Titration of poly(dA-dT).poly(dA-dT) in solution at variable NaCl concentration

CD and uv absorption data showed that high molecular weight poly(dA-dT) poly(dA-dT), at 298 K, undergoes an acid-induced transition from B-double helix to random coil in NaCl solutions of different concentrations, ranging from 0.005 to 0.600M. Similarly, titration of the polynucleotide with a strong base causes duplex-to-single strands transition. The base- and acid-induced transitions were both reversible by back-titration (with an acid or, respectively, with a base): the apparent pKa were the same in both directions. However, the number of protons per titratable site (adenine N1) required to reach half-denaturation was in great excess over the stoichiometric value; to a much larger extent…

Titration of poly(dA-dT) · poly(dA-dT) in solution at variable NaCl concentration

CD and uv absorption data showed that high molecular weight poly(dA-dT) . poly(dA-dT), at 298 K, undergoes an acid-induced transition from B-double helix to random coil in NaCl solutions of different concentrations, ranging from 0.005 to 0.600M. Similarly, titration of the polynucleotide with a strong base causes duplex-to-single strands transition. The base- and acid-induced transitions were both reversible by back-titration (with an acid or, respectively, with a base): the apparent pKa were the same in both directions. However, the number of protons per titratable site (adenine N1) required to reach half-denaturation was in great excess over the stoichiometric value; to a much larger exte…

ChemInform Abstract: COMPLEXES OF ORGANOMETALLIC COMPOUNDS PART 42, SPECTROSCOPIC STUDIES OF N,N′-ETHYLENEBIS(ACETYLACETONEIMINE) AND N,N′-ETHYLENEBIS(SALICYLIDENEIMINE) ADDUCTS OF ORGANOLEAD(IV) AND ORGANOTHALLIUM(III)

Abstract The nature of the 1 1 adducts formed from the ligands N,N′-ethylenebis(acetylacetonemine) and N,N′-ethylenebis(salicylideneimine) with Ph2PbCl2 and PhTlCl2 was investigated in the solid state and in methanol solution by IR, electronic and PMR spectroscopy, and by osmometry and conductivity. The adducts exist only in the solid state and dissociate fully into the parent compounds in solution. Polymeric structures are proposed for the solids, in which bis-monodentate ligands bridge the organometallic moieties.

Selective, homogeneous hydrogenation of cycloheptatriene to cycloheptene catalyzed by (η4-cycloocta-1,5-diene)(η6-cyclohepta-1,3,5-triene)ruthenium(0)

Abstract In the presence of small amounts of [Ru(η 4 -COD)](η 6 -C 8 H 10 )] (1), cycloheptatriene is hydrogenated to cycloheptene, under one atmosphere of hydrogen at room temperature in homogeneous phase. The formation of a small amount of cyclooctene and the existence of an induction period, which do not occur when [Ru(η 4 -COD)(η 6 -C 7 H 8 )] (2) is used as the catalyst, suggest that 2 is the real catalyst. The selectivity of this hydrogenation is 100% in n-hexane as solvent, 99.5% in THF, and low in ethanol. Conversion is quantitative in THF and ethanol, but not more than 65% in n-hexane. In the presence of 1 or 2, cycloheptene is rapidly hydrogenated to cycloheptane in THF and ethano…

PolyAT chemical denaturation in w/o microemulsion

CD and UV spectroscopies have been used to investigate the effects caused by the addition of either strong acid-or base-containing microemulsions on the behaviour of the synthetic polynucleotide polyAT entrapped in the aqueous core of a cationic quaternary water-in-oil microemulsion (μE). The titrations were performed in the presence of variable concentrations of NaCl, in the range 0.00 to 0.60 M. In both cases, the primary effect was the reversible transition from B-double helix to random coil of the guest polynucleotide. However, in the microemulsive medium, the number of moles of protons (RH) and hydroxide ions (ROH) per mole of titrable sites are independent of the salt concentration bu…

On the interaction of doxorubicin with polynucleotides

The interaction of doxorubicin (DX) with model polynucleotides poly(dG-dC)·poly(dG-dC) (polyGC), poly(dA-dT)·poly(dA-dT) (poly-AT), and calf thymus DNA has been studied by several spectroscopic techniques in phosphate buffer aqueous solutions. UV−vis, circular dichroism, and fluorescence spectroscopic data confirm that intercalation is the prevailing mode of interaction, and also reveal that the interaction with AT-rich regions leads to the transfer of excitation energy to DX not previously documented in the literature. Moreover, the DX affinity for AT sites has been found to be on the same order of magnitude as that reported for GC sites.

Effect of alkaline cations on the stability of the model polynucleotide poly(dG-dC).poly(dG-dC).

Ruolo della mobilità dell’acqua sulla stabilità e la conformazione dei polinucleotidi in microemulsione

Questa memoria mostra i risultati preliminari ottenuti nello studio dell’influenza della mobilità dell’acqua e dell’importanza di questa sul comportamento dei polinucleotidi in sistemi confinati. L’acqua nei sistemi biologici svolge un ruolo determinante sulla stabilità e il polimorfismo del DNA. I tempi di rilassamento protonici, T1 e T2, determinati mediante tecniche NMR a bassa risoluzione, permettono di ottenere informazioni sulla mobilità dell’acqua. Il sistema modello utilizzato per simulare il comportamento dell’acqua endocellulare è la microemulsione ternaria BHDC/benzene/acqua, costituita dal tensioattivo cationico BHDC (cloruro di benzilesadecildimetilammonio) che in assenza di co…

Interaction of Doxorubicin with Polynucleotides. A Spectroscopic Study

The interaction of doxorubicin (DX) with model polynucleotides poly(dG-dC)·poly(dG-dC) (polyGC), poly(dA-dT)·poly(dA-dT) (polyAT), and calf thymus DNA has been studied by several spectroscopic techniques in phosphate buffer aqueous solutions. UV-vis, circular dichroism, and fluorescence spectroscopic data confirm that intercalation is the prevailing mode of interaction, and also reveal that the interaction with AT-rich regions leads to the transfer of excitation energy to DX not previously documented in the literature. Moreover, the DX affinity for AT sites has been found to be on the same order of magnitude as that reported for GC sites.

Is There Still a Role for Endocrine Therapy Alone in HR+/HER2- Advanced Breast Cancer Patients? Results from the Analysis of Two Data Sets of Patients Treated with High-Dose Fulvestrant as First-Line Therapy in the Real-World Setting: The EVA and GIM-13 AMBRA Studies

<b><i>Background:</i></b> Different studies suggest that fulvestrant 500 mg every 28 days (HD-FUL) could be an active treatment in HR+ advanced breast cancer (ABC) patients even treated with aromatase inhibitors in the adjuvant setting. The aim of this analysis is to describe the outcome of ABC patients treated with HD-FUL as first-line treatment in terms of median duration of treatment and the overall response rate in a real-world setting. <b><i>Methods:</i></b> For the purpose of the present analysis, we considered two data sets of HR+ ABC patients collected in Italy between 2012 and 2015 (EVA and GIM-13 AMBRA studies). <b><i>Res…

Circular dichroism of polynucleotides: Interactions of NiCl2 with poly(dA-dT).poly(dA-dT) and poly(dG-dC).poly(dG-dC) in a water-in-oil microemulsion.

The thermal behavior of the synthetic, high molecular weight, double stranded polynucleotides poly(dA-dT)·poly(dA-dT) [polyAT] and poly(dG-dC)·poly(dG-dC) [polyGC] solubilized in the aqueous core of the quaternary water-in-oil cationic microemulsion CTAB|n-pentanol|n-hexane|water in the presence of increasing amounts of NiCl2 at several constant ionic strength values (NaCl) has been studied by means of circular dichroism and electronic absorption spectroscopies. In the microemulsive medium, both polynucleotides show temperature-induced modifications that markedly vary with both Ni(II) concentration and ionic strength. An increase of temperature causes denaturation of the polyAT duplex at lo…

Alkaline titrations of poly(dG-dC).poly(dG-dC): microemulsion versus solution behaviour

PolyGC was titrated with a strong base in the presence of increasing concentrations of NaCl (from 0.00 to 0.60M) either in water solution or with the polynucleotide solubilized in the aqueous core of reverse micelles, i.e., the cationic quaternary water-in-oil microemulsion CTAB/n-hexane/n-pentanol/water. The results for matched samples in the two media were compared. CD and UV spectroscopies and, for the solution experiments, pH measurements were used to follow the course of deprotonation. In both media the primary effect of the addition of base was denaturation of the polynucleotide, reversible by back-titration with a strong acid. In solution, the apparent pK(a) of the transition decreas…

Interactions of the alternating double stranded copolymer poly(dA-dT).poly(dA-dT) with NiCl2 and CdCl2: solution behaviour

The thermal denaturation of the synthetic high molecular weight double stranded polynucleotide poly(dA-dT) x poly(dA-dT) has been studied in aqueous buffered solution (Tris 1.0 mM; pH 7.8+/-0.2) in the presence of increasing concentrations of either Ni(2+) (borderline cation) or Cd(2+) (soft cation) at four different constant ionic strength values (NaCl), making use of UV and circular dichroism (CD) spectroscopies. The experimental results show that the B-type double helix of the polymer is stabilized against thermal denaturation in the presence of both cations at low concentrations, relative to the systems where only NaCl is present, in the same conditions of ionic strength and pH. The eff…

Selective homogeneous hydrogenation of cycloocta-1,5, and cycloocta-1,3-diene to cyclooctene in the presence of (η4-cycloocta-1,5-diene)(η6-cycloocta-1,3,5-triene)ruthenium(0)

Cyclooctadiene isomers (1,3- and 1,5-COD) are selectively, homogenously hydrogenated to cyclooctene (C8H14) in tetrahydrofuran (THF) solution, under mild conditions of temperature (20 °C) and hydrogen pressure (1 atm), in the presence of catalytic amounts of (cycloocta-1,5-diene)(cycloocta-1,3,5,-triene)ruthenium(0), [Ru(η4-COD)(η6-C8H10)] (1). The rate of hydrogenation is higher when 1,3-COD is the substrate. Evidence for the isomerization 1,5-COD → 1,3-COD is reported. Similar studies carried out in several alcoholic solutions, although showing a decreased selectivity in the hydrogenation, confirm the isomerization 1,5-COD → 1,3-COD, and allow a discrimination between the isomerization an…

Effect of the Alkaline Cations on the Stability of the Model Polynucleotide Poly(dG-dC)·Poly(dG-dC)

When the model polynucleotide poly(dG-dC)∙poly(dG-dC) [polyGC] is titrated with a strong acid (HCl) in unbuffered aqueous solutions containing the chlorides of the alkali metals in the concentration range 0.010 M-0.600 M, two transitions in the absorbance vs. pH plots are evidenced, characterized by the constants pK(a(₁)) and pK(a(₂)). The limiting values at infinite saline concentrations of these two constants, namely pK(∞)(a(₁)) and pK(∞)(a(₂)) obtained making use of the "one site saturation constant" equation or, in turn, of the double logarithmic plot: pK(a) vs. log([salt]⁻¹), exhibit a clear dependence on the nature of the cations. The effects of the different alkali cations on the pK(…

Circular dichroism of polynucleotides. Interactions of NiCl2 with poly(dA-dT).poly(dA-dT) and poly(dG-dC).poly(dG-dC): solution vs microemulsion behaviour.

Effect of cadmium ions on poly(dA-dT) in cationic microemulsion

Interaction of the Alternating Double Stranded Copolymer poly(dA-dT)·poly(dA-dT) with NiCl2and CdCl22: Solution Behavior

The thermal denaturation of the synthetic high molecular weight double stranded polynucleotide poly(dA-dT) x poly(dA-dT) has been studied in aqueous buffered solution (Tris 1.0 mM; pH 7.8+/-0.2) in the presence of increasing concentrations of either Ni(2+) (borderline cation) or Cd(2+) (soft cation) at four different constant ionic strength values (NaCl), making use of UV and circular dichroism (CD) spectroscopies. The experimental results show that the B-type double helix of the polymer is stabilized against thermal denaturation in the presence of both cations at low concentrations, relative to the systems where only NaCl is present, in the same conditions of ionic strength and pH. The eff…

Acid Titrations of poly(dG-dC).poly(dG-dC) in Aqueous Solution and in a w/o Microemulsion

The model polynucleotide poly(dG-dC).poly(dG-dC) (polyGC) was titrated with a strong acid (HCl) in aqueous unbuffered solutions and in the quaternary w/o microemulsion CTAB/n-pentanol/n-hexane/water. The titrations, performed at several concentrations of NaCl in the range 0.005 to 0.600 M, were followed by recording the modifications of the electronic absorption and of the CD spectra (210or = lambdaor =350 nm) upon addition of the acid. In solution, the polynucleotide undergoes two acid-induced transitions, neither of which corresponds to denaturation of the duplex to single coil. The first transition leads to the Hoogsteen type synG.C+ duplex, while the second leads to the C+.C duplex. The…

Polynucleotides solubilised in a water-in-oil microemulsion: the case of poly(dG-dC). poly(dG-dC)