Revealing compounds unstable during gas chromatographic separation. Non-substituted hydrazones of carbonyl compounds

Evaluating the content of contemporary GC-MS databases (including the NIST database) allows revealing compounds not enough characterized both mass spectra, and GC retention indices (RI). Among relatively simple objects of this type there are the products of carbonyl compounds interaction with hydrazine – non-substituted hydrazones and azines. Revealing the reasons for the lack of reference information for these compounds indicates that non-substituted hydrazones are thermally unstable and converts into azines inside chromatographic column during separation. It is resulted in the appearance of specific profiles of chromatograms and leads to irreproducibility of relative peak areas of these compounds, strong variations of retention times and, hence, low reproducibility of their retention indices. Nevertheless, more then dozen of non-substituted hydrazones and the same number of corresponding azines were characterized first time by standard EI mass spectra and RI values on standard non-polar polydimethyl siloxane stationary phases. On the example of reaction mixtures of alkyl aryl ketones with hydrazine (under medium conversion of substrates into derivatives) the new effect in chromatography is revealed. The chromatograms of these samples contain the diffused zones of hydrazones with retention times less then retention times of such hydrazones from reaction mixtures. The explanation of this anomaly is the formation of volatile hydrazine during hydrazine decomposition, followed by its secondary interaction with initial carbonyl compound taking place in another part of chromatographic column.Контроль содержания современных баз хромато-масс-спектрометрических данных (в том числе базы NIST) позволяет выявлять соединения, недостаточно подробно охарактеризованные как масс-спектрами, так и газохроматографическими индексами удерживания (RI). Среди сравнительно простых соединений к ним относятся продукты взаимодействия карбонильных соединений с гидразином – незамещенные гидразоны и азины. Выяснение причин отсутствия подробной справочной информации для соединений этих классов показало, что незамещенные гидразоны термически нестабильны и превращаются в азины в хроматографической колонке в процессе их разделения, что проявляется в характерных профилях хроматограмм. Кроме того, это приводит к невоспроизводимости относительных площадей пиков гидразонов и азинов, заметным вариациям времен удерживания и, следовательно, невысокой воспроизводимости их индексов удерживания. Тем не менее, стандартными масс-спектрами с электронной ионизацией и значениями RI на стандартных неполярных полидиметилсилоксановых неподвижных фазах впервые охарактеризованы более десяти незамещенных гидразонов и столько же соответствующих им азинов. На примере реакционных смесей алкиларилкетонов с гидразином (при невысокой степени конверсии карбонильных соединений в производные) выявлен не наблюдавшийся ранее в хроматографии эффект. На хроматограммах регистрируются размытые зоны гидразонов в областях времен удерживания, меньших времен удерживания таких гидразонов, присутствующих в реакционных смесях. Установлено, что причиной такой аномалии является образование летучего гидразина в ходе деструкции гидразона и его последующее вторичное взаимодействие с исходным карбонильным соединением, но уже в другой области хроматографической колонки

Methodical Approach to the Selection of a Rational Variant of the Allocation of Financial Resources for the Foreign Patenting of the Results of Intellectual Activity

Subject. The subject of the research in this article are the results of intellectual activity, obtained during the implementation of research and development work under the state defense order. Purpose. The purpose of the research is to ensure the effective use of financial resources for the legal protection of the results of intellectual activity created within the framework of the state defense order abroad, in the interests of protection against unauthorized copying of domestic military products, increasing its competitiveness and export volumes. Methodology. The article uses the existing methodology for estimating the cost of licenses based on royalties, for the base of which the cost of a single sample of military products is accepted. Results. Within the framework of the article, an approach to choosing a rational variant of the allocation of financial resources for foreign patenting of the results of intellectual activity is proposed, which ensures the maximum revenue from the sale of licenses for granting the right to use the results of intellectual activity owned by the state and the production of weapons samples. Conclusions. The developed methodical approach has a practical focus, it also is consistent with domestic and international legislation in the field of intellectual property protection, it takes into consideration the organizational and economic aspects of the disposition of intellectual property rights created under the state defense order. The methodological provisions formulated in the article are aimed at increasing the level of legal protection of the results of intellectual activity contained in exported military products, intensifying innovation activity in the Russian Federation and increasing the flow of funds to the federal budget from the disposal of intellectual property owned by the state

Homogenization of the p-Laplacian with nonlinear boundary condition on critical size particles: identifying the strange term for the some non smooth and multivalued operators

We extend previous papers in the literature concerning the homogenization of Robin type boundary conditions for quasilinear equations, in the case of microscopic obstacles of critical size: here we consider nonlinear boundary conditions involving some maximal monotone graphs which may correspond to discontinuous or non-Lipschitz functions arising in some catalysis problems.The research of the first two authors was partially supported as members of the Research Group MOMAT (Ref. 910480) of the UCM. The research of J.I. Diaz was partially supported by the project ref. MTM 2014-57113 of the DGISPI (Spain). The research of D. Gómez-Castro was supported by a FPU Grant from the Ministerio de Educación, Cultura y Deporte (Spain)

Characterizing the strange term in critical size homogenization: Quasilinear equations with a general microscopic boundary condition

The aim of this paper is to consider the asymptotic behavior of boundary value problems in n-dimensional domains with periodically placed particles, with a general microscopic boundary condition on the particles and a p-Laplace diffusion operator on the interior, in the case in which the particles are of critical size. We consider the cases in which 1<p<n{1<p<n}, n≥3{n\geq 3}. In fact, in contrast to previous results in the literature, we formulate the microscopic boundary condition in terms of a Robin type condition, involving a general maximal monotone graph, which also includes the case of microscopic Dirichlet boundary conditions. In this way we unify the treatment of apparently different formulations, which before were considered separately. We characterize the so called “strange term” in the homogenized problem for the case in which the particles are balls of critical size. Moreover, by studying an application in Chemical Engineering, we show that the critically sized particles lead to a more effective homogeneous reaction than noncritically sized particles

Homogenization of the p-Laplacian with nonlinear boundary condition on critical size particles: Identifying the strange term for the some non smooth and multivalued operators

We extend previous papers in the literature concerning the homogenization of Robin type boundary conditions for quasilinear equations, in the case of microscopic obstacles of critical size: here we consider nonlinear boundary conditions involving some maximal monotone graphs which may correspond to discontinuous or non-Lipschitz functions arising in some catalysis problems