History of chitin and chitosan investigations in Russia
At the beginning of the 1870’s, fishermen fished for crab in Peter in Great Bay and off the Far East’s shores. Perhaps then, as it is now, cooked crab din not need much in the way of promotion to be an entree on any festive menu.
Founded in Primorye’s Gaidamak Bay, the first Russian crab cannery produced its first output in 1908. Two years later, another cannery was put into operation in Nakhodka Bay.
After 1914, when crabbing in the Russian Far East had supplied 730 crates of crab, there was a break in fishing and production. During the upheavals of the Revolution, Russia cared nothing for the production of delicacies.
Soviet canned crab appeared on the international market in 1923. However, it could not yet compete with Japanese seafood. By that time, Primorye’s eastern neighbor had six factory ships fishing for crab off their own coast, along the entire Kurile chain of Islands, off southern Sakhalin Island, Kamchatka and Primorye.
In 1927, Japanese companies leased from the Soviet Union almost 90 percent of all its crab areas. But, some two years later, the situation changed abruptly.
The owner of the Japanese ship, “Tayamaru”, built in 1913, could hardly have seen that his ordinary cargo ship would make history, by giving rise to the Russian crabbing fleet. The ship was selected by Soviet officials as suitable for holding a cannery line.
The ship raised the Soviet flag on March 15, 1928. The ship’s new name was the First Crabber. Shortly thereafter, on April 5, the First Crabber left Vladivostok for western Kamchatka. The ship was quite big: nearly 100 meters long, with a 2750-ton cargo capacity and eight motor boats. Its productivity was 400 crates per day. Her first captain was A. I. Dudnik.
Another crab cannery ship, the Kamchatka, was acquired from the United States, by Kamchatka-based, joint-stock Aktsionernoye Kamchatskoye Obschestvo.
Eight months later, in October, the First Crabber returned to the port having made over 20,000 crates of canned crab for the season. They were shipped to the London market immediately. The first experience was a success and from that moment on, Russian crabbing set off on the road to complete supremacy of the world crab market, an honor that they retain up to this very day.
The large amount of crab, shrimp waste, as well as some insects and plants (such as seaweeds) are used currently for preparation of chitin and chitosan. These natural polysaccharides have found numerous applications in food and medicine industries, biotechnological and agricultural needs, cosmetics and veterinary.
As for numerous other cases, the science of chitin was born in Europe. This polysaccharide was discovered in 1811 by Henry Braconnot a French researcher working on mushrooms. The actual name “chitin” was given for the first time by A. Odier and a third French scientist, C. Roget, isolated chitosan in 1894. In the first part of XX century chitin and its derivatives attracted great attention of scientists. In particular, three Nobel prize winner dealt with it: F. Fischer (1903) synthesized glucosamine; P. Karrer (1929) degraded chitin with chitinases; W. N. Haworth (1939) had established the absolute configuration of glucosamine.
In Russia first researches on chitin and chitosan have started in 1930s.
First works, directed to the chitin modification, were provided by academician of USSR Academy of Science – Pavel P. Shorigin (1881-1939) – famous organic chemist. He had discovered metalation reaction and intermolecular regroupings: carbonyl and phenol, which now named after him. In 1934-1935 research works on methylation, acetylation and nitration reactions well studied on cellulose were published [1, 2, 3]. Low reactive capacity of chitin was found in these processes. Unfortunately, this investigation was stopped on this stage.
Soviet scientists carried out series of research works concerned with Crustacea (Amphipoda, Gammaridae) from 1930 to 1970 at the Black Sea. At that time conversion of chitin under the action of sea bacteria has been investigated . F. E. Copp and E. M. Markianovich have revealed chitin-destroying bacteria at a depth of 100 to 2000 metres, the bulk of microorganisms were detected at the hydrosulphuric zone . Authors arrived to a conclusion that degradation of chitin by bacteria occurred at anaerobic conditions mainly. But the next investigation of E. M. Markianovich displayed that destruction of chitin happen both at oxygenic and hydrosulphuric zones of the Black Sea. This circumstance characterized these bacteria as facultative aerobes .
In 1941 Fedor I. Sadov had tried to utilize chitosan in practical needs. He used chitosan solutions for printing tissues dyeing [7, 8].
Systematic investigation of chitin, chitosan and its derivatives as well as their utilization have started in the mid of 1950 under the leadership of by academician of Academy of Sciences of USSR – Stepan N. Danilov (1889-1978) in the Institute of Macromolecular Compounds (IMC, Leningrad). He is known to be working in the field of classic organic chemistry, applied chemistry and chemistry of high molecular compounds. Fundamental researches on chitosan were conducted in his laboratory. They have determined the following physico- chemical properties of this biopolymer: heat capacity; heat swelling; internal surface of native chitin; radioactive destruction of chitin; chitin sorbtion capacity on uranium ions .
They have synthesized for the first time esters and other derivatives of chitin [9-13].
In 1970s in accordance to the laboratory technology the first batches of chitosan were put on sale on Moscow factory of chemical compounds named after Voikov.
Furthermore investigations of physico-chemical properties of chitin/chitosan were provided. It was shown that paper treated by chitosan and cyanoethylchitosan solutions become more firm and dielectric properties of condensation paper become higher. Chitosan was shown to be useful for cancer treatment. Special self dissolving bandages on the base of chitosan were prepared for surgeon. All of these investigations were provided on chitin/chitosan from crabs and shrimps waste material. Furthermore a raw material base became wider [14 – 18].
Since 1961 investigations on chitin/chitosan have been started in Moscow by Boris P. Belousov in Institute of Biophysics in USSR. Boris P. Belousov has found a fluctuation reaction known as reaction of Belousov-Zhabotinsky (1951). He and his collaborators investigated chitosan action on radioactive rayed organisms such as dogs, monkeys and some more. It was shown that its intravenous animal injection before fatal irradiation completely prevented their death. Injection after fatal irradiation increased their survival to 45%. All of these works were under the secret [19-22]. Despite this a medical form of this preparation was elaborated and a medical permission of its utilization was received.
In 1980s in USSR because of the increased fishing out of Antarctic krill a problem of raw utilization was originated. All-Union complex program “Kril” was worked up. The head organization was VNIRO (Russian Federal Research Institute of Fisheries & Oceanography) under the leadership – Vladimir P. Bykov (1931 – 1998). This program includes following Research Institutes:
- Moscow – A.N. Kosygin Moscow State Textil Academy, A.N. Nesmeyanov Institute of Organo-Element Compouds RAS, Institute of Microbiology RAS;
- Leningrad – Russian Federal Research Institute of Biological Pure Preparations, Gyprorybflot Institute;
- Murmansk – PINRO, Sevtehrybflot
- Kalyningrad – AtlantNIRO
- Vladivostok – Dalrybvtuz, Daltechrybprom, Pacific Oceanology Institute Far Eastern DivRAS (TINRO)
as well as in Ukraine and Latvia.
The development of chitin production technology and its utilization in practical needs were the aim of this investigation.
The first conference devoted to utilization of chitin/chitosan from crabs raw and other crawfishes took place in 1983 in Vladivostok. More than 40 reports were presented here.
In the middle of 80s pilot installations of chitin/chitosan production were constructed in Vladivostok and Murmansk and a first batch of paper modified with chitosan was produced.
The second meeting for chitin and chitosan utilization took place in 1987 in Murmansk.
Third and forth conferences took place in Moscow in 1991 and 1995. The common direction in this field was a utilization of these biopolymers in medicine, pharmacy, cosmetic and agricultural needs. Construction of factory with 35 tons per year productivity was under the process during these years.
The fifth conference took place in 1999 in Moscow region, Schelkovo. It was the most representative one. More than 150 scientists from 30 places of Russia, as well as Ukraine, Byelorussia, Uzbekistan, Latvia, Lithuania and Poland presented their researches devoted to chitin/chitosan effect on plant, animal, human protective properties, production of medical forms and dietary additives of these biopolymers and many other subjects.
The organizing committee included Center of Bioengineering RAS, Russian Federation Research Institute of Fisheries & Oceanography (VNIRO), Russian Federation Research and Technological Institute of Biological Industry RAAS.
RUSSIAN CHITIN SOCIETY was decided to be established on V conference for coordination of all investigations on chitin & chitosan. This was realized in 2000 on 15 of May in Schelkovo (Moscow Region).
The sixth conference took place in 2001 in Moscow region, Schelkovo. It was the first conference from this series in XXI century. Our scientists received a number of interesting results concerned fundamental investigations in the field of chitin and chitosan as well as practical aspects of usage of these unique biopolymers in all directions.
The seventh conference took place in 2003 in Leningad region, Repino. More than 150 scientists from Russia, Ukraine, Belarus, Uzbekistan, Latvia, Lithuania, Poland, France, Slovakia and Portugal presented their investigations in the field of medico-biological problems, phytoimmunity of cultivated plants, analyzing of chitin and its modifications, as well as numerous aspects of practical application of these biopolymers. Until recently Russian chitinology achieved much success. A whole series of preparations on the basis of chitosan registered in Russian Federation and produced in the role of biologically active food additives and environmentally appropriate biopesticides.
- P.P. Schorigin, E.W. Heit , Uber die Nitrierung von Chitin // Berichte, 1934, v.67, p. 1712-1714
- P.P. Schorigin, E.W. Heit, Uber die Methylether des Chitins // Berichte, 1935, v.68, p. 971-973
- P.P.Schorigin, N.N. Makarova-Semljanskaja, Uber die Acetylierung des Chitins, Berichte, 1935, v. 68, p. 969-971
- B.L. Isachenko, Î razlozhenii hitina microbiologicheskim putem, Priroda , 1939, 2 , 97-98 [Article in Russian]
- F. E. Copp, E. M. Markianovich, Î razrushayuschih hitin bacteriyah v Chernom more, DÀN SSSR, 1950, 75, 6, 859-862 [In Russian]
- E. M. Markianovich, Î chitinrazrushayuschih bacteriyah v Chernom more, Trudy Sevastopol,skoy biol. stantsii, 1959, 12, 18-27 [In Russian]
- F.I. Sadov, Noviy material dlya nesmyvayemogo appreta, Text. Promyshlennost,, 1941, 2, 52-54 [Article in Russian]
- F.I. Sadov, G.B. Markova, Hitozan dlya shlihtovaniya, Text. Promyshlennost,, 1954, 10, 36-38 [Article in Russian]
- S.N. Danilov, Å.À. Plisko, Izycheniye hitina. I. Deystviye na hitin kislot i schelochey, Zhurnal obschey himii, 1954, 24, 1761-1769 [Article in Russian]
- S.N. Danilov, Å.À. Plisko, Izycheniye hitina. II. Glytserinoviye ephiry hitina, Zhurnal obschey himii, 1954, ò.24, 2071-2075 [Article in Russian]
- L.A. Nud,ga, Å.À. Plisko, S.N. Danilov, Polucheniye hitozana i izucheniye yego fraktsionnogo sostava, Zhurnal obschey himii, 1971, 41, 2555-2558 [Article in Russian]
- L.A. Nud,ga, Å.À. Plisko, S.N. Danilov, Î-Àlkilirovaniye hitozana, Zhurnal obschey himii, 1973, 43, 2752-2756 [Article in Russian]
- L.A. Nud,ga, Å.À. Plisko, S.N. Danilov, N-Àlkilirovaniye hitozana, Zhurnal obschey himii, 1973, ò.43, 2756-2760 [Article in Russian]
- Avt. Svid. SSSR ¹ 428053, Bumaga electrotehnicheskogo naznacheniya, 1974, B.I. ¹ 18 [In Russian]
- V.N. Baranova, Å.À. Plisko, L.A. Nud,ga, I.L. Suhareva, Primeneniye hitozana v proizvodstve bumagi, Tsellyuloza. Bumaga. Karton, 1975, 6, 8-9 [In Russian]
- V.N. Baranova, Å.À. Plisko, L.A. Nud,ga, Modifitsyrovanniy hitozan v proizvodstve bumagi, Bumazhnaya promyshlennost,, 1976, 7, 9-10 [Article in Russian]
- Å.À. Plisko, L.I. Schelkunova, L.A. Nud,ga, Izmeneniye svoystv hitozana pod deystviyem gamma-izlucheniya, Zhurnal prikladnoy himii, 1977, 50, 2040-2044 [Article in Russian]
- Å.À. Plisko, L.A. Nud,ga, S.N. Danilov, Hitin i yego himicheskiye prevrascheniya, Uspehi himii, 1977, 46, 1470-1487 [Article in Russian]
- P.D. Gorizontov, V.D. Rogozkin, V.A. Razorenova, I.E. Àndrianova, Ì.V. Tyhomirova, Radiozaschitnaya i lechebnaya effectivnost, preparata RS-10 v opytah na sobakah, B, ul. Radiatsionnoy Meditsiny, 1967, 1, 12-25 [Article in Russian]
- V.A. Razorenova, Hitozan (preparat RS-10) noviy radioprotector i sredstvo rannego lecheniya ostroy luchevoy bolezni, Dissertatsiya, 1969 [In Russian]
- P.D. Gorizontov, V.D. Rogozkin, V.A. Razorenova, I.E. Àndrianova, Nekotoriye itogi izucheniya lechebnogo deystviya RS-11 v experimente, B, ul. Radiatsionnoy Meditsiny, 1974, 3, 3-10 [Article in Russian]
- G.A. Chernov, V.P. Yevdakov, V.A. Kabanov, Protivoluchevoy effect ionogennykh polymerov, B, ul. Radiatsionnoy Meditsiny, 1975, 3, 3-10 [Article in Russian]