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Surface imprinting used for protein recognition in functional cavities is highly effective in imprinting biomacromolecules to avoid template encapsulation during the formation of a molecularly imprinted polymer (MIP) matrix. Herein, we introduce a facile surface-imprinting method based on two-step spin-coating and photopolymerization to design highly efficient imprinted sites on polymeric films to detect trypsin (TRY). Well-distributed template imprinting is successfully achieved for maximized sensing responses by controlling the composition of functional monomers and crosslinkers in the precursor solution and the concentration of TRY in the imprinting solution. The MIP film exhibits higher sensitivity (−841 ± 65 Hz/(μg/mL)) with a coefficient of determination of 0.970 and a higher imprinting factor of 4.5 in a 0.24 µg/mL TRY solution compared to the nonimprinted polymer (NIP) film. Moreover, the limit of detection and limit of quantification are calculated to be 25.33 and 84.42 ng/mL, respectively. Finally, the selectivity coefficient is within the range of 3.90–6.78 for TRY against other proteins. These sensing properties are superior to those of the corresponding nonimprinted polymer matrix. Thus, the proposed facile surface-imprinting method is highly effective for protein imprinting with high sensitivity and selectivity.

Surface imprinting used for template recognition in nanocavities can be controlled and improved by surface morphological changes. Generally, the lithographic technique is used for surface patterning concerning sensing signal amplification in molecularly imprinted polymer (MIP) thin films. In this paper, we describe the effects of silanized silica molds on sensing the properties of MIP films. Porous imprinted poly(MAA–co–EGDMA) films were lithographically fabricated using silanized or non-treated normal silica replica molds to detect 2,4-dichlorophenoxyacetic acid (2,4-D) herbicide as the standard template. The silanized mold MIP film (st-MIP) (Δf = −1021 Hz) exhibited a better sensing response than the non-treated normal MIP (n-MIP) (Δf = −978 Hz) because the imprinting effects, which occurred via functional groups on the silica surface, could be reduced through silane modification. Particularly, two non-imprinted (NIP) films (st-NIP and n-NIP) exhibited significantly different sensing responses. The st-NIP (Δfst-NIP = −332 Hz) films exhibited lower Δf values than the n-NIP film (Δfn-NIP = −610 Hz) owing to the remarkably reduced functionality against nonspecific adsorption. This phenomenon led to different imprinting factor (IF) values for the two MIP films (IFst-MIP = 3.38 and IFn-MIP = 1.86), which was calculated from the adsorbed 2,4-D mass per poly(MAA–co–EGDMA) unit weight (i.e., QMIP/QNIP). Moreover, it was found that the st-MIP film had better selectivity than the n-MIP film based on the sensing response of analogous herbicide solutions. As a result, it was revealed that the patterned molds’ chemical surface modification, which controls the surface functionality of imprinted films during photopolymerization, plays a role in fabricating enhanced sensing properties in patterned MIP films.

This study successfully fabricated BPA-imprinted poly(4-vinylpyridine-co-ethylene glycol dimethacrylate) (poly(4-VP-co-EGDMA)) quartz crystal microbalance (MIP-QCM) sensors on a silica skeleton surface and gold pinholes of silica inverse opal through surface-initiated atom transfer radical polymerization (SI-ATRP). The sensing features of the two MIP films on the structured silica surface and nano-scale local gold surface were investigated by measuring the resonant frequency change (∆f) in QCM sensors. The ∆f values for the p-MIP (MIP on gold pinholes) and s-MIP films (MIP on silica skeleton surface) were obtained with the ∆f value of −199 ± 4.9 Hz and −376 ± 19.1 Hz, respectively, whereas for p-/s-NIP films, the ∆f values were observed to be −115 ± 19.2 Hz and −174 ± 5.8 Hz by the influence of non-specific adsorption on the surface of the films. Additionally, the imprinting factor (IF) appeared to be 1.72 for p-MIP film and 2.15 for s-MIP film, and the limits of quantitation (LOQ) and detection (LOD) were 54.924 and 18.125 nM (p-MIP film) and 38.419 and 12.678 nM (s-MIP film), respectively. Using the Freundlich isotherm model, the binding affinity of the BPA-imprinted films was evaluated. This was measured in an aqueous solution of BPA whose concentration ranged between 45 and 225 nM. It was found that the p-MIP film (m = 0.39) was relatively more heterogeneous than the s-MIP film (m = 0.33), both of which were obtained from the slope of the linear regressions. Finally, the selectivity of the MIP-QCM sensors for BPA detection was determined by measuring the effect of other analogous chemicals, such as bisphenol F (BPF), bisphenol AP (BPAP), and bisphenol B (BPB), in aqueous solutions. The selectivity coefficients (k*) of the two MIP films had ~1.9 for the p-MIP and ~2.3 for the s-MIP films, respectively. The results reveal that, with respect to signal amplification of the QCM sensors, the s-MIP film has better sensing features and faster detection responses than the p-MIP film.

Surface imprinting is an effective and simple method to fabricate and retain imprinted templates and recognizable nanocavities after template extraction. The imprinted effects can be controlled depending on the surface morphological changes. In general, a planar film has a limited area compared to a structured film with relatively higher surface-to-volume (S/V) ratio (A/A0), leading to the conventional sensing response upon the functionality of monomers in a fixed chemical composition. To increase the limited sensing properties and develop simple fabrication of porous arrays on a large area, we herein demonstrate the 2,4-dichlorophenoxyacetic acid (2,4-D, herbicide)-imprinted porous thin film lithographically patterned using photopolymerization and silica colloidal array as a master mold, derived by a unidirectional rubbing method. The resonant frequency changes with respect to the adsorption of 2,4-D molecules on a template-extracted porous poly(MAA-co-EGDMA) (MIP) film in a 10−1 mM aqueous solution of 2,4-D for 1 h, and when compared to the planar MIP film, the higher sensing response (Δf = −283 ± 7 Hz ≈ 1543 ± 38 ng/cm2) appears on the porous MIP film due to the specific recognition toward the more accessible templated cavities of the structured porous array, indicating an imprinting effect (If) value of 3.5. In addition, a higher selectivity for 2,4-D was also displayed on the porous MIP film compared to other herbicides. From these results, it was revealed that these improved sensing properties can be determined from the effects of various parameters (template functionality, film structuring, hydroxyl groups of silica colloids, etc.).

PURPOSE. The purpose of this preliminary study was to investigate the effects of adding 4,4'-bis(N,Ndiethylamino) benzophenone (DEABP) as a co-initiator to a binary photoinitiating system (camphorquinoneamine) to analyze on the degree of conversion (DC) of a light-cured resin for dental 3D printing. MATERIALS AND METHODS. Cylindrical specimens (N=60, n=30 per group, ø5 mm × 1 mm) were fabricated using bisphenol A glycerolate dimethacrylate (BisGMA) both with and without DEABP. The freshly mixed resins were exposed to light in a custom-made closed chamber with nine light-emitting diode lamps (wavelength: 405 nm; power: 840 mW/cm2) for polymerization at each incidence of light-irradiation at 10, 30, 60, 180, and 300 seconds, while five specimens at a time were evaluated at each given irradiation point. Fourier-transform infrared (FTIR) spectroscopy was used to measure the DC values of the resins. Two-way analysis of variance and the Duncan post hoc test were used to analyze statistically significant differences between the groups and given times (a=.05). RESULTS. In the DEABP-containing resin, the DC values were significantly higher at all points in time (P<.001), and also the initial polymerization velocity was faster than in the DEABP-free resin. CONCLUSION. The addition of DEABP significantly enhanced the DC values and, thus, could potentially become an efficient photoinitiator when combined with a camphorquinone-amine system and may be utilized as a more advanced photopolymerization system for dental 3D printing. [ABSTRACT FROM AUTHOR]

Novel detection method has been developed to explore changes in mechanical bending angles on a bilayer of polyethylene terephthalate (PET) and molecularly imprinted polymer (MIP). For an ovalbumin (OVA)-imprinted hydrogel layer, functional monomers were employed to achieve sufficient binding effect in the polymer matrix. The OVA amount added in the MIP precursor solution and the dimensions of OVA-imprinted hydrogel (MIH) strips were controlled to maximize the change in bending angles as an OVA sensing response within a valid detection range. The sensing behaviors were determined by monitoring the difference in the bending angles via protein adsorption based on the swelling-induced deformation of the OVA-extracted hydrogel (E-MIH) strip. The equilibrium adsorption capacity of the E-MIH strip was calculated via the Bradford protein assay. The detection limit, quantification limit, and imprinting factor were calculated. To compare the selectivity coefficients, the adsorption behaviors of three proteins were investigated. Finally, the reusability of the E-MIH strip was explored via repeated adsorption and extraction. Based on the results, the E-MIH strips demonstrated a promising protein sensing platform monitoring mechanical bending angles affected by swelling deformation. [ABSTRACT FROM AUTHOR]

The use of affinity peptide displaying on the surface of M13 phage has emerged as a promising alternative to antibody-based detection methods owing to its diverse structure, mass production, easy purification, and genetic manipulation, as well as excellent stability. In this study, we aimed to identify highly selective and sensitive peptide-displayed M13 phage for thrombin detection using phage display technology. Phage display was conducted using two different phage libraries (linear and cyclic forms of peptides), which displayed affinity peptides capable of binding specifically to thrombin. Throughout the biopanning process, two phage clones that displayed both peptides (WGQSFWGYQHYS and CWKLLTPWC) were selected. After the characterization of their binding abilities using enzyme-linked immunosorbent assay, whole phage particles were covalently attached to a gold electrode using MUA-EDC/NHS coupling chemistry. The thrombin detection mechanism was based on signal inhibition, and the results revealed that the specific interactions between the phage-tethered gold electrode and thrombin are critical factors affecting the decrease in the peak current of the sensor. In addition, under optimal conditions, the fabricated phage-based electrochemical sensors were capable of highly sensitive and specific thrombin detection with a good binding affinity (Kd = 17 nM for 12mer 3–17 and 14 nM for C7C 3–5) and limit of detection (4 nM for 12mer 3–17 and 10 nM for C7C 3–5), resulting in good reproducibility, even in artificial human plasma samples. This study may provide an alternative and more efficient method of detecting thrombin with desirable sensitivity, selectivity, and feasibility for the diagnosis and prognosis of coagulation disorder-related diseases. [ABSTRACT FROM AUTHOR]

Surface imprinting used for protein recognition in functional cavities is highly effective in imprinting biomacromolecules to avoid template encapsulation during the formation of a molecularly imprinted polymer (MIP) matrix. Herein, we introduce a facile surface-imprinting method based on two-step spin-coating and photopolymerization to design highly efficient imprinted sites on polymeric films to detect trypsin (TRY). Well-distributed template imprinting is successfully achieved for maximized sensing responses by controlling the composition of functional monomers and crosslinkers in the precursor solution and the concentration of TRY in the imprinting solution. The MIP film exhibits higher sensitivity (−841 ± 65 Hz/(μg/mL)) with a coefficient of determination of 0.970 and a higher imprinting factor of 4.5 in a 0.24 µg/mL TRY solution compared to the nonimprinted polymer (NIP) film. Moreover, the limit of detection and limit of quantification are calculated to be 25.33 and 84.42 ng/mL, respectively. Finally, the selectivity coefficient is within the range of 3.90–6.78 for TRY against other proteins. These sensing properties are superior to those of the corresponding nonimprinted polymer matrix. Thus, the proposed facile surface-imprinting method is highly effective for protein imprinting with high sensitivity and selectivity. [ABSTRACT FROM AUTHOR]

I Polymers i was able to uphold its high standards for published papers due to the outstanding efforts of our reviewers. Thanks to the efforts of our reviewers in 2022, the median time to first decision was 13 days and the median time to publication was 33 days. Regardless of whether the articles they examined were ultimately published, the editors would like to express their appreciation and thank the following reviewers for the time and dedication that they have shown I Polymers i : y those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). [Extracted from the article]

Regardless of whether the articles they examined were ultimately published, the editors would like to express their appreciation and thank the following reviewers for the time and dedication that they have shown I Molecules i olely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). Thanks to the efforts of our reviewers in 2022, the median time to first decision was 14 days and the median time to publication was 34 days. I Molecules i was able to uphold its high standards for published papers due to the outstanding efforts of our reviewers. [Extracted from the article]

In this study, a novel fibrous-like molecularly imprinted polymer film (F-MIP)-based QCM sensor was developed for the detection of methyl-4-chlorophenoxyacetic acid (MCPA). An electrospinning process was used to create a poly(N-tert-butylacrylamide) (TBAm) nanofiber membrane that would be used as the master mold for the creation of a polydimethylsiloxane (PDMS) replica mold. Further, this replicated mold was used for the fabrication of an F-MIP film on a gold-coated quartz crystal (QC) substrate via microcontact imprinting. One of the well-known functional monomers, methacrylic acid (MAA), and ethylene glycol dimethacrylate were used as functional monomer and crosslinker for the F-MIP films, respectively. The imprinted polymer network from the MIP precursor solution including the MCPA template was formed via photopolymerization during mold contact on the QC substrate. The diameter of the poly(TBAm) nanofiber used as a membrane mold controlled the fibrous morphology on the MIP film, which was investigated using field emission scanning electron microscopy. The binding behaviors of MCPA on the MIP-QCM sensor were evaluated by measuring the change in resonant frequency (Δf) values of F-MIP/NIP films with analyte adsorption in MCPA solution with a concentration range of 0.02–200 ng/mL. Furthermore, the sensing responses on the film were used to calculate the limit of detection, the limit of qualification, and the imprinting factor. The selectivity of the films was determined by comparing their sensing responses to similar herbicides. Despite the effect of nonspecific adsorption on both films due to the functional groups on MAA monomer, the imprinted film exhibited higher sensing properties and amplified sensing responses due to the fibrous-like MIP film's increased surface area. As a result, this sensor is expected to be a better option than another analytical method for detecting herbicides. [ABSTRACT FROM AUTHOR]

A visual observation of the bending angle changes for the novel and easy detection of proteins is introduced in this study by fabricating bovine serum albumin (BSA) imprinted hydrogel strips with a one sided 3D porous structure using a combination of polystyrene colloidal crystal templating and the molecular imprinting approach using BSA as the template protein and several functional monomers. [ABSTRACT FROM AUTHOR]

In this study, molecularly imprinted films with concave and convex hemispherical patterns were fabricated using soft lithography and photopolymerization, and their dynamic sensing properties were compared using the gravimetric detection of caffeine. [ABSTRACT FROM AUTHOR]

Surface imprinting used for template recognition in nanocavities can be controlled and improved by surface morphological changes. Generally, the lithographic technique is used for surface patterning concerning sensing signal amplification in molecularly imprinted polymer (MIP) thin films. In this paper, we describe the effects of silanized silica molds on sensing the properties of MIP films. Porous imprinted poly(MAA–co–EGDMA) films were lithographically fabricated using silanized or non-treated normal silica replica molds to detect 2,4-dichlorophenoxyacetic acid (2,4-D) herbicide as the standard template. The silanized mold MIP film (st-MIP) (Δf = −1021 Hz) exhibited a better sensing response than the non-treated normal MIP (n-MIP) (Δf = −978 Hz) because the imprinting effects, which occurred via functional groups on the silica surface, could be reduced through silane modification. Particularly, two non-imprinted (NIP) films (st-NIP and n-NIP) exhibited significantly different sensing responses. The st-NIP (Δfst-NIP = −332 Hz) films exhibited lower Δf values than the n-NIP film (Δfn-NIP = −610 Hz) owing to the remarkably reduced functionality against nonspecific adsorption. This phenomenon led to different imprinting factor (IF) values for the two MIP films (IFst-MIP = 3.38 and IFn-MIP = 1.86), which was calculated from the adsorbed 2,4-D mass per poly(MAA–co–EGDMA) unit weight (i.e., QMIP/QNIP). Moreover, it was found that the st-MIP film had better selectivity than the n-MIP film based on the sensing response of analogous herbicide solutions. As a result, it was revealed that the patterned molds' chemical surface modification, which controls the surface functionality of imprinted films during photopolymerization, plays a role in fabricating enhanced sensing properties in patterned MIP films. [ABSTRACT FROM AUTHOR]

This study successfully fabricated BPA-imprinted poly(4-vinylpyridine-co-ethylene glycol dimethacrylate) (poly(4-VP-co-EGDMA)) quartz crystal microbalance (MIP-QCM) sensors on a silica skeleton surface and gold pinholes of silica inverse opal through surface-initiated atom transfer radical polymerization (SI-ATRP). The sensing features of the two MIP films on the structured silica surface and nano-scale local gold surface were investigated by measuring the resonant frequency change (∆f) in QCM sensors. The ∆f values for the p-MIP (MIP on gold pinholes) and s-MIP films (MIP on silica skeleton surface) were obtained with the ∆f value of −199 ± 4.9 Hz and −376 ± 19.1 Hz, respectively, whereas for p-/s-NIP films, the ∆f values were observed to be −115 ± 19.2 Hz and −174 ± 5.8 Hz by the influence of non-specific adsorption on the surface of the films. Additionally, the imprinting factor (IF) appeared to be 1.72 for p-MIP film and 2.15 for s-MIP film, and the limits of quantitation (LOQ) and detection (LOD) were 54.924 and 18.125 nM (p-MIP film) and 38.419 and 12.678 nM (s-MIP film), respectively. Using the Freundlich isotherm model, the binding affinity of the BPA-imprinted films was evaluated. This was measured in an aqueous solution of BPA whose concentration ranged between 45 and 225 nM. It was found that the p-MIP film (m = 0.39) was relatively more heterogeneous than the s-MIP film (m = 0.33), both of which were obtained from the slope of the linear regressions. Finally, the selectivity of the MIP-QCM sensors for BPA detection was determined by measuring the effect of other analogous chemicals, such as bisphenol F (BPF), bisphenol AP (BPAP), and bisphenol B (BPB), in aqueous solutions. The selectivity coefficients (k*) of the two MIP films had ~1.9 for the p-MIP and ~2.3 for the s-MIP films, respectively. The results reveal that, with respect to signal amplification of the QCM sensors, the s-MIP film has better sensing features and faster detection responses than the p-MIP film. [ABSTRACT FROM AUTHOR]

Surface imprinting is an effective and simple method to fabricate and retain imprinted templates and recognizable nanocavities after template extraction. The imprinted effects can be controlled depending on the surface morphological changes. In general, a planar film has a limited area compared to a structured film with relatively higher surface-to-volume (S/V) ratio (A/A0), leading to the conventional sensing response upon the functionality of monomers in a fixed chemical composition. To increase the limited sensing properties and develop simple fabrication of porous arrays on a large area, we herein demonstrate the 2,4-dichlorophenoxyacetic acid (2,4-D, herbicide)-imprinted porous thin film lithographically patterned using photopolymerization and silica colloidal array as a master mold, derived by a unidirectional rubbing method. The resonant frequency changes with respect to the adsorption of 2,4-D molecules on a template-extracted porous poly(MAA-co-EGDMA) (MIP) film in a 10−1 mM aqueous solution of 2,4-D for 1 h, and when compared to the planar MIP film, the higher sensing response (Δf = −283 ± 7 Hz ≈ 1543 ± 38 ng/cm2) appears on the porous MIP film due to the specific recognition toward the more accessible templated cavities of the structured porous array, indicating an imprinting effect (If) value of 3.5. In addition, a higher selectivity for 2,4-D was also displayed on the porous MIP film compared to other herbicides. From these results, it was revealed that these improved sensing properties can be determined from the effects of various parameters (template functionality, film structuring, hydroxyl groups of silica colloids, etc.). [ABSTRACT FROM AUTHOR]