Theorems of Large Deviations in the Approximation by the Compound Poisson Distribution

The paper is devoted to the research of large deviation probabilities in the approximation by compound Poisson law.     

Effect of protonation exothermicity on the chemical ionization mass spectra of some alkylbenzenes

The H₂, N₂/H₂, CO₂/H₂, N₂O/H₂, CO/H₂ and CH₄ chemical ionization mass spectra of thirteen C₈ to C₁₁ alkylbenzenes are reported. Characteristic hydride and alkide ion abstraction reactions are observed with all reagent gases. The major fragmentation reactions of [MH]⁺ are olefin elimination to form a protonated arene and arene elimination to form an alkyl ion. From the effect of structure and protonation exothermicity it is concluded that rearrangement of primary alkyl groups to the more stable secondary or tertiary structure occurs prior to alkyl ion formation. A detailed fragmentation mechanism for protonated arenes is proposed. The ‘effective’ proton affinity of the methane-derived reagent system is estimated to be ～556 kJ mol^?1.     

Development of optimised synthesis of 4-amino-N-(4-carbamoylphenyl)benzamide for industrial application

An efficient two-step synthetic route for preparation of the important Pigment Yellow 181 intermediate 4-amino-N-(4-carbamoylphenyl)benzamide is described. The synthetic pathway reflects requirements that are important for industrial applications. Optimisation of the reaction steps was performed to improve yields and procedures. The overall yield was higher than 78 %.     

House-of-security approach to measurement in analytical chemistry: quantification of human error using expert judgments

A new technique for quantification of human errors in chemical analysis using expert judgments is described. This technique is based on the house-of-security approach developed recently in the field of safety and security for prevention of terrorist and criminal attacks against an organization. The following relative quantification parameters (expressed in %) are proposed in the technique: (a) likelihood score of human error in a chemical analytical measurement/testing method, (b) severity score of human error for reliability of the test results, (c) importance score of a component of a laboratory quality system, and (d) effectiveness score of the quality system as a whole in preventing/blocking human error. As an example, 34 scenarios of human error in pH measurement of groundwater are discussed and quantified.     

Monitoring of the Proton Electrochemical Gradient in Reconstituted Vesicles: Quantitative Measurements of Both Transmembrane Potential and Intravesicular pH by Ratiometric Fluorescent Probes

Proteoliposomes carrying reconstituted yeast plasma membrane H⁺-ATPase in their lipid membrane or plasma membrane vesicles are model systems convenient for studying basic electrochemical processes involved in formation of the proton electrochemical gradient (Δμ_H ⁺) across the microbial or plant cell membrane. Δψ- and pH-sensitive fluorescent probes were used to monitor the gradients formed between inner and outer volume of the reconstituted vesicles. The Δψ-sensitive fluorescent ratiometric probe oxonol VI is suitable for quantitative measurements of inside-positive Δψ generated by the reconstituted H⁺-ATPase. Its Δψ response can be calibrated by the K⁺/valinomycin method and ratiometric mode of fluorescence measurements reduces undesirable artefacts. In situ pH-sensitive fluorescent probe pyranine was used for quantitative measurements of pH inside the proteoliposomes. Calibration of pH-sensitive fluorescence response of pyranine entrapped inside proteoliposomes was performed with several ionophores combined in order to deplete the gradients passively formed across the membrane. Presented model system offers a suitable tool for simultaneous monitoring of both components of the proton electrochemical gradient, Δψ and ΔpH. This approach should help in further understanding how their formation is interconnected on biomembranes and even how transport of other ions is combined to it.     

Quantification of measurement uncertainty in the sequential determination of <Superscript>210</Superscript>Pb and <Superscript>210</Superscript>Po by liquid scintillation counting and alpha-particle spectrometry

Methodologies for the quantification of measurement uncertainties associated with the determination of ²¹⁰Pb- and ²¹⁰Po-specific activities by liquid scintillation counting (LSC) and alpha-particle spectrometry are presented, and are demonstrated using the soil reference material IAEA-326. Major contributors to the combined uncertainty associated with the measurement result of ²¹⁰Pb were the uncertainties of net count rates in the ²¹⁰Pb energy region of the sample spectrum and in the ²¹⁰Bi energy region of the blank spectrum. The predominant sources of uncertainty in the measurement of ²¹⁰Po were the uncertainties of net count rates in the regions of interest of ²⁰⁹Po and ²¹⁰Po. The relative standard uncertainty of ²¹⁰Po exponentially increases with the time interval between the sampling date and the separation date of Po, and this effect is strongly dependent on the ²¹⁰Po/²¹⁰Pb activity ratio. When the specific activity of ²¹⁰Pb is much higher than that of ²¹⁰Po in the sample, the relative standard uncertainty of the ²¹⁰Po determination increases significantly within a short time interval between the sampling date (or reference date) and the separation date of Po in samples.     

Generating sublocales by subsets and relations: a tangle of adjunctions

Generalizing the obvious representation of a subspace \({Y \subseteq X}\) as a sublocale in Ω(X) by the congruence \({\{(U, V ) | U\cap Y = V \cap Y\}}\), one obtains the congruence \({\{(a, b) |\mathfrak{o}(a) \cap S = \mathfrak{o}(b) \cap S\}}\), first with sublocales S of a frame L, which (as it is well known) produces back the sublocale S itself, and then with general subsets \({S\subseteq L}\). The relation of such S with the sublocale produced is studied (the result is not always the sublocale generated by S). Further, we discuss in general the associated adjunctions, in particular that between relations on L and subsets of L and view the aforementioned phenomena in this perspective.     

Few associative triples,isotopisms and groups

Let Q be a quasigroup. For \(\alpha ,\beta \in S_Q\) let \(Q_{\alpha ,\beta }\) be the principal isotope \(x*y = \alpha (x)\beta (y)\). Put \(\mathbf a(Q)= |\{(x,y,z)\in Q^3;\) \(x(yz)) = (xy)z\}|\) and assume that \(|Q|=n\). Then \(\sum _{\alpha ,\beta }\mathbf a(Q_{\alpha ,\beta })/(n!)^2 = n^2(1+(n-1)^{-1})\), and for every \(\alpha \in S_Q\) there is \(\sum _\beta \mathbf a(Q_{\alpha ,\beta })/n! = n(n-1)^{-1}\sum _x(f_x^2-2f_x+n)\ge n^2\), where \(f_x=|\{y\in Q;\) \( y = \alpha (y)x\}|\). If G is a group and \(\alpha \) is an orthomorphism, then \(\mathbf a(G_{\alpha ,\beta })=n^2\) for every \(\beta \in S_Q\). A detailed case study of \(\mathbf a(G_{\alpha ,\beta })\) is made for the situation when \(G = \mathbb Z_{2d}\), and both \(\alpha \) and \(\beta \) are “natural” near-orthomorphisms. Asymptotically, \(\mathbf a(G_{\alpha ,\beta })>3n\) if G is an abelian group of order n. Computational results: \(\mathbf a(7) = 17\) and \(\mathbf a(8) \le 21\), where \(\mathbf a(n) = \min \{\mathbf a(Q);\) \( |Q|=n\}\). There are also determined minimum values for \(\mathbf a(G_{\alpha ,\beta })\), G a group of order \(\le 8\).     

Novel synthetic approach to alfaprostol key intermediates via Stille coupling with an alkyne

Novel intermediates based on the Corey skeleton for preparation of the ω-chain of non-halogenated unnatural prostaglandin analogues containing a triple bond at position 13–14 (PG numbering) were synthesized. The utilization of a novel synthetic approach towards a new tin intermediate, and subsequent Stille coupling opens up new possibilities for preparing these important pharmaceutical intermediates.