Source: CORNELL UNIVERSITY submitted to
NANOTECHNOLOGY AND BIOSENSORS
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
Reporting Frequency
Annual
Accession No.
1004621
Grant No.
(N/A)
Cumulative Award Amt.
(N/A)
Proposal No.
(N/A)
Multistate No.
NC-_old1194
Project Start Date
Oct 1, 2014
Project End Date
Sep 30, 2016
Grant Year
(N/A)
Program Code
[(N/A)]- (N/A)
Recipient Organization
CORNELL UNIVERSITY
(N/A)
ITHACA,NY 14853
Performing Department
Fiber Science & Apparel Design
Non Technical Summary
Fibers 100 times thinner than human hairs will be designed to perform separation, concentration and mixing tasks within diagnostic devices. These nanoscale fibers can be used to purify and concentrate a sample to be analyzed by a wide range of biosensor technologies. The nanofibers can be incorporated into common diagnostic platforms including lateral flow assays or microfluidic devices.
Animal Health Component
40%
Research Effort Categories
Basic
40%
Applied
40%
Developmental
20%
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
71250102020100%
Goals / Objectives
Construct and characterize self-assembled nanostructures Develop devices and systems incorporating microfabrication and nanotechnology
Project Methods
Nanofibers will be incorporated into microfluidic channels as components of lab-on-chip systems. Many types of nanofibers designed for sample purification/filtration, specific pathogen capture or reagent mixing have already been developed in our laboratory. Pathogen capture has been achieved via electrostatic charge, chemical affinity or specific DNA binding at the nanofiber surface. New nanofiber functions can be developed rapidly via phase separation and self-assembly during the electrospinning process. Functional fibers are achieved by incorporating functional materials in solution with a fiber forming polymer and applying a high voltage to solution droplets. As the nanofiber forms, solvent evaporation, thermodynamics of mixing and the electrostatic charge at the fiber surface drive separation of the active ingredient to the fiber surface. Nanofibers can be patterned directly into portions of microfluidic channels or placed in channels after formation. Multiple types of functional nanofibers can be incorporated in either the same microfluidic channel or in different channel sections of an overall device. The nanofiber structure provides large surface area per volume and enhances dispersive mixing at low Reynold's number flows. This technology will be investigated as a compatible component with sensing systems including micro and nano-optical arrays for non-labeled sensing and fluorescent and luminescent based chemical and biological sensing of trace contaminants, toxins, and biological signaling molecules.

Progress 10/01/14 to 09/30/16

Outputs
Target Audience:Methods and early results were presented to a broad range of scientific audiences at PITTCON '16 in Atlanta, GA, Gordon Conference on Biosensors in Newport, RI, the 75th anniversary meeting of the Fiber Society in Mulhouse, FR. L. Shepherd, "Increasing Surface Available Biotin and Improving WaterStability of PLA/PLA-b-PEG Nanofibers", Mulhouse, FR M.W. Frey, 'Electrospun nanofibers for analyte purification', Gordon Research Conference on Bioanalytical Sensors, Newport, RI, June 2016. M.W. Frey, 'Nanofiber chemistry and synthesis and the impact on analytical systems', PITTCON, Atlanta, March 2016. Additionally, 3 manuscripts have been submitted to peer reviewed journals (1 published and 2 under review as of reporting date): González, Edurne, Shepherd, Larissa M, Saunders, Laura, & Frey, Margaret W. (2016). Surface Functional Poly (lactic Acid) Electrospun Nanofibers for Biosensor Applications. Materials, 9(1), 47. Larissa M. Shepherd, Edurne González, Esther X. Chen, and Margaret W. Frey, Increasing Stability of Biotin Functionalized Electrospun Fibers for Biosensor Applications, ACS Applied Materials & Interfaces Article ASAP, DOI: 10.1021/acsami.6b14348 Edurne González, Margaret W. Frey, Synthesis, characterization and electrospinning of poly (vinyl caprolactam-co-hydroxymethyl acrylamide) to create stimuli-responsive nanofibers, Polymer, 108(13) 154-162, ISSN 0032-3861, http://dx.doi.org/10.1016/j.polymer.2016.11.053. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Undergraduate students associated with this project were trained in laboratory methods, data analysis and report writing by post-doctoral associates. One undergraduate was participated in the NSF funded Cornell Center for Materials Research, Research Experience for Undergraduates program (DMR-1460428 and DMR-1120296). Post docs and undergraduates presented research in group meetings and at meetings on the Cornell University Campus Post docs participated in professional development workshops on teaching, grant writing and preparing academic job applications. These workshops were offered via the Cornell University Graduate School. How have the results been disseminated to communities of interest?Results have been disseminated via peer reviewed publications and conference presentations as noted above. What do you plan to do during the next reporting period to accomplish the goals?Additional functional polymers have been developed which respond to both temperature and pH by changing from hydrophiic to hydrophobic. This polymers will be electrospun into nanofiber mats to create materials that can absorb and release chemicals based on environmental stimuli (heat or pH). Additionally, nanocoatings of these materials will be applied to cotton fabrics to add these environmentally responsive properties to cotton. We have started exploring a new NMR characterization technique for measuring polymer coatings on fabrics which we expect will provide insight into the nature of chemical binding and property development in these systems. Additionally, arrays of fibers with surface positive and negative charges will be tested for synergistic removal of contaminants from aqueous media.

Impacts
What was accomplished under these goals? Phase changing and biotinylated nanofibers were produced and self assembly during the electrospinning process was investigated. Ability of the resulting nanofiber systems to respond to environmental stimuli was tested. Poly (vinyl caprolactam) (PVCL) is an especially attractive temperature-responsive polymer due to its biocompatibility and the fact that its lower critical solution temperature (LCST) is in the physiological range (32e34 C). Here, PVCL was copolymerized with hydroxymethyl acrylamide (NMA) and electrospun to create PVCL based temperature-responsive chemical hydrogel nanofibers for the first time. Field emission scanning electron microscopy (FESEM) was used to study fiber morphology. The thermal curing process of the nanofibers was analyzed by attenuated total reflectance-fourier transform infrared spectroscopy (ATR-FTIR), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The created "smart" hydrogel nanofibers responded quickly and reversibly to changes in temperature and showed a temperature controlled rhodamine B dye release. The unique properties offered by these novel materials show promise for applications in biosensors, controlled drug delivery and microfluidic systems.

Publications

  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Gonz�lez, Edurne, Shepherd, Larissa M, Saunders, Laura, & Frey, Margaret W. (2016). Surface Functional Poly (lactic Acid) Electrospun Nanofibers for Biosensor Applications. Materials, 9(1), 47.
  • Type: Journal Articles Status: Accepted Year Published: 2016 Citation: Edurne Gonz�lez, Margaret W. Frey, Synthesis, characterization and electrospinning of poly(vinyl caprolactam-co-hydroxymethyl acrylamide) to create stimuli-responsive nanofibers, Polymer, 108(13) 154-162, ISSN 0032-3861, http://dx.doi.org/10.1016/j.polymer.2016.11.053.
  • Type: Journal Articles Status: Accepted Year Published: 2017 Citation: Larissa M. Shepherd, Edurne Gonz�lez, Esther X. Chen, and Margaret W. Frey, Increasing Stability of Biotin Functionalized Electrospun Fibers for Biosensor Applications, ACS Applied Materials & Interfaces Article ASAP, DOI: 10.1021/acsami.6b14348
  • Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: L. Shepherd, "Increasing Surface Available Biotin and Improving WaterStability of PLA/PLA-b-PEG Nanofibers", Mulhouse, FR
  • Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: M.W. Frey, 'Electrospun nanofibers for analyte purification', Gordon Research Conference on Bioanalytical Sensors, Newport, RI, June 2016.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: M.W. Frey, 'Nanofiber chemistry and synthesis and the impact on analytical systems', PITTCON, Atlanta, March 2016.


Progress 10/01/14 to 09/30/15

Outputs
Target Audience:Materials based on functional nanofibers were developed with potential application for waste water remediation. In particular functionality targeting removal or decolorization of textile dye waste or capture and detection of residual chemotherapy drugs were developed. Results were reported to audiences at the American Chemical Society Northeast Regional Meeting in June, and the American Chemical Society Green Chemistry & Engineering conference in July 2015. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?This project has supported training and professional development of undergraduate students, graduate students and a post-doctoral research associate. Training in peer review, scientific writing, presentation and preparation of graphics has been facilitated by this project. How have the results been disseminated to communities of interest?The work has been disseminated via presentation at scientific conferences, publication in peer reviewed journals and an article in the popular press: http://www.news.cornell.edu/stories/2015/08/nano-style-sheets-may-aid-health-shield-ecosystem What do you plan to do during the next reporting period to accomplish the goals?In the next reporting period we will build on successful development of hydrophilic, non-water soluble polymers. Additional functionality will be added to the surface of these high specific surface area, high porosity materials to specifically capture and concentrate residual chemotherapy drugs from water. These drugs represent a highly toxic emerging pollutant and also have similar chemical structure and properties to chemical warfare agents. Additionally, phase switching properties will be added to the surfaces to create materials that switch from hydrophilic to hydrophobic in response to temperature or environmental conditions.

Impacts
What was accomplished under these goals? Carboxylic acid coated iron oxide nanoparticles (CA-Fe3O4 NPs) were applied to Nylon 6 nanomembranes by three different techniques: (1) simultaneous electrospinning/electrospraying, (2) layer-by-layer (LbL) assembly, and (3) chemical grafting. These membranes have potential use toward clean-up of polluted rivers due to the multi-functional properties of the NPs. However, it is critical to evaluate particle retention and stability on fibers to reduce human health and environmental concerns. This study evaluates the NP treatment uniformity, and particle retention of the membranes based on knowledge of the preparation process. Electron microscopy and CIELAB spectrophotometry revealed that the NPs were uniformly dispersed via the electrospun/electrosprayed and grafted methods while non-uniformity was observed on LbL treated membranes. The membranes were washed in solutions of various pH levels (pH54, 7, 10) to investigate NP release and retention. Inductively coupled plasma-atomic emission spectroscopy results indicate particle release is driven by pH-dependent, bonding interactions between the NPs and the Nylon 6 fibers. Over 97% of NPs were retained on all treated membranes after washing for 60 min. Biotin surface functionalized hydrophilic non-water-soluble biocompatible poly(lactic acid) (PLA) nanofibers are created for their potential use as biosensors. Varying concentrations of biotin (up to 18 weight total percent (wt %)) were incorporated into PLA fibers together with poly(lactic acid)-block-poly(ethylene glycol) (PLA-b-PEG) block polymers. While biotin provided surface functionalization, PLA-b-PEG provided hydrophilicity to the final fibers. Morphology and surface-available biotin of the final fibers were studied by Field Emission Scanning Electron Microscopy (FESEM) and competitive colorimetric assays. The incorporation of PLA-b-PEG block copolymers not only decreased fiber diameters but also dramatically increased the amount of biotin available at the fiber surface able to bind avidin. Fiber water stability tests revealed that both biotin and PLA-b-PEG, migrated to the aqueous phase after relatively extended periods of water exposure. The functional hydrophilic nanofiber created in this work shows a potential application as a biosensor for point-of-care diagnostics.

Publications

  • Type: Journal Articles Status: Accepted Year Published: 2015 Citation: A comparative study on electrosprayed, layer?by?layer, and chemically grafted nanomembranes loaded with iron oxide nanoparticles NK Trejo, M Frey Journal of Applied Polymer Science 132 (41)
  • Type: Journal Articles Status: Accepted Year Published: 2016 Citation: Surface Functional Poly(lactic acid) Electrospun Nanofibers for Biosensor Applications Edurne Gonz�lez, Larissa Shepherd , Laura Saunders , Margaret Frey * Materials