1. Discovery of materials specific peptides (Nature 2000)

Virus and Nanotechnology

2. Alignment quantum dots directed by M13 virus (Science 2002)

3. Synthesis of magnetic and semiconducting nanowires (Science 2004)

4. Nanowires for lithium ion battery electrodes (Science 2006)

5. Fabrication of high-power Li-ion batteries using virus (Nature 2009)

(Developed by Angela Belcher Group at DMSE, MIT)

Organic-Inorganic Interface of Abalone

Nacre is made of aragonite (CaCO3) & organic materials (only a few wt %)Nacre has 3000 times higher fracture toughness than a single crystal of pure aragonite

Discovery of materials specific peptides

TMRTMRTMRTMR

Line = GaAs

Space = SiO2

TMR = tetramethyl rhodamine

Morphology of M13 Virus

6.6 nm

880 nm

pIII unit

Phage Display

Repeated 5 times

A7-phase: Cys-Asn-Asn-Pro-Met-His-Gln-Asn-Cys

By 106

5 times

Amino Acid Structure

Amino Acids

Nonpolar & hydrophobic

Polar &

http://www.bioss.ac.uk/~dirk/genomeOdyssey/go_1955_to_66.html

Polar & hydrophilic

Carboxyl group: acidic

Amino group: basic

Amino-acid sequence bound to GaAs(100)

• Shades � Amino acids with functional group that can donate electrons to the GaAs surface (STNQ rich region)

• Grey � Nonpolar amino acids• Grey � Nonpolar amino acids

Preferably bind to GaAs(111)A (Ga-rich) to GaAs(111)B (As-rich)

Specifically bind to GaAs(100) but not to Al0.98Ga0.02As(100)

Specifically bind to GaAs(100)but not to Si(100)

Binds both to GaAs(100) and InP(100)

Specific Binding

G1-3 clone with AuNP (20 nm) tag

1. GaAs (100)

2. Si (100)

Crystal Composition SpecificCrystal Composition SpecificCrystal Composition SpecificCrystal Composition Specific

1. GaAs (100)

2. GaAs (111) A: Ga-rich

3. GaAs (111) B: As-rich

XPS: Gold 4f-electron signal

Different chemical reactivity �selectivity

Crystal Face SpecificCrystal Face SpecificCrystal Face SpecificCrystal Face Specific

Phage Recognition of Semiconductor Heterostructures

G12-3 on GaAs (zinc zinc zinc zinc blendeblendeblendeblendesurface)

SiO2

G12-3 on GaAs

No G12-3 on Al0.98Ga0.02N

Similar lattice constant, (5.66 Å vs. 5.65 Å) both zinc blende,

chemical compositionchemical compositionchemical compositionchemical compositionis different � element specific

20 nm AuNP tagged to G12-3

G1-3 phage on InP(100)

On GaAs

InP InP InP InP ---- Another zincAnother zincAnother zincAnother zinc----blende blende blende blende structure, great ionic structure, great ionic structure, great ionic structure, great ionic charactercharactercharactercharacter

Selective binding due to Selective binding due to Selective binding due to Selective binding due to chemical, structural, or chemical, structural, or chemical, structural, or chemical, structural, or electronic ? atom size, electronic ? atom size, electronic ? atom size, electronic ? atom size, charge, polarity, crystal charge, polarity, crystal charge, polarity, crystal charge, polarity, crystal structure ???structure ???structure ???structure ???

500 nm

PIII protein

Direct Nanopaticles to Specific Location

Bivalent synthetic peptide

Alignment quantum dots directed by M13 Virus

Procedure

Tris buffered saline (TBS) 0.1% TWEEN-20 (to reduce phage-phage interaction)

1hr rocking

Wash with TBS at pH7.5 and TWEEN-20 ~0.5%

Elution – glycine-HCl pH2.2, neutralization with Tris-HCl pH 9.1

A7-phase: Cys-Asn-Asn-Pro-Met-His-Gln-Asn-Cys

Liquid Crystal Alignment

SmecticSmecticSmecticSmectic

SmecticDifferential interference contrast (DIC)

127 mg/ml127 mg/ml127 mg/ml127 mg/ml

CholestericCholestericCholestericCholesteric

76 mg/ml76 mg/ml76 mg/ml76 mg/ml

AFMAFMAFMAFM

Liquid Crystallinity

Cholesteric phase

A7-phage and ZnS nanocrystalsA7 = CNNPMHQNC

1 mM ZnCl2 and Na2S

A7-ZnS Viral Film

PL

POMPOMPOMPOM

A7-ZnS Viral Film

Synthesis of Magnetic and Semiconducting Nanowires

Virus-Templated Nanowire Formation

NucleationNucleationNucleationNucleation

OrderingOrderingOrderingOrdering

AnnealingAnnealingAnnealingAnnealing

Modification of gP8

5 genetically modifiable proteins: gP3, gP6, gP7, gP8, gP9

gP8 – protein form the capsid of the virus (~ 2700: major coat proteins)

Nucleating Peptide Sequences

• A7; ZnS = CNNPMHQNC

• J140; CdS = SLTPLTTSHLRS

• FP12; FePt = HNKHLPSTQPLA• FP12; FePt = HNKHLPSTQPLA

• CP7; CoPt = CNAGDHANC

DNA

DNA

• Single stranded DNA (ssDNA) and double stranded (dsDNA)

• Each strand is made of Adenine (A), Guanine (G), Cytocine (C), Thymine (T)

Phosphaste end 5’

Sugar end 3’

Base Pair

5’5’5’5’

3’3’3’3’

1’1’1’1’

Transcription

Translation

Codon

Formation of ZnS single crystal nanowire

annealing

ZnS and CdS single crystal nanowires

ZnS NW

CdS NW

CoPt Nanowires (prior to annealing)

With virus

before annealing

CoCl2 + H2PtCl6 + NaBH4

Reduction of Co and Pt salts without virus � Precipitation

Magnetic Nanowires

CoPt NW

FePt NW

FeCl2 + H2PtCl6 + NaBH4

unanealedunanealedunanealedunanealed

Nanowires for Lithium Ion Battery Electrodes

Virus Enabled Synthesis of Nanowires

Tetraglutamate (EEEE-) motif (negatively charged)

i) Interact with various positive metal ions, important in biomineralization

ii) Blocking motif for Au nanoparticles, prevent non-specific Au binding

iii) Good for electrostatically driven assembly with a (+) charged polymer

Formation of Co3O4

i) 1 mM Cobalt chloride solution for 30 min

ii) Reduction with NaBH4

iii) Spontaneous oxidation in water

Virus Enabled Assembly of Nanowires

Characterization of Viral Co3O4

Nanowires

Different Texture of Co3O4

Nanowires

branchlike nanowire structurebranchlike nanowire structurebranchlike nanowire structurebranchlike nanowire structure::::Higher cobalt chloride concentration ~ 5 mM with 10 mM NaBH4

Discrete Nanoparticles:Discrete Nanoparticles:Discrete Nanoparticles:Discrete Nanoparticles:Synthesized at low T (~ 4 oC) 1 mM Co ion, 5 mM NaBH4

Hybrid Structure (Au_NP/Co3O4_NW)

Phage display � Au binding motif

Au

Hybrid structureAu_NPs

• High electrical conductivity

• Thermodynamically stable interface with Co3O4

• Catalyze electrochemical reactions at nanoscale

Enhanced Electrochemical Properties

Cyclic voltammograms

Liquid Crystalline Ordering of Co3O4 Viral Nanowires

CoCoCoCo3333OOOO4444 viral NWs viral NWs viral NWs viral NWs on LPEI/PAAon LPEI/PAAon LPEI/PAAon LPEI/PAA

100 nm Cu

Co3O4

NW/Li cell

Fabrication of high-power Li-ion batteries using virus

• Ion phosphate based Li ion battery– Low toxicity, low cost, and improved safety

– Kinetic limitations: poor charge- and discharge-rate capability

• One solution– Reducing particle size � decrease in ionic and electronic

path within the particles: currently 20 ~ 40 nm

– This work: 10 ~ 20 nm

• Result– Power performance of a-FePO4/SWNT is comparable to that

of state-of-the-art c-LiFePO4

Characterization of a-FePO4

cathode

a-FePO4 NWs on E4 viruses

Ag loaded E4 - anhydrous

Discharge curves at different rates

Ragone plot

E4 virus: Modified M13 virus that has tetraglutamate (EEEE) on pVIII major coat proteinSynthesis of a-FePO4: incubation with FeCl3·6H2O followed by reaction with Na3PO4

C-rate in Li-ion battery

http://www.maxell.co.jp/e/products/industrial/battery/li_ion/The charge and discharge current of a battery is measured in C-Rate. Most portable batteries (with the exception of the SLA) are rated at 1C. A discharge of 1C draws a current equal to the rated capacity. For example, a battery rated at 1000mAh provides 1000mA for one hour if discharged at 1C rate. The same battery discharged at 0.5C would provide 500mA for two hours, or at 2C it would deliver 2000mA for 30 minutes. 1C is often also referred to as a one hour discharge rate; a 0.5C would be a two hour, and a 0.1C a 10 hour discharge rate. http://www.allegromicro.com/techpub2/cadex/index332.htm

Genetic Engineering & Biomolecular Recognition

Major coat Major coat Major coat Major coat

• Fabrication of positive electrodes: mixing a-FePO4 + Super P carbon black + polytetrafluoroethylene (PTFE) binder

proteinproteinproteinprotein

Minor coat proteinMinor coat proteinMinor coat proteinMinor coat protein

a-FePO4 grown on Viruses/SWNT

SWNT onlySWNT onlySWNT onlySWNT only aaaa----FePOFePOFePOFePO4444 + SWNT+ SWNT+ SWNT+ SWNT

aaaa----FePOFePOFePOFePO4444

NW on VirusNW on VirusNW on VirusNW on Virus

Electrochemical Properties: Rate capabilities and capacity retention

• E4: one gene system virus with no insert on pIII

• EC#1: virus is a two-gene system virus with the moderate biding affinity to SWNTs

• EC#2: virus is a two-gene system virus with the strongest biding affinity (5 wt % SWNT)