Direct nitroxide mediated (co)polymerization of 4-vinylphenylboronic acid as route towards sugar sensors

Sulfonphthaleine dyes are an important class of pH indicators, finding applications in novel (textile) sensors. In this paper, we present a combined experimental and theoretical study to elucidate the halochromic behaviour of a large set of sulfonphthaleine compounds. Starting from an experimental analysis consisting of UV/Vis spectroscopy, the pH region and the absorption wavelengths related to the colour shift are obtained and pK a values are derived. The effect of the substituents on the pH region can be traced back to their electron donating/withdrawing properties. Time-Dependent Density Functional Theory (TD-DFT) is able to adequately produce the trend in experimental wavelengths. Proton affinities are used to assess the effect of substituents on the pH region. The combination of theory and experiment is able to give a better understanding of the pH sensitivity; the methodology in this work will be useful in future dye design and is applicable to other dye classes as well.

show abstract

“…This is part of a larger research field, namely functionalized polymers. [13][14][15][16] It has been shown that pH…”

Section: Introductionmentioning

confidence: 99%

Substituent effects on absorption spectra of pH indicators: An experimental and computational study of sulfonphthaleine dyes

Meyer

Hemelsoet²,

Speybroeck³

et al. 2014

Dyes and Pigments

View full text Add to dashboard Cite

show abstract

“…The VPBA segments of the copolymer were not soluble in aqueous solution due to strong hydrogen bonding between the boronic acid moieties and the transition to the tetragonal anionic form that occurs around pH 8 to 10 in the presence of glucose. 57 As expected, the CPT decreased with an increase of VPBA content in the final copolymer and it was 28.0 to 36.4 8C (at 0.5 wt % solution concentration) with F VPBA 5 0.045 to 0.13 (approximately a degree decrease in CPT per 1 mol % of increase in VPBA content). In previous studies of a similar system where MEMA was copolymerized with VBK via NMP, the CPTs of the resulting copolymers were affected by composition and ranged between 37 and 43 8C.…”

Section: Complexation Of Boron With the Tertiary Aminementioning

confidence: 63%

“…Controlled homopolymerization of VPBA by NMP has been reported in the presence of BlocBuilder initiator previously. 57 Figure 2 shows the characteristic kinetic plots of log ((1 2 X) 21 ), versus time and Figures 3 and 4 shows M n and -D, respectively, versus conversion for all copolymerizations.…”

Section: Resultsmentioning

confidence: 99%

“…For instance, VPBA homopolymer is only soluble in the presence of glucose between pH 9 and 10; otherwise, the polymer is not soluble due to strong hydrogen bonding between the boronic acid moieties. 57 Protonation of the tertiary amine groups occurs between pH 4-6 for MEMA residues (pK a 4.9), 29 and DI decreases from about 89% to 7% with an increase in pH in this range. As the repulsive forces between the charged units become less dominant in the molecule conformation, the chains become more compact and hydrophobic at higher pH, resulting in lowering of the CPT.…”

mentioning

confidence: 98%

See 1 more Smart Citation

Vinyl phenylboronic acid controlling co‐monomer for nitroxide mediated synthesis of thermoresponsive poly(2‐N morpholinoethyl methacrylate)

Savelyeva

Chondon

Marić

2015

J. Polym. Sci. Part A: Polym. Chem.

View full text Add to dashboard Cite

Low concentrations of 4-vinylphenylboronic acid (VPBA) were copolymerized with 2-N-morpholinoethyl methacrylate (MEMA) by nitroxide mediated polymerization using BlocBuilder TM unimolecular initiator at 80 to 90 8C. The MEMA/VPBA copolymerizations were performed at initial feed compositions (f VPBA,0 ) of 0.05 to 0.10 VPBA, with f VPBA,0 5 0.10 using dimethylacetamide (DMAc) solvent being most effective, as seen by a linear increase in number average molecular weight, M n , versus conversion and low dispersity, -D < 1.40. The copolymers were further chain-extended with a second batch of VPBA, resulting in a block copolymer with monomodal molecular weight distribution and -D 5 1.66. For MEMA/VPBA copolymers, increases in VPBA composition and polymer solution concentration resulted in decreases in the cloud point temperature (CPT, typically varied between 27.4-37.8 8C) and CPT increased from 31.2 to 33.8 8C to about 88 8C with decreases in pH from 7 to 4. Rheological tests with small angle light scattering (SALS) confirmed CPTs measured by UV-Vis and DLS. These copolymers were targeted as models to combine possible glucose-sensing boronic acid functionality the thermoresponsiveness provided by MEMA groups. V C 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016Chem. , 54, 1560Chem. -1572

show abstract

“…This translational mechanism has mostly been used for the creation of polymeric thermometers with examples including a 1,8-naphthalimide-decorated thermoresponsive copolymer like poly( N -isopropylacrylamide) showing fluorescent enhancement upon precipitation [83] or Disperse Red 1 (DR1)-oligoethyleneglycol acrylate copolymers showing a bathochromic shift [84,85]. The possibility of using a solvatochromic dye for the creation of polymeric sensors for glucose was published by our group in 2012 where the pH-induced polymer precipitation of a P(4-VBA) was translated into a color change by incorporating DR1 [86]. …”

Section: Sensory Applicationsmentioning

confidence: 99%

Responsive Boronic Acid-Decorated (Co)polymers: From Glucose Sensors to Autonomous Drug Delivery

Vancoillie

Hoogenboom

2016

Sensors

Self Cite

View full text Add to dashboard Cite

Boronic acid-containing (co)polymers have fascinated researchers for decades, garnering attention for their unique responsiveness toward 1,2- and 1,3-diols, including saccharides and nucleotides. The applications of materials that exert this property are manifold including sensing, but also self-regulated drug delivery systems through responsive membranes or micelles. In this review, some of the main applications of boronic acid containing (co)polymers are discussed focusing on the role of the boronic acid group in the response mechanism. We hope that this summary, which highlights the importance and potential of boronic acid-decorated polymeric materials, will inspire further research within this interesting field of responsive polymers and polymeric materials.

show abstract

Direct nitroxide mediated (co)polymerization of 4-vinylphenylboronic acid as route towards sugar sensors

Cited by 46 publications

References 26 publications

Substituent effects on absorption spectra of pH indicators: An experimental and computational study of sulfonphthaleine dyes

Substituent effects on absorption spectra of pH indicators: An experimental and computational study of sulfonphthaleine dyes

Vinyl phenylboronic acid controlling co‐monomer for nitroxide mediated synthesis of thermoresponsive poly(2‐N morpholinoethyl methacrylate)

Responsive Boronic Acid-Decorated (Co)polymers: From Glucose Sensors to Autonomous Drug Delivery

Contact Info

Product

Resources

About