Ternary Rhenium(I) Complexes: from Fluorescent Reporters to Interesting Scaffolds for Dual-Imaging Heterobimetallic Probes

Five ternary tricarbonylrhenium(I) complexes based on a pyridinetriazole moiety, so called pyta, were synthesized and spectroscopically characterized. The photophysical properties of these cationic complexes of general formula, [Re(CO)3(pyta-COOMe)L] (L = substituted pyridine derivatives) have been investigated, as well. Three of them are fluorescent and could be considered as interesting scaffolds for the preparation of dual-imaging heterobimetallic species

Різнолігандні комплекси ренію(i): від флуоресцентних міток до гетеробіметалічних зон- дів з цікавою топологією для подвійної візуалізації

In this paper, five new ternary tricarbonylrhenium(I) complexes based on a pyridinetriazole moiety, the so-called pyta, have been investigated. These cationic complexes of the general formula [Re(CO)3(pyta-COOMe)L] (L = substituted pyridine derivatives) combine a carboxylate functionalization, for further biomolecule conjugation, with a metal chelating site – a pyta-based tricarbonylrhenium moiety – which can act as a fluorescent reporter. The complexes have been prepared using a two-steps pathway involved the activation of [Re(CO)3Cl(bipy)] with triflate silver salts in the presence of acetonitrile followed by the thermally activated substitution of the acetonitrile adduct by commercially available substituted pyridine derivatives. They have been prepared from modest to good yields, fully characterized by means of NMR, IR and mass spectrometry, and their photophysical properties have been investigated. Upon excitation into the MLCT band of each complex (absorption band at ca. 300 nm), three of them exhibit a bright green luminescence centered at c.a. 494 nm, with a quantum yield of 0.60% in acetonitrile. These interesting photophysical features make them potential fluorescent cellular imaging agents. Moreover, thank to their ancillary ligand, they could be also considered as interesting scaffolds for the preparation of dual-imaging heterobimetallic species.В данной работе представлены результаты исследований пяти новых разнолигандных трис-карбонильных комплексов рения(I) на основе пиридинтриазольных производных, так называемых pyta. Такие катионные комплексы общей формулы [Re(CO)3(pyta-COOMe)L] (L = производные пиридина) сочетают в себе карбоксилатную функциональную группу для дальнейшего биомолекулярного связывания с хелатированным металлсодержащим фрагментом – на основе pyta-трискарбонильных комплексных частиц, которые могут выступать в качестве флуоресцентного центра. Комплексы были получены двухстадийной реакцией, основанной на активации [Re(CO)3Cl(bipy)] трифлатом серебра в присутствии ацетонитрила с дальнейшим взаимодействием термически активированного ацетонитрильного аддукта с коммерчески доступными замещенными пиридинпроизводными. Координационные соединения были получены с разными выходами, исследованы методами ЯМР-, ИК- и масс-спектроскопии и изучены их фотофизические свойства. При использовании длины волны возбуждения, соответствующей центру полосы переноса заряда металл-лиганд (MLCT) для каждого комплекса (полоса поглощения ~ 300 нм), три из них проявляют ярко-зеленую люминесценцию в ацетонитриле с центром ~ 494 нм и квантовым выходом 0,60%. Такие фотофизические особенности делают их потенциальными флуоресцентными биовизуализирующими агентами. Кроме того, благодаря дополнительным лигандам они могут быть использованы как основа для получения гетеробиметаллических частиц для двойственной визуализации.В даній публікації представлені результати досліджень п’яти нових різнолігандних трис-карбонільних комплексів ренію(I) на основі піридинтриазольних похідних, так званих pyta. Такі катіонні комплекси загальної формули [Re(CO)3(pyta-COOMe)L] (L = похідні піридину) поєднують карбоксилатну функціональну групу, яка може бути використана для подальшого біомолекулярного зв’язування з хелатованим металовмісним фрагментом на основі pyta-трис-карбонільних комплексних часточок, які можуть виступати в якості флуоресцентного центру. Комплекси були отримані двостадійною реакцією, заснованою на активації [Re(CO)3Cl(bipy)] трифлатом срібла в присутності ацетонітрилу з подальшою взаємодією термічно активованого ацетонітрильного аддукту з комерційно доступними заміщеними піридинпохідними. Координаційні сполуки були отримані з різними виходами, охарактеризовані методами ЯМР-, ІЧ- та мас-спектроскопії і досліджені їх фотофізичні властивості. При використанні довжини хвилі збудження, яка відповідає центру смуги переносу заряду метал-ліганд (MLCT) для кожного комплексу (смуга поглинання ~300 нм), три з них виявляють яскраво-червону люмінесценцію в ацетонітрилі з центром ~494 нм та квантовим виходом 0,60%. Такі фотофізичні особливості роблять їх потенційними флуоресцентними біовізуалізуючими агентами. До того ж, завдяки додатковим лігандам вони можуть бути використані як основа для створення гетеробіметалічних часточок для подвійної візуалізації

On the scientific status of quantum psychology

Introduction. The present paper analyses the origination of the quantum psychology concept, its main proposition and features, which correspond to the status of marginal science (parapsychology). Particular attention is paid to psychological characteristics of the individuals who study parapsychological phenomena. Theoretical Basis. In the second half of the 20th century postmodern changes have contributed to the decrease in the axiological status of science. Furthermore, Western scientific rationality has drawn near to Oriental mysticism. Discoveries in quantum mechanics have determined drastic changes in the view of the physical world. These discoveries were in contradiction with classical physics and common sense. Changes in the world view have been combined with postmodern transformations of science. The role of implicit knowledge, interpretative thinking, and the fundamental nonremovability of subjectivity in results of scientific knowledge has increased significantly. The application of the quantum corpuscular-wave laws to brain and psychic activity was a theoretical basis for the concept of quantum psychology. The direct use (instead of metaphorical application) of quantum effects in psychology is groundless from the point of view of academic physics and psychology. According to psychological characteristics quantum psychology is a parapsychological field of psychic phenomena, as it recognizes transmission of information without known sense organs, as well as mental influence on physical objects. From a philosophical point of view the quantum concept of consciousness is a kind of contemporary physiological (physical) reductionism, which was defined as “vulgar materialism” in the past. The study (a) analyses the reasons for a person to be interested in the paranormal, which results in the popularity of ideas of quantum psychology; (b) presents a classification of the psychological characteristics and motivation of the individuals interested in psychic phenomena; (c) highlights various negative consequences of a high social activity among authors of parapsychological concepts and practices. Conclusion. Quantum psychology has no scientific grounds for being considered as a “normal” science. Nowadays theoretical and methodological grounds for quantum psychology are discussed. Quantum psychology is considered as a marginal science

Supramolecular Approaches To Control Activity and Selectivity in Hydroformylation Catalysis

The hydroformylation reaction is one of the most intensively explored reactions in the field of homogeneous transition metal catalysis, and many industrial applications are known. However, this atom economical reaction has not been used to its full potential, as many selectivity issues have not been solved. Traditionally, the selectivity is controlled by the ligand that is coordinated to the active metal center. Recently, supramolecular strategies have been demonstrated to provide powerful complementary tools to control activity and selectivity in hydroformylation reactions. In this review, we will highlight these supramolecular strategies. We have organized this paper in sections in which we describe the use of supramolecular bidentate ligands, substrate preorganization by interactions between the substrate and functional groups of the ligands, and hydroformylation catalysis in molecular cages

Brønsted Acid Promoted Reduction of Tertiary Phosphine Oxides

Recently, Brønsted acids, such as phosphoric acids, carboxylic acids, and triflic acid, were found to catalyze the reduction of phosphine oxides to the corresponding phosphines. In this study, we fully characterize the HCl, HOTf, and Me2SiHOTf adducts of triphenylphosphine oxide and find that the thermally stable adduct Ph3POH+OTf– is efficiently converted into triphenylphosphine at 100 °C in the presence of readily available hydrosiloxanes. Under the same reaction conditions, also Ph3POSiMe2H+OTf– selectively affords triphenylphosphine indicating that silylated phosphine oxides are likely intermediates in this process

C(sp3)–H Bond Acylation with N-Acyl Imides under Photoredox/ Nickel Dual Catalysis

International audienceA novel Ni/photoredox-catalyzed acylation of aliphatic substrates, including simple alkanes and dialkyl ethers, has been developed. The method combines C–N bond activation of amides with a radical relay mechanism involving hydrogen-atom transfer. The protocol is operationally simple, employs bench-stable N-acyl imides as acyl-transfer reagents, and permits facile access to alkyl ketones under very mild conditions