# US 8,568,872 B2 · Catechol functionalized polymers and method for preparing them > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,568,872 B2 - Document ID: US8568872B2 - Status: Granted - Kind: B2 - Application number: 12/064,564 - Filed: 2005-08-24 - Published: 2009-04-09 - Granted: 2013-10-29 - Earliest claimed: 2005-08-24 - Assignees: ETH Zurich - Applicants: Marcus Textor; Stefan Zürcher; Karl Gademann; Samuele Tosatti - Inventors: Marcus Textor; Stefan Zürcher; Karl Gademann; Samuele Tosatti - Web page: https://patentgrep.com/patent/US8568872B2 ## CPC - C08G 65/3315: {aromatic} - A61K 47/60: the organic macromolecular compound being a polyoxyalkylene oligomer, polymer or dendrimer, e.g. PEG, PPG, PEO or polyglycerol - C08G 65/329: with organic compounds - Y10T 428/265: 1 mil or less - Y10T 428/31511: Of epoxy ether - Y10T 428/31663: As siloxane, silicone or silane - Y10T 428/31725: Of polyamide - Y10T 428/31855: Of addition polymer from unsaturated monomers - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - A61K: PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES (devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms A61J3/00; chemical aspects of, or use of materials for deodorisation of air, for disinfection or sterilisation, or for bandages, dressings, absorbent pads or surgical articles A61L; soap compositions C11D) - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract Described are compounds that are capable of forming adlayers, the compounds comprising at least one headgroup A, an optional linker B, a polymer C, a terminal group D and an optional crosslinking group R, wherein the headgroup A is a compound of the following formula wherein X is independently selected from an acidic group, Y is a group derived from a convenient coupling group, Z1, Z3, and Z4 are C or N+ Z2, Z5 and Z6 are C-L1 or N+-L, wherein L1 is H or an electron withdrawing group, L is C1-C6 alkyl, in particular C1-C4 alkyl L2 and L3 are independently selected from H or C1-C6 alkyl, or L2 may form together with L1 or L of Z6 a heterocycle, in particular a positively charged heterocycle, n is 0, or 1, or 2, or 3, m is 0 or 1. ## Claims ### Claim 1 A compound capable of forming adlayers and having one of the general formulas (A) to (C) below: wherein A designates at least one headgroup A, B designates an optionally present linker B, C designates a polymer C, D designates an optionally present terminus D and R designates an optionally present crosslinker R, and wherein the headgroup A is a compound of the following formula wherein X is independently from each other selected from an acidic group comprising OH, SH, phosphate, phosphonate, and N+R2H, wherein the R are independently from each other selected from H or C1-C6 alkyl, Y is a group derived from a convenient coupling group comprising NL3, or N+(L3)2, Z1, Z3, and Z4 are C or N+ Z2, Z5 and Z6 are C-L1 or N+-L, wherein L1 is H or an electron withdrawing group, whereby in the case of L1═NR1R2R3+, each of R1, R2, R3 may be selected from C1-C6 alkyl or C5 or C6 aryl, L is C1-C4-alkyl, L2 and L3 are independently selected from H or C1-C6 alkyl, or L2 may form together with L1 or L of Z6 a heterocycle, n is 0, or 1, or 2, or 3, m is 0 or 1 with the proviso that at most one of Z1 to Z6 is N+ and that in case that Z1 is N+, L2 may additionally be an ester, an amide, or a heterocycle, the optional linker B refers to one of the general formulas I, II, III or IV below where m and n are independently from each other 0, 1, 2, 3, 4, or 5, A refers to the headgroup A described above, and C refers to the polymer C, said polymer C being either of the general formula I or II wherein X is a group which can be chemically coupled to either A or the optional linker B, Y is a polymer, or an alkyl chain, Z is a functional group suitable for coupling to a terminus D, and the optional terminus D is either an inert group or a reactive group, and the optional crosslinker R is any molecule capable of crosslinking, and wherein in the headgroup A, L1 bound to Z6 is NR1R2R3+, or NO2, or F or CxFy, whereby in the case of L1═NR1R2R3+, each of R1, R2, R3 may independently from each other be selected from C1-C6 alkyl or C5 or C6 aryl. ### Claim 2 (depends on 1) The compound of claim 1, wherein each of R1, R2, R3 may independently from each other be selected from methyl, ethyl, n-propyl or iso-propyl, or wherein one of R1 or R2 or R3 and L2 form together a 5-membered or 6-membered heterocycle. ### Claim 3 (depends on 1) The compound of claim 1, wherein the headgroup A either refers to I, or II or III, or IV wherein R1, R2, L2, L3 and n are as defined above, wherein L2 may also be an ester or amide, but not CO2H and wherein the deprotonated group indicates the improved deprotonation characteristics of the groups of formula II, III and IV. ### Claim 4 (depends on 1) The compound of claim 1, wherein the terminus D is either an inert group selected from the group consisting of alkyl, aryl, allyl, alkenyl, alkinyl, or polyalkylsilyl group, or a fluorescent marker, a biologically active compound selected from the group consisting of proteins, peptide sequences, and sacharides, or any other biologically active compound, or mixtures thereof, or a reactive group, selected from the group consisting of vinylsulfone, maleimide, acrylate, azide, alkine group or mixtures thereof. ### Claim 5 (depends on 1) The compound of claim 1, wherein the crosslinker R is selected from the group consisting of catechol, styrene, acrylates, thioles, thiophene, pyrrole, and combinations thereof. ### Claim 6 (depends on 1) The compound of claim 1 comprising more than one headgroup A per polymer C. ### Claim 7 (depends on 1) The compound of claim 1 comprising a terminus D. ### Claim 8 (depends on 1) The compound of claim 1 comprising a linker B. ### Claim 9 (depends on 1) The compound of claim 1 comprising a crosslinker R. ### Claim 10 (depends on 1) The compound of claim 1 comprising a headgroup A, a polymer C, and a terminus D. ### Claim 11 (depends on 1) The compound of claim 1 comprising one headgroup A, a linker B, a polymer C, and a terminus D. ### Claim 12 (depends on 1) The compound of claim 1 comprising two or three headgroups A, a linker B, a polymer C, and a terminus D. ### Claim 13 (depends on 1) The compound of claim 1 having the formula wherein R1 and R2 are as defined above. ### Claim 14 (depends on 1) The compound of claim 1 having the formula wherein R1 and R2 are as defined above. ### Claim 15 (depends on 1) The compound of claim 1 having the formula ### Claim 16 (depends on 1) The compound of claim 1 wherein Z1 is N+ and L2 is selected from the group consisting of C1-C4 alkyl, amide, and ester. ### Claim 17 (depends on 1) The compound of claim 1 having the formula ### Claim 18 A compound having a pKa1 of at most 9.9, said compound being capable of forming adlayers and having one of the general formulas (A) to (C) below: wherein A designates at least one headgroup A, B designates an optionally present linker B, C designates a polymer C, D designates an optionally present terminus D and R designates an optionally present crosslinker R, and wherein the headgroup A is a compound of the following formula wherein X is an acidic group and is independently from each other, X comprising OH, SH, phosphate, phosphonate, N+R2H, wherein both R independently from each other are selected from H or C1-C6 alkyl, Y is a group comprising the polymer C and the optionally present linker B, the optionally present terminus D and the optionally present crosslinker R, Z1, Z3, and Z4 are C or N+, Z2, Z5 and Z6 are C-L1 or N+-L, whereby L1 is H or an electron withdrawing group and L is a neutral group, and wherein in the headgroup A, L1 bound to Z6 is NR1R2R3+, or NO2, or F or CxFy whereby in the case of L1═NR1R2R3+, each of R1, R2, R3 may independently from each other be selected from C1-C6 alkyl or C5 or C6 aryl. ### Claim 19 (depends on 1, 18) The compound of claim 18, wherein said compound is a compound according to claim 1. ### Claim 20 (depends on 18) The compound of claim 18, wherein X are both OH. ### Claim 21 (depends on 1) The compound of claim 1, wherein X are both OH. ### Claim 22 (depends on 1) The compound of claim 1, wherein L1 is L1═NR1R2R3+, each of R1, R2, R3 may be selected from methyl, ethyl, n-propyl or iso-propyl. ### Claim 23 (depends on 1) The compound of claim 1, wherein L2 forms together with L1 or L of Z6 a positively charged heterocycle. ### Claim 24 (depends on 1) The compound of claim 1, wherein Y is an alkyl chain comprising a (CR2) chain with n being at least 3 and R being independently from each other H or F.