Acoustic Sensing with Dissipation: Real-TimeAnalysis of Surface/Chemical Interactions
Mark Poggi, Ph.D.Territory Manager
Q-Sense Inc.
Mark Poggi, Ph.D.University of Kentucky
August 22nd, 2007
Outline
• Brief Q-Sense History• Introduction to Quartz Crystal Microbalance
(QCM)• The QCM with the Dissipation monitoring
principle.• Applications• Applications
• Polymers• Biochemical• Electrochemical
• Concluding Remarks• Discussions
Brief History• 1976: Start of QCM-D research at Chalmers
• 1995: QCM-D patented
• 1996: Q-Sense AB founded
• 1999: Product development, prototype sales
• 2000: Commercial focus, 1:st generation product launched
• 2001: US Subsidiary, Newport Beach, CA
• 2005: 2nd Generation product launch, Q-Sense E4
• 2006: US Office moved to the east coast, systems in 25 countries
Q-Sense is a subsidiary of Biolin AB, a public company listed on theStockholm Stock Exchange. Biolin AB is an R&D and development basedcompany that invests capital, as well as competence, in order to create valuegrowth in high tech companies within life sciences and related areas.
• 2006: Biolin AB acquires CoAT AB
• 2006: Biolin AB acquires KSV
• 2007: Over 270+ scientific publications
Laboratories Utilizing QCM-D
• Harvard University, Prof. Whitesides
• Stanford University, Prof Curtis Frank
• Rutgers University, Prof J. Kohn
• Yale University, Prof P. Van Tassel
Academic
• Procter and Gamble (2)
• Medtronic, Inc.
• Nippon Paper Industries, JP
• 3M (Dental)
Industrial
• Boston University, Dr. Brown
• Georgia Tech, Prof. Henderson
• Chalmers University of Technology, SE, Prof. B. Kasemo
• Cambridge University, Cavendish lab, UK, Prof. A. Donald
• Max-Planck Institute, DE, Prof. W. Knoll
• Amgen
• Johnson & Johnson
QuartzQuartz is the only material known that possesses the following
combination of properties:
• Piezoelectric ("pressure-electric"; piezein = to press, in Greek)
• Zero temperature coefficient cuts exist
• Stress compensated cut exists
• Low loss (i.e., high Q)
• Easy to process; low solubility in everything, under "normal" conditions,except the fluoride etchants; hard but not brittle
• Abundant in nature; easy to grow in large quantities, at low cost, andwith relatively high purity and perfection. Of the man-grown singlecrystals, quartz, at ~3,000 tons per year, is second only to silicon inquantity grown (3 to 4 times as much Si is grown annually, as of 1997).
Jiri Janata, Principles Of Chemical Sensors. 1989.
QCM Timeline
Undeformed lattice
X++
++++
+++
++++++
+ +++++
____ __ ______ __
______
Y
_
Strained lattice
+++
+++
+++
++++++
++
++++
____ __ __
_____ __
___
___
-+
Y
_ fn
Cm 1
1880 1921 1959 1980 1996
++++ ___ _
Starts as research tool
Sauerbrey
• The ”Mandatory” reference for QCMapplications
1Linear relationship between frequency and mass:
fn
Cm 1
overtonen
sngcmC
127,17
Sauerbrey, G Z. Phys. 155 (1959) 206.
Military & AerospaceCommunicationsNavigationIFFRadarSensorsGuidance systemsFuzesElectronic warfare
IndustrialCommunicationsTelecommunicationsMobile/cellular/portableradio, telephone & pagerAviationMarineNavigationInstrumentation
ConsumerWatches & clocksCellular & cordlessphones, pagers
Radio & hi-fi equipmentColor TVCable TV systemsHome computersVCR & video camera
Acoustic Sensor Applications
Electronic warfareSonobouys
Research & MetrologyAtomic clocksInstrumentsAstronomy & geodesySpace trackingCelestial navigation
InstrumentationComputersDigital systemsCRT displaysDisk drivesModemsTagging/identificationUtilitiesSensors
VCR & video cameraCB & amateur radioToys & gamesPacemakersOther medical devices
AutomotiveEngine control, stereo,
clockTrip computer, GPS
John R. Vig, U.S. Army Communications-Electronics Command
The QCM-D sensor
Mass Sensitivity D-factorMass Sensitivity D-factor
in air (1 bar) ~0.2 ng/cm2
in water (25 C) ~0.9 ng/cm2
~410-8
~110-7
• Detection range in viscoelastic films: nm - m
• Temperature Range 15-45° C; long term stability +/- 0.02° C
QCM layout
Metallicelectrodes
Active electrode(reactionsubstrate)
Crystal, sensor, QCMCounter electrode
Contact electrodes
Vibration Modes
Induced withan AC Voltage
QCM-D ping principle: Teachingan Old Dog New Tricks
Δf is related to the massof the attached film(Sauerbrey relation)
ΔD is related to the
viscoelasticity
Instrument operation: Frequencyand Dissipation
5Mhz 15Mhz 25Mhz 35Mhz 5Mhz time
Features•Sequential multi frequency measurement•Freely oscillating crystal=true crystal frequency•Enables multiple frequencies & viscoelastic modeling
driving freq ~10 ms decay recording ~2 ms data communication ~13ms
Crystal non-oscillating 50% of the time
Note: QCM-D can sample viscoelastic changes over 100 times/sec.Compared to approximately one data point per 30 seconds whenusing impedance analysis.
The Quartz Crystal Microbalance withDissipation monitoring (QCM-D) technique
A(t)=A0exp(-t/)sin(2ft+)
D=1/ f
Mathematical representation
of the decay curve
Frequency change (Df):
Time ( s)
A f
mD stiffness
Frequency change (Df): adsorbed amount: Dm=-C·Df
(Sauerbrey equation)
Voinova et al., Physica Scripta 59 (1999) 391
Energy Dissipation (DD): rigidity
Multiple frequency modeling: shear viscosity and elasticity
ΔD Provides Insight Into:
• Verify validity of Sauerbrey relation
• Monitoring swelling/hydration
• Viscoelastic modeling
• Insight into structural changes• Insight into structural changes
Surfaces, Surfaces, Surfaces
Metals & OxidesSome Examples
SiO2, Al2O3, TiO2
W, Ir, Ta, Pt, Fe
Au, Ag, Cu, Cr
Spin-CoatedPolymers
PS
PC
PMMA
Protocols Immobilization
Streptavidin on SLB
Streptavidin on biotin-BSA
NTA on SLB
SiC, FeC3, TaN
Many More!
Custom made onrequest
Quartz
Metal-/ oxide
PMMA
Custom made onrequest
Quartz
Gold
Polymer
Surface Chemistry
SAM (Thiols & Silanes)
UVO Treatment
The Q-Sense E4 System
www.q-sense.com
•4 Sensors
•Peltier Thermal Control
•Baseline stability of 0.2 Hz in liquid!
•Electrochemistry Module
•Flow / stagnant mode
•Wide range of chip coatings
Removable flow module
Quartz crystal
Flow channelsfor temperaturestabilization
Inlet
Outlet
Cross section of flow module
So, What Can QCM-D Measure???
oxidized goldvesicle adsorption
SiO2
two steps to bilayer
26 Hz
-40
-20
0
freq
uen
cy(H
z)
gold with alkane thiolmonolayer adsorption
13 Hz
Lipid VesicleAdsorption
Ø 25 nm
Pfeiffer and Hook. Analytical Chemistry. 2006, 78, 7493-7498
400 500 600 700 800time (s)
90 Hz
300 400 500 600 700time (s)
-1
0
1
2
3
4
400 500 600 700 800
Dis
sipat
ion
(10-6
)
time (s)
-80
-60
freq
uen
cy(H
z)
C.A. Keller and B. Kasemo, Biophysical J. 75 (1998) 1397.
Antibody Detection of AlbuminAdsorbed on a TiO2 Surface
Albumin Antibody
C.W. Frank et al. Colloids and Surfaces B: Biointerfaces. 50 (2006) 76–84Höök, F., Rodahl, M., Kasemo, B. and Brzezinski, P. (1998) Proc Natl Acad Sci, 95 (21), 12271-12276.
Adsorption and Cross-linking
of a Mussel AdhesiveProtein
Release Dm (Ellipsometry / SPR):
Mefp-180
n=1
Time (min)
Rinsing
QCM-D:
-70
-60
-50
-40
-30
-20
-10
0
0 20 40 60
fn=1
Dn=1
f
(Hz)
Time (min)
Exposure to Mefp-1
0
2
4
6
8
10
12
14
100 120 140
D
(10
-6)Exposure to
NaIO4
Fant, C & Höök, F; Anal. Chem. (2001), 73, 5796-5804
NaIO4
Release
of Water
DmQCM = 1200 ngcm-2
Dm (Ellipsometry / SPR):
0
40
80
120
160
m (ELM)
0 20 40 60 80 100 120 140
m
(ng/c
m2)
Exposure to Mefp-1 Rinsing Exposure toNaIO
4
Time (min)
Polyelectrolyte Multilayer
- - - - - A – Negative charge
++ +
++ + B – Positive charge
Raw data indicate mass loss
[(POD-PSS)c] and oppositelycharged (PAH)
SiO2
- - - - - - - -
++ +
++ +- - - - -
++ +
++ +
MP
0,0
1,0
2,0
3,0
4,0
5,0
6,0
7,0
8,0
A 1st layer A 2nd layer A 3rd layer A 4th layer A 5th layer NaCl Water
thic
kness
[nm
]
Sauerbrey
Model
Modeling reveals swelling
Caruso et al. Chem. Mater. 2005, 17, 171-175
Moisture Uptake of ThermoresponsiveHydrogel Films: Impact of Cross-link Density
vs.
Tamirisa et al. Macromolecules 2006, 39, 7092-7097
The Effect of Silica Nanopartice Coatings onProtein Adsorption
vs.
Lord et al. Biomaterials 27 (2006) 4856–4862
Complexation Chemistry for Tuning Releasefrom Polymer Coatings
Co-polymer (PVM) + Cu2+
vs.
MedetomidineRelease
Fant et al. J. Phys. Chem B. (2006).
vs.
Co-polymer (PVM) + Zn2+
PVM = Poly-vinyl-methacrylate
Plotting D vs f – Dextran on SiO2 and Al2O3
Dextran behavesdifferently on a Al2O3
substrate (black) than ona SiO2 substrate (grey).
Two-phase process
indicated on Al O .Al2O3
SiO2
indicated on Al2O3.
Phase 1
Phase 2
Kwon et al, Environ Sci Technology 2006, 40, 7739-7744
Al2O3
Lipase-Mediated Lipid DegradationMechanism
Detergent with Enzyme (lipase)
Stain (lipids)
Fabric
Water Water
Fabric
Stain (lipids)
JacketGreasy stain
Stain (lipids)
Crystal
Water
Lipase activity study
In. Situ, QCM-D
Stain (lipids)
Crystal
Water
Snabe et al. Chemistry and Physics of Lipids 125(2003), 69-82
Lipase solution
~100 nm
Practical Example:
Lipase (E.C. 3.1.1.3)Molecular Weight ~30kDaConcentration 1 μg/ml
Lipoprime (lipase)
Quartz crystal
Lipid film ~100 nmConcentration 1 μg/ml
Formula: C57H104O6
Molecular Weight: 885.43 DaCAS Registry Number: 122-32-7
Triolein (triacylglycerol)
Snabe et al. Chemistry and Physics of Lipids 125(2003), 69-82
0
1
2
3
4
5
6
Vis
c(k
gm
-1s-1
)o
rE
lasti
cit
y(1
05
Pa)
0
20
40
60
80
100
120
Fil
mT
hic
kn
ess
(nm
)
A B CD
Enzymatic Degradation of Lipids
4
5
6
)o
rE
las
tic
ity
(105
80
100
120
Fil
mT
hic
kn
es
s(n
m)
A
D
BC
4
5
6
)o
rE
las
tic
ity
(105
80
100
120
Fil
mT
hic
kn
es
s(n
m)
A
D
BC
0
0 1 2Time (min)
0
Quartz Crystal
Lipid film
A
A) Adsorption of lipase
Quartz crystal
Lipid film
B
B) Cluster formation
Quartz Crystal
Lipid film
C
C) Mass ejection
Quartz Crystal
Lipid film
D
D) Lipid layer removal
0
1
2
3
0 5 10 15 20
Time (min)
Vis
c(k
gm
-1s-1
)o
rE
las
tic
ity
(10
Pa
)
0
20
40
60
Fil
mT
hic
kn
es
s(n
m)
0
1
2
3
0 5 10 15 20
Time (min)
Vis
c(k
gm
-1s-1
)o
rE
las
tic
ity
(10
Pa
)
0
20
40
60
Fil
mT
hic
kn
es
s(n
m)
viscositythickness elasticity
Snabe et al. Chemistry and Physics of Lipids 125(2003), 69-82
Biomaterial Protein Resistancy
Eye
Contac lens
Eye
Tear fluid
Contact lens polymer
Protein film (unwanted)
Crystal
Tear fluid
Protein resistance optimization
Crystal
In. Situ, QCM-D
Contact lens
Contac lens Contact lens material (HEMA)
Lord et. al. Biomaterials 2005
Protein resistant modification
E4 Electrochemistry Module
Module SpecificationsSensor crystals All Q-Sense crystals can be usedInternal volume ~ 600 mLCleaning Simple, can be disassembled
ElectrodesWorking electrode The sensor crystal itselfWorking electrode The sensor crystal itselfCounter electrode Platinum discReference electrode Custom modified Ag/AgCl
Common application areas
Surface(QCM-D)
Drug development
Surfactants
Biofouling
Biosensors(QCM-D)
Biomaterials
Drug discovery
Polymers
Concluding Remarks
• QCM-D provides not only mass uptake butalso viscoelastic properties of thin films.
• Real-time surface sensitive technique
• Overtones (different sensitivity, modeling)• Overtones (different sensitivity, modeling)
• Surface interaction/reaction
The Q-Sense QCM-D Solution
Education&Training
Turn key QCM-D systemAdvanced Modeling
Q-Sense E4Turn key QCM-D system
Advanced Modelingsoftware
Data evaluationsupport
Annual User meetings
User’s 19 Countries
Thank You!
Mark A. Poggi, Ph.D.Territory ManagerQ-Sense, Inc808 Landmark Drive, Suite 124Glen Burnie, MD 21061
Direct #: 404-863-4257Office #: 877-773-6730
DiscussionDiscussion
E-Chem moduleCounter electrode99.95% Pt
Reference electrodeReference electrodeAg/AgCl
Left or Right hand configuration1 or 2 modules can be used with one E4
QTools SoftwareTheoretical Modeling of the QCM-D Response (Viscoelastic
Modeling)
Δf=f1(n,ηf,ρf,μf,δf)
ΔD=f2(n,ηf,ρf,μf,δf) Fluid(ρ l, l)
n=1n=3
n=...
ρ: density, (kg/m3)
η: viscosity (G’’/ω), (kg/ms)
Crystal
Adlayer(ρ f, f, f)
δf
Voinova et al., Physica Scripta 59 (1999) 391
G = G' + jG''= m + j2πf
η: viscosity (G’’/ω), (kg/ms)
μ: elasticity (G’), (Pa)
δ: thickness, (m)
Viscoelastic model -Assumptions
Homogeneous Adlayer
Maxwell
viscoelastic fluid
Voight
viscoelastic solid
Newtonian Fluid
G = G' + jG''= m + jw