Sustained release ionic conjugate
Abstract
A METHOD OF SPHERIFICATION OF AN IONIC CONJUGATE OF PROLONGED RELEASE CONTAINING A BIODEGRADABLE POLYMER WITH A FREE CARBOXYL GROUP AND A PHARMACO THAT CONTAINS A FREE AMINO GROUP WHICH IS LINKED IONICALLY BETWEEN IF.
Term
Term ended
Projected expiry passed 22 April 2017, 9.4 years ago.
- Priority
- Filed
- Published
- Projected expiry
- Today
49 claims: 16 independent, 33 dependent
- 1ES 2 200 172 T3 REIVINDICACIONES 1. Un método para producir micropartículas de un conjugado iónico de liberación sostenida que contiene un polímero biodegradable que contiene grupos carboxilo libres y un fármaco que contiene grupos amino libres que están iónicamente unidos los unos a los otros, comprendiendo el método:obtener una primera solución en la que dicho conjugado se disuelve, en la que dicha solución comprende acetona, acetonitrilo, acetato de etilo, tetrahidrofurano o glima (éter dimetílico de etilenglicol);mezclar dicha primera solución con un primer líquido para formar una primera dispersión, en la que dicho primer líquido es miscible con dicha primera solución, y dicho conjugado no es soluble en dicho primer líquido y precipita fuera de dicha primera dispersión;y aislar dicho conjugado de dicha primera dispersión.
- 2Un método de acuerdo con la reivindicación 1, en el que dicha primera solución se añade a dicho primer líquido en forma de gotitas pequeñas.
- 3Un método de acuerdo con la reivindicación 2, en el que dicha primera solución se añade a dicho primer líquido mediante una boquilla de pulverización.
- 4Un método de acuerdo con una cualquiera de las reivindicaciones 1-3, en el que dicho fármaco es un péptido.
- 5Un método de acuerdo con cualquier reivindicación anterior, en el que dicho polímero biodegradable es un poliéster hecho de ácido láctico, ácido ε-caproico, ácido glicólico, carbonato de trimetileno, o p-dioxanona;o uno de sus copolímeros.
- 6Un método de acuerdo con cualquier reivindicación anterior, en el que dicho fármaco es soluble en dicho primer líquido.
- 7Un método de acuerdo con cualquier reivindicación anterior, en el que dicho polímero biodegradable es un poliéster que comprende ácido láctico, o ácido glicólico;o uno de sus copolímeros.
- 8Un método de acuerdo con la reivindicación 7, en el que dicho poliéster contiene además ácido málico, ácido tartárico, ácido cítrico, ácido succícino o ácido glutárico.
- 9Un método de acuerdo con una cualquiera de las reivindicaciones 4-8, en el que dicho péptido es somatostatina o LHRH.
- 10Un método de acuerdo con cualquier reivindicación anterior, en el que dicho primer líquido es alcohol o agua;o una de sus mezclas.
- 11Un método de acuerdo con la reivindicación 10, en el que dicho primer líquido es etanol mantenido entre aproximadamente 0°C y -30°C o alcohol isopropílico mantenido entre aproximadamente 0°C y -70°C.
- 12Un método de acuerdo con cualquier reivindicación anterior, en el que dicha primera solución contiene acetona o acetonitrilo.
- 13Un método de acuerdo con cualquier reivindicación anterior, en el que dicha primera solución se obtiene al:disolver dicho polímero biodegradable en un segundo líquido para formar una segunda solución;disolver dicho fármaco en un tercer líquido para formar una tercera solución, en la que dicho tercer líquido es miscible con dicho primer líquido y dicho segundo líquido;y mezclar dicha segunda solución y dicha tercera solución para formar dicha primera solución, en la que dicha mezcla causa que dicho fármaco se una iónicamente a dicho polímero biodegradable y forme dicho conjugado en dicha primera solución.
- 14Un método de acuerdo con la reivindicación 13, en el que se añade NaOH o KOH a la segunda solución antes de mezclar dicha segunda solución y dicha tercera solución.
- 15Un método de acuerdo con la reivindicación 13 ó 14, en el que dicho segundo líquido es acetona;y dicho tercer líquido es agua o acetona;o una de sus mezclas.
- 16Un método de acuerdo con una cualquiera de las reivindicaciones 1-12, en el que dicha primera solución se obtiene al disolver dicho polímero biodegradable y dicho fármaco en un segundo líquido para formar dicha primera solución, formándose así dicho conjugado en dicha primera solución. ES 2 200 172 T3
- 17Un método de acuerdo con la reivindicación 16, en el que dicho segundo líquido es acetona o una mezcla de acetona y agua.
- 18Un método de acuerdo con la reivindicación 17, en el que dicho polímero biodegradable primero se disuelve en dicho segundo líquido, después se añade una base a dicha segunda solución, y se disuelve dicho fármaco posteriormente en dicho segundo líquido.
- 19Un método de acuerdo con cualquier reivindicación anterior, en el que dicho conjugado se aisla por centrifugación o filtración de dicha primera dispersión.
- 20Un método de acuerdo con la reivindicación 19, en el que dicha primera solución se evapora parcialmente o completamente de dicha primera dispersión antes de aislar dicho conjugado.
- 21Un método de acuerdo con la reivindicación 20, en el que dicho conjugado aislado se mezcla con una solución de manitol acuosa antes de secar al vacío.
- 22Un método para dar forma esférica a un conjugado iónico de liberación sostenida que comprende un polímero biodegradable que contiene grupos carboxilo libres y un fármaco que contiene grupos amino libres que se unen iónicamente los unos a los otros, comprendiendo dicho método:mezclar dicho conjugado con un primer líquido para formar una primera dispersión, en la que dicho conjugado tiene la forma de una micropartícula y no es soluble en dicho primer líquido;calentar dicha primera dispersión a una temperatura mayor que la Tg o la Tm de dicho conjugado;enfriar dicha primera dispersión por debajo de la Tg o la Tm de dicho conjugado;mezclar dicha primera dispersión con un segundo líquido para formar una segunda dispersión, en la que dicho segundo líquido es miscible con dicho primer líquido y dicho conjugado no es soluble en dicho segundo líquido;y aislar dicho conjugado de dicha segunda dispersión.
- 23Un método de acuerdo con la reivindicación 22, en el que dicho conjugado tiene la forma de una microcápsula que tiene un diámetro medio de entre 5 μιη a 200 μιη antes de mezclar con dicho primer líquido y dicha primera dispersión se agita antes de dicho calentamiento o refrigeración.
- 24Un método de acuerdo con la reivindicación 22 ó 23, en el que dicho polímero biodegradable es un poliéster hecho de ácido láctico o ácido glicólico;o uno de sus copolímeros.
- 25Un método de acuerdo con una cualquiera de las reivindicaciones 22-24, en el que dicho fármaco es un péptido.
- 26Un método de acuerdo con una cualquiera de las reivindicaciones 22-25, en el que dicho primer líquido es un aceite y dicho segundo líquido es hexano.
- 27Un método de acuerdo con una cualquiera de las reivindicaciones 22-26, que además comprende:lavar dicho conjugado aislado con dicho segundo líquido;y secar al vacío dicho conjugado lavado.
- 28Un método de acuerdo con la reivindicación 27, en el que dicho conjugado aislado se mezcla con una solución de manitol acuosa antes de secar al vacío.
- 29Un método para dar forma esférica a un conjugado iónico de liberación sostenida que contiene un polímero biodegradable que contiene grupos carboxilo libres y un fármaco que contiene grupos amino libres que están unidos iónicamente los unos a los otros, comprendiendo dicho método:disolver dicho conjugado en un primer líquido para formar una primera solución;agitar dicha primera solución con un segundo líquido para formar una primera dispersión, en la que dicho segundo líquido es inmiscible con dicha primera solución;evaporar dicho primer líquido de dicha primera dispersión para precipitar dicho conjugado de dicha primera dispersión;y aislar dicho conjugado precipitado de dicha primera dispersión. ES 2 200 172 T3
- 30Un método de acuerdo con la reivindicación 29, en el que dicha primera solución se añade a dicho segundo líquido en forma de pequeñas gotitas.
- 31Un método de acuerdo con la reivindicación 29 ó 30, en el que dicho primer líquido es acetonitrilo y dicho segundo líquido es un aceite.
- 32Un método de acuerdo con la reivindicación 31, en el que dicho aceite es aceite de silicona, aceite mineral, aceite de sésamo o un aceite vegetal.
- 33Un método de acuerdo con una cualquiera de las reivindicaciones 29-32, en el que dicho polímero biodegradable es un poliéster que comprende ácido láctico o ácido glicólico;o uno de sus copolímeros.
- 34Un método de acuerdo con una cualquiera de las reivindicaciones 29-33, en el que dicho fármaco es un péptido.
- 35Un método de acuerdo con una cualquiera de las reivindicaciones 29-34, que además comprende lavar dicho conjugado aislado con un tercer líquido que es miscible con dicho segundo líquido y no es un disolvente para dicho conjugado aislado.
- 36Un método de acuerdo con la reivindicación 35, en el que dicho tercer líquido es hexano, heptano u octano.
- 37Un método de acuerdo con una cualquiera de las reivindicaciones 29-36, en el que dicho conjugado aislado se mezcla con una solución de manitol acuosa antes de secar al vacío.
- 38Un método de acuerdo con la reivindicación 8, en el que dicho poliéster comprende ácido láctico, ácido glicólico y ácido tartárico.
- 39Un método de acuerdo con la reivindicación 28, en el que dicho poliéster comprende ácido láctico, ácido glicólico y ácido tartárico.
- 40Un método de acuerdo con la reivindicación 37, en el que dicho poliéster comprende ácido láctico, ácido glicólico y ácido tartárico.
- 41Un polímero biodegradable formado a partir de un monómero seleccionado de ácido láctico, ácido ε-caproico, ácido glicólico, carbonato de trimetileno, p-dioxanona o uno de sus copolímeros y el monómero ácido tartárico.
- 42El polímero biodegradable de acuerdo con la reivindicación 41, que comprende ácido láctico, ácido glicólico y ácido tartárico.
- 43El polímero biodegradable de acuerdo con la reivindicación 42, en el que la relación de ácido láctico a ácido glicólico y a ácido tartárico es de aproximadamente 66 a aproximadamente 33 a aproximadamente 1, repectivamente.
- 44El polímero biodegradable de acuerdo con la reivindicación 42, en el que la relación de ácido láctico a ácido glicólico y a ácido tartárico es de aproximadamente 66 a aproximadamente 32 a aproximadamente 2, repectivamente.
- 45Micropartículas que comprenden un polímero biodegradable de acuerdo con una cualquiera de las reivindicaciones 41-44.
- 46Micropartículas de un conjugado iónico de liberación sostenida que comprenden el polímero biodegradable de acuerdo con una cualquiera de las reivindicaciones 41-44 y un fármaco que contiene uno o más grupos amino libres, en el que el polímero y el fármaco están unidos iónicamente.
- 47Micropartículas de acuerdo con la reivindicación 46, en el que dicho fármaco se selecciona del grupo que consiste en péptido liberador de la hormona del crecimiento, hormona liberadora de la hormona luteinizante, adrenomedulina, hormona del crecimiento, somatostatina, bombesina, péptido liberador de gastrina, calcitonina, bradiquinina, galanina, hormona estimuladora de melanocitos, factor liberador de la hormona del crecimiento, amilina, taquiquininas, secretina, hormona paratiroides, encefalina, endotelina, péptido liberador del gen de la calcitonina, neuromedinas, proteína relacionada con la hormona paratiroides, glucagón, neurotensina, hormona adrenocorticotrófica, péptido YY, péptido liberador de glucagón, péptido intestinal vasoactivo, péptido activador de la adenilato-ciclasa de la glándula pituitaria, motilina, sustancia P, neuropéptido Y, y TSH, y sus análogos y fragmentos.
- 48Micropartículas de acuerdo con la reivindicación 47, en las que dicho fármaco es somatostatina o LHRH o uno de sus análogos o fragmentos. ES 2 200 172 T3
- 49Micropartículas de acuerdo con la reivindicación 48, en las que dicho análogo de somatostatina es D-e-Nal-c [Cys-Tyr-D-Trp-Lys-Val-Cys]-Thr-NH2. NOTA INFORMATIVA:Conforme a la reserva del art. 167.2 del Convenio de Patentes Europeas (CPE) y a la Disposición Transitoria del RD 2424/1986, de 10 de octubre, relativo a la aplicación del Convenio de Patente Europea, las patentes europeas que designen a España y solicitadas antes del 7-10-1992, no producirán ningún efecto en España en la medida en que confieran protección a productos químicos y farmacéuticos como tales. Esta información no prejuzga que la patente esté o no incluida en la mencionada reserva.
Independent claims49
82 paragraphs in 14 sections, as filed
IS 2 200 172 T3
DESCRIPTION
Sustained release ionic conjugate.
Technical field
This invention relates to sustained release drug delivery systems and, in particular, to a method of producing microparticles of a sustained release ionic conjugate.
Background of the technique
Polymeric and biodegradable drug delivery formulations have been developed and used for controlled drug delivery in vivo. See, for example, US Patents No.<sup>you</sup> . 3,773,919 and 4,767,628 and WO-A-9317668. Such biodegradable polymeric formulations are designed to allow an entrapped drug to slowly diffuse through a polymer matrix or coating when the biodegradable polymer is depolymerized.
International Publication No. WO 94/15587 describes ionic molecular conjugates of polyesters and sustained release drugs. Because polyester degradation is a key step in the release process, the surface area of the conjugate particles can govern the drug release profile of the conjugate. Thus, the conjugated particles must be of similar size and shape to ensure that the surface area is minimal and reproducible, for example, as is the case with microspheres.
Description of the invention
In one aspect, this invention shows a method of producing microparticles of a sustained release ionic conjugate containing a biodegradable polymer containing free carboxyl groups (a polyester made of monomers such as lactic acid, ε-caproic acid, glycolic acid, carbonate of trimethylene, or p-dioxanone, or one of its copolymers; the monomers can be optical isomers or racemates) and a drug containing free amino groups (eg, a peptide drug such as somatostatin or LHRH) that is ionically bound to each other. The method includes the steps of (1) obtaining a first solution in which the conjugate dissolves; (2) mixing the first solution (added as small droplets, for example, through a spray nozzle such as an ultrasound spray nozzle, a pneumatic spray nozzle, a rotary sprayer, or a pressure sprayer) with a first liquid to form a first dispersion, wherein the first liquid is miscible with the first solution, and the conjugate is not soluble in the first liquid and precipitates out of the first dispersion; and (3) isolating the conjugate from the first dispersion.
In one embodiment, the drug is soluble in the first liquid, which can be an alcohol (eg, ethanol or isopropyl alcohol), hexane, or water; or one of its mixtures. When ethanol is used as the first liquid, it can be kept between about 0 ° C and -30 ° C when in use. When isopropyl alcohol is used, it can be kept between about 0 ° C and -70 ° C, for example, cooled by the addition of carbon dioxide ice.
The first solution, which can contain acetone, dichloromethane, acetonitrile, ethyl acetate, tetrahydrofuran, or glyme, or one of their mixtures can be obtained by (1) dissolving the biodegradable polymer in a second liquid (for example, acetone, tetrahydrofuran, glycon , ethyl acetate, methyl acetate, acetonitrile, ethyl formate, or glyme; or a mixture thereof) to form a second solution; (2) dissolve the drug in a third liquid (eg, water or acetone; or a mixture thereof) to form a third solution, in which the third liquid is miscible with the first liquid and the second liquid; and (3) mixing the second solution and the third solution to form the first solution, wherein the mixture causes the drug to ionically bind to the biodegradable polymer and form the conjugate in the first solution. The first solution may comprise up to 40% by weight of the conjugate (eg, between 25 and 35 percent by weight of the conjugate). In one example, a base, eg, NaOH or KOH, can be added to the second solution before mixing the second solution and the third solution. The neutralization of the carboxyl groups of the biodegradable polymer with the base facilitates the formation of ionic conjugate.
Alternatively, the first solution is made by dissolving the biodegradable polymer and drug in a second liquid (for example, acetone or a mixture of acetone and water) to form the first solution, whereby the conjugate is formed in the first solution. . According to this method, the biodegradable polymer can first be dissolved in the second liquid, a base is then added to the second solution, and the drug is subsequently dissolved in the second liquid. Also, if desired, the first solution may be partially or completely evaporated from the first dispersion prior to isolation of the conjugate. The suitably treated conjugate can be isolated by centrifugation or filtration of the first dispersion, and the isolated conjugate can be mixed with an aqueous mannitol solution before drying under vacuum (eg, by lyophilization). The isolated conjugate can furthermore be produced in the form of a film or in strips. The isolated conjugate can also be produced in spherical shape to give 5 to 200 µm mean diameter microspheres, for example, as described herein. By "spherical-shaped" or "spherical-shaped" is meant the processing of a microparticle into a sphere-like shape.
In another aspect, this invention shows a method for spherical shaping of an ionic release conjugate.
ES 2 200 172 T3 held as mentioned above. The method includes the steps of (1) mixing the conjugate with a first liquid (for example, an oil such as silicone oil, mineral oil, sesame oil, or a vegetable oil) to form a first dispersion, in which the conjugate is in the form of a microparticle and is not soluble in the first liquid; (2) heating the first dispersion to a temperature greater than the Tg or Tm of the conjugate; (3) cooling the first dispersion below the Tg or Tm of the conjugate; (4) mixing the first dispersion with a second liquid (for example, hexane, heptane, isopropyl myristate, or an alcohol such as ethanol or isopropyl alcohol) to form a second dispersion, in which the second liquid is miscible with the first liquid and the conjugate is not soluble in the second liquid; and (5) isolating the conjugate from the second dispersion. The conjugate may be in the form of a microcapsule with a mean diameter of between 5 µm to 200 µm before mixing with the first liquid, and the first dispersion thus formed is vigorously stirred while heated to aid in the separation of the particles. Once the conjugate has been isolated, it can be washed with the second liquid and then dried under vacuum. Optionally, it can also be mixed with an aqueous mannitol solution before vacuum drying. A third aspect of this invention shows a method of spherical shaping of the sustained release ionic conjugate described above (eg, a microcapsule having a mean diameter of between 5 µm to 200 µm). The method includes the steps of (1) mixing the conjugate in a first liquid (eg, water) to form a first dispersion, wherein the conjugate is in the form of microparticles and the conjugate is not soluble in the first liquid; (2) shake the first dispersion; (3) mixing the stirred dispersion with a second liquid (eg, dichloromethane or chloroform) in such an amount so as to be absorbed by the conjugate, but without solubilizing the conjugate, wherein the second liquid is miscible with the first liquid; (4) evaporating the second liquid from the first dispersion; and (5) isolating the precipitated conjugate from the first dispersion. If necessary, the method may further include the step of adding a surfactant (eg, lecithin, Tween 20, polysorbate, or lauryl sulfate) to the first dispersion to aid stabilization of the first dispersion, and the isolated conjugate can be washed with the first liquid and vacuum drying. Again, the isolated conjugate can be mixed with an aqueous mannitol solution before drying under vacuum.
In a further aspect of this invention, this invention features a method of spherical shaping of the sustained release ionic conjugate described above. The method includes the steps of (1) dissolving the conjugate in a first liquid (eg, acetonitrile) to form a first solution; (2) agitating the first solution with a second liquid (eg, oil) to form a first dispersion, in which the second liquid is immiscible with the first solution; (3) evaporating the first liquid from the first dispersion to precipitate the conjugate from the first dispersion; and (4) isolating the precipitated conjugate from the first dispersion. In the stirring stage, the first solution can be added to the second liquid in the form of small droplets.
The above method may further include the step of washing the isolated conjugate with a third liquid (eg, hexane, heptane, or octane) that is miscible with the second liquid and is not a solvent for the isolated conjugate. If desired, the isolated conjugate can be mixed with an aqueous mannitol solution before drying under vacuum.
The biodegradable polymer in the conjugate described above may contain at least one free carboxyl group (eg, two to ten free carboxyl groups per polymer chain). Examples of carboxylic acid containing biodegradable polymers include polyesters containing lactic acid units, ε-caproic acid, pdioxanone, ε-caprionic acid, substituted and unsubstituted trimethylene carbonate, 1,5-dioxepan-2-one, 1, 4-dioxepan2-one, glycolic acid, alkylene oxylate, cycloalkylene, cycloalkylene oxylate, alkylene succinate, or 3-hydroxy butyrate in optically active forms or as racemates; or copolymers of any of the above. Additional free carboxylic acid groups can be incorporated into the biodegradable polyester by reaction, for example, ring opening polymerization or polycondensation, with polycarboxylic acids such as malic acid, tartaric acid, pamoic acid, citric acid, succinic anhydride, and glutaric anhydride. Thus, the biodegradable polymer can be a water insoluble polyester including lactic acid units with or without glycolic acid units. Other biodegradable polymers such as polyorthoesters, polyorthocarbonates, and polyantals can also be used. The biodegradable polymer can have an average degree of polymerization, for example, average number of monomers per polymer chain, between 10 and 300.
The drug has one or more (eg, one to ten) free amino groups. In one embodiment, the drug is an acid stable peptide. Examples of suitable acid stable peptides include growth hormone releasing peptide (GHRP), luteinizing hormone releasing hormone (LHRH), adrenomedullin, growth hormone, somatostatin, bombesin, gastrin releasing peptide (GRP), calcitonin, bradykinin, galanin, melanocyte stimulating hormone (MSH), growth hormone releasing factor (GRF), amylin, adrenomedullin, tachykinins, secretin, parathyroid hormone (PTH), enkephalin, endothelin, calcitonin gene releasing peptide (CGRP), neuromedins, parathyroid hormone related protein (PTHrP), glucagon, neurotensin, adrenocorticotrophic hormone (ACTH), peptide YY (PYY), glucagon releasing peptide (GLP) , vasoactive intestinal peptide (VIP), pituitary gland adenylate cyclase activating peptide (PACAP), motilin, substance P, neuropeptide Y (NPY), TSH, and their analogs and fragments. The drug can be soluble (eg more concentrated than 0.1 mg / ml; preferably more concentrated than 1.0 mg / ml) in the first liquid.
Other features and advantages of the present invention will be apparent from the detailed description and claims.
IS 2 200 172 T3
The best ways to carry out the invention
Example 1
18.0 g of the 6,000 g / mol 66/32/2 poly (L-lactic-co-glycolic-co-D, L-malic acid), (66% Lactic acid, 32% glycolic acid) were dissolved percent, and 2 percent malic acid; acid number 0.373 milliequivalents / g) in 180 g of acetone (10% by weight copolymer solution). 14.4 ml of aqueous 0.5 N NaOH was added to form the sodium carboxylate of the polymer. 4.28 g of the acetate salt of the Lanreotide peptide were dissolved<sup>®</sup> (Kinerton, Dublin, Ireland; D-Nal-c [Cys-Tyr-D-Trp-Lys-Val-Cys] -Thr-NH2; acetate content = 9.60 weight percent) separately in a mixture of 10 g of acetone and 10 g of deionized water. The amount of peptide dissolved corresponded to the stoichiometric ratio of acid groups of the copolymer (for example, one) and the free amino groups for the peptide (for example, two). The peptide solution was then added dropwise to the copolymer solution, and the resulting solution was stirred for two hours to allow salt exchange and the resulting formation of the polymer / peptide ion conjugate (PPIC).
Example 2
In a temperature controlled jacketed reactor (Schott Glass, AGB, Dublin, Ireland), a two liter bath of deionized water was pre-cooled to 0 ° C and vigorously stirred. The above PPIC solution from Example 1 was then slowly added to the reactor using a Masterflex pump (Bioblock Scientific, Illkvch, France) producing a flow rate of 10-15 ml / min through a silicone tubing fitted with a measuring needle. 19 at its tip. The PPIC solution was fed through the needle which was placed over a 0 ° C water bath. PPIC precipitated in the bath as small, solid particles. The solid particles were then separated from the supernatant by centrifugation (30 minutes at 5000 rpm and 0-5 ° C), washed with fresh deionized water, suspended in water again, centrifuged again, and then lyophilized. The isolated conjugate was filtered through a 100 µm sieve to remove any large particles that were not capable of being injected through a 21 gauge needle. An analysis of the resulting particle sizes is described in Table I.
Example 3
The PPIC solution from Example 1 was also precipitated as described above in Example 2, but a -20 ° C ethanol bath was used instead of a 0 ° C water bath. An analysis of the resulting particle sizes is described in Table I.
Example 4
The PPIC solution from Example 1 was also dispersed at a controlled flow rate of 4 ml / min through a spray nozzle and containing a hollow tip (Bioblock; 50 watts, 20 kHz) in a -10 ° ethanol bath. C in a temperature controlled jacketed reactor. In this spraying procedure, the copolymer solution was released from the probe as a fine mist of small droplets. The small droplets fell into the ethanol bath, causing the deionized water and acetone to drain out of the droplets. Consequently, the copolymer droplets hardened into small, solid particles. The particles were then recovered by centrifugation and lyophilized. An analysis of the resulting particle sizes is represented in Table I. What is meant by Diameter-10 (that is, D 0.1), Diameter-50 (that is, D 0.5), or Diameter-90 (that is, D 0.9) is the smallest diameter that it is greater than 10%, 50%, and 90% of the total particles, respectively. What is meant by specific area is the average specific area of the resulting particles.
TABLE I
<td>Example</td><td>Diameter-10 (μιη)</td><td>Diameter 50 (um)</td><td>Diameter 90 (um)</td><td>Specific area (m<sup>2</sup>/ g)</td>
<td> 2</td><td> 10</td><td> 30</td><td> 62</td><td> 18,64</td>
<td> 3</td><td> 9</td><td> 37</td><td> 89</td><td> 6,42</td>
<td> 4</td><td> 13</td><td> 46</td><td> 95</td><td> 22,61</td>
Example 5
5.0 g of the PPIC described above in Example 4 was dissolved in 20 g of acetone (PPIC concentration 20% by weight). This solution was then sprayed at a flow rate of 4.0 ml / min into 500 ml of ethanol bath at -10 ° C as described in Example 4. After preparation of the PPIC particles in the bath, they were added 500 ml of deionized water to the bath, and the bath was then brought to 0 ° C. The bath was then stirred for 30 minutes, brought to 20 ° C, and stirred for an additional 30 minutes. The PPIC particles were then recovered by filtration and dried under vacuum at room temperature. An analysis of the resulting particles is depicted in Table II.
IS 2 200 172 T3
TABLE II
<td>Example</td><td>Diameter-10 (um)</td><td>Diameter 50 (um)</td><td>Diameter 90 (um)</td><td>Specific area (m<sup>2</sup>/ g)</td>
<td> 4</td><td> 13</td><td> 46</td><td> 95</td><td> 22,61</td>
<td> 5</td><td> 50</td><td> 99</td><td> 180</td><td> 0,11</td>
As shown in Table II, different particle morphologies were obtained. The particles of Example 4 were larger and had a lower specific area. As indicated by scanning electron microscopy, the particles obtained in Example 4 were also more porous, probably due to the frozen water remaining on the particles during precipitation. When the bath dispersion returned to room temperature, the water was thawed and allowed to flow into the ethanol bath, leaving open channels in the microparticles. Consequently, these particles were the generated and most fragile fragments of small size.
Example 6
A PPIC solution described above in Example 5 was sprayed at 2.5 ml / min in 1.5 liters of deionized water at 0 ° C. An analysis of the resulting particle sizes is depicted in Table III.
Example 7
A PPIC solution described above in Example 5 was sprayed at 2.5 ml / min in 1.5 liters of ethanol at -10 ° C. An analysis of the resulting particle sizes is depicted in Table III.
TABLE III
<td>Example</td><td>D 0.1 (um)</td><td>D 0.5 (um)</td><td>D 0.9 (um)</td><td>Specific area (m<sup>2</sup> / g)</td>
<td>N ° 6</td><td> 53,4</td><td> 154,3</td><td> 329,1</td><td>n / a</td>
<td>N ° 7</td><td> 42,4</td><td> 87,2</td><td> 170,1</td><td> 0,20</td>
Example 8
Two PPIC solutions were prepared in acetone as described above in Example 5. The first solution had a PPIC concentration of 15% while the second solution had a PPIC concentration of 20%. The solutions were sprayed in an ethanol bath at -10 ° C at flow rates of 2.5, 3.5, and 5.0 ml / min as described in Example 5. A resulting particle size analysis is depicted in Table IV.
TABLE IV
<td>Concentration</td><td>Feed rate (ml / min)</td><td>D 0.1 (um)</td><td>D 0.5 (um)</td><td>D 0.9 (um)</td><td>Specific area (m<sup>2</sup>/ g)</td>
<td> 15%</td><td> 2,5</td><td> 35,9</td><td> 81,6</td><td> 191,1</td><td> 4,455</td>
<td> 15%</td><td> 3,5</td><td> 34,4</td><td> 80,2</td><td> 188,3</td><td> 8,336</td>
<td> 15%</td><td> 5,0</td><td> 49,4</td><td> 163,6</td><td> 397,8</td><td>n / a</td>
<td> 20%</td><td> 2,5</td><td> 33,3</td><td> 73,8</td><td> 145,6</td><td> 0,199</td>
<td> 20%</td><td> 3,5</td><td> 50,8</td><td> 112,7</td><td> 241,9</td><td> 0,579</td>
<td> 20%</td><td> 5,0</td><td> 108,3</td><td> 219,1</td><td> 395,9</td><td>n / a</td>
Analysis of the particles using the scanning electron microscope revealed that the particle size and specific area increased with increasing feed rate.
IS 2 200 172 T3
Example 9
5.0 g of PPIC microparticles from Example 4 were dissolved in 45 g of acetone (concentration 10% by weight). The solution was then added dropwise into 500 ml of hexane stirred vigorously at room temperature. The n-hexane solution became cloudy when the PPIC particles precipitated. The PPIC was removed by filtration and dried under vacuum at room temperature.
Example 10
In a jacketed reactor, 3.0 g of the PPIC microparticles described in Example 2 were dispersed into 250 ml of vigorously stirred 12,500 cs medical grade silicone oil (Dow Coming, Midlan, Mich.) (1% by weight of PPIC). After stirring, the mixture was then heated to 120 ° C, which is earlier than the Tg of 55 ° C for PPIC, and held at this temperature for 30 minutes. During this heating, the isolated individual particles melted to form spherical droplets. The dispersion was then cooled to 20 ° C and then diluted with 1,250 ml of hexane. The microspheres were subsequently hardened, recovered by filtration, washed with fresh hexane, and finally dried under vacuum. The characteristics of the microspheres obtained are described in Table V. The final microspheres had a small diameter compared to those of Example 2 as a consequence of compaction of the particles during melting.
TABLE V
<td>Example</td><td>D 0.1 ίμηη</td><td>D 0.5 (um)</td><td>D 0.9 (um)</td><td>Specific area (m<sup>2</sup>/ g)</td>
<td> 2</td><td> 10</td><td> 30</td><td> 62</td><td> 18,64</td>
<td> 7</td><td> 2</td><td> 10</td><td> 47</td><td> <0,33</td>
Example 11
0.2 g of the PPIC microparticles described in Example 2 were dispersed in 5 ml of deionized water and stirred vigorously with a vortex mixer. Then 100 microliters of dichloromethane (DCM) was added to the stirred dispersion. The addition of a small amount of DCM caused swelling of the surface of the PPIC particles. Stirring was maintained at room temperature for 4 hours, allowing evaporation of DCM and consequent hardening of the swollen surface of the particles. A scanning electron microscope showed that the resulting particles were spherical in shape with a smoother surface compared to the starting material. As a consequence of the increased particle density the particle size distribution narrowed and the maximum particle size was reduced.
Example 12
One liter of sesame seed oil (Vitamins, Inc., Chicago, IL.) Was placed in a 2 liter three-necked bottle immersed in a water bath. The oil was stirred at 600 rpm using a Teflon stirring paddle.<sup>®</sup> coupled with a high agitation motor. 500 mg of the surfactant, soy lecithin, (Sigma Chemicals, St. Louis, MO.) Was added to the sesame seed oil, and the mixture was stirred for 10 minutes. Then 10 g of a PPIC formulation was dissolved in 100 ml of acetonitrile to give a clear solution. PPIC compositions were made using Lanreotide<sup>®</sup> conjugated to one of the following three polymers: poly-DL-lactic-coglycolic acid-D copolymer, L-malic 64/34/2 (mean MW 6,000) (Composition 1); 74/24/2 poly-DL-lactic-co-glycolic D, L-malic acid copolymer (mean MW 6,000) (Composition 2); and 98/2 poly-DL-lactic acid-co-D, L-malic acid copolymer (Composition 3).
This clear PPIC solution was added dropwise through an addition funnel. When the addition was complete, the temperature of the external water bath was increased to 40 ° C, and the oil was stirred for 20 h. One liter of hexane was then added to dilute the sesame seed oil, and the oil was filtered through a medium porous funnel. The collected microspheres in the filter funnel were further washed several times with 500 ml in total volume of hexane. The particles were dried at 36 ° C for two days under vacuum. The characteristics of the resulting microspheres are presented in Table VI.
IS 2 200 172 T3
TABLE VI
<td>Composition</td><td>D 0.1 (um)</td><td>D 0.5 (um)</td><td>D 0.9 (um)</td><td>Specific area (m<sup>2</sup>/ g)</td>
<td> 1</td><td> 13</td><td> 28</td><td> 57</td><td> 0,1426</td>
<td> 2</td><td> 13</td><td> 25</td><td> 59</td><td> 0,1395</td>
<td> 3</td><td> 14</td><td> 25</td><td> 51</td><td> 0,1480</td>
Example 13
The reactor was charged with glycolide monomers (Purac Biochem, The Netherlands, 84.83 g), lactide (Purac Biochem, The Netherlands, 210.67 g) and L (+) - tartaric acid (Riedel-de Haen, Seelze, Germany , product number 33,801, 4.50
g) and stannous 2-ethylhexanoate (Sigma, St. Louis, Missouri, USA, product number S-3252) in a solution (0.1025 M, 4.34 ml) of toluene (Riedel-de Haen, Seelze, Germany). The L (+) - tartaric acid was pre-dried over phosphorous pentoxide (Riedel-de Haen, Seelze, Germany) in an Abderhalden dryer for 10 hours. The reactor (connected for pumping via a liquid nitrogen trap) was then placed under vacuum (0.04 mbar, 4 Pa) with stirring for 50 minutes to remove toluene. The reactor, under an atmosphere of oxygen-free nitrogen (BOC gases, Dublin, Ireland, 8 VPM moisture content), was then immersed in an oil bath (Temperature = 200 ° C) and stirring was increased to 125 rpm. Before diving, a heating tape (type 45500 Thermolyne<sup>®</sup>, inlet control setting = 4) was placed on the lid of the reactor. The time it took for the reactor contents to completely melt was noted, typically 10 minutes for a load of 300 g at 200 ° C. The samples were taken every hour during the synthesis and analyzed by GPC to determine the percentage of residual monomer and obtain values of the average molecular weight in number (Mn) and in weight (Mw). Typical reaction times are on the order of 6 hours.
An amorphous copolymer was obtained comprising 66.21% lactide units, 33.11% glycolide units, and 0.68% tartaric acid units (66/33/1 PLGTA). The acid number of the titration was determined as 0.303 milliequivalents / g (mequ./g; the normality of NaOH multiplied by the volume of the NaOH solution required to neutralize one gram of polyester). The number average molecular weight of the copolymer had a value of 10,250, the weight average molecular weight of the copolymer was 11,910 giving a Mw / Mn value of 1.16.
41.32 g of the above 10,000 g / mol poly-L-lactic-co-glycolic-co-L (+) - tartaric acid copolymer 66/32/2 (acid number = 0.303 meq / g) was dissolved in 165.52 g of acetone (Riedel-de Haen, Seelze, Germany) by sonication in a Branson sonication bath (Branson, Danbury, Connecticut, USA) to give a solution with a concentration of 19.98% by weight by PLGTA.
To this solution, 37.6 ml of 0.2N sodium carbonate (Aldrich, Gillingham, Dorset, UK) was added thus providing a 1.2-fold excess of sodium over the carboxyl groups of the copolymer. The solution was allowed to stir for 30 minutes to aid sodium salt formation. It was then fed to a spray nozzle at 8.0 ml / min using a Masterflex pump.<sup>®</sup> (Cole Parmer, Barrington, Illinois, USA). The solution was sprayed into a 6 L jacketed reactor containing 2 L of deionized water cooled to 2.5 ° C using a circulating bath (Huber, Offenburg, Germany). This water was stirred at 350 rpm using a 4 blade paddle attached to a stirrer motor.
After spraying was complete, the dispersion was placed in 6 centrifuge bottles and spun at 5000 rpm for 30 minutes in a Sorvall centrifuge (DuPont Sorvall<sup>®</sup> Products, Wilmington, Delaware, USA). The resulting spin-settled cakes were resuspended in deionized water and spun again. The supernatant was discarded and the cakes were frozen in a freezer overnight before being dried in a small scale freeze dryer (Edwards, Crawley, West Sussex, UK) the next day. 33.16 g of the washed copolymer were recovered representing a yield of 80.24%.
4.92 g of the poly-L-lactic acid-co-glycolic-co-D, L-tartaric copolymer 66/33/1 of 10,000 g / mol above (66 percent L-lactic acid, 33 percent) was dissolved percent glycolic acid, and 1 percent tartaric acid) in 11.58 g acetonitrile (Ridel-de Haen, Seelze, Germany; HPLC grade) by sonication in a Branson sonication bath<sup>®</sup> (Branson, Danbury, CT, USA) and stirred on a stir plate resulting in a solution with a concentration of 29.82% by weight of PLGTA.
This copolymer / acetonitrile solution was fed into a glass reservoir through a spray nozzle using a rotary piston pump from FMI (FMI, Oyster Bay, New York, USA) set at 2.0 ml / min. . The power output of the sprayer was set at 50 W with 80% amplitude. The solution was sprayed into a 6 L jacketed reactor containing 1.5 L of the general isopropyl alcohol reagent (Labscan, Dublin, Ireland), cooled to -70 ° C by solid CO2 pellets (AIG, Dublin, Ireland), and stirred at 300 rpm with a 4 blade paddle attached to a stirrer motor. The temperature of the isopropyl alcohol remained at or near -70 ° C throughout the spray which lasted approximately 8 minutes.
IS 2 200 172 T3
After the spraying was complete, the dispersion was allowed to warm to 10 ° C by itself over a period of 5.5 hours. It was then filtered on Whatman® No. 1 filter paper (9 cm diameter) with the aid of vacuum. The filter paper and cake were placed in a desiccator with silica gel drying beads and evacuated by an automatic cooling trap at -110 ° C. After 24 hours, 4.24 g of the material was recovered. An analysis of the resulting particles is depicted in Table VII.
TABLE VII
<td>Example</td><td>D 0.1 (um)</td><td>D 0.5 (um)</td><td>D 0.9 (um)</td><td>Specific area (m<sup>2</sup>/ g)</td>
<td> 13</td><td> 31</td><td> 68</td><td> 139</td><td> 0,16</td>
Contents14
54 members in 29 offices
Priority claims2
| Document | Office | Kind | Date |
|---|---|---|---|
| 19960000308 | Ireland | – | |
| 960308 | Ireland | A |
Members54
| Document | Office | Kind | |
|---|---|---|---|
| CA2252826A1 | Canada | A1 | |
| WO9739738A2 | World Intellectual Property Organization (WIPO) | A2 | |
| IE960308A1 | Ireland | A1 | |
| AU2575197A | Australia | A | |
| WO9739738A3 | World Intellectual Property Organization (WIPO) | A3 | |
| IS4869A | Iceland | A | |
| NO984924D0 | Norway | D0 | |
| NO984924L | Norway | L | |
| TR199802125T2 | Türkiye | T2 | |
| CZ329998A3 | Czechia | A3 | |
| SK145598A3 | Slovakia | A3 | |
| PL329606A1 | Poland | A1 | |
| EP0904062A2 | European Patent Office (EPO) | A2 | |
| EE9800349A | Estonia | A | |
| CN1216465A | China | A | |
| JPH11508609A | Japan | A | |
| IL126619D0 | Israel | D0 | |
| BG102947A | Bulgaria | A | |
| YU46598A | Yugoslavia, later Serbia and Montenegro (until 2006) | A | |
| BR9708818A | Brazil | A | |
| HK1018748A1 | Hong Kong, China | A1 | |
| KR20000010621A | Republic of Korea | A | |
| NZ332893A | New Zealand | A | |
| HU0000122A2 | Hungary | A2 | |
| HUP0000122A2 | Hungary | A2 | |
| AU721433B2 | Australia | B2 | |
| HU0000122A3 | Hungary | A3 | |
| HUP0000122A3 | Hungary | A3 | |
| RU2173137C2 | Russian Federation | C2 | |
| US2002041893A1 | United States of America | A1 | |
| JP2003026606A | Japan | A | |
| JP3390177B2 | Japan | B2 | |
| EP0904062B1 | European Patent Office (EPO) | B1 | |
| IL126619A | Israel | A | |
| AT245970T | Austria | T | |
| ATE245970T1 | Austria | T1 | |
| DE69723833D1 | Germany | D1 | |
| DK0904062T3 | Denmark | T3 | |
| PT904062E | Portugal | E | |
| IL155756D0 | Israel | D0 | |
| ES2200172T3This record | Spain | T3 | |
| DE69723833T2 | Germany | T2 | |
| CZ293822B6 | Czechia | B6 | |
| CZ293965B6 | Czechia | B6 | |
| CN1186012C | China | C | |
| PL188517B1 | Poland | B1 | |
| US2005074492A1 | United States of America | A1 | |
| HU224036B1 | Hungary | B1 | |
| CN1626243A | China | A | |
| US6911218B2 | United States of America | B2 | |
| PL189319B1 | Poland | B1 | |
| US7026431B2 | United States of America | B2 | |
| US2006121120A1 | United States of America | A1 | |
| US7179490B2 | United States of America | B2 |
Numbers
- Publication
- 2200172
- Application
- 97917391
Titles2
- Spanish
- CONJUGADO IONICO DE LIBERACION SOSTENIDA.
- English
- IONIC CONJUGATE OF SUSTAINED LIBERATION.
Classification
- CPC, 11
- A61K9/1641
- A61K9/16
- A61K9/1647
- A61K9/167
- A61K9/1694
- A61K38/31
- A61K38/08
- A61K47/593
- A61K47/6927
- Y10T428/2985
- A61K47/50
- IPC, 9
- A61K47 34
- A61K9 14
- A61K9 16
- A61K9 26
- A61K9 52
- A61K38 00
- A61K38 08
- A61K38 22
- A61K47 48