By Acad. Valentin PARMON, Boreskov Institute of Catalysis (director), president of the Joint Scientific Council on Chemical Sciences, Siberian Branch of the Russian Academy of Sciences (SB RAS)
The West-Siberian Branch of the USSR Academy of Sciences founded in 1943 had four research centers (institutes) under its wing, the Chemical and Metallurgical Institute among them. Its present name is the Institute of Solid State Chemistry and Mechanochemistry, and it is among eleven active chemical research centers of the Siberian Branch of the Russian Academy of Sciences (SB RAS). Most of them date back to 1957 - 1958. However, new challenges have brought to life new research bodies as well. Thus, the International Tomography Center was set up at Novosibirsk Akademgorodok about twenty years ago; and closer to our days, in 2001, the Institute of Chemical and Energetic Technologies was established in the town of Biysk, Altai Territory.
Six research centers are located directly at Novosibirsk Akademgorodok (Academic Township). These are the Boreskov Institute of Catalysis, Nikolayev Institute of Inorganic Chemistry, Vorozhtsov Institute of Organic Chemistry, the Institute of Chemical Kinetics and Combustion as well as the Institute of Solid State Chemistry and Mechanochemistry, and the International Tomography Center. The other five are working elsewhere in Siberia - in Tomsk (Institute of Oil Chemistry), Krasnoyarsk (Institute of Chemistry and Chemical Technology), Omsk (Institute for Problems of Hydrocarbons Processing), Irkutsk (Favorsky Institute of Chemistry) and at Biysk (the Institute of Chemical and Energetic Technologies, the youngest). These centers are different in scale: while the staff of the Institute of Catalysis is nearly 1,000 (the largest chemical research center east of the Urals), the International Tomography Center has but about 80 on its staff. All told SB RAS employs 3,300 chemists and people of related specialities, with 1,360 research scientists among them. This makes up nearly a quarter of the total number of chemists working for the Russian Academy of Sciences (RAS).
We are going to touch only on some of the results that go to the SB RAS credit.
NEW PHYSICAL METHODS OF RESEARCH
The accomplishments of the Moscow school of Acad. Nikolai Semenov (Nobel Prize, 1956) in the theory of mechanisms and rates of chemical reactions brought this area to the forefront of research way back in the 1940s and 1950s. At the Siberian Branch of the USSR Academy of Sciences this line was further continued by Acad. Vladislav Voyevodsky (1917 - 1967), one of Semenov's pupils who stood at the cradle of the Institute of Chemical Kinetics and Combustion (ICKC). Acad. Voevodsky was also among the pioneers of chemical radiospectroscopy in this country. At ICKC this line of research was developed in the method of electronic spin echo (ESE)*; this country's and Europe's first ESE spectrometer was built at ICKC in 1965 by a team led by Yuri Tsvetkov (elected to RAS in 1997). This device opened up broad opportunities for research into the physics and chemistry of free radicals. Modifications of this technique suggested at ICKC allow to study the motion of spin-tagged lipid molecules in biological membranes and their permeability; they also allow to determine the conformation of proteins (that is the form and mutual orientation of their fragments) and study electron transport in photosynthesis.
ICKC research scientists, Acads. Yuri Molin and Renad Sagdeyev above all (the latter heading the International Tomography Center), have made a substantial contribution to "spin chemistry", a new discipline explaining the effect of a magnetic field on interactions of active intermediate particles in the course of many types of chemical conversions. Lately particular attention has been given to radical reactions in weak fields comparable to the earth's magnetic field. These results are important to magneto-biology. As to superfast processes in ion-radical pairs taking place in solutions within billionth fractions of a second, these are registered by another method evolved at ICKC, the spectroscopy of "quantum beats" in recombinational luminescence.
In another development, the Nikolayev Institute of Inorganic Chemistry has built a laptop spectrometer NMR-micro (NMR standing for Nuclear Magnetic Resonance) for studying nano-size pairs and the dynamics of nanoliquids within them. Using this device and quantum chemistry methods, researchers have studied many characteristics of metal nanoclusters, proton and superion conductors, superconducting systems, and nanoporous crystals. The results thus obtained hold good prospects for the technologies of photolithography, and for cartridges of superhigh-resolution jet printers and memory cells.
Nuclear Magnetic Resonance (NMR) is making good progress among other radiospectroscopy techniques. NMR is widely employed by medical doctors and in studying the functional activity of the brain. It has found useful applications in chemistry, too, making it possible to study the internal structure and behavior of objects in noninvasive techniques. In their joint works the International Tomography Center and the Boreskov Institute of Catalysis have shown that NMR tomography is indispensable in studying processes implicated in the mass transfer of gases and liquids within porous catalysts, adsorbents, sub-
* Spin-intrinsic momentum of a microparticle, which is of quantum origin and not connected with the particle's motion as a whole. - Ed.
Magnetic interactions (fields: external magnetic and resonance microwave ones, those of magnetic nuclei) alter the mutual orientation of electronic spins and the capability of chemical interaction between two radicals.
strates and porous layers. The multiphase catalytic hydrogenation reaction has been studied - in real time for that matter - by NMR tomography in the world's pioneering effort. The International Tomography Center has many other achievements to its credit. One is a unique method for visualization of the dynamics of the peristaltic movement of free liquids within hollow biostructures and for assessing parameters of physiological rhythms.
From the very start we at our department have been exploring the structure of compounds, their electronic structure including. For this purpose the Nikolayev Institute of Inorganic Chemistry has come up with a new line of research - X-ray and X-ray electronic spectroscopy.
MECHANISMS OF CHEMICAL REACTIONS
Such mechanisms are a priority for as good as all chemical research centers of Siberia. First of all we should mention the school of Acad. Valentin Koptiug (1931 - 1997), who has made a crucial contribution in developing the rearrangement theory for molecules of organic compounds: such rearrangements occur via formation of carbonium ions, or positively charged particles on a carbon atom. These rearrangements are of great practical interest, too, for they are involved in the formation of rather complex substances. The mechanism implicated in the migration of substitutes in molecules of aromatic compounds* has been determined using the method of labeled atoms. In superacidic media at low temperatures it became possible to stabilize many intermediate particles in rearrangements, identify their structure and kinetic characteristics, and thus clear the way for their quantitative description and prediction of the velocity of multistage reactions of aromatic and aliphatic compounds.** Of particular importance in elucidating the mechanisms implicated in such conversions were "identical conversion" processes, when the initial and the resultant carboniums have the same structure. Thereby Siberian chemists have accomplished a major breakthrough in organic chemistry, and passed from the stage of mere accumulation of results to a quantitative description of phenomena.
At the Institute of Solid State Chemistry and Mechanochemistry the school of Acad. Vladimir Boldyrev has discovered the impact of defects in a solid body on the mechanism of many solid phase conversions. A proper selection of methods for obtaining solid substances, crystals in particular, and of their pretreatment techniques allow to change the concentration of those particular defects within them to which a given reaction is most sensitive. By using special mechanoactivators we can make certain solid-phase processes waste free, and even achieve a dramatic cut in the number phases and time in a technological cycles - this time may be down to decimal fractions.
Processes involved in the formation of nanoparticles in an explosion have been the latest target of research at this center. Such studies have been made with the use of synchrotron radiation in real time. This is a major achieve-
* Aromatic compounds - hydrocarbons and their derivatives (e.g. aniline, phenol, etc.) whose molecules contain cycles (benzene rings) composed of 6 carbon atoms involved in the formation of a single system of conjugated bonds. They are chiefly obtained from petroleum refinement products and coal-tar pitch. - Ed.
** Aliphatic compounds-saturated hydrocarbons and their derivatives (e.g. carbonic acids) in whose molecules carbon atoms form open linear or branched chains. - Ed.
Liquid phase redistribution dynamics within a catalyst's granule, a process observed by the method of nuclear magnetic resonance (NMR) tomography. The intensity of a NMR signal corresponds to liquid phase volume.
merit. The purpose of this work carried out jointly by Novosibirsk researchers at the Budker Institute of Nuclear Physics and the Lavrentiev Institute of Hydrodynamics is to gain a better understanding of fast processes, and develop effective methods of controlling nanodiamond synthesis by explosion.
ICKC is also closely concerned with photochemical reactions and reactivity of intermediate particles thus formed. We are pinning big hopes on our laser operating on free electrons - developed jointly with Budker Nuclear Physics Institute. This is a large specialized electron accelerator generating powerful radiation in the terahertz (submillimeter) frequency band. We owe it pioneering results indeed. We have demonstrated that biological macromolecules on the surface of a substrate can be converted to a gaseous phase without its destruction and denaturation.
CATALYSIS AND TARGETED SYNTHESIS
Now catalysis is one of the most science-intensive and promising interdisciplinary areas of research involving chemistry and physics, biology and mathematics. It is an important part of problem solving in scientific research, technology and ecology related to the large-scale production of organic substances and to control of vital biological processes in a living cell. Its application range is really immense. The works of Acad. Georgi Boreskov (1907 - 1984), the very first director of the Siberia-based Institute of Catalysis, and his following have gained world renown. What Acad. Boreskov and his pupils have accomplished in the mathematical modeling of catalytic processes and methods of transition from laboratory studies to commercial apparatuses means a dramatic change in the approach to designing corresponding reactors, and in the ways of intensification of state-of-the-art technological processes. What concerns new physical methods of obtaining catalysts and unorthodox techniques of catalytic reactions, the search in this area is being continued by the schools of Acads. Kirill Zamarayev (1939 - 1996) and Valentin Parmon. They have explored the structure of reactive centers in numerous catalytic reactions, and developed techniques of stimulating such reactions by light and ionizing radiation. And they have made a substantial contribution in elucidating and modeling of astrocatalytic processes implicated in the synthesis of organic compounds on cosmic dust particles at the very birth of the solar system.*
The Catalysis Institute has obtained high-efficiency titanium-magnesium catalysts for the production of a superhard polymer, the super-high molecular polyethylene. This structural material of a new generation is remarkable for unique physico-technical characteristics, and is irreplaceable under extreme conditions, and also for the making of armor. The pilot batches of this material produced in the Tomsk R&D Advancement Zone have been tested with much success by domestic consumers.
Joining hands with colleagues from the Institute for Problems of Hydrocarbons Processing, our research center has developed new catalysts involved in two basic oil refining processes-cracking and reforming.** This
* See: V. Parmon, "Autocatalysis: Go-ahead to Life?", Science in Russia, No. 4, 2004. - Ed.
** Reforming - here with reference to petroleum refining for the production of high-octane gasolines, aromatic hydrocarbons and technical hydrogen. - Ed.
Spin transitions in unorthodox systems-chain-polymer complexes of bivalent copper with nitroxyl radicals (left). Shorthand of decomposition of a system of exchange clusters in molecular magnetics (right).
work was done within the framework of an innovational national project in 2003 - 2006. These catalysts have allowed to streamline the production of motor fuels at homeland enterprises. The money gained from the sales of new catalysts and motor fuel topped 8 billion rubles by the end of 2006, while only 500 million was initially invested.
Synthetic chemistry and chemical design of complex systems is yet another important line where actually all chemical research institutes of SB RAS are working. The Irkutsk-based Favorsky Institute of Chemistry (up until 1997, the Irkutsk Institute of Organic Chemistry) is among them as one of this country's largest centers researching in organic and heterorganic chemistry. This research center has reared a leading scientific school carrying on the traditions of the outstanding organic chemist Alexei Favorsky (1860 - 1945), who has made a large contribution in many areas of organic chemistry, in particular, in studying acetylene and its derivatives. Using acetylene it is possible to synthesize many products put out by the chemical industry today. That is why acetylene chemistry is still a dominant area in the programs of the Irkutsk Chemistry Institute which, among other things, is also concerned with organic silicon compounds of extraordinary valency.
Irkutsk scientists have discovered new chemical reactions like the reaction of ketoximes (a class of organic compounds) with acetylene producing pyrroles - the key fragments of vital composite metal systems (chlorophyll and haemoglobin); this reaction has been entered in monographs and manuals as the Trofimov reaction*; another reaction involving elemental sulfur and halogensubstituted hydrocarbons of different composition has been named after Voronkov** (the Voronkov reaction); it opens a direct way to sulfide heterocycles.
The Favorsky Institute has innovated in chemical processes and technologies alongside commercially valuable products and materials, such as medical drugs, ecologically safe pesticides, plant growth regulators, polymers, fragrant substances, sorbents, ionites, corrosion inhibitors, additives to fuels and oils (to improve their properties), corrosion inhibitors, materials for microelectronics and lithium accumulators of a new generation, and high-energy substances for rocket fuels.
And now it would be in place to mention the latest line of research, and this is supramolecular chemistry concerned with large molecular ensembles self-assembling from fragments matching one another geometrically and chemically; this process is similar to self-assembly of most complex spatial structures in biological systems. Such compounds are exemplified by complexes in which the "host molecule" (cavitand), which has a hollow cavity within, is capable of taking in a "guest's" molecule fitting in size.
The Nikolayev Institute of Inorganic Chemistry has studied reactions whereby complexes of transition metals are incorporated into hydrophobic cavities of nanometer dimensions-some kind of molecular containers called cucurbituryls. It has been demonstrated experimentally that molecules getting into such hollows may change their physical and chemical characteristics substantially. Cucurbituryls can be used for obtaining metal complexes characterized by extraordinary oxidation and reactivity levels.
* Boris Trofimov. director of the A. E. Favorsky Institute of Chemistry (SB RAS) in Irkutsk; elected to RAS in 2000. - Ed.
** Mikhail Voronkov, in 1970 to 1994 director of the Irkutsk Institute of Organic Chemistry; elected to RAS in 1990. - Auth.
Quite recently, the Nikolayev Institute and our research center came up with methods for synthesizing coordination polymers on the basis of zinc ions and optically active (homochiral) organic compounds of easily available lactic acid; such polymers can be used as specialized sorbents and catalysts.
The Novosibirsk-based Vorozhtsov Institute of Organic Chemistry and the International Tomography Center have amassed vast experience in the synthesis of a very wide range of stable nitroxyl radicals. Using paramagnetic metal ions and such radicals as ligands* it became possible to obtain diverse coordination compounds - the heterospin systems, which are a novel type of magnetoactive objects. As a matter of fact, the design of molecular magnetics is one of the most actively developing areas of chemistry. It is in this field that research scientists of the International Tomography Center have carried out pioneering works on the first layered-polymer and network structures. An essentially new class of objects has been discovered, and these are "breathing" crystals that change their volume significantly with the change of magnetic state and temperature.
At the very beginning of its activity the Novosibirsk Institute of Organic Chemistry under Acad. Nikolai Vorozhtsov (1907 - 1979) suggested a general approach to obtaining polyfluorinated aromatic compounds; this method is based on the interaction of perchlorated aromatic compounds with anhydrous potassium fluoride at 300 - 550°C. The method of obtaining such key products as hexafluorobenzene and chlorpentafluorobenzene from technically available chlorine derivatives, a technique adopted on a commercial scale back in the 1960s, has gained great practical significance. This country has thus created a raw material base of fluorine-aromatic compounds, something that has enabled SB researchers to launch major research projects in this area of chemistry.
Now back to the Nikolayev Institute of Inorganic Chemistry. As early as the mid-1960s it concentrated on physicochemical research into materials for electronic hardware. A large amount of work was done by Acad. Feodor Kuznetsov's school. They came up with methods for a quantitative inquiry into chemical precipitation from the gaseous phase - a technique much used for the commercial making of microelectronic devices. Subsequently, proceeding from putative thermodynamic characteristics of substances and processes, they evolved a targeted synthesis of volatile compounds of most metals in the Periodic Table that could be used for obtaining functional materials. Another spin-off from basic research conducted at the Nikolaev Institute is the technology of growing crystals for lasers and detection of emissions.
Coming to high-energy materials, we should mention the Institute of Chemical Kinetics and Combustion (ICKC) once again. At the initial stage its first director Alexander
* Ligand - relative to complexation: molecules and ions linked to the central complex-forming atom. - Ed.
Kowalski (1906 - 1978), corresponding member of the USSR Academy of Sciences, was interested chiefly in the combustion of solid fuels. He demonstrated that inflammation of gunpowders attends chemical processes in the condensation phase. These ideas came as a first step in visualization of combustion in a departure from the orthodox theories of the day. Studies into combustion processes in high-energy liquids are still on as a major line in the Institute's work. Kowalski's followers have succeeded in bringing together the uncoordinated parts of the theory of gaseous phase and heterogenic filtration combustion, an achievement that facilitates predicting the risk factor in reactors under emergency conditions. Further-more, this allows to interpret the transition from smoldering to inflammation in peatbog fires. Ultimately precise techniques were devised for fire and explosion protection safeguards.
The Institute for Problems of Chemical and Energetic Technologies, one of the youngest research centers at SB RAS, is making a tangible contribution in the production of new high-energy substances. Acad. Gennady Sakovich, its present research head, and his school have obtained solid rocket fuel propellants with record-high characteristics.
CHEMISTRY OF MEDICINES
Synthesis of medical drugs is an important area for chemical research centers of SB RAS working in close collaboration with medical researchers of the Siberian Branch of the Russian Academy of Medical Sciences (SB RAMS) and other bodies.
In Novosibirsk, a research team under Acad. Heinrich Tolstikov (N. N. Vorozhtsov Institute of Organic Chemistry) has synthesized new derivatives of betulonic acid, a compound obtained from birch bark. Jointly with the R&D Association VECTOR, it found that peptides of this acid, which contain fragments of long-chained amino acids, evolve as active inhibitors of HIV. They account for 90% suppression of the virus even at nanomolar concentrations, and thus are ten times as effective as azidothymidine, a preparation used widely for AIDS treatment. Such peptides also check the growth of malignancies and offer good prospects for chemotherapy of oncological cases.
The Vorozhtsov Institute has synthesized a group of high-efficiency analgetics (pain killers) of polycyclic type. They have no negative effect on the chardiovascular and respiratory systems, and are more persistent in their anaesthetic action than analogs.
The Irkutsk-based A. E. Favorsky Institute of Chemistry has developed a range of new medical drugs now in full-scale production. One is ACIZOL, a preparation highly effective as an antidote* to carbon monoxide (coal-gas) even in worst cases of intoxication. This medicine is indispensable in bad emergencies.
Another new medical preparation, KOBAZOL, is an active hemopoietic (blood-making) stimulant comparable and even superior to vitamin B12 in effect and spectrum of action. This medication is meant for the treatment of various anemias, including those caused by ionizing radiation. In radiation diseases cases it helps restore the amount of leukocytes, erythrocytes and hemoglobin in the organism.
ANAVIDIN, an antiseptic and disinfectant of a new generation, is superior even to such foreign analogs as chlorhexydin, bigluconate, septabic and other medicaments. ANAVIDIN is now produced on a commercial scale.
The Russian Federation Pharmacological Committee has given permission for the synthesis and clinical uses of TREKREZAN (universal stimulant), FERACRYL (hemostatic) and DIHYDROQUERCETIN, an antioxidant and capillaroprotector.
PERCHLOROZON, a new anti-TB medication, is undergoing clinical tests. Judging by initial results, it is effective for persisting forms of the disease resistant to other remedies.
* Antidote - a medicine or other remedy to counteract the effects of a poison. - Ed.
RAW MATERIALS PROCESSING AND ECOLOGY
Searching for ecologically safe methods of raw materials processing is a priority objective for chemists of Siberia, a very mineral-rich land of Russia's. This applies both to natural and Russia's renewable raw materials. For instance, the Institute of Chemistry and Chemical Technology has gained good experience in getting all the various products from plant biomass - particularly, obtaining microcrystallic cellulose from wood wastes. Cooperating with the Biophysics Institute (SB RAS) and the National Academy of Sciences of the Republic of Kazakhstan, this research center has developed a technology for the processing of "hard" arsenious coaly ores containing gold. The new beneficiation technology makes it possible to concentrate as much as 94 - 95 percent of gold and utilize harmful wastes. The town of Ust-Kamenogorsk in Kazakhstan has built a plant working on this very technology, one that is capable of concentrating 100,000 tons of gold-containing ore annually.
Making use of microscopic coenospheres (hollow alumosilicate microspheres) contained in ash produced by coal-burning power stations, we have obtained microspheric sorbents for purification of liquid radioactive wastes at nuclear plants and effluents at hydrometallurgical enterprises from radionuclides, and ions of nonferrous and noble metals.
The Institute of Oil Chemistry (SB RAS) is working on science-intensive energy-saving technologies for increasing the productive capacity of pay. The full-scale industrial uses of the proposed methods prolong the commercial exploitation of old oil deposits and those where mining is hard because of the high viscosity of oil. Work is underway to improve state-of-the-art physicochemical, hydrodynamic, hot steam and microbiological techniques of bed stimulation.
Environmental monitoring is yet another significant part of research and practical activities of SB RAS-affiliated centers. Years ago a team led by Alexander Kowalski at ICKC took up the physics and chemistry of aerosols, and this research has been making good headway. Optimal aerosol technologies have been developed and assimilated for the use of chemicals to protect farm crops against pests, weeds and diseases, and for the use of biopreparations, growth regulators and microelements. Only as little as one-fifth of such agents has to be expended, and this cuts down costs and minimizes the environmental hazards involved.
The Boreskov Institute of Catalysis likewise prioritizes ecofriendly technologies. We have come up with new techniques for detoxification of wastes discharged by industrial enterprises, power stations and transportation facilities. These methods are now applied on a wide scale. The "reverse-process" developed by Georgi Boreskov and coworkers (unorthodox technology of catalytic purification of outgoing gases, and of conversion of toxic impurities into harmless substances) is much in use both in Russia and abroad - in the United States, Bulgaria, Japan, China, Australia and other countries. Adopted at the integrated metallurgical PECHENGANICKEL plant in European Russia's north, this technology has been instrumental in protecting the Kola Peninsula from sulfur dioxide discharges; worldwide each year over 1 mln tons of sulfur dioxide, formerly wasted into the atmosphere, is utilized this way.
Since the foundation of the Siberian Branch of the national Academy of Sciences fifty years ago research workers of its chemical institutes have merited many prizes: 5 Lenin Prizes; 6 State Prizes of the USSR; 2 State Prizes of the Russian Soviet Socialist Federative Republic (RSFSR): 4 Prizes of the Council of Ministers of the USSR; 7 Prizes of the Russian Federation; 3 Prizes of the Russian Federation's Government. All this speaks volumes.
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