI) contamination of the environment with distance from the tannery were statistically significant (). Similarly, significant difference in the levels of Cr among the tested vegetables was recorded. The levels increased with decreasing distance from the effluent channel. Dereje Homa, Ermias Haile, and Alemayehu P. Washe Copyright © 2016 Dereje Homa et al. All rights reserved. Corrigendum to “Extraction of HCV-RNA from Plasma Samples: Development towards Semiautomation” Tue, 29 Nov 2016 06:34:42 +0000 Imran Amin, Tania Jabbar, Fawad Ali, and Muhammad Saeed Akhtar Copyright © 2016 Imran Amin et al. All rights reserved. Cauliflower Leave, an Agricultural Waste Biomass Adsorbent, and Its Application for the Removal of MB Dye from Aqueous Solution: Equilibrium, Kinetics, and Thermodynamic Studies Tue, 15 Nov 2016 08:44:29 +0000 Cauliflower leaf powder (CLP), a biosorbent prepared from seasonal agricultural crop waste material, has been employed as a prospective adsorbent for the removal of a basic dye, methylene blue (MB) from aqueous solution by the batch adsorption method under varying conditions, namely, initial dye concentration, adsorbent dose, solution pH, and temperature. Characterization of the material by FTIR and SEM indicates the presence of functional groups and rough coarse surface suitable for the adsorption of methylene blue over it. Efforts were made to fit the isotherm data using Langmuir, Freundlich, and Temkin equation. The experimental data were best described by Freundlich isotherm model, with an adsorption capacity of 149.22 mg/g at room temperature. To evaluate the rate of methylene blue adsorption onto CLP, pseudo-first-order, pseudo-second-order, and intraparticle diffusion models were employed. The experimental data were best described by the pseudo-second-order kinetic model. Evaluation of thermodynamic parameters such as changes in enthalpy, entropy, and Gibbs’ free energy showed the feasible, spontaneous, and exothermic nature of the adsorption process. On the basis of experimental results obtained, it may be concluded that the CLP prepared from agricultural waste has considerable potential as low-cost adsorbent in wastewater treatment for the removal of basic dye, MB. Seraj Anwar Ansari, Fauzia Khan, and Anees Ahmad Copyright © 2016 Seraj Anwar Ansari et al. All rights reserved. Innovative Monitoring of Atmospheric Gaseous Hydrogen Fluoride Thu, 13 Oct 2016 08:07:34 +0000 Hydrogen fluoride (HF) is a basic raw material for a wide variety of industrial products, with a worldwide production capacity of more than three million metric tonnes. A novel method for determining particulate fluoride and gaseous hydrogen fluoride in air is presented herewith. Air was sampled using miniaturised 13 mm Swinnex two-stage filter holders in a medium-flow pumping system and through the absorption of particulate fluoride and HF vapours on cellulose ester filters uncoated or impregnated with sodium carbonate. Furthermore, filter desorption from the holders and the extraction of the pentafluorobenzyl ester derivative based on solid-phase microextraction were performed using an innovative robotic system installed on an xyz autosampler on-line with gas chromatography (GC)/mass spectrometry (MS). After generating atmospheres of a known concentration of gaseous HF, we evaluated the agreement between the results of our sampling method and those of the conventional preassembled 37 mm cassette (±8.10%; correlation coefficient: 0.90). In addition, precision (relative standard deviation for , 4.3%), sensitivity (0.2 μg/filter), and linearity (2.0–4000 μg/filter; correlation coefficient: 0.9913) were also evaluated. This procedure combines the efficiency of GC/MS systems with the high throughput (96 samples/day) and the quantitative accuracy of pentafluorobenzyl bromide on-sample derivatisation. Stefano Dugheri, Alessandro Bonari, Ilenia Pompilio, Alessandro Monti, Nicola Mucci, and Giulio Arcangeli Copyright © 2016 Stefano Dugheri et al. All rights reserved. Quantitative Scrutinization of Aflatoxins in Different Spices from Pakistan Mon, 03 Oct 2016 13:40:36 +0000 The current research work aimed to access the contamination level of aflatoxins B1, B2, G1, and G2 in the household spices that are widely consumed in huge amounts. 200 different spice samples, 100 packed and 100 unpacked, were analyzed for the aflatoxins profile by HPLC with an incidence of 61.5% contamination out of which 53.66% samples exceed the EU limit. The results disclosed that the unpacked samples are more contaminated as compared to the packed samples except for white cumin seeds. Among packed and unpacked samples of spices, the maximum value of aflatoxins was detected in fennel, that is, 27.93 μg/kg and 67.04 μg/kg, respectively. The lowest concentration of aflatoxin was detected in cinnamon in packed form (0.79 μg/kg) and in the unpacked samples of white cumin seeds which is 1.75 μg/kg. Caraway seeds and coriander in its unpacked form showed positive results whereas black pepper (packed and unpacked) was found free from aflatoxins. This is the first report on the occurrence of aflatoxins in packed and unpacked samples of spices from Pakistan. To ensure safe consumption of spices, there should be constant monitoring of aflatoxin and more studies need to be executed with the intention of preventing mycotoxin accretion in this commodity. Narjis Naz, Aiza Kashif, Kinza Kanwal, Abdul Muqeet Khan, and Mateen Abbas Copyright © 2016 Narjis Naz et al. All rights reserved. A High-Throughput Size Exclusion Chromatography Method to Determine the Molecular Size Distribution of Meningococcal Polysaccharide Vaccine Mon, 05 Sep 2016 16:24:54 +0000 Molecular size distribution of meningococcal polysaccharide vaccine is a readily identifiable parameter that directly correlates with the immunogenicity. In this paper, we report a size exclusion chromatography method to determine the molecular size distribution and distribution coefficient value of meningococcal polysaccharide serogroups A, C, W, and Y in meningococcal polysaccharide (ACWY) vaccines. The analyses were performed on a XK16/70 column packed with sepharose CL-4B with six different batches of Ingovax® ACWY, a meningococcal polysaccharide vaccine produced by Incepta Vaccine Ltd., Bangladesh. A quantitative rocket immunoelectrophoresis assay was employed to determine the polysaccharide contents of each serogroup. The calculated distribution coefficient values of serogroups A, C, W, and Y were found to be , , , and , respectively, and met the requirements of British Pharmacopeia. The method was proved to be robust for determining the distribution coefficient values which is an obligatory requirement for vaccine lot release. Imran Khan, K. M. Taufiqur Rahman, S. M. Saad Us Siraj, Mahbubul Karim, Abdul Muktadir, Arpan Maheshwari, Md Azizul Kabir, Zebun Nahar, and Mohammad Mainul Ahasan Copyright © 2016 Imran Khan et al. All rights reserved. The Development of DNA Based Methods for the Reliable and Efficient Identification of Nicotiana tabacum in Tobacco and Its Derived Products Thu, 18 Aug 2016 08:10:57 +0000 Reliable methods are needed to detect the presence of tobacco components in tobacco products to effectively control smuggling and classify tariff and excise in tobacco industry to control illegal tobacco trade. In this study, two sensitive and specific DNA based methods, one quantitative real-time PCR (qPCR) assay and the other loop-mediated isothermal amplification (LAMP) assay, were developed for the reliable and efficient detection of the presence of tobacco (Nicotiana tabacum) in various tobacco samples and commodities. Both assays targeted the same sequence of the uridine 5′-monophosphate synthase (UMPS), and their specificities and sensitivities were determined with various plant materials. Both qPCR and LAMP methods were reliable and accurate in the rapid detection of tobacco components in various practical samples, including customs samples, reconstituted tobacco samples, and locally purchased cigarettes, showing high potential for their application in tobacco identification, particularly in the special cases where the morphology or chemical compositions of tobacco have been disrupted. Therefore, combining both methods would facilitate not only the detection of tobacco smuggling control, but also the detection of tariff classification and of excise. Sukumar Biswas, Wei Fan, Rong Li, Sifan Li, Wenli Ping, Shujun Li, Alexandra Naumova, Tamara Peelen, Esther Kok, Zheng Yuan, Dabing Zhang, and Jianxin Shi Copyright © 2016 Sukumar Biswas et al. All rights reserved. Nanotechnology-Based Surface Plasmon Resonance Affinity Biosensors for In Vitro Diagnostics Wed, 10 Aug 2016 14:33:18 +0000 In the last decades, in vitro diagnostic devices (IVDDs) became a very important tool in medicine for an early and correct diagnosis, a proper screening of targeted population, and also assessing the efficiency of a specific therapy. In this review, the most recent developments regarding different configurations of surface plasmon resonance affinity biosensors modified by using several nanostructured materials for in vitro diagnostics are critically discussed. Both assembly and performances of the IVDDs tested in biological samples are reported and compared. Riccarda Antiochia, Paolo Bollella, Gabriele Favero, and Franco Mazzei Copyright © 2016 Riccarda Antiochia et al. All rights reserved. Development of an Ion-Pairing Reagent and HPLC-UV Method for the Detection and Quantification of Six Water-Soluble Vitamins in Animal Feed Sun, 31 Jul 2016 10:57:24 +0000 A novel and simple method for detecting six water-soluble vitamins in animal feed using high performance liquid chromatography equipped with a photodiode array detector (HPLC/PDA) and ion-pairing reagent was developed. The chromatographic peaks of the six water-soluble vitamins were successfully identified by comparing their retention times and UV spectra with reference standards. The mobile phase was composed of buffers A (5 mM PICB-6 in 0.1% CH3COOH) and B (5 mM PICB-6 in 65% methanol). All peaks were detected using a wavelength of 270 nm. Method validation was performed in terms of linearity, sensitivity, selectivity, accuracy, and precision. The limits of detection (LODs) for the instrument employed in these experiments ranged from 25 to 197 μg/kg, and the limits of quantification (LOQs) ranged from 84 to 658 μg/kg. Average recoveries of the six water-soluble vitamins ranged from 82.3% to 98.9%. Method replication resulted in intraday and interday peak area variation of <5.6%. The developed method was specific and reliable and is therefore suitable for the routine analysis of water-soluble vitamins in animal feed. Ho Jin Kim Copyright © 2016 Ho Jin Kim. All rights reserved. The Influence of Crown Ether and Alcohol on Unsaturation and Molar Mass of Poly(propylene oxide)s Prepared by Use of Potassium t-Butoxide: Reinvestigation of Chain Transfer Reactions Tue, 26 Jul 2016 13:26:29 +0000 Potassium t-butoxide dissolved in tetrahydrofuran effectively initiates homogeneous polymerization of propylene oxide at room temperature. Unsaturation and molar mass () of the polymers prepared depend on the presence of additives, such as macrocyclic ligand 18-crown-6 (L) and t-butanol. Application of the ligand alone results in distinct increase of unsaturation and decrease of , whereas use of t-BuOH leads to simultaneous decrease of unsaturation and . Activation of t-BuOK/t-BuOH system with the ligand causes further decrease of unsaturation, that is, from 12.0 to 3.5 mol % for OK/OH (1/3) and OK/OH/L (1/3/2) systems, respectively. Unexpectedly, of the polymers obtained does not practically change (~4800). This result differs from that reported earlier for neat PO polymerization initiated potassium 1-methoxy-2-propoxide/1-methoxy-2-propanol, in which in the presence of the same ligand increases to ~12 400 for the same ratio of reagents. The mechanism of studied processes was discussed. Zbigniew Grobelny, Andrzej Swinarew, Justyna Jurek-Suliga, Kinga Skrzeczyna, Jadwiga Gabor, and Marta Łężniak Copyright © 2016 Zbigniew Grobelny et al. All rights reserved. Characterization and Uncertainty Assessment of a Certified Reference Material of Chloramphenicol in Methanol (GBW(E)082557) Wed, 13 Jul 2016 09:33:35 +0000 Prior to preparation of CRM candidate of chloramphenicol in methanol with a concentration of 100 mg/L, two independent methods including mass balance (MB) and quantitative nuclear magnetic resonance (qNMR) were employed to precisely measure the mass fraction of pure chloramphenicol materials. The mass fraction was assigned to be 99.8% with uncertainty of 0.3%. Homogeneity testing and stability study of chloramphenicol in methanol were examined by using high performance liquid chromatography. Additionally, the uncertainties originating from the process of CRM development were comprehensively evaluated. The experimental results indicate that the property value of this CRM is homogeneous and stable at 4°C for at least six months. The new CRM (GBW(E)082557) can be applicable to calibration of instrument and assurance of accuracy and comparability of results in routine measurement. Mengrui Yang, Min Wang, Jian Zhou, Yinqing Song, and Tongtong Wang Copyright © 2016 Mengrui Yang et al. All rights reserved. Recent Advances in the Synthesis and Stabilization of Nickel and Nickel Oxide Nanoparticles: A Green Adeptness Sun, 19 Jun 2016 11:22:34 +0000 Green protocols for the synthesis of nanoparticles have been attracting a lot of attention because they are eco-friendly, rapid, and cost-effective. Nickel and nickel oxide nanoparticles have been synthesized by green routes and characterized for impact of green chemistry on the properties and biological effects of nanoparticles in the last five years. Green synthesis, properties, and applications of nickel and nickel oxide nanoparticles have been reported in the literature. This review summarizes the synthesis of nickel and nickel oxide nanoparticles using different biological systems. This review also provides comparative overview of influence of chemical synthesis and green synthesis on structural properties of nickel and nickel oxide nanoparticles and their biological behavior. It concludes that green methods for synthesis of nickel and nickel oxide nanoparticles are better than chemical synthetic methods. Muhammad Imran Din and Aneela Rani Copyright © 2016 Muhammad Imran Din and Aneela Rani. All rights reserved. Selective Sensing of Tyrosine Phosphorylation in Peptides Using Terbium(III) Complexes Wed, 08 Jun 2016 11:22:37 +0000 Phosphorylation of tyrosine residues in proteins, as well as their dephosphorylation, is closely related to various diseases. However, this phosphorylation is usually accompanied by more abundant phosphorylation of serine and threonine residues in the proteins and covers only 0.05% of the total phosphorylation. Accordingly, highly selective detection of phosphorylated tyrosine in proteins is an urgent subject. In this review, recent developments in this field are described. Monomeric and binuclear complexes, which emit notable luminescence only in the presence of phosphotyrosine (pTyr), have been developed. There, the benzene ring of pTyr functions as an antenna and transfers its photoexcitation energy to the ion as the emission center. Even in the coexistence of phosphoserine (pSer) and phosphothreonine (pThr), pTyr can be efficintly detected with high selectivity. Simply by adding these complexes to the solutions, phosphorylation of tyrosine in peptides by protein tyrosine kinases and dephosphorylation by protein tyrosine phosphatases can be successfully visualized in a real-time fashion. Furthermore, the activities of various inhibitors on these enzymes are quantitatively evaluated, indicating a strong potential of the method for efficient screening of eminent inhibitors from a number of candidates. Jun Sumaoka, Hiroki Akiba, and Makoto Komiyama Copyright © 2016 Jun Sumaoka et al. All rights reserved. Simultaneous Determination of Four Active Ingredients in Sargentodoxa cuneata by HPLC Coupled with Evaporative Light Scattering Detection Sun, 29 May 2016 14:15:55 +0000 A HPLC coupled with evaporative light scattering detection method had been developed for the simultaneous determination of 3,4-dihydroxyphenylethyl alcohol glycoside, salidroside, chlorogenic acid, and liriodendrin in the stem of Sargentodoxa cuneata. With a C18 column, the analysis was performed using acetonitrile and 0.2% formic acid aqueous solution as mobile phase in gradient program at a flow rate of 0.9 mL/min. The optimum drift tube temperature of evaporative light scattering detection was at 105°C with the air flow rate of 2.5 L/min. The calibration curves showed good linearity during the test ranges. This method was validated for limits of detection and quantification, precision, and reproducibility. The recoveries were within the range of 96.39%–104.64%. The relative standard deviations of intraday and interday precision were less than 2.90% and 3.30%, respectively. The developed method can be successfully used to quantify the four analytes in the stem of Sargentodoxa cuneata from various regions in China. Di-Hua Li, Yuan-Shan Lv, Jun-Hong Liu, Lei Yang, Yan Wang, Shu-Kun Zhang, and Yu-Zhen Zhuo Copyright © 2016 Di-Hua Li et al. All rights reserved. Morphological Analysis of White Cement Clinker Minerals: Discussion on the Crystallization-Related Defects Wed, 25 May 2016 06:32:16 +0000 The paper deals with a formation of artificial rock (clinker). Temperature plays the capital role in the manufacturing process. So, it is useful to analyze a poor clinker to identify the different phases and defects associated with their crystallization. X-ray fluorescence spectroscopy was used to determine the clinker’s chemical composition. The amounts of the mineralogical phases are measured by quantitative XRD analysis (Rietveld). Scanning electron microscopy (SEM) was used to characterize the main phases of white Portland cement clinker and the defects associated with the formation of clinker mineral elements. The results of a study which focused on the identification of white clinker minerals and defects detected in these noncomplying clinkers such as fluctuation of the amount of the main phases (alite (C3S) and belite (C2S)), excess of the free lime, occurrence of C3S polymorphs, and occurrence of moderately-crystallized structures are presented in this paper. Mohamed Benmohamed, Rabah Alouani, Amel Jmayai, Abdesslem Ben Haj Amara, and Hafsia Ben Rhaiem Copyright © 2016 Mohamed Benmohamed et al. All rights reserved. The Size of the Human Proteome: The Width and Depth Thu, 19 May 2016 17:15:16 +0000 This work discusses bioinformatics and experimental approaches to explore the human proteome, a constellation of proteins expressed in different tissues and organs. As the human proteome is not a static entity, it seems necessary to estimate the number of different protein species (proteoforms) and measure the number of copies of the same protein in a specific tissue. Here, meta-analysis of neXtProt knowledge base is proposed for theoretical prediction of the number of different proteoforms that arise from alternative splicing (AS), single amino acid polymorphisms (SAPs), and posttranslational modifications (PTMs). Three possible cases are considered: PTMs and SAPs appear exclusively in the canonical sequences of proteins, but not in splice variants; PTMs and SAPs can occur in both proteins encoded by canonical sequences and in splice variants; all modification types (AS, SAP, and PTM) occur as independent events. Experimental validation of proteoforms is limited by the analytical sensitivity of proteomic technology. A bell-shaped distribution histogram was generated for proteins encoded by a single chromosome, with the estimation of copy numbers in plasma, liver, and HepG2 cell line. The proposed metabioinformatics approaches can be used for estimation of the number of different proteoforms for any group of protein-coding genes. Elena A. Ponomarenko, Ekaterina V. Poverennaya, Ekaterina V. Ilgisonis, Mikhail A. Pyatnitskiy, Arthur T. Kopylov, Victor G. Zgoda, Andrey V. Lisitsa, and Alexander I. Archakov Copyright © 2016 Elena A. Ponomarenko et al. All rights reserved. Use of the Relaxometry Technique for Quantification of Paramagnetic Ions in Aqueous Solutions and a Comparison with Other Analytical Methods Tue, 17 May 2016 06:43:41 +0000 We have demonstrated that the relaxometry technique is very efficient to quantify paramagnetic ions during in situ electrolysis measurements. Therefore, the goal of this work was to validate the relaxometry technique in the determination of the concentration of the ions contained in electrolytic solutions, Cu2+, Ni2+, Cr3+, and Mn2+, and compare it with other analytical methods. Two different NMR spectrometers were used: a commercial spectrometer with a homogeneous magnetic field and a home-built unilateral sensor with an inhomogeneous magnetic field. Without pretreatment, manganese ions do not have absorption bands in the UV-Visible region, but it is possible to quantify them using relaxometry (the limit of quantification is close to 10−5 mol L−1). Therefore, since the technique does not require chemical indicators and is a cheap and robust method, it can be used as a replacement for some conventional quantification techniques. The relaxometry technique could be applied to evaluate the corrosion of metallic surfaces. Bruna Ferreira Gomes, Juliana Soares da Silva Burato, Carlos Manuel Silva Lobo, and Luiz Alberto Colnago Copyright © 2016 Bruna Ferreira Gomes et al. All rights reserved. Multianalytical Method Validation for Qualitative and Quantitative Analysis of Solvents of Abuse in Oral Fluid by HS-GC/MS Wed, 04 May 2016 13:41:24 +0000 The use of oral fluid as a biological matrix to monitor the use of drugs of abuse is a global trend because it presents several advantages and good correlation to the blood level. Thus, the present work aimed to develop and validate an analytical method for quantification and detection of solvents used as inhalants of abuse in oral fluid (OF), using Quantisal™ as collector device by headspace and gas chromatography coupled with a mass detector (HS-GC/MS). Chromatographic separation was performed with a ZB-BAC1 column and the total time of analysis was 11.8 min. The method showed good linearity (correlation coefficient higher than 0.99 for all solvents). The limits of detection ranged from 0.05 to 5 mg/L, while the lower limits of quantification ranged from 2.5 to 12.5 mg/L. Accuracy, precision, matrix effect, and residual effect presented satisfactory results, meeting the criteria accepted for the validation of bioanalytical methods. The method showed good selectivity considering that, for solvents coeluting at the same retention time, resolution was performed by the mass detector. The method developed proved to be adequate when applied in OF samples from users of drugs and may be used to monitor the abuse of inhalants in routine forensic analyses. Bruna Claudia Coppe, Bruna Tassi Borille, Taís Regina Fiorentin, Ana Laura Bemvenuti Jacques, Ana Claudia Fagundes, Stela Maris de Jezus Castro, Lysa Silveira Remy, Flavio Pechansky, and Renata Pereira Limberger Copyright © 2016 Bruna Claudia Coppe et al. All rights reserved. Comparison of Three Solid Phase Materials for the Extraction of Carboxylic Acids from River Water Followed by 2D GC × GC-TOFMS Determination Wed, 04 May 2016 13:39:05 +0000 The extraction and determination of aliphatic and aromatic carboxylic acids as well as their influence on the aromaticity and molecularity relationship of natural organic matter (NOM) in water are reported in this study. Three solid phase extraction (SPE) sorbents were used and their extraction efficiencies evaluated after chromatographic determinations (using gas chromatography with a time of flight mass spectrometer (GC × GC-TOFMS) and liquid chromatography with organic carbon detector (LC-OCD)). More than 42 carboxylic acids were identified in raw water from the Vaal River, which feeds the Lethabo Power Generation Station, South Africa, with cooling water. The aromatic carboxylic acid efficiency (28%) was achieved by using Strata™ X SPE while the highest aliphatic carboxylic acid efficiency (92.08%) was achieved by silica SPE. The hydrophobic nature of NOM in water depends on the nature of organic compounds in water, whether aromatic or aliphatic. The LC-OCD was used to assess the hydrophobicity levels of NOM as a function of these carboxylic acids in cooling water. The LC-OCD results showed that the aromatic nature of NOM in SPE filtered water followed the order Silica>Strata X>C-18. From the results, the hydrophobicity degree of the samples depended on the type and number of carboxylic acids that were removed by the SPE cartridges. G. O. Bosire, J. C. Ngila, and H. Parshotam Copyright © 2016 G. O. Bosire et al. All rights reserved. Determination of Natamycin in Turkish Yoghurt Tue, 03 May 2016 11:06:51 +0000 This study was aimed at developing RP-HPLC method for determination of natamycin in Turkish yoghurt. Chromatographic separation was achieved on a C8 column (150 mm × 4.6 mm × 5 µm) with a mobile phase of methanol : water : acetic acid (12 : 8 : 1 v/v/v), at 1 mL/min flow rate with a detection of 303 nm. Natamycin was spiked into handmade yoghurt samples and used for validation. The method has been fully validated according to ISO 9233-2, 2007 (IDF 140-2, 2007). It was successfully applied to determination of 28 different Turkish yoghurt products. Findings dealing with the presence of natamycin in cheese samples are presented. Dilek Bilgic Alkaya and Ozlem Karalomlu Copyright © 2016 Dilek Bilgic Alkaya and Ozlem Karalomlu. All rights reserved. Study on Colloidal Model of Petroleum Residues through the Attraction Potential between Colloids Tue, 19 Apr 2016 14:17:50 +0000 The samples of DaGang atmospheric residue (DG-AR), Middle East atmospheric residue (ME-AR), TaHe atmospheric residue (TH-AR), and their thermal reaction samples were chosen for study. All the samples were fractioned into six components separately, including saturates plus light aromatics, heavy aromatics, light resins, middle resins, heavy resins, and asphaltenes. The dielectric permittivity of the solutions of these components was measured, and the dielectric permittivity values of the components can be determined by extrapolation, which increased steadily from saturates plus light aromatics to asphaltenes. Moreover, the Hamaker constants of the components were calculated from their dielectric permittivity values. The Van der Waals attractive potential energy between colloids corresponding to various models could be calculated from the fractional composition and the Hamaker constants of every component. It was assumed that the cores of colloidal particles were formed by asphaltenes and heavy resins mainly; the other fractions acted as dispersion medium. For the three serials of thermal reaction samples, the Van der Waals attraction potential energy between colloids for this kind of model was calculated. For TH-AR thermal reaction samples, the Van der Waals attraction potential energy presented the maximum as thermal reaction is going on, which was near to the end of coke induction period. Long-li Zhang, Guo-hua Yang, Chao-he Yang, and Guo-he Que Copyright © 2016 Long-li Zhang et al. All rights reserved. Masking Agents Evaluation for Lead Determination by Flow Injection-Hydride Generation-Atomic Fluorescence Spectrometry Technique: Effect of KI, L-Cysteine, and 1,10-Phenanthroline Mon, 11 Apr 2016 14:32:14 +0000 Hydride generation (HG) of lead technique presents interferences from foreign ions of complex matrix samples. In order to minimize these interferences, the effect of masking agents such as KI, L-cysteine, and 1,10-phenanthroline was studied in the absence and in the presence of selected interfering species (As, Cr, Cu, and Fe). Different modes of addition of masking agents were accomplished, that is, to either sample or KBH4 reducing solution. The lead determinations were performed using a flow injection analysis (FIA) system coupled to HG and atomic fluorescence spectrometry (AFS). The linearity of calibration curves (1–10 μg Pb L−1) was not affected by the addition of the masking agents. The use of KI in the reducing solution diminished interferences from concentrations of As and Cu, while 1,10-phenanthroline showed a positive effect on the interference by As. Moreover, Cr and Cu appeared to be the most serious interfering ions for plumbane (PbH4), because they drastically reduced the analytical signal of lead. Fe did not present any interference under the employed experimental conditions, even at high levels. The accuracy was established through the analysis of certified reference material (i.e., BCR-610, groundwater) using KI as masking agent. The detection limit reached by FIA-HG-AFS proposed methodology was 0.03 μg Pb L−1. Blanca G. Beltrán, Luz O. Leal, Laura Ferrer, and Víctor Cerdà Copyright © 2016 Blanca G. Beltrán et al. All rights reserved. Core-Shell Columns in High-Performance Liquid Chromatography: Food Analysis Applications Sun, 10 Apr 2016 06:18:33 +0000 The increased separation efficiency provided by the new technology of column packed with core-shell particles in high-performance liquid chromatography (HPLC) has resulted in their widespread diffusion in several analytical fields: from pharmaceutical, biological, environmental, and toxicological. The present paper presents their most recent applications in food analysis. Their use has proved to be particularly advantageous for the determination of compounds at trace levels or when a large amount of samples must be analyzed fast using reliable and solvent-saving apparatus. The literature hereby described shows how the outstanding performances provided by core-shell particles column on a traditional HPLC instruments are comparable to those obtained with a costly UHPLC instrumentation, making this novel column a promising key tool in food analysis. Raffaella Preti Copyright © 2016 Raffaella Preti. All rights reserved. Measurement of Circulating 1,25-Dihydroxyvitamin D: Comparison of an Automated Method with a Liquid Chromatography Tandem Mass Spectrometry Method Tue, 05 Apr 2016 09:35:51 +0000 Background. The clinical relevance of circulating 1,25-dihydroxyvitamin D (1,25(OH)2D) is probably underappreciated, but variations in the measurement of this difficult analyte between different methods limit comparison of results. Methods. In 129 clinical samples, we compared a new automated assay with a commercially available liquid chromatography tandem mass spectrometry (LC-MS/MS) kit. Results. Median (interquartile range) 1,25(OH)2D concentrations with the automated assay and the LC-MS/MS method were 26.6 pg/mL (18.5–39.0 pg/mL) and 23.6 pg/mL (16.1–31.3 pg/mL), respectively (). Using the method-specific cut-offs for deficient 1,25(OH)2D levels (<20 pg/mL for the automated assay and <17 pg/mL for the LC-MS/MS method), the percentage of patients classified as 1,25(OH)2D deficient was 28.7% and 27.1%, respectively. However, concordance between the two methods for deficient levels was only 62% and the concordance correlation coefficient was poor (0.534). The regression equation resulted in an intercept of −1.99 (95% CI: −7.33–1.31) and a slope of 1.27 (95% CI: 1.04–1.52) for the automated assay. The mean bias with respect to the mean of the two methods was −3.8 (1.96 SD: −28.3–20.8) pg/mL for the LC-MS/MS method minus the automated assay. Conclusions. The two methods show only modest correlation and further standardization is required to improve reliability and comparability of 1,25(OH)2D test procedures. Armin Zittermann, Jana B. Ernst, Tobias Becker, Jens Dreier, Cornelius Knabbe, Jan F. Gummert, and Joachim Kuhn Copyright © 2016 Armin Zittermann et al. All rights reserved. Direct Analysis of Low-Volatile Molecular Marker Extract from Airborne Particulate Matter Using Sensitivity Correction Method Mon, 04 Apr 2016 08:30:49 +0000 Molecular marker analysis of environmental samples often requires time consuming preseparation steps. Here, analysis of low-volatile nonpolar molecular markers (5-6 ring polycyclic aromatic hydrocarbons or PAHs, hopanoids, and n-alkanes) without the preseparation procedure is presented. Analysis of artificial sample extracts was directly conducted by gas chromatography-mass spectrometry (GC-MS). After every sample injection, a standard mixture was also analyzed to make a correction on the variation of instrumental sensitivity caused by the unfavorable matrix contained in the extract. The method was further validated for the PAHs using the NIST standard reference materials (SRMs) and then applied to airborne particulate matter samples. Tests with the SRMs showed that overall our methodology was validated with the uncertainty of ~30%. The measurement results of airborne particulate matter (PM) filter samples showed a strong correlation between the PAHs, implying the contributions from the same emission source. Analysis of size-segregated PM filter samples showed that their size distributions were found to be in the PM smaller than 0.4 μm aerodynamic diameter. The observations were consistent with our expectation of their possible sources. Thus, the method was found to be useful for molecular marker studies. Satoshi Irei Copyright © 2016 Satoshi Irei. All rights reserved. Quantification of Sterol and Triterpenol Biomarkers in Sediments of the Cananéia-Iguape Estuarine-Lagoonal System (Brazil) by UHPLC-MS/MS Mon, 21 Mar 2016 08:11:08 +0000 Sterols and triterpenols present in sedimentary cores from 12 stations along the Cananéia-Iguape estuarine-lagoonal system were investigated by ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS). Ten sterols and three triterpenols were identified and quantified, indicating both natural and anthropogenic sources. The relative distributions of sterol and triterpenol showed that the study area is submitted to organic matter (OM) from the Ribeira de Iguape River, seawater, surrounding vegetation, and plankton production. The contribution of these sources depends on the region of the estuarine-lagoonal system and the depth of sediment. Regarding anthropogenic sources, only the samples submitted to freshwater flow from the Ribeira de Iguape River presented concentration of coprostanol higher than the threshold value and diagnostic ratios, coprostanol/(coprostanol + cholestanol) and coprostanol/cholesterol, that indicate moderate contamination by domestic sewage in that area of the estuarine-lagoonal system. Therefore, the approach used herein identified the OM sources and its transport along the Cananéia-Iguape estuarine-lagoonal system (Brazil), which is a complex of lagoonal channels located in a United Nations Educational, Scientific and Cultural Organization (UNESCO) Biosphere Reserve. Giovana Anceski Bataglion, Hector Henrique Ferreira Koolen, Rolf Roland Weber, and Marcos Nogueira Eberlin Copyright © 2016 Giovana Anceski Bataglion et al. All rights reserved. Gas Chromatography/Atmospheric Pressure Chemical Ionization-Fourier Transform Ion Cyclotron Resonance Mass Spectrometry of Pyrolysis Oil from German Brown Coal Tue, 15 Mar 2016 09:46:56 +0000 Pyrolysis oil from the slow pyrolysis of German brown coal from Schöningen, obtained at a temperature of 500°C, was separated and analyzed using hyphenation of gas chromatography with an atmospheric pressure chemical ionization source operated in negative ion mode and Fourier transform ion cyclotron resonance mass spectrometry (GC-APCI-FT-ICR-MS). Development of this ultrahigh-resolving analysis method is described, that is, optimization of specific GC and APCI parameters and performed data processing. The advantages of GC-APCI-FT-ICR-MS hyphenation, for example, soft ionization, ultrahigh-resolving detection, and most important isomer separation, were demonstrated for the sample liquid. For instance, it was possible to separate and identify nine different propylphenol, ethylmethylphenol, and trimethylphenol isomers. Furthermore, homologous series of different acids, for example, alkyl and alkylene carboxylic acids, were verified, as well as homologous series of alkyl phenols, alkyl dihydroxy benzenes, and alkoxy alkyl phenols. Jan Zuber, Marius M. Kroll, Philipp Rathsack, and Matthias Otto Copyright © 2016 Jan Zuber et al. All rights reserved.