Phenalene-1-one-containing photosensitizer composition, phenalene-1-one compound and the use thereof
11186545 · 2021-11-30
Assignee
Inventors
Cpc classification
C07C217/10
CHEMISTRY; METALLURGY
C07C69/76
CHEMISTRY; METALLURGY
C07D309/14
CHEMISTRY; METALLURGY
C07C225/18
CHEMISTRY; METALLURGY
C07C317/22
CHEMISTRY; METALLURGY
C07C233/31
CHEMISTRY; METALLURGY
C07C217/08
CHEMISTRY; METALLURGY
C07C271/16
CHEMISTRY; METALLURGY
C07C49/755
CHEMISTRY; METALLURGY
C07C69/56
CHEMISTRY; METALLURGY
C07C233/20
CHEMISTRY; METALLURGY
C07C233/38
CHEMISTRY; METALLURGY
C07C217/12
CHEMISTRY; METALLURGY
C07C271/20
CHEMISTRY; METALLURGY
C07C69/54
CHEMISTRY; METALLURGY
C07C233/18
CHEMISTRY; METALLURGY
International classification
C07C233/18
CHEMISTRY; METALLURGY
C07C49/755
CHEMISTRY; METALLURGY
C07F7/18
CHEMISTRY; METALLURGY
C07C69/56
CHEMISTRY; METALLURGY
C07C69/76
CHEMISTRY; METALLURGY
C07C317/22
CHEMISTRY; METALLURGY
C07C233/20
CHEMISTRY; METALLURGY
Abstract
A phenalene-1-one compound, a photosensitizer composition including the phenalene-1-one compound, an article including the phenalene-1-one compound and/or photosensitizer composition and the use thereof.
Claims
1. A photosensitizer composition comprising (a) at least one phenalen-1-one compound with the general formula (1): ##STR00160## wherein the residues R1 to R8, which respectively independently of one another may be identical to or different from each other, respectively represent hydrogen, halogen, alkyl containing 1 to 12 C atoms, alkylaryl containing 5 to 20 C atoms, aryl containing 5 to 20 C atoms, *—O-alkyl containing 1 to 12 C atoms, *—O-alkylaryl containing 5 to 20 C atoms, *—O-aryl containing 5 to 20 C atoms, ether containing 2 to 12 C atoms, a residue with the formula *—O—C(═O)—R.sup.(Ia), a residue with the formula *—C(═O)—R.sup.(Ib), or an organic residue W1 which contains at least one reactive functional group, with the proviso that at least one of the residues R1 to R7 is an organic residue W1, wherein the organic residue W1 respectively independently of each other represents a residue with the general formula (2) to (6):
*—[(C(D)(E)).sub.d—B].sub.a—(C(D)(E)).sub.m—X (2)
*-A—[(C(D)(E)).sub.d—B].sub.c—(C(D)(E)).sub.m—X (3)
*—(C(D)(E)).sub.d-AR—(C(D)(E)).sub.n—X (4)
*—[(C(D)(E)).sub.d—B].sub.b—(C(D)(E)).sub.g-AR—(C(D)(E)).sub.n—X (5)
*-A—[(C(D)(E)).sub.d—B].sub.f—(C(D)(E)).sub.g-AR—(C(D)(E)).sub.n—X (6) wherein A respectively independently of each other represents oxygen, sulphur or a residue with the general formula (10a) to (11a): ##STR00161## wherein *.sup.ph respectively denotes a linkage from the residue with the general formula (10a) to (11a) to a C atom of the phenalene ring and *.sup.c respectively denotes a linkage from the residue with the general formula (10a) to (11a) to a C atom of the residue (C(D)(E)), and wherein the residue B respectively independently of each other represents oxygen, sulphur or a residue with the general formula (10) to (14): ##STR00162## wherein the residues R.sup.(Ia), R.sup.(Ib), R.sup.(11a), R.sup.(12a), R.sup.(13a), R.sup.(14a), and R.sup.(14b), respectively independently of each other, represent hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, n-pentyl, phenyl or benzyl, and wherein phenyl and benzyl respectively independently of each other may be unsubstituted or substituted with one or more residues selected from the group which consists of halogen, amino, hydroxyl, *—O-alkyl which may be linear or branched, containing 1 to 3 carbon atoms, alkyl which may be linear or branched, containing 1 to 3 carbon atoms, hydroxyalkyl which may be linear or branched, containing 1 to 3 carbon atoms and 1 to 3 OH groups, halogenoalkyl which may be linear or branched, containing 1 to 3 carbon atoms and 1 to 3 halogen groups, and combinations thereof, wherein Y.sup.− is an anion which respectively independently of each other represents fluoride, chloride, bromide, iodide, sulphate, hydrogen sulphate, phosphate, hydrogen phosphate, dihydrogen phosphate, at least one carboxylate anion of a carboxylic acid containing 1 to 15 carbon atoms, at least one sulphonate anion of a sulphonic acid containing 1 to 12 C atoms, or a combination thereof, and wherein the residues D and E respectively independently of each other represent hydrogen, halogen, hydroxyl, alkyl which may be linear or branched, containing 1 to 5 carbon atoms, hydroxyalkyl which may be linear or branched, containing 1 to 5 carbon atoms and 1 to 5 OH groups, phenyl, benzyl, a residue with the formula *-L—R .sup.(II), a residue with the formula *-L—C(=L)-R.sup.(III), a residue with the formula *—(CH.sub.2).sub.q—X, a residue with the formula *-L—(CH.sub.2).sub.q—X, or a residue with the formula *—(CH.sub.2).sub.s-L—(CH.sub.2).sub.t—X, wherein the residue L respectively independently of each other represents oxygen or sulphur, wherein the residues R.sup.(II) and R.sup.(III) respectively independently of each other, represent hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, n-pentyl, phenyl or benzyl, and wherein phenyl and benzyl respectively independently of each other may be unsubstituted or substituted, the indices q, s and t respectively independently of each other representing a whole number from 1 to 5, wherein the indices a, c, f, g and n respectively independently of each other represent a whole number from 0 to 5, and wherein the indices b, d and m respectively independently of each other represent a whole number from 1 to 5, wherein the residue Ar respectively independently of each other represents a substituted or unsubstituted aromatic residue or a substituted or unsubstituted heteroaromatic residue, and wherein the residue X respectively independently of each other is a reactive functional group denoted by *—N(R.sup.(VI))(R.sup.(VII)), *—OH, *—SH, *—NCO, *—NCS, *—Si(R.sup.(VIII))(R.sup.(IX))—[O—Si(R.sup.(X))(R.sup.(XI))].sub.p—Z, or a residue with the general formula (20) to (24): ##STR00163## wherein the residues R.sup.(20a), R.sup.(20b), R.sup.(20c), R.sup.(21a), R.sup.(22a), R.sup.(22b), R.sup.(22c), R.sup.(23a), R.sup.(24a), R.sup.(24b), and R.sup.(24c) respectively of each other, represent hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, or n-pentyl, and wherein the indices l and k respectively independently of each other represent a whole number from 0 to 4, wherein the residues R.sup.(VI) and R.sup.(VII) respectively independently of each other represent hydrogen, alkyl which may be linear or branched, containing 1 to 5 carbon atoms, phenyl or benzyl, wherein phenyl and benzyl respectively independently of each other may be unsubstituted or substituted with one or more residues selected from the group consisting of chlorine, bromine, fluorine, methyl, ethyl, n-propyl, iso-propyl, methoxy, ethoxy, and combinations thereof, wherein the residues R.sup.(VIII), R.sup.(IX), R.sup.(X) and R.sup.(XI) respectively independently of each other represent hydrogen, alkyl which may be linear or branched, containing 1 to 5 carbon atoms, *—O-alkyl which may be linear or branched, containing 1 to 5 carbon atoms, phenyl or benzyl, wherein phenyl and benzyl respectively independently of each other may be unsubstituted or substituted with one or more residues selected from the group consisting of chlorine, bromine, fluorine, methyl, ethyl, n-propyl, iso-propyl, methoxy, ethoxy, and combinations thereof, wherein the residue Z respectively independently of each other represents halogen, hydroxyl, alkoxyl containing 1 to 4 carbon atoms or alkylcarboxyl containing 1 to 4 carbon atoms, and wherein the index p respectively independently of each other represents a whole number from 0 to 4, and (b) at least one polymeric component and/or precursor thereof, wherein the at least one polymeric component and/or precursor thereof is selected from the group which consists of polymers and/or copolymers of acrylic acid and esters thereof, methacrylic acid and esters thereof, cyanoacrylic acid and esters thereof, acrylamide, methacrylamide, styrene, siloxanes and esters thereof, melamine, acrylonitrile, 1,3-butadiene, epichlorohydrin, polyols, polyisoprenes, polyethers, polyetherimides, polyvinyl acetates, polycarbonates, polyether sulphones, carboxymethyl cellulose, alginate, and combinations thereof.
2. The photosensitizer composition as claimed in claim 1, wherein the residue Ar respectively independently of each other represents a residue with the general formula (25a) to (31): ##STR00164## ##STR00165## ##STR00166## wherein the residues R25, R26, R27, R28, R29, R26.sup.a, R26.sup.b, R27.sup.a, R27.sup.b, R28.sup.a, R28.sup.b, R29.sup.a, R29.sup.b, R30.sup.a and R30.sup.b respectively independently of each other represent hydrogen, hydroxy, amino, alkyl which may be linear or branched, containing 1 to 5 carbon atoms, *—O-alkyl which may be linear or branched, containing 1 to 5 carbon atoms, phenyl or benzyl, wherein phenyl and benzyl respectively independently of each other may be unsubstituted or substituted with one or more residues selected from the group consisting of chlorine, bromine, fluorine, methyl, ethyl, n-propyl, iso-propyl, methoxy, ethoxy, and combinations thereof, and wherein the residue R30 respectively independently of each other represents hydrogen or alkyl which may be linear or branched, containing 1 to 5 carbon atoms, and wherein the residues R33.sup.a and R33.sup.b respectively independently of each other represent hydrogen, hydroxy, amino, alkyl which may be linear or branched, containing 1 to 5 carbon atoms, perfluoralkyl which may be linear or branched, containing 1 to 5 carbon atoms, *—O-alkyl which may be linear or branched, containing 1 to 5 carbon atoms, phenyl, benzyl or, when taken together, a cycloalkyl which may be linear or branched, containing 4 to 9 carbon atoms, or a 9H-fluoren-9-ylidene residue, and wherein Y.sup.− is an anion which respectively independently of each other represents fluoride, chloride, bromide, iodide, sulphate, hydrogen sulphate, phosphate, hydrogen phosphate, dihydrogen phosphate, at least one carboxylate anion of a carboxylic acid containing 1 to 15 carbon atoms, at least one sulphonate anion of a sulphonic acid containing 1 to 12 C atoms, or a combination thereof.
3. The photosensitizer composition as claimed claim 1, wherein the at least one organic residue W1 respectively independently of each other represents a residue with the general formula (40) to (67) or (72) to (98e): ##STR00167## ##STR00168## ##STR00169## ##STR00170## ##STR00171## ##STR00172## wherein Y.sup.− is an anion which respectively independently of each other represents fluoride, chloride, bromide, iodide, sulphate, hydrogen sulphate, phosphate, hydrogen phosphate, dihydrogen phosphate, at least one carboxylate anion of a carboxylic acid containing 1 to 15 carbon atoms, at least one sulphonate anion of a sulphonic acid containing 1 to 12 C atoms, or a combination thereof.
4. The photosensitizer composition as claimed in claim 1, comprising: (a) at least one phenalen-1-one compound with the general formula (1), which is selected from the group which consists of compounds with formula (100) to (127), (132) to (166): ##STR00173## ##STR00174## ##STR00175## ##STR00176## ##STR00177## ##STR00178## ##STR00179## ##STR00180## ##STR00181## ##STR00182## ##STR00183## and combinations thereof, and (b) said at least one polymeric component and/or precursor thereof.
5. The photosensitizer composition as claimed in claim 1, comprising: (a) at least one phenalen-1-one compound with the general formula (1) which is a phenalen-1-one compound with the general formula (1a): ##STR00184## wherein the residues R1.sup.a to R8.sup.a, which respectively independently of one another may be identical to or different from each other, respectively represent hydrogen, halogen, alkyl containing 1 to 12 C atoms, alkylaryl containing 5 to 20 C atoms, aryl containing 5 to 20 C atoms, *—O-alkyl containing 1 to 12 C atoms, *—O-alkylaryl containing 5 to 20 C atoms, **—O-aryl containing 5 to 20 C atoms, ether containing 2 to 12 C atoms, a residue with the formula *—O—C(═O)—R.sup.(Ia), a residue with the formula *—C(═O)—R.sup.(Ib), or an organic residue W1a which contains at least one reactive functional group, with the proviso that at least one of the residues R1.sup.a or R2.sup.a is an organic residue W1a, wherein the organic residue W1a respectively independently of each other represents a residue with the general formula (2a) to (6a):
*—[(C(D)(E)).sub.d—B].sub.e—(C(D)(E)).sub.m—X.sup.a (2a)
*-A—[(C(D)(E)).sub.d—B].sub.c—(C(D)(E)).sub.m—X.sup.a (3a)
*—(C(D)(E)).sub.d-AR—(C(D)(E)).sub.n—X.sup.a (4a)
*—[(C(D)(E)).sub.d—B].sub.b—(C(D)(E)).sub.g-AR—(C(D)(E)).sub.n—X.sup.a (5a)
*-A—[(C(D)(E)).sub.d—B].sub.f—(C(D)(E)).sub.g-AR—(C(D)(E)).sub.n—X.sup.a (6a) wherein the residue A respectively independently of each other represents oxygen, sulphur or a residue with the general formula (10a) to (11a): ##STR00185## wherein *.sup.ph respectively denotes a linkage from the residue with the general formula (10a) to (11a) to a C atom of the phenalene ring and *.sup.c respectively denotes a linkage from the residue with the general formula (10a) to (11a) to a C atom of the residue (C(D)(E)), wherein the residue B respectively independently of each other represents oxygen, sulphur or a residue with the general formula (10) to (12): ##STR00186## and wherein the residues R.sup.(Ia), R.sup.(Ib), R.sup.(11a) and R.sup.(12a) respectively independently of each other represent methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, n-pentyl, phenyl or benzyl, and wherein phenyl and benzyl respectively independently of each other may be unsubstituted or substituted with one or more residues selected from the group consisting of chlorine, bromine, fluorine, methyl, ethyl, n-propyl, iso-propyl, methoxy, ethoxy, and combinations thereof, and wherein the residues D and E respectively independently of each other represent hydrogen, halogen, hydroxyl, alkyl which may be linear or branched, containing 1 to 5 carbon atoms, hydroxyalkyl which may be linear or branched, containing 1 to 5 carbon atoms and 1 to 5 OH groups, phenyl, benzyl, a residue with the formula *-L—R .sup.(II), a residue with the formula *-L—C(=L)-R.sup.(III), a residue with the formula *—(CH.sub.2).sub.q—X.sup.a, a residue with the formula *-L —(CH.sub.2).sub.q—X.sup.a, or a residue with the formula *—(CH.sub.2).sub.s-L—(CH.sub.2).sub.t—X.sup.a, wherein the residue L respectively independently of each other represents oxygen or sulphur, wherein the residues R.sup.(II) and R.sup.(III) respectively independently of each other, represent hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, n-pentyl, phenyl or benzyl, and wherein phenyl and benzyl respectively independently of each other may be unsubstituted or substituted with one or more residues selected from the group consisting of chlorine, bromine, fluorine, methyl, ethyl, n-propyl, iso-propyl, methoxy, ethoxy, and combinations thereof, the indices q, s and t respectively independently of each other representing a whole number from 1 to 5, wherein the indices c, g, f and n respectively independently of each other represent a whole number from 0 to 5, and wherein the indices b, d, e and m respectively independently of each other represent a whole number from 1 to 5, wherein the residue Ar respectively independently of each other represents a substituted or unsubstituted aromatic residue or a substituted or unsubstituted heteroaromatic residue which contains no N atoms, and wherein the residue X.sup.a respectively independently of each other represents a reactive functional group *—OH, *—SH, *—NCO, *—NCS, *—Si(R.sup.(VIII)(R.sup.(IX))—[O—Si(R.sup.(X))(R.sup.(XI))].sub.p—Z, or a residue with the general formula (20) to (24): ##STR00187## wherein the residues R.sup.(20a), R.sup.(20b), R.sup.(20c), R.sup.(21a), R.sup.(22a), R.sup.(22b), R.sup.(22c), R.sup.(23a), R.sup.(24a), R.sup.(24b), and R.sup.(24c) respectively independently of each other, represent hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, or n-pentyl, and wherein the indices l and k respectively independently of each other represent a whole number from 0 to 4, wherein the residues R.sup.(VIII), R.sup.(IX), R.sup.(X), R.sup.(XI) respectively independently of each other represent hydrogen, alkyl which may be linear or branched, containing 1 to 5 carbon atoms, —O-alkyl which may be linear or branched, containing 1 to 5 carbon atoms, phenyl or benzyl, wherein phenyl and benzyl respectively independently of each other may be unsubstituted or substituted with one or more residues selected from the group consisting of chlorine, bromine, fluorine, methyl, ethyl, n-propyl, iso-propyl, methoxy, ethoxy, and combinations thereof, wherein the residue Z respectively independently of each other represents halogen, hydroxyl, alkoxyl containing 1 to 4 carbon atoms or alkylcarboxyl containing 1 to 4 carbon atoms, and wherein the index p respectively independently of each other represents a whole number from 0 to 4, and (b) said at least one polymeric component and/or precursor thereof.
6. The photosensitizer composition as claimed in claim 1, wherein the composition furthermore comprises at least one crosslinking agent, which contains at least one polyisocyanate, a blocked isocyanate, at least one alkyl diisocyanate or cycloalkyl diisocyanate or aryl diisocyanate, a compound with the general formula SiZ.sub.4, (R.sup.XII)SiZ.sub.3, (R.sup.XII).sub.2SiZ.sub.2, a compound containing at least two epoxy residues, a compound containing at least two acrylamide residues, a compound containing at least two acrylate residues, a compound containing at least two aldehyde residues, a compound containing at least two alcohol groups, a compound containing at least two amine residues, a divinylsulphone, or combinations thereof, wherein the residue R.sup.XII respectively independently of each other represents alkyl which may be linear or branched, containing 1 to 5 carbon atoms, phenyl or benzyl, and wherein the residue Z respectively independently of each other represents halogen, hydroxyl, alkoxyl containing 1 to 4 carbon atoms or alkylcarboxyl containing 1 to 4 carbon atoms.
7. The photosensitizer composition as claimed in claim 1, wherein the at least one phenalen-1-one compound with the general formula (1) is electrostatically bonded to the at least one polymeric component and/or precursor thereof.
8. The photosensitizer composition as claimed in claim 1, wherein the photosensitizer composition is a paint, a varnish, an emulsion paint, a latex paint, a silicate paint, or a chalk paint.
9. The photosensitizer composition as claimed in claim 1, wherein the photosensitizer composition is a granulate.
10. An article comprising a hardened photosensitizer composition produced by hardening a photosensitizer composition according to claim 1, wherein the at least one phenalene-1-one compound with the general formula (1) is covalently or electrostatically bonded to the at least one polymeric component ##STR00188## ##STR00189## ##STR00190## ##STR00191##
11. The article as claimed in claim 10, wherein the at least one phenalene-1-one compound is a compound of formula (1a) ##STR00192## wherein the residues R1.sup.a to R8.sup.a, which respectively independently of one another may be identical to or different from each other, respectively represent hydrogen, halogen, alkyl containing 1 to 12 C atoms, alkylaryl containing 5 to 20 C atoms, aryl containing 5 to 20 C atoms, *—O-alkyl containing 1 to 12 C atoms, *—O-alkylaryl containing 5 to 20 C atoms, **—O-aryl containing 5 to 20 C atoms, ether containing 2 to 12 C atoms, a residue with the formula *—O—C(═O)—R.sup.(Ia), a residue with the formula *—C(═O)—R.sup.(Ib), or an organic residue W1a which contains at least one functional group, with the proviso that at least one of the residues R1.sup.a or R2.sup.a is an organic residue W1a, wherein the organic residue W1a respectively independently of each other represents a residue with the general formula (2a) to (6a):
*—[(C(D)(E)).sub.d—B].sub.e—(C(D)(E)).sub.m—X.sup.a (2a)
*-A—[(C(D)(E)).sub.d—B].sub.c—(C(D)(E)).sub.m—X.sup.a (3a)
*—(C(D)(E)).sub.d-AR—(C(D)(E)).sub.n—X.sup.a (4a)
*—[(C(D)(E)).sub.d—B].sub.b—(C(D)(E)).sub.g-AR—(C(D)(E)).sub.n—X.sup.a (5a)
*-A—[(C(D)(E)).sub.d—B].sub.f—(C(D)(E)).sub.g-AR—(C(D)(E)).sub.n—X.sup.a (6a) wherein the residue A respectively independently of each other represents oxygen, sulphur or a residue with the general formula (10a) to (11a): ##STR00193## wherein *.sup.ph respectively denotes a linkage from the residue with the general formula (10a) to (11a) to a C atom of the phenalene ring and *.sup.c respectively denotes a linkage from the residue with the general formula (10a) to (11a) to a C atom of the residue (C(D)(E)), wherein the residue B respectively independently of each other represents oxygen, sulphur or a residue with the general formula (10) to (12): ##STR00194## and wherein the residues R.sup.(Ia), R.sup.(Ib), R.sup.(11a) and R.sup.(12a) respectively independently of each other represent methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, n-pentyl, phenyl or benzyl, and wherein phenyl and benzyl respectively independently of each other may be unsubstituted or substituted with one or more residues selected from the group consisting of chlorine, bromine, fluorine, methyl, ethyl, n-propyl, iso-propyl, methoxy, ethoxy, and combinations thereof, and wherein the residues D and E respectively independently of each other represent hydrogen, halogen, hydroxyl, alkyl which may be linear or branched, containing 1 to 5 carbon atoms, hydroxyalkyl which may be linear or branched, containing 1 to 5 carbon atoms and 1 to 5 OH groups, phenyl, benzyl, a residue with the formula *-L-R.sup.(II), a residue with the formula *-L—C(=L)-R.sup.(III), a residue with the formula *—(CH.sub.2).sub.q—X.sup.a, a residue with the formula *-L—(CH.sub.2).sub.q—X.sup.a, or a residue with the formula *—(CH.sub.2).sub.s-L—(CH.sub.2).sub.t—X.sup.a, wherein the residue L respectively independently of each other represents oxygen or sulphur, wherein the residues R.sup.(II) and R.sup.(III) respectively independently of each other, represent hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, n-pentyl, phenyl or benzyl, and wherein phenyl and benzyl respectively independently of each other may be unsubstituted or substituted with one or more residues selected from the group consisting of chlorine, bromine, fluorine, methyl, ethyl, n-propyl, iso-propyl, methoxy, ethoxy, and combinations thereof, the indices q, s and t respectively independently of each other representing a whole number from 1 to 5, wherein the indices c, g, f and n respectively independently of each other represent a whole number from 0 to 5, and wherein the indices b, d, e and m respectively independently of each other represent a whole number from 1 to 5, wherein the residue Ar respectively independently of each other represents a substituted or unsubstituted aromatic residue or a substituted or unsubstituted heteroaromatic residue which contains no N atoms, and wherein the residue X.sup.a respectively independently of each other represents a reactive group *—OH, *—SH, *—NCO, *—NCS, *—Si(R.sup.(VIII))(R.sup.(IX))—[O—Si(R.sup.(X))(R.sup.(XI))].sub.p—Z, or a residue with the general formula (20) to (24): ##STR00195## wherein the residues R.sup.(20a), R.sup.(20b), R.sup.(20c), R.sup.(21a), R.sup.(22a), R.sup.(22b), R.sup.(22c), R.sup.(23a), R.sup.(24a), R.sup.(24b), and R.sup.(24c) respectively independently of each other, represent hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, or n-pentyl, and wherein the indices l and k respectively independently of each other represent a whole number from 0 to 4, wherein the residues R.sup.(VIII), R.sup.(IX), R.sup.(X) and R.sup.(XI) respectively independently of each other represent hydrogen, alkyl which may be linear or branched, containing 1 to 5 carbon atoms, —O-alkyl which may be linear or branched, containing 1 to 5 carbon atoms, phenyl or benzyl, wherein phenyl and benzyl respectively independently of each other may be unsubstituted or substituted with one or more residues selected from the group consisting of chlorine, bromine, fluorine, methyl, ethyl, n-propyl, iso-propyl, methoxy, ethoxy, and combinations thereof, wherein the residue Z respectively independently of each other represents halogen, hydroxyl, alkoxyl containing 1 to 4 carbon atoms or alkylcarboxyl containing 1 to 4 carbon atoms, and wherein the index p respectively independently of each other represents a whole number from 0 to 4, or a combination thereof.
12. The article as claimed in claim 10, wherein the hardened polymer composition is in the form of a coating, a self-supporting film, a fabric or a shaped article.
13. A method for inactivation of microorganisms selected from the group consisting of viruses, archaea, bacteria, bacterial spores, biofilms of bacteria, fungi, fungal spores, protozoa, algae, blood-borne parasites and combinations thereof, and/or a biofilm thereof, wherein the method comprises the following steps: (A) bringing the microorganisms and/or a biofilm thereof into contact with at least one coating which has been produced by hardening a photosensitizer composition as claimed in claim 1, wherein the at least one phenalene-1-one compound with the general formula (1) is covalently or electrostatically bonded to the at least one polymeric component ##STR00196## ##STR00197## ##STR00198## ##STR00199## and/or at least one article comprising at least one hardened polymer composition which has been produced by hardening a photosensitizer composition as claimed in claim 1, wherein the at least one phenalene-1-one compound with the general formula (1) is covalently or electrostatically bonded to the at least one polymeric component ##STR00200## ##STR00201## ##STR00202## ##STR00203## and (B) irradiating the microorganisms and/or a biofilm thereof and the at least one phenalen-1-one compound contained in the coating and/or the article with electromagnetic radiation of a suitable wavelength and energy density.
14. A photosensitizer composition comprising (a) at least one phenalen-1-one compound with the general formula (1): ##STR00204## wherein the residues R1 to R8, which respectively independently of one another may be identical to or different from each other, respectively represent hydrogen, halogen, alkyl containing 1 to 12 C atoms, alkylaryl containing 5 to 20 C atoms, aryl containing 5 to 20 C atoms, *—O-alkyl containing 1 to 12 C atoms, *—O-alkylaryl containing 5 to 20 C atoms, **—O-aryl containing 5 to 20 C atoms, ether containing 2 to 12 C atoms, a residue with the formula *—O—C(═O)—R.sup.(Ia), a residue with the formula *—C(═O)—R.sup.(Ib), or an organic residue W1 which contains at least one functional group, with the proviso that at least one of the residues R1 to R7 is an organic residue W1, wherein the organic residue W1 respectively independently of each other represents a residue with the general formula (2) to (6):
*—[(C(D)(E)).sub.d—B].sub.a—(C(D)(E)).sub.m—X (2)
*-A—[(C(D)(E)).sub.d—B].sub.c—(C(D)(E)).sub.m—X (3)
*—(C(D)(E)).sub.d-AR—(C(D)(E)).sub.n—X (4)
*—[(C(D)(E)).sub.d—B].sub.b—(C(D)(E)).sub.g-AR—(C(D)(E)).sub.n—X (5)
*-A—[(C(D)(E)).sub.d—B].sub.f—(C(D)(E)).sub.g-AR—(C(D)(E)).sub.n—X (6) wherein A respectively independently of each other represents oxygen, sulphur or a residue with the general formula (10a) to (11a): ##STR00205## wherein *.sup.ph respectively denotes a linkage from the residue with the general formula (10a) to (11a) to a C atom of the phenalene ring and *.sup.c respectively denotes a linkage from the residue with the general formula (10a) to (11a) to a C atom of the residue (C(D)(E)), and wherein the residue B respectively independently of each other represents oxygen, sulphur or a residue with the general formula (10) to (14): ##STR00206## wherein the residues R.sup.(Ia), R.sup.(Ib), R.sup.(11a), R.sup.(12a), R.sup.(13a), R.sup.(14a), and R.sup.(14b), respectively independently of each other, represent hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, n-pentyl, phenyl or benzyl, and wherein phenyl and benzyl respectively independently of each other may be unsubstituted or substituted with one or more residues selected from the group which consists of halogen, amino, hydroxyl, *—O-alkyl which may be linear or branched, containing 1 to 3 carbon atoms, alkyl which may be linear or branched, containing 1 to 3 carbon atoms, hydroxyalkyl which may be linear or branched, containing 1 to 3 carbon atoms and 1 to 3 OH groups, halogenoalkyl which may be linear or branched, containing 1 to 3 carbon atoms and 1 to 3 halogen groups, and combinations thereof, wherein Y.sup.− is an anion which respectively independently of each other represents fluoride, chloride, bromide, iodide, sulphate, hydrogen sulphate, phosphate, hydrogen phosphate, dihydrogen phosphate, at least one carboxylate anion of a carboxylic acid containing 1 to 15 carbon atoms, at least one sulphonate anion of a sulphonic acid containing 1 to 12 C atoms, or a combination thereof, and wherein the residues D and E respectively independently of each other represent hydrogen, halogen, hydroxyl, alkyl which may be linear or branched, containing 1 to 5 carbon atoms, hydroxyalkyl which may be linear or branched, containing 1 to 5 carbon atoms and 1 to 5 OH groups, phenyl, benzyl, a residue with the formula *-L—R .sup.(II), a residue with the formula *-L—C(=L)-R.sup.(III), a residue with the formula *—(CH.sub.2).sub.q—X, a residue with the formula *-L—(CH.sub.2).sub.q—X, or a residue with the formula *—(CH.sub.2).sub.s-L—(CH.sub.2).sub.t—X, wherein the residue L respectively independently of each other represents oxygen or sulphur, wherein the residues R.sup.(II) and R.sup.(III) respectively independently of each other, represent hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, n-pentyl, phenyl or benzyl, and wherein phenyl and benzyl respectively independently of each other may be unsubstituted or substituted, the indices q, s and t respectively independently of each other representing a whole number from 1 to 5, wherein the indices a, c, f, g and n respectively independently of each other represent a whole number from 0 to 5, and wherein the indices b, d and m respectively independently of each other represent a whole number from 1 to 5, wherein the residue Ar respectively independently of each other represents a substituted or unsubstituted aromatic residue or a substituted or unsubstituted heteroaromatic residue, and wherein the residue X respectively independently of each other is a functional group denoted by *—N(R.sup.(VI))(R.sup.(VII)), *—OH, *—SH, *—NCO, *—NCS, *—Si(R.sup.(VIII))(R.sup.(IX))—[O—Si(R.sup.(X))(R.sup.(XI))].sub.p—Z, or a residue with the general formula (20) to (24): ##STR00207## wherein the residues R.sup.(20a), R.sup.(20b), R.sup.(20c), R.sup.(21a), R.sup.(22a), R.sup.(22b), R.sup.(22c), R.sup.(23a), R.sup.(24a), R.sup.(24b), and R.sup.(24c) respectively independent of each other, represent hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, or n-pentyl, and wherein the indices l and k respectively independently of each other represent a whole number from 0 to 4, wherein the residues R.sup.(VI) and R.sup.(VII) respectively independently of each other represent hydrogen, alkyl which may be linear or branched, containing 1 to 5 carbon atoms, phenyl or benzyl, wherein phenyl and benzyl respectively independently of each other may be unsubstituted or substituted with one or more residues selected from the group consisting of chlorine, bromine, fluorine, methyl, ethyl, n-propyl, iso-propyl, methoxy, ethoxy, and combinations thereof, wherein the residues R.sup.(VIII), R.sup.(IX), R.sup.(X) and R.sup.(XI) respectively independently of each other represent hydrogen, alkyl which may be linear or branched, containing 1 to 5 carbon atoms, *—O-alkyl which may be linear or branched, containing 1 to 5 carbon atoms, phenyl or benzyl, wherein phenyl and benzyl respectively independently of each other may be unsubstituted or substituted with one or more residues selected from the group consisting of chlorine, bromine, fluorine, methyl, ethyl, n-propyl, iso-propyl, methoxy, ethoxy, and combinations thereof, wherein the residue Z respectively independently of each other represents halogen, hydroxyl, alkoxyl containing 1 to 4 carbon atoms or alkylcarboxyl containing 1 to 4 carbon atoms, and wherein the index p respectively independently of each other represents a whole number from 0 to 4, and (b) at least one polymeric component and/or precursor thereof, wherein the at least one polymeric component and/or precursor thereof is selected from the group which consists of polymers and/or copolymers of acrylic acid and esters thereof, methacrylic acid and esters thereof, cyanoacrylic acid and esters thereof, acrylamide, methacrylamide, styrene, siloxanes and esters thereof, melamine, acrylonitrile, 1,3-butadiene, epichlorohydrin, polyols, polyisoprenes, polyethers, polyetherimides, polyvinyl acetates, polycarbonates, polyether sulphones, carboxymethyl cellulose, alginate, and combinations thereof, wherein the at least one phenalen-1-one compound with the general formula (1) is covalently bonded to the at least one polymeric component and/or precursor thereof.
15. The photosensitizer composition as claimed in claim 14, wherein the residue Ar respectively independently of each other represents a residue with the general formula (25a) to (31): ##STR00208## ##STR00209## ##STR00210## ##STR00211## wherein the residues R25, R26, R27, R28, R29, R26.sup.a, R26.sup.b, R27.sup.a, R27.sup.b, R28.sup.a, R28.sup.b, R29.sup.a, R29.sup.b, R30.sup.a and R30.sup.b respectively independently of each other represent hydrogen, hydroxy, amino, alkyl which may be linear or branched, containing 1 to 5 carbon atoms, *—O-alkyl which may be linear or branched, containing 1 to 5 carbon atoms, phenyl or benzyl, wherein phenyl and benzyl respectively independently of each other may be unsubstituted or substituted with one or more residues selected from the group consisting of chlorine, bromine, fluorine, methyl, ethyl, n-propyl, iso-propyl, methoxy, ethoxy, and combinations thereof, and wherein the residue R30 respectively independently of each other represents hydrogen or alkyl which may be linear or branched, containing 1 to 5 carbon atoms, and wherein the residues R33.sup.a and R33.sup.b respectively independently of each other represent hydrogen, hydroxy, amino, alkyl which may be linear or branched, containing 1 to 5 carbon atoms, perfluoralkyl which may be linear or branched, containing 1 to 5 carbon atoms, *—O-alkyl which may be linear or branched, containing 1 to 5 carbon atoms, phenyl, benzyl or, when taken together, a cycloalkyl which may be linear or branched, containing 4 to 9 carbon atoms, or a 9H-fluoren-9-ylidene residue, and wherein Y.sup.− is an anion which respectively independently of each other represents fluoride, chloride, bromide, iodide, sulphate, hydrogen sulphate, phosphate, hydrogen phosphate, dihydrogen phosphate, at least one carboxylate anion of a carboxylic acid containing 1 to 15 carbon atoms, at least one sulphonate anion of a sulphonic acid containing 1 to 12 C atoms, or a combination thereof.
16. The photosensitizer composition as claimed claim 14, wherein the at least one organic residue W1 respectively independently of each other represents a residue with the general formula (40) to (67) or (72) to (98e): ##STR00212## ##STR00213## ##STR00214## ##STR00215## ##STR00216## ##STR00217## ##STR00218## wherein Y.sup.− is an anion which respectively independently of each other represents fluoride, chloride, bromide, iodide, sulphate, hydrogen sulphate, phosphate, hydrogen phosphate, dihydrogen phosphate, at least one carboxylate anion of a carboxylic acid containing 1 to 15 carbon atoms, at least one sulphonate anion of a sulphonic acid containing 1 to 12 C atoms, or a combination thereof.
17. The photosensitizer composition as claimed in claim 14, comprising: (a) at least one phenalen-1-one compound with the general formula (1), which is selected from the group which consists of compounds with formula (100) to (127), (132) to (166): ##STR00219## ##STR00220## ##STR00221## ##STR00222## ##STR00223## ##STR00224## ##STR00225## ##STR00226## ##STR00227## ##STR00228## ##STR00229## ##STR00230## and combinations thereof, and (b) said at least one polymeric component and/or precursor thereof.
18. The photosensitizer composition as claimed in claim 14, comprising: (a) at least one phenalen-1-one compound with the general formula (1) which is a phenalen-1-one compound with the general formula (1a): ##STR00231## wherein the residues R1.sup.a to R8.sup.a, which respectively independently of one another may be identical to or different from each other, respectively represent hydrogen, halogen, alkyl containing 1 to 12 C atoms, alkylaryl containing 5 to 20 C atoms, aryl containing 5 to 20 C atoms, *—O-alkyl containing 1 to 12 C atoms, *—O-alkylaryl containing 5 to 20 C atoms, **—O-aryl containing 5 to 20 C atoms, ether containing 2 to 12 C atoms, a residue with the formula *—O—C(═O)—R.sup.(Ia), a residue with the formula *—C(═O)—R.sup.(Ib), or an organic residue W1a which contains at least one functional group, with the proviso that at least one of the residues R1.sup.a or R2.sup.a is an organic residue W1a, wherein the organic residue W1a respectively independently of each other represents a residue with the general formula (2a) to (6a):
*—[(C(D)(E)).sub.d—B].sub.e—(C(D)(E)).sub.m—X.sup.a (2a)
*-A—[(C(D)(E)).sub.d—B].sub.c—(C(D)(E)).sub.m—X.sup.a (3a)
*—(C(D)(E)).sub.d-AR—(C(D)(E)).sub.n—X.sup.a (4a)
*—[(C(D)(E)).sub.d—B].sub.b—(C(D)(E)).sub.g-AR—(C(D)(E)).sub.n—X.sup.a (5a)
*-A—[(C(D)(E)).sub.d—B].sub.f—(C(D)(E)).sub.g-AR—(C(D)(E)).sub.n—X.sup.a (6a) wherein the residue A respectively independently of each other represents oxygen, sulphur or a residue with the general formula (10a) to (11a): ##STR00232## wherein *.sup.ph respectively denotes a linkage from the residue with the general formula (10a) to (11a) to a C atom of the phenalene ring and *.sup.c respectively denotes a linkage from the residue with the general formula (10a) to (11a) to a C atom of the residue (C(D)(E)), wherein the residue B respectively independently of each other represents oxygen, sulphur or a residue with the general formula (10) to (12): ##STR00233## and wherein the residues R.sup.(Ia), R.sup.(Ib), R.sup.(11a), R.sup.(12a) respectively independently of each other represent methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, n-pentyl, phenyl or benzyl, and wherein phenyl and benzyl respectively independently of each other may be unsubstituted or substituted with one or more residues selected from the group consisting of chlorine, bromine, fluorine, methyl, ethyl, n-propyl, iso-propyl, methoxy, ethoxy, and combinations thereof, and wherein the residues D and E respectively independently of each other represent hydrogen, halogen, hydroxyl, alkyl which may be linear or branched, containing 1 to 5 carbon atoms, hydroxyalkyl which may be linear or branched, containing 1 to 5 carbon atoms and 1 to 5 OH groups, phenyl, benzyl, a residue with the formula *-L—R .sup.(II), a residue with the formula *-L—C(=L)-R.sup.(III), a residue with the formula *—(CH.sub.2).sub.q—X.sup.a, a residue with the formula *-L —(CH.sub.2).sub.q—X.sup.a, or a residue with the formula *—(CH.sub.2).sub.s-L—(CH.sub.2).sub.t—X.sup.a, wherein the residue L respectively independently of each other represents oxygen or sulphur, wherein the residues R.sup.(II) and R.sup.(III) respectively independently of each other, represent hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, n-pentyl, phenyl or benzyl, and wherein phenyl and benzyl respectively independently of each other may be unsubstituted or substituted with one or more residues selected from the group consisting of chlorine, bromine, fluorine, methyl, ethyl, n-propyl, iso-propyl, methoxy, ethoxy, and combinations thereof, the indices q, s and t respectively independently of each other representing a whole number from 1 to 5, wherein the indices c, g, f and n respectively independently of each other represent a whole number from 0 to 5, and wherein the indices b, d, e and m respectively independently of each other represent a whole number from 1 to 5, wherein the residue Ar respectively independently of each other represents a substituted or unsubstituted aromatic residue or a substituted or unsubstituted heteroaromatic residue which contains no N atoms, and wherein the residue X.sup.a respectively independently of each other represents a functional group *—OH, *—SH, *—NCO, *—NCS, *—Si(R.sup.(VIII))(R.sup.(IX))—[O—Si(R.sup.(X))(R.sup.(XI))].sub.p—Z, or a residue with the general formula (20) to (24): ##STR00234## wherein the residues R.sup.(20a), R.sup.(20b), R.sup.(20c), R.sup.(21a), R.sup.(22a), R.sup.(22b), R.sup.(22c), R.sup.(23a), R.sup.(24a), R.sup.(24b), and R.sup.(24c) respectively independent of each other, represent hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, or n-pentyl, and wherein the indices l and k respectively independently of each other represent a whole number from 0 to 4, wherein the residues R.sup.(VIII), R.sup.(IX), R.sup.(X) and R.sup.(XI) respectively independently of each other represent hydrogen, alkyl which may be linear or branched, containing 1 to 5 carbon atoms, —O-alkyl which may be linear or branched, containing 1 to 5 carbon atoms, phenyl or benzyl, wherein phenyl and benzyl respectively independently of each other may be unsubstituted or substituted with one or more residues selected from the group consisting of chlorine, bromine, fluorine, methyl, ethyl, n-propyl, iso-propyl, methoxy, ethoxy, and combinations thereof, wherein the residue Z respectively independently of each other represents halogen, hydroxyl, alkoxyl containing 1 to 4 carbon atoms or alkylcarboxyl containing 1 to 4 carbon atoms, and wherein the index p respectively independently of each other represents a whole number from 0 to 4, and (b) said at least one polymeric component and/or precursor thereof.
19. The photosensitizer composition as claimed in claim 14, wherein the composition furthermore comprises at least one crosslinking agent, which contains at least one polyisocyanate, a blocked isocyanate, at least one alkyl diisocyanate or cycloalkyl diisocyanate or aryl diisocyanate, a compound with the general formula SiZ.sub.4, (R.sup.XII)SiZ.sub.3, (R.sup.XII).sub.2SiZ.sub.2, a compound containing at least two epoxy residues, a compound containing at least two acrylamide residues, a compound containing at least two acrylate residues, a compound containing at least two aldehyde residues, a compound containing at least two alcohol groups, a compound containing at least two amine residues, a divinylsulphone, or combinations thereof, wherein the residue R.sup.XII respectively independently of each other represents alkyl which may be linear or branched, containing 1 to 5 carbon atoms, phenyl or benzyl, and wherein the residue Z respectively independently of each other represents halogen, hydroxyl, alkoxyl containing 1 to 4 carbon atoms or alkylcarboxyl containing 1 to 4 carbon atoms.
20. The photosensitizer composition as claimed in claim 14, wherein the photosensitizer composition is a paint, a varnish, an emulsion paint, a latex paint, a silicate paint, or a chalk paint.
21. The photosensitizer composition as claimed in claim 14, wherein the photosensitizer composition is a granulate.
Description
(1) The invention will now be explained by means of figures and examples without being limited in any way thereto.
BRIEF DESCRIPTION OF DRAWINGS
(2)
(3)
(4)
(5)
DESCRIPTION OF PREFERRED EMBODIMENTS
(6) All of the chemicals used were purchased from established suppliers (Thermo Fisher Scientific, Polysciences Europe GmbH, Sigma Aldrich, TCI, ABCR, Acros, Merck and Fluka) and used without further purification. Solvents were distilled prior to use and, if necessary, were dried in the usual manner. Dry DMF was purchased from Fluka (Taufkirchen, DE).
(7) Thin layer chromatography was carried out on thin layer aluminium foil coated with 60 F254 silica gel from Merck (Darmstadt, DE). Preparative thin layer chromatography was carried out on commercially available glass plates coated with silica gel 60 (20 cm×20 cm, Carl Roth GmbH & Co. KG, Karlsruhe, DE)). The compounds were detected using UV light (λ=254 nm, 333 nm) and sometimes detected with the naked eye or stained with ninhydrin. Chromatography was carried out using silica gel (0.060-0.200) from Acros (Waltham, US).
(8) NMR spectra were measured on a Bruker Avance 300 spectrometer (300 MHz [1H-NMR]) (Bruker Corporation, Billerica, US).
(9) All of the chemical displacements are given in δ [ppm] relative to an external standard (tetramethylsilane, TMS). The coupling constants are respectively given in Hz; characterization of signals: s=singlet, d=doublet, t=triplet, m=multiplet, dd=doublet of doublets, br=broad. Integration determined the relative number of atoms. The unequivocal determination of the signals in the carbon spectrum was carried out using the DEPT method (pulse angle: 135°). Error limits: 0.01 ppm for .sup.1H-NMR and 0.1 Hz for coupling constants. The solvent used is recorded for each spectrum.
(10) The IR spectra were recorded on a Biorad Excalibur FTS 3000 spectrometer (Bio-Rad Laboratories GmbH, Munich, DE).
(11) ES-MS spectra were measured using a ThermoQuest Finnigan TSQ 7000 spectrometer, all HR-MS spectra were determined on a ThermoQuest Finnigan MAT 95 spectrometer (each from Thermo Fisher Scientific Inc, Waltham, US), and argon was used as the ionization gas for FAB.
(12) The melting points were determined with the aid of the Büchi SMP-20 melting point measuring instrument (Büchi Labortechnik GmbH, Essen, DE) using a glass capillary.
(13) All of the UV/vis spectra were recorded using a Varian Cary 50 bio UV/VIS spectrometer, and fluorescence spectra were recorded with a Varian Cary Eclipse spectrometer (both from Agilent Technologies, Santa Clara, US).
(14) The solvents for the absorption and emission measurements were purchased from Acros or Baker or Uvasol from Merck in special spectroscopic grades. Millipore water (18MΩ, Milli QPlus) was used for all measurements.
EXAMPLE 1
Production of the Phenalen-1-One Derivatives
(15) ##STR00039## 1. Production of 2-chloromethyl-1H-phenalen-1-one
(16) 2-chloromethyl-1H-phenalen-1-one was obtained using the method described in Example 1 of US 2014/039184 A1. The NMR spectrum corresponded to the values disclosed in US 2014/039184 A1. 2. General Specification a):
(17) TABLE-US-00003 Substituted pyridine in overview 1, step a) MW Weight Product [g/mol] [mg] Formula Designation 2.1 4-pyridine methanol (Sigma-Aldrich) R.sup.a = *—CH.sub.2OH 109.13 270 .fwdarw.
(18) 2-chloromethyl-1H-phenalen-1-one (115 mg, 0.5 mmol) was placed in acetonitrile (6 mL). The substituted pyridine given above (2.5 mmol) was respectively added slowly in small portions. The suspension was stirred for 3 days at room temperature in the dark.
(19) For purification, the suspension was divided into two polypropylene tubes with conical bases (nominal volume 15 mL, Greiner Bio-One GmbH, Frickenhausen, DE) and precipitated by adding diethyl ether up to 15 mL per tube. The product was centrifuged (60 mins, 4400 rpm, 0° C.) and the supernatant was discarded. The precipitate was suspended in diethyl ether. After the product had settled out, in each case, the supernatant was discarded. The purification step was repeated once more and the product was then dried. 3. General Specification b):
(20) TABLE-US-00004 Substituted dimethylamine in overview 1, step b) MW Weight Product [g/mol] [mg] Formula Designation 3.1 N,N- dimethylallylamine (Sigma-Aldrich) R.sup.b1 = 2-propen-1-yl R.sup.b2, R.sup.b3 = methyl 85.16 170 .fwdarw.
(21) 2-chloromethyl-1H-phenalen-1-one (115 mg, 0.5 mmol) was placed in acetonitrile (6 mL). The substituted dimethylamine given above (2 mmol) was respectively added slowly in small portions. The suspension was stirred for 48 h at room temperature in the dark.
(22) For purification, the suspension was divided into two polypropylene tubes with conical bases (nominal volume 15 mL, Greiner Bio-One GmbH) and precipitated by adding diethyl ether up to 15 mL per tube. The product was centrifuged (60 mins, 4400 rpm, 0° C.) and the supernatant was discarded. The precipitated was suspended in diethyl ether. After the product had settled out, in each case, the supernatant was discarded. The purification step was repeated once more and the product was then dried. 4. Specification c): Production of 2-hydroxymethyl-1H-phenalen-1-one [Designation: PNOH, compound (100)]
(23) ##STR00057##
(24) 2-chloromethyl-1H-phenalen-1-one (230 mg, 1 mmol) was dissolved in 20 mL of toluene. Aqueous sodium hydroxide (4N, 5 mL) and the phase transfer catalyst tetrabutylammonium hydrogen sulphate (100 mg) were added. The reaction mixture was stirred vigorously for 6 h at room temperature. A yellow-brown precipitate was formed. The precipitate was filtered off and washed with water (4 times, 20 mL), toluene and petroleum ether (respectively 1 time, 20 mL). The product was dried in air to constant weight. 5. General specification d):
(25) TABLE-US-00005 Carboxylic acid in overview 1, step d) MW Weight Product [g/mol] [mg] Formula Designation 5.1 acrylic acid (Sigma-Aldrich) R.sup.d = *—CH═CH.sub.2 72.06 72 .fwdarw.
(26) Variation 1:
(27) The carboxylic acids given above (1 mmol) were respectively neutralized with an equimolar quantity of sodium hydroxide and the sodium salt of the carboxylic acid obtained was isolated by freeze drying.
(28) 2-chloromethyl-1H-phenalen-1-one (115 mg, 0.5 mmol) was dissolved in toluene (3 mL). The sodium salt of the carboxylic acid given above, hydroquinone (11 mg, 0.1 mmol) and Adogen® 464 (200 mg) were added and the reaction mixture was refluxed for 4 h with vigorous stirring. After cooling to room temperature, it was diluted with toluene (20 mL) and shaken with water (30 mL). The aqueous phase was extracted twice with acetic acid ethyl ester (20 mL). The organic phases were combined, washed with water (50 mL) separated and dried over magnesium sulphate.
(29) After filtration and concentration under reduced pressure, the raw product was purified by flash chromatography (DCM/PE 2:1).
(30) Variation 2:
(31) Compound (100) (65 mg, 0.3 mmol) was dissolved in dry THF (1 mL). The aforementioned carboxylic acid, hydroquinone (11 mg, 0.1 mmol), DMAP (61 mg, 0.5 mmol) and DCC (103 mg, 0.5 mmol) were added at 2-5° C. The reaction mixture was stirred vigorously for 4 h at RT. It was diluted with acetic acid ethyl ester (20 mL) and shaken with water (30 mL). The aqueous phase was extracted twice with acetic acid ethyl ester (20 mL). The organic phases were combined, washed with water (50 mL), separated and dried over magnesium sulphate.
(32) After filtration and concentration under reduced pressure, the raw product was purified by flash chromatography (DCM/PE 2:1). 6. General specification e):
(33) TABLE-US-00006 Substituted alcohol in overview 1, step e) MW Weight Product [g/mol] [mg] Formula Designation 6.1 allyl alcohol (Sigma-Aldrich) R.sup.e = 2-propen-1-yl 58.08 58 .fwdarw.
(34) 2-chloromethyl-1H-phenalen-1-one (115 mg, 0.5 mmol) was placed in toluene (4 mL). The aforementioned substituted alcohol (1 mmol), hydroquinone (11 mg, 0.1 mmol) and tetrabutylammonium hydrogen sulphate (100 mg) were added. 2 mL of aqueous 4N sodium hydroxide was added to the vigorously stirred solution at 2-5° C. The ice bath was removed and the reaction mixture was stirred vigorously for a further 6 h. It was diluted with 30 mL DCM and shaken several times with water (4 times, each time 20 mL).
(35) The organic phase was separated out and dried over magnesium sulphate. After filtration and concentration under reduced pressure, the raw product was purified by flash chromatography (DCM/PE 2:1). 7. General specification t):
(36) TABLE-US-00007 Substituted silyl chloride in overview 1, step f) MW Weight Product [g/mol] [mg] Formula Designation 7.1 Triethoxychlorosilane (Sigma-Aldrich) R.sup.f1, R.sup.f2, R.sup.f3 = ethoxy 198.72 76 .fwdarw.
(37) 2-hydroxymethyl-1H-phenalen-1-one (70 mg, 0.3 mmol) was placed together with imidazole (30 mg, 0.4 mmol) in dry DCM (3 mL) in a 10 mL round bottomed flask with a septum, under nitrogen. The aforementioned substituted silyl chloride (0.4 mmol) in 2 mL of dry DCM was slowly added dropwise through the septum using a syringe, at approximately 0° C. The ice bath was removed and the reaction mixture was stirred at room temperature overnight. It was diluted with 30 mL DCM and shaken several times with water (4 times, 20 mL each time). The organic phase was separated and dried over magnesium sulphate. After filtration and concentration under reduced pressure, the raw product was purified using flash chromatography (DCM/PE 2:1). 8. General specification g):
(38) TABLE-US-00008 Carboxylic acid in overview 1, step g) MW Weight Product [g/mol] [mg] Formula Designation 8.1 acrylic acid R.sup.g = *—CH═CH.sub.2 72.06 53 .fwdarw.
(39) 3-hydroxy-phenalen-1-on (Sigma-Aldrich) (100 mg, 0.5 mmol) was placed together with triphenylphosphine (50 mg, 1 mmol) and the aforementioned carboxylic acid (0.6 mmol) in dry THF (5 mL) in a 10 mL round bottomed flask with a septum, under nitrogen. DCC (103 mg, 0.5 mmol) in dry THF (1 mL) was slowly added dropwise through the septum using a syringe, at approximately 0° C. After stirring for 2 h in the ice bath, a further portion of DCC (103 mg, 0.5 mmol) in dry THF (1 mL) was added dropwise. The reaction mixture was stirred in the thawing ice bath, then at room temperature for 6 h. The THF was withdrawn, the residue was taken up in 30 mL of DCM and shaken several times with water (4 times, 20 mL).
(40) The organic phase was separated and dried over magnesium sulphate. After filtration and concentration under reduced pressure, the raw product was purified using flash chromatography (DCM/PE 2:1). 9. General specification h):
(41) TABLE-US-00009 Substituted alcohol in overview 1, step h) MW Weight Product [g/mol] [mg] Formula Designation 9.1 allyl alcohol R.sup.h = 2-propen-1-yl 58.08 23 .fwdarw.
(42) 3-hydroxy-phenalen-1-on (60 mg, 0.3 mmol) was placed together with triphenylphosphine (30 mg, 0.6 mmol) in DCM (3 mL) and the aforementioned substituted alcohol (0.4 mmol) in a 10 mL round bottomed flask with a septum, under nitrogen. DEAD in toluene (40%, 0.2 mL, 0.4 mmol) was slowly added dropwise using a syringe via the septum, at approximately 0° C. The reaction mixture was stirred in the thawing ice bath, then at room temperature for 6 h. It was diluted with 30 mL of DCM and shaken several times with water (4 times, 20 mL). The organic phase was separated and dried over magnesium sulphate. After filtration and concentration under reduced pressure, the raw product was purified using flash chromatography (DCM/PE 2:1). 10. Specification k): Production of 2-(N-methylamino)methyl-1H-phenalen-1-one hydrochloride [Designation: SAPN-02c, compound (158)]
(43) ##STR00079##
(44) 2-chloromethyl-1H-phenalen-1-one (113 mg, 0.5 mmol) in methanol (10 mL) was added dropwise to an ice cold solution of the amine in methanol (10 mL, 5M) over 2 h. After stirring vigorously for 1 h at room temperature, the solvent together with the surplus amine was driven off in the stream of nitrogen. The residue was dissolved in as little DCM/ethanol 4:1 as possible and precipitated by adding diethyl ether. The product was centrifuged (60 mins, 4400 rpm, 0° C.) and the supernatant was discarded. The precipitate was suspended in diethyl ether and centrifuged again. The purification step was repeated once more and the product was then dried. 11. General specification I):
(45) TABLE-US-00010 Carboxylic acid chloride in overview 1, step l) MW Weight Product [g/mol] [mg] Formula Designation 11.1 acrylic acid chloride (Merck-Millipore) R.sup.k = methyl R.sup.l = 2-ethen-1-yl 90.5 36 .fwdarw.
(46) 2-(N-methylamino)methyl-1H-phenalen-1-one hydrochloride (80 mg, 0.3 mmol) was dissolved with triethylamine (100 mg, 1 mmol) in DCM (3 mL) and stirred in an ice bath with the exclusion of moisture. The corresponding carboxylic acid chloride (0.4 mmol) in DCM (0.5 mL) was added dropwise. The reaction mixture was stirred in the thawing ice bath, then at room temperature for 4 h. It was diluted with 30 mL of DCM and shaken several times with water (4 times, 20 mL). The organic phase was separated and dried over magnesium sulphate. After filtration and concentration under reduced pressure, the raw product was purified using flash chromatography. 12. Synthesis of compound (127) [Designation: PN-AMO-01]
(47) ##STR00082##
(48) 2-chlormethyl-1H-phenalen-1-one (230 mg, 1.0 mmol) in acetonitrile (20 mL) was added dropwise to a solution of 3-aminopropanol (1.5 mL, 20 mmol) in acetonitrile (50 mL) over 30 min. After stirring overnight at room temperature, triethylamine (2.02 g, 2.66 mL, 20 mmol) was added and the solution was stirred in an ice bath. Acetic acid anhydride (3.06 g, 2.83 mL, 30 mmol) was added dropwise at approximately 0° C. The reaction mixture was stirred for 2 h at room temperature, then heated to 50° C. for 1 h. All of the volatile components were removed under reduced pressure.
(49) The product was purified by column chromatography using dichloromethane/ethanol 20:1. 261 mg of a yellow syrup was obtained. This material was dissolved in methanol (2 mL). Aqueous sodium hydroxide (1M, 0.5 mL) was added and the mixture was stirred overnight at room temperature. The alcohol was withdrawn and the remaining solution was diluted with water (10 mL). The product was extracted with dichloromethane (2×10 mL). The organic phases were dried over magnesium sulphate, filtered and concentrated under reduced pressure. The product was a yellowish, greasy solid (215 mg, 69%, 0.69 mmol). 13. Deprotection of the Boc group
(50) TABLE-US-00011 Product Protected phenalenone derivative Formula Designation 13.1
(51) The corresponding tert-butyloxycarbonyl (Boc-protected phenalenone derivative was placed in dichloromethane (3 mL per 100 mg). A saturated solution of hydrochloric acid in diethyl ether (0.5 mL per mmol Boc group) was added dropwise. The batch was stirred for 3 h with the exclusion of moisture. The product was precipitated by adding 30 mL of diethyl ether. The precipitate was centrifuged and washed thoroughly with diethyl ether. The product was dried under reduced pressure.
(52) The respective calculated molecular weight (MW) and molecular formula (MF) as well as the data for the measured mass spectra (MS) and .sup.1H NMR spectra are given below for the compounds produced.
(53) TABLE-US-00012 Molecular weight Substance (MW) / Molecular No. Structure formula (MF) Mass spectrum (MS) NMR 2.1 SAPN-19a
EXAMPLE 2
Production of Antimicrobial Surface Coatings
(54) The photosensitizers produced in Example 1 were tested in a variety of paint systems, as follows. 1) 2-component (2-C) polyurethane paint, containing solvent
(55) The respective photosensitizer (0.06 mmol) was dissolved in 100 mL of clear basic paint (polyisocyanate cross-linkable, hydroxyl group-containing acrylic resin, 20% in xylene/n-butyl acetate). The cross-linking agent (hexamethylene diisocyanate (HDI)—containing polymer, 20% in xylene/n-butyl acetate, “Desmodur® N75” from Covestro AG, Leverkusen, DE) was mixed with the basic paint in a ratio of 5:1 (v/v). The viscous, pale yellow solution was applied to a variety of degreased surfaces using a spray gun. The tested substances were PMMA, PVC, glass, aluminium, stainless steel and wood. After drying for 4 h at room temperature, complete hardening was obtained by heating to 60° C. for 30 min.
(56) The following photosensitizers were processed using this method:
(57) ##STR00136## ##STR00137##
(58) Result: transparent, pale yellow, homogeneous coating; layer thickness between 20 and 40 μm. 2) 1-component (1-C) polyurethane paint, water-based
(59) The respective photosensitizer (0.05 mmol) was dissolved in the water-based paint (100 mL, acrylic-polyurethane emulsion, fatty acid-modified, 20% in water). The mixture was vigorously stirred for 30 min at room temperature. The paint was applied evenly to i) an untreated wooden board, ii) PMMA plates or iii) PVC plates using a brush. Alternatively, the paint was applied using a spray gun, evenly from a distance of approximately 30 cm. The coating was allowed to dry in air and was allowed to harden overnight at room temperature.
(60) The following photosensitizers were processed using this method:
(61) ##STR00138##
(62) Result: transparent, matte, pale yellow, homogeneous coating; layer thickness approximately 50 μm. 3) 2-C epoxy resins
(63) Composition of Basic Resins (Typical Technical Products): Formulation I (resin with reactive diluent): bisphenol-A-epichlorohydrin resin with mean molecular weight of <700 g/mol (25-50%) C12-C14 aliphatic glycidyl ether (25-50%) alkylglycidyl ether (5-25%) Formulation II (resin with reactive diluent): bisphenol-A-epichlorohydrin resin with mean molecular weight of <700 g/mol (60-80%) 1,4-bis(2,3-epoxypropoxy)butane (20-40%) Formulation III (resin with reactive diluent): bisphenol-A-epichlorohydrin resin with mean molecular weight of <700 g/mol (75-90%) hexanediol diglycidyl ether (10-25%) Formulation IV (resin with reactive diluent): bisphenol-A-epichlorohydrin resin with mean molecular weight of <700 g/mol (50-90%) bisphenol F epoxy resin (25-50%) C12-C14 aliphatic glycidyl ether (10-20%) 1,4-bis(2,3-epoxypropoxy)butane (10-20%)
(64) Composition of Hardener (Typical Technical Products): Formulation I (normal hardener): isophorone diamine (aminomethyl-3,5,5-trimethyl-cyclohexylamine) (10-25%) benzyl alcohol (25-50%) 2,2,4-trimethylhexane-1,6-diamine (3-10%) Formulation II (normal hardener): isophorone diamine (aminomethyl-3,5,5-trimethyl-cyclohexylamine) (44%) xylidene diamine (10%) trimethylhexamethylene diamine (5%) salicylic acid (1%) polyethylene amine (10%) benzyl alcohol (30%) Formulation III (rapid hardener): diaminocyclohexane (18%) pentamethylene diamine (25%) salicylic acid (2%) polyethylene amine (20%) benzyl alcohol (35%) Optionally with accelerator/catalyst: N-benzyldimethylamine (BDMA) and/or N,N,N,N-tetramethyl-1,3-butanediamine (TMBDA) and/or 2-methyl imidazole (2MI)
(65) Variation a)
(66) The respective photosensitizer (0.05 mmol) was dissolved in 25 mL of the clear hardener (formulation I or II). From the basic resin (formulation II, Ill or IV), 75 mL was mixed with the hardener. The viscous, pale yellow solution was applied to degreased surfaces formed from i) PMMA or ii) PVC using a spray gun.
(67) Alternatively, the mixture was applied with a brush several times in even coats to untreated wood, in order to obtain an antimicrobial seal. After hardening for 12h at room temperature, post-hardening was carried out by heating to 40° C. for 6h.
(68) The following photosensitizers were processed using this method:
(69) ##STR00139##
(70) Result: transparent, pale yellow, homogeneous coating; layer thickness between 20 and 40 μm.
(71) Variation b)
(72) The respective photosensitizer (0.05 mmol) was dissolved in 30 mL of the clear hardener (formulation II or III). From the basic resin (formulation I), 70 mL was mixed with the hardener. A flat stainless steel pan was evenly coated with release wax. In it, i) a glass fibre mat, ii) a piece of CFRP fabric or iii) a piece of aramid fabric (each 20×20 cm.sup.2) was evenly impregnated with the resin mixture with a brush so that the fabric could completely take up the mixture. After hardening for 24 hours at room temperature, post-hardening was carried out by slowly heating to 60° C. and holding for 30 min.
(73) The following photosensitizers were processed using this method:
(74) ##STR00140##
(75) Result: stiff, limited flexibility fibrous mat; intrinsic colour of colorant could not be discerned.
(76) Variation c)
(77) The respective photosensitizer (0.05 mmol) was dissolved in 70 mL of the basic resin (formulation II, Ill or IV). Of the hardener (formulation III), 30 mL was mixed in. The viscous, pale yellow solution was applied with a spray gun to degreased surfaces formed from i) PMMA or ii) roughened glass.
(78) Alternatively, the mixture was applied to untreated wood several times in even coats with a brush, in order to obtain an antimicrobial seal. After hardening for 6h at room temperature, post-hardening was carried out by heating to 40° C. for 3h. The following examples were processed using this method:
(79) ##STR00141##
(80) Result: transparent, pale yellow, homogeneous coating; layer thickness between 20 and 40 μm, when brush used: >50 μm. 4) Room temperature-vulcanizing 1-component (RTV-1) silicone,
(81) Typical composition of the silicone (technical product from Wacker): polydimethylsiloxane diol and polydimethylsiloxane as a mixture with silicon dioxide (filler) and triacetoxymethylsilane (cross-linking agent, <5%)
(82) Variation a)
(83) Clear sanitary silicone (1-C, room temperature-crosslinking, acid-crosslinking, 5.0 g) was dissolved in hexane (10 mL). A solution of the respective photosensitizer (0.012 mmol) in dry dichloromethane (20 mL) was mixed in. The slightly opaque, pale yellow, viscous solution was evenly applied to i) a degreased glass plate, ii) a degreased PMMA plate, iii) a ceramic plate or iv) a polyester film. After approximately 15 min at room temperature, the coating had dried; approximately 10 min later, skin formation had commenced. After 6h at room temperature, the approximately 0.1 mm thick layer had hardened all the way through.
(84) Result: transparent, matte, pale yellow, homogeneous, rubber-like coating.
(85) Variation b)
(86) The respective photosensitizer (0.02 mmol) was dissolved in dry ethyl acetate (100 mL). Clear sanitary silicone (1-C, room temperature-crosslinking, acid-crosslinking, 8.0 g) was added and the solution was stirred until it was homogeneous. The slightly opaque, pale yellow solution was evenly applied to i) a clay plate, ii) a ceramic tile, iii) a degreased PE plate or iii) an aluminium plate, using a spray gun. After approximately 20 min at room temperature the coating had dried; approximately 10 min later, skin formation had commenced. After 6 h at room temperature the approximately 0.1 mm thick layer had hardened all the way through.
(87) Result: transparent, matte, pale yellow, homogeneous, rubber-like coating.
(88) Variation c)
(89) The finely powdered photosensitizer (0.012 mmol) was stirred into clear sanitary silicone (1-C, room temperature-crosslinking, acid-crosslinking, 5.0 g) in a SpeedMixer™ DAC 600 (Hauschild Engineering, Germany) mixer at room temperature, until a macroscopically homogeneous paste was obtained. The pale yellow, viscous mass was evenly applied using a disposable syringe to i) a tile grout or ii) to bond two glass plates which were stacked vertically one on top of the other. After approximately 30 min at room temperature the silicone had dried; approximately 20 min later, skin formation had commenced. After 6h at room temperature, the layer had hardened all the way through.
(90) The following photosensitizers in the three variations were processed into pale yellow, rubber-like silicone grouts:
(91) ##STR00142##
(92) Result: transparent, matte, pale yellow, homogeneous, rubber-like grout. 5) Room temperature-vulcanizing 2-component (RTV-2) silicone
(93) Typical composition of the silicone (technical product from Wacker): component A) oligomeric silane containing vinyl groups/vinylsilane and component B) polydimethylsiloxane as a mixture with silicon dioxide (filler) and adjuvants and platinum catalyst.
(94) The base polymer (A) was mixed with the crosslinking agent (B) in a ratio of 9:1.
(95) The finely powdered photosensitizer (0.05 mmol) was stirred into 90 g of the base polymer (A) at room temperature, until a macroscopically homogeneous paste was obtained. The pale yellow, viscous mass was mixed with the crosslinking agent (B) in a ratio of 9:1 with the aid of a flat spatula, evenly applied to i) a polyester film, ii) a ceramic tile, a degreased glass plate, iv) a degreased PE plate or v) an aluminium plate (50 mL per m.sup.2).
(96) After approximately 30 min at room temperature, initial skin formation had occurred. After 8 h at room temperature the layer had hardened all the way through.
(97) The following photosensitizers were processed into silicone coatings:
(98) ##STR00143## ##STR00144##
(99) Result: transparent, matt, pale yellow, homogeneous, rubber-like coating. 6) Polyacrylate, 1-C
(100) The finely powdered photosensitizer (0.05 mmol) was dissolved in 100 mL of methacrylic acid ethyl ester (dry conditions). Camphor quinone (1.7 mg, 0.01 mmol) and 4-dimethylaminobenzoic acid methyl ester (0.9 mg, 0.005 mmol, amine accelerator) were added and the mixture was stirred for 15 min in the dark. The solution could be kept for weeks in the dark.
(101) The solution was applied to i) wood with a brush or ii) absorbed into a filter paper or iii) sprayed evenly onto a degreased PMMA plate.
(102) In the second step, illumination was carried out using a polymerization lamp (LED Bluephase; IvoclarVivadent AG, at 650 mW/cm.sup.2) for 30 seconds. After production, the test specimens were stored in a drying cabinet at 37° C. for 24 h in order to complete the polymerization. The following photosensitizers were used in the experiments:
(103) ##STR00145## ##STR00146##
(104) Result: the following were obtained: i) transparent, polymeric seal, ii) a partially flexible, pale yellow platelet or iii) transparent, pale yellow, paint-like coating. 7) Polyacrylate, 2-C
(105) Variation a)
(106) The respective photosensitizer (0.05 mmol) was dissolved in 100 mL of methacrylic acid methyl ester (methyl methacrylate, MMA, Sigma Aldrich) (solution A). Tert-butyl peroxybenzoate (Peroxan PB, 0.5 g) was dissolved in THF (2 mL) (solution B). Solution B was added to solution A and the mixture was heated for 15 min at 90° C. in a water bath. The slightly viscous solution was i) applied to a degreased PMMA plate or ii) sprayed onto a degreased glass plate or iii) applied to pine wood and distributed evenly with a brush (50 mL per m.sup.2). To completely harden the acrylic glass coating, the support was stored for 24 hours at 60° C. in a drying cabinet. A pale yellow, clear synthetic material coating or polymeric seal for the wood was obtained.
(107) Result: transparent, homogeneous, paint-like coating; in i) and ii), the yellow intrinsic colour of the layer was barely detectable, in iii), the intrinsic colour could not be distinguished from the background.
(108) Variation b)
(109) The respective photosensitizer (0.05 mmol) was dissolved in 100 mL of methacrylic acid methyl ester (methyl methacrylate, MMA, Sigma Aldrich) (solution A). Benzoyl peroxide (0.5 g) was dissolved in THF (2 mL) (solution B). Solution B was added to solution A and the mixture was heated for 20 min at 80° C. in a water bath. With the mixture, i) approximately 6 mm thick cotton fleece or ii) an approximately 6 mm thick felt mat or iii) a piece of aramid fabric (each 20×20 cm.sup.2) was impregnated evenly with a brush, so that the fabric could take up the mixture in its entirety.
(110) In order to harden the acrylic glass completely, the fibrous mats were dried for 12 hours at 60° C. A solid yellowish plate was obtained. The following photosensitizers were processed:
(111) ##STR00147## ##STR00148##
(112) Result: stiff, limited flexibility fibrous mat; intrinsic colour of colorant could only just be discerned in i).
(113) 8) Polyacrylamide
(114) A 40% solution of acrylamide/bis-acrylamide (37.5:1) in water (2.5 mL) was mixed with Tris buffer (3.75 mL, 1M, pH 8.8) and propylene glycol (0.6 mL). The respective photosensitizer (0.005 mmol) in distilled water (3.0 mL) was added. The solution was degassed for 5 minutes with a vacuum pump (5-10 mbar) and then TEMED was added (10 μL). Finally, 0.05 mL of ammonium persulphate (10% in water) was added, with stirring.
(115) Next, i) a 3 mm thick cassette (plates previously cleaned with 70% alcohol) was filled with the mixture and carefully overlaid with isopropanol. After polymerization for 30 min at room temperature, the gel was solid and the supernatant could be poured away. After removing the chamber plates, a flexible, thick pale yellow film was obtained. Alternatively, ii) the mixture was evenly applied to a fleece.
(116) During the polymerization, the material was covered with cling film. After polymerization for 30 min at room temperature, the gel was solid and the film was carefully removed. A gel-like yellowish coating was obtained.
(117) The following photosensitizers were polymerized in this manner:
(118) ##STR00149## ##STR00150##
(119) Result: i) rubber-like, slightly opaque, pale yellow mat; ii) transparent, matt, pale yellow, homogeneous, rubber-like coating. 9) Cyanoacrylate
(120) Variation a)
(121) The respective photosensitizer (0.01 mmol) was dissolved in 100 mL of dichloromethane (dried over calcium chloride). 0.2 g of commercial cyanoacrylate (Loctite, Henkel AG & Co. KGaA, Düsseldorf, DE) was added to 1 g of the solution (dry conditions). The mixture was evenly sprayed onto a) a degreased glass plate or b) dry spruce wood. At room temperature and with a humidity of between 20% and 70%, the layer hardened completely within 20 min.
(122) Variation b)
(123) The respective photosensitizer (0.01 mmol) was dissolved in 100 mL of dry methylethylketone. Commercial cyanoacrylate (Loctite.) was mixed with 10 g of the solution in a ratio of 1:5 (w/w). The solution was evenly applied to a substrate cleaned with isopropanol, for example i) glass or ii) PE or iii) melamine plate. After evaporation of the solvent, the coating cured in the moisture of the air (approximately 15 min, humidity between 20% and 70%).
(124) The following photosensitizers were processed in accordance with the respective variation:
(125) ##STR00151## ##STR00152##
(126) Result: transparent, slightly opaque, pale yellow, homogeneous coating; layer thickness between 20 and 40 μm. 10) Polystyrene
(127) The respective photosensitizer (0.01 mmol) was dissolved in 20 mL of freshly distilled polystyrene (Sigma Aldrich) (solution A). Benzoyl peroxide (0.5 g) was dissolved in THF (2 mL) (solution B). Solution B was added to solution A and the mixture was heated for 20 min at 80° C. in a water bath. 5 to 6 mL of the mixture was painted evenly onto i) a clean, untreated chipboard or ii) a degreased PMMA plate or iii) a degreased glass plate (each 20×20 cm.sup.2) with a brush. The support was left for 12 hours at 60° C. in order to dry fully. A solid yellow plate was obtained. The following photosensitizers were processed:
(128) ##STR00153## ##STR00154## 11) Carboxymethyl cellulose coatings
(129) The respective photosensitizer (0.05 mmol) was dissolved in 100 mL of water along with finely crushed carboxymethyl cellulose (4.0 g, Akzo Nobel). 5 to 6 mL of the clear, somewhat viscous solution was painted evenly onto i) a clean, untreated chipboard or ii) a degreased PMMA plate (each 20×20 cm.sup.2) using a brush.
(130) Alternatively, iii) a cotton fleece (20×20 cm.sup.2) could be evenly impregnated with a brush, so that the fabric could take up the mixture in its entirety. To harden, the support was left to dry for 3 hours at room temperature. The following photosensitizers were processed:
(131) ##STR00155##
(132) Result: i) transparent, polymeric seal without any detectable intrinsic colour; ii) transparent, slightly opaque, pale yellow, homogeneous coating; iii) stiff, limited flexibility fibrous mat; the intrinsic colour of the photosensitizer was barely detectable. 12) Alginate coatings
(133) Sodium hydroxide (850 mg, 21.25 mmol) was dissolved in 95 mL distilled water. 5 g of alginic acid (Sigma Aldrich) was added to the warm solution (approximately 35° C.) and stirred for 3 h. A viscous, clear solution was formed. A stock solution of the respective photosensitizer (5 mL, 12 mmol/L) was added dropwise, with stirring. Using the yellow, slightly viscous solution, i) a piece of paper or ii) a piece of cotton fleece or iii) a paper towel/pad (each 20×20 cm.sup.2) was impregnated. The surplus solution was allowed to drip out. The wet support was quickly immersed in a 1% calcium chloride solution. The material was allowed to drain well, it was then carefully swabbed and dried at room temperature in air for 3 hours.
(134) The following photosensitizers were processed:
(135) ##STR00156##
(136) Result: stiff, limited flexibility fibrous mat or piece of paper; the intrinsic colour of the photosensitizer was barely detectable.
EXAMPLE 3
Testing the Activity of the Antimicrobial Surface Coatings
(137) 1.) Production of sample supports
(138) The following photosensitizer was used for the tests below:
(139) ##STR00157##
(140) The photosensitizer was dissolved in the respective paint system and applied to various square sample supports (width: 4 cm, length: 4 cm, thickness: 3 mm) formed from PVC or PMMA and then dried. After drying the coating, a specific quantity of bacteria from the species Staphylococcus aureus ATCC 25923 was applied to the surface.
(141) In this regard, firstly, an overnight (ON) culture of S. aureus in 5 mL of Mueller Hinton broth (Carl Roth GmbH+Co. KG, Karlsruhe, DE) was inoculated with a single colony from an agar plate and incubated at 37° C. and 180 rpm on a shaker for 18-20 hours.
(142) On the day of the test, in each case 1 mL of ON culture was centrifuged (Hettich Universal 320 R centrifuge (Andreas Hettich GmbH & Co.KG, Tuttlingen, DE); swing-out rotor 1494; 10 Min, 3000 rpm, RT). The supernatant was discarded and the pellet was re-suspended in 1 mL of Milli-Q water, which is commercially available from Merck (KGaA, Darmstadt, DE) (designation “Milli-Q Integral Ultra-pure Water (Type 1)”).
(143) After determining the optical density at 600 nm (“Specord 50 plus”, spectrometer, Analytik Jena), the re-suspended bacteria were diluted with Milli-Q-water to a cell count of 10.sup.5 bacteria/mL. From the dilution, in each case 100 μL was dripped onto the sample support using a pipette (droplet size approximately 1 cm.sup.2).
(144) This resulted in approximately 10.000 bacteria per cm.sup.2 on the surface of the respective sample support. The sample support was then dried in air under a clean bench in the dark for approximately 2 hours, until water could no longer be seen on the surface. 2.) Irradiation and quantitative determination of the colony forming units (CFU)/mL
(145) The respective sample supports were irradiated with monochrome light at a wavelength of 405 nm with the aid of a LED module (test area 5×5 cm homogeneously illuminated; high power LEDs) or with room lighting (Osram Lumilux Cool White, colour temperature 4000 K) at the intensities and for the irradiation periods given below. Directly after irradiation, the bacteria were wiped from the surface of the respective sample support with a sterile cloth and re-suspended in 1 mL of Mueller-Hinton broth.
(146) Next, the sample was serially diluted (1:10 dilution stages: 180+20 μL; to dilution stage 10.sup.−5).
(147) For each dilution stage (100 to 10.sup.−5), 3×respectively 20 μL of broth was dripped onto a Mueller-Hinton agar plate (Carl Roth GmbH+Co. KG) using a pipette, and spread. The agar plates were then incubated at 37° C. ON.
(148) On the following day, the colonies from all of the dilution stages which could be counted of an experiment were counted and the CFU/mL was calculated.
(149) Dilution stages which exhibited a bacterial lawn or no colonies at all were denoted with “∞” or “0” and were not included in the calculation of the CFU/mL.
(150) Next, from the value for the CFU/mL, the log.sub.10 eradication rate was calculated. The reference point in each experiment was the reference control (=100% count of bacteria employed).
(151) A test was composed of the following: coated sample support: without photosensitizer, not irradiated (“reference control”) coated sample support: with photosensitizer, not irradiated (“dark control”) coated sample support: without photosensitizer and irradiated (“light control”) coated sample support: with photosensitizer and irradiated (“sample”) 3.) Paint systems used and irradiation parameters 3.1.) 2-C polyurethane paint, solvent butyl acetate/xylene from Example 2.1
(152) Coated material: PMMA, 3 mm thickness, 4×4 cm
(153) Drying time approximately 1 hour
(154) Drying temperature 15-30° C.
(155) Application with a spray gun
(156) Concentration of photosensitizer used: 200 μm (61.55 mg/L)
(157) Irradiation conditions:
(158) TABLE-US-00013 Irradiation Irradiation Test No. Irradiation source intensity duration 3.1.1 LED module (405 nm) 10 mW/cm.sup.2 2 min 3.1.2 LED module (405 nm) 20 mW/cm.sup.2 2 min 3.1.3 LED-module (405 nm) 0.7 mW/cm.sup.2 0 to 150 min 3.2.) 1-C polyurethane paint, water-based, from Example 2.2
(159) Coated material: PVC, 3 mm thickness, 4×4 cm
(160) Drying time approximately 2 hours
(161) Drying temperature 15-30° C.
(162) Relative humidity for the drying time 30-70%
(163) Application with a spray gun
(164) Concentration of photosensitizer used: 200 μm (61.55 mg/L)
(165) Irradiation conditions:
(166) TABLE-US-00014 Irradiation Irradiation Irradiation Test No. source intensity duration 3.2.1 LED module (405 nm) 10 mW/cm.sup.2 10 min 3.3) Room temperature-vulcanizing 2-component (RTV-2) silicone from Example 2.5
(167) Coated material: PVC, 3 mm thickness, 4×4 cm
(168) Drying time approximately 2 hours
(169) Drying temperature 15-30° C.
(170) Relative humidity for the drying time 30-70%
(171) Application with a spray gun
(172) Concentration of photosensitizer used: 200 μm (61.55 mg/L)
(173) Two grades of silicone hardness (known as “Shores”): A=10 Shore; B=45 Shore
(174) Irradiation conditions:
(175) TABLE-US-00015 Irradiation Irradiation Test No. Irradiation source intensity duration 3.3.1 LED module (405 nm) 10 mW/cm.sup.2 5 min 3.3.2 LED module (405 nm) 10 mW/cm.sup.2 10 min 4.) Results and evaluation 4.1.) 2-C polyurethane paint (solvent: butyl acetate/xylene) from Example 2.1
(176) In a first study with the 2-C paint system, firstly, high intensities of 10 and 20 mW/cm.sup.2 were used in order to test the activity of the photosensitizer SAPN-19c used against S. aureus. The results are shown in
(177)
(178)
(179) Subsequently, the effectivity at low intensities of 0.7 mW/cm.sup.2 was determined. The results are shown in
(180)
(181) The irradiation was carried out using 0.7 mW/cm.sup.2 for up to 150 minutes (corresponds to an energy density of up to 6.3 J/cm.sup.2). The mean value for the reference control (no light, no catalyst) was 3.2×10.sup.4 bacteria per mL. The light and dark controls were only measured at 150 minutes.
(182) The reduction in the colony forming units with respect to a non-irradiated sample (0 min) was measured at intervals, wherein after the times shown in
(183) The mean value for the reference control (no light, no catalyst) was 3.2×10.sup.4 bacteria per mL. The light and dark controls were only measured at 150 minutes.
(184)
(185) When irradiated with an artificial light source, the 2-C paint system exhibited a biological activity against S. aureus, both at high intensities and low irradiation times (
(186) A first test with a high intensity (10 mW/cm.sup.2) and a long irradiation period (10 minutes) demonstrated the activity of the 1-C paint system.
(187) The results are shown in
(188)
(189) The experiments with the 1-C paint system clearly show that only an interaction of light and the photodynamic catalyst brings about an effective eradication of S. aureus on the coated surface. Three independent tests exhibited a mean eradication of 3.0 log.sub.10 units for an energy density of 6 J/cm.sup.2.
(190) The light control in the experiments exhibited a mean reduction of 1.2 log.sub.10 units, which presumably is due to the dark sample support. 3.3) Room temperature-vulcanizing 2-component (RTV-2) silicone from Example 2.5
(191) A first test with a high intensity (10 mW/cm.sup.2) and an irradiation period of 5 minutes or 10 minutes demonstrated the activity of the RTV-2 silicone system.
(192) The results are shown in
(193)
(194) In the paint systems tested (2-C PUR paint system; 1-C PUR paint system, RTV-2 silicone), the photosensitizer SAPN-19c which was used exhibited a biological activity against S. aureus on the painted surface coating.
(195) Higher light intensities and/or longer irradiation periods produced more singlet oxygen, which resulted in a faster and more effective eradication of microorganisms on the surface.
(196) The concentration of 200 μM (61.55 mg/L) used in both paint systems was not visible on coloured surfaces. Furthermore, at a light intensity of 6 J/cm.sup.2, the coating achieved a reduction of 3 log.sub.10 units (=99.9%) of the bacteria involved.
EXAMPLE 4
Testing the Phototoxic Effect of a Coated Surface in Office Lighting (Neon Tubes)
(197) In a subsequent test, the 2-C paint system was irradiated with room lighting. In this regard, the photoactive surfaces produced in Example 2.1 with the photosensitizers SAPN-19c and SAPN-19 were additionally stored exposed in areas with normal office lighting (standard fluorescent lights, Osram Cool White, 840) and the phototoxic action on S. aureus with the same pathogen counts as in Example 3 was analysed after specific periods. In this regard, the photoactive layers were distanced from the light source by approximately 40 cm.
(198) It was shown that for the photosensitizer SAPN-19c, after storage for 24 h under standard office lighting conditions with an illumination period of 12 h, that all pathogens on the surface had been completely eradicated (approximately 5.5 log.sub.10 units, corresponding to >99.999% reduction).
EXAMPLE 5
Long-Term Test of Photoactive Stability
(199) In order to test the stability of the lacks produced, a long term test was carried out.
(200) The test surfaces were pre-irradiated for different time periods (5, 25, 50, 75 h) at an output of 5 mW cm.sup.−2 in order to establish whether the respective photosensitizer in PUR was affected in a manner such that the phototoxic activity of the surface was reduced:
(201) TABLE-US-00016 Applied “Irradiation energy [J cm.sup.−2] 5 mW cm.sup.−2 0.7 mW cm.sup.−2 days” 90 5 h 35.70 h 7 days (d) 450 25 h 178.5 h 36 d 900 50 h 357.0 h 71 d 1350 75 h 535.5 h 107 d
(202) Following the pre-irradiation, the surfaces as described above were contaminated with S. aureus then irradiated for 2 h (corresponds to 5 mW cm.sup.−2) and the phototoxic efficiency was measured.
(203) ##STR00158##
(204) The TPP sensitizer WBII/2 was produced using the method described in Felgenträger A., Maisch T., Späth A., Schröder J. A., Bäumler W., “Singlet oxygen generation in porphyrin-doped polymeric surface coating enables antimicrobial effects on Staphylococcus aureus.”, (Phys Chem Chem Phys. 2014 Oct. 14; 16(38):20598-607. doi: 10.1039/c4cp02439g.).
(205) For the porphyrin-doped surfaces tested (TPP sensitizer WBII/2), there was a noticeable reduction in the phototoxic efficiency. In this regard, after one month, the test surfaces had discoloured significantly and they lost phototoxic activity.
(206) This may be because the ring of the colorant breaks under the influence of the active oxygen, whereupon bilirubin analogues are formed:
(207) ##STR00159##
(208) For SAPN-19c, there was no difference as regards phototoxic efficiency up to a pre-irradiation of 75 h with 5 mW cm.sup.−2.
(209) This corresponds to an extrapolated 312 days of irradiation (d), assuming that office lighting tubes with a power of 100 μW cm.sup.−2 (at the office workspace) are continuously illuminated for 12 hours per day.