Thermal instability of monoalkyl esters of phthalic acid during their gas chromatographic separation

Моноалкиловые эфиры бензол-1,2-дикарбоновой (фталевой) кислоты являются основными продуктами метаболизма (частичного гидролиза) диалкилфталатов, широко применяющихся в качестве пластификаторов полимерных композиций. Проверка возможностей газохроматографического и хромато-масс-спектрометрического анализа простейших моноалкиловых (С₁-С₇) эфиров показала, что эти соединения термически нестабильны и разлагаются в хроматографической колонке, что может осложнять их обнаружение в различных образцах. Установлено, что основное направление деструкции моноалкилфталатов в газохроматографической колонке аналогично известному процессу их пиролиза с образованием соответствующих спиртов и фталевого ангидрида. По этой причине для разделения моноэфиров фталевой кислоты необходимо использовать максимально короткие колонки с тонкими пленками стандартных неполярных неподвижных фаз при минимальной скорости программирования температуры, что позволит снизить температуры удерживания таких аналитов и, следовательно, минимизировать их термическое разложение. Высказано предположение, что именно разложение с образованием фталевого ангидрида объясняет высокую токсичность (в том числе эндокринную) моноалкилфталатов для человека и животных.Monoalkyl esters of benzene-1,2-dicarboxylic (phthalic) acid are the main metabolites (products of the partial hydrolysis) of dialkyl phthalates widely used as ingredients of polymeric compositions. Testing the possibilities of GC and GC-MS analysis of the simplest monoalkyl (C₁-C₇) esters indicates these compounds are thermally unstable and decompose in a chromatographic column during separation that may complicate their determination. The principal way of monoalkyl phthalate decomposition is similar to the known process of their pyrolysis with formation of corresponding alkanols and phthalic anhydride. It is concluded that GC analysis of these monoesters can be provided using short WCOT columns with thin layers of non-polar stationary phases at the smooth temperature ramps. It allows to reduce retention temperature of such analytes and, hence, to minimize their thermal decomposition. It is proposed that just the possibility of phthalic anhydride formation in the result of decomposition explains us high toxicity (including endocrine disruptions) of monoalkyl phthalates for mammals

Features of the gas chromatographic analysis of aliphatic dicarboxylic acids

Изучение литературных данных свидетельствует, что результаты прямого газохроматографического анализа таких труднолетучих полярных соединений как алифатические дикарбоновые кислоты отличаются заметной невоспроизводимостью. Значительная часть опубликованных индексов удерживания этих соединений характеризуется существенным разбросом и представляется ошибочной. Подобная же невоспроизводимость присуща значениям и других их физико-химических свойств (температура плавления, растворимость в воде и т.д.). Выполнена экспериментальная проверка возможностей газохроматографического и хромато-масс-спектрометрического анализа простейших дикарбоновых кислот на стандартных неполярных полидиметилсилоксановых неподвижных фазах (BPX-1, RTX-5). Установлено, что некоторые соединения этого ряда (например, глутаровая кислота) определяются без разложения, для других характерно взаимодействие с растворителем (щавелевая), а в некоторых случаях единственными регистрируемыми компонентами являются продукты термической деструкции (лимонная). Так, при анализе раствора щавелевой кислоты в изопропиловом спирте зафиксировано образование двух сложных эфиров - моноизопропил- и диизопропилоксалатов.The literature data indicates that the results of gas chromatographic analysis of such low-volatile polar compounds as aliphatic dicarboxylic acids are characterized by high irreproducibility. Most of the previously published GC retention indices seem to be very spread out and appear to be erroneous. Similar irreproducibility is typical for some other physicochemical properties of these acids, namely melting temperatures, water solubility, etc. The experimental testing of the possibilities of gas chromatographic and/or GC-MS analysis of simplest dicarboxylic acids using standard non-polar polydimethylsiloxane stationary phases (BPX-1, RTX-5) has been fulfilled. It indicates that some compounds of this series (e.g., glutaric acid) are determined without decomposition, for others the interaction with solvent is typical (oxalic acid), and in some cases the single compounds observed are the products of thermal destruction (citric acid). Namely, the analysis of the solution of oxalic acid in isopropyl alcohol permits us to detect two esters - monoisopropyl and diisopropyl oxalates

Spectral Duality Between Heisenberg Chain and Gaudin Model

In our recent paper we described relationships between integrable systems inspired by the AGT conjecture. On the gauge theory side an integrable spin chain naturally emerges while on the conformal field theory side one obtains some special reduced Gaudin model. Two types of integrable systems were shown to be related by the spectral duality. In this paper we extend the spectral duality to the case of higher spin chains. It is proved that the N-site GL(k) Heisenberg chain is dual to the special reduced k+2-points gl(N) Gaudin model. Moreover, we construct an explicit Poisson map between the models at the classical level by performing the Dirac reduction procedure and applying the AHH duality transformation.Comment: 36 page

Spectral Duality in Integrable Systems from AGT Conjecture

We describe relationships between integrable systems with N degrees of freedom arising from the AGT conjecture. Namely, we prove the equivalence (spectral duality) between the N-cite Heisenberg spin chain and a reduced gl(N) Gaudin model both at classical and quantum level. The former one appears on the gauge theory side of the AGT relation in the Nekrasov-Shatashvili (and further the Seiberg-Witten) limit while the latter one is natural on the CFT side. At the classical level, the duality transformation relates the Seiberg-Witten differentials and spectral curves via a bispectral involution. The quantum duality extends this to the equivalence of the corresponding Baxter-Schrodinger equations (quantum spectral curves). This equivalence generalizes both the spectral self-duality between the 2x2 and NxN representations of the Toda chain and the famous AHH duality

Resonant Raman Scattering of ZnS, ZnO, and ZnS/ZnO Core/shell quantum dots

Resonant Raman scattering by optical phonon modes as well as their overtones was investigated in ZnS and ZnO quantum dots grown by the Langmuir–Blodgett technique. The in situ formation of ZnS/ZnO core/shell quantum dots was monitored by Raman spectroscopy during laser illumination

Deformed planar topological open string amplitudes on Seiberg-Witten curve

We study refined B-model via the beta ensemble of matrix models. Especially, for four dimensional N=2 SU(2) supersymmetric gauge theories with N_f=0,1 and 2 fundamental flavors, we discuss the correspondence between deformed disk amplitudes on each Seiberg-Witten curve and the Nekrasov-Shatashvili limit of the corresponding irregular one point block of a degenerate operator via the AGT correspondence. We also discuss the relation between deformed annulus amplitudes and the irregular two point block of the degenerate operator, and check a desired agreement for N_f=0 and 1 cases.Comment: 27 pages. v2: minor changes and references added. v3: minor corrections and one reference adde

S-duality as a beta-deformed Fourier transform

An attempt is made to formulate Gaiotto's S-duality relations in an explicit quantitative form. Formally the problem is that of evaluation of the Racah coefficients for the Virasoro algebra, and we approach it with the help of the matrix model representation of the AGT-related conformal blocks and Nekrasov functions. In the Seiberg-Witten limit, this S-duality reduces to the Legendre transformation. In the simplest case, its lifting to the level of Nekrasov functions is just the Fourier transform, while corrections are related to the beta-deformation. We calculate them with the help of the matrix model approach and observe that they vanish for beta=1. Explicit evaluation of the same corrections from the U_q(sl(2)) infinite-dimensional representation formulas due to B.Ponsot and J.Teshner remains an open problem.Comment: 21 page