# US 2019/0169456 A1 · Supramolecular encrypted fluorescent security ink compositions > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2019/0169456 A1 - Document ID: US20190169456A1 - Status: Published application - Kind: A1 - Application number: 16/269,311 - Filed: 2019-02-06 - Published: 2019-06-06 - Earliest claimed: 2014-09-29 - Assignees: Northwestern University; Innotune LLC - Applicants: Northwestern University; Innotune LLC - Inventors: James Fraser Stoddart; Xisen Hou; Chenfeng Ke; Roger B. Pettman - Web page: https://patentgrep.com/patent/US20190169456A1 ## CPC - C09D 11/50: Sympathetic, colour changing or similar inks - C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D) ## Abstract Fluorescent dyes, ink compositions comprising the dyes, methods and devices for printing the ink compositions, images printed using the ink compositions and methods for authenticating the printed images are provided. The fluorescent dyes are heterorotaxanes that include large macrocyclic rings around fluorophores and are capable of emitting solid-state fluorescence. When the heterorotaxanes are combined with encapsulating agents and competitive binding agents in aqueous solution, the resulting ink composition exhibits a complex, dynamic equilibrium that provides a tunable fluorescence emission spectrum with a non-linear response to the dye concentration. ## Claims ### Claim 1 A fluorescent ink composition comprising: (a) a heterorotaxane comprising: (i) a substantially linear molecule comprising a central fluorophoric group, a first fluorophoric end group on one end of the substantially linear molecule, and a second fluorophoric end group on the opposite end of the substantially linear molecule; (ii) a first macrocyclic ring encircling the central fluorophoric group; (iii) a second macrocyclic ring encircling a portion of the substantially linear molecule between the first fluorophoric end group and the central fluorophoric group; and (iv) a third macrocyclic ring encircling a portion of the substantially linear molecule between the second fluorophoric end group and the central fluorophoric group; and (b) an encapsulating agent comprising a macrocyclic ring encapsulating one or both of the first and second fluorophoric end groups. ### Claim 2 (depends on 1) The composition of claim 1, further comprising: (c) a competitive binding agent that competes with one or both of the first and second fluorophoric end groups for binding the encapsulating agent. ### Claim 3 (depends on 1) The composition of claim 1, wherein the heterorotaxane has the structure: where X is the first fluorophoric end group, Y is the central fluorophoric group and Z is the second fluorophoric end group; N+ is a quarternary nitrogen cation; n is selected from 6, 7 and 8; R1, R2, R3 and R4 are selected independently from the group consisting of H, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, OH, NH2, SH, F, Cl, Br, I, PR′2, CHO, COOR′, COOM, CH2OR′, CH2OM, OR′, NHCOR′, CONHR′, CONHM, CONR′2, N3, NO2, B(OR′)2, B(OM)2, CN, NR′3+, PR′3+, POR′2, and OM, where R′ is selected independently from the group consisting of H, alkyl groups, alkenyl groups, alkynyl groups, and aryl groups and M is selected independently from the group consisting of Li, Na, K, Rb, and Cs; and C− is an organic or inorganic negatively charged ion. ### Claim 4 (depends on 2) The composition of claim 2, wherein the heterorotaxane has the structure: where X is the first fluorophoric end group, Y is the central fluorophoric group and Z is the second fluorophoric end group; N+ is a quarternary nitrogen cation; n is selected from 6, 7 and 8; R1, R2, R3 and R4 are selected independently from the group consisting of H, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, OH, NH2, SH, F, Cl, Br, I, PR′2, CHO, COOR′, COOM, CH2OR′, CH2OM, OR′, NHCOR′, CONHR′, CONHM, CONR′2, N3, NO2, B(OR′)2, B(OM)2, CN, NR′3+, PR′3+, POR′2, and OM, where R′ is selected independently from the group consisting of H, alkyl groups, alkenyl groups, alkynyl groups, and aryl groups and M is selected independently from the group consisting of Li, Na, K, Rb, and Cs; and C− is an organic or inorganic negatively charged ion. ### Claim 5 (depends on 4) The composition of claim 4, wherein where X, Y and Z are selected from the group consisting of pyrene, anthracene, coumarin, acridine, 9-aminoacridine, fluorescein, naphthofluorescein, resofurin, rhodamine B, rhodamine 6G, perylene diimide, naphthalene diimide, propidium, boron difluoride dipyrromethene, phthalocyanine, cyanine, porphyrin, biphenyl, a group having the structure: N+ is selected from the group consisting of NH2+ ammonium cations, methyl ammonium cations, dimethyl ammonium and pyridinium cations; and C− is selected from the group consisting of F−, Cl−, Br−, I−, PF6−, BF4−, CF3COO−, CH3COO−, SO42−, SO32−, NO3−, NO2−, CO32−, HCO3−, ClO4−, PO43−, HPO42−, H2PO4−, CN−, and SCN−. ### Claim 6 (depends on 4) The composition of claim 4, wherein X and Z are 1-pyrenylmethyl and Y has the structure ### Claim 7 (depends on 1) The composition of claim 1, wherein the encapsulating agent comprises a γ-cyclodextrin. ### Claim 8 (depends on 2) The composition of claim 2, wherein the encapsulating agent comprises a γ-cyclodextrin. ### Claim 9 (depends on 8) The composition of claim 8, wherein the competitive binding agent comprises 2-adamantylamine hydrochloride. ### Claim 10 (depends on 1) A printhead comprising a plurality of different ink channels, the different ink channels containing fluorescent ink compositions comprising the composition of claim 1 and (c) optionally, a competitive binding agent that competes with one or both of the first and second fluorophoric end groups for binding the encapsulating agent. ### Claim 11 (depends on 10) The printhead of claim 10, wherein the fluorescent ink compositions in the different ink channels have different concentrations of heterorotaxane, encapsulating agent and, if present, competitive binding agent, such that the fluorescent ink compositions in the different ink channels have different fluorescence emission spectra. ### Claim 12 (depends on 10) The printhead of claim 10, wherein the fluorescent ink compositions in the different ink channels contain different competitive binding agents, such that the fluorescent ink compositions in the different ink channels have different fluorescence emission spectra. ### Claim 13 (depends on 1) A method of printing an image on a substrate, the method comprising applying one or more fluorescent ink compositions onto a surface of the substrate and allowing the one or more applied fluorescent ink composition to dry, wherein the one or more fluorescent ink compositions comprise the composition of claim 1 and (c) optionally, a competitive binding agent that competes with one or both of the first and second fluorophoric end groups for binding the encapsulating agent. ### Claim 14 (depends on 13) The method of claim 13 comprising applying a plurality of the fluorescent ink compositions onto the surface of the substrate and allowing the plurality of applied fluorescent ink compositions to dry, wherein different fluorescent ink compositions within the plurality of the fluorescent ink compositions have different concentrations of heterorotaxane, encapsulating agent and, if present, competitive binding agent, such that the image printed on the substrate is a polychromic image. ### Claim 15 (depends on 13) The method of claim 13 comprising applying a plurality of the fluorescent ink compositions onto the surface of the substrate and allowing the plurality of applied fluorescent ink compositions to dry, wherein different fluorescent ink compositions within the plurality of the fluorescent ink compositions contain different competitive binding agents, such that the image printed on the substrate is a polychromic image. ### Claim 16 A printed substrate comprising: a substrate; and one or more fluorescent inks on the surface of the substrate, the fluorescent inks comprising: (a) a heterorotaxane comprising: (i) a substantially linear molecule comprising a central fluorophoric group, a first fluorophoric end group on one end of the substantially linear molecule, and a second fluorophoric end group on the opposite end of the substantially linear molecule; (ii) a first macrocyclic ring encircling the central fluorophoric group; (iii) a second macrocyclic ring encircling a portion of the substantially linear molecule between the first fluorophoric end group and the central fluorophoric group; and (iv) a third macrocyclic ring encircling a portion of the substantially linear molecule between the second fluorophoric end group and the central fluorophoric group; (b) an encapsulating agent comprising a macrocyclic ring encapsulating one or both of the first and second fluorophoric end groups; and (c) optionally, a competitive binding agent that competes with one or both of the first and second fluorophoric end groups for binding the encapsulating agent. ### Claim 17 (depends on 16) The printed substrate of claim 16 comprising a plurality of the fluorescent inks on the surface of the substrate, wherein different fluorescent inks within the plurality of the fluorescent inks have different concentrations of heterorotaxane, encapsulating agent and, if present, competitive binding agent, such that the different fluorescent inks are different colors when viewed under ultraviolet light. ### Claim 18 (depends on 16) The printed substrate of claim 16 comprising a plurality of the fluorescent inks on the surface of the substrate, wherein different fluorescent inks within the plurality of the fluorescent inks contain different competitive binding agents, such that the different fluorescent inks are different colors when viewed under ultraviolet light. ### Claim 19 A method of authenticating a printed substrate, the printed substrate comprising: a substrate; and a plurality of fluorescent inks forming a polychromic image on the surface of the substrate, the fluorescent inks comprising: (a) a heterorotaxane comprising: (i) a substantially linear molecule comprising a central fluorophoric group, a first fluorophoric end group on one end of the substantially linear molecule, and a second fluorophoric end group on the opposite end of the substantially linear molecule; (ii) a first macrocyclic ring encircling the central fluorophoric group; (iii) a second macrocyclic ring encircling a portion of the substantially linear molecule between the first fluorophoric end group and the central fluorophoric group; and (iv) a third macrocyclic ring encircling a portion of the substantially linear molecule between the second fluorophoric end group and the central fluorophoric group; (b) an encapsulating agent comprising a macrocyclic ring encapsulating one or both of the first and second fluorophoric end groups; and (c) optionally, a competitive binding agent that competes with one or both of the first and second fluorophoric end groups for binding the encapsulating agent; the method comprising: applying an authentication reagent over the polychromic image, wherein the authentication reagent induces a change in the fluorescence emission spectrum of the polychromic image; and comparing the change in the fluorescence emission spectrum of the polychromic image against a known fluorescence emission spectrum change for an authentic printed substrate. ### Claim 20 (depends on 19) The method of claim 19, wherein the authentication reagent comprises a non-fluorescent encapsulating agent, a non-fluorescent competitive binding agent, or a combination thereof. ### Claim 21 (depends on 19) The method of claim 19, wherein the authentication reagent comprises a fluorescent competitive binding agent. ### Claim 22 (depends on 19) The method of claim 19, wherein the authentication reagent comprises a salt. ### Claim 23 (depends on 19) The method of claim 19, wherein the authentication reagent is water.