CA2339271A1 - Device for photoactivated production of singlet oxygen and method for the production of the device - Google Patents
Device for photoactivated production of singlet oxygen and method for the production of the device Download PDFInfo
- Publication number
- CA2339271A1 CA2339271A1 CA002339271A CA2339271A CA2339271A1 CA 2339271 A1 CA2339271 A1 CA 2339271A1 CA 002339271 A CA002339271 A CA 002339271A CA 2339271 A CA2339271 A CA 2339271A CA 2339271 A1 CA2339271 A1 CA 2339271A1
- Authority
- CA
- Canada
- Prior art keywords
- formed body
- photosensitiser
- production
- granulate
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Medicines Containing Plant Substances (AREA)
- Materials For Medical Uses (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Peptides Or Proteins (AREA)
- Separation By Low-Temperature Treatments (AREA)
- Meat, Egg Or Seafood Products (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
Abstract
The invention pertains to a device for the production of singlet oxygen. At least one photosensitizer is mixed with at least one polymeric or monomeric material. Subsequently, a shaped body that may be used in the production of singlet oxygen is produced from said mixture.
Description
Device for photoactivated production of ringlet oxygen and method for manufacture of the det~tce The invention concerns a device for production of ringlet oxygen anal a method for manufacture of the device.
Oxygen exists in the normal state as a triplet molecule and can be converted, by supplying energy, into the activated ringlet state. Activated ringlet oxygen is particularly reactive and is used for example in chemical process engineering, i_n. medicine and in water treatment.
Up till now, ringlet oxygen has been produced either by means of chemical reactions or by means of irradiation of a photosensitive layer, which is situated in contact with air or pure oxygen. By quenching the fluorescence, the triplet oxygen molecules are transferred into the acaivated ringlet state via a radiatioxzless transition. Since ringlet oxygen has oxzly a very short life-span in solution, it it generally brought to the place of use in the gaseous state.
When producing ringlet oxygen with the aid of photosensitisers it is disadvantageous that a series of photosensitisers are unsuitable as coating matex-ial.. One of these photosensitisers which is unsuitable as coating material is for example copper(II~phthalocyanine. This dyestuff is insoluble in. water and hence difficult for the body to absorb. Therefore this dyestuff is particularly suitable for medicinal applications such as for example in inhalation apparatus for ringlet oxygen. Up till now, copper(II)phthaloc,yanine and a series of further photosensitisers have however hardly been used for the photoactivated production of ringlet oxygen for reasons of their costly processing.
Proceeding from these problems, the object of tlse invention is to indicate a device which permits the photoactivated production of ringlet oxygen without requiring to fall back upon a coating method for the preparation of the photosensitiser. Fu,rtb.ermore, the object is to indicate a method for the manufacture of such a device.
Oxygen exists in the normal state as a triplet molecule and can be converted, by supplying energy, into the activated ringlet state. Activated ringlet oxygen is particularly reactive and is used for example in chemical process engineering, i_n. medicine and in water treatment.
Up till now, ringlet oxygen has been produced either by means of chemical reactions or by means of irradiation of a photosensitive layer, which is situated in contact with air or pure oxygen. By quenching the fluorescence, the triplet oxygen molecules are transferred into the acaivated ringlet state via a radiatioxzless transition. Since ringlet oxygen has oxzly a very short life-span in solution, it it generally brought to the place of use in the gaseous state.
When producing ringlet oxygen with the aid of photosensitisers it is disadvantageous that a series of photosensitisers are unsuitable as coating matex-ial.. One of these photosensitisers which is unsuitable as coating material is for example copper(II~phthalocyanine. This dyestuff is insoluble in. water and hence difficult for the body to absorb. Therefore this dyestuff is particularly suitable for medicinal applications such as for example in inhalation apparatus for ringlet oxygen. Up till now, copper(II)phthaloc,yanine and a series of further photosensitisers have however hardly been used for the photoactivated production of ringlet oxygen for reasons of their costly processing.
Proceeding from these problems, the object of tlse invention is to indicate a device which permits the photoactivated production of ringlet oxygen without requiring to fall back upon a coating method for the preparation of the photosensitiser. Fu,rtb.ermore, the object is to indicate a method for the manufacture of such a device.
This object is achieved by a device according to claim. 1 and a method according to claim 8. The sub-clams concern preferred and advantageous embodiments of the invention.
According to the invention, it is proposed to mix one or more photosensitxsers with one or more polymer or monomer materials ~u~.d to manufacture a formed body of arbitrary geometry from the mixture. The i:ormed body then contains at least one photosensitises embedded in a polymer matrix which comprises the polymer material. or the polymerised monomer material. Triplet oxygen is able to come into contact with the photosensitises on 2ua. exterior or interior surface of the formed body and, by means of photoactivation, be activated to singlet oxygen.
In this m~mner, photosensitisers which cannot, or only with difficulty, be applied with the coating method can also be immobilised and used for the photoactivated production of ringlet oxygen. The device according to the invention is however not restricted to photosens:itisers of the type which are unsuitable as a coating material.. Rather, any ph~otosensitisers can be used in this manner for the production of ringlet oxygen.
In. many cases it is advantageous to subject at least one part of a surface of the formed body to a mechanical or chemical surface; treatment. In this way, the portion of the photosensitises which is exposed on the formed body surfaces can be increased. In. addition, the photosensitises can be exposed in this manner if first only matrix material. is disposed on the formed body surfaces due to the mutual wetting behaviour of the photosensitises and matrix material after the manufacture of the formed body. In. every case, the surface treatment (for example roughening by means of grinding, sand blasting, cutting, etching, dissolving etc.) effects an increase in the production of ringlet oxygen.
A further increase in production of ringlet oxygen can be achieved if polymer materials which have a high oxygen permeation are used as matrix.
According to the invention, it is proposed to mix one or more photosensitxsers with one or more polymer or monomer materials ~u~.d to manufacture a formed body of arbitrary geometry from the mixture. The i:ormed body then contains at least one photosensitises embedded in a polymer matrix which comprises the polymer material. or the polymerised monomer material. Triplet oxygen is able to come into contact with the photosensitises on 2ua. exterior or interior surface of the formed body and, by means of photoactivation, be activated to singlet oxygen.
In this m~mner, photosensitisers which cannot, or only with difficulty, be applied with the coating method can also be immobilised and used for the photoactivated production of ringlet oxygen. The device according to the invention is however not restricted to photosens:itisers of the type which are unsuitable as a coating material.. Rather, any ph~otosensitisers can be used in this manner for the production of ringlet oxygen.
In. many cases it is advantageous to subject at least one part of a surface of the formed body to a mechanical or chemical surface; treatment. In this way, the portion of the photosensitises which is exposed on the formed body surfaces can be increased. In. addition, the photosensitises can be exposed in this manner if first only matrix material. is disposed on the formed body surfaces due to the mutual wetting behaviour of the photosensitises and matrix material after the manufacture of the formed body. In. every case, the surface treatment (for example roughening by means of grinding, sand blasting, cutting, etching, dissolving etc.) effects an increase in the production of ringlet oxygen.
A further increase in production of ringlet oxygen can be achieved if polymer materials which have a high oxygen permeation are used as matrix.
Advantageously, there can be added to the mixture a substance which can be washed out again after the manufacture of the formed body. Because of the interior surfaces in the form of pores which arise by means of the crashing-out, the active surface can furthermore be increased and/ or a porous formed body can be manufactured, which permits the through-~Low of fluid or gaseous media.
The formed body surfaces according to the invention have a high chemical resistance, which permits the use of the device according to the invention in medical technology (for example in endoscopy), in water treatment and in chemical process engineering. Use of the device in fluids is possible.
Further details and advantages of the invention are apparent from the subsequent description of embodiments, given by «ay of example.
According to a first embodiment, a photosensitiser such as copper(II)phthalocyanin.e can be embedded in a matrix made of fluorinated hydrocarbons. To this is mixed the photosensitiser with PTFE granulate and the mixture is then pressed. The proportion of the photosensitiser in the formed body is preferably less than 50% by weight and particularly preferred less than 10% by weight. Subsequent to the pressing, a temperature-controlled sinter process is carried out in order to manufacture a formed body which can be mechanically processed. In. the scope of the sinter process, the pressed mixture is slowly heated over a few days to temperatures of over 300 °C and preferably to a peak temperature of 380 °C. Thereafter, the sintered formed body is again left to slowly cool. Finally, the formed body is subjected to a mechanical surface processing.
Surprisingly, it was found that formed bodies produced in this way and containing copper(II)phthalocyanin.e for the production of singlet oxygen have an extremely high thermal stability up to 300 °C, without the onset of a thermal degradation of the photosensitiser.
The formed body surfaces according to the invention have a high chemical resistance, which permits the use of the device according to the invention in medical technology (for example in endoscopy), in water treatment and in chemical process engineering. Use of the device in fluids is possible.
Further details and advantages of the invention are apparent from the subsequent description of embodiments, given by «ay of example.
According to a first embodiment, a photosensitiser such as copper(II)phthalocyanin.e can be embedded in a matrix made of fluorinated hydrocarbons. To this is mixed the photosensitiser with PTFE granulate and the mixture is then pressed. The proportion of the photosensitiser in the formed body is preferably less than 50% by weight and particularly preferred less than 10% by weight. Subsequent to the pressing, a temperature-controlled sinter process is carried out in order to manufacture a formed body which can be mechanically processed. In. the scope of the sinter process, the pressed mixture is slowly heated over a few days to temperatures of over 300 °C and preferably to a peak temperature of 380 °C. Thereafter, the sintered formed body is again left to slowly cool. Finally, the formed body is subjected to a mechanical surface processing.
Surprisingly, it was found that formed bodies produced in this way and containing copper(II)phthalocyanin.e for the production of singlet oxygen have an extremely high thermal stability up to 300 °C, without the onset of a thermal degradation of the photosensitiser.
According to a further embodiment, a photosensitiser (for example chosen from porphyrines, phthalocyanines, chlorins, tetraphenylporpbyr~n.es, ~benzoporphyrine derivatives, purpurines, pheophorbides and their metal complexes, copper(II)phthalocyan:in.e, rose bengal anal 5-aminolevulinic acid) is mixed with a polymer granulate, monomers (for ex<~mple acrylate monomers) or resins (for example polyester resins). The mixture can then be further processed into a granulate. By means of injection moulding, extrusion, curing or polymerisation, a formed body can be manufactured from the mixture or from the granulate, which body can be mechanically processed. Since the maximum occurring temperatures during these manufacturing methods are substantially less than those temperatures arising during sintering according to the brst embodiment, photosensitisers, which are less temperature-stable, can also be used in the scope of the second embodiment.
The use of a transparent matrix is preferred. This makes possible the activation of the photosensitiser by illumination also from the rear side by means of artificial light or sunlight. The embodiment of the formed body as a transparent foil can be used as covering over floors in order to improve the floor quality by means of direct influence of singlet oxygen and by means of selective activation of the growth of aerobic bacteria. As a~ covering for bodies of water (aquaria, ponds, lakes), the water quality is improved by means of the singlet oxygen. In the field of dermatology and of plastic ;surgery, transparent foils can be used in order to promote healing processes.
A thin, flat formed body which contains a transparent matrix can be applied for example to windows or function as windows and, by using sunlight or artificial light, be used for the production of singiet oxygen in order to improve air quality in rooms.
The use of a transparent matrix is preferred. This makes possible the activation of the photosensitiser by illumination also from the rear side by means of artificial light or sunlight. The embodiment of the formed body as a transparent foil can be used as covering over floors in order to improve the floor quality by means of direct influence of singlet oxygen and by means of selective activation of the growth of aerobic bacteria. As a~ covering for bodies of water (aquaria, ponds, lakes), the water quality is improved by means of the singlet oxygen. In the field of dermatology and of plastic ;surgery, transparent foils can be used in order to promote healing processes.
A thin, flat formed body which contains a transparent matrix can be applied for example to windows or function as windows and, by using sunlight or artificial light, be used for the production of singiet oxygen in order to improve air quality in rooms.
Claims (17)
1. Formed body for photoactivated production of singlet oxygen, characterised in that the formed body is obtained by means of pressing and subsequent sintering, injection moulding, extrusion, curing or polymerisation from a mixture made of at least one photosensitiser and polymer, the photosensitiser being embedded in a polymer matrix.
2. Formed body according to claim 1, characterised in that the proportion of photosensitiser of the formed body is less than 50% by weight.
3. Formed body according to claim 1 or 2, characterised in that the photosensitiser is chosen from porphyrines, phthalocyanines, chlorins, tetraphenylporphyrines, benzoporphyrine derivatives, purpurines, pheophorbides and their metal complexes.
4. Formed body according to one of the claims 1 to 3, characterised in that the photosensitiser is chosen from copper(II)phthalocyanine, rose bengal and 5-aminolevulinic acid.
5. Formed body according to one of the claims 1 to 4, characterised in that the matrix is transparent.
6. Formed body according to one of the claims 1 to 5, characterised in that the formed body is porous and/or has a rough surface.
7. Formed body according to one of the claims 1 to 6, characterised in that the formed body is a foil.
8. Method for manufacture of a formed body for photoactivated production of singlet oxygen, characterised in that at least one photosensitiser is mixed with at least one polymer or monomer material and the formed body is manufactured from the mixture by means of pressing and subsequent, sintering, injection moulding, extrusion, curing or polymerisation.
9. Method according to claim 8, characterised in that a granulate is manufactured from the mixture, which granulate is used for the manufactures of the formed body.
10. Method according to claim 8 or 9, characterised in that the formed body is subjected at least in regions to a surface treatment.
11. Method according to one of the claims 8 to 10, characterised in that the mixture has in addition a substance added which is washed out again. after the manufacture of the formed body.
12. Method according to one of the claims 8 to 11, characterised in that the photosensitiser is mixed with polymer granulate, monomers and/ or resins.
13. Method according to one of the claims 8 to 12, characterised in that the photosensitiser is mixed with fluorinated hydrocarbons.
14. Method according to one of the claims 8 to 13, characterised in that the photosensitiser is mixed with PTFE granulate.
15. Method according to claim 14, characterised in that the sintering is carried out at temperatures of over 300 °C.
16. Use of a formed body according to claim 7 in order to cover surfaces.
17. Use according to claim 16, characterised in that floors, bodies of water or skin surfaces are covered.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19835457.6 | 1998-08-05 | ||
| DE19835457A DE19835457A1 (en) | 1998-08-05 | 1998-08-05 | Device for the photoactivated production of singlet oxygen and method for producing the device |
| PCT/EP1999/005668 WO2000007934A1 (en) | 1998-08-05 | 1999-08-05 | Device for photoactivated production of singlet oxygen and method for the production of the device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2339271A1 true CA2339271A1 (en) | 2000-02-17 |
Family
ID=7876597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002339271A Abandoned CA2339271A1 (en) | 1998-08-05 | 1999-08-05 | Device for photoactivated production of singlet oxygen and method for the production of the device |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP1115652B1 (en) |
| JP (1) | JP2002522210A (en) |
| AT (1) | ATE236851T1 (en) |
| BR (1) | BR9912752A (en) |
| CA (1) | CA2339271A1 (en) |
| DE (2) | DE19835457A1 (en) |
| NO (1) | NO20010554L (en) |
| WO (1) | WO2000007934A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10048153A1 (en) * | 2000-09-28 | 2002-04-25 | Natural Energy Solutions Ag | Device for generating singlet oxygen |
| DE10064064A1 (en) * | 2000-12-21 | 2002-07-18 | Fraunhofer Ges Forschung | Process for accelerating biocatalytic and / or hormonal processes and its use |
| EP1852391A1 (en) * | 2006-05-02 | 2007-11-07 | Medical Biophysics GmbH | Apparatus and process for the generation of fluid activated by singlet oxygen |
| DE102013220210A1 (en) * | 2013-10-07 | 2015-04-09 | Lr Health & Beauty Systems Gmbh | Apparatus and method for generating singlet oxygen |
| DE102021114704B3 (en) * | 2021-06-08 | 2022-09-08 | Jassen - Kunststoffzentrum Gmbh - Apparatebau, Zuschnitte Und Formung | Apparatus and method for converting ammonia from an aqueous liquid containing ammonia into molecular nitrogen |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4315998A (en) * | 1974-06-12 | 1982-02-16 | Research Corporation | Polymer-bound photosensitizing catalysts |
| US4579837A (en) * | 1984-10-22 | 1986-04-01 | Kms Fusion, Inc. | Solid phase photosensitizer for generation of singlet oxygen |
| US4849076A (en) * | 1987-10-13 | 1989-07-18 | Neckers Douglas C | Continuous oxidation method |
| DE3836759A1 (en) * | 1988-10-28 | 1990-05-03 | Wolters Werner | Catalyst for activating molecular oxygen |
| US4915804A (en) * | 1988-12-20 | 1990-04-10 | Allied-Signal Inc. | Titanate bound photosensitizer for producing singlet oxygen |
| ES2113547T3 (en) * | 1992-07-31 | 1998-05-01 | Behringwerke Ag | PHOTOACTIVABLE CHEMIOLUMINISCENT MATRICES. |
-
1998
- 1998-08-05 DE DE19835457A patent/DE19835457A1/en not_active Ceased
-
1999
- 1999-08-05 EP EP99939451A patent/EP1115652B1/en not_active Expired - Lifetime
- 1999-08-05 DE DE59904986T patent/DE59904986D1/en not_active Expired - Fee Related
- 1999-08-05 JP JP2000563571A patent/JP2002522210A/en active Pending
- 1999-08-05 WO PCT/EP1999/005668 patent/WO2000007934A1/en active IP Right Grant
- 1999-08-05 CA CA002339271A patent/CA2339271A1/en not_active Abandoned
- 1999-08-05 AT AT99939451T patent/ATE236851T1/en not_active IP Right Cessation
- 1999-08-05 BR BR9912752-0A patent/BR9912752A/en not_active IP Right Cessation
-
2001
- 2001-02-01 NO NO20010554A patent/NO20010554L/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| EP1115652A1 (en) | 2001-07-18 |
| EP1115652B1 (en) | 2003-04-09 |
| WO2000007934A1 (en) | 2000-02-17 |
| DE59904986D1 (en) | 2003-05-15 |
| BR9912752A (en) | 2001-05-15 |
| ATE236851T1 (en) | 2003-04-15 |
| JP2002522210A (en) | 2002-07-23 |
| NO20010554L (en) | 2001-04-05 |
| DE19835457A1 (en) | 2000-02-17 |
| NO20010554D0 (en) | 2001-02-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued | ||
| FZDE | Discontinued |
Effective date: 20040805 |