A theory of topological constraints in polymer networks

Summary This paper presents an investigation of the dependence of harmonic-like topological constraints in entangled and moderately crosslinked polymer networks on segment and crosslink density and on the deformation of the sample. The approach is an extension of a theory developed for the highly crosslinked case and for polymer melts. The results are used to discuss the influence of topological constraints on the mechanical properties of different types of rubberelastic networks.     

Application of active coke in processes of SO2- and NOx-removal from flue gases

In the field of flue gas cleaning, active coke plays an important role as adsorbant and catalyst. In the temperature range usually prevailing downstream of the air preheater of power plants, SO₂ becomes adsorbed on carbonaceous materials and in a consecutive step is catalysed by the carbonaceous surface and converted to sulphuric acid. The quality demands for a cyclic regenerative process for SO₂ removal are fulfilled by the active coke which is used in the BF-process. The same active coke catalyses the reaction of NO with NH₃ to N₂ and steam. This is the basis for processes for simultaneous SO₂ and NO_x removal. By the addition of ammonia the SO₂ removal by active coke is improved. Two processes are described and results from the laboratory and from the demonstration plant for the BF-process are presented. These show that SO₂ removal efficiences exceed 95% and NO conversions of > 80% can be realized without problems. The cost of the processes using active coke with ammonia addition are comparable with those of wet flue gas desulphurization processes without any additional equipment should NO have to be removed.     

<Emphasis Type="Bold">Stefan Hügel</Emphasis> transparenz.arbeit.kontrolle,Gemeinsame Jahrestagung von FIfF und DVD

DuD ReportVeranstaltungsbesprechungen

Stefan Hügel transparenz.arbeit.kontrolle, Gemeinsame Jahrestagung von FIfF und DVD K?ln, 5.–7. November 2010     

Immunsuppressiva-Antigen-Konjugate. VIII. Darstellung von 6-Mercaptopurin-Protein-Konjugaten nach dem Azid-Verfahren

Immunosuppressant-Antigen Conjugates. VIII. Preparation of 6-Thiopurine-Protein Conjugates by the Azide Method 6-Carboxymethyl-thiopurine was coupled with human serum albumin (HSA) and bovine serum globuline in the presence of a water soluble carbodiimide. Under these conditions, reaction of HSA with the carbodiimide led to electrophoretically detectable changes. Therefore, further conjugates were prepared by the azide method. The used azides, N-(6-benzylthiopurin- and 6-methylthiopurin-9-yl)-acetyl azide, were obtained from the hydrazides. The prepared conjugates contained upto 4.2% thiopurine, determined by spectrophotometry. It was not possible to obtain an azide from purinyl-(6)-thioacethydrazide.     

Pulsed field gradient n.m.r. measurements and theoretical interpretation of the self-diffusion of polystyrene in solution

The self-diffusion coefficients of polystyrene dissolved in C₆D₆ were measured by means of pulsed field gradient n.m.r.. The dependence on the molecular weight was of the power of -2 in accordance with the reptation model. The concentration dependence was theoretically calculated within the blob concept which shows that in the crossover region the self-diffusion coefficient is determined only by the blob dimensions and the monomeric friction coefficient is constant. The calculated concentration dependence agrees well with that observed by the authors.     

Quasielastic scattering from dilute polymer solutions

The initial slope $\text{Ω(q)}$ of the time-dependent scattering function and the static structure factor S(q) of macromolecules in good solvents are calculated without using the Gaussian assumption. For S(q), the scaling relation S(q)～q^?1.7 is confirmed in the intermediate q range, whereas no q dependent cross-over behaviour can be observed. The calculation of $\text{Ω(q)}$ reveals a q³ dependence in this range and no evidence is seen for an exponent apart from 3. The time-dependent scattering function S(q,t) is treated within the framework of the Gaussian assumption. Hydrodynamic as well as excluded volume interactions are incorporated. It has been found that excluded volume effects decrease the decay of the scattering function in comparison with the Gaussian chain.     

Effect of Melt Processing on Crystallization Behavior and Rheology of Poly(3‐hydroxybutyrate) (PHB) and its Blends

Poly(3‐hydroxybutyrate) (PHB) is sensitive to high processing temperatures. This leads to a decrease in molar mass as well as a lower melt viscosity. The crystallization temperature shifts to lower values, and crystallization kinetics is slow. A mixture was developed in order to improve the manufacturing properties and the final product. The blends exhibit a slight reduction in molar mass because they have a lower melting point than pure PHB, and can be extruded at their melt temperature of 170 to 180°C. Then they immediately crystallize at 125 to 100°C. Differential scanning calorimetry (DSC) shows the effect of holding time in the melt on crystallization behavior. It has been shown that the crystallization time has to be longer in the case of PHB and shorter for the blends. Thermal degradation of PHB and its blends has been investigated using thermogravimetry analysis (TG). Derivative thermogravimetry coupled with TG (TG/DTG) curves show three decomposition stages for blends at 290, 340 and 445°C, respectively. Acetic acid, water, carbon dioxide and methane are produced by degradation at a higher temperature.     

Synthesis of 6‐amino acid substituted 4,6,7,12‐tetrahydro‐4‐oxoindolo[2,3‐a]quinolizines

In the presence of Na₂CO₃ (1S,3S)‐ and (1R,3S)‐1‐(2,2‐dimethoxyethyl)‐2‐(1,3‐dioxobutyl)‐3‐(1,3‐dioxo‐butyl)oxymethyl‐1,2,3,4‐tetrahydrocarboline ( 1 ) were transformed into (1S,3S)‐ and (1R,3S)‐1‐(2,2‐dimethoxyethyl)‐2‐(1,3‐dioxobutyl)‐3‐hydroxymethyl‐1,2,3,4‐tetrahydrocarboline ( 2 ), which were cyclized to (6S)‐3‐acetyl‐6‐hydroxymethyl‐4,6,7,12‐tetrahydro‐4‐oxoindolo[2,3‐a]quinolizine ( 4 ), via(6S,12bS)‐ and (6S,12bR)‐3‐acetyl‐2‐hydroxyl‐6‐hydroxymethyl‐1,2,3,4,6,7,12,12b‐octahydro‐4‐oxoindolo[2,3‐a]quinoline ( 3 ). (6S)‐ 4 was coupled with Boc‐Gly, Boc‐L‐Asp(β‐benzyl ester), or Boc‐L‐Gln to give 6‐amino acid substituted (6S)‐3‐acetyl‐4,6,7,12‐tetrahydro‐4‐oxoindolo[2,3‐a]quinolizines 5a , 5b , or 5c , respectively. After the removal of Boc from (6S)‐ 5a (6S)‐3‐acetyl‐6‐glycyl‐4,6,7,12‐tetrahydro‐4‐oxoindolo[2,3‐a]quinolizine ( 6 ) was obtained. The anticancer activities of (6S)‐ 5 and (6S)‐ 6 in vitro were tested.