Untersuchung des einflusses molekularer parameter auf morphologie und eigenschaften von polyethylenen niedriger dichte

Based on the example of PE-LD grades and on model substances obtained by preparative fractionation (fractions in the molecular weight range M?_w = 1.2 ? 390·10⁴ g/mol), comprehensive investigations regarding the problems of structure/properties have been carried out. The correlations of M?_w with 15 physical and application technological perameters have been investigated taking into account the reaction mechanism during the manufacturing of PE-LD in the tubular and agitated autoclave reactor, resulting in the formation of so-called primary structure perameters M?_n, M?_w, molar mass distribution, short chain branching and long chain branching. For the interpretation of the results, among other factors, also the morphological conditions have been taken into consideration, which in connection with the molecular parameters reveal — for specific M?_w-ranges — strong changes and saturation ranges, resp., for the physical and application technological properties.     

Mutation of herpesvirus thymidine kinase to generate ganciclovir-specific kinases for use in cancer gene therapies

Understanding the functional and mechanistic properties of themulti-substrate herpes simplex virus type-1 thymidine kinase(HSV-1 TK) remains critical to defining its role as a majorpharmacological target in herpesvirus and gene therapies forcancer. An inherent limitation of the activity of HSV-TK isthe >70-fold difference in the K_ms for phosphorylation ofthymidine over the pro-drug ganciclovir (GCV). To engineer anHSV-1 TK isoform that is specific for GCV as the preferred substrate,16 site-specific mutants were generated. The mutations wereconcentrated at conserved residues involved in nucleoside basebinding, Gln125 and near sites 3 and 4 involved in catalysisand substrate binding. The substrate preferences of each mutantenzyme were compared with wild-type HSV-1 TK. One mutant, termedQ7530 TK, had a lower K_m for GCV than thymidine. Expressionof the Q7530 TK in tumor cells indicated comparable metabolismto and improved sensitivity to GCV over wild-type HSV-1 TK,with minimal thymidine phosphorylation activity. A molecularmodeling simulation of the different HSV-1 TK active-sites wasdone for GCV and thymidine binding. It was concluded that mutationsat Gln125 and near site 4, especially at Ala168, were responsiblefor loss of deoxypyrimidine substrate binding.     

Synthese von substituierten benzotriazolen zur stabilisierung aromatischer polyamide gegen UV-licht

2-(2′-Hydroxyphenyl)-benzotriazoles, containing a carbonamide group in 5- or 5′-position, were synthesized to stabilize polyamides. The influence of the ortho-positioned hydroxy group for the stabilizing effect of these substances was examined by methylating it. The synthesized benzotriazoles were characterized, especially with regard to their UV-absorption-spectra. The photolytic resistance of poly-(m-phenyleneisophthalamide), containing these stabilizers, for example 2-(2′-hydroxy-5′-tert-butylphenyl)-benzotriazol-5-carbonic acid anilide, was examined by measuring the viscosity.     

The oxidation and self-heating of metal sulphides as an electrochemical corrosion phenomenon

Experiments with a representative number of technically interesting metal sulphides trace out hydrogen peroxide as the reactive intermediate of sulphide oxidation. It is formed through an electrochemical reduction of molecular oxygen. The formation of sulphur or sulphate as the final state of oxidation is determined by consecutive reactions which are critically dependent on the catalytical properties of the surface and the solution for hydrogen peroxide decomposition. The individual steps of the reaction are discussed in some detail. Conclusions with respect to a possible control of the autogeneous heating are drawn.     

Fabrication of Patterned Inorganic–Organic Hybrid Film for the Optical Waveguide by Microfluidic Lithography

Inorganic–organic hybrid materials for the optical waveguide were synthesized by the sol–gel process starting from the acid-catalyzed solutions of phenyltrimethoxysilane, methyltriethoxysilane, and tetraethylorthosilicate. The control of the refractive index in the organically modified silicate films was achieved by varying the content of phenyltrimethoxysilane incorporated as a refractive index modifier. A single spin-coating with the precursor solution produced a crack-free buffer layer of 22-μm thickness with a dense microstructure. For the fabrication of the patterned guiding layer on top of the buffer layer, the microfluidic lithography method was used. The patterned microlines of the linewidth of 20–35 μm with a sharp edge definition could form by filling the precursor solutions into the microchannels associated with the polydimethylsiloxane microfluidic device. The patterned guiding layer was optically transparent as similar as the bare quartz glass at the wavelength above 500 nm and had a low propagation loss of 0.77 dB/cm at 1310 nm.     

Amelioration of mechanical brittleness in hyperbranched polymer. 1. Macroscopic evaluation by dynamic viscoelastic relaxation

Hyperbranched poly(ether ketone)-b-linear poly(ether ketone)-b-hyperbranched poly(ether ketone) (HLHPEK) triblock copolymers with two different block compositions were prepared as an approach to improve the mechanical brittleness of hyperbranched poly(ether ketone) (HPEK). From the time-temperature superposition of dynamic shear moduli, G′(ω) and G″(ω), of HPEK and two HLHPEKs, it was investigated that the junction points between G′(ω) and G″(ω) shifted to the higher frequencies and the rubbery plateau region spread wider over the reduced frequency axis as the linear blocks were introduced and their compositions were increased. Such changes in viscoelastic response were consequences of increase in the amount of chain entanglements additionally formed by the linear blocks. In order to verify the effect of the linear block incorporation on amelioration of the mechanical brittleness, the degree of brittleness and its improvement were evaluated from the temperature dependence of the shift factors, a_Ts, experimentally obtained during the superposition of the dynamic moduli and of the average viscoelastic relaxation times, τ_HNs, determined with empirical Havriliak-Negami distribution function. From the nonlinear curve fittings of the a_Ts and the τ_HNs by the Vogel-Tamman-Fulcher equation, the degree of brittleness for HPEK and HLHPEK triblock copolymers were quantified as values of the material parameter D, an indicative of deviation from the linear Arrhenius behavior and a measure of fragility of the given material. The tendency of increasing D values with the linear block compositions confirmed substantial improvement of the mechanical brittleness in the HLHPEK triblock copolymers compared to HPEK. Therefore, the approach to copolymerize HPEK with its chemically analogous linear counterpart was verified to be an effective strategy to impart molecular entanglements and hence ameliorate the mechanical brittleness on the basis of macroscopic rheological evaluation.     

Hybrid systems in seawater desalination—practical design aspects, present status and development perspectives

Ever since seawater desalination has been applied on an industrial scale, and particular in the countries of the Arabian Gulf, the application of desalination processes in dual-purpose facilities—water and power—as a hybrid configuration has been discussed in many feasibility investigations and also planning concepts. It is above all the combination of reverse osmosis with thermal processes that has found increasing interest with the aim of ensuring, as economically as possible, uniform water supplies under the specific, greatly varying load conditions in the Gulf countries. Such design concepts for hybrid configurations encompass straightforward structures with a low degree of coupling between membrane and thermal desalination processes, but range up to very complex configurations with strong interconnections on both the water side and thermally, as well as with several desalination processes connected in series or in parallel. Classical hybrid concepts in which the permeate from an RO desalination component is mixed with distillate from thermal desalination have already been implemented in Saudi Arabian dual-purpose plants, like Jeddah and Yanbu-Medina. Although hybrid systems of greater complexity have been addressed in many design studies and publications, up to now none has been brought to fruition. Coming into consideration asthe design basis for determining the capacity shares of the various desalination processes operated in a hybrid configuration are: arrangement of thermal cycle of the power plant component; water/power ratio of the dual-purpose seawater desalination and power plant; provision of undiminished water production of the desalination plant as electricity generation varies; provision of a specified drinking water quality with regard to composition and salt content; combination of all these aspects. Also gaining in importance are concerns of environmental pollution and sustainable development when selecting seawater desalination and power plant configurations, as well as their optimization when considering desalination and electricity generation as a whole. In the practical design of hybrid membrane and thermal systems, aspects come to light, though, that restrict linking of the two systems and joint utilization of facilities, as conceived in studies and conceptual design investigations. This applies both for common utilization of intakes and the use of heated up cooling water from thermal processes as a feed stream for the RO part of the desalination process. Additionally, requirements of drinking water composition, particularly chloride content, TDS and compliance with a specific residual content of boron, influence specifically the design of the membrane process part and its share in the total desalination capacity. Such practical aspects have greatly influenced the design and configuration of the Fujairah hybrid plant for which, from a total desalination capacity of 100 MIGD (454,600 m³/d), the share of 37.5 MIGD (170,500 m³/d) makes its seawater RO plant the biggest currently being constructed anywhere in the world. From the findings of the engineering of this plant and the idea that, by increasing interconnection between the two processes on the water side, it is possible to advance a hybrid configuration of this type with regard to cost optimization in the membrane installation, but also by joint utilization of the intake equipment, perspectives result for applied research efforts over the near and long terms, for example: long-term behavior of membranes at elevated temperatures; tendency for biofouling in membrane process with common utilization of cooling water and brine; influences of such interconnections on the overall availability of the facility. But also for the operation and maintenance organization of such large facilities, consequences can be foreseen for the future development of hybrid plants, particularly for operation management and organisation of the interplay of the different power plant and desalination systems, monitoring of SWRO membrane replacement and cleaning, as well as controlling water quality.