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Biomimetics Learning from Nature

Biomimetic Synthesis of Nanoparticles: Science, Technology Applicability3uperparamagnetismange of 1-10nm In the pif an external magnetic field, the material behavestism with an exception that the magnetic moment of the entireQuantum confinement occurs when one or more dimensions of the nanoparticle is maderery small so that it apn exciton in the bulk material called the bohrciton radius the idea behind confinement is toelectronic properties Scientists at the Washington University have studied theectronic and optical changes in the material whenOnm or lethe property of quantum confinementof special properties that nanoparticles exhibit when compared to thebulk are the lack of malleability and ductility of copper nanoparticles lesser than 50nm Zincknown to have superior UV blocking properties compared to the31 Classification of nanoparticlesparticles

Organic nanoparticlesincludeparticles(fullerenes) whilef theparticles may includenanoparticles(like gold and silver)and semiconductor nanoparticles (like titanium dioxided zinc oxideThere isrganic nanoparticles as they providevailable chemical imaging drugs agents and drugs, inorganic nanoparticles have beenxamined as potential tools for medical imaging as well as for treating diseases Inorganicavailability, rich functionality, good biocompatibility, capability of targeted drugdelivery and controlleddrugs (Xu et al, 2006) For example mesoporousined with molecular machines prove to be excellentystems Gold nanoparticles have been used extensively in imaging, as drug carriers and inhermo therapy of biological targets(Cheon Horace, 2009) Inorganic nanoparticles(suchmetallic and semiconductor nanoparticles)exhibit intrinsic optical properties which mayenhance the transparency of polymer- particle composites For such reasons, inorganicave found special inin studies devoted to optical properties inesdependant colour of gold nanoparticles has been used tolour glass for centuries( Caseri, 2009)esTraditionallyarticles were produced only by physical and chemical methods Some ofthesis, reduction and sotechnique Basically there are twoly the Bottom up approach and the Top down approachIn the Top down approach, scientists try to formulateirect their assembly, The bottompproach is a process that builds towards larger and

Biomimetics, Learning from Naturore complex systems by starting at the molecular level and maintaining precise control ofysical and chemical methods of nanoparticle synthesischemical temetal oxides from a chemical solution whinetwork (gel)of discrete particles or polymersdeposited on the substrate to form a film, cast intrature route in whichothermalhe solubility of reactants increases significantlyenabling reaction to take place atturee)Chemical reduction, which is the reduction of an ionic salt in an appropriatein the presence of surfactant using reducing agents Some of thematerial from a solid surface birradiating with a laser beam At low laser flux, the material is heated by absorbedlaser energy and evaporates or sublimates At higher flux, the material is convertedto plasma

The depth over which laser energy is absorbed and the amount ofand the laser wavelength Carbon nanotubes can be produced by this methoe) Inert gasn,where different metals are evaporateinside an ultra high vacuum chamber filled with heliuchamber, theated metallose their kinetic energy and condense in theform of small crystals whichulate on liquid nitrogen filled cold finger Egold nanoparticles have been synthesized from gold wirebihesis of nanoparticles rose as the physical and chemicalDer pathways for nanoparticle synthesis,coOrgfor synthesis Nature has devisefor the synthesisneth scaled inorganic materials which havelargely unexploredbased on the biosynthesisals(Mohanpuria et al, 2007)Biosynthesis of nanoparticles is a kind of bottom up approach where the main reactioncurring is reduction/oxidation The microbial enzymes or the plant phytochemicals withanti oxidant or reducing propertieusually responsible for reduction of metalpounds into their respective nanoparticlegreen chemistry perspective are the choice of the solvent medium used for the synthesis, the

Biomimetic Synthesis of Nanoparticles: Science, Technology Applicabilitynoice of an environmentally benign reducing agent and the choice of a non toxic materialthe synthetic methods reported to date relyheavily onsolvents This is mainly due to the hydrophobicity of the capping agentsdran ef aL, 2002)

Synthebio-chemistry principles: the bio-organism is()eco-friendly as are (ii) the reducing agentmployed and (iii) the capping agent in the reaction (Li et al, 2007) Often chemicalnthesis methods lead to the presence of some toxic chemical species adsorbed on thenot an issue when it comes to biosynthesized nanoparticles as they are eco friendly andbiocompatible for pharmaceutical applicatietics involves boredtially bacteria were used to synthesize nanopartind thislater succeeded withthe use of fungi, actinomycetes and more recently plantschart for Nanobiosynthesism bacteriaMetaNanopartide powdeoach for the synnanoparticles Although the efforts directed towards theetals have been well documented and the ability of microorgaextract andcommercial biotechnologbioremediation(Gericke Pinches, 200acteria are known to proerials either intra cellularly or extra cellularly Microorganisms are considered

Biomimetics, Learning from NaturSome well known examples of bacteria synthesizing inorganic materials includeactic bacteria (synthesizing magnetic nanoparticles) and s layer bacteria whichand calcarbonate layers(Shankar et al, 2004)and grow even at highn concentrationheir resistance to the metal The mechanisms involve: efflux systems, alteration ofbiosorption, bioaccumulation, extracomplexation or precipif metals and lack of specific metal trag Pseudomonas stutzeri AG 259 isolated from silver mbeen shown to produce silver nanoparticles(Mohanpuria et al, 2007)Many microorganisms are known to produce nanostructured mineral crystals and metallicnoparticles with properties similar to chemically synthesized materials, while exercisingstrict control over size, shapeformation of magianoparticles by magnetotactic bacteria, the production of silnanopartidespace of Pseudomonas stutzeri and the fte reducing bacteria in the piectron donor (Gericke &cbioreduction process, some studies have indicated it otherwise Studies indicate thatthe processes of bioreduction were probablnon enzymatic For eg dried cells of Bacillus megaterium Do1, Lactobacillus sp

A09 werens by then of the silver ions with the groups on there produced by treating dried cells of Corynebacterium sp SHog with diammine silvermplex The ionized carboxyl group of amino acid residues and the amide of peptidechains were the main groups trapping(Ag(NH3)2+)onto the cell wafound that the reaction progressed sled could be accelerated in the pice of oh( Fu et al, 2006)of bacteria, most metal ions are toxic and therefore the reduction of ions or thea defense mechanism developed by the bacteriaovercome such toxicity (Sastry23 Use of actinomycetes to synthesize nanoparticactinomycetesmicroorganisms that share important characteristics of fungi andprokaryotes such as bacteria Even though they are classified as prokaryotes, they werexceptional ability to producndary metabolites such as antibiotichas been observed thavel alkalothermophilic actinomycete, Thermonles extracellularly when exposed to gold ions under alkaline2003) In an effort to elucidate the mechanism or the processethe formation of monodisperse gold nanoparticles by Thermomonospora sp and concludedat extreme biological conditions such as alkaline and slightly elevated temperature

Biomimetic Synthesis of Nanoparticles: Science, Technology Applicabilityynthesis of monodisperse gold nanoparticles by Ahmad et al(2003) In this study it wasrticles were more on the cytoplasmicbraneThis could have been due to the reduction of metal ions by thepresent in the cellwall and on the cytoplasmic membrane but not in the cytosofound to be non toxic to the cells which continued to multipl42 4 Use of fungi to synthesize nanoparticlesFungi have been widely used for the biosynthesis of nanoparticles and the mechanisticaspects governing the nanoparticle formation have also been documented for a few of thenIn addition to monodispersity, nanoparticles with well defined dimensionsusing fungi Compared to bacteria, fungi could be used as a source for the production off nanoparticles Thisto the fact that fungi secreteYeast, belonging to the class asynthesis of nanoparticles Gold nanoparticles have been synthesized intracellularthe fungi V

luteomibu Heparticle formation and thereforenanoparticles could to an extentnipulated by controlling parameters such as pHmperature, gold concentration and exposure time a biological process with the ability totrictly control the shape of the particlesa considerable advantage(GerickeExtracellular secretion of the microorganisms offers the advantage of obtaininquantities in a relatively pte free from other cellulr downstream processing Mycelia free spent meditparticlestedtracellularly, It was hypothesized that proteinaccharides and organicreleased by the fungusable to differentiate different crystal shapes anddirect their growth into extended spherical crystals(Balaji et al, 2009)as responsible for the reduction of silver ions andarticles, However Fiparticles either intracellularly or extracellularly even thoughand extracellular reductases in the sanon as Fusanum oxyspofungi culture, isolated proteins from themalso been used successfullynanoparticles production Nanocrystalline zirconia was produced at room temperature bypecific enzymes secreted by fungi in the synthesis of nanoparticles appearspromising Understanding the nature of the biogenic nanoparticle would be equally

Biomimetics, Learning from NaturThis would lead to the possibility of genetically engineering microorganisms toeducing molecules and capping agents and therebyf the biogenic nanoparticles(Balaji et al, 2009)hthan that observedt extracts are used This is one of the major drawbacks of biological synthesis ofusing microorganisms and must be correrected if it must compete with other425 Use of plants to synthesize nanoparticlesilable stage of using plants for the synthesis of nanoparticles is that they are easilavailable, safe to handle and posA numberbeingicles Gold nanoparticles with a sizeof 2-20 nm have been synthesized usinghe live alfaalfa plants(Torresday et al

, 2002) Nanoparticles of silver, nickel, cobalt, zind copper have also been synthesized inside the live plants of Brassica juncea(Indianmustard), Medicago sativa(Alfa alfa) and Heliantusare termed as hypemulators Of the plants investigated Bjuncea had better metalaccumulating ability and later assing it as nanoparticles(Baliluch work has been done with regard to plant assisted reduction of metal(Hydrophytes)were studied for their role in the synthesisf silver nanoparticles The Xerophytes were found to contain emodin, an anthraquinoneredial tautomerization leading to the formation of silver nanoparticleMesophyte studied contained three types of benzoquinones, namely, cyperoquinoneIt was suggested that gentle warming fncubation resulted in the activation of quinones leading to particle size reduction Catechd protocatechualdehyde were reported in the hydrophyte studied along with otherytochemicals, It was reported that catechol under alkaline conditions gets transformedinto protocatechaldehynd finally into protocatecheuic acid Both these processesberated hydrogen anduggested that it playednanoparticles The size of the nanoparticles synthRecently gold nanoparticles have been synthesized using the exf Magnolia kobus andDiopyros kaki leaf extracts, The effect of temperatureof 5- 300nmas obtained at lower temperature while a higher temperature supported the formation ofWhile fungi and bacteria require a comparatively longer incubation time for the reduction ofetal ions, water soluble phytochemicals do it in a much lesser time Therefore compared to

Biomimetic Synthesis of Nanoparticles: Science, Technology Applicabilitybacteria and fungi, plants are better candidates for the synthesis of nanoparticlesynthesize metallic as well as oxide nanoparticles on an industrial scale once issues like themetaboltus of the plarproperly addressed26 Work on the biomimetic synthesis of nanoparticles in Indian India in the fieldf nanoparticles More research has been found to be concentrated in the area of biomimeticthesis using plantsIt has been observed that a novel alkalothermophilic actinomysynthesized gold nanoparticles extracellularly when exposed to gold ions under alkalineonditions (Sastry et al, 2003) The use of algae for the biosynthesis of nanoparticlesrmationRecently stable gold nanoparticles have been synthesized using the marine algusing the seaweed An important potential benefit of the method of synthesis was that theast, belonging to the class ases of fungi has shown to have good potential for theparticles

Schizosaccharomyces pombe cellsds nanocrystals and the productivity was maximum during the midphase of growth Addition of Cd in the initial exponential phase of yeast growth affected therticlesand the tolerance of the organism towards Sb O3 has also been assessed Particles with a sizechallenged with silversolution Monodisperse silver nanoparticles withalso found that a protein from theed as a capping agent on the nanoparticles (vigneshwaran et al, 200as abiosynthesis of silver nanoparticles The advantage of using this organismhat thequite rapid with the n

anoparticlcontact with the cell filtrate particles withrange of 525nm couldbe obtained using this organism(Bhainsa D Souza, 2006)zirconia nanopartiIt has been reported that cationic proteins withliar in nature to silf the nanoparticlesRecently, scientists in India have reported the green synthesis of silver nanoparticles usinghe leaves of the obnoxious weed, Parthenium hysterophorus Particles in the size range of 30-80nm were obtained after 10 min of reaction The use of this noxious weed has an added

Biomimetics, Learning from Naturadvantage in that it can be used by nanotechnology processing industries(Parashar et al2009) Mentia piperita leaf extract has also beeparticles Nanoparticles in the size range of 10-25obtained within 15 min ofthe reaction(Parashar et al, 2009) Table 1 denotesynthesis of nanoparticlessynthesizedExtracellularBacteriumExtracellular Hussein et al,(2007)Bacillus subtilis5-60nmExtracellularSaiffudin ef al (2009bioplasmical,(2000200nmKlaus ef al,(1999)Ag0-75nm Extracellular Sanghi &xdeclan10-60nm Extracellular basavarajaFusarium oxysporum15nmp/MenerochiaeAExtracellular Vigneshwaran e! al,(2006chrysosporiumAspergillus favustracellular vigneshwa62nnAzadirachta indicaAg, Au, Ag/ Au 50-100nm Extracellular Shankar et al

,(2003)bimetallicTripathy et al,(2009)pelargonium16-40nmExtracellularellularal,②2007)Table 1 Use of bial entities for the synthesis of various nanoparticlesbimetallic (silver and gold)les Studies indicated that the reducinginly of terpenoids It was found that thesereducing components also served as capping and stabilizing agents in addition to reductionas revealed from FT IR studies The major advantage of using the neem leaves is that it is ainal plant and the antibacterial activity of the biosynthesizesilver nanoparticle might have been enhanced as it was capped with the neem leaf extract

Biomimetic Synthesis of Nanoparticles: Science, Technology ApplicabilityThe major chemical constituents in the extract were identifieShankar ef al, 2004, Tripathy ef al, 2009) Figure 2 and 3 show thebiosynthesized silver nanoparticles (unpublished data, Prathna TC et al, 2009)Fig 2 Transmneem leaf extract (unpublished data, Prathna T

C et al, 2009)Fig 3 Transmission electron micrograph showing silver nanoparticles synthesized usingeem leaf extract(unpublished data, Prathna T C et al, 2009)427 Some of the mistic aspects ofbacteria, there is very little information available regarding the mechanistic aspects of

Biomimetics, Learning from Naturcumulation by cyanobacteria(Plectonema boryanum UTEX 485)chloride soluhave been studied and it is found that interactith aqueous gold (Ilr) chloride initially promoted the precipitation ofamorphous gm of octahedral (Ill) platelets near cell surfaces and in solutions( Lengke et althe cells of Klebsiella pneumoniae They hypothesize that the reduction of the metallic ions inhe solution by the cell free supernatant is most likely due twhich is produced by some members of Enterobacteriaceae It has been widely studied thatRecentlv cadmiIfide nanoparticles have been biosynthesized using the photosyntheticteria, Rhodopseudomonas palustris The work indicated that the cysteine desulfhydrase(Cyase) could control crystalthrough the action of C-S lyase The content of C-S lyase in R palustris was suggested to beted that r palustristracellularly, later discharging it( Bai et aL, 2009)cells were found to synthesize semiconductor Cds nanocrystalsnd the productinmum during the mid log phase of growth AddCd inthe orKowshik ef al

, 2002) A possible mechanism for this could be that when Cdadded, it causes stress to the organism triggering a series of biochemical reactions Firstly,n enzyme phytochelatin synthaseactivated to syze phytochelatins(PC)thatansport themthe vacuolar membrane by an atp binding cassette typin tbrane protein(HMT-1) In addition to Cd, sulfide could also be added to this complexbrane and this could result in the formation of high molecular weight PC- Cascomplex that alleto be ultimately sequestered into the vacuole(Mohanpuria et al) has been reportedtranstSb O3 nanoparticles and the tolerance of them towards sb203 hasalso been assessed Particles with a size range of 2- 10 nm were obtained It has beend that membrane bound oxido reductases and quinones may have played a rolend work in ala lower ph, oxidase getsted while a higher pH valreductase Thisnumber of simple hydroxy/ methoxy derivatives of benzoquinonesluquinones mainly found in lower fungi(and hypothesized to be present in yeastfacilitate the redox reaction due to its tautomerization The transformation appears to begotiateddiately after the additionSbcl3 solution which triggers tautomerization of quinones and lownsitive oxidaseswhich thereby makes molecular oxygen available for transformation Also when Sbl+enters

BI口 MIMETICSEARNING FR口MNAEditedbyTechintechweb org

In-TehAbstracting and non-profit use of the material is permitted with credit to thee statements anduthor or editor, and the make other personal use of the work

8 2010 In-tehFirst published March 20Technical editelsBN98-953-3070254

PrefaceHumans have always been fascinated by nature and have constantly made efforts tode him to act beyond rather thanst mimicking nature He has now begun to understand and implement natures principlesive helped him to understand the related phenomena in order to engineerdevicesnd design techniques to improve their capability, This field is now called as biomimeticsbio-inspired technology The term biomimetics is deg life andmeaning to imitate While some of nature's designs can be copiedare best adapted if they are to serve as an inspiration using man made capabilities

Therecharacteristics thauniquely identify a biomimetic mechanism and a majcaracteristic is to function autonomously in a complex environment, being adaptable topredictable changes and to perform multifunctional taskstaking inspiration from the lotus effect, photovoltaic cells that have beenped byudying the photosynthesis mechanism of bacteria, airplanes constructed mimicking theThis book is a compilation of knowledge of several authors who have contributed in variousapplications in the field of biomimetics The book is divided into twenty five chaptersThe first part of the book is entirely devoted toand technolonanoparticle synthesis and identifying the various mechanisms adapted by nature Chaptersdevoted for the various strategies and applications of nanoparticles synthesized usingliving organisms, mimicking the various features of physiological membranes, studyingfeatures of photosyenergy converntrol and learning, biomimetic oxidation catalyzemetalloporphyrins and dethe role of carbonic anhydrase in the biomimeticvaticThe second part of the book deals withaspects of fabrication of materials drawinginspiration from nature It discusses the assembly of organic/ inorganic nanocompositesbased on nacre, hydroxyapatite microcapsules, apatite nuclei and apatite related biomaterialsdetail the dent of biomimeticheraophobic surfaces based on lotus effect, micro robots with fabricated functional surfaces,trochemical sensors based on biomimetics, use of biomimetics in dental application

gnd the development of space and earth drills drawing inspifrom the wood waspThe editor would like to thank the authors for their valuable contributions and to all thosewho were directly or indirectly involved in bringing out this work

Last but not the least, weindebted to Vedran Kordic who was responsible for coordinating ththat readers would greatly benefit from this book by keeping abreast the research and latestadvances in this fieldAmitava Mukherje

ContentsBiomimetic Synthesis of NanoparScience, Technology ApplicabilityPrathna T C Lazar Mathew, N ChandrasekaranDaniel H Murgida, Peter Hildebrandt and Smilja Todorovicergei K Zhamukhamedov, vyacheslaroshi Nishihara, Mamoru Mimuro, Robert Carpentier and Toshi Nagata4

Neurobiologically inspired distributed and hierarchical systemand Kazutaka Takahashi5 Function-Based Biology Inspired Concept GenerationJ K Strobe Nagel6 Biomimetic chemistry: radical reactions in vesicle suspensions117Chryssostomos Chatgilialoglu and Carla FerreBiomimeticneous oxidation catalyzed by metalloporphyrinsHong-Bing Ji and xian- Tai zhou8 The Carbonic Anhydrase as a Paragon: Theoretical and ExperimentalInvestigation of Biomimetic Zinc-catalyzed Activation of CumulenesBurkhard o, Jahn wilhelm Aand Ernst Anders

VI24Sondi and2 A Biomimetic Study of Discontinuous-Constraint MetamorphicMechanism for Gecko- Like RobotZhen Dong Dai and HongKai3 Biomimetic Fabrication of Hydroxyapatite Microcapsules by using Apatite Nuclei 273akeshi Yao and Takeshi yabutsukatite related biomaterials89akuya Matsumoto, Masayuki Okazaki,Atsushi Nakahira anSohm5ic aryltetralpreparatio305e Bruno RindoneSaliu6 Superhydrophobicity, Learn from the Lotus LeafMengnan Qu, Jinmei He and Junyan Zhang7 Micro Swimming Robots Based on Small Aquatic Creatures8

Bio-Inspired Water Strider Robots with Microfabricated Functional Surfaces3639 Electrochemical sensor based on biomimetic recognition utilizingcularly imprinted polymer receptor85ering: a new approach to dental tissue reconstructionlisa battistella siBiomimetic Porous Titanium Scaffolds for Orthopedic and Dental Applicationse Examplee“MothTheobald Lohmueller Robert Band Joachim P Spatz23 Wood wasp inspired planed earth dril467Thibault Gouache, Yang Gao, Yves Gourinat and Pierre CosteJianming Li, Sean Connell and Riyi Shi25 Lipid-based Biomimetics in Drug and vaccine DeliveryRibeiro

Biomimetic Synthesis of NanoparticlesScience, Technology ApplicabilityPrathna T C Lazar mathew,n ChandrasekaranAshok m raichurt and amSchool of bioepartment of Materials Engg, Indian Institute of sciNanotechnology emerges from the physical, chemical, biological and engi10-9m is defined as a small object thatbehaves as a whole unit in terms of its transport and properties

The science andngineering of nanosystems is one of the most challenging and fastest growing sectors ofattempts to explain the diversity of the field, starting with the history ofnanotechnology, the physics of the nanoparticle, various strategies of synthesis, the variousadvantages and disadvantages of different methods, the possible mechperspectives Though there are a few good reviews dealing with the synthesis andchanistic aspects of nanoparticle formation This review attempts to fill theons,In section 2, we discuss about the early historydescribe about therticles, their classificatioand significance of inorganic nanoparticles The next section discusses about the variousd theThe last sectionhighlights the recent advances and possible applications of nanparticlesyThe concept of nanotechnology thoughartisans ofpotamia to generate a二一has its historyes of gold and silver were used by theect to pots The first scientific description1 857 by Michael Faraday in his famouspaper"Experimental relations of gold (and other metals)to light"(Faraday, 185

Biomimetics, Learning from NaturIn 1959, Richard Feynman gave a talk describing molecular machines built with atomicThis was entitled"Therof space at the bottomthe world turning its focus towards thene field of drug delivery One of the pioneers in this field was Professor Peter PaulHis research group at first investigated polyacrylic beads for oral administration,used on microcapsules and in the late 1960s developed the first nanoparticlelivery purposetems for drug delivery like (for eg the development ofanoparticles for the transport of drugs athe blood brain barrial,,(19/7) bound 5-fluorouracil to the albumin nanoparticles, and found denaturationemperature dependent differences in drug release as well as in the body distribution inintravenous tail vein injection An increase in life spantraperitoneal injection of the nanopartito Ehrlich Ascites Carcinoma-bearing miceKreuter 2007The nano- revolution conceptually started in thenanotechnology being published in 1981 by K Eric Drexler of Space SysterMassachuetts instf Technology This was entitled"An approach to the developmentWith gradual advancements such as the invention of techniques like TEM, AFM, DLs etcanology today has reachedered as the future to alhnologies3 Unique properties of nanopartinumber of physical phenomena becemore pronounced as the size of the systemdecreases

Certain phenomena may not come into play as the system moves from macro tolevel but may be significant at thescale One example is the increase in surfacethe surface of the particlethat of those in the interior of thearticle, thus altering the properties The electronic and optical properties and the chemicaleactivity of small clusters are completely different from the better known property of eachmponent in the bulk or at extended surfaces Some of the size dependant properties ofnanoparticles are quantum confinement in semiconductors, Surface Plasmon Resonance inmetallic nanoparticles anders to the collective oscillations of the conduction electrons inesonance with the light field The surface plasmon modefromonfinement in the nanoparticle The surface plasmon resonance frequencybut also on the shape and size of the nanoparticle and the dielectriproperties of the surrounding medium ain ef aL, 2007) For example, noble metalspecially gold and silver nanoparticles exhibit unique and tunable optical properties onResouperparamagnetism is a form of magnetism that is a special charaferromagnetic or ferromagiparticles In such superparamagnetic nanopartiandomly change direction under the influence of temperature