Investigation of complexes of DNA with synthetic peptide fragments of the N-end of histone H2B

The nature of the interaction of high- and low-molecular-weight DNAs (6×10⁶ and 3×10⁵ daltons) with synthetic oligopeptides of the N-end of histone H2B having the sequences 1–21, 1–10, 1–13, 11–21, and 14–21, differing in molecular weight and amino acid composition, as a function of the amount of peptide component in the complex and the ionic strength of the solution has been studied by the methods of UV and CD spectroscopy and the spectrophotometric analysis of melting curves. It has been shown that of all the peptides studied only the 1–21 peptide possesses the capacity of condensing DNA. This capacity depends on the amount of peptide component in the complex, the molecular weight of the DNA, and the ionic strength of the solution. The interaction with peptides under all the conditions studied, without changing the conformational parameters of the DNA, stabilizes its secondary structure in relation to the action of the temperature, which depends on the number of lysine residues in the peptides.N. I. Nikitin Institute of Chemistry of the TadzhSSR Academy of Sciences, Dushanbe. Institute of Cytology of the USSR Academy of Sciences, Leningrad. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 708–713, September–October, 1987.     

Conformational features of peptide fragments of the C-end of histone H1

The conformational possibilities of four synthesized oligopeptides with the amino acid sequences 165–172, 173–184, 152–172, and 152–184 of the C-end of histone H1 of calf thymus above been studied in solution under various conditions by the method of circular dichroism. V. I. Nikitin Institute of Chemistry, Academy of Sciences of the Tadchik SSR, Dushanbe. Institute of Cytology, Academy of Sciences of the USSR, Leningrad. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 793–798, November–December, 1990.     

Conformational features of peptide fragments of the C-end of histone H1

The conformational possibilities of four synthesized oligopeptides with the amino acid sequences 165–172, 173–184, 152–172, and 152–184 of the C-end of histone H1 of calf thymus above been studied in solution under various conditions by the method of circular dichroism.V. I. Nikitin Institute of Chemistry, Academy of Sciences of the Tadchik SSR, Dushanbe. Institute of Cytology, Academy of Sciences of the USSR, Leningrad. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 793–798, November–December, 1990.     

Theoretical Investigation of the C2H2B2 Potential Energy Surface

Fifteen unique energy minima and thirteen transition states on the C ₂H₂B₂ potential surface have been located and optimized at the MP2 level of theory with the 6-311G(d,p) basis set. The planar four-membered ring isomer , 1, an analog of cyclobutadiene, is a transition state lying 37 kcal/mol above the nonplanar four-membered ring , 3. The planar , 10, is the second most stable species found, lying 72.2 kcal/mol below 3. The nonplanar, butterfly-shaped ring, 4, is a local minimum 33.7 kcal/mol more stable than 3. A four-membered ring isomer with alternating boron–carbon locations, , 5, lies 67.0 kcal/mol below 3 and 33.3 kcal/mol below 4. The ring of 5 is planar with one hydrogen above and one below the plane (C _2h symmetry). The borylene-substituted boracyclopropene, , 8, is a planar local minimum lying 36.0 kcal/mol above 5. The most stable C₂H₂B₂ isomer found was the planar, four-membered ring system 22 (D _2h symmetry) composed of two BCC three-membered rings fused across the C-C bond. Structure 22 lies 22.2 kcal/mole below 10, 105.4 kcal/mol below 3, 71.7 kcal/mol below 4, and 38.2 kcal/mol below 5. Isomer 22 is the structural analog of the trialene form of C₄H₂. The most stable linear isomer, HB BH, 26, was surprisingly 50.5 kcal/mol less stable than 22. The stabilities of the two most stable cyclic isomers 10 and 22 may be explained by aromaticity.     

Oxorhenium phosphinophenolato complexes with model peptide fragments: synthesis, characterization, and stability considerations

The synthesis and characterization of a series of mixed-ligand oxorhenium(V) complexes containing the o-diphenylphosphinophenolato ligand (HL) and model peptide fragments acting as the tridentate coligand are reported. Thus, by reacting equimolar amounts of tiopronin, Gly-Gly, Gly-L-Phe, or glutathione (GSH) peptides on the [(n-C4H9)4N][ReOCl3(L)] precursor in refluxing MeCN/MeOH or aqueous MeCN/MeOH mixtures, the following complexes were obtained: ReO([SC(CH3)CONCH2COO][L])[(n-C4H9)4N], 1, ReO([H2NCH2CONCH2COO][L]), 2, ReO)[H2NCH2CONCH(CH2C6H5)COO][L]), 3, and ReO([SCH2CH(NHCOCH2CH2CHNH2COOH)CONCH2COO][L])Na, 4. The compounds are closed-shell 18-electron oxorhenium species adopting a distorted octahedral geometry, as demonstrated by classical spectroscopical methods including multinuclear NMR. X-ray diffraction analyses for 1 and 2 are also reported. By comparative stability studies of complexes 1-3 against excess GSH it was shown that complex 3 containing the bulky C6H5CH2 substituent adjacent to the coordinated carboxylate group of Phe is the most stable complex.     

Comparative investigation of the structure of complexes of DNA with the polypeptide fragment 152–184 of histone H1 and the polypeptide (Lys-Ala-Ala)n

The interactions with DNA of a synthetic peptide fragment of histone H1 33 amino acid residues long the sequence of which corresponds to fragment 152–184 and of a synthetic polypeptide (Lys-Ala-Ala)_n modeling the properties of the C-terminal fragments of histone H1 have been studied by the CD method. The use of the CD method for recording the spectra of the polypeptides under investigation in the free state and of the artificial complexes of DNA formed with them has permitted the characterization of different structural possibilities of the polypeptides in solution and of their complexes with DNA, and the conformational changes of the components of the complex under various ionic conditions.     

Racemization at proline residues during peptide bond formation : A study of diastereomeric mixtures of synthetic alamethicin fragments by 270 MHz 1H NMR

The stepwise synthesis of amino terminal pentapeptide of alamethicin, Z-Aib-Pro-Aib-Ala-Aib-OMe, by the dicyclohexylcarbodiimide mediated couplings leads to extensive racemization at the Ala and Pro residues. Racemization is largely suppressed by the use of additives like N-hydroxysuccinimide and 1-hydroxybenzotriazole. The presence of diastereomeric peptides may be detected by the observation of additional methyl ester and benzylic methylene signals in the 270 MHz ¹H NMR spectra. Unambiguous spectral assignment of the signals to the diastereomers has been carried out by the synthesis and NMR studies of the D-Ala tetra and pentapeptides. The racemization at Pro is of particular relevance in view of the reported lack of inversion at C-terminal Pro on carboxyl activation.     

Interaction of Cu(II) and Ni(II) with the 63-93 fragment of histone H2B

Chromatin proteins are believed to represent reactive sites for metal ion binding. We have synthesized the 31 amino acid peptide Ac-NSFVNDIFERIAGEASRLAHYNKRSTITSRE-NH2, corresponding to the 63-93 fragment of the histone H2B and studied its interaction with Cu(II) and Ni(II). Potentiometric and spectroscopic studies (UV-vis, CD, NMR and EPR) showed that histidine 21 acts as an anchoring binding site for the metal ion. Complexation of the studied peptide with Cu(II) starts at pH 4 with the formation of the monodentate species CuH2L. At physiological pH values, the 3N complex (N(Im), 2N(-)), CuL is favoured while at basic pH values the 4N (N(Im), 3N(-)) coordination mode is preferred. Ni(II) forms several complexes with the peptide starting from the distorted octahedral NiH2L at about neutral pH, to a square planar complex where the peptide is bound through a (N(Im), 3N(-)) mode in an equatorial plane at basic pH values. These results could be important in revealing more information about the mechanism of metal induced toxicity and carcinogenesis.     

A study of the behavior of histone H1 and its complex with DNA by the spin-label method

The behavior of the tyrosine-72 residue of histone H1 has been studied by the spin-label method as a function of the ionic strength of the solution and of the temperature and on its interaction with DNA. It has been shown that in the formation of complexes of histone H1 with DNA the globular part of the protein not directly interacting with the nucleic acid retains a definite conformation enabling it to participate in various processes taking place in the chromatin.     

乙硼烷离子和自由基结构的量子化学研究

用B₃LYP/6-311G(d,p)密度泛函方法对B₂H₅⁺阳离子和B₂H₅^·自由基的几何异构体的空间构型进行了优化,并在此基础上用QCISD(T)/6-311++G(3df,2p)偶合簇法进行了单点能计算和零点能校正.结果表明,B₂H₅⁺单态有2种稳定的几何构型(D_3h,C₁),其中C₁构型是新发现的.B₂H₅⁺三重态阳离子除已知C_s构型外,又发现两种稳定构型(C₁).对于B₂H₅^·自由基体系,共有4种异构体(包括两种新发现的构型C_s),其中,具有单桥结构的C_2v最稳定.用二级多体微扰理论和密度泛函方法对前人所认为稳定的B₂H₅⁺单态的C_2v构型进行了全优化,结果发现该构型始终具有一个虚频,不是稳定构型.对B₂H₅^-阴离子体系的单态和三重态进行的全优化,理论上得出单态时具有C_2v和C_s两种稳定构型,而三重态只有C_2v一种稳定构型.     

Sandwich iridium complexes with the monoanionic carborane ligand [9-SMe2-7,8-C2B9H10]−

The reaction of the [(η-9-SMe₂-7,8-C₂B₉H₁₀)IrBr₂]₂ complex with Tl[Tl(η-7,8-C₂B₉H₁₁)] afforded the iridacarborane compound (η-9-SMe₂-7,8-C₂B₉H₁₀)Ir(η-7,8-C₂B₉H₁₁). The cationic complex [Cp*Ir(η-9-SMe₂-7,8-C₂B₉H₁₀)]⁺PF₆ ⁻ (5 · PF₆, Cp* is pentamethylcyclopentadienyl) was synthesized by the reaction of [Cp*IrCl₂]₂ with Na[9-SMe₂-7,8-C₂B₉H₁₀]. The structures of (η-9-SMe₂-7,8-C₂B₉H₁₀)Ir(η-cod) (cod is 1,5-cyclooctadiene) and 5 · PF₆ were established by X-ray diffraction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 81–84, January, 2006.     

A synthetic cycle for H2/CO activation and allene synthesis using recyclable zirconium complexes

The zirconium complexes supported by the anisole-bridged bis(phenoxide) ligands serve as an easily recycled auxiliary for converting H2 and CO into allene and hexamethyldisiloxane under mild conditions. Hydrogenolysis of the zirconium benzyl complexes followed by treatment with CO led to formation of oxo-bridged complexes and allene. Deoxygenation of the resulting oxo-bridged complexes with trimethylsilyltrifluoromethanesulfonate and trimethylsilyl chloride and subsequent treatment with benzylmagnesium chloride re-formed the starting benzyl complexes.