Solid‐phase microextraction for the human biomonitoring of environmental chemicals: Current applications and future perspectives

Sample preparation is one of the crucial steps in the analytical chemistry including human biomonitoring studies. Although there are several traditional approaches available, solid‐phase microextraction is emerged as one of the pioneering techniques due to its simplicity, rapidness, wide applicability, and miniaturization of traditional sample preparation (e.g., use of less or no organic solvents). There are few earlier review articles available on the advancements in solid‐phase microextraction and its use for the measurement of environmental chemicals in various types of environmental samples. However, a collective information on applicability and current usage of solid‐phase microextraction for the human biomonitoring of environmental chemicals are scarce, nonetheless, rising demands on innovative analytical approaches for human biomonitoring studies. Hence, in this review article, we covered the application of solid‐phase microextraction as extraction/purification methods for more than 15 classes of environmental chemicals to assess their respective exposure levels and associated health outcomes in various human population reported across the globe. Further, a detailed discussion on various types of matrix used, nature of coupled analytical instrumentations, and limitations and future perspectives of solid‐phase microextraction for human biomonitoring studies is presented in this review.     

Solution of Schrodinger Equation for Two-Dimensional Complex Ouartic Potentials

We investigate the quasi-exact solutions of the Schrodinger wave equation for two-dimensional non-hermitian complex Hamiltonian systems within the frame work of an extended complex phase space characterized by x = x1 ＋ ip3, y = x2 ＋ ip4, px= p1＋ ix3, py= p2 ＋ ix4. Explicit expressions of the energy eigenvalues and the eigenfunctions for ground and first excited states for a complex quartic potential are obtained. Eigenvalue spectra of some variants of the complex quartic potential, including PT-symmetrie one, are also worked out.     

Propane σ‐Complexes on PdO(101): Spectroscopic Evidence of the Selective Coordination and Activation of Primary CH Bonds

Achieving selective C? H bond cleavage is critical for developing catalytic processes that transform small alkanes to value‐added products. The present study clarifies the molecular‐level origin for an exceptionally strong preference for propane to dissociate on the crystalline PdO(101) surface via primary C? H bond cleavage. Using reflection absorption infrared spectroscopy (RAIRS) and density functional theory (DFT) calculations, we show that adsorbed propane σ‐complexes preferentially adopt geometries on PdO(101) in which only primary C? H bonds datively interact with the surface Pd atoms at low propane coverages and are thus activated under typical catalytic reaction conditions. We show that a propane molecule achieves maximum stability on PdO(101) by adopting a bidentate geometry in which a H? Pd dative bond forms at each CH₃ group. These results demonstrate that structural registry between the molecule and surface can strongly influence the selectivity of a metal oxide surface in activating alkane C? H bonds.     

Manganese(II) zero-field interaction in cambialistic and manganese superoxide dismutases and its relationship to the structure of the metal binding site

The Mn(II) high-magnetic-field electron paramagnetic resonance (HFEPR) spectra of five different superoxide dismutases (SODs) were measured at 190 and 285 GHz. The native E. coli manganese SOD was found to be distinct from the other SODs by virtue of its large zero-field E-value. The two wild-type cambialistic proteins from Porphyromonas gingivalis and Rhodobacter capsulatus were also distinct. However, the Gly155Thr mutant of the P. gingivalis SOD changed the Mn(II) spectrum so that it closely resembled the spectrum of manganese reconstituted E. coli iron SOD. This observation paralleled enzyme activity measurements that show that this mutation causes the loss of activity with manganese and enhanced activity with iron indicating a conversion from a cambialistic to an iron-specific protein. The Mn(II) magnetic parameters were determined by simultaneously fitting the multifrequency data. Simulations were carried out by numerically diagonalizing the spin Hamiltonian and explicitly calculating all possible transition probabilities. The relationship between the Mn(II) zero-field interaction and structure of the metal binding site is also discussed.     

Determination of the isomeric composition of an ionic mixture using collision cross-sections

A theory has been developed for the determination of the isomeric composition of an ionic mixture. The probability theory describing the collisionally activated decomposition (CAD) which was developed previously provided a general foundation for the present theory. Quantification was based on the cross-sections for the collisional production of daughter ions as observed in the mass-analysed ion kinetic energy Spectrometry (MIKES). Experimental details for the implementation of the theory have also been developed. The method has been applied to the case of C₂H₄O^+· generated from butane-l,3-diol, which is known to be a mixture of more than one isomeric structure. The results seem to be far superior to those based on previous methods, as evidenced by the excellent internal consistency.     

Resonance characteristics of localized plasmonic structures with periodic ZnO nano-patterns

Localized plasmonic structures with the periodic ZnO nano-patterns are demonstrated to increase the sensing characteristics of plasmonic sensor. The ZnO nano-patterns with 30 and 50 nm thicknesses are formed on the Au thin film of 50 nm, which have the periodic nano-patterns of 300 nm. Localized plasmonic structures are optimized using the three-dimensional finite-difference time-domain method as a function of incident angle for the width and thickness of the ZnO nano-structures. Localized plasmonic structures with the periodic ZnO nano-holes are fabricated using the double exposure technique by laser interference lithography. The measured resonance angles of 47.5° and 54° are obtained in the localized plasmonic structures with the periodic ZnO nano-patterns of 30 and 50 nm thicknesses, respectively.     

Experimental demonstration of 10 Gbit/s transmission with an optical backplane system using optical slots

A practical optical backplane system was prepared with transmitter-receiver processing boards and an optical backplane made from polymeric-waveguide-embedded optical printed-circuit boards. Optical slots were used as connection components between the transmitter-receiver processing boards and the backplane board to permit easy and repeatable insertion and extraction of the boards with micrometer precision. We report 10 Gbit/s data transmission between an optical backplane and the transmitter-receiver processing boards.     

Sensitivity of tyrosyl radical g-values to changes in protein structure: a high-field EPR study of mutants of ribonucleotide reductase.

The local electrostatic environment plays a critical role in determining the physicochemical properties of reactive radicals in proteins. High-field electron paramagnetic resonance (HF-EPR) spectroscopy has been used to determine the sensitivity of the tyrosyl radical g-values to local electrostatic environment. Site-specific mutants of ribonucleotide reductase from Escherichia coli were used to study the effect of introducing a charge group on the HF-EPR spectrum of the stable tyrosyl (Y122) radical. The changes affected by the mutations were small, but measurable. Mutation of isoleucine-74 to an arginine (I74R) or lysine (I74K) induced disorder in the hyperfine interactions. Similar effects were observed for the mutation of valine-136 to an arginine (V136R) or asparagine (V136N). For five or six mutants studied, the g(x)() component of the g-tensor was distributed. For the isoleucine-74 to lysine (I74K) and leucine-77 to phenylalanine (L77F) mutants, a shift of 1 x 10(-)(4) in g(x)() value was also detected. For the I74K mutant, it is shown that the shift is consistent with the introduction of a charged residue, but cannot be distinguished from changes in the electrostatic effect of the nearby diiron center. For the L77F mutant, the shift is induced by the diiron center. Using existing tyrosyl radical g-tensor measurements, we have developed a simple effective charge model that allows us to rationalize the effect of the local electrostatic environments in a number of proteins.