nanostructured materials in biological and artificial systems · nanostructured materials in...

Review

R&D Review of Toyota CRDL, Vol.45 No.1 (2014) 31-41

© Toyota Central R&D Labs., Inc. 2014 http://www.tytlabs.com/review/

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Special Review

11th Toyota Conference, Mesoporous Materials, Neutron Quasi-elastic Scattering, FuelCellMembrane,ArtificialEnzyme,ArtificialPhotosynthesisSystem, Bio-mineralization,Yohen-Temmokubowl

Report received on Feb. 3, 2014

YoshiakiFukushima

Nanostructured Materials in Biological and Artificial Systems

Selected research examples from the last decade at theTOYOTACRDL, INC. fornanostructuredmaterialswerereviewedusingthecomparisonintroducedatthe11th Toyota Conference held in1997.Theresultsofmesoporousmaterials,characterizationsusingneutronscattering,approachestoanartificialenzyme,aphotosynthesissystemandbio-mineralizationwereincluded.Theresultswerediscussedfromtheviewpointsoftruenanostructuredmaterialandtherelationshipbetweenthecharacteristicsandproperties.

1. Introduction

We organized the 11th Toyota Conference entitled “NanostructuredMaterialsinBiologicalandArtificialSystems” on November 5–8, 1997, sponsoredby TOYOTA MOTOR CORPORATION. Theconferencecoveredmodeling,analyses,synthesesandapplications of mesoporous materials, nanoparticles, colloids, films and layers produced in natural orartificial processes. The reports at the conferencewerepublished as a special issueofSupramolecularScience Volume 5, Number 3–4, 1998. When wewere planning the conference, one of the membersoftheorganizingcommittee,ProfessorT.J.Pinnaviaof Michigan State University, proposed that wedefine“nanostructured”materials.HeaskeduswhatNANOSTRUCTUREDmaterialsare.Hewrotemethefollowingletter.“Historicallyanumberofnanosizedmaterialshavebeenreportedtodatesuchascolloids,nanocrystals and cluster compounds.Although theyhave exhibited interesting properties, most of themare simply nanosized particles. Their properties areinvariantwhenthesizesarechangedfromatomic toconventional scales. True nanostructured materials,whichwewould like todefinehere,areoneswhosestructures and compositions can neither be described nor characterized by anything else than terms of ananometer-length scale”. As this statementwas fullofprofoundmeaning,weacceptedhiscommentand

quoteditintheprefaceofthespecialissue.(1)However,thelatterpartofthisstatement,wherehetriedtodefinea truenanostructuredmaterial,washard to interpret.One of the motivations for this review is to try toansweragainhisquestion,whatistruenanostructuredmaterial.

The nanostructured materials and their related subjects are still studied in the world and also atToyotaCentralR&DLabs.,Inc.(TOYOTACRDL,INC.).In this review, I selected some topics that wereproposed in the 11th Toyota Conference as an origin of studywith comparisonsof some recentoutcomesofTOYOTACRDLINC.Iwouldliketodiscusstheproblem of the true nanostructured material from theviewpointofmyowninterest.Theperformancesofmaterials for automobile bodies, electricwires orcatalystsaredirectlyconcernedwiththeirproperties,suchasmechanical strength, electricconductivityorcatalyticactivity.Forunderstandingandcontrollingtheproperties,itisnecessarytoknowtheircharacteristics,such as crystal structure, morphology of grains, electrical and magnetic structures, diffusion constant, and surfacemorphology and structure.Although thedifferencesbetween“performance”,“properties”and“characteristics”arenotclear, Iwould like todefinetheminthisreview.Asmyinteresthasbeentherelationof properties and atomic architecture, the question for “true nanostructured material” could be replaced by the “necessity of the nanometer-scale structure for

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realizingaspecificproperty”,whichisaviewpointofthisreview.

2. Characterization Methods

In the research of materials, we should alwaysfollow the design-synthesis-characterization (DSC)cycle.Informationregardingapplicationneedsshouldbeoneofthemostimportanttasksforthedesignstep.Aspartofthiscycle,propertyandperformancechecksare included in thematerial development processes.Structural analyses using quantum beams from X-rays, electrons, light or neutrons are the principal methods of characterization.We focused on structure on thenanometerscale,aswellassmall-anglescattering(2,3) and electron diffraction and electron microscopy(4)

techniquesattheToyotaconference.

2. 1 Design-synthesis-characterization (DSC) Cycle in Research of Mesoporous Materials

We have been collaborating with Prof. Terasaki,who proposed a strategy for characterizingnanostructured materials using electron diffraction, electronmicroscopyandmodeling.(4)Wecouldfollowthe characterization (C) of mesoporous silica,(5)by followingadesign (D)of thenoblematerial andattemptingsynthesis(S).BesidestheDCScycles,wealso found characteristic properties of mesoporous silica, such as catalysis,(6-10) by collaboration withProf.Ichikawa,whoreportedthecatalyticbehaviorsofthe nanostructured materials at the Toyota conference, along with adsorption properties,(11-12) stabilizedenzymes(13-15) and organic molecules included in the nano-spaces.(16,17) Some interesting properties led to proposalsfornewapplicationssuchasacatalystsforafuel cell(18)oranadsorptionheat-pump.(19) Continuous research following the DSC cycle achieved theinnovativeresultofaperiodicmesoporousorganosilica(PMO),(20,21)whichwasrecognizedinoneofthecorepaperstoopenanewchemistryandmaterialssciencefront and promote new researchwork in the world.The noble properties(22) of the hybrid mesoporous materialsareexpectedtohaveinnovativeapplications.

2. 2 Complementary Approaches in Material Characterization

At the 11th Toyota Conference, two examples of

small-angle neutron scattering for emulsions and polymergelswereintroduced.Prof.KanayaofKyotoUniversity proposed the complementary approachusing wide-angle neutron scattering, small-angleneutron scattering, ultra-small-angle neutron scattering andlightscatteringtoadvancethenanostructure.(3) Since 1997, thesuperphotonringat the8GeV(SPring-8)facilitywasopenedforcommonuse,andconsequentlytheworld’s strongestX-rayshavebeenavailable forcharacterizationofthematerials.Thecomplementaryuse of X-rays and neutrons is a powerful methodfor structural analysis.TheKanayagroup confirmedthe unique Shishi-kebab structure (Fig. 1) of flowmoldedpolyethylenebyusingsmall-andwide-angleX-ray scattering, small-angle neutron scattering, light scattering and an optical microscopy.(23-25) The informationofawide-scalestructurefrom0.1nmto0.1mmmadeitpossibletounderstandtheabnormalstrength: about 300 kg・mm–2 of polyethylene fiber.The nanosize of the kebab part with the crystallamellae and their nm scale periodically arrayed along theshishpartwiththestretchedmolecularchainmicrofibrilscontributedtotheirmechanicalproperties.Herewehaveatypicalexampleofnanostructuredmaterialwhose property or performance was realized by itsnanometer-scalestructure.

2. 3 Connection of Character with Property: Neutron Scattering

Understanding the structure of matters is the basis for materialresearch.However,thecharacteristicscannot

Fig. 1 Shishi-kebabmodel for the structure of themeltdrawingpolyethylene.(23)

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directlybeconnectedwithpropertieswithoutourownimagination or modeling using computer simulations and calculations.We can measure the properties ofbulkmaterials such as electric conductivity, thermalconductivity, magnetization or mechanical strength,and also check performances of a catalysts, fuelcell,batteryorautomobilebody.However,thereis still a significant gap between the micro- ormeso-scale character and the intrinsic properties of the materialsduetotheinfluencesofmeasuringmethods,impurities,defectsandinterfaces.Recentdevelopmentin computer modeling methods is one of the most helpfultoolsforourimagination.Iamexpectingthatthemost advanced neutron scattering and theX-rayfreeelectronlaserwillconnectthenanostructureandintrinsicproperties.We are using two aspects of quantum beams,

wavelength and energy, for the characterizations ofthematerials.AsthewavelengthofanX-rayisseveralangstroms, which is comparable to the distancebetweenatomsorthelatticeperiodicityincondensedmatter,itissuitabletocharacterizethestaticstructureofmatterbyusingwaveinterference.Energychangesbetween an incident and a scattering beam provideuswith informationabout adynamic structure, suchasvibrationordiffusion.Astheenergyofinfraredorvisible light is comparable with the vibration modeof the usual chemical bonds in condensed matter or molecules, infrared and Raman spectroscopies arepowerfultoolstocharacterizethedynamicstructures.The g-ray,X-ray,ultraviolet,visibleandinfraredraysare electromagnetic waves that follow Plank’s rule,asshown inFig. 2.Figure2alsoshows the relation

betweenenergyandwavelengthforparticlerayssuchas electron and neutron beams,which follow the deBroglie rule. Neutron beams with wavelengths ofseveral angstroms are suitable for characterizingthe static structure of solids and liquids. Neutronbeams have an energy of several tens to hundredsmeV,which is suitable for dynamic structures.Coldand thermal neutron scattering has been expected to provide the vibration or diffusion properties withintheregionofnanometersizeandthepico-secondtimescale. The vibration or diffusion behaviors withinregionsofthissizeandtimescalewouldbeusefultounderstand the relation of the static structure and the intrinsicproperties such as catalytic activitiesor iondiffusion.Recentdevelopmentsoftheneutronfacilityin the Japan ProtonAccelerator Research Complex(J-PARC) make possible a high flux of cold andthermalneutrons,whichcanapplyneutronscatteringforthecharacterizationofmaterials.Besides the energy-wavelength relationship,

neutronshavethecharacteristicofhydrogenorprotonscattering. As the incoherent scattering length ofneutrons for hydrogen or protons is about ten times larger than that for other atoms, neutron scattering is suitable to analyze thedynamicsofhydrogenandmolecules containing hydrogen. The quasi-elasticneutron scattering (QENS) spectrum is related toself-diffusion and local jumpmotion. When water,hydroxide or protons in a sample are tightly bound to solid surfaces and their movement is restricted,incident neutron energy is not modified by thescattering and only the same profiles of scatteringneutronswithanincidentneutronbeamareobserved.This is called elastic scattering. The movementsof the hydrogen modify the neutron spectrum and diffuse the quasi-elastic spectra around the elastic peak,asshowninFig. 3.Theratiooftheelasticpeakandthequasi-elasticpeakcorrespondstotheratioofrestrictedandmovingmolecules.Thespectrumfortheadsorbedwater in themesoporous silica shows thatwatermoleculesinthefirstlayeronthesilicasurfacecould not move, although other water molecules inthe mesopore-space could move. Further precisecurve-fittinganalysesof thebroadquasi-elasticpeakprovided theaveragedstaying timeat trappingsites,thejumpinglengthbetweenneighboringtrappingsitesandtheself-diffusionconstantofthewatermolecules.The jumping mechanism and diffusion constant of the watermoleculeinthenano-spacesweredifferentfrom

Fig. 2 Characterizations of static and dynamic structureusingneutron.

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thoseofbulkwater.Since proton diffusion is one of the most important

properties for fuel cell development, proton, waterand hydronium diffusion behavior in solid protonconductive materials(26,27) and hydrated polymer films(28-30) have been analyzed by QENS. Perovskite(SrCe(Yb)O3) has attracted attention as a proton conductive solid.(26) Models for the proton motions around the –OHgroup in the solid shown inFig. 4 were proposed(27) and analyzed by quasi-elastic andinelastic neutron scattering.(31,32) The quasi-elastic spectrum suggested the four jumping modes of H+: rotating around Ce4+ -O (tR), trapping at the Ce4+ -O site for t sec followed by jumping about 0.3 nm tothe neighboring Ce4+ -Osite, trappingat theYb3+ -O site for t0 sec followedby jumpingabout0.3nm tothe Ce4+ -Osite, and trappingat theYb3+ -O site for t1 sec followed by jumping about 1 nm to theYb3+ -O site. The research studies proposed that theprotondiffusionconstantinthisoxidewasrelatedtothejumpsbetweenYb3+ -O sites, and the combination ofjumpsbetweenCe4+-Ositeswithloweractivationenergyisattributabletothehighprotonconductivity.Thewatercontentinanorganicpolymermembrane

changes with relative humidity, which changes thenanometer-scale structure of the water clusters.Themolecularmotions and vibrations of thematrixpolymerchainsalsoaffectthediffusionofprotons(H+), water (H2O),hydronium ions (H3O+) and hydronium cluster(H7O3

+).Thestructure,vibrationanddiffusionpropertieshavebeenanalyzedbyX-rayandsmall-angleneutron scattering, infrared, and inelastic neutron and quasi-elasticneutronspectroscopy.(28-30) AsshowninFig. 5,thefollowingfivemodesofprotonsandprotonmovementwereproposed.a)TightlyboundH+ to SO4

– group on the surface of thepolymermembrane.b)Jumpingbetweentheneighboringtrapsites.c)MovinginthewaterclustershydratedwithSO4

– groups.d)Movinginthewaterdomainssurroundedbythepolymerchains.e)Jumpingbetweenthewaterdomains.Itisnecessaryforunderstandingtheprotondiffusionmechanismtoanalyzethestaticanddynamicstructureinthespacerangefromseveralangstromstoseveralhundreds of mm,and in the time range fromseveralpico-sectoseveraltensofnano-seconds.Althoughthephenomenaaretoocomplicatedtorealizeanacceptablemodel,thishasbeenchallengingandimportantwork.Increasing acid density is expected to increase the

protondiffusivityeveninalowhumidityenvironment.However, increasing theSO4

– groups in the polymer chainalsoraisesexcessswellingwithwatertoweaken

Fig. 3 Energyspectrumofincidentandscatteredneutroninquasi-elasticneutronscatteringexperiment.

Fig. 5 Proton diffusion modes in a swollen polymermembrane.

Fig. 4 Modelforjumpingdiffusionmodesinaperovskiteoxide.

H+ H+ H+ H+

τ0

τ1

τ

H+O O O O O O

Ce4+ Ce4+ Ce4+ Yb3+Yb3+

τR

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the mechanical properties and durability. Althoughmesoporous silica with SO4

– groups on the inner surface (Fig. 6) is expected to be a suitable material to control the acid density without modification ofthe swelling property, intrinsic proton conductivitycouldnotbeevaluatedduetothepowdermorphology.Complementary analyses of quasi-elastic neutron scattering, X-Ray diffraction, electron microscopeobservation and proton conductivity measurementconfirmed the direct jump between the acid siteseven in the low humidity environment.(33) The characteristicsandthepropertiesofthismaterialwerewellestablishedtoproposethepossibilityofexcellentperformance for a fuel cellmembrane. Besides theproton dynamics, those of other ions such as lithium andsodiumionwerealsoanalyzedbyQENS(34,35)and offered valuable information for secondary batterydevelopment. Following theopeningof theneutronfacilitiesinJ-PARCandtheX-rayfacilitiesinSPring-8,muon-spin rotation and muon-spin relaxation (m+SR)facilities and the X-ray free electron laser facility, the SPring-8AngstromCompact free electronLaser(SACLA)hasbeenopenedforpublicuseandofferedus dynamic structure(36,37) and nanoscale structure(38)information. Developments of the characterizationmethod are expected to broaden our knowledge ofmaterials.

3. Nanostructured Materials in Biological Systems and Bio-inspired Research

In the natural system, highly selective andhigh-speed proton diffusions are realized bycontrolling the pore size and the surface propertiesofthechannels,asshowninFig. 7.Itwasproposedthatthepinpointsofnarrowspaceswithahydrophilic

surface and the relatively wide channels with ahydrophobicsurfacewouldcontributetotheexcellentproton transfer property in proteins.(39) In the designprocessofthematerials,assembliesofthepartswithspecificfunctionsarenecessaryforobtainingexcellentmaterialsforusefulsystems,whichwasproposedasaclosingremarkof the11thToyotaConference. In thecaseoftheprotonchannelinFig.7,combinationsofa hydrophilic part and a hydrophilic part should be mimickedinartificialdevelopments.

3. 1 Artificial Enzymes

Abiologicalcatalyst,anenzyme,hastheremarkableabilityof selectivity andprovides a lower activationenergy(higherreactionrateconstant).Weconfirmedtheexcellentperformanceofanenzymebypreparingan enzyme fuel cell, in which the suitable enzymesfor anode and cathode reactions and a porous carbon electrodewithsuitableporesizetoincludetheenzymeswere assembled.(40) Application of the enzyme fuelcell was limited due to the poor durability and low

Fig. 6 Structuremodel of amesoporous silicamodifiedwith–SO3Hgroup.

Fig. 7 Watertransfermodelinbio-membranechannel.(39)

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activesitedensityoftheenzymes.However,thelowactivationenergyforthefuelcellreactionwasaffirmedin this enzyme catalysis system, which is expectedtobemimicked in an artificial system.The requiredparts for reaction, adsorption, introducing reactants, removing products and controlling the reactionare assembled in the enzymes. The moleculesare self-assembled in nanometer spaces prepared by proteins,inwhichthenanometerscaleisimportantforenergy and electron transfer between the moleculesandquickmovementofhydratedmolecules.

Chlorophyll a (C55H72MgN4O5) is one of the most important pigments in chloroplasts for the photosynthesissysteminplants.Chlorophyllacannotworkalonebutaggregatestoformalight-harvestingcomplexantenna that realizes effectivephotoelectricconversion, durability for light radiation and along-lived active state. A hydrophilic phytol(C20H39OH)groupandametalorganiccomplexMg-porphyrin were bound to form the chlorophyll amolecule. The porphyrin part is an active site forphotoelectricconversionandthephytolgrouphelpstoself-assemblethearrangementoftheantenna.Whenmesoporous silica with a suitable pore size and asuitable solvent for chlorophyll a is present, thechlorophyll was selectively adsorbed in the nano-space of the mesoporous silica. The adsorbedmoleculeswerearrayedinthemesoporesasshownin Fig. 8.(16) The arrangement where the porphyrinmolecules are oriented face-to-face within 1 nmdistance would allow energy transfer between theporphyrinmolecules.(41) Ametalporphyrinwhich issimilar in structure to the chlorophyll a is used in natural enzymes such as hemoglobin or myoglobin.AlthoughHeme,Fe2+ -porhyrin,wasnotadsorbed in

the mesoporous silica and had little activity as acatalyst, the phytol modified Heme molecules wereadsorbed in the mesoporous silica to form the same molecular arrangement shown in Fig. 8 with ananalogouseffectofthenaturalenzymemyoglobin.(17) These results suggest that the control of the local nanometer-sized environment around the activationsite of Fe2+ was necessary to realize the excellentcatalytic activities, which were brought by thearrangement of the protein globin in the natural enzymeandalsoby themolecular assemblies in thenano-spaces of the mesoporous silica. The artificialenzymehasbeenoneofthemostattractiveapproachesinnanostructuredmaterialscience.(42)

3. 2 Approach to Artificial Photosynthesis

Artificialphotosynthesisisoneofthemostdesiredtechnologies to address globalwarming and to savefutureenergy.UsefulhydrocarbonsareproducedfromCO2andH2O by using the energy of sunlight in natural photosynthesis. Although ultraviolet light energy issuitable for the reaction,natural leavesprefernot touse the ultraviolet, but instead prefer to use visiblelightwithlowerenergyduetotheeffectiveutilizationof sunlight and protection of their own bodies andsystems against light radiation. As the visible lightenergy is not enough to generate hydrocarbon from CO2 and H2O, the leaves prepare two photoelectricconversion elements called photosystems I and II,which are connected to obtain enough energy. Wetried to assemble the artificial photosystems I andII. One photosystem is a complex(43) of organic photo-activemoleculesandmolecularnano-sheetsofquasi-TiO2 proposedbyDr.Sasaki.(44) The other is a complexofvisiblelightactiveorganicmoleculeswithmesoporoussilica.Wefocusedontheelectronorholetransferbetweenthetwomodelsystems.(45,46) Although this assembly has not been developed as a usefulphotosynthesis system, the challenge for assembling photochemical active semiconductors, oxidationand reduction catalysts has been continued at the TOYOTACRDL,INC.Inthephotosynthesissystem,elementsforlightharvesting,photoelectricconversionand catalysis for oxidation ofH2O and reduction of CO2areused. Theassemblyof theseelementswithefficientelectron,hole,andmasstransfers,forwhichthe arrangements on the nanometer scale hold the key,isoneofthemostimportantchallenges.Periodic

Fig. 8 Model of the arrangement of chlorophyll a in the mesoporoussilica.(16)

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mesoporousorganosilica(PMO)withachromophoregroupintheframeworkisexpectedtobeacandidateforthelight-harvestingelement. Anefficientenergytransferfromtheframeworkchromophoretotheguestdye(47) and CO2 reduction catalysis(48) in the mesopore spaceswereconfirmed.Intheseassemblies,organic-inorganic hybrid frameworks served not only as aphotoelectricconversionelementbutalsoasaprotectivecoveringforthefunctionalorganicmoleculesagainstradiation of ultraviolet light.(48) Another approach at the TOYOTA CRDL, INC., which demonstratedartificialhydrocarbonphotosynthesisusingonlyH2O, CO2andvisiblelight,isthepreparationofacatalysiselementforselectiveHCOO– formation in an aqueous system,hybridizedwithaninorganicsemiconductor(49) and followed by the conjugate with H2O oxidation photocatalysis.(50,51)Wecouldhaveatypicalexampleof a nanoscale assembly technology of nano-parts to obtainausefulsystem,andTOYOTACRDL,INC.hasbeeninthepositiontoleadinthisfield.

3. 3 Bio-mineralization

Research on organic/inorganic hybrids or complexmaterialsisinspiredbythebio-mineralizationprocess.In biological systems, organic/inorganic hybrids orcomplex materials have produced many interestingnano-magnets,(52) nano-hybrids in shells(53) and plant bodies.(54) An example of the nano-magnet particle is shownonthefrontcoveroftheproceedingsofthe11th Toyota Conference. Calcium carbonate (CaCO3) minerals are one of the most important minerals on our earth, because of their role of fixing CO2 in the environment and serving as a source ofmaterial forshells, plant bodies, industrial concrete and plasters.Although bio-mimetic approaches to make uniquecomposites were tried,(55) materials with excellentproperties such as abalone shells have not beenartificially obtained. We studied the influence oforganicpolymerfilmsontheformationofCaCO3 and obtained an organic CaCO3 composite film.(56) The effects of the lowmolecular weight organic aminesand aminoacids on CaCO3 precipitation have beenstudied,(57,58) but the preparation of polyamide CaCO3 hybrids is challenging. The process to makenanostructuredmaterialsinspiredbybio-mineralizationwasdevelopedinotherdirectionstoprepareorderednano-hetero-metallic materials from organic blockcopolymers.(59)

4. Typical Nanostructure Material in Traditional Technology

In biological systems, we have many examplesof nanostructured materials and assemblies, whicharouseourinterestbutwhicharestillhardtoimitateartificially. I also found an example in traditionaltechnology. Jian ware bowls created at the Songdynasty (10th–13thcenturies)areknownasTemmokuwareinJapan.TheinnerbrilliantblackglazingoftheYohen-Temmoku bowls is splashed with spots, anda sparkling lazuline border surrounds the spots.Thecolorof thebordervariesdependingon the incidentlightandviewingposition.Therearethreeexamplesof Yohen-Temmoku bowls in the world, and thesethreebowlsareaJapaneseNationalTreasure.OnlyafewraresampleswiththiskindofbrilliantglazeeffecthavebeenfoundattheJiankilnsite.Fortunately,Ihadtheopportunitytoobserveoneoftheshardsbyelectronmicroscopy,electrondiffractionandenergydispersiveX-rayspectroscopy.(60)Theglazingwastheglassphaseexcept for the magnetite polycrystalline of the surface layer,whichwasabout40nmin thickness. Crinklepatternsofabout0.1mmpitch,asshowninFig. 9, play theroleofsurfacegratingforvisiblelightdiffraction,whichcontributestothevariedcolorchangefromtheYoheneffect.Ananometer-scale ironoxidefilmwasformed at the surface, followed by hardening of theinner glass phase during the cooling process. Thecrinkling patterns are formed during this process.

Fig. 9 TEM image of glazing layer of ancient chinaTENMOKU,preparedfromasamplefromtheJiankilnsite.

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Although many trials have tried to reproduce thisbrilliant pattern for more than a thousand years, no one hasreachedthetechnologyofYohen-Temmoku.Herewe have another excellent nanostructured material,whosecharacterwasunderstoodbyrecenttechnology.

5. Conclusions

Wehavemanyexcellentexamplesofnanostructuresin natural, biological, earth and cosmic sciences, and alsoinancientandmoderntechnology.Wehavebeentrying tounderstand theiressencebyusingavailableresearch methods. The gap between natural system/artificial system, character/property/performance ofmaterials,andnoblediscovery/application,hasyettobeclosed.However,wehavemademanyconsiderableachievements,asshowninthisreviewonbothsidesofscience and technology, as a result of complementary worksunderinterrelatedinfluences.Ihadaninterestingmeeting at the 11th Toyota Conference over a broadrange of scientific and engineering activities, ofcharacterization, synthesis, assembling and applyingofnanostructuredmaterialsinbiologicalandartificialsystems.Smallbutinterestingandsuccessfulcasesoftruenanostructuredmaterialsinthelatestdecadewereintroducedinthisreview.Ihopetobeabletocontinuecharacterizationsoforganic/inorganicinteractionsandchallengestobio-mineralizationmimics.

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Yoshiaki FukushimaResearchFields: -OrganicandInorganicHybrids -Bio-mineralization AcademicDegree:Dr.Eng. Academic Societies: -TheChemicalSocietyofJapan -TheJapanInstituteofMetalsandMaterials -TheClayScienceSocietyofJapan -TheJapaneseSocietyforNeutronScience -JapanSocietyofPowderandPowderMetallurgyAwards: -TheJapanSocietyofPowderandPowderMetallurgy AwardforResearchDevelopment,1994 -TheCeramicSocietyofJapanAwardfor Ceramography, 1997 - The Secretary of Science and Technology Agency AwardforDistinguishedReserch,1998 -TheChemicalSocietyofJapanAwardforTechnical Development,2000 -TheClayScienceSocietyofJapanAward,2000 -JapanFineCeramicAssociationAwardforTechnical Development,2005 -AIPEA(InternationalAssociationforStudyofClays)

Medal, 2009 -TheChemicalSocietyofJapanFellow,2010

nanostructured materials in biological and artificial systems · nanostructured materials in...

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