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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)
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