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1.
Sandwich ELISA methods have been widely used for biomarker and pathogen detection because of their high specificity and sensitivity. However, the main drawbacks of this assay are the cost, the time-consuming procedure for the isolation of antibodies and their poor stability. To overcome these restrictions, we herein fabricated artificial antibodies based on imprinting technology and developed a sandwich ELISA for pathogen detection. Both the capture and detection antibodies were obtained via an in situ method, with simplicity, rapidity and low cost. The peroxidase mimics, the CeO2 nanoparticles, as signal generators were integrated with the detection antibody. The fabricated artificial antibodies exhibited not only natural antibody-like binding affinities and selectivities, but also superior stability and reusability. The detection limit was about 500 CFU mL–1, which is much lower than that of traditional ELISA methods (104 to 105 CFU mL–1). Furthermore, the capture antibody can disinfect pathogens in situ.  相似文献   

2.
The photophysics of a covalently linked perylenediimide–diketopyrrolopyrrole–perylenediimide acceptor–donor–acceptor molecule (PDI–DPP–PDI, 1) were investigated and found to be markedly different in solution versus in unannealed and solvent annealed films. Photoexcitation of 1 in toluene results in quantitative charge separation in τ = 3.1 ± 0.2 ps, with charge recombination in τ = 340 ± 10 ps, while in unannealed/disordered films of 1, charge separation occurs in τ < 250 fs, while charge recombination displays a multiexponential decay in ∼6 ns. The absence of long-lived, charge separation in the disordered film suggests that few free charge carriers are generated. In contrast, upon CH2Cl2 vapor annealing films of 1, grazing-incidence X-ray scattering shows that the molecules form a more ordered structure. Photoexcitation of the ordered films results in initial formation of a spin-correlated radical ion pair (electron–hole pair) as indicated by magnetic field effects on the formation of free charge carriers which live for ∼4 μs. This result has significant implications for the design of organic solar cells based on covalent donor–acceptor systems and shows that long-lived, charge-separated states can be achieved by controlling intramolecular charge separation dynamics in well-ordered systems.  相似文献   

3.
We induce and study reactions of polyoxometalate (POM) molecules, [PW12O40]3− (Keggin) and [P2W18O62]6− (Wells–Dawson), at the single-molecule level. Several identical carbon nanotubes aligned side by side within a bundle provided a platform for spatiotemporally resolved imaging of ca. 100 molecules encapsulated within the nanotubes by transmission electron microscopy (TEM). Due to the entrapment of POM molecules their proximity to one another is effectively controlled, limiting molecular motion in two dimensions but leaving the third dimension available for intermolecular reactions between pairs of neighbouring molecules. By coupling the information gained from high resolution structural and kinetics experiments via the variation of key imaging parameters in the TEM, we shed light on the reaction mechanism. The dissociation of W–O bonds, a key initial step of POM reactions, is revealed to be reversible by the kinetic analysis, followed by an irreversible bonding of POM molecules to their nearest neighbours, leading to a continuous tungsten oxide nanowire, which subsequently transforms into amorphous tungsten-rich clusters due to progressive loss of oxygen atoms. The overall intermolecular reaction can therefore be described as a step-wise reductive polycondensation of POM molecules, via an intermediate state of an oxide nanowire. Kinetic analysis enabled by controlled variation of the electron flux in TEM revealed the reaction to be highly flux-dependent, which leads to reaction rates too fast to follow under the standard TEM imaging conditions. Although this presents a challenge for traditional structural characterisation of POM molecules, we harness this effect by controlling the conditions around the molecules and tuning the imaging parameters in TEM, which combined with theoretical modelling and image simulation, can shed light on the atomistic mechanisms of the reactions of POMs. This approach, based on the direct space and real time chemical reaction analysis by TEM, adds a new method to the arsenal of single-molecule kinetics techniques.

We induce and study reactions of polyoxometalate (POM) molecules, [PW12O40]3− (Keggin) and [P2W18O62]6− (Wells–Dawson), at the single-molecule level, utilising TEM as an analytical tool, and nanotubes as test tubes.  相似文献   

4.
Deoxynivalenol (DON) is one of the most common mycotoxins in grains, causing gastrointestinal inflammation, neurotoxicity, hepatotoxicity and embryotoxicity, even at a low quantity. In this study, a facile electrochemical aptasensor was established for the rapid and sensitive determination of DON based on a multifunctional N-doped Cu-metallic organic framework (N–Cu–MOF) nanomaterial. The N–Cu–MOF, with a large specific surface area and good electrical conductivity, served not only as an optimal electrical signal probe but also as an effective supporting substrate for stabilizing aptamers through the interactions of amino (-NH2) and copper. Under the optimal conditions, the proposed sensor provided a wide linear concentration range of 0.02–20 ng mL−1 (R2 = 0.994), showing high sensitivity, with a lower detection limit of 0.008 ng mL−1, and good selectivity. The sensor’s effectiveness was also verified in real spiked wheat samples with satisfactory recoveries of 95.6–105.9%. The current work provides a flexible approach for the rapid and sensitive analysis of highly toxic DON in food samples and may also be easily extended to detect other hazardous substances with alternative target-recognition aptamers.  相似文献   

5.
A novel nanosized biological active multilayer film composed of polyoxometalate (POM) anion α-[SiW11O39Co(H2PO4)]7−(abbr. SiW11Co-PO4) and poly(diallyldi methylammonium chloride) (abbr. PDDA) was fabricated by layer-by-layer self-assembly (LBL). The composition and growth processes of the films have been determined by X-ray photoelectron spectra (XPS) and ultraviolet-visible absorption spectra (UV). The composite film was formed by the alternate adsorption of SiW11Co-PO4 and PDDA, and the deposition process was quantitative and highly reproducible from layer to layer. The morphology of the film was studied by atomic force microscopy (AFM), which showed that the film was relatively uniform and smooth, and POM anions aggregated into nanoclusters distributing on the surface uniformly. The film exhibited favorable electrochemical behavior of POM indicated by cyclic voltammetry (CV). The film can immobilize the DNA molecules via Mg2+-bridging medium.  相似文献   

6.
Polyoxometalates (POMs) demonstrate potential for application in the development of integrated smart energy devices based on bifunctional electrochromic (EC) optical modulation and electrochemical energy storage. Herein, a nanocomposite thin film composed of a vanadium-substituted Dawson-type POM, i.e., K7[P2W17VO62]·18H2O, and TiO2 nanowires were constructed via the combination of hydrothermal and layer-by-layer self-assembly methods. Through scanning electron microscopy and energy-dispersive spectroscopy characterisations, it was found that the TiO2 nanowire substrate acts as a skeleton to adsorb POM nanoparticles, thereby avoiding the aggregation or stacking of POM particles. The unique three-dimensional core−shell structures of these nanocomposites with high specific surface areas increases the number of active sites during the reaction process and shortens the ion diffusion pathway, thereby improving the electrochemical activities and electrical conductivities. Compared with pure POM thin films, the composite films showed improved EC properties with a significant optical contrast (38.32% at 580 nm), a short response time (1.65 and 1.64 s for colouring and bleaching, respectively), an excellent colouration efficiency (116.5 cm2 C−1), and satisfactory energy-storage properties (volumetric capacitance = 297.1 F cm−3 at 0.2 mA cm−2). Finally, a solid-state electrochromic energy-storage (EES) device was fabricated using the composite film as the cathode. After charging, the constructed device was able to light up a single light-emitting diode for 20 s. These results highlight the promising features of POM-based EES devices and demonstrate their potential for use in a wide range of applications, such as smart windows, military camouflage, sensors, and intelligent systems.  相似文献   

7.
The 3-Iodo-1-nitrosonaphthalene-2-ol (I-NON) was obtained by the copper(II)-mediated iodination of 1-nitroso-2-naphthol (NON). The suitable reactants and optimized reaction conditions, providing 94% NMR yield of I-NON, included the usage of Cu(OAc)2·H2O and 1:2:8 CuII/NON/I2 molar ratio between the reactants. The obtained I-NON was characterized by elemental analyses (C, H, N), high-resolution ESI+-MS, 1H and 13C{1H} NMR, FTIR, UV-vis spectroscopy, TGA, and X-ray crystallography (XRD). The copper(II) complexes bearing deprotonated I-NON were prepared as follows: cis-[Cu(I-NON–H)(I-NON)](I3) (1) was obtained by the reaction between Cu(NON-H)2 and I2 in CHCl3/MeOH, while trans-[Cu(I-NON–H)2] (2) was synthesized from I-NON and Cu(OAc)2 in MeOH. Crystals of trans-[Cu(I-NON–H)2(THF)2] (3) and trans-[Cu(I-NON–H)2(Py)2] (4) were precipitated from solutions of 2 in CHCl3/THF and Py/CHCl3/MeOH mixtures, respectively. The structures of 1 and 3–4 were additionally verified by X-ray crystallography. The characteristic feature of the structures of 1 and 3 is the presence of intermolecular halogen bonds with the involvement of the iodine center of the metal-bound deprotonated I-NON. The nature of the I···I and I···O contacts in the structures of 1 and 3, correspondingly, were studied theoretically at the DFT (PBE0-D3BJ) level using the QTAIM, ESP, ELF, NBO, and IGM methods.  相似文献   

8.
In the present work, a new ligandless-dispersive liquid-liquid microextraction (LL-DLLME) method has been developed for preconcentration trace amounts of copper as a prior step to its determination by flame atomic absorption spectrometry. In the proposed approach 1,2-dicholorobenzene and ethanol were used as extraction and dispersive solvents, respectively. Some factors influencing on the extraction efficiency of copper and its subsequent determination were studied and optimized, such as the extraction and dispersive solvent type and volume, pH of sample solution, extraction time and salting out effect. Under the optimal conditions, the calibration curve was linear in the range of 1.0 ng mL−1-0.6 μg mL−1 of copper with R2 = 0.9985. Detection limit was 0.5 ng mL−1 in original solution (3Sb/m) and the relative standard deviation for seven replicate determination of 0.2 μg mL−1 copper was ±1.4%. The proposed method has been applied for determination of copper in standard and water samples with satisfactory results.  相似文献   

9.
The chemical composition of three Citrus limon oils: lemon essential oil (LEO), lemon terpenes (LT) and lemon essence (LE), and their influence in the virulence factors production and motility (swarming and swimming) of two Pseudomonas aeruginosa strains (ATCC 27853 and a multidrug-resistant HT5) were investigated. The main compound, limonene, was also tested in biological assays. Eighty-four compounds, accounting for a relative peak area of 99.23%, 98.58% and 99.64%, were identified by GC/MS. Limonene (59–60%), γ-terpinene (10–11%) and β-pinene (7–15%) were the main compounds. All lemon oils inhibited specific biofilm production and bacterial metabolic activities into biofilm in a dose-dependent manner (20–65%, in the range of 0.1–4 mg mL−1) of both strains. Besides, all samples inhibited about 50% of the elastase activity at 0.1 mg mL−1. Pyocyanin biosynthesis decreases until 64% (0.1–4 mg mL−1) for both strains. Swarming motility of P. aeruginosa ATCC 27853 was completely inhibited by 2 mg mL−1 of lemon oils. Furthermore, a decrease (29–55%, 0.1–4 mg mL−1) in the synthesis of Quorum sensing (QS) signals was observed. The oils showed higher biological activities than limonene. Hence, their ability to control the biofilm of P. aeruginosa and reduce the production of virulence factors regulated by QS makes lemon oils good candidates to be applied as preservatives in the food processing industry.  相似文献   

10.
Accurate measurement of sulfated steroid metabolite concentrations can not only enable the elucidation of the mechanisms regulating steroid metabolism, but also lead to the diagnosis of various related diseases. The present study describes a simple and sensitive method for the simultaneous determination of four sulfated steroid metabolites in saliva, pregnenolone sulfate (PREGS), dehydroepiandrosterone sulfate (DHEAS), cortisol sulfate (CRTS), and 17β-estradiol-3-sulfate (E2S), by online coupling of in-tube solid-phase microextraction (IT-SPME) and stable isotope dilution liquid chromatography–tandem mass spectrometry (LC–MS/MS). These compounds were extracted and concentrated on Supel-Q PLOT capillary tubes by IT-SPME and separated and detected within 6 min by LC–MS/MS using an InertSustain swift C18 column and negative ion mode multiple reaction monitoring systems. These operations were fully automated by an online program. Calibration curves using their stable isotope-labeled internal standards showed good linearity in the range of 0.01–2 ng mL−1 for PREGS, DHEAS, and CRTS and of 0.05–10 ng mL−1 for E2S. The limits of detection (S/N = 3) of PREGS, DHEAS, CRTS, and E2S were 0.59, 0.30, 0.80, and 3.20 pg mL−1, respectively. Moreover, intraday and interday variations were lower than 11.1% (n = 5). The recoveries of these compounds from saliva samples were in the range of 86.6–112.9%. The developed method is highly sensitive and specific and can easily measure sulfated steroid metabolite concentrations in 50 μL saliva samples.  相似文献   

11.
Rare earth europium(III) complex with α‐thenoyltrifluoroacetone and triphenylphosphine oxide (Eu (TTA)3(TPPO)2, shortened as EuTT) was synthesized in this paper, then blended with polylactide (PLA) and poly(butylene adipate‐co‐terephthalate) (PBAT) to prepare the biodegradable agricultural films. Through the optical performance, mechanical properties, and other research, the results showed that the rare earth complex could convert the sun's ultraviolet light to red light when doped polymer. Moreover, the relative intensity ratio of 5D0/7F2 to 5D0/7F1 of PLA/PBAT/EuTT film could reach 3.79, which implied that the film had strong fluorescence intensity and high color purity. The highest tensile strength of the film could reach 36.7/25.2 MPa, and the elongation at break was 462.8/483.0% in the machine and in the transverse direction when the added amount of Eu (TTA)3(TPPO)2 was 0.1 wt%. The tensile strength of the film was 33.3/20.1 MPa, and the elongation at break could reach 535.8/413.6% when the added amount of Eu (TTA)3(TPPO)2 was increased up to 0.3 wt%. Gel permeation chromatography showed that the Eu (TTA)3(TPPO)2 could cause depolymerization of polylactide, resulting in a decrease in the molecular weight of PLA. Furthermore, the crystallization ability of PLA was also improved. In this paper, the biodegradable films exhibited excellent ultraviolet light conversion ability and mechanical properties.  相似文献   

12.
Renal cell carcinoma is the most lethal cancer of the urological system due to late diagnosis and treatment resistance. Propolis, a beehive product, is a valuable natural source of compounds with bioactivities and may be a beneficial addition to current anticancer treatments. A Portuguese propolis sample, its fractions (n-hexane, ethyl acetate, n-butanol and water) and three subfractions (P1–P3), were tested for their toxicity on A498, 786-O and Caki-2 renal cell carcinoma cell lines and the non-neoplastic HK2 kidney cells. The ethyl acetate fraction showed the strongest toxicity against A498 (IC50 = 0.162 µg mL−1) and 786-O (IC50 = 0.271 µg mL−1) cells. With similar toxicity against 786-O, P1 (IC50 = 3.8 µg mL−1) and P3 (IC50 = 3.1 µg mL−1) exhibited greater effect when combined (IC50 = 2.5 µg mL−1). Results support the potential of propolis and its constituents as promising coadjuvants in renal cell carcinoma treatment.  相似文献   

13.
Active and passive smoking are serious public health concerns Assessment of tobacco smoke exposure using effective biomarkers is needed. In this study, we developed a simultaneous determination method of five tobacco-specific nitrosamines (TSNAs) in hair by online in-tube solid-phase microextraction (SPME) coupled to liquid chromatography-tandem mass spectrometry (LC–MS/MS). TSNAs were extracted and concentrated on Supel-Q PLOT capillary by in-tube SPME and separated and detected within 5 min by LC–MS/MS using Capcell Pak C18 MGIII column and positive ion mode multiple reaction monitoring systems. These operations were fully automated by an online program. The calibration curves of TSNAs showed good linearity in the range of 0.5–1000 pg mL–1 using their stable isotope-labeled internal standards. Moreover, the limits of detection (S/N = 3) of TSNAs were in the range of 0.02–1.14 pg mL–1, and intra-day and inter-day precisions were below 7.3% and 9.2% (n = 5), respectively. The developed method is highly sensitive and specific and can easily measure TSNA levels using 5 mg hair samples. This method was used to assess long-term exposure levels to tobacco smoke in smokers and non-smokers.  相似文献   

14.
Extraordinary low-temperature vapor-phase synthesis of SnS thin films from single molecular precursors is attractive over conventional high-temperature solid-state methods. Molecular-level processing of functional materials is accompanied by several intrinsic advantages such as precise control over stoichiometry, phase selective synthesis, and uniform substrate coverage. We report here on the synthesis of a new heteroleptic molecular precursor containing (i) a thiolate ligand forming a direct Sn-S bond, and (ii) a chelating O^N^N-donor ligand introducing a “launch vehicle”-effect into the synthesized compound, thus remarkably increasing its volatility. The newly synthesized tin compound [Sn(SBut)(tfb-dmeda)] 1 was characterized by single-crystal X-ray diffraction analysis that verified the desired Sn:S ratio in the molecule, which was demonstrated in the direct conversion of the molecular complex into SnS thin films. The multi-nuclei (1H, 13C, 19F, and 119Sn) and variable-temperature 1D and 2D NMR studies indicate retention of the overall solid-state structure of 1 in the solution and suggest the presence of a dynamic conformational equilibrium. The fragmentation behavior of 1 was analyzed by mass spectrometry and compared with those of homoleptic tin tertiary butyl thiolates [Sn(SBut)2] and [Sn(SBut)4]. The precursor 1 was then used to deposit SnS thin films on different substrates (FTO, Mo-coated soda-lime glass) by CVD and film growth rates at different temperatures (300–450 °C) and times (15–60 min), film thickness, crystalline quality, and surface morphology were investigated.  相似文献   

15.
A novel class of quinolinol-based dimeric indium complexes (1–6) was synthesized and characterized using 1H and 13C(1H) NMR spectroscopy and elemental analysis. Compounds 1–6 exhibited typical low-energy absorption bands assignable to quinolinol-centered π–π* charge transfer (CT) transition. The emission spectra of 1–6 exhibited slight bathochromic shifts with increasing solvent polarity (p-xylene < tetrahydrofuran (THF) < dichloromethane (DCM)). The emission bands also showed a gradual redshift, with an increase in the electron-donating effect of substituents at the C5 position of the quinoline groups. The absolute emission quantum yields (ΦPL) of compounds 1 (11.2% in THF and 17.2% in film) and 4 (17.8% in THF and 36.2% in film) with methyl substituents at the C5 position of the quinoline moieties were higher than those of the indium complexes with other substituents.  相似文献   

16.
Nacobbus aberrans ranks among the “top ten” plant-parasitic nematodes of phytosanitary importance. It causes significant losses in commercial interest crops in America and is a potential risk in the European Union. The nematicidal and phytotoxic activities of seven plant extracts against N. aberrans and Solanum lycopersicum were evaluated in vitro, respectively. The chemical nature of three nematicidal extracts (EC50,48h ≤ 113 µg mL−1) was studied through NMR analysis. Plant extracts showed nematicidal activity on second-stage juveniles (J2): (≥87%) at 1000 µg mL−1 after 72 h, and their EC50 values were 71.4–468.1 and 31.5–299.8 µg mL−1 after 24 and 48 h, respectively. Extracts with the best nematicidal potential (EC50,48h < 113 µg mL−1) were those from Adenophyllum aurantium, Alloispermum integrifolium, and Tournefortia densiflora, which inhibited L. esculentum seed growth by 100% at 20 µg mL−1. Stigmasterol (1), β-sitosterol (2), and α-terthienyl (3) were identified from A. aurantium, while 1, 2, lutein (4), centaurin (5), patuletin-7-β-O-glucoside (6), pendulin (7), and penduletin (8) were identified from A. integrifolium. From T. densiflora extract, allantoin (9), 9-O-angeloyl-retronecine (10), and its N-oxide (11) were identified. The present research is the first to report the effect of T. densiflora, A. integrifolium, and A. aurantium against N. aberrans and chemically characterized nematicidal extracts that may provide alternative sources of botanical nematicides.  相似文献   

17.
Antimicrobial active films based on poly(lactic acid) (PLA) were prepared with poly(ε‐caprolactone) (PCL) and thymol (0, 3, 6, 9, and 12 wt%) by solvent casting methods. The films were characterized by thermal, structural, mechanical, gas barrier, and antimicrobial properties. Scanning electron microscopy analysis revealed that the surface of film became rougher with certain porosity when thymol was incorporated into the PLA/PCL blends. Thymol acted as plasticizers, which reduce the intermolecular forces of polymer chains, thus improving the flexibility and extensibility of the films. The addition of PCL into the pure PLA film decreased the glass transition temperature of the films. The presence of thymol decreased the crystallinity of PLA phase, but did not affect the thermal stability of films. Water vapor barrier properties of films slightly decreased with the increase of thymol loading. The antimicrobial properties of thymol containing films showed a significant activity against Escherichia coli and Listeria monocytogenes. The results indicated the potential of PLA/PCL/thymol composites for applications in antimicrobial packaging. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

18.
Poly(lactic acid) (PLA)/poly(propylene carbonate) (PPC)/mica composites with different amount of chain extender (CE) were melt compounded and then processed via two routes (compression molding and uniaxial stretching) into sheets and films. The tensile, thermal, and oxygen barrier properties of all the samples were investigated. Tensile test showed that the tensile strength and elongation at break of all films were much higher than that of all sheets, especially for PLA/PPC/mica with 0.9‐wt% CE composite (CM3(CE)0.9) film. The crystallinity of all films increased significantly after uniaxial stretching of sheet samples. The Fourier transform infrared spectroscopy (FTIR) results proved the chemical reactions occurred between PLA/PPC and CE. Scanning electron microscope (SEM) analysis revealed that compatibility and interfacial adhesion of all samples were improved after adding mica and CE, and they were further enhanced after uniaxial stretching. The addition of CE was not favorable to improve the oxygen barrier performance of PLA/PPC/mica sheet samples. However, the oxygen barrier performance of film samples was significantly improved after uniaxial stretching. In particular, the CM3(CE)0.9 film had the lowest oxygen permeability coefficient (1.4 × 10?15 cm3·cm/(cm2·s·Pa)), and this was the best oxygen barrier properties reported in the literature for PLA‐based composites, which was comparable with PA film. This study demonstrated the high efficiency of uniaxial stretching on improvement of properties of composites, which would promote the application of biodegradable polymers in oxygen sensitive food packaging.  相似文献   

19.
Using investigations of the copper(I)–1,10-phenanthroline system as an example, it is shown that thermal lensing can be used for determining stability constants at a level of concentrations one–two orders of magnitude lower compared to conventional spectrophotometry, with better precision of measurements. The values of stability constants are log2= 11.7 ± 0.7 without regard for stepwise chelation, and logK 1= 5.9 ± 0.3, logK 2= 5.4 ± 0.3, and log2= 11.3 ± 0.6 taking into account stepwise chelation. It is shown that, when shifting from microgram to nanogram amounts of reactants in the determination of stability constants by thermal lensing, changes in the kinetic parameters of the reaction studied should be taken into account. The thermal-lens limit of detection of copper(I) is 2 × 10–8M; the linear calibration range is 4 × 10–8–2 × 10–5M (488.0 nm, pump power 120 mW). The data obtained were used for determining copper(I) in the hydrogen sulfide layer of the Baltic Sea.  相似文献   

20.
A simple and rapid spectrophotometric technique has been designed for the trace copper analysis employing 1-(2-Thiazolylazo)-2-naphthol (TAN) reagent in aqueous micellar solution of cetyl trimethylammonium bromide (CTAB) as a surfactant. Copper complexed with 1-(2-Thiazolylazo)-2-naphthol to form bis[1-(2-Thiazolylazo)-2-naphthol]copper. The present spectrophotometric technique was very important since the micellar system was used in place of the toxic, high cost and time-consuming solvent extraction steps. The technique showed an enhanced detection efficiency, specificity, and molar absorptivity. It was found that the molar absorption coefficient and sensitivity of Sandel were ε 2.45 × 104 L mol?1cm?1 and 2.6 ngcm?2 at λmax 578.4 nm. A linear calibration plot in the range 0.12–5.0 μg mL?1 was obtained; a stoichiometric metal ligand ratio [M:L] of 1:2 was found for the formation of Cu-[TAN]2. The complex was formed at pH 9.5 and was stable up to 24 h. The proposed technique has been employed to study copper from different alloys, biological, environmental and pharmaceutical samples.  相似文献   

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