Research Areas

The Berrie lab investigates how the properties of materials are influenced by nanoscale modification of the composition or topography of the materials. The overarching goal of our work is to elucidate the factors that control these properties at the nanoscale to enable the design of materials with specific capabilities. This work has covered a wide range of materials and applications including sensing, molecular electronics, photovoltaic devices, and catalysis. In order to investigate the nanoscale variation in properties, we use scanning probe methods to not only measure the topography, but also to manipulate the materials at the nanoscale to create nanoscale patterns in either the chemistry or topography. In addition, the heterogeneity of the materials properties such as friction, electrical conductivity, and surface potential is mapped concurrently with the topography. While scanning probe methods of nanoscale fabrication allow precise fabrication of features in nearly any pattern, they are relatively slow, and therefore we have also investigated methods for creating metal nanostructures using particle lithography-based methods. Some of the recent projects in the group are highlighted in the sections below.

Fabrication of Materials at the Nanoscale

Our group has developed methods for the fabrication of metal nanostructures with precise control over size, shape, spacing, and exact relative position. These methods have included the use of both AFM- and particle lithography-based methods for the fabrication of features from a few nanometers to microns in dimension. The goal of this work is development of nanostructured platforms that can be used both for fundamental investigations and applications including sensing, cell signaling, electronics, and photovoltaics.

Images of metal nanodots fabricated using particle lithography, metal nanowires created with AFM-based methods, a nanoscale KU fabricated using the AFM, and metal nanostructures created with novel salt-based resist materials.

 

Ulapane, S. B.; Doolin, J. L.; Okeowo, M. K.; Berrie, C. L., Atomic Force Microscopy-Based Static Plowing Lithography Using CaCO3 Nanoparticle Resist Layers as a Substrate-Flexible Selective Metal Deposition Resist, J. Phys. Chem. C 2021, 125 (42), 23490-23500.

Edwards, C. M.; Ulapane, S. B.; Kamathewatta, N. J. B.; Ashberry, H. M.; Berrie, C. L.* Fabrication and Growth Control of Metal Nanostructures through Exploration of Atomic Force Microscopy-Based Patterning and Electroless Deposition Conditions, J. Phys. Chem. C 2020, 124, 25588–25601.

Ulapane, S. B.; Kamathewatta, N. J. B.; Borkowski, A. K.; Steuart, S. J.; Berrie, C. L.* Periodic Silver and Gold Nanodot Array Fabrication on Nanosphere Lithography-Based Patterns using Electroless Deposition, J. Phys. Chem. C 2020, 124, 15646–15655.

Protein Immobilization at Interfaces

In collaboration with Prof. Candan Tamerler (KU Mechanical Engineering) and Prof. Mark Richter (KU Molecular Biosciences) the Berrie group has been investigating the use of genetically engineered peptides for the immobilization of enzymes at interfaces. These combinatorially selected short peptide sequences have a high affinity for a particular material and can therefore in principle be used for the selective immobilization of biomolecules at interfaces. We have demonstrated that not only the amount of adsorption, but also the conformation or orientation of the enzyme at the interface can be significantly altered by incorporation of a small gold binding peptide sequence . As part of an NSF funded project, we are investigating the use of such peptides to coassemble multiple enzymes for the potential investigation of cascade enzyme activity, and what factors affect the coupled activity of systems of enzymes. Coupled with the nanostructure fabrication work, this allows a detailed investigation of the assembly and activity of such systems as a function of spacing between enzymes, the details of the environment around the enzyme, and also the shape and curvature of the nanoscale immobilization sites. We are also investigating the influence of the peptide sequence as well as the spacer length in the assembly of not only the peptide itself, but also the peptide labelled enzymes.

 

AFM images showing the changes in binding of putrescine oxidase to a gold surface upon incorporation of a gold binding peptide tag.

 

We have also applied these principles to the immobilization of multidomain enzymes such as the F1-ATPase to allow for the immobilization of functionally active motor proteins at interfaces and developed a widely applicable method for the use of his tags on enzymes to be used for the selective immobilization of enzymes. In another collaborative project with Prof. Paulette Spencer, we have used a variety of methods to probe the surface composition of dental polymer adhesives and control their properties, including engineering for enzyme inhibition which is thought to contribute to the degradation of the material. 

Kamathewatta, N. J. B.; Nguyen, T. M.; Lietz, R.; Hughes, T.; Taktak Karaca, B.; Deay, D. O.; Richter, M. L.; Tamerler, C.*; Berrie, C. L.* Probing Selective Self-Assembly of Putrescine Oxidase with Controlled Orientation Using a Genetically Engineered Peptide Tag, Langmuir 2021, 37, 7536–7547. 

Kamathewatta, N. J. B.; Deay III, D. O.; Karaca, B. T.; Seibold, S.; Nguyen, T. M.; Tomás, B.; Richter, M. L.; Berrie, C. L.*; Tamerler, C.* Self-Immobilized Putrescine Oxidase Biocatalyst System Engineered with a Metal Binding Peptide, Langmuir 2020, 36, 11908-11917.

Tucker, J. K.; McNiff, M. L.; Ulapane, S. B.; Spencer, P.; Laurence, J. S.; Berrie, C. L.* Mechanistic Investigations of Matrix Metalloproteinase-8 Inhibition by Metal Abstraction Peptide, Biointerphases 2016, 11, 021006.

Dixit, N.; Settle, J. K.; Ye, Q.; Berrie, C. L.; Spencer, P.; Laurence, J. S.* Grafting MAP Peptide to Dental Polymer Inhibits MMP-8 Activity, J. Biomed. Mater. Res. B: Appl. Biomater. 2015, 103, 324-331.

Optoelectronic Properties of Materials

The effect of nanoscale structure on the optoelectronic properties of materials have been investigated in a number of projects in the Berrie group. In collaboration with Prof. Judy Wu (KU Physics) we have demonstrated that both the nanoscale topography and local chemical modification influence both the electronic and optical properties of graphene. We are currently investigating the local heterogeneity of electronic properties of graphene and graphene like materials and the nanoscale changes in the electronic properties induced in the graphene due to local doping of the materials upon adsorption of small molecules such as the exquisitely tunable substituted azulenes synthesized by our collaborator, Prof. Mikhail Barybin’s (KU Chemistry) laboratory. Use of such molecules for molecular electronics applications is of longstanding interest, and the assembly of azulene-based molecules through either thiol or isocyano junction groups at gold surfaces has been investigated extensively. 

Applegate, J. C.; Okeowo, M. K.; Erickson, N. R.; Neal, B. M.; Berrie, C. L.; Gerasimchuk, N. N.; Barybin, M. V.* First π-Linker Featuring Mercapto and Isocyano Anchoring Groups within the Same Molecule: Synthesis, Heterobimetallic Complexation and Self-assembly on Au(111), Chem. Sci. 2016, 7, 1422-1429. 

Liu, J.; Xu, G.; Rochford, C.; Lu, R.; Wu, J.; Edwards, C. M.; Berrie, C. L.; Chen, Z.; Maroni, V. A.* Doped Graphene Nanohole Arrays for Flexible Transparent Conductors, Appl. Phys. Lett. 2011, 99, 023111.

Sensors and Catalysis

In collaboration with Prof. Judy Wu (KU Physics) and her research group we have carried out measurements to aid in the understanding of the properties of both 2D chalcogenide and carbon nanotube based sensors. Detailed measurements of the sizes and distribution of such materials in functional sensors at the nanoscale is critical in understanding their sensing and catalytic activity. In addition, we have coupled UHV SPM characterization directly to growth chambers where state of the art devices are fabricated using ALD and MBE methods for detailed in situ characterization of the materials at each step of the growth process.

Ghopry, S. A.; Sadeghi, S. M.; Berrie, C. L.; Wu, J. Z., MoS2 Nanodonuts for High-Sensitivity Surface-Enhanced Raman Spectroscopy. Biosensors (Basel) 2021, 11 (12)

Alamri, M; Liu, B.; Walsh, M.; Doolin, J. L.; Berrie, C. L.; Wu, J. Z.* Enhanced H2 Sensitivity in Ultraviolet-activated Pt Nanoparticle/SWCNT /Graphene Nanohybrids, IEEE Sensors Journal, 2021, 21, 19762-19770.

Liu, B.; Alamri, M.; Walsh, M.; Doolin, J. L.; Berrie, C. L.; Wu, J. Z.* Development of an ALD-Pt@SWCNT/Graphene 3D Nanohybrid Architecture for Hydrogen Sensing, ACS Appl. Mater. Interfaces 2020, 12, 53115-53124.