( 12 ) United States Patent
Total Page:16
File Type:pdf, Size:1020Kb
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. Abdullah M . et al. , “ Preparation of Oxide Particles With Ordered B01J 35 / 04 ( 2006 .01 ) Macropores by Colloidal Templating and Spray Pyrolysis ” , Acta Materialia 52 : 5151 - 5156 ( 2004 ) . B01J 37 /02 ( 2006 .01 ) Azevedo A . M . et al. , “ Horseradish Peroxidase : A Valuable Tool in CO2F 1 / 48 ( 2006 .01 ) Biotechnology ” , Biotechnology Annual Review 9 : 199 - 247 ( 2003 ) . CO2F 3 /00 ( 2006 . 01 ) Chalkias N . G . et al . , “ Activity Increase of Horseradish Peroxidase C02F 3 /34 ( 2006 .01 ) in the Presence ofMagnetic Particles” , J . Am . Chem . Soc . 130 :2910 C07C 1 / 12 ( 2006 .01 ) 2911 ( 2008 ) . C07G 1 /00 ( 2011. 01 ) Corgie S . C . et al. , “ Self - Assembled Complexes of Horseradish C08F 14/ 00 ( 2006 .01 ) Peroxidase with Magnetic Nanoparticles Showing Enhanced C08F 18 / 00 ( 2006 . 01 ) Peroxidase Activity ” , Advanced Functional Materials 22 : 1940 1951 ( Feb . 15 , 2012 ) . C07D 301 / 22 ( 2006 .01 ) Corvini P . F . X . et al ., “ Lance : Laccase -Nanoparticle Conjugates for C12N 11 / 14 ( 2006 . 01 ) the Elimination of Micropollutants ( Endocrine Disrupting Chemi C12P 7 / 22 ( 2006 . 01 ) cals ) from Wastewater in Bioreactors ” , Rev Environ Sci Biotechnol C12N 9 / 02 ( 2006 . 01) 9 : 23 - 27 ( 2010 ) . C12N 9 /04 ( 2006 . 01 ) Davis M . et al ., “ Formation of Three - Dimensional Ordered Hier C12N 9 / 08 ( 2006 .01 ) archically Porous Metal Oxides Via a Hybridized Epoxide Assisted / C12N 13 / 00 ( 2006 . 01) Colloidal Crystal Templating Approach ” , ACS Applied Materials & C12P 7 / 04 ( 2006 . 01 ) Interfaces 5 :7786 -7792 (2013 ) . C12P 17 /02 ( 2006 .01 ) Huang J. et al. , “ Zinc Tetraaminophthalocyanine -Fe304 Nanoparticle Composite for Laccase Immobilization ” , Interna B01J 35 / 00 ( 2006 . 01 ) tional Journal of Nanomedicine 2 ( 4 ) :775 -784 ( 2007 ) . B01J 8 / 00 ( 2006 .01 ) Luo X - L et al. , “ Electrochemically Deposited Chitosan Hydrogel CI2N 11 /08 ( 2006 .01 ) for Horseradish Peroxidase Immobilization Through Gold B01J 35 / 10 (2006 .01 ) Nanoparticles Self - Assembly " , Biosensors and Bioelectronics CO2F 101/ 32 ( 2006 .01 ) 21: 190 - 196 ( 2005 ) . (52 ) U .S . CI. Morrison M . et al. , “ Peroxidase - Catalyzed Halogenation ” , Annual CPC .. C02F 2305 /08 ( 2013 .01 ) ; C12Y 101/ 03004 Review of Biochemistry 45 : 861 -888 ( Jul . 1976 ) , abstract. Niu T . et al . , “ Preparation of Meso -Macroporous a — Alumina ( 2013 .01 ) ; C12Y 111/ 01 (2013 . 01 ) ; YO2P Using Carbon Nanotube as the Template for the Mesopore and Their 20 / 588 ( 2015 . 11) Application to the Preferential Oxidation of CO in HZ- Rich Gases” , J Porous Mater 20 : 789 - 798 ( 2013 ) . (56 ) References Cited Seelan S . et al. , “ Macroporous Ceramics Coated With Mesoporous Layer for Enzyme Encapsulation ” , Key Engineering Materials U . S . PATENT DOCUMENTS 317 - 318 :717 - 722 ( 2006 ) . 7 ,459 , 145 B2 12 / 2008 Bao et al . Tang D . et al ., “ Direct Electrochemical Immunoassay Based on 7 , 485 , 367 B2 2 / 2009 Chen et al. Immobilization of Protein -Magnetic Nanoparticle Composites on to 9 ,597 ,672 B2 * 3 / 2017 Corgie . B82Y 30 / 00 Magnetic Electrode Surfaces by Sterically Enhanced Magnetic 2006 /0289354 Al 12 / 2006 Zhou et al. Field Force” , Biotechnology Letters 28 :559 -565 (2006 ) . 2008 / 0305048 A1 12 / 2008 Josephson et al. Veitch N . C . , “ Horseradish Peroxidase: A Modern View of a Classic 2010 / 0056360 A1 3 / 2010 Lee Enzyme” , Phytochemistry 65 : 249 - 259 ( 2004 ) . 2010 / 0056816 A1 3 / 2010 Wallin et al. Wang F . et al. , “ Magnetic Mesoporous Silica Nanoparticles : Fab 2014 / 0004583 A1 * 1/ 2014 Corgie . .. .. .. B82Y 30 / 00 rication and Their Laccase Immobilization Performance ” , 435 / 156 Bioresource Technology 101: 8931 -8935 ( 2010 ) . Yang H - H et al ., “ Magnetite - Containing Spherical Silica FOREIGN PATENT DOCUMENTS Nanoparticles for Biocatalysis and Bioseparations” , Analytical Chemistry 76 ( 5 ) : 1316 - 1321 (Mar . 1 , 2004 ) . CN 101198255 A 6 /2008 Yang L . et al. , “ Robust MacroporousMaterials of Chiral Polyaniline KR 2011 /033575 A * 3 / 2011 Composites” , Chem . Mater . 18 ( 2 ) :297 - 300 (2006 ) . SU 1000098 A 2 / 1983 International Search Report dated Oct . 10 , 2012 received from the WO WO 2012 / 122437 A2 9 / 2012 Korean Intellectual Property Office from Application No. PCT/ US2012 /028392 . OTHER PUBLICATIONS International Search Report dated Feb . 20 , 2014 received from Application No . PCT/ US2013 / 063441. Wang , F . et al. Magnetic Mesoporous Silica Nanoparticles . Ping , Z . et al ., “ Research and application of magnetic fluidized Bioresource Technology vol. 101 8931 - 5 , 2010 . * bed ” , Chemical Industry and Engineering Progress , ( Apr. 25 , 2006 ) , Kim J . et al. A Magnetically Separable Highly Stable Enzyme pp . 371 - 377 , with English abstract. System Based on Nanocomposites of Enzymes . Small 1 ( 12 ) Chinese Office Action dated Mar . 23 , 2016 issued in corresponding 1203 - 7 , 2005. * Chinese Patent Application No . 201380063389 . 8 with English Kim , M . et al. Colorimetric Quantification of Galactose Using a language translation . Nanostructured Multicatalyst System . Analyst 137 ( 5 ) 1137 - 1143 , Supplementary Partial European Search Report dated Apr. 29 , 2016 2012 . * issued in EP 13844083 . 9 . Lee J . et al . Magnetically Separable and Higly Stable Enzyme Supplementary European Search Report dated Sep