A study of the parameters affecting the accuracy of the total pore blocking method

We report on a study wherein we investigate the different factors affecting the accuracy of the total pore blocking method to determine the interstitial volume of reversed-phase packed bed columns. Octane, nonane, decane and dodecane were all found to be suitable blocking agents, whereas heptane already dissolves too well in the applied fully aqueous buffers. The method of moments needs to be used to accurately determine the elution times, and a proper correction for the frit volume is needed. Failing to do so can lead to errors on the observed interstitial volume of the order of 2% or more. It has also been shown that the application of a high flow rate or a high pressure does not force the blocking agent out of the mesopores of the particles. The only potential source of loss of blocking agent is dissolution into the mobile phase (even though this is a buffered fully aqueous solution). This effect however only becomes significant after the elution of 400 geometrical column volumes, i.e., orders more than needed for a regular total pore blocking experiment.     

Future of high pressure liquid chromatography: do we need porosity or do we need pressure?

Making a theoretical study supported by experiments of the kinetic advantages of increased inlet pressures versus increased external porosity using impedance plots of analysis time versus required plate number, it is found that both approaches more or less have the same effect on the kinetic performance. The need to change a given system to one with an increased inlet pressure or with an increased external porosity can best be assessed from the optimal plate number (N(opt)) of the system. When the pursued application requires a plate number that is larger than N(opt), any increase in inlet pressure and external porosity is beneficial. When the required plate number is smaller than N(opt), any increase in inlet pressure and external porosity should preferentially be accompanied by an overall reduction of the feature sizes of the support. The degree to which this feature size reduction can be realized in practice will to a large extent determine which of the two approaches will be the dominant system of the future.     

The link between nanoscale feature development in a negative resist and the Hansen solubility sphere

By systematically studying development of a high resolution, negative electron beam resist, hexa‐methyl acetoxy calix(6)arene, we have elicited a more general understanding of the underlying development mechanisms for negative resists. Using the three dimensional Hansen solubility parameters for more than 40 solvents, we have constructed a Hansen solubility sphere (HSS). From this sphere, we have estimated the Flory Huggins interaction parameter for solvents with hexa‐methyl acetoxy calix(6)arene and found a correlation between resist development contrast, nanoscale patterned feature quality, and the polymer‐solvent solubility. Conducting Atomic Force Microscopy (AFM) in a liquid cell, we have measured swelling for hexa‐methyl acetoxy calix(6)arene in four solvents. The swelling measurements indicate that the HSS gives an indication of the Flory‐Huggins interaction parameter. These measurements provide new insights into the development behavior of nanoscale features – necessary for obtaining the ultimate lithographic resolution. In addition, it demonstrates a methodology for choosing appropriate polymer‐solvent combinations for nanoscience applications. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2091–2105, 2009     

Sorption isotherm measurements by NMR

An experimental setup is described for the automated recording of sorption isotherms by NMR experiments at precisely defined levels of relative humidity (RH). Implementation is demonstrated for a cotton fabric; Bloch decays. T1 and T2* relaxation times were measured at predefined steps of increasing and decreasing relative humidities (RHs) so that a complete isotherm of NMR properties was obtained. Bloch decays were analyzed by fitting to relaxation functions consisting or a slow- and a fast-relaxing component. The fraction of slow-relaxing component was greater than the fraction of sorbed moisture determined from gravimetric sorption data. The excess slow-relaxing component was attributed to plasticized segments of the formerly rigid cellulose matrix. T1 and T2* sorption isotherms exhibit hysteresis similar to gravimetric sorption isotherms. However, correlating RH to moisture content (MC) reveals that both relaxation constants depend only on MC, and not on the history of moisture exposure.     

Vector-meson-dominance model for radiative decays involving light scalar mesons

We study a vector-dominance model which predicts quite a large number of currently interesting decay amplitudes of the types S-->gammagamma, V-->Sgamma, and S-->Vgamma, where S and V denote scalar and vector mesons, in terms of three parameters. As an application, the model makes it easy to study in detail a recent proposal to boost the ratio Gamma(phi-->f(0)gamma)/Gamma(phi-->a(0)(0)gamma) by including the isospin violating a(0)(0)-f(0) mixing. However, we find that this effect is actually small in our model.