NITRILIUM DERIVATES OF NIDO-CARBORANE IN SYNTHESIS OF TRANSITIONAL METAL COMPLEXES

This work was supported by Russian Science Foundation, project № 21-73-10199

ПУТИ ПОВЫШЕНИЯ СПЕЦИФИЧНОСТИ РЕАКЦИИ ЛАТЕКСНОЙ АГГЛЮТИНАЦИИ

The article describes research on the development of new diagnostic test systems operating on the basis of latex agglutination reaction, in which polymer microspheres are used as bioligand carriers instead of erythrocytes. Polymeric microspheres to be used as bioligand carriers must satisfy the following requirements: narrow size distribution, diameter of 5 microns. Besides, they must be characterized by aggregative stability in water and buffer solutions and be contained functional groups in the surface layer for linking with the functional groups of the protein. They are crosslinked particles obtained by copolymerization of styrene and divinylbenzene on polystyrene seed particles 1.5 microns in diameter with a narrow size distribution followed by modification by chloromethylation and amination by ethylenediamine. To increase the hydrophilicity of the surface of the polymer microspheres and to reduce nonspecific adsorption of proteins dextran was immobilized on the surface of the particles by covalent binding with amino groups of particles using Maillard reaction. It was found that diagnostic test systems, where modified dextran particles were used as carriers of the bioligand (Vi-antigen), are characterized by insufficient specificity and require additional modification of the surface of the polymer microspheres to eliminate its non-specific interaction with the surface of the polymer plate used for the latex agglutination reaction. A nonionic surfactant (Tween 80) proposed for the surface modification and used in a certain concentration provides the best reaction specificity.Статья посвящена описанию и обсуждению исследований по созданию новых диагностических тест-систем, работающих на основе реакции латексной агглютинации. Диагностические тест-системы, где в качестве носителя биолиганда (Vi-антигена) использовались модифицированные декстраном полимерные микросферы, характеризовались недостаточной специфичностью и нуждались в дополнительном модифицировании поверхности микросфер для исключения ее неспецифического взаимодействия с поверхностью полимерных планшет, в которых проводится реакция латексной агглютинации. Показано, что модифицирование поверхности полимерных частиц неионным ПАВ (Твин-80), взятым в определенной концентрации, обеспечивает повышение специфичности реакции

СИНТЕЗ АМИНОСОДЕРЖАЩИХ ПОЛИМЕРНЫХ МИКРОСФЕР ЗАТРАВОЧНОЙ СОПОЛИМЕРИЗАЦИЕЙ ДЛЯ ПРИМЕНЕНИЯ В БИОТЕХНОЛОГИИ

This paper presents the results of studies of seed copolymerization of glycidyl methacrylate with ethylene glycol poly(glycidyl methacrylate) on seed particles in order to obtain partially crosslinked polymer microspheres with a diameter of about 3.5 microns for use in immunochemical reactions, as carriers of bioligands. The physico-chemical properties of polymeric microspheres obtained under different conditions were studied by the following methods: the diameters of the particles - by electron scanning and light microscopy; the wetting angle - bу the method of "lying droplets"; the sedimentation velocity - by the macromethod in a capillary tube by the movement of the (polymer slurry)/water phase boundary (buffer solution); the zeta-potential - by dynamic light scattering. Having studied the physical-chemical properties of all polymer slurries we concluded that the optimal particles to create on the basis of their diagnostic test systems with high sensitivity working on the principle of latex agglutination reaction are poly(glycidyl methacrylate) particles with equal percentage of glycidyl methacrylate and ethylene glycol dimethacrylate aminated with hexamethylendiamine in the environment of n-propanol, because they have a sufficient number of amino groups and do not lose their sedimentation properties after all stages of the synthesis.В данной работе представлены результаты по изучению затравочной сополимеризации глицидилметакрилата с этиленгликольдиметакрилатом на затравочных полиглицидилметакрилатных частицах c целью получения частично сшитых полимерных микросфер с диаметром порядка 3.5 мкм для их использования в иммунохимических реакциях в качестве носителей биолигандов. Физико-химические свойства полимерных микросфер, полученных в разных условиях, были изучены следующими методами: диаметры частиц - методами электронной сканирующей и световой микроскопии, краевой угол смачивания - методом «лежащей капли», скорость седиментации - макрометодом в капилляре по движению границы раздела фаз полимерная суспензия/вода (буферный раствор), дзета-потенциал - методом динамического светорассеяния. Изучив физико-химические свойства всех полимерных суспензий, был сделан вывод, что оптимальными частицами для создания на их основе диагностической тест-системы с высокой чувствительностью, работающей по принципу реакции латексной агглютинации, являются полиглицидилметакрилатные частицы с равным процентным содержанием глицидилметакрилата и этиленгликольдиметакрилата, аминированные гексаметилендиамином в среде н-пропанола, так как они обладают достаточным количеством аминогрупп, не теряют седиментационных свойств после всех стадий синтеза

Crystal Structure of 9-Dibenzylsulfide-7,8-dicarba-nido-undecaborane 9-Bn2S-7,8-C2B9H11

The crystal structure of 9-dibenzylsulfide-7,8-dicarba-nido-undecaborane 9-Bn2S-7,8-C2B9H11 was determined by a single-crystal X-ray diffraction. One of the benzyl groups is located above the open face of the carborane cage with a short H···H distance (2.29 and 2.71 Å for two symmetrically independent molecules) between the BHB-bridging hydrogen atom of the carborane fragment and the ortho-CH group of the aromatic ring. Topological analysis has revealed the existence of a critical bond point with a calculated energy of −0.8 kcal/mol in accordance with an X-ray diffraction molecular geometry. The crystal packing analysis revealed that this benzyl group is also involved in π-stacking interactions, while another benzyl group participates in numerous weak H···π, H···H and van der Waals interactions

Synthesis of Boronated Amidines by Addition of Amines to Nitrilium Derivative of Cobalt Bis(Dicarbollide)

A series of novel cobalt bis(dicarbollide) based amidines were synthesized by the nucleophilic addition of primary and secondary amines to highly activated B-N+≡C–R triple bond of the propionitrilium derivative [8-EtC≡N-3,3′-Co(1,2-C2B9H10)(1′,2′-C2B9H11)]. The reactions with primary amines result in the formation of mixtures of E and Z isomers of amidines, whereas the reactions with secondary amines lead selectively to the E-isomers. The crystal molecular structures of E-[8-EtC(NMe2)=HN-3,3′-Co(1,2-C2B9H10)(1′,2′-C2B9H11)], E-[8-EtC(NEt2)=HN-3,3′-Co(1,2- C2B9H10)(1′,2′-C2B9H11)] and E-[8-EtC(NC5H10)=HN-3,3′-Co(1,2-C2B9H10)(1′,2′-C2B9H11)] were determined by single crystal X-ray diffraction

Silver and Copper Complexes with closo-Polyhedral Borane, Carborane and Metallacarborane Anions: Synthesis and X-ray Structure

Synthesis and structure of silver and copper salts and complexes with polyhedral boron hydride anions, including closo-decaborate [B10H10]2−, closo-dodecaborate [B12H12]2−, 1-carba-closo- decaborate [1-CB9H10]−, carba-closo-dodecaborate [CB11H12]−, and cobalt bis(dicarbollide) [3,3′-Co(1,2-C2B9H11)2]− anions and their derivatives, are reviewed. The complexes demonstrate a wide variety of structural types, relating to both the metal coordination environment and coordination modes of boron hydride anions. The latter can range from strong coordination via the polyhedron triangular face including formation of 3c-2e MHB bonds in the case of the [B10H10]2− dianion, the structure of which contains two four-coordinated boron atoms, to very weak M…H interactions with the hydride atoms in the case of bulky [3,3′-Co(1,2-C2B9H11)2]− monoanion

Coordination Ability of 10-EtC(NHPr)=HN-7,8-C2B9H11 in the Reactions with Nickel(II) Phosphine Complexes

The complexation reactions of nido-carboranyl amidine 10-PrNHC(Et)=HN-7,8-C2B9H11 with different nickel(II) phosphine complexes such as [(PR2R’)2NiCl2] (R = R’ = Ph, Bu; R = Me, R’ = Ph) were investigated. As a result, a series of novel half-sandwich nickel(II) π,σ-complexes [3-R’R2P-3-(8-PrN=C(Et)NH)-closo-3,1,2-NiC2B9H10] with the coordination of the carborane and amidine components was prepared. The acidification of obtained complexes with HCl led to the breaking of the Ni-N bond with formation of nickel(II) π-complexes [3-Cl-3-R’R2P-8-PrNH=C(Et)NH-closo-3,1,2-NiC2B9H10]. The crystal molecular structure of [3-Ph3P-3-(8-PrN=C(Et)NH)-closo-3,1,2-NiC2B9H10] was determined by single crystal X-ray diffraction