RESUMO
A facile and practical ratiometric fluorescence probe based on two CdTe quantum dots (QDs) coated with molecularly imprinted polymers (MIPs) was prepared for the detection of trace malachite green (MG) in fish. Two CdTe QDs coated with MIPs were fabricated by a one-pot method using MG, (3-aminopropyl) triethoxysilane (APTES) and tetraethyl orthosilicate (TEOS) as template, functional monomer, and cross-linker, respectively. CdTe QDs with λem 530 nm (gQDs) and 630 nm (rQDs) were used as the referential fluorophore and target sensitive fluorophore, respectively. The fluorescence intensity of gQDs remained unchanged in the presence of MG, while the fluorescence of rQDs could be quantitatively quenched by MG based on the strategy of fluorescence resonance energy transfer. The ratiometric fluorescence probe (MIPs@gQDs&rQDs) was characterized by transmission electron microscopy and Fourier transform infrared spectroscopy. The linear range of MG detection was 0.1-32 µmol L-1 with a detection limit of 8.8 µg kg-1. The constructed probe has been successfully applied to the detection of MG in fish with the recoveries of 92.3-109.1%, which were validated by the method of HPLC. The result indicated that the probe possessed rapid response, wide linear range, high sensitivity, and relatively high selectivity, and was low-cost and easy in operation in the detection of MG in fish samples.
Assuntos
Compostos de Cádmio/química , Peixes , Fluorometria/métodos , Impressão Molecular , Pontos Quânticos , Corantes de Rosanilina/química , Telúrio/química , Animais , Estrutura Molecular , Reprodutibilidade dos Testes , Sensibilidade e Especificidade , Espectroscopia de Infravermelho com Transformada de FourierRESUMO
A specific and sensitive colorimetric aptasensor is described for the determination of Malachite Green (MG). It is exploiting the inhibition of the peroxidase-like activity of gold nanoparticles (AuNPs). The AuNPs act as enzyme mimics that catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by H2O2 to yield a dark blue solution. The catalytic activity is inhibited by hexadecyl trimethyl ammonium ion, specifically by cetyltrimethylammonium bromide (CTAB), which causes the aggregation of AuNPs. If a (negatively charged) RNA-aptamer against MG is added, it binds to the positively charged CTAB and prevents aggregation. This enhances the enzyme mimicking activity of the AuNPs and leads to the formation of a dark blue solution. However, in the presence of MG, the aptamer binds to MG, and leads to the aggregation of AuNPs again. The aggregated AuNPs possess a light blue color. A colorimetric method (best performed at 650 nm) was work out that can detect MG in a concentration range from 10 to 500 nmol L-1. The detection limit based on 3σ/k criterion is 1.8 nmol L-1. The assay is highly specific and accurate. Recoveries from spiked real samples (aquaculture water) ranged from 80% to 120%. Graphical abstract Based on the inhibition of cetyltrimethyal ammonium ion and the enhancement of RNA-aptamer, the differences of the peroxidase-like activities of AuNPs can be greatly enlarged with and without MG, by which a colorimetric aptasensor can be constructed for the detection of Malachite Green (MG).
Assuntos
Aptâmeros de Nucleotídeos/química , Cetrimônio/química , Colorimetria/métodos , Ouro/química , Nanopartículas Metálicas/química , Peroxidase/química , Corantes de Rosanilina/análise , Benzidinas/química , Catálise , Cor , Peróxido de Hidrogênio/química , Limite de Detecção , OxirreduçãoRESUMO
Due to complex matrixes and specific reagent deficiency, the rapid detection of histamine is still a challenge to date. Based on the high peroxidase-like activity of iron-cobalt co-doped carbon dots, an indirect competitive enzyme-linked immunosorbent assay (ic-ELISA) was established for histamine detection using the mimic enzyme labeled with histamine antibody (His-Ab). Through the competitive binding of the labeled His-Ab to solid-phase and sample antigens, histamine content was detected with a linear range of 2.5-150 µg mL-1. The detection limit based on 3σ/K was 0.50 mg kg-1, which was much lower than those of commercial His-kit and HPLC methods. The ic-ELISA method was applied to histamine detection in fish samples with the recovery of (103.4 ± 0.5)%, which was in accord with those of commercial His-kit and HPLC methods. The results indicated that the established ic-ELISA method was suitable for rapid detection of histamine in fish samples with high accuracy, sensitivity and stability.
Assuntos
Peixes/metabolismo , Histamina/análise , Pontos Quânticos/química , Animais , Anticorpos/química , Anticorpos/imunologia , Carbono/química , Cobalto/química , Ensaio de Imunoadsorção Enzimática , Histamina/imunologia , Ferro/química , Limite de Detecção , Reprodutibilidade dos Testes , Alimentos Marinhos/análiseRESUMO
A fluorescence probe was delicately designed for the detection of malachite green (MG) in water and fish samples. Through the electrostatic self-assembly of CdTe QDs on the surface of polystyrene (PS) microspheres, the fluorescence signal was amplified. After grafting molecularly imprinted film, the fluorescence probe of MIP@PS@CdTe was fabricated and applied to the detection of MG based on fluorescence quenching. The linear range of MG detection was 0.01-20 µmol L-1, and the detection limit was 4.7 nmol L-1 (3σ, n = 9) which was much lower than those of the previous reports. The recoveries of MG in aquaculture water and fish samples ranging from 87.6% to 105.4% illustrated that the detection by MIP@PS@CdTe probe was accurate and reliable.
Assuntos
Compostos de Cádmio , Monitoramento Ambiental/métodos , Impressão Molecular , Poliestirenos/química , Pontos Quânticos , Corantes de Rosanilina/análise , Telúrio , Animais , Microesferas , Modelos Químicos , Espectrometria de FluorescênciaRESUMO
A method for the aptamer-based determination of chloramphenicol (CAP) was developed by exploiting the peroxidase mimicking activity of hemin. The method includes two hemin-modified DNA probes termed P1 and P2. P1, which was modified at its 5' end with one hemin monomer, contains the CAP-binding sequence. The hybridization between P1 and P2 brings the two hemin monomers in close proximity, resulting in the formation of a hemin dimer with low peroxidase mimicking activity. The duplex structure was dehybridized in the presence of CAP. The formed hemin monomer featured a strong peroxidase mimicking activity and catalyzed the conversion of non-fluorescent tyramine into fluorescent dityramine by hydrogen peroxide. Fluorescence (with an excitation/emission maxima at 320 and 410 nm, respectively) increased linearly in the 0.1 ng mL-1 to 10 ng mL-1 CAP concentration range. The detection limit based on the 3σ/k criterion reached 0.07 ng mL-1. The proposed assay was successfully employed for CAP detection in (spiked) honey samples with recoveries of 94.3-117.2%. Given its high sensitivity and good stability, this method shows potential in providing a platform for antibiotic detection.
Assuntos
Biomimética , Técnicas de Química Analítica , Cloranfenicol , Hemina , Peroxidase , Aptâmeros de Nucleotídeos , Técnicas de Química Analítica/métodos , Cloranfenicol/análise , Fluorometria , Análise de Alimentos/métodos , Hemina/metabolismo , Mel/análise , Limite de Detecção , Peroxidase/metabolismoRESUMO
A dichromatic label-free aptasensor was described for sulfadimethoxine (SDM) detection. Compared with the binding of SDM-aptamer to SDM, the higher affinity of aptamer to cDNA may result in the hybridization of dsDNA. In the presence of SDM, the aptamer specifically binds to SDM, leading to a blue color of AuNPs in deposit and fluorescence at 530â¯nm in supernatant after adding cDNA and SGI. With no target of SDM, AuNPs protected with the aptamer re-disperse in PBS with a red color, and no fluorescence occurs in supernatant. Based on the principle, SDM can be quantitatively detected through both fluorescent emission and AuNPs color changes with recoveries ranging from 99.2% to 102.0% for fish and from 99.5% to 100.5% for water samples. An analytical linear range of 2-300â¯ngâ¯mL-1 was achieved with the detection limits of 3.41â¯ngâ¯mL-1 for water and 4.41â¯ngâ¯g-1 for fish samples (3σ, nâ¯=â¯9).
Assuntos
Aptâmeros de Nucleotídeos/química , DNA/química , Corantes Fluorescentes/química , Nanopartículas Metálicas/química , Compostos Orgânicos/química , Espectrometria de Fluorescência/métodos , Sulfadimetoxina/análise , Animais , Benzotiazóis , Diaminas , Peixes/metabolismo , Ouro/química , Limite de Detecção , Quinolinas , Água/químicaRESUMO
In this paper, molecular imprinting and photonic crystal techniques were combined to construct a four-channel sensor array for the simultaneous identification of various sulfonamides. The assay was composed of four units. Three of these units were prepared using sulfaguanidine, sulfamethazine, or sulfathiazole as template molecules. The fourth unit was prepared without a template molecule. The preparation was optimized to obtain maximum identification with a molar ratio of template, monomer, and cross-linker of 1:50:10. The response time was as short as 10 min. For demonstration, six sulfonamides were selected as analytes. The Bragg diffraction patterns of analytes at different concentrations were measured using the sensor array. Data obtained were analyzed using linear discrimination analysis (LDA) and principal component analysis (PCA). LDA can be applied for SAs discrimination. The message ratios of 87.6%, 94.4%, and 95.8% for six SAs at 10-4 mol L-1, 10-6 mol L-1, and 10-8 mol L-1 were achieved using LDA. The sensor array identified the mixture containing various SAs with an LDA coefficient of 86.1%, thereby indicating that the sensor array had a strong anti-interference ability. The sensor array was used to identify six SAs in fish samples. The measured data in spiked samples were consistent with the fingerprint collected from standard solutions. The accuracy rate reached 90.9%, indicating that the array can be used to identify SAs from food samples.
Assuntos
Polímeros/química , Sulfonamidas/análise , Animais , Análise Discriminante , Peixes , Contaminação de Alimentos/análise , Limite de Detecção , Impressão Molecular/métodos , Análise de Componente Principal , Alimentos Marinhos/análise , Dióxido de Silício/química , Espectrofotometria Ultravioleta/métodos , Sulfonamidas/químicaRESUMO
Fluorescence-based aptasensors possess high sensitivity but are complicated and usually require multistep labeling and modification in method design, which severely limit the practical applications. Here, a label-free fluorescence-based aptasensor, consisting of aptamer, gold nanoparticles (AuNPs), and cadmium telluride (CdTe) quantum dots (QDs), was developed for the detection of sulfadimethoxine (SDM) in water and fish based on the specific recognition of SDM-aptamer and the inner filter effect of QDs and AuNPs. In the absence of a target, AuNPs dispersed in salt solution because of the aptamer protection, which could effectively quench the fluorescence emission of QDs, while in the presence of SDM, AuNPs aggregated due to the specific recognition of SDM-aptamer to SDM, which resulted in fluorescence recovery. A linear response of SDM concentrations in the range of 10-250 ng mL-1 ( R2 = 0.99) was obtained, and the detection limit was 1.54 ng mL-1 (3σ, n = 9), far below the maximum residue limit (100 ng mL-1) of SDM in edible animal tissues regulated by China and the European Commission. The fluorescence-based aptasensor was applied to the detection of SDM in aquaculture water and fish samples with high accuracy, excellent precision, and ideal selectivity. The results indicated that the developed aptasensor was simple in design, easy to operate, and could be used to detect rapidly and accurately SDM in water and fish samples.
Assuntos
Aptâmeros de Nucleotídeos/química , Peixes/metabolismo , Espectrometria de Fluorescência/métodos , Sulfadimetoxina/análise , Água/química , Animais , Técnicas Biossensoriais , Compostos de Cádmio/química , Ouro/química , Limite de Detecção , Nanopartículas Metálicas/química , Pontos Quânticos/química , Telúrio/químicaRESUMO
A magnetic fluorescent probe of CdTe QDs/nano-Fe3O4@MIPs was prepared using CdTe QDs and Fe3O4 nanoparticles as co-nucleus and molecularly imprinted polymers (MIPs) as specific recognition sites based on a reverse microemulsion method. With the specific enrichment and magnetic separation properties, the probe of CdTe QDs/nano-Fe3O4@MIPs was used to detect malachite green (MG) in fish samples. The TEM analysis showed that the particles of CdTe QDs/nano-Fe3O4@MIPs were spherical with average diameter around 53nm, and a core-shell structure was well-shaped with several Fe3O4 nanoparticles and CdTe QDs embedded in each of the microsphere. Quick separation of the probes from solutions could be realized with a magnet, indicating the excellent magnetic property of CdTe QDs/nano-Fe3O4@MIPs. The probe exhibited high specific adsorption towards MG and excellent fluorescence emission at λem 598nm. The fluorescence of CdTe QDs/nano-Fe3O4@MIPs could be linearly quenched by MG at the concentrations from 0.025 to 1.5µmolL-1. The detection limit was 0.014µmolL-1. The average recovery of spiked MG in fish samples was 105.2%. The result demonstrated that the as-prepared CdTe QDs/nano-Fe3O4@MIPs could be used as a probe to the detection of trace MG in fish samples.
Assuntos
Compostos de Cádmio/química , Resíduos de Drogas/análise , Corantes Fluorescentes/química , Nanopartículas de Magnetita/química , Corantes de Rosanilina/análise , Alimentos Marinhos/análise , Telúrio/química , Animais , Peixes/metabolismo , Limite de Detecção , Modelos Lineares , Impressão Molecular , Pontos Quânticos/química , Espectrometria de FluorescênciaRESUMO
A novel fluorescence-based sensor combining synchronous fluorescence spectroscopy (SFS) with molecularly imprinted polymers (MIPs) was fabricated with reverse microemulsion method. Tetracycline (TC), (3-aminopropyl) triethoxysilane (APTES), tetraethyl orthosilicate (TEOS) and carbon quantum dots (CDs) were used as template, functional monomer, cross-linker and signal sources respectively in the probe preparation. A synchronous fluorescence emission (λem) at 355nm was observed for the prepared MIP-coated CDs (MIP@CDs) particles when the wavelength interval (Δλ) was set as 70nm, and the synchronous fluorescence intensity could be rapidly and efficiently quenched by TC based on inner filter effect (IFE). The quenching efficiencies of synchronous fluorescence intensity was linearly fitted with tetracycline (TC) concentrations ranging from 0.1 to 50µmolL-1 with a detection limit (DL) of 9nmolL-1 (3σ, n=9). The MIP@CDs was used as a probe to detect TC in fish samples with the recoveries ranging from 98.4% to 103.1% and the relative standard deviation less than 6.0%. The results illustrated that the as-prepared MIP@CDs could be applied to the detection of trace TC in fish samples with rapidity, high sensitivity and accuracy.
Assuntos
Carbono/química , Peixes/metabolismo , Impressão Molecular/métodos , Pontos Quânticos/química , Dióxido de Silício/química , Tetraciclinas/análise , Adsorção , Animais , Fluorescência , Pontos Quânticos/ultraestrutura , Espectrometria de Fluorescência , Espectrofotometria Ultravioleta , Espectroscopia de Infravermelho com Transformada de FourierRESUMO
A highly selective and sensitive enzyme-linked immunosorbent assay (ELISA) was developed for the detection of malachite green (MG) using a molecularly imprinted polymer (MIP) film as bionic antibody. The MIP film, based on the self-polymerization of dopamine, was fabricated on the surfaces of a 96-well microplate. It showed specific recognition for MG in aqueous solution. A direct competitive ELISA method was established with the sensitivity reaching 10.31µgL-1 and the detection limit being 0.3µgL-1. The cross-reactivity of two structural analogues to MG was less than 10%. The average recovery tested by MG standard spiking was 88.8% for bass and 90.4% for water, and the relative standard deviations were less than 3.6%. All the above results indicated that the developed method could be used to detect MG in fish and water samples rapidly, specifically and accurately.
Assuntos
Anticorpos , Ensaio de Imunoadsorção Enzimática/métodos , Peixes , Impressão Molecular/métodos , Polímeros/química , Corantes de Rosanilina/análise , Animais , Biomimética , Produtos Pesqueiros , Corantes de Rosanilina/imunologia , Sensibilidade e EspecificidadeRESUMO
A sensitive fluorescence sensor for the detection of malachite green (MG) was fabricated by grafting molecularly imprinted polymers (MIPs) onto the surface of CdTe quantum dots (QDs). The MIP-coated QDs were synthesized via a reverse microemulsion method using (3-aminopropyl)triethoxysilane (APTES) and tetraethyl orthosilicate (TEOS) as functional monomer and cross-linker, respectively. The optimum molar ratio of MG, functional monomer and cross-linker was 1:3:10. The MIP-coated QDs exhibited uniform spheres with diameter around 49nm and excellent fluorescence emission at λex 370nm. A linear relationship with two segments between the relative fluorescence intensities and the MG concentrations ranging from 0.08 to 20µmol·L-1 could be obtained with a detection limit of 12µg·kg-1. The fluorescent probe was successfully applied to the determination of MG in fish samples with the spiked recoveries ranging from 94.3% to 109.5% which were in accordance with those of the measurement by HPLC-UV.
Assuntos
Compostos de Cádmio/química , Contaminação de Alimentos , Impressão Molecular/métodos , Pontos Quânticos/química , Corantes de Rosanilina/análise , Dióxido de Silício/química , Telúrio/química , Animais , Peixes , Limite de DetecçãoRESUMO
Magnetic molecularly imprinted polymers (MMIPs) were synthesized through precipitation polymerization using malachite green (MG) as template, methacrylic acid as monomer, ethylene dimethacrylate as crosslinker, and Fe3O4 magnetite as magnetic component. MMIPs were characterized by scanning electron microscopy, Fourier transform infrared spectrometry, and vibrating sample magnetometry. Under the optimum condition, the MMIPs obtained exhibited quick binding kinetics and high affinity to MG in the solution. Scatchard plot analysis revealed that the MMIPs contained only one type of binding site with dissociation constant of 24.0 µg mL(-1). The selectivity experiment confirmed that the MMIPs exhibited higher selective binding capacity for MG than its structurally related compound (e.g., crystal violet). As a sorbent for the extraction of MG in sample preparation, MMIPs together with the absorbed analytes could easily be separated from the sample matrix with an external magnet. After elution with methanol/acetic acid (9:1, v/v), MG in the eluent was determined by high-performance liquid chromatography coupled with UV detector with recoveries of 94.0-115%. Results indicated that the as-prepared MMIPs are promising materials for MG analysis in aquatic products.
Assuntos
Cromatografia Líquida de Alta Pressão/métodos , Impressão Molecular/métodos , Polímeros/química , Corantes de Rosanilina/químicaRESUMO
A direct competitive enzyme-linked immunosorbent assay (ELISA) method was used for the detection of malachite green (MG) with a high sensitivity and selectivity using magnetic molecularly imprinted polymers (MMIPs) as a bionic antibody. MMIPs were prepared through emulsion polymerization using Fe3O4 nanoparticles as magnetic nuclei, MG as a template, methacrylic acid (MAA) as a functional monomer, ethylene glycol dimethacrylate (EGDMA) as a crosslinking agent and span-80/tween-80 as mixed emulsifiers. The MMIPs were characterized by scanning electron micrographs (SEM), thermal-gravimetric analyzer (TGA), Fourier transform infrared spectrometer (FT-IR) and vibrating sample magnetometer (VSM), respectively. A high magnetic saturation value of 54.1emug-1 was obtained, resulting in rapid magnetic separation of MMIPs with an external magnet. The IC50 of the established ELISA method was 20.1µgL-1 and the detection limit (based on IC85) was 0.1µgL-1. The MMIPs exhibited high selective binding capacity for MG with cross-reactivities less than 3.9% for MG structural analogues. The MG spiking recoveries were 85.0%-106% with the relative standard deviations less than 4.7%. The results showed that the biomimetic ELISA method by using MMIPs as bionic antibody could be used to detect MG rapidly in fish samples with a high sensitivity and accuracy.
Assuntos
Biomimética , Ensaio de Imunoadsorção Enzimática/métodos , Impressão Molecular , Polímeros/química , Corantes de Rosanilina/química , Adsorção , Microscopia Eletrônica de VarreduraRESUMO
The paper reports a new molybdenum phosphate (NH3CH2CH2NH3)7H2[NaMo12O30(PO4)2(HPO4)5(H2PO4)].7H2O containing Mo(V) which is hydrothermally synthesized and spectrally characterized by FTIR, Raman and UV/Vis DRS. The result indicates long Mo(V)-O bonds and innumerable hydrogen bonds in compound cause the red shift of characteristic vibrations in IR spectrum of title compound.
Assuntos
Molibdênio/química , Fosfatos/química , Ácidos Fosfóricos/síntese química , Ácidos Fosfóricos/química , Espectrofotometria Ultravioleta , Espectroscopia de Infravermelho com Transformada de Fourier , Análise Espectral RamanRESUMO
Three novel organic-molybdenum phosphates with [(PO4)2Mo5O15], namely (NH3CH2CH2NH3)2.5[(PO4)(HPO4) Mo5O15].7.5H2O (I), (H3NCH2CH2NH3)3.[(PO4)2Mo5O15].3H2O (II) and (H3NCH2CH2NH3)2.[Cu(en)] [(PO4)2Mo5O15].5H2O (III), were synthesized. The relationship between their properties and structures were studied by using FTIR, NIR-Raman, UV-Vis DRS and fluorescence spectra. Among these compounds, compound I and II possess isolating [(PO4)2Mo5O15] cage, while compound III is rather novel whose [(PO4)2Mo5O15] cages are bridging into chains by [Cuen] groups. The characteristic vibrational frequencies of molybdenum phosphates are related to the structures of these compounds. In the UV-Vis DRS spectra, there are two characteristic peaks of heteropoly compounds at 200 and 260 nm. The fluorescence spectra of these three compounds have been studied, which have emission peaks at about 400 nm excited by 240 nm, which are caused by O mu-Mo, while compound III produces 604 nm emission excited by 570 nm, which is caused by the LMCT of [Cuen] group.
Assuntos
Molibdênio/química , Compostos Organometálicos/química , Fosfatos/química , Cristalização , Compostos Organometálicos/síntese química , Fosfatos/síntese química , Espectrometria de Fluorescência , Espectrofotometria Ultravioleta , Espectroscopia de Infravermelho com Transformada de Fourier , Análise Espectral RamanRESUMO
Five novel organic-molybdenum phosphates with [(PO4)4Mo6(V)O15]12- cluster, Na x (H4TETA)3 x (H3O)5 x {Zn[(HPO4)2(PO4)2Mo6O15]2} (2), (H2en)7 x (H3O)4 x {Cu[(HPO4)2(PO4)2Mo6O15]2} x H2O (3), (H3DETA)2 x (H3O)3 x {Co0.5[(HPO4)2(PO4)2Mo6O15]} x H2O (4), [Co(H3TETA)]2{Co0.5[(HPO4)(PO4)3Mo6O15] x 3.5H2O (5) and (H3DETA) x (H3O)4 x {Co1.5 [(HPO4)2(PO4)2Mo6O15]} x 0.5H2O (6), have been synthesized. The relationship between their properties and structures was studied by using FTIR, NIR FT-Raman, UV-Vis DRS and fluorescence etc. In these compounds, every two [(PO4)4Mo6O15] clusters are coordinated by a metal atom to form a {M[(PO4)4Mo6O15]2} dimer. In compound 2, 3 and 4, {M[(PO4)4Mo6O15]2} dimers are hydrogen-bonded by the organic molecules and water molecules to form a three-dimensional expended framework, respectively. In compound 5 and 6, {Co[(PO4)4Mo6O15]2} dimers are coordinated by [Co(H3TETA)] groups and [CoO4] tetrahedra to form a network, respectively. These characteristic vibrational frequencies of the molybdenum phosphates are related to the structure of these compounds. Three characteristic bands in UV-Vis DRS spectra of these compounds have to be attributed to the absorptions of O(d) --> Mo, O(mu) --> Mo and O --> M charge transfer, respectively. These compounds exhibit strong fluorescence emission bands at about 410 nm when excited by 240 nm, which are caused by O(mu) --> Mo charge transfer.
RESUMO
The structural and electrical properties of a metal-halide cubic perovskite, CH(3)NH(3)SnI(3), have been examined. The band structure, obtained using first-principles calculation, reveals a well-defined band gap at the Fermi level. However, the temperature dependence of the single-crystal electrical conductivity shows metallic behavior down to low temperatures. The temperature dependence of the thermoelectric power is also metallic over the whole temperature range, and the large positive value indicates that charge transport occurs with a low concentration of hole carriers. The metallic properties of this as-grown crystal are thus suggested to result from spontaneous hole-doping in the crystallization process, rather than the semi-metal electronic structure. The present study shows that artificial hole doping indeed enhances the conductivity.