Industrial applications of supercritical fluid chromatography: polymer analysis

Summary Polymers can be difficult to fully characterize by conventional chromatographic methods [i.e., gas chromatography (GC), high performance liquid chromatography (HPLC) and size exclusion chromatography (SEC)] due to temperature instability, detector incompatibility, nonvolatility, molecular weight considerations or insufficient chromatographic efficiency. Capillary supercritical fluid chromatography (SFC) offers several advantages for polymer analysis. Complex distributions can be resolved, low temperatures can be used and individual oligomers can be detected, allowing differences in molecular weight distributions to be quantitatively and qualitatively measured. In this paper, results will be shown for the analysis of various types of polymers demonstrating how changes in chromatographic parameters affect the analysis

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Industrielle Anwendungen der Chromatographie mit überkritischen fluiden Phasen: Polymeranalyse

     

Charged hadron multiplicities and inclusive π− distributions in inelastic ep scattering

Electroproduction of hadrons is studied in the kinematic region W < 2.8 GeV and 0.3 < Q² < 1.4 GeV² using the DESY streamer chamber. Prong cross sections, charged-particle multiplicities and inclusive π^? distributions are presented. The average charged multiplicity is found to be independent of Q² in the Q² range studied here; however it is lower than in photoproduction. The fraction of forward π^? is found to be significantly less in electroproduction than in photoproduction. The 〈p_⊥²〉 for inclusive π^? is, for all x values, similar to that found in photoproduction.     

Determination of promethazine in human plasma by automated high-performance liquid chromatography with electrochemical detection and by gas chromatography-mass spectrometry

A highly specific and sensitive method using automated high-performance liquid chromatography with electrochemical detection (HPLC-ED) and a method using gas chromatography-mass spectrometry (GC-MS) have been developed for the quantitative determination of promethazine in plasma. The lowest detectable concentration by HPLC-ED is 0.1 ng/ml of plasma and by GC-MS 0.5 ng/ml of plasma. The HPLC-ED method incorporates a valve switching unit to prevent all of the electroactive impurities from entering the electrode compartment, thus maintaining the sensitivity of the detector for the analyses of large numbers of samples. The GC-MS method incorporates the highly specific selected-ion monitoring technique. Plasmas derived from healthy subjects each given a single 50-mg oral dose of promethazine were analyzed by both HPLC-ED and GC-MS. The two methods compare favorably with a correlation coefficient of 0.92 and a slope of 1.059. While both methods are suitable for studying single-dose pharmacokinetics of promethazine, the automated HPLC-ED method has a decided advantage in being more sensitive and suitable for unattended overnight analyses of the large number of samples encountered in pharmacokinetic studies. The specificity of the HPLC-ED method is demonstrated by comparison to the GC-MS analysis of biological samples.     

Remarks on bang-bang control in a Hilbert space

The control of a linear system, whose performance index is the sum of a linear term and a quadratic term, is considered. A necessary and sufficient condition is given for the optimal control to be bang-bang, and this is used to extend and clarify the results of Refs. 1–2. As an illustration, an application to an elliptic boundary-value problem is given.This research was supported by the SFB 72 of the DFG, West Germany.     

Mechanistic studies on the Heck-Mizoroki cross-coupling reaction of a hindered vinylboronate ester as a key approach to developing a highly stereoselective synthesis of a C1-C7 Z,Z,E-triene synthon for viridenomycin

Mechanistic studies of the Heck-Mizoroki reaction of a vinylboronate ester with electronically different (four-substituted) aryl iodides shows that electron donors accelerate the cross-coupling, demonstrating that the oxidative addition step is not rate determining and that there is development of some degree of positive charge in the rate determining step. These results were used as a basis to allow the development of reaction conditions for the Heck-Mizoroki coupling of a hindered vinylboronate ester with electron deficient methyl cis-2-iodoacrylate. The resulting dienylboronate ester was converted through a series of highly stereoselective iodo-deboronations and Heck-Mizoroki reactions into a trienyl iodide precursor for further application in the total synthesis of viridenomycin.     

Resonant formation measurements of dt\mu via time of flight

Solid hydrogen in the form of an inhomogeneous layered target offers several experimental advantages when compared with liquid or gas. Beams of non-thermalized muonic hydrogen atoms allow us to explore resonant molecular ion formation processes near eV kinetic energies. Isotopically specific layers make it possible to separate competing and confusing interactions and to employ the time of flight for comparison with predictions based on theoretical energy dependences. Unambiguous charged fusion product detection simplifies absolute intensity measurements. The systematic uncertainties encountered in resonant molecular ion formation measurements, using solid hydrogen target layers, are being investigated with simulations which use the many calculated energy-dependent rates and cross-sections which are now available. The importance of the rates for processes such as muon transfer and elastic scattering are discussed, and results of some recent analyses are presented. This revised version was published online in August 2006 with corrections to the Cover Date.