Molecularly imprinted polymers and their application as environmental sensors

Carbon Dots ◽

Environmental Sensors ◽

Imprinted Polymer ◽

Molecularly Imprinted ◽

Imprinted Polymers

Molecularly imprinted polymers are specialty polymers with ability of selectively capturing target molecules. They show great potential to be environmental sensors for the detection of specific contaminant. The overall research objective is to investigate the sensing ability of MIPs based on two mechanisms fluorescence quenching and reflectance for two example contaminants 2, 4-dinitrotoluene and 2-butoxylethanol, which are fingerprinting contaminant of explosive manufacturing and hydraulic fracking. The water chemistry effects are explored on MIPs for their potential use as in-situ sensors in complex aquatic environments. Fluorescent carbon dots with different surface functionality were fabricated and their environmental fate was explored. Amino-functionalized carbon dots (AC-dots) were applied to fluorescently label a molecularly imprinted polymer (MIP) for 2, 4-dinitrotoluene (DNT) as a template. DNT is specifically captured by the cavities in the MIP and interact with AC-dots on the surface, resulting in quenching of the fluorescence of the AC-dots. Response to DNT reaches equilibrium within [about]30 min. The method has a dynamic range that extends from 1 to 15 ppm, and allows for quantitation of DNT in aqueous solutions, with a detection limit of 0.28 ppm. Selectivity tests conducted in presence of DNT analogs demonstrated the specific recognition of DNT. The effect of sample water chemistry on carbon dots labeled molecularly imprinted polymer (AC-MIP) sensor the detection of 2, 4-dinitrotoluene (DNT) was investigated. With the increase of ionic strength from 1 mM to 100 mM, the quenching amount of MIPs decreased about 19% and 30% with NaCl and CaCl2 respectively. In the range of pH from 4 to 9, quenching effect is slightly higher at basic environment for both MIPs and non-imprinted polymers (NIPs) resulting from swelling properties of the films. NOM added the quenching amount to the sensor with a modified equation developed with NOM as a variable. In both lake water and tap water, DNT concentrations read by the sensors were very close to the HPLC measured DNT concentrations with the range from 72% to 105%. Molecularly imprinted polymers (MIPs) sensors for detection of 2-butoxyethanol (2BE), a pollutant associated with hydraulic fracturing contamination, were developed based on the combination of a colloidal crystal templating method and a molecular imprinting technique. MIPs exhibited higher binding than non-imprinted films (NIPs) due to the specific adsorption provided by molecular imprinting with imprinting efficiencies around 2. Optical tests were performed because of the uniformly ordered porous structure. The reflectance spectra of the sensors showed Bragg's peaks, which responded to the presence of 2BE; peaks presented increasing red shifts up to 50 nm with 2BE concentrations in the range of 1 ppb to 100 ppm, which allowed quantitative estimates of present 2BE concentration in aqueous solutions. The material has the potential for early detection of hydraulic fracturing sites contamination.

Ferric Iron-Containing Molecularly Imprinted Polymer as an Adsorbent for Cholesterol

Adsorption Science & Technology ◽

10.1260/026361703322404403 ◽

2003 ◽

Vol 21 (3) ◽

pp. 261-268 ◽

Cited By ~ 4

Author(s):

K. Sreenivasan ◽

R. Sivakumar

Keyword(s):

Adsorption Capacity ◽

Molecular Imprinting ◽

Ferric Iron ◽

Imprinted Polymer ◽

Molecularly Imprinted ◽

Functional Monomers ◽

Imprinted Polymers ◽

Chemically Modified

Molecular imprinting is an elegant approach to the synthesis of polymers with predetermined recognition properties, the technique of molecular imprinting involving arranging the functional monomers around the print molecules prior to polymerisation. Molecularly imprinted polymers (MIPs) show a remarkable ability to bind print molecule from a mixture of entities which are close in structure. One of the serious drawbacks of MIPs is their low adsorption capacity and one approach to improving this relies on the use of chemically modified monomers in the synthesis of the MIPs. This report discusses the synthesis and evaluation of an MIP based on ferric acrylate as an adsorbent for cholesterol.

Factors Affecting Preparation of Molecularly Imprinted Polymer and Methods on Finding Template-Monomer Interaction as the Key of Selective Properties of the Materials

Molecules ◽

10.3390/molecules26185612 ◽

2021 ◽

Vol 26 (18) ◽

pp. 5612

Author(s):

Aliya Nur Hasanah ◽

Nisa Safitri ◽

Aulia Zulfa ◽

Neli Neli ◽

Driyanti Rahayu

Keyword(s):

Molecular Imprinting ◽

Magic Angle Spinning ◽

Proton Nuclear Magnetic Resonance ◽

Magic Angle ◽

Imprinted Polymer ◽

Molecularly Imprinted ◽

Imprinted Polymers ◽

Vis Spectroscopy

Molecular imprinting is a technique for creating artificial recognition sites on polymer matrices that complement the template in terms of size, shape, and spatial arrangement of functional groups. The main advantage of Molecularly Imprinted Polymers (MIP) as the polymer for use with a molecular imprinting technique is that they have high selectivity and affinity for the target molecules used in the molding process. The components of a Molecularly Imprinted Polymer are template, functional monomer, cross-linker, solvent, and initiator. Many things determine the success of a Molecularly Imprinted Polymer, but the Molecularly Imprinted Polymer component and the interaction between template-monomers are the most critical factors. This review will discuss how to find the interaction between template and monomer in Molecularly Imprinted Polymer before polymerization and after polymerization and choose the suitable component for MIP development. Computer simulation, UV-Vis spectroscopy, Fourier Transform Infrared Spectroscopy (FTIR), Proton-Nuclear Magnetic Resonance (1H-NMR) are generally used to determine the type and strength of intermolecular interaction on pre-polymerization stage. In turn, Suspended State Saturation Transfer Difference High Resolution/Magic Angle Spinning (STD HR/MAS) NMR, Raman Spectroscopy, and Surface-Enhanced Raman Scattering (SERS) and Fluorescence Spectroscopy are used to detect chemical interaction after polymerization. Hydrogen bonding is the type of interaction that is becoming a focus to find on all methods as this interaction strongly contributes to the affinity of molecularly imprinted polymers (MIPs).

Recent developments in molecularly imprinted polymer nanofibers and their applications

Analytical Methods ◽

10.1039/c5ay01609f ◽

2015 ◽

Vol 7 (18) ◽

pp. 7406-7415 ◽

Cited By ~ 16

Author(s):

Shabi Abbas Zaidi

Keyword(s):

Imprinted Polymer ◽

Polymer Nanofibers ◽

Molecularly Imprinted ◽

Imprinted Polymers ◽

Recent Developments ◽

Analyte Detection

Molecularly imprinted polymers (MIPs) have been potential and versatile candidates for analyte detection.

Reusable molecularly imprinted polymeric nanospheres for diclofenac removal from water samples

Journal of Chemical Research ◽

10.1177/1747519820925998 ◽

2020 ◽

pp. 174751982092599

Author(s):

Noha Amaly ◽

Georges Istamboulie ◽

Ahmed Y El-Moghazy ◽

Thierry Noguer

Keyword(s):

Water Samples ◽

Imprinted Polymer ◽

Molecularly Imprinted ◽

Imprinted Polymers ◽

Residue Removal ◽

Pharmaceutical Pollutants ◽

Polymer Nanospheres ◽

Average Size

The preparation of efficient molecularly imprinted polymers materials (MIPs) for pharmaceutical residue removal is still a challenging task. Herein, we design uniformly molecularly imprinted polymer nanospheres via a precipitation polymerization method using methacrylic acid (MAA) as functional monomer and N,N-methylenebis(acrylamide) (MBAA) as a crosslinker for removal of diclofenac (DFC) as a model for pharmaceutical pollutants. Nanospheres with average size 200 nm were prepared with MAA:MBAA at a ratio of 1:7 and acetonitrile/toluene (1:1) as a porogenic solvent. The successful synthesis is evidenced by Fourier transform infrared spectroscopy, scanning electron microscopy, and with a particle size analyzer. The rebinding experiments confirmed that the more introduction of the carboxyl groups from MAA could remarkably improve the imprinting effect with a significantly increased imprinting factor and specific rebinding capacity reached 450 mg/g after 15 min. Furthermore, the adsorption capacity of the molecularly imprinted polymers is maintained above 85% after seven regeneration cycles, indicating that the molecularly imprinted polymers can be used multiple times. Moreover, the developed molecularly imprinted polymers show promising DFC removal efficiency from real water samples, which suggests that the prepared molecularly imprinted polymer nanospheres are promising in DFC separation.

Molecularly Imprinted Polymer and Computational Study of (E)-4-(2- cyano-3-(dimethylamino)acryloyl)benzoic Acid from Poly(ethylene terephthalate) Plastic Waste

Current Analytical Chemistry ◽

10.2174/1573411015666190131123843 ◽

2020 ◽

Vol 16 (2) ◽

pp. 119-137 ◽

Cited By ~ 1

Author(s):

Asmaa M. Fahim ◽

Bartłomiej Wasiniak ◽

Jerzy P. Łukaszewicz

Keyword(s):

Benzoic Acid ◽

Ethylene Terephthalate ◽

Computational Study ◽

Imprinted Polymer ◽

Molecularly Imprinted ◽

Imprinted Polymers ◽

Poly Ethylene Terephthalate ◽

Poly Ethylene

Background: Molecularly imprinted polymers (MIPs) are utilized in the separation of a pure compound from complex matrices. A stable template-monomer complex generates MIPs with the highest affinity and selectivity for the template. In this investigation, degradation of Poly(ethylene terephthalate) PET afforded the (E)-4-(2-cyano-3-(dimethylamino) acryloyl) benzoic acid (4) (TAM) which used TAM as template which interacts with Methacrylic Acid (MAA) monomer, in the presence of CH3CN as progen. The TAM-MMA complex interactions are dependent on stable hydrogen bonding interaction between the carboxylic acid group of TAM and the hydroxyl group of MMA with minimal interference of porogen CH3CN. The DFT/B3LYP/6-31+G model chemistry was used to optimize their structures and frequency calculations. The binding energies between TAM with different monomers showed the most stable molar ratio of 1:4 which was confirmed through experimental analysis. Methods: The present work describes the synthesis of (E)-4-(2-cyano-3-(dimethylamino) acryloyl) benzoic acid (4) (TAM) from PET waste and formation of molecularly imprinted polymer from TAM with the methacrylic acid monomer. The optimization of molecular imprinted was stimulated via DFT/B3LYP/6-31G (d). The imprinted polymer film was characterized via thermal analysis, pore size, FT-IR and scanning electron microscopy. Results: The most stable molecularly imprinted polymers (MIPs) showed binding energy of TAM(MMA4)=-2063.456 KJ/mol with a small value of mesopores (10-100 Å). Also, the sorption capability of TAM-MIPs showed 6.57 mg/g using STP-MIP-9VC. Moreover, the average pore size ranged between 0.2-1 nm with the BET surface about 300 m2/g. Conclusion: The proposed TAM exhibited a high degree of selectivity for MMA in comparison with other different monomers through hydrogen bond interaction, which was thermally stable, good reproducibility and excellent regeneration capacity and elucidated in the computational study and analytical analysis.

Synthesis and Evaluation of a Molecularly Imprinted Polymer Selective to 2,4,6-Trichlorophenol

Australian Journal of Chemistry ◽

10.1071/ch04004 ◽

2004 ◽

Vol 57 (8) ◽

pp. 759 ◽

Cited By ~ 34

Author(s):

Lachlan Schwarz ◽

Clovia I. Holdsworth ◽

Adam McCluskey ◽

Michael C. Bowyer

Keyword(s):

Competitive Binding ◽

Imprinted Polymer ◽

Binding Studies ◽

Molecularly Imprinted ◽

Imprinted Polymers ◽

Target Molecule ◽

High Preference ◽

Structural Analogues

Molecularly imprinted polymers (MIPs) selective for the phenolic contaminant 2,4,6-trichlorophenol (2,4,6-TCP) were prepared and evaluated in three porogens of differing character (hexane, acetonitrile, dichloromethane). Rebinding of 2,4,6-TCP was found to be most effective in dichloromethane (imprinting factor: 13.2). Competitive binding studies performed against a range of close structural analogues showed a high preference for the target molecule, although partial recognition towards 2,4-dichlorophenol was also observed. Specificity was found to be dependent upon the presence of ring chlorine on the target, which suggested that these atoms participate in secondary binding interactions that are essential for successful recognition in the polymer cavity.

Boronate-affinity hollow molecularly imprinted polymers for the selective extraction of nucleosides

New Journal of Chemistry ◽

10.1039/c7nj00148g ◽

2017 ◽

Vol 41 (15) ◽

pp. 7133-7141 ◽

Cited By ~ 18

Author(s):

Yue Hu ◽

Wei Huang ◽

Yukui Tong ◽

Qinfei Xia ◽

Miaomiao Tian

Keyword(s):

Selective Extraction ◽

Imprinted Polymer ◽

Molecularly Imprinted ◽

Imprinted Polymers ◽

Selective Enrichment

Preparation of a boronate-affinity hollow molecularly imprinted polymer and its application as an SPE adsorbent for the selective enrichment of nucleosides.