EP2292329A1 - Polymer substrate with fluorescent structure, method for production of same and application of same - Google Patents
Polymer substrate with fluorescent structure, method for production of same and application of same Download PDFInfo
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- EP2292329A1 EP2292329A1 EP09011507A EP09011507A EP2292329A1 EP 2292329 A1 EP2292329 A1 EP 2292329A1 EP 09011507 A EP09011507 A EP 09011507A EP 09011507 A EP09011507 A EP 09011507A EP 2292329 A1 EP2292329 A1 EP 2292329A1
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- 229920000307 polymer substrate Polymers 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 21
- 230000005855 radiation Effects 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 4
- 238000011084 recovery Methods 0.000 claims description 11
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 4
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 3
- 229910052805 deuterium Inorganic materials 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920003232 aliphatic polyester Polymers 0.000 claims description 2
- 230000001427 coherent effect Effects 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 238000003384 imaging method Methods 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims 4
- 239000004713 Cyclic olefin copolymer Substances 0.000 claims 2
- 239000007858 starting material Substances 0.000 claims 2
- 238000004806 packaging method and process Methods 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract description 5
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 abstract 2
- 229910052727 yttrium Inorganic materials 0.000 abstract 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 abstract 2
- VZPPHXVFMVZRTE-UHFFFAOYSA-N [Kr]F Chemical compound [Kr]F VZPPHXVFMVZRTE-UHFFFAOYSA-N 0.000 abstract 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052724 xenon Inorganic materials 0.000 abstract 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 12
- 230000005284 excitation Effects 0.000 description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 238000000799 fluorescence microscopy Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000006059 cover glass Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 238000000386 microscopy Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000012963 UV stabilizer Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000012822 chemical development Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
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- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002073 fluorescence micrograph Methods 0.000 description 1
- 229920001109 fluorescent polymer Polymers 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010330 laser marking Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/54—Labware with identification means
- B01L3/545—Labware with identification means for laboratory containers
Abstract
Description
Die Erfindung betrifft mit Fluoreszenzmerkmalen versehene Polymersubstrate, in denen durch UV-Bestrahlung photochemisch Fluoreszenzmerkmale, d.h. fluoreszierende Strukturen, erzeugt werden. So können in Polymersubstraten mit einer geringen Eigenfluoreszenz durch geeignete UV-Bestrahlung Fluorophore erzeugt werden, die bei Anregung mit Licht geeigneter Wellenlänge eine markante und detektierbare Emission zeigen. Wird eine derartige Bestrahlung strukturiert durchgeführt, können auf diese Weise in Polymersubstraten Emissionsmuster erzeugt werden, die z.B. als Wiederfindungsgitter in der Fluoreszenz-Mikroskopie angewendet werden können. Ein weiteres Anwendungsfeld betrifft die Produkt-Authentifizierung, die durch die erfindungsgemäßen mit Fluoreszenzmerkmalen versehenen Polymersubstrate ermöglicht wird.The invention relates to polymer substrates provided with fluorescence features in which fluorescence characteristics, ie fluorescent structures, are produced photochemically by UV irradiation. For example, in polymer substrates with a low intrinsic fluorescence, suitable fluorophors can be produced by suitable UV irradiation, which exhibit marked and detectable emission upon excitation with light of suitable wavelength. If such irradiation is carried out in a structured manner, emission patterns can be generated in this way in polymer substrates, which can be used, for example, as a recovery grid in fluorescence microscopy. Another field of application relates to product authentication, which is made possible by the polymer substrates provided with fluorescence features according to the invention.
Auf dem Gebiet der Kultivierung von Zellen werden unterschiedlichste Probenkammern verwendet. Diese sind zumeist polymerbasiert und reichen von der Zellkulturflasche über Objektträger und µ-Slides der Firma ibidi bis hin zu Multiwellplatten.In the field of culturing cells, a wide variety of sample chambers are used. These are mostly polymer-based and range from the cell culture bottle to slides and μ-slides from ibidi to multiwell plates.
Diese Probenkammern können zusammenhängende Flächen, auf denen Zellen wachsen, von 1 mm2 bis 100 cm2 aufweisen. Da Zellen typischerweise einen Durchmesser von 1 µm bis 30 µm aufweisen, ist das Wiederfinden einzelner Zellen in großflächigen Kammern ohne Wiederfindungsstrukturen fast unmöglich.These sample chambers can have contiguous areas on which cells grow from 1 mm 2 to 100 cm 2 . Since cells typically have a diameter of 1 .mu.m to 30 .mu.m, finding individual cells in large-area chambers without recovery structures is almost impossible.
So ist aus der
Ein weiterer Bereich des Standes der Technik, der der vorliegenden Erfindung zugrunde liegt, betrifft die Authentifizierung von Produkten, insbesondere Konsumprodukten.Another area of the prior art underlying the present invention relates to the authentication of products, especially consumer products.
Die Authentifizierung von Produkten erfolgt derzeit im Stand der Technik durch das Aufbringen von fluoreszierendem Material auf Polymerfolien mittels diverser Druckverfahren. Andere Methoden zur Authentifikation von Produkten sehen vor, dass eine Charakterisierung der Eigenfluoreszenz von Polymeren erfolgt, wobei bei der Herstellung der Polymere Fluoreszenzfarbstoffe als Dopanden beigefügt wurden (
Weiterhin kann in Folien die Fluoreszenz strukturiert werden, indem eine bestehende Eigenfluoreszenz ausgeblichen wird.Furthermore, in fluorescence films can be structured by bleaching existing autofluorescence.
Ebenso sind Verfahren zur Strukturierung von Fluoreszenz bekannt, bei denen Polymere eingesetzt werden, die kovalent gebundene Precursor enthalten oder denen solche als Dopanden zugesetzt werden müssen.Likewise, methods for structuring fluorescence are known in which polymers are used which contain covalently bonded precursors or to which such must be added as dopants.
Ebenso sind komplexere Systeme bekannt, die Fluoreszenz als Mittel der Authentifikation nutzen, wobei jedoch Formveränderungen der Folienkombinationen erforderlich sind (
Ausgehend hiervon war es Aufgabe der vorliegenden Erfindung, mit Fluoreszenzmerkmalen versehene Polymersubstrate bereitzustellen, die einfach herzustellen sind und eine einfache Erkennung oder Detektion ermöglichten.Based on this, it was an object of the present invention to provide fluorescent polymer substrates, which are easy to prepare and allow easy detection or detection.
Diese Aufgabe wird durch das Polymersubstrat mit den Merkmalen des Anspruchs 1 und das Verfahren zu dessen Herstellung mit den Merkmalen des Anspruchs 17 gelöst. In den Ansprüchen 24 bis 28 werden erfindungsgemäße Verwendungen des Polymersubstrats aufgeführt. Ebenso wird eine Probenkammer gemäß Anspruch 7 bereitgestellt, die dieses Polymersubstrat aufweist. Die weiteren abhängigen Ansprüche zeigen vorteilhafte Weiterbildungen auf.This object is achieved by the polymer substrate having the features of claim 1 and the process for its preparation having the features of claim 17. In claims 24 to 28 uses according to the invention of the polymer substrate are listed. Likewise, a sample chamber according to claim 7 is provided which comprises this polymer substrate. The other dependent claims show advantageous developments.
Erfindungsgemäß wird ein Polymersubstrat mit einer fluoreszierenden Struktur als integralen Bestandteil bereitgestellt, wobei in dem Polymersubstrat bereichsweise eine fluoreszierende Struktur photochemisch erzeugt wird. Bei den bevorzugten Polymersubstraten handelt es sich um Polymere mit einer geringen Eigenfluoreszenz, d.h. mit einer Eigenfluoreszenz in der Größenordnung eines Deckglases im Anregungs-und Emmissionsbereich von 200 nm bis 1.000 nm. Dazu gehören insbesondere COC, COP, PMMA, aliphatische Polyester und Polyurethane sowie Polyether. Besonders gut sind Polymere ohne UV-Stabilisatoren geeignet. Für die optische Mikroskopie sind insbesondere Polymere mit einem Brechungsindex zwischen 1,4 und 1,6 insbesondere mit 1,51 und/oder einer Abbezahl über 50 und/oder mit einer geringen Doppelbrechung geeignet.According to the invention, a polymer substrate having a fluorescent structure is provided as an integral constituent, wherein a fluorescent structure is generated photochemically in regions in the polymer substrate. The preferred polymer substrates are low intrinsic fluorescence polymers, i. with an intrinsic fluorescence on the order of a cover glass in the excitation and emission range from 200 nm to 1000 nm. These include in particular COC, COP, PMMA, aliphatic polyesters and polyurethanes, and also polyethers. Particularly good polymers are suitable without UV stabilizers. For optical microscopy, in particular polymers with a refractive index between 1.4 and 1.6, in particular with 1.51 and / or a Abbe number over 50 and / or with a low birefringence are suitable.
Unter einer fluoreszierenden Struktur werden dabei Strukturen bis hin zur optischen Auflösungsgrenze verstanden. Typischerweise werden aber Strukturen mit einer lateralen Auflösung von mehreren µm verwendet. Bevorzugt soll die fluoreszierende Struktur mindestens eine doppelt so hohe Intensität wie die nicht fluoreszierende Struktur aufweisen. Für klassische Anwendungen soll die Struktur eine so hohe Intensität aufweisen, dass diese bereits bei Belichtungszeiten unter einer Sekunde mit handelsüblichen Forschungsfluoreszenzmikroskopen gut zu erkennen ist. Dies ist bei einem Faktor 10 bereits gegeben.A fluorescent structure is understood to mean structures up to the optical resolution limit. Typically, however, structures with a lateral resolution of several μm are used. Preferably, the fluorescent structure should have at least twice as high intensity as the non-fluorescent structure. For classical applications, the structure should have such a high intensity that it can be easily recognized even at exposure times of less than one second with commercial fluorescence microscopes. This is already the case with a factor of 10.
Erfindungsgemäß sind die erzeugten Fluorophore, die die fluoreszierende Struktur bilden, fest im dem Polymersubstrat gebunden und bilden mit ihm eine Einheit. Die fluoreszierenden Strukturen sind somit ein integraler Bestandteil des Trägers. Das so modifizierte Polymer zeichnet sich dadurch aus, das sowohl die fluoreszierenden Bereiche als auch die nicht fluoreszierenden Bereiche aus dem identischen Ursprungsmaterial bestehen. Deshalb können die Fluorophore darüber hinaus auch nicht diffundieren oder ausschwitzen. Diese Eigenschaften grenzen die erzeugten Strukturen z.B. deutlich von einer aufgedruckten, anderweitig aufgebrachten Struktur (z.B. einer eingeprägten oder eingelaserten Struktur) oder Farbstoffdotierten Polymersystemen ab. Es müssen zudem keine, eventuell zelltoxischen, Fluoreszenzfarbstoffe verwendet werden, die auf das Polymer aufgebracht werden.According to the invention, the fluorophores which form the fluorescent structure are firmly bound in the polymer substrate and form a unit with it. The fluorescent structures are thus an integral part of the carrier. The modified polymer is characterized by the fact that both the fluorescent regions and the non-fluorescent regions consist of the identical original material. Therefore, the fluorophores also can not diffuse or sweat out. These properties clearly delimit the structures produced, for example, from a printed, otherwise applied structure (eg an embossed or lasered structure) or dye-doped polymer systems. In addition, no, possibly cell toxic, fluorescent dyes have to be used, which are applied to the polymer.
Erfindungsgemäß wird eine Strukturierung des Polymersubstrates mit fluoreszenten Bereichen erzeugt. Hierzu wird bevorzugt eine Maske oder eine lokal positionierbare Strahlungsquelle eingesetzt. Wird die UV-Bestrahlung strukturiert vorgenommen, so fluoreszieren signifikant nur die Bereiche, die bestrahlt wurden. In den unbestrahlten Bereichen jedoch wird keine wesentliche Erhöhung der Grundemission erzielt. Auf diese Weise können Muster erzeugt werden, die bei Anregung mit Licht geeigneter Wellenlänge sichtbar werden. Eine so erfolgte photochemische Strukturierung erzeugt musterhaft fluoreszierende Bereiche, die langzeitstabil und stabil gegenüber Umwelteinflüssen sind. Weiterhin zeichnen sie sich dadurch aus, dass sie ihre Kantenschärfe nicht durch Diffusion oder ähnliche Prozesse verlieren. Außerdem lassen sich die so erzeugten Merkmale nicht spurenfrei entfernen. Vorzugsweise besteht die fluoreszierende Struktur im Polymersubstrat aus mehreren Elementen in Form von Strichen, Linien, Zeichen, Figuren, Interferenzmustern oder Kombinationen hiervon.According to the invention, a structuring of the polymer substrate with fluorescent regions is produced. For this purpose, a mask or a locally positionable radiation source is preferably used. If the UV irradiation is carried out in a structured manner, only the areas that have been irradiated will fluoresce significantly. In the non-irradiated areas, however, no substantial increase in the base emission is achieved. In this way, patterns can be generated which become visible upon excitation with light of suitable wavelength. Such a photochemical structuring produces patterned fluorescent areas that are long-term stable and stable to environmental influences. Furthermore, they are characterized by the fact that they do not lose their edge sharpness by diffusion or similar processes. In addition, the features thus produced can not be removed without trace. Preferably, the fluorescent structure in the polymer substrate consists of several elements in the form of bars, lines, characters, figures, interference patterns, or combinations thereof.
Wie oben beschrieben können fluoreszierende Strukturen mit nur durch die Substratgröße beschränkter Gesamtausdehnung des Musters erzeugt werden. Die laterale Auflösung der Elemente der fluoreszierenden Struktur wird nur von der Methode der Einbringung und der Lichtwellenlänge beschränkt. Die einzelnen Strukturelemente der Fluoreszenzmuster besitzen jedoch typischerweise eine laterale Ausdehnung von weniger als 100 µm, vorzugsweise weniger als 10 µm.As described above, fluorescent structures can be generated with only limited by the substrate size limited overall extent of the pattern. The lateral resolution of the elements of the fluorescent structure is limited only by the method of introduction and the wavelength of the light. However, the individual structural elements of the fluorescence pattern typically have a lateral extent of less than 100 μm, preferably less than 10 μm.
Erfindungsgemäß wird ebenso ein Verfahren zur Herstellung des zuvor beschriebenen Polymersubstrates bereitgestellt, bei dem ein Polymersubstrat zumindest bereichsweise einer Bestrahlung im Wellenlängenbereich unterhalb von 300 nm zur Erzeugung von fluoreszierenden Strukturen unterzogen wird.According to the invention, a method is also provided for producing the polymer substrate described above, in which a polymer substrate is at least partially subjected to irradiation in the wavelength range below 300 nm to produce fluorescent structures.
Gemäß einer erfindungsgemäßen Variante erfolgt dabei die Herstellung der fluoreszierenden Strukturen durch UV-Bestrahlung unter Verwendung von Masken durch Abbildung oder Kontaktbelichtung.According to a variant of the invention, the preparation of the fluorescent structures by UV irradiation using masks by imaging or contact exposure takes place.
Als Maske zur Strukturierung werden vorzugsweise Platten verwendet, die eine musterhafte Variation von Bereichen, die für das verwendete Bestrahlungslicht entweder transparent oder nicht-transparent sind, aufweisen. Bevorzugt werden metallische Platten eingesetzt, die musterhafte Durchbrechungen besitzen. Besonders bevorzugt werden Masken aus Chrom auf Kieselglas.As a mask for structuring, it is preferable to use plates which have an exemplary variation of regions that are either transparent or non-transparent to the irradiation light used. Preference is given to using metallic plates which have patterned openings. Particularly preferred are masks made of chrome on silica glass.
Es können zur Strukturierung alternativ zu Masken sowohl Strahlungsquellen mit kohärentem (Laser-Direktschreiben) als auch fokussiertem Strahl (Probenpositionierung) eingesetzt werden.As an alternative to masks, both radiation sources with coherent (laser direct writing) and focused beam (sample positioning) can be used for structuring.
Als Strahlungsquellen werden vorzugsweise Strahlungsquellen mit Emissionswellenlängen oder Emissionswellenlängenbereichen im Bereich unterhalb von 300 nm eingesetzt. Hierzu zählen insbesondere Deuterium-Lampen, Excimer-Lampen (Xe), Excimer-Laser (F2, ArF, KrF) oder Festkörper-Laser (Nd: YVO4/YLF).Radiation sources used are preferably radiation sources with emission wavelengths or emission wavelength ranges in the range below 300 nm. These include, in particular, deuterium lamps, excimer lamps (Xe), excimer lasers (F 2 , ArF, KrF) or solid-state lasers (Nd: YVO 4 / YLF).
Als Polymersubstrat wird vorzugsweise eine Polymerfolie eingesetzt.The polymer substrate used is preferably a polymer film.
Die UV-generierte Erzeugung der Fluorophoren kann im Absorptionsspektrum des Polymersubstrates durch eine Zunahme der Extinktion im UV-Bereich verfolgt werden. Diese Veränderungen beeinträchtigen jedoch nicht wesentlich die optische Durchlässigkeit im für das menschliche Auge sichtbaren Bereich des Lichtes. Die Polymersubstrate können beschädigungsfrei auf der Vorder- oder Rückseite mit Fluoreszenzmerkmalen versehen werden. Ihre Erzeugung erfordert keinen Ausschluss vom Luftsauerstoff.The UV-generated generation of the fluorophores can be monitored in the absorption spectrum of the polymer substrate by an increase in the extinction in the UV range. However, these changes do not significantly affect the optical transmissivity in the visible region of the light to the human eye. The polymer substrates can be provided without damage on the front or back with fluorescent features. Their production requires no exclusion of atmospheric oxygen.
Aufgrund einer hohen Bandbreite von Absorption und Emission der erzeugten Fluorophore können unterschiedliche Fluoreszenzfarben entsprechend den Anregungsbedingungen generiert werden.Due to a high range of absorption and emission of the generated fluorophores, different fluorescence colors can be generated according to the excitation conditions.
Die Fluoreszenzmerkmale zeichnen sich weiterhin dadurch aus, dass sie direkt in Materialien erzeugt werden, die ohnehin für Produkte aus verschiedenen Bereichen verwendet werden. Es sind keine zusätzlichen Beschichtungen, Bedruckungen oder anderes Aufbringen von Fluorophoren, Fluoreszenz-Labeln oder deren Precursoren nötig. Dadurch, dass die Merkmale direkt im verwendeten Material erzeugt werden, vereinfacht und verbilligt sich Herstellung dieser beträchtlich gegenüber anderen Verfahren. Darüber hinaus handelt es sich um einen voll-optischen Prozess, der keinerlei nasschemische Entwicklungsprozesse erfordert.The fluorescent features are further characterized by the fact that they are generated directly in materials that are used anyway for products from different areas. There are no additional coatings, imprints or other application fluorophores, fluorescent labels or their precursors. The fact that the features are produced directly in the material used, makes it much easier and cheaper to manufacture this compared to other methods. In addition, it is a fully optical process that does not require any wet-chemical development processes.
Solche Emissionsmuster können genutzt werden, um Substrate für die Fluoreszenz-Mikroskopie mit einem Wiederfindungsgitter zu versehen. Typischerweise sind die Wiederfindungsgitter als Gitterraster ausgeführt, das auch mit Zahlen oder Buchstaben versehen ist. Diese Wiederfindungsgitter erleichtern das Wiederfinden bestimmter Probenareale dadurch, dass diese anhand des Gitterrasters genau charakterisierbar sind. Die Wiederfindungsgitter beeinflussen biologische Prozesse nicht wesentlich und sind ausreichend stabil, um längere Beobachtungen an biologischen und anderen Proben bei höherer Zuverlässigkeit und Reproduzierbarkeit durchführen zu können.Such emission patterns can be used to provide substrates for fluorescence microscopy with a recovery grid. Typically, the recovery grids are designed as a grid, which is also provided with numbers or letters. These recovery grids facilitate the retrieval of certain sample areas by being precisely charac- terised by the grid grid. The recovery grids do not significantly affect biological processes and are sufficiently stable to perform longer observations on biological and other samples with greater reliability and reproducibility.
Die beschriebenen, photochemisch erzeugten Merkmale eignen sich aufgrund ihrer Absorptions- und Emissionseigenschaften sehr gut für typische Anregungsbedingungen bei der Fluoreszenzmikroskopie, sie sind in allen Fluoreszenzkanälen sichtbar (blau, grün, gelb und rot). Die laterale Auflösung bei derartig erzeugten Merkmalen ist ausreichend hoch, um z.B. ein kartiertes Beobachten von Zellen verschieden Typs zu ermöglichen.Due to their absorption and emission properties, the described, photochemically generated characteristics are very well suited for typical excitation conditions in fluorescence microscopy; they are visible in all fluorescence channels (blue, green, yellow and red). The lateral resolution in such produced features is sufficiently high, e.g. to allow a mapped observation of cells of different types.
Kammern, in die solche Gitter eingebracht werden können, sind in der
Dabei handelt es sich im Wesentlichen um Kammern, die mindestens aus einem Oberteil und einem Unterteil bestehen. Dabei weist das Oberteil mindestens eine Aussparung auf. Durch das Verbinden mit dem Unterteil wird ein Reservoir gebildet. Je nach Geometrie der Aussparung des Oberteils ist das Reservoir dann als ein geschlossener Kanal/Röhre oder als nach oben offenes Behältnis ausgebildet.These are essentially chambers which consist of at least one upper part and one lower part. In this case, the upper part has at least one recess. By connecting to the lower part of a reservoir is formed. Depending on the geometry of the recess of the upper part of the reservoir is then designed as a closed channel / tube or as an open-topped container.
Der durch das Unterteil gebildete Boden kann eine Folie oder ein beschichteter Glasträger sein. Der Boden hat eine bevorzugte Dicke von 50 µm bis 250 µm und/oder eine Abbe-Zahl größer 50 und/oder einen Brechungsindex zwischen 1,2 und 1,8 insbesondere zwischen 1,45 und 1,55. Diese Eigenschaften sind besonders gut für die (hochauflösende) Mikroskopie geeignet. Der Boden oder die Folie kann sowohl von der Seite, auf welcher später die Zellen kultiviert werden sollen, als auch von der entsprechend gegenüberliegenden Seite bestrahlt werden, um fluoreszierende Strukturen zu erzeugen. Bei Verwendung hochauflösender Mikroskopietechniken mit einer entsprechend geringen Tiefenschärfe (ca. unter 50 µm, typischerweise unter 10 µm) ist es vorteilhaft, die Seite fluoreszenzzumarkieren, auf der später die wiederzufindenden Zellen wachsen werden. Dadurch befinden sich die Zellen und das Gitter gleichzeitig im optischen Fokus, wobei das fluoreszierende Element integraler Bestandteil des Polymerträgers ist.The bottom formed by the base may be a foil or a coated glass carrier. The bottom has a preferred thickness of 50 .mu.m to 250 .mu.m and / or an Abbe number greater than 50 and / or a refractive index between 1.2 and 1.8, in particular between 1.45 and 1.55. These properties are particularly well suited for (high-resolution) microscopy. The bottom or film can be irradiated both from the side on which the cells are to be cultivated later and from the corresponding opposite side in order to produce fluorescent structures. When using high-resolution microscopy techniques with a correspondingly low depth of field (approximately less than 50 μm, typically less than 10 μm), it is advantageous to fluorescently mark the side on which the cells to be recovered will later grow. As a result, the cells and the lattice are simultaneously in optical focus, the fluorescent element being an integral part of the polymer carrier.
Wird die gegenüberliegende Seite bestrahlt, können auch bereits gedeckelte mikrofluidische Analysekammern mit entsprechenden Merkmalen versehen werden.If the opposite side is irradiated, already covered microfluidic analysis chambers can be provided with corresponding features.
Es können auch Verbundfolien aus verschiedenen Materialien verwendet werden, bei denen mindestens eine Komponente die gewünschten Eigenschaften besitzt.It is also possible to use composite films of different materials in which at least one component has the desired properties.
Insbesondere können auch beschichtete Glasträger verwenden werden. So können z.B. Glasdeckgläser mit einer COP- oder COC-Schicht beschichtet werden, um dann in diese Schicht über das beschriebene Verfahren Fluoreszenzgitter einzubringen. Die Schicht kann z.B. durch Spincoaten etc. aufgebracht werden.In particular, coated glass supports can also be used. Thus, e.g. Glass cover glasses are coated with a COP or COC layer to then introduce into this layer via the method described fluorescent grating. The layer may e.g. be applied by spincoating etc.
Ein weiteres Feld der Anwendung betrifft die Produkt-Authentifizierung. So können Label, Etiketten und Produkte aus Polymeren durch die strukturierte UV-Bestrahlung mit einem Merkmal versehen werden, das erst durch Anregung mit Licht geeigneter Wellenlänge und Intensität deutlich sichtbar wird. Auf diese Weise erhöht sich die Fälschungssicherheit des Produktes und es kann eine nicht-löschbare Produktindividualisierung zum Beispiel über Barcodes vorgenommen werden. Dies kann durch ein Laserbeschriftungssystem realisiert werden, wobei das Merkmal auch elektronisch gelesen werden kann.Another field of application concerns product authentication. Thus, labels, labels and products made of polymers can be provided with a feature by the structured UV irradiation, which becomes clearly visible only by excitation with light of suitable wavelength and intensity. In this way, the counterfeiting security of the product increases and a non-erasable product individualization can be carried out, for example via barcodes. This can be realized by a laser marking system, wherein the feature can also be read electronically.
Anhand der nachfolgenden Figuren und Beispiele soll der anmeldungsgemäße Gegenstand näher erläutert werden, ohne diesen auf die hier gezeigten speziellen Ausführungsformen einschränken zu wollen.With reference to the following figures and examples, the object according to the application is intended to be explained in more detail, without wishing to restrict it to the specific embodiments shown here.
In
Auf eine COC-Folie wird eine Maske (musterhaft Chrom auf Kieselglas) befestigt, so dass die Maske mit der Chromseite schlüssig aufliegt. Es erfolgt eine Bestrahlung mit einer 30W Deuterium-Lampe für 3 Stunden. Anschließend wird die Maske entfernt und das Emissionsmuster kann durch Anregung bei 365 nm sichtbar gemacht.On a COC film, a mask (pattern chrome on silica glass) is attached, so that the mask rests with the chrome side. It is irradiated with a 30W deuterium lamp for 3 hours. Then the mask is removed and the emission pattern can be visualized by excitation at 365 nm.
Auf eine COC-Folie wird eine Maske (musterhaft Chrom auf Kieselglas) befestigt, so dass die Maske mit der Chromseite schlüssig aufliegt. Es erfolgt eine Bestrahlung mit einem ArF-Excimer-Laser (193 nm) für 10 Sekunden. Anschließend wird die Maske entfernt und das Emissionsmuster kann durch Anregung bei 365 nm, 436 nm oder 515 nm sichtbar gemacht werden.On a COC film, a mask (pattern chrome on silica glass) is attached, so that the mask rests with the chrome side. It is irradiated with an ArF excimer laser (193 nm) for 10 seconds. The mask is then removed and the emission pattern can be visualized by excitation at 365 nm, 436 nm or 515 nm.
Claims (29)
wobei die fluoreszierende Struktur photochemisch erzeugt ist.Polymer substrate having a fluorescent structure as an integral component,
wherein the fluorescent structure is photochemically generated.
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EP09011507.2A EP2292329B1 (en) | 2009-09-08 | 2009-09-08 | Polymer substrate with fluorescent structure, method for production of same and application of same |
US12/876,881 US9597688B2 (en) | 2009-09-08 | 2010-09-07 | Polymer substrate with fluorescent structure, method for the production thereof and the use thereof |
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Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4241663A1 (en) * | 1992-12-04 | 1994-06-09 | Borus Spezialverfahren | Procedure for marking and recognizing an object |
FR2755902A1 (en) * | 1996-11-20 | 1998-05-22 | Sarl Ind Laser Partner | Marking procedure for use with merchandise liable to be fraudulently copied |
DE10004135A1 (en) | 2000-01-31 | 2001-08-09 | Reinhard Galneder | Chamber for cultivating and microscoping cells, comprises a lower section which acts as a base, and an upper section which acts as a cover. |
DE10105711A1 (en) | 2001-02-08 | 2002-09-05 | Ibidi Gmbh | Sample holder for chemical and biological samples |
WO2003101755A1 (en) | 2002-05-31 | 2003-12-11 | Ucb, S.A. | Authentication means |
US20040055492A1 (en) * | 2000-07-12 | 2004-03-25 | Van Den Elshout Wihelmus H.H.A. | Irreversible application of an invisible marking to polymer mouldings |
WO2004087795A1 (en) | 2003-04-02 | 2004-10-14 | Ucb, S.A. | Authentication means |
WO2005054830A1 (en) | 2003-11-26 | 2005-06-16 | General Electric Company (A New York Corporation) | Fluorescence tag based method of authentificating polymers, authenticatable polymers, methods of making authenticatable polymers and authenticatable articles, and articles made there from |
FR2909922A1 (en) * | 2006-12-14 | 2008-06-20 | Att Advanced Track & Trace Sa | Object and material marking method for use in package of e.g. watch, involves marking surface and core of zone of material with laser for representing code on zone so that zone is imperceptible to naked eye |
EP2008715A1 (en) | 2007-06-25 | 2008-12-31 | ibidi GmbH | Sample chamber |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3068483B2 (en) * | 1996-02-08 | 2000-07-24 | 株式会社東芝 | Pattern reading method and optical signal reading device |
EP1343973B2 (en) * | 2000-11-16 | 2020-09-16 | California Institute Of Technology | Apparatus and methods for conducting assays and high throughput screening |
JP2002239484A (en) * | 2001-02-16 | 2002-08-27 | Ushio Inc | Apparatus for treating substrate by using dielectric barrier discharge lamp |
AU2002338795A1 (en) | 2001-09-28 | 2003-04-14 | Ibidi Gmbh | Flow chamber |
US8206666B2 (en) * | 2002-05-21 | 2012-06-26 | Battelle Memorial Institute | Reactors having varying cross-section, methods of making same, and methods of conducting reactions with varying local contact time |
JP4945893B2 (en) * | 2004-11-11 | 2012-06-06 | 大日本印刷株式会社 | Pattern forming substrate |
EP2255881B1 (en) | 2005-07-05 | 2013-03-13 | ibidi GmbH | Microfluidic device for generating diffusion gradients and method therefor |
EP1880764B1 (en) | 2006-07-20 | 2012-09-05 | ibidi GmbH | Sample carrier for examining cell growth |
US20100186524A1 (en) * | 2008-02-05 | 2010-07-29 | Enertechnix, Inc | Aerosol Collection and Microdroplet Delivery for Analysis |
-
2009
- 2009-09-08 EP EP09011507.2A patent/EP2292329B1/en active Active
-
2010
- 2010-09-07 US US12/876,881 patent/US9597688B2/en active Active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4241663A1 (en) * | 1992-12-04 | 1994-06-09 | Borus Spezialverfahren | Procedure for marking and recognizing an object |
FR2755902A1 (en) * | 1996-11-20 | 1998-05-22 | Sarl Ind Laser Partner | Marking procedure for use with merchandise liable to be fraudulently copied |
DE10004135A1 (en) | 2000-01-31 | 2001-08-09 | Reinhard Galneder | Chamber for cultivating and microscoping cells, comprises a lower section which acts as a base, and an upper section which acts as a cover. |
US20040055492A1 (en) * | 2000-07-12 | 2004-03-25 | Van Den Elshout Wihelmus H.H.A. | Irreversible application of an invisible marking to polymer mouldings |
DE10105711A1 (en) | 2001-02-08 | 2002-09-05 | Ibidi Gmbh | Sample holder for chemical and biological samples |
WO2003101755A1 (en) | 2002-05-31 | 2003-12-11 | Ucb, S.A. | Authentication means |
WO2004087795A1 (en) | 2003-04-02 | 2004-10-14 | Ucb, S.A. | Authentication means |
WO2005054830A1 (en) | 2003-11-26 | 2005-06-16 | General Electric Company (A New York Corporation) | Fluorescence tag based method of authentificating polymers, authenticatable polymers, methods of making authenticatable polymers and authenticatable articles, and articles made there from |
FR2909922A1 (en) * | 2006-12-14 | 2008-06-20 | Att Advanced Track & Trace Sa | Object and material marking method for use in package of e.g. watch, involves marking surface and core of zone of material with laser for representing code on zone so that zone is imperceptible to naked eye |
EP2008715A1 (en) | 2007-06-25 | 2008-12-31 | ibidi GmbH | Sample chamber |
Non-Patent Citations (3)
Title |
---|
BAKER A.K. ET AL.: "Refractive-index modification of polymethylmethacrylate (PMMA) thin films by KrF-laser irradiation", APPLIED PHYSICS A (SOLIDS AND SURFACES), vol. A57, no. 6, December 1993 (1993-12-01), Germany, pages 543 - 544, XP002581837, ISSN: 0721-7250 * |
CARLSSON D.J. ET AL.: "Photooxidation of polypropylene films. V. Origin of preferential surface oxidation", MACROMOLECULES, vol. 4, no. 2, 1971, pages 179 - 184, XP002581836 * |
QIN C.-L. ET AL.: "Blue light emission from pulsed laser ablated polyethylene", OPTOELECTRONICS LETTERS, vol. 4, no. 1, January 2008 (2008-01-01), XP002581835 * |
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US9597688B2 (en) | 2017-03-21 |
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EP2292329B1 (en) | 2014-11-12 |
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