Combined isolation and purification procedures prior to the high-performance liquid chromatographic-ion-trap tandem mass spectrometric determination of estrogens and their conjugates in river sediments

A fast and sensitive analytical procedure has been developed for the simultaneous separation and determination of alpha-estradiol, beta-estradiol, estriol, estrone and ethynylestradiol and their sulfate, glucuronide and acetate conjugates in river sediments. The procedure includes a microwave-assisted extraction (MAE) with aqueous methanol (25:75, v/v) at 100 degrees C in 10 min, a clean-up on Oasis WAX cartridge and a high-performance liquid chromatography-ion-trap tandem mass spectrometry (HPLC-IT-MS/MS) with electrospray ionization. The recovery for each compounds ranged from 83 to 107% and the repeatability represented as RSDs ranged from 4.9 to 9.6%. The limits of detection (LODs) were down to 1 ng g(-1). The analytical performance of the method was evaluated using determination of free and conjugated estrogens in river sediments.     

High-performance liquid chromatographic/ion-trap mass spectrometric speciation of aquatic mercury as its pyrrolidinedithiocarbamate complexes

Mercury-pyrrolidinedithiocarbamate complexes are first time used for speciation of aquatic mercury with high-performance liquid chromatographic/ion trap-mass spectrometric method utilizing atmospheric pressure chemical ionization (APCI). The separation of the four mercury species was achieved in less than 5 min with a linear gradient profile of aqueous methanol from 70 up to 100% (v/v) in 4th min, isocratic elution at 100% up to 5th min and followed by a negative gradient to 70% in 6th min. The best separation was achieved on a reverse phase Zorbax Eclipse XDB C18 column (50 mm × 2.1 mm i.d., 1.8 μm particle size). The on-column limits of detection (injection volume 1 μL) were 370 pg for methylmercury (MeHg⁺), 280 pg for ethylmercury (EtHg⁺), 250 pg for phenylmercury (PhHg⁺) and 90 pg for inorganic mercury (Hg²⁺) when the data were collected in selective ion monitoring (SIM) mode. A method of isolation and preconcentration of the mercury species using a “home-made” C18 solid phase extraction (SPE) microcolumns was developed to enhance sensitivity of the method. The preconcentration factor as much as 2500 was achieved with on-column complex formation of mercury-pyrrolidinedithiocarbamate. Methanol (100%) was chosen for elution of preconcentrated mercury species. The method was applied for the determination of mercury species in river water samples.     

External inversion,internal inversion,and reflection invariance

Having in mind that physical systems have different levels of structure we develop the concept of external, internal and total improper Lorentz transformation (space inversion and time reversal). A particle obtained from the ordinary one by the application of internal space inversion or time reversal is generally a different particle. From this point of view the intrinsic parity of a nuclear particle (elementary particle) is in fact the external intrinsic parity, if we take into account the internal structure of a particle. We show that non-conservation of the external parity does not necessarily imply noninvariance of nature under space inversion. The conventional theory of beta-decay can be corrected by including the internal degrees of freedom to become invariant under total space inversion, though not under the external one.     

Novel bicyclisation of unsaturated polyols in PdCl2-CuCl2-AcOH catalytic system

Novel type of Pd(II)-catalysed transformation of sugar-derived alkenitols furnishing 7-benzyloxy-2,5-dioxabicyclo[2.2.1]heptanes was discovered. The investigated bicyclisation displays an exceptional substrate selectivity towards xylo-configured unsaturated polyols. Moreover, a newly build stereogenic centre is formed in a diastereospecific cis-manner. The observed stereochemical preference was corroborated by modelling of pertinent transition states at the semiempirical level of theory (PM5). In addition, the single crystal X-ray analysis of an acylated analogue d-glycero-l-gulo-21 was done in order to establish the relative configuration of related bicyclic products.     

Single atom hot-spots at Au-Pd nanoalloys for electrocatalytic H2O2 production

A novel strategy to direct the oxygen reduction reaction to preferentially produce H(2)O(2) is formulated and evaluated. The approach combines the inertness of Au nanoparticles toward oxidation, with the improved O(2) sticking probability of isolated transition metal "guest" atoms embedded in the Au "host". DFT modeling was employed to screen for the best alloy candidates. Modeling indicates that isolated alloying atoms of Pd, Pt, or Rh placed within the Au surface should enhance the H(2)O(2) production relative to pure Au. Consequently, Au(1-x)Pd(x) nanoalloys with variable Pd content supported on Vulcan XC-72 were prepared to investigate the predicted selectivity toward H(2)O(2) production for Au alloyed with Pd. It is demonstrated that increasing the Pd concentration to 8% leads to an increase of the electrocatalytic H(2)O(2) production selectivity up to nearly 95%, when the nanoparticles are placed in an environment compatible with that of a proton exchange membrane. Further increase of Pd content leads to a drop in H(2)O(2) selectivity, to below 10% for x = 0.5. It is proposed that the enhancement in H(2)O(2) selectivity is caused by the presence of individual surface Pd atoms surrounded by gold, whereas surface ensembles of contiguous Pd atoms support H(2)O formation. The results are discussed in the context of exergonic electrocatalytic H(2)O(2) synthesis in Polymer Electrolyte Fuel Cells for the simultaneous cogeneration of chemicals and electricity, the latter a credit to production costs.     

Path and path deviation equations for <Emphasis Type="Italic">p</Emphasis>-branes

Path and path deviation equations for neutral, charged, spinning and spinning charged test particles, using a modified Bazanski Lagrangian, are derived. We extend this approach to strings and branes. We show how the Bazanski Lagrangian for charged point particles and charged branes arises à la Kaluza-Klein from the Bazanski Lagrangian in 5-dimensions.     

Relativisticp-branes without constraints and their relation to the wiggly extended objects

The invariant evolution parameter is often used in the formulation of a so-called unconstrained relativistic quantum theoryof a point particle. Such a theory is very elegant, and contains the usual Klein-Gordon or the Dirac particle as a special case. In the present paper we extend the unconstrained theory to describe a continuous set of point particles forming a string or, in general, a membrane of arbitrary dimension p.The action of this system is not invariant with respect to reparametrizations of the evolution parameter and therefore there is no constraints among the dynamical variables, and no need for ghosts in the quantized theory. Then we show that such an unconstrained membrane is equivalent to a wiggly membranewhich has variable tension on its (p+1)-dimensional worldsheet. The equations of motion admit the usual well-known Dirac-Nambu-Goto membranes as particular solutions.On leave from J. Stefan Institute, University of Ljubljana, 61111 Ljubljana, Slovenia.     

Comment on the analysis of angle-dependent X-ray magnetic circular dichroism in systems with reduced dimensionality

The magnetic dipole term T appearing in the X-ray magnetic circular dichroism (XMCD) spin sum rule can be eliminated from the analysis within the spin sum rule by angle-dependent XMCD spectroscopy if the effects of spin–orbit coupling are small so that T_x+T_y+T_z≈0. It is shown by the ab initio electron theory for the extreme case of a low-dimensional system, i.e., for a free-standing monatomic Co wire that this relation is strongly violated, indicating that the determination of T by the angle-dependent XMCD is possibly not very reliable for low-dimensional magnetic systems.