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Hierarchical thin film architectures for enhanced sensor performance: liquid crystal-mediated electrochemical synthesis of nanostructured imprinted polymer films for the selective recognition of bupivacaine.

Suriyanarayanan S, Nawaz H, Ndizeye N, Nicholls IA - Biosensors (Basel) (2014)

Bottom Line: Nanostructured bupivacaine-selective molecularly imprinted 3-aminophenylboronic acid-p-phenylenediamine co-polymer (MIP) films have been prepared on gold-coated quartz (Au/quartz) resonators by electrochemical synthesis under cyclic voltammetric conditions in a liquid crystalline (LC) medium (triton X-100/water).Detection was possible at 100 nM (30 ng/mL), and discrimination of bupivacaine from closely related structural analogs was readily achieved as reflected in the corresponding stability constants of the MIP-analyte complexes.The facile fabrication and significant enhancement in sensor sensitivity together highlight the potential of this LC-based imprinting strategy for fabrication of polymeric materials with hierarchical architectures, in particular for use in surface-dependent application areas, e.g., biomaterials or sensing.

View Article: PubMed Central - PubMed

Affiliation: Bioorganic and Biophysical Chemistry Laboratory, Linnæus University Centre for Biomaterials Chemistry and Department of Chemistry and Biomedical Sciences, Linnæus University, SE-391 82 Kalmar, Sweden; E-Mails: esusu@lnu.se (S.S.), nawazhazrat@gmail.com (H.N.); natacha.ndizeye@lnu.se (N.N.).

ABSTRACT
Nanostructured bupivacaine-selective molecularly imprinted 3-aminophenylboronic acid-p-phenylenediamine co-polymer (MIP) films have been prepared on gold-coated quartz (Au/quartz) resonators by electrochemical synthesis under cyclic voltammetric conditions in a liquid crystalline (LC) medium (triton X-100/water). Films prepared in water and in the absence of template were used for control studies. Infrared spectroscopic studies demonstrated comparable chemical compositions for LC and control polymer films. SEM studies revealed that the topologies of the molecularly imprinted polymer films prepared in the LC medium (LC-MIP) exhibit discernible 40 nm thick nano-fiber structures, quite unlike the polymers prepared in the absence of the LC-phase. The sensitivity of the LC-MIP in a quartz crystal microbalance (QCM) sensor platform was 67.6 ± 4.9 Hz/mM under flow injection analysis (FIA) conditions, which was ≈250% higher than for the sensor prepared using the aqueous medium. Detection was possible at 100 nM (30 ng/mL), and discrimination of bupivacaine from closely related structural analogs was readily achieved as reflected in the corresponding stability constants of the MIP-analyte complexes. The facile fabrication and significant enhancement in sensor sensitivity together highlight the potential of this LC-based imprinting strategy for fabrication of polymeric materials with hierarchical architectures, in particular for use in surface-dependent application areas, e.g., biomaterials or sensing.

No MeSH data available.


Related in: MedlinePlus

RAIR spectra of the bupivacaine MIP and REF films.
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biosensors-04-00090-f002: RAIR spectra of the bupivacaine MIP and REF films.

Mentions: The chemical functionalities of the films were studied by refractive angle infrared (RAIR) spectroscopy. Figure 2 shows the RAIR spectra for MIP and REF films prepared in aqueous and LC medium. Discernible bands at 829, 1288, 1396, 1508, 1567, 3027, 3208, 3314, and 3442 cm−1 depict the ring bending, ν(C–N), ν(B–O), ν(C=C), δ(N–H), ν(C–H), ν(B–OH) and ν(N–H) IR-active vibrational modes present in the backbone of the copolymer [41,42,43,44]. In addition, the band at 1396 and broad bands around 3350 cm−1 corresponds to the stretching vibrations of –B–O [45] in 3-APBA and –NH2 moieties in p-PD, respectively, validate the copolymerization. The spectral features of the polymer films prepared in both media were very similar indicating that the polymerization reactions had incorporated both the monomers into the copolymer films. Interestingly, the lack of a significant difference between the spectra of the MIP and REF films indicates that the template does not affect the polymerization process and the copolymer composition. Furthermore, the absence of vibrational bands for the amide carbonyl (C(=O)NH) and ether (C–O–C) functionalities support the conclusion that the bupivacaine template and Triton X-100 were both efficiently removed from the polymer films.


Hierarchical thin film architectures for enhanced sensor performance: liquid crystal-mediated electrochemical synthesis of nanostructured imprinted polymer films for the selective recognition of bupivacaine.

Suriyanarayanan S, Nawaz H, Ndizeye N, Nicholls IA - Biosensors (Basel) (2014)

RAIR spectra of the bupivacaine MIP and REF films.
© Copyright Policy
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4264373&req=5

biosensors-04-00090-f002: RAIR spectra of the bupivacaine MIP and REF films.
Mentions: The chemical functionalities of the films were studied by refractive angle infrared (RAIR) spectroscopy. Figure 2 shows the RAIR spectra for MIP and REF films prepared in aqueous and LC medium. Discernible bands at 829, 1288, 1396, 1508, 1567, 3027, 3208, 3314, and 3442 cm−1 depict the ring bending, ν(C–N), ν(B–O), ν(C=C), δ(N–H), ν(C–H), ν(B–OH) and ν(N–H) IR-active vibrational modes present in the backbone of the copolymer [41,42,43,44]. In addition, the band at 1396 and broad bands around 3350 cm−1 corresponds to the stretching vibrations of –B–O [45] in 3-APBA and –NH2 moieties in p-PD, respectively, validate the copolymerization. The spectral features of the polymer films prepared in both media were very similar indicating that the polymerization reactions had incorporated both the monomers into the copolymer films. Interestingly, the lack of a significant difference between the spectra of the MIP and REF films indicates that the template does not affect the polymerization process and the copolymer composition. Furthermore, the absence of vibrational bands for the amide carbonyl (C(=O)NH) and ether (C–O–C) functionalities support the conclusion that the bupivacaine template and Triton X-100 were both efficiently removed from the polymer films.

Bottom Line: Nanostructured bupivacaine-selective molecularly imprinted 3-aminophenylboronic acid-p-phenylenediamine co-polymer (MIP) films have been prepared on gold-coated quartz (Au/quartz) resonators by electrochemical synthesis under cyclic voltammetric conditions in a liquid crystalline (LC) medium (triton X-100/water).Detection was possible at 100 nM (30 ng/mL), and discrimination of bupivacaine from closely related structural analogs was readily achieved as reflected in the corresponding stability constants of the MIP-analyte complexes.The facile fabrication and significant enhancement in sensor sensitivity together highlight the potential of this LC-based imprinting strategy for fabrication of polymeric materials with hierarchical architectures, in particular for use in surface-dependent application areas, e.g., biomaterials or sensing.

View Article: PubMed Central - PubMed

Affiliation: Bioorganic and Biophysical Chemistry Laboratory, Linnæus University Centre for Biomaterials Chemistry and Department of Chemistry and Biomedical Sciences, Linnæus University, SE-391 82 Kalmar, Sweden; E-Mails: esusu@lnu.se (S.S.), nawazhazrat@gmail.com (H.N.); natacha.ndizeye@lnu.se (N.N.).

ABSTRACT
Nanostructured bupivacaine-selective molecularly imprinted 3-aminophenylboronic acid-p-phenylenediamine co-polymer (MIP) films have been prepared on gold-coated quartz (Au/quartz) resonators by electrochemical synthesis under cyclic voltammetric conditions in a liquid crystalline (LC) medium (triton X-100/water). Films prepared in water and in the absence of template were used for control studies. Infrared spectroscopic studies demonstrated comparable chemical compositions for LC and control polymer films. SEM studies revealed that the topologies of the molecularly imprinted polymer films prepared in the LC medium (LC-MIP) exhibit discernible 40 nm thick nano-fiber structures, quite unlike the polymers prepared in the absence of the LC-phase. The sensitivity of the LC-MIP in a quartz crystal microbalance (QCM) sensor platform was 67.6 ± 4.9 Hz/mM under flow injection analysis (FIA) conditions, which was ≈250% higher than for the sensor prepared using the aqueous medium. Detection was possible at 100 nM (30 ng/mL), and discrimination of bupivacaine from closely related structural analogs was readily achieved as reflected in the corresponding stability constants of the MIP-analyte complexes. The facile fabrication and significant enhancement in sensor sensitivity together highlight the potential of this LC-based imprinting strategy for fabrication of polymeric materials with hierarchical architectures, in particular for use in surface-dependent application areas, e.g., biomaterials or sensing.

No MeSH data available.


Related in: MedlinePlus