Ueber die Haltbarkeit der Salzs?ure als Reagens

Ohne Zusammenfassung     

A rheological and structural study of a discotic side chain polymer solution

The structural and dynamical properties of a physical network in a discotic side-chain polymer solution have been studied. For that purpose, use has been made of rheological measurements and a statistical network model for the crosslinking of polymer. The goal of the investigation was to gain more insight into processes playing important roles in the subtle interactions between discotic side-chain polymers. A relatively simple mechanical model is presented to describe the mechanical behaviour of the solutions. Moreover, results are shown for the specific dynamic as well as structural properties of the physical networks in these solutions.     

Large-scale purification of factor VIII by affinity chromatography: optimization of process parameters

The optimization of a new process for the extraction of human coagulation factor VIII (FVIII) from plasma with the tailor-made affinity matrix dimethylamino-propylcarbamylpentyl-Sepharose CL-4B (C3-C5 matrix) is described. First, plasma is applied to DEAE-Sephadex A-50 anion exchanger in order to separate a number of proteins, including coagulation factors II, IX and X (prothrombin complex), from FVIII. Subsequently, the unbound fraction of the ion exchanger, containing FVIII, is contacted with the C3-C5 affinity matrix. Optimization of the FVIII affinity chromatographic procedure is accomplished in terms of the ligand density of the matrix, adsorption mode (batch-wise versus column-wise adsorption and matrix to plasma ratio), and conditions of pH and conductivity to be applied on washing and desorption. In scale-up experiments, by processing 20 l of plasma, the recovery (340 U VIII:C/kg plasma) and the specific activity (s.a.) (1.2 U VIII:C/mg protein) are better than those obtained by cryoprecipitation (recovery 300 U VIII:C/kg plasma, s.a. 0.3 U VIII:C/mg protein). The newly developed process using the specially designed C3-C5 affinity matrix has potential application in the process-scale purification of FVIII.     

Investigation into the ageing process in gels of gelatin/water systems by the measurement of their dynamic moduli

Summary This second paper on the ageing of aqueous gelatin gels (1–5%) deals with the mechanism of the renaturation process. The maximum gelation temperature, i. e. the gel temperature, increases with increasing concentration. For the heat of cross-linking a value of H° = - 442 kJ/mol was found, corresponding with mono-helices of 24 windings and a length of 230 Å. The influence of the thermal history is considerable, and the heat of activation of the rate determining step is very small. Hence, the temperature dependence of the degree of ageing is not caused by temperature dependence of the reaction rate constant, but by the increase in stability of small structures which accompanies a decrease in temperature.

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Zusammenfassung Diese zweite Veröffentlichung betreffs der Alterung von 1–5% Lösungen von Gelatin in Wasser behandelt den Mechanismus des Renaturationprozesses. Die maximale Gelierungstemperatur, d. h. die Geltemperatur, nimmt zu mit zunehmender Konzentration. Für die Verknüpfungswärme wurde gefunden H° = -442 kJ/mol. Dieser Wert korrespondiert mit Monohelices von 24 Windungen und einer Länge von 230 Å. Die Abhängigkeit von der thermischen Geschichte ist bedeutend und die Aktivierungsenergie des geschwindigkeitsbestimmenden Reaktionsschrittes ist sehr klein. Demnach wird die Temperaturabhängigkeit des Alterungsgrades nicht verursacht durch die Temperaturabhängigkeit der Reaktionsgeschwindigkeitskonstante, sondern durch die Zunahme der Stabilität kleiner Strukturen mit abnehmender Temperatur.

     

A first principles calculations and experimental study of the ground- and excited-state properties of ladder oligo(p-aniline)s

The molecular structure of three ladder oligo(p-aniline)s, 5,11-diethyl-6,12-dimethylindolo[3,2-b]carbazole (DIMER 2P), 14-ethyl-5,8-dihydro-diindolo[3,2-b:2',3'-h]carbazole (TRIMER 2P), and 5,8,14-triethyl-diindolo[3,2-b:2',3'-h]carbazole (TRIMER 3P) were investigated by first principles calculations at the Hartree-Fock (HF6-31G*) and density functional theory (DFTB3LYP6-31G*) levels. It is found that the agreement between theoretical and x-ray geometrical parameters is good and rather similar for both theoretical methods. The nature and the energy of the first two singlet-singlet electronic transitions have been obtained by Zerner intermediate neglect of differential overlap/spectroscopy semiempirical calculations performed on the HF6-31G* and DFTB3LYP6-31G* optimized geometries, as well as time-dependent density functional theory (TDDFT) calculations performed on the DFTB3LYP6-31G* optimized structures. For all the compounds and for all the theoretical approaches, it is observed that the S(1)<--S(0) electronic transition (pipi*) is weakly allowed and polarized along the short axis (y) of the molecule. On the other hand, the S(2)<--S(0) electronic transition of each oligomer possesses a much larger oscillator strength and is polarized along the long (x) molecular axis. It is found that TDDFT calculations provide the best overall agreement between the energies and the corresponding optical transitions obtained from the absorption bands (0-0 peaks) measured in dichloromethane as well as providing a good evaluation of the bathochromic shifts caused by the increase in the conjugation length or by the presence of extra alkyl chains on the nitrogen atoms in TRIMER 3P compared to TRIMER 2P.     

Theoretical study of the association of glycine molecules on ionic crystals NaCl,KI, LiF in aqueous solution

Summary The adsorption of glycine on different crystals (namely NaCl, KI, LiF) is studied in an isolated state and in water by methods of theoretical chemistry in view of determining the preferential adsorption sites, the modifications of adsorbing crystal properties, and the role played by the electronic structure of the adsorbed molecule, by the solvent and by the parametric concordance on various sites of the structure.     

Preparation of ortho-aryl-benzaldehyde derivatives via free-radical ipso-substitution of an amidomethyl group

Preparation of 2-biarylcarbaldehydes using an intramolecular free-radical ispo-substitution is described. The two aryl moieties to be coupled are pre-associated using a glycolamide derivative. An unusual amidomethyl leaving group was successfully employed in this process.