Institute Of Chemistry Research Articles

Front Cover: Helquats as Promoters of the Povarov Reaction: Synthesis of 1,2,3,4‐Tetrahydroquinoline Scaffolds Catalyzed by Helicene‐Viologen Hybrids (ChemPlusChem 10/2020)

The Front Cover shows how helquat molecules (shown as solar panels) can be used as organocatalysts in the Povarov reaction. The background combines historical monuments of Prague and the new research centre of the Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, while the yellow plants represent alternative fuels. More information can be found in the Full Paper by P. E. Reyes-Gutiérrez, L. Pospíšil, and co-workers.

Destruction of Co-EDTA Complexes by the Electrochemical Treatment of Water-Based Solutions

This work reports the main findings of the studies related to the problem of liquid radioactive waste utilization conducted at the Institute of Chemistry, Far Eastern Branch, Russian Academy of Sciences, in 2013–2018. It has been shown that, during the electrochemical treatment of model aqueous solutions containing Co-EDTA, the complex is destroyed and cobalt precipitates in the form of oxides, hydroxides, and spinel of variable compositions.

Preface

IX International Scientific Conference “Innovative engineering technologies, equipment and materials - 2019” has been hosted by the exhibition center “Kazan Fair” within the framework of the 19th international specialized exhibition “Mechanical engineering. Metalworking. Kazan” and 13th specialized exhibition “TechnoWelding” on the 4th and 6th of December, 2019The conference program was including 6 sections of work:Section 1 - Innovative materials, technologies and equipment in mechanical engineeringSection 2 - Innovative developments and economics in engineeringSection 3 - Chemical EngineeringSection 4 - Mathematical and physical modeling of information, technical, technological and management systems and processesSection 5 - Innovative Welding Technologies in IndustrySection 6 - Reliability, efficiency and safety of objects of the fuel and energy complexParticipants and guests of the conference discussed the scientific and technical achievements in the field of development, design and manufacture of engineering products. See the results of studies of the country’s leading universities in the field of robotics, new materials (including on the basis of production waste), waste management and recycling, mechanical engineering, energy, fuel cells, manufacturing economy.Presidium of the seсsions headed by Director of the Institute of Engineering Prof. Nail Faikovich Kashapov and Director Engineering center «Energoprogress» Almaz Lyabisovich Garaev. The Presidium also included: Deputy. Director of the Institute for educational activities Ildar Hafizov Ilsurovich, Deputy Director of the Institute for Science Gilmanshin Iskander Rafailevich and director's advisor of Engineering center «Energoprogress» Linar Salihzanovich Sabitov.Research and Innovation have been presented by the staff of the Engineering Institute of KFU, Institute of Naberezhnye Chelny, Institute of Chemistry named after A.M. Butlerov, Kazan State Power Engineering University and Kazan National Research Technical University named after A. N. Tupolev – KAI, Kazan State University of Architecture and Engineering. Representatives of Uzbekistan, Vietnam, Kazakhstan, Russian cities: Moscow, St. Petersburg, Voronezh, Yekaterinburg, Kazan, Nizhny Novgorod, Naberezhnye Chelny, Cheboksary, Lipetsk, Khimki, Tambov, etc., became participants of the IMTOM-2019. breakout sessions and round tables were made more than 200 reports, the total number of participants was 372 people.Active participation in the conference were graduate students and students of the Engineering Institute. The experience of live communication with scientists, practitioners, representatives of the real economy will allow buduyuschim experts to determine its scientific direction for a successful solution of important problems of import substitution and enhancing competitiveness assigned to the engineering industry of our country.

Production of rich aluminum master alloys containing scandium, yttrium and zirconium for non-ferrous and ferrous metallurgy

The method for the synthesis of aluminum based master alloys and alloys, which employs the high-temperature exchange reaction between fluoridechloride melt of alkaline or alkaline-earth elements and fluoride, oxide or oxyfluoride of the corresponding metal (scandium, yttrium, zirconium) with molten aluminum metal, is considered. The use of high temperatures leads to a large loss of fluoride-chloride salts of alkaline metals, and experiments for the enhancement of the percentage of alloying component finally result in an abrupt reduction of direct metallurgical yield. The mass ratio of salt melt to aluminum melt determined by the solubility of chosen compounds is established. At the salt : metal ratio less than 1:1, the process of reduction of introduced metal is retarded. The study of the kinetics of high-temperature exchange reactions of metals from salt melt at different temperatures shows that after the beginning of melting of fusible components of salt flux (~580 oC) the interaction with still hard aluminum already begins. However, this solid-phase reaction dies down quickly because the aluminum particles are covered by reaction products. The subsequent melting of aluminum is accompanied by a rapid destruction of the oxide film and acceleration of the exchange reaction, which also fades out quickly due to impediments connected with diffusion — the compounds, formed on liquid aluminum, block the way to initial substances. This limits the amount of metal introduced in aluminum using high-temperature exchange reactions. Scandium, yttrium and zirconium rich aluminum master alloys were obtained by the centrifugation methods. Al – Sc master alloy with scandium content 25 wt.% was produced by filtering of aluminum-scandium melt through graphitized fabrics. The manufacturability of the centrifugation method for the production of aluminum-scandium, aluminum-yttrium and aluminum-zirconium rich master alloys was shown.This research has been carried out in accordance with the governmental assignment, as well as the research plan by the Institute of Solid State Chemistry of the Ural Branch of the Russian Academy of Sciences.

BÁRBARA CARINE SOARES PINHEIRO: QUÍMICA, MÃE, NORDESTINA E MILITANTE NEGRA

Bárbara Carine Soares Pinheiro was born in 1987, on the suburbs of Salvador. She is the great-granddaughter of Vicença, the granddaughter of Djanira Soares and the daughter of Teresinha Soares de Jesus. She grew up free on the streets of her neighbourhood - she still remembers very well feeling the smell of red clay after rainfall. She graduated in 2010 at the Federal University of Bahia (UFBA) and obtained the title of Master’s Degree in 2012 and PhD in 2014. She is a professor at the Institute of Chemistry at UFBA. Today, Bárbara defines herself as: critical-decolonial researcher, anti-racist, north-eastern feminist, pagodeira, bisexual, cis black woman, mother. On the other hand, she does not define herself: she opens up in a constant movement of self-building or, perhaps, or yet to be built.

SONIA GUIMARÃES

Sonia Guimarães, born in São Paulo in 1956, daughter of an upholsterer and a housewife. She was always the second in the class in all subjects and was passionate about teachers of Mathematics, Physics and Chemistry. In 1974, she finished high school and then entered the São Paulo High School of Arts and Crafts, where she took the technical course in buildings. She enters the Bachelor of Science course at the Federal University of São Carlos (UFSCar) and concludes it in 1979. Then, in 1983, she completed her master's degree in Applied Physics at the São Carlos Institute of Physics and Chemistry, University of São Paulo (USP). In 1989, Sonia obtained a Ph.D. in electronic materials from the University of Manchester Institute of Science and Technology. In 1993, Sonia became a professor of physics at the Technological Institute of Aeronautics (ITA). (ITA). She is currently an employee of the Ministry of Defense of Brazil, in the Department of Aerospace Science and Technology (DCTA), as an adjunct professor at ITA. &nbsp

ANITA CANAVARRO: ENEGRECENDO A QUÍMICA

Professor Anna Maria Canavarro Benite is a PhD and Master in Science, also owning a Degree in Chemistry from the Federal University of Rio de Janeiro (UFRJ, Unviersidade Federal do Rio de Janeiro). Coordinator of the Research Laboratory in Chemical Education and Inclusion (LPEQI) and Coletivo Negro Ciata, from the Chemistry Institute of the Federal University of Goiás. In addition, she is the creator of the Investiga Menina Project, which seeks to inspire black students to pursue careers in the exact and scientific areas.

Network Pharmacology to Identify the Pharmacological Mechanisms of a Traditional Chinese Medicine Derived from Trachelospermum jasminoides in Patients with Rheumatoid Arthritis

BackgroundThis study used a network pharmacology approach to identify the pharmacological mechanisms of a traditional Chinese medicine derived from Trachelospermum jasminoides (Lindl.) Lem. in patients with rheumatoid arthritis (RA).Material/MethodsKnown compounds of T. jasminoides were obtained from the Traditional Chinese Medicine Systems Pharmacology (TCMSP) database, the Shanghai Institute of Organic Chemistry of Chinese Academy of Science, Chemistry (CASC) database, and a literature search. Putative targets of identified compounds were predicted by SwissTargetPrediction. RA-related targets were achieved from the Therapeutic Target database, Drugbank database, Pharmacogenomics Knowledgebase, and Online Mendelian Inheritance in Man database. The protein-protein interaction (PPI) network was built by STRING. CluGO was utilized for Kyoto Encyclopedia of Genes and Genomes (KEGG) and Gene Ontology (GO) enrichment analysis.ResultsA total of 354 potential targets were predicted for the 17 bioactive compounds in T. jasminoides; 69 of these targets overlapped with RA-related targets. A PPI network was composed and 2 clusters of 59 and 42 nodes each were excavated. GO and KEGG enrichment analysis of the overlapping targets and the 2 clusters was mainly grouped into immunity, inflammation, estrogen, anxiety, and depression processes.ConclusionsOur study illustrated that T. jasminoides alleviates RA through the interleukin-17 signaling pathway, the tumor necrosis factor signaling pathway, and other immune and inflammatory-related processes. It also may exert effects in regulating cell differentiation and potentially has anti-anxiety, anti-depression, and estrogen-like effects.

Golden Jubilee of Singapore National Institute of Chemistry (1970–2020): Celebrating its Partnership with Wiley‐VCH

Golden Jubilee of Singapore National Institute of Chemistry (1970–2020): Celebrating its Partnership with Wiley‐VCH

3D LASER SCANNING SURVEY FOR CULTURAL HERITAGE. A FLEXIBLE METHODOLOGY TO OPTIMIZE DATA COLLECTION

Abstract. The paper describes an operational working methodology to be applied for surveys with phase-shift laser scanning, which allows defining a guidelines system to optimize in-field data collection. While reducing the number of scan positions still using the same quality, it is possible to obtain smaller files, in order to limit the computational requirements during editing and post-production. Nonetheless, this methodology guarantees results that are qualitatively comparable to the standard data collection process. Consequently, the angle ranges have been analyzed to find a value that guarantees for the survey a point cloud lighter and more manageable and, at the same time, that maintains a reasonable accuracy. Subsequently, two parameters were defined, “redundancy” and “closeness”, to find an operational process that allows to schematize what is usually achieved with the help of experience in the field: to evaluate the minimum number of scan points that can ensure the necessary overlap for optimal coverage of the entire building surveyed. After defining the study of the ideal situation, the model is applied in a case study, situated in a densely built context, typical of European historical urban centers: the main façade of the G. Ciamician Institute of Chemistry of the University of Bologna (Italy).

Development of Innovative Photoactive Admixtures for Concrete and Cement-Based Plaster Finishes, to Create Self-Cleaning Surfaces

This article presents research and development on innovative photoactive admixtures for concrete and cement-based plasters for the finishing of concrete surfaces. The goal is to provide the resulting surfaces of these newly developed materials with a self-cleaning ability stemming from photocatalytic reaction during exposure to UV radiation. This research and development is currently underway as part of a project supported by the Czech Ministry of Industry and Trade, in the TRIO programme; and in cooperation with BETOSAN s.r.o., the Technical University of Liberec, the Institute of Inorganic chemistry of the Czech Academy of Sciences and the J. Heyrovsky Institute of Physical Chemistry of the Czech Academy of Sciences. The first type of material under development is a photocatalytically active admixture in powder form, allowing the preparation of concrete surfaces with photocatalytic properties. The second type of material under development is a photocatalytically active cement-based plaster, intended primarily for application to a concrete substrate. The preparation of two or more final versions is to be expected for both types of materials. In the case of the plaster this includes the preparation of two colour variants, specifically white and grey. For the powdered cement admixture we expect the preparation of various types based on their application. This could mean different types of admixtures mixed throughout the entire volume of the concrete or only in the surface layer of the concrete. We envisage exterior applications on the self-cleaning outer shell of buildings, as well as treatment of the surface layer of various structures such as bridges, noise barriers, traffic barriers and tunnels. The materials created could also be used in interiors under specific conditions, with anticipated uses in the health care and food processing industries.

Научная и организационная деятельность лаборатории хроматографии Института физической химии с момента её образования

В 2020 г. лаборатория хроматографии и хромато-масс-спектрометрии в ИФХЭ РАН отмечает 70-летие со дня её основания. В статье рассказывается об организации лаборатории хроматографии в СССР, её становлении и перспективах развития. Приведены данные о наиболее важных результатах научной и организационной деятельности заведующих и сотрудников лаборатории на протяжении нескольких десятилетий. Пионером создания хроматографии в СССЗ как научного направления стал заведующий кафедрой физической и коллоидной химии Тимирязевской сельскохозяйственной академии (ТСХ) профессор Евгений Никитович Гапон (1891-1950). Значимость хроматографии в 1950 году в области научных и прикладных исследований была подтверждена созданием специальной лаборатории в Институте физической химии АН СССР. Первым научным руководителем лаборатории хроматографии был назначен профессор Константин Васильевич Чмутов. Под его руководством были изучены закономерности статики, динамики и кинетики на цеолитах и ионитах с целью внедрения хроматографических процессов в производство. После ухода из жизни в 1979 году Константина Васильевича достойным продолжателем его научных исследователей стал д.х.н. Олег Георгиевич Ларионов (1932-2013). О.Г. Ларионовым и его сотрудниками были выполнены основополагающие работы в области жидкостно-адсорбционной хроматографии, барохроматографии и хроматографического титрования. В 1984 году лаборатория физико-химических основ хроматографии пополнилась сотрудниками безвременно ушедшего всемирно известного физико-химика д.х.н. Андрея Владимировича Киселева Любовью Дмитриевной Беляковой, Юрием Анатольевичем Эльтековым, Натальей Петровной Платоновой. В 2004 году лаборатория пополнилась учеными масс-спектроскопистами из лаборатории спектроскопии ИФХЭ РАН. Одним из них был д.х.н. Алексей Константинович Буряк, который стал заведующим новой объединенной лаборатории физико-химических основ хроматографии и хроматомасс-спектроскопии. В настоящее время в лаборатории ведутся исследования по совершенствованию методов удерживания в условиях газовой хроматографии, а также выполняется теоретическое моделирование и экспериментальная проверка удерживания на углеродных хроматографических сорбентах для жидкостной и газовой хроматографии. Один из методов предсказания газохроматографических индексов удерживания на основе структуры аналита лег в основу современных методов искусственного интеллекта (в глубоких сверточных нейронных сетях).

TO THE 90th ANNIVERSARY OF STEPAN BUTSKO

Stepan Stepanovich Butsko was born on June 3, 1930 in the city of Mukachevo into a family of teachers. In 1948 he graduated from Mukachevo Secondary School № 1. He continued his studies at the Faculty of Chemistry of Uzhhorod State University, from which he graduated in 1953.In November 1953 S.S. Butsko gained the admission to the doctoral program at the Institute of Physical Chemistry named by L.V. Pisar-zhevsky of the USSR Academy of Sciences. Under the tutelage of Professor B.Ja. Dajno S.S. Butsko studied the redox properties of chlorophyll. After finishing his studies, he worked in various positions in the Department of Photochemistry and Radiation Chemistry of the same institute. In 1962 he defended his doctoral dissertation on "Dark and photochemical interactions of chlorophyll with iron salts." DOI: 10.24144/2414-0260.2020.1.5 S.S. Butsko started his teaching activity at Uzhhorod State University in 1963 as a senior lecturer at the Department of General and Inorganic Chemistry. From 1964 to 1966 S.S. Butsko taught chemistry at the University College of Cape Coast in the Republic of Ghana. In 1966 S.S. Butsko returns to work at Uzhhorod State University and heads the Department of General and Inorganic Chemistry. Under his leadership, the scientific direction of the department was formed, which was related to the researches in the field of coordination chemistry. In 1968 the department launches a postgraduate program in inorganic chemistry. From 1973 to 1975 S.S. Butsko works as a senior officer of the department of scientific and technical information of the House of Soviet Science and Culture in Budapest (Hungary). After returning from abroad S.S. Butsko continues to head the Department of General and Inorganic Chemistry. From 1980 to 2008 he works at the Department of Chemical Technology and Industrial Ecology. Since 2008 S.S. Butsko has been working at the Ferenc Rakoczi II Transcarpathian Hungarian College of Higher Education. Since 2011 he has been heading the Department of Biology and Chemistry of this university, where he works up to now.S.S. Butsko is a well-known scientist in the field of photochemistry, chemistry of complex compounds, bioinorganic chemistry and of complex processing technologies of raw materials. S.S. Butsko is the author of more than 150 scientific publications. The lines of scientific researches founded by S.S. Butsko in the field of coordination chemistry were continued by his stu-dents – DrSc., Prof. Chundak S.Yu., PhD, Assoc. Prof. Shmanko P.I., PhD, Assoc.Prof. Buzash V.M. and PhD, Assoc. Prof. Dobrjanszka L.P.As an outstanding scientist and teacher, S.S. Butsko at different times was a member of the Scientific Council on Inorganic Chemistry of the USSR Academy of Sciences, Scientific Councils of the Academy of Sciences of Ukraine on Inorganic Chemistry, Chemical Kinetics and Structure, Surface Chemistry and Disperse Oxide Modification Technology, Scientific and Methodological Council on Chemistry of the Ministry of Higher Education of Ukraine, "Chemical Problems of Ecology” Scientific and Technical Council, and was Chairman of the Transcarpathian Regional Branch of the Ukrainian Chemical Society. The outstanding merits of S.S. Butsko's before the state were honored by the Ministry of Education and Science and the National Academy of Sciences of Ukraine.

Nickel- and Brønsted Acid-Catalyzed Redox-Neutral Coupling of 1,3-Dienes and Aldehydes for Synthesis of Dienols

Dienols are important structural motifs in organic molecules, but most of the traditional synthetic methods required multistep prefunctionalization of substrates, leading to stoichiometric waste an...

Justification of stripping and development of a modular mine site for a combined coal mining method in Kuzbass on the example Baikaimskaya mine site

The article considers one actual method for development coal deposits in the Kuzbass by open-underground mining. The scientific and practical advantages of the proposed method due to the use of common infrastructure of coal mine and a modular mine site (subsequently transformed into a mining and technological structure operating according to the mine – longwall scheme) are presented. Currently, a development strategy for Kuzbass until 2035 has been developed. As part of the strategy, a draft program for subsoil use is being formed in the coal industry department. The program should take into account all the positive and negative aspects associated with coal mining in cities and municipal areas and also their prospects. In the Kuznetsk coal basin, 42 mines and 52 opencast mines are mining, of which 12 enterprises use partially unified infrastructure. According to the results of open-underground mining work conducted by the laboratory of the Institute of Coal and Coal Chemistry of the Siberian Branch of the Russian Academy of Sciences (Institute of Coal SB RAS), the list of sites includes favorable mining and geological conditions with incidence angles of up to 18 degrees. As open-pit coal production increases, many sites encounter such a parameter as maximum allowable (boundary) strip ratio. At the stage of preparing the feasibility study for the development of a coal deposit, this coefficient is calculated first of all, since duration of enterprise’s work and its economic component depend on it. In order to increase parameters, it is necessary to carry out transition from open works to underground. As a result, coal mine will not work at a loss, providing production with an economically disadvantageous strip ratio.

Reaction: The Impact of the AIE Concept

Xinggui Gu received his PhD from the Institute of Chemistry of the Chinese Academy of Sciences and conducted his postdoctoral research at Hong Kong University of Science & Technology. In 2017, he became a professor at Beijing University of Chemical Technology. Deqing Zhang is currently a research professor at the Institute of Chemistry of the Chinese Academy of Sciences. He received his PhD from Ruprecht-Karls University Heidelberg in 1996. His research interests include the design and synthesis of organic conjugated molecules toward optoelectronics and the development of external stimuli-responsive molecular systems for molecular switches, logic gates, and chemo- and biosensors.

Grand Challenges and Opportunities for Greener Chemical Alternatives in Hydraulic Fracturing: A Perspective from the ACS Green Chemistry Institute Oilfield Chemistry Roundtable

Formulated products used in hydraulic fracturing are designed to address specific subsurface challenges during oil and gas well completion and are intended for the treatment of a myriad of issues i...

Identification of Novel Carbonic Anhydrase IX Inhibitors Using High-Throughput Screening of Pooled Compound Libraries by DNA-Linked Inhibitor Antibody Assay (DIANA).

The DNA-linked inhibitor antibody assay (DIANA) has been recently validated for ultrasensitive enzyme detection and for quantitative evaluation of enzyme inhibitor potency. Here we present its adaptation for high-throughput screening of human carbonic anhydrase IX (CAIX), a promising drug and diagnostic target. We tested DIANA's performance by screening a unique compound collection of 2816 compounds consisting of lead-like small molecules synthesized at the Institute of Organic Chemistry and Biochemistry (IOCB) Prague ("IOCB library"). Additionally, to test the robustness of the assay and its potential for upscaling, we screened a pooled version of the IOCB library. The results from the pooled screening were in agreement with the initial nonpooled screen with no lost hits and no false positives, which shows DIANA's potential to screen more than 100,000 compounds per day.All DIANA screens showed a high signal-to-noise ratio with a Z' factor of >0.89. The DIANA screen identified 13 compounds with Ki values equal to or better than 10 µM. All retested hits were active also in an orthogonal enzymatic assay showing zero false positives. However, further biophysical validation of identified hits revealed that the inhibition activity of several hits was caused by a single highly potent CAIX inhibitor, being present as a minor impurity. This finding eventually led us to the identification of three novel CAIX inhibitors from the screen. We confirmed the validity of these compounds by elucidating their mode of binding into the CAIX active site by x-ray crystallography.

Ullmann‐Ma Reaction: Development, Scope and Applications in Organic Synthesis†

SummaryCopper‐catalyzed cross‐couplings of aryl halides and nucleophiles, traditionally called Ullmann‐type coupling reactions, were initially reported by Ullmann et al. from 1901—1929. A seminal report in 1998 by Ma et al. from Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences revealed an accelerating effect caused by amino acids, which brought Ullmann‐type coupling reactions into a ligand‐accelerating era. From 1999 to the first 10 years of 2000s, the first‐generation ligands were developed by many researchers and promoted Ullmann‐type coupling reactions of aryl iodides and bromides under relatively mild conditions. Amino acid ligands, developed by Ma and coworkers, are one class of the most important first‐generation ligands. In the second 10 years of 2000s, Ma et al. led the discovery of second‐generation ligands for copper‐catalyzed cross‐coupling reactions. Two great breakthroughs have been realized by using second‐generation oxalic diamide and related amide ligands, with aryl chlorides as general coupling partner and with low catalyst loadings. Now copper‐catalyzed cross coupling reactions of aryl halides and nucleophiles with amino acids or oxalic diamides and related amides as ligands are recognized as Ullmann‐Ma reactions and have found extensive applications in organic synthesis.

Daniel Bailey wins Peter J. Dunn Award

Daniel Bailey of Takeda Pharmaceuticals is the recipient of the Peter J. Dunn Award for Green Chemistry and Engineering Impact in the Pharmaceutical Industry. The award, established by the ACS Green Chemistry Institute Pharmaceutical Roundtable, recognizes excellence in the research, development, and execution of new green chemistry technologies in the pharmaceutical industry. Bailey developed a technology for greener reaction conditions that reduces a six-step synthesis to four. In addition to shortening the synthetic route, Bailey and his team were able to reduce the amount of raw materials needed to make a final product. Bailey will present his technology during the 24th Green Chemistry & Engineering Conference, which will take place virtually June 15–19. Please send announcements of awards to l_wang@acs.org.