Innovatival Functionalized Nanomaterials for Biomedicalm Sensing and Composites Applications

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Electrochemical

pH

Ionic Strength

Biological

Mechanical Electrical

Magnetic

Light

Temperature

What is “SMART”?

External S+muli

Internal S+muli

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Increase stability and promote an ordered

architecture

Decrease extensive surface functionalization

for eventual degradation

Hard

Soft

Inorganic

Organic

Hybrid Materials

Hybrid Materials

Yang, X.; Moosa, B.; Deng, L.; Zhoa, L; Khashab, N. M. * “Polymer Chemistry 2011, 2, 2543–2547.

Biomedical: pH-Triggered Micellar Membrane for Controlled Release Microchips

!

0 5 10 15 200

10

20

30

40

50b

time (h)

DO

X re

leas

e (w

t %)

pH=4.0 pH=5.0 pH=6.0 pH=7.0 pH=8.0 pH=9.0

!

General Scheme

Assembly and Application

Deng, Lin; Wang, Guangchao; Ren, Jian; Zhang, Bei; Yan, Jingjing; Li, Wengang; Khashab, N. M. * RSC adv. 2012, 2, 12909–12914

Biomedical: Enzymatically Triggered System Based on Hyaluronic Acid Micelles

General Scheme

Deng, Lin; Wang, Guangchao; Ren, Jian; Zhang, Bei; Yan, Jingjing; Li, Wengang; Khashab, N. M. * RSC adv. 2012, 2, 12909–12914.

Biomedical: Enzymatically Triggered System Based on Hyaluronic Acid Micelles

Biomedical: Magnetically Triggered Theranostic Platform for Remote Cancer Cells Therapy and Imaging

!

General Scheme

Zhang, W.; Deng, L.; Wang, G.; Guo, X.; Li, Q.; Zhang, J.; Khashab, N. M. * Part. Pat. Syst. Charact. 2014, 31, 985–993.

Biomedical: Magnetically Triggered Theranostic Platform for Remote Cancer Cells Therapy and Imaging

!

Zhang, W.; Deng, L.; Wang, G.; Guo, X.; Li, Q.; Zhang, J.; Khashab, N. M. * Part. Pat. Syst. Charact. 2014, 31, 985–993.

Biomedical: Photo-Triggered Membrane Based on Inter-particle Crosslinking for Decreasing Diffusion Rates

PHCA microspheres

EC membrane

IrradiationDrug Reservoir Drug Reservoir

Lower Efflux

Crosslinking

(A)Membrane

PMMA device

Reservoir for drug loading

(B)

(C1) (C3)(C2)

bc

a

d

(A)

(B)

Song, L., Moosa, M., Li, W.; Khashab, N. M.* J. Mater. Chem. B 2015, 3, 1208–1216.

Deng, L.; Li, Q.; Yang, Y.;Omar, H; Tang, N.; Zhang,J.; Nie, Z.; Khashab, N. M.* Chem. Eur. J. 2015, accepted (chem.201502522) .

Biomedical: Graphene Oxide-Wrapped Gold Nanorods

General Scheme

!

“Two-Step” Raman Imaging-Guided Chemo-Photothermal Cancer Therapy



!



SERS mapping of Doxorubicin (a) and Graphene oxide (b) on AuNRs, ratio of Doxorubicin to graphene oxide (c), and overlap image (d) in Hela cell

Biomedical: Photoresponsive Bridged Silsesquioxane Nanoparticles with Tunable Morphology

1hν laser H

+

+

+

+

+ +

+

+

+ +

+

- - -

- - -

- - -

- - -

- - - -

- -

- - -

- - -

- - -

- - -

- - -

- - -

- -

- - -

- -

- -

- - - -

-

Fatieiev, Y.; Croissant, J.; Julfakyan, K.; Deng, L.; Anjum, D.H.; Gurinov, A.; Khashab, N.M. Nanoscale 2015, DOI: 10.1039/C5NR03065J

BS NPs

Hollow BS NPs

200 nm

100 nm

H +

+

+

+

+ +

+

+

+ +

+

H +

+

+

+

+ +

+

+

+ +

+

H2O

H2O

EtOH

Origin

Irradiated

Origin Irradiated

e

Origin

Irradiated

Origin Irradiated

e

4.05 ppm

Origin

Irradiated

Origin Irradiated

e

4.00 3.75

Origin

Irradiated

Origin Irradiated

e

4.00 3.75

O + − + O −

+

1hν laser

1hν laser

Positive Zeta potential Negative Zeta potential


Hollow BS NPs

DNA

1hν laser

Zeta Potential (mV)

Cha

rge

Dis

t. (a

.u.)

-100 -50 0 50 100

-39 mV +46 mV

1hν

H +

+

+

+

+ +

+

+

+ +

+

- - -

- -

-

- - -

- - - - -

- - -

-

- - -

- - -

- - -

- - -

- - -

- - -

- -

- - - -

-

- - - - -

- -

H +

+

+

+

+ +

+

+

+ +

+


Angew. Chem. Int. Ed. 2015, accepted DOI: 10.1002/anie.201501615R1 and 10.1002/ange.201501615R1 (Cover image, Highlighted by Nature Middle East)

Biomedical: Light Triggered Colloidosomes

-+-+

-+-+-+

-+

-+-+

- +- + - +

-+

--

--

------

--

----

- -- - - -

--

hv

Stable colloidosome

Unstable colloidosomeDissociation of colloidosome

NBSN-2

NBSN-1

-+

+

- -+-+

+

-+ -

-+

+-

+

Oil phase Water

phase

Emulsion with two types of NPs

A

---

-

---

-

-

-

--

-- -

--

-

- -

--

--

C

B

-100-80-60-40-20020406080100

Before Irradiation After Irradiation

SN(control)

Zeta Poten

tial (mV)

NBSN-1 NBSN-2 SN-NH2(control)

hν Positive

Neutral

- -

+

NP- NP+ NB+

SURFACE CHARGE OF NP- & NP+ NANOBUILDING BLOCKS COMPATIBLE WITH THE COLLOIDOSOME ASSEMBLY/DISASSEMBLY

28

Biomedical: Light Triggered Colloidosomes

3 µm 500 nm

500 nm 200 nm 29

hν

500 nm

ELECTROSTATIC DISASSEMBLY OF COLLOISOMES UPON LASER IRRADIATION

30

0

20

40

60

80

100

0 5 10 15 20

Release (%

)

Time (min)

Cargo loaded

Colloidosomes

OFF ON OFF ON

hν hν

- + - +

- + -

+ - +

- +

- + - +

- + - + - +

- +

- -

- - - -

- -

- -

-

-

hν - -

-

- -

-

31 Angew. Chem. Int. Ed. 2015, accepted DOI: 10.1002/anie.201501615R1 and 10.1002/ange.201501615R1 (Cover image, Highlighted by Nature Middle East)

Biomedical: AuNC@BSA Gated MSNs

+

+

+

+

+

+

+

+

FluorescentAuNC@BSAn-

Cargo3loadedMSN3NH3

+

+-

+

+

+

+

+

+

+--

+

+

++

+

+

+

++

+

H+

pH 7.4

pH 5.0

Release9(%

)

pH 5.0

pH 7.4

b

Time9(h)

a

!

a b

3 µm

c d

50 nm 50 nm

100 nm

!

Size%Distrib

ution%(%

)

Diameter%(nm)

2.5%nm

!


Cell Viab

ility (%

)

NPs Concentration (µg.mL-‐1)

100

80

60

40

20

00 10 20 30 50 100 150

Cell$Viab

ility$(%

)

MSN$NH2+DOXMSN$AuNC@BSA+DOX

DOX$Concentration$(µg.mL91) !


!

Absorption

Wavelength1(nm)

Emission

645$nm364$nm

496$nm

!


Red$Channel$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$Blue$Channel$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$Merged

Salin

eCo

ntrol

Hoe4load

ed$

MSN

4AuN

C@BS

A

a

b

!


S

L

T

K

Lu

Salin

eCo

ntrol

a Merged222222222222222222222222Red2Channel22222222222 Blue2Channel2 Red+Blue2Channel222222222222222

L

T

KLu

b

Hoe9loaded2

MSN

9AuN

C@BSA

!

Submitted


Sensing: Protein-Directed Synthesis of Highly Fluorescent Gold Nanoclusters

Xie, J.; Zheng, Y.; Ying, J. Y. J. Am. Chem. Soc., 2009, 131, 888


Hu, L.; Deng, L.; Alsaiari, S.; Zhang, D.; Khashab, N. M. Anal. Chem., 2014, 86, 4989–4994.

Sensitivity

Selectivity



Biomedical: Zippered Release from Polymer Gated Carbon Nanotubes

!

Mashat, A.; Deng, L; Altawashi, A.; Sougrat, R.; Wang, G.; Khashab, N. M. * “Zippered Release from Polymer Gated Carbon Nanotubes” J. Mater. Chem. 2012, 22, 11503–11508.

General Scheme

Biomedical: Zippered Release from Polymer Gated Carbon Nanotubes

Mashat, A.; Deng, L; Altawashi, A.; Sougrat, R.; Wang, G.; Khashab, N. M. * “Zippered Release from Polymer Gated Carbon Nanotubes” J. Mater. Chem. 2012, 22, 11503–11508.

! !

Chen, Ye; Tao, Jing; Deng, Lin; Li, Liang; Li, Jun; Yang, Yang; Khashab, N. M.* ACS App. Mater. Inter. 2013, 5, 7478–7484. .

Composites: PEI/Bucky Gels Nanocomposites with Superior Conductivity and Thermal Stability

!

General Scheme

Chen, Ye; Tao, Jing; Deng, Lin; Li, Liang; Li, Jun; Yang, Yang; Khashab, N. M.* ACS App. Mater. Inter. 2013, 5, 7478–7484.

Composites: PEI/Bucky Gels Nanocomposites with Superior Conductivity and Thermal Stability

!

Chen, Ye; Tao, Jing; Song, Li; Khashab, N. M. * ACS App. Mater. Inter. 2014, 6, 9013–9022.

Composites: Polyfluorene Wrapped Carbon nanotubes for Enhanced Interfacial Interactions

General Scheme

Chen, Ye; Tao, Jing; Song, Li; Khashab, N. M. * ACS App. Mater. Inter. 2014, 6, 9013–9022.

Composites: Polyfluorene Wrapped Carbon nanotubes for Enhanced Interfacial Interactions

Composites: Surface Modification of Multiwall Carbon Nanotubes with Cationic Conjugated Polyelectrolytes

General Scheme

Ezzeddine, A.; Chen, Z.; Schanze, K. S.; Khashab, N. M. ACS Appl. Mater. Interfaces, 2015, 7 , 12903–12913.

Composites: Surface Modification of Multiwall Carbon Nanotubes with Cationic Conjugated Polyelectrolytes

Ezzeddine, A.; Chen, Z.; Schanze, K. S.; Khashab, N. M. ACS Appl. Mater. Interfaces, 2015, 7 , 12903–12913.

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Innovatival Functionalized Nanomaterials for Biomedicalm Sensing and Composites Applications

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