Skip to main content
SpringerLink
Log in

Catalytic activity of various pepsin reduced Au nanostructures towards reduction of nitroarenes and resazurin

  • Research Paper
  • Published:
Journal of Nanoparticle Research Aims and scope Submit manuscript

Abstract

Pepsin, a digestive protease enzyme, could function as a reducing as well as stabilizing agent for the synthesis of Au nanostructures of various size and shape under different reaction conditions. The simple tuning of the pH of the reaction medium led to the formation of spherical Au nanoparticles, anisotropic Au nanostructures such as triangles, hexagons, etc., as well as ultra small fluorescent Au nanoclusters. The activity of the enzyme was significantly inhibited after its participation in the formation of Au nanoparticles due to conformational changes in the native structure of the enzyme which was studied by fluorescence, circular dichroism (CD), and infra red spectroscopy. However, the Au nanoparticle-enzyme composites served as excellent catalyst for the reduction of p-nitrophenol and resazurin, with the catalytic activity varying with size and shape of the nanoparticles. The presence of pepsin as the surface stabilizer played a crucial role in the activity of the Au nanoparticles as reduction catalysts, as the approach of the reacting molecules to the nanoparticle surface was actively controlled by the stabilizing enzyme.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  • Anson ML (1938) The estimation of pepsin, trypsin, papain and cathepsin with haemoglobin. J Gen Physiol 22:79–89

    Article  Google Scholar 

  • Astruc D (2008) Nanoparticles and Catalysis. Wiley, New York

    Google Scholar 

  • Au L, Lim B, Colletti P, Jun Y-S, Xia Y (2010) Synthesis of gold microplates using bovine serum albumin as a reductant and a stabilizer. Chem Asian J 5:123–129

    Article  Google Scholar 

  • Baruah B, Gabriel GJ, Akbashev MJ, Booher ME (2013) Facile synthesis of silver nanoparticles catalyzed by cationic polynorbornenes and their catalytic activity in the reduction of 4-nitrophenol. Langmuir 29:4225–4234

    Article  Google Scholar 

  • Bawaked S, Dummer NF, Dimitratos N, Bethell D, He Q, Kiely CJ, Hutchings G (2009) Solvent free selective epoxidation of cyclooctene using supported gold catalysts. Green Chem 11:1037–1044

    Article  Google Scholar 

  • Bhattacharya T, Sarma TK, Samanta S (2012) Self-assembled monolayer coated gold-nanoparticle catalyzed aerobic oxidation of α-hydroxy ketones in water: an efficient one-pot synthesis of quinoxaline derivatives. Catal Sci Technol 2:2216–2220

  • Biondi I, Laurenczy G, Dyson PJ (2011) Synthesis of gold nanoparticle catalysts based on a new water-soluble ionic polymer. Inorg Chem 50:8038–8045

    Article  Google Scholar 

  • Burda C, Chen X, Narayanan R, El-Sayed MA (2005) Chemistry and properties of nanocrystals of different shapes. Chem Rev 105:1025–1102

    Article  Google Scholar 

  • Campos LA, Sancho J (2003) The active site of pepsin is formed in the intermediate conformation dominant at mildly acidic pH. FEBS Lett 538:89–95

    Article  Google Scholar 

  • Choudhary TV, Goodman DW (2005) Catalytically active gold: the role of cluster morphology. Appl Catal A 291:32–36

  • Ciganda R, Li N, Deraedt C, Gatard S, Zhao P, Salmon L, Hernández R, Ruiz J, Astruc D (2014) Gold nanoparticles as electron reservoir redox catalysts for 4-nitrophenol reduction: a strong stereoelectronic ligand influence. Chem Commun 50:10126–10129

    Article  Google Scholar 

  • Coppage R, Slocik JM, Dakhel HR, Bedford NM, Heinz H, Naik RR, Knecht MR (2013) Exploiting localized surface binding effects to enhance the catalytic reactivity of peptide-capped nanoparticles. J Am Chem Soc 135:11048–11054

    Article  Google Scholar 

  • Corma A, Garcia H (2008) Supported gold nanoparticles as catalysts for organic reactions. Chem Soc Rev 37:2096–2126

    Article  Google Scholar 

  • Cuenya BR (2010) Synthesis and catalytic properties of metal nanoparticles: size, shape, support, composition, and oxidation state effects. Thin Solid Films 518:3127–3150

    Article  Google Scholar 

  • Cuenya BR (2013) Metal nanoparticle catalysts beginning to shape up. Acc Chem Res 46:1682–1691

    Article  Google Scholar 

  • Dai H, Cao N, Yang L, Su J, Luo W, Cheng G (2014) AgPd nanoparticles supported on MIL-101 as high performance catalysts for catalytic dehydrogenation of formic acid. J Mater Chem A 2:11060–11064

    Article  Google Scholar 

  • Dee D, Pencer J, Nieh M-P, Krueger S, Katsaras J, Yada RY (2006) Comparison of solution structures and stabilities of native, partially unfolded and partially refolded pepsin. Biochemistry 45:13982–13992

    Article  Google Scholar 

  • Deka J, Paul A, Chattopadhyay A (2012) Modulating enzyme activity in presence of gold nanoparticles. RSC Adv 2:4736–4745

    Article  Google Scholar 

  • Edwards JK, Ntainjua E, Carley AF, Herzing AA, Kiely CJ, Hutchings G (2009) Direct synthesis of H2O2 from H2 and O2 over gold, palladium, and gold–palladium catalysts supported on acid-pretreated TiO2. Angew Chem Int Ed 48:8512–8515

    Article  Google Scholar 

  • Fu H, Yang X, Jiang X, Yu A (2013) Bimetallic Ag-Au nanowires: synthesis, growth mechanism, and catalytic properties. Langmuir 29:7134–7142

    Article  Google Scholar 

  • Haruta M (1997) Size-and support-dependency in the catalysis of gold. Catal Today 36:153–166

    Article  Google Scholar 

  • Hashmi ASK (2007) Gold-catalyzed organic reactions. Chem Rev 107:3180–3211

    Article  Google Scholar 

  • Ishida T, Haruta M (2007) Gold catalysts: towards sustainable chemistry. Angew Chem Int Ed 46:7154–7156

    Article  Google Scholar 

  • Kawasaki H, Hamaguchi K, Osaka I, Arakawa R (2011) ph-dependent synthesis of pepsin-mediated gold nanoclusters with blue, green and red fluorescent emission. Adv Funct Mater 21:3508–3515

    Article  Google Scholar 

  • Kundu S, Lau S, Liang H (2009a) Shape-controlled catalysis by cetyltrimethylammonium bromide terminated gold nanospheres, nanorods, and nanoprisms. J Phys Chem C 113:5150–5156

    Article  Google Scholar 

  • Kundu S, Wang K, Liang H (2009b) Size-selective synthesis and catalytic application of polyelectrolyte encapsulated gold nanoparticles using microwave irradiation. J Phys Chem C 113:5157–5163

    Article  Google Scholar 

  • Kuo C-H, Huang MH (2010) Morphology controlled synthesis of Cu2O nanocrystals and their properties. Nano Today 5:106–116

    Article  Google Scholar 

  • Lakowicz JR (2006) Principles of fluorescence spectroscopy. Springer, New York

    Book  Google Scholar 

  • Li Y, Tang Z, Prasad PN, Knecht MR, Swihart MT (2014) Peptide-mediated synthesis of gold nanoparticles: effects of peptide sequence and nature of binding on physicochemical properties. Nanoscale 6:3165–3172

    Article  Google Scholar 

  • Liang M, Wang L, Liu X, Qi W, Su R, Huang R, Yu Y, He Z (2013) Cross-linked lysozyme crystal template synthesis of Au nanoparticles as high-performance recyclable catalysts. Nanotechnology 24:245601

    Article  Google Scholar 

  • Liu H, Liu Y, Li Y, Tang Z, Jiang H (2010) Metal − organic framework supported gold nanoparticles as a highly active heterogeneous catalyst for aerobic oxidation of alcohols. J Phys Chem C 114:13362–13369

    Article  Google Scholar 

  • Mikami Y, Dhaksinamoorthy A, Alvaro M, Garcia H (2013) Catalytic activity of unsupported gold nanoparticles. Catal Sci Technol 3:58–69

    Article  Google Scholar 

  • Narayanan R, El-Sayed MA (2005) Catalysis with transition metal nanoparticles in colloidal solution: nanoparticle shape dependence and stability. J Phys Chem B 109:12663–12676

    Article  Google Scholar 

  • Rangnekar A, Sarma TK, Singh AK, Deka J, Ramesh A, Chattopadhyay A (2007) Retention of enzymatic activity of α-amylase in the reductive synthesis of gold nanoparticles. Langmuir 23:5700–5706

    Article  Google Scholar 

  • Rashid MH, Mandal TK (2008) Templateless synthesis of polygonal gold nanoparticles: an unsupported and reusable catalyst with superior activity. Adv Funct Mater 18:2261–2271

    Article  Google Scholar 

  • Sardar R, Funston MA, Mulvaney P, Murray RW (2009) Gold nanoparticles: past, present, and future. Langmuir 25:13840–13851

    Article  Google Scholar 

  • Scott D, Toney M, Muzikar M (2008) Harnessing the mechanism of glutathione reductase for synthesis of active site bound metallic nanoparticles and electrical connection to electrodes. J Am Chem Soc 130:865–874

    Article  Google Scholar 

  • Sharma B, Mandani S, Sarma TK (2013) Biogenic growth of alloys and core-shell nanostructures using urease as a nanoreactor at ambient conditions. Sci Rep 3:2601. doi:10.1038/srep02601

    Google Scholar 

  • Sharma B, Mandani S, Sarma TK (2014) Enzymes as bionanoreactors: glucose oxidase for the synthesis of catalytic Au nanoparticles and Au nanoparticle–polyaniline nanocomposites. J Mater Chem B 2:4072–4079

    Article  Google Scholar 

  • Shimizu K-I, Miyamoto Y, Kawasaki T, Tanji T, Tai Y, Satsuma A (2009) Chemoselective hydrogenation of nitroaromatics by supported gold catalysts: mechanistic reasons of size- and support- dependent activity and selectivity. J Phys Chem C 113:17803–17810

    Article  Google Scholar 

  • Stratakis M, Garcia H (2012) Catalysis by supported gold nanoparticles: beyond aerobic oxidative processes. Chem Rev 112:4469–4506

    Article  Google Scholar 

  • Tan X, Deng W, Liu M, Zhang Q, Wang Y (2009) Carbon nanotube-supported gold nanoparticles as efficient catalysts for selective oxidation of cellobiose into gluconic acid in aqueous medium. Chem Commun 7179–7181

  • Tang J, Sepulveda P, Marciniszyn J Jr, Chen KCS, Huang W-Y, Tao N, Liu D, Lanier JP (1973) Amino-acid sequence of porcine pepsin. Proc Nat Acad Sci USA 70:3437–3439

    Article  Google Scholar 

  • Tsunoyama H, Sakurai H, Ichikuni N, Negishi Y, Tsutuda T (2004) Colloidal gold nanoparticles as catalyst for carbon − carbon bond formation: application to aerobic homocoupling of phenylboronic acid in water. Langmuir 20:11293–11296

    Article  Google Scholar 

  • Virkutyte J, Varma RS (2011) Green synthesis of metal nanoparticles: biodegradable polymers and enzymes in stabilization and surface functionalization. Chem Sci 2:837–846

    Article  Google Scholar 

  • Wei Y, Liu J, Zhao Z, Chen Y, Xu C, Duan A, Jiang G, He H (2011) Highly active catalysts of gold nanoparticles supported on three-dimensionally ordered macroporous LaFeO3 for soot oxidation. Angew Chem Int Ed 50:2326–2329

    Article  Google Scholar 

  • Wu S, Dzubiella J, Kaiser J, Drechsler M, Guo X, Ballauff M, Lu Y (2012) Thermosensitive Au-PNIPA yolk–shell nanoparticles with tunable selectivity for catalysis. Angew Chem Int Ed 51:2229–2233

    Article  Google Scholar 

  • Wunder S, Polzer F, Lu Y, Mei Y, Ballauff M (2010) Kinetic analysis of catalytic reduction of 4-nitrophenol by metallic nanoparticles immobilized in spherical polyelectrolyte polymer brushes. J Phys Chem C 114:8814–8820

    Article  Google Scholar 

  • Xia B, Fang H, Li L (2013) Preparation of bimetallic nanoparticles using a facile green synthesis method and their application. Langmuir 29:4901–4907

    Article  Google Scholar 

  • Xie J, Zhang Y, Ying JY (2009) Protein-directed synthesis of highly fluorescent gold nanoclusters. J Am Chem Soc 131:888–889

    Article  Google Scholar 

  • Xu R, Wang D, Zhang J, Li Y (2006) Shape-dependent catalytic activity of silver nanoparticles for the oxidation of styrene. Chem Asian J 1:888–893

    Article  Google Scholar 

  • Xu W, Kong JS, Yeh Y-TE, Chen P (2008) Single-molecule nanocatalysis reveals heterogeneous reaction pathways and catalytic dynamics. Nat Mater 7:992–996

  • Xu Y, Sherwood J, Qin Y, Crowley D, Bonizzoni M, Bao Y (2014) The role of protein characteristics in the formation and fluorescence of Au nanoclusters. Nanoscale 6:1515–1524

    Article  Google Scholar 

  • Yan W, Mahurin SM, Pan Z, Overbury SH, Dai S (2005) Ultrastable gold nanocatalyst supported on surface-modified TiO2 nanocrystals. J Am Chem Soc 127:10480–10481

    Article  Google Scholar 

  • Yu T, Xeng J, Lim B, Xia Y (2010) Aqueous-phase synthesis of Pt-CeO2 hybrid nanostructures and their catalytic properties. Adv Mater 22:5188–5192

    Article  Google Scholar 

  • Zayats M, Baron R, Popov I, Willner I (2005) Biocatalytic growth of Au nanoparticles: from mechanistic aspects to biosensors design. Nano Lett 5:21–25

    Article  Google Scholar 

  • Zhang N, Qiu H, Liu Y, Wang W, Li Y, Wang X, Gao J (2011) Fabrication of gold nanoparticle/graphene oxide nanocomposites and their excellent catalytic performance. J Mater Chem 21:11080–11083

    Article  Google Scholar 

  • Zheng N, Stucky GD (2006) A general synthetic strategy for oxide-supported metal nanoparticle catalysts. J Am Chem Soc 128:14278–14280

    Article  Google Scholar 

  • Zhou X, Xu W, Liu G, Panda D, Chen P (2010) Size dependent catalytic activity and dynamics of gold nanoparticles at the single-molecule level. J Am Chem Soc 132:138–146

    Article  Google Scholar 

Download references

Acknowledgments

This work is supported by SERB, DST India research project no. SR/S1/PC-32/2010. B.S and S.M thank UGC (India) and CSIR (India), respectively, for fellowships. TEM facility provided by SAIF, NEHU, Shillong is gratefully acknowledged. We are also thankful to Mr. Anupal Gogoi for technical support.

Author information

Authors and Affiliations

  1. Discipline of Chemistry, School of Basic Sciences, Indian Institute of Technology Indore, IET Campus-DAVV, Khandwa Road, Indore, 452017, India

    Bhagwati Sharma, Sonam Mandani & Tridib K. Sarma

Authors
  1. Bhagwati Sharma
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Sonam Mandani
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Tridib K. Sarma
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Tridib K. Sarma.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (PDF 1057 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Sharma, B., Mandani, S. & Sarma, T.K. Catalytic activity of various pepsin reduced Au nanostructures towards reduction of nitroarenes and resazurin. J Nanopart Res 17, 4 (2015). https://doi.org/10.1007/s11051-014-2835-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s11051-014-2835-y

Keywords

Search

Navigation