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TRANSCRIPT
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
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
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
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)