research highlights 2016 - university of minnesota...inert biodegradable surfaces with “...
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Research Highlights
2016
Biocatalysis and Biotechnology (BB)Investigator Department ExpertisePing Wang* BBE Enzymology and biocatalysis, bioconversion and
biosynthesis, biomaterials and functional coatings, bioelectrochemical processing, biosensors.
Mark Distefano Chem Organic and biochem., protein conjugates for therapeutic and biotechnology applications.
Mikael Elias Biochem Protein engineering and evolution, molecular modelling andrecognition, bioremediation and quorum quenching strategies.
Wei-Shou Hu CEMS Systems biotechnology, biochemical engineering, cell culture bioprocessing, stem cell technology
Romas Kazlauskas Biochem Biocatalytic synthesis of chemical intermediates and biofuels, enzyme modification for new reactions.
Lawrence Wackett Biochem Enzymes in biotechnology, immobilization technology, bioremediation, computer prediction tools for biocatalysis
Kechun Zhang CEMS Synthetic biology, metabolic engineering, protein engineering, biofuels, renewable chemicals.
*Program Leader (Email: [email protected]; Phone: 612-624-4792)
Chemical and fuel bioprocessing; Biocatalyst engineering; Biotransformation and Bioremediation; Enzyme evolution; Bio-based polymers and biocoatings; Pathway engineering; Synthetic biology; Systems biotechnology; Cell culture bioprocessing
Enzymatic Protein Labeling
Mark Distefano is exploring how proteinsaccelerate chemical reactions and howproteins recognize other molecules with highspecificity. This information is useful for drugdesign and biotechnology applications.
http://www.bti.umn.edu/faculty/biodistefano.html
Distefano Lab
Fluorescent labeling of CNTF
Protein prenylation is a ubiquitous post-translational modification
Systems Design and Cell Engineering
Hu Lab
Genome engineering for biomanufacturing, genome technology for CHO cells
Stem cell engineering for hepatic applications, biomanufacturing, for cell therapy
Biofilm and antibiotic resistance transmission, microbial invasion
Chinese hamster
Chinese hamster iPSC
Enterocuccus facaelis
Kazlauskas Lab
- engineers enzymes tobe more stable, to havehigher selectivity andeven to catalyze newreactions.
http://www.umn.edu/~rjk
Reconstructed ancestral esterases and hydroxynitrile lyases are more promiscuous than modern enzymes
Protein Engineering
Ancestral catalyze new reactions
Nano Biocatalysis and Biomaterials
Wang Lab
Conceiving and realizing nature-inspiredmultienzyme reaction pathways, ImmobilizedBiocatalysts, Bioproducts and Biopolymers,Bioenergy, Biosensors and Biomaterials.
http://www.bti.umn.edu/faculty/biowang.html
Bioproducts Innovations and Pathway Engineering
Our research program combinesprinciples of chemistry, biologyand engineering to achievebiosynthesis beyond nature
http://www.cems.umn.edu/about/people/faculty.id21395.html
Zhang Lab
Biomedical and Pharmaceutical Materials (BPM)
• Biomaterials for drug delivery, medical device coatings, and tissue engineering
• Drug/medical device combinations, characterization of drug/materials interactions
• Cell-based fabrication of bioartificial tissues
• Novel tissue mechanical testing and analysis methods
Investigator Department Expertise
Ron Siegel* Phm1/BME2 hydrogels, drug delivery systems, microfabrication
Effi Kokkoli CEMS3 bioadhesion and drug targeting
Jayanth Panyam Phm multifunctional nanodelivery vehicles
Wei Shen BME bioactive materials
Calvin Sun Phm drug crystal and particle engineering
Raj Suryanarayanan Phm solid state properties of drugs, stability of drug/biomaterial formulations
Bob Tranquillo BME/CEMS fabrication and characterization of bioartificial cardiovascular replacement tissues
Chun Wang BME bio-molecular materials, polymer-based DNA and drug delivery, protein-based tissue
scaffolds*Program Leader (Email:[email protected])Affiliated Investigators: Chris Macosko,3 Marc Hillmyer,4 Theresa Reineke,4 Tom Hoye.41Pharmaceutics; 2Biomedical Engineering; 3Chemical Engineering and Materials Science, 4Chemistry
Inert Biodegradable Surfaces with “Artificial Mucus”
Wenshou Wang, Ronald A. Siegel, and Chun Wang, ACS Biomaterials Science & Engineering, 2, 180-187 (2016)
Hydrophobic graft (PCL)Hydrophilic core (HA)
TCP PCL
PCL/(1% HA-g-PCL) PCL/(3% HA-g-PCL)
0
20
40
60
80
100
120
TCP PCL PCL/1%HA-g-PCL
PCL/3%HA-g-PCL
Cel
l cou
nt
1 week4 weeks
1 week
Medical device surface
Biodegradable matrix
Medical device surface
Active nanostructured
particles
Biocompatible surface coating
Medical device surface
Biodegradable matrix
Medical device surface
Active nanostructured
particles
Biocompatible surface coating
Medical device surface
Biodegradable matrix
Medical device surface
Active nanostructured
particles
Biocompatible surface coating
(PCL)
(1) Addition of a cell mixture on thecapture substrate.
(2) Capture of target cells.(3) Washing of non-target cells.(4) Release of captured cells using the
molecular trigger B-PEG.
(4)(2) (3)
Targetcell
(1)
Non-targetcell
Cell surface antigen
Capture antibody Coiled-coil A
Coiled-coil B
PEG
Efficient Release of Affinity-Captured Cells Using Coiled-Coil-Based Molecular Triggers
Selective capture of endothelial cells
Efficient release of the captured endothelial cells by B-PEG
A label-free, affinity-based cell separation platformcomposed of a capture substrate and a cell-releasingmolecular trigger. The capture substrate is functionalizedwith a capture antibody and a coiled-coil A. The cell-releasing molecular trigger B-PEG, a conjugate of coiled-coil B and polyethylene glycol, can drive efficient andgentle release of the captured cells. No excessive shearstress or enzymes are involved, and the released cellshave neither external molecules attached nor endogenouscell-surface molecules cleaved, which might be critical forthe viability, phenotype, and function of sensitive cells.Wei Shen laboratory
Spacer between single stranded DNA (ssDNA) and hydrophobic tail affects self-assembly, secondary
structure and binding.
Depending on the spacer used ssDNA-amphiphiles self-assemble into spherical micelles and bilayer nanotapes. The nanotapes progress from twisted nanotapes to helical nanotapes to nanotubes.
We can control the diameter and length of the ssDNA nanotubes, and we are exploring both ssDNA micelles and nanotubes for the targeted delivery of oligonucleotides.
200 nmHelical
Tube
200 nm
Twisted
Helical
Tim Pearce1 and Efie Kokkoli21Department of Biomedical Engineering
2Department of Chemical Engineering and Materials Science
Modulating Tabletability by Coating
Lab webpage: http://www.pharmacy.umn.edu/faculty/sun_changquancalvin/index.htm
0
1
2
3
4
5
6
7
Tabl
et T
ensi
le S
tren
gth
(MPa
) B
C
D
E
F
A
A
B C
D E
Osei-Yeboah & Sun, J. Pharm. Sci. , 2015
PI: Changquan Calvin Sun
70 µm
Coating Process Fundamentals — CPF
Investigator Expertise
Lorraine F. Francis* Solidification, stress development, microstructure, printing
Satish Kumar* Transport processes, interfacial phenomena, microfluidics
Marcio S. Carvalho** Fluid mechanics, rheology, numerical methods
Alon V. McCormick Curing, thermodynamics & kinetics, NMR, stress development
C. Daniel Frisbie Printing processes, printed electronics
Chris W. Macosko Rheology, polymer processing
Xiang Cheng Colloids, polymers, rheology, visualization
Michael Tsapatsis Zeolite and particulate coatings, membranes, separations
Wieslaw Suszynski*** Coating process experiments, apparatus, flow visualization
*Program Co-Leaders
**Pontifica Universidade Catolica, Rio de Janeiro
***Research Engineer and Coating Process and Visualization Laboratory Manager
Trapping of liquid may be detrimental to coating quality
Model ProblemFlow of a liquid film on rotating cylinders
r
y
StentsAuto Bodies
Contact Lenses
Challenge: Non-uniform coating thickness due to surface curvature
3D Printed Parts Lens
Imposed Surface Topography & Complex Cross-section Shape
g
Reverse Flows
Increasing Film Thickness
Smooth coatings will likely require simultaneous rotation and drying
Film Rupture
Liquid Shedding
Incr
easin
g Ro
tatio
n Ra
te
Patterned Cylinders
Slender Cylinders
Coating of Rotating Discrete Objects with Complex Surface Geometry
Weihua Li (Kumar)
Self-Aligned Capillarity-Assisted Lithography for Electronics (SCALE)*
* Mahajan, A.; Hyun, W. J. et al.Adv. Electron. Mater. 1, 1500137 (2015)A. Mahajan, W. J. Hyun (Frisbie, Francis)
Fabrication of an organic thin-film transistor (OTFT) by the SCALE process
Features of SCALE-processed OTFTs Charge carrier mobility: 0.8 ± 0.4 cm2V-1s-1
On/off current ratio: 105.3 ± 0.3
Threshold voltage: -0.3 ± 0.0 V
Nanocrystal Coatings by Aerosol Jet Printing and Compaction
Objective
Develop continuous-amenable process for nanocrystal coatings
Results
Coating morphology depends on aerosol flow rate
Nanocrystal agglomerates form a continuous coating
Compaction increases density
Thermal annealing creates the desired microstructure
Increasing carrier gas flow rate
Williams et al. ACS Applied Materials & Interfaces 2015.Bryce Williams (Francis, Aydil)
Coating Patches: Analysis of Shutdown Process
D. Maza (Carvalho)
Goal: Study the effect of process conditions and die lip design on the trailing edgeof patches coated with slot die.
Method: Solve the transient Navier-Stokes equations for free surface flows using the finite element method.
Main Result:
Minimized trailing edge on patches coated withslot coating process.
Maza D. and Carvalho M.S., AIChE Journal, submitted for publication, 2016.
Slot Coating of Particle Suspensions
R. Reboucas and I. Siqueira (Carvalho)
Goal: Evaluate effect of particle concentration and size on process limits and particle distribution and orientation on the coated film.
Method: Solve the Navier-Stokes equations for free surface flows coupled with particle concentration and conformation transport equations using the finite element method
Reboucas, Siqueira, Souza Mendes and Carvalho, JNNFM, sub., 2016
Main Result:
Accurate prediction of process limits of particle suspension coating.
Effect of flow conditions on particle distribution and alignment on coated film.
Electronic Materials and Devices (EMD)
Investigator Department ExpertiseSteven Koester* ECE (program leader) Electronic devices, semiconductors
Chris Leighton CEMS Electronic/magnetic properties, film/layer growth
Paul Crowell Physics Magnetism, transport, ultra-fast spectroscopy
Steve Campbell ECE Thin-film photovoltaics, 2D materials
Bharat Jalan CEMS Complex oxides, molecular beam epitaxy
Renata Wentzcovitch CEMS Electronic structure theory
CollaboratorsAndre Mkhoyan (CEMS), Dan Frisbie (CEMS), Xiaodong Xu (U. Washington), Ludwig Bartels (UCR), Chris Palmstrøm (UCSB), Chris Kim (ECE)
Synthesis, structural and chemical characterization of materials relevant for a wide range of electronic, optical and magnetic devices. Particular emphasis is placed on the understanding of the fundamentals of electronic structure and transport in electronic and magnetic materials, in addition to the materials science, physics and chemistry of the interfaces and nanostructures that play a vital role in device operation.
• Temperature and gate bias windows for effective gating carefully established.• Stark asymmetry in electrostatic vs. electrochemical gate response with bias polarity, with
important implications for electrolyte gating of n-type vs. p-type oxides.• Electrical control over transport, Curie temperature, etc., probed via anomalous Hall effect.
Walter, Wang, Luo, Frisbie and Leighton,Submitted, ACS Nano (2016).
• Electrolytes can be used as unconventional gate dielectrics in transistors, generating unprecedented surface charge densities, and controlling electronic and magnetic properties. This has been studied here in LSCO.
Leighton / Frisbieresearch.cems.umn.edu/leighton
Understanding Electrolyte Gating to Understand Complex Oxides: La0.5Sr0.5CoO3-δ (LSCO)
• Spin injection from Co2MnSi and Co2FeSi into GaAs and detection at room temperature. Demonstration of spin pumping and large spin Hall magneto-resistance in heterostructures based on Co2FeAl/Pt.
• Heusler alloys have important applications in memory and logic applications as well as high-sensitivity magnetic sensors.
Heusler Alloy-Based Spintronic Devices
• Developing spintronic devices based on highly-polarized Heusler alloy ferromagnets integrated with semiconductors as well as high-Z metals (e.g. Pt):
Spin pumping devicesMicrowave detection of spin accumulation
C. Liu et al., Nature Communications 7, 10296 (2016).
Crowell
2D Materials• Developed black phosphorus growth
• Developing growth system for transition metal dichalcogenides (TMDs):
SulfidesSelenidesHeterojunctions
Photovoltaics• Developed wide gap, low trap
density CuInAlGaSe process
• Developed technique to control in-situ MoSe2 orientation to prevent delamination
• Developed method for measuring interface trap density in materials with bulk traps
Energy from Valence Band (eV)
Inte
rfac
e Tr
ap D
ensi
ty (c
m-2
/eV)
Wide gap layerCu-deficient layer
Narrow gap layer
Novel Semiconductors
Campbell
• Applications in flexible electronics and thin-film solar cells.
S. A. Campbell, MRS, 2015.
SnS Nanosheets – Another “2D” Semiconductor?
• SnS is a 2D semiconductor with similar crystal structure to black phosphorus:
• Synthesized large (up to 10 µm wide and as thin as 3.5 nm) nanoplates. Raman / XRD consistent with orthorhombic SnS. applications in optoelectronics and printed electronics.
research.cems.umn.edu/aydil
5 µm
300
322
340
In
tens
ity (A
rb. U
nits
)
20 30 40 50 60 70
SnS SnS2
2θ (degrees)
Aydil
bare Cu Gr, short pre-anneal Gr, long pre-anneal0.00
0.05
0.10
0.15
0.20
Cor
rosi
on R
ate
(mm
/yr)
Material
~ 10x
Graphene Coatings for Corrosion Protection
• Developed growth process for graphene directly on copper wires:
• Used Tafel analysis to quantify corrosion rate in PBS electrolyte solution.
• Demonstrated 10x reduction in corrosion rate compared to bare Cu.
• Applications for medical electronics.
www.ece.umn.edu/users/skoester
Schematic diagram showing graphene-coated copper wire
-0.4 -0.3 -0.2 -0.1
10-7
10-6
10-5
10-4
Cur
rent
den
sity
(A/c
m2 )
Pentential vs. reference (V)
Bare Cu Gr/Cu - short pre-anneal Gr/Cu - long pre-anneal
Q. Su and S. Koester, to be published.
Koester
Faculty Member Department ExpertiseRussell J. Holmes CEMS Thin films, LEDs, solar cells
David Blank CHEM Ultrafast spectroscopy
Chris Douglas CHEM Molecular synthesis
C. Daniel Frisbie CEMS TFTs and printed electronics
P. Paul Ruden ECE Device modeling, transport theory
*Program Leader
Flexible Electronics and Photovoltaics (FEP)
Interested in the design of materials, device architectures, and processes for the realization of flexible electronics and optoelectronics based on organic
and hybrid organic-inorganic materials
NPD588.7 g/mol
Pvap~0.7-7 Pa forT=260°C-290°C
Purification of specialty electronic materials
0 10 20 30 40 50 60 700
2
4
6
8
10
12
14
16
18
Inve
rse
Sub
limat
ion
Rat
e (h
r/g)
Distance to Collection Zone (cm)
NPD
Transport
Deposition
• Thermal gradient sublimation is used in industry to purify high value, small molecule organic semiconductors
• Identified rate limited steps as transport down the tube to the deposition zone and a resistance to physical vapor deposition
• Developed model has been used to optimize separation efficiency for multicomponent feeds and predict conditions for scale-up
Morgan, N. et al. AIChE Journal, 60, 1347 (2014) and Morgan, N. et al. Org. Electron., 24, 212 (2015)
PI: Cussler, Holmes and Dow Chemical Co.
Acce
ptor
= Host Donor (SubPc)= Guest Donor (SubNc)
Broad absorbing, cascade organic solar cells
NB
N
N N
N
N
Cl
N
BN
N N
N
N
Cl
SubPc, Guest
10 nm 25 wt. % SubNc in SubPc
ITO10 nm MoOX
3 nm SubNc42 nm C60
10 nm Blocking layerAl
-0.2 0.0 0.2 0.4 0.6 0.8 1.0-10
-8
-6
-4
-2
0
2
Cur
rent
Den
sity
(mA
/cm
2 )
Voltage (V)
Neat SubNc / C60
Dilute SubNc:UGH2 / C60
Dilute SubNc:SubPc / C60
Dilute SubNc:SubPc / C70
Performance at an intensity of 100 mW/cm2 under AM 1.5G solar simulated illumination
Host Acceptor ηP [%]
None C60 2.0 ± 0.1
None C70 2.2 ± 0.1
UGH2(Non-absorbing) C60 2.8 ± 0.1
SubPc C60 3.2 ± 0.1
SubPc C70 4.3 ± 0.2
SubNc, Host
• SubPc and SubNc have complementary optical absorption
• Excitons are generated on both materials with transport occurring on SubNc – Energy cascade between SubPc and SubNc
• Diffusion on SubNc can be engineered via dilution
Performance of host-guest cascade cell exceeds that of conventional devices that do not use a composite donor layer as well as those with a non-absorbing host
Menke, S.M. and Holmes, R.J., ACS Appl. Mater. Interfaces, 7, 2912 (2015)
PI: Holmes
2 µm 1 µm
SEM cross-sections showing Ag seed layer on the channel walls(left) anda channel completely filled with Cu metal (right)
Ag seed layer Electroless Plated Cu Line width and spacing down
to 2 µm Conductivity 60 % of bulk
metal Additive Roll-to-roll compatible
Major Process Attributes
New Approach for High-Resolution Printed Electronics
Inkjet-printed Ag ink is wicked into microimprinted channels on a plastic substrate, followed by a Cu electroless plating step. Ag metal inside the channel acts as a seed layer for selective deposition of Cu .
Mahajan, A. et al. ACS Appl. Mater. Interfaces 7, 1841-1847 (2015)
PI: Frisbie and Francis (CPF)
Unwind Coating Imprint Metrology Rewind
• Manufactured by Carpe Diem Technology
• Line Speed: 4-800 inches per minute
• Web Width: 4-6 inches
R2R Nanoimprint at Minnesota
Second R2R Line: Multimaterials, Slot, Gravure, Aerosol Jet
•Forward – reverse operation, multiple web paths
•Fully enclosed, HEPA filtered air
Unwind
Aerosol jet and drop on demandprinter
Gravure printing
Photonic sintering unit
Rewind
Slot coating
4 ft
IR heater
Corona
Microstructured Polymers (MP)
Investigator Department ExpertiseFrank S. Bates CEMS Thermodynamics, scattering, synthesis
Marc A. Hillmyer* CHEM Polymer synthesis and characterization(Director: Polymer Synthesis Facility)
Timothy P. Lodge CHEM/CEMS Polymer dynamics, solutions, scattering
Chris Macosko CEMS Rheology, processing
Mahesh Mahanthappa CEMS Synthesis, morphology, self-assembly
David C. Morse CEMS Theory and modeling
Theresa Reineke CHEM Biomedicine, Diagnostics, Targeted Delivery
Collaborators include:Lorraine Francis (CEMS), Dan Frisbie (CEMS), Tom Hoye (CHEM), Chris Leighton (CEMS), Ron Siegel (PHRM), Bill Tolman (CHEM)
*Program Leader
Synthesis, characterization, dynamics, processing, properties, and theory
Toughening Poly(lactide) with Block Copolymer Micelles
Tuoqi Li, Jiuyang Zhang, Deborah K. Schneiderman, Lorraine Francis and Frank S. Bates (ACS Macro Letters 2016)
1 µm
5 wt% EB-1
• Low molecular weight poly(ethylene oxide)-b-poly(butylene oxide) (EB) diblock copolymer forms micelles in poly(L-lactide) (PLLA)
EB diblock copolymer
PLLA
Izod impact strength Tensile strength
• Dispersion of micelles in PLLA is due to a negative χ parameter between poly(ethylene oxide) and PLLA.
• Micelles impart outstanding impact and tensile toughness at relatively low loadings without compromising modulus, Tg or optical clarity
33
0.2 μm
2000 3000 4000 5000
Cou
nts
Energy (eV)
SnLα
SnLβ
interface
inclusion
PLA
HDPE
Thurber Lodge, Macosko, ACS Macro Letters, 2015, 1, 30-33
60 / 30 / 10 / 0.4 HDPE / HO-PE-OH / PLA / SnOct2
1 μm
d = 0.26 ± 0.04 μm
1 μm
90 / 10 HDPE / PLA
d = 0.77 ± 0.20 μm
1 μm
TEM +EDS
Catalyst Localized at Interface in Polymer Blends
Versatile ion gels for plastic electronics
Choi, Gu, Hong, Xie, Frisbie, and Lodge, ACS Appl. Mater. Int., 6, 19275-19281 (2014)Moon, Lodge, and Frisbie, Chem. Mater., 26, 5358-5364 (2014)Moon, Lodge, and Frisbie, Chem. Mater. 27, 1420-1425 (2015) Ueki, Nakamura, Usui, Kitazawa, So, Lodge, and Watanabe, Angew. Intl. Ed., 54, 3018-3022 (2015)Choi, Xie, Gu, Frisbie, and Lodge, ACS Appl. Mater. Interfaces, ASAP (2015)
ABA triblock copolymers swollen with ionic liquids are excellent candidates for organictransistor gate dielectrics, polymer gel electrolytes, and luminescent devices, among others.This versatility stems from a combination of attributes, including tunable mechanical strength,high throughput printability, high ionic conductivity, high capacitance, and thermal stability.
Electrochromic ion gel operating at only 1 V. Methyl viologen is the chromophore, in an ion gel containing PS-PMMA-PS and [EMI][TFSI]
(H. C. Moon)
Photoreversible ion gel consisting of P(NIPAm-ran-AzoMA)-PMMA-P(NIPAm-ran-AzoMA) in [EMI][PF6], operating under alternating UV and visible irradiation (T. Ueki)
PCHE–PEO Block Polymer for Metal Oxide Templating
Schulze, Sinturel, & HillmyerACS Macro Lett., 4, 1027, 2015
2. Selectively Deposit Inorganic Precursors within PEO domain
3. Oxidize Inorganic and Remove BP Template
UV/Ozone
Spincoat Inorganic Precursor Solution
1. Solvent anneal PCHE–PEO Film
PS–PEO
On O
Hm
PCHE–PEO
On O
Hm
Approach• Anionic polymerization and hydrogenation for the
synthesis of new block polymer PCHE-PEO
• PEO selectively imbibes sol-gel reactants/metal ions
Outcome• Large χ enabled self-assembly at low N
• Formation of ultra-small particles (6 ± 1 nm)
• Versatile templating of silica, iron oxide, titania
100 nm
TiO2 Particles
Highlighted in MRS Bulletin, 11, 900, 2015.
Elastomers and PSAs from Isosorbide-Based Block Polymers
J. J. Gallagher, M. A. Hillmyer, T. M. Reineke, ACS Sustainable Chem. Eng. 2015, 2016 University of Minnesota, Department of Chemistry
OO
BTCBA, AIBN
AAI, AIBN OOO
OO
O O
OH
H
Z
O O O
OO
OO
OH
H
ZR
OO
Z
O O
ZR
OHO
O
O
O
OS S
S
SS
S 1010
BTCBA
70 °C, 2 h
DMF, 70 °C, 2h
PolymerMn, th. Mn, SEC Mn, NMR Đ wt% PAAI
(kg/mol) (kg/mol) (kg/mol) (NMR)PAAI-PnBA-PAAI
(53k, 12%) 51.7 53.3 49.8 1.09 12
PAAI-PnBA-PAAI (60k, 17%) 56.1 60.2 65.6 1.12 17
PAAI-PnBA-PAAI(70k, 21%) 59.5 69.2 67.5 1.15 21
PSA Peel Test
Nanostructural Materials and Processes (NMP)
Investigator Department ExpertiseAlon McCormick CEMS Materials and Emulsions Synthesis; Spectroscopy and
CryoMicroscopyC. Daniel Frisbie CEMS Molecular Materials and Interfaces; Molecular
ElectronicsWayne Gladfelter CHEM Materials Chemistry; Inorganic Chemistry; Scanning
Probe MicroscopyGreg Haugstad CHARFAC AFM Scanning Probe Microscopy
(Director, Characterization Facility)R. Lee Penn CHEM Environmental Solid State ChemistryIlja Siepmann CHEM Predictive Modeling of Phase and Sorption EquilibriaAndreas Stein CHEM Solid State Chemistry of Porous MaterialsMichael Tsapatsis CEMS Materials Synthesis, Structure Elucidation Joe Zasadzinski CEMS Microscopy of Complex Fluids
Associated Investigators: Frank Bates, Lorraine Francis, Christy Haynes, Eric Kaler, Chris Macosko, Wei Zhang
synthesis, phase behavior, structure, and performance of surfactants and self-assembled molecular and colloid systems
Contact-mode height image… (steric, “frictionless” contact)
In situ colloid probe AFM: “Hyperspectral” force mapping methods (here on crosslinked, oriented fibrin gel) Haugstad (Anne Ellis, Bob Tranquillo)
blue green
yellow
redorange
Elasticity histogram
Young’s modulus (MPa)
Hertzian modelR = 3.3 um probek = 0.08 N/m cantilever
Topography
Young’s Modulus
interlaced with force spectroscopy
Hysteresis: modulus correlation“Force spectroscopy”: Normal force vs. Z
Soft location Stiff location
84-nm shear-modulation, 100 Hz
Shear force
6.6 um
Mechanical hysteresis loops
Goal: Quantify mechanical anisotropyNeed: hyperspectral dataset analysis (large)
Simultaneously: shear response
Guido and Tranquillo, “A methodology for the systematic and quantitative study of cell contact guidance in oriented collagen gels…”, J Cell Sci, 1993
Morin and Tranquillo, “Guided sprouting from endothelial spheroids in fibrin gels aligned by magnetic fields and cell-induced gel compaction”, Biomaterials, 2011
32x32 = 1024 sites over 20x20 μm image
2.Surfactant mixtures for dispersionExample: Span 80 effect on crude oil dispersion
Dispersion processes (McCormick group with collaborators)
1. Cryo-EM Monitoring
Multi-lamellar
Lee, H.; Morrison, E.; Frethem, C.; Zasadzinski, J.; and McCormick, A. Cryogenic electron microscopy study of nanoemulsion formation from microemulsions, Langmuir, 2014, 30 (36), 10826-10833. doi: 10.1021/la502207f
Example of nanoemulsion with non-ionic surfactant
Lee, H.; Arunagirinathan, M.; Vagias, A.; Lee, S.; Bellare, J.; Davis, H.; Kaler, E.; McCormick, A.; and Bates, F. Almost Fooled Again: New Insights into Cesium Dodecyl Sulfate Micelle Structures, Langmuir, 2014, 30 (43). 12743-12747. doi:10.1021/la502809y
Riehm, D.; McCormick, A. The role of dispersants’ dynamic interfacial tension in effective crude oil spill dispersion. Mar. Pollut. Bull., 2014, 84, 155-163. doi:10.1016/j.marpolbul.2014.05.018
0102030405060708090
0.0001
0.001
0.01
0.1
1
0 10 20 30 40 50 60
Effe
ctiv
enes
s (%
)
Initi
al
wt% Span 80
OPT
IMU
M
Inte
rfac
ial T
ensi
on (m
N/m
)
10wt% 50wt% 60wt%
Dyna
mic
cree
p ov
er m
inut
es
Sphere (ellipsoids) to cylinder transition
Characterizing the dynamics of aggregation in reactive systems (PENN)
pH 3.5
pH 5.5
CRYO-TEM images of nanoparticles in liquid media.
WATER
WATER: after aging.
TetrahydrofuranIsopropanol
Burrows, Talmon, Penn; 2013
Yuwono, Burrows, Soltis, Penn (JACS, 2010)
Yuwono, Burrows, Soltis, Penn(Faraday Trans 2012)
U60 clustersin waterSoltis et al., JACS, 2016
Predictive Modeling of Separation Processes and Nanostructured Materials– Siepmann
Funding from NSF (CBET, CHE, SI2), DOE (MGI, SciDAC, EFRC, EERE), Industry & IPRIMEDiscovery of Zeolites for Sweetening of Sour Natural Gas•Hierarchical screening of all known zeolites for binary H2S/CH4 and H2S/C2H6 mixtures and of 16 top--performing zeolites for four-- and five--component mixtures•Simula'ons yield direct informa'on on selec'vity, capacity & number of adsorp'on stagesShah, Tsapatsis & Siepmann, Angew. Chem. Intl. Ed. 55, 5938 (2016)
AngewandteChemie
5938
International Edition: DOI: 10.1002/anie.201600612 H2S Capture
Identifying Optimal Zeolitic Sorbents for Sweetening of Highly Sour Natural GasMansi S. Shah, Michael Tsapatsis, and J. Ilja Siepmann*
AngewandteChemieCommunications
⌫ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2016, 55, 5938 –5942
Understanding Transport in Hierarchical Zeolites• MD elucidate the complex diffusion of sorbates in house--of--cards
nanosheets where the large free energy penalty for transfer frommicropores to mesopores leads to a tortuous diffusion pathway
Bai, …, Tsapatsis & Siepmann, ACS Nano, submi9ed
Sensitivity of Nucleation FreeEnergies to Force Fields•This work demonstrates that the sensi'vity of predicted nuclea'on rates to details of the molecular models can be dramatically reduced by comparing nucleation at the same relative state pointKeasler & Siepmann, J. Chem. Phys. 143, 164516 (2015)
Industrial Fellows
2016
IPrime Industrial Fellows (8)
Company Employee Research Topic Faculty
Asahi Kasei Ryo Katayama Effect of Drying Conditions on Particle Distribution Lorraine Francis/ Satish Kumar
Boston Scientific Bruce Forsyth High sensitivity alpha-particle detectors Steve Koester
Dai Nippon Printing Koichi Nakano Coating flow of non-Newtonian liquid in tensioned-web-over-
slot die coatingLorraine Francis/
Satish Kumar
Ecolab Stephan Hubig Evaluation of Nano Coatings for Surface Modification: Development of a tool kit for performance testing Alon McCormick
Evonik Industries Alex Todd Synthesis and self-assembly of model semi-crystalline blockpolymers Marc Hillmyer
Medtronic Carl Schu Ion Sensor applications to new products Andreas Stein
Toray Yu Abe An Analysis of the Drying State in Multi-layer Coating Xiang Cheng/Lorraine Francis
Valspar Tessie Panthani Film Formation and Stress Development Lorraine Francis
Industrial Fellow
Ryo KatayamaAsahi Kasei
IPrime ProgramCoating Process Fundamentals
Faculty Sponsors Satish Kumar & Lorraine Francis
Effect of drying conditions on particle distribution
IPrime ProgramElectronic Materials and Devices
Faculty SponsorSteve Koester
Research ProjectHigh sensitivity alpha-particle detectors
Industrial Fellow
Bruce ForsythBoston Scientific
PhotoPending
IPrime ProgramCoating Process Fundamentals
Faculty SponsorSatish Kumar &Lorraine Francis
Research ProjectCoating flow of non-Newtonian liquid in tensioned-web-over-slot die coating
Industrial Fellow
Koichi NakanoDai Nippon Printing
IPrime ProgramNanostructural Materials and Processes
Faculty SponsorsAlon McCormick
Research ProjectEvaluation of nano coatings for surface modification: development of a tool kit for performance testing
Industrial Fellow
Stephan HubigEcolab
IPrime ProgramMicrostructured Polymers
Faculty SponsorMarc Hillmyer
Research ProjectSynthesis and self-assembly of model semi-crystalline block polymers
Industrial Fellow
Alex ToddEvonik Industries
IPrime ProgramNanostructural Materials Processes
Faculty SponsorAndreas Stein
Research ProjectIon Sensor applications to new products
Industrial Fellow
Carl SchuMedtronic
IPrime ProgramCoating Process Fundamentals
Faculty SponsorXiang Cheng & Lorraine Francis
Research ProjectAn analysis of the drying state in multi-layer coating
Industrial Fellow
Yu AbeToray
IPrime ProgramCoating Process Fundamentals
Faculty SponsorLorraine Francis
Research ProjectFilm formation and stress development
Industrial Fellow
Tessie PanthaniValspar
PhotoPending