BIOMIMETIC BASED APPLICATIONS Edited by Anne George Biomimetic Based Applications Edited by Anne George Published by InTech Janeza Trdine 9, 51000 Rijeka, Croatia Copyright © 2011 InTech All chapters are Open Access articles distributed under the Creative Commons Non Commercial Share Alike Attribution 3.0 license, which permits to copy, distribute, transmit, and adapt the work in any medium, so long as the original work is properly cited. After this work has been published by InTech, authors have the right to republish it, in whole or part, in any publication of which they are the author, and to make other personal use of the work. Any republication, referencing or personal use of the work must explicitly identify the original source. Statements and opinions expressed in the chapters are these of the individual contributors and not necessarily those of the editors or publisher. No responsibility is accepted for the accuracy of information contained in the published articles. The publisher assumes no responsibility for any damage or injury to persons or property arising out of the use of any materials, instructions, methods or ideas contained in the book. Publishing Process Manager Ivana Lorkovic Technical Editor Teodora Smiljanic Cover Designer Martina Sirotic Image Copyright Tischenko Irina, 2010. Used under license from Shutterstock.com First published March, 2011 Printed in India A free online edition of this book is available at www.intechopen.com Additional hard copies can be obtained from orders@intechweb.org Biomimetic Based Applications, Edited by Anne George p. cm. ISBN 978-953-307-195-4 free online editions of InTech Books and Journals can be found at www.intechopen.com Chapter 1 Chapter 2 Chapter 3 Chapter 4 Chapter 5 Chapter 6 Chapter 7 Preface IX Biomimetic Epoxidation of Olefins Catalyzed by Metalloporphyrins with Molecular Oxygen 1 Hong-Bing Ji and Xian-Tai Zhou Biomimetic Oxidation of Hydrocarbons with Air over Metalloporphyrins 31 Guofang Jiang, Qiang Liu and Cancheng Guo Homogeneous and Heterogeneous Free-Based Porphyrins Incorporated to Silica Gel as Fluorescent Materials and Visible Light Catalysts Mimic Monooxygenases 59 Mariusz Trytek, Marek Majdan and Jan Fiedurek Physicochemical Peculiarities of Iron Porphyrin - Containing Electrodes in Catalase - and Peroxidase - Type Biomimetic Sensors 105 T.M.Nagiev Design of Biomimetic Models Related to the Active Sites of Fe-Only Hydrogenase 123 Yu-Chiao Liu, Ling-Kuang Tu, Tao-Hung Yen and Ming-Hsi Chiang The Improvement of LC-MS/MS Proteomic Detection with Biomimetic Affinity Fractionation 141 Rong-Xiu Li, Qing-Qiao Tan and De-Xian Dong Green Oxidation Reactions of Drugs Catalyzed by Bio-inspired Complexes as an Efficient Methodology to Obtain New Active Molecules 163 Emerson Henrique de Faria, Gustavo Pimenta Ricci, Frederico Matias Lemos, Marcio Luis Andrade e Silva, Ademar Alves da Silva Filho, Paulo Sérgio Calefi, Eduardo José Nassar and Katia Jorge Ciuffi Contents Contents VI Chemical Indices of the Biomimetic Models of Oxyhemocyanin and Oxytyrosinase 183 Yu Takano, Kizashi Yamaguchi and Haruki Nakamura Bioactive Microarc Oxidized TiO2-based Coatings for Biomedical Implication 201 Daqing Wei and Yu Zhou Antimicrobial Biomimetics 227 Ana Maria Carmona-Ribeiro, Lilian Barbassa and Letícia Dias de Melo Biomimetic Adsorbents: Enrichment of Trace Amounts of Organic Contaminants (TAOCs) in Aqueous Solution 285 Chao-Hai Wei, Xiao-Xuan Zhang, Yuan Ren and Xu-Biao Yu Spectro-Electrochemical Investigation of the bc 1 Complex from the Yeast Saccharomyces cerevisiae using Surface Enhanced B-Band Resonance Raman Spectroscopy 311 Denise Schach, Marc Großerüschkamp, Christoph Nowak, Carola Hunte, Wolfgang Knoll and Renate L. C. Naumann Self-Oscillating Gel as Novel Biomimetic Materials 333 Ryo Yoshida Non-Calcium Inorganic Materials Fabrication by Surface-Immobilized Organic Molecular Template 349 Peng Yang, Wantai Yang, Xu Zhang and Jinchun Chen Biomimetic Applications of Metal Systems Supported by Scorpionates 385 Maura Pellei and Carlo Santini Analogue CMOS Cochlea Systems: A Historic Retrospective 429 Andreas Katsiamis and Emmanuel Drakakis Design Considerations for Magnetically Actuated Biomimetic Cilia 473 Benjamin Evans and Rich Superfine Monitoring the Intertidal Environment with Biomimetic Devices 499 Fernando P. Lima, Nicholas P. Burnett, Brian Helmuth, Nicole Kish, Kyle Aveni-Deforge and David S. Wethey Nanoparticle Synthesis in Vesicle Microreactors 523 Peng Yang and Rumiana Dimova Chapter 8 Chapter 9 Chapter 10 Chapter 11 Chapter 12 Chapter 13 Chapter 14 Chapter 15 Chapter 16 Chapter 17 Chapter 18 Chapter 19 Contents VII Biologically Inspired Locomotion Control of a Climbing Robot 553 Reinaldo de Bernardi, Arturo Forner-Cordero and José Jaime Da Cruz Chapter 20 Pref ac e !"#$"$%&"'() "() &*%) ('"%+'%) #,) %$ /&"+0) +/&-1%2() 3%("0+4) 5+) +/&-1%6) ."7"+0) #10/+"($() (8+&*%("9%)$"+%1/."9%3)&"((-%()/+3)&*"():1#'%(()#,);"#$"+%1/."9/&"#+)"()-+3%1)(&1"'&);"#< .#0"'/.)'#+&1#.4)5&)"+7#.7%()&*%)"+&%1/'&"#+()#,)(%7%1/.);"#.#0"'/.)$/'1#$#.%' %()/$#+0) &*%$(%.7%()/+3)="&*)&*%)$"+%1/.)'#$:#+%+&(4)>%+%1/ 86)+/&-1%()3%("0+):1"+'":.%()/1%) ;/(%3)#+)/)?!#Ĵ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ě)%'&)#,)+/+#(&1-'&-1%()/+3)+/+#< &#:#01/:*"%()/+3)&*%"1)%ě)%'&)#+)&*%)3%7%.#:$%+&)#,)/)+%=)0%+%1/&"#+)#,);"#$/&%1"/.() "+' 3"+0)/37/+'%3)$ &",-+'&"#+/.)('/ě)#.3(),#1)&"((-%)%+0"+%%1"+0)/1%)3"('-((%34)E*%) J)7# $%()'#+&/"+)/1&"'.%()&*/&)'#7%1)/)="3%)(:%'&1-$)#,)(-;K%'&)$/Ĵ)%1)(-'*)/()3"ě)%1%+&) /(:%'&()#,)&*%)3%7%.#:$%+&)#,)('/ě)#.3()/+3)'#/&"+0()="&*)%+*/+'%3):%1,#1$/+'%)/+3) ;"#/'&"7"&86)"+' 3"+0)"+7%(&"0/&"#+()#,)$/&%1"/.)(-1,/'%<'% )"+&%1/'&"#+(4 Anne George @+"7%1("&8)#,)5 "+#"()/&)I*"'/0#6 H%:/1&$%+&)#,)L1/.)!"#.#086 I*"'/0#6) @BC [...]... = k4[PorMnII][RCO3H] - k5[MnIV=O][cyclohexene] (16) (17) d[RCO3H]/dt = k2[RCO3 ][RCHO] - k4[PorMnII][RCO3H] Based on pathways A and B, the total rate equation of epoxide (Re) can be expressed as: Re = d[epoxide] /dt = k5[MnIV=O][cyclohexene] + k6[RCO3 ][cyclohexene] (18) 16 Biomimetic Based Applications Through the pseudo steady state hypothesis for the Mn(IV) high-valent intermediate and RCO3H, eqs.16,... epoxide was not produced and zinc was hardly consumed Moreover, a larger amount of epoxide was obtained by adding 1-MeIm further (> 10-2 M) A plausible mechanism was proposed as shown in Figure 3 4 Biomimetic Based Applications N N M N R N O(CH2)x N+ R= N+ CH3 Scheme 2 Structure and abbreviation of covalently linked manganese(III) porphyrinsviologen 6 4 -3 [Epoxide]/10 M 5 3 2 1 0 0 5 10 15 Reaction time/h... of olefins using dioxygen as oxidant under ambient conditions The process involved use of -diketonate complexes of Ni2+, Co2+, and Fe3+ as catalysts and an aldehyde as oxygen acceptor.[64-66] 6 Biomimetic Based Applications Subsequently, many metal catalysts e.g manganese complex, cobalt-containing molecular sieves and metalloporphyrins demonstrated highly catalytic performance for the aerobic oxidation... oxidized, the conversion rates of styrene, trans- -methylstyrene and trans-stilbene were 95%, 89% and 86% after reacting for 4.5, 7.0 and 8.0 h, again demonstrating a steric effect (entries 4-6) 8 Biomimetic Based Applications MnTPP (0.1 ppm) CH2Cl2 (50 mL), isobutyraldehyde (0.1mol), O2 (1 atm), 10 h, r.t 20 mmol O isolated yield: 90% TON: 731,470,480 TOF: 1.2x106 min-1 N N Mn N N MnTPP Scheme 4 Manganese... isobutyraldehyde (0.01mol), CH2Cl2 (5 mL), O2 bubbling, r.t Table 2 Epoxidation of alkenes catalyzed by manganese meso-tetraphenylporphyrin in the presence of molecular oxygen and isobutyraldehydea 10 Biomimetic Based Applications Conversion of cyclohexene (%) 100 80 60 10000ppm 100ppm 10ppm 1ppm 0.1ppm 40 20 0 0 1 2 3 4 5 Time/h Fig 4 Conversion rates profile of cyclohexene oxide with different amounts of... presence of Mn(TPP)Cl and isobutyraldehyde: concentration of cyclohexene, 0.4 M; concentration of isobutyraldehyde, 2.0 M; concentration of catalyst, 4 10-5 M; O2 bubbling; room temperature 12 Biomimetic Based Applications In contrary to Kaneda’s results, the metalloporphyrins catalyst is absolutely necessary for the epoxidation of cyclohexene from the fact that only 13% yield of epoxide can be obtained... Mn(TPP)Cl as catalyst is a combination of oxidation of aldehyde and epoxidation of cyclohexene Following the reaction mechanism given in Figure 6, the reaction equations can be listed as below: 14 Biomimetic Based Applications 350 400 450 500 550 Wavelength (nm) Fig 8 In situ UV-vis spectra of the aerobic epoxidation of cyclohexene catalyzed by Mn(TPP)Cl (0.04 mM) in dichloromethane solution (time scan:... the electronic structure of one of the partners Living systems mainly use enzymes like cytochromes P-450 to modify the electronic structure of dioxygen to form which is adapted for the desired 2 Biomimetic Based Applications O2 CH3 H2C CH H3C C CH2 H N N Fe N N CH3 H3C H2C H2C CH2 CO2- S C O protein C H2C C CO2H2 NH2 SH Fig 1 Prosthetic of cysteinato-heme enzymes: an iron(III) protoporphyrin-IX covalently... increasing of isobutyraldehyde concentration from 0.8 to 2.4 M resulted in an increase of the initial rate of epoxidized cyclohexene from 1.11 10-3 to 3.41 103 mol L-1 min-1 as shown in Table 6 18 Biomimetic Based Applications 4.5 3.5 3.0 -3 -1 R/10 mol L min -1 4.0 R=0.997 2.5 2.0 0.8 1.0 1.2 1.4 1.6 0.5 -2 1.8 2.0 0.5 [Mn(TPP)Cl] /10 , M Fig 10 Effect of the concentration of Mn(TPP)Cl catalyst on the... the amount of catalyst was only 0.01 ppm (entry 2) The optimal amount of catalyst for the epoxidation was 0.05ppm (entry 3) On the contrary, attempts for enhancing the yield by increasing the 20 Biomimetic Based Applications amount of catalyst were unsuccessful The yield decreased with the increase of catalyst amount (entries 4-6) This is the typical characteristics of metalloporphyrins-catalyzed oxidation, . BIOMIMETIC BASED APPLICATIONS Edited by Anne George Biomimetic Based Applications Edited by Anne George Published by InTech Janeza. at www.intechopen.com Additional hard copies can be obtained from orders@intechweb.org Biomimetic Based Applications, Edited by Anne George p. cm. ISBN 978-953-307-195-4 free online editions. modify the electronic structure of dioxygen to form which is adapted for the desired Biomimetic Based Applications 2 N N N N Fe CH CH 3 CH 3 H 2 C CH 2 H 3 C H 3 C H 2 C H 2 C CO 2 - C H 2 CO 2 - C H CH 2 S C C NH 2 H 2 C SH O O 2 protein