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1.
Epitope imprinting is a promising technique for fabrication of novel diagnostic tools. In this study, an epitope imprinted methodology for recognition of target epitope sequence as well as targeted protein infused by bacterial infection in blood samples of patients suffering from brain fever is developed. Template sequence chosen is a ferric iron binding fbp A protein present in Neisseria meningitidis bacteria. To orient the imprinting template peptide sequence on gold surface of electrochemical quartz crystal microbalance (EQCM), thiol chemistry was utilized to form the self‐assembled monolayer on EQCM electrode. Here, synergistic effects induced by various noncovalent interactions extended by multiple monomers (3‐sulfopropyl methacrylate potassium‐salt and benzyl methacrylate) were used in fabricating the imprinting polymeric matrix with additional firmness provided by N,N‐methylene‐bis‐acrylamide as cross‐linker and azo‐isobutyronitrile as initiator. Extraction of template molecule was carried out with phosphate buffer solution. After extraction of epitope molecules from the polymeric film, epitope molecularly imprinted polymeric films were fabricated on EQCM electrode surface. Nonimprinted polymers were also synthesized in the similar manner without epitope molecule. Detection limit of epitope molecularly imprinted polymers and imprinting factor (epitope molecularly imprinted polymers/nonimprinted polymers) was calculated 1.39 ng mL?1 and 12.27 respectively showing high binding capacity and specific recognition behavior toward template molecule. Simplicity of present method would put forward a fast, facile, cost‐effective diagnostic tool for mass health care.  相似文献   

2.
A major limitation of MnO2 in aqueous Zn/MnO2 ion battery applications is the poor utilization of its electrochemical active surface area. Herein, it is shown that by generating oxygen vacancies (VO) in the MnO2 lattice, Gibbs free energy of Zn2+ adsorption in the vicinity of VO can be reduced to thermoneutral value (≈0.05 eV). This suggests that Zn2+ adsorption/desorption process on oxygen‐deficient MnO2 is more reversible as compared to pristine MnO2. In addition, because of the fact that fewer electrons are needed for Zn? O bonding in oxygen‐deficient MnO2, more valence electrons can be contributed into the delocalized electron cloud of the material, which aids in enhancing the attainable capacity. As a result, the stable Zn/oxygen‐deficient MnO2 battery is able to deliver one of the highest capacities of 345 mAh g?1 reported for a birnessite MnO2 system. This excellent electrochemical performance suggests that generating oxygen vacancies in MnO2 may aid in the future development of advanced cathodes for aqueous Zn ion batteries.  相似文献   

3.
A novel molecular imprinting electrochemiluminescence sensor for detecting chiral cinchonine molecules was developed with a molecularly imprinted polymer membrane on the surfaces of magnetic microspheres. Fe3O4@Au nanoparticles modified with 6‐mercapto‐beta‐cyclodextrin were used as a carrier, cinchonine as a template molecule, methacrylic acid as a functional monomer and N ,N ′‐methylenebisacrylamide as a cross‐linking agent. Cinchonine was specifically recognized by the 6‐mercapto‐beta‐cyclodextrin functional molecularly imprinted polymer and detected based on enhancement of the electrochemiluminescence intensity caused by the reaction of tertiary amino structures of cinchonine molecules with Ru(bpy)32+. Cinchonine concentrations of 1 × 10?10 to 4 × 10?7 mol/L showed a good linear relationship with changes of the electrochemiluminescence intensity, and the detection limit of the sensor was 3.13 × 10?11 mol/L. The sensor has high sensitivity and selectivity, and is easy to renew. It was designed for detecting serum samples, with recovery rates of 98.2% to 107.6%.  相似文献   

4.
《Chirality》2017,29(7):340-347
Acrylamide (AM) was copolymerized with ethylene glycol dimethacrylate (EGDMA) in the presence of (R )‐1,1′‐binaphthalene‐2‐naphthol (BINOL) as the template molecules on the surface of silica gel by a free radical polymerization to produce a chiral stationary phase based on the surface molecularly imprinted polymer (SMIP‐CSP). The SMIP‐CSP showed a much better separation factor (α = 4.28) than the CSP based on the molecularly imprinted polymer (MIP‐CSP) without coating on the silica gel (α = 1.96) during the chiral separation of BINOL enantiomers by high‐performance liquid chromatography. The influence of the pretreatment temperature and the content of the template molecule ((R )‐BINOL) of the SMIP‐CSP, and the mobile phase composition on the separation of the racemic BINOL were systematically investigated.  相似文献   

5.
A novel fluorescent nanosensor using molecularly imprinted silica nanospheres embedded CdTe quantum dots (CdTe@SiO2@MIP) was developed for detection and quantification of chloramphenicol (CAP). The imprinted sensor was prepared by synthesis of molecularly imprinting polymer (MIP) on the hydrophilic CdTe quantum dots via reverse microemulsion method using small amounts of solvents. The resulting CdTe@SiO2@MIP nanoparticles were characterized by fluorescence, UV–vis absorption and FT‐IR spectroscopy and transmission electron microscopy. They preserved 48% of fluorescence quantum yield of the parent quantum dots. CAP remarkably quenched the fluorescence of prepared CdTe@SiO2@MIP, probably via electron transfer mechanism. Under the optimal conditions, the relative fluorescence intensity of CdTe@SiO2@MIP decreased with increasing CAP by a Stern–Volmer type equation in the concentration range of 40–500 µg L–1. The corresponding detection limit was 5.0 µg L–1. The intra‐day and inter‐day values for the precision of the proposed method were all <4%. The developed sensor had a good selectivity and was applied to determine CAP in spiked human and bovine serum and milk samples with satisfactory results. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

6.
In this study, a high fluorescence sensitivity and selectivity, molecularly imprinted nanofluorescent polymer sensor (MIP@SiO2@QDs) was prepared using a reverse microemulsion method. 2,4,6‐Trichlorophenol (2,4,6‐TCP) was detected using fluorescence quenching. Tetraethyl orthosilicate (TEOS), quantum dots (QDs) and 3‐aminopropyltriethoxysilane (APTS) were used as cross‐linker, signal sources and functional monomer respectively. The sensor (MIP@SiO2@QDs) and the non‐imprinted polymer sensor (NIP@SiO2@QDs) were characterized using infra‐red (IR) analysis, X‐ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The selectivity of MIP@SiO2@QDs was examined by comparing 2,4,6‐TCP with other similar functional substances including 2,4‐dichlorophenol (2,4‐DCP), 2,6‐dichlorophenol (2,6‐DCP) and 4‐chlorophenol (4‐CP). Results showed that MIP@SiO2@QDs had better selectivity for 2,4,6‐TCP than the other compounds. Fluorescence quenching efficiency displayed a good linear response at the 2,4,6‐TCP concentration range 5–1000 μmol/L. The limit of detection (LOD) was 0.9 μmol/L (3σ, n = 9). This method was equally applicable for testing actual samples with a recovery rate of 98.0–105.8%. The sensor had advantages of simple pretreatment, good sensitivity and selectivity, and wide linear range and could be applied for the rapid detection of 2,4,6‐TCP in actual samples.  相似文献   

7.
Mn oxides are highly important electrode materials for aqueous electrochemical energy storage devices, including batteries and supercapacitors. Although MnO2 is a promising pseudocapacitor material because of its outstanding rate and capacity performance, its electrochemical instability in aqueous electrolyte prevents its use at low electrochemical potential. Here, the possibility of stabilizing MnO2 electrode using SiO2‐confined nanostructure is demonstrated. Remarkably, an exceptionally good electrochemical stability under large negative polarization in aqueous (Li2SO4) electrolyte, usually unattainable for MnO2‐based electrode, is achieved. Even more interestingly, this MnO2–SiO2 nanostructured composite exhibits unique mixed pseudocapacitance‐battery behaviors involving consecutive reversible charge transfer from Mn(IV) to Mn(II), which enable simultaneous high‐capacity and high‐rate characteristics, via different charge‐transfer kinetic mechanisms. This suggests a strategy to design and stabilize electrochemical materials that are comprised of intrinsically unstable but high‐performing component materials.  相似文献   

8.
Earth‐abundant amorphous nanomaterials with rich structural defects are promising alternative catalysts to noble metals for an efficient electrochemical oxygen evolution reaction; however, their inferior electrical conductivity and poor morphological control during synthesis hamper the full realization of their potency in electrocatalysis. Herein, a rapid surface‐guided synthetic approach is proposed to introduce amorphous and mixed‐metal oxyhydroxide overlayers on ultrathin Ni‐doped MnO2 (Ni? MnO2) nanosheet arrays via a galvanic replacement mechanism. This method results in a monolithic 3D porous catalyst with a small overpotential of only 232 mV to achieve a current density of 10 mA cm?2 in 1 m KOH, which is much lower than the corresponding value of 307 mV for the Ni? MnO2 reference sample. Detailed structural and electrochemical characterization reveal that the unique Ni? MnO2 ultrathin nanosheet arrays do not only provide a large surface area to guide the formation of active amorphous catalyst layers but also ensure the effective charge transport owing to their high electron conductivity, collectively contributing to the greatly improved catalyst activity. It is envisioned that this highly operable surface‐guide synthetic strategy may open up new avenues for the design and fabrication of novel 3D nanoarchitectures integrated with functional amorphous materials for broadened ranges of applications.  相似文献   

9.
It has become clear that cycling lithium‐oxygen cells in carbonate electrolytes is impractical, as electrolyte decomposition, triggered by oxygen reduction products, dominates the cell chemistry. This research shows that employing an α‐MnO2/ramsdellite‐MnO2 electrode/electrocatalyst results in the formation of lithium‐oxide‐like discharge products in propylene carbonate, which has been reported to be extremely susceptible to decomposition. X‐ray photoelectron data have shown that what are likely lithium oxides (Li2O2 and Li2O) appear to form and decompose on the air electrode surface, particularly at the MnO2 surface, while Li2CO3 is also formed. By contrast, cells without α‐MnO2/ramsdellite‐MnO2 fail rapidly in electrochemical cycling, likely due to the differences in the discharge product. Relatively high electrode capacities, up to 5000 mAh/g (carbon + electrode/electrocatalyst), have been achieved with non‐optimized air electrodes. Insights into reversible insertion reactions of lithium, lithium peroxide (Li2O2) and lithium oxide (Li2O) in the tunnels of α‐MnO2, and the reaction of lithium with ramsdellite‐MnO2, as determined by first principles density functional theory calculations, are used to provide a possible explanation for some of the observed results. It is speculated that a Li2O‐stabilized and partially‐lithiated electrode component, 0.15Li2α‐LixMnO2, that has Mn4+/3+ character may facilitate the Li2O2/Li2O discharge/charge chemistries providing dual electrode/electrocatalyst functionality.  相似文献   

10.
Although the Li‐excess layered‐oxide Li2MnO3 has a high theoretical capacity, structural transformations within the oxide during electrochemical cycling lead to relatively low experimental capacities, hindering its use in practical applications. Here, aberration‐corrected scanning transmission electron microscopy/electron energy loss spectroscopy and high‐resolution X‐ray diffraction are used to characterize the oxide following electrochemical cycling. Microscopy reveals the coexistence of regions with local monoclinic, spinel, and rock‐salt symmetries, indicating localized and inhomogeneous structural evolutions. Crystal structure transformations are observed both at the particle surface and in the bulk. At the surface, these transformed regions resemble spinel Mn3O4 or rock‐salt MnO, consistent with oxygen loss. In the bulk, the regions resemble defect spinels, such as the layered‐spinel LixMn4/3O4, which suggest a partial phase transformation consistent with oxygen retention. Both microscopy and diffraction data of the cycled sample indicate areas of pristine Li2MnO3; the presence of such areas, in close proximity to LixMn4/3O4 areas, suggests that the layered to spinel structure transformation is partially reversible. Spinel, disordered rock salt, and pristine areas are also observed in Li2MnO3 samples intentionally damaged by electron beam irradiation. This observation indicates that the dynamic processes resulting in phase transformations can be studied for a variety of oxide systems by a judicious selection of irradiation conditions.  相似文献   

11.
Rechargeable aqueous Zn/MnO2 batteries are very attractive large‐scale energy storage technologies, but still suffer from limited cycle life and low capacity. Here the novel adoption of a near‐neutral acetate‐based electrolyte (pH ≈ 6) is presented to promote the two‐electron Mn4+/Mn2+ redox reaction and simultaneously enable a stable Zn anode. The acetate anion triggers a highly reversible MnO2/Mn2+ reaction, which ensures high capacity and avoids the issue of structural collapse of MnO2. Meanwhile, the anode‐friendly electrolyte enables a dendrite‐free Zn anode with outstanding stability and high plating/stripping Coulombic efficiency (99.8%). Hence, a high capacity of 556 mA h g?1, a lifetime of 4000 cycles without decay, and excellent rate capability up to 70 mA cm?2 are demonstated in this new near‐neutral aqueous Zn/MnO2 battery by simply manipulating the salt anion in the electrolyte. The acetate anion not only modifies the surface properties of MnO2 cathode but also creates a highly compatible environment for the Zn anode. This work provides a new opportunity for developing high‐performance Zn/MnO2 and other aqueous batteries based on the salt anion chemistry.  相似文献   

12.
Li2MnO3 is the parent compound of the well‐studied Li‐rich Mn‐based cathode materials xLi2MnO3·(1‐x)LiMO2 for high‐energy‐density Li‐ion batteries. Li2MnO3 has a very high theoretical capacity of 458 mA h g?1 for extracting 2 Li. However, the delithiation and lithiation behaviors and the corresponding structure evolution mechanism in both Li2MnO3 and Li‐rich Mn‐based cathode materials are still not very clear. In this research, the atomic structures of Li2MnO3 before and after partial delithiation and re‐lithiation are observed with spherical aberration‐corrected scanning transmission electron microscopy (STEM). All atoms in Li2MnO3 can be visualized directly in annular bright‐field images. It is confirmed accordingly that the lithium can be extracted from the LiMn2 planes and some manganese atoms can migrate into the Li layer after electrochemical delithiation. In addition, the manganese atoms can move reversibly in the (001) plane when ca. 18.6% lithium is extracted and 12.4% lithium is re‐inserted. LiMnO2 domains are also observed in some areas in Li1.63MnO3 at the first cycle. As for the position and occupancy of oxygen, no significant difference is found between Li1.63MnO3 and Li2MnO3.  相似文献   

13.
Electrochemical detection of glucose in alkaline solution was performed on La0.88Sr0.12MnO3 (LSMO) nanofibers modified carbon paste electrode. Perovskite-type oxide LSMO nanofibers were prepared by an electrospinning and calcination process. The morphologies, structures, and electrochemical behavior of the nanofibers were characterized by scanning electron microscope, energy dispersive spectrometer, X-ray diffraction, Fourier transform infrared spectrum, and cyclic voltammetry. The modified electrode shows excellent electrocatalytic activity toward glucose. Under optimal conditions, the linear response was obtained in the range of 0.05–100 μM with high sensitivity and rapid response.  相似文献   

14.
Molecular imprinting is a technique for the fabrication of biomimetic polymeric recognition sites or “plastic antibodies/receptors” which is attracting rapidly increasing interest. By this technology, recognition matrices can be prepared which possess high substrate selectivity and specificity. In the development of this technology, several applications have been foreseen in which imprinted materials may be exchanged for natural recognition elements. Thus, molecularly imprinted polymers have been used as antibody/receptor binding mimics in immunoassay-type analyses, as enzyme mimics in catalytic applications and as recognition matrices in biosensors. The best developed application area for imprinted materials, though, has been as stationary phases for chromatography, in general, and chiral chromatography, in particular. This review seeks to highlight some of the more intriguing advantages of the technique as well as pointing out some of the difficulties encountered. The prospects for future development will also be considered. Chirality 10:195209, 1998. © 1998 Wiley-Liss, Inc.  相似文献   

15.
A molecularly imprinted electrochemical sensor was fabricated based on gold electrode decorated by chitosan-platinum nanoparticles (CS-PtNPs) and graphene-gold nanoparticles (GR-AuNPs) nanocomposites for convenient and sensitive determination of erythromycin. The synergistic effects of CS-PtNPs and GR-AuNPs nanocomposites improved the electrochemical response and the sensitivity of the sensor. The molecularly imprinted polymers (MIPs) were prepared by HAuCl(4), 2-mercaptonicotinic acid (MNA) and erythromycin. Erythromycin and MNA were used as template molecule and functional monomer, respectively. They were first assembled on the surface of GR-AuNPs/CS-PtNPs/gold electrode by the formation of Au-S bonds and hydrogen-bonding interactions. Then the MIPs were formed by electropolymerization of HAuCl(4), MNA and erythromycin. The sensor was characterized by cyclic voltammetry (CV), scanning electron microscope (SEM), UV-visible (UV-vis) absorption speactra and amperometry. The linear range of the sensor was from 7.0×10(-8)mol/L-9.0×10(-5)mol/L, with the limit of detection (LOD) of 2.3×10(-8)mol/L (S/N=3). The sensor showed high selectivity, excellent stability and good reproducibility for the determination of erythromycin, and it was successfully applied to the detection of erythromycin in real spiked samples.  相似文献   

16.
Diazomethane (CH2N2) was used to methylate the non‐specific binding sites after molecularly imprinted polymer particles were prepared using methacrylic acid as the functional monomer, ethylene glycol dimethacrylate as the cross‐linker and bisphenol A (BPA) as the template. After diazomethane treatment and subsequent removal of BPA by triethylamine, the treated molecularly imprinted polymer (TMIP) particles were tested for binding selectivity toward BPA and other organic compounds by capillary electrophoresis with ultraviolet detection. Even in the presence of compounds that were positively charged, neutral or negatively charged in the background electrolyte, BPA was selectively bound with the highest efficiency. A significant decrease in the affinity for metformin (MF, a positively charged compound), along with 13C nuclear magnetic resonance spectra and electrophoretic mobility data, provided strong evidence for the elimination of non‐specific –COOH binding sites in the TMIP particles. Only 8% of MF and 16% of diclofenac sodium salt (a negatively charged compound) remained as non‐specific bindings because of hydrophobic interactions. Further comparison with poly(methyl methacrylate) revealed the true merits of the TMIP, which exhibited minimal non‐specific bindings while preserving a high level of specific binding owing to molecular recognition. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

17.
The aim of this work was to produce a thin, flexible and diffusion able molecularly imprinted polymeric matrix with good template accessibility. Membranes were prepared using a non‐covalent molecular imprinting approach and their physical characteristics and binding capabilities investigated. Two materials were used, a poly(tri‐ethyleneglycol dimethyacrylate‐co‐methyl methacrylate‐co‐methacrylic acid) copolymer containing 14% cross‐linker and a monomer (g) to porogen (ml) ratio of 1:0.5 (A), and a blend of poly(TEGMA‐co‐MAA) and polyurethane (B). The polyurethane was added to improve membrane flexiblity and stability. The polymers were characterized using AFM, SEM and nitrogen adsorption, whilst binding was evaluated using batch‐rebinding studies. For all membranes the specific surface area was low (<10 m2/g). MIP (A) films were shown to bind specifically at low concentrations but specific binding was masked by non‐specific interactions at elevated concentrations. Selectivity studies confirmed specificity at low concentrations. KD approximations confirmed a difference in the population of binding sites within NIP and MIP films. The data also indicated that at low concentrations the ligand‐occupied binding site population approached homogeneity. Scanning electron microscopy images of membrane (B) revealed a complex multi‐layered system, however these membranes did not demonstrate specificity for the template. The results described here demonstrate how the fundamental parameters of a non‐covalent molecularly imprinted system can be successfully modified in order to generate flexible and physically tolerant molecularly imprinted thin films. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

18.
Several amino acid chiral ionic liquids were introduced as functional monomers to prepare molecularly imprinted polymers for specific recognition of L‐phenylalanine. Among them, the imprinted polymers L‐Phe@MIPs based on [ViImC3][L‐Pro] showed the best selective recognition ability for L‐phenylalanine. A series of experiments such as dynamic adsorption, static adsorption, and competitive adsorption were conducted to investigate the specific recognition ability and adsorption capacity of the L‐Phe@MIPs. It is found that the adsorption efficiency to L‐phenylalanine on L‐Phe@MIPs was 3.11 times higher than that to D‐phenylalanine. All the results demonstrated that the L‐Phe@MIPs possessed good recognition and relatively high adsorption efficiency for L‐phenylalanine. Besides, the recovery of L‐phenylalanine was above 98%, and the L‐Phe@MIPs exhibited good reusability.  相似文献   

19.
2D nanostructures with high surface area and flexibility are regarded as a promising building platform for flexible supercapacitors that are attracting tremendous attention due to their potential applications in various wearable technologies. Notably, although pseudocapacitive metal oxides are widely accepted as a very important class of electrochemically active materials, the utilization of 2D metal oxide sheets in the preparation of flexible supercapacitors is very rare. The scarcity of a suitable filler with the integrated properties of both high conductivity and excellent hydrophilicity is probably to blame. In this work, by introducing a recently discovered intriguing material, Ti3C2 sheets, a novel MnO2/Ti3C2 hybrid with a molecularly stacked structure is developed using a simple and scalable mixing and filtration method. Their individual advantages are combined in the hybrid, thus delivering excellent electrochemical performances. A highly flexible and symmetric supercapacitor based on the novel hybrid electrode manifests top‐class electrochemical performance with maximum energy and power densities of 8.3 W h kg?1 (at 221.33 W kg?1) and 2376 W kg?1 (at 3.3 W h kg?1), respectively, regardless of the various bending states, suggesting enormous possibilities for applications in future flexible and portable micropower systems.  相似文献   

20.
New biosourced chiral cross‐linkers were reported for the first time in the synthesis of methyltestosterone (MT) chiral molecularly imprinted polymers (cMIPs). Isosorbide and isomannide, known as 1,4:3,6‐dianhydrohexitols, were selected as starting diols. The cMIPs were synthesized following a noncovalent approach via thermal radical polymerization and monitored by Raman spectroscopy. These cross‐linkers were fully characterized by 1H and 13C nuclear magnetic resonance (NMR) spectroscopy and high‐resolution mass spectrometry. The cross‐polarization magic angle spinning 13C NMR, Fourier transform infrared spectroscopy, scanning electron microscopy, and specific surface areas following the Brunauer‐Emmett‐Teller (BET) method were used to characterize the cMIPs. The effect of stereochemistry of cross‐linkers on the reactivity of polymerization, morphology, and adsorption‐recognition properties of the MIP was evaluated. The results showed that the cMIP exhibited an obvious improvement in terms of rebinding capacity for MT as compared with the nonimprinted polymer (NIP). The highest binding capacity was observed for cMIP‐Is (27.298 mg g−1) for high concentrations (500 mg L−1). However, the isomannide homologue cMIP‐Im showed higher recovery—up to 65% and capacity for low concentrations (15 mg L−1). The experimental data were properly fitted by the Freundlich adsorption isothermal model.  相似文献   

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