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WO2011131677A1 - Matériau polymère photoactivé et son utilisation pour la préparation de dispositifs médicaux - Google Patents

Matériau polymère photoactivé et son utilisation pour la préparation de dispositifs médicaux Download PDF

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Publication number
WO2011131677A1
WO2011131677A1 PCT/EP2011/056246 EP2011056246W WO2011131677A1 WO 2011131677 A1 WO2011131677 A1 WO 2011131677A1 EP 2011056246 W EP2011056246 W EP 2011056246W WO 2011131677 A1 WO2011131677 A1 WO 2011131677A1
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Prior art keywords
medical device
group
tube
compound
catheter
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Ceased
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PCT/EP2011/056246
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English (en)
Inventor
Simone D'onofrio
Paolo Pellegrini
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Invatec SpA
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Invatec SpA
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Priority to JP2013505459A priority Critical patent/JP6005627B2/ja
Priority to EP11714992.2A priority patent/EP2560695B1/fr
Publication of WO2011131677A1 publication Critical patent/WO2011131677A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/04—Macromolecular materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment

Definitions

  • the present invention relates to a medical device.
  • the present invention relates to a catheter having a surface endowed with improved properties .
  • the present invention relates to a catheter tube having a surface endowed with improved properties.
  • the present invention relates to a catheter tube of a catheter for endovascular interventions, said catheter tube having a surface endowed with improved properties.
  • the present invention relates to a catheter guide wire tube having an inner surface endowed with a low friction coefficient.
  • the present invention relates to an inflation tube or an aspiration tube of a catheter for endovascular interventions, said inflation or aspiration tube having an inner surface endowed with improved properties.
  • angioplasty is a procedure for opening narrowed or even blocked blood vessels and restoring the normal blood flow.
  • Angioplasty is successfully used also for treating coronary arteries, e.g. for treating coronary stenoses present therein.
  • a catheter e.g. an angioplasty catheter
  • a blood vessel of the patient the blood vessel of an arm or of the groin, for instance
  • the intervention site e.g. an occluded or partially occluded blood vessel (vein or artery)
  • a guide wire is firstly inserted into the blood vessel (optionally in combination with a guiding catheter) for allowing the correct positioning of the endovascular catheter, such as a balloon catheter, a stent delivery system, a clot extraction catheter, a multipurpose catheter.
  • the subsequent operations of inflating and deflating the balloon result in the plaque obstructing the vessel to be flattened against the vessel inner wall for re-establishing an acceptable blood flow .
  • Pushability refers to the possibility of the catheter to be easily pushed by the physician through the vascular system to the intervention site, while slidability relates to the capability of the catheter (and specifically of the catheter tube) to suitably slide over the guide wire.
  • Slidability can be improved also by operating on the catheter tube material and/or structure.
  • a multilayered catheter guide wire tube can be used, the outer layer of which provides for the requested mechanical resistance while the inner layer provides for the necessary slidability of the guide wire tube over the guide wire.
  • An example of a multilayered guide wire tube structure is a tri-layered guide wire tube formed of PEBA-polyethylene resin-HDPE where the HDPE layer is the tube inner layer.
  • PA12 mono-layered polyamide 12
  • polyamide 12 is endowed with suitable mechanical properties in terms of flexibility, chemical resistance, robustness, as well as with welding and workability properties.
  • polyamide 12 has poor slidability properties.
  • at least two main procedures for the surface modification of polymers are known in the art .
  • the surface of a polymeric material can be modified by acting on its composition and/or microstructure .
  • US 5, 714, 360 discloses the covalent linkage of a target molecule, selected among synthetic polymers, especially polyvinylpirrolidone , carbohydrates, proteins, lipids, nucleic acids, drugs, dyes and fluorescent compounds, capable of conferring a particular property to a substrate through a photoactivating linking agent.
  • a target molecule selected among synthetic polymers, especially polyvinylpirrolidone , carbohydrates, proteins, lipids, nucleic acids, drugs, dyes and fluorescent compounds, capable of conferring a particular property to a substrate through a photoactivating linking agent.
  • US 6,551,267 discloses a plastic material article coated with a crosslinked hydrogel permanently bound to the inner wall of the tube.
  • US 6, 120, 904 discloses the formation of a po 1 yurethane /po 1 yurea hydrogel coating onto a plasma treated surface.
  • US 5,415,619 describes the modification of a polyester surface with the reaction of sulphuric acid which originates negative charges;
  • Polyamide surfaces may also be modified according to the method disclosed in Polymer (2006, vol.47, 14, 4916-4924) with the use of a strong base like potassium terbutylate ; the potassium salt thus formed may bind other useful molecules .
  • the method of applying a coating may be performed by dipping or spraying as taught, for instance, in US 5,061,738 wherein a mixture of a silicone resin and heparin is applied to a tube surface.
  • extrusion and co-extrusion techniques may be used, wherein a lubricating hydrophilic polymer immiscible with the tube material and the tube material are co-extruded, as disclosed for instance in US 6, 506, 333.
  • the applied coating being not very stable, can be removed, damaged or degraded, such as delaminated or peeled, while the tube is being used.
  • plasma treatments which modify the surface of the tube material, may cause damages to the surface itself and do not provide reproducible results.
  • the Applicant has perceived the need of providing a reliable and reproducible method which is suitable for modifying the surface of a medical device, in particular the inner surface thereof.
  • the Applicant has perceived the need of providing a reliable and reproducible method which is suitable for decreasing the friction coefficient of the surface of a medical device, particularly of the inner surface of a catheter tube.
  • said photoactivation may impart either hydrophobic or hydrophilic properties to the surface of a catheter.
  • the present invention discloses the use of substituted aromatic azides for the photoactivation of polymeric surfaces .
  • Fig. 1 shows the mechanism of insertion of the para-substituted arylazide compounds of the invention into a C-H containing surface.
  • Fig. 2 shows the TLC obtained for the preparation of a compound according to EXAMPLE 4.
  • Fig. 3-8 show the spectra obtained with XPS analysis of samples treated according to the present invention.
  • Fig. 9 shows the reaction mechanism for light excitation of arylazides of the invention.
  • Fig. 10 shows the TLC obtained for the preparation of the compounds according to EXAMPLE 14.
  • a medical device particularly a catheter, comprises a hollow body made of a polymeric material and has an outer and an inner surface, wherein said inner surface has been modified by the insertion of hydrophilic or hydrophobic moieties.
  • said catheter is a catheter guide wire tube, an inflation tube of a balloon catheter or an aspiration tube.
  • guide wire tube includes any catheter component which defines and possesses a lumen suitable for receiving a guide wire there into.
  • the guide wire tube extends for the whole catheter length and it is coaxially arranged with respect to the catheter shaft, the guide wire tube being internal to the catheter shaft.
  • the guide wire tube includes the shaft catheter portion forming the guide wire lumen and the actual guide wire tube starting at the balloon proximal end.
  • inflation tube includes any catheter component which defines and possesses a lumen suitable for receiving an inflation fluid which allows inflation and deflation of a catheter balloon.
  • aspiration tube any catheter component which defines and possesses a lumen suitable for the aspiration of clots, thrombi, ...
  • the term "inner surface" of a catheter tube refers to the surface of a lumen which is suitable for receiving a guide wire, an inflation fluid or an aspirated material (clot, thrombi, ..), respectively.
  • a medical device as above disclosed has, in addition or in alternative to the inner surface , the outer surface which is modified by the insertion of hydrophilic or hydrophobic moieties.
  • the friction under consideration is the one between the guide wire outer surface and the guide wire tube inner surface (inside of which the guide wire is caused to slide) .
  • the guide wire is usually provided with a hydrophobic PTFE coating
  • the inner surface of the guide wire tube is photoactivated with substituted aromatic azides suitable for imparting hydrophobic properties to said inner surface. In this way, in fact, the friction between the two contacting hydrophobic materials can be kept advantageously low.
  • the catheter tube is an inflation tube as above disclosed, particularly a balloon catheter for angioplasty
  • the inflation tube inner surface modified according to the present invention advantageously improves the distribution and the sliding of the inflation fluid along the inflation tube. This aspect favourably affects the balloon inflation and deflation times, which can be advantageously reduced.
  • a decrease of the balloon inflation time, and especially of the balloon deflation time, is particularly advantageous for applications where long balloons (e.g. up to 300mm) or valvuloplasty balloons, which have relevant radial dimensions in comparison with the longitudinal ones, are used.
  • both the guide wire tube and the inflation tube inner surfaces may be modified by the insertion of hydrophilic moieties.
  • the inflation fluid which moves in the space between the inflation tube (catheter shaft) and the guide wire tube, is advantageously made sliding with low friction forces.
  • hydrophilic properties may also be imparted according to the present invention to the inner surface of an aspiration tube of a medical device, such as a clot extraction catheter.
  • a medical device such as a clot extraction catheter.
  • the aspiration tube inner surface thus modified advantageously contributes in increasing the aspiration efficiency of the aspiration catheter, especially in case of very dense material (clots, thrombi, ...) to be aspirated from a blood vessel.
  • the inner surface of a guide wire tube as above disclosed may be modified in order to impart hydrophilic properties.
  • the friction between the latter and the hydrophilic inner surface of the guide wire tube is advantageously and surprisingly low.
  • the guide wire is wetted with a liquid solution, typically an aqueous solution of heparin, in order to avoid that blood coagulation occurs on the guide wire outer surface.
  • the modified inner surface of the guide wire tube according to the invention is capable of attracting the wetting solution and generating the thin liquid layer above mentioned.
  • PA12 has a contact angle ⁇ of about 85°; therefore, a surface modification which increases this angular value makes the PA12 material more hydrophobic while a surface modification which decreases this angular value makes the PA12 material more hydrophilic.
  • hydrophilic groups are -OH, -COOH, -S0 3 , -P0 4 , -NH 2 , -NH 4 + , PEG (poly (ethylene glycol)), PEO (polyethylene oxide).
  • PTFE polytetraf luoroe thylene
  • biopolymers are particularly suitable as the polymeric material for manufacturing the catheter tube.
  • a biocompatible polymeric material or a biopolymer is intended to encompass those materials which may be suitably placed in contact with a body surface or tissue and especially with the blood, without triggering the formation of blood clotting or thrombi. Hydrophilic surfaces have in fact been demonstrated to slow the blood macromolecules and corpuscles absorption.
  • the polymeric material which is suitable for the present invention comprises C-H or C-X functional groups, where X is an heteroatom.
  • X is selected from the group comprising nitrogen, oxygen, sulphur, phosphorous, boron, chloride, bromine and iodine.
  • biocompatible polymers which are suitable for the present invention include, for instance, polyamides, polyester-polyamide copolymers, the polyamide-based copolymers of general formula
  • the polymeric material may be an elastomer obtained by the polymerization of a polyamide forming block compound selected in the group comprising an aminocarboxylic acid of formula (1) below and a lactam of formula (2) below
  • Rl, R2 and R3 are each binding groups comprising a hydrocarbon chain therein, which may be interrupted by one or more amide groups and wherein Rl and R2 comprise independently an alkylene group having 2 to 20 carbon atoms and amide bonds and R3 comprises an alkylene group having 1 to 20 carbon atoms and wherein x may change from 1 to 20, preferably from 1 to 18, more preferably from 1 to 16, wherein y may change from 4 to 50, preferably from 5 to 45, more preferably from 8 to 30 and z may change from 1 to 20, preferably from 1 to 18, more preferably from 1 to 12 and wherein m is 0 or 1 as disclosed in WO 2007/132485, whose content, with respect to the compounds and preparation methods, is herewith incorporated by reference.
  • a particularly preferred polymer of the present invention is polyamide and, more in particular, polyamide PA12 and PEBAX ® .
  • the modification of the polymer surface is obtained by the insertion of moieties capable of modifying the wetting properties of the material surface.
  • a substituted aromatic azide bearing a R group under UV light produces the extremely reactive intermediate phenylnitrene .
  • the nitrene radical takes an hydrogen from a substrate having C-H bonds thus giving two radical moieties, which then combine together. There results that the azide molecule is inserted into the substrate .
  • the polymeric inner surface of a catheter tube is rendered hydrophilic, or at least more hydrophilic than before, by covalently bounding to said inner surface groups of formula
  • R 1 independently from each is H or F
  • R 2 is selected from H, F, a Z group selected from C(0)NH-R a , -S(0) 2 NH-R a and -P(0) 2 NH-R a wherein R a is C 1 -C4 linear or branched saturated alkyl chain optionally substituted with one or more polar functional groups like -OH, -COOH, -SO3, -PO4, -NH 2 , -NH4+ and the like or with a -(CF 2 ) m -CF 3 perfluoroalkyl group wherein m is 1 to 70; or wherein R a is - (CHRCH 2 0) n -X wherein n is 1 to 70, R is H or -CH 3 and X is selected from H, saturated branched or linear C 1 -C4 alkyl chain or a - (CH 2 ) P -0- (CH 2 ) q -W group wherein W is H, -CH 3 or -NH 2 and wherein
  • R3 is selected from -N0 2 or a Z group as above defined.
  • R a being a linear or branched saturated alkyl chain, it can be selected from the group comprising hydrocarbon chains, polyethylene, polypropylene and polyolefins, while when R a is an aromatic group, it can be selected among the group comprising xylene, polystyrene and acrylonitrile butadiene styrene.
  • a preferred perfluoroalkyl R a group is -(CF 2 ) n CF 3 , wherein n is 1 to 70 or polytetrafluoroethylene .
  • the sliding properties of the inner surface of a catheter tube can also be improved by carrying out a hydrophobic treatment.
  • a hydrophobic treatment allows to minimise the interaction between the catheter tube inner surface and the fluid layer surrounding the guide wire, so that the catheter tube suitably and advantageously slides over said layer.
  • the Applicant has found that in spite of the fact that the surface to be treated is not exposed to light - being an inner surface of a catheter tube - the photoactivation can be successfully carried out. To this aim, it is necessary to select the wavelength of the UV light source as well as the polymeric material to be treated so that no absorbance of the radiation may occur. It has been found that the photoactivating wavelength of the above azide compounds does not interfere with the absorbance wavelength of the materials normally used for catheter tubes.
  • an alcoholic solution of methanol or ethanol or acetone or an acetonitrile or a chloroform solution of a para-substituted arylazide compound is prepared and the inner surface to be treated is contacted with said solution.
  • the solution may be made flowing inside the catheter tube, i.e. through the catheter tube lumen.
  • the treated surface is activated by light of a suitable wavelength capable of photoact ivating the para-substituted arylazide and irradiation is performed for a suitable period of time.
  • the light wavelength for a given para-substituted arylazide is selected as the wavelength which substantially corresponds to the maximum absorption for that specific para-substituted arylazide.
  • the light wavelength is comprised from about 200 nm to about 600 nm.
  • the light wavelength is comprised from about 250 nm to about 350 nm and even more preferably is comprised from about 230 nm to about 300 nm.
  • the photoact ivat ion reaction is carried out in a dark environment, at room temperature, i.e. about 25°C, and the reaction time is typically comprised from 0.5-1 hour.
  • the outer surface of a medical device can be modified in order to impart hydrophilic or hydrophobic properties.
  • the Applicant has also found that the photoactivation reaction can also occur by causing the solution of azide compound to flow continuously within the catheter tube. This aspect is particularly advantageous since a continuous process avoids all the drawbacks that are typical of a batch process, in particular in terms of time and costs saving, as well as in terms of uniformity and homogeneity of the treated surface .
  • the catheter tube inner surface is preferably washed in order to remove any impurities from the surface. Typically, after the photoreaction treatment has occurred, the catheter tube inner surface is washed again until all the unbound molecules have been removed. Monitoring of the washing solution is generally carried out by UV.
  • a catheter tube e.g. a guide wire catheter tube, an inflation tube of a balloon catheter or an aspiration tube of a clot extraction catheter - which is modified.
  • a catheter tube e.g. a guide wire catheter tube, an inflation tube of a balloon catheter or an aspiration tube of a clot extraction catheter - which is modified.
  • the light wavelength is comprised within the visible spectra and is selected according to the activating molecule used.
  • the wavelength of maximum absorbance of the substituted arylazide compound is used. For instance, a 254 nm wavelength can be advantageously used since the polymeric materials typically used in the manufacture of catheter tubes are transparent to this light wavelength.
  • composition of the inner surface material of the catheter tube treated according to the method of the present invention may be analysed by XPS ( Pho toelect ron Spectroscopy) or ESCA (Electron Spectroscopy for Chemical Analysis) .
  • XPS Pho toelect ron Spectroscopy
  • ESCA Electron Spectroscopy for Chemical Analysis
  • the title compound was then prepared by solubilising the N- (tris (hydroxymethyl) ) -4- aminobenzenesulphanylamide in an aqueous solution of chloride acid (rate 5:1) and was stirred for 15 min in an ice bath at 0°C. Then, a solution obtained dissolving sodium nitrite in the minimum amount of water (nitrite : aniline rate 1:1) was added dropwise bringing the temperature to -5/-10°C with an ice bath. Then, the reaction was left for 30 min under stirring. The a 3 was solubilised (molar ratio sodium azide : aniline 1:3) into the minimum water amount and then quenched. It was then added dropwise to the solution and was left reacting for 1 hour at room temperature under stirring. A white precipitate formed, which was filtered and re- crystallized with aqueous methanol (1:1 solution) .
  • the title compound was then obtained by solubilising the 4-amino-N- (2-hydroxyethyl) - benzamide into an aqueous solution of chloridic acid (rate 5:1) and was stirred for 15 min in an ice bath at 0°C. Then, a solution obtained dissolving sodium nitrite in the minimum amount of water (nitrite : aniline rate 1:1) was added dropwise bringing the temperature to -5/-10°C with an ice bath. Then, the reaction was left for 30 min under stirring. The a 3 was solubilised (molar ratio sodium azide : aniline 1:3) into the minimum water amount and then quenched.
  • N- (2-hydroxyethyl )-4-nitrobenzenesulphonamide was dissolved in ethanol into a Erlenmeyer flask and Pd/C was added as the catalyst (N- (2-hydroxyethyl) -4- nitrobenzenesulphonamide : Pd/C 5:1 weight ratio).
  • a brownish-yellowish solid was obtained which was re-crystallized in 100% ethyl acetate.
  • a brownish-yellowish crystalline solid of N- (2- hydroxyethyl) -4-aminobenzenesulphonamide was obtained. Melting point: 95°C (literature: 95-97°C)
  • the title compound was prepared solubilising the N- (2- hydroxyethyl) -4-aminobenzenesulphonamide into an aqueous solution of chloridic acid (rate 5:1) and was stirred for 15 min in an ice bath at 0°C.
  • the oil is solubilised into the minimum quantity of cycloesane and is deposited in the column.
  • the first eluted compound (Rf TLC: 0.87) is the white crystalline solid of ethyl-4-nitrobenzoate ; the other three eluted products all are N- (Jeffamine® M-600) -4- nitrobenzamide .
  • N- (Jeffamine® M-600) -4-nitrobenzamide was solubilised in ethanol and Pd/C was added as the catalyst (N- (Jeffamine® M-600) -4-nitrobenzamide : Pd/C 5:1 weight ratio).
  • N-(Jef famine® M- 600 ) -4-aminob e n z a m i d e was solubilised into an aqueous solution of chloridic acid (rate 5:1) and was stirred for 15 min in an ice bath at 0°C. Then, a solution obtained dissolving sodium nitrite in the minimum amount of water (nitrite : aniline rate 1:1) was added dropwise bringing the temperature to -5/-10°C with an ice bath. Then, the reaction was left for 30 min under stirring. The a 3 was solubilised (molar ratio sodium azide : aniline 1:3) into the minimum water amount and then quenched. It was then added dropwise to the solution and was left reacting for 1 hour at room temperature under stirring. Two phases formed by adding chloroform: a yellowish oil was obtained.
  • the solution was placed in darkness to stir overnight.
  • the sample was brought to dry with a Rotavapor and vacuum pump (one night) .
  • the product was a yellow crystalline solid .
  • the solvent used for sample ii) was methanol. This comparative sample was tested in order to evaluate if the solvent is capable of influencing the surface wettability .
  • control sample has been tested three times in three different positions (side, centre, side portions of the sample) .
  • the obtained results show that the azide compounds treatment according to the invention is able to modify the properties of the PA12 surface.
  • the surface treatments with iv, vi and vii decrease the value of contact angle with respect to the comparative samples 1 and 2.
  • the surface treatment with viii increases the value of contact angle with respect to the comparative samples 1 and 2, thereby rendering the PA12 surface more hydrophobic.
  • composition of the surface which underwent photoactivation has further been analysed by ESCA in order to determine the composition of the outer layers of the treated material for 8-10 nm depth and evaluating possible surface modifications.
  • ESCA Perkin Elmer PHI 5400 ESCA System
  • Mg anode X-ray source and a pressure within the analysis chamber of about 10 ⁇ 9 Torr. 1 cm samples were tested immediately after cutting and put into the chamber without any additional treatment.
  • PA12 (theoretical composition) 7.1 85.7 7.1 - -
  • PA12 (measured composition) 13.1 80.0 3.4 - -
  • PA12 UV processed 11.6 82.7 2.2 0.3 -
  • a diluted solution of an azide compound of the present invention into a solvent was prepared.
  • the solvent can be selected from methanol, ethanol, acetone, acetonitrile, chloroform or mixture thereof.
  • the solution was then introduced into a tube having inner diameter of 0.43 mm, external diameter of 0.60 mm and a length of 500 mm.
  • the first is a static method according to which, after the tube has been filled with the above solution, firstly the tube ends are closed (e.g. welded), then the tube is placed into a dark chamber and irradiated for 1 hour with a 254 nm wavelength. The tube ends are successively opened and then the inner tube cavity is washed with water, methanol and acetone until no azide is detected into the wash water. The tube is then left drying in air.
  • the second is a dynamic method according to which one end of the tube guide catheter is connected to a dark recipient containing the alcoholic solution of the azide.
  • the device is placed inside a chamber provided with four lamps irradiating at a wavelength of 254 nm. Irradiation is performed for 1 hour while the alcoholic solution passes through the inside cavity of the tube. The thus treated inner surface is washed with water, methanol and acetone until no photoactivating compound is detected into the wash water. The tube is then left drying in air.
  • An extraction test was carried out in order to evaluate the force necessary for extracting a guide wire from a guide wire tube.
  • the extraction test was performed for evaluating the effect of the modification of the inner surface of a guide wire tube treated according to the present invention.
  • the guide wire tube inner surface was treated according to the teachings of Example 12 (dynamic method) .
  • the guide wire and the guide wire tube were previously wetted with water. Then the guide wire was placed inside the guide wire tube so that the guide wire tip protruded of about 530 mm from the distal end of the guide wire tube. The guide wire tube and the guide wire were then introduced into a device provided with a tortuous path (so as to mimic a tortuous blood vessel) so that the guide wire exited of about 30 mm from the end portion of the tortuous path. The device was then clamped for ensuring blockage thereof. A dynamometer cell load was clamped to the guide wire tip exiting from the device and then the guide wire was extracted for a length of 850 mm at a speed of 60 mm/min. The extraction force was thus recorded.
  • the guide wire tubes had all the following sizes:
  • Guide wire tubes a) , b) and from d) to 1) were made from a single polymeric layer, while only guide wire tube c) was a tri-layered tube.
  • Model 1 SKIPPER guide wire; manufactured by Brivant and commercialized by Invatec S.p.A.; usable length of 950 mm; Tip: floppy J; compliance: 0.014" (0,36 mm);
  • the modification of the inner surface of a PEBAX guide wire tube allows a lower force to be required for extracting the guide wire (Model 2) .
  • the modification with N- (tris (hydroxymethyl) ) -4- azidobenzenesulphonylamide and N- (2-hydroxyethyl) -4- azidobenzenesulphonylamide advantageously leads to a performance which is even better than the performance of the comparative tri-layered guide wire tube.
  • arylazide (1) undergoes loss of molecular nitrogen and transient formation of singlet arylnitrene (2S) .
  • This unstable compound may rapidly react by insertion on hydrocarbons (3) or by internal rearrangement to 1 , 2-azacycloheptatetraene (4).
  • This is an electrondeficient species and it reacts predominantly with nucleophiles (Nu) , forming azepine adducts (5) .
  • Nu nucleophiles
  • Triplet nitrene is essentially a diradical species that is capable of hydrogen-radical abstraction and covalent binding to hydrocarbon substrates (7) .
  • the azepine formation is the major reaction path while only a small part of the singlet arylnitrene (2s) is slowly converted into hydrocarbon substrates (3) or into triplet nitrene (2T) .
  • Example 8 N- (tris (hydroxymethyl) -5-azido-2-nitrobenzoate of Example 9 and N- ( Dodecaethylene glycol monomethyl ether) -5-azido-2-ni trobenzoate of Example 10 have shown to provide good reaction rate and yield.
  • the solvent used for the samples was methanol.
  • a PA12 surface has been immersed in each solution, and the samples have been irradiated with a light wavelength of 254 nm.
  • the disclosed photoactivated polymers can be used for the preparation of medical devices such as, for instance, balloon catheters, stent delivery systems, clot extraction catheters, multipurpose catheters.
  • the inflation time and especially the deflation time of the balloon can be favourably improved (i.e. decreased) .
  • treated inner surface of the present invention a reduced friction between the inflation fluid and the inner surface of the balloon inflation tube is obtained, thereby resulting in a very easy and quick sliding of the inflation fluid along the inflation tube.
  • the disclosed para-substituted arylazide compounds are used in order to modify the properties of a polymeric inner surface of a catheter tube.
  • the catheter tubes produced according to the invention are provided with a hydrophilic inner surface.
  • the inner surface may be rendered either more hydrophilic or more hydrophobic according to the need by changing the nature of the para substitutent in the arylazide compound.
  • the Applicant has found that a catheter tube treated according to the present invention advantageously has a reduced thickness with respect to a tri-layered catheter tube known in the art, without the mechanical resistance of the catheter tube being negatively affected.
  • the method of the invention allows: a) to decrease the outer diameter of the tube (guide wire tube) , thereby increasing the cross-section area dedicated to the passage of the inflation fluid, and/or b) to increase the inner diameter of the tube (guide wire tube) without modifying the outer diameter thereof, thereby providing a larger passageway for the guide wire and reducing the friction risks between the guide wire and the tube (guide wire tube) .
  • the reduced thickness of the tube allows either to reduce the external diameter of the catheter (and thus the radial dimension thereof) or to increase the aspiration area and efficiency without modifying the catheter outer diameter.

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  • Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Abstract

La présente invention concerne un dispositif médical, en particulier un tube de cathéter ou un cathéter à ballonnet pour l'angioplastie, ayant une surface interne améliorée.
PCT/EP2011/056246 2010-04-19 2011-04-19 Matériau polymère photoactivé et son utilisation pour la préparation de dispositifs médicaux Ceased WO2011131677A1 (fr)

Priority Applications (2)

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JP2013505459A JP6005627B2 (ja) 2010-04-19 2011-04-19 光活性化高分子材料及びその医療機器作製への使用
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