SINGLE- and DOUBLE-STRAND BREAK FORMATION IN DOUBLE-STRANDED DNA UPON NANOSECOND LASER-INDUCED PHOTOIONIZATION

Double-stranded (ds) calf thymus DNA (0.4 mM), excited by 20 ns laser pulses at 248 nm, was studied in deoxygenated aqueous solution at room temperature and pH 6.7 in the presence of a sodium salt (10 mM). The quantum yields for the formation of hydrated electrons (phi c-), single-strand breaks (phi ssb) and double-strand breaks (phi dsb) were determined for various laser pulse intensities (IL). phi c- and phi ssb increase linearly with increasing IL; however, phi ssb has a tendency to reach saturation at high IL (greater than 5 X 10(6) Wcm-2). The ratio phi ssb/phi c-, representing the number of ssb per radical cation, is about 0.08 at IL less than or equal to 5 X 10(6) Wcm-2. For comparison, the number of ssb per OH radical reacting with dsDNA is 0.22. On going from argon to N2O saturation, phi ssb and phi dsb become larger by factors of approximately 5 and 10-15, respectively. This enhancement is produced by attack on DNA bases by OH radicals generated by N2O-scavenging of the photoelectrons. While phi ssb is essentially independent of the dose (Etot), phi dsb depends linearly on Etot in both argon- and N2O-saturated solutions. The linear dependence of phi dsb implies a square dependence of the number of dsb on Etot. This portion of dsb formation is explained by the occurrence of two random ssb, generated within a critical distance (h) in opposite strands. For both argon- and N2O-saturated solutions h was found to be of the order of 40-70 phosphoric acid diester bonds. On addition of electron scavengers such as 2-chloroethanol (or N2O plus t-butanol), phi dsb is similar to that in neat, argon-saturated solutions. Thus, hydrated electrons are not involved in the chemical pathway leading to laser-pulse-induced dsb of DNA.     

Two-dimensional condensation in camphor-10-sulphonic acid films at the mercury/electrolyte interface

The electrosorption properties of camphor-10-sulphonic acid (CS) in different electrolytes (Na₂SO₄, LiClO₄, KNO₃, KCl, KBr, KJ) were investigated experimentally by ac polarographic measurements at different temperatures. Depending on the type of electrolyte and on the temperature, film condensation was observed.The Frumkin interaction coefficient, determined from the critical degree of coverage, does not depend linearly on the reciprocal temperature as would be the case in correspondence to the temperature dependence of the pit width. This contradiction does not occur if the interaction coefficient is determined from the critical degree of coverage using the lattice gas model. The temperature dependence of the pit width of the differential capacity-potential curves, found in the experiment, can be theoretically described by both these models. The interaction coefficient in the models is inversely proportional to the temperature. Furthermore, the parameters of the standard free energy of adsorption, the interaction energy, the interaction coefficient of the Frumkin isotherm, the adsorption coefficient, and the maximal surface concentration of CS in the film were estimated and compared.     

Iminophosphanes: Unconventional Compounds of Main Group Elements

The large number of known stable compounds in which phosphorus has a low coordination number makes it clear that such compounds can no longer be regarded as “exotic” in main group chemistry. While the rich chemistry of P? C multiply bonded systems makes clear their affinity to their organic congeners, iminophosphanes in particular are also of increasing importance. The linkage of a phosphinidine fragment with an imine fragment via a multiple bond gives rise to a class of compounds with an unusually wide range of structural types. This in turn leads to a broad spectrum of chemical behavior which makes iminophosphanes extremely useful synthetic building blocks in organoelement chemistry.     

The characterization of silica microparticles by electrophoretic mobility measurements

Summary Electrophoretic mobility measurements in the pH 2‐10 range are described for several commercial HPLC silica microparticles and a laboratory-produced product. The content of metal impurities for the silicas was also determined by AAS. An acidic/hydrothermal treatment was used to generate a more homogenous surface for some of the silicas. The zero points of charge (zpc) for both a native and a treated silica plus several commercial HPLC silicas were compared. The electrophoretic mobility method may be useful in predicting the utility of certain types of silica supports for chromatographic separations.     

Pore formation during the pyrolysis of C-Nb2O5 and C-Ta2O5 xerogels

Binary organic-inorganic gels have been prepared by mixing a carbonaceous hydrosol and a Nb₂O₅ or Ta₂O₅ sol derived by hydrolysis of the alkoxides. The gels are pyrolyzed under an inert atmosphere into precursors in which carbon and the metal oxides are mixed very intimately. High temperature treatment converts the precursors into the cubic face centered carbides. The precursors as well as the carbides have been shown to be micro- and mesoporous materials. Measurements of nitrogen adsorption reveal a characteristic change of the shapes of the isotherms (Type I Type IV) and of the hysteresis loops (H4H2H1) during the thermal processes. Pore widening has been observed with rising temperature. The phenomena of crystallization, carbothermal reduction and sintering were found to control the pore shape and size. The results of the adsorption measurement correlate well with those of the thermoanalytical and X-ray diffraction studies.Dedicated to Professor Dr. rer.nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

Investigations of precipitates in heat treated AgPd30/CuSn6 layers

The subject of the investigations are precipitation zones, which grew as a result of chemical diffusion in AgPd30/CuSn6 bimetals. These precipitation zones have been characterized by metallography, electron probe microanalysis and x-ray diffraction. The growth of precipitation zones in the plating layer and in the substrate layer in dependence on time have been determined. The use of x-ray diffraction alone for the identification of the precipitates could not supply satisfying results in every case. This problem was solved by the application of electron probe microanalysis using a correction method, which allows the estimation of the chemical composition of small particles.Dedicated to Professor Dr. rer. nat. Dr. h. c. Hubertus Nickel on the occasion of his 65th birthday     

Stereoisomeric flavor compounds,part LVIII: The use of heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)-β-cyclodextrin as a chiral stationary phase in flavor analysis

The characteristics of the new chiral stationary phase heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)-β-cyclodextrin are outlined and compared with permethyl- and perethyl-β-cyclodextrins.