Simultaneous determination of perfluoroalkyl phosphonates, carboxylates, and sulfonates in drinking water

A trace analytical method based on high performance liquid chromatography coupled to quadrupole time-of-flight high resolution mass spectrometry was developed for simultaneous determination of perfluoroalkyl phosphonates (PFPAs, carbon chain lengths C6,8,10), perfluoroalkyl carboxylates (PFCAs, C5-12), and perfluoroalkyl sulfonates (PFSAs, C4,6,8,10) in drinking water (tap water). Analytes were enriched on a mixed mode co-polymeric sorbent (C8+quaternary amine) using solid phase extraction. Chromatographic separation was achieved on a Zorbax Extend C18 reversed phase column using a mobile phase gradient consisting of water, methanol, and acetonitrile containing 2mM ammonium acetate and 5 mM 1-methyl piperidine. The mass spectrometer was operated in electrospray negative ion mode. Use of 1-methyl piperidine in the mobile phase resulted in a significant increase in instrument sensitivity for PFPAs through improved chromatographic resolution, background suppression, and increased ionization efficiency. Method detection limits for extraction of 500 mL tap water were in the ranges of 0.095-0.17 ng/L, 0.027-0.17 ng/L, and 0.014-0.052 ng/L for PFPAs, PFCAs, and PFSAs, respectively. Whole method recoveries at a spiking level of 0.5 ng/L to 500 mL HPLC grade water were 40-56%, 56-97%, and 55-77% for PFPAs, PFCAs, and PFSAs, respectively. A matrix effect (signal enhancement) was observed in the detection of PFPAs in tap water extracts, leading to calculated recoveries of 249-297% at a 0.5 ng/L spiking level. This effect resulted in an additional improvement of method sensitivity for PFPAs. To compensate for the matrix effect, PFPAs in tap water were quantified using matrix-matched and extracted calibration standards. The method was successfully applied to the analysis of drinking water collected from six European countries. PFPAs were not detected except for perfluorooctyl phosphonate (PFOPA) at close to the detection limit of 0.095 ng/L in two water samples from Amsterdam, the Netherlands. Highest levels were found for perfluorobutane sulfonate (PFBS, 18.8 ng/L) and perfluorooctanoate (PFOA, 8.6 ng/L) in samples from Amsterdam as well as for perfluorooctane sulfonate (PFOS, 8.8 ng/L) in tap water from Stockholm, Sweden.     

Fluorescent zinc(II) complex exhibiting "on-off-on" switching toward Cu2+ and Ag+ ions

Binuclear zinc(II) and copper(II) complexes based on a new Schiff base ligand N,N'-bis(2-hydroxybenzilidene)-2,4,6-trimethylbenzene-1,3-diamine (H(2)L) have been synthesized. The ligand H(2)L and complexes under investigation have been characterized by elemental analyses, spectral (FT-IR, (1)H, (13)C NMR, ESI-MS, electronic absorption, emission), and electrochemical studies. The structures of H(2)L and complexes [{Zn(C(23)H(18)N(2)O(2))}(2)] (1) and [{Cu(C(23)H(18)N(2)O(2))}(2)]·H(2)O (2) have been determined crystallographically. Selective "On-Off-On" switching behavior of the fluorescent complex 1 has been studied. The fluorescence intensity of 1 quenches (turns-off) upon addition of Cu(2+), while enhances (turns-on) in the presence of Ag(+) ions. The mechanisms of "On-Off-On" signaling have been supported by (1)H NMR, ESI-MS, electronic absorption, and emission spectral studies. Job's plot analysis supported 1:1 and 1:2 stoichiometries for Cu(2+) and Ag(+) ions, respectively. Association and quenching constants have been estimated by the Benesi-Hildebrand method and Stern-Volmer plot. Moreover, 1 mimics a molecular keypad lock that follows correct chemical input order to give maximum output signal.     

Effects of exponential volume fraction law on the natural frequencies of FGM cylindrical shells under various boundary conditions

In the present work, vibration characteristics of thin functionally graded cylindrical shells are studied under the influence of various boundary conditions. Fabrication of FGM cylindrical shell is carried out by using exponential volume fraction law. Strain- and curvature-displacements relationships are taken from Love’s thin shell theory. The frequency equation in the form of eigenvalue problem is obtained by adapting the Rayleigh-Ritz method. Characteristic beam functions are assumed to approximate the axial modal dependence. Effects of exponential volume fraction law on the natural frequencies of the FGM cylindrical shells for various boundary conditions are studied against circumferential wave number, length to radius ratio and thickness to radius ratio for different values of power law exponents. Results evaluated show good agreement with those available in the literature.     

The growth of nanoscale periodic and dot-like structures on the surface of stainless steel with femtosecond laser pulses in the dry and wet ambient environment

The present work deals with growth of nanoscale periodic and dot-like structures on the surface of stainless steel (SS) by the irradiation of femtosecond laser pulses. For this purpose Ti: Sapphire femtosecond laser pulses (wavelength of 800 nm, pulse length of 25 fs and pulse repetition rate of 1 kHz) were employed in a dry (air) and liquid confined (deionized water and ethanol) environments. The targets were exposed to 1000 succeeding pulses for various fluences ranging from 50 to 150 mJ?cm^?2. Nanoscale structures including ripples, and dots were observed by SEM analysis. The growth and dependence of structure-formation on the ambient environment and laser fluence in both central as well as peripheral ablated areas is systematically investigated. The development of nanostructures and nanoripples is correlated with structural analysis carried out by micro Raman spectroscopy.     

Semi-empirical formula for Λ-binding energies in ground states of light hypernuclei

Starting with a Λ-nucleus potential, we have obtained a semi-empirical formula, which gives a fairly satisfactory account of the ground state Λ-binding energy of light hypernuclei, if the very light nuclei are ignored.     

Entanglement conditions for two-mode states

We provide a class of inequalities whose violation shows the presence of entanglement in two-mode systems. We initially consider observables that are quadratic in the mode creation and annihilation operators and find conditions under which a two-mode state is entangled. Further examination allows us to formulate additional conditions for detecting entanglement. We conclude by showing how the methods used here can be extended to find entanglement in systems of more than two modes.     

Classification of Teleparallel Homothetic Vector Fields in Cylindrically Symmetric Static Space-Times in Teleparallel Theory of Gravitation

In this paper we classify cylindrically symmetric static space-times according to their teleparallel homothetic vector fields using direct integration technique. It turns out that the dimensions of the teleparallel homothetic vector fields are 4, 5, 7 or 11, which are the same in numbers as in general relativity. In case of 4, 5 or 7 proper teleparallel homothetic vector fields exist for the special choice to the space-times. In the case of 11 teleparallel homothetic vector fields the space-time becomes Minkowski with all the zero torsion components. Teleparallel homothetic vector fields in this case are exactly the same as in general relativity. It is important to note that this classification also covers the plane symmetric static space-times.     

Converses of the Jensen inequality derived from the Green functions with applications in information theory

Jensen integral inequality has got much importance regarding their applications in different fields of mathematics. In this paper, two converses of Jensen integral inequality for convex function are obtained. The results are applied to establish converses of Hölder and Hermite-Hadamard inequalities as well. At the end, some useful applications in information theory of the obtained results are given. The idea used in this paper may inculcate further research.