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The Sallanlatva massif belongs to the group of Paleozoic alkaline-ultrabasic complexes wide spread in the Kola Region (the northwestern part of the Fennoscandian Shield). In the central part of this massif, the host ijolite and urtites contain calcite, ankerite, ankerite-dolomite and siderite carbonatites. The explosive processes that led to the formation of carbonatite breccias in the calcite and ankerite-dolomite carbonatites occurred in Sallanlatva massife in the last stages of the carbonatite magmatism. There are two types of explosive carbonatite breccias in the Sallanlatva massif: (1) glimmerite-calciocarbonatite breccias, and (2) siderite-dolomite breccias. Analysis of the mineral composition of fragments and matrix and the shape of fragments in breccias has shown that the first material to intrude into the host calcite and ankerite-dolomite carbonatites was calcite melt. After that, dolomite melt penetrated through the fracture zones, which resulted in the formation of siderite-dolomite breccias. The differences in the mineral composition of the breccia matrix suggest that the residual carbonatite melts originate from separate magma chambers. The chamber with calcite melt was located at great depth, and some captured glimmerite fragments were abraded during the melt upwelling. Silicate-dolomite melts lifted from a shallower depth; the captured fragments of siderite carbonatites retained their angular shape. Late hydrothermal processes yielded veins and caverns with Ba-Sr-P-S-Ti-REE mineralization in the breccias and host rocks.

The objects of the study are apocarbonatitic titanium metasomatites ("titanium carbonatites") associated with the rare earth carbonatites of the Petyayan-Vara area of the Vuoriyarvi complex (the Kola region). In this paper, the following mechanism for the formation of these rocks has been substantiated based on the agreed results of mineralogical and geochemical studies. Prior to the onset of carbonatite genesis, a fluorine-enriched fluid phase originated in the lower horizons of the complex passed along the deep-permeating fracture system of several hundred meters length up to the level of the modern erosion surface. It transported Al, Fe2+, Mg, Ti, P into the pyroxenites and Si, Ca and Na out of them, as a result of which the pyroxenites were transformed into giant-grained phlogopite rocks – glimmerites. The most probable source of this fluid is alkaline aluminosilicate magma. Then carbonate melts intruded along the same fractures. In the course of carbonatite genesis, F-fluid caused a local migration of K, Al, Si, Fe, P, Ti, Nb, Ta, Zr, Hf and HREE out of glimmerites into igneous dolomite carbonatites, which led to the formation of apocarbonatitic titanium metasomatites. They represent several paragenetic associations superimposed on each other, the mineral composition and the formation sequence of which correspond to the metasomatic column zones directly observed within the contact "carbonatite – altered pyroxenite". The separation of HFSE and REE is controlled by the same metasomatic column: Ti, Nb and Ta were accumulated in titanium carbonatites, i. e. in associations of the frontal and intermediate zones, and Zr, Hf and HREE – in apatitized fields corresponding to the rear zone of the column. Accordingly, the fractionation of these elements occurred due to the "fluid – rock" interaction. Subsequently, the same long-lived fractures served as a channel for REE-Sr-Ba-S fluids, but the recrystallization caused by K-Al-Si-Ti-F-metasomatism made titanium carbonatites dense and fine-grained in texture, what, in most cases, "protected" these rocks from the influences of later processes.

The results of complex petro-mineragraphic, Raman and isotope- geochemical study of three types of graphite- bearing rocks circulated at different distances from the alkaline granites: (1) kyanite schists of Bolshiye Keivy, sampled at a considerable distance from a contact with alkaline gran ites; (2) sillimanite schists, sampled close to the contact, and (3) silexites, located in the inner part of th e alkaline granite massif Western Keivy have been presented. Five morphogenetic types of graphite have been revealed in the rocks under consideration: fine- grained Gr-1, intergranular Gr-2, nest-shaped Gr-3, vein Gr- 4 and spherulitic Gr-5. Current study demonstrates that these five types of graphite distinctly vary not only i n morphology, but also in temperature of crystallization, as determined by RSCM-Raman geothermometer, and in carbon isotop e composition. The most likely source for the anomalous "light" graphite Gr-1 and Gr-2 [δ 13 C(PDB) = −43...−45 ‰] from kyanite schists is a water- methane fluid originating from sedimentary rocks with org anic compounds. The carbon of graphite Gr-5 of the silexites selected at the inner part of alkaline granite massif West ern Keivy, on the contrary, proved to be most "heavy" [δ 13 C(PDB) = −8 ‰], which indicates its origin from the lower crustal or mantle carbon dioxide fluid. Thus, carbon extracted into the rocks of Keivy structure from at least two contrasting isotope sources. Graphite Gr-3, that makes up the bulk of graphite of exocontact sil limanite schists, is also isotopically light, but not anomalously [δ 13 C(PDB) = −17...−28 ‰]. The crystallization temperature of the gi ven graphite (435−520 ºC), and its structural relationships with other minerals of th e rock evidence of its synmetamorphic origin. The presence of veinlets of isotopically heavy [δ 13 C(PDB) = −10 ‰...−11 ‰] high-temperature (570−670 ºC) graphite intersecting minerals of the metamorphic paragenesis (i ncluding Gr-3) indicates that the introduction of the granites occurred into the previously metamorphosed strat a and was accompanied by thermal and fluid influence on these strata.

The polypeptide sequence of the unmodified catalase from Penicillium vitale containing 696 amino acid residues was deduced. The sequences of 76 tryptic peptides of the unmodified catalase, 63 tryptic peptides of the catalase with modified Lys residues, 48 peptides resulting from catalase cleavage by the Staphylococcus aureus V8 protease, and 9 fragments obtained by BrCN-treatment were considered, and a comparison with the sequences of other catalases was made.

The relative percentage of type III to type I collagen, the ratio of alpha 1(I) to alpha 2(I) collagen chains and the ratio of dimers (beta-chains) to monomers (alpha-chains) in type I collagen have been measured in solubilized collagen fractions from keloids and hypertrophic scars aged about 1-7 years after burn. In tissue samples the content of crosslink with structure of pyridinoline were analyzed and expressed as mole of crosslink per mole of collagen. A comparison between hypertrophic and keloid scars has shown that the young (about 1 year) hypertrophic scars have higher ratios alpha 1(I)/alpha 2(I) and beta 11 + beta 12/alpha 1(I) + alpha 2(I). The increased proportion of beta-chains in the younger hypertrophic scars approximated to the same level as in normal skin within 7 years after lesion. There was no decrease in the ratio dimers/monomers of collagen type I with age of keloid scar tissue. The relative amount of collagen type III in young keloid scars was found decreased as compared to age-matched hypertrophic scars (13 +/- 3 and 17 +/- 7 respectively), but was similar in the older scars. The average pyridinoline crosslinks content per mole of collagen in keloids was 2 times as high as in hypertrophic scars. The data support the suggestion that general, as well as peculiar disturbances of collagen metabolism are involved in the development of keloids and hypertrophic scars.

Collagenolytic activity was estimated in primary focuses of melanoma, in preparations of normal skin surrounding the tumor, in benign pigmentary neoplasms (nevus) as well as in normal and metastatic lymph nodes. Both metal-dependent and -independent collagenolytic activity was significantly increased in tumoral tissues as compared with that of healthy tissues. At the same time, the collagenolytic activity was considerably lower in benign pigmentary neoplasms than that of melanoma primary focuses. Importance of the collagenolytic enzymes in the processes of melanoma invasion and metastatic spreading is discussed.

The changes in the content of mature crosslinks with pyridinoline structure and soluble/insoluble collagen ratio in the costal cartilage tissue of human beings aged from 1 month to 57 years were found to be age-dependent. The effect of the pyridinoline crosslink content on the soluble/insoluble collagen ratio in human costal cartilage tissue may constitute no less than 67% of the total influence of the sum of all factors. The pronounced nonlinearity of the studied dependencies points to a possible involvement of a factor(s) other than the pyridinoline crosslink content.

Catabolism of collagen was studied in 25 children with keloid and hypertrophic scars by means of evaluation of total and polypeptide-bound hydroxyproline excreted with urine. Formation of postburn pathological scars led to an increase in excretion of collagen degradation products, the rate of the increase depended on area and age of scar. In hypertrophic cicatrization rate of collagen metabolites excretion correlated with the scar age reversely, demonstrating the tendency to decrease of the scar collagen metabolites with its ageing. Excretion of collagen metabolites with urine in patients with keloid scars depended on area of the scar and only slightly on its age. Besides, in patients with keloids rather high, statistically distinct correlation (r = 0.855) was found between the ratio macrophages/neutrophils under studies using "skin window" as well as between the ratio of hydroxyproline content in the polypeptide fractions with molecular mass above 1,500 and in the fraction containing oligopeptides and free hydroxyproline. This correlation was not found in patients with hypertrophic scars. Interaction of macrophages, neutrophils and, probably, eosinophiles appears to have a definite importance in regulation of collagen degradation, impairment of which may be substantial for scars formation.

Excretion of pyridinoline and polypeptide-bound hydroxyproline with urine was studied in 27 children with hereditary impairment of connective tissue. At the same time, effects of beta-adrenoblocking agents and vitamin complex, prescribed during preoperation period before thoracoplasty in hereditary chest deformation, were investigated. Clinical efficiency of the treatment depended distinctly on the initial value of ratios pyridinoline/creatinine and polypeptide-bound hydroxyproline/creatinine. Total positive effect of the therapeutic course, considering also echocardiographic examination and postoperational complications, was observed in 44% of patients with Ehlers-Dunlop syndrome and in 75% of patients with Marfan syndrome.

Increased rate of pyridinoline excretion with urine was detected in patients with focal sclerodermia: the ratio pyridinoline/creatinine was equal to 0.094 +/- 0.049 as compared with that of 0.073 +/- 0.049 in controls. Concentration of mature collagen cross-links involving pyridinoline structure in urine of patients with focal sclerodermia did not depend on the patients age and the disease duration. However, this pattern correlated distinctly with clinical form of the disease (0.073 +/- 0.049 in local form and 0.013 +/- 0.017 in generalized form of sclerodermia) as well as correlated reversely with the rate of activity of natural killer cells (r = -0.977).

Natural physiological alterations in excretion of pyridoline (total hydroxypyridoline and lysyl pyridoline) with urine were studied in children and adults depending on age (1-86 years old) and sex. Age-dependent alterations of pyridoline excretion with urine had apparently four phases: an increase, a decrease, stabilization and secondary increase. Distinct dissimilarity between men and women in the rate of pyridoline excretion was found only in the age group of 16-21 years old.

Collagens were analyzed in skin and rib cartilage of 9 patients with Ehlers-Danlos syndrome of the II type. Electrophoresis and CNBr-peptide mapping showed that extended inserts and deletions as well as rough impairments of post-translation processing were not detected in collagens of the I, II and III types from these patients. In the patients with Ehlers-Danlos syndrome of the II type distinct increase was observed both in the total ratio of collagens III/I (P = 0.95) and in the ratio of intact collagens III/I free of cross-links. A decrease in content of dimers beta 11 and beta 12 was found in two patients. The data obtained suggest that the Ehlers-Danlos syndrome of the II type involved deteriorations in the structure of collagens I responsible for decrease in stability and sometimes for impairments in cross-link formation. Increase in content of collagen II fraction, predisposed to proteolytic hydrolysis of terminal sites, as well as elevated sensitivity of collagen II to pepsin hydrolysis were found in collagens of rib cartilage from patients with the syndrome and with funnel chest deformation. This suggests the lowered stability of collagen II from rib cartilage in funnel chest deformation.

A procedure is described for immobilization of partially purified histidase by means of covalent binding of the enzyme with amino ethyl cellulose activated by glutaraldehyde. The preparation obtained was stable within 6 months at 5 degrees and within 40 days at 39 degrees. The preparation of immobilized histidase might be used for enzymatic synthesis of urocanic acid from histidine.

A molecule of Penicillium vitale catalase is shown to dissociate into subunits with the molecular weight 75-80 kDalton. When hemin is splitted off the molecule also disintegrates into subunits equalling 1/4 of the enzyme molecule. The amino acid composition and fingerprints of the catalase subunits were studied. It is supposed that N-terminal residue of the subunit is blocked.

A mixture of pH 3.5-soluble trypsin peptides of inclusion bodies proteins of moth nuclear polyedrosis virus was fractionated by means of ionic exchange chromatography on Dowex 50X2 and purified by paper electrophoresis-chromatography. 32 peptides are isolated, their amino acid composition being studied.

Skin and rib cartilage collagens were studied in patient 1.I.K. with isolated form of pigeon chest as well as in a group of children without any impairments of connective tissue. Distinct decrease in stability of collagen I, an increase in the ration of alpha 1 (I)/alpha 2(I) chains and impairment in formation of beta 12 dimers were detected in the patient with pigeon chest. In the patient skin total ratio between collagens I and III, calculated from a content of BrCN-peptides, was similar to normal level, whereas the proportion was markedly increased between intact molecules of collagens III and I free of cross-links, which was calculated from the ratio of alpha 1(III)/alpha 2(I) chains. Presence of cross-links between alpha 1 (III) and alpha 2 (I) chains as well as between alpha 1 (III) and alpha 2 (I) chains was detected after peptide mapping of polypeptides arranged in the region of beta 11 and beta 12 dimers. All the collagen I preparation, extracted from skin of the patient 1.I.K., contained molecules with unstabilized N-terminal sites. These results suggest that mutation occurred in the N-terminal region of alpha 1(I) chain. Analysis of collagen from the patient 1.I.K. rib cartilage demonstrated a slight decrease in total stability of collagen II as well as elevated concentration of collagen II molecules containing unstabilized N-terminals. Mechanisms responsible for formation of cross-links between polypeptide chains of collagens I and III detected in human skin are discussed.

Using SDS electrophoresis and subsequent densitometry, isolated collagen proteins of infantile rib and knee joint hyaline cartilage were characterized. Both the normal samples and hyaline cartilages of children with osteochondrodysplasias were shown to contain collagens type I and II as well as collagen proteins with Mr 160 (A), 150 (B), 140 (C), 120 (D), 110 (E) and 39 kD (F), whose content in normal samples varied, depending on the donor age. An analysis of normal and pathological samples revealed the following biochemical markers of intensive chondrocyte proliferation: an increased content of collagen proteins A--F and a decreased number of intramolecular cross-links of collagen type II. Conversely, the increased number of intramolecular cross-links in collagen type II and the elevation of the relative content of collagen type I in lethal forms of osteochondrodysplasias and funnel chest may testify to chondrocyte dedifferentiation. It was assumed that collagen proteins D and E correspond to proteins 1 alpha and 2 alpha, whereas proteins A, B, C and F are the products of hydrolysis by pepsin type M of collagen detected previously only in animal cartilages. Mapping of collagen type II CNBr-peptides and electron microscopic analysis of its SLS-form were carried out. The experimental results are suggestive of the involvement of collagen proteins in the pathogenesis of human osteochondridysplasias as well as of the pronounced biochemical heterogeneity of the disease.

A method for estimation of amino acid composition and collagen-specific amino acids was developed. The assay was based on the precolumn reaction of amino acids with phenylisothiocyanate. The phenylthiocarbamyl derivatives were analyzed by means of reverse-phase chromatography on octadecyl sorbents, which involved gradient elution with ethanol and sodium or ammonium acetate. The method was used for effective separation of collagen-specific and main amino acids in cartilage hydrolysate from healthy persons and of patients with funnel chest and Ehlers-Danlos syndrome and also for determination of amino acid composition in creatine phosphokinase B- and M-subunits.

The electrophoretical analysis and CNBr-peptide mapping of the collagens, isolated from the costal cartilage of 30 patients with non-classified and syndromal forms of pex excavatum (funnel chest) (27 patients) and pex carinatum (3 patients) was carried out. In case of one patient with the nonclassified form of funnel chest the electrophoretical mobility of CB 9.7-peptide was found to be decreased. The electrophoretical mobilities of other peptides are not markedly changed. The data obtained allow one to suggest the mutation causing the defect in the region about 160 amino acid residues distant from the C-end of alpha 1 (II) chain of type II collagen of the patient.

Amino acid composition, partial or complete sequence of 43 tryptic peptides of pelyhedral protein of nuclear polyhedrosis virus is investigated. These peptides include 327 amino acid residues. There are 28 peptides with unique sequences containing 240 amino acid residues. It conforms to polypeptide chain molecular weight ca. 28000 and coincides with earlier reported data on polyacrylamide gel electrophoresis.

The nuclear polyhedrosis virus of the silkworm B. mori was obtained by dissolution of polyhedra at pH 10,5. It was shown that the virus particles contain a protease, which cleaves a few virion polypeptides during the dissolution of polyhedra under alkaline conditions. The proteolytic activity is inactivated by polyhedra treatment with phenylmethylsulfonylfluoride, diisopropylfluorophosphate, HgCl2 and at 80 degrees. Sodium dodecyl sulfate polyacrylamide gel electrophoresis revealed 18 virion polypeptides with molecular weights ranging between 10000-110000. It was assumed that the virion includes the polyhedral protein and its fragments. A possible role of the polyhedral protein and its fragments in the virion is discussed.

A dependence of activity of histidase from rat liver and skin on the agents affecting the activity of the adenylate cyclase systeme was studied in vitro. Under conditions optimal for the activity of liver phosphorylase protein kinase the skin extract histidase was activated 2-3-fold. This is indicative of a possibility of regulation of the skin histidase activity via the adenylate cyclase system by modification of enzyme by phosphorylation-dephosphorylation, which is performed by 3':5'-AMP-dependent protein kinase. Theophylline at concentrations of 10(-4) M and 10(-3) M activates partially purified histidase (both liver and skin forms), probably in the course of direct interaction with the enzyme.

Highly purified L-asparaginase having a specific activity of 500+/- +/-40 IU./mg protein is isolated from Pseudomonas fluorescens AG cells. The purification procedure includes isopropanol fractionation, gel filtration through Sephadex G-100, chromatography on hydroxylapatite and DEAE-cellulose columns. The asparaginase preparation is homogenous on the basis of polyacrylamide gel electrophoresis data. The pH optimum is found to be 8.0-9.0, isoelectric point and molecular weight are 4.5+/-0.05 and 70,000+/-5,000 respectively, Km for L-asparagine being-4.1-10(-4)M. The enzyme does not hydrolyse L-glutamine. The hydrolysis rate of D-glutamine is less than 1% of the deamydation rate of L-isomer. p-Chloro-mercurium benzoate at a concentration of 10(-4) M completely inhibits the asparaginase activity. Asparaginase from Ps. fluorescens AG possesses and antileucosic activity, inhibiting 3H-thymidine incorporation into DNA of Berkit lymphoma cells.

Study of the effects of pepsin treatment on soluble collagens type I of the skin and collagens type II of the costal cartilage of healthy subjects revealed the presence of two classes of molecules differing in the stability of their three-helical structure. In collagen molecules possessing a low stability (their number may amount to 20-30%) within the temperature range of 4-30 degrees C pepsin causes a split-off of N-terminal sites with the formation of short chains, i.e., alpha 1(I), alpha 2(II), and alpha 1(II), whereas at higher temperatures (33 degrees C for collagens type I and 37 degrees C for collagens type II) a complete degradation of these molecules takes place. It was found that collagens types I and II molecules contain a high number of three-helical sites with a high susceptibility to pepsin. The putative functional role of structural heterogeneity of collagen molecules is discussed.

The role of glutaminase activity of microbial deamidases in the immunodepressant action of these enzymes was studied. Escherichia coli asparaginase, asparagin and glutamin deamidases from Pseudomonas fluorescens and Mycobacterium album were found to have an inhibitory effect on the PHA-stimulated lymphocyte blast transformation. The inhibitory activity of deamidases with the asparaginase-glutaminase ratios 1 : 1.5 and 1 : 1.3 was one order of magnitude higher than that of Escherichia coli asparaginase with the ratio 1 : 0.02. It is assumed that glutaminase activity plays an essential role in the immunodepressant action of deamidases .

The process of oxidation of deamidase of asparagine-glutamine from Pseudomonas fluorescens sensitized with dyes has been studied. Oxidation brings about complete inactivation of the enzyme which, however, retains the quaternary structure. In the course of photooxidation, tryptophan residues are first destroyed and then those of histidine. Possibilities of the participation of these amino acid residues in catalysis and maintenance of active conformation of the enzyme are discussed.

Using disc polyacrylamide gel electrophoresis, the molecular weights of polyhedral proteins of nuclear polyhedrosis viruses (NPV) of Porthetria dispar, Mamestra brassicae, and Aporia crataegi were found to be 28000 +/- 3000. It was shown that NPV polyhedra of Bombyx mori, Galleria mellonella, P. dispar, and M. brassicae contain a protease. During dissolution of the polyhedra at pH 10,5 this protease specifically cleaves the matrix protein into 2--5 fragments. The amino acid compositions of NPV polyhedral proteins of P. dispar, M. brassicae, A. crataegi, Hyphantria cunae were shown to be very similar. It was found that tyrosine is a C-terminal amino acid of NPV polyhedral proteins of P. dispar, M. brassicae, and A. crataegi.

Content of collagen and relative content of unextractable collagen were increased by 35% and 50%, respectively, while the content of immobilized water was decreased in costal cartilage of children with the isolated form of funnel chest or with the deformation accompanied by Ehlers-Danlos syndrome. These anomalies may be considered as indicators of the cartilage premature ageing. In skin of the children with isolated form of funnel chest the ratio of collagen extracted with acetic acid was increased 2-fold.

Asparaginases from Escherichia coli and Erwinia caratovora were isolated and purified by column chromatography with a specific sorbent (sepharose, covalently bound to N-alpha-(6-aminohexyl)-D-asparagine). Homogenous asparaginase from E. coli was isolated by one-step procedure, while the enzyme from Er. carotovara was 50-60-fold purified. Asparaginase from Mycobacterium n. sp. was found not to bind with the specific sorbent.