A comparison of covalent and non-covalent imprinting strategies for the synthesis of stigmasterol imprinted polymers

Hashim, Shima N Siti; Boysen, Reinhard I; Schwarz, Lachlan J.; Danylec, Basil; Hearn, Milton Thomas William

doi:10.1016/j.chroma.2014.07.034

Cited by 53 publications

(26 citation statements)

References 26 publications

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“…The observed binding was largely associated with non-specific interactions. These studies confirmed an earlier report on the failure of the monomers MAA and 4-VP to generate by non-covalent self-assembly approaches stigmasterol-imprinted polymers with acceptable imprinting factors [28]. This outcome can be attributed to an inability to form a stable pre-polymerisation complex, involving the functional monomers and the sterol template, owing to the presence of only a single A-ring C-3β-hydroxyl group of the sterol capable of forming a hydrogen bond with, for example, the N,N -dimethylamido group of the N,N -DMAAM monomer.…”

Section: Resultssupporting

confidence: 79%

“…Upon polymerisation with N,N -dimethylacrylamide (N,N -DMAAM) as the co-monomer, the molecular template, stigmasteryl-3-O-methacrylate, generated a MIP which can be hydrolyzed to afford a complimentary cavity housing carboxylic acid and N,N -dimethylamido group functionalities as hydrogen bonding recognition units [17,28]. On the basis of molecular modelling investigations, it was anticipated that this MIP would be able to recognize not only stigmasterol but also the more valuable campesterol and brassicasterol.…”

Section: Selection Of the Molecular Templatementioning

confidence: 99%

“…Stigmasterol was converted to the polymerisable template stigmasteryl methacrylate (18) via a dicyclohexylcarbodiimide (DCC)-mediated reaction [28] between stigmasterol and methacrylic acid (Scheme 4) based on conditions similar to those used for generation of cholesterol-based templates [15]. Further details of the synthesis of (18) …”

Section: Synthesis Of the Polymerisable Molecular Templatementioning

confidence: 99%

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Phytosterol Recognition via Rationally Designed Molecularly Imprinted Polymers

Schwarz

Leung

Danylec

et al. 2018

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Abstract:Molecularly imprinted polymers (MIPs) prepared via a semi-covalent imprinting strategy using stigmasteryl methacrylate as a polymerisable template have been evaluated by static binding methods for their ability to selectively capture other valuable phytosterol targets, including campesterol and brassicasterol. Design criteria based on molecular modelling procedures and interaction energy calculations were employed to aid the selection of the co-monomer type, as well as the choice of co-monomer:template ratios for the formation of the pre-polymerisation complex. These novel hybrid semi-covalently imprinted polymers employed N,N -dimethylacryl-amide (N,N -DMAAM) as the functional co-monomer and displayed specific binding capacities in the range 5.2-5.9 mg sterol/g MIP resin. Their binding attributes and selectivities towards phytosterol compounds were significantly different to the corresponding MIPs prepared via non-covalent procedures or when compared to non-imprinted polymers. Cross-reactivity studies using stigmasterol, ergosterol, cholesterol, campesterol, and brassicasterol as single analytes revealed the importance of the A-ring C-3-β-hydroxyl group and the orientational preferences of the D-ring alkyl chain structures in their interaction in the templated cavity with the N,N -dimethylamide functional groups of the MIP. Finally, to obtain useful quantities of both campersterol and brassicasterol for these investigations, improved synthetic routes have been developed to permit the conversion of the more abundant, lower cost stigmasterol via a reactive aldehyde intermediate to these other sterols.

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Section: Resultssupporting

confidence: 79%

Section: Selection Of the Molecular Templatementioning

confidence: 99%

Section: Synthesis Of the Polymerisable Molecular Templatementioning

confidence: 99%

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Phytosterol Recognition via Rationally Designed Molecularly Imprinted Polymers

Schwarz

Leung

Danylec

et al. 2018

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“…15,16 This approach provides polymers with homogeneous distribution of binding sites, high selectivity, and eliminates nonspecific binding sites which results from excess use of functional monomers. 17 However, the approach is not widely applied because of slow rebinding process of the polymers, 13,18 the need for a pre-step process of designing a stable template-monomer composite through covalent bond formation, and limitation of the approach to diols, ketones, aldehydes, carboxylic acids, and amines. 16,18 The third approach is the so called intermediate approach or the semi-covalent approach and takes advantage of both noncovalent and covalent interactions.…”

Section: Molecular Imprinting Processmentioning

confidence: 99%

Molecularly imprinted polymers—A closer look at the control polymer used in determining the imprinting effect: A mini review

Ndunda

2020

J of Molecular Recognition

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Molecular recognition displayed by naturally occurring receptors has continued to inspire new innovations aimed at developing systems that can mimic this natural phenomenon. Since 1930s, a technology called molecular imprinting for producing biomimetic receptors has been in place. In this technology, tailor made binding sites that selectively bind a given target analyte (also called template) are incorporated in a polymer matrix by polymerizing functional monomers and cross-linking monomers around a target analyte followed by removal of the analyte to leave behind cavities specific to the analyte. The success of the imprinting process is defined by two main

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“…In the case of molecularly imprinted polymers prepared using non-covalent interactions, a key step in the polymer synthesis is the formation of the complex between the template and functional monomer(s). It is commonly accepted that the stronger the interactions between the template and monomers are, the more stable of the host-guest complex prior to polymerization is [13], and consequently the better imprinting efficiency of the resulted polymers is. Many theoretical [14] and experimental studies [15]- [17] focused on the formation and stability of pre-polymerization complexes.…”

Section: Introductionmentioning

confidence: 99%

Template-Monomer Interaction in Molecular Imprinting: Is the Strongest the Best?

Fu¹,

Yang²,

Zhou³

et al. 2015

OJOPM

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Molecularly imprinted polymers (MIPs) represent a new class of materials possessing high selectivity and affinity for the target molecule. They have been utilized as sensors, catalysts, sorbents for solid-phase extraction, stationary phase for liquid chromatography, mimics of enzymes, receptors, and antibodies. In this research, molecular imprinted polymers (MIPs) for luteolin were prepared using acrylamide, 4-vinylpyridine and 1-allyl-piperazine as functional monomers and ethylene glycol dimethacrylate as cross-linker by non-covalent imprinting method. UV-visible spectra were used to evaluate the interaction strength between the template and the monomers. The composites of the polymers were calculated from elementary analysis. The porous properties of the imprinted polymers have been determined from nitrogen adsorption-desorption isotherms. The imprinting efficiency of the prepared MIPs was evaluated by selective adsorption for luteolin and its structural analogues. Although the interaction strength of monomers to the template was in the order 1-ALPP > 4-VP > AA, the binding affinity of the imprinted polymers towards luteolin was in the order MIP 2 > MIP 3 > MIP 1. Our results demonstrated that the imprinting efficiency was depending not only on the interaction strength between the template and the monomer, but also on the fidelity in transferring the complex into the polymer.

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A comparison of covalent and non-covalent imprinting strategies for the synthesis of stigmasterol imprinted polymers

Cited by 53 publications

References 26 publications

Phytosterol Recognition via Rationally Designed Molecularly Imprinted Polymers

Phytosterol Recognition via Rationally Designed Molecularly Imprinted Polymers

Molecularly imprinted polymers—A closer look at the control polymer used in determining the imprinting effect: A mini review

Template-Monomer Interaction in Molecular Imprinting: Is the Strongest the Best?

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