Fluorescence spectroscopy and multivariate analysis as a greener monitoring tool: characterization of the curing kinetics of bioinspired polymers

Ledesma, Julieta; Bortolato, Santiago Andrés; Martino, Debora Marcela; Boschetti, Carlos E.

doi:10.1080/17518253.2015.1073798

Cited by 3 publications

(5 citation statements)

References 27 publications

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“…In contrast, after 18 min of blue‐LED irradiation in the presence of Ru(bpy) 3 2+ /S 2 O 8 2− in both N 2 ‐ and air‐saturated solutions, the FEEM spectrum of the protein in each case was distorted with the appearance of an extra red‐shifted band with an excitation/emission maximum at approximately 320 nm/410 nm, respectively. However, the ratio of emission fluorescence intensity between the shoulder at 410 nm and the maximum at 340 nm was almost twice as high for the N 2 ‐purged solution as for the air‐saturated one.Multivariate curve resolution‐alternating least squares (MCR‐ALS) algorithm was applied to separate the individual spectral contribution of each fluorophore residue, [38,39] and the normalized excitation and emission spectra contributing to each FEEM obtained by the MCR‐ALS analysis with a misfit of only <5 % are shown in Figure 6B.…”

Section: Resultsmentioning

confidence: 99%

Photosensitized Formation of Soluble Bionanoparticles of Lysozyme

et al. 2021

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Photosensitized crosslinking of hen egg‐white lysozyme (LZ) in buffer solutions was obtained by blue‐LED excitation of ruthenium (II) tris‐bipyridyl dication (Ru(bpy)32+) in a molar excess of persulfate anion (S2O82−), both in the absence and presence of dissolved oxygen. The results show a rapid monomer consumption of >75 %, with sequential formation of soluble LZ nanoparticles, e. g., dimers (LZ2),…n‐mers (LZn≥6) with diameters from 6 to 13 nm, regardless of the presence of dissolved oxygen in solution. The bionanoparticles are crosslinked through 3,3'‐dityrosine (diTyr) bonds, by the recombination of tyrosyl radicals of Y20, Y23, and Y53 residues of different protein molecules, produced by intermediated oxidants Ru(bpy)33+ and SO4.− generated after excitation. Furthermore, under aerobic conditions, photosensitized formation of singlet molecular oxygen (1O2) also results in the oxidative transformation of tryptophan residues into fluorescent kynurenine‐type derivatives. These findings may contribute to the rational development of functional protein bionanoparticles.

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Section: Resultsmentioning

confidence: 99%

Photosensitized Formation of Soluble Bionanoparticles of Lysozyme

et al. 2021

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Section: Resultsmentioning

confidence: 99%

“…Despite the molecular complexity of both polyelectrolytes due to the presence of VBA or VPS units, which vibrational transitions overlap with some frequencies of interest, it has been proved that upon UV irradiation the VBT unit is photodegraded. [18,34] Therefore, some positive bands of either FTIR or Raman difference spectrum (i. e. UVB-dark) generate information regarding the formation of the VBT photo-dimers, e. g. CPD-like and 6-4PP-like; while some negative bands suggest the degradation of the VBT copolymer. Accordingly, the negative bands at 1630 cm À 1 [29] and 1602 cm À 1 [28] in the FTIR and Raman difference spectra ( Figures 3C and 3D), respectively, confirm the VBT degradation due to the destruction of the C(5) = C(6) double bond in the thymine moiety.…”

Section: Uv-induced Dimerization Of the Vbt Copolymer In The Microcapmentioning

confidence: 99%

Fabrication and Characterization of Hollow Microcapsules from Polyelectrolytes Bearing Thymine Pendant Groups for Ultraviolet‐B (UVB)‐Induced Crosslinking

et al. 2019

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DNA – bioinspired polyelectrolytes poly[vinylbenzylthymine (VBT)‐4‐vinylbenzyltriethylammonium chloride (VBA)] and poly[vinylbenzylthymine (VBT)‐4‐vinylphenylsufonate (VPS)] were used for the preparation of hollow microcapsules (HMC) using the layer‐by‐layer method and CaCO3 microspheres as removable molds. Stable aqueous suspensions of spherical‐shaped HMCs with a shell composed of six layers of VBA‐based polyelectrolytes were obtained, of approximately (7.0±1.5) μm diameter and a shell thickness of 1 μm. Ultraviolet‐B irradiation of the HMC suspensions induces an efficient crosslinking between adjacent polyelectrolyte chains through the formation of thymine photodimers, such as the cyclobutane pyrimidine dimer (CPD) and the (6–4) pyrimidine–pyrimidone photoproduct (6–4PP). This process resulted in a reduction of the average interstitial mesh size of the HMC shells, modulating their permeability properties and increasing the mechanical stability of the HMC without a noticeable modification of size and shape. Thus, the DNA‐bioinspired polyelectrolytes are promising materials for the preparation of UVB‐responsive HMCs.

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“…), the photo-induced crosslinking process within the copolymer can be monitored as a function of irradiation time and simulated mathematically. UV irradiation does not modify the VBA monomer, while it induces the thymine moiety to react with other neighbor thymine, leading to crosslinking of the chains (31). Consequently, the crosslinking degree "α" can be defined as follows:…”

Section: Theory: Mathematical Modelmentioning

confidence: 99%

“…The KM considers that the crosslinking process is a second order reaction with respect to the molar concentration of thymine ([Ty]) (31). Thus, the evolution of thymine concentration can be found from the following balance:…”

Section: Theory: Mathematical Modelmentioning

confidence: 99%

Experimental studies and mathematical modeling of the curing reaction of bioinspired copolymers

Chen

Lee

Bortolato

et al. 2018

Green Chemistry Letters and Reviews

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Polymer curing is a complex process that significantly delineate the final properties of the synthetized material. In this work, the photo-induced crosslinking reaction of synthetic "bioinspired" copolymers based on thymine and ionic groups was studied by gel permeation chromatography and UV absorption spectroscopy. A mathematical model for the curing process based on statistical techniques and coupled to the kinetics of crosslinking was developed. The model allows to predict both, the evolution of the crosslinking degree as a function of curing time and the gel times as a function of the molecular structure of the copolymer and the curing conditions. The theoretical values showed a very good agreement with the UV-Vis and GPC spectroscopy experimental results for all the copolymers studied. A better knowledge of the curing kinetics of thymine-based biopolymers will enable to develop materials with pre-specified properties and to improve their applications.

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Fluorescence spectroscopy and multivariate analysis as a greener monitoring tool: characterization of the curing kinetics of bioinspired polymers

Cited by 3 publications

References 27 publications

Photosensitized Formation of Soluble Bionanoparticles of Lysozyme

Photosensitized Formation of Soluble Bionanoparticles of Lysozyme

Fabrication and Characterization of Hollow Microcapsules from Polyelectrolytes Bearing Thymine Pendant Groups for Ultraviolet‐B (UVB)‐Induced Crosslinking

Experimental studies and mathematical modeling of the curing reaction of bioinspired copolymers

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