Synthetic erythropoietic proteins: tuning biological performance by site-specific polymer attachment

Chemical synthesis in combination with precision polymer modification allows the systematic exploration of the effect of protein properties, such as charge and hydrodynamic radius, on potency using defined, homogeneous conjugates. A series of polymer-modified synthetic erythropoiesis proteins were constructed that had a polypeptide chain similar to the amino acid sequence of human erythropoietin but differed significantly in the number and type of attached polymers. The analogs differed in charge from +5 to -26 at neutral pH and varied in molecular weight from 30 to 54 kDa. All were active in an in vitro cell proliferation assay. However, in vivo potency was found to be strongly dependent on overall charge and size. The trends observed in this study may serve as starting points for the construction of more potent synthetic EPO analogs in the future.     

Simultaneous quantification of terpenelactones and flavonol aglycones in hydrolyzed ginkgo biloba extract by liquid chromatography with inline ultraviolet and evaporative light scattering detection

We report here a liquid chromatography (LC) method with inline ultraviolet/evaporative light scattering (UV/ELS) detection for the simultaneous quantification of the terpenelactones and flavonol aglycones in a single sample of hydrolyzed Ginkgo biloba extract (GBE). The sample is hydrolyzed by a rapid and convenient oven heating method for 1 h at 90 degrees C with 10% hydrochloric acid. The 1 h hydrolysis was found to be equivalent to the 2.25 h reflux treatment for dry powder extract, where total flavonol glycosides were 28.4 and 28.1%, respectively. Acceptable precision was achieved for total terpenelactones [relative standard deviation (RSD) = 4.8%] by ELS detection, and total flavonol aglycones (RSD = 2.3%) by UV detection. The analytical range was 1.5 to 7.3% (w/w) for the individual terpenelactones (ELS) and 2.5 to 15.0% (w/w) for the individual glycosides (UV) calculated from the aglycones quercetin, kaempferol, and isorhamnetin. This improved method allows for the first time high throughput sample preparation coupled with the quantification of the predominant compounds generally used for quality control of GBE in a single assay.     

Assessment of supporting electrolyte contributions in electrochemically modulated liquid chromatography

This paper reports the results of an investigation on the role of the supporting electrolyte in separations using electrochemically modulated liquid chromatography (EMLC) with a porous graphitic carbon stationary phase. With respect to the identity of the supporting electrolyte, the elution strength of the electrolyte anion increased as F- < OH- < BF4- < ClO4- < PF6- for injections of negatively charged aromatic molecules, whereas a 10-fold increase in electrolyte concentration induced a 60% change in retention for the same solutes. Furthermore, both the concentration and composition of the supporting electrolyte affected retention in a manner that varied with the charge of the analyte and applied potential. This behavior is explained using Gouy-Chapman diffuse double layer theory, coupled with comparisons of this theory with closely related models for ion-pair chromatography. Insights into the retention mechanism reveal that an ion-exchange mechanism controls the retention of negatively charged solutes at applied potentials removed from the potential of zero charge (PZC). At potentials close to the PZC, the electrostatic model is less effective with the predominant retention mechanism likely involving hydrophobic interactions with the carbonaceous stationary phase. The combined effects of these findings are demonstrated by using a temporal gradient in supporting electrolyte concentration to optimize an EMLC separation.     

An optical study of phase transitions of poly (ethylene terephthalate-co-p-hydroxybenzoic acid) liquid crystal

The copolyester containing 40 mol % ethylene terephthalate (PET) and 60 mol % p-hydroxybenzoate (HB) units has been reported by several investigators to be biphasic in the solid and the liquid states. The reported thermal transitions in the two phases, however, are in part contradictory, perhaps partly due to different polymerization conditions. The present work is a study of the transitions in each of the two phases of this copolyester by polarized light microscopy and by light transmission measurements. By light transmission measurements, the two phases were found to have two different glass transition temperatures for the onset of segmental motion, consistent with two assignable temperatures (T.). Cold crystallization and melting in each of the two different phases was also detected. The results help clarify the nature of transitions and agree with the results of dynamic mechanical analysis on the same thermotropic liquid crystalline copolyester.     

A new approximation method for scattering by long finite arrays

The scattering of water waves by a long array of evenly spaced,rigid, vertical circular cylinders is analysed under the usualassumptions of linear theory. These assumptions permit the reductionof the problem to that of solving the Helmholtz equation intwo dimensions, with appropriate circular boundaries. Our primarygoal is to show how solutions obtained for semi-infinite arrayscan be combined to provide accurate and numerically efficientsolutions to problems involving long, but finite, arrays. Theparticular diffraction problem considered here has been chosenboth for its theoretical interest and for its applicability.The design of offshore structures supported by cylindrical columnsis commonplace and understanding how the multiple interactionsbetween the waves and the supports affect the field is clearlyimportant. The theoretical interest comes from the fact that,for wavelengths greater than twice the geometric periodicity,the associated infinite array can support Rayleigh–Blochsurface waves that propagate along the array without attenuation.For a long finite array, we expect to see these surface wavestravelling back and forth along the array and interacting withthe ends. For particular sets of parameters, near-trapping haspreviously been observed and we provide a quantitative explanationof this phenomenon based on the excitation and reflection ofsurface waves by the ends of the finite array.     

Some Isoperimetric Inequalities in Electrochemistry and Hele Shaw Flows

Isoperimetric inequalities are applied to a moving-boundaryproblem for doubly-connected domains. This problem occurs forexample in electrochemistry, in which case the domains in questionare the electrolyte of an electrolytic cell. The two electrodessurrounding the electrolyte are assumed to grow or dissolve,at different rates in general, by electrochemical reaction.We obtain optimal estimates showing, for example, that the leastchange in volume of each electrode always occurs in sphericalsymmetry.     

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     

Mercury speciation in air-coal and oxy-coal combustion: A modelling approach

In this study, a mechanism for mercury chlorination in flue gases resulting from the combustion of pulverised coal has been presented. Arrhenius parameters of the gas-phase elementary reactions in the Hg–Cl sub-mechanism have been updated and are mainly based on recent experimental and quantum mechanical rate determinations. The mechanism is validated by comparison to accurate experimental data that is unbiased by Hg oxidation in the impinger solutions of aqueous chemistry methods. Solid-phase retention of Hg⁰ has been studied in parallel to char combustion; the heterogeneous model describes condensation of mercury on fly ash particles. The combined homogeneous–heterogeneous model predictions show comparable trends to those of power plant data. This approach aims to provide an improved prediction of mercury speciation from coal-fired power plants and to shed light on the chemical kinetic changes encountered during oxy-coal operation.