Laser photolysis of interaction of poly-guanylic acid (5'''') with anthraquinone-2-sulfonate

The electron transfer reaction between triplet anthraquinone-2-sulfonate and poly-guanylic acid (5') in CH3CN-H2O (97 : 3) has been investigated by 248 nm (KrF) laser flash photolysis. The transient absorption spectra and kinetics obtained from the interaction of triplet anthraquinone-2-sulfonate and poly[G] demonstrate that the primary ionic radical pair, radical cation of poly[G] and radical anion of anthraquinone-2-sulfonate have been detected simultaneously. The free energy changes in the process of the electron transfer were also calculated.     

Study on inclusion interaction of hydrophilic 2-chloromandelic acid with hydroxypropyl-β-cyclodextrin

The inclusion interaction between hydroxypropyl-β-cyclodextrin (HP-β-CD) and hydrophilic 2-chloromandelic acid (CMA) was studied by ultraviolet (UV) absorption spectrophotometer. A reliable determination of the complex stoichiometry was provided by the continuous variation technique. ¹H NMR spectrum and Thermo-gravimetric/differential thermal analyzer (TG/DTA) techniques were explored to further characterize the inclusion complex, and molecular modeling was used to investigate the mechanism of inclusion interaction. The results showed that HP-β-CD reacted with R,S-CMA to form inclusion complexes, with 1:1 stoichiometry and inclusion stability constants K_R and K_S were 24 and 39 L/mol determined from UV data by the method of Benesi-Hildebrand’s. Molecular modeling confirmed experimental observation and indicated that the hydrogen bonding interaction plays an important role in the interactive inclusion between HP-β-CD and CMA. Besides, compared with the HP-β-CD, molecular modeling showed R, S-CMA interact with β-CD through different binding modes, in which Vander Waals is the main intermolecular force between β-CD and R-CMA (or S-CMA) while without obvious hydrogen bonding interaction.     

2′,5′-寡核苷酸C_(2′P_5′)C_(2′P_5′)A的合成

近年来发现用干扰素处理过的细胞胞浆提取物和双链RNA、ATP一起培养,可以生成一个低分子量的蛋白合成抑制剂,即5′-三磷酸-三聚2′,5′-腺苷酸(Ⅰ)。由于(Ⅰ)具有天然核酸中不存在的2′,5′-磷酸酯链以及它的抗病毒活性,因此引起不少化学家的兴趣,已有不少文章报导了(Ⅰ)及其类似物的合成,同时也发现不含三磷酸的三聚2′,5′-腺苷酸(Ⅱ)也同样具有活性。为了进一步研究(Ⅰ)的结构与活性关系,本文报导了用胞嘧啶碱基代替腺嘌呤碱基的(Ⅱ)的类似物C_(2′P5′)C_(2′P5′)A(Ⅲ)的合成。     

Laser flash photolysis of fullerols of C_(60) and of C_(70) in aqueous solutions

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Vibration-rotation infrared spectrum of ν2 of methyl iodide—Coriolis interaction with ν5

Vibration-rotation i.r. spectrum of ν₂ of methyl iodide was measured with a resolution of 0.08 cm⁻¹. The spectrum was analyzed by taking account of an xy-type Coriolis interaction between ν₂ and ν₅ and a Fermi resonance between ν₅ and ν₃ + ν₆. The analysis gave values of spectroscopic parameters which include (ν₀)₂ 1251.193 cm⁻¹, A₂-A₀ 0.02030 cm⁻¹, (D_J)₂ 2.08 × 10⁻⁷ cm⁻¹, (D_JK)₂ 3.2 × 10⁻⁶ cm⁻¹ and ζ_2,5a^y −0.630₅.     

A convenient automated solid-phase synthesis of PNA-(5′)-DNA-(3′)-PNA chimera

An automated online solid-phase synthesis of Ac-cac ct T¹GG TC t¹ac ct-Gly-OH¹ using standard DNA and appropriately protected PNA building blocks (2–5) is described. This chimera forms stable duplexes with complementary DNA and RNA.     

A radiation-chemical and quantum-chemical study of ascorbic acid interaction with α-hydroxyethyl radicals

The effect of ascorbic acid and its analogue 5,6-O-isopropylidenyl-2,3-O-dimethylascorbic acid (I), which has been synthesized for the purpose and does not contain mobile hydrogen atoms, on the formation of the products of continuous radiolysis of deaerated ethanol and its aqueous solutions has been studied. The ionization potentials, the molecular orbital energies, the enthalpies of homolytic dissociation of C-H and O-H bonds, and the enthalpies of H atom addition to the C=O group of the test compounds have been calculated by ab initio methods. The array of the experimental and calculated theoretical data suggests that both ascorbic acid in the undissociated form and compound I can oxidize α-hydroxyethyl radicals, whereas the monoanion of ascorbic acid acts as a reducing agent in the reactions with these transient radicals. The reduction of α-hydroxyethyl radicals in aqueous solutions by the ascorbic acid monoanion can follow both the hydrogen transfer and electron transfer mechanisms.     

Role of tautomerism and rotational isomerism in the interaction of α-hydroxyanthraquinones with boric acid

The products of reaction of α-hydroxyanthraquinones with boric acid are mixtures of 9,10-, 1,10 -, 1,4- and 1,5-quinoid tautomeric complexes of boric acid and borate esters differing by the coordination bonds with carbonyl groups existing in the dynamic equilibrium. The deepening of the reagents color in the presence of boron does not a result only of the complexation, but in the accompanying shift of the tautomeric equilibria.     

Influence of amino acid sequence on the interaction of short peptides containing 3-[2-(9-anthryl)benzoxazol-5-yl]-alanine with β-cyclodextrin

The influence of peptide sequence and Leu chirality in linear and cyclic peptides containing 3-[2-(9-anthryl)benzoxazol-5-yl]alanine on interaction with β-cyclodextrin were studied using fluorescence and NMR spectroscopy. The analysis of enthalpy-entropy compensation effect (α=1.05±0.02 and TΔS₀ ⁰=15.1±0.5 kJ mol^?1) indicates that the entropic contribution connected with the solvent reorganization is the major factor governing the peptides-β-cyclodextrin complexation. Moreover, spatial orientation of guest-host molecule depends more than association constant on Leu residue configuration. However, the cyclization of the peptide chain substantially decrease the association constant with β-CD. An analysis of 2D NMR spectra reveals that inclusion complex is formed by penetration of cyclodextrin cavity from wider and narrow rims by anthryl group in the case of Box(Ant)-SPKL or anthryl and Leu residues for Box(Ant)-SPK(D)L analogue.      

Reaction of arylidene-2-naphthylamines with the ethyl ester of (2-quinolyl)-β-oxopropionic acid

The reaction of arylidene-2-naphthylamines with the ethyl ester of (2-quinolyl)--oxopropionic acid results in the synthesis of ethyl esters of 1-(2-quinolyl)-3-arylbenzo[f]quinoline-2-carboxylic acids. All the theoretically possible intermediate reaction products were isolated: the amino esters of 2-quinoline--oxopropionic acid, the hydroxy esters of tetrahydro- and esters of dihydrobenzo[f]quinoline-2-carboxylic acid, as well as the by-products — the ethyl ester of 2-quinolyl--(R-benzylidene)--oxopropionic acid. The IR, UV, and mass spectra of the synthesized compounds are discussed.Institute of Physical Organic Chemistry, Belorussian Academy of Sciences, Minsk 220603. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1406–1410, October, 1994. Original article submitted October 5, 1994.     

Laser flash photolysis and pulse radiolysis study on chemical activity of VP-16 and podophyllotoxin

Time-resolved laser flash photolysis and pulse radiolysis have been used to study the chemical activity of podophyllotoxin(PPT) and etoposide(VP-16). The mechanism of photoioniza-tion of etoposide and podophyllotoxin has been confirmed and illustrated. It is demonstrated that VP-16 and PPT in aqueous solution can be photoionized at 248 nm to give hydrated electron and neutral radical resulting from rapid deprotonation of radical cation of VP-16 and PPT. The quantum yield for the photoionization of VP-16 and PPT with single-photo is 0.21 and 0.61, respectively. In addition, they can react with hydrated electron, hydrogen radical and hydroxyl radical. This will give chemists some advice on synthesizing new derivatives of podophyllotoxin in cancer treatment.     

Reaction of amino acid derivatives with C_(60)

Ammo acid derivatives react with C60 at 110-120℃to form adduct compounds.The products were isolated by column chromatography and were identified by FD-MS,UV-Vis,FT-IR and 13C NMR spectroscopies.     

Furylvinylhalogenides,XII: Reactions of β-chloro-α-cyano-β-(5-nitrofur-2-yl)-acrylic acid derivatives with malonic acid derivatives

Summary Reactions of -chloro--cyano--(5-nitrofur-2-yl)-acrylic acid derivatives with malonic acid derivatives in the presence of collidine yield the allyl anions3a–d. The pyridines4, 8 or9 are formed by cyclization of3 under acidic conditions. The 2-chloropyridine4a reacts with nucleophiles under substitution. The treatment of ethyl dichloropropionate1b with C-H-acidic compounds provided the cyclopropanes11 or12, the configurations of which were determined by¹³C-NMR spectroscopy. The results of the X-ray structure analysis of8c are discussed.

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Furylvinylhalogenide, 12. Mitt.: Reaktionen von -Chlor--(5-nitrofur-2-yl)--cyanacrylsäurederivaten mit Malonsäurederivaten

Zusammenfassung Die Umsetzung von -Chlor--cyan--(5-nitrofur-2-yl)-acrylsäurederivaten mit Malonsäurederivaten in Gegenwart von Collidin führt zu Allylanionen3a–d. Unter sauren Bedingungen cyclisiert3 zu den Pyridinen4, 8 oder9. Das 2-Chlorpyridin4a reagiert mit Nukleophilen unter Substitution. Setzt man den Dichlorpropionsäureester1b mit C-H-aciden Verbindungen in Gegenwart von Collidin um, so werden die Cyclopropane11 bzw.12 gebildet, deren Konfigurationen mit Hilfe der¹³C-NMR-Spektroskopie bestimmt wurden. Die Ergebnisse der Röntgenkristallstrukturanalyse von8c werden diskutiert.

     

Reactions of Laser Ablation-magnesium Plasma with Methanol Clusters

IntroductionReactions of metal ions with neutral molecules orclusters produce a variety of metal complex ions andother new series of cluster ions including cations andanions.The laser ablation-molecular beam(LA-MB)method has marked its relevance in the st…     

Transient species of fullerenes studied with pulse radiolysis and laser photolysis

The excited triplet of C60 or C70 is generated via either direct excitation by laser light or energy transfer from excited states of solvent to C60 and C70. The cation radical of C60 is produced either via hole transfer from cation radical of CCl4 to C60 or via electron transfer from excited triplet of C60 to CCl4. C60 and C70 could be added to trichloromethyl radical to produce adduct radicals with different mechanisms.     

Interaction of 3-β-chloro-Δ5-steroids with trifluoroperacetic acid

It has been established that the reaction of 3--chloro-⁵-steroids with trifluoroperactic acid forms not only the 5a,6-peroxides (3a,d), but also the 5a,6-diols (5a,b,d) and their 6-trifluoroacetates.Institute of Bioorganic Chemistry of the National Academy of Sciences of Belarus, 220141, Minsk, ul. Akad. Kuprevicha, 5/2. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 94–99, January–February, 1999.     

Thermochemical study of the reactions of acid–base interaction in an aqueous solution of α-aminobutyric acid

The heat effects of the interaction between a solution of α-aminobutyric acid and solutions of HNO₃ and KОН are measured by means of calorimetry in different ranges of рН at 298.15 K and values of ionic strength of 0.25, 0.5, and 0.75 (KNO₃). The heat effects of the stepwise dissociation of the amino acid are determined. Standard thermodynamic characteristics (Δ_r H ⁰, Δ_r G ⁰, and Δ_r S ⁰) of the reactions of acid–base interaction in aqueous solutions of α-aminobutyric acid are calculated. The connection between the thermodynamic characteristics of the dissociation of the amino acid and the structure of this compound is considered.     

Three-component condensation of 2-aminothiophene-3-carboxylic acid derivatives with aldehydes and Meldrum’s acid

New approach to the synthesis of 4,7-dihydro-5H-thieno[2,3-b]pyridin-6-ones using 2-aminothiophenes unsubstituted at position 3 of the thiophene ring has been developed. Labile 2-aminothiophenes have been obtained by the in situ decarboxylation of unstable 2-amino-3-thiophenecarboxylic acids. The three-component condensation of 2-aminothiophenes with aromatic aldehydes and the Meldrum’s acid is the key step of the process.     

Synthesis,characterization, and interaction with DNA of Cu(II) and Zn(II) complexes with 2,2′-bipyridyl-6,6′-dicarboxylic acid

Two transition metal complexes, [Cu₂(bpdc)₂H₂O]·2H₂O (1) and Zn(bpdc)(H₂O)₂ (2) (H₂bpdc?=?2,2′-bipyridine-6,6′-dicarboxylic acid), were synthesized and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. Complex 1 is dinuclear with two five-coordinate cupric ions and 2 is mononuclear with one six-coordinate zinc. Interactions of 1 and 2 with DNA have been investigated using UV–Vis absorption spectra. The cleavage reaction on DNA has been monitored by agarose gel electrophoresis.     

Alkylation of [Pt2(μ-S)2(PPh3)4] with boronic acid derivatives

The reactivity of the metalloligand [Pt₂(μ-S)₂(PPh₃)₄] with the boron-functionalized alkylating agents BrCH₂(C₆H₄)B(OR)₂ (R = H or C(CH₃)₂) was investigated by electrospray ionization mass spectrometry (ESI-MS) in real time using pressurized sample infusion (PSI). The macroscopic reaction of [Pt₂(μ-S)₂(PPh₃)₄] with one mole equivalent of alkylating agents BrCH₂(C₆H₄)B{OC(CH₃)₂}₂ and BrCH₂(C₆H₄)B(OH)₂ gave the dinuclear monocationic μ-sulfide thiolate complexes [Pt₂(μ-S){μ-SCH₂(C₆H₄)B{OC(CH₃)₂}₂}(PPh₃)₄]⁺ and [Pt₂(μ-S){μ-S⁺CH₂(C₆H₄)B(OH)(O^?)}(PPh₃)₄]. The products were isolated as the [PF₆]^? salt and zwitterion, respectively, and fully characterized by ESI-MS, IR, ¹H and ³¹P NMR spectroscopy, and single-crystal X-ray structure determinations.