Skip directly to content

Minimize RSR Award Detail

Research Spending & Results

Award Detail

Awardee:THE UNIVERSITY OF AKRON
Doing Business As Name:University of Akron
PD/PI:
  • Ali N Dhinojwala
  • (330) 972-6246
  • ali4@uakron.edu
Award Date:05/16/2011
Estimated Total Award Amount: $ 500,000
Funds Obligated to Date: $ 500,000
  • FY 2011=$125,000
  • FY 2013=$125,000
  • FY 2012=$125,000
  • FY 2014=$125,000
Start Date:06/01/2011
End Date:05/31/2016
Transaction Type:Grant
Agency:NSF
Awarding Agency Code:4900
Funding Agency Code:4900
CFDA Number:47.049
Primary Program Source:040100 NSF RESEARCH & RELATED ACTIVIT
Award Title or Description:Understanding Acid-Base Interactions using Interface-Sensitive Spectroscopy
Federal Award ID Number:1105370
DUNS ID:045207552
Parent DUNS ID:045207552
Program:POLYMERS
Program Officer:
  • Andrew Lovinger
  • (703) 292-4933
  • alovinge@nsf.gov

Awardee Location

Street:302 Buchtel Common
City:Akron
State:OH
ZIP:44325-0001
County:Akron
Country:US
Awardee Cong. District:11

Primary Place of Performance

Organization Name:University of Akron
Street:302 Buchtel Common
City:Akron
State:OH
ZIP:44325-0001
County:Akron
Country:US
Cong. District:11

Abstract at Time of Award

TECHNICAL SUMMARY The objective of this NSF project is to exploit the interface sensitivity of infrared-visible sum frequency generation spectroscopy (SFG) to measure acid-base interactions at solid-solid interfaces. An understanding of polar interactions is important in the areas of adhesion, friction, and wetting. In-situ characterization of acid-base interactions and their role in adhesion of these coatings at the molecular level and under kinetic conditions (for example: during sliding and mechanical contact) pose a formidable challenge to scientists. The principal investigator (PI), Professor Dhinojwala, proposes to directly probe the acid-base interactions for polymers in contact with inorganic sapphire substrate or sapphire modified with self-assembled monolayers with acidic or basic end groups to understand these interactions at the molecular level. SFG instrumentation is used to directly monitor the shifts in the vibrational peaks of the acidic and basic groups and correlate them with interaction energies to study exchange kinetics at polymer-solid interface as a function of time, temperature, and composition. This proposal explores the kinetics and thermodynamics of surface segregation driven by acid-base interactions. In addition, this proposal focuses on blends and copolymers to study the role of these interaction energies on the segregation of near solid-solid interfaces and dynamics during sliding and peel-off. The study of interaction energies and its experimental results have important implications in understanding friction and adhesion hysteresis. These interaction energies will be compared with adhesion measurements using the Johnson-Kendall- Roberts (JKR) geometry. In addition to these experiments, the PI will also conduct atomistic molecular dynamics simulations (MD) and quantum calculations to understand the magnitude of the frequency shift and its effect on segregation. The SFG, MD, and quantum calculations of these experiments will be used in conjunction to understand the influence of surface concentration, steric constraints, and surface roughness on acid-base interactions and the consequences on adhesion energies. NON-TECHNICAL SUMMARY The fundamental understanding of acid-base interactions helps in predicting the adhesion of polymers to substrates and in developing the next generation of enhanced coatings and adhesives for applications in multiple areas, including, but not limited to, electronics, bio-mineralization, peptide-based surface recognition, nano-composites and solar cells. This project will support two graduate students who will work together as a group with experts in the areas of surface science, MD simulations, and industrial research. The students working with this broad multidisciplinary group will be provided training to work as a team. Additionally, the graduate students will also have the opportunity to supervise NSF-REU students during the summer. As a volunteer Director of District 5 Science Day, the PI will continue his outreach to host District Science Day at The University of Akron (UA). The PI has also initiated a mentorship program where he brings together scientists from industries and academia to mentor the science projects. This mentorship program was started in the city of Hudson, Ohio, and the PI plans to make this program available to all schools in District 5. In collaboration with UA's business school and Austen Bio-innovation Institute in Akron, the PI is helpping in developing a multidisciplinary Bio-design class offered to UA students in physical sciences, business, and medicine with a goal of observation or experimental based approach to solve problems. This class will be taught in collaboration with professors from UA's business and medicine schools.

Publications Produced as a Result of this Research

Note: When clicking on a Digital Object Identifier (DOI) number, you will be taken to an external site maintained by the publisher. Some full text articles may not yet be available without a charge during the embargo (administrative interval).

Some links on this page may take you to non-federal websites. Their policies may differ from this site.

Xiao, M. and Li, Y. and Allen, M. C. and Deheyn, D. D. and Yue, X. and Zhao, J. and Gianneschi, N. C. and Shawkey, M. D. and Dhinojwala, A. "Bio-Inspired Structural Colors Produced via Self-Assembly of Synthetic Melanin Nanoparticles" ACS Nano, v.9, 2015, p.5454-5460. doi:10.1021/acsnano.5b01298 

Badge, Ila and Stark, Alyssa Y. and Paoloni, Eva L. and Niewiarowski, Peter H. and Dhinojwala, Ali "The role of surface chemistry in adhesion and wetting of gecko toe pads." Sci Rep, v.4, 2014, p.6643. doi:10.1038/srep06643 

Niewiarowski, P. H. and Stark, A. Y. and Dhinojwala, A. "Sticking to the story: outstanding challenges in gecko-inspired adhesives" J. Exp. Biol, v.219, 2016, p.912-919. doi:10.1242/jeb.080085 

Badge, I. and Stark, A. Y. and Paoloni, E. L. and Niewiarowski, P. H. and Dhinojwala, A. "The Role of Surface Chemistry in Adhesion and Wetting of Gecko Toe Pads" Sci., v.4, 2014, p.1-8.

Michael C. Heiber and Ali Dhinojwala "Dynamic Monte Carlo modeling of exciton dissociation in organic donor-acceptor solar cells" Journal of Chemical Physics, v.137, 2012, p.014903. doi:http://dx.doi.org/10.1063/1.4731698 

Jha, Kshitij C. and Zhu, He and Dhinojwala, Ali and Tsige, Mesfin "Molecular structure of poly(methyl methacrylate) surface II: Effect of stereoregularity examined through all-atom molecular dynamics." Langmuir, v.30, 2014, p.12775--12. doi:10.1021/la5023328 

Zhu, H. and Dhopatkar, N. and Dhinojwala, A "Effect of Acid-Base Interactions on Conformation of Adsorbed Polymer Chains" ACS Macro Lett., v.5, 2016, p.45-49. doi:10.1021/acsmacrolett.5b00834 

Xiao, M. and Dhinojwala, A. and Shawkey, M. D. "Nanostructural basis of rainbow-like iridescence in common bronzewing Phaps chalcoptera feathers" Opt. Express, v.22, 2014, p.14625-146. doi:10.1364/OE.22.014625 

Sahni, V. and Miyoshi, T. and Chen, K. and Jain, D. and Blamires, S. J. and Blackledge, T. A. and Dhinojwala, A. "Direct Solvation of Glycoproteins by Salts in Spider Silk Glues Enhances Adhesion and Helps To Explain the Evolution of Modern Spider Orb Webs" Biomacromolecules, v.15, 2014, p.1225-1232. doi:10.1021/bm401800y 

Defante, Adrian P. and Burai, Tarak N. and Becker, Matthew L. and Dhinojwala, Ali "Consequences of water between two hydrophobic surfaces on adhesion and wetting." Langmuir, v.31, 2015, p.2398--240. doi:10.1021/la504564w 

Vasav Sahni, Jared Harris, Todd Blackledge, and Ali Dhinojwala "Cobweb-weaving spiders produce different attachment discs for locomotion and prey capture" Nature Communication, v.3, 2012, p.1106. doi:DOI: 10.1038/ncomms2099 

Yimer, Y. Y. and Dhinojwala, A. and Tsige, M. "Interfacial properties of free-standing poly(3-hexylthiophene) films" J. Chem. Phys., v.137, 2012, p.1-12. doi:http://dx.doi.org/10.1063/1.4736571 

Nanjundiah, K. and Dhinojwala, A. "Melting of Linear Alkanes between Swollen Elastomers and Solid Substrates" Langmuir, v.29, 2013, p.12168-121. doi:10.1021/la402884g 

Heiber, M. C. and Dhinojwala, A. "Estimating the Magnitude of Exciton Delocalization in Regioregular P3HT" J. Phys. Chem. C, v.117, 2013, p.21627-216. doi:10.1021/jp403396v 

Jain, D. and Stark, A. Y. and Niewiarowski, P. H. and Miyoshi, T. and Dhinojwala, A. "NMR spectroscopy reveals the presence and association of lipids and keratin in adhesive gecko setae" Sci. Rep., v.5, 2015, p.1-8.

Zhu, H. and Jha, K. C. and Bhatta, R. S. and Tsige, M. and Dhinojwala, A. "Molecular Structure of Poly(methyl methacrylate) Surface. I. Combination of Interface-Sensitive Infrared--Visible Sum Frequency Generation, Molecular Dynamics Simulations, and ab Initio Calculations" Langmuir, v.30, 2014, p.11609-116. doi:10.1021/la502333u 

Shishir Prasad; He Zhu; Anish Kurian; Ila Badge; Ali Dhinojwala "Interfacial Segregation in Polymer Blends Driven by Acid?Base Interactions" Langmuir, v.29, 2013, p.15727.

Stark, Alyssa Y. and Wucinich, Nicholas A. and Paoloni, Eva L. and Niewiarowski, Peter H. and Dhinojwala, Ali "Self-drying: a gecko's innate ability to remove water from wet toe pads." PLoS One, v.9, 2014, p.e101885. doi:10.1371/journal.pone.0101885 

Blamires, Sean J. and Sahni, Vasav and Dhinojwala, Ali and Blackledge, Todd A. and Tso, I-Min "Nutrient deprivation induces property variations in spider gluey silk." PLoS One, v.9, 2014, p.e88487. doi:10.1371/journal.pone.0088487 

Vasav Sahni, Toshikazu Miyoshi, Kelley Chen, Dharamdeep Jain, Sean J. Blamires, Todd A. Blackledge,and Ali Dhinojwala "Direct Solvation of Glycoproteins by Salts in Spider Silk Glues Enhances Adhesion and Helps To Explain the Evolution of Modern Spider Orb Webs" Biomacromolecules, v., 2014, p..

Li, G. and Dhinojwala, A. and Yeganeh, M. S. "Interference Effect from Buried Interfaces Investigated by Angular-Dependent Infrared?Visible Sum Frequency Generation Technique" J. Phys. Chem. C, v.115, 2011, p.7554-7561. doi:10.1021/jp2000249 

Stark, A. Y. and Subarajan, S. and Jain, D. and Niewiarowski, P. H. and Dhinojwala, A. "Superhydrophobicity of the gecko toe pad: biological optimization versus laboratory maximization" Phil. Trans. R. Soc. A, v.374, 2016, p.20160184. doi:10.1098/rsta.2016.0184 

Prasad, S. and Zhu, H. and Kurian, A. and Badge, I. and Dhinojwala, A. "Interfacial Segregation in Polymer Blends Driven by Acid-Base Interactions" Langmuir, v.29, 2013, p.15727-157. doi:10.1021/la403418h 

Alyssa Y. Starka, Ila Badgeb, Nicholas A. Wucinicha, Timothy W. Sullivana, Peter H. Niewiarowski, and Ali Dhinojwala "Surface wettability plays a significant role in gecko adhesion underwater" Proceedings of National Academy of Sciences, v.110, 2013, p.6243. doi:doi:10.1073/iti1613110 

Jain, Dharamdeep and Stark, Alyssa Y. and Niewiarowski, Peter H. and Miyoshi, Toshikazu and Dhinojwala, Ali "NMR spectroscopy reveals the presence and association of lipids and keratin in adhesive gecko setae." Sci Rep, v.5, 2015, p.9594. doi:10.1038/srep09594 

Dharamdeep Jain, Vasav Sahni, Ali Dhinojwala "Synthetic Adhesive Attachment Discs Inspired by Spider?s Pyriform Silk Architecture" Journal of Polymer Science Polymer Physics, v., 2014, p..

Alyssa Y. Starka, Ila Badge, Nicholas A. Wucinich, Timothy W. Sullivan, Peter H. Niewiarowski, and Ali Dhinojwala "Surface wettability plays a significant role in gecko adhesion underwater" Proceedings of National Academy Science, v.110, 2013, p.6340.

Ila Badge, Sarang Bhawalkar, Li Jia, and Ali Dhinojwala "Tuning surface wettability using single layered and hierarchically ordered arrays of spherical colloidal particles" Soft Matter, v.9, 2013, p.3032. doi:DOI: 10.1039/c2sm27773e 

Jain, D. and Sahni, V. and Dhinojwala, A. "Synthetic adhesive attachment discs inspired by spider's pyriform silk architecture" J. Polym. Sci. Part B: Polym. Phys., v.52, 2014, p.553-560.

Zhou, J. and Anim-Danso, E. and Zhang, Y. and Zhou, Y. and Dhinojwala, A. "Interfacial Water at Polyurethane--Sapphire Interface" Langmuir, v.31, 2015, p.12401-124. doi:10.1021/acs.langmuir.5b03263 

Defante, A. P. and Burai, T. N. and Becker, M. L. and Dhinojwala, A. "Consequences of Water between Two Hydrophobic Surfaces on Adhesion and Wetting" Langmuir, v.31, 2015, p.2398-2406. doi:10.1021/la504564w 

Heiber, M. C. and Dhinojwala, A. "Dynamic Monte Carlo modeling of exciton dissociation in organic donor-acceptor solar cells" J. Chem. Phys., v.137(1), 2012, p.1-11. doi:http://dx.doi.org/10.1063/1.4731698 

Kurian, A. and Prasad, S. and Dhinojwala, A. "Direct Measurement of Acid?Base Interaction Energy at Solid Interfaces" Langmuir, v.26, 2010, p.17804-178. doi:10.1021/la103591f 

Sean J. Blamires, Vasav Sahni2, Ali Dhinojwala, Todd A. Blackledge, I-Min Tso "Nutrient Deprivation Induces Property Variations in Spider Gluey Silk" PLoS One, v.9, 2014, p.e88487.

Zhu, He and Jha, Kshitij C. and Bhatta, Ram S. and Tsige, Mesfin and Dhinojwala, Ali "Molecular structure of poly(methyl methacrylate) surface. I. Combination of interface-sensitive infrared-visible sum frequency generation, molecular dynamics simulations, and ab initio calculations." Langmuir, v.30, 2014, p.11609--11. doi:10.1021/la502333u 

Badge, I. and Bhawalkar, S. P. and Jia, L. and Dhinojwala, A. "Tuning surface wettability using single layered and hierarchically ordered arrays of spherical colloidal particles" Soft Matter, v.9, 2013, p.3032-3040. doi:10.1039/C2SM27773E 

Jha, K. C. and Dhinojwala, A. and Tsige, M. "Local Structure Contributions to Surface Tension of a Stereoregular Polymer" ACS Macro Lett., v.4, 2015, p.1234-1238. doi:10.1021/acsmacrolett.5b00612 

Sahni, Vasav and Miyoshi, Toshikazu and Chen, Kelley and Jain, Dharamdeep and Blamires, Sean J. and Blackledge, Todd A. and Dhinojwala, Ali "Direct solvation of glycoproteins by salts in spider silk glues enhances adhesion and helps to explain the evolution of modern spider orb webs." Biomacromolecules, v.15, 2014, p.1225--123. doi:10.1021/bm401800y 

Jha, K. C. and Zhu, H. and Dhinojwala, A. and Tsige, M. "Molecular Structure of Poly(methyl methacrylate) Surface II: Effect of Stereoregularity Examined through All-Atom Molecular Dynamics" Langmuir, v.30, 2014, p.12775-127. doi:10.1021/la5023328 

Zhou, Jinjun and Defante, Adrian P. and Lin, Fei and Xu, Ying and Yu, Jiayi and Gao, Yaohua and Childers, Erin and Dhinojwala, Ali and Becker, Matthew L. "Adhesion properties of catechol-based biodegradable amino acid-based poly(ester urea) copolymers inspired from mussel proteins." Biomacromolecules, v.16, 2015, p.266--274. doi:10.1021/bm501456g 

Xiao, Ming and Dhinojwala, Ali and Shawkey, Matthew "Nanostructural basis of rainbow-like iridescence in common bronzewing Phaps chalcoptera feathers." Opt Express, v.22, 2014, p.14625--14.

Michael C. Heiber and Ali Dhinojwala "Estimating the Magnitude of Exciton Delocalization in Regioregular P3HT" Journal of Physical Chemistry C, v.117, 2013, p.21627.

Stark, A. Y. and Dryden, D. M. and Olderman, J. and Peterson, K. A. and Niewiarowski, P. H. and French, R. H. and Dhinojwala, A. "Adhesive interactions of geckos with wet and dry fluoropolymer substrates" J. R. Soc. Interface, v.12, 2015, p.20150464. doi:10.1098/rsif.2015.0464 

Kumar Nanjundiah and Ali Dhinojwala "Melting of Linear Alkanes between Swollen Elastomers and Solid Substrates" Langmuir, v.29, 2013, p.12168. doi:10.1021 

Bhatta, R. S. and Prasad, I. P. and Dhinojwala, A. and Tsige, M. "A brief review of Badger-Bauer rule and its validation from a first-principles approach" Mod. Phys. Lett. B, v.28, 2014, p.1-16. doi:10.1142/S0217984914300142 

Kurian, A. and Prasad, S. and Dhinojwala, A. "Unusual Surface Aging of Poly(dimethylsiloxane) Elastomers" Macromolecules, v.43, 2010, p.2438-2443. doi:10.1021/ma902624s 

Heiber, M. C. and Dhinojwala, A. "Efficient Generation of Model Bulk Heterojunction Morphologies for Organic Photovoltaic Device Modeling" Phys. Rev. Applied, v.2, 2014, p.1-10. doi:10.1103/PhysRevApplied.2.014008 

Stark, A. Y. and Wucinich, N. A. and Paoloni, E. L. and Niewiarowski, P. H. and Dhinojwala, A. "Self-drying: a gecko's innate ability to remove water from wet toe pads" PLOS ONE, v.9, 2014, p.e101885.

Zhu, H. and Dhinojwala, A. "Thermal Behavior of Long-Chain Alcohols on Sapphire Substrate" Langmuir, v.31, 2015, p.6306-6313. doi:10.1021/acs.langmuir.5b01330 

Stark, Alyssa Y. and McClung, Brandon and Niewiarowski, Peter H. and Dhinojwala, Ali "Reduction of water surface tension significantly impacts gecko adhesion underwater." Integr Comp Biol, v.54, 2014, p.1026--103. doi:10.1093/icb/icu066 

Stark, A. Y. and Badge, I. and Wucinich, N. A. and Sullivan, T. W. and Niewiarowski, P. H. and Dhinojwala, A. "Surface wettability plays a significant role in gecko adhesion underwater" Proc. Natl. Acad. Sci. U.S.A, v.110, 2013, p.6340-6345. doi:10.1073/pnas.1219317110 

Hsu, P. Y. and Dhinojwala, A. "Contact of Oil with Solid Surfaces in Aqueous Media Probed Using Sum Frequency Generation Spectroscopy" Langmuir, v.28, 2012, p.2567-2573. doi:10.1021/la203228t 

Sahni, V. and Harris, J. and Blackledge, T. A. and Dhinojwala, A. "Cobweb-weaving spiders produce different attachment discs for locomotion and prey capture" Nat. Commun., v.3, 2012, p.1-7.


Project Outcomes Report

Disclaimer

This Project Outcomes Report for the General Public is displayed verbatim as submitted by the Principal Investigator (PI) for this award. Any opinions, findings, and conclusions or recommendations expressed in this Report are those of the PI and do not necessarily reflect the views of the National Science Foundation; NSF has not approved or endorsed its content.

Project Outcome (DMR-1105370 (2011-2016), Understanding Acid-Base Interactions using Interface-Sensitive Spectroscopy

Intellectual Merit: The objective of this proposal was to exploit the interface sensitivity of infrared-visible sum frequency generation spectroscopy (SFG) to measure acid-base interactions at solid-solid interfaces.  To design coatings that stick to solid surfaces or creating multilayer coatings require a fundamental understanding of the interaction of molecules at interfaces. The focus of this proposal was to understand the formation of acid-base bonds at interfaces and relate it to surface segregation and adhesion. Acid-base interactions play an important in the areas of adhesion, friction, and wetting.  In-situ characterization of acid-base interactions and their role in adhesion of these coatings at the molecular level and under kinetic conditions (for example: during sliding and mechanical contact) pose a formidable challenge to scientists.  In this grant the PI has designed SFG experiments to study contact of polymer films with an acidic sapphire substrate. They were able to quantify the segregation of more basic groups next to a more acidic sapphire substrate by monitoring the shift in vibration of the surface OH groups. This allowed them to quantify the amount and orientation of these functional groups at the interface. In addition, the PI has developed novel approaches to monitor the changes taking place as a function of humidity, temperature, and during sliding. To improve the understanding of the spectroscopy results, the PI has collaborated with Dr. Tsige to perform molecular dynamics simulations (MD) and quantum calculations to compute SFG spectra for polymer-air interface. These theoretical spectra were compared directly with the experimental results to validate the theoretical models. The validated MD results were then be used to determine important structural differences of polymers as a function of tacticity. This grant has resulted in thirty published papers and filling of eight patent applications.

Broader Impact: Adhesion is a multi-billion dollar industry and the development of formulations for optimum performance is mostly based on intuition. Even with the advances in the chemistry, our adhesives perform very poorly in wet and humid conditions. They also use toxic additives to improve bonding with substrates. Understanding the bonding mechanism and how it withstands exposure to moisture will help in designing adhesives that are more effective in wet environments. The grant allowed the PI to train four PhD. students in the area of adhesion and surface science (Mike Heiber, Ila Badge, He Zhu and Adrian Defante). As part of the outreach activities, the PI has been organizing District 5 Science Day from last eighteen years (http://www2.uakron.edu/cpspe/wrsd/wrsd.htm).  This activity involves around 350 poster presentation from middle and high school students. The best 100 posters are selected for participating at the annual State Fair held in Columbus, Ohio. The PI and his students have mentored undergraduate and high school students. The graduate students gave demonstrations at local schools, metro parks, and also participated as judges during Science Day. The PI has also contributed as a program chair of the adhesion society meeting in 2016; is currently a Vice-Chair for the Gordon conference on adhesion; and co-PI of the new biomimicry center at the University of Akron.

 


Last Modified: 10/17/2016
Modified by: Ali N Dhinojwala

For specific questions or comments about this information including the NSF Project Outcomes Report, contact us.