WO2002033383A1 - Procede et dispositif pour la collecte de donnees par fluorescence - Google Patents

Procede et dispositif pour la collecte de donnees par fluorescence Download PDF

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Publication number
WO2002033383A1
WO2002033383A1 PCT/US2000/028439 US0028439W WO0233383A1 WO 2002033383 A1 WO2002033383 A1 WO 2002033383A1 US 0028439 W US0028439 W US 0028439W WO 0233383 A1 WO0233383 A1 WO 0233383A1
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WO
WIPO (PCT)
Prior art keywords
excitation
emission
fiber
optic bundle
fiber optic
Prior art date
Application number
PCT/US2000/028439
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English (en)
Inventor
Radislav Alexandrov Potyrailo
John Patrick Lemmon
Original Assignee
General Electric Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by General Electric Company filed Critical General Electric Company
Priority to PCT/US2000/028439 priority Critical patent/WO2002033383A1/fr
Publication of WO2002033383A1 publication Critical patent/WO2002033383A1/fr

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/47—Scattering, i.e. diffuse reflection
    • G01N21/4738—Diffuse reflection, e.g. also for testing fluids, fibrous materials
    • G01N21/474—Details of optical heads therefor, e.g. using optical fibres
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/645—Specially adapted constructive features of fluorimeters
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/47—Scattering, i.e. diffuse reflection
    • G01N21/4738—Diffuse reflection, e.g. also for testing fluids, fibrous materials
    • G01N21/474—Details of optical heads therefor, e.g. using optical fibres
    • G01N2021/4742—Details of optical heads therefor, e.g. using optical fibres comprising optical fibres
    • G01N2021/4747—Concentric bundles

Definitions

  • the present invention is directed to a method and apparatus for obtaining fluorescence data and, more specifically, to a method and apparatus for rapid in situ quantification of target species in a reactor.
  • the interfacial method for making polycarbonate has several inherent disadvantages. First, it can be a disadvantage to operate a process that requires phosgene as a reactant. Second, the process utilizes large amounts of an organic solvent, which can require expensive precautionary measures to prevent deleterious environmental effects. Third, the interfacial method requires significant capital investment in equipment. Fourth, polycarbonate produced by the interfacial process is prone to exhibiting inconsistent color, high levels of particulates, and high chloride concentration.
  • melt process involves the transesterification of a carbonate diester (e.g., diphenylcarbonate) with a dihydroxy compound (e.g., bisphenol-A). This reaction is typically performed without a solvent and is driven to completion by mixing the reactants under reduced pressure and high temperature with simultaneous distillation of the phenol produced by the reaction.
  • Polycarbonate produced by the melt process is typically referred to as LX grade polycarbonate.
  • the melt process provides many advantages over the interfacial process. More specifically, the melt process does not employ phosgene; it does not require a solvent; and it uses less equipment. Moreover, the polycarbonate produced by the melt process does not contain chlorine contamination from the reactants; it has lower particulate levels; and it has a more consistent color. Therefore, in certain circumstances, it can be highly desirable to use the melt process in production facilities.
  • the melt process tends to produce polycarbonate with significantly higher level of branching than that produced by the interfacial process.
  • This branching is the result of a side reaction called the Fries rearrangement, which involves the conversion of a phenolic ester into corresponding ortho and para hydroxyketones.
  • the rearrangement is based on the Fries rule, which postulates that the most stable form of a polynuclear compound is that arrangement which has the maximum number of rings in the benzenoid form.
  • the Fries rearrangement product in polycarbonate is typically the result of exposure to elevated temperatures in the presence of an active catalyst.
  • the primary Fries product is a salicylate ester that, under melt polymerization conditions, can further react to form a tri-functional molecule that acts as a branch point for the resulting polymer.
  • the generation of the Fries branch point structure can lead to polymer branching, thereby generating inconsistent melt behavior. In various applications, this branching significantly increases the ductility of the polycarbonate and is, therefore, undesirable.
  • the present invention is directed to a method and apparatus for obtaining fluorescence data from a specimen.
  • the apparatus includes an electromagnetic radiation source, an optical analyzer, and a fiber optic bundle.
  • the fiber optic bundle has an excitation fiber in optical communication with the electromagnetic radiation source and a plurality of emission fibers in optical communication with the optical analyzer.
  • the optical analyzer can have multiple channels, including a fluorescence-emission channel in optical communication with the emission fibers.
  • the fiber optic bundle can further contain at least one reflection fiber in optical communication with an absorbance/reflectance channel.
  • the method and apparatus can also be utilized to directly determine the concentration of a target species in parallel polycarbonate reactor systems.
  • FIG. 1 is a schematic view of an aspect of an embodiment of the present invention
  • FIG. 2 is a cross-sectional view of an aspect of an embodiment of the present invention
  • FIG. 3 is a schematic view of an aspect of an embodiment of the present invention.
  • FIG. 4 is a schematic view of an aspect of an embodiment of the present invention.
  • FIG. 5 is a schematic view of an aspect of an embodiment of the present invention
  • FIG. 6 is an excitation-emission spectrum of solid LX melt polycarbonate
  • FIG. 7 is a graphical representation of fluorescence spectra of various concentrations of Fries product in polycarbonate
  • FIG. 8 is a graphical representation of fluorescence spectra of various concentrations of Fries product in polycarbonate.
  • the present invention is directed to a method and apparatus for obtaining fluorescence data. It is contemplated that the method and apparatus can be especially useful, ter alia, for directly determining the concentration of a target species in a composition comprising aromatic carbonate chain units. Such a composition may be the product of a melt polymerization reaction or an interfacial polymerization reaction. The method may be performed during a reaction or upon the final product of the reaction. It is further contemplated that the method and apparatus can be used on polycarbonate compositions that have been subjected to further processing. The method is capable of determining the concentration of a target species, such as Fries product or the like, by direct fluorescence measurements.
  • the direct analytical method can be performed on polycarbonate compositions in various forms including, for example, films, pellets, sheets, solutions, suspensions, or blends containing polycarbonate.
  • the disclosed method and apparatus eliminates the need for extensive sample preparation as required by other detection methods.
  • polycarbonate depolymerization followed by liquid chromatography analysis requires a time consuming (30-60 minutes) sample preparation step involving dissolution of the polycarbonate.
  • it can take 2 hours or more to complete a single measurement using NMR methodology, thereby effectively eliminating the opportunity to quantify a target species in real time during a reaction or in connection with parallel combinatorial screening.
  • polycarbonate polycarbonate composition
  • composition comprising aromatic carbonate chain units includes compositions having structural units of the formula (I): o
  • R 6 groups are aromatic organic radicals and the balance thereof are aliphatic, alicyclic, or aromatic radicals.
  • R 6 is an aromatic organic radical and, more preferably, a radical of the formula (II):
  • each of A 1 and A 2 is a monocyclic divalent aryl radical and Y 1 is a bridging radical having one or two atoms which separate A 1 from A 2 .
  • one atom separates A 1 from A 2 .
  • radicals of this type are -O-, -S-, -S(O)- or -S(O 2 )-, -C(O)-, methylene, cyclohexyl- methylene, 2-[2.2.1]-bicycloheptylidene, ethylidene, isopropylidene, neopentylidene, cyclohexyhdene, cyclopentadecylidene, cyclododecylidene, and adamantylidene.
  • the bridging radical Y 1 can be a hydrocarbon group or a saturated hydrocarbon group such as methylene, cyclohexyhdene or isopropylidene.
  • Polycarbonates can be derived from dihydroxy compounds in which only one atom separates A 1 and A 2 .
  • dihydroxy compound includes, for example, bisphenol compounds representative of general formula (III) as follows:
  • R a and R b each represent a halogen atom or a monovalent hydrocarbon group and may be the same or different.
  • the p and q variables represent integers from 0 to 4.
  • the X a variable represents one of the following groups:
  • Variables R c and R d each independently represent a hydrogen atom or a monovalent hydrocarbon group. Variables R c and R d may form a ring structure. Variable R e is a divalent hydrocarbon group.
  • suitable dihydroxy compounds include the dihydroxy-substituted aromatic hydrocarbons disclosed by name or formula (generic or specific) in U.S. Patent 4,217,438.
  • a nonexclusive list of specific examples of the types of bisphenol compounds that may be represented by formula (III) includes the following: 1 , 1 -bis(4-hydroxyphenyl) methane; l,l-bis(4-hydroxyphenyl) ethane;
  • BPA 2,2-bis(4-hydroxyphenyl) propane
  • 2,2-bis(4-hydroxy- 1 -methylphenyl) propane 1,1 -bis(4-hydroxy-t-butylphenyl) propane; bis(hydroxyaryl) alkanes such as 2,2-bis(4-hydroxy-3-bromophenyl) propane; l,l-bis(4-hydroxyphenyl) cyclopentane; and bis(hydroxyaryl) cycloalkanes such as l,l-bis(4-hydroxyphenyl) cyclohexane.
  • Preferred LX polycarbonates are bisphenol A polycarbonates, in which each of A 1 and A 2 is p-phenylene and Y 1 is isopropylidene.
  • the average molecular weight of the initial polycarbonate ranges from about 5,000 to about
  • 100,000 ; more preferably from about 10,000 to about 65,000, and most preferably from about 15,000 to about 35,000.
  • Fries and “Fries product” denote a repeating unit in polycarbonate having the following formula:
  • FIG. 1 A portion of an exemplary embodiment of the apparatus is shown in FIG. 1.
  • the portion shown is an optical probe 10, wherein a fiber optic bundle 11 is partially enclosed within a probe housing 12.
  • a focusing lens 14 and a collimating lens 16 are also disposed within probe housing 12.
  • fiber optic bundle 11 comprises a plurality of emission fibers 52, which are disposed around an excitation fiber 54.
  • the excitation fiber is placed in optical communication with an electromagnetic radiation source (not shown), and the emission fibers are placed in optical communication with an optical analyzer (not shown).
  • an excitation signal passes through excitation fiber 54 and into a specimen 18 (FIG.
  • the specimen emits an emission signal, which passes through emission fibers 52 and to the optical analyzer.
  • the apparatus is used to obtain fluorescence data from reaction products during the course of a reaction, which requires optical access to the reaction zone through a viewing window 19 (FIG. 1), a translucent reactor wall, or the like.
  • the configuration shown provides increased signal levels at significant distances from the probe.
  • Conventional fluorescence probes for remote monitoring utilize a single optical fiber or a bifurcated fiber-optic bundle.
  • an excitation light is delivered from a source to a target location. Emission from the target is collected with the same or another fiber or fibers and guided to a detector which measures fluorescence signal (intensity or lifetime).
  • the excitation light leaves the excitation fiber or fibers as a cone defined by the numerical aperture of the fiber. Fluorescence emission is captured by the numerical aperture of the same or another fiber or fibers.
  • FIG. 3 An embodiment of the apparatus of the present invention is presented in FIG. 3.
  • the apparatus is useful for parallel monitoring of Fries product in multiple polymerization reactors and the like. It is contemplated that the apparatus shown can also be useful for combinatorial screening of catalysts and the like.
  • the apparatus includes a white light source 20, a collimator 22, an excitation optical filter 24, a beam splitter 26, a focusing lens 28, a fiber optic bundle 11, a plurality of polymerization reactors 32, and a plurality of optical probes 10 (as described supra), an emission optical filter 36, a second focusing lens 38, and an imaging photo- detector 40.
  • both excitation optical filter 24 and emission optical filter 36 preferably comprise two filter elements 42, 44 with each of the filter elements having a continuous linear variation of either cut-on or cut-off wavelength.
  • Such optical filter elements are commercially available, for example, from Coherent, Inc. of Auburn, CA.
  • White light 46 can be converted to colored light by using an opposed pair of these filter elements. The bandwidth of white light 46 can be adjusted by counter rotating the elements, while coordinated rotation changes the center wavelength. In this manner, incoming white light 46 can be converted to constant-bandwidth, variable wavelength output light 48.
  • the filtered light passes through beam splitter 26 and is focused onto the tip of fiber-optic bundle 11. Light travels through excitation fiber 54
  • FIG. 2 of fiber-optic bundle 11 and is delivered to the reaction zone via optical probes 10.
  • the emission signal passes through emission fibers 52 and is directed through beam splitter 26 and emission optical filter 36 having variable edge-pass optical filter elements 42, 44 (FIG. 5) before being focused into imaging photo-detector 40, such as, e.g., a CCD camera or the like.
  • imaging photo-detector 40 such as, e.g., a CCD camera or the like.
  • excitation-emission fluorescence matrices can be collected simultaneously from each reactor 32.
  • excitation optical filter 24 is set to transmit white light
  • the absorbance/reflectance spectra are collected from each reactor 32 by the coordinated rotation of emission filter elements 42, 44.
  • Imaging photo-detector 40 is used for monitoring the fluorescence at each of the multiple measurement locations.
  • fiber optic bundle 11 can be provided with an optional third fiber 56 to deliver white light to a measurement location while one or more reflectance fibers 58 can be provided to deliver the back propagated portion of light to an optical analyzer.
  • These absorption/reflection measurements can be used to compensate for variations in fluorescence signal due to primary and secondary inner filter effects.
  • the configuration of the probe allows excitation and absorbance/reflection measurements to be obtained in rapid sequence without changing the position of any portion of the apparatus relative to the specimen, thereby allowing effective real time monitoring of the specimen.
  • the term "inner filter effect" includes the significant absorption of the excitation or emission radiation as the radiation travels through the medium where the target species is located.
  • primary inner filter effect denotes significant absorption of the excitation radiation
  • secondary inner filter effect denotes significant abso ⁇ tion of the emission radiation.
  • inner filter effects can affect the relationship between luminescence signal and analyte concentration, and correction factors can be calculated from absorbance and scatter at the excitation and emission wavelengths in order to compensate for the loss of optical signal at these wavelengths.
  • Use of the probe shown in FIGs. 1 and 2 can also compensate for variations in the refractive index of the optical medium.
  • FIG. 4 Another apparatus for parallel on-line monitoring of Fries product in multiple polymerization reactors is shown in FIG. 4.
  • the apparatus includes a multichannel spectrometer 60 having an absorbance/reflectance channel 62, a fluorescence- excitation channel 64, and a fluorescence-emission channel 66.
  • a fiber-optic bundle 11 is placed in optical communication with spectrometer 60 and a plurality of optical probes 10 (as described above), which can be located proximate reactors 32 (non- invasive) or immersed in reactors 32 (invasive, as shown).
  • Two of the channels 64, 66 are provided with optical filters 24, 36 (described supra).
  • Emission fibers 52 are placed in optical communication with fluorescence-emission channel 66.
  • Reflectance fiber 58 is placed in optical communication with absorbance/reflectance channel 62.
  • multichannel spectrometer 60 is capable of measuring the excitation and emission fluorescence spectra and absorbance/reflectance from each reactor 32 in rapid sequence. Measurements in multiple reactors can be accomplished using the art-recognized time-domain multiplexing approach or having a miniature spectrometer for each of the reactors.
  • the present method is capable of directly determining the concentration of a target species (e.g., Fries product) in a composition comprising aromatic carbonate chain units.
  • the method includes the steps of providing an apparatus having an electromagnetic radiation source, an optical analyzer, and a fiber optic bundle.
  • the bundle contains an excitation fiber in optical communication with the electromagnetic radiation source and a plurality of emission fibers in optical communication with the optical analyzer.
  • a portion of the composition is irradiated with electromagnetic radiation at an excitation wavelength sufficient to cause the target species to emit a fluorescence spectrum.
  • the method further includes the steps of detecting at least a portion of the fluorescence spectrum and determining the concentration of the target species from the fluorescence spectrum.
  • the composition is preferably irradiated at an excitation wavelength that allows the target species to fluoresce at a detectable level that provides differential emission between the target species and interfering species.
  • the present method permits quantification of Fries product during a melt polymerization reaction in the presence of fluorescent, absorbing, and scattering interfering species.
  • the conditions used allow for selective excitation of the Fries product in the polycarbonate material; collection of its fluorescence emission; and relation of the measured fluorescence signal to Fries concentration.
  • the range of excitation wavelengths for quantification of Fries product is preferably selected to satisfy at least two criteria: (1) appreciable absorbance of the selected excitation wavelengths by Fries product and (2) minimal absorbance of the selected excitation wavelengths by interfering species.
  • the range of emission wavelengths for quantification of Fries product is preferably selected to satisfy at least two criteria: (1) Fries product emits fluorescence and (2) interfering species do not appreciably emit fluorescence.
  • interfering species include non-branched Fries end-groups, non-Fries end-groups, and cyclics. Also, different contaminant species may potentially emit fluorescence.
  • a typical excitation-emission spectrum of a solid LX material (119 ppm of Fries product) is presented in FIG. 6 to illustrate the complexity of the fluorescence spectrum of a solid LX material obtained after a melt polymerization reaction.
  • a suitable excitation wavelength is between about 250 nm and about 500 nm; preferably between about 300 ran and about 400 nm; more preferably between about 320 nm and about 350 nm; and most preferable about 340 nm.
  • Other portions of the excitation and emission fluorescence spectra can be collected for calibration, normalization, and scaling purposes.
  • Compensation for the variation in absorbance and scattering effects of the measured regions at the excitation and emission wavelengths can be accomplished by at least two compensation methods.
  • the first compensation method comprises measuring the absorption spectrum of the probed region of polycarbonate over the spectral range that covers the excitation and emission wavelengths.
  • the second compensation method comprises using second order Rayleigh scattering effects in the emission and excitation spectra for scaling the spectral features.
  • the collected fluorescence intensity can be affected by a number of instrumental and sample parameters not related to the concentration of the fluorescent product.
  • various embodiments of the disclosed method allow for compensation to provide reproducible signals from single or multiple polymerization reactors during monitoring of the progress of, e.g., a polycarbonate melt polymerization reaction.
  • Second-order Rayleigh scattering effects are typically undesirable in conventional spectrometers for general applications because they distort the true spectral features of the measured samples.
  • These second order effects in the emission and excitation spectra can be eliminated by various techniques. For example, it is common to use excitation and emission filters that block the respective spectral portion of radiation from entering the measurement device (spectrometer).
  • second order effects are used to scale spectral features.
  • FIG. 7 An example of second-order effects is shown in FIG. 7, where the peaks at 680 nm in both recorded spectra of solid polycarbonate samples are second-order effects resulting from excitation at 340 nm. These second order peaks are measured and used as reference excitation intensity. As shown in FIG.

Abstract

L'invention concerne, à titre d'exemple, un dispositif à source de rayonnement électromagnétique, analyseur optique et faisceau de fibres optiques. Ce faisceau comporte une fibre d'excitation reliée optiquement à la source, et plusieurs fibres d'émission reliées optiquement à l'analyseur. Cet analyseur peut avoir plusieurs canaux, y compris un canal à fluorescence relié optiquement aux fibres d'émission. Eventuellement, le faisceau peut comporter au moins une fibre de réflexion reliée optiquement à un canal d'absorption/réflexion. On peut ainsi déceler un produit de Fries dans des matériaux formés à base de polycarbonate, mais aussi déterminer directement la concentration d'une espèce cible dans des systèmes de réaction parallèles à polycarbonate.
PCT/US2000/028439 2000-10-13 2000-10-13 Procede et dispositif pour la collecte de donnees par fluorescence WO2002033383A1 (fr)

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PCT/US2000/028439 WO2002033383A1 (fr) 2000-10-13 2000-10-13 Procede et dispositif pour la collecte de donnees par fluorescence

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10314848A1 (de) * 2002-06-28 2004-01-15 Jenoptik Laser, Optik, Systeme Gmbh Messeinrichtung zur Detektion von laserinduzierter Fluoreszenzstrahlung
US8718948B2 (en) 2011-02-24 2014-05-06 Gen-Probe Incorporated Systems and methods for distinguishing optical signals of different modulation frequencies in an optical signal detector
US9458451B2 (en) 2007-06-21 2016-10-04 Gen-Probe Incorporated Multi-channel optical measurement instrument

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4678326A (en) * 1983-05-30 1987-07-07 Labsystems Oy Apparatus for the measurement of fluorescence, turbidity, luminescence or absorption
US5128882A (en) * 1990-08-22 1992-07-07 The United States Of America As Represented By The Secretary Of The Army Device for measuring reflectance and fluorescence of in-situ soil
US5926262A (en) * 1997-07-01 1999-07-20 Lj Laboratories, L.L.C. Apparatus and method for measuring optical characteristics of an object
WO2001022065A1 (fr) * 1999-09-20 2001-03-29 General Electric Company Procede de mesure directe de compositions de polycarbonate par fluorescence

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4678326A (en) * 1983-05-30 1987-07-07 Labsystems Oy Apparatus for the measurement of fluorescence, turbidity, luminescence or absorption
US5128882A (en) * 1990-08-22 1992-07-07 The United States Of America As Represented By The Secretary Of The Army Device for measuring reflectance and fluorescence of in-situ soil
US5926262A (en) * 1997-07-01 1999-07-20 Lj Laboratories, L.L.C. Apparatus and method for measuring optical characteristics of an object
WO2001022065A1 (fr) * 1999-09-20 2001-03-29 General Electric Company Procede de mesure directe de compositions de polycarbonate par fluorescence

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HOYLE C E ET AL: "PHOTOCHEMISTRY OF BISPHENOL-A BASED POLYCARBONATE: THE EFFECT OF THE MATRIX AND EARLY DETECTION OF PHOTO-FRIES PRODUCT FORMATION", JOURNAL OF POLYMER SCIENCE, POLYMER CHEMISTRY EDITION,JOHN WILEY AND SONS. NEW YORK,US, vol. 30, no. 8, July 1992 (1992-07-01), pages 1525 - 1533, XP000978610, ISSN: 0887-624X *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10314848A1 (de) * 2002-06-28 2004-01-15 Jenoptik Laser, Optik, Systeme Gmbh Messeinrichtung zur Detektion von laserinduzierter Fluoreszenzstrahlung
US9458451B2 (en) 2007-06-21 2016-10-04 Gen-Probe Incorporated Multi-channel optical measurement instrument
US10086342B2 (en) 2007-06-21 2018-10-02 Gen-Probe Incorporated Multi-channel optical measurement instrument
US8718948B2 (en) 2011-02-24 2014-05-06 Gen-Probe Incorporated Systems and methods for distinguishing optical signals of different modulation frequencies in an optical signal detector
US9915613B2 (en) 2011-02-24 2018-03-13 Gen-Probe Incorporated Systems and methods for distinguishing optical signals of different modulation frequencies in an optical signal detector
US10641707B2 (en) 2011-02-24 2020-05-05 Gen-Probe Incorporated Systems and methods for distinguishing optical signals of different modulation frequencies in an optical signal detector

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