scholarly journals Self-assembly Synthesis of Molecularly Imprinted Polymers for the Ultrasensitive Electrochemical Determination of Testosterone

Biosensors ◽  
2020 ◽  
Vol 10 (3) ◽  
pp. 16 ◽  
Author(s):  
Kai-Hsi Liu ◽  
Danny O’Hare ◽  
James L. Thomas ◽  
Han-Zhang Guo ◽  
Chien-Hsin Yang ◽  
...  

Molecularly imprinted polymers (MIPs) can often bind target molecules with high selectivity and specificity. When used as MIPs, conductive polymers may have unique binding capabilities; they often contain aromatic rings and functional groups, which can undergo π-π and hydrogen bonding interactions with similarly structured target (or template) molecules. In this work, an electrochemical method was used to optimize the synthetic self-assembly of poly(aniline-co-metanilic acid) and testosterone, forming testosterone-imprinted electronically conductive polymers (TIECPs) on sensing electrodes. The linear sensing range for testosterone was from 0.1 to 100 pg/mL, and the limit of detection was as low as ~pM. Random urine samples were collected and diluted 1000-fold to measure testosterone concentration using the above TIECP sensors; results were compared with a commercial ARCHITECT ci 8200 system. The testosterone concentrations in the tested samples were in the range of 0.33 ± 0.09 to 9.13 ± 1.33 ng/mL. The mean accuracy of the TIECP-coated sensors was 90.3 ± 7.0%.

Author(s):  
Kai-Hsi Liu ◽  
Danny O’Hare ◽  
James L. Thomas James L. Thomas ◽  
Han-Zhang Guo ◽  
Chien-Hsin Yang ◽  
...  

Molecularly imprinted polymers (MIPs) can often bind target molecules with high selectivity and specificity. When used as MIPs, conductive polymers may have unique binding capabilities; they often contain aromatic rings, which have a great tendency to undergo covalent and hydrogen bonding interactions with similarly structured target (or template) molecules. In this work, an electrochemical method was used to optimize the synthetic self-assembly of poly(aniline-co-metanilic acid) and testosterone, forming testosterone-imprinted polymers (TIPs) on sensing electrodes. The linear sensing range for testosterone ranged from 0.1 to 100 pg/mL, and the limit of detection was as low as ~pM. Random urine samples were collected and diluted 1000 fold to measure testosterone concentration using the above TIP sensors in comparison with a commercial ARCHITECT ci 8200 system. The testosterone concentrations in the tested samples were in the range of 0.33± 0.09 to 9.13±1.33 ng/mL. The mean accuracy of the TIP-coated sensors was 90.3 ±7.0 %.


Author(s):  
Tongchang Zhou ◽  
Arnab Halder ◽  
Yi Sun

In this work, we firstly explored a mild, clean, and highly efficient approach for the synthesis of graphene quantum dots (GQDs). GQDs with carboxyl groups or amino groups, were prepared from one-pot environmentally friendly method assisted by hydrogen peroxide, respectively. It was proved that carboxyl groups played an important role in the fluorescence quenching. Based on these findings, we developed a novel fluorescent nanosensor by combining molecularly imprinted polymers (MIPs) with carboxyl functionalized GQDs for the determination of tetracycline (TC) in aqueous samples. The nanocomposite was prepared using a sol-gel process. GQDs-MIPs showed strong fluorescent emission at 410 nm when excited at 360 nm, which was subsequently quenched in the presence of TC. Under optimum conditions, the fluorescence intensity of GQDs-MIPs decreased in response to the increase of TC concentration with good linearity rage of 1.0-104 µg L-1. The limit of detection was determined to be 1 µg L-1. The fluorescence intensity of GQDs-MIPs was more strongly quenched by TC compared to the corresponding non-imprinted polymers, GQDs-NIPs. With the high sensitivity, the material was also successfully worked for the detection of TC in real spiked milk samples.


2020 ◽  
Vol 16 (3) ◽  
pp. 196-207 ◽  
Author(s):  
Yeşeren Saylan ◽  
Adil Denizli

Introduction: A molecular imprinting is one of the fascinating modification methods that employ molecules as targets to create geometric cavities for recognition of targets in the polymeric matrix. This method provides a broad versatility to imprint target molecules with different size, three-dimensional structure and physicochemical features. In contrast to the complex and timeconsuming laboratory surface modification procedures, this method offers a rapid, sensitive, inexpensive, easy-to-use, and selective approach for the diagnosis, screening and monitoring disorders. Owing to their unique features such as high selectivity, physical and chemical robustness, high stability, low-cost and reusability of this method, molecularly imprinted polymers have become very attractive materials and been applied in various applications from separation to detection. Background: The aims of this review are structured according to the fundamentals of molecularly imprinted polymers involving essential elements, preparation procedures and also the analytical applications platforms. Finally, the future perspectives to increase the development of molecularly imprinted platforms. Methods: A molecular imprinting is one of the commonly used modification methods that apply target as a recognition element itself and provide a wide range of versatility to replica other targets with a different structure, size, and physicochemical features. A rapid, easy, cheap and specific recognition approach has become one of the investigation areas on, especially biochemistry, biomedicine and biotechnology. In recent years, several technologies of molecular imprinting method have gained prompt development according to continuous use and improvement of traditional polymerization techniques. Results: The molecularly imprinted polymers with excellent performances have been prepared and also more exciting and universal applications have been recognized. In contrast to the conventional methods, the imprinted systems have superior advantages including high stability, relative ease and low cost of preparation, resistance to elevated temperature, and pressure and potential application to various target molecules. In view of these considerations, molecularly imprinted systems have found application in various fields of analytical chemistry including separation, purification, detection and spectrophotometric systems. Conclusion: Recent analytical methods are reported to develop the binding kinetics of imprinted systems by using the development of other technologies. The combined platforms are among the most encouraging systems to detect and recognize several molecules. The diversity of molecular imprinting methods was overviewed for different analytical application platforms. There is still a requirement of more knowledge on the molecular features of these polymers. A next step would further be the optimization of different systems with more homogeneous and easily reachable recognition sites to reduce the laborious in the accessibility in the three-dimensional polymeric materials in sufficient recognition features and also better selectivity and sensitivity for a wide range of molecules.


NANO ◽  
2020 ◽  
Vol 15 (08) ◽  
pp. 2050105
Author(s):  
Min Wang ◽  
Manjie Gao ◽  
Linlin Deng ◽  
Xun Kang ◽  
Lijuan Yang ◽  
...  

A new fluorescence composite material for the sensitive and selective determination of 4-nitrophenol (4-NP) was developed based on molecularly imprinted polymers (MIPs) incorporated with carbon dots (CDs). First, fluorescent CDs with a high quantum yield (QY) of 51.8% were prepared by hydrothermal synthesis method by using anhydrous citric acid as carbon source and AEAPMS as surface modifier. Then, CDs were fabricated with MIPs (CDs@MIPs) by sol–gel method using 4-NP as template, (3-aminopropyl) triethoxysilane (APTES) as functional monomer, tetraethoxysilane (TEOS) as cross-linker and CDs as signal sources, respectively. The CDs@MIPs exhibited strong fluorescence property and high selectivity to 4-NP as it incorporated merits of CDs and MIPs. Under optimized conditions, the relative fluorescence intensity of CDs@MIPs decreased linearly with the concentration of 4-NP from 0.025[Formula: see text][Formula: see text]g[Formula: see text]mL[Formula: see text] to 5[Formula: see text][Formula: see text]g[Formula: see text]mL[Formula: see text]. The limit of detection (LOD) of 4-NP was 5[Formula: see text]ng[Formula: see text]mL[Formula: see text] (35[Formula: see text]nM). Specificity and selectivity experiments showed that CDs@MIPs can selectively detect 4-NP with rare interference of other competitive analogs and metal ions. Finally, CDs@MIPs was successfully used to detect 4-NP in river water samples with the recoveries ranging from 94.0% to 103.4%. The results demonstrated that the prepared CDs@MIPs can be applied to the selective and sensitive detection of trace 4-NP in real samples.


2017 ◽  
Vol 95 (7) ◽  
pp. 799-805 ◽  
Author(s):  
Shaoming Yang ◽  
Lingling Li ◽  
Xiaorong Zhang ◽  
Peiling Shang ◽  
Shaoqing Ding ◽  
...  

The preparation and application of reagentless electrochemical thrombin molecularly imprinted sensors were studied using multiwalled carbon nanotubes as sensitivity-enhanced materials. The molecularly imprinted polymer film was prepared by the electropolymerization of o-phenylenediamine with thrombin as the template molecule onto the surface of multiwalled carbon nanotubes modified glassy carbon electrode. After removing thrombin, the poly-o-phenylenediamine molecularly imprinted film was obtained with specific recognition for thrombin. Using the poly-o-phenylenediamine molecularly imprinted polymers as the electron probe, the electrochemical molecularly imprinted sensor was fabricated for the detection of the protein thrombin. Under optimized experimental conditions, the sensor exhibited a good linear response from 10.0 fg/mL to 1.0 μg/mL for thrombin, with correlation coefficient 0.999 and a low detection limit of 1.7 fg/mL. The fabricated molecularly imprinted sensor can be applied to the detection of thrombin in actual sample bovine serum with satisfactory results.


2009 ◽  
Vol 62 (8) ◽  
pp. 751 ◽  
Author(s):  
Marc Bompart ◽  
Karsten Haupt

Molecularly imprinted polymers (MIPs) are tailor-made biomimetic receptors that are obtained by polymerization in the presence of molecular templates. They contain binding sites for target molecules with affinities and specificities on a par with those of natural receptors such as antibodies, hormone receptors, or enzymes. A great majority of the literature in the field describes materials based on polymers obtained by free radical polymerization. In order to solve general problems associated with MIPs, in particular their heterogeneity in terms of inner morphology and distribution of binding site affinities, it has been suggested to use modern methods of controlled/living radical polymerization for their synthesis. This also facilitates their generation in the form of nanomaterials, nanocomposites, and thin films, a strong recent trend in the field. The present paper reviews recent advances in the molecular imprinting area, with special emphasis on the use of controlled polymerization methods, their benefits, and current limitations.


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