ROLE OF SURFACE COATING ON ACCUMULATION OF CADMIUM SULFIDE QUANTUM DOTS IN SOYBEAN PLANTS AND STRESS MECHANISMS SANGHAMITRA MAJUMDAR

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ROLE OF SURFACE COATING ON ACCUMULATION OF CADMIUM SULFIDE QUANTUM DOTS IN SOYBEAN PLANTS AND STRESS MECHANISMS SANGHAMITRA MAJUMDAR Jason C. WHITE (The Connecticut Agricultural Experiment Station) Arturo KELLER (Bren School, UCSB) 6TH SUSTAINABLE NANOTECHNOLOGY ORGANIZATION CONFERENCE LOS ANGELES, CA November 06, 2017

QUANTUM DOTS: BRIGHT AND VERSATILE Zero dimensional, few nanometers wide High photoluminescence quantum yield Broad absorption coupled with narrow emission, and strong photostability Semiconductor core (CdSe, CdS, CdTe) encapsulated at times in a shell eg. ZnS), and further functionalized with ligands depending on application Fontes et al. 2012 Park et al. 2017 Majumdar Nov 6, 2017 2

QUANTUM DOT APPLICATIONS 1.5 nm 5 nm Park et al. 2017 Colloidal quantum dots irradiated with a UV light. Different sized quantum dots emit different color light due to quantum confinement. Pathogen and contaminant detection in plants Gao X, Nie S. Anal. Chem. 2004 Majumdar Nov 6, 2017 3

QD MARKET IS GROWING FAST!! Quantum bits: This camera sensor chip contains a layer of quantum dots that absorbs light before it reaches the silicon. Majumdar Nov 6, 2017 4

EXPERIMENTAL DESIGN: NANOMATERIAL Drs. Marco Villani, Andrea Zappettini Cadmium sulfide QDs (QD) o QD-Bare (Uncapped) o QD-TOPO (trioctylphosphine oxide) o QD-PVP (polyvinylpyrrolidone) o QD-MAA (mercaptoacetic acid) Non-specific binding o QD-GLY (glycine) Trioctylphosphine oxide Polyvinylpyrrolidone Mercaptoacetic acid Glycine neutral steric hindrance negative amino group Majumdar Nov 6, 2017 5

EXPERIMENTAL DESIGN: PLANT EXPOSURE Soybean plants grown in vermiculite for 14 days Treatments Control 50, 100, 200 mg Cd/L vermiculite for each QD 100 mg Cd/L vermiculite: CdS bulk 10 mg Cd/L vermiculite: CdCl 2 2 min sonication Physiological parameters Cd content in tissues Cd content in subcellular compartments Macro and micro nutrients Photosynthetic pigment Antioxidant enzymes: SOD, CAT, APX, GPX FTIR of soybean roots Lignin content Total Phenol and flavonoid contents Gene expression by qrt- PCR Majumdar Nov 6, 2017 6

CHARACTERIZATION OF THE CdS QDs X-ray diffraction of the CdS QDs FTIR spectra of the CdS QDs C=O C=O C-S C-N P=O C-O Alkynyl C=C C-H Amide O-H Trioctylphosphine oxide Polyvinylpyrrolidone Mercaptoacetic acid Glycine Majumdar Nov 6, 2017 7

NANOMATERIAL CHARACTERIZATION IN WATER HYDRODYNAMIC SIZE ZETA POTENTIAL DISSOLUTION + Majumdar Nov 6, 2017 8

CADMIUM UPTAKE AND ACCUMULATION No nanospecific effect CdS associated more with the roots than the Cd 2+ ions Majumdar Nov 6, 2017 9

CADMIUM TRANSLOCATION Low dissolution, still high conc. in shoots at 100 mg/l for comparison Majumdar Nov 6, 2017 10

Control 10 100 50 100 200 50 100 200 50 100 200 50 100 200 50 100 200 Plant length (cm) PHYSIOLOGICAL RESPONSE 70 60 50 40 30 20 10 0 CdCl2 CdS bulk QD-Bare QD-TOPO QD-PVP QD-MAA QD-GLY Treatments (mg/l) Majumdar Nov 6, 2017 11

ROOT MORPHOLOGY Majumdar Nov 6, 2017 12

mg/g cell wall LIGNIN CONTENT IN SOYBEAN ROOTS 160 140 120 100 80 60 40 20 0 Majumdar Nov 6, 2017 13

SUBCELLULAR LOCALIZATION OF CADMIUM Majumdar Nov 6, 2017 14

OXIDATIVE STRESS RESPONSE Enzymatic antioxidants Activity increased: Superoxide dismutase Ascorbate peroxidase Guaiacol peroxidase Catalase Majumdar Nov 6, 2017 15

GENE EXPRESSION IN EXPOSED SOYBEANS ROOTS SHOOTS Majumdar Nov 6, 2017 16

CONCLUSION QD-TOPO had highest dissolution compared with to other QDs QD-MAA was the most stable in solution Except QD-PVP, translocation of all QDs decreased with dose, more adsorption on roots (steric properties did not restrict QD-PVP); Cd accumulation in roots subcellular compartments: Cell wall: MAA >Bulk >GLY >CdCl2 >Bare >PVP >TOPO Cell membrane: TOPO >Bare >GLY >Bulk >PVP >CdCl2 > MAA Organelles: PVP>CdCl2>GLY>Bulk>Bare >MAA >TOPO Lignin in roots enhances in all the QD treatment to protect the plants Superoxide dismutase in roots effectively combats the oxidative stress in roots Heavy metal transporter genes in roots of QD-Gly was downregulated unlike QD-Bare Unlike CdCl2, all QD treatments showed upregulation of another heavy metal transporter, NRAMP6 All Cd treatments had downregulation of pathogenesis related gene Majumdar Nov 6, 2017 17

ACKNOWLEDGEMENTS Dr. Jason C. White White research group Dr. Arturo Keller Keller research group Dr. Luca Pagano Dr. Chuanxin Ma Dr. Marco Villani Dr. Andrea Zappettini Dr. Nubia Zuversa-Mena Majumdar Nov 6, 2017 18

THANK YOU!!! 19

CdS QD 20