CN101212987B - Self-sterilizing products - Google Patents
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- CN101212987B CN101212987B CN2006800240846A CN200680024084A CN101212987B CN 101212987 B CN101212987 B CN 101212987B CN 2006800240846 A CN2006800240846 A CN 2006800240846A CN 200680024084 A CN200680024084 A CN 200680024084A CN 101212987 B CN101212987 B CN 101212987B
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Abstract
Self-sterilising products, and in particular novel products comprising phthaloeyanine derivatives bound to polymers, a process for the preparation of said products and their use for preparing self-sterilising industrial and medical articles or devices, are described.
Description
Technical field:
The present invention relates to phthalocyanine derivates, particularly have the new product from the characteristic that sterilizes, the phthalocyanine derivates of wherein following general formula (I) is bound on the polymer.
Background technology:
For the mankind, much infect by contact transmission.This is true especially for the infection relevant with using medical equipment (for example catheter, implant, plastics contact lens and similar).In fact, under nearly all situation the infection that causes by microorganism, these microorganisms that have been grown on the foreign material of equipment are fatal especially and have resistance for standard inactivation treatment and working standard antibiotic.
All developed in known a lot of microorganism for antibiotic drug resistance, medical circle and people experience anxiety to this.Whether in addition, this relates to has new antibiotic can effectively resist the problem that may occur in the future fast.The new antibiotic of known exploitation is very expensive and consuming time, in the meantime microorganism in face of based on the antibiotics of known action mechanism because evolution pressure causes the drug resistance can be more and more stronger.
Therefore the research that continues is based on new role principle and replacement method so that eradicate possible microbial antigen.
Germ-resistant known method for medical article and equipment comprises different processing, for example with gaseous state or the processing of liquid cellular toxic substance, high-energy radiation or heat treated.
Unfortunately, such bactericidal level that reaches can only be temporary transient, and must be when equipment uses and with after repeat above-mentioned processing to recover bactericidal effect.In other words, the sterilization that known method provided is not permanent, must carry out new sterilization cycles before reusing after the first use of material.
Therefore there is keen interest to pay close attention to and makes the material that is suitable for, described material itself has sterilization and disinfective action, is suitable for preparing can be used for medical article and equipment or being applicable to any field that need keep long-term bactericidal effect and maintenance effect lastingly at equipment and article surface.
Summary of the invention:
The applicant finds that surprisingly the phthalocyanine derivates of following general formula (I) has bactericidal activity, can be solidificated in polymer surfaces and keep its bactericidal activity.
Therefore theme of the present invention is to comprise the polymerization product that binding has the polymer of general formula (I) phthalocyanine derivates.
Wherein M is selected from 2H and is selected from and comprises Zn, Si (OR ')
2, Ge (OR ')
2And the metal of the group of AlOR ', wherein R ' is selected from H and the alkyl with 1-15 carbon atom.
R is selected from H, comprises the group of at least one quaternary ammonium-substituted base, comprises the amino substituent group of at least one aliphatic, and is fit to and the bonded group of specific support,
R
1Identical or different with R, be selected from H, comprise the amino substituent group of at least one aliphatic, comprise the amino substituent group of at least one aliphatic,
R
2And R
3, be same to each other or different to each other, be selected from H, a 1-10 carbon atom alkoxyl, have the thio alkoxy of 1-10 carbon atom, the group that comprises the amino substituent group of at least one aliphatic and comprise at least one quaternary ammonium-substituted base,
And following restriction arranged:
A) as R, R
1, R
2And R
3Be when comprising the amino substituent group of at least one aliphatic or comprising the group of at least one quaternary ammonium-substituted base, R, R
1, R
2And R
3In at least one group that comprises the amino substituent group of at least one aliphatic or comprise at least one quaternary ammonium-substituted base, perhaps R and R
2Be the group that comprises the amino substituent group of at least one aliphatic or comprise at least one quaternary ammonium-substituted base, and R
1And R
3Be H, describedly comprise the amino substituent group of at least one aliphatic or the described group that comprises at least one quaternary ammonium-substituted base is identical;
B) as R and R
1Be not H, they are positioned at 1,4 or 2,3, otherwise, R and R
1In when having only one to be not H, it is positioned at 1 or 2;
C) work as R
2And R
3Be not H, they are positioned at 8,11, and 15,18,22,25 or 9,10,16,17,23,24, otherwise, work as R
2And R
3In when having only one to be not H, it is positioned at 8 (11), 15 (18), 22 (25) or 9 (10), 16 (17), 23 (24),
And the acceptable salt of materia medica.
Another theme of the present invention is the method for preparing the aforementioned polymer product, and it is used for preparation or applies from germ-resistant industry and medical article or equipment, and described article and equipment have at least one surface and comprises aforesaid polymeric articles.
Characteristics of the present invention and advantage will elaborate in description subsequently.
Description of drawings:
Fig. 1 such as example 13 are described, concentration of recovering after the chemical compound 9 usefulness DMF desorption (μ M) and concentration (mM) contrast at the solution that is used for preparing coating.
The specific embodiment:
Phthalocyanine derivates is known to be the heliosensitivity molecule, is used for the optical dynamic therapy (or title " PDT ") of known tumor and bacterial infection.Phthalocyanine is considered to be arranged in the chemical compound of eucaryon alive or protokaryon species for a long time, and can absorb light to produce active oxygen (ROS) (being meant oxygen base and singlet oxygen especially) thus destroy the cell that relates in the light dynamic process (.Int.J Radiat.Biol. such as Ben-Hur E., Vol 47, pp.145-147,1985).
By the phthalocyanine derivates sample description of applicant preparation in U.S. Patent No. 5,965, in 598.These products are used to prepare the pharmaceutical composition that is used for the bacterial infection processing, and with the parenteral of solution form, or with the form topical of frost, gel, cream and washing liquid, but up to the present also be not used to bind or in conjunction with the polymer that is suitable for preparing article and equipment.The characteristic of macro ring and substituent existence have influenced the preparation of active oxygen (ROS) consumingly, so their ability makes inactivation of bacteria.
The generation of active oxygen (ROS) also depends on the environment of finding phthalocyanine strongly.Particularly, the high more and polymerization therefrom of the concentration of phthalocyanine in solution then can be got over poor efficiency in photosensitive process.When reducing the negative effect that also observes when the replacement of its mobility (for example because the atom steric restriction) on phthalocyanine nucleus takes place heliosensitivity.
Phthalocyanine derivates of the application of the invention and preparation method thereof, the applicant finds that surprisingly their bactericidal activity (being mediated by active oxygen (ROS) generation) is still effective after phthalocyanine derivates is solidificated in polymer surfaces.Particularly, the applicant observes after the phthalocyanine modification by general formula (I), and the polymer surfaces that contacts with microorganism becomes from germ-resistant.
Polymeric articles of the present invention at the bacillary biomembrane of deactivation, can be transplanted to the allos system that catheter, artificial heart valve, dentistry are filled up the comprehensive and good organization on agent and other non-life surfaces, and biological tissue, human tissue for example, the particularly tissue of injured infection, and chronic ulcer also is effective.
Compare biomembrane with the cell of the attitude of swimming and demonstrate unique phenotypic characteristic; Particularly, they have the more high drug-resistance of some orders of magnitude for most of conventional sterilization agent treatment, and this is because multiple drug resistance mechanism causes the chronic infection relevant with bacterial biof iotalm to be difficult to be uprooted.
" bactericidal activity " means and comprises bacteriostatic activity and bactericidal activity in the present invention.Polymeric articles particularly of the present invention for Gram-positive and negative bacteria and fungus, mycoplasma, protozoacide, parasite and virus effectively.
Depend on the phthalocyanine derivates and the concentrate thereof that use at polymer surfaces, bactericidal activity can be by showing under the situation that is exposed to visible light even does not have to shine.Under first kind of situation, bactericidal activity maintains overall optical according to duration of existence and recovery when one section light of after date when dark shines once more.Molecule of the present invention can day light intensity or artificial light under effectively absorb visible light.It is near 400nm and 700nm that ultraviolet-visible (UV-Vis) spectrum demonstrates two wave bands with strong absorbance, promptly at spectrographic visible light wave range, so these two light sources can be used to the irradiation will be by germ-resistant polymer or material.
Demonstrate bactericidal activity when product of the present invention is exposed under visible light and the low-energy light, the harmful effect of described bactericidal activity can not cause by the change of germ-resistant properties of materials yet.
Because it also is effective under non-illuminate condition, polymeric articles of the present invention has extra advantage, the substitute that promptly is used for inside of human body, support and similar medical article can be by preparation of product of the present invention, and they are used for inside of human body, therefore do not have visible light, can not influence their sterilization characteristic certainly.
Be meant one preferred (X) based on what is called of the present invention " comprise at least one quaternary ammonium-substituted base or the amino substituent group of aliphatic "
pR
4Group, wherein X be selected from O ,-CH
2-, CO, S, SO and-NR
5, R wherein
5Be selected from H and C
1-C
15Alkyl; R
4Be
Wherein
Y is selected from C
1-C
10Alkyl and phenyl can replace, and perhaps Y and its Z group of binding form a saturated or unsaturated heterocycle, and described heterocycle can be substituted and can comprise maximum two hetero atoms that are selected from N, O and S;
Z is selected from-N ,-CH
2N and-CONHCH
2CH
2N;
R
6And R
7, be same to each other or different to each other, be selected from C
1-C
15Alkyl and phenyl, or form saturated or unsaturated heterocycle with Z group that it is bound, described heterocycle can be substituted and can comprise maximum two hetero atoms that are selected from N, O and S;
R
8And R
9, be same to each other or different to each other, be selected from H, C
1-C
15Alkyl, R
10COOEt or R
10COOMe group, wherein R
10Be C
1-C
15Alkyl;
M, n, p, w, t and u, independently of one another, and be 0 or 1; And
V is the integer of 1-3,
And restricted condition is n, and w has only one to be 0 among t and the u.
Based on the present invention, the group that comprises at least one quaternary ammonium-substituted base is selected from following preferred group:
Based on the present invention, comprise the amino substituent group of at least one aliphatic and be preferably selected from following group:
Comprise that following group is particularly preferred in the amino substituent group of at least one aliphatic:
Comprise that following group is particularly preferred in the group of at least one quaternary ammonium-substituted base:
Based on preferred embodiment of the present invention M is Zn.
Term " saturated or be not full of heterocycle " preferably is meant the heterocycle that selects morpholine, piperidines, pyridine, pyrimidine, piperazine, pyrrolidine, pyrrolin, imidazoles, aniline and julolidine.
Term " is suitable for the group in conjunction with specific support " and is meant any covalency that is suitable for and is tied to group on the biological organic carrier, and for example aminoacid, polypeptide, protein, polysaccharide and oligonucleoside part can be so that bind described phthalocyanine on solid phase; Aforesaid implication preferably is meant and is selected from-COOH ,-SH ,-NH
2,-CO-CH
2-Br ,-S0
2The group of Cl, maleimide, hydrazine, phenol, imido, biotin is preferably by proper spacing body (X)
p-W is tied to the phthalocyanine core, wherein X and p as defined above, W is selected from C
1-C
10Alkyl, aromatic radical and C
1-C
5Aralkyl.
When R be one as described above definition be suitable for group in conjunction with specific support, R
1Be preferably H, R
2And R
3Be selected from H, comprise the amino substituent group of at least one aliphatic and comprise the group of at least one quaternary ammonium-substituted base and R at least
2And R
3In one be not H.
The phthalocyanine derivates of structural formula (I) can be by corresponding aminoderivative preparation, it can be purchased product from commerce successively and prepares by known method, as applicant's U.S. Patent No. 5,965,598, described in European patent No.1 164 135 and the European patent No.1 381 611.
The polymer that is used for product of the present invention is selected from insoluble material in water and biological fluid.
The example of the polymer that is fit to based on the present invention is can be synthesized or naturally occurring, but be not limited to: cotton, viscose, polystyrene, polyethylene, polypropylene, polyacrylamide, polyamide, polyvinyl alcohol, polysaccharide, cellulose esters (for example cellulose acetate), silicon derivative, and their mixture, they can be processed into solid, fiber, yarn fabric or form of film.
The polymer of water soluble or biological fluid, for example glucosan and derivant thereof, protein and metabolic derivative thereof, protein hydrolysate and analog thereof also can comprise in the present invention, mix with aforementioned insoluble polymer or wrap up thereon.
Product of the present invention can be used for preparing and wrap up and be used for medical science and the article of industry and the technology of equipment, and described article and equipment are fixed against phthalocyanine derivates makes the surface have from sterilizing characteristic.
Items and equipment include but not limited to: catheter, conduit, probe, cardiac valve, soft tissue repair thing, animal organ's restoration, artificial tendon/bone/cardiovascular alternative, contact lens, blood oxygenator, artificial kidney/heart/pancreas/liver, blood bag, Eustachian tube, surgical apparatus, filtration system, laboratory equlpment, be used to cultivate and container, peptide/protein/antibody supporter, domestic and hospital that cell/tissue is rebuild with clinical relief product, the container that is used for cosmetics and instrument.
Self-sterilizing products of the present invention can be used to make article (comprising complex article) and coating, thin film and fiber; Fiber can be transferred to textile, knitting then or is used to prepare supatex fabric, is used for for example dressing and the binder of wound.
Product of the present invention also can comprise one or more materia medica effective ingredient, for example is selected from following composition: antibiotic, anti-infective, antimicrobial drug, antiviral agents, cytostatics, antitumor agent, anti-inflammatory agent, Wound-healing agent, cholinomimetic or adrenaline excitant or antagonist, antithrombotic, anticoagulant, hemorrhage, fibrinolysis, thrombolytics, protein or its fragment, polypeptide, polynucleotide, somatomedin, enzyme and vaccine.
Phthalocyanine derivates of the present invention can by physics and/or being tied on the polymer of covalency.Substitute as a kind of, the surface can be pretreated and immobilization can be implemented in and be used for pretreated material.
Product of the present invention can carry out polyreaction then by phthalocyanine derivates (I) and monomer reaction and prepare, or will realize that the polymer of preparation and phthalocyanine derivates (I) react and make.
Specific reaction conditions depends on the surface of polymer and the characteristic of phthalocyanine nucleus replacement in the heart, but reacts under each situation and can realize by using routine techniques well known to those skilled in the art.
The phthalocyanine derivates of structural formula (I) can be directly bound to polymer surfaces or bind by an interval body; Under this situation, can use suitable difunctional dose, carbodiimides for example, glutaraldehyde, 1,1 '-carbonyl dimidazoles chlorotriazine, Bromine cyanide., mixed anhydride, imino-ester and maleimide derivatives; Otherwise the use adulterant, for example acid reagent such as acrylic acid is incorporated in the polymer or in second step of reaction and is added into.
In another embodiment of the present invention, polymer surfaces is at first wrapped up by protein solution, makes phthalocyanine to be fixed on the protein coat by physics or chemical method.
As an alternative, phthalocyanine is tied to by carboxyl and forms an amide group on the aminoderivative of polymer.
Perhaps, other functional group's industry can import photosensitive compounds by appropriate chemical methods, for example: be used for the solidified carboxyethyl group of physical property, can be hydrolyzed, the carboxyl functional group of gained is activated by being converted into corresponding chloric acid, azide or Acibenzolar, is incorporated in the polymerization product with nucleophilic displacement of fluorine base by known chemical method then.
Under each situation, reaction is carried out between polymer (or monomer) and phthalocyanine solution, described polymer or monomer can be wrapped or derivatization, and described phthalocyanine solution is the phthalocyanine of structural formula (I) or its salt (for example iodine salt or villaumite) to be dissolved in the appropriate solvent get.
The amount of phthalocyanine derivates that is tied to polymer surfaces is optimised, to reach varied concentration in wide region.Light deactivation microorganism is based on the amount of existing phthalocyanine, and this amount changes according to institute's light requirement sterilization and sterilisation level.
For obtaining effective self-sterilizing products, the concentration of phthalocyanine is 10 μ M-10mM in the solution, is preferably 1mM.
Compare product of the present invention with known method for disinfection and have following advantage: control the generation of active oxygen in the sterilization process (ROS) easily by the photosensitive agent concentration that changes the surface, the type of used light and intensity: irradiation can be used artificial light and available light or the selected interior specific wavelength of limit of visible spectrum.Further advantage is not needing to realize particular device or instrument also not to need to use traditional antibacterial to sterilize.
Following non-limiting example can the present invention will be described.
Example 1
The diiodide of the phthalocyanine derivates of preparation structural formula (I), wherein M is Zn, R
1
=R
2
=R
3
=H, and
And R=1,3-pair-(Trimethylamine)-2-propoxyl group 2[chemical compound 1 on the throne]
0.272g 4-[1,3-is two-(dimethylamino)-2-propoxyl group]-1,1 of 2-benzene dinitrile (1mmol) and 0.384g, 2-benzene dinitrile (3mmol) is dissolved in the small amount of methanol; In gained solution, add to Zn (AcO)
2(0.176g; 0.96mmol) and DBU (0.66ml; 0.42mmol).Under inert atmosphere mixture be heated to 150 ℃ 3 hours 30 minutes again.Blue mixture is dissolved among the DMF, and with the alkaline water redeposition several times, purifies with the flash chromatography on the silica gel then, uses Et
2O/DMF (4: 1), EtOAc/DMF (4: 1), EtOAc/DMF (1: 1), EtOAc/DMF (1: 2) and DMF elution.
Products therefrom is structural formula (I) chemical compound, and wherein M is Zn, R
1=R
2=R
3=H and R=1,3-pair-(dimethylamino) 2-propoxyl group 2[chemical compound on the throne 1bis]; This product of 10mg (0.014mmol) is dissolved in the N-N-methyl-2-2-pyrrolidone N-of 2.5ml, and the excessive Mel of reuse handles, and reactant mixture at room temperature stirred 15 hours.
Product is by Et
2O is precipitated out from mixture, and recover the filtration back, uses the organic solvent washing and precipitating several times to purify then, obtains described product 2[1 like this, 3-pair-(Trimethylamine)-2-propoxyl group] zinc (II) phthalocyanine diiodide; Blue powder.
UV-vis(DMF)λ
max(ε，M
-1，cm
-1)：343，607，672(1.9275×10
5)
1H-NMR(300MHz，DMSO-d
6)：δ(ppm)＝9.95-9.40(m，7H)，9.23(s，1H)，8.42-8.35(m，6H)，8.25-8.15(m，1H)，6.30-6.10(m，1H)，4.45-4.10(m，4H)，3.55(s，18H)。
ESI-MS：m/z?375.3[M-2I]
2+
Example 2
Phthalocyanine derivates eight iodide of preparation structural formula (I), wherein M is Zn, R
1
=R
2
=H, and R
=R
3
=1,3-pair-(dimethyl-ethyl acetate-amine)-2-propoxyl group on the throne 2,9 (10), 16 (17), 23 (24)
[chemical compound 2]
Title compound prepares by following method as described in Example 1, originates in 4-[1,3-pair-(dimethylamino)-2-propoxyl group]-1, the 2-benzene dinitrile is to obtain the chemical compound of structural formula (I), and wherein M is Zn, R
1=R
2=H, and R=R
3=1,3-pair-(dimethylamino)-2-propoxyl group 2,9 (10), 16 (17), 23 (24) [chemical compound 2bis] on the throne.
0.5ml ICH
2COOEt is added to the 5mg aminoderivative and is dissolved in the 1mlN-methyl pyrrolidone gained solution, and mixture is stirred 3 days.Product is by Et
2The O precipitation, solid phase is cleaned several times to remove residual solvent and impurity by ether.
Product is finally absorbed by DMF, by Et
2The O precipitation, and by Et
2O and CHCl
3Clean several times.
1H-NMR(300MHz，DMSO-d
6)δ(ppm)9.5(t，4H，J＝8.5Hz)，9.1(m，4H)，6.2(m，4H)，4.7(m，16H)，4.4-4.3(b.m.，16H)，4.0(q，16H，J＝6.8Hz)，3.5(s，48H)，1.0(t，24H，J＝6.8Hz).
13C-NMR(300MHz，DMSO-d
6)δ(ppm)＝165.3?156.1?153.1?140.8?134.5125.0?120.7?112.5?69.6?65.4?62.7?53.8?39.3?14.2
UV-vis(DMF)λ
max(ε，M
-1，cm
-1)：678，354。
Example 3
Preparation structural formula (I) phthalocyanine derivates diiodide, wherein M is Zn, R
1
=R
2
=R
3
=H, and
R=1,3-pair-(dimethyl-ethyl acetate-ammonium)-2-propoxyl group 2[chemical compound 3 on the throne]
With 2 described same procedure as a rule, the preparation title compound, the NMR analysis result of gained chemical compound is as follows:
1H-NMR(300MHz，DMSO-d
6)δ(ppm)9.5-9.3(m，6H)，9.1(s，2H)，8.1-8.3(m，7H)，6.2(m，1H)，4.75(m，4H)，4.5(b.d.，2H，J＝12Hz)，4.3(b.d.，2H，J＝12Hz)，4.05(q，4H，J＝10Hz)，3.5(s，12H)，1.0(t，6H，J＝10Hz).
13C-NMR(300MHz，DMSO-d
6)δ(ppm)165.4?155.9?154.2?154.0?153.8153.4?140.9?138.6?134.3?130.6?124.9?123.2?120.9?112.1?69.3?65.6?62.853.5?39.3?14.2。
Example 4
Phthalocyanine derivates eight iodide of preparation structural formula (I) wherein M are Zn, R
1
=R
2
=H abandons
R=R
3
=1,3-is two-and (dimethyl-(2-hydroxyl carbonyl) ethyl-ammonium)-2-propoxyl group is on the throne 2,9 (10), 16 (17),
23 (24) [chemical compounds 4]
According to same procedure as described in example 2, but use alkylating agent ICH
2COOH obtains corresponding acid derivative.
Example 5
The phthalocyanine derivates diiodide of preparation structural formula (I) wherein M is Zn, R
1
=R
2
=R
3
=H, and
And R=1,3-pair-(dimethyl-(2-hydroxyl carbonyl) ethyl-ammonium)-2-propoxyl group 2[chemical compound 5 on the throne]
According to same procedure as described in Example 3, but use alkylating agent ICH
2COOH obtains corresponding acid derivative.
Example 6
The phthalocyanine derivates teriodide of preparation structural formula (I) wherein M is Zn, R
1
=R
3
=H, R=4-hydroxyl carbonyl
Phenoxy group is on the throne 2, and R
2
=[3-(N, N, N-Trimethylamine) phenoxy group] is on the throne 9 (10), 16 (17),
23 (24) [chemical compounds 6]
According to identical method as described in example 1, be [4-(4-hydroxyl carbonyl)-phenoxy group]-phthalocyanine and 4 (3-dimethylamino phenoxy group)-phthalocyanine but use original material, obtain the title compound of structural formula (I).
Example 7
The phthalocyanine derivates teriodide of preparation structural formula (I) wherein M is Zn, R
1
=R
3
=H, R=4-hydroxyl carbonyl
Phenoxy group is on the throne 2, and R
2
=[3-(N, N, N-Trimethylamine) phenoxy group] is on the throne 8 (11), 15 (18),
22 (25) [chemical compounds 7]
According to same procedure as described in example 1, but the original material that uses is [4-(4-hydroxyl carbonyl)-phenoxy group]-phthalocyanine and 3 (3-dimethylamino phenoxy group)-phthalocyanine, obtains the title compound of structural formula (I).
Example 8
The phthalocyanine derivates tetraiodide of preparation structural formula (I) wherein M is Zn, R
1
=R
3
=H, R=R
2
=[3-
(N, N, N-Trimethylamine) phenoxy group], and R and R
2
On the throne 2,9 (10), 16 (17), 23 (24) [chemical compounds
8]
A) Synthetic 2,9 (10), 16 (17), 23 (24)-four [3-(N, N-dimethylamino) phenoxy group] zinc phthalocyanine salts [is changed
Compound 8bis]
DBU (29ml-194mmol) and anhydrous Zn (OAc)
2(3.48g-19mmol) be added to 3-(N, N-dimethylamino) phenoxy group] phthalocyanine (10g-38mmol); The gained mixture is heated to 160 ℃ and kept this temperature 4 hours, keeps stirring, and under inert atmosphere, and lucifuge.Mixture returns to after the room temperature deionized water with 200ml and handles, and the gained solid phase is separated and by water and washed with methanol.The gained crude product is with chromatograph purify (silica gel, CH
2Cl
2/ MeOH 98/2v/v).Eluate contains described chemical compound, and it is spissated position different structure mixture, is dissolved in CH
2Cl
2In, and redeposition goes out from normal hexane, obtains 7.629 the pure mixture of isomery (productive rate=72%).
UV-Vis(DMF)λ
max(nm)681(ε＝70300M
-1cm
-1)612，356
1H-NMR(200MHz，DMSO-d
6)δppm?9.01-8.90(m，4H)，8.51-8.45(m，4H)，7.82-7.73(m，4H)，7.49-7.36(m，4H)，6.85-6.73(m，12H)，3.05-3.02(m，24H).
13C-NMR(300MHz，DMSO-d
6)δppm?159.71，159.47，158.33，158.21，153.06，152.53，152.23，152.03，151.77，151.36，139.91，132.89，131.16，131.02，124.23，120.32，110.76，109.17，107.97，107.83，104.59
FAB-MS?m/z?1117[M+H]
+.
B)
Synthetic 2,9 (10), 16 (17), 23 (24)-four [3-(N, N, N-Trimethylamine) phenoxy group] zinc phthalocyanine salts The tetraiodide
Add excess iodine methane (16ml) to zinc 2,9 (10), 16 (17), 23 (24)-four [3-(N, the N-dimethylamino) phenoxy group] phthalocyanine salts (6.32g-5.65mmol) is dissolved in NMP (158ml) the gained solution, mixture keeps stirring 120 hours, and room temperature and lucifuge are handled with ether (1.3I) by methanol (320ml) dilution back then, obtain green precipitate, corresponding with required product, be isomer mixture form (9g, 95% productive rate).
UV-Vis(DMF)λ
max(nm)677(ε＝161000M
-1cm
-1)，609，353；
1H-NMR(200MHz，DMSO-d
6)δppm?9.55-9.43(m，4H)，9.09-9.02(m，4H)，8.22-8.15(m，4H)，8.07-7.76(m，12H)，7.62-7.52(m，4H)3.77and3.75(2s，36H)
13C-NMR(200MHz，DMSO-d
6)δppm?157.84，157.67，152.50(m)，148.85，140.00(m)，134.00，131.77，124.70，121.30(m)，120.18，119.89，115.99，115.80，112.70，112.42，56.60
ESI-MS?m/z?388[M-4I-CH
3]
3+，573[M-4I-2CH
3]
2+，1132[M-4I-3CH
3]
+.
Use is in example 12 described methods, preparation phthalocyanine derivates chloride is begun by corresponding iodide, described as the International Application PCT/EP2006/062059 the applicant, the phthalocyanine derivates of structural formula (I) and corresponding aminoderivative intermediate are produced then:
Example 9
The phthalocyanine derivates tetrachloride of structural formula (I), wherein M is Zn, R
1=R
3=H, R=R
2=[3-(N, N, N-Trimethylamine) phenoxy group], and R and R
21,8 (11), 15 (18), 22 (25) [chemical compound 9] on the throne and
The phthalocyanine derivates of structural formula (I), wherein M is Zn, R
1=R
3=H, R=R
2=[3-(N, N-dimethylamino) phenoxy group] 1,8 (11), 15 (18), 22 (25) [chemical compound 9bis] on the throne
Example 10
The phthalocyanine derivates tetrachloride of structural formula (I), wherein M is Zn, R
1=R
3=H, R=R
2=[4-(N, N, N-Trimethylamine) phenoxy group], and R and R
21,8 (11), 15 (18), 22 (25) [chemical compound 10] on the throne and
The phthalocyanine derivates of structural formula (I) wherein M is Zn, R
1=R
3=H, R=R
2=[4-(N, N-dimethylamino) phenoxy group] 1,8 (11), 15 (18), 22 (25) [chemical compound 10bis] on the throne
Example 11
Eight chlorides of the phthalocyanine derivates of structural formula (I), wherein M is Zn, R=R
1=R
2=R
3=[3-(N, N, N-Trimethylamine) phenoxy group], and R, R
1, R
2, R
3On the throne 2,3,9,10,16,17,23,24[chemical compound 11] and
The phthalocyanine derivates of structural formula (I) wherein M is Zn, R=R
1=R
2=R
3=[3-(N, N-dimethylamino) phenoxy group] is on the throne 2,3,9,10,16,17,23,24[chemical compound 11bis]
Example 12
Phthalocyanine derivates eight chlorides of structural formula (I), wherein M is Zn, R=R
1=R
2=R
33-==[(N, N, N-methyl diethyl ammonium) phenoxy group], and R, R
1, R
2, R
3On the throne 2,3,9,10,16,17,23,24[chemical compound 12] and
The phthalocyanine derivates of structural formula (I), wherein M is Zn, R=R
1=R
2=R
3=[3-(N, N-lignocaine) phenoxy group] is on the throne 2,3,9,10,16,17,23,24[chemical compound 12bis]
Example 13
Polystyrene side's body (2cm * 2cm, 0.2cm is thick) is soaked in the solution of the chemical compound 1 of preparation as described in example 1, and solution concentration is 1mM (being dissolved among the DMSO), 4 ℃ of cultivations whole night.Remove solution then, polystyrene fully cleans with the second alcohol and water.The products therefrom drying for standby.
Similar, chemical compound 2,3,8 and 9 is solidificated on the polystyrene according to same procedure.By at 4 ℃ at H
2O/CH
3OH (4: 1) thus in to cultivate whole night at the polystyrene parcel be to be implemented by the petri diss of this material preparation as the loading scope of the chemical compound 9 of preparation as described in the example 9.Be absorbed in the amount of the chemical compound in the polystyrene, measure that the concentration of chemical compound 9 assesses after with the DMF desorption by spectrophotography (690nm).Solid phase apparatus result is the function of coating concentration (promptly in the concentration of chemical compound 9 at the initial soln that is used for preparing coating), as shown in Figure 1.
Example 14
The lens of making by Nefilcon A and PVA (day throwing type, Solecare company product) and silicon catheter (aseptic two-chamber 15-French Nelaton, Maersk Medical Sdn company, Malaysia) by example 1 prepared chemical compound 1 coating, this is by respectively at the H of the chemical compound 1 of 1mM and 1 μ M
2O/CH
3Get whole night 4 ℃ of cultivations in OH (4: the 1) solution, use aseptic PBS rinsing then.
Example 15
The polystyrene orifice plate is handled by BSA solution (0.1mg/ml), cultivates 1 hour at 37 ℃ then.Remove solution, with the PBS cleaning orifice solution-treated of the prepared chemical compound 1 of use-case 1 immediately then.Solution is removed solution 4 ℃ of cultivations whole night, and orifice plate fully cleans with the second alcohol and water, drying for standby.
Similarly, the prepared chemical compound 8-12 of routine 8-12 is connected on the polystyrene with identical method, obtains identical result.
Example 16
The polystyrene orifice plate is handled by glutaraldehyde solution (0.1%PBS), and cultivates 1 hour at 37 ℃.Remove glutaraldehyde solution, after orifice plate is cleaned by PBS immediately use-case 1 prepared chemical compound 1bis (1mg/ml) handle.Solution 4 ℃ of cultivations whole night, it is standby to remove solution after drying orifice plate.
With identical method, example 2, the prepared chemical compound 2bis of 8-12 as described above, 8bis, 9bis, 10bis, 11bis and 12bis are used to do coating.
Example 17
Silicone tube is handled with glutaraldehyde solution (0.1%PBS) and 0.01% human serum albumin (HSA), cultivates 1 hour at 37 ℃.Remove solution, the pipe after cleaning with PBS immediately the prepared chemical compound 1 of use-case 1 at DMSO and H
2O/CH
3(ratio is 10 to different solutions in the OH mixture: 90-90: 10) handle.
Solution 4 ℃ of cultivations whole night, remove solution after scavenge pipe up to not detecting heliosensitivity, the pipe of gained has the photosensitive compounds molecular coatings like this.
Previous example 2,3, the chemical compound 2,3 and the 8-12 of 8-12 preparation apply with aforementioned same procedure, and gained comes to the same thing.
Example 18
With 3 hours at room temperature consuming time of 2N HCl solution to the local simplely depolymerization of nylon tube.The surface uses N-succimide base-3-(2-pyridine radicals sulfur)-propionic ester (SPDP) to handle with the sodium bicarbonate solution neutralization then.The effective ethanol in reaction back fully cleans, again by dithiothreitol dithio (1mM) handle with obtain being solidificated in reagent on the nylon tube-the SH free state, subsequently by by measuring the reaction of 2-mercaptopyridine chromophore spectrophotography.
Modification in advance is to be used for example 5,6 and 7 chemical compounds 5,6 and 7 that prepare that the succinimide group imports the phthalocyanine part to solidify by traditional method (Hermanson, Bioconjugate Techniques, Academic Press 1996).
Described method causes the phthalocyanine derivates covalency to attach on the surface that is modified.
Example 19
Staphylococcus aureus (taphylococcus aureus (bacterial strain 6538ATCC)) is being grown under aerobic environment under 37 ℃ in the tryptic soy broth (Difco company product).At stable phase cell is taken out from culture fluid, clean twice, in same buffer, be diluted to 1 * 10 then with PBS
4The sterilization contact lens of making by Nelficon A and PVA (day throwing type, Solecare company) and according to the silicon sterilization two-chamber 15-French Nelaton of example 14 preparations (Maersk Medical Sdn, Malaysia) catheter is used.
Contact lens or catheter fragment are placed in the 6-hole tissue culture dish, add 2ml staphylococcus aureus suspension in each hole.At 37 ℃ culture plate was cultivated 5 minutes, then irradiation (600-700nm, 30J/cm
2).After the irradiation, the 100 μ l suspensions that take out from the hole are put pancreatin soy agar (TSA) then by 10 times of serial dilutions.Pancreatin soy agar dish was cultivated 24 hours at 37 ℃, calculated group, and their numerical statement is shown CFU/ml.
The test matched group carries out on the equipment of being untreated
All tests are carried out 3-5 time, and the gained result adds up in following table 1,2.
Table 1
Table 2
Claims (29)
1. polymeric articles, it comprises directly or the polymer of the phthalocyanine derivates by interval body binding general formula (I)
Wherein M is selected from 2H and is selected from Zn, Si (OR ')
2, Ge (OR ')
2And the metal of AlOR ', wherein R ' is selected from the alkyl of H and 1-15 carbon atom;
R is selected from H, comprise the group of at least one quaternary ammonium-substituted base, comprise the amino substituent group of at least one aliphatic, be fit to and the bonded group of specific support, and the described group that is suitable in conjunction with specific support is selected from-COOH ,-SH ,-NH
2,-CO-CH
2-Br ,-SO
2Cl, maleimide, hydrazine, phenol, imido, biotin can pass through interval body (X)
p-W is tied to phthalocyanine nucleus, wherein X be selected from O ,-CH
2-, CO, S, SO and-NR
5, p is 0 or 1, W is selected from C
1-C
10Alkyl, aromatic radical, C
1-C
5Aralkyl;
R
1Identical or different with R, as to be selected from H, to comprise the amino substituent group of at least one aliphatic and comprise at least one quaternary ammonium-substituted base group,
R
2And R
3Be same to each other or different to each other, be selected from the alkoxyl of H, a 1-10 carbon atom, the thio alkoxy of a 1-10 carbon atom, the group that comprises the amino substituent group of at least one aliphatic and comprise at least one quaternary ammonium-substituted base,
And restricted condition is:
A) as R, R
1, R
2And R
3Be when comprising the amino substituent group of at least one aliphatic or comprising the group of at least one quaternary ammonium-substituted base, R, R
1, R
2And R
3In at least one group that comprises the amino substituent group of at least one aliphatic or comprise at least one quaternary ammonium-substituted base, perhaps R and R
2Be the group that comprises the amino substituent group of at least one aliphatic or comprise at least one quaternary ammonium-substituted base, and R
1And R
3Be H, describedly comprise the amino substituent group of at least one aliphatic or the described group that comprises at least one quaternary ammonium-substituted base is identical;
B) as R and R
1Be not H, they are positioned at 1,4 or 2,3, otherwise, R and R
1In when having only one to be not H, it is positioned at 1 or 2;
C) work as R
2And R
3Be not H, they are positioned at 8,11, and 15,18,22,25 or 9,10,16,17,23,24, otherwise, work as R
2And R
3In when having only one to be not H, it is positioned at 8 (11), 15 (18), 22 (25) or 9 (10), 16 (17), 23 (24),
Wherein said polymer is water insoluble and polymer biological fluid, and it can be mixed with or be enclosed with the polymer of water soluble or biological fluid, and the acceptable salt of materia medica.
2. polymeric articles according to claim 1, wherein said insoluble polymer is selected from cotton, viscose, polystyrene, polyethylene, polypropylene, polyacrylamide, polyamide, polyvinyl alcohol, polysaccharide, cellulose esters, silicon derivative, and composition thereof.
3. polymeric articles according to claim 1, wherein said soluble polymer are selected from glucosan and derivant, protein and methylate derivant and protein hydrolysate.
4. polymeric articles according to claim 1 wherein saidly comprises at least one quaternary ammonium-substituted base or the amino substituent group of aliphatic is (X)
pR
4Group, wherein X be selected from O ,-CH
2-, CO, S, SO and-NR
5, R wherein
5Be selected from H and C
1-C
15Alkyl; R
4Be
Wherein
Y is selected from C
1-C
10Alkyl and phenyl can be substituted, and perhaps Y and its Z group of binding form saturated or unsaturated heterocycle, and described heterocycle can be substituted and can comprise maximum two hetero atoms that are selected from N, O and S;
Z is selected from-N ,-CH
2N and-CONHCH
2CH
2N;
R
6And R
7, be same to each other or different to each other, be selected from C
1-C
15Alkyl and phenyl, or form saturated or unsaturated heterocycle with Z group that it is bound, described heterocycle can be substituted and can comprise maximum two hetero atoms that are selected from N, O and S;
R
8And R
9, be same to each other or different to each other, be selected from H, C
1-C
15Alkyl, R
10COOEt or R
10COOMe group, wherein R
10Be C
1-C
15Alkyl;
M, n, p, w, t and u are 0 or 1 and independently of one another;
V is the integer of 1-3,
And restricted condition is to have only one to be 0 among n, w, t and the u.
5. polymeric articles according to claim 1, the wherein said group that comprises at least one quaternary ammonium-substituted base is selected from:
6. polymeric articles according to claim 1, the wherein said group that comprises at least one quaternary ammonium-substituted base is selected from:
7. polymeric articles according to claim 1, the wherein said amino substituent group of at least one aliphatic that comprises is selected from:
8. polymeric articles according to claim 1, the wherein said amino substituent group of at least one aliphatic that comprises is selected from:
9. polymeric articles according to claim 1, wherein M is Zn in the phthalocyanine derivates of structural formula (I).
10. polymeric articles according to claim 1 is wherein said saturated or be not full of heterocycle and be selected from morpholine, piperidines, pyridine, pyrimidine, piperazine, pyrrolidine, pyrrolin, imidazoles, aniline and julolidine.
11. polymeric articles according to claim 1, wherein working as R is the group that is suitable in conjunction with specific support, R
1Be H, R
2And R
3Be selected from H, comprise the amino substituent group of at least one aliphatic, comprise the group of at least one quaternary ammonium-substituted base, and R
2And R
3In at least one is different from H.
12. polymeric articles according to claim 1, the phthalocyanine derivates of wherein said general formula (I) is selected from following chemical compound:
The phthalocyanine derivates diiodide of-structural formula (I), wherein M is Zn, R
1=R
2=R
3=H, and R=1,3-pair-(Trimethylamine)-2-propoxyl group 2[chemical compound 1 on the throne]
The phthalocyanine derivates of-structural formula (I), wherein M is Zn, R
1=R
2=R
3=H and R=1,3-pair-(dimethylamino)-2-propoxyl group 2[chemical compound on the throne 1bis];
Phthalocyanine derivates eight iodide of-structural formula (I), wherein M is Zn, R
1=R
2=H, and R=R
3=1,3-pair-(dimethyl-ethyl acetate-amine)-2-propoxyl group 2,9 (10), 16 (17), 23 (24) [chemical compound 2] on the throne
The phthalocyanine derivates of-structural formula (I), wherein M is Zn, R
1=R
2=H, and R=R
3=1,3-pair-(dimethylamino)-2-propoxyl group 2,9 (10), 16 (17), 23 (24) [chemical compound 2bis] on the throne
The phthalocyanine derivates diiodide of-structural formula (I), wherein M is Zn, R
1=R
2=R
3=H, R=1,3-pair-(dimethyl-ethyl acetate-amine)-2-propoxyl group 2[chemical compound 3 on the throne]
Phthalocyanine derivates eight iodide of-structural formula (I), wherein M is Zn, R
1=R
2=H, and R=R
3=1,3-pair-(dimethyl-(2-hydroxyl carbonyl) ethyl-ammonium)-2-propoxyl group 2,9 (10), 16 (17), 23 (24) [chemical compound 4] on the throne
The phthalocyanine derivates diiodide of-structural formula (I), wherein M is Zn, R
1=R
2=R
3=H, and R=1,3-pair-(dimethyl-(2-hydroxyl carbonyl) ethyl-ammonium)-2-propoxyl group 2[chemical compound 5 on the throne]
The phthalocyanine derivates teriodide of-structural formula (I), wherein M is Zn, R
1=R
3=H, R=4-hydroxyl carbonyl phenoxy group is on the throne 2, and R
2=[3-(N, N, N-Trimethylamine) phenoxy group] 9 (10), 16 (17), 23 (24) [chemical compound 6] on the throne
The phthalocyanine derivates teriodide of-structural formula (I), wherein M is Zn, R
1=R
3=H, R=4-hydroxyl carbonyl phenoxy group is on the throne 2, and R
2=[3-(N, N, N-Trimethylamine) phenoxy group] iodide 8 (11), 15 (18), 22 (25) [chemical compound 7] on the throne
The phthalocyanine derivates tetraiodide of-structural formula (I), wherein M is Zn, R
1=R
3=H, R=R
2=[3-(N, N, N-Trimethylamine) phenoxy group] 2,9 (10), 16 (17), 23 (24) [chemical compound 8] on the throne
The phthalocyanine derivates of-structural formula (I), wherein M is Zn, R
1=R
3=H, R=R
2=[3-(N, N-dimethylamino) phenoxy group] 2,9 (10), 16 (17), 23 (24) [chemical compound 8bis] on the throne
The phthalocyanine derivates tetrachloride of-structural formula (I), wherein M is Zn, R
1=R
3=H, R=R
2=[3-(N, N, N-Trimethylamine) phenoxy group] 1,8 (11), 15 (18), 22 (25) [chemical compound 9] on the throne
The phthalocyanine derivates of-structural formula (I) wherein M is Zn, R
1=R
3=H, R=R
2=[3-(N, N-dimethylamino) phenoxy group] 1,8 (11), 15 (18), 22 (25) [chemical compound 9bis] on the throne
The phthalocyanine derivates tetrachloride of-structural formula (I), wherein M is Zn, R
1=R
3=H, R=R
2=[4-(N, N, N-Trimethylamine) phenoxy group] 1,8 (11), 15 (18), 22 (25) [chemical compound 10] on the throne
The phthalocyanine derivates of-structural formula (I) wherein M is Zn, R
1=R
3=H, R=R
2=[4-(N, N-dimethylamino) phenoxy group] 1,8 (11), 15 (18), 22 (25) [chemical compound 10bis] on the throne
Phthalocyanine derivates eight chlorides of-structural formula (I), wherein M is Zn, R=R
1=R
2=R
3=[3-(N, N, N-Trimethylamine) phenoxy group] is on the throne 2,3,9,10,16,17,23,24[chemical compound 11]
The phthalocyanine derivates of-structural formula (I) wherein M is Zn, R=R
1=R
2=R
3=[3-(N, N-dimethylamino) phenoxy group] is on the throne 2,3,9,10,16,17,23,24[chemical compound 11bis]
Phthalocyanine derivates eight chlorides of-structural formula (I), wherein M is Zn, R=R
1=R
2=R
3=[3-(N, N, N-methyl diethyl ammonium) phenoxy group] is on the throne 2,3,9,10,16,17,23,24[chemical compound 12]
The phthalocyanine derivates of-structural formula (I) wherein M is Zn, R=R
1=R
2=R
3=[3-(N, N-lignocaine) phenoxy group] is on the throne 2,3,9,10,16,17,23,24[chemical compound 12bis].
13. polymeric articles according to claim 1, wherein said interval body is derived from described phthalocyanine derivates and described polymer by suitable difunctional dose of formed connection, described difunctional dose be selected from carbodiimides, glutaraldehyde, 1,1 '-carbonyl dimidazoles chlorotriazine, Bromine cyanide. mixed anhydride, imino-ester and maleimide derivatives.
14. as the purposes of polymeric articles as described in arbitrary among the claim 1-13, it is used for preparation or applies from germ-resistant industry and medical article or equipment.
15. article and equipment, it is by forming as arbitrary described polymeric articles among the claim 1-13, and described polymeric articles can be accepted active substance with one or more materia medicas and combine.
16. article and equipment, it has at least one by the surface that applies as arbitrary described polymeric articles among the claim 1-13.
17. described article of claim 15 and equipment, be selected from catheter, conduit, probe, cardiac valve, soft tissue repair thing, animal organ's restoration, artificial tendon/bone/cardiovascular alternative, contact lens, blood oxygenator, artificial kidney/heart/pancreas/liver, blood bag, Eustachian tube, surgical apparatus, filtration system, laboratory equlpment, be used to cultivate and container, peptide/protein/antibody supporter, domestic and hospital that cell/tissue is rebuild with clinical relief product, the container that is used for cosmetics and instrument.
18. described article of claim 16 and equipment, be selected from catheter, conduit, probe, cardiac valve, soft tissue repair thing, animal organ's restoration, artificial tendon/bone/cardiovascular alternative, contact lens, blood oxygenator, artificial kidney/heart/pancreas/liver, blood bag, Eustachian tube, surgical apparatus, filtration system, laboratory equlpment, be used to cultivate and container, peptide/protein/antibody supporter, domestic and hospital that cell/tissue is rebuild with clinical relief product, the container that is used for cosmetics and instrument.
19. preparation comprises the steps: as the method for arbitrary described polymeric articles among the claim 1-13
I) phthalocyanine salts with structural formula (I) is dissolved in the appropriate solvent to obtain phthalocyanine solution;
Monomer and step I that ii) described polymer is corresponding) gained phthalocyanine (I) solution reaction, to obtain having the monomer derived thing of phthalocyanine;
Iii) from step I i) the polymerization of monomer derived thing.
20. preparation comprises the steps: as the method for arbitrary described polymeric articles among the claim 1-13
I ') phthalocyanine salts with structural formula (I) is dissolved in the appropriate solvent to obtain phthalocyanine solution;
Ii ') step I ') polymer reaction of gained phthalocyanine (I) solution and pre-preparation, method pretreatment and/or derivatization that described polymer can be suitable.
21. method according to claim 19, wherein said step I i ') polymer is by adulterant or protein solution pretreatment.
22. method according to claim 21, wherein said adulterant is an acrylic acid.
23. method according to claim 20, wherein said polymer are in advance by difunctional dose of suitable derivatization, to obtain the required interval body between described polymer and described phthalocyanine derivates.
24. method according to claim 23, wherein said difunctional dose be selected from carbodiimides, glutaraldehyde, 1,1 '-carbonyl dimidazoles chlorotriazine, Bromine cyanide. mixed anhydride, imino-ester and maleimide derivatives.
25. method according to claim 19, wherein step I i ') described in polymer by suitable amino in advance derivatization so that form amido link with the carboxyl of phthalocyanine.
26. method according to claim 20, the concentration of phthalocyanine in the wherein said solution (I) are 10 μ M-10mM.
27. method according to claim 21, the concentration of phthalocyanine in the wherein said solution (I) are 10 μ M-10mM.
28. method according to claim 26, phthalocyanine in the wherein said solution (I) concentration is 1mM.
29. method according to claim 27, phthalocyanine in the wherein said solution (I) concentration is 1mM.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US69575205P | 2005-06-29 | 2005-06-29 | |
| US60/695,752 | 2005-06-29 | ||
| ITFI20060089 ITFI20060089A1 (en) | 2006-04-04 | 2006-04-04 | SELF-STERILIZING PRODUCTS |
| ITFI2006A000089 | 2006-04-04 | ||
| PCT/EP2006/063695 WO2007000472A1 (en) | 2005-06-29 | 2006-06-29 | Self-sterilizing products |
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| CN101212987B true CN101212987B (en) | 2011-02-02 |
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| IT1395907B1 (en) * | 2009-07-30 | 2012-11-02 | Molteni E C Dei Flii Alitti Societa Di Esercizio Spa L | FTALOCYANIC DERIVATIVE CONSISTING OF A MIXTURE OF FOUR ISOMERS |
| CN102675325B (en) * | 2012-06-01 | 2014-06-25 | 福州大学 | Phthalocyanine metal complex containing piperazine ethyoxyl modification group and preparing method thereof |
| CN102702210B (en) * | 2012-06-01 | 2014-09-10 | 福州大学 | Application of phthalocyanine metal complex containing piperazine ethyoxyl modified groups |
| EP3553062A1 (en) * | 2018-04-09 | 2019-10-16 | Chemical Intelligence Limited | Antimicrobial and anticancer cationic phthalocyanine compounds |
| CN108607151B (en) * | 2018-05-21 | 2021-06-01 | 青岛杰圣博生物科技有限公司 | Antibacterial catheter and preparation method thereof |
| CN111072679B (en) * | 2020-01-16 | 2022-07-01 | 福州大学 | Non-peripheral quaternary ammonium group modified zinc phthalocyanine and preparation method and application thereof |
| CN113018500B (en) * | 2021-03-10 | 2022-04-12 | 西华师范大学 | Synergistic chemical and photodynamic antibacterial and antiviral coating and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0186404B1 (en) * | 1984-12-18 | 1991-02-27 | Imperial Chemical Industries Plc | Optical recording medium |
| US5281616A (en) * | 1988-05-23 | 1994-01-25 | Georgia State University Foundation, Inc. | Porphyrin and phthalocyanine antiviral compositions |
| EP0906758A1 (en) * | 1997-08-14 | 1999-04-07 | MOLTENI L. & C. dei Fratelli Alitti Società di Esercizio S.P.A. | Zinc-phthalocyanines and corresponding conjugates, their preparation and use in photodynamic therapy and as diagnostic agents |
| EP1164135B1 (en) * | 2000-06-15 | 2004-02-18 | L. MOLTENI & C. DEI FRATELLI ALITTI SOCIETA' DI ESERCIZIO SOCIETA' PER AZIONI | Substituted metal-phthalocyanines, their preparation and the use thereof |
| EP1356813B1 (en) * | 2002-04-25 | 2005-07-20 | L. MOLTENI & C. DEI FRATELLI ALITTI SOCIETA' DI ESERCIZIO SOCIETA' PER AZIONI | Antibacterial compositions comprising metal phthalocyanine analogues |
-
2006
- 2006-06-29 ES ES06777523T patent/ES2367371T3/en active Active
- 2006-06-29 CN CN2006800240846A patent/CN101212987B/en active Active
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2008
- 2008-01-25 ZA ZA200800787A patent/ZA200800787B/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0186404B1 (en) * | 1984-12-18 | 1991-02-27 | Imperial Chemical Industries Plc | Optical recording medium |
| US5281616A (en) * | 1988-05-23 | 1994-01-25 | Georgia State University Foundation, Inc. | Porphyrin and phthalocyanine antiviral compositions |
| EP0906758A1 (en) * | 1997-08-14 | 1999-04-07 | MOLTENI L. & C. dei Fratelli Alitti Società di Esercizio S.P.A. | Zinc-phthalocyanines and corresponding conjugates, their preparation and use in photodynamic therapy and as diagnostic agents |
| EP1164135B1 (en) * | 2000-06-15 | 2004-02-18 | L. MOLTENI & C. DEI FRATELLI ALITTI SOCIETA' DI ESERCIZIO SOCIETA' PER AZIONI | Substituted metal-phthalocyanines, their preparation and the use thereof |
| EP1356813B1 (en) * | 2002-04-25 | 2005-07-20 | L. MOLTENI & C. DEI FRATELLI ALITTI SOCIETA' DI ESERCIZIO SOCIETA' PER AZIONI | Antibacterial compositions comprising metal phthalocyanine analogues |
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| CN101212987A (en) | 2008-07-02 |
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