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Welcome to the Spring 2009 QCM-D Training Workshop at The University of Kentucky
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Quantifying Changes at Material Interfaces Using Dissipative Quartz Crystal Microbalance (QCM-D)Mark Poggi, Ph.D., Archana Jaiswal, Ph.D., and Matthew Dixon, Ph.D.
Q-SenseGlen Burnie, MD
The University of KentuckyApril 8th 2009
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Outline• Brief Q-Sense History• The QCM with the Dissipation monitoring
principle.• Applications• Discussions• Lunch! (Approx. Noon)• Demonstration
Note: Quartz Crystal Microbalance = QCM
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Who, What and Where?
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Brief Q-Sense History• 1995: QCM-D patented
• 1996: Q-Sense AB founded
• 1999: Product development, prototype sales
• 2000: Commercial focus, 1st generation product launched (D300)
• 2001: US Subsidiary, Newport Beach, CA
• 2005: Application Research Labs Established in MD.
• 2005: 2nd Generation product launch, Q-Sense E4
• 2007: E1 Product Launch, Module Launches (4)
• 2008: >500 Technical publications using QCM-D
• 2009: Systems in 28 countries (~150 in North America)
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Who uses QCM-D?
• 3M
• Genentech
• BASF
• Kimberly Clark
• Medtronic
• Procter and Gamble (4)
• Rohm and Haas (2)
• Boston Scientific
• Amgen
• Unilever
• SC Johnson
Industrial
• University of Illinois
• MIT
• EPA
• University of Kentucky
• USDA / EPA
• Georgia Tech
• Purdue University
• Lawrence Berkeley National Labs
• Virginia Tech (2)
• Max-Planck Institute
Academic/Government
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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, and with relatively high purity and perfection. Of the man-grown single crystals, quartz, at ~3,000 tons per year, is second only to silicon in quantity grown (3 to 4 times as much Si is grown annually, as of 1997).
Jiri Janata, Principles Of Chemical Sensors. 1989.
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QCM TimelineCu
rie b
roth
ers
disc
over
piez
oele
ctric
ity
1880
Firs
t qua
rtz c
ryst
al
cont
rolle
d os
cilla
tor
1921 1959
Saue
rbre
y re
late
s
frequ
ency
and
mas
s1980
Firs
t QCM
ope
ratin
g in
liqui
d
1996
QCM
-D P
aten
t file
d
Undeformed lattice
X++
++++
+++
++++++
+ +++++
____ __ ______ __
______Y
_
Strained lattice
+++
+++
+++
++++++
+ +++++
____ __ _______ __
______
••-+
Y
_ fn
Cm Δ−=Δ1
Starts as research tool
Sauerbrey, G Z. Phys. 155 (1959) 206.
Gas and vapor analysis
Liquid analysis
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The QCM-D sensor
Mass Sensitivity D-factor
in air (1 bar) ~0.2 ng/cm2
in water (25 °C) ~0.9 ng/cm2~4×10-8
~1×10-7
• Detection range in viscoelastic films: nm - μm
• Temperature Range 15-65° C; long term stability +/- 0.02° C
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The QCM-D SensorQuartz
Gold Electrode
diam. 14mm
5MHz
Contact electrodes
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Why is There a Notch in the Quartz Crystal?
diam.14mm
Thickness (δ) given by 1/fand νq = 3340 m/sSo for 5 MHz δ ~ 330 μm
10.5 mm
radius = 140 mm
Notch IndicatesOscillation Direction
Cross section(Plano-plano with beveled edges)
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Surfaces supplied by Q-Sense
Au sensor
metals, oxidesSiO2, Al2O3, Ti, Pt, Ag, W, Cu, Cr, Ir, Ta, FeC3, TaN, CeO2, Fe, Zn, ZnO2, Fe2O3, ZnS, FeS, Stainless steel, ..., and custom made
polymersPS, PC, PMMA, Fluoropolymer, PE, PPUsers can coat with own polymers
hydroxyapatitenanocrystalline, RMS ~2 nm
Hard Model Surfaces available from Q-Sense: •Glass, ceramics (SiO2)•Plastics (PE, PP, PS and PVC)•Stainless steel
On-Request Model Surfaces can be supplied by Q-Sense:Such as starch, grease/fat and many polymers
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QCM-D ping principle: Teaching an Old Dog New Tricks
Δf is related to the massof the attached film(Sauerbrey relation)
ΔD is related to theviscoelasticity
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Instrument operation: Frequency and Dissipation
driving freq ~10 ms decay recording ~2 ms data communication ~13ms
5Mhz 15Mhz 25Mhz 35Mhz 5Mhz
Crystal non-oscillating 50% of the time
time
Features•Sequential multi frequency measurement•Freely oscillating crystal=true crystal frequency •Enables multiple frequencies & viscoelastic modeling
Note: QCM-D can sample viscoelastic changes over 200 times/sec.
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The Quartz Crystal Microbalance with Dissipation monitoring (QCM-D) technique
Time ( s)μ
AΔ ∝f
ΔΔ ∝
mD stiffness
A(t)=A0⋅exp(-t/τ)⋅sin(2πft+φ)
D=1/ πfτ
Mathematical representationof the decay curve
Frequency change (Δf):adsorbed amount: Δm=-C·Δf
(Sauerbrey equation)
Voinova et al., Physica Scripta 59 (1999) 391
Energy Dissipation (∆D):rigidity
Multiple frequency modeling:shear viscosity and elasticity
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The Q-Sense E4 System
• 4 Sensors (simultaneous studies)• Peltier Thermal Control• 2 Weeks Learning time• Flow / stagnant mode• Wide range of chip coatings• Parallel Modules
www.q-sense.com
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The E4 MeasurementChamber
parallel 2 by 2 parallel
serial 2 by 2 serial
Examples of Experimental Design
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4 Removable Flow Modules
Inlet
Outlet
Quartz crystalFlow channels for temperature stabilization
Cross section of flow module
• Volume above sensor – 40 μL• Minimum sample volume – 200 μL• Temperature – 15-65 °C (± 0.02 °C)• Programmable temperature ramping• Easy access for cleaning
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The Q-Sense E-Series Modules
•Standard FlowModule
•Electrochemistry Cell
•Window Module
•Humidity Module
•Open Module
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QCM-D Technology OverviewWide Range of Crystal Surfaces
Metals Polymers/Lipids Metal Oxides HydroxyapatiteReactive Surfaces Custom Surfaces
t
MassThicknessDensityViscosity/RheologyShear modulus
Real Time Measurement of Δf and ΔD
Wide Range of Sample Possibilities
14 mm diam.5 MHz
Surfaces
Data
Samples
Measured Simultaneously
SAMS, surfactants, detergentsPeptides, lipids, membranesProteins/DNA, antibodies, enzymesPolymers, polyelectrolytesViruses, phage display, biofilmsBacteria, yeastMammalian Cells
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Reactions or Structural Changes•Crosslinking events (polymers)•Structural properties of materials/thin films•Detergent activity•Conformation changes (receptor conformation)•Hydration/Swelling (polymers and other thin films)•Degradation/Dissolution kinetics
H2O
InteractionsMolecule-molecule and molecule-surface•Small molecule-surface interactions•Polyelectrolyte multilayer buildup •Biomolecular interactions (Biofilm growth)•Protein deposition or fouling
Bulk Characterisation•Viscoelastic properties of fluids (protein solutions, surfactants etc...)
Application Areas
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Combined QCM-D and microscopy• New window module fits
under microscope
• Examples of applications:fluorescence, light or irradiation sensitive processes
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QCM-D Technology OverviewWide Range of Crystal Surfaces
Metals Polymers/Lipids Metal Oxides HydroxyapatiteReactive Surfaces Custom Surfaces
t
MassThicknessDensityViscosity/RheologyShear modulus
Real Time Measurement of Δf and ΔD
Nanoparticles, self-assembling molecules, polymers, surfactants, detergents, Peptides, lipids, membranesProteins/DNA, antibodies, enzymesViruses, phage displayBacteria, yeastMammalian Cells
Wide Range of Sample Possibilities
14 mm diam.5 MHz
Surfaces
Data
Samples
Measured Simultaneously
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So, What can QCM-D Measure?
Materials
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Polyelectrolyte Multilayers
SiO2
- - - - - - - -+
+ + + + +- - - - -+
+ + + + +
- - - - - A – Negative charge
++ + + + + B – Positive charge
Raw data indicate mass loss
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
knes
s [n
m]
SauerbreyModel
Modeling reveals swelling
Caruso et al. Chem. Mater. 2005, 17, 171-175
[(POD-PSS)c] and oppositely charged (PAH)
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Anti-fouling Development
Medetomidine Uptake
Medetomidine Release
Fant et al. J. Phys. Chem B. (2006).
Crystal
Water
Polymer (w/ Nanoparticles)
Developing tailored materials
- controlled uptake
- controlled release
= Medetomidine
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Cooperative Adsorption of Functionalized Nanoparticles onto Silica
S. Smoukov et al., J. AM. CHEM. SOC. 2007, 129, 15623-15630 (2007)
- Single functionalized particle-type will NOT assemble.
- When functionalized NPs are mixed with oppositely charged functionalized NPs…assembly DOES occur!
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Adsorption of Functionalized Nanoparticles onto Silica (cont)
S. Smoukov et al., J. AM. CHEM. SOC. 2007, 129, 15623-15630 (2007)
Coating density impacted by immersion?
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Using QCM-D to Follow the Adsorption of Functionalized Nanoparticles onto Silica
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Adsorption Rate of Deposition as Determined with QCM-D
M.A. Poggi et. al, J. Phys. Chem. C. submitted (2008)
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So, What can QCM-D Measure?
Biological
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Single Mismatch Detection During PNA (15-mer) and DNA (15-mer) Hybridization
Single mismatch detection during hybridization
Höök, F. et al. Langmuir 2001, 17, 8305-8312
Specificprotein binding
Nucleotidehybridization
TIMESLB formation
Biotinylated bilayer and subsequent streptavidin binding
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Fant, C & Höök, F; Anal. Chem. (2001), 73, 5796-5804
Adsorption and Cross-linking of Polymers
NaIO4
Release
of Water
Mefp-1
80
me (min)
Rinsing
QCM-D:
-70
-60
-50
-40
-30
-20
-10
0
0 20 40 60
Δfn=1
ΔDn=1
Δf (
Hz)
Time
Exposure to Mefp-1
0
2
4
6
8
10
12
14
100 120 140
ΔD (10
-6)
Exposure to NaIO
4
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Fibrinogen Adsorbed to the Surface of Biopolymers
Crystal
Water
Polymer
Crystal
Water
Polymer
Weber et al. Langmuir 2007, 23, 3298-3304
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Fibrinogen adsorption (cont.)
A = PLLA
B = Steel
C = poly(PEG) graft
Weber et al. Langmuir 2007, 23, 3298-3304
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Rapid Screening of Protein Adsorption onto Different Surface Chemistries
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Hovgaard et al. Biophysical Journal, 93, 2162-2169, 2007
T.P.J. Knowles et al. PNAS, 104, 10016-10021, 2007
Surface mass density quantified at different stages of fibrillation.
500 nm
500 nm
1 µm
1 µm
∆D
Growth of peptide macrostructures Case study: glucagon monomer
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Bone Stem Cells on Ta & Cr Surfaces
Cell attachment stronger and more spread on Ta surface then Cr
Modin et al. Biomaterials 27 (2006) 1346–1354
QuartzCr
QuartzTa
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Monitoring/Quantifying the Formation of Biofilms (cont.)
Fluorescence Microscopy QCM-D
Bacteria: Leuconostoc mesenteroides
Surface: Steel
H. Green Q-Sense AB. 2004.
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Monitoring/Quantifying the Formation of Biofilms (cont.)
Time
6 hr
Time
12 hr
H. Green Q-Sense AB. 2004.
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Monitoring/Quantifying the Formation of Biofilms (cont.)
Exopolysacharides
H. Green Q-Sense AB. 2004.
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QCM-D Fundamental Training
Experimental Planning and Methods
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Outline
Measurement requirementsSurfacesCleaning protocolsSample preparationTech Tips
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QCM-D Experiment PlanningS.S.I
Surface
What type of surface?How will I clean/prepare the surface?
What buffer (solvent)?Which concentration(s)?What Temperature?Do I need to degas my samples?
Samples
How do I cleaning/prepare the instrument?What liquid path am I going to use?What about solvent compatibility?Flow rate/Batch mode?
Instrument
PBS
1
2
34
parallel
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Methods & Protocols
Collection of preparation and cleaning methods for surfaces and instrument
Cleaning Au Cleaning SiO2SAM preparation Instrument cleaningCleaning PS
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Wide Range of Crystal Surfaces
Metals & Metal OxidesAu, SiO2, Al2O3, Ti, Stainless steel, Pt
Ag, W, Cu, Cr, Ir, Ta, FeC3, TaN, CeO2, Fe, Zn, ZrO2, SiOC, Iron oxide, Si3N4 etc
Other coatings can be made on request
Spin Coated PolymersIn stock: Polystyrene
Other polymers on requestExamples: PC, PMMA, PP, PE, PVC
Users can coat sensors with their own polymers/materials
Quartz Sensor crystal
Gold
Polymer
Unique Inorganic Coating
Hydroxyapatite (nanocrystalline, RMS roughness ~2-3 nm)
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Surfaces - Polymeric
sensor
dω/dt≠0
sensor
ω
sensor
ω
ωsensor
sensor
Deposition(full coverage)
EvaporationFluid thinningAcceleration
Spin coating
Spin coated polymersMany polymers can be spin coated:PS, PC, PMMA
QuartzGold
Polymer
Thickness range:100nm-1μm
Other methods•Surface attached polymerization
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NTA/Lipid
Biotin/Lipid
Surfaces – Specific Chemistry
•Biotin immobilization surface Protocol
•SLB NTA modified surface for His linkeageProtocol
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Clean Sensor (and tweezers)
ultrasonicbath
+
Gold
Amonia, Peroxide Mix (TL1, Piranha) UV/Ozone
SiO2
SDS
Thick films/Heavy contaminated
+ UV/Ozone
O2
O3
O2 O2
O2
O O3
OO
hν1
hν2
CO2, H2O, N2 …O3
UV-lamp(185nm + 254nm)
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Chemical Treatment, APM, TL1Surface: gold
Deposits: lipids, thiols, proteins in molecular layers
W. Kern et al., RCA Review 31 (1970) 187
Method:• UVO-treatment (10 min)• Heat 5:1:1-mixture of mQ-water, ammonia (25%) and hydrogen peroxide (30%) to 75°C•Immerse sensors in solution using a cleaning holder (5 min)•Clean tweezer in the same beaker• Rinse in mQ-water, dry with N2
• UVO-treatment (10 min)
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Cleaning Surfaces – UVO-Treatment
sensor surface
O2
O3
O2 O2
O2
O O3
OO
UV-lamp(185nm + 254nm)hν1
hν2d
(few mm)
organic contaminants
CO2, H2O, N2 …O3
• effective in air• exposure time: 5..10 min
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Sensors Dry and Dust FreeRinse washing solution off Dry with a clean gas
N2Ar2CO2
Never use compressed air!
Keep tweezer below sensor
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QCM-D Experiment PlanningS.S.I
Surface
What type of surface?How will I clean it?
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Pure SamplesWater:18,3 MΩ MilliQ
Buffers:Prepare your own buffers, do not trust the ”kitchen”!
? ? – Water, PBS, HEPES, MES, ACETAT, .....
sterile≠clean
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Concentrations
0.1-100 ug/ml
low high
No/slow responseDiffusion / Depletion
Bulk effectToo rapid kinetics
Costly
Optimal concentration region
Typical ConcetrationsProtein 0.1-100 μg/mlAntibody 0.01-10 μg/mlCells 104 - 106 CFU/mlDNA pmol-nmol
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-10
-5
0
5
10
-3
-2
-1
0
1
2
0 5 10 15 20
f3 (Hz)f5 (Hz)f7 (Hz)
D3 (1E-6)D5 (1E-6)D7 (1E-6)
Δf (H
z)
ΔD (10
-6)
time (min)
Bulk effects – “Buffer step”
Effect:offset in baseline of f and D when changing solution
Cause: bulk properties
- density & viscosity -influence f and D
ΔD
off
Δf of
f
buffer 1buffer 2
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QCM-D Temperature Responsein air in water
-60
-40
-20
0
20
40
60
80
100
6
6.5
7
7.5
8
0 5 10 15 20
Δf3 (Hz) ΔD
3 (10-6)
time (min)
10
20
30
40
T (C)
-140
-120
-100
-80
-60
-40
-20
0
130
140
150
160
170
180
190
0 5 10 15 20
Δf3 (Hz) ΔD
3 (10-6)
time (min)
10
20
30
40
T (C)
(clean sensor with thin rigid coating)
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T Response of Our QCM-D
• E4 has T control +/- 0.02 oC• D300 has T control +/- 0.03 oC
Zelenka, J. Piezoelectric Resonators and their Applications; Elsevier: Amsterdam-Oxford-New York-Tokyo, 1986; Chapter 6.
TfCf T Δ−=Δ 0CT = constant depending on design and manufacturing of crystal
~ 4x10-7 deg-1 (for crystal with radius 5 mm and thickness 0.2 mm)f0 = fundamental frequency
For a 5 MHz crystal with ΔT = 1 oC Δf = - 2 Hz
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P Response of Our QCM-D
Stockbridge, C. D. In Vacuum Microbalance Techniques; Behmdt, K. H.,Ed.; Plenum Press: New York, 1966; Vol. 5, p 147.
PCf PΔ−=ΔCP = constant independent of nature of gas in torr
= 1x10-9 * f0f0 = fundamental frequency
For a 5 MHz crystal with ΔP = 760 torr Δf = - 3.8 Hz
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Degas Samples
Origin• Buffer
Hydrophobic surfaces more problematic!
Degassing samples• Sonicator• Heat (Tsample>Tinstrument)
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QCM-D Experiment PlanningS.S.I
Surface
What type of surface?How will I clean it?
What buffer (solvent)?Which concentration(s)?Temperature?Degassing
Samples
PBS
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Instrument Cleaning
Cleaning solutions:Hellmanex IISDS 2%Roche cleaner
Always end with a water rinse and store chamber dry!
Replace rubber parts when worn out or every year.
Clean the instrument before and after every experiment !!
Quartz crystalFlow channels for temperature stabilization
Cross section of flow module
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Liquid Path (E4)1
2
3
4
parallel
1
2
2 by 2 parallel
1
serial
1
2
2 by 2 serial
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Solvent CombatibilityE4
Liquid interfacing materials -(standard configuration)
Titanium oxideVitonPTFE
Check Appendix – Chemical Compatibility Chart!
IsmatcPeristaltic
pump
Tygon
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Mass Transport Limitations
F1:5 1000ug 100 ul/min F2:5 1000ug 400 ul/min F3:5 1000ug 800 ul/min F4:5 1000ug 25 ul/min
Time6050403020100
F1:5
100
0ug
100
ul/m
in
0
-1
-2
-3
-4
-5
-6
-7
-8
-9
-10
-11
Antibody interaction
Increasin
g flow sp
eed
Diffusion controlled interaction
Affinity controlled interaction
25 μl/min100 μl/min400 μl/min800 μl/min
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SummarySurface
What type of surface?How will I clean it?
What buffer (solvent)?Which concentration(s)?Temperature?Degassing
Samples
CleaningLiquid pathSolvent compatibilityFlow rate
Instrument
PBS
1
2
34
parallel
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Measurement Time Line
PBS
•Surface•Sample•Instrument
0
F1:5
/5 H
z
3
2
1
0
-1
-2
-3
-4
-5
-6
-7
-8
-9
-10
-11
-12
-13
-14
-15
-16
-17
-18
-19
2) Establish base line in
blank (buffer)
1) S.S. I.)
New 1:
100806040200
F1:5
/5 H
z
3
2
1
0
-1
-2
-3
-4
-5
-6
-7
-8
-9
-10
-11
-12
-13
-14
-15
-16
-17
-18
-19
3) Introduce sample
New 1: 2006-03-21 16:24:11
No name 1240220200180160140120100806040200
3
2
1
0
-1
-2
-3
-4
-5
-6
-7
-8
-9
-10
-11
-12
-13
-14
-15
-16
-17
-18
-19
4) Rinse with blank (buffer)
5) Save file and clean instrument
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Tech Tips
• Always start in blank (buffer, water etc)• Avoid difference in bulk properties• Bubble = trouble• Do your own sample preparation!
Thank you for your attention!
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Software Primer
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Raw Data of Demo experimentsModules 1 and 2: lard removal by two different commercially available surfactantsModules 3 and 4: surfactant adsorption from Millipore (3) and tap (4) water
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Example Modeled Data of Module 1Blue lines = frequencyRed lines = dissipationBlack symbols are the fits
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Module 1Modeled Thickness (red) and Viscosity (green)
Lard coating in water(note thickness is ~40 nm)
Lard coating removed(note thickness is ~ 0and viscosity ~ water)
Inject surfactants Rinse with water
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Lard coating in water(note thickness is ~40 nm)
Lard coating removed towards very end of rinse(note thickness is ~ 0and viscosity ~ water)
Module 2Modeled Thickness (red) and Viscosity (green)
Inject surfactants Rinse with water
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Comparing Thickness of Module 1 (red) and Module 2 (green)
Inject surfactant rinse
Note they both end up at zero
but 2 takes longer
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QTools Software
• Q-Sense Adapted Graphics and Plots Fully exportable and customizable
• Sauerbrey – thickness δ
• Models (Voight & Maxwell) – thickness δ, shear viscosity η, and a shear elasticity μ
• Kinetics – Koff, KA, and Kon
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QTools SoftwareTheoretical Modeling of the QCM-D Response (Viscoelastic
Modeling)
Δf=f1(n,ηf,ρf,μf,δf) ΔD=f2(n,ηf,ρf,μf,δf)
Crystal
Adlayer(ρ f, ηf, μf)
δf
Fluid(ρ l, ηl) n=1
n=3
n=...
Voinova et al., Physica Scripta 59 (1999) 391
G = G' + jG'' = m + j2πfη
ρ: density, (kg/m3)
η: viscosity (G’’/ω), (kg/ms)
μ: elasticity (G’), (Pa)
δ: thickness, (m)
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time (s)
Δf (
Hz) ΔD
(10-6)
Information extracted from modeling (15 & 25 MHz)
fitted data
time (s)
d(n
m)
time (s)
η(1
0-3
Ns/
m2 ) μ
(103N
/m2)
η
μ
f3
f5
D5
D3
thickness
viscosity & shear modulus
input: ρ = 1050 g/dm3
(estimated by QCM-D & SPR)
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Concluding Remarks
• QCM-D provides not only mass changes but also viscoelastic properties of chemical systems.
• Real-time, sensitive technique• Surface interaction/reaction• QCM-D provides the ability to quantify
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The Q-Sense QCM-D Solution
Q-Sense E4
Education & Training
Turn key QCM-D systemAdvanced Modeling
software
Data evaluation support
Annual User Meetings
User’s 28 Countries
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Thank You!Mark A. Poggi, Ph.D.Territory ManagerQ-Sense, Inc808 Landmark Drive, Suite 124Glen Burnie, MD 21061
Direct #: 404-863-4257Office #: 877-773-6730E-mail: [email protected]
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Demo experiment polymeric adsorption on metallic surfaces
ObjectiveTo demonstrate adsorption of a water soluble polymer: Diethylaminoethyl-Dextran to different surfaces.
Materials•Au, SiO2, PS and Al2O3 crystals
•PBS Buffer pH 7.4 150 mM NaCl (Sigma)
•DEAE Dextran (50 µg/ml in PBS)