Molecularly imprinted polymeric membranes, containing artificial recognition sites for a number of benzylphosphonic acid derivatives, were prepared by the polymerization of titanium(IV) butoxide in the presence of a titanium(IV) phosphonate complex. Reference polymers were prepared in the same manner but in the absence of the phosphonate template. FTIR spectroscopy was used to follow the formation of a benzylphosphonic acid-Titanium(IV) oxide complex during the imprinting process, and upon the association of the substrate in the imprinted TiO2 thin film. The imprinted polymers were examined as sensing membranes in an ion-sensitive field-effect transistors (ISFETs). The sensors reveal selectivity towards analyzing the imprinted substrates, yet the recognition ability of the sensors strongly depends on the substituents associated with the phosphonic acid structures. The response time of the sensors is ca. 45 s, and the sensors reveal unaffected stability for at least 2 weeks. Also, imprinted TiO2 films for thiophenol, and para-nitrothiophenol were generated on ISFET devices, and the respective substrates were selectively sensed by the functional devices. 相似文献
TiO(2) nano-thin films with imprinted (R)- and (S)-enantiomers of propranolol, 1,1'-bi-naphthol, and 2-(4-isobutylphenyl)-propionic acid were fabricated on quartz plates by spin-coating their solutions with Ti(O-(n)Bu)(4) in a toluene-ethanol mixture (1:1, v/v). After template removal, the imprinted films showed better binding for original templates than to the corresponding enantiomers. The assessment of template incorporation, template removal, and re-binding was conducted through UV-vis measurements. Significant enhancement of enantioselectivity was achieved by optimization of the film thickness and by heat-treatment of the imprinted films. After subtraction of non-specific binding, the optimized films provided chiral recognition with the enantioselectivity of almost 100% for (R)-propranolol and 95% for (S)-propranolol. 相似文献
Crosslinked films consisting of the acrylamide-acrylamidophenylboronic acid copolymer that are imprinted with recognition sites for β-nicotinamide adenine dinucleotide (NAD+), β-nicotinamide adenine dinucleotide phosphate NADP+, and their reduced forms (NAD(P)H), are assembled on Au-coated glass supports. The binding of the oxidized cofactors NAD+ or NADP+ or the reduced cofactors NADH or NADPH to the respective imprinted sites results in the swelling of the polymer films through the uptake of water. Surface plasmon resonance (SPR) spectroscopy is employed to follow the binding of the different cofactors to the respective imprinted sites. The imprinted recognition sites reveal selectivity towards the association of the imprinted cofactors. The method enables the analysis of the NAD(P)+ and NAD(P)H cofactors in the concentration range of 1×10−6 to 1×10−3 M. The cofactor-imprinted films associated with the Au-coated glass supports act as active interfaces for the characterization of biocatalyzed transformations that involve the cofactor-dependent enzymes. This is exemplified with the characterization of the biocatalyzed oxidation of lactate to pyruvate in the presence of NAD+ and lactate dehydrogenase using the NADH-imprinted polymer film. 相似文献
For the first time, the feasibility of a molecularly imprinted liquid phase deposition (LPD) thin film has been demonstrated. Thin films of titanium oxide imprinted with L-glutamic acid were prepared by the LPD method on a gold-coated quartz crystal microbalance. The imprinted molecule could be removed upon treatment with immersion in deionized water. A sensor was developed on the basis of this method and showed good sensitivity, selectivity, and reproducibility to the template molecule. An equation was deduced to characterize the interaction between molecularly imprinted films and the template by virtue of Scatchard analysis. X-ray photoelectron spectroscopy was introduced to show the evidence for the molecular imprinting phenomenon. The linear relationship between the frequency shifts and the concentration of analyte in the range of 10-200 microM was obtained. LPD proves to be a powerful method for imprinting titanium oxide thin films. 相似文献
A new chromium(III)-imprinted 3-(2-aminoethylamino) propyltrimethoxysilane (AAPTS)-functionalized silica gel sorbent was synthesized by a surface imprinting technique and was employed as a selective solid-phase extraction material for speciation analysis of chromium in environmental water samples prior to its determination by inductively coupled plasma mass spectrometry (ICP-MS). The prepared Cr(III)-imprinted silica gel shows the selectivity coefficient of more than 700 for Cr(III) in the presence of Mn(II). The static adsorption capacity of the ion-imprinted and non-imprinted sorbent for Cr(III) were 30.5 mg g(-1) and 13.4 mg g(-1). It was also found that Cr(VI) could be adsorbed at low pH by the prepared imprinted silica gel, and this finding makes it feasible to enrich and determine Cr(VI) at low pH without adding reducing reagents. The imprinted silica gel sorbent offered a fast kinetics for the adsorption and desorption of both chromium species. Under the optimized conditions, the detection limits of 4.43 pg mL(-1) and 8.30 pg mL(-1) with the relative standard deviations (R.S.D.s) of 4.44% and 4.41% (C=0.5 ng mL(-1), n=7) for Cr(III) and Cr(VI) were obtained, respectively. The proposed method was successfully applied to the speciation of trace chromium in environmental water samples. To validate the proposed method, two certified reference materials were analyzed and the determined values were in a good agreement with the certified values. The developed method is rapid, selective, sensitive and applicable for the speciation of trace chromium in environmental water samples. 相似文献
Layer-by-layer assembled polyelectrolyte multilayer films of poly(acrylic acid) (PAA)/poly(allylamine hydrochloride) (PAH) have been successfully patterned by room-temperature imprinting using a Norland Optical Adhesives (NOA 63) polymer mold. The proper amount of water in the PAA/PAH multilayer film can decrease the viscosity of the film and facilitate the imprinting. Many factors, such as imprinting pressure, length of imprinting time, and the structure and size of the patterns in the polymer mold, can produce an influence on the final imprinted pattern structures on multilayer films. A high imprinting pressure of 100 bar and elongated imprinting time of several hours is needed to achieve a patterned PAA/PAH multilayer film with a feature size of several tens of micrometers. With a twice imprinting, grid structures can be successfully produced when a NOA 63 mold having line structures is used. Room-temperature imprinting by using polymer NOA 63 mold provides a facile way to fabricate layered polymeric films with various kinds of pattern structures. 相似文献
The application of novel electrosynthesized polydopamine (PDA)-imprinted film as a recognition element for the capacitive sensing of nicotine is reported. The PDA-imprinted film was electropolymerized directly on the gold electrode surface in the presence of nicotine without an additional self-assembled thiol sublayer. The compact PDA film has various functional groups that aid the imprinting procedure. Furthermore, the film shows good capacitive response since it is insulating in nature and ultrathin. The sensor’s linear response range for nicotine was between 1–25 μmol L−1, with a detection limit of 0.5 μmol L−1. The proposed molecularly imprinted polymer capacitive (MIPC) sensor exhibited good selectivity for nicotine. The reproducibility and repeatability of the MIPC senor were all found to be satisfactory. The results from sample analysis confirmed the applicability of the MIPC sensor to quantitative analysis. 相似文献
We present hybrid films consisting of a composite prepared from polystyrene (PS) and titanium dioxide (titania; TiO2) and molecularly imprinted with 1-pyrenebutyric acid (PBA). The interaction of PBA with the polymer is shown to occur via binding of the carboxylic group to TiO2 and hydrophobic interaction of the pyrene moiety with the PS network. We investigated the effects of the PS fraction on morphology, imprinting properties, and guest binding. The template could be completely removed by incubating the films in an acetonitrile solution of pyrene, which is due to the stronger π–π interaction between PBA and pyrene than the interaction between PBA and its binding site. A guest binding study with pyrene, 1-aminopyrene, pyrenemethanol, and anthracene-9-carboxylic acid showed that the hybrid films possessed selectivity and much higher binding capacity for PBA. This study demonstrates the first case of clear PS-assisted imprinting, where the π–π interaction of the template with a linear (non-crosslinked) polymer creates selective binding sites and enhances the binding capacity. This is a driving force for guest binding in addition to the interaction of the template/analyte with TiO2. All molecularly imprinted films displayed better binding, repeatability and reversibility compared to the respective non-imprinted films.
Figure
Illustration of the fabricated polystyrene/titania hybrids imprinted with 1-pyrenebutyric acid providing the interaction between the organic and inorganic components through the pyrene and carboxylic moieties 相似文献
We present hybrid films consisting of a composite prepared from polystyrene (PS) and titanium dioxide (titania; TiO2) and molecularly imprinted with 1-pyrenebutyric acid (PBA). The interaction of PBA with the polymer is shown to occur via binding of the carboxylic group to TiO2 and hydrophobic interaction of the pyrene moiety with the PS network. We investigated the effects of the PS fraction on morphology, imprinting properties, and guest binding. The template could be completely removed by incubating the films in an acetonitrile solution of pyrene, which is due to the stronger π–π interaction between PBA and pyrene than the interaction between PBA and its binding site. A guest binding study with pyrene, 1-aminopyrene, pyrenemethanol, and anthracene-9-carboxylic acid showed that the hybrid films possessed selectivity and much higher binding capacity for PBA. This study demonstrates the first case of clear PS-assisted imprinting, where the π–π interaction of the template with a linear (non-crosslinked) polymer creates selective binding sites and enhances the binding capacity. This is a driving force for guest binding in addition to the interaction of the template/analyte with TiO2. All molecularly imprinted films displayed better binding, repeatability and reversibility compared to the respective non-imprinted films.
This work reports a surface ion imprinting strategy in electropolymerized microporous poly(2-mercaptobenzothiazole) (MPMBT) films at the surface of glassy carbon electrode (GCE) for the electrochemical detection of Hg(II). The Hg(II)-imprinted MPMBT/GCE exhibits larger binding to functionalized capacity, faster binding kinetics and higher selectivity to template Hg(II) due to their high ratio of surface-imprinted sites, larger surface-to-volume ratios, the complete removal of Hg(II) templates and larger affinity to Hg(II). The square wave anodic stripping voltammetry (SW ASV) response of the Hg(II)-imprinted MPMBT/GCE to Hg(II) is ca. 3.0 and 5.9 times larger than that at the direct imprinted poly(2-mercaptobenzothiazole) modified GCE and non-imprinted MPMBT/GCE sensor, respectively; and the detection limit for Hg(II) is 0.1 nM (which is well below the guideline value given by the World Health Organization). Excellent wide linear range (1.0–160.0 nM) and good repeatability (relative standard deviation of 2.5%) were obtained for Hg(II). The interference experiments showed that mercury signal was not interfered in the presence of Pb(II), Cd(II), Zn(II), Cu(II) and Ag(I), respectively. These values, particularly the high sensitivity and excellent selectivity compared favorably with previously reported methods in the area of electrochemical Hg(II) detection, demonstrate the feasibility of using the prepared Hg(II)-imprinted MPMBT/GCE for efficient determination of Hg(II) in aqueous environmental samples. 相似文献
Human body is greatly exposed to aluminum due to its high abundance in the environment. This nonessential metal is a threat to the patients of chronic renal disorders, as it is easily retained in their plasma and quickly accumulates in different tissues. Thus, there is great need to remove it from the aqueous environment. In this study, Al3+ imprinted semiinterpenetrating polymer network (semi-IPN)-based cryogel composite was prepared and applied for the purification of environmental and drinking water samples from aluminum. Poly (2-hydroxyethyl methacrylate) (pHEMA) discs were produced via cryogenic treatment and imprinted semi-IPN was introduced to the 3-(trimethoxysilyl) propyl acrylatemodified macroporous cryogel discs. The adsorption properties and selectivity of the aluminum (III) imprinted semi-IPN cryogel composite were studied in detail. The imprinted semi-IPN cryogel composite showed good selectivity towards aluminum (III) ions with the imprinting factor (IF) of 76.4 in the presence of competing copper (II), nickle (II), and iron (III) ions. The maximum adsorption capacity of 271 μmol g-1 was obtained for aluminum (III) at pH 7.0 within 10 min using imprinted semi-IPN cryogel composite. The good selectivity and reusability of aluminum (III)-imprinted semi-IPN cryogel composite makes this material an eligible candidate for the purification of drinking water from aluminum (III) leaving important minerals remained in the water. 相似文献
Thin films with enantioselective properties for electrochemically active chiral probes were developed. Enantioselectivity was accomplished via molecular imprinting. The films were fabricated through the sol-gel technique and were spin-coated on ITO electrodes. The chiral selectivity recognition was detected using two enantiomer pairs: D- and L-3,4-dihydroxyphenylalanine (D- and L-dopa) and (R)- and (S)-N,N'-dimethylferrocenylethylamine [(R)-Fc and (S)-Fc]. A defined chiral cavity was obtained by selection of functional monomers that interact with the template molecule, followed by its removal. Chiral selection properties were measured by cyclic voltammetry and square wave voltammetry. For both template molecules, very good chiral recognition was revealed by electrochemical measurement. The nonspecific adsorption measured for reference nonimprinted films was negligible (less than 5%). Dopa imprinted films revealed both high sensitivity, by the detection of 1 nM (0.2 ppb) concentration, and excellent selectivity, when challenged with a series of catechol derivatives. Fc-imprinted films were able to detect ca. 2 ppm of the target molecule, with very good enantioselectivity and low nonspecific adsorption. To our knowledge, this is the first report of successful molecular imprinting of a ferrocene derivative. 相似文献
In this article we report the introduction of the cooperativity of various specific interactions combined with photo-cross-linking of the interlayers to yield binding sites that can realize better selectivity and imprinting efficiency of a surface molecularly imprinted LbL film (SMILbL), thus providing a new approach toward fabrication of nanostructured molecularly imprinted thin films. It involves preassembly of poly(acrylic acid) (PAA) conjugated of the theophylline residue template via a disulfide bridge, denoted as PAAtheo 15, in solution, and layer-by-layer (LbL) assembly of PAAtheo 15 and a positively charged photoreactive diazo resin (DAR) to form multilayer thin film with designed architecture. After photo-cross-linking of the film and template removal, binding sites specific to 7-(beta-hydroxyethyl)theophylline (Theo-ol) molecules are introduced within the film. Binding assay demonstrates that the SMILbL has a high selectivity of SMILbL to Theo-ol over caffeine. A control experiment demonstrates that the selectivity of SMILbL derives from nanostructured recognition sites among the layers. The imprinting amount per unit mass of the film can be 1 order of magnitude larger than that of the conventional bulk molecular imprinting systems. As this concept of construction SMILbL can be easily extended to the other molecules by the following similar protocol: its applications in building many other different molecular recognition systems are greatly anticipated. 相似文献
[structures: see text] A class II aldolase-mimicking synthetic polymer was prepared by the molecular imprinting of a complex of cobalt (II) ion and either (1S,3S,4S)-3-benzoyl-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one (4a) or (1R,3R,4R)-3-benzoyl-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one (4b) in a 4-vinylpyridine-styrene-divinylbenzene copolymer. Evidence for the formation of interactions between the functional monomer and the template was obtained from NMR and VIS titration studies. The polymers imprinted with the template demonstrated enantioselective recognition of the corresponding template structure, and induced a 55-fold enhancement of the rate of reaction of camphor (1) with benzaldehyde (2), relative to the solution reactions, and were also compared to reactions with a series of reference polymers. Substrate chirality was observed to influence reaction rate, and the reaction could be competitively inhibited by dibenzoylmethane (6). Collectively, the results presented provide the first example of the use of enantioselective molecularly imprinted polymers for the catalysis of carbon-carbon bond formation. 相似文献
A bulk polymerization method was used to easily and efficiently prepare homoveratric acid (3,4-dimethoxyphenylacetic acid)-imprinted polymers from eight basic monomers: 2-vinylpyridine, 4-vinylpyridine, 1-vinylimidazole, N-allylaniline, N-allylpiperazine, allylurea, allylthiourea, and allylamine, in the presence of homoveratric acid as a template in N,N-dimethylformamide as a porogen. The imprinted polymer prepared from allylamine had the highest affinity to the template, showing an imprinting factor of 3.43, and allylamine polymers MIP8/NIP8 were selected for further studies. Their binding properties were analyzed using the Scatchard method. The results showed that the imprinted polymers have two classes of heterogeneous binding sites characterized by two pairs of K(d), B(max) values: K(d)(1) = 0.060 μmol/mL, B(max)(1) = 0.093 μmol/mg for the higher affinity binding sites, and K(d)(2) = 0.455 μmol/mL, B(max)(2) = 0.248 μmol/mg for the lower affinity binding sites. Non-imprinted polymer has only one class of binding site, with K(d) = 0.417 μmol/mL and B(max) = 0.184 μmol/mg. A computational analysis of the energies of the prepolymerization complexes was in agreement with the experimental results. It showed that the selective binding interactions arose from cooperative three point interactions between the carboxylic acid and the two methoxy groups in the template and amino groups in the polymer cavities. Those results were confirmed by the recognition studies performed with the set of structurally related compounds. Allylamine polymer MIP8 had no affinity towards biogenic amines. The obtained imprinted polymer could be used for selective separation of homoveratric acid. 相似文献