4.7 Article

In-Capillary Photodeposition of Glyphosate-Containing Polyacrylamide Nanometer-Thick Films

Journal

ACS APPLIED POLYMER MATERIALS
Volume -, Issue -, Pages -

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acsapm.2c01461

Keywords

confocal micro-Raman spectroscopy; glyphosate; fused silica microcapillary; microfluidics; nanofilm; photopolymerization; polyacrylamide; silanization

Funding

  1. European Community (European Union)
  2. National Centre for Research and Development of Poland (European Union)
  3. European Community [PhotonicSensing/1/2018]
  4. National Centre for Research and Development of Poland [PhotonicSensing/1/2018]
  5. European Commission [857543]
  6. International Research Agendas Programme of the Foundation for Polish Science - European Union under the European Regional Development Fund [MAB/2020/14]
  7. European Commission
  8. Foundation for Polish Science [POIR.04.04.00-00-16ED/18]

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The present research reports on the in-water, site-specific photodeposition of glyphosate-containing polyacrylamide nanofilms. The successful photodeposition was confirmed through material characterization and analysis. Additionally, the study found that glyphosate had an impact on polymer gelation. These findings are important for the development of glyphosate-based nanomaterials and chemical sensors.
The present research reports on in-water, site-specific photodeposition of glyphosate (GLP)-containing polyacrylamide (PAAGLP) nanometer-thick films (nanofilms) on an inner surface of fused silica (fused quartz) microcapillaries presilanized with trimethoxy(octen-7yl)silane (TMOS). TMOS was chosen because of the vinyl group presence in its structure, enabling its participation in the (UV light) activated free-radical polymerization (UV-FRP) after its immobilization on a fused silica surface. The photodeposition was conducted in an aqueous (H2O/ACN; 3:1, v/v) solution, using UV-FRP (lambda = 365 nm) of the acrylamide (AA) functional monomer, the N,N & PRIME;-methylenebis(acrylamide) (BAA) cross-linking monomer, GLP, and the azobisisobutyronitrile (AIBN) UV-FRP initiator. Acetonitrile (ACN) was used as the porogen and the solvent to dissolve monomers and GLP. Because of the micrometric diameters of microcapillaries, the silanization and photodeposition procedures were first optimized on fused silica slides. The introduction of TMOS, as well as the formation of PAA and PAA-GLP nanofilms, was determined using atomic force microscopy (AFM), scanning electron microscopy with energy-dispersive X-ray (SEM-EDX) spectroscopy, and confocal micro Raman spectroscopy. Particularly, AFM and SEM-EDX measurements determined nanofilms' thickness and GLP content, respectively, whereas in-depth confocal (micro-Raman spectroscopy)-assisted imaging of PAA-and PAA-GLP-coated microcapillary inner surfaces confirmed the successful photo deposition. Moreover, we examined the GLP impact on polymer gelation by monitoring hydration in a hydrogel and a dried powder PAA-GLP. Our study demonstrated the usefulness of the in-capillary micro Raman spectroscopy imaging and in-depth profiling of GLP-encapsulated PAA nanofilms. In the future, our simple and inexpensive procedure will enable the fabrication of polymer-based microfluidic chemosensors or adsorptive-separating devices for GLP detection, determination, and degradation.

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