Abstract: A field flow fractionator to separate particles contained within an injected sample aliquot is described. As required, said fractionator may be used to capture, for subsequent removal, specific predefined classes of such particles. Based upon the cross flow or asymmetric flow field flow fractionators, the fractionator disclosed contains means to vary the applied transverse flows at a plurality of locations along the length of its separating channel. One embodiment utilizes a plurality of separated compartments, each lying below a distinct and corresponding membrane supporting permeable frit segment, are provided individual means to control the localized flow through the membrane section thereabove. A corresponding concentric compartment implementation achieves the same type of compartmentalized cross flow when integrated with a hollow fiber fractionator.

Abstract: A method is described for separating and processing liquid-borne particles within an aliquot thereof following injection into a field flow fractionator. Said fractionation method may be employed also to capture, for subsequent segregation, specific predefined classes of such particles. The unique fractionation method disclosed contains means to control the applied transverse flow at each designated location along the length of said channel. In one embodiment of the method a separate compartment lies below each distinct location and corresponding membrane supporting permeable frit segment of the fractionator, providing the individual means to control the localized flow through the membrane section thereabove. Employment of a corresponding concentric compartment implementation achieves the same type of compartmentalized cross flow when applied to a hollow fiber fractionation means.

Abstract: A new method is presented for characterizing the associative properties of a solution of macromolecules at high concentration. Sample aliquots spanning a range of concentrations are injected sequentially into a light scattering photometer. Equilibrium association constants and association stoichiometry are derived from an analysis of the angular and concentration dependence of the scattering signals. Thermodynamic nonideality, which becomes important at high concentrations, is dealt with in the analysis in a simplified manner which is applicable to multiple associated species.

Abstract: A field flow fractionator to separate particles contained within an injected sample aliquot is described. As required, said fractionator may be used to capture, for subsequent removal, specific predefined classes of such particles. Based upon the cross flow or asymmetric flow field flow fractionators, the fractionator disclosed contains means to vary the applied transverse flows at a plurality of locations along the length of its separating channel. A plurality of separated compartments, each lying below a distinct and corresponding membrane supporting permeable frit segment, are provided individual means to control the localized flow through the membrane section thereabove. A corresponding concentric compartment implementation achieves the same type of compartmentalized cross flow when integrated with a hollow fiber fractionator.

Abstract: A sample cell for making light scattering measurements, incorporating an exterior surface acting as both a lateral and vertical lens, is described. This unique structure permits greatly improved measurement of the light scattered by molecules and particles suspended in a fluid contained therein or flowing therethrough while illuminated by a fine light beam incident thereon. The resultant lensed structure of the cell, when integrated into a scattered light photometer and combined with suitable apertures before each scattered light collecting detector, reduces significantly stray light from entering each such detector.

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: 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. 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 method and apparatus is described by which means molecules in suspension may be characterized in terms of the size and mass distributions present. As a sample solution is separated by centrifugal means, it is illuminated at a particular radial distance from the axis of rotation by a fine, preferably monochromatic, light beam. Despite the high resolution of such devices, a key problem associated with most separators based upon use of centrifugal forces is the difficulty in deriving the absolute size and/or molar mass of the separating molecules. By integrating means to detect light scattered, over a range of scattering angles, from samples undergoing centrifugal separation, molecular sizes in the sub-micrometer range may be derived, even in the presence of diffusion. Adding a second light beam at a displaced rotational angle, preferably of an ultraviolet wavelength, that intersects the sample at the same radial region as the first beam permits determination of the molecular concentration at that region.

Abstract: An improved cell for a walk-off refractometer is disclosed that permits measurement of the differential refractive index, DRI, between a sample fluid and a reference fluid. In addition, the new cell design permits the measurement of the refractive index, RI, of a fluid relative to the refractive index of the material comprising or surrounding the flow cell. Thus a single instrument may be used to measure separately the RI of a sample fluid and the DRI between a sample fluid and a reference fluid. The new flow cell contains two chambers, typical of a DRI instrument, but an asymmetric internal angle in either the sample or the reference chamber. By the provision of this unique structure, it is an objective of this invention to be able to measure the refractive index of a fluid relative to the refractive index of the material comprising the flow cell or relative to the medium surrounding the flow cell, either of which may be considered a measurement of the RI of the fluid.

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 sensitivity-enhanced flow cell to be used in the determination of the differential refractive index increment of a sample fluid relative to a reference fluid is disclosed. The invention permits the use of smaller sample amounts without sacrificing overall sensitivity. Equally important, said improved flow cell produces measurements of increased precision without requirement for increased sample amount. This is achieved by means of two chambers within said cell whose volumes are different. The sample fluid chamber is the smaller of the two with the reference fluid chamber constructed so that the incident illumination beam, upon passage through said sample chamber and displacement by the partition element located therebetween said sample and reference chambers, passes through said reference chamber without grazing any of the confining walls or striking corners of said sensitivity-enhanced flow cell.

Abstract: A method and apparatus are described by which previously identified aerosol particles that may have precipitated onto surfaces and/or into specific physical regions are detected, removed from said regions, and stored for later examination or destruction. The method includes means such as an ultrasonic probe to loosen said aerosol particles from the surfaces to which they have precipitated and then withdraw them into an optical read head for measurement. The optical read head illuminates each particle, previously diluted and entrained in a sheath flow, as it passes therethrough with a fine beam of light such as produced by a laser. The scattered light produced by each such particle is collected over a range of scattering angles, converted into a digital representation for each value collected, and stored in a computer means.

Abstract: A method for determining absolute number densities of particles in a solution is disclosed based on a light scattering method. A light scattering photometer is calibrated to produce the Rayleigh ratio at each angle measured with respect to light scattered per unit incident intensity, per unit volume illuminated within the field of view of each detector per steradian subtended by said detector. In order that the numbers calculated be accurate, the illuminated particles should be effectively monodisperse. From the excess Rayleigh ratios measured at a plurality of angles with respect to the incident light beam illuminating said sample particles, an effective size is calculated which, in turn, is used to calculate the differential scattered intensity at each angle. The number of particles per unit volume element is then determined from the measured excess Rayleigh ratio divided by the corresponding differential scattered intensity.

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: An aerosol hazard classification and early warning network is composed of a large number of detector and analysis units, called “detector stations,” which are deployed throughout a region to be warned of a potentially hazardous aerosol intrusion. Such aerosol threats may originate from fires, volcanic eruptions, or overt releases of biological and chemical agents dispersed in aerosol form. Among the former are the characteristic toxic aerosols released during refinery fires or explosions. The latter biological agents include bacterial spores, lyophilized bacterial cells, and virus preparations, whereas chemical agents might include various forms of nerve gasses and other anti-personnel gasses such as mustard, all commonly deployed in aerosol form.

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: A method is described to determine the 2nd virial coefficient of an ensemble of molecules dissolved in a selected solvent. Two distinct classes are described: monodisperse and polydisperse molecules. If the molecules are monodisperse, they must be prepared for a chromatographic separation and suitable columns selected. Following standard chromatographic separation procedures such as exemplified by the method of size exclusion chromatography, the sample passes through the separation columns, a multiangle light scattering detector, and a concentration detector. The effect of the columns is to produce a concentration profile of said sample that appears as a peak as it passes through the light scattering and concentration detectors. For each elution interval, &ngr;i, a corresponding concentration value ci and set of excess Rayleigh ratios Ri(&thgr;j) is measured for each scattering angle &thgr;j.

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.