peT
`WORLD INTElLECTUAL PROPERTY ORGANIZATION
`International Bureau
`INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
`WO 94/24962
`
`(51) International Patent Classification 5 :
`A61F 2/06, A61B 17/22
`
`At
`
`(11) International Publication Number:
`
`(43) International Publication Date:
`
`10 November 1994 (10.11.94)
`
`'"
`
`(21) International Application Number:
`
`PCTIUS94/04824
`
`(22) International Filing Date:
`
`28 April 1994 (28.04.94)
`
`Georgetown, MA 01833 (US). BERRIGAN, Kevin, M.
`[USIUS]; 10 Manning S11'ee1:, Woburn, MA 01833 (US).
`JARRETT, Peter, K. [USIUS]; 1063 Georges Hill Road,
`Southbury, cr 06488 (US). COURY, Arthur, J. [USIUS];
`154 Warren Avenue, Boston, MA 02116 (US).
`
`(30) Priority Data:
`08/054,385
`
`28 April 1993 (28.04.93)
`
`US
`
`(74) Agent: OYER, Timothy, J.; Wolf, Greenfield & Sacks, 600
`Atlantic Avenue, Boston, MA 02210 (US).
`
`(60) Parent Application or Grant
`(63) Related by Continuation
`US
`Filed on
`
`08/054,385 (CIP)
`28 April 1993 (28.04.93)
`
`(71) Applicant (jor all designated States except US): FOCAL, INC.
`[USIUS]; One Kendall Square, Cambridge, MA 02139 (US).
`
`(72) Inventors; and
`(75) Inventors/Applicants (jor US only):
`PATHAK, Chan-
`drashekhar, P. [INIUS]; 3102 Steams Hill Road, Waltham.
`MA 02154 (US). SA WHNEY, Amarpree1:, S. [INIUS];
`148 Church S11'ee1:, Newton, MA 02158 (US). HUBBElL,
`Jeffrey, A. [USIUS]; 413 Silver Hill Road, Concord, MA
`01742 (US). HERMAN, Stephen, J. [USIUS]; 28 Summer
`S11'oo1:, Andover, MA 01810 (US). ROTH, Laurence, A.
`[USIUS]; 8 Jackman Ridge Road, Windham, NH 03087
`(US). CAMPBElL, Patrick, K. [USIUS]; 45 East S11'ee1:,
`
`(81) Designated States: AT, AU, BB, BG, BR, BY, CA, CH, CN,
`CZ, DE, DK, ES, PI, GB, GE, HU, JP, KG, KP, KR,
`KZ, LK, LU, LV, MD, MG, MN, MW, NL, NO, NZ, PL,
`PT, RO, RU, SD, SE, SI, SK, TJ, TT, UA, US, uz, VN,
`European patent (AT, BE, CH, DE, DK, ES, FR, GB, GR,
`IE, IT, LU, MC, NL, PT, SE), OAPI patent (BF, BJ, CF,
`CG, CI, CM, GA, GN, MI., MR, NE, SN, TD, TO).
`
`Published
`With international search report.
`Before the expiration of the time limit for amending the
`claims and to be republished in the event of the receipt of
`amendments.
`
`(54) Title: APPARATUS AND METHODS FOR INTRALUMINAL PHOTOTHERMOFORMING
`
`(57) Abstract
`
`A method and apparatus for molding polymeric s1rUctures in vivo is disclosed. The structures comprise polymers that may be heated
`to their molding temperature by absorption of visible or near-visible wavelengths of light. By providing a light source that produces
`radiation of the wavelength absorbed by the polymeric material, the material may be selectively heated and shaped in vivo without a
`corresponding heating of adjacent tissues or fluids to unacceptable levels. The apparatus comprises a catheter (10) having a shaping element
`(12) positioned near its distal end. An emitter (15) provided with light from at least one optical fiber (18) is positioned within the shaping
`element The emitter serves to provide a moldable polymeric article (19) positioned on the shaping element with a substantially uniform
`light field, thereby allowing the article to be heated and molded at a desired 11'eatment site in a body lumen.
`
`STRYKER CORPORATION v. ORTHOPHOENIX, LLC
`
`IPR2014-01519
`
`STRYKER EXHIBIT 1003, p. i
`
`

`

`FOR THE PURPOSES OF INFORMATION ONLY
`
`Codes used to identify States party to the PCT on the front pages of pamphlets publishing international
`applications under the PCT.
`
`AT
`AU
`BB
`BE
`BF
`BG
`BJ
`BR
`BY
`CA
`CF
`CG
`CD
`CI
`CM
`CN
`CS
`CZ
`DE
`DK
`ES
`FI
`FR
`GA
`
`Austria
`Australia
`Barbados
`Belgium
`Burkina Paso
`Bulgaria
`Benin
`Brazil
`Belarus
`Canada
`Central African Republic
`Congo
`Switzerland
`COte d'[voinl .
`Cameroon
`Qlina
`Czechoslovakia
`Czech Republic
`Germany
`DenmaIt
`Spain
`Finland
`France
`Gabon
`
`GB
`GE
`GN
`GR
`au
`IE
`IT
`JP
`KE
`KG
`KP
`
`KR
`KZ
`LI
`LK
`LV
`LV
`MC
`MD
`MG
`ML
`MN
`
`United Kingdom
`Georgia
`Guine4
`Greece
`Hungary
`Ireland
`Italy
`Japan
`Kenya
`Kyrgystan
`Democratic People's Republic
`of Korea
`Republic of Korea
`Kazakhstan
`Liechtenstein
`Sri Lanka
`Luxembourg
`LatviA
`Mooaco
`Republic of Moldova
`Madagascar
`Mali
`Mongolia
`
`MR
`MW
`NE
`NL
`NO
`NZ
`PL
`PT
`RO
`RU
`SD
`SE
`SI
`SK
`SN
`TD
`TG
`TJ
`IT
`UA
`US
`UZ
`VN
`
`Mauritania
`Malawi
`Niger
`Netherlands
`Norway
`New Zealand
`Poland
`Portugal
`Romania
`Russian Federation
`Sudan
`Sweden
`Slovenia
`Slovakia
`Senegal
`Clad
`Togo
`Tajikistan
`Trinidad .00 Tobago
`Ukraine
`United States of America
`Uzbekistan
`VietNam
`
`STRYKER EXHIBIT 1003, p. ii
`
`

`

`WO 94/24962
`
`PCT /uS94/04824
`
`-
`
`1 -
`
`..
`
`APPARATUS AND METHODS FOR INTRALUMINAL
`PHOTOTHERMOFORMING
`
`FIELD OF THE INVENTION
`This invention pertains to devices for intraluminal
`implantation of polymeric materials in a human or animal
`patient and methods for delivering such materials.
`
`BACKGROUND OF THE INVENTION
`The application of polymeric materials to body tissues of
`human or animal patients is becoming increasingly important
`in medicine. Among the proposed uses of such materials are
`the alteration of tissue; the creation or preservation of
`lumens, channels or reservoirs for the passage or collection
`of fluids; the creation of matrices for the growth of tissue;
`the control of undesirable tissue growth; the delivery of
`therapeutic agents to a tissue surface; the ability to join a
`tissue surface to another tissue or an artificial implant;
`the ability to isolate or protect tissue or lesions to enable
`or mediate healing; and the ability to mediate the rate of
`substances or energy passing into, out of, or through tissue.
`Although it has been recognized that the use of polymeric
`materials in vivo may offer significant therapeutic effects,
`to date such applications have met many limitations. For
`example, the methods for applying such polymers to tissue
`surfaces often require the use of pressure, heat or
`electrical energy exceeding limits of tolerability at the
`tissue site. Likewise various chemica! effects associated
`
`STRYKER EXHIBIT 1003, pg. 1
`
`

`

`WO 94/24962
`
`PCT /uS94/04824
`
`- 2 -
`
`with such polymers have been found to be physiologically
`unacceptable.
`Numerous methods for reshaping polymeric materials in
`vivo are known in the prior ar:.
`In particular, U.S. Patent
`No. 5,213,580 and International Publication WO 90/01963, both
`to Slepian et al., the entire disclosures of which are
`incorporated herein by reference, describe methods in which
`polymers having melting points slightly above physiological
`temperatures are implanted into a patient and in which such
`polymers are melted via contact with heated fluids and shaped
`using mechanical force provided by a balloon catheter.
`Unfortunately, many of the methods known in the art suffer
`from the need to use energy levels beyond those which are
`physiologically tolerable l or from the inability to
`sufficiently control the shape change and/or temperature of
`the polymeric material.
`Typically, the primary limitation in prior art methods
`for the delivery of energy to an implanted device is the
`inability to direct the energy specifically ":0 the device,
`while minimizing energy delivery to body tissue. For
`example, it is known in the prior ar't that polymeric devices
`such as stents may be delivered to specific locations in vivo
`using a balloon catheter. Such stents may be heated at the
`site by filling the balloon with a heated fluid.
`In that
`method, heat is conducted from the fluid in ~he balloon,
`through the balloon material, and into the stent. Since
`conduction is a relatively slow process and the balloon has a
`relative large thermal mass, energy is transferred not only
`to the stent, but also to the surrounding body tissues and
`fluids. The result is that undesired amounts of heat are
`transferred into the surrounding body tissues and fluids.
`Accordingly, a need exists for apparatus for implanting
`polymeric materials in vivo that avoids the problems
`associated with the prior art. A need also exists for
`methods for delivering and reshaping materials in vivo which
`allow a physician to safe:y and easily introduce the materia:
`
`STRYKER EXHIBIT 1003, pg. 2
`
`

`

`WO 94/24962
`
`PCT /uS94/04824
`
`- 3 -
`
`into a patient, configure the material as des:red, and
`deposit the material at a desi:ed loca~ion for a~ leas~ a
`therapeutically desirable period of time. A further need
`exists for materials and methods for reshaping such ma~erials
`in vivo that offer the ability to reshape the materials while
`minimizing the amount of energy that is transferred to
`surrounding tissues and physiological fluids.
`
`SUMMARY OF THE INVENTION
`The present invention pertains to apparatus and methods
`for the delivery of polymeric material in vivo, and more
`particularly to the implantation of polymeric material into
`tissue lumens of human or animal patients. More particularly
`the invention relates to methods for photothermoforming a
`polymeric article in vivo, that is, modifying the shape of a
`polymeric article in vivo by using light to selectively heat
`the article to a temperature at which it is fluent, molding
`the article into a desired conformation, and allowing the
`article to become non-fluent in the desired conformation.
`Material from which the article is made is selected such that
`it is moldable at a temperature at which substantial damage
`to adjacent or proximate tissue does not occur.
`the
`Heating is achieved by irradiating, or illuminating
`article with light of a wavelength or within a wavelength
`range at which the polymeric material readily absorbs, or at
`which adjacent tissue or body fluids do not significantly
`absorb. According to one aspect of the invention, the
`article is irradiated at a wavelength or within a wavelength
`range at which the polymeric material readily absorbs and at
`which adjacent tissue or fluids do not significantly absorb.
`This is achieved by providing polymeric material that
`relatively strongly absorbs the radiation provided, or by
`loading the polymeric material with a chromophore that
`readily absorbs the radiation.
`It is preferred that the
`light used to thermoform the polymer be of a wavelength that
`is not readily absorbed by body tissues or fluids, ~hereby
`
`STRYKER EXHIBIT 1003, pg. 3
`
`

`

`WO 94/24962
`
`peT /uS94/04824
`
`-
`
`4:
`
`minimizing the amount of light absorbed by, and hea~
`geherated in, ~he tissue or fluid
`the region of :he
`thermoforming, According to one aspect of the invention
`visible or near-infrared light is provided locally to the
`polymeric material by an optical tip assembly on a delivery
`device,
`The resulting shaped article provides a therapeutic
`benefit by acting, in one embodiment, as a stent to maintain
`patency through a blood vessel, Numerous other therapeutic
`shapes are contemplated as well.
`According to one embodiment, the polymeric material has a
`chromophore such as a dye or pigment compounded therein, The
`chromophore is selected, in conjunction with a particular
`light source, to absorb light that is produced by the light
`source, The absorbed light is converted to thermal energy
`which acts to heat the polymer. According to one aspect of
`the invention, the chromophore is thermochromic. As an
`alternative to compounding the polymer with a chromophore,
`polymers that naturally absorb the wavelength spectrum of the
`light produced by the source may be used. The natural
`absorption spectrum of the material may result from the
`polymer in its native state, or alternatively, by the
`incorporation of one or more chromophores into the polymeric
`backbone or side-chains.
`In each case, however, it is
`necessary that the polymer satisfies other selection criteria
`such as biocompatibility and moldability.
`By selecting a chromophore, or polymeric material, having
`maximum absorption characteristics at or near a particular
`wavelength or spectral range, in conjunction with a light
`source that emits at or near the particular wavelength or
`spectral range, the polymer is provided with the ability to
`be efficiently heated via light absorption.
`In this way,
`selective heating of the polymer with minimal heating of
`surrounding body tissues and fluids may be achieved.
`Broadly~ the apparatus comprises a catheter having a
`shaping elemen~ positioned near its distal end. The
`
`,
`
`STRYKER EXHIBIT 1003, pg. 4
`
`

`

`WO 94/24962
`
`peT IUS94/04824
`
`-
`
`5 -
`
`polymeric material is positioned adjacent or ~ear the shaping
`eleme~t, illuminated by light delivered jy the cat~e~er and
`thus heated to render it fluent, and molded by the shaping
`element into contact with a tissue lumen.
`In one embodiment, the apparatus comprises a balloon
`dilatation catheter having an associated optical tip
`assembly. The polymeric material is positioned on the
`balloon, preferably in the form of a tube or sleeve which
`surrounds the balloon. The optical tip assembly serves to
`direct light to the polymeric material. The light may be
`provided from an external source. Upon absorption of the
`light, the polymeric material is heated to a temperature at
`which it becomes moldable.
`Inflation of the balloon causes
`the moldable polymeric material to expand outwardly, thereby
`pressing the polymer into contact with the tissue lumen.
`Alternatively, in cases in which the polymeric material can
`be reconfigured prior to molding (i.e., the polymeric
`material comprises a rolled sheet or a tube having axial
`pleats), the material is reconfigured using the balloon and
`then heated to mold it into conformance with an adjace~t
`tissue surface.
`According to another embodiment, the apparatus further
`includes a retractable sheath which is designed to
`encapsulate the polymeric material on the balloon as the
`material is guided to a treatment location in vivo. Once
`positioned, the sheath is retracted to expose the material
`and to allow the material to be heated and molded as
`described above. The sheath may include a tapered distal
`tip, formed of a flexible polymer, which expands radially
`over the balloon and polymeric material as the sheath is
`withdrawn over those structures. As an alternative, the tip
`may include at least one longitudinal slit which allows
`radial expansion of the tip.
`
`BRIEF DESCRIPTION OF TEE DRP.WINGS
`FIG. 1 illustrates one embodiment of a laser ba:loon
`polymeric ma:e:lc._;
`catheter s~itable for de:l.ive::-y
`
`STRYKER EXHIBIT 1003, pg. 5
`
`

`

`WO 94/24962
`
`PCT IUS94/04824
`
`-
`
`6 -
`
`FIGS. 2a and 2b illustrate one embodime~~ of a lase:
`balloorr cathete= suitable for delivery of a polymeric
`material;
`FIG. 3 is an illus~ration of a laser balloon catheter
`showing two embodiments of an optical emitte=;
`FIGS. 4a and 4b illustrate a second embodiment of a lase=
`balloon catheter suitable for delive=y of a polymeric
`material;
`FIGS. 5a and 5b illustrate a retractable sheath suitable
`for use with the laser balloon catheters of FIGS. 1, 2 and 4;
`FIGS. 6a and 6b are schematic illustrations of anothe=
`embodiment of a device for providing a thick polymeric film
`on a luminal wall; and
`FIGS. 7a and 7b are schematic representations of an
`optical emitter catheter for use with the device of FIG. 6b.
`
`DETAILED DESCRIPTION OF THE INVENTION
`The ability to selectively heat an implanted polymeric
`material using light in the visible or near-visible spectrum
`can be achieved using a light source which produces a
`wavelength spectrum that is not readily absorbed by body
`tissue. Light from the source is used to heat a polyrr.eric
`material that is at least partially absorptive of the light
`in the spectral range.
`Even if only a portion of the light
`(e.g., 50%) is absorbed by the polymer, transmitted light
`will not be readily absorbed by the surrounding tissue and
`will have a minimal heating effect on that tissue.
`In this
`case, light which is not absorbed by the polymer is absorbed
`by a relatively large area of tissue as it penetrates beyond
`the polymer. As such, resultant heating occurs throughout a
`much larger volume of tissue. Since the temperature rise in
`the tissue is a function of energy absorbed within a unit
`volume of tissue, localized heating is significantly lowe= as
`compared to the heating caused by wave:engths that are
`~ . ,
`b"-b ",'
`b
`' 1""
`I
`rea~l~y a so~ e~, 1.e., y a sma~ e_ vo urne 0_ .lssue.
`to'
`.t:
`~ne
`"T'l'
`requirement for wavele:1gths which have lov..' tiSS·:..l8 absorption
`
`STRYKER EXHIBIT 1003, pg. 6
`
`

`

`WO 94/24962
`
`PCT fUS94/04824
`
`- 7 -
`
`characteristics is necessary only to the ex~en: that excess
`heatir.g of the tissue does not occur or is undes:rable at __ he
`particular treatment location.
`Alternatively, it is possible to use light having a
`spectrum that is absorbed by body tissues and fluids provided
`that the polymeric material is highly absorptive of light in
`the spectral range.
`In this case, the polyme: will absorb
`substantially all of the light, thereby minimizing the amount
`that is transferred to the body tissue and minimizing the
`heating effect of that light on tissue.
`The polymeric materials of the present invention must
`satisfy various criteria, including molding temperature,
`crystallinity, absorption characteristics, bioerodability,
`physical strength, biocompatibility and light transmission
`and absorption characteristics. Each of these are discussed
`below.
`
`Molding Temperature
`The material must become either moldable or molten at a
`temperature that is not significantly injurious to tissue or
`surrounding physiological fluids if maintained at that
`temperature for the amount of time required to implant and
`shape the material. Additionally, the material must become
`moldable at a temperature above about 40 degrees C. That
`temperature has been selected as being a temperature that is
`greater than body temperatures associated with hyperthermia
`or fever (approximately 38-40 degrees C). The requirement of
`the minimum molding temperature is to prevent the material
`from spontaneously softening or melting in response to
`elevated, physiologically occurring body temperatures.
`As used herein, the term "molding temperature" is used to
`describe a minimum melting temperature, Tm' or a glass
`transition temperature, Tg , at which the polymer may be
`plastically deformed using physiologically acceptable
`forces. Likewise, the melting or glass transition
`temperat~re must be below that at which signi:icant
`
`STRYKER EXHIBIT 1003, pg. 7
`
`

`

`WO 94/24962
`
`PCT ruS94/04824
`
`8 -
`
`mecha:1ical or thermal damage to body tissues occurs . The
`term . , thermof ormi:1q-' is used to desc:ibe the process 'tJhere i:1
`a polymeric article is heated to at least its molding
`temperature and then reshaped by external or inte:-nal forces.
`
`crystallinity and Physical Strength
`It is preferred that the material have a substantially
`crystalline or semi-crystalline structure so that when heated
`to its melting temperature, it will undergo a rapid
`transition to a viscous fluid that will flow readily, yet
`remain cohesive, when subjected to molding forces associated
`with thermoforming. As an alternative, the material may be
`glassy or have a glassy component.
`In that case, if heated
`sufficiently above its glass transition temperature, the
`material will also flow readily and remain cohesive when
`subjected to molding forces.
`The materials useful in the invention are termed "fluent"
`when in their moldable state. The actual viscosity of the
`fluent material that allows the material to be molded without
`significant mechanical disruption of the tissue depends upon
`the particular tissue and the method by which the material is
`mol~ed. In general, it is preferred that the material be
`such that, once heated to its molding temperature, (i.e.,
`rendered fluent), the material may be shaped or formed using
`a physiologically acceptable amount of force. Likewise, it
`is preferred that the molding temperature be low enough to
`prevent significant thermal damage during the molding
`process. The ability to be molded using a minimum amount of
`force reduces the possibility of tissue injury potentially
`occurring as a result of misuse or structural failure of the
`polymeric material or the force-supplying component.
`Determination of an acceptable amount of force and
`thermal load depends upon at least a) the viscosity of the
`material in its moldable state, b) the length and/or
`thickness of the material, c) the geometric configuration of
`the material, and d) the temperature at which the material
`
`STRYKER EXHIBIT 1003, pg. 8
`
`

`

`WO 94/24962
`
`peT /uS94/04824
`
`-
`
`9 -
`
`becomes sufficiently fluent. Additionally, forces and
`thermal loads that may be physiologically acceptable on one
`type of tissue may no~ be acceptable en another. Fer
`example, physiologically acceptable forces and temperatures
`within bone tissue may far exceed the amount of force and
`heat that is physiologically acceptable on a blood vessel or
`other soft tissue. Thus, the physical characteristics of
`both the polymeric material and the tissue site must be
`considered in determining maximum physiologically acceptable
`forces and temperatures for molding the polymer,
`It is preferred that the selected polymeric material be
`such that the amount of thermal energy needed to heat the
`material to its molding point can be transferred within a
`practical amount of time to thereby minimize the length of
`time required for the surgical procedure and to minimize the
`amount of heat conducted out of the material and into the
`tissue.
`In one embodiment, the material is intended to provide
`mechanical support to tissue structures.
`In that embodiment,
`the material itself, and the ultimate therapeutic shape of
`the material, must provide a structure having sufficient
`mechanical strength to withstand forces exerted upon the
`shaped material during its functional lifetime in vivo. This
`requirement is especially significant when using materials
`that are expected to be biodegradeable after their
`mechanically functional lifetime, Alternatively, the
`material need not be intended for structural support.
`Rather, the material may be used as a protective layer, a
`barrier layer, as an adhesive, or as a carrier of therapeutic
`agents,
`In that case, the material must be selected so that
`its function is not impaired either by biodegradation during
`its functional lifetime in vivo or by the process used to
`shape the material during implantation, The ability to
`provide varied degrees of mechanical support can be achieved
`by selecting differing polymeric materials or by altering the
`molecular weight distribution of materials comprisi~g more
`
`STRYKER EXHIBIT 1003, pg. 9
`
`

`

`WO 94/24962
`
`peT /uS94/04824
`
`- 10 -
`
`In gene~al, materials having highe:
`than one polymer.
`molecular weights will provide a higher modulus and gr~ater
`support than those materials having a lower molecular
`weight. Additionally, the material must be selected such
`that the heating and reformation of the material do not
`degrade or otherwise alter the release characteristics of the
`material toward any therapeutic agents that may be
`incorporated into the material,
`In some applications it is preferred that the material
`not completely cover, but only partially cover an area of
`tissue to be supported or otherwise addressed by the
`material. For example, the material may be applied to
`support a portion of a tissue lumen, rather than the entire
`lumen. The physical form may be varied to suit the final
`application. While relatively thin solid films or sheets are
`preferred for many applications, fenestrated or microporous
`sheets may also be,used. Spun webs, with or without
`melt-bonding or calendaring, may also be of use. The
`material can include predefined perforations or apertures
`once transformed from a delivery configuration to its
`therapeutic configuration.
`If the device is intended to be
`delivered in the form of a hollow cylinder, the cylinder may
`be provided with a plurality of perforations which open or
`remain open once the cylinder has been expanded to a la,rger,
`therapeutic configuration.
`If the material is used as a
`support structure for an artery, the perforations may allow
`increased axial flexibility to faci~itate delivery and reduce
`tissue erosion during and after implementation, improved
`perfusion of side branch vessels by decreasing the likelihood
`of obstruction of such vessels, and increased ingrowth of
`tissue for anchoring and encapSUlation of the material.
`
`Absorption Characteristics
`The polyme~ic material should preferably absorb light
`within a wavelength range that is not readily absorbed by
`tissue, blood elemen~s, physiolog:ca: fluids, or water.
`
`STRYKER EXHIBIT 1003, pg. 10
`
`

`

`WO 94/24962
`
`peT /uS94/04824
`
`- 11 -
`
`Although wavelengths in the spectral range of aboct 250-1300
`nm may be used, wavelengths !n the range of about 300-1000 ~rn
`are preferred, and wavelengths in the range of about 500-850
`are especially preferred.
`In the case in which a chromophore
`such as a dye or pigment is incorporated into the polyme:ic
`material, the material itself must be sufficiently
`transparent to allow the light to reach and be absorbed by
`the dye or pigment.
`For both the bioerodable and non-bioerodable polymers,
`chromophores and light sources suitable for use in the
`invention may be selected from dye or pigment materials and
`lasers corresponding to those materials including, but no:
`limited to, the following:
`Wavelength (nm)/laser
`
`Dve/Maximum Absorption
`
`457 Argon Ion
`
`488 Argon Ion
`
`Acramine Yellow (420 nm)
`
`Acridine Orange (489 nm),
`Fluorescein (491 nm)
`
`514 Argon Ion
`
`Eosin Y (514 nm)
`
`676 Argon/Krypton
`
`Methylene Blue (661 nm)
`
`647 Krypton
`676
`
`694 Ruby
`
`780 Semiconductor
`780
`810
`820
`830
`850
`870
`
`532 Neodymiurn:YAG
`(frequency X2)
`
`355 Neodymiurn:YAG
`(frequency X3)
`
`Neodymium:YAG
`(frequency X4)
`
`266,
`"" , :
`~ ... -
`
`Jenner stain (651 nm),
`Methylene Blue (661 nm)
`
`Prussian blue (694 nm),
`
`Copper Phthalocyanine
`(795 nm in sulfuric acid),
`Indocyanine Green (775nm)
`
`Ethyl Eosin (532 nm in
`ethanol); Erythrosin B
`(525 nm); Eosin Y (514 nm)
`
`Acridine (358 nm)
`
`Prussian blue (260 nm),
`
`Carbon black
`
`STRYKER EXHIBIT 1003, pg. 11
`
`

`

`WO 94/24962
`
`PCT /uS94/04824
`
`- 12 -
`
`The selection of ligtt source and chromophore is not
`i~~ended to be limited solely to those spe:i:ied above,
`Rather, any combination that yields sufficient heating to
`rende~ the polymeric material fluent may be used,
`Any of a variety of methods known in the art of pol~.er
`processing may be used to form the polymeric material into
`its predeployment configuration and, if necessary, to
`compound chromophores into the material. Among the polymer
`processing methods contemplated are solvent casting,
`injection molding, extrusion, solvent extraction and
`compression molding.
`The heating method of the present invention may be
`contrasted with conductive heating methods which use a
`heating element, as such techniques tend to require a greater
`thermal load and to heat more slowly, thereby having the
`potential to transfer significant amounts of heat to the
`surrounding body tissue or fluids. As noted previously
`however, absorption of light allows the polymeric article to
`be heated while transferring a minimum of energy to the
`surrounding tissue and fluids. This is achieved by selecting
`either a wavelength spectrum that is not readily absorbed by
`body tissue, a polymeric composition that absorbs
`substantially all incident energy in the wavelength spectrum,
`or a combination of these characteristics.
`In one embodiment, the upper limit of the polymer
`temperature can be controlled using a dye which substantially
`stops absorbing optical energy once it reaches a certain
`temperature. Such so-called "thermochromic" dyes are
`commercially available from Clark R&D Limited of Arlington
`Heights, Illinois. Thermochromic dyes exhibit a constant
`absorption below a lower critical temperature TL. Between
`TL and an upper critical temperature TU the absorption
`decreases from a constant value to nearly zero.
`Thermochromic dyes are further characterized generally in
`that the change of absorption with temperature is fully
`reversible. The incorporation of thermochromic dyes into
`
`STRYKER EXHIBIT 1003, pg. 12
`
`

`

`WO 94/24962
`
`peT /uS94/04824
`
`- 13 -
`
`polymeric ma~e=ials allows constant absorp:ion of ene=gy when
`:he polyme~ is cool with a decreasing ene~gy absorptio~ as
`the polymer is heatec.
`It is expected tha~ the po~ymer
`temperature will reach a steady state at some point between
`TL and TU resulting from a balance between the energy
`absorbed by heat input from the light source and the energy
`lost by heat output to the surrounding tissue.
`For example, Type 47 thermochromic dye available from
`Clark R&D absorbs, at room temperature, light in the
`wavelength spectrum between about 600 and about 850 nm. The
`dye has a TL of 44 degrees C and a Tu of 58 degrees C.
`If this dye is compounded into a polymer having a melting
`temperature (TM) that falls between TL and TU' the
`resulting polymeric material will absorb light in the 600-850
`nm spectrum and begin to heat. Once the polymeric material
`is heated to a temperature above TL, the absorption of the
`dye will decrease, thereby decreasing the rate of polymeric
`heating and preventing the polymeric material from achieving
`a temperature that may be harmful to it, and adjacent body
`tissue or surrounding body fluids. Once the temperature of
`the polymeric material reaches TM, the polymer melts,
`allowing it to pave an adjacent tissue surface. Howeve=,
`since the temperature rise will decrease and reach a steady
`state level where the energy input (reduced due to decreased
`dye absorption) equals the energy output (mediated by thermal
`boundary conditions) an upper thermal limit is achieved.
`Thermochromism thus is essentially a feedback mechanism for
`obtaining uniform heating of the entire article despite
`possible non-uniformity of illumination. The hottest regions
`of the polymer will absorb less light, allowing other areas
`of the device to "catch up" in temperature during the heating
`stage. Thermochromic dyes can render instrumentation to
`measure temperature of the polymeric material unnecessary.
`In addition, the use of thermochromic dyes may offer
`advantages if the enitter is eccentrically located inside a
`shaping element suc~ as a ballocn. Since powe~ density :=o~
`
`STRYKER EXHIBIT 1003, pg. 13
`
`

`

`WO 94/24962
`
`PCT IUS94/04824
`
`- 14 -
`
`the emitter is approxima~ely related to the :~verse or the
`inverse square of the dis~ance between the e~!~~e: and the
`polymeric material, the power density would be much highe:
`for a portion of polymeric material close ~o the emitter than
`for a portion of the material that is further away. When
`using conventional dyes, the result can be a non-uniform
`temperature around the shaping element, resulting in one
`portion of the polymeric material being much warmer than
`another. However, if a thermochromic dye is incorporated
`into the polymeric material, the material tha~ is located
`closer to the emitter would rapidly reach its maximum
`temperature and level off, while material on a further
`portion of the polymeric material would reach the same
`maximum temperature, although more slowly. The result is
`that ultimately the entire polymeric article would reach a
`uniform temperature. Likewise, different thermal boundary
`conditions at the surface onto which the polymeric article is
`being applied could also, if conventional dyes are used,
`cause the polymeric article to become warmer in some sections
`than in others. This difference can also be reduced if
`thermochromic dyes are employed.
`In still another embodiment, a thermochromic dye can be
`used in combination with a conventional dye. Thus, rather
`than reaching a steady state condition in which the thermal
`input is equal to the thermal output as a result of near zero
`dye absorption, a combination of thermochromic and
`conventional dyes would cause the heating to slow as the
`absorption of the thermochromic dye decreases. However, even
`if the thermochromic dye reaches a state of zero absorption,
`the heating level would continue to increase as a result of
`the presence of the conventional dye until a steady state is
`reached. By varying the relative proportions of conventional
`dye to thermochromic dye, the heating of the polymeric
`article can be tailored to a specific application.
`
`STRYKER EXHIBIT 1003, pg. 14
`
`

`

`WO 94/24962
`
`'peT /US94/04824
`
`- 15 -
`
`3ioerodabilitv
`Although not intended to be limited as such. :n one