Interaction of Zn(2+) ions with single-stranded polyU and polyC in neutral solutions.

Effect of Zn(2+) ions on the conformation of single-stranded polynucleotides polyU and polyC in a wide temperature range at pH 7 was studied by differential UV spectroscopy and by thermal denaturation. The atoms coordinating Zn(2+) ions were determined (O4 and N3 in polyU and N3 in polyC). A three-dimensional phase diagram and its two-dimensional components were constructed for a polyC-Zn(2+) system. The phase diagram revealed a region in which ordered single-stranded structures, stabilized by Zn(2+)-mediated cross-links involving N3 atom of cytosine, are formed. The phase diagram also demonstrated that the behavior of the polyC-Zn(2+) system is similar to the effect of retrograde condensation observed in some binary solutions of simple liquids. A dependence of Zn(2+)-polyC binding constant on the metal ion concentration was obtained. The reason why zinc-induced transition of the sequences with adenine-uracil (AU) base pairs from A-form geometry to a metallized m-form requires higher pH compared to the sequences comprised of guanine-cytosine (GC) base pairs is explained. This information can be useful for the development of possible technological applications based on m-DNA.

Effect of Zn2+ and temperature on the conformational equilibrium of single-stranded polyA in neutral solutions.

Effect of Zn(2+) ions on the conformation of polyA in cacodilic buffer at pH 7 was investigated by differential UV spectroscopy (DUV) and by thermal denaturation. The shapes of the DUV spectra and melting curves suggest a transition of polyA into a more ordered "metallized", possibly double-helical conformation at Zn(2+) concentrations above 3×10(-5) M. A phase diagram of polyA complexes with Zn(2+) was constructed for the temperature range from 20 °C to 95 °C and Zn(2+) concentrations between 10(-5) M and 5×10(-4) M. It was found that the transition of a single strand into the "metallized" form is possible only if the length of the disordered single-stranded region becomes larger than a certain critical value, ranging between 98% and 78% as the metal concentration increases from 3×10(-5) to 5×10(-4) M.

Specific features of Zn²âº, Co²âº and Ni²âº ion binding to DNA in alkaline solutions.

Dependence of DNA metallization degree during B-DNA transition into the metallized (m) form on DNA concentration has been studied by visible and differential UV-spectroscopy in the presence of Zn(2+), Co(2+) and Ni(2+) ions in tetraborate buffer (pH 8.5) with and without ethidium bromide. Constants of Mt(2+) binding to double stranded DNA were calculated. The obtained binding constants corresponded to the formation of inter-strand metal bridges stabilizing m-form. Thermodynamic origin of higher efficiency of Zn(2+) ions in DNA metallization compared to Co(2+) and Ni(2+) was revealed. Increase of the DNA helix-coil transition temperature by up to 10°Ð¡ upon formation of m-form in the presence of Zn(2+) ions was observed and rationalized. Furthermore, a strong cooperative decrease (up to 30°Ð¡) of the temperature of В→m transition induced by heating in the presence of Zn(2+) was found and its nature was explained.

DNA conformational equilibrium in the presence of Zn2+ ions in neutral and alkaline solutions.

Effect of Zn(2+) ions on DNA transition from B-form to a metallized form (m-DNA) in Tris and tetraborate buffers at pH 8.5 has been studied by visible and differential UV-spectroscopy and by thermal denaturation. The results have been compared to those obtained at pH 6.5 in cacodylate buffer. It was found that in alkaline solutions Zn(2+) ions induced a hypochromicity of the DNA absorption in the whole spectral range monitored, which was attributed to DNA transition from B- to the m-form. Complete metallization occurred only upon heating the DNA solutions containing more than ~2×10(-4) M of Zn(2+) ions. Phase diagrams of the DNA-zinc complexes at pH 6.5 and 8.5 have been obtained for the first time. The m-DNA form showed higher thermal stability compared to B-DNA.

Divalent metal ion effect on helix-coil transition of high molecular weight DNA in neutral and alkaline solutions.

Effect of Mg(2+), Ca(2+), Ni(2+) and Cd(2+) ions on parameters of DNA helix-coil transition in sodium cacodylate (pH 6.5), Tris (pH 8.5) and sodium tetraborate (pH 9.0) buffers have been studied by differential UV-visible spectroscopy and by thermal denaturation. Anomalous behavior of the melting temperature T(m) and the melting interval ΔT in the presence of MgCl(2) was observed in Tris, but not in cacodylate or tetraborate buffers. Changes in the buffer type and pH did not influence T(m) and ΔT dependence on Ca(2+) and Cd(2+) concentrations. Decrease of the T(m) and ΔT of DNA in the presence of Ni(2+) and Cd(2+) was caused by preferential ion interaction with N7 of guanine. This type of interaction was also found for Mg(2+) in Tris buffer. The anomalous decrease in the T(m) and ΔT values was connected to formation of complexes between metal ions and Tris molecules. Transition of DNA single-stranded regions into a compact form with the effective radius of the particles of 300±100 Å was induced by Mg(2+) ions in Tris buffer.

Acute thoracic aortic pathology in practice of the cardiovascular surgeon.

Acute thoracic aortic pathology is a relatively new term. The experience gained in treatment of thoracic aorta pathology has shown the importance of early diagnosis of the disease of this localization. Improved resolution of modern diagnostic medical equipment has made it possible to recognize early forms of aortic lesions and accordingly to optimize management of this cohort of patients. The present article is based on the review of the pertinent literature, summarizing the data on aetiology, pathophysiology, clinical patterns, and present-day therapeutic strategy employed in the three most frequently encountered forms of an acute aortic lesion, i. e., aortic dissection, aortic intramural haematoma, and penetrating atherosclerotic ulcer of the aortic wall.

[Stereotactic radiosurgery in treatment of patients with hypothalamic hamartomas].

Hypothalamic hamartoma (HH) is malformation of the brain manifesting by paroxysmal disorders (gelastic seizures) and endocrine disorders (mostly precocious sexual development). Surgical resection of HH is associated with the risk of severe neurological and neuroendocrine complications. Alternative ways of treatment are being investigasted. Stereotactic radiosurgery is one of the leading techniques in treatment of pharmacoresistant seizures due to high effectiveness and low complication rate. Since 2005 till 2009 7 patients with HH were treated in Burdenko Moscow Neurosurgical Institute. Age of patients varied between 9 months and 20 years 9 mean - 8.5 years). In all cases the disease manifested by gelastic seizures with frequency differing between 2-3 per months and 17 per day. All patients received long-term combined anticonvulsant treatment (using valproates, carbamazepine, lamotrigine, oxcarbazepine, topiramate) with temporary and insufficient effect or without any effect. In 4 patients frequency of seizures increased during anticonvulsant therapy. I patient had been operated (partial resection of HH) with temporary effect which consisted of decrease in frequency of seizures for 8 months; later frequency of paroxysms increased. Main indications to radiosurgical treatment included progressive course of disease, low effectiveness of anticonvulsant therapy and high risk of direct surgical treatment. 6 patients were treated using linear accelerator "Novalis" and 1 using "Cyber-knife". Treatment was performed under pharmacological sedation (midazolam, ketamine). Marginal dose was 11-18 Gy (mean 15.7 Gy). Volume of hamartomas was 0.3-3 cm3. Follow-up period varied between 3 and 50 months. Decreased frequency of seizures was observed in 100% of cases. Stereotactic radiosurgery is an effective and safe method of treatment for HH and may be considered as treatment of choice for pharmacoresistant seizures caused by HH.

Role of "hybrid" operation in the surgical management of type I aortic dissection. Early experience.

Persistent or recurrent aortic dissection after successful surgical treatment of acute type I aortic dissection is well-known complication. Persistence of the false lumen in the arch or descending aorta can result in a fatal complication and has an undesirable impact on long term prognosis. Endovascular stenting has showed promising result for patients with type III aortic dissection. The role of stenting in management of complex persistent aortic dissection is not well established. In the article we reviewed our early result of combine surgical and endovascular treatment of persistent type I aortic dissection. In our series we did not have mortality. Analysis of early and long term postoperative period showed promising result.

[The nature of different influence of Cd2+ ions on the conformation of three-stranded polyU-polyA-polyU and polyI-polyA-polyI in aqueous solution].

The methods of UV (DUV) spectroscopy and thermal denaturation were used to study the effect of Cd2+ ions on the conformational equilibrium of three-stranded (A21, A2U) and single-stranded (poly U, poly A and poly I) polynucleotides in aqueous solutions containing 0.1 M Na+ (pH 7). An analysis of the form and intensities of DUV-spectra of poly A, poly I and A2I revealed the presence of two types of complexes: interaction with N7 of purines, resulting in the formation of macrochelates and binding to N1 of poly A and poly I. Cd2+ ions do not bind to heteroatoms of A2U nitrogen bases, and, therefore, the conformation of its structure remains unchanged up to a concentration of Cd2+ 0.01 M. A "critical" concentration (1.5x10(-4) M) of Cd2+ ions exists above which A2I transits cooperatively into a new helical conformation, which has a lower thermostability. It is supposed that, during the formation of metallized A2I, Cd2+ ions form bridges between the adenine and hypoxanthine of its homopolynucleotide circuits, being arranged inside the triple helix.

Mg2+ and Ni2+ ion effect on stability and structure of triple poly I.poly A.poly I helix.

The effects of Mg2+ and Ni2+ ions on the absorption spectra of IMP, single-stranded poly I and three-stranded A2I in solutions with 0.1 M Na+ (pH 7) have been studied. In contrast to Mg2+ ions, the Ni2+ ions affect the absorption spectra of these polynucleotides and IMP. The concentration dependences of the intensity at the extrema in the differential UV spectra suggest that in the region of high Ni2+ concentrations ionic complexes with poly I and A2I are formed, which are characterized by the association constants K'''I = 2000 M(-1) and K'''A2I = 550 M(-1), respectively. The shape of the DUV spectra prompts the conclusion that these complexes are formed due to the inner-sphere interaction of Ni2+ ions with N7 of poly I and A2I presumably due to the outer-sphere Ni2+-O6 interaction. The formation of the complexes leads to destruction of A2I triplexes. The dependences of the melting temperature (T(m)) of A2I on Mg2+ and Ni2+ concentrations have been measured. The thermal stability is observed to increase at the ionic contents up to 0.01 M Mg2+ and only to 2x10(-4) M Ni2+. At higher contents of Ni2+ ions, T(m) lowers and the cooperativity of A2I melting decreases continuously. In all the cases the melting process is the A2I-->A+I+I (3-->1) transition. According to the "ligand" theory, these effects are generated by the energy-advantageous Ni2+ binding to single-stranded poly I (K'''A2I < K'''I) and by the greater number of binding sites which appears during the 3-->1 transition and is entropy-advantageous.

[Interaction of divalent metal ions with four-stranded polyriboinosinic acid]. / Vzaimodeistvie ionov dvukhvalentnykh metallov s chetyrekhtsepochechnoi poliriboinozinovoi kislotoi.

Interaction of Mg2+, Ca2+, Cu2+ ions with the four-stranded poly(I) was studied using differential UV and visible spectroscopies. It was shown that, up to concentrations of approximately 0.1 M, Mg2+ and Ca2+ ions do not bind to heteroatoms of hypoxanthine of the four-stranded poly(I). Cu2+ ions interact with N7 (and/or N1) and O6 (through the water molecule of the hydrate shell of the ion). The latter seems to induce the enolization of hypoxanthine the deprotonation of N1, and, as a result, the transition of the four-stranded helix to single-stranded coils. Single-stranded chains form compact particles with an effective radius of about 100 A.

[Interaction of Ag+ ions with DNA and its monomers]. / Vzaimodeistvie ionov Ag+ s DNK i ee monomerami.

Differential UV spectra of DNA and its monomers that were induced by Ag+ ions were measured, and the effect of ions on the parameters of the helix-coil transition was studied. The data obtained confirm the existence of "strong" and "weak" modes of binding of Ag+ to DNA. The earlier proposed proton transfer from N1G to N3C, which is determined by the interaction of Ag+ with N7G (a "strong" complex), follows immediately from the shape of the differential UV spectra. The positive cooperativity of the binding of Ag+ to DNA upon the formation of a "weak" complex is due to the cooperativity of the transition of DNA to a new double-helical conformation. A model of this conformation is proposed which suggests the formation of Hougsteen GC and AT pairs.

[Interaction of Ag+ ions with ribonucleotides of canonical bases]. / Vzaimodeistvie ionov Ag+ s ribonukleotidami kanonicheskikh osnovanii.

The interaction of Ag+ ions with ribonucleotides of canonical bases in aqueous solution was studied by differential UV spectroscopy. Atoms coordinating silver ions (N7, O6 of guanosine 5'-monophosphate, N3, O2 of cytidine 5'-monophosphate, N7, N1, N3 of adenosine 5'-monophosphate and N3 of uridine 5'-monophosphate) and the binding constants characterizing the formation of appropriate complexes were determined. The differences in the relative affinity of Ag+ ions for the atoms of nucleotide bases correlate with the potential on them.

[Interaction of divalent cadmium ions with nucleotides and native DNA]. / Izuchenie vzaimodeistviia ionov dvukhvalentnogo kadmiia s nukleotidami i prirodnoi DNK.

Complex formation of Cd2+ ions with 2'-deoxy-5'-phosphates of canonical bases and their riboanalogues in water solution is studied by the method of differential UV-spectroscopy. It is stated that the atoms coordinating Cd2+ in complexes are N7 of dGMP and GMP, dAMP and AMP, N1 of adenine derivatives, N3 of dCMP. No interaction with base heteroatoms of UMP and dTMP is found. O2' present in the structure of the sugar ring has a weak influence on the Cd2+ ion binding to purine nucleotides. It manifests itself strongly in the complexes with cytosine derivatives: cadmium does not interact with N3 of CMP and poly-C practically. In the last case O2 is a centre coordinating Cd2+ ions. The interaction with this atom induces the melting of polynucleotide helical parts. At the high cadmium concentration poly-C forms compact particles. The main centre binding Cd2+ ions in DNA is N7 of guanines. Noncooperative interaction with these centres results in the internal protonation of N3C of GC-pairs. This is not followed with the disordering of the DNA helical structure.

[The "condensation" and "ligand" theory in describing DNA helix-coil transition: comparative analysis]. / Teorii "kondensatsii" i "skrepok" pri opisanii perekhoda spiral'-klubok DNK: sravnitel'nyi analiz.

Experimental data on DNA melting in the presence of magnesium and calcium ions are compared with the calculated results by the "ligand" theory and "condensation" theory developed by de Marky and Manning (TMM). The maximum is observed in TMM dependences of DNA melting temperature change (delta Tm) on the ion concentration (D), absent in the experimental dependences and the "ligand" theory. The main cause of the discrepancy of calculated and experimental dependences delta Tm (D) is the fact that TMM neglects Na+ ion effects on Me2+ ion binding ("condensation") to DNA. The results obtained show that in comparison with TMM the "ligand" theory describes more adequately DNA helix-coil transition in the presence of divalent metal ions in the region of both low and high ionic strengths of solution.

Interaction of bivalent copper, nickel, manganese ions with native DNA and its monomers.

UV differential spectroscopy is applied to study the interaction of Cu2+, Ni2+, Mn2+ ions with deoxyribonucleotides of canonic bases (dGMP, dAMP, dCMP, dTMP) and native DNA. Heteroatoms of the bases, coordinating ions, and binding constants which characterize the formation of metal complexes are found. The affinity of the ions is lower for the deoxyribonucleotide bases than for the ribonucleotide ones. This indicates that 02' of ribose participates in the stabilization of the metal complex even under conditions close to the neutral one (pH 6). Unlike the Cu2+ ions, Ni2+ and Mn2+ ions do not interact with N3C both in monomers and polymers. This seems to be the main factor explaining why copper makes DNA transform into a structure with a quasi-Hoogsteen pairing of GC pairs. No transformations of this kind of helix-coil transitions are caused by manganese and nickel up to concentrations 4 X 10(-2) M.

[Interaction of divalent copper ions with native DNA and its monomers]. / Vzaimodeistvie ionov dvukhvalentnoi medi s prirodnoi DNK i ee monomerami.

The complex formation of Cu2+ ions with the 2'-deoxynucleotide-5'-phosphates of bases in water solution by the UV-spectroscopy method has been established. It was obtained that the N7-atom in dGMP and N3-atom in dTMP are coordinated with copper (Cu) in complexes. The deoxyribonucleotide C can not subtract with the copper (Cu). The constants (K) of Cu-bases binding have been obtained. The K-value for purines is greater than for pyrimidines independent of the ribose structure. The ions Cu2+ at formation of complexes with separate nucleotides or natural DNA can cause the conformational transitions in these molecules. Thus the ions Cu2+ interact as with N7 and O6 G, as with N3 and O2 C. It is agreed with model, in which guanosine passes from anti to sin-conformation. The interactions of Cu-ions with G, C and A base pairs in single stranded DNA have been registered.

[Structural and physicochemical characteristics of DNA from animal tissue subjected to chronic irradiation in the Chernobyl area]. / Strukturnye i fiziko-khimicheskie kharakteristiki DNK iz tkanei zhivotnykh, podvergavshikhsia dlitel'nomu khronicheskomu oblucheniiu v zone chernobylia.

The properties of animal DNAs exposed to prolonged irradiation in the Chernobyl zone, have been studied by the methods of viscometry, thermal denaturation, IR-spectroscopy, and electrophoresis. High content of low-molecular fractions have been observed in the preparations of DNA from liver and spleen, their quantities increasing with age and generation of animals. This effect is especially strong in DNA from liver. Low-molecular fraction of DNA is shown to be enriched with G-C pairs and to consist of the following four fractions: 1) approximately 500 base pairs (B.p.), 2) approximately 1.5 divided by 2 thousand B.p., 3) approximately 4 divided by 5 thousand B.p. and 4) a mixture of approximately 20 thousand B.p. fragments. Further, it has been observed that the DNA preparations from the tissues of experimental animals contain about ten times higher contents of Fe, Zn, Se and other elements as compared to the control preparations.

[Interaction of DNA with divalent metal ions]. / Izuchenie vzaimodeistviia DNK s ionami dvukhvalentnykh metallov.

The interaction between the native DNA macromolecules and Ca2+, Mn2+, Cu2+ ions in solutions of low ionic strength (10(-3) M Na+) is studied using the methods of differential UV spectroscopy and CD spectroscopy. It is shown that the transition metal ions Mn2+ exercise binding to the nitrogen bases of DNA at concentrations approximately 5 x 10(-6) M and form chelates with guanine of N7-Me(2+)-O6 type. Only at high concentrations in solution (5 x 10(-3) M) do Ca2+ ions interact with the nitrogen bases of native DNA. In the process of binding to Ca2+ and Mn2+ the DNA conformation experiences some changes under which the secondary structure of the biopolymer is within the B-form family. The DNA transition to the new conformation is revealed by its binding to Cu2+ ions.