Gilbert Ling

Poster Award Presentation

The Role of Water in the Antifouling

Properties of Ultrathin Organic Adlayers:
Experimental & Computational Evidence
Sonia Sheikh
October 12, 2014
9th Annual Conference on the Physics, Chemistry & Biology of Water
Pamporovo, Bulgaria

The Ubiquitous Problem of Fouling

Undesirable adsorption/accumulation of species (proteins, cells,
organisms) on artificial surfaces from surrounding environment

Some examples of fouling in everyday life:

Food processing, water purification systems

Marine equipment

Biotechnology: biomedical/surgical equipment &

implants; biosensors (non-specific adsorption)
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Biomedical & Bioanalytical Concerns

(A) In vivo biomaterial applications: Foreign body reaction
Fibrous capsule

Blood

Synthetic
Implant

Implant

Adsorbed protein
Foreign body
giant cell

(B) Biosensor applications: Non-specific adsorption

Biosensing Platform

Indistinguishable signal
False positives
False negatives

Biological sample:
Target analyte
Matrix interferents

Specific binding (target analyte)

&
Non-specific adsorption (interferents)

Surface Passivation: Surface Chemistry

Surface modifiers are short organic molecules designed to
spontaneously attach to substrates and form ultrathin adlayers

Surface modifiers
Antifouling adlayer

Blaszykowski, C.; Sheikh, S.; Thompson, M. Chem. Soc. Rev. 2012, 41, 5599

Surface Modifiers for Customized Surfaces

Head function

Any (chemically compatible) organic group

Functionalizable for subsequent
biomolecule immobilization

Linkers for
biosensors

Alkyl: (CH2)n
Oligoethylene glycol (OEG): (OCH2CH2)n
Backbone

Perfluoroalkyl: (CF2)n
Peptides: (NHCHRCO)n

Anchoring function
Substrate

Trichlorosilyl (Cl3Si), thiol (SH), ...

Quartz (piezoelectric), gold (electrical/optical),
plastics (flexible), ...
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Examples of Surface Modifiers

Cl

Cl Si
Cl

Cl

F
O

Cl

O
O

OTS

Cl
Cl

Si

MEG-OMe
F
Cl

Cl

Cl

Cl Si
Cl

O
O

Cl

TFE

OEG-TTTA

PFP-TTTA

Si

Cl

TTTA
Cl Si
Cl

Cl

Si

Cl

F
O

OTS-TFA

PFP

F
F

Cl
Cl
Cl

Si

MEG-TFA

F
F

Transducer & Detection: EMPAS Technology

ElectroMagnetic Piezoelectric Acoustic Sensor (EMPAS) is an

analytical flow-through device able to detect on-surface biomolecular
interactions in a real-time and label-free manner

Remotely triggers acoustic resonance within thin, electrode-free quartz

discs using an external electromagnetic field generated by a coil
Quartz disc

Secondary electric
field

Thickness:
83 m

Electromagnetic
field

AC-powered copper coil

Thompson, M.; Ballantyne, S. M.; Cheran, L.-E.; Stevenson, A. C.; Lowe, C. R. Analyst 2003, 128, 1048

Resonant Frequency Shift

Biomolecule adsorption / interaction
=
Change in resonant frequency

Biosensors:
Sample
injection

biorecognition & nonspecific adsorption (NSA)

Biomaterial Coatings:
antifouling behaviour
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Motivation, Objectives & Strategy

Couple surface chemistry with EMPAS technology to develop
organic coatings able to minimize fouling occurring upon
exposure to biological fluids (e.g. blood serum & plasma)

Bioanalytical:
Biosensors

Biomedical:
Biomaterials

Design & synthesis of new trichlorosilane surface modifiers

Prepare & characterize organosilane adlayers on quartz

Evaluate the antifouling (& biorecognition) properties of the

resulting molecular assemblies with the EMPAS
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Unimolecular
Antifouling Adlayers

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Fouling of Bare Quartz by Serum

944.460

Frequency (MHz)

944.450

944.440

34 kHz
944.430

Full serum injection

944.420

944.410
0

500

1000

1500

2000

Time (s)
Sheikh, S.; Yang, D. Y.; Blaszykowski, C.; Thompson, M. Chem. Commun. 2012, 48, 1305

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Systematic Structural Modification

quartz

quartz

MEG family

quartz

--------------------------------------------------

1/1 (v/v) H2O/MeOH

room temp., overnight

quartz

quartz

Alkyl family

Sheikh, S.; Yang, D. Y.; Blaszykowski, C.; Thompson, M. Chem. Commun. 2012, 48, 1305

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Antifouling Behaviour Against Serum

Through the use of structurally simple surface modifiers, the
frequency shift due to the adsorption of goat serum was
substantially reduced from 31 kHz for bare quartz to below
3 kHz for MEG-OH coatings

Sheikh, S.; Yang, D. Y.; Blaszykowski, C.; Thompson, M. Chem. Commun. 2012, 48, 1305

13

Adlayer Characterization: CAM & XPS

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MEG-OH

90

MEG-TFA

Cleaned quartz

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Sheikh, S.; Yang, D. Y.; Blaszykowski, C.; Thompson, M. Chem. Commun. 2012, 48, 1305

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Comparing EMPAS Profiles

Frequency (MHz)

Bare quartz profile:

Bare quartz

sharp initial drop

gradual decrease

no rinse-off

irreversible adsorption

comparatively limited
initial drop

gradual and extensive

rinse-off

reversible adsorption

Frequency (MHz)

MEG-OH coating profile:

MEG-OH coating

Sheikh, S.; Yang, D. Y.; Blaszykowski, C.; Thompson, M. Chem. Commun. 2012, 48, 1305

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Frequency (MHz)

Surface Hydration? EMPAS Experiments

overnight soaking in 1/1 (v/v) H2O/MeOH

(15% RSD, N = 6)

no treatment
(8% RSD, N = 5)

Sheikh, S.; Yang, D. Y.; Blaszykowski, C.; Thompson, M. Chem. Commun. 2012, 48, 1305

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Water, Surface Hydration & Antifouling

Water is crucial

Antifouling properties linked to (the state of) surface hydration

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Neutron Reflectometry

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Probing Surface Hydration with NR (1/2)

Stratified model to study surface hydration
Contrast variation

Bulk water (D2O/H2O), SLDB = 3.54 x 10-6 -2

Layer 1

1-B
Transitional water
Silane adlayer

SLD1

SiO2, SLDSiO2 = 3.48 x 10-6 -2

Enhance scattering
contrast of Layer 1

d1

SiO2-1
dSiO2

Si-SiO2
Si, SLDSi = 2.07 x 10-6 -2

Match the SLD of bulk

water to SiO2 substrate

Data fitting: adjustment of

d = thickness
= interfacial roughness
SLD = scattering length density

Pawlowska, N. M.; Fritzsche, H.; Blaszykowski, C.; Sheikh, S.; Mansoor, V.; Thompson, M.
Langmuir 2014, 30, 1199

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NR: Experimental Overview

WATER

Reflectivity Data
NR

SLD Profile

Sample

Modelling
+
Data Fitting

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Probing Surface Hydration with NR (2/2)

MEG-OH vs. OTS-OH hydration

SLD profiles
SiO2

Layer 1

Bulk
water

Layer 1 not well defined for MEG-OH

compared to OTS-OH (as seen by the
sharpness of the peaks)

Ability to absorb water?

MEG-OH: SLD value near the SiO2

interface close to that of bulk water
suggesting water absorption

OTS-OH: SLD value near the SiO2

interface deviates from that of bulk
water suggesting water does not absorb

|F| < 3 kHz

MEG-OH
OTS-OH

Water organization?

|F| ~ 22 kHz

MEG-OH: long-range (~40) & less

structured (higher SLD)

OTS-OH: shorter-range (~20) & more

structured (lower SLD)

Pawlowska, N. M.; Fritzsche, H.; Blaszykowski, C.; Sheikh, S.; Mansoor, V.; Thompson, M.
Langmuir 2014, 30, 1199

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Two Distinct Hydration Patterns

not to scale

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Molecular Dynamics Simulation

Computational approach to investigate the molecularlevel structuration of water within and atop various
antifouling adlayers (MEG versus alkyl family)

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MD Simulations: Models
Surface functionalization
of -quartz with residue

Solvated
simulation cell:
Quartz slab:
1.97 x 1.97 x 0.90 nm

Full 5 x 5 coverage

~23,000 atoms

The atom colour code is as follows:

yellow (silicon), turquoise (carbon),
red (oxygen), and white (hydrogen)

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Radial Distribution Function (RDF)

The RDF describes the probability of finding water molecules

organized at a certain distance from a reference

Seen as distinct peaks with proportional magnitude

Hydration innermost film

Hydration top film

Sheikh, S.; Blaszykowski, C.; Nolan, R.; Thompson, D.; Thompson, M. J. Colloid Interface Sci. 2015, 437, 197

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Water Dynamicity: MEG-OH System (1/2)

Water dynamicity refers to the lability & mobility of water molecules
within and atop an adlayer

MD simulations with the MEG-OH

system revealed:

multiple molecules of water absorb

simultaneously around the internal
ether atoms of oxygen (A, C, D)

full assortment of possible H-bonding

interactions of water with the internal
ether or/and distal hydroxyl moieties

Sheikh, S.; Blaszykowski, C.; Nolan, R.; Thompson, D.; Thompson, M. J. Colloid Interface Sci. 2015, 437, 197

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Water Dynamicity: MEG-OH System (2/2)

9 ns
1 ns
1 ns

Water clustering

Water residency time within the

adlayer well into the ns regime

As we move closer to the top of

the adlayer, then away from it:

27 ns

interfacial water is more

labile & mobile

bulk water diffuses freely

Sheikh, S.; Blaszykowski, C.; Nolan, R.; Thompson, D.; Thompson, M. J. Colloid Interface Sci. 2015, 437, 197

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Antifouling & Surface Hydration:

Basic Requirements
Adlayer internal
& interfacial
hydrophilicity

Molecular-level
water structuration

Tightly-bound
hydration water

Limited
dynamicity
for hydration
water

Sheikh, S.; Blaszykowski, C.; Nolan, R.; Thompson, D.; Thompson, M. J. Colloid Interface Sci. 2015, 437, 197

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Summary & Conclusions

Water via surface hydration (and its state) plays a key role in
surface antifouling/protein repellency

Molecular-level mechanism rationalized in terms of a set of

basic requirements: internal & interfacial hydrophilicity, water
structuration, hydration strength, water dynamicity (lability &
mobility)

The antifouling mechanism postulated for such ultrathin

structures concurs with that generally invoked in the literature,
and accounts for the uniqueness of the MEG-OH nanogel
surface chemistry

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Acknowledgments
Supervisor:

Professor M. Thompson

Collaborators:
Current

Drs. C. Blaszykowski and D. Thompson, Ms. N. Pawlowska

and former members of the Bioanalytical Research Group

Funding:

Ontario Graduate Scholarship (OGS) Program, IrelandCanada

Dobbin Scholarship, Department of Chemistry and the University of Toronto

Organizing

Committee of the 9th Annual Conference on the Physics,

Chemistry & Biology of Water

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Thank You for Your Attention

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