EMISSION SPECTRA FROM SYNTHETIC POLYNUCLEOTIDES AND DEOXYRIBONUCLEIC ACID IN AQUEOUS SOLUTIONS†

A study has been made of the emission spectra at 77°K from poly A, poly U, poly C, their complexes, and from native and heat-denatured DNA in buffered aqueous solutions containing 0·25 per cent glucose: no emission was observed from these polynucleotides at room temperature. The spectra differed from those obtained in the polyalcoholic glasses used by other workers. The principal differences between the emission spectra of poly A and adenosine at pH 7 in a water-glucose mixture were: (a) a decrease in both P/F and the overall intensity in poly A; (b) absence of the structure normally found in adenosine phosphorescence; and (c) appearance of a new short-lived component in the phosphorescence decay. Further changes in the emission characteristics (e.g. the increase of P/F, the proportional increase of the short-lived component in the phosphorescence decay) from poly A were observed at pH 5. These can not be explained solely by protonization of adenosine residues, but rather appear to depend upon exciton interactions of the most intense π–π* transition in double-stranded poly A. and perturbation of the lowest-lying emitting band. When poly A or poly C is complexed with poly U or poly I the luminescence intensity decreases in two-strand complexes and is completely quenched in poly (A + 2U), poly (A+2I) and poly (C⁺+I); no emission was observed from either, single-strand poly I or poly U. Identical emission patterns were obtained from native and heat-denatured samples of DNA. The comparison of polynucleotide emission spectra in the water-glucose medium with those obtained from polyalcoholic glasses leads to the conclusion that the emission spectra depend most critically upon the relative proportions of base-solvent and base-base interactions in each environment: the possible importance of proton tunneling and/or triplet-triplet transfer mechanisms is briefly discussed.     

Determination of the energy of the bond formed by carbon with the surface of a nickel catalyst

Summary Calculations were made of the energy of the bond formed by carbon with the surface of a nickel catalyst on the assumtion that the excess of free energy of the surface compounds is determined mainly by the excess of free energy of the surface of the catalyst.We express our deep thanks to A. A. Balandin for his interest in our work.     

Crystal structure,Mössbauer,and magnetic behavior of mixed valence compounds in the BaFeS system: Ba3(Ba1−xAlx)Fe2S6[S1−y(S2)y]

The compounds $\text{Ba}{}_4\text{Fe}{}_2\text{S}{}_6\text{[S}{}_{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}\text{(}\text{S}{}_2\text{)}{}_{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}\text{]}$ and Ba_3.6Al_0.4Fe₂S₆[S_0.6(S₂)_0.4], designated I and II, were prepared by reacting BaS, Fe, and S powders and Al foils in graphite containers sealed in evacuated quartz ampoules at approximately 1100°C. The crystal structure of I was determined using 1682 independent, nonzero X-ray reflections, while 3589 were used for II. They are triclinic, $\text{A}\text{l}$:

$\text{a=9.002(2)}\text{A}\text{?}\text{,b=6.7086(8)}\text{A}\text{?}\text{,c=24.658(4)}\text{A}\text{?}\text{α91.49(2)°,}$

$\text{β=105.10(2)°y=90.74(2)°,ψ}{}_{\mathrm{calc}}\text{=4.15g/cm}{}^3\text{,for I:}$

$\text{a=8.993(6)}\text{A}\text{?}\text{,b=6.708(7)}\text{A}\text{?}\text{,c=24.70(1)}\text{A}\text{?}\text{α91.11(6)°,}$

$\text{β=105.04(6)°y=90.90(9)°,ψ}{}_{\mathrm{calc}}\text{=3.90g/cm}{}^3\text{,for II:}$

BaS₆ trigonal prisms share edges to form distorted hexagonal rings which form one-dimensional chains leaving two free lateral edges. The chains link in a stairstep manner with the rings offset along the [301] direction. These stairsteps join in a complicated manner to form a three-dimensional network. Fe ions are in two sites forming isolated FeS₄ tetrahedra and isolated Fe₂S₆ dimers by edge-sharing tetrahedra. The Al substitution occurs in the trigonal prisms which have free edges with Al replacing Ba. Room-temperature Mössbauer isomer shifts are 0.20 mm/sec. for I and 0.30 mm/sec for II. These data indicate that upon Al substitution charge compensation occurs by reducing Fe³⁺. Valence calculations indicate that Fe in edge-sharing tetrahedra are reduced while the Fe in the isolated tetrahedron remains unchanged. The effective charge distribution in the Al substituted compound is approximately Fe³⁺, Fe^2.5+ with electron delocalization across the shared edge. Room temperature electrical resistivity is 10⁵ ohm/cm. The compositions of the crystals are best represented by the formulas $\text{[}\text{Ba}{}_4\text{Fe}{}_2\text{S}{}_7\text{]}{}_{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}\text{·[}\text{Ba}{}_4\text{Fe}{}_2\text{S}{}_6\text{(S}{}_2\text{)]}{}_{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}$ and [Ba₃AlFe₂S₇]_0.4·[Ba₄Fe₂S₇]_0.2·[Ba₄Fe₂S₆(S₂)]_0.4. The replacement of a sulfide by a disulfide ion is thought to be strongly dependent on the sulfur activity during the preparation.     

Homolytic substitutions in indolinone nitroxide radicals—I: Reaction with aroyloxyl radicals

Indolinone nitroxides undergo a homolytic substitution with aroyl oxyl radicals, leading to two isomers, 7-aroyloxy- and 5-aroyloxy-derivative, respectively, whose structures were assigned on the basis of the ESR hfccs and of the ¹H NMR spectra of the corresponding amines. The presence of aroyl oxyl radicals in the reaction medium was demonstrated by thermal decomposition of benzoyl peroxide in the presence of aromatic acids.     

Kinetics of two-phase bulk polymerization. II. The influence of dissolved polymer

The effect of dissolved polybutadiene on the initial rate of polymerization of styrene was investigated by using high-precision dilatometric techniques. The dissolved polymer reduced the rate of polymerization by amounts greater than can be accounted for by a reduction in monomer concentration. Rate reductions increased with the amount of dissolved polybutadiene and with its molecular weight and were greater for benzoyl peroxide initiator than for equal concentrations of azobisisobutyronitrile. Surprisingly, analogous rate reductions were observed when polystyrene were substituted for the polybutadienes, except that at high polystyrene concentrations, the expected autoacceleration was observed. These rate reductions showed no correlation with the viscosity of the reaction mass, nor did the dissolved polymer affect initiator efficiency. At a given level of a particular dissolved polybutadiene, rate reductions were diminished by increasing levels of each initiator, and by adding a chain-transfer agent. Good quantitative agreement was obtained with the number-average length of the growing polymer chains, whether varied by using different initiators, changing initiator level, or adding chain-transfer agent. These results are inconsistent with a chemical mechanism, but they are explained by a proposal originated by North and Reed whereby the dissolved polymer makes the reaction mass a “poorer” solvent for the growing polymer chains, reducing their overall coil dimensions and enhancing their rate of diffusion together for termination.     

Mechanism of vinyl chloride polymerization

An overall mechanistic scheme for the suspension polymerization of vinyl chloride is presented. The process can be resolved into five discrete stages, each of which presents a unique environment for the interaction of the systems parameters. It is shown that the surface area of the polymer formed during the reaction is not a major factor in autoacceleration and that the increase of kinetic chain length with conversion is due to a radical dilution effect. The latter is a direct result of the difference in rates between polymerization and radical formation, the former being greater. The increase of the initial polymerization rate and the reduction of autoacceleration brought about by chain transfer agents can be explained by the lower diffusion rate and greater bulkiness of the chain transfer agent radical relative to that of the monomer radical. The chaintransfer agent CBr₄ is preferentially absorbed by PVC from solution in vinyl chloride. With lauryl peroxide as initiator it is shown that the “hot spot” is the result of a build-up of initiator in the monomer caused by its exclusion from the polymer phase. Vinyl chloride was found to dissolve 0.03% PVC at ambient temperature and to have no effect on the decomposition rate of lauryl peroxide.     

Structures of 2-hydroxypyridine and its vinyl derivatives

The PMR, Raman, and UV absorption spectra of 2-hydroxypyridine and its vinyl derivatives were investigated. Their electrochemical reduction was studied, and a quantum-chemical analysis of them was performed. It was concluded that the structure of 2-hydroxypyridine in proton-donor solvents is mesomeric, and its wave function, to a first approximation, is a linear combination of the wave functions of the 2-pyridone and zwitterion models. The contribution of the wave functions of each of the models depends substantially on the concentration of the solution and the nature of the solvent. An assumption was made regarding the presence of dynamic conjugation between the vinyl group and the ring in vinyl derivatives of 2-hydroxypyridine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 95–102 January, 1972.     

Studies on the exchange characteristics of [Co(NH3)6]3+ in amberlite IRC-50

Summary The exchange of Co(NH₃)₆]³⁺-ions on amberlite IRC-50 resin has been studied at room temperature. For this exchange process the cations are effective in the order: Cs⁺<Rb⁺<K⁺<Na⁺<Li⁺<NH₄ ⁺<Mg²⁺ <Ca²⁺<H⁺ and (C₂H₅)₄N<(CH₃)₄N⁺ ≪Cetyltrimethylammonium-ion <Cetylpyridinium-ion. The logarithm of the selectivity coefficient gives linear graphs when plotted against the radius of the hydrated ions or the reciprocals of theDebye-Hückel parameter?.     

Researches on benzodiazines

2-R-Quinazolones have been synthesized (R=Me, Ph,-pyridyl,-furyl), and subsequently the 4-chlorides and the corresponding 2-R-4-hydrazinoquinazolines were obtained. By the reaction of orthoformic ester and nitric acid on the hydrazines, 5-R- [3, 4-c]-s-triazoloquinazolines and 5-R- [1, 5-c] tetrazoloquinazolines were prepared, respectively. The compounds in which R=Me differ considerably from compounds with other groups, both in color and stability of intermediate reaction products. 5-R- [1, 5-c] tetrazoloquinazolines are hydrolyzed by HCl into quinazol-4-ones.For Part IV see [1].