Virus and Nanotechnology

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1 Virus and Nanotechnology 1. Discovery of materials specific peptides (Nature 2000) 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)

2 Organic-Inorganic Interface of Abalone Nacre is made of aragonite (CaCO 3 ) & organic materials (only a few wt %) Nacre has 3000 times higher fracture toughness than a single crystal of pure aragonite

3 Discovery of materials specific peptides TMR Line = GaAs Space = SiO 2 TMR = tetramethyl rhodamine

4 Morphology of M13 Virus 6.6 nm 880 nm piii unit

5 Phage Display Repeated 5 times By 10 6 A7-phase: Cys-Asn-Asn-Pro-Met-His-Gln-Asn-Cys

6 Amino Acid Structure

7 Amino Acids Nonpolar & hydrophobic Polar & hydrophilic Carboxyl group: acidic Amino group: basic

8 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 Preferably bind to GaAs(111)A (Ga-rich) to GaAs(111)B (Asrich) Specifically bind to GaAs(100) but not to Al 0.98 Ga 0.02 As(100) Specifically bind to GaAs(100) but not to Si(100) Binds both to GaAs(100) and InP(100)

9 Specific Binding Crystal Composition Specific G1-3 clone with AuNP (20 nm) tag 1. GaAs (100) 2. Si (100) Crystal Face 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

10 Phage Recognition of Semiconductor Heterostructures G12-3 on GaAs (zinc blende surface) SiO 2 No G12-3 on Al 0.98 Ga 0.02 N G12-3 on GaAs Similar lattice constant, (5.66 Å vs Å) both zinc blende, chemical composition is different element specific 20 nm AuNP tagged to G12-3

11 G1-3 phage on InP(100) PIII protein On GaAs 500 nm InP - Another zinc-blende structure, great ionic character Selective binding due to chemical, structural, or electronic? atom size, charge, polarity, crystal structure???

12 Direct Nanopaticles to Specific Location Bivalent synthetic peptide

13 Alignment quantum dots directed by M13 Virus

14 Procedure Tris buffered saline (TBS) 0.1% TWEEN-20 (to reduce phagephage 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

15 Liquid Crystal Alignment Smectic Differential interference contrast (DIC) Smectic 127 mg/ml Cholesteric 76 mg/ml AFM

16 Liquid Crystallinity Cholesteric phase

17 A7-phage and ZnS nanocrystals A7 = CNNPMHQNC 1 mm ZnCl 2 and Na 2 S

18 A7-ZnS Viral Film PL POM

19 A7-ZnS Viral Film

20 Synthesis of Magnetic and Semiconducting Nanowires

21 Virus-Templated Nanowire Formation Nucleation Ordering Annealing

22 Modification of gp8 5 genetically modifiable proteins: gp3, gp6, gp7, gp8, gp9 gp8 protein form the capsid of the virus (~ 2700: major coat proteins)

23 Nucleating Peptide Sequences A7; ZnS = CNNPMHQNC J140; CdS = SLTPLTTSHLRS FP12; FePt = HNKHLPSTQPLA CP7; CoPt = CNAGDHANC

24 DNA

25 DNA Single stranded DNA (ssdna) and double stranded (dsdna) Each strand is made of Adenine (A), Guanine (G), Cytocine (C), Thymine (T) Sugar end 3 Phosphaste end 5

26 Base Pair 5 1 3

27 Transcription

28 Translation

29 Codon

30

31 Formation of ZnS single crystal nanowire annealing

32 ZnS and CdS single crystal nanowires ZnS NW CdS NW

33 CoPt Nanowires (prior to annealing) With virus Reduction of Co and Pt salts without virus Precipitation before annealing CoCl 2 + H 2 PtCl 6 + NaBH 4

34 Magnetic Nanowires CoPt NW unanealed FePt NW FeCl 2 + H 2 PtCl 6 + NaBH 4

35 Nanowires for Lithium Ion Battery Electrodes

36 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 Co 3 O 4 i) 1 mm Cobalt chloride solution for 30 min ii) Reduction with NaBH 4 iii) Spontaneous oxidation in water

37 Virus Enabled Assembly of Nanowires

38 Characterization of Viral Co 3 O 4 Nanowires

39 Different Texture of Co 3 O 4 Nanowires branchlike nanowire structure: Higher cobalt chloride concentration ~ 5 mm with 10 mm NaBH 4 Discrete Nanoparticles: Synthesized at low T (~ 4 o C) 1 mm Co ion, 5 mm NaBH 4

40 Hybrid Structure (Au_NP/Co 3 O 4 _NW) Phage display Au binding motif Au High electrical conductivity Thermodynamically stable interface with Co 3 O 4 Catalyze electrochemical reactions at nanoscale Au_NPs Hybrid structure

41 Enhanced Electrochemical Properties Cyclic voltammograms

42 Liquid Crystalline Ordering of Co 3 O 4 Viral Nanowires 100 nm Cu Co 3 O 4 NW/Li cell Co 3 O 4 viral NWs on LPEI/PAA

43 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-fepo 4 /SWNT is comparable to that of state-of-the-art c-lifepo 4

44 Characterization of a-fepo 4 cathode a-fepo 4 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 protein Synthesis of a-fepo 4 : incubation with FeCl 3 6H 2 O followed by reaction with Na 3 PO 4

45 C-rate in Li-ion battery 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.

46 Genetic Engineering & Biomolecular Recognition Major coat protein Minor coat protein Fabrication of positive electrodes: mixing a-fepo 4 + Super P carbon black + polytetrafluoroethylene (PTFE) binder

47 a-fepo 4 grown on Viruses/SWNT SWNT only a-fepo 4 + SWNT a-fepo 4 NW on Virus

48 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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