The heterometric microdetermination of mercury with mercaptobenzthiazole in the presence of an excess of foreign metals

1. A general method is presented for the determination of 1–2 mg mercuric mercury, in the absence of complexing agents, in 20 ml solution, with an error of 0–3 %. The solution may contain: Ca, Ba, Mg, Zn, Mn, Ni, Co or Cd as nitrate of sulphate in a concentration of 0.2M. The concentration of Pb should be <0.1M and that of Al, Cr or Fe ?0.05M. 2. A special method is presented for the determination of mercury (1–2 mg Hg in 20 ml) in the presence of large excesses of bismuth (?98%) by using ethylendiammetetraacetate. Error 0–3 %. 3. A method is presented for the determination of mercury in excesses of copper in an acetic acid solution which contains ethylendiaminetetraacetate. 4. A special method is presented which permits the determination of 1–2 mg mercury in 30 ml solution which contains large excesses of copper (up to 98% or more). The titration is carried out in an alkaline solution of trisodiumcitrate. The titration proceeds rapidly. Error 0–2%.     

Absolute characterization of laser-induced breakdown spectroscopy detection systems

A quantitative comparison of the performance of four different laser-induced breakdown spectroscopy detection systems is presented. The systems studied are an intensified photodiode array coupled with a Czerny–Turner spectrometer, an intensified CCD coupled with a Czerny–Turner spectrometer, an intensified CCD coupled to an Echelle spectrometer, and a prototype multichannel compact CCD spectrometer system. A simple theory of LIBS detection systems is introduced, and used to define noise-equivalent spectral radiance and noise-equivalent integrated spectral radiance for spectral detectors. A detailed characterization of cathode noise sources in the intensified systems is presented.     

Analysis of Spontaneous Electrochemical Oscillations by the Wavelet Transformation Method

A new way of analyzing current oscillations that accompany anodic metal dissolution is presented. A wavelet transformation is used for separation and spectral analysis of singular courses—elementary components of electrochemical oscillation recordings. A method of obtaining oscillation energy distribution analogous to the spectral power density function is presented. It is shown that the chaotic component (Shil'nikov chaos) can be separated from the deterministic component of the described process.     

Preliminary study of mechanism of action of SN38 derivatives. Physicochemical data,evidence of interaction and alkylation of DNA octamer d(GCGATCGC)2

The synthesis of water‐soluble SN38 derivatives is presented, and their stability in solutions used during drug development studies has been investigated. A preliminary study of mechanism of action of 9‐aminomethyl SN38 is presented. Using NMR techniques, the interaction of the oligomer d(GCGATCGC)₂ is studied, showing that the terminal GC base pairs are the main site of interaction. Using pulsed field gradient spin echo and mass spectroscopy, evidence of a spontaneous alkylation reaction of the DNA oligomer with SN38 derivatives is presented. A proposed mechanism of reaction is suggested. Copyright © 2016 John Wiley & Sons, Ltd.     

Configuration interaction by the method of bonded functions,some preliminary calculations

A resumé of Boys' approach to configuration interaction calculations is presented, and a program suitable to perform such calculations is described in some detail. The results of a preliminary calculation on water, together with some timings are presented.     

Accuracy in the Determination of Recovery in HPLC

Abstract

A method for the determination of the recovery in RP-HPLC using fluorescence and UV-detection is presented and compared with radioisotope experiments. A sensitive and specific detection is necessary in order to obtain accurate results.     

On the use of the mean squared error as a proficiency index

The mean squared error is presented as a convenient parameter to be used in assessing laboratories participating in proficiency tests. Its main advantages and disadvantages are presented and compared with the z score and the normalized error. A proficiency index is proposed as the ratio of an estimate of the mean squared error over a reference uncertainty.     

A spectral and polarographic study of the acid--base and complexing behaviour of bromazepam.

A method for the microdetermination of periodate in the presence of iodate is presented. It is based on reduction of periodate to iodate by leucothionine generated in situ by photochemical reaction between EDTA and blue thionine. Biamperometric curves are used for evaluation, representing reduction time for the periodate versus the current generated in the oxidation of the T_red in excess after the end-point. A polarographic study of the process is presented. An applied potential of 100 mV is suitable for the biamperometric measurements with Pt—Pt electrodes. The method is applicable for 0.4–45 ppm periodate. Iodate does not interfere up to IO^-₃ : IO^-₄ ratios of 100:1.     

Enantioselective Michael reactions. Stereoselective addition of enolates of phenmenthol esters to crotonates

A method is described for enantioselective synthesis which is based on the stereoselective Michael addition of phenmenthol enolates such as 5 to $\text{E}$-crotonate esters. A stereomechanistic rationale is presented.     

Towards a new class of ferroelectric liquid crystal molecules for nonlinear optical applications

The synthesis of a new molecule specifically designed to exhibit both ferroelectric and nonlinear optical properties is presented. This molecule possesses an optically active phenyl sulphinic group, which introduces a dipole moment directly linked to the chromophore group, with a nitro group in the meta -position. The rest of the molecule comprises a tolane and a benzoate group. Such a structure results in an enantiotropic smectic C*-smectic A phase sequence in its polymorphism. A first measurement of the spontaneous polarization shows a high value. The polymorphism of the racemic homologous molecule possessing the nitro group in the ortho-position is also presented, and also shows the smectic C-smectic A phase sequence.     

Radiochemical analysis of radionuclides difficult to measure for waste characterization in decommissioning of nuclear facilities

Some radiochemical analytical methods for the determination of important beta-radionuclides for decommissioning are presented. An analytical method is briefly described, which is used for the determination of ³H and ¹⁴C in steel and aluminum by combustion using commercial oxidizer. A leaching method was developed for the determination of ³H in the contaminated silica gel. A simple distillation method is presented for the determination of ¹⁴C in heavy water and wastewater sample. A method developed for the simultaneous determination of ³H, ¹⁴C, ³⁶Cl, ⁵⁵Fe, ⁶³Ni, ⁴¹Ca and ¹²⁹I in concrete, graphite, aluminium, lead, and steel is presented. The developed methods have been successfully used to analyse various materials for characterization of the waste during the decommissioning of Danish nuclear reactors.     

Evaluation of photodynamic therapy (PDT) procedures using microfluidic system

A hybrid PDMS/glass microfluidic system for evaluation of the efficiency of photodynamic therapy is presented. 5-aminolevulinic acid (ALA) was used as a precursor of photosensitizer. The geometry of the microdevice presented in this paper enables to test different concentrations of the photosensitizer in a single assay. The viability of the A549 cells was determined 24 h after PDT procedure (irradiation with light which induced a photosensitizer accumulated in carcinoma cells, λ = 625 nm). The presented results confirmed the possibility to perform the photodynamic therapy process in vitro in microscale and the possibility to assess its effectiveness. Moreover, because two identical microstructures on a single chip were performed, the microchip can be used for examination simultaneously various cell lines (carcinoma and normal) or various photosensitizers.     

Diastereoselective synthesis of substituted prolines via 5-endo-trig cyclisations of aza-[2,3]-Wittig sigmatropic rearrangement products

The major diastereoisomers of aza-[2,3]-Wittig sigmatropic rearrangement products from α-amino acid derivatives are susceptible to a rare nucleophilic 5-endo-trig cyclisations of an amine onto a non-conjugated vinylsilane in high yield and complete diastereocontrol. Five examples are presented, with cyclisation yields between 35 and 87%. A rationale for the stereoselectivity of the cyclisation is forwarded based upon the steric control factors that have been documented for the aza-[2,3]-Wittig sigmatropic rearrangement. A discussion of the mechanism in the context of the reaction conditions is also presented. Oxidation of the silyl group to a hydroxyl group and complete removal were demonstrated for synthetic utility.     

Ab initio molecular calculations with pseudopotentials: calculations of double-zeta quality on BeH2, BH3, CH4, and C2H6

A new form of pseudopotential for applicaiton in ab initio molecular calculations is described. A method for determining pseudopotential parameters is suggested and pseudopotential parameters of double-zeta quality are presented for the first row atoms of the periodic table. The pseudopotential is especially well suited for incorporation into the floating-spherical-Gaussian-orbital (FSGO ) method, though it is not restricted to any particular method. Applications of the resulting pseudo-FSGO method to BeH₂, BH₃, CH₄, and C₂H₆ are presented.     

Validation of a new method for spectrophotometric determination of polyethylenimine

A new method of determination of polyethylenimine (PEI) is presented. The method is fast, reliable, and easy to perform. It is based on a creation of a complex between Cu²⁺ and PEI and its absorption in UV–VIS spectrum. The complex has a distinct absorption peak in UV part of electromagnetic spectrum and the measurement is optimal at 285 nm. A method is thoroughly analyzed in various concentrations of both PEI and Cu²⁺, temperatures, times of creation of a complex, ionic strengths, background electrolytes types, and pH values. Analytical parameters of the presented method such as linearity, sensitivity, limit of detection (LOD), limit of quantification (LOQ), repeatability, and intermediate precision were also determined.     

Determination of the heterogeneity factor in the Frumkin adsorption isotherm from the width of capacity peaks

An appraisal of the various known surface preparations for the single crystal TiO₂ as used in solar photoelectrolysis cells is presented. The results presented are derived from photocurrent-voltage characteristics and interpretations of the surface behaviour are made on the basis of these measurements and their deviations from theoretically “ideal” behaviour. A novel preparation procedure is also introduced, producing results that represent the closest approach to the theoretically ideal surface known to date.     

Effects of sample matrix on detection limits in analytical inductively coupled plasma-Fourier transform spectrometry

The feasibility of making analytical atomic spectrometry measurements by inductively coupled plasma-Fourier transform spectrometry (ICP-FTS) is demonstrated. Analytical working curves and detection limits are presented for Al, Ni, Fe and Ca. The effects of sample matrix composition on detection limits for analytical ICP-FTS are investigated. It is shown that a multiplex disadvantage may occur in the case of a spectral bandpass encompassing stroog emission lines of a matrix element. A “worse case” example of this problem is presented. Possible approaches to overcoming the multiplex disadvantage in analytical ICP-FTS and some ideal criteria for ICP-FTS instrumentation are presented.     

Synthesis of carbohydrate‐segmented polydimethylsiloxanes by hydrosilylation

Carbohydrate‐modified polysiloxanes have been presented several times within the last decade. In this work, a new route to carbohydrate‐segmented polysiloxanes is presented. A series of allyl‐group‐containing bifunctional carbohydrate derivatives was synthesized and reacted with hydrodimethylsilyl‐terminated polysiloxane in hydrosilylation reactions with Speier's catalyst. The carbohydrate monomers and the resulting materials were fully characterized with ¹H and ¹³C NMR spectroscopy. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3814–3822, 2005     

Graphical unitary group approach to arbitrary spin representations

A graph theoretic approach to the representation of N particle systems involving arbitrary single-particle spin is presented. The method is a generalization of the Distinct Row Table (DRT ) technique employed by Shavitt in developing the graphical unitary group approach (GUGA ) to electronic spin-orbitals. A detailed analysis of the DRT and GUGA representations is presented based on several theoretical considerations and computer-tested implementations. The use of the representation to establish rules concerning the evaluation of the matrix elements of the group generators is also discussed.     

Temperature dependence of the quasiclassical reactivity for vibrationally excited hydrogen molecules colliding with hydrogen atoms

A discussion of reactants vibrational energy and temperature dependence of reactive rate constants for the hydrogen atom hydrogen molecule reaction is presented for a matrix of values calculated at 0 < v <10 and temperatures in the range from 300 K to 4000 K. A parametrization ofthe results is attempted. A comparison with rate constant values obtained from an approximate quantum treatment is also reported.