# US 11,439,150 B2 · Methods and compositions for treating algae using metal phenolic networks > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,439,150 B2 - Document ID: US11439150B2 - Status: Granted - Kind: B2 - Application number: 17/087,004 - Filed: 2020-11-02 - Published: 2022-05-05 - Granted: 2022-09-13 - Earliest claimed: 2020-11-02 - Assignees: The Administrators of the Tulane Educational Fund - Applicants: The Administrators of the Tulane Educational Fund - Inventors: Vijay T. John; Igor K. M. Tsengam - Web page: https://patentgrep.com/patent/US11439150B2 ## CPC - A01N 59/16: Heavy metals; Compounds thereof - A01P 13/00: Herbicides; Algicides - A01N 31/08: Oxygen or sulfur directly attached to an aromatic ring system - A01N 43/16: with oxygen as the ring hetero atom - A01N: PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF (preservation of food or foodstuff A23); BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES (preparations for medical, dental or toiletry purposes which kill or prevent the growth or proliferation of unwanted organisms A61K); PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS - A01P: BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS ## Abstract The disclosure relates to a metal phenolic network (MPN) composition for treating algae in an aqueous environment, in particular to entrap/capture, flocculate, and settle or otherwise remove the algae from a location where it damages the aqueous environment and/or harms organisms in the aqueous environment. The MPN composition includes a metal phenolic network (MPN) film and a secondary flocculant such as a clay material or ionic flocculant. Application of the MPN composition to an aqueous environment, for example a marine environment containing a harmful algal bloom (HAB) induces flocculation of the algae with the MPN composition and sedimentation of the resulting floc. Algae removed from a surface region of the aqueous environment in this way eventually kills the algae at least due to a lack of sunlight, and reduces or eliminates the ability of the algae to further damage the aqueous environment until its eventual death. ## Claims ### Claim 1 A metal phenolic network (MPN) composition for treating algae in an aqueous environment, the composition comprising: a metal phenolic network (MPN) film comprising a polyphenol and a multivalent metal ion coordinated to the polyphenol; a flocculant comprising at least one of (i) clay nanoplatelets; (ii) clay nanotubes comprising an algaecide contained within an interior volume of the clay nanotubes; and (iii) an ionic flocculant comprising polyaluminum chloride; and water; wherein the MPN composition is in the form of an aqueous suspension with the MPN film and the flocculant dispersed in the water. ### Claim 2 (depends on 1) The MPN composition of claim 1, wherein: the polyphenol comprises tannic acid, and the multivalent metal ion comprises iron (III). ### Claim 3 (depends on 1) The MPN composition of claim 1, wherein the flocculant comprises the clay nanoplatelets. ### Claim 4 (depends on 1) The MPN composition of claim 1, wherein the flocculant comprises the clay nanotubes comprising the algaecide contained within the interior volume of the clay nanotubes. ### Claim 5 (depends on 1) The MPN composition of claim 1, wherein the flocculant comprises the ionic flocculant comprising polyaluminum chloride. ### Claim 6 (depends on 1) The MPN composition of claim 1, wherein a weight ratio of the MPN film relative to the flocculant is in a range of 0.1 to 10. ### Claim 7 A metal phenolic network (MPN) composition for treating algae in an aqueous environment, the composition comprising: a metal phenolic network (MPN) film comprising a polyphenol and a multivalent metal ion coordinated to the polyphenol; a flocculant comprising at least one of clay particles and an ionic flocculant; a networking biopolymer comprising at least one hydrogen-bonding functional group, wherein the networking biopolymer forms bridging links between different MPN films via hydrogen-bonding between (i) the hydrogen-bonding functional group of the networking biopolymer and (ii) at least one hydrogen-bonding functional group of the MPN film; and water; wherein the MPN composition is in the form of an aqueous suspension with the MPN film and the flocculant dispersed in the water. ### Claim 8 (depends on 7) The MPN composition of claim 7, wherein the networking biopolymer comprises chitosan. ### Claim 9 (depends on 7) The MPN composition of claim 7, wherein a weight ratio of the MPN film relative to the networking biopolymer is in a range of 1 to 50. ### Claim 10 A metal phenolic network (MPN) kit for treating algae in an aqueous environment, the kit comprising: an aqueous suspension comprising: (i) water, and (ii) a metal phenolic network (MPN) film or component thereof dispersed in the water, the MPN film comprising a polyphenol and a multivalent metal ion coordinated to the polyphenol; and a flocculant in the form of a dried powder, the flocculant comprising at least one of clay particles and an ionic flocculant. ### Claim 11 A method for treating algae in an aqueous environment, the method comprising: providing a metal phenolic network (MPN) composition comprising: (i) a metal phenolic network (MPN) film comprising a polyphenol and a multivalent metal ion coordinated to the polyphenol, (ii) a flocculant comprising at least one of clay particles and an ionic flocculant, and (iii) water, wherein the MPN composition is in the form of an aqueous suspension with the MPN film and the flocculant dispersed in the water; and applying the MPN composition to an aqueous environment containing algae, thereby contacting the algae with the MPN composition and flocculating the algae (i) to form a floc comprising the MPN composition and a plurality of algal cells and (ii) to sediment the floc. ### Claim 12 (depends on 11) The method of claim 11, wherein at least 80 wt. % of the algae in the aqueous environment treated by the MPN composition are captured and sedimented in the floc. ### Claim 13 (depends on 11) The method of claim 11, wherein the algae are in the form of an algal bloom on a surface of the aqueous environment. ### Claim 14 (depends on 11) The method of claim 11, wherein the algae are selected from the group consisting of cyanobacteria, dinoflagellates, and diatoms. ### Claim 15 (depends on 11) The method of claim 11, wherein the aqueous environment is a freshwater marine environment. ### Claim 16 (depends on 11) The method of claim 11, wherein the aqueous environment is a saltwater marine environment. ### Claim 17 (depends on 10) The kit of claim 10, wherein: the polyphenol comprises tannic acid, and the multivalent metal ion comprises Fe(III). ### Claim 18 (depends on 10) The kit of claim 10, wherein the flocculant comprises the clay particles, and the clay particles comprise clay nanoplatelets. ### Claim 19 (depends on 10) The kit of claim 10, wherein the flocculant comprises the clay particles, and the clay particles comprise clay nanotubes. ### Claim 20 (depends on 19) The kit of claim 19, further comprising an algaecide contained within an interior volume of the clay nanotubes. ### Claim 21 (depends on 10) The kit of claim 10, wherein the flocculant comprises the ionic flocculant, and the ionic flocculant comprises polyaluminum chloride. ### Claim 22 (depends on 10) The kit of claim 10, wherein the aqueous suspension comprises the MPN film, and a weight ratio of the MPN film relative to the flocculant is in a range of 0.1 to 10. ### Claim 23 (depends on 10) The kit of claim 10, wherein further comprising a networking biopolymer comprising at least one hydrogen-bonding functional group, wherein the networking biopolymer forms bridging links between different MPN films via hydrogen-bonding between (i) the hydrogen-bonding functional group of the networking biopolymer and (ii) at least one hydrogen-bonding functional group of the MPN film. ### Claim 24 (depends on 23) The kit of claim 23, wherein the networking biopolymer is chitosan. ### Claim 25 (depends on 11) The method of claim 11, wherein: the polyphenol comprises tannic acid, and the multivalent metal ion comprises Fe(III).