University of California Davis

20min 30min 45min 1hour 1hour30min

HO

O8

N

OP

O O

OH

O

O

O

O

14

14

Peg8S

DPPC

0min 1min 2min 3min 10min

Time evolution studies of metastable DPPC/PEG8S domains

Pressure-area isotherm of DPPC/PEG8S

Langmuir trough coupled to an imaging ellipsometer

Lipid/Polymer Mixtures at Air/Water InterfaceLipid/Polymer Mixtures at Air/Water Interface

Si

O

O

O O O

n

Alkyl chain (can also be Cholesterol)

Poly(ethylene glycol)

Trichlorosilane

pH 9.0

pH 4.0

Silicon waferFlorescent glassNIPAAMNaMAAInitiatorLipid

Gramicidin A

FITC doped glass will fluoresce differently depending of changes in pH.

pH sensitive copolymer expands and compresses as H+ pumps through the membrane via the gramicidin ion channel.

Building BiosensorsBuilding Biosensors

Directed Assembly using Patterned Brushes and Composite Directed Assembly using Patterned Brushes and Composite NanoparticlesNanoparticles

Polymer-coated nanoparticles patterned onto a gold surfaceGeneral

Scheme

TEM image of polymer encapsulated nanoparticles Detail of RAFT-based tethering methodology

CdS

SiO2

S

S

CN

NH

O

O

N

S11

n

Si

O

Neutron Surface Reflectivity of Dry and Solvated Neutron Surface Reflectivity of Dry and Solvated ATRP Grafted Polystyrene on Si and SiOATRP Grafted Polystyrene on Si and SiO22 Wafers Wafers

R-X + Mtn/L R* + X-Mtn+1/Lkact

kdeact

Monomer

kp

CA after ATRP initiator deposition : 71ºCA after ATRP initiator deposition : 71ºGPC: MGPC: Mnn = 11,000 g/mol, PDI = 1.11 = 11,000 g/mol, PDI = 1.11

CA after polymerization : 112ºCA after polymerization : 112º

Evacuation/backfill portEvacuation/backfill portKrytox ® Krytox ® grease coated grease coated ground glass ground glass jointjoint

Surface platformSurface platform

Addition and Addition and sampling armsampling arm

CuBr : CuBrCuBr : CuBr2 2 : Styrene : PMDETA : EbiB = 9.6 : 0.48 : 960 : 10.8 : 1: Styrene : PMDETA : EbiB = 9.6 : 0.48 : 960 : 10.8 : 1

O

Si

O

Si

O

Si

O

Si

O

O

O

O

O

O

Br

n+CuBr, CuBr2, PMDETA

90 oC

Br

Si

Si

O

Si

O

Si

O

Si

O

Si

O

O

O

O

O

O

Br

Br

106

106

Si

Si

Brush compression vs. brush interdigitationBrush compression vs. brush interdigitation

0 1 2 3 4 50

10

20

30

40

50

60

Mn x

(10

-3)

Time (h)

9-96

Honey regionHoney region

Glue regionGlue region

Coffee regionCoffee region

Bulk polymerization of styrene MBulk polymerization of styrene Mnn vs. time vs. time

Atom Transfer Radical Polymerization (ATRP) SchematicAtom Transfer Radical Polymerization (ATRP) Schematic

0

1

2

3

-100 -50 0 50 100 150 200 250

10-5 Chi^2=1.92

Sca

tte

rin

g L

eng

th D

en

sity

, b x

10-6

Å-2

Z, Distance (Å)

Silicon

Na

tive

Oxi

de

PS

Air

Air

PS

PS

SiO

SiO

22

Si

Si

Scattering length density vs. dry thicknessScattering length density vs. dry thickness

ATRP of styrene “grafting from” Si waferATRP of styrene “grafting from” Si wafer

Polymerization reaction vesselPolymerization reaction vessel

10-12

10-11

10-10

10-9

10-8

0 0.05 0.1 0.15 0.2 0.25 0.3

10-5

Ref

lect

ivity

, RQ

4

Q (Å-1)

Reflectivity plotReflectivity plot

0 10 20 30 40 50 60 70 80

100

200

300

400

500

600

700

800

Th

ickn

ess

(Å)

Mn x (10-3)

(SLD) 10-5 (1.3) 10-6 (1.3) 10-62 (1.3) 10-66 (1.54) 10-67 (1.3) Linear Fit (R=0.9948)

PS brush thickness vs. MPS brush thickness vs. Mnn

Pre-elastomer coating on Pre-elastomer coating on stretched PDMS substratestretched PDMS substrate

Imprint epoxy mold master Imprint epoxy mold master A

Cure / Mold removalCure / Mold removal

ContractionContraction

Epoxy PDMS mold replication Epoxy PDMS mold replication BB

Epoxy master mold Epoxy master mold BB removal removal

Imprint epoxy master mold Imprint epoxy master mold BB on pre- on pre-elastomer coated stretched PDMS elastomer coated stretched PDMS substratesubstrate

Cure / Mold removalCure / Mold removal

ContractionContraction

High-Efficiency Stepwise Contraction and Adsorption High-Efficiency Stepwise Contraction and Adsorption Nanolithography (h-SCAN)Nanolithography (h-SCAN)

http://www.tdk.co.jp/teaah01/aah17200.htmhttp://www.tdk.co.jp/teaah01/aah17200.htm

Statistical analysis of AFM imageStatistical analysis of AFM image

Peak width (nm)Peak width (nm) 1,855 ± (37.87)1,855 ± (37.87)

Valley width (nm)Valley width (nm) 1,979 ± (32.81)1,979 ± (32.81)

Peak height (nm)Peak height (nm) 516.7 ± (7.804)516.7 ± (7.804)

Peak width (nm)Peak width (nm) 1,430 ± (35.33)1,430 ± (35.33)

Valley width (nm)Valley width (nm) 1,774 ± (31.28)1,774 ± (31.28)

Peak height (nm)Peak height (nm) 560 ± (16.6)560 ± (16.6)

Peak width (nm)Peak width (nm) 679.2 ± (43.14)679.2 ± (43.14)

Valley width (nm)Valley width (nm) 1,498 ± (31.62)1,498 ± (31.62)

Peak height (nm)Peak height (nm) 572.9 ± (30.26)572.9 ± (30.26)

Peak width (nm)Peak width (nm) 183.2 ± (7.500)183.2 ± (7.500)

Valley width (nm)Valley width (nm) 120.9 ± (5.670)120.9 ± (5.670)

Peak height (nm)Peak height (nm) 21.59 ± (3.400)21.59 ± (3.400)

Statistical analysis of AFM imageStatistical analysis of AFM imageStatistical analysis of AFM imageStatistical analysis of AFM image

Statistical analysis of AFM imageStatistical analysis of AFM image

AFM image of mold CAFM image of mold C Diagram of the layers of a DL Blue-ray disc Diagram of the layers of a DL Blue-ray disc AFM image of BD-RAFM image of BD-R

AFM image of mold AAFM image of mold A AFM image of mold BAFM image of mold B

Epoxy PDMS mold replication Epoxy PDMS mold replication CC

Erik Woodbury John Ell

Rita El-khouri Jennifer Cash

Prof. Timothy Patten