Simultaneous multiresidue determination of 48 pesticides in Yeongsan and Sumjin River water using GC-NPD and confirmation via GC-MS

In a continuation of our earlier work, a multiresidual analytical method using 48 frequently used neutral pesticides in a water matrix was developed and validated in this study. The samples were extracted with dichloromethane and the pesticides were analyzed via GC-NPD followed by confirmation with GC-MS. Good linearity was detected over a concentration range of 0.01-1.0 microg/mL with correlation coefficients (r(2) ) in excess of 0.982. The recoveries were measured between 70.7 and 111.4% for the majority of the targeted pesticides with relative standard deviations (RSDs) of less than 20%. The LODs and LOQs were in ranges of 0.1-2 and 0.33-6.6 microg/L, respectively. A total of 66 water samples were collected from different locations in Yeongsan and the Sumjin River, Republic of Korea, and were analyzed in accordance with the developed method. None of the water samples were determined to contain any of the targeted pesticides. The method has been shown to be simpler, faster, and more cost-effective than the method established by the Environmental Protection Agency (EPA).     

The nature of in-plane skeleton Raman modes of P3HT and their correlation to the degree of molecular order in P3HT:PCBM blend thin films

The nature of main in-plane skeleton Raman modes (C=C and C-C stretch) of poly(3-hexylthiophene) (P3HT) in pristine and its blend thin films with [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) is studied by resonant and nonresonant Raman spectroscopy and Raman simulations. Under resonant conditions, the ordered phase of P3HT with respect to its disordered phase is identified by (a) a large shift in the C=C mode peak position to lower wavenumber (~21 cm(-1) shift), (b) a narrower fwhm of the C=C mode (~9 cm(-1) narrower), (c) a larger intensity of the C-C mode relative to the C=C mode (~56% larger), and (d) a very small Raman dispersion (~5 cm(-1)) of the C=C mode. The behavior of the C=C and C-C modes of the ordered and disordered phases of P3HT can be explained in terms of different molecular conformations. The C=C mode of P3HT in P3HT:PCBM blend films can be reproduced by simple superposition of the two peaks observed in different phases of P3HT (ordered and disordered). We quantify the molecular order of P3HT after blending with PCBM and the subsequent thermal annealing to be 42 ± 5% and 94 ± 5% in terms of the fraction of ordered P3HT phase, respectively. The increased molecular order of P3HT in blends upon annealing correlates well with enhanced device performance (J(SC), -4.79 to -8.72 mA/cm(2) and PCE, 1.07% to 3.39%). We demonstrate that Raman spectroscopy (particularly under resonant conditions) is a simple and powerful technique to study molecular order of conjugated polymers and their blend films.     

Cationic nucleolipids as efficient siRNA carriers

We synthesized five novel uridine-based cationic nucleolipids, introducing basic amino acid residues at the 5' position of uridine, through 1,3-dipolar cycloaddition, and hydrophobic alkyl moieties at the 2' and 3' positions, through carbamate linkages. Their lipoplexes delivered siRNAs efficiently to cells, in vitro, without any severe toxicity.     

Enzyme-magnetic nanoparticle conjugates as a rigid biocatalyst for the elimination of toxic aromatic hydrocarbons

An enzyme-magnetic nanoparticle conjugate is prepared via conjugation of Ni(2+) ions onto the surface of magnetic nanoparticles to interact with a six histidine-tagged enzyme. The catalytic properties and enzyme rigidification of the conjugates are more stable at high concentrations of aromatic hydrocarbons.     

Benzene sorption complex of fully dehydrated fully Mn2+-exchanged zeolite Y (FAU) and its single-crystal structure

The single-crystal structure of a benzene sorption complex of fully dehydrated fully Mn²⁺-exchanged zeolite Y, |Mn_37.5(C₆H₆)₂₄|[Si₁₁₇Al₇₅O₃₈₄]-FAU, has been determined by single-crystal synchrotron X-ray diffraction techniques in the cubic space group Fd $ \overline{3} $ m at 100(1) K. A fully dehydrated and fully Mn²⁺-exchanged zeolite Y (|Mn_37.5|[Si₁₁₇Al₇₅O₃₈₄]-FAU, Si/Al = 1.56) was treated with zeolitically dried benzene at 297(1) K for 3 days. The structure was refined using all intensities to the final error indices (using the 544 reflections for which F _o > 4??(F _o)) R ₁ = 0.050 (based on F) and wR ₂ = 0.147 (based on F ²). In this structure, Mn²⁺ ions occupy four crystallographic sites: 13.5 Mn²⁺ ions are at the centers of the double 6-rings; 4 Mn²⁺ ions are in the sodalite cavity opposite to the double 6-rings; the remaining 20 Mn²⁺ ions are found at two non-equivalent threefold axes in the sodalite cavity and supercage with occupancies of 2 and 18, respectively. The 24 benzene molecules are found at two distinct positions within the supercages. Eighteen benzene molecules are found on the threefold axes in the supercages where each interacts facially with one of site-II Mn²⁺ ions (Mn²⁺-benzene center = ca. 2.53 Å). The remaining six benzene molecules lie on the planes of the 12-rings where each is stabilized by multiple weak electrostatic and van der Waals interactions with framework oxygens.     

The application of Py-GC/MS for the catalytic upgrading of oil separated from summer food waste leachate

The catalytic cracking of oil fractions separated from summer food waste leachate was investigated over BEA zeolite and Al-SBA-15 catalysts. In this study, a mixture of food waste oil fractions and catalyst was directly introduced to pyrolysis gas chromatography/mass spectrometry (Py-GC/MS), with the resulting vapor phase products being simultaneously analyzed. Various acid compounds, including oleic acid, produced by the non-catalytic pyrolysis of food waste leachate were reformed into valuable compounds, such as oxygenates, hydrocarbons, and aromatics. The BEA zeolite catalyst showed higher selectivity for hydrocarbon compounds, especially aromatics, within the gasoline range due to its superior cracking ability originating from its highly acidic sites. Conversely, the cracking performance of the Al-SBA-15 catalyst, possessing mild acidic sites, was lower than that of the BEA zeolite. Increasing the amount of Al-SBA-15 catalyst enhanced the cracking activity and resulted in higher selectivity for hydrocarbons.     

Interfacial synthesis and characterization of camphor sulfonic acid doped poly(aniline-co-2,5-dimethoxyaniline)

Polyaniline doped with camphor sulfonic acid, poly(2,5-dimethoxyaniline) and their copolymers were synthesized by interfacial method. The FT-IR spectra, UV-Vis absorption spectra and X-ray diffraction patterns were used to characterize the molecular structures of the polymers. The morphology of the polymers was studied by using SEM and TEM. Voltammetric study was done to investigate the electrochemical behavior of these polymers. The results show that the polymers were in microscale with the different shapes such as rod, flake and sphere, respectively. All the homopolymers and copolymers had a poor crystallinity. The conductivity of the copolymers of aniline with 2,5-dimethoxyaniline decreased with increase of 2,5-dimethoxy-aniline molar content.     

Continuous separation of breast cancer cells from blood samples using multi-orifice flow fractionation (MOFF) and dielectrophoresis (DEP)

Circulating tumor cells (CTCs) are highly correlated with the invasive behavior of cancer, so their isolations and quantifications are important for biomedical applications such as cancer prognosis and measuring the responses to drug treatments. In this paper, we present the development of a microfluidic device for the separation of CTCs from blood cells based on the physical properties of cells. For use as a CTC model, we successfully separated human breast cancer cells (MCF-7) from a spiked blood cell sample by combining multi-orifice flow fractionation (MOFF) and dielectrophoretic (DEP) cell separation technique. Hydrodynamic separation takes advantage of the massive and high-throughput filtration of blood cells as it can accommodate a very high flow rate. DEP separation plays a role in precise post-processing to enhance the efficiency of the separation. The serial combination of these two different sorting techniques enabled high-speed continuous flow-through separation without labeling. We observed up to a 162-fold increase in MCF-7 cells at a 126 μL min(-1) flow rate. Red and white blood cells were efficiently removed with separation efficiencies of 99.24% and 94.23% respectively. Therefore, we suggest that our system could be used for separation and detection of CTCs from blood cells for biomedical applications.     

Differential pulse anodic stripping voltammetric determination of Cd and Pb at a bismuth glassy carbon electrode modified with Nafion, poly(2,5-dimercapto-1,3,4-thiadiazole) and multiwalled carbon nanotubes

A simple, cheap, and nonpolluting method was developed for the cloud point extraction of gold (Au) and palladium (Pd). It is based on the complexation reaction of Au and Pd with 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) and micelle mediated extraction of the complex using the non-ionic surfactant poly(ethylene glycol) mono-p-nonylphenyl ether (PONPE 7.5). Under the optimized experimental conditions, the enrichment factors are 16 and 17 for Au and Pd, respectively, for 15?mL of preconcentrated solution. The limits of detection are 3.8???g?L^?1 and 1.8???g?L^?1 for Au and Pd, respectively. The relative standard deviations are 1.4% for Au and 0.6% for Pd (n?=?11). The method was successfully applied to the determination of Au and Pd in certified reference materials and mine samples.

A novel anti-interference and pH-modulation device: application to enzyme-free glucose detection

We report on a novel anti-interference and pH-modulation device (herein after referred to as ??device??). It is based on electrodialysis and can continuously increase the pH value of the carrier solution and - at the same time - remove interfering analytical signals obtained for ascorbic acid (AA) and uric acid (UA). The ??device?? was coupled to the FIA-amperometric detection of glucose. The linear range is from 1???mol?L^?1 to 0.4?mmol?L^?1, with a sensitivity of 213???A?cm^?2?mM^?1 and a detection limit of 1???mol?L^?1 at a signal-to-noise ratio of 3. The method was used to sucessfully determine glucose in serum. This study represents a novel technique for overcoming analytical interference and is expected to find applications in liquid chromatography, for example in on-line pH-modulation if different pH values are needed for separation and detection.