Abstract: A new method is presented for measuring the molecular properties of an unfractionated solution of macromolecules. Sample aliquots spanning a range of concentrations are injected sequentially into a stream of solution and flow towards the detectors. Each aliquot produces, thereby, an effective “peak” whose elements correspond to different concentrations of the diluted aliquot. The weight averaged molar mass, the mean square radius, and the second virial coefficient of the macromolecules in solution are derived from an analysis of the angular and concentration dependence of the scattering signals throughout the corresponding peaks. In contrast to earlier on-line methods, better accuracy is achieved, while using a smaller quantity of sample. A similar method for determining cross virial coefficients between two distinct species of macromolecules is also presented.

Abstract: A new method is presented for measuring the molecular properties of an unfractionated solution of macromolecules. Sample aliquots spanning a range of concentrations are injected sequentially into a stream of solution and flow towards the detectors. Each aliquot produces, thereby, an effective “peak” whose elements correspond to different concentrations of the diluted aliquot. The weight averaged molar mass, the mean square radius, and the second virial coefficient of the macromolecules in solution are derived from an analysis of the angular and concentration dependence of the scattering signals throughout the corresponding peaks. In contrast to earlier on-line methods, better accuracy is achieved, while using a smaller quantity of sample. A similar method for determining cross virial coefficients between two distinct species of macromolecules is also presented.

Abstract: Chromatographic separations are often characterized by multiple detectors through which the sample flows serially. As the sample flows between detectors, it becomes progressively diluted due to mixing and diffusion. This phenomenon is traditionally called interdetector “band broadening” and often results in significant distortion of the sample's derived physical properties such as molar mass. This method to characterize the broadening present in a chromatographic system, and an algorithm whereby the narrow peaks of the upstream detector are numerically broadened so they can be compared to the broadened peaks of the downstream detector, is described. Although the technique results in some loss of resolution, its stability and generality allow it a broad range of application. Examples are presented for data collected by dRI, MALS, UV, and viscometric detectors.

Abstract: Chromatographic separations are often characterized by multiple detectors through which the sample flows serially. As the sample flows between detectors, it becomes progressively diluted due to mixing and diffusion. This phenomenon is traditionally called interdetector “band broadening” and often results in significant distortion of the sample's derived physical properties such as molar mass. A method to characterize the broadening present in a chromatographic system, and an algorithm whereby the narrow peaks of the upstream detector are numerically broadened so they can be compared to the broadened peaks of the downstream detector, is described. Although the technique results in some loss of resolution, its stability and generality allow it a broad range of application. Examples are presented for data collected by dRI, MALS, UV, and viscometric detectors.

Abstract: A thermally controlled stage is connected within one arm of a bridge of a capillary bridge viscometer so that the bridge can be balanced in situ to provide accurate measurement signals. The thermally controlled stage includes a tuning capillary tubing portion that is wrapped around a thermally conductive core. A resistance heater or a Peltier thermoelectric device is located in close proximity to the capillary tubing portion. The heater or Peltier device and the capillary tubing portion are located within a thermally insulated housing. The heater or Peltier device varies the temperature of the capillary tubing portion to cause a corresponding change in the flow impedance of the tuning capillary tubing portion of the arm of the bridge in which the thermally controlled stage is connected. The temperature of the tuning capillary tubing portion is monitored and adjusted until any pressure differential across the bridge is eliminated, whereby to trim in the balance of the bridge.

Abstract: An improved differential refractometer incorporating a photodetector array is disclosed. Using a multi-element photo array provides the basis for measurement of differential refractive index values with a heretofore unattainable combination of sensitivity of measurement and concurrent range of measurement. Within the large dynamic range attainable, the detector structure provides equal sensitivity irrespective of deflection within the range. The transmitted light beam is tailored to provide a spatial variation of the light intensity at the array improving thereby the precision of measurement of its displacement. This in turn results in improved precision in the reported differential refractive index and in the calculation of the differential refractive index increment dn/dc. Integrating the detector array into the flow cell structure of the parent case results in a detector of exceptional sensitivity and range for sample quantities far smaller than required by conventional differential refractometers.

Abstract: A new method is presented for measuring the molecular properties of an unfractionated solution of macromolecules. Sharing some similarities with the standard Zimm plot technique, the method begins with the preparation of several sample aliquots spanning a range of concentrations. The aliquots are then injected sequentially into a stream such as provided by a liquid chromatograph. Each aliquot produces, thereby, an effective “peak” whose elements correspond to different concentrations of the diluted aliquot. By analyzing the angular and concentration dependence of the scattering signals throughout the corresponding peaks, the weight averaged molar mass, the mean square radius, and the second virial coefficient may be derived. In contrast to earlier on-line methods, better accuracy is achieved, while using a smaller quantity of sample.

Abstract: Optical flow cells used, for example, for making scattered light measurements on liquid borne samples, are often affected by particulate materials that adhere to the internal optical surfaces. These contaminating particulates can cause distortions of the scattered light signals to be measured from the illuminated samples within the flow cell. Such particulates are difficult to remove, especially while the cell is assembled. A method for dislodging and removing such particulate contaminants is described that consists of attaching externally to the flow cell an ultrasonic generator whose frequency of operation may be tuned to couple most effectively with the internal structures of the flow cell itself. Such ultrasonic coupling must be accompanied by an impressed flow through the cell that can remove from the cell particulates that have been dislodged. In order to assure good mechanical action, the impressed ultrasonic frequency is swept over a range of frequencies.

Abstract: Optical flow cells used, for example, for making scattered light measurements on liquid borne samples, are often affected by particulate materials that adhere to the internal optical surfaces. These contaminating particulates can cause distortions of the scattered light signals to be measured from the illuminated samples within the flow cell. Such particulates are difficult to remove, especially while the cell is assembled. A method for dislodging and removing such particulate contaminants is described that consists of attaching externally to the flow cell an ultrasonic generator whose frequency of operation is swept initially over a range that would couple most effectively with the internal structures of the flow cell itself. The optimal frequency is then selected automatically by monitoring the power dissipated and fixing the ultrasonic frequencies of operation at those values corresponding to regions of maximum power dissipation.

Abstract: An improved channel for separation of molecular and particulate samples by means of electrical field flow fractionation (FFF) is disclosed. The electrodes therein are made of metal oxide coated flat glass plates and permit the achievement, thereby, all of the seven most desirable features for such an electrical FFF channel, viz. 1) hardness, 2) flatness, 3) smoothness, 4) chemical inertness, 5) durability (does not generate particles), 6) high conductivity, and 7) transparency. In addition, the design of the clamping plates permits high precision in aligning the electrodes for parallelism.

Abstract: A method and apparatus is disclosed for measuring the refractive index difference between a reference and sample liquid based on an interferometric design. The resultant device has an almost unlimited range of operation in contrast to a conventional interferometric refractometer of the so-called polarization type whose dynamic range is restricted to a relatively narrow range of refractive indices. The measurement of the refractive index difference between a sample and reference cell is achieved by measuring the angle through which the plane of polarization of a combined beam has rotated. For the conventional device, this angle is restricted to about .pi. radians which corresponds to a half wavelength shift between the reference and sample components of said combined beam. The extended range device disclosed permits this angle to be tracked and measured accurately over many rotations.