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Page 1: Have Questions? - American Chemical Society · 11/7/2019  · Recordings are an exclusive ACS member benefit and are made available to registrants via an email invitation once the

11/6/2019

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1

Type them into questions box!

“Why am I muted?”Don’t worry. Everyone is muted except the presenter and host. Thank you and enjoy the show.

Contact ACS Webinars ® at [email protected]

Have Questions?

2

http://bit.ly/ACSnewmember

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http://bit.ly/ACSnewmember

Benefits of ACS Membership

Chemical & Engineering News (C&EN) The preeminent weekly digital and print news source.

NEW! ACS SciFinder ACS Members receive 25 complimentary SciFinder® research activities per year.

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Contact ACS Webinars ® at [email protected]

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@AmerChemSociety

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@AmerChemSociety

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Be a featured fan on an upcoming webinar! Write to us @ [email protected] 5

“Safety content is always timely and important. Getting the message out is always a challenge and this ACS Webinar presented some good ideas on safety communication that I will apply at our institution.”

Henry VanBrocklin, PhDProfessor, Radiology and Biomedical Imaging, Chair, Chemistry and Environmental Safety Committee, University of California, San FranciscoACS member for 36 years strong!

http://bit.ly/labsafetyACS

6

www.acs.org/acswebinars

Learn from the best and brightest minds in chemistry! Hundreds of webinars on diverse topics presented by experts in the chemical sciences and enterprise.

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http://acsoncampus.acs.org

What is ACS on Campus?

ACS visits campuses across the world offering FREE seminars on how to be published, find a job, network and use essential tools like SciFinder. ACS on Campus presents seminars and workshops focused on how to:

8

www.acs.org/heroes

#HeroesofChemistryACS Heroes of Chemistry Award

The ACS Heroes of Chemistry Award is the Annual award sponsored by the American Chemical Society that recognizes talented industrial chemical scientists whose work has led to the development of successful commercialized products ingrained with chemistry for the benefit of humankind.

2018 Winners:

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https://chemidp.acs.org

An individual development planning tool for you!

10

Upcoming ACS Webinar!www.acs.org/acswebinars

https://www.acs.org/content/acs/en/acs-webinars/technology-innovation/phase-separation.html

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11

Resources from Industry Member Programs!

T H I S A C S W E B I N A R W I L L B E G I N S H O R T L Y . . .

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Presentation slides available now! Recordings are an exclusive ACS member benefit.

Combating Climate Change with New Nanobugs: Teaching Bacteria to Eat Carbon Dioxide and Light with Quantum Dots

13www.acs.org/acswebinarsThis ACS Webinar is co-produced with the ACS Industry Member Programs

Mark JonesExecutive External Strategy and

Communications Fellow, Dow Chemical

Prashant NagpalAssistant Professor, University of

Colorado Boulder and the Co-Founder, Antimicrobial Regeneration Consortium

Combating Climate Change with New Nanobugs: Teaching Bacteria to Eat Carbon Dioxide and Light with Quantum Dots

Prashant NagpalDepartment of Chemical and Biological Engineering

Renewable and Sustainable Energy Institute (RASEI)

Materials Science and Engineering

University of Colorado Boulderwww.colorado.edu/lab/nagpal

Antimicrobial Regeneration Consortium, ARC www.amrconsortium.org

14

Page 8: Have Questions? - American Chemical Society · 11/7/2019  · Recordings are an exclusive ACS member benefit and are made available to registrants via an email invitation once the

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Combating Climate Change: Feasible?

15

https://climate.nasa.gov/evidence

Combating Climate Change: Feasible?

https://climate.nasa.gov/evidence

16

CO2 at 408 ppm: Highest in 3 million years

17/18 warmest years since 2000

800 million people: 11% of the world’s

population vulnerable to climate change

Global carbon emissions 2018:

All-time high of 37.1bn tonnes

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Combating Climate Change: Feasible?

17

70% of Earth’s oxygen comes

from oceans…

By 2050, plastic > fish in

oceans by weight

We produce ~381 million

tonnes of plastic each year

https://www.unenvironment.org/interactive/beat-plastic-pollution

The amount of plastic waste each year (381 million tonnes) is equivalent to the weight of how many people?

Audience Survey QuestionANSWER THE QUESTION ON BLUE SCREEN IN ONE MOMENT

• Few thousand people

• Population of a large city

• Population of a large country

• Almost entire human population

18

* If your answer differs greatly from the choices above tell us in the chat!

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Combating Climate Change: Feasible?

Answer: Almost entire human population

19

381 million tonnes= 381×109 kg

Assuming an average human weight of 75 kg

381 million tonnes= 381×109 /75=5.08 billion people

or ~2/3 of entire human population

Solar Power

CO2, H2O, N2 …

Inorganic

Photocatalysts

Photosynthetic

Organisms

QDs-microbes

Nanobiohybrid

Biomass

Pre-treatment

Hydrolysis

Fermentation

Valuable Chemicals: H2, CxHy, CxHyOz, NH3 …

Low Selectivity Low Efficiency High Efficiency, Selectivity?

Strong light absorption

High carrier mobility

Mixed productsLimited to simple products

Highly specific

Complex chemicals

Limited AbsorptionLengthy processes

Strong light absorption

High carrier mobility

Highly specificComplex chemicals

20

H2O

CO2

N2

Singh, Beltran, Ribot, Nagpal*, Nano Lett., 14, 597 (2014)Alivov, Singh, Ding, Cerkovnik, Nagpal*, Nanoscale, 6, 18039 (2014)Sun, Ding, Goodman, Funke, Nagpal*, Nanoscale, 6, 12450 (2014)

Ding, Bertram, Eckert, Bommareddy, Patel, Conradie,Bryan, Nagpal*, J. Am. Chem. Soc., 141, 10272 (2019)

20

Ding, Nagpal*, Nanoscale, 8, 17496 (2016)Ding, Nagpal*, Phys. Chem. Chem. Phys., 19, 10042 (2017)

Page 11: Have Questions? - American Chemical Society · 11/7/2019  · Recordings are an exclusive ACS member benefit and are made available to registrants via an email invitation once the

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QDs uptake by microbesSite-selective QDs-

enzyme binding

Light-activatede-h generation

Electron injectionto enzyme

Red2

Ox2

Ox1

Red1

Redox Reactions

21

How can we make Nanobugs

21

Challenges

• Quantum Dot (QD) uptake

• Site-specific QDs-enzyme binding

• Efficient electron transfer

• QDs Stability

• Low QDs Toxicity

• Balanced Electron Flux…

Ding, Bertram, Eckert, Bommareddy, Patel, Conradie, Bryan, Nagpal*, J. Am. Chem. Soc., 141, 10272 (2019)Levy, Chowdhury, Nagpal*, J. Biol. Eng., 13:48 (2019)Goodman, Levy, Li, Ding, Courtney, Chowdhury, Erbse, Chatterjee, Nagpal*, Front. Chem., 6,46,1 (2018)Ding, Nagpal*, Phys. Chem. Chem. Phys., 19, 10042 (2017)Courtney, Goodman, Nagy, Levy, Bhusal, Madinger, Detweiler, Nagpal*, Chatterjee*, Science Adv., 3, e1701776 (2017)Courtney, Goodman, McDaniel, Madinger, Chatterjee*, Nagpal*, Nature Materials, 15, 529 (2016)Ding, Nagpal*, Nanoscale, 8, 17496 (2016)Goodman, Noh, Singh, Cha, Nagpal*, Appl. Phys. Lett.,106, 083109 (2015)Goodman, Siu, Singh, Nagpal*, Nanoscale, 7, 18435 (2015)Goodman, Singh, Ribot, Chatterjee, Nagpal*, J. Phys. Chem. Lett., 5,3909 (2014) Singh, Beltran, Ribot, Nagpal*, Nano Lett., 14, 597 (2014)

22

Page 12: Have Questions? - American Chemical Society · 11/7/2019  · Recordings are an exclusive ACS member benefit and are made available to registrants via an email invitation once the

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Living QD-A. vinelandii Nanobugs

• Gram-negative diazotroph

• Utilizes dinitrogen from air

• Can fix nitrogen aerobically

Nitrogen Fixation: Methods and Protocols, Springer, 2011

e-

23

Choosing QDs: Material and Size

CdX1 CdX2 CdX3

QDs + Purified MFN (1:1, 1 μM)

Argon Atmosphere

100 mM L-ASC, HEPES (pH 7.4)

400 nm LED Irradiation

TON ~ 10,000 (30 min)

Ding, Bertram, Eckert, Bommareddy, Patel, Conradie, Bryan, Nagpal*, J. Am. Chem. Soc., 141, 10272 (2019)

24

Page 13: Have Questions? - American Chemical Society · 11/7/2019  · Recordings are an exclusive ACS member benefit and are made available to registrants via an email invitation once the

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Choosing QDs: Material and Size

Visible Light AbsorptionCdX1 CdX2 CdX3

QDs + Purified MFN (1:1, 1 μM)

Argon Atmosphere

100 mM L-ASC, HEPES (pH 7.4)

400 nm LED Irradiation

TON ~ 10,000 (30 min)

Ding, Bertram, Eckert, Bommareddy, Patel, Conradie, Bryan, Nagpal*, J. Am. Chem. Soc., 141, 10272 (2019)

25

Choosing QDs: Material and Size

Visible Light AbsorptionCdX1 CdX2 CdX3

Ding, Bertram, Eckert, Bommareddy, Patel, Conradie, Bryan, Nagpal*, J. Am. Chem. Soc., 141, 10272 (2019)

26

3.0

2.5

2.0

1.5

1.0

0.5

0.0

-0.5

-1.0

-1.5

CdTe1~3CdSe1~3

O2/H

2O

Vo

lta

ge

vs N

HE

(V

) H+/H

2

pH ~ 7

CdS1~3Tunable Band-edge

Page 14: Have Questions? - American Chemical Society · 11/7/2019  · Recordings are an exclusive ACS member benefit and are made available to registrants via an email invitation once the

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Choosing QDs: Material and Size

Tunable Band-edge

CdX1 CdX2 CdX3

Ding, Bertram, Eckert, Bommareddy, Patel, Conradie, Bryan, Nagpal*, J. Am. Chem. Soc., 141, 10272 (2019)

CdS1CdS2

CdS3

CdSe1

CdSe2

CdSe30.0

3.0x103

6.0x103

9.0x103

1.2x104

H2 T

ON

(m

ol / m

ol M

FN

)

Argon

27

Selective QDs-Enzyme Coupling: Zn-Histidine

CdS CdS@ZnS (CZS)

Zn-NTAin IMAC

MFN His-MFN

A. vinelandiiDJ995

(7x Histidineat N-terminal)

Page 15: Have Questions? - American Chemical Society · 11/7/2019  · Recordings are an exclusive ACS member benefit and are made available to registrants via an email invitation once the

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Selective QDs-Enzyme Coupling: Zn-Histidine

MFN Non-MFN0

2

4

6

8

10

12

Cd

2+ d

ete

cte

d (

pp

b)

QDs + Lysate QDs + MFN

CdSe@ZnS (CZSe)

FL FL StainStain

Selective QDs-Enzyme Coupling: Zn-Histidine

QDs + Cell Lysate

Argon Atmosphere

Light Irradiation

Yield increase significantly

after ZnS coating

Page 16: Have Questions? - American Chemical Society · 11/7/2019  · Recordings are an exclusive ACS member benefit and are made available to registrants via an email invitation once the

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If a nanobug has ~10,000 copies of an enzyme of interest, and chosen QD has molecular weight of 120 g/mol, how much QDs are required to make 1 mol of nanobugs?

Audience Survey QuestionANSWER THE QUESTION ON BLUE SCREEN IN ONE MOMENT

• 1200 kg of QDs

• 6.023×1024 kgs

• 120 kg

• Need more information

31

* If your answer differs greatly from the choices above tell us in the chat!

How much QDs are required to make a nanobug?

Answer: 1200 kgs

32

1 mol of nanobugs requires 10,000 mols of QDs (to saturate

every enzyme)

Using QD molecular weight (120 g/mol)

To make 1 mol of nanobugs= 10,000×120g =1200 kgs

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17

Tuning the Shell Thickness

0ML 1ML 2ML 3ML

Effective Surface PassivationSmall Electron Transport Barrier

33

Ding, Nagpal*, Nanoscale, 8, 17496 (2016)Ding, Bertram, Eckert, Bommareddy, Patel, Conradie, Bryan, Nagpal*, J. Am. Chem. Soc.,141, 10272 (2019)

33

0ML 1ML 2ML 3ML0

200

400

600

800

Ne

t H

2 g

en

era

tio

n (

nm

ol / m

l C

L)

30 minImidazole:

Competitively binds to zinc

Higher acidity:Protonates histidine

Light-driven QD-Enzyme Biocatalysis

0.0

0.2

0.4

0.6

0.8

pH = 7.4

Imidazole pH = 5.9

Ne

t H

2 G

en

era

tio

n (m

ol / m

l C

L)

pH = 7.4

30 min

CdS@ZnS 2ML

2H+ + 2e− + nhυ → H2

0.0

0.2

0.4

0.6

0.8

pH = 7.4

Imidazole

Ne

t H

2 G

en

era

tio

n (m

ol / m

l C

L)

pH = 7.4

30 min

CdS@ZnS 2ML

34

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0ML 1ML 2ML 3ML0

200

400

600

Ne

t H

2 o

r N

H3 g

en

era

tion

(nm

ol / m

l C

L)

H2

NH3

Dinitrogen

30 min

Light-driven Air-Water Reduction

N2 + 8H+ + 8e− + nhυ→ 2NH3 + H2

Ding, Bertram, Eckert, Bommareddy, Patel, Conradie, Bryan, Nagpal*, J. Am. Chem. Soc., 141, 10272 (2019)

35

---

-

--

-------

--

--MPA

++++

+

+++

+ ++

++

+

++ CAMPA CYS CA

0

10

20

30

40

QD

s U

pta

ke

(%

)

200 nM

CYS--+

-

-+-

+-

-

-+

+

+

+

+

MPA0

10

20

30

40

QD

s U

pta

ke

(%

)

200 nM

MPA -- CA0

10

20

30

40

QD

s U

pta

ke

(%

)

200 nM

Intracellular Uptake of QDs

36

Courtney, Goodman, McDaniel, Madinger, Chatterjee*, Nagpal*, Nature Materials, 15, 529 (2016)Courtney, Goodman, Nagy, Levy, Bhusal, Madinger, Detweiler, Nagpal*, Chatterjee*, Science Adv., 3, e1701776 (2017)Goodman, Levy, Li, Ding, Courtney, Chowdhury, Erbse, Chatterjee , Nagpal*, Front. Chem., 6, 46 (2018)Levy, Chowdhury, Nagpal*, J. Biol. Eng., 13:48 (2019)Ding, Bertram, Eckert, Bommareddy, Patel, Conradie, Bryan, Nagpal*, J. Am. Chem. Soc., 141, 10272 (2019)

36

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MPA (-): Some toxicityCYS (+-): Non-toxicCA (+): Highly toxic

0 200 400 600 800 1000

0.0

0.2

0.4

0.6

0.8

1.0

MPA

CYS

CA

Gro

wth

Inh

ibitio

n

QDs Concentration (nM)

0 200 400 600 800 1000

0.0

0.2

0.4

0.6

0.8

1.0

MPA

CYS

Gro

wth

Inh

ibitio

n

QDs Concentration (nM)

0 200 400 600 800 1000

0.0

0.2

0.4

0.6

0.8

1.0

MPA

Gro

wth

Inh

ibitio

n

QDs Concentration (nM)

Maintaining Cell Viability

37

0 200 400 600 800 1000

20

40

60

80

100

120

140

MPA

CYS

CA

Ce

ll V

iab

ility

(%

)

QDs Concentration (nM)

MPA (-): Toxic at high concentrationCYS (+-): Non-toxic

CA (+): Toxic even at low concentration

0

10

20

30

40

50

Co

lon

y F

orm

ing

Un

it

0

20

40

60

80

100

CACYSMPA

Ce

ll V

iab

ility

(%

)500 nM

No QDs

Maintaining Cell Viability

38

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0 200 400 600 800 10000.0

1.0

2.0

3.0

NH

3 T

ON

(m

ol / m

ol cell)

QDs Concentration (nM)

MPA

CYS

CA

x 107

30 min

MPA (-):Low uptake

Toxicity at high conc.

CA (+):High uptakeHighly Toxic

CYS (+-):Moderate uptake

Non-toxic

Light-driven Selective Catalysis by Nanobugs

39

Expand the Absorption Spectrum

400 500 600 700 800

Extin

ctio

n (

a.u

.)

Wavelength (nm)

CZS1

CZS2

CZSe1

CZSe2

CZSe3

IPZS

CZTS

400 500 600 700

Ph

oto

lum

ine

sce

nce

(a

.u.)

Wavelength (nm)

CZS1 CZS2 CZSe1

CZSe2 CZSe3 IPZS

40

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21

CZS1CZS2

CZSe1

CZSe2

CZSe3IPZS

CZTS0.0

0.5

1.0

1.5

2.0

NH

3 T

ON

(m

ol / m

ol cells

)A. vinelandii

x 107

Expand the Absorption Spectrum

41

0 1 2 3

0.0

1.0

2.0

3.0

4.0

NH

3 o

r H

2 T

ON

(m

ol / m

ol ce

ll)

Time (h)

NH3

H2

x 107

Nanobug Factories

8730 for NH3

4350 for H2

TOF (s-1) in 1 h:

Ding, Bertram, Eckert, Bommareddy, Patel, Conradie, Bryan, Nagpal*, J. Am. Chem. Soc., 141, 10272 (2019)

Total QY: ~ 13 %

Like Solar Cells

42

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0 3 6 9 12

0

1

2

3

4

x 1017

TO

N (

mol / m

ol cells

)

Absorbed Photon

A. Vinelandii DJ995x 107

0

4

8

12

Tota

l Q

ua

ntu

m Y

ield

(%

)

H2

NH3

Nanobug Factories

Ding, Bertram, Eckert, Bommareddy, Patel, Conradie, Bryan, Nagpal*, J. Am. Chem. Soc., 141, 10272 (2019)

Conversion Limited by Enzyme turnover Max theoretical QY: 16-20%

43

Total QY: ~ 13 %

Nanobug Factories

Ding, Bertram, Eckert, Bommareddy, Patel, Conradie, Bryan, Nagpal*, J. Am. Chem. Soc., 141, 10272 (2019)

0.0 1.0 2.0 3.0

0.0

2.0

4.0

6.0

8.0

C2H

4 T

ON

(m

ol / m

ol cells

)

Absorbed Photon

TONx 106

0.0

0.2

0.4

0.6

C. Necator

pBBR1-efe

Quan

tum

Yie

ld (

%)

QY

x 1020

CZS

IPZS

• Range of fuels, fertilizers, preservatives, bioplastics

• Nanobugs utilize CO2, air, and sunlight

• Process can be scaled up efficiently

• Tandem Cells for optimal utilization of sunlight

44

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Nanobug Factories

Ding, Bertram, Eckert, Bommareddy, Patel, Conradie, Bryan, Nagpal*, J. Am. Chem. Soc., 141, 10272 (2019)

45

• Range of fuels, fertilizers, preservatives, bioplastics

• Nanobugs utilize CO2, air, and sunlight

• Process can be scaled up efficiently

• Tandem Cells for optimal utilization of sunlight

Nanobug Factories

Ding, Bertram, Eckert, Bommareddy, Patel, Conradie, Bryan, Nagpal*, J. Am. Chem. Soc., 141, 10272 (2019)

46 46

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Nanobug Factories

Ding, Bertram, Eckert, Bommareddy, Patel, Conradie, Bryan, Nagpal*, J. Am. Chem. Soc., 141, 10272 (2019)

47 47

If we convert all emitted CO2/year (37.1 bn tonnes) using nanobugs, how much volume of nanobugs would it require?

Nanobugs TON (7.3×1010 mol PHB/mol cells/year)

Audience Survey QuestionANSWER THE QUESTION ON BLUE SCREEN IN ONE MOMENT

• A small reservoir or pond

• A large lake

• A whole sea

• An entire ocean

48

* If your answer differs greatly from the choices above tell us in the chat!

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Approximately a large lake (e.g. Navajo Reservoir, Colorado,

Lake Minnetonka or Calhoun,

Minneapolis)

Combating Climate Change with Nanobugs?

Answer: A large lake

37.1 bn tonnes= 37.1×1012 kg= 37.1×1015/44 mol CO2

=8.43×1014 mol CO2

Using PHB = 5×108× 365 days/2.5day run/mol cells

TON (5×108 mol PHB/mol cells/run) = 7.3×1010 mol PHB/year

= 7.3×1010×4 mol CO2/year/mol cells (C4H6O2)

Total mol cells required= 8.43×1014 / 7.3×1010×4=2887 mol

Volume of 1 cell~1 μm3 or 10-15 L

Total volume of cells reqd.=1×10-18m3×2887×6.023×1023

=1.74×109m3=1.74 km3

49

Combating Climate Change with Nanobugs

Ding, Bertram, Eckert, Bommareddy, Patel, Conradie, Bryan, Nagpal*, J. Am. Chem. Soc., 141, 10272 (2019)Goodman, Levy, Li, Ding, Courtney, Chowdhury, Erbse, Chatterjee, Nagpal*, Front. Chem., 6,46,1 (2018)Ding, Nagpal*, Phys. Chem. Chem. Phys., 19, 10042 (2017)Courtney, Goodman, McDaniel, Madinger, Chatterjee*, Nagpal*, Nature Materials, 15, 529 (2016)Ding, Nagpal*, Nanoscale, 8, 17496 (2016)Goodman, Noh, Singh, Cha, Nagpal*, Appl. Phys. Lett.,106, 083109 (2015)Goodman, Siu, Singh, Nagpal*, Nanoscale, 7, 18435 (2015)Goodman, Singh, Ribot, Chatterjee, Nagpal*, J. Phys. Chem. Lett., 5,3909 (2014) Singh, Beltran, Ribot, Nagpal*, Nano Lett., 14, 597 (2014)

• Efficiency like solar-cells

• Scalable, low-cost fuel and chemical generation

• Easy to implement technology

• Sustainable Nanobug factories

50

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26

Graduate Students:

– Sam Goodman (PhD., 2016)

– Yuchen Ding (Ph.D., 2017)

– Lee Erik Korshoj

– Partha Chowdhury (Ph.D. 2018)

– Ibrahim Saleh (Ph.D. 2019)

– Max Levy

– John R. Bertram

– Ameya Prabhune

– Shane Bassett

Postdocs:

– Dr. Yuchen Ding

Acknowledgements

Nagpal Group members

Alumni :

– Dr. Vivek Singh

– Dr. Qi Charles Sun

– Dr. Sajida A. Khan

– Dr. Sepideh Afsari

Alumni :

– Dr. Gary Abel

– Dr. Yahya Alivov

– Dr. D.M. Sagar

– Dr. FeiFei Li

Financial support:

– NSF CAREER Award

– W.M. Keck Foundation Research Award

– NSF MRSEC (DMR) IRG-II

– Army Research Office DURIP Award

– NSF-MRI

– NASA-TRISH

– DOE-BER

51

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Combating Climate Change with New Nanobugs: Teaching Bacteria to Eat Carbon Dioxide and Light with Quantum Dots

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