US009765324B2 (12 ) United States Patent ( 10 ) Patent No. : US 9 ,765 , 324 B2 Corgie et al. (45 ) Date of Patent: Sep. 19, 2017 (54 ) HIERARCHICAL MAGNETIC ( 2013 .01 ) ; C12N 11/ 14 ( 2013 .01 ); C12N 13/ 00 NANOPARTICLE ENZYME MESOPOROUS ( 2013 .01 ) ; C12P 7 /04 ( 2013 . 01 ) ; C12P 7 / 22 ASSEMBLIES EMBEDDED IN ( 2013 . 01 ) ; C12P 17 /02 ( 2013 .01 ) ; B01J MACROPOROUS SCAFFOLDS 35 / 1061 ( 2013 .01 ) ; B01J 35 / 1066 (2013 .01 ) ; BOIJ 2208 /00805 ( 2013 . 01 ) ; B01J 2219 /0854 (71 ) Applicant: CORNELL UNIVERSITY , Ithaca , NY ( 2013 .01 ) ; BOIJ 2219 /0862 ( 2013 .01 ) ; CO2F (US ) 2101/ 327 (2013 .01 ) ; CO2F 2209 / 006 (2013 . 01 ) ; CO2F 2303 /04 (2013 .01 ) ; (72 ) Inventors : Stephane C . Corgie , Ithaca , NY (US ) ; Xiaonan Duan , Ithaca, NY (US ) ; ( Continued ) Emmanuel Giannelis , Ithaca , NY (US ) ; (58 ) Field of Classification Search Daniel Aneshansley , Ithaca , NY (US ) ; None Larry P . Walker , Ithaca , NY (US ) See application file for complete search history . (73 ) Assignee : CORNELL UNIVERSITY , Ithaca , NY (56 ) References Cited (US ) U . S . PATENT DOCUMENTS ( * ) Notice : Subject to any disclaimer, the term of this 4 , 152, 210 A 5 / 1979 Robinson et al. patent is extended or adjusted under 35 6 , 440 , 711 B18 / 2002 Dave U . S . C . 154 ( b ) by 73 days. (Continued ) ( 21) Appl. No .: 14 /433 , 242 FOREIGN PATENT DOCUMENTS CN 1580233 A * 2 / 2005 ( 22 ) PCT Filed : Oct. 4 , 2013 CN 101109016 A 1 / 2008 ( 86 ) PCT No .: PCT/ US2013 / 063441 (Continued ) $ 371 ( c ) ( 1 ), OTHER PUBLICATIONS ( 2 ) Date : Apr. 2 , 2015 Corgie S . et al . Self Assembled Complexes of Horseradish (87 ) PCT Pub . No. : WO2014 / 055853 Peroxidase with Magnetic Nanoparticles Showing Enhanced Peroxidase Activity . Advanced Functional Materials vol. 22, 1940 PCT Pub . Date : Apr. 10 , 2014 1951, Feb . 15 , 2012 .* (65 ) Prior Publication Data (Continued ) US 2015 /0252352 A1 Sep . 10 , 2015 Primary Examiner — Ralph Gitomer (74 ) Attorney , Agent, or Firm — Scully Scott Murphy & Related U . S . Application Data Presser (60 ) Provisional application No . 61 /710 , 110 , filed on Oct . 5 , 2012 , provisional application No. 61/ 767 ,477 , filed ( 57 ) ABSTRACT on Feb . 21 , 2013 . A hierarchical catalyst composition comprising a continuous or particulate macroporous scaffold in which is incorporated (51 ) Int . Cl. mesoporous aggregates of magnetic nanoparticles , wherein B01J 31 /00 ( 2006 . 01 ) an enzyme is embedded in mesopores of the mesoporous C12N 11 /04 ( 2006 .01 ) aggregates of magnetic nanoparticles . Methods for synthe A62D 3 / 02 ( 2007 . 01 ) sizing the hierarchical catalyst composition are also B01J 19 / 12 ( 2006 .01 ) described . Also described are processes that use the recov B01J 31 /02 ( 2006 .01 ) erable hierarchical catalyst composition for depolymerizing (Continued ) lignin , remediation of water contaminated with aromatic (52 ) U . S . CI. substances, polymerizing monomers by a free -radical ??? .. .. C12N 11 /04 ( 2013 .01 ) ; A62D 3 / 02 mechanism , epoxidation of alkenes, halogenation of phe (2013 .01 ) ; B01J 8 / 00 ( 2013 .01 ) ; B01J 19 / 12 nols , inhibiting growth and function of microorganisms in a ( 2013 .01 ) ; B01J 31 /003 ( 2013 . 01 ) ; B01J solution , and carbon dioxide conversion to methanol. Fur 31 /02 ( 2013 .01 ) ; B01J 35 /0033 (2013 .01 ) ; ther described are methods for increasing the space time B01J 35 / 04 ( 2013 . 01 ) ; B01J 37 / 02 ( 2013 . 01 ) ; yield and / or total turnover number of a liquid - phase chemi CO2F 1 /484 ( 2013 .01 ) ; C02F 3 / 00 ( 2013 .01 ) ; cal reaction that includes magnetic particles to facilitate the CO2F 3 /342 ( 2013 . 01 ) ; C07C 1 / 12 (2013 . 01) ; chemical reaction , the method comprising subjecting the CO7D 301 /22 (2013 .01 ) ; C07G 1/ 00 chemical reaction to a plurality ofmagnetic fields of selected ( 2013. 01 ) ; C08F 14 / 00 ( 2013 . 01 ) ; C08F 18/ 00 magnetic strength , relative position in the chemical reaction , ( 2013 .01 ) ; C12N 9 / 0004 ( 2013 .01 ) ; C12N and relative motion . 970006 ( 2013 .01 ) ; C12N 9 /0061 (2013 .01 ) ; C12N 9 / 0065 (2013 .01 ) ; C12N 11/ 08 25 Claims, 22 Drawing Sheets US 9 ,765 , 324 B2 Page 2 (51 ) Int . Cl. 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