| 1. |
- Adam, Stefan, et al.
(författare)
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Quartz crystal microbalance with coupled Spectroscopic Ellipsometry-study of temperature-responsive polymer brush systems
- 2017
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Ingår i: Applied Surface Science. - : ELSEVIER SCIENCE BV. - 0169-4332 .- 1873-5584. ; 421, s. 843-851
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Tidskriftsartikel (refereegranskat)abstract
- Using a combined setup of quartz crystal microbalance with dissipation monitoring together with spectroscopic ellipsometry, the thermo-responsive behavior of two different brush systems (poly(N-isopropyl acrylamide) and poly(2-oxazoline)s) was investigated and compared to the behavior of the free polymer in solution. Poly(2-oxazoline)s with three different hydrophilicities were prepared by changing the content of a hydrophilic comonomer. While both polymer types exhibit a sharp, discontinuous thermal transition in solution, in the brush state the transition gets broader in the case of poly(N-isopropyl acrylamide) and is transformed into a continuous transition for poly(2-oxazoline)s. The position of the transition in solution is influenced by the degree of hydrophilicity of the poly(2-oxazoline). The difference in areal mass detected by quartz crystal microbalance and by spectroscopic ellipsometry, has been attributed to the chain segment density profile of the polymer brushes. Applying this density profile information, for poly(N-isopropyl acrylamide) two different swelling stages could be identified, while for poly(2-oxazoline) the transition between a parabolic and more step-wise profile is found continuous. The different swelling characteristics were attributed to the different miscibility behavior types, with the brush state acting similar to a crosslinked system. (C) 2017 Elsevier B.V. All rights reserved.
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| 2. |
- Bittrich, Eva, et al.
(författare)
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Morphology of Thin Films of Aromatic Ellagic Acid and Its Hydrogen Bonding Interactions
- 2020
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Ingår i: The Journal of Physical Chemistry C. - : AMER CHEMICAL SOC. - 1932-7447 .- 1932-7455. ; 124:30, s. 16381-16390
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Tidskriftsartikel (refereegranskat)abstract
- Ellagic acid (EA), an antioxidant from fruits or other plants, has recently evoked interest in the field of organic electronics because of its weak electron donor properties. In this work, the preparation of uniaxial pi-stacked EA films by thermal evaporation on different surfaces is reported for the first time. The (102) lattice plane of the pi-electron system was confirmed as the contact plane for one monolayer equivalent on Ag(111) by low-electron energy diffraction. X-ray and atomic force microscopy measurements revealed nanocrystalline grains with an average inplane size of 50 nm and considerably smaller average out-of-plane crystallite sizes (16-25 nm) in films of 16-75 nm thickness. The influence of different substrates was minor compared to the effect of the film thickness. An increase in the in-plane density of grains at larger film thicknesses was deduced from the trend in their uniaxial optical properties. Weak and strong intermolecular H-bonding interactions were identified in the EA crystal lattice, while a surplus of weak H-bonding was observed for the nanocrystallites in thin films, as compared to bulk EA. Finally, EA was coevaporated with the semiconducting thiophene molecule DCV4T-Et-2 to demonstrate principle interactions with a guest molecule by H-bonding analysis. Our results illustrate the feasibility of applying EA films as alignment layers for templating other semiconducting organic films used in organic electronic devices.
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| 3. |
- Chae, Soosang, et al.
(författare)
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Stretchable Thin Film Mechanical-Strain-Gated Switches and Logic Gate Functions Based on a Soft Tunneling Barrier
- 2021
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Ingår i: Advanced Materials. - : Wiley-Blackwell. - 0935-9648 .- 1521-4095. ; 33:41
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Tidskriftsartikel (refereegranskat)abstract
- Mechanical-strain-gated switches are cornerstone components of material-embedded circuits that perform logic operations without using conventional electronics. This technology requires a single material system to exhibit three distinct functionalities: strain-invariant conductivity and an increase or decrease of conductivity upon mechanical deformation. Herein, mechanical-strain-gated electric switches based on a thin-film architecture that features an insulator-to-conductor transition when mechanically stretched are demonstrated. The conductivity changes by nine orders of magnitude over a wide range of tunable working strains (as high as 130%). The approach relies on a nanometer-scale sandwiched bilayer Au thin film with an ultrathin poly(dimethylsiloxane) elastomeric barrier layer; applied strain alters the electron tunneling currents through the barrier. Mechanical-force-controlled electric logic circuits are achieved by realizing strain-controlled basic (AND and OR) and universal (NAND and NOR) logic gates in a single system. The proposed material system can be used to fabricate material-embedded logics of arbitrary complexity for a wide range of applications including soft robotics, wearable/implantable electronics, human-machine interfaces, and Internet of Things.
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| 4. |
- Ferrand-Drake Del Castillo, Gustav, 1990, et al.
(författare)
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Enzyme Immobilization in Polyelectrolyte Brushes: High Loading and Enhanced Activity Compared to Monolayers
- 2019
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Ingår i: Langmuir. - : American Chemical Society (ACS). - 1520-5827 .- 0743-7463. ; 35:9, s. 3479-3489
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Tidskriftsartikel (refereegranskat)abstract
- Catalysis by enzymes on surfaces has many applications. However, strategies for efficient enzyme immobilization with preserved activity are still in need of further development. In this work, we investigate polyelectrolyte brushes prepared by both grafting-to and grafting-from with the aim to achieve high catalytic activity. For comparison, self-assembled monolayers that bind enzymes with the same chemical interactions are included. We use the model enzyme glucose oxidase and two kinds of polymers: anionic poly(acrylic acid) and cationic poly(diethylamino)methyl methacrylate. Surface plasmon resonance and spectroscopic ellipsometry are used for accurate quantification of surface coverage. Besides binding more enzymes, the "3D-like" brush environment enhances the specific activity compared to immobilization on self-assembled monolayers. For grafting-from brushes, multilayers of enzymes were spontaneously and irreversibly immobilized without conjugation chemistry. When the pH was between the pI of the enzyme and the pK a of the polymer, binding was considerable (thousands of ng/cm 2 or up to 50% of the polymer mass), even at physiological ionic strength. However, binding was observed also when the brushes were neutrally charged. For acidic brushes (both grafting-to and grafting-from), the activity was higher for covalent immobilization compared to noncovalent. For grafting-from brushes, a fully preserved specific activity compared to enzymes in the liquid bulk was achieved, both with covalent (acidic brush) and noncovalent (basic brush) immobilization. Catalytic activity of hundreds of pmol cm -2 s -1 was easily obtained for polybasic brushes only tens of nanometers in dry thickness. This study provides new insights for designing functional interfaces based on enzymatic catalysis.
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| 5. |
- Kananizadeh, Negin, et al.
(författare)
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Visualization of label-free titanium dioxide nanoparticle deposition on surfaces with nanoscale roughness
- 2019
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Ingår i: ENVIRONMENTAL SCIENCE-NANO. - : ROYAL SOC CHEMISTRY. - 2051-8153 .- 2051-8161. ; 6:1, s. 248-260
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Tidskriftsartikel (refereegranskat)abstract
- Understanding the transport of engineered nanoparticles (ENPs) and their interaction with environmental surfaces is critical to predicting their fate and environmental implications. Here, we report an innovative technique to visualize and quantify the deposition of titanium dioxide nanoparticles (TiO2NP) on engineered surfaces with nanoscale roughness, i.e., slanted columnar thin films (SCTFs). The attachment of TiO2NP on the surface of SCTFs changed the optical property of SCTFs, which was detected using a generalized ellipsometry (GE)-based instrument, an anisotropy contrast optical microscope (ACOM). An anisotropic effective medium model was applied to quantitatively analyze ACOM images of SCTF surfaces, which provided the mass distribution of TiO2NP. The TiO2NP mass measured by ACOM was in good agreement with the known amount of TiO2NP mass dispersed by controlled piezoelectric plotting. The detection of a few picograms of nanoparticle mass by an individual pixel measuring 7 x 7-micrometer squared was demonstrated. Further, a glass microfluidic channel with SCTF embedded was developed. The areal mass density of attached TiO2NP on SCTF surfaces as they flow through the channel under various flow rates was quantitatively measured in situ. At the end of the experiment, the distribution of the attached TiO2NP on the SCTF surface was visualized. The averaged mass density estimated by integrating the distribution map was in close agreement with the estimation from dynamic measurements and between repeating experiments. The capability of this novel technique to sense, quantify and visualize the mass distribution of TiO2NP provides a valuable approach to investigate the behavior of nanoparticles at the interface of flow and rough surfaces.
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| 6. |
- Koenig, Meike, et al.
(författare)
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Salt Sensitivity of the Thermoresponsive Behavior of PNIPAAm Brushes
- 2018
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Ingår i: Langmuir. - : AMER CHEMICAL SOC. - 0743-7463 .- 1520-5827. ; 34:7, s. 2448-2454
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Tidskriftsartikel (refereegranskat)abstract
- We report investigations on the salt sensitivity of the thermoresponsive behavior of PNIPAAm brushes applying the quartz crystal microbalance coupled with spectroscopic ellipsometry technique. This approach enables a detailed study of the optical and mechanical behavior of the polymer coatings. Additional conclusions can be drawn from the difference between both techniques due to a difference in the contrast mechanism of both methods. A linear shift of the phase transition temperature to lower temperatures with the addition of sodium chloride was found, similar to the behavior of free polymer chains in solution. The thermal hysteresis was found to be decreased by the addition of sodium chloride to the solution, hinting to the interaction of the ions with the amide groups of the polymer, whereby the formation of hydrogen bonds is hindered. The results of this study are of relevance to the application of PNIPAAm brushes in biological fluids and demonstrate the additional potential of the ion sensitivity besides the better known thermosensitivity.
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| 7. |
- Mantz, Amy, et al.
(författare)
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Free Polyethylenimine Enhances Substrate-Mediated Gene Delivery on Titanium Substrates Modified With RGD-Functionalized Poly(acrylic acid) Brushes
- 2019
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Ingår i: Frontiers in Chemistry. - : FRONTIERS MEDIA SA. - 2296-2646. ; 7
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Tidskriftsartikel (refereegranskat)abstract
- Substrate mediated gene delivery (SMD) is a method of immobilizing DNA complexes to a substrate via covalent attachment or nonspecific adsorption, which allows for increased transgene expression with less DNA compared to traditional bolus delivery. It may also increase cells receptivity to transfection via cell-material interactions. Substrate modifications with poly(acrylic) acid (PM) brushes may improve SMD by enhancing substrate interactions with DNA complexes via tailored surface chemistry and increasing cellular adhesion via moieties covalently bound to the brushes. Previously, we described a simple method to graft PM brushes to Ti and further demonstrated conjugation of cell adhesion peptides (i.e., RGD) to the PM brushes to improve biocompatibility. The objective of this work was to investigate the ability of Ti substrates modified with PM-RGD brushes (PM-RGD) to immobilize complexes composed of branched polyethyleneimine and DNA plasmids (bPEI-DNA) and support SMD in NIH/3T3 fibroblasts. Transfection in NIH/3T3 cells cultured on bPEI-DNA complexes immobilized onto PM-RGD substrates was measured and compared to transfection in cells cultured on control surfaces with immobilized complexes including Flat Ti, PM brushes modified with a control peptide (RGE), and unmodified PM. Transfection was two-fold higher in cells cultured on PM-RGD compared to those cultured on all control substrates. While DNA immobilization measured with radiolabeled DNA indicated that all substrates (PM-RGD, unmodified PM, Flat Ti) contained nearly equivalent amounts of loaded DNA, ellipsometric measurements showed that more total mass (i.e., DNA and bPEI, both complexed and free) was immobilized to PM and PM-RGD compared to Flat Ti. The increase in adsorbed mass may be attributed to free bPEI, which has been shown to improve transfection. Further transfection investigations showed that removing free bPEI from the immobilized complexes decreased SMD transfection and negated any differences in transfection success between cells cultured on PM-RGD and on control substrates, suggesting that free bPEI may be beneficial for SMD in cells cultured on bPEI-DNA complexes immobilized on PM-RGD grafted to Ti. This work demonstrates that substrate modification with PM-RGD is a feasible method to enhance SMD outcomes on Ti and may be used for future applications such as tissue engineering, gene therapy, and diagnostics.
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