Synthetic Mechanism of Molecular Imprinting at the Solid Phase

Cowen, Todd; Stefanucci, Enrico; Piletska, Elena; Marrazza, Giovanna; Canfarotta, Francesco; Piletsky, Sergey A.

doi:10.1021/acs.macromol.9b01913

Cited by 36 publications

(32 citation statements)

References 60 publications

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“…As far as we know, though these facts have been acknowledged, their consequences on the properties of MIPs have not been considered so far. This is the purpose of the present work [9].…”

Section: Introductionmentioning

confidence: 95%

“…To this end, computer simulations were used to estimate the monomer-template interaction energies. However, caution should be taken in their direct application to real systems; the most suitable estimation which takes into account the complexity of the real medium must be empirically derived [9]. Besides the interaction between the functional monomer and the template, the functional monomer should also be chosen on the basis of its reactivity in the radical copolymerization with the cross-linking agent.…”

Section: Introductionmentioning

confidence: 99%

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Design of Molecularly Imprinted Polymeric Materials: The Crucial Choice of Functional Monomers

Anene¹,

Kalfat²,

Chevalier

et al. 2020

Chemistry Africa

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The choice of the functional monomer is addressed in the present study. It is not only dictated by its ability to interact with the template molecule. Its reactivity towards the cross-linker in the radical polymerization reaction is also to be considered in order to yield a suitable distribution of the monomer bearing binding groups within the material and also to adjust the cross-linking degree which provides rigidity to MIP network. MIPs prepared using two functional monomers of very different reactivity in radical polymerization allowed to investigate the criteria for the optimum choice of the functional monomer. MIPs were made of cross-linked poly(methacrylic acid) or poly(maleic acid) bound as thin films to a silica solid support. Ethylene glycol dimethacrylate was the cross-linker. Calculations of the composition drift of the copolymer material from monomers reactivity ratios give new insights into the control of MIP properties by the choice of the functional monomer. As a consequence of the lower reactivity of maleic acid than methacrylic acid for copolymerization with methacrylic esters, the incorporation of maleic acid is low, the cross-linking density is very high, the polymer coating is very thin, and the specific area is high. The final structure of the MIP network with a predominance of isolated functional units closely surrounded by cross-links yields a rigid material capable of preserving the memory of the model molecule of patulin in molecular imprints. Low reactivity of the functional monomer has beneficial effects regarding the binding selectivity for the target molecule compared to materials prepared from the more reactive methacrylic acid which lead to the formation of flexible polymer formed of short poly(methacrylic acid) sequences.

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“…As far as we know, though these facts have been acknowledged, their consequences on the properties of MIPs have not been considered so far. This is the purpose of the present work [9].…”

Section: Introductionmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

Design of Molecularly Imprinted Polymeric Materials: The Crucial Choice of Functional Monomers

Anene¹,

Kalfat²,

Chevalier

et al. 2020

Chemistry Africa

View full text Add to dashboard Cite

show abstract

Section: Discussionmentioning

confidence: 99%

“…When they grow further, cross-linking increases until they exceed their solubility limit, giving rise to nanogel particles, which may further grow and aggregate to finally form the bulk polymer. As recently demonstrated in the case of imprinted polymers prepared by solid-phase synthesis [28], the interactions between the template molecules and the pre-polymerization mixture can lead to three different outcomes: (a) When template molecules are present in the pre-polymerization mixture from the start, they will find a reaction medium that is very rich in functional monomers, but with no oligomers. Because the polymerization process is fast and dominated by cross-linking steps, weak complexes between template molecules and functional monomers will prevail by producing an MIP with a relatively low imprinting effect.…”

Section: Discussionmentioning

confidence: 99%

Delayed Addition of Template Molecules Enhances the Binding Properties of Diclofenac-Imprinted Polymers

et al. 2020

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It has been reported that in the molecular imprinting technique, the use of preformed oligomers instead of functional monomers increases the stability of the non-covalent interactions with the template molecule, providing a sharp gain in terms of binding properties for the resulting imprinted polymer. Based on this theory, we assumed that the delayed addition of template molecules to a polymerization mixture enhances the binding properties of the resulting polymer. To verify this hypothesis, we imprinted several mixtures of 4-vinylpyridine/ethylene dimethacrylate (1:6 mol/mol) in acetonitrile by adding diclofenac progressively later from the beginning of the polymerization process. After polymerization, the binding isotherms of imprinted and non-imprinted materials were measured in acetonitrile by partition equilibrium experiments. Binding data confirm our hypothesis, as imprinted polymers prepared by delayed addition, with delay times of 5 and 10 min, showed higher binding affinity (Keq = 1.37 × 104 L mol−1 and 1.80 × 104 L mol−1) than the polymer obtained in the presence of template at the beginning (Keq = 5.30 × 103 L mol−1). Similarly, an increase in the imprinting factor measured vs. the non-imprinted polymer in the binding selectivity with respect to mefenamic acid was observed. We believe that the delayed addition approach could be useful in prepar imprinted polymers with higher binding affinity and increased binding selectivity in cases of difficult imprinting polymerization.

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“…For this purpose, special automated UV photochemical reactor prototypes were designed by Piletsky and co‐workers. [ 172 ] Very recently, they proposed a synthetic mechanism for molecular imprinting in the solid phase [ 173 ] that is in contrast to mechanisms previously proposed in other studies. The main disadvantage of solid‐phase imprinting is the low yield of MIPs (high E‐factor).…”

Section: Green Strategies For Benign Mipsmentioning

confidence: 99%

Molecular Imprinting: Green Perspectives and Strategies

et al. 2021

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Large quantities of organic solvents and reagents are usually required in the fabrication of these materials. Moreover, the use of excess reagents in solvent extraction, purification, filtration/ centrifugation, and cleaning processes is essential for adequate product purity. Because of the numerous practical applications of advanced materials, some are synthesized on a large scale and commercialized. [3] The excessive consumption of nonrenewable, hazardous chemicals is an unsustainable practice and a prominent criticism of these materials. Nonetheless, the use of advanced materials in sensing applications, medicine, electronics, and catalysis is inevitable. [4] During various research activities, such as fabricating advanced materials, as well as in the subsequent stage, i.e., industrial operations, new challenges have arisen that impact not only almost every aspect of human life but also other living creatures and ecosystems. It is estimated that the impact of these practices will endure into the next century. [5] Since the advancement of science, industry, and technology is inevitable, scientists have been persuaded to search for methods to counteract or minimize the negative impacts of human activities. [6] Thus, green chemistry has advanced and green principles have been defined for most sciences, including synthesis, [7] analytical chemistry, [8] engineering, [9] and pharmaceutical science. [10] Fortunately, contemporary society has great awareness of deleterious environmental side effects, resulting in a sense Advances in revolutionary technologies pose new challenges for human life; in response to them, global responsibility is pushing modern technologies toward greener pathways. Molecular imprinting technology (MIT) is a multidisciplinary mimic technology simulating the specific binding principle of enzymes to substrates or antigens to antibodies; along with its rapid progress and wide applications, MIT faces the challenge of complying with green sustainable development requirements. With the identification of environmental risks associated with unsustainable MIT, a new aspect of MIT, termed green MIT, has emerged and developed. However, so far, no clear definition has been provided to appraise green MIT. Herein, the implementation process of green chemistry in MIT is demonstrated and a mnemonic device in the form of an acronym, GREENIFICATION, is proposed to present the green MIT principles. The entire greenificated imprinting process is surveyed, including element choice, polymerization implementation, energy input, imprinting strategies, waste treatment, and recovery, as well as the impacts of these processes on operator health and the environment. Moreover, assistance of upgraded instrumentation in deploying greener goals is considered. Finally, future perspectives are presented to provide a more complete picture of the greenificated MIT road map and to pave the way for further development.

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Synthetic Mechanism of Molecular Imprinting at the Solid Phase

Cited by 36 publications

References 60 publications

Design of Molecularly Imprinted Polymeric Materials: The Crucial Choice of Functional Monomers

Design of Molecularly Imprinted Polymeric Materials: The Crucial Choice of Functional Monomers

Delayed Addition of Template Molecules Enhances the Binding Properties of Diclofenac-Imprinted Polymers

Molecular Imprinting: Green Perspectives and Strategies

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