Röntgenkleinwinkeluntersuchungen an Lösungen eines Polystyrolpräparates mit enger Molekulargewichtsverteilung

Zusammenfassung Es wurde das Streuverhalten von Polystyrol im thermodynamisch schlechten Lösungsmittel Cyclohexan zwischen Entmischungstemperatur und-Temperatur untersucht. Beim -Punkt und nahe dabei liegt das Verhalten eines statistisch verknäuelten Fadenmoleküls vor. Unterhalb der-Temperatur beginnt eine Aggregation. Knapp oberhalb der Entmischungstemperatur entspricht das Molekulargewicht etwa einer Verhängung zweier Fadenmoleküle. Ein Auftreten von kompakten Polymerknäueln ist bei dieser Temperatur nicht festzustellen. Der Einfluß des Fadenquerschnitts auf die Streukurve ist beträchtlich, da der Querschnitt nicht viel kleiner als die Persistenzlänge ist. Trotzdem läßt sich die Persistenzlänge (a=12,2 Å) aus dem Übergangspunkt zwischen den etwa 1/(2)² und 1/(2) proportionalen Bereichen bestimmen, da der Knick im Übergangsbereich infolge der großen Anzahl von Persistenzlängen pro Molekül sehr ausgeprägt ist.

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X-Ray small-angle investigations on solutions of a polystyrene sample with a narrow molecular weight distribution

Investigations were made of the scattering behaviour of polystyrene in the thermodynamically bad solvent cyclohexane between precipitation-temperature and-temperature. At the-point and close to it the behaviour of a statistically coiled chain molecule is found. Below-temperature an aggregation is beginning. Just above precipitation-temperature the molecular weight corresponds to an entanglement of two chain molecules. Appearance of compact polymer coils could not be noted at this temperature. The influence of the chain crosssection upon the scattering curve is considerable as the crosssection is not much smaller than the persistence length. Nevertheless, the persistence length (a=12.2 Å) may be determined from the transition point between the ranges roughly proportional to 1/(2)² and 1/(2) as the break within the transition range is very distinct on account of the great number of persistence lengths per molecule.

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Mit 3 Abbildungen

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Herrn Prof. Dr.E. Broda zum 60. Geburtstag gewidmet.     

Preparation of ultramicro-, micro-, and supermicroporous carbon adsorbents by template procedure

The new template procedure for preparing ultramicro-, micro-, and supermicroporous carbon adsorbents is proposed on the basis of the use of two polymers with different thermal stabilities as a template matrix and a carbonizable carbon source. The polymeric template matrix is removed by thermal decomposition in the low-temperature pyrolysis of the polymer mixture, whereas the second polymer component of a mixture is transformed into a carbonizate. The resultant monolithic carbonizate is the polymeric matrix replica and represents a molecular-sieve ultramicroporous carbon adsorbent, which adsorbs water vapor at 293 K and does not adsorb nitrogen vapor at 77 K. The activation of this carbonizate with water vapor leads to a series of micro-and supermicroporous carbon adsorbents with a broad range of the parameters of a pore structure: BET specific surface area S _BET is 610–2130 m²/g, micropore volume W ₀ is 0.20–0.69 cm³/g, micropore half-width x ₀ (slit model) is 0.20–0.70 nm, mesopore specific area S _me is 20–1000 m²/g, and characteristic adsorption energy E ₀ is 15.6–27.4 kJ/mol. Original Russian Text ? O.K. Krasil’nikova, A.M. Voloshchuk, A.E. Evsyukhin, N.Y. Lomovsakaya, 2006, published in Kolloidnyi Zhurnal, 2006, Vol. 68, No. 2, pp. 207–213.     

A search for a thermal spike effect in sputtering

The temperature dependence of the sputtering yield was measured for lOOkeV per atom bombardment of silver with molecular and atomic antimony ions. No exponential increase of the yield was found in the temperature range from 25° to 775 °C, although a pronounced nonlinear effect is observed when the yield of these projectiles is compared,Y(Sb ₂ ⁺ )≈ 1.5×[2Y(Sb⁺)]. We conclude that there is no influence of the lattice temperature on collision spikes.     

Resonance-enhanced multiphoton ionization (2+1) of the\tilde B and\tilde C' states of ammonia

Resonance-enhanced multiphoton ionization (REMPI) of the \(\tilde B\) and \(\tilde C'\) states of NH₃ in a pulsed supersonic molecular beam was observed at 304–340 nm, using the multiphoton-ionization mass-spectrometer system described herein. The observed features are the result of a 2+1 MPI process and correspond quite well with the reported 3+1 MPI of NH₃ in the literature from the ground state of opposite parity.     

Systems Tl2MoO4-E(MoO4)2, where E = Zr or Hf, and the crystal structure of Tl8Hf(MoO4)6

Systems Tl₂MoO₄-E(MoO₄)₂ (E = Zr, Hf) are studied using X-ray powder diffraction, DTA, and IR spectroscopy. Compounds Tl₈E(MoO₄)₆ and Tl₂E(MoO₄)₂ are found in these systems. T-x diagrams for the Tl₂MoO₄-Zr(MoO₄)₂ system are designed. Single crystals are grown and structure is solved for Tl₈Hf(MoO₄)₆. The compound crystallizes in a monoclinic structure with the unit cell parameters a = 9.9688(6) Å, b = 18.830(1) Å, c = 7.8488(5) Å, β = 108.538(1)°, Z = 2, space group C2/m. The main structural fragment is a [HfMo₆O₂₄]^8? isle group. Three crystallographically independent types of Tl polyhedra uniformly fill spaces between [HfMo₆O₂₄]^8? fragments to form a three-dimensional framework.     

Synthesis of pyrimidine betaines with phosphonium and cycloammonium cations

Previously undescribed pyrimidine betaines with cycloammonium and triphenylphosphonium cations were obtained. A study of the UV, IR, PMR, and mass spectra made it possible to draw a conclusion regarding the noncyclic structure of betaines stabilized by an intramolecular donor-acceptor interaction of the charge-transfer complex (CTC) type.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1687–1690, December, 1978.     

Haloaldehyde polymers. IX. Polybromodichloroacetaldehyde

Bromodichloroacetaldehyde was synthesized by two methods. The first synthesis started from chloral, which was allowed to react with Ph₃P and the resultant compound brominated and hydrolyzed to give bromodichloroacetaldehyde in an overall yield of 60%. Purification by repeated distillation from P₂O₅ gave polymerization grade bromodichloroacetabldehyde. Bromodichloroacetaldehyde could also be synthesized by bromination of dichloroacetaldehyde diethyl acetal. The yields of this synthesis were only 20–30%, and the aldehyde could not be purified readily to give polymerization grade monomer. Bromodichloroacetaldehyde could be homopolymerized at ?30°C with anionic and also some cationic initiators to a polymer which was insoluble and did not melt but degraded to monomer above 200°C. The ceiling temperature of the polymerization was ?15°C in 1M solution. Bromodichloroacetaldehyde could also be copolymerized with isocyanates, primarily aryl isocyanates, and also with chloral.     

ULTRAVIOLET IRRADIATION OF NUCLEIC ACIDS COMPLEXED WITH HEAVY ATOMS—III. INFLUENCE OF Ag + AND Hg 2+ ON THE SENSITIVITY OF PHAGE AND OF TRANSFORMING DNA TO ULTRAVIOLET RADIATION

Abstract— We have studied the influence of the heavy metal ions Ag⁺ and Hg²⁺ on the photoinactivation and photodimerization of transforming DNA and of bacteriophage. The rate of inactivation of Haemophilus influenzae transforming DNA by ultraviolet (UV) radiation was enhanced by a factor of 30 when it was complexed with Ag⁺. This enhancement was correlated with a comparable increase in the rate of thymine dimerization. In contrast, mercuric ions led to a reduction in the rates of both inactivation and dimerization. When we examined the effects of these metal ions on the photobiology of bacteriophage, we again found that Ag⁺ enhanced and Hg²⁺ reduced the rate of ultraviolet inactivation. These results demonstrate that heavy metals may be useful tools for studying the photochemistry and photobiology of nucleic acids.     

Synthesen in der Carotinoid-Reihe. 22. Mitteilung. Totalsynthese von Rhodoxanthin

The total synthesis of rhodoxanthin according to the scheme C₁₄ + C₁₂ + C₁₄ is reported.