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UV-Cured Green Polymers for Biosensorics: Correlation of Operational Parameters of Highly Sensitive Biosensors with Nano-Volumes and Adsorption Properties.

ABSTRACT: The investigated polymeric matrixes consisted of epoxidized linseed oil (ELO), acrylated epoxidized soybean oil (AESO), trimethylolpropane triglycidyl ether (RD1), vanillin dimethacrylate (VDM), triarylsulfonium hexafluorophosphate salts (PI), and 2,2-dimethoxy-2-phenylacetophenone (DMPA). Linseed oil-based (ELO/PI, ELO/10RD1/PI) and soybean oil-based (AESO/VDM, AESO/VDM/DMPA) polymers were obtained by cationic and radical photopolymerization reactions, respectively. In order to improve the cross-linking density of the resulting polymers, 10 mol.% of RD1 was used as a reactive diluent in the cationic photopolymerization of ELO. In parallel, VDM was used as a plasticizer in AESO radical photopolymerization reactions. Positron annihilation lifetime spectroscopy (PALS) was used to characterize vegetable oil-based UV-cured polymers regarding their structural stability in a wide range of temperatures (120-320 K) and humidity. The polymers were used as laccase immobilization matrixes for the construction of amperometric biosensors. A direct dependence of the main operational parameters of the biosensors and microscopical characteristics of polymer matrixes (mostly on the size of free volumes and water content) was established. The biosensors are intended for the detection of trace water pollution with xenobiotics, carcinogenic substances with a very negative impact on human health. These findings will allow better predictions for novel polymers as immobilization matrixes for biosensing or biotechnology applications.

SUBMITTER: Gozdziuk M

PROVIDER: S-EPMC9572821 | biostudies-literature | 2022 Sep

REPOSITORIES: biostudies-literature

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UV-Cured Green Polymers for Biosensorics: Correlation of Operational Parameters of Highly Sensitive Biosensors with Nano-Volumes and Adsorption Properties.

Goździuk Magdalena M Kavetskyy Taras T Roquero Daniel Massana DM Smutok Oleh O Gonchar Mykhailo M Královič David P DP Švajdlenková Helena H Šauša Ondrej O Kalinay Pavol P Nosrati Hamed H Lebedevaite Migle M Grauzeliene Sigita S Ostrauskaite Jolita J Kiv Arnold A Zgardzińska Bożena B

Materials (Basel, Switzerland) 20220923 19

The investigated polymeric matrixes consisted of epoxidized linseed oil (ELO), acrylated epoxidized soybean oil (AESO), trimethylolpropane triglycidyl ether (RD1), vanillin dimethacrylate (VDM), triarylsulfonium hexafluorophosphate salts (PI), and 2,2-dimethoxy-2-phenylacetophenone (DMPA). Linseed oil-based (ELO/PI, ELO/10RD1/PI) and soybean oil-based (AESO/VDM, AESO/VDM/DMPA) polymers were obtained by cationic and radical photopolymerization reactions, respectively. In order to improve the cros ...[more]

PMID: 36233949

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Project description:A scaling theory is developed for selective adsorption of polymers induced by the strong binding between specific monomers and complementary surface adsorption sites. By "selective" we mean specific attraction between a subset of all monomers, called "sticky", and a subset of surface sites, called "adsorption sites". We demonstrate that, in addition to the expected dependence on the polymer volume fraction ϕbulk in the bulk solution, selective adsorption strongly depends on the ratio between two characteristic length scales, the root-mean-square distance l between neighboring sticky monomers along the polymer, and the average distance d between neighboring surface adsorption sites. The role of the ratio l/d arises from the fact that a polymer needs to deform to enable the spatial commensurability between its sticky monomers and the surface adsorption sites for selective adsorption. We study strong selective adsorption of both telechelic polymers with two end monomers being sticky and multisticker polymers with many sticky monomers between sticky ends. For telechelic polymers, we identify four adsorption regimes at l/d < 1 that are characterized by the fraction of occupied adsorption sites and whether the dominant conformation of adsorbed chains is a single-end-adsorbed "mushroom" or double-end-adsorbed loop. For l/d > 1, we expect that the adsorption layer at exponentially low ϕbulk consists of separated unstretched loops, while as ϕbulk increases the layer crosses over to a brush of extended loops with a second layer of weakly overlapping tails. For multisticker chains, in the limit of exponentially low ϕbulk, adsorbed polymers are well separated from each other. As l/d increases, the conformation of an individual polymer changes from a single-end-adsorbed "mushroom" to a random walk of loops. For high ϕbulk, adsorbed polymers at small l/d are mushrooms that cover all the adsorption sites. At sufficiently large l/d, adsorbed multisticker polymers strongly overlap. We anticipate the formation of a self-similar carpet and with increasing l/d a two-layer structure with a brush of loops covered by a self-similar carpet. As l/d exceeds the threshold determined by the adsorption energy, the brush of loops under the carpet reaches a saturated state, resulting in a l/d-independent brush-under-carpet structure, which can also be applied to describe adsorbed multisticker polymers in nonselective adsorption where a sticker can strongly bind to any place on the adsorption surface. We examine the adsorbed amount Γ of multisticker polymers in different regimes for selective adsorption. If the adsorbed multisticker polymers are nonoverlapping mushrooms, the adsorbed amount Γ increases linearly with the surface density of adsorption sites Σ ≈ 1/d2. In the self-similar carpet regime, Γ increases sublinearly as Σ0.15 in a good solvent, while only logarithmically in a theta solvent. Formation of a brush layer under the carpet contributes an additional adsorbed amount. This additional amount increases linearly with Σ and eventually dominates the overall adsorbed amount Γ before saturating at a plateau value controlled by the adsorption energy.

Project description:BackgroundThere is a growing interest in the green synthesis of silver nanoparticles (AgNPs) using plant extract because the technique is cost effective, eco-friendly and environmentally benign. This is phasing out the use of toxic and hazardous chemical earlier reported. Tithonia diversifolia is a wild sunflower that grows widely in the western part of Nigeria with a proven medicinal benefit. However, several studies carried out have left doubts on the basic operational parameters needed for the green synthesis of AgNPs. The objective of this work was to carry out green synthesis of AgNPs using T. diversifolia extract via an eco-friendly route through optimization of various operational parameters, characterization, and antimicrobial studies.MethodGreen synthesis of TD-AgNPs was done via bottom-up approach through wet chemistry technique using environmentally benign T. diversifolia plant extract as both reducing and stabilizing agent. Phytochemical Screening of the TD plant extract was carried out. Experimental optimization of various operational parameters-reaction time, concentration, volume ratio, and temperature was investigated. TD-AgNPs were characterized by UV-Vis spectroscopy, FTIR Spectroscopy, SEM/energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and transmission electron microscopy (TEM). Antimicrobial studies against multi drug resistant microorganisms (MDRM) were studied using the agar well diffusion method.ResultsThis study reveals the importance of various operational parameters in the synthesis of TD-AgNPs. Excellent surface plasmon resonance peaks (SPR) were obtained at optimum experimental factors of 90 min reaction time under room temperature at 0.001M concentration with the volume ratio of 1:9 (TD extract:Ag ion solution). The synthesis was monitored using UV-Vis and maximum wavelength obtained at 430 nm was due to SPR. The morphology and elemental constituents obtained by TEM, SEM, and EDX results revealed a spherical shape of AgNPs with prominent peak of Ag at 3.0 kV in EDX spectrum. The crystallinity nature was confirmed by XRD studies. FTIR analysis proved presence of biomolecules functioning as reducing, stabilizing, and capping agents. These biomolecules were confirmed to be flavonoid, triterpenes, and saponin from phytochemical screening. The antimicrobial studies of TD-AgNPs were tested against MDRM-Escherichia coli, Salmonella typhi, Salmonella enterica, and Bacillus subtilis.DiscussionThe variation of reaction time, temperature, concentration, and volume ratio played substantive and fundamental roles in the synthesis of TD-AgNPs. A good dispersion of small spherical size between 10 and 26 nm was confirmed by TEM and SEM. A dual action mechanism of anti-microbial effects was provided by TD-AgNPs which are bactericidal and membrane-disruption. Based on the antimicrobial activity, the synthesized TD-AgNPs could find good application in medicine, pharmaceutical, biotechnology, and food science.

Dataset Information

UV-Cured Green Polymers for Biosensorics: Correlation of Operational Parameters of Highly Sensitive Biosensors with Nano-Volumes and Adsorption Properties.

Publications

UV-Cured Green Polymers for Biosensorics: Correlation of Operational Parameters of Highly Sensitive Biosensors with Nano-Volumes and Adsorption Properties.

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