Search

The article is devoted to the identification and analysis of the source documents used by land surveyors to compile Economic Notes to the General Land Survey plans. The landmarking on the Crimean Peninsula began in the late 18th century, but by the early 19th century it was judged premature and suspended until development of special rules taking into account the peculiarities of land use in the region. And yet the field notes of land surveyors on the Crimean Peninsula of the turn of the 19th century preserve primary economic information to a greater extent than those on other territories of the Russian Empire. This information is presented in the “Skazki to the Economic Land Survey,” data collected from the local population. Skazki (“tales”) containing initial data for Economic Land Survey remain a poorly studied and rarely encountered source. Their identification in these field notes makes it possible to verify the accuracy of the Economic Land Survey and to restore the information excluded from the Brief Economic Notes and descriptions of specific lands in the lost Full and Cameral Economic Notes. The discovered “Skazki to the Economic Notes” on the Tauride gubernia are a unique source that makes it possible to assess the economy of Crimea at the turn of 19th century. They characterize natural environment, economic activities on the peninsula and occupations of its population, provide information on the soil conditions, available water resources, common species of trees, animals, birds, and fish. In their structure, they coincide with the skazki compiled in other regions of Russia, but have characteristic features that are associated with the identity of the Crimea and its economic condition in the late 18th century. The process of the Crimea development made its own adjustments to the land survey documentation. Unlike other regions, here the authors of the skazki were not only landowners’ attorneys, but also land owners themselves — local beys and murzes. The introduction of the skazki into scientific use opens opportunities for comparing their data with the preserved texts of the Economic Notes and for studying the history of the region at the micro level of individual settlements.

Physiological and biomedical experiments were performed. We estimated the parameters of tree main levels of physiological systems as a response of an organism to stress. Mechanisms of physiological defense of an organism against stress should be considered systemically. The response of physiological systems of animal organism was modeled by the activation of latent functional reserves by various exposures to stress (abdominal surgery, cranial electrotherapy stimulation, cranial electrotherapy stimulation with simultaneous administration of droperidol, aminazine, vetranquil, and carbacholine).

Condensation of 2-ethoxypropenal with diaminoethylene in different solvents (CHCl3, MeCN, H2O, DMSO) at room temperature gives an equilibrium mixture (1:1–1.5) of tautomeric 2-(1′-ethoxyvinyl)-1,3-imidazolidine and 2-aminoethylimine of 2-ethoxypropenal as well as 1,2-bis(2′-ethoxypropenyl-ideneamino)ethylene. The latter is readily prepared in quantitative yield using a twofold excess of the aldehyde. 1H NMR was used to demonstrate the effect of heating on the dynamics of the ring-chain tautomeric equilibrium. Reaction of the 2-alkoxypropenals with N-methyl- and N,N′-diphenyl-1,2-diaminoethylenes and with N-phenylaminoethanol gives only the corresponding substituted imidazolidines in 43–95% yield.

2,5-Bis(alkylsulfanyl)-2,3-dihydro-4H-pyran-2carbaldehydes exhibit bacteriostatic effect [1]. 2,5-Bis(butylsulfanyl)-2,3-dihydro-4H-pyran-2-carbaldehyde is known as a strong and safe antiseptic [2]. We examined its reactions with alcohols in order to obtain new potential biologically active derivatives. Unlike 2,5-dialkoxy-2,3-dihydro-4H-pyran-2-carbaldehydes [3] which take up alcohols at the endocyclic double bond, the reaction of sulfur-containing analog I with alcohols in acid medium at room temperature (i.e., under comparable conditions) occurred at the carbonyl group. However, apart from the expected symmetric dialkyl acetal II, diastereoisomeric mixed acetals III and IV were always formed, regardless of the acid taken as catalyst (p-TsOH, HClO4, CF3COOH) or alcohol (MeOH, EtOH); the products are readily detected by gas chromatography–mass spectrometry. To determine the product structure, isomer mixture obtained in the reaction of aldehyde I with methanol were separated by high-performance liquid chromatography (HPLC). The reaction with methanol was selected as model process, taking into account more facile identification of methyl derivatives by NMR spectroscopy. Judging by the intensities of signals from the acetal CH protons at δ 4.27 (IIa), 4.53 (IIIa), and 4.47 ppm (IVa) in the H NMR spectra, the product ratio changed from 2 : 1 : 1 to 1 : 1 : (1–2) in 7–10 days, the conversion of the initial aldehyde being 80–100%. Analysis of the H and C NMR spectra of the first isomer allowed us to identify it as symmetric dimethyl acetal IIa. Formalistically, two other isomers IIIa and IVa result from exchange of OMe and SBu groups in the vicinal acetal and hemithioketal moieties (at the C and C atoms).

Reactions of 2-alkoxypropenals with 2-aminoalkanols afforded tautomeric mixtures of previously unknown 2-(1-alkoxyvinyl)oxazolidines and imino alcohols. The condensation takes 2 h at room temperature (89-100%) or 1-5 min under microwave irradiation. The tautomeric equilibrium shifts toward the open-chain structure with increase in the solvent polarity (CDCl3, CD2OD, DMSO-d6, D2O) and temperature. The presence of substituents in the oxazolidine ring raises the stability of the cyclic tautomer.

The reaction of 2-alkoxypropenals with organylthiols in the presence of small amounts of a base afforded 3-organylsulfanyl-2-alkoxypropanals. The regiochemistry follows the 1,4-addition pattern and contrasts the orientation of the Markovnikov addition, which takes place in the absence of a base. Microwave irradiation accelerates the 1,4-addition reaction.

The reaction of 2-alkoxypropenals with ethane-1,2-dithiols and propane-1,3-dithiols under various conditions was studied by 1H NMR and chromato-mass spectrometry. Under kinetically controlled conditions at 20° in the absence of catalysts the addition of dithiols takes place according to the Markovnikov rule. The primary adducts are unstable and are quickly converted into the corresponding substituted 1,4-dithiacycloheptane or 1,4-dithiane. The latter in turn can be converted under the reaction conditions or at high temperature into a thiolane derivative. The reaction of 2-ethoxypropenal with a twofold excess of ethane-1,2-dithiol at 60°C in the presence of p-toluenesulfonic acid leads to 2-methyl-2,2'-bi(dithiolane)

We have studied the effects of chlorpromazine, acepromazine, droperidol, and transcranial electroanesthesia upon evacuation function of the stomach in piglets and the effects of leu-enkephalin and glycyl-proline upon secretory activity of the stomach in dogs and rats during surgical stress to optimize anesthetic dosage. All pharmaceutical and nonpharmaceutical methods of anesthesia used in the experiments were implemented by actiovating stress-limiting systems in post-operational period. Leu-enkephalin, apart from stimulating the stress-limiting factors of neurohumoral systems of the organism, shifted the vector ratio of aggressive and protective factors of gastric mucosa toward strengthening of the latter. The opposite trends of changes in the secretory activity of the stomach of rats in response to surgical stress can be leveled using glycyl-proline as a component of anesthesia.

The reaction between 2-alkoxypropenals and 2-mercaptoethanol was studied at 20 and 60°C by means of 1HNMR and GC-MS methods. Under kinetically controlled conditions (20°C, 7-30 days) with no catalyst the addition of 2-mercaptoethanol to 2-alkoxypropenals occurs along Markownikoff rule. The arising 2'-hydroxyethylthio-2-alkoxypropanal undergoes isomerization into the 2-hydroxy-3-alkoxy-3-methyl-1,4-oxathiane that at heating in the presence of catalytic amounts of acids is converted into 2-methyl-2-formyl-1,3-oxathiolane. The reaction of 2-alkoxypropenals with 2-mercaptoethanol at heating (60°C, 3 h) in the presence of acids affords 2-methyl-2,2'-bi(1,3-oxathiolane) even at 2-mercaptoethanol deficit. At the double excess of the latter the 2-methyl-2,2'-bi(1,3-oxathiolane) was obtained in quantitative yield. The presumable schemes of conversion of 2-hydroxy-3-alkoxy-3-methyl-1,4-oxathiane into 2-methyl-2-formyl-1,3-oxathiolane and 2-acetyl-1,3-oxathiolane are discussed.

The kinetics of 2-alkylthiopropenals cyclodimerization was studied in the temperature range from -7 to +42 °C in heptane and at 20 °C in various solvents. The rate constants for cyclodimerization of 2-alkylthiopropenals are four orders of magnitude higher than those for dimerization of the oxygen-containing analogs, 2-alkoxypropenals, and are independent of the solvent polarity and substituent steric constant. The activation parameters for 2-butylthiopropenal cyclodimerization were estimated. The distribution of electron density in the 2-methoxy- and 2-methylthiopropenals molecules was calculated by the ab initio method. From comparison of the HOMO and LUMO energies for these aldehydes it was concluded that the ratio between the cyclodimerization rates for 2-alkylthio-, 2-ethoxypropenals, and propenal is determined by the HOMO–LUMO gap.

The first stage of the reactions of alcohols with α-alkoxyacroleins in an acidic medium at 20°C under kinetically controlled conditions is the Markovnikoff addition at the C=C bond to form 2,2-dialkoxypropanals (methylglyoxal ketals). Under conditions of thermodynamic control, subsequent acetalization of the aldehyde group occurs to form 1,1,2,2-tetraalkoxypropanes. When the duration of the reaction is further increased in the absence of a water acceptor, the ketal group undegroes hydrolysis and methylglyoxal acetals are formed. A method was developed for the preparation of methylglyoxal ketals.

Monomeric α-alkylthioacroleins were obtained by the reaction of alkylthioacetaldehydes with formaldehyde and diethylamine hydrochloride. The structures of the α-alkylthioacroleins were confirmed by NMR spectroscopy and mass spectrometry as well as by chemical transformations of these compounds.

Cyanosilylation of α-butylthioacrolein with trimethylsilyl cyanide occurs as 1,2-addition. Concurrent rapid dimerization of α-butylthioacrolein occurred both in the presence and in the absence of H2PtCl6·6H2O as a catalyst to give 2,5-dibutylthio-2,3-dihydro-4H-pyran-2-carbaldehyde, whose cyanosilylation afforded the corresponding cyanohydrin. The latter is prone to retrodiene degradation upon heating.

Under kinetically controlled conditions, the addition of organylthiols to 2-ethoxypropenal follows the Markovnikov rule to give 2-ethoxy-2-organylthiopropanals which spontaneously isomerize to 1-ethoxy-1-organylthiopropanones in storage or in the presence of an acid catalyst.

Methods for the synthesis of new aldehydes and acetals have been developed. The antimicrobial activity of the synthesized compounds against Staphylococcus aureus and Escherichia coli was estimated.

2-Butylsulfanyl-2-alkenals react with alcohols at room temperature in the presence of acid catalysts to give 45–90% of the corresponding acetals. Acetals derived from 2-butylsulfanylpropenal readily undergo hydrolysis at the vinylsulfanyl group (20°C, catalysis by HCl or TsOH) with formation of 2-oxopropionaldehyde O,O- or O,S-acetals in 70–90% yield. Unlike 2-butylsulfanyl-2-propenal O,O-dialkyl acetals, the initial aldehydes and 2,4-dinitrophenylhydrazones derived therefrom are stable to hydrolysis under analogous conditions: the vinyl sulfide moiety remains unchanged even under considerably more severe conditions (100°C, 3 h; HCl, H2SO4, CF3SO2OH, or TiCl4).

Monomeric α-alkylthioacroleins were obtained by the reaction of alkylthioacetaldehydes with formaldehyde and diethylamine hydrochloride. The structures of the α-alkylthioacroleins were confirmed by NMR spectroscopy and mass spectrometry as well as by chemical transformations of these compounds.

Addition of thiols to 2-alkoxypropenal in neutral medium at 20°C in the absence of a catalyst occurs regioselectively, following the Markownikoff pattern. The resulting 2-alkoxy-2-R-thiopropanals are capable of undergoing spontaneous isomerization to 1-alkoxy-1-R-thiopropanones. The addition and isomerization processes are accelerated by heating to 60°C or in the presence of acid catalysts (TsOH, HCl). The reaction is also accompanied by partial disproportionation of 2-oxopropanal O,S-acetals to give O,O- and S,S-acetals.

The reaction of 2-alkoxypropenals with ethane-1,2-dithiols and propane-1,3-dithiols under various conditions was studied by 1H NMR and chromato-mass spectrometry. Under kinetically controlled conditions at 20° in the absence of catalysts the addition of dithiols takes place according to the Markovnikov rule. The primary adducts are unstable and are quickly converted into the corresponding substituted 1,4-dithiacycloheptane or 1,4-dithiane. The latter in turn can be converted under the reaction conditions or at high temperature into a thiolane derivative. The reaction of 2-ethoxypropenal with a twofold excess of ethane-1,2-dithiol at 60°C in the presence of p-toluenesulfonic acid leads to 2-methyl-2,2'-bi(dithiolane)

A method for assessment of the infective activity of HIV using plaque formation method with human diploid cells (strains L-65, L-68, L-72) has been developed. This method is not inferior to plaque formation with poly-L-lysine in sensitivity, but superior to it in reproducibility of results and standardization of the test conditions. The method is fit for titration of HIV and virus-neutralizing antibodies, as well as for assessment of the activity of anti-HIV preparations.

The anti-HIV activity of a cationic detergent myramistin and nonionic detergent dezintegron-0 (d-0) was studied using HIV-1 strains III B/H9 and BRU in lymphoblastoid cells MT-4 and Jurkat-tat. Myramistin in a concentration of 0.075 mg/ml was shown to prevent HIV-1 replication in MT-4 when these cells were cocultivated with the cells preinfected and treated with the detergent. Myramistin in concentrations from 0.030 to 0.050 mg/ml delayed the accumulation of virus antigens in the cells by 4 and 14 days, respectively, without preventing the infection of intact cells. Nonionic d-0 prevented HIV-1 infection of intact Jurkat-tat cells at a concentration of 12.5 mg/ml.

A high rate of HIV carrier state was observed in seropositive children with early symptoms of HIV infection. The virus was also isolated from 2 seropositive adults (mothers) showing no clinical manifestations. The intervals of virus manifestation in culture varied from 6 to 30 days with maximal frequency of detection in the 2nd week. Different modifications of the procedure for HIV isolation were assayed, and it was shown that the efficacy of isolation (shortening of the period of virus detectability and increase in the number of the antigen-containing cells) could be improved by the addition to the culture of the Jurkat-tat III line expressing the product of the tat gene important for virus reproduction.

Both variants of HIV-1 reported in the literature: slow/low and rapid/high types, were detected among the strains isolated from the subjects examined in 4 foci of HIV-1 infection in the south of the RSFSR and Byelorussia. All the 17 strains isolated in the southern RSFSR foci belonged to the slow/low type and had a low and unstable replication potential in donor peripheral blood mononuclear cells and in MT-4 cell line. All of them were isolated from subjects with asymptomatic infection and from children with initial clinical manifestations of the disease. Only one strain isolated in Byelorussia belonged to the rapid/high type. Its replicative activity was very similar to that of the classical HIV-1--HTLV-IIIB strain. Long-term (up to 7 months) propagation of slow/low strains did not result in any increase of their replicative activity. The capacity to form syncytia was found not only in the rapid/high type strains but also in the majority of slow/low strains under study.

The rate constants for cyclodimerization of α-alkylthioacroleins were determined. They are two orders of magnitude higher than those for dimerization of α-alkoxyacroleins.

The nucleophilic or radical addition of thiols to α-alkoxyacroleins leads to 2-alkoxy-3-organylthiopropanals. Depending on the reaction conditions, the product of the electrophilic reaction of the same reagents is a 2-alkoxy-2-organylthiopropanal or 1-alkoxy-1-organylthiopropanone.

1. The reaction of sodium alkanethiolates with the acetals of α-halo-substituted α, β-unsaturated aldehydes leads to the correspondingβ-alkylthio-substituted derivative independent of the nature of the halogen or of the presence of an alkyl group in theβ position, and also independent of the character of the employed solvent. 2. In acid medium theβ-alkylthio-substituted acetals ofα, β-unsaturated aldehydes are hydrolyzed at room temperature without cleaving the C-S linkage to give the correspondingβ-alkylthio-substitutedα, β-unsaturated aldehydes. The latter under mild conditions form derivatives at the carbonyl group without changing the carbon skeleton. This reaction when run with heating leads to cyclization and the formation of pyrazole derivatives. Prolonged heating of the butylthioacrolein with excess butanethiol leads to the reaction product at the two reaction centers, and specifically to 1,1,3,3-tetrabutylthiopropane.

The authors studied the morphology of the following cells: renal cells ofMacacus rhesus, cardiac cells ofMacacus cinomolgus, and of different lines of malignant HeLa and Hep cells. All these cells were cultured on mica films in the liquid nutrient medium. Although the dynamics of the cytological changes of the cultures were similar, each one of them had certain growth peculiarities reflected in the curves of mitotic activity. In 122 experiments this activity in the renal cells was low. Evidently, the cellular reproduction here occurs by amitosis. Irregular mitoses are encountered in all four cultures as a manifestation, of intensive cellular reproduction. The growth dynamics and morphology of the renal culture vary depending on the cells originating directly from the body or from a subculture. The culture of a cinornolgus heart differs by a number of signs (dynamics of mitotic activity, the shape of the nuclei) from the cultures of malignant cells, with which it has certain morphological similarities.

An inquiry was made into the size of the nuclei and the mitotic activity of the transplantable cellular lines HeLa, Hep-2 and cinomolgus heart (SCH) during prolonged cultivation (for about 40 months). Each of the cultures studied was characterized by a definite size of the nuclei. For 40 months the SCH culture was characterized byconstant morphology, degree of mitotic activity and sensitivity to the action of poliomyelities virus. These data are in favor of a marked stability of the transplantable cellular line. However, in individual cases considerable changes were seen in the morphology and mitotic activity of the same transplantable cellular line, depending on the conditions of cultivations.

A complex investigation of the phenotype of a stable strain of LHC—162 cells derived from a spontaneous abortus was carried out. The karyotype, of the strain was 47,XY,+C. The extra chromosome was identified by Giemsa staining as a No. 7. The strain was subjected to cytomorphological, autoradiographic, immunochemical and virological examination in comparison with diploid cell strains. The cells of the LHC—162 strain had no oncogenic activity. Their susceptibility to the three types of poliomyelitis virus did not differ from those of diploid strains. The growth of the LHC—162 cells was poorly organized, and they had a reduced capacity for the formation of histotypical structures. There was low collagen production, poor accumulation of lipid granules, high acid phosphatase, activity, and high glycogen content. Radioautographic investigation of cell cycle revealed lengthening of the mitotic cycle in the G2, period which was twice as long as in diploid strains. Immunochemical investigation showed that fibroblasts of both trisomic and diploid strains synthesized proteins in α1 and α2 globulin zones. However, the synthesis of a protein in α1 zone was considerably more intensive and in α2 zone less intensive in the LHC—162 cells than in the diploid strain.

The authors studied the effect of polio virus upon the morphology of the cells obtained from subculture of the renal tissue (Macacus rhesus), heart (Macacus cynomolgus) and HeLa and HEp-2 malignant cells. The changes become noticeable in individual cells after an 8–12-hour action and are marked in 24 hr. These changes are manifested in the chromatin redistribution, the loss of nuclear membrane turgor, the change of the cellular shape and cytoplasmic eosinophilia. The most sensitive to the action of the virus are the cultures during the initial stages of growth, and the youngest and the most active cells in a given culture. The following changes occur in the cultures of transplantable strains acted upon by the virus: at first decomplexation of the stratum is noted with the formation of roundish cellular accumulations, and only later the changes in the individual cells are seen. Temporary stimulation of mitotic activity is noted in the cells of the transplantable strains on the second day of the viral action

A number of new 2,5-dialkylthio-2-formyl-2, 3-dihydro-γ-pyrans was synthesized via the Mannich reaction using alkylthioacetaldehydes.

It is shown that polarization of the endocyclic double bond in the electrophilic addition of alcohols and water to 2-formyl-2,5-dialkoxy-2,3-dihydro-γ-pyrans is directed toward the carbon atom in the 6 position.

1. Depending on the reaction conditions, the hydrolysis ofβ-ethylthiocrotonaldehyde diethyl acetal leads either toβ-ethylthiocrotonaldehyde or to methylβ-ethylthiovinyl ketone. 2. The 2,4-dinitrophenylhydrazones ofβ-ethylthiocrotonaldehyde and methylβ-ethylthiovinyl ketone when heated in an acid medium are respectively converted to the 5-methyl and 5-methyl derivatives of 1-(2,4-dinitrophenyl)pyrazole.

Alkylthioacetaldehydes under the conditions of the aminomethylation reaction giveα-alkylthioacro-leins, which under the synthesis conditions are dimerized to 2-formyl-2,5-dialkylthio-2,3-dihydro-γ-pyrans.

Experiments were performed on pathogenicity of LPV oncornavirus and Mason-Pfizer-like virus for monkeys Macaca mulatta. The mixture of culture fluid and cell homogenate ultrafiltrates of virus-producing T-9 cell line was used as a source of LPV virus. The same materials derived from HEp-2 continuous cell line served as a source of Mason-Pfizer-like virus. As a control monkeys were inoculated with ultrafiltrates from human diploid cells. The clinical and pathomorphological analysis of experimental results leads to the conclusion, that only LPV virus induced different forms of haemacytoblastosis in monkeys that confirms our previous observations.

The alkaline phosphatase activity was studied in embryonic lung human fibroblasts grown in vitro. The total enzyme activity per flask was constant during the log-phase of culture growth to increase significantly after confluence. The increase in the activity did not depend on the rate of culture growth, and was seen to start after the mean density equal to (37.5 +/- 5.9) X 10(3) cells/cm2 flask surface. The stimulation of cell growth may presumably slow down the synthesis of alkaline phosphatase, which resumes after the contact inhibition of DNA replication.