Fabrication of metal nanocomposites based on proteins and their self-assemblies as templates
(2.School of Food and Biological Engineering, Zhengzhou University of Light Industry, Zhengzhou, Henan, China 450001)
(3.State Key Laboratory of Chemical Engineering, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, Zhejiang, China 310027)
【Abstract】Fabrication of functional metal nanocomposites by using protein and its self-assemblies as template has aroused the interest of the researchers. Protein and its self-assemblies generally exhibit various morphological structures and possess specific molecular recognition as well as biomimetic mineralization capabilities. These characteristics make them play an important role of structural orientation and morphology control during the assisted synthesis of metal nanostructures. And the fabricated protein–metal nanostructure composites exhibit broad prospect of applications in catalytic conversion, biosensing, medical imaging and so on. Based on the differences in structural characteristics of proteins and their assemblies, this review summarizes the recent progress in the construction of metal nanocomposites based on protein single subunits, protein multi-subunit super assembled structures and three-dimensional protein crystals. The direction of research and development is forecasted. Furthermore, the future research direction in this field is prospected.
【Keywords】 protein; self-assembly; protein crystal; metal nanostructure; composite materials;
 VOET A R, TAME J R. Protein-templated synthesis of metal-based nanomaterials [J]. Current Opinion in Biotechnology, 2017, 46 (1): 14–19.
 LI N, TITTL A, YUE S, et al. DNA-assembled bimetallic plasmonic nanosensors [J]. Light: Science & Applications, 2014, 3 (1): e226.
 LIANG M. Fabrication and catalytic application of metal nanocrystals within porous proteinbased materials [D]. Tianjin: Tianjin University, 2014 (in Chinese).
 JONES O G, MEZZENGA R. Inhibiting, promoting, and preserving stability of functional protein fibrils [J]. Soft Matter, 2012, 8 (4): 876–895.
 LAGZIEL-SIMIS S, COHEN-HADAR N, MOSCOVICH-DAGAN H, et al. Protein-mediated nanoscale biotemplating [J]. Current Opinion in Biotechnology, 2006, 17 (6): 569–573.
 ABE S, MAITY B, UENO T. Design of a confined environment using protein cages and crystals for the development of biohybrid materials [J]. Chemical Communications, 2016, 52 (39): 6496–6512.
 LI C, CHEN H, CHEN B, et al. Highly fluorescent gold nanoclusters stabilized by food proteins: from preparation to application in detection of food contaminants and bioactive nutrients [J]. Critical Reviews in Food Science and Nutrition, 2016, 58 (5): 1–11.
 PALMAL S, JANAN R. Gold nanoclusters with enhanced tunable fluorescence as bioimaging probes [J]. Wiley Interdisciplinary Reviews: Nanomedicine and Nanobiotechnology, 2014, 6 (1): 102–110.
 YANG W T, GUO W S, ZHANG B B, et al. Synthesis of noble metal nanoclusters based on protein and peptide as a template [J]. Journal of the Chinese Chemical Society, 2014, 72 (12): 1209–1217 (in Chinese).
 WANG X, LI Y, ZHONG C. Amyloid–directed assembly of nanostructures and functional devices for bionanoelectronics [J]. Journal of Materials Chemistry B, 2015, 3 (25): 4953–4958.
 GOSWAMI N, ZHENG K, XIE J. Bio-NCs the marriage of ultrasmall metal nanoclusters with biomolecules [J]. Nanoscale, 2014, 6 (22): 13328–13347.
 MAITY B, FUJITA K, UENO T. Use of the confined spaces of apoferritin and virus capsids as nanoreactors for catalytic reactions [J]. Current Opinion in Chemical Biology, 2015, 25 (1): 88–97.
 MELDRUMFC, WADEVJ, NIMMODL, et al. Synthesis of inorganic nanophase materials in supramolecular protein cages [J]. Nature, 1991, 349 (6311): 684–687.
 KASYUTICH O, ILARI A, FIORILLO A, et al. Silver ion incorporation and nanoparticle formation inside the cavity of pyrococcus furiosus ferritin: structural and size-distribution analyses [J]. Journal of the American Chemical Society, 2010, 132 (10): 3621–3627.
 SHIN Y, DOHNALKOVA A, LIN Y. Preparation of homogeneous gold–silver alloy nanoparticles using the apoferritin cavity as a nanoreactor [J]. The Journal of Physical Chemistry C, 2010, 114 (13): 5985–5989.
 UENO T, SUZUKI M, GOTO T, et al. Size-selective olefin hydrogenation by a Pd nanocluster provided in an apo-ferritin cage [J]. Angewandte Chemie International Edition, 2004, 43 (19): 2527–2530.
 FAN R, CHEW S W, CHEONG V V, et al. Fabrication of gold nanoparticles inside unmodified horse spleen apoferritin [J]. Small, 2010, 6 (14): 1483–1487.
 ZHANG W, LIU X, WALSH D, et al. Caged-protein-confined bimetallic structural assemblies with mimetic peroxidase activity [J]. Small, 2012, 8 (19): 2948–2953.
 XIE J, LEE J Y, DANIEL I C W. Synthesis of single-crystalline gold nanoplates in aqueous solutions through biomineralization by serum albumin protein [J]. The Journal of Physical Chemistry C, 2007, 111 (28): 10226–10232.
 CHEN L, WANG N, WANG X, et al. Protein-directed in situ synthesis of platinum nanoparticles with superior peroxidase-like activity, and their use for photometric determination of hydrogen peroxide [J]. Microchimica Acta, 2013, 180 (15/16): 1517–1522.
 SHARMA A K, PANDEY S, KHANM S, et al. Protein stabilized fluorescent gold nanocubes as selective probe for alkaline phosphatase via inner filter effect [J]. Sensors and Actuators B: Chemical, 2018, 259 (1): 83–89.
 CHAKRABORTY I, FELIU N, ROY S, et al. Protein-mediated shape control of silver nanoparticles [J]. Bioconjugate Chemistry, 2018, 29 (4): 1261–1265.
 HART C, ABULADEL N, BEE M, et al. Protein-templated gold nanoparticle synthesis: protein organization, controlled gold sequestration, and unexpected reaction products [J]. Dalton Transactions, 2017, 46 (47): 16465–16473.
 WILLNER I, BARON R, WILLNERR B. Growing metal nanoparticles by enzymes [J]. Advanced Materials, 2010, 18 (9): 1109–1120.
 EBY D M, SCHAEUBLIN N M, FARRINGTON K E, et al. Lysozyme catalyzes the formation of antimicrobial silver nanoparticles [J]. ACS Nano, 2009, 3 (4): 984–994.
 SHARMA B, MANDANI S, SARMA T K. Biogenic growth of alloys and core-shell nanostructures using urease as a nanoreactor at ambient conditions [J]. Scientific Reports, 2013, 3 (37): 2601.
 ZOU L, QI W, HUANG R, et al. Green synthesis of a gold nanoparticle–nanocluster composite nanostructures using trypsin as linking and reducing agents [J]. ACS Sustainable Chemistry & Engineering, 2013, 1 (11): 1398–1404.
 ROTH K L, GENG X, GROVE T Z. Bioinorganic interface: mechanistic studies of protein-directed nanomaterial synthesis [J]. The Journal of Physical Chemistry C, 2016, 120 (20): 10951–10960.
 AN D, SU J, WEBER J K, et al. Apeptide-coated gold nanocluster exhibits unique behavior in protein activity inhibition [J]. Journal of the American Chemical Society, 2015, 137 (26): 8412–8418.
 XIE J, ZHENG Y, YING J Y. Protein-directed synthesis of highly fluorescent gold nanoclusters [J]. Journal of the American Chemical Society, 2009, 131 (3): 888–889.
 YU Y, LUO Z, TEO C S, et al. Tailoring the protein conformation to synthesize different-sized gold nanoclusters [J]. Chemical Communications, 2013, 49 (84): 9740–9742.
 CHUANG K T, LIN Y W. Microwave-assisted formation of gold nanoclusters capped in bovine serum albumin and exhibiting red or blue emission [J]. The Journal of Physical Chemistry C, 2017, 121 (48): 26997–27003.
 XU Y, SHERWOOD J, QIN Y, et al. The role of protein characteristics in the formation and fluorescence of Au nanoclusters [J]. Nanoscale, 2014, 6 (3): 1515–1524.
 ZANG J, LI C, ZHOU K, et al. Nanomolar Hg2+ detection using β-lactoglobulin-stabilized fluorescent gold nanoclusters in beverage and biological media [J]. Analytical Chemistry, 2016, 88 (20): 10275–10283.
 XAVIER P L, CHAUDHARI K, BAKSI A, et al. Protein-protected luminescent noble metal quantum clusters: an emerging trend in atomic cluster nanoscience [J]. Nano Reviews, 2012, 3 (1): 19–24.
 YU Y, NEW S Y, XIE J, et al. Protein-based fluorescent metal nanoclusters for small molecular drug screening [J]. Chemical Communications, 2014, 50 (89): 13805–13808.
 KANBAK-AKSU S, NAHID H M, HAGEN W R, et al. Ferritin-supported palladium nanoclusters: selective catalysts for aerobic oxidations in water [J]. Chemical Communications, 2012, 48 (46): 5745–5747.
 SUN C, YANG H, YUAN Y, et al. Controlling assembly of paired gold clusters within apoferritin nanoreactor for in vivo kidney targeting and biomedical imaging [J]. Journal of the American Chemical Society, 2011, 133 (22): 8617–8624.
 KAWASAKI H, HAMAGUCHI K, OSAKA I, et al. pH-dependent synthesis of pepsin-mediated gold nanoclusters with blue freen and red fluorescent emission [J]. Advanced Functional Materials, 2011, 21 (18): 3508–3515.
 CHEN T H, TSENG W L. (Lysozyme type Ⅵ)-stabilized Au8 clusters: aynthesis mechanism and application for sensing of glutathione in a single drop of blood [J]. Small, 2012, 8 (12): 1912–1919.
 LI Z, PENG H, LIU J, et al. Plant protein-directed synthesis of luminescent gold nanocluster hybrids for tumor imaging [J]. ACS Applied Materials & Interfaces, 2018, 10 (1): 83–90.
 MOHANTY J S, XAVIER P L, CHAUDHARI K, et al. Luminescent, bimetallic Au–Ag alloy quantum clusters in protein templates [J]. Nanoscale, 2012, 4 (14): 4255–4262.
 ZHAI Q, XING H, ZHANG X, et al. Enhanced electrochemiluminescence behavior of gold–silver bimetallic nanoclusters and its sensing application for mercury (II) [J]. Analytical Chemistry, 2017, 89 (14): 7788–7794.
 ZHANG N, SI Y, SUN Z, et al. Rapid, selective, and ultrasensitive fluorimetric analysis of mercury and copper levels in blood using bimetallic gold–silver nanoclusters with “silver effect”-enhanced red fluorescence [J]. Analytical Chemistry, 2014, 86 (23): 11714–11721.
 ZHOU Q, LIN Y, XU M, et al. Facile synthesis of enhanced fluorescent gold–silver bimetallic nanocluster and its application for highly sensitive detection of inorganic pyrophosphatase activity [J]. Analytical Chemistry, 2016, 88 (17): 8886–8892.
 PANG S, LIU S. Lysozym-stabilized bimetallic gold/silver nanoclusters as a turn-on fluorescent probe for determination of ascorbic acid and acid phosphatase [J]. Analytical Methods, 2017, 9 (47): 6713–6718.
 GAO Z, SU R, QI W, et al. Copper nanocluster-based fluorescent sensors for sensitive and selective detection of kojic acid in food stuff [J]. Sensors and Actuators B: Chemical, 2014, 195 (1): 359–364.
 GHOSH R, SAHOO A K, GHOSH S S, et al. Blue-emitting copper nanoclusters synthesized in the presence of lysozyme as candidates for cell labeling [J]. ACS Applied Materials & Interfaces, 2014, 6 (6): 3822–3828.
 FENG J, CHEN Y, HAN Y, et al. pH-regulated synthesis of trypsin-templated copper nanoclusters with blue and yellow fluorescent emission [J]. ACS Omega, 2017, 2 (12): 9109–9117.
 ZETH K, OFFERMANN S, ESSEN L O, et al. Iron-oxo clusters biomineralizing on protein surfaces: structural analysis of halobacterium salinarum DpsA in its low- and high-iron states [J]. Proceedings of the National Academy of Sciences of the United States of America, 2004, 101 (38): 13780.
 UENO T, ABE S, KOSHIYAMA T, et al. Elucidation of metal-ion accumulation induced by hydrogen bonds on protein surfaces by using porous lysozyme crystals containing Rh (III) ions as the model surfaces [J]. Chemistry (Weinheim an der Bergstrasse, Germany), 2010, 16 (9): 2730.
 HE N P, LU S F, ZHAO W G, et al. Fabrication of the self-assembly systems based on protein molecules [J]. Progress in Chemistry, 2014, 26 (12): 303–309 (in Chinese).
 ZHANG L, LI N, GAO F, et al. Insulin amyloid fibrils: an excellent platform for controlled synthesis of ultrathin superlong platinum nanowires with high electrocatalytic activity [J]. Journal of the American Chemical Society, 2012, 134 (28): 11326–11329.
 TAO L, GAO Y, WU P, et al. Insulin templated synthesis of single crystalline silver nanocables with ultrathin Ag cores [J]. RSC Advances, 2015, 5 (47): 37814–37817.
 HOU L, NIU Y, WANG Y, et al. Controlled synthesis of Pt–Pd nanoparticle chains with high electrocatalytic activity based on insulin amyloid fibrils [J]. Nano, 2016, 11 (6): 1650063.
 ZHOU X, LI R, DAI B, et al. The fabrication and electrical characterization of protein fibril-templated one-dimensional palladium nanostructures [J]. European Polymer Journal, 2013, 49 (8): 1957–1963.
 BOLISETTY S, ARCARI M, ADAMCIK J, et al. Hybrid amyloid membranes for continuous flow catalysis [J]. Langmuir, 2015, 31 (51): 13867–13873.
 NYSTROM G, FEMANDEZRONCO M P, BOLISETTY S, et al. Amyloid templated gold aerogels [J]. Advanced Materials, 2016, 28 (3): 472–478.
 HUANG R, ZHU H, SU R, et al. Catalytic membrane reactor immobilized with alloy nanoparticle-loaded protein fibrils for continuous reduction of 4-nitrophenol [J]. Environmental Science & Technology, 2016, 50 (20): 11263–11273.
 JAVED I, SUN Y, ADAMCIK J, et al. Co-fibrillization of pathogenic and functional amyloid proteins with gold nanoparticles against amyloidogenesis [J]. Biomacromolecules, 2017, 18 (12): 4316–4322.
 XU Z, LI L, LI H, et al. Synthesis of self-assembled noble metal nanoparticle chains using amyloid fibrils of lysozyme as templates [J]. Nanomaterials and Nanotechnology, 2016, 6 (4): 1–7.
 JUAREZ J, CAMBON A, GOYLOPEZ S, et al. Obtention of metallic nanowires by protein biotemplating and their catalytic application [J]. The Journal of Physical Chemistry Letters, 2010, 1 (18): 2680–2687.
 TAHERI R A, AKHTARI Y, MOGHADAM T T, et al. Assembly of gold nanorods on HSA amyloid fibrils to develop a conductive nanoscaffold for potential biomedical and biosensing applications [J]. Europe PMC, 2018, 8 (1): 9333.
 LEE D, CHOE Y J, CHOI Y S, et al. Photoconductivity of pea-pod-type chains of gold nanoparticles encapsulated within dielectric amyloid protein nanofibrils of α-synuclein [J]. Angewandte Chemie, 2011, 50 (6): 1332–1337.
 CHEN C L, ZHANG P, ROSI N L. A new peptide-based method for the design and synthesis of nanoparticle superstructures: construction of highly ordered gold nanoparticle double helices [J]. Journal of the American Chemical Society, 2008, 130 (41): 13555–13557.
 SHARMA N, TOP A, KIICK K, et al. One-dimensional gold nanoparticle arrays by electrostatically directed organization using polypeptide self-assembly [J]. Angewandte Chemie International Edition, 2009, 48 (38): 7078–7082.
 YANG T, ZHANG Y, LI Z. Formation of gold nanoparticle decorated lysozyme microtubes [J]. Biomacromolecules, 2011, 12 (6): 2027–2031.
 LARA C, HANDSCHIN S, MEZZENGA R. Towards lysozyme nanotube and 3D hybrid self-assembly [J]. Nanoscale, 2013, 5 (16): 7197–7201.
 LARA C, ADAMCIK J, JORDENS S, et al. General self-assembly mechanism converting hydrolyzed globular proteins into giant multistranded amyloid ribbons [J]. Biomacromolecules, 2011, 12 (5): 1868–1875.
 FU W C, OPAZO M A, ACUNA S M, et al. New route for self-assembly of α-lactalbumin nanotubes and their use as templates to grow silver nanotubes [J]. Plos One, 2017, 12 (4): e0175680.
 GOTO S, AMANO Y, AKIYAMA M, et al. Gold nanoparticle inclusion into protein nanotube as a layered wall component [J]. Langmuir, 2013, 29 (46): 14293–14300.
 CARRENOFUENTES L, PLASCENCIAVILLA G, PALOMARES L A, et al. Modulating the physicochemical and structural properties of gold-functionalized protein nanotubes through thiol surface modification [J]. Langmuir, 2014, 30 (49): 14991–14998.
 FALKNER J C, AL-SOMALI A M, JAMISON J A, et al. Generation of size-controlled, submicrometer protein crystals [J]. Chemistry of Materials, 2005, 17 (10): 2679–2686.
 TAKAFUMI U. Porous protein crystals as reaction vessels [J]. Chemistry—A European Journal, 2013, 19 (28): 9096–9102.
 VILENCHIK L Z, GRIFFITH J P, CLAIR N S, et al. Protein crystals as novel microporous materials [J]. Journal of the American Chemical Society, 1998, 120 (18): 4290–4294.
 FALKNER J C, TURNER M E, BOSWORTH J K, et al. Virus crystals as nanocomposites caffolds [J]. Journal of the American Chemical Society, 2005, 127 (15): 5274–5275.
 ABE S, TSUJIMOTO M, YONEDA K, et al. Porous protein crystals as reaction vessels for controlling magnetic properties of nanoparticles [J]. Small, 2012, 8 (9): 1314–1319.
 WEI H, WANG Z, ZHANG J, et al. Time-dependent, protein-directed growth of gold nanoparticles within a single crystal of lysozyme [J]. Nature Nanotechnology, 2011, 6 (2): 93–97.
 WEI H, LU Y. Catalysis of gold nanoparticles within lysozyme single crystals [J]. Chemistry—An Asian Journal, 2012, 7 (4): 680–683.
 GULI M, LAMBERT E, LI M, et al. Template-directed synthesis of nanoplasmonic arrays by intracrystalline metalization of cross-linked lysozyme crystals [J]. Angewandte Chemie, 2010, 49 (3): 520–523.
 MUSKENS O L, ENGLAND M W, DANOS L, et al. Plasmonic response of Ag- and Au-infiltrated cross-linked lysozyme crystals [J]. Advanced Functional Materials, 2013, 23 (3): 281–290.
 LIANG M, WANG L, SU R, et al. Synthesis of silver nanoparticles within cross-linked lysozyme crystals as recyclable catalysts for 4-nitrophenol reduction [J]. Catalysis Science & Technology, 2013, 3 (8): 1910–1914.
 LIANG M, WANG L, LIU X, et al. Cross-linked lysozyme crystal templated synthesis of Au nanoparticles as high-performance recyclable catalysts [J]. Nanotechnology, 2013, 24 (24): 245601.
 LIU M, WANG L, HUANG R, et al. Superior catalytic performance of gold nanoparticles within small cross-linked lysozyme crystals [J]. Langmuir, 2016, 32 (42): 10895–10904.