CN103814169A - Product for release of active substance - Google Patents

Abstract

A delivery system for an active substance, comprising a substrate on which the substance is loaded for subsequent release,wherein: (i) the substrate has been at least partially coated with a polymer using plasma deposition (preferably pulsed plasma deposition); (ii) the active substance is present as a guest molecule within a cyclodextrin inclusion complex; and (iii)the inclusion complex is bound to the polymer through a chemical linkage formed between a hydroxyl group on the cyclodextrin and a functional group on the polymer. The system may be used to control the release of an active substance such as a perfume. Also provided are methodsfor preparing (a) the delivery system and (b) a functionalised substrate for use as part of the system, in which the polymer is suitably reacted with a cyclodextrin using an S N 2 nucleophilic substitution reaction, in particular a Williamson ether synthesis reaction.

Description

The product discharging for active material

Invention field

The present invention relates to load substrate and preparation and the purposes of active material, and the functionalized substrate of available active material filling.

background of invention

Known by encapsulating active substance control in entity, it discharges, for example micro-capsule of described entity or micella.In this way, can delayed release until cause applicable future, or allow to carry out within the time extending, or controlled in addition.In some cases, the entity of sealing can be fixed on solid substrate.

May need the active material of controlling in this way release to comprise for example medicine and spices.

People's sensory perception general relevant with freshness with the cleannes of the consumer goods [1] of volatile aromatic molecule (or spices).In fact, keep the perfume delivery system of fragrance sensation to receive the concern [2,3] of smart fabric industry through time expand.

For example, in available a lot of differences substitute (, micro-capsule [4], microparticle [5] and polymer micelle [6]), be considered to have very much prospect [7] by Host-guest inclusion complex dynamic release spices.(this comes from affects between the object of rate of release and host molecule strong binding interactions, hydrophobic effect and Van der Waals interact) shortage [8], and send and need embedding in the substrate and physics or chemistry cause from micro-capsule or microparticle---for example, external force, in time degraded or pH change---to impel spices to discharge [9,10].The in the situation that of Host-guest inclusion complex, naturally replace guest molecule to complete spices by other less molecule from surrounding environment (being generally water or little amine) and discharge [11].

Due to its intrinsic cavity geometry, cyclodextrin is particularly well suited to Host-guest inclusion complex and interacts.Their basic structure is made up of cyclic oligosaccharide, the most available have 6,7 or 8 glucopyranose units (be respectively α-, β-, gamma-cyclodextrin).Compound sugar ring forms holder shape or " cylinder " shape, and wherein glucose unit primary hydroxyl presents to narrow end, and secondary hydroxyl is positioned near wider portion [12].Multiple object thing class can form inclusion complex in cylinder cavity, produce the surperficial related application of certain limit, comprise drug delivery control [13,14,15,16], chromatography [17,18] the selective transmission [23 that, fixing [19,20] of reactive chemical, dissolubility improve [21,22], compound, 24] and spices discharge [25,26].

This type of application often needs main body or guest molecule to be fixed on the surface of solids, and wherein important prerequisite is that suitable surface orientation, the guest molecule of cyclodextrin " cylinder " easily enters a cavity and the high density on surface, below is adhered to.Existing trial at the directed supporting course that forms cyclodextrin comprises Langmuir-Bu Luojieta (Langmuir-Blodgett) film [27,28], the self-assembled monolayer of mercaptan cyclodextrine derivatives (SAM) [29 in gold surface, 30,31,32] and Cyclodextrin Chemistry be adsorbed onto [33,34] on Polymer-supported support body.For example, due to its intrinsic complexity (, needing particular solid substrate), relatively low density, intrinsic low surface area and/or the inadequate sense hold facility of adhering to, these methods live through limited success.Therefore, need to be applied to the improved selective release official energy coating of a series of substrates.

Research early shows, by with the epoxy reaction of poly-(glycidyl methacrylate) of pulse plasma deposition, the amine-functionalized variant of-cyclodextrin, 6-amino-6-deoxidation-beta-schardinger dextrin-can successfully be fixed on plasma chemical layer.The cyclodextrin structure obtaining can form Host-guest inclusion complex [35] with cholesterine (bile acid) and DMF.But this process need cyclodextrin molecular is functionalized before it can be attached to polymeric layer.

WO-2010/021973 describes a kind of multilayer controlled release system that can decompose film that comprises on substrate.Film has the polymer layer of at least two different electric charges, and active material can in succession be degraded by polymer and be discharged from these layers in applicable liquid medium.Layer must comprise hydrolyzable electrolyte, also has " polymeric cyclodextrins ", that is, have cyclodextrin skeleton or have the polymer of the Cyclodextrin groups that dangles.Active material is incorporated in cyclodextrin host molecule before deposited polymer layer, and this can limit the technology that can be used for deposited polymer, particularly for responsive active material.Another defect of this system is that active material discharges the degraded that needs related polymer layer, therefore hinders it to use subsequently again.

Le Thuaut etc. (Journal of Applied Polymer Science, the 77th volume: 2118-2125) describe cyclodextrin and are fixed on non-woven polypropylene supporter, for the preparation of " reactive filter ".Their technology comprises glycidyl methacrylate graft is aggregated on carrier, subsequently polymer by epoxy radicals be attached to α-, β-and gamma-cyclodextrin.

The object of this invention is to provide active material (specifically volatile active matter, for example, spices) is loaded into the technology for discharging subsequently on substrate.Object be to provide can overcome or at least relax the problems referred to above and can effective Cyclodextrin inclusion complex as the technology of the main body of active material molecule.

invention statement

According to a first aspect of the invention, provide a kind of delivery system for active material, described system comprises the substrate of filling active material for discharging subsequently on it, wherein:

(i) substrate has used plasma deposition to be aggregated thing coating in its surperficial at least a portion;

(ii) active material is present in Cyclodextrin inclusion complex as guest molecule; And

(iii) by the chemical bond forming between the functional group on hydroxyl and polymer on cyclodextrin, Cyclodextrin inclusion complex is attached to polymer.

Cyclodextrin inclusion complex is adapted at exposing on the surface of polymer coating, and to promote from inclusion complex release of active agent, and polymer is not degraded or removed.

In this article, " delivery system " refers to and is applicable to carry active material and subsequently at desired locations delivery of active substances or active material is delivered to the system of desired locations.

In one embodiment, chemical bond is direct chemical bond,, between the functional group on hydroxyl and the polymer on cyclodextrin, does not comprise connection base, for example methacrylate (for example, glycidyl methacrylate) or vulcabond that is.Select in embodiment a confession, chemical bond is included between the functional group on hydroxyl and the polymer of cyclodextrin and uses applicable coupling part, as described below.

In one embodiment, between the functional group on primary hydroxyl and the polymer on cyclodextrin, form chemical bond.It is adapted at forming between the hydroxyl (particularly primary hydroxyl) on non-derivative cyclodextrin molecular.

In one embodiment, chemical bond is ehter bond.Find, this type of ehter bond can easily form between the alkanisation group on the hydroxyl on cyclodextrin molecular (particularly primary hydroxyl) and polymer molecule by Williamson ether synthetic reaction.This is a kind of S _n2 reactions, for example generally occur in, between alkoxide ion and alkylating agent (, primary alkyl halogen).It can allow cyclodextrin by being fixed on the substrate of polymer-coated with the simple reaction in-situ of polymer.

In addition, because ether synthetic reaction is tended to, at primary hydroxyl, (these are than more nucleophilic of secondary hydroxyl, also there is larger spatial degrees of freedom) occur, therefore, this mode that can contribute to improve its acceptance and discharge guest molecule ability makes cyclodextrin molecular orientation, and wherein the thicker end of each " cylinder " is away from substrate and more accessible surrounding environment.

Can use other form of chemical bond.As an example, can make cyclodextrin hydroxyl and coupling part (for example, succinyl oxide) reaction, then can be further with polymer on the hydroxyl reaction that exists, for example, in the time of the polymer that uses hydroxyl to replace, for example poly-(acrylic acid 2-hydroxy methacrylate).

Other of chemical bond may form comprise ester bond (having acid or anhydride base on polymer) and alkyl or aryl sulfonic acid ester bond (for example having sulfonic acid halide on polymer).

Once be incorporated into polymer by chemical bonded refractory, available active material filling cyclodextrin, to form the Host-guest inclusion complex of known type.In this way, active material (" object " molecule) can capture on substrate, but can discharge from cyclodextrin host molecule according to conventional releasing mechanism subsequently.Such release can easily realize, if particularly cyclodextrin host molecule exposes at the substrate surface of polymer-coated.With cyclodextrin molecular filling active material or from cyclodextrin release of active agent, conventionally do not need depolymerization or removal, as in prior art systems, the system of for example WO-2010/021973.Similarly, once release of active agent, cyclodextrin host molecule just can relatively easily recharge with other active material, thereby system of the present invention can be used again.

Find that the Cyclodextrin inclusion complex generating in this way allows guest molecule to extend and discharges." prolongation discharges " is released in lasting generation in a period of time described in referring to after loading inclusion complex with guest molecule (active material), for example 30 or more days, or 60 or more days, or 70 or 80 or more days, or in some cases 3 or 5 and even 8 or more months.Such release can for example continue maximum 10 months or maximum 9 or 8 or 7 months.As above discuss, discharge generally by generally carrying out compared with little molecular replacement guest molecule from other of surrounding environment.But other releasing pattern is possible, as described in more detail below.

Therefore, the present invention can make from substrate gradually release of active agent become possibility, this can have wide range of application.In fact, the present invention can provide polymer coated on substrate, polymer coated through functionalized, to allow filling and release of active agent subsequently.

In delivery system of the present invention, according to desired use, substrate can be formed by any applicable material (being generally solid).In one embodiment, substrate is selected from textile material (by weaving or non-woven, natural or synthetic fiber are made); Metal; Glass; Pottery; Semiconductor; Cellulosic material; Paper and plate; Wood; Structural polymer, for example polytetrafluoroethylene (PTFE), polyethylene, polypropylene and polystyrene; And combination.In one embodiment, substrate can be textile material (weave or non-woven).It can be any object that active material release coat will be coated to, and comprises self being applicable to and/or adapting to and/or expection is administered to lip-deep thin substrate or the film of another object.

In one embodiment, substrate comprises open architecture, and for example, network of fibers, can be used as the support of the derivative polymer coating of cyclodextrin.

Polymer is coated to substrate by plasma deposition.Plasma (or plasma chemical) deposition process is well known, and (be for example included in exciting media, plasma) deposited monomer (polymer precursor) on inherent substrate, this causes precursor molecule polymerization in the time that they deposit.Plasma activation polymer deposition method extensively proved in the past, referring to, for example J P S Badyal, Chemistry in Britain 37 (2001): 45-46.

Plasma deposition method can be carried out in gas phase, generally lower than under atmospheric pressure, or at liquid monomer or be loaded with in the medium of monomer and carry out, described in WO-03/101621.

In one embodiment, polymer is coated to substrate with pulse plasma deposition process.In one embodiment, with the coating of atomized liquid spraying plasma deposition method, wherein can form equally plasma pulse.

Pulsed discharge can produce the good coating limiting in structure.Mechanically, this makes to open the cycle (being generally microsecond) in short operation cycle, avtive spot (being mainly free radical) result from monomer in electric discharge mutually in, and be also created in the thin polymer film surface of growth.After this, in the case of the damage without any by UV, ion or electronic induction, carry out conventional flowcollector aggregation scheme FlowCollector in whole relatively long (being generally millisecond) the operation cycle cycle of closing.

Use the advantage of (pulse) plasma deposition can comprise the potential applicability to wide region substrate material and geometry, and the sedimentary deposit obtaining is complied with the surface of below well.This technology can provide the direct effective ways that make the surface of solids functionalized, and this is the method for single stage, solvent-free and irrelevant substrate.The inherent reactivity matter of electric discharge can guarantee to be attached to well substrate by the free radical site at generation of interfaces during plasma ignition.In addition, between pulse plasma depositional stage, the level of surface functionality can regulate by article on plasma operation cycle pre-programmed simply.

Past is successfully prepared the sense film of the good restriction that comprises acid anhydride [36], carboxylic acid [37], cyano group [38], epoxy [39], hydroxyl [40], furfuryl group [41], mercaptan [42], amine [43], perfluoroalkyl [44], perfluor methylene [45] and trifluoromethyl [46] with pulse plasma deposition technique; also comprise aldehyde radical [McGettrick, J D; Schofield, W C E; Garrod, R P; Badyal, J P S, Chem Vap Deposition 2009,15:122], halogen [Teare, D O H; Barwick, D C; Schofield, W C E; Garrod, R P; Ward, L J; Badyal, J P S, Langmuir, 2005,21:11425; R P Garrod; L G Harris; W C E Schofield; J McGettrick; L J Ward; D O H Teare; J P S Badyal, Langmuir, 2007,23:689; McGettrick, J D; Crockford, T; Schofield, W C E; Badyal, J P S, Appl Surf Sci, 2009,256:S30], ester group [Teare, D O H; Schofield, W C E Garrod, R P; Badyal, J P S, J Phys Chem B, 2005,109:20923] and pyridine radicals [Bradley, T J; Schofield, W C E; Garrod, R P; Badyal, J P S, Langmuir 2006,22:552; Schofield, W C E; Badyal, J P S, ACS Applied Materials and Interfaces, 2009,1:2763].Pulse plasma deposition official can film other previous example comprise poly-(glycidyl methacrylate), poly-(acrylic acid bromine ethyl ester), poly-(vinyl aniline), poly-(vinyl chloride), poly-(allyl sulfhydrate), poly-(N-acryloyl methyl amimoacetic acid methyl esters), P4VP and poly-(hydroxyethyl methylacrylate).

According to the character of required coating on monomer and substrate, any applicable condition can be used for polymer plasma deposition to substrate.As an example, especially using when pulsed plasma and/or polymer during for polyvinyl polymer, for example, poly-(vinyl benzyl halogen), can use one or more following conditions:

A. pressure is 0.1-1 millibar, or 0.1-0.5 millibar, for example approximately 0.2 millibar.

B. temperature is 5-50 ℃, or 10-30 ℃, for example room temperature (can be about 18-25 ℃, for example approximately 20 ℃).

C. power (or the in the situation that of pulsed plasma, peak power) is 10-70W, or 20-50W, for example about 30-40W.

D. the in the situation that of pulsed plasma, the operation cycle unlatching cycle is 10-200 μ s, or 50-150 μ s, for example approximately 100 μ s.

E. the in the situation that of pulsed plasma, the operation cycle cycle of closing is 0.5-20ms, or 1-10ms, or 1-5ms, for example about 4ms.

F. the in the situation that of pulsed plasma, it is 0.001-0.05 with the ratio in the cycle of closing that operation cycle is opened the cycle, or 0.01-0.05, for example approximately 0.025.

Be coated to the general demonstration of the polymer adhesion strength good to substrate surface of substrate with plasma deposition.The general conduct of polymer of coating evenly conformal coating is formed on the whole region of substrate that is exposed to relevant monomer during deposition process, no matter and substrate geometry or configuration of surface.This polymer generally also shows that the high-level structure of relevant monomer retains, and particularly, in the time that polymer deposits with relatively high flow velocity and/or low average power, for example, can realize with pulse plasma deposition or atomized liquid spraying plasma deposition.

In delivery system of the present invention, the exposed surface that cyclodextrin molecular is adapted at coating is attached to polymer coating.Polymer can single coating form be coated to substrate.Polymer coating can have any applicable thickness.It can for example have 1nm or larger thickness, or 10 or 50nm or larger, or 75 or 100nm or larger, or 0.5 or 1 or 10 μ m or larger in some cases.This thickness can be the highest 100 μ m, or the highest 10 or 1 μ m, or the highest 500 or 200nm.For example, it can be 1nm-100 μ m, or 50-500nm, or 50-200nm, or 75-200nm, or 100-200nm.

Cyclodextrin derived polymer can comprise one or more holes, particularly macropore: in the case, Cyclodextrin inclusion complex can expose at the inner surface in hole.Porous cyclodextrin derived polymer layer can show the porosity gradient reducing to substrate interface from outer surface, to help to improve the mass transfer of guest molecule.Particularly, it can have than in the less hole of outside polymer surfaces being positioned at or approaching substrate-polymer interface place.

Form water-in-oil emulsion by induction in cyclodextrin derived polymer layer, can obtain (greatly) pore structure.Find that this for example, is possible in the case of not needing other emulsion stabilizer (surfactant), as long as overall derived polymer system be amphipathic characteristic (, in conjunction with hydrophilic and hydrophobic entities the two, for example, be connected to the hydrophilic cyclodextrin molecular that dangles of hydrophobic polymer (for example, poly-(vinyl benzyl) polymer)).In fact, in this type systematic, spontaneous emulsification can occur during polymer-cyclodextrin key forms, and can produce poly-HIPE (High Internal Phase Emulsion) structure of macropore, wherein dangle-Cyclodextrin groups is present in hole and both exposed surfaces of outer polymer surface.

In one embodiment, this porous series turnkey is drawn together three layers of graded porous structure, (aperture is generally the nano-porous structure (cyclodextrin cavity) of approximate number μ on m) in conjunction with being supported in poly-HIPE structure for described structure, described poly-HIPE structure and then be fixed on open base sheet rack, for example, there is the network of fibers of spacing between approximately hundreds of μ m fibers.

For this emulsification is occurred, may be necessary to make the polymer coating of deposition to there is certain minimum thickness, for example 150nm or larger.

The ability that forms the derivative porous polymer coating of cyclodextrin of the present invention can be brought remarkable benefit.It can be functionalized by plasma chemical (irrelevant substrate, solvent-free single stage deposition process) Inherent advantage and the spontaneous of beta-schardinger dextrin-derived polymer layer combine without stabilizing agent emulsification.Therefore, existence may be applied to other high surface substrate by this classification macropore to nano-pore structure method.High surface (greatly) pore polymer may be manufactured difficulty and/or costliness.Conventional poly-HIPE by water-in-oil emulsion containing water around matrix polymerization form, this need to be with applicable surfactant-stabilized.On the contrary, the present invention can to being used as, high loading capacity active material be caught and/or the derivative poly-HIPE structure of the cyclodextrin of delivery system provides relatively simple and cheap route.

In the context of the present invention, term " polymer " " also comprise copolymer.According to the present invention, in order to produce required chemical bond, polymer should comprise can with cyclodextrin molecular on hydroxyl (or with the derivative of this group, for example alkoxide ion) reaction substituting group (, functional group, for example acid, aldehyde or alkyl halide).In one embodiment, polymer comprises and can be applicable under condition and the alkanisation group of cyclodextrin hydroxyl or derivatives reaction, for example, and by Williamson ether synthetic reaction.Alkanisation group is applicable to comprising leaving group, and the nucleophile (for example, alkoxide ion) that leaving group can be formed by cyclodextrin hydroxyl replaces.In one embodiment, leaving group is halide, for example chloride.Therefore, polymer can be the polymer of the polymer, particularly chlorination of halogenation.Its alkanisation group is suitably for primary alkyl or aryl-alkyl halide, comprises for example benzyl halide.

In a specific embodiments of the present invention, polymer is the polyvinyl of polyvinyl, particularly halogenation.In one embodiment, polymer is poly-(vinyl benzyl halogen), for example, and poly-(4-vinyl chloride).

In another embodiment, polymer is the polymer that hydroxyl replaces, for example, and the acrylate that hydroxyl replaces, for example, poly-(acrylic acid 2-hydroxy methacrylate).

In one embodiment, on polymer, at least 40% of related functional group be incorporated into cyclodextrin molecular by chemical bonded refractory.In one embodiment, at least 50% such combination of related functional group, or in some cases at least 60%.Compared with using the attainable capacity of the delivery system based on cyclodextrin of prior art, may use the present invention to realize polymer-cyclodextrin relatively high on substrate surface and adhere to density and carry capacity with therefore relative high active material.

Active material can carry for discharging subsequently and can remaining on any material in Cyclodextrin inclusion complex as guest molecule for being desirably on substrate.It can for example comprise and is selected from following material: pharmaceutically active substances (comprising antimicrobial, for example antiseptic or antifungal agent), flavor enhancement, spices, dyestuff, cosmetics and their mixture.In one embodiment, it comprises volatile materials, for example, and spices.

In one embodiment, active material comprises lipophilic substance or has the material of one or more lipophilic substituents.This can help to improve it and absorb in main body cyclodextrin molecular, more discusses in detail as follows.In one embodiment, active material comprises essential oil (also referred to as volatile oil, essential oil or volatile oil (aetherolea)).In one embodiment, it comprises and is selected from following essential oil: lavender, santal, jasmine, rosemary, Xue MingRosma rinus officinalis, lemon, vanilla and their mixture; Or santal, jasmine, rosemary, Xue MingRosma rinus officinalis, vanilla and their mixture; Or santal, rosemary, Xue MingRosma rinus officinalis, vanilla and their mixture; Or jasmine, rosemary, Xue MingRosma rinus officinalis, vanilla and their mixture; Or rosemary, Xue MingRosma rinus officinalis, vanilla and their mixture.

In one embodiment, active material comprises aromatic compounds, that is, and and the compound that comprises one or more virtues (for example, phenyl) ring.

The cyclodextrin using in the present invention can be selected from α-,-and gamma-cyclodextrin and their mixture.In one embodiment, it is-cyclodextrin.

According to second aspect, the invention provides and on it, can load the method for active material for the functionalized substrate that discharges subsequently a kind of preparation, described method comprises:

(i) provide substrate, described substrate has used plasma deposition to be aggregated thing and has applied in its surperficial at least a portion; With

(ii) polymer is reacted with cyclodextrin molecular, to produce chemical bond between the functional group on hydroxyl and polymer on cyclodextrin molecular.

Reaction is applicable to making cyclodextrin molecular to expose on the surface of polymer coating subsequently, and to promote that active material filling enters cyclodextrin molecular and/or active material discharges from cyclodextrin molecular, and polymer is not degraded or removed.

Chemical bond can also be direct chemical bond.It can be ehter bond.It can be formed between the functional group on primary hydroxyl and the polymer on cyclodextrin.

Reactions steps (ii) can be S _n2 nucleophilic substitutions.In one embodiment, it is Williamson ether synthetic reaction.In order to make the hydroxyl on cyclodextrin change into alkoxide ion, this reaction is adapted at carrying out under alkali condition, for example, under alkali exists, for example NaOH or potassium hydroxide or carbonic acid (hydrogen) sodium.Reaction can be carried out in solution, for example, and in the aqueous solution.Applicable solvent, temperature and reaction time and catalyst (if being suitable for) depend on the character of polymer naturally.

In one embodiment, reaction is carried out until at least 40% of related functional group be incorporated into cyclodextrin molecular by chemical bonded refractory on polymer, or at least 50 or 60%.In one embodiment, reaction is carried out until the cyclodextrin molecular that polymer surfaces is connected by chemistry is saturated, or at least 98 or 95 or 90 or 80 or 70% saturated.

The method of a second aspect of the present invention also can be included in reactions steps (ii) before by the polymer-coated substrate that arrives.As mentioned above, this can comprise use pulse plasma deposition process.

Method can be included in after reactions steps (ii) and load cyclodextrin with active material, to produce the Cyclodextrin inclusion complex that is attached to polymer that comprises active material guest molecule.Filling step can be undertaken by any appropriate methodology, for example, by making substrate immerse active material or immersing solution or the dispersion liquid of active material, or rinses polymer coating with active material or its solution or dispersion liquid.Available the method is prepared the delivery system of filling active material according to a first aspect of the invention.

Functionalized substrate can be in a similar manner with (or another kind of) active material filling of amount in addition.Therefore,, once a certain amount of active material discharges from cyclodextrin host molecule, substrate just can be effectively be used how identical active material and/or " recharge " with another kind of active material.

A third aspect of the present invention provides a kind of functionalized substrate, it is as preparing according to a part for the delivery system of first aspect and/or according to the method for second aspect, described substrate has used plasma deposition to be aggregated thing and has applied in its surperficial at least a portion, and wherein polymer is attached to cyclodextrin molecular by the chemical bond (particularly ehter bond) forming between the functional group on hydroxyl and polymer on cyclodextrin.The surface that cyclodextrin molecular is also adapted at polymer coating exposes, and to promote that active material filling enters cyclodextrin molecular and/or active material discharges from cyclodextrin molecular, and polymer is not degraded or removed.

In one embodiment, available this functionalized substrate " is caught " active material from environment.Active material can be caught as the guest molecule in cyclodextrin molecular.This material can be removed from environment, enters in cyclodextrin molecular, and subsequently, if be applicable to, from wherein discharging, after this, functionalized substrate can be used further to catch other active material.

A fourth aspect of the present invention provides a kind of method that the first active material is caught from the first environment that comprises it, described method comprises to first environment introduces functionalized substrate according to a third aspect of the invention we, and allows the first active material to enter cyclodextrin molecular as guest molecule.

Therefore, available the present invention removes active material from the environment that comprises it.

The method of a fourth aspect of the present invention can comprise subsequently and discharges the first active material or its at least a portion from cyclodextrin host molecule.

Can be by any appropriate methodology from cyclodextrin host molecule (, from Cyclodextrin inclusion complex) release of active agent.In one embodiment, active material extraction can be entered to applicable solvent system, for example, by rinse functionalized substrate or delivery system with solvent system.In one embodiment, can be by following release of active agent: in some way to its modification, the modified form of material is not too well suitable for, and (for example, on energy and/or space, being applicable to) is present in cyclodextrin host molecule: the pH of the environment that this modification can for example be exposed to by change active material realizes.In one embodiment, can be by the better competition molecular replacement active material that is suitable for occupying cyclodextrin host molecule: such competition molecule can be for example water, for example, atmospheric water, and can compatibly be less than active material.

(the key factor that support body-object inclusion complex forms (" catching ") relates to heterogeneity, beta-schardinger dextrin-, object and solvent) between thermodynamic interaction, this generation forces guest molecule to come to the net energy driving force of cyclodextrin cavity.If this driving force can be overcome, just can realize release and/or the replacement of guest molecule.For most of guest molecules, (, wherein the pH of surrounding medium is greater than the pK of molecule with the unionized of molecule or neutral form _a) compare, the ionization of molecule or charged form are by the poor combination showing cyclodextrin.

Also can promote active material to discharge from delivery system according to a first aspect of the invention with this releasing mechanism.

Method according to a forth aspect of the invention re-uses functionalized substrate after can being included in and discharging the first active material subsequently, so that the second active material (can be identical or different with the first active material) is caught from the second environment that comprises this second active material.Second environment can be identical or different with first environment.In this way, can use functionalized substrate, and by expecting to re-use any number of times.

According to a fifth aspect of the invention, provide one (for example to prepare active material delivery system, system according to a first aspect of the invention) method, described method comprises active material is loaded into according on the functionalized substrate of the third aspect, to produce the Cyclodextrin inclusion complex that comprises active material that is attached to polymer.Also can " recharge " in this way functionalized substrate or delivery system, as mentioned above.

A sixth aspect of the present invention provides a kind of product, described product by form below or in conjunction with below: (a) according to the delivery system of first aspect, (b) according to the functionalized substrate of the third aspect and/or (c) use according to second, the 4th or the functionalized substrate (optionally loading with active material) prepared of the method for the 5th aspect.Product can be for example clothes, footgear or ornament (comprising jewelry article).It can be utensil (comprising vehicle seat) or upholstery (for example curtain, or wall or floor covering) article.It can be household products, for example, and air freshener or laundry treatment product.It can be beauty treatment or cosmetic product; Wrapping or health product; Or deodorising product, comprise for example shoe-insert, for example shoe-pad.It can be connection with wrapping of piece, for example packaging for foodstuff.It can be the supporting structure for organizational project.Product can be in conjunction with one or more other active materials, for example antimicrobial (comprising antifungal agent), deodorant or anti-perspirant.

In certain embodiments of the invention, active material can load and enter any applicable host molecule, particularly cryptand, for example cyclodextrin.Host molecule can be incorporated into polymer by the chemical bonded refractory forming between the functional group on the functional group on host molecule (particularly hydroxyl) and polymer.Key can be direct chemical bond, and it can be ehter bond.

Available delivery system of the present invention, functionalized substrate or method, for controlling the release of (particularly time delay) active material from substrate.It can be used for environment from comprising active material catches the object of active material.

In the whole explanation and claims of this description, word " comprises " and the variant (for example " comprising (comprising) " and " comprising (comprises) ") of " comprising " and word refers to " including but not limited to ", and does not get rid of other parts, additive, component, integer or step.In addition, singulative comprises plural number, unless context separately has needs: particularly, using when indefinite article, this explanation is interpreted as having expected plural number and odd number, unless context separately has needs.

The preferred feature of each side of the present invention can be described about any other side.Other features of the present invention will be become apparent by following examples.In general, the present invention expands to any new feature or any new combination of open feature in this description (comprising any claims and accompanying drawing).Therefore, feature, integer, characteristic, compound, chemical part or the group described about concrete aspect of the present invention, embodiment or embodiment are interpreted as can be applicable to any other side as herein described, embodiment or embodiment, unless incompatible with it.In addition, unless otherwise mentioned, disclosed any feature can be by replacing for the alternative features of identical or similar object in this article.

Proposing when upper and lower bound for character, for example, for concentration or the temperature of component, also can refer to the number range that the combination of any upper limit and any lower limit limits.

With reference now to following non-limiting example and accompanying drawing, further describe the present invention, wherein:

Fig. 1 illustrates to show method of the present invention;

Fig. 2 is presented at the curve map that polymer surfaces cl concn (x-ray photoelectron spectroscopy) changes with beta-schardinger dextrin-solution concentration after the reacting of surface aggregate thing layer in following examples 1 and beta-schardinger dextrin-solution;

The infrared spectrum of the material using in Fig. 3 and 4 demonstration embodiment 1 and prepare;

Fig. 5 is presented at vanillic aldehyde and is exposed in embodiment 1 quartz crystal microbalance carrying out during the derivative and non-derived polymer layer of the cyclodextrin of preparation and measures;

Fig. 6 shows that the cyclodextrin of preparation from embodiment 1 derives and the vanillic aldehyde rate of release of non-derived polymer layer; And

Fig. 7 is presented in embodiment 2 essential oil filling degree in the derived polymer layer of preparation and at the rate of change between the storage life subsequently.

describe in detail

Fig. 1 scheme

Fig. 1 demonstration, according to the present invention, how-cyclodextrin " cylinder " 1 can be attached to substrate 2 by intermediate polymer layer 3.

First, with for example pulse plasma deposition technique, thin polymer is deposited on substrate.In the case, polymer is poly-(4-vinyl chloride), and it presents the benzyl chloride group 4 dangling on substrate surface.

Then make polymeric layer and-cyclodextrin for example, have lower reaction at alkali (, hydroxide).Alkali makes the primary hydroxyl in-situ transesterification on cyclodextrin change into alkoxide ion, alkoxide ion then with polymer on benzyl chloro experience Williamson ether synthetic reaction, replace chlorine, to form ehter bond, as shown in 5 [47].

Then, for example, with active material (spices) filling fixing cyclodextrin cylinder (not being shown in Fig. 1) thus, for discharging subsequently.

With to utilize in the early time 6-amino-6-deoxidation-beta-schardinger dextrin-cylinder to be attached to poly-(glycidyl methacrylate) of pulse plasma deposition contrary, method permission provided by the invention is the immobilization carrier as active material with unmodified cyclodextrin.

Fig. 1 illustrates to show how cyclodextrin molecular takes the approximate shapes of axially extended holder or hollow frustum of a cone.The ehter bond of the narrow end of molecule by related polymer benzyl is towards polymer surfaces orientation.Guest molecule so just can be accepted and discharge to thicker end, away from surface, better.Therefore, ether synthetic reaction---together with intrinsic space pliability of polymeric layer 3---helps Cyclodextrin inclusion complex suitably directed, and wherein the axle of frustum of a cone is approximately perpendicular to polymer/substrate surface.

In following examples, with the spices filling substrate of preparation as shown in fig. 1.Object-main body between perfume molecules and fixing beta-schardinger dextrin-cylinder interacts and characterizes by infrared spectrum, quartz crystal microbalance (QCM) and people's sensory test, proves that spices is from Cyclodextrin inclusion complex prolongation release.

embodiment 1

1 experiment

Electrodeless cylindrical glass reactor (5cm diameter, the 520cm that surround at faraday cup ³volume, basic pressure 1 × 10 ^-3millibar, leak rate is better than 1.8 × 10 ^-9kg s ^-1) in carry out 4-vinyl chloride (+98%, Aldrich, with several freezing-pump inhales-melts circulatory purification) pulse plasma deposition.Chamber is equipped with gas access, Pi Lani (Pirani) pressure gauge, is connected to the 30L min of liquid cold-trap ^-1secondary rotary pump and the outside copper coil (4mm diameter, 9 circles, from precursor entrance 8-15cm span) that is wound around.All joints do not have lubricant grease.

Make the output impedance compatible portion ionized gas load of 13.56MHz radio frequency (RF) power generator with L-C network.RF power triggers by signal generator, and monitors pulse shape with oscillograph.Before each test, by with detergent wash and in water and propan-2-ol rinsing make reactor chamber clean, oven drying subsequently.And then assembling evacuation system.Further clean and within 30 minutes, form by move air plasma under 0.2 millibar of pressure and 50W power.

Next step, by the silicon of polishing (100) sheet (MEMC Electronics Materials, ultrasonic cleaning in 50/50 propan-2-ol/cyclohexane solvent mixture) or non-woven polypropylene cloth (Corovin GmbH) insertion reactor middle part, and will under the suction of chamber pump, roll back basic pressure.In this stage, before igniting electric discharge, introduce 4-vinyl chloride monomer vapor 5 minutes with 0.2 millibar of pressure.The optimum condition retaining for functional group is corresponding to 40W peak power and 100 μ s operation cycle opening time and 4ms shut-in times.Deposition is carried out 10 minutes, to obtain the layer that 150 ± 5nm is thick.After plasma disappearance, make precursor vapor continue to pass through system 3 minutes again, then will under the suction of chamber, roll back basic pressure.

Poly-(4-vinyl chloride) layer of pulse plasma deposition derives the different beta-cyclodextrin solution (5 – 40 μ M) that need to make to immerse through coated substrates 25 μ M NaOH with the surface of beta-schardinger dextrin-(Fluka Chemicals).This produces the Surface filling density of certain limit.Cultivate after 72 hours in room temperature (approximately 20 ℃), sample is thoroughly thoroughly cleaned in high purity water, ethanol and propan-2-ol, to remove any unconjugated beta-schardinger dextrin-, and the alkoxide groups of any not use is transformed get back to primary alcohol group again.

By soaking the time of maximum 72 hours, prepare the inclusion complex between the derivative beta-schardinger dextrin-in object vanillic aldehyde (3-methoxy-4-hydroxybenzaldehyde, Aldrich) molecule and surface in 75mM ethanol vanillic aldehyde solution.Clean with ethanol and propan-2-ol subsequently, in baking oven, at 35 ℃, be dried 60 minutes subsequently, remove any unconjugated guest molecule.

Nkd-6000 spectrophotometer for measured film thickness (Aquila Instruments Ltd) carries out.Transmissivity-the reflectance curve (350 – 1000nm wave-length coverage) obtaining is fitted in Cauchy (Cauchy) model of the dielectric material that utilizes Lai Wenbai-mark spy (Levenberg-Marquardt) method [48] of revising.On the VG ESCALAB instrument of the hemisphere analyzer that is equipped with polyenergetic Mg K α X-ray source (1253.6eV) and operate with constant analyzer energy model (CAE, by energy=20eV), carrying out the x-ray photoelectron spectroscopy (XPS) of layer analyzes.Suppose Linear Background and equal full width at half maximum (FWHM) (fwhm) Gauss's component peaks [49], minimize software matching XPS core level spectra with Ma Kuate (Marquardt).Use instrumental sensitivity (multiplication) factor of measuring from chemical standard thing C (1s): O (1s): Cl (2p)=1.00:0.45:0.38 to calculate concentration of element.To think to have indicated the layer of free of pinholes on the thickness that exceedes XPS sampling depth (2 – 5nm) to cover [50,51] from below substrate without any Si (2p) signal.

Use is equipped with across 700 – 4000cm ^-1the Perkin-Elmer Spectrum One spectrometer of the cooled with liquid nitrogen MCT detector of wave-number range operation carries out Fourier transform infrared (FTIR) analysis to the layer in each stage of reaction.The angle annex that is set in 66o (Specac Inc) that use has KRS-5 polarizer (it is adapted for and removes s-polarization component) reflects-absorbs (RAIRS) detection.At 4 cm ^-1resolution ratio, through 5000 average all spectrums of scanning.

After object-main body interacts in real time, vanillic aldehyde steam was exposed to quartz crystal detector (Varian 985-7013 type under 0.2 millibar of pressure through 345 seconds, use 5MHz AT to cut quartzy 13mm diameter crystal), detector with poly-(the 4-vinyl chloride) of pulse plasma deposition (with do not have 20 μ M beta-schardinger dextrin-s functionalized both) apply.Expose and this after during 60 seconds, within every 5 seconds, get quality reading.

2. result

2.1 β the surface of-cyclodextrin is fixed

The XPS analysis of poly-(4-vinyl chloride) layer of pulse plasma deposition proves that carbon and chlorine are present in surface (seeing following table 1).After reacting with beta-schardinger dextrin-, there is the appearance at O (1s) peak and follow the decay at Cl (2p) peak.

Table 1 (XPS atomic percentage)

Find, can be by the Surface filling density of the beta-schardinger dextrin-cylinder of change reaction condition control combination.After Fig. 2 is presented at and reacts with beta-schardinger dextrin-at the XPS on polymeric layer surface cl concn (% Cl) function as solution concentration: can see, it is saturated that the beta-schardinger dextrin-solution concentration of 20 μ M and Geng Gao produces surface, and lower dilution obtains sub-individual layer covering.

Table 1 and Fig. 2 show jointly, under higher beta-schardinger dextrin-solution concentration, in deposited polymer layer utilize surperficial cl radical have at least 66% derivative.

Fig. 3 shows the infrared spectrum of obtaining from poly-(4-vinyl chloride) layer of pulse plasma deposition.Trace (a) is corresponding to polymeric layer (P _p=40W; t _open=100 μ s; t _close=4ms; 10 minutes); (b) corresponding to the polymeric layer (P of 20 μ M solution reactions of beta-schardinger dextrin- _p=40W; t _open=100 μ s; t _close=4ms; 10 minutes); (c) corresponding to beta-schardinger dextrin-.

Point out as follows spectrum [53]: 1263cm ^-1halide degree of functionality (CH ₂sway mode, corresponding to CH ₂-Cl), 1446cm ^-1polymer backbone CH ₂scissors stretch, and at 1495cm ^-1and 1603cm ^-1contraposition substituted benzene basic ring stretch.In addition, with precursor comparison, at 1629cm ^-1do not have vinyl double bond to stretch consistent with the monomer that experiences polymerization.

Poly-(4-vinyl chloride) layer of pulse plasma deposition causes at 754cm with the derivative of beta-schardinger dextrin- ^-1, 1045cm ^-1, 1085cm ^-1and 1160cm ^-1occur several new infrared bands [54], these are all relevant to beta-schardinger dextrin-.Notice, after Williamson ether synthetic reaction, at 1263cm ^-1poly-(4-vinyl chloride) CH ₂-Cl absorbance is with respect at 1446cm ^-1polymer backbone peak in intensity significantly decline.Any remaining CH detecting after surface conjunction ₂-Cl group is corresponding to the unreacted CH surperficial ₂-Cl group (for successful combination, not all primary hydroxyls center on beta-schardinger dextrin-cylinder need to be attached to surface), or they are positioned at the lower face region of poly-(4-vinyl chloride) layer of pulse plasma deposition.Via center greatly about 3250cm ^-1broadband, it is also obvious that the O-H relevant to beta-schardinger dextrin-cylinder stretches.

2.2 spices discharges

Fig. 4 shows following infrared spectrum: (a) with the derivative polymeric layer of 20 μ M beta-schardinger dextrin-solution, and (b) vanillic aldehyde, and (c) be exposed to derivative polymeric layer after 75mM vanillic aldehyde solution.

Can see, vanillic aldehyde Host-guest inclusion complex of poly-(4-vinyl chloride) layer formation depositing with the derivative pulse plasma of beta-schardinger dextrin-is created in 1665cm ^-1(aldehyde C=O stretching, extension) and 1587cm ^-1two new remarkable INFRARED ABSORPTION that (phenyl ring C=C stretching, extension) [55] occur, these are the marks that comprise respectively aldehyde and aryl in vanillic aldehyde molecular structure.

Measure the beta-schardinger dextrin-cylinder of real-time tracking surface conjunction with quartz crystal microbalance and catch gas phase vanillic aldehyde molecule.The results are shown in Fig. 5.Trace (a) is exposed to poly-(4-vinyl chloride) layer (P of pulse plasma deposition at vanillic aldehyde _p=40W; t _open=100 μ s; t _close=4ms; 10 minutes) during produce, and trace (b) represents that vanillic aldehyde is exposed to the derivative pulse plasma of 20 μ M beta-schardinger dextrin-s poly-(4-vinyl chloride) layer (P _p=40W; t _open=100 μ s; t _close=4ms; 10 minutes).

The quality that quartz crystal microbalance detects increases fast after surface conjunction beta-schardinger dextrin-cylinder is exposed to vanillic aldehyde, after approximately 55 seconds, reaches capacity.Stop vanillic aldehyde charging, find time subsequently, and produce and decline from the relevant quality reading of beta-schardinger dextrin-cylinder loss vanillic aldehyde molecule under vacuum.Utilize perpendicular to surface alignment to promote the cylinder (referring to Fig. 1) of Host-guest interaction of molecules, available 1.77nm ²beta-schardinger dextrin-surface area occupy-place [56] calculate 5.65 × 10 ¹³individual molecule cm ^-2theoretical monolayer cover level.Quartz crystal microbalance measures approximately 4.54 × 10 ¹³individual vanillic aldehyde molecule cm ^-2, equal about 80% cyclodextrin cylinder surface coverage.Be exposed to for the second time vanillic aldehyde charging and record to such an extent that overall inclusion complex formation ability declines and is less than 2%, thus the beta-schardinger dextrin-of illustration surface anchoring recharge performance.

Use the check experiment demonstration of non-derivative pulse plasma poly-(4-vinyl chloride) layer to interact with the minimum of vanillic aldehyde probe molecule, wherein detect that little quality rises, this quality rises and in the time finding time, loses (trace (a) in Fig. 5).

Use another illustration of daily substrate (non-woven polypropylene cloth) to show; when contrasting non-derivative pulse plasma (poly-4-vinyl chloride) layer relatively time on non-woven polypropylene cloth sample with being coated to, vanillic aldehyde height in time loads horizontal retention rate (detecting by solvent extraction).The results are shown in Fig. 6, Fig. 6 to vanillic aldehyde from have and do not have beta-schardinger dextrin-(CD) functionalized both be deposited on pulse plasma non-woven polypropylene cloth poly-(4-vinyl chloride) layer (P _p=40W; t _open=100 μ s; t _close=4ms; 10 minutes) rate of release mapping.Rate of release detects with the UV-Vis spectroscopic methodology of solvent extract.

Can see from Fig. 6, although initially load quite, the rate of release of control sample (2 weeks latter 82%, 8 week rear 99%) is more faster than beta-schardinger dextrin-functionalized surfaces (2 weeks latter 5%, 8 week rear 35%).

embodiment 2

1 experiment

Inclusion complex between preparation is following: (a) several essential oils of knowing (lavender, santal, jasmine, rosemary, Xue MingRosma rinus officinalis, lemon and vanilla, The Body Shop Co Ltd) and (b) the functionalized pulse plasma deposition poly-(4-vinyl chloride) of 20 μ M beta-schardinger dextrin-s on non-woven polypropylene cloth, as preparation in embodiment 1.Be exposed to relevant oily 75mM ethanolic solution by the cloth that functionalized polymeric is applied and within 72 hours, prepare inclusion complex.Clean with ethanol and propan-2-ol subsequently, be dried 60 minutes at 35 ℃ subsequently, remove any unconjugated guest molecule.Load concentration by following calculating essential oil guest molecule: use ethanol/water (50:50 volume/volume) mixture extraction 12 hours, carry out UV-vis absorption spectrum measurement (the absorption maximum of the essential oil of all researchs) with Fixed Time Interval at 276nm wavelength subsequently.

The fragrance activity of new inclusion complex of filling is assessed by sensory test, and test must be placed in functionalized non-woven polypropylene cloth between the heat insulation of room temperature storage.In order to detect fragrance, smell and hear their (, hearing taste) with fixed intervals.Spices is deposited to the control sample comparison of poly-(4-vinyl chloride) layer from the emission levels of inclusion complex with comprise non-derivative pulse plasma at non-woven polypropylene cloth.Carry out two groups of fragrance news according to single blind experiment condition [52] by several individuals and smell assessment, the wherein fragrance between the each heat insulation of correct identification before assessing by flavor strength.

2 result

The present embodiment further shows robustness and the general applicability of of the present invention-functionalized substrate of cyclodextrin.

Monitored the rate of release of essential oil from non-woven polypropylene cloth through 10 months.The results are shown in Fig. 7, Fig. 7 describes six kinds of oil in the relative filling rate that is deposited on the beta-schardinger dextrin-derived polymer layer in non-woven polypropylene.Essential oil is labeled as: (1) lavender; (2) santal; (3) jasmine; (4) rosemary, Xue MingRosma rinus officinalis; (5) lemon; (6) vanilla.For every kind of oil, the vertical bar of order is corresponding to 0,2,4,6,8 and 10 months storage times in unlimited laboratory (20 ℃).

Can see from Fig. 7, essential oil filling rate reduces in a controlled manner, reaches approximately 81% ± 4% and discharge after 10 months.On the contrary, after control experiment (wherein identical essential oil is loaded on poly-(4-vinyl chloride) layer of non-derivative pulse plasma deposition on non-woven polypropylene cloth) is presented at 2 weeks, approximately 82% ± 6% discharges, and after 2 months, approximately 99% ± 1% discharges.

Table 2 shows the people sensory evaluation result of carrying out with the beta-schardinger dextrin-derived polymer layer of these essential oil fillings.The result of the flavor strength that reflection is sent from test substrate shows to continue smell 240 days (approximately 8 months).

By comparison, contrast after non-derived polymer layer (being also deposited on non-woven polypropylene cloth) is presented at 14 days and there is no fragrance.Beta-schardinger dextrin-derives the degeneration that did not produce people's induction aspect through 280 days subsequently each experimental periods that recharges of sample.

Table 2

The discussion of embodiment 1 and 2

These embodiment show, by forming ehter bond [57] by Williamson ether synthetic reaction, can realize the combination of beta-schardinger dextrin-cylinder to poly-(4-vinyl chloride) surface of pulse plasma deposition.Under NaOH exists, the primary hydroxyl on beta-schardinger dextrin-easily experiences in-situ transesterification and changes into alkoxide groups, and then alkoxide groups can form ehter bond (seeing Fig. 1 and 3) by the nucleophilic displacement of fluorine that comprises Lv center in polymer film.

The high Surface filling density demonstration beta-schardinger dextrin-cylinder of being measured the beta-schardinger dextrin-cylinder of (80% individual layer coverage rate) deduction by quartz crystal microbalance is compatibly orientated had both accepted also to discharge guest molecule.This may be the flexible result in overall intrinsic space of below polymeric linkers layer, and this can make wider surface orientation, forms and maximizes with help agent-object inclusion complex.

Reported for use chemisorbed beta-schardinger dextrin-cylinder previous trial [63] (for example, beta-schardinger dextrin-chemistry is fixed to naturally occurring fabric with bridging agent, bridging agent is triazine radical chlorine, chloropropylene oxide or polybasic carboxylic acid for example), be presented at unsettled spices in the time between 1 month and 6 months and retain [1,5,58].By comparison, find that surface conjunction beta-schardinger dextrin-cylinder of the present invention performance aspect the release of control volatile spice molecule is better, even exceeded 10 months (seeing Fig. 6 and 7).

All essential oils comprise lipophilicity (lard type) alkane fragment [59], and described fragment, as cholesterine (fat binding molecule), can form inclusion complex [60,61] in beta-schardinger dextrin-cavity.The driving force forming towards inclusion complex is that non-polar-nonpolar interaction (between object and cyclodextrin cavity) (for example interacts to high enthalpy polar-nonpolar, at nonpolar cyclodextrin cavity and be initially between the polar water molecules of cyclodextrin internal solvent) replacement [1], this destruction by hydrone and loss cause.Due to hydrone along with the time get involved between object and main body nonpolar-apolar interaction, guest molecule slowly discharges [62] subsequently, thereby causes the volatility of guest molecule.

Active material filling substrate of the present invention, carries cyclodextrin functionalized polymeric (for example those polymer of preparation in embodiment 1 and 2), can have the potential application of wide region.Only as an example, beta-schardinger dextrin-can add sock laying and help perspiration removing, to suppress growth of microorganism and stench [1,5,63]: according to the present invention, cyclodextrin can be supported on substrate, and with spices filling, allows perfume releasing gradually, perspiration removing simultaneously.Other products, for example fabric and the goods of being made up of them, can provide " intelligence " double-unit system spices to discharge in a similar manner, and wherein large object perfume molecules is by smelly little molecular replacement, to help masking stimulus smell.These products can be remained valid the several months, and if necessary, and available spices " recharges " for use more subsequently, for example, and during cleaning process.

In addition, by by the Inherent advantage of functionalized plasma chemical (irrelevant substrate, there is no solvent and low spillage of material) and the ability combination of cyclodextrin cylinder that easily recharges combination, the present invention can control more application that molecule discharges potentiality are being provided for relating in the future.

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Claims (15)

1. for a delivery system for active material, described system comprises the substrate of the described active material of filling for discharging subsequently on it, wherein:

(i) described substrate has used plasma deposition to be aggregated thing coating in its surperficial at least a portion;

(ii) described active material is present in Cyclodextrin inclusion complex as guest molecule; And

(iii) by the chemical bond forming between the functional group on the hydroxyl on described cyclodextrin and described polymer, described Cyclodextrin inclusion complex is attached to described polymer.

2. the delivery system of claim 1, between the functional group on primary hydroxyl and the described polymer of wherein said formation of chemical bond on described cyclodextrin.

3. the delivery system of claim 1 or 2, wherein said chemical bond is ehter bond.

4. the delivery system of any one in aforementioned claim, wherein said polymer is deposited and is coated on described substrate by pulse plasma.

5. the delivery system of any one in aforementioned claim, wherein said polymer comprises alkanisation group, particularly primary alkyl or aryl-alkyl halide, and described alkanisation group can react with cyclodextrin hydroxyl or its nucleophile derivative.

6. the delivery system of any one in aforementioned claim, wherein said active material comprises spices, lipophilic substance or has the material of one or more lipophilic substituents.

7. the delivery system of any one in aforementioned claim, wherein said cyclodextrin is-cyclodextrin.

8. its upper active material that can load of preparation is for the method for the functionalized substrate of release subsequently, and described method comprises:

(i) provide substrate, described substrate has used plasma deposition to be aggregated thing and has applied in its surperficial at least a portion; And

(ii) described polymer is reacted with cyclodextrin, to produce chemical bond between the functional group on the hydroxyl on described cyclodextrin and described polymer.

9. the method for claim 8, wherein reactions steps (ii) is S _n2 nucleophilic substitutions, particularly Williamson ether synthetic reaction.

10. the method for claim 8 or 9, described method be also included in reactions steps (ii) before with plasma deposition by described polymer-coated to described substrate.

11. 1 kinds of functionalized substrates, the method preparation that it is used as part of the delivery system of any one in claim 1 to 7 and/or has used any one according to Claim 8 to 10, described substrate has used plasma deposition to be aggregated thing and has applied in its surperficial at least a portion, and wherein by the chemical bond forming between the functional group on the hydroxyl on described cyclodextrin and described polymer, described polymer scale is incorporated into described cyclodextrin molecular.

12. 1 kinds of methods for the first active material is caught from the first environment that comprises it, described method comprises functionalized substrate from claim 11 to described first environment that introduce, and allows described the first active material to enter cyclodextrin molecular as guest molecule.

Prepare the method for active material delivery system for 13. 1 kinds, described method comprises active material is loaded on the functionalized substrate of claim 11, to produce the Cyclodextrin inclusion complex that comprises active material that is attached to described polymer.

14. 1 kinds of products, described product by form below or in conjunction with below: (a) delivery system of any one in claim 1 to 7, (b) the functionalized substrate of claim 11, and/or (c) the functionalized substrate (being optionally filled with active material) prepared by the method for any one in claim 8 to 10,12 or 13.

In 15. claims 1 to 7, in the functionalized substrate of the delivery system of any one, claim 11 or claim 8 to 10,12 or 13, the method for any one is used for controlling the purposes of (particularly extending) active material from the release of substrate.

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