When electron exchange is chemical exchange-assignment of 1H NMR spectra of paramagnetic cobalt(II)-2,2':6'2''-terpyridine complexes

Electron exchange between [Co(terpy)2]3+ and [Co(terpy)2]2+ can be monitored by 1H NMR exchange spectroscopy and allows the cobalt(II) spectra to be fully assigned.     

Relation between steady shear flow and dynamic rheology

Summary The relationships between steady shear flow and dynamic rheology are investigated at relatively high shear rates and frequencies. A useful empirical relationship in this region predicts that the magnitude of the complex dynamic viscosity | ^*| should be compared with the shear viscosity at equal values of frequency and shear rate (Cox-Merz-rule). Polystyrenes (PS) and Polyacrylamides (PAAm) have been investigated over a wide range of concentration and molecular weight. Only in case of PAAm/H₂O solutions we have found that the results do not coincide with Cox-Merz-rule. As far as we know this is the first time that deviations from Cox-Merz-rule were observed in a homogeneous system. A molecular interpretation is given.

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Zusammenfassung Die Beziehung zwischen der Scherviskosität und der komplexen (dynamischen) Viskosität bei relativ hohen Schergeschwindigkeiten und Frequenzen wurde untersucht. Eine geeignete empirische Beziehung in diesem Bereich sagt aus, daß der Betrag der komplexen Viskosität | ^*| mit der Scherviskosität bei gleichen Werten von Frequenz und Schergeschwindigkeit vergleichbar ist (Cox-Merz-Regel). Polystyrole (PS) and Polyacrylamide (PAAm) wurden über einen weiten Bereich der Konzentration und des Molekulargewichts untersucht. Nur im Fall der PAAm/H₂O-Lösungen wurden Abweichungen von der Cox-Merz-Regel gefunden. Soweit uns bekannt, ist es das erste Mal, daß Abweichungen von der Cox-Merz-Regel in einem homogenen System gefunden wurden. Eine molekulare Erklärung wird gegeben.

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Presented at the IUPAC 26^th International Symposium on Macromolecules, Mainz, September 17–21, 1979.

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With 4 figures and 1 table     

Hydrogels based on carboxymethyl cassava starch cross-linked with di- or polyfunctional carboxylic acids: Synthesis, water absorbent behavior and rheological characterizations

Carboxymethyl cassava starch (CMS) was synthesized and its hydrogels were prepared by cross-linking it with di- or polyfunctional carboxylic acids using glutaric (CASXGLU), suberic (CASXSUB), pimelic (CASXPIM) and butanetetracarboxylic acids (CASBTC) as the cross-linkers. The characterization of the CMS showed that its degree of substitution was 0.86, average molar mass (M_w) was 5.6 × 10⁶ g mol⁻¹ and the ¹³C NMR showed strong peak at δ = 180.42 ppm which was assigned to the CO carbon in the carboxymethyl group. The absorption under load (AUL) and free swelling capacity (FSC) studies showed that the hydrogels have fast swelling properties and that they reached equilibrium after 1 h. Furthermore, all the hydrogels were sensitive to the increasing salt concentrations and pH of the medium. Both AUL and FSC reduced in saline solution while their values increased in alkaline buffer solutions. The result indicate that the difunctional carboxylic acids produced hydrogels with stronger material functions compared with the polyfunctional carboxylic acid and the order of increases in both AUL and FSC was CASXBTC, CASXPIM, CASXSUB and CASXGLU.     

Viscoelastic properties of liquid crystals of aqueous biopolymer solutions

The formation of aqueous, lyotropic phases of the biopolymers xanthan (M = 1.6·10⁶) and schizophyllan (M _W = 335 000) is investigated with stationary shear flow and oscillatory measurements, as well as with the aid of polarization microscopy, because these polymers show very different viscoelastic properties from coiled vinyl polymers. Xanthan and schizophyllan exhibit the same typical behavior observed in anisotropic solutions when the viscosity is plotted as a function of concentration and of shear rate. It has also been observed that the first normal stress difference for concentrated xanthan solutions shows a saturation effect at increasing shear rate. In oscillatory measurements only schizophyllan exhibits an maximum for the storage modulus. The absence of a such an elasticity maximum in the case of the xanthan solution may be attributed to the significantly higher flexibility of the xanthan helix. A comparison of the critical concentrations calculated according to Flory's theory and the experimentally determined values shows that the two-phase region is distinctly broader than the theory predicts. This deviation cannot be attributed to the flexibility of the polymer, but can, however, be explained by intermolecular interactions. In contrast to the non-charged schizophyllan the polyelectrolyte xanthan is affected in addition to the attractive interactions (H-bonds) by electrostatic repulsion forces.This paper was partly presented at the 198th ACS National Meeting in Miami Beach, Florida, Sept. 10–15, 1989 .     

Chiral Diselenides from Benzylamines: Catalysts in the Diethylzinc Addition to Aldehydes

A series of new chiral diselenides with a N-atom in the side chain was prepared by a short synthetic sequence (Scheme 1). Only 1 mol-% of these diselenides catalyzed very effectively the diethylzinc addition to various aromatic and α,β-unsaturated aldehydes yielding the secondary alcohols in up to 98% ee (Scheme 2 and Tables 1 and 2). An asymmetric amplification was observed with these catalysts. Detailed NMR studies were performed to characterize the catalytically active species.     

Synthesis of 4′-C-Acylated Thymidines

Two synthetic pathways towards 4′-C-acylthymidines are presented. These modified mononucleosides are precursors of the 2′-deoxyribonucleotide 4′-C-radical. They were converted into their corresponding 3′-O-[(2-cyanoethyl) N,N-diisopropylphosphoramidites] 3a–c and incorporated in oligonucleotides by solid-phase synthesis. The structure of some modified nucleosides was revealed by X-ray crystal-structure analysis.     

Bestimmung der Molmassenverteilung sowie der Stabilitätsgrenze von Polyacrylamiden unter Benutzung einer kombinierten Ausschlußchromatographie/Kleinwinkel-Laser-Streulichtphotometer Anlage

The molecular weight distribution including the calculation ofM _n, M_w andM _z of polyacrylamide in aqueous 0.1 M sodium sulphate-solution has been determined by simultaneously and continuously monitoring the effluent from a size-exclusion chromatographic (SEC) column filled with porous glasses with a low-angle-laser-light-scattering (LALLS) photometer. The recorder traces of the scattering intensity and the refractive index difference have been digitalized in about 400 steps corresponding to 200l fractions. Each fraction has been assumed to be monodisperse. This method gives absolute data rather than relative data obtained from any calibration method. The investigations clearly show a flow-rate dependent degradation of samples with relatively low molar masses (M _w =500 000 g/mol atM _w/M_n=2.5) at typical flow rates Q1 ml/min. A discussion of some problems encountered using aqueous SEC and a way to determine the critical molar mass, below which no degradation could be observed, based on elongational flow theories is given.

Verzeichnis der Abkürzungen a Exponent der Mark-Houwink-Beziehung - A _c Querschnittsfläche der Säule - A ₂ Zweiter Virialkoeffizient - c Konzentration - c ₁ ^* kritische Konzentration nach Einstein - c ₂ ^* kritische Konzentration aus Lichtstreumessungen - D Säulendurchmesser - De Deborahzahl - d Partikeldurchmesser - d _equ,[n] Polymerknäueldurchmesser nach Einstein - (dn/dc ) Brechungsindexincrement - K Faktor der Mark-Houwink-Beziehung - k Faktor der Lichtstreuung - K1 Formfaktor - LALLS Kleinwinkel-Laserlichtstreuung - M _i monodisperse Molmasse einer Einzelfraktion - M _n, M_w, M_z verschiedene Mittelwerte der Molmasse - N _L Loschmidtsche Zahl - n Brechungsindex des Lösungsmittels - np Porosität - P Streufunktion - Q Volumengeschwindigkeit - R allgemeine Gaskonstante - Re Reynoldszahl - R Streulichtintensität - R _G ² > ^1/2 Gyrationsradius - SEC Ausschlußchromatographie - T Temperatur - V _e Elutionsvolumen - ¯ v mittlere Strömungsgeschwindigkeit Griechische Symbole Scherrate - Dehnrate - Viskosität - [] Staudingerindex - Widerstandskennzahl - Wellenlänge des Lichtes - _M Relaxationszeit der Porenmatrix - ₁₂ Schubspannung - Relaxationszeit - Beobachtungswinkel der Lichtstreuung - Dichte Wir danken dem Fonds der Chemischen Industrie auch an dieser Stelle für die finanzielle Unterstützung der Arbeit.     

Prediction of the non-Newtonian viscosity and shear stability of polymer solutions

The structure-property relationships derived here permit the prediction of both the zero-shear viscosity ₀, as well as the shear rate dependent viscosity . Using this molecular modeling it is now possible to predict over the whole concentration range, independently of the molecular weight, polymer concentration and imposed shear rate. However, the widely accepted concept: dilute — concentrated, is insufficient. Moreover it is necessary to take five distinct states of solution into account if the viscous behavior of polymeric liquids is to be described satisfactorily. For non-homogeneous, semi-dilute (moderately concentrated) solutions the slope in the linear region of the flow curve (= must be standardized against the overlap parameterc · []. As with the ₀-M-c-relationship, a-M -c- relationship can now be formulated for the complete range of concentration and molecular weight. Furthermore, it is possible to predict the onset of shear induced degradation of polymeric liquids subjected to a laminar velocity field on the basis of molecular modeling. These theoretically obtained results lead to the previously made ad hoc conclusion (Kulicke, Porter [32]) that, experimentally, it is not possible to detect the second Newtonian region.Roman and Italian symbols a exponent of the Mark-Houwink relationship - b exponent of the third term of the ₀-M -c relationship - c concentration /g · cm^–3 - E number of entanglements per molecule - F(r) connector tension - f function - G _i ^A shear modulus; A indicates that it /Pa has been evaluated by a transient shear flow experiment; i is the shear rate to whichG ^A refers to - G storage modulus /Pa - G _p plateau modulus /Pa - H() relaxation spectrum /Pa - h shift factor (₀/_r) - K _H Huggins constant - K _b third constant of the ₀-M -c relationship - K constant of the Mark-Houwink relationship - M molecular weight /g · mol^–1 - M _e molecular weight between two /g · mol^–1 entanglement couplings - N number of segments per molecule - n slope in the power-law region of the flow curve - p p-th mode of the relaxation time spectrum - R gas constant /8.314 J·K^–1·mol^–1 - r direction vector - T temperature /K Greek symbols ß reduced shear rate - shear rate /s^–1 - shear viscosity /Pa·s - _s solvent viscosity /Pa·s - _sp specific viscosity - ₀ zero-shear viscosity /Pa·s - apparent viscosity at shear rate - reduced viscosity - viscosity of polymeric liquid in /Pa·s the second Newtonian region - [] intrinsic viscosity/cm³·g^–1 - screening length/m - /g·cm ^–3 density - relaxation time/s - ₀ experimentally derived relaxation time/s - angular frequency of oscillation Indices conc concentrated - corr slope corrected - cr critical - deg degradation - e entanglement - exp experimental - mod moderately concentrated/semi-dilute - n number average - p polymer - R Rouse - rep reptation - s solvent - sp specific - theo theoretical - weight average - relaxation time - o experimental or steady state - * critical - ** transition moderately conc. — conc. - + transition dilute — moderately cone. Paper presented at the 2nd bilateral U.S.-West German Polymer Symposium, Yountville, the 7th–11th September 1987.