Electron spin echo study of long-lived radicals which cause mutation in gamma-ray irradiated mammalian cells

Long-lived radicals, produced by gamma-ray irradiation of mammalian cells at room temperature, cause mutation and morphological transformation in the cells. The local environment near the long-lived radicals in irradiated cells was investigated here by the analysis of electron spin echo envelope modulation (ESEEM) spectra. The number of hydrogen (deuterium) atoms surrounding the long-lived radical, which may correspond to the number of water molecules, was estimated roughly as one or two. It is postulated that the long-lived radicals are generated in the interior of biopolymers. The radicals are not produced by the reaction of OH radicals, but mainly by the decomposition of biopolymer which absorbed directly the energy of the ionizing radiation.     

Generation, reactions, and kinetics of sterically congested triplet diphenylcarbenes. Effects of bromine groups.

A series of polybrominated diphenylcarbenes (DPCs) are generated by irradiation of the corresponding precursor diazomethanes, and their reactivities are investigated by means of low-temperature spectroscopies as well as laser flash photolysis. Triplet bis(2,4,6-tribromophenyl)carbene was shown to decay by undergoing dimerization and to have a half-life of 1 s in a degassed benzene solution at room temperature, some 6 orders of magnitude longer-lived than the parent DPC. Anomalous effects of para substituents on the stability of the triplet are noted. Thus, while the replacement of a 4-bromine group with a methyl group resulted in a sharp decrease in the lifetime, introduction of a tert-butyl group resulted in a dramatic increase in the lifetime; triplet bis(2,6-dibromo-4-tert-butylphenyl)carbene was shown to have a half-life of 16 s in solution at room temperature. Attempts to increase the stability of these polybrominated DPCs by buttressing effects of a m-bromine group and by the synergetic effect of bromine and methyl groups are also described.     

Enantioselective Reactions of Configurationally Unstable alpha-Thiobenzyllithium Compounds

Too unstable for asymmetric deprotonation, alpha-sulfenyl carbanions can undergo asymmetric substitution reactions with high stereoselectivity [Eq. (1)]. The key to the asymmetric induction is the dynamic kinetic resolution of the complex formed between the organolithium compound and a chiral ligand, the most effective of which were bisoxazoline derivatives.     

Synthesis of isocorrole and the higher homologues

Bis(azafulvene) derivative of gem-dimethyldipyrrylmethane reacted with 2,2′-bipyrrole under neutral conditions without catalyst to give a mixture of expanded isocorroles in ca. 50% total yields. GPC separation gave eleven porphyrinoids containing 4, 8, 12, 16, 20, 24, 28, 32, 36, 40, and 44 units of pyrrole.     

The reducive amination of phthalaldehyde by tetracarbonylhydridoferrate : Synthesis of 2-arylisoindoles

Phthalaldehyde reacted with primary amines in the presence of tetracarbonylhydridoferrate under mild conditions to give 2-substituted isoindoles and/or isoindolines in good to excellent yields. Aliphatic amines gave selectively the isoindolines but aromatic amines had a great tendency to the isoindoles. 2-(2-Tolyl)-, 2-(4-tolyl)-, 2-(4-methoxyphenyl)-, 2-(3-chlorophenyl)-, 2-(4-chlorophenyl)- and 2-(3,4-dichlorophenyl)-isoindole were prepared by this method.     

Electrocapillary phenomena at oil-water interfaces

Summary In order to discuss the structure of the electrical double layer at the oil-water interface, we measured the electrocapillary curves for various inorganic electrolyte aqueous solutions (aq. phase) in contact with the oil phase containing surface active agents (oil phase). When the aqueous phase contained the potassium halide, the depression of the interfacial tension over the cathodic polarization range due to the adsorption of the surface active agent, i. e. cetyl pyridinium chloride or cytyltrimethylammonium chloride, was suppressed strongly. The suppression was larger for the anion of larger crystal radius. This phenomenon indicated that the adsorbed surface active ion was neutralised by the binding of counter-ions. When the oil phase contained sodium dodecylbenzenesulphonate, the interfacial tension was depressed over the anodic polarization region. This depression was again suppressed by the counter-ion binding. The order of this suppression for various divalent cations agreed with that of the binding ability to chondroitin sulphate. Moreover, high valent cations had strong binding ability. These counter-ion binding support the idea of the penetration of polar groups of orientated surface active agents into the aqueous phase at the oil-water interface.

---

Zusammenfassung Um Aussagen über die Struktur der elektrischen Doppelschicht an Öl-Wasser-Grenzflächen zu erhalten, wurden die Elektrokapillaritätskurven von wässerigen Lösungen verschiedener anorganischer Salze in Kontakt mit der Ölphase, die grenzflächenaktive Stoffe enthielt, gemessen.Die durch Cetylpyridiniumchlorid oder cetyltrimethylammoniumchlorid in der Ölphase bewirkte Erniedrigung der Grenzflächenspannung wurde im Bereich der kationischen Polarisation durch Kaliumhalogenide in der wässerigen Phase aufgehoben. Die Wirkung des anorganischen Salzes wurde mit zunehmendem Anionenradius stärker.Die durch Natriumdodecylbenzolsulfonat bewirkte Erniedrigung der Grenzflächenspannung wurde durch die Kaliumhalogenide im Bereich der anodischen Polarisation aufgehoben. Die Wirkung zweiwertiger Kationen lief parallel mit der Bindungsfestigkeit dieser Ionen an Chondroitinsulfat.Diese Ergebnisse weisen darauf hin, daß die adsorbierten grenzflächenaktiven Ionen in ihrer Wirkung durch die Bindung von Gegenionen neutralisiert werden und daß die polaren Gruppen der an der Öl-Wasser-Grenzfläche orientierten grenzflächenaktiven Molekeln in die wässerige Phase eindringen.

---

---

With 7 figures and 1 table     

Mössbauer and ESR study of pyridine-inactive phthalocyanineiron (II) in zeolite supercage

Pyridine-treated phthalocyanineiron (II) (FePc) was synthesized in a NaY-zeolite supercage. Mössbauer spectra indicated the presence of pyridine-inactive FePc without any change of Mössbauer parameters. The relative yield of the inactive complex was not simply dependent on the amount of iron doped and the temperature during reduction for preparation. Spin-spin interaction may have broadened the ESR signal at g=6 for FePc in zeolite, suggesting that the FePc molecules are located close together in zeolite. It is postulated that two types of FePc in zeolite particle were formed, in accordance with the reactivity of FePc to pyridine adduct formation.     

Radiation-induced terpolymerization of tetrafluoroethylene with propylene and isobutylene in bulk

Terpolymerization of tetrafluoroethylene (TFE) with propylene (P) and isobutylene (iB) by γ radiation at temperatures of ?78 to 40°C, a dose rate of 5 × 10⁴?5 × 10⁵ rad/hr, and an iB/P molar ratio of 40/10?5/45 in the monomer mixture was carried out. Alternating copolymers of TFE and α-olefins, that is, P and iB, were formed at various monomer compositions. No crystalline structure was observed in the terpolymer obtained below an iB/P molar ratio of 15/35 in the monomer mixture but a partly crystalline order increased with the amounts of iB in terpolymer. The crystal lattice of the TFE–iB copolymer was affected by the introduction of P. The dose rate dependencies of the polymerization rate and inherent viscosity were 0.8 and ?0.2, respectively. The activation energy of polymerization was 2.4 kcal/mole, and the relative reactivity ratio of iB and P for a TFE radical chain end was estimated as 4.50 by the treatment of the free propagating mechanism.