RESUMO
A novel molecularly imprinted nanomaterial (Eu (BTC)-MPS@MIP) was synthesized on the surface of silanized europium-based metal-organic frameworks (Eu (BTC)-MPS) using 1, 3, 5-benzotrioic acid (H3BTC) as a ligand. The resulting Eu (BTC)-MPS@MIP was applied to constructing a smartphone sensing platform for the sensitive and selective detection of clothianidin (CLT) in vegetables. The synthesized Eu (BTC)-MPS@MIP demonstrated the successful formation of a typical core-shell structure featuring a shell thickness of approximately 70 - 80 nm. The developed sensing platform based on Eu (BTC)-MPS@MIP exhibited sensitivity in CLT detection with a detection limit of 4 µg/L and a linear response in the range 0.01 - 10 mg/L at excitation and emission wavelengths of 365 nm and 617 nm, respectively. The fluorescence sensing platform displayed excellent specificity for CLT detection, as evidenced by a high imprinting factor of 3.1. This specificity is primarily attributed to the recognition sites in the molecularly imprinted polymer (MIP) layer. When applied to spiked vegetable samples, the recovery of CLT ranged from 78.9 to 102.0%, with relative standard deviation (RSD) values falling between 2.2 and 6.2%. The quenching mechanism of Eu (BTC)-MPS@MIP toward CLT can be attributed to the inner filter effect (IFE), resulting from the optimal spectral overlap between the absorption spectrum of CLT and the excitation spectra of Eu (BTC)-MPS@MIP. The proposed method has the potential for extension to the detection of other pesticides by replacing the MIP recognition probes.
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A turn-on fluorescent aptasensor based on a paper-based microfluidic chip was developed to detect arsenite via aptamer competition strategy and smartphone imaging. The chip was prepared by wax-printing hydrophilic channels on filter paper. It is portable, low-cost, and environmentally friendly. Double-stranded DNA consisting of aptamer and fluorescence-labeled complementary strands was immobilized on the reaction zone of the paper chip. Due to the specific strong binding between aptamer and arsenite, the fluorescent complementary strand was squeezed out and driven by capillary force to the detection area of the paper chip, so that the fluorescent signal arose in the detection area under the excitation wavelength of 488 nm. Arsenite can be quantified by using smartphone imaging and RGB image analysis. Under the optimal conditions, the paper-based microfluidic aptasensor exhibited excellent linear response over a wide range of 1 to 1000 nM, with a detection limit as low as 0.96 nM (3σ).
Assuntos
Arsenitos , Smartphone , Oligonucleotídeos , Corantes , Dispositivos Lab-On-A-ChipRESUMO
Due to the threat to health of heavy metal contamination, simple and rapid detection methods for heavy metals are an urgent needed in environment protection and food safety. In this work, we have developed a fluorescent aptasensor for the 'turn-off' model detection of Pb2+ . The key feature of the aptasensor is that the dye-labelled nucleic acid strand can be folded into a G-quadruplex structure in the presence of Pb2+ . This conformational change induces photoinduced electron transfer (PET) between a G-quadruplex-hemin complex and 6-carboxyrhodamine X (ROX), which results in fluorescence quenching of ROX. We systematically investigated the interaction mechanism between Pb2+ and the aptasensor and the effects of several environmental parameters were also studied. Under the optimum conditions, the proposed method exhibited a good liner relationship between the concentration of Pb2+ and fluorescence quenching efficiency in the range 25-500 nM and the limit of detection was 1.02 nM. In addition, this method also manifested good performance in spiked lettuce samples with satisfactory recoveries of 87.10-109.6%. This target-induced PET platform can be further expanded to other heavy metal analysis.
Assuntos
Aptâmeros de Nucleotídeos , Técnicas Biossensoriais , Quadruplex G , Elétrons , Hemina , Chumbo , Limite de DetecçãoRESUMO
The improper conformation of oligonucleotides on gold nanoparticle surfaces is caused by unintended base adsorption, which hinders DNA hybridization and lowers colloidal stability. In this work, we treated spherical nucleic acids with Br- , which serves as an efficient backfilling agent, to adjust the DNA conformation by displacing bases from the gold surface. To investigate the effect of DNA conformation on interfacial recognition, a kanamycin fluorescent aptasensor was constructed with bromide backfilled-treated spherical nucleic acids. In the presence of kanamycin, the anchored aptamer binds with the target and the partially complementary reporter strand is dissociated from the surface of the gold nanoparticles, resulting in the fluorescence recovery of labelled fluorophore on the reporter strand. Under optimum conditions, the apparent binding affinity of the aptasensor with bromide backfilling was 2.2-fold that without backfilled one. The proposed aptasensor exhibited a good liner relationship between the concentration of kanamycin and fluorescence intensity change in the range 200 nM to 10 µM and the limit of detection was calculated to be 71.53 nM. Moreover, this aptasensor was also successfully applied in a spiked milk sample assay and the satisfactory recoveries were obtained in the range 96.94-101.57%, which demonstrated its potential in practical applications.
Assuntos
Aptâmeros de Nucleotídeos , Técnicas Biossensoriais , Nanopartículas Metálicas , Ácidos Nucleicos , Animais , Canamicina/análise , Canamicina/química , Ouro/química , Brometos , Ácidos Nucleicos/análise , Nanopartículas Metálicas/química , Aptâmeros de Nucleotídeos/química , Leite/química , Conformação de Ácido Nucleico , Técnicas Biossensoriais/métodos , Limite de DetecçãoRESUMO
A novel hydrophilic As(V) ion-imprinted cryogel (IIC) was green prepared by cryogelation in aqueous environment which was coincident with the adsorption condition and can improve the specific recognition performance. The methacrylamido propyl trimethyl ammonium chloride (MPTAC) was selected as the functional monomer and the saturated adsorption capacity of the prepared IIC and NIC were 55.0 mg/g and 29.4 mg/g, and with high imprinting factor of 1.87. Additionally, the prepared IIC showed admirable reusability and high selectivity, and the recovery was in the range 81.2-97.9% with RSD range of 1.9-4.3%, which was similar to the value obtained by hydride generation atomic absorption spectrometry. IIC can be used as solid material for colorimetric detection at the ultraviolet wavelength of 858 nm without color interference of material matrix, in the range 5-200 µg/L (R2 = 0.990) with a detection limit of 0.970 µg/L. Obviously, this synthetic strategy provides a simple, efficient, and green method for the preparation of water-compatible ion-imprinted polymers providing selective separation and detection of trace As(V) in real complex samples.
Assuntos
Impressão Molecular , Impressão Molecular/métodos , Criogéis/química , Colorimetria , Água , AdsorçãoRESUMO
Kanamycin fluorescence aptasensors were created using a series of di-block oligonucleotide modified gold nanoparticles with various lengths of poly-adenine. In the presence of kanamycin, the double strand structure of the aptamer-reporter strand complex is disrupted, and the dye-labelled reporter strand detaches from the surface of gold nanoparticles, resulting in fluorescence recovery (Ex/Em = 485/520 nm). By adjusting the number of consecutive adenines, the programable aptamer density can be implemented on the gold nanoparticle surface, and the conformation of nucleic acid changed from lying-down to up-right. The apparent binding constant, binding kinetics, and limit of detection of the prepared aptasensors were carefully examined to explore the influence of surface density. Under the optimum condition, the aptasensor had a tenfold lower limit of detection than the thiolated aptamer modified one, as low as 23.6 nM, when a di-block oligonucleotide with twenty consecutive adenines tailed. In addition, satisfactory recoveries ranging from 96.33 to 99.47% were achieved in spiked milk samples with relative standard deviation of 1.2-6.9% (n = 3). This surface density regulation strategy holds great promise in other aptamer-based interfacial recognition and sensing. Schematic presentation of di-block oligonucleotide modified gold nanoparticle with different surface densities and its kanamycin sensing application.
Assuntos
Nanopartículas Metálicas , Ácidos Nucleicos , Animais , Ouro/química , Canamicina/análise , Nanopartículas Metálicas/química , Leite/química , Ácidos Nucleicos/análise , Oligonucleotídeos/análise , Poli ARESUMO
Lead contamination in aquatic products is one of the main hazard factors. The aptasensor is a promising detection method for lead ion (Pb(II)) because of its selectivity, but it is easily affected by pH. The combination of ion-imprinted polymers(IIP) with aptamers may improve their stability in different pH conditions. This paper developed a novel electrochemical biosensor for Pb(II) detection by using aptamer-imprinted polymer as a recognition element. The glassy carbon electrode was modified with gold nanoparticles and aptamers. After the aptamer was induced by Pb(II) to form a G-quadruplex conformation, a chitosan-graphene oxide was electrodeposited and cross-linked with glutaraldehyde to form an imprint layer, improving the stability of the biosensor. Under the optimal experimental conditions, the current signal change (∆I) showed a linear correlation of the content of Pb(II) in the range of 0.1-2.0 µg/mL with a detection limit of 0.0796 µg/mL (S/N = 3). The biosensor also exhibited high selectivity for the determination of Pb(II) in the presence of other interfering metal ion. At the same time, the stability of the imprinted layer made the sensor applicable to the detection environment with a pH of 6.4-8.0. Moreover, the sensor was successfully applied to the detection of Pb(II) in mantis shrimp.
Assuntos
Aptâmeros de Nucleotídeos , Técnicas Biossensoriais , Grafite , Nanopartículas Metálicas , Polímeros/química , Ouro/química , Chumbo , Grafite/química , Aptâmeros de Nucleotídeos/química , Técnicas Biossensoriais/métodos , Técnicas Eletroquímicas/métodos , Limite de Detecção , EletrodosRESUMO
Due to the threat of lead pollution to health, environmental and food safety, developing simple and fast detection methods is highly required. Whereas, traditional single-mode probe suffers from limited application scenario. In this study, a colorimetric and fluorometric dual-mode probe for Pb2+ determination was constructed by using bifunctional G-quadruplex-hemin complex. In this dual-mode probe, enzyme strand and substrate strand of 8-17 DNAzyme are labeled with G-quadruplex-hemin complex and fluorophore, respectively. In the absence of Pb2+, the self-assembly of enzyme strand and substrate strand inhibits intrinsic mimic peroxidase of G-quadruplex-hemin complex by base-pairing, which also quench the fluorescence via in proximity effect. When the DNAzyme is activated by Pb2+, the quenched fluorescence is restored as well as the inherent peroxidase mimetic activity, leading to dual signal output. Under optimal conditions, this dual-mode probe exhibit a good linear relationship between logarithm of Pb2+ concentration and signal difference within the range from 1.5 nM to 20 nM and 0.5 nM to 10 nM for colorimetric and fluorescence mode, respectively. The detection limits for the corresponding mode were estimated to be 1.29 nM and 0.16 nM, respectively. This dual-mode probe also successfully applied for the spiked river water assay with satisfactory recovery in the range of 93.2 %-115.3 %. This work paves a new way for DNAzyme based dual-mode probe construction.
Assuntos
Técnicas Biossensoriais , DNA Catalítico , Quadruplex G , Hemina , Chumbo , Colorimetria/métodos , Corantes , Peroxidases , Técnicas Biossensoriais/métodosRESUMO
Owing to advantage in high sensitivity and fast response, aptamer based electrochemical biosensors have attracted much more attention. However, inappropriate interfacial engineering strategy leads to poor recognition performance, which ascribe to the following factors of immobilized oligonucleotide strand including steric hindrance, interchain entanglement, and unfavorable conformation. In this work, we proposed a DNA tetrahedron based diblock aptamer immobilized strategy for the construction of label-free electrochemical biosensor. The diblock aptamer sequence is composite of T-rich anchor domain and recognition domain, where T-rich domain enabling anchored on the edge of DNA tetrahedron via Hoogsteen hydrogen bond at neutral condition. The DNA tetrahedron scaffold offers an appropriate lateral space for target recognition of diblock aptamer. More importantly, this trivalent aptamer recognition interface can be regenerated by simply adjusting the pH environment to alkaline, resulting in the dissociation of diblock aptamer. Under the optimum condition, proposed electrochemical aptasensor manifested a satisfied sensitivity for aminoglycosides antibiotic, kanamycin with a limit of detection of 0.69 nM, which is 45-fold lower than traditional Au-S immobilization strategy. Moreover, the proposed aptasensor had also successfully been extended to ampicillin detection by changing the sequence of recognition domain in diblock aptamer. This work paves a new way for the rational design of aptamer-based electrochemical sensor.
Assuntos
Aptâmeros de Nucleotídeos , Técnicas Biossensoriais , Antibacterianos , Técnicas Biossensoriais/métodos , Aptâmeros de Nucleotídeos/química , DNA/química , Canamicina , Técnicas Eletroquímicas , Limite de Detecção , Ouro/químicaRESUMO
The oily wastewater and heavy metal ions have been increasingly discharged into water environment, posting a serious threat to ecosystems and human health. However, it remains challenging to use single separation technology to effectively remove oil and heavy metal ions in oil-water mixtures simultaneously. Herein, novel hydrophobic/hydrophilic composites (HHC) were successfully prepared by using A4 paper-derived hydrophilic cellulose as the modified matrix, modifying the polydopamine layer and in-situ growth nanoscale zero-valent iron as active adsorption materials, combined with oleic acid-modified hydrophobic magnetic hollow carbon microspheres, which were used to efficiently and rapidly adsorb heavy metals and oil in oil-water mixtures. Under the optimal adsorption conditions, the adsorption amounts of As(III), As(V), Pb(II) and Cu(II) were 289.6 mg/g, 341.9 mg/g, 241.2 mg/g and 277.5 mg/g, respectively, and the mass transfer rate of HHC to the target ions is fast. The HHC have efficient separation performance for layered oil-water mixtures and emulsified oil-water mixtures, with separation efficiency of 97 % and 92 %. At the same time, due to the abundant adsorption sites, the HHC also exhibit splendid regeneration performance for the four ions after multiple adsorption utilization. Our work designed a approach to achieving promising oil and heavy metal adsorbents with higher adsorption capacity and better regenerative properties.
RESUMO
An ultra-sensitive and selective electrochemical sensor was proposed through the combination of carbon disulfide-functionalized graphene oxide (GOCS) composite with high conductivity and cadmium ion-imprinted polymer (IIP). Using pyrrole as the functional monomer and Cd2+ as the template ion, the IIP was formed by in situ electropolymerization on GOCS composite. Under the optimized experimental conditions, the sensor exhibited a good linear relationship in the range of 0.5-50 µg/L Cd2+ concentration, with the lowest detection limit of 0.23 µg/L. The sensor exhibited not only good selectivity for the determination of Cd2+, but also good repeatability with current response remaining 87.6 % after four cycles. Furthermore, the sensor exhibited similar sensing performance in lettuce, orange and peach with recovery ranging from 82.6 % to 110.63 %. This work is expected to provide an electrochemical sensor with excellent selectivity, good stability and sensitivity for the detection of trace amounts of Cd2+ in real samples.
Assuntos
Impressão Molecular , Polímeros , Cádmio , Técnicas Eletroquímicas , Limite de Detecção , EletrodosRESUMO
Alkaline phosphatase (ALP) as an important biomarker as well as an index for the pasteurization degree of dairy food. However, there is a dilemma between the sensitivity and time-cost of ALP determination based on nucleic acid amplification approach. Herein, an ultrasensitive and rapid detection method for the ALP assay was developed based on entropy-driven DNA machine. In our design, the ALP catalyzed dephosphorylation of detection probe, which inhibited the digestion effect of lambda exonuclease. The remaining probe as a linker to tether the walking strand proximity to the surface of track strand modified gold nanoparticle, activating entropy-driven DNA machine. Accompany with walking strand moving, a large amount of assembled dye-labelled strand dissociated from gold nanoparticle with fluorescence recovery. More importantly, to further improve the walking efficiency, butanol was introduced to accelerated the signal amplification at interface, which short the incubation time from several hours to 5 min. Under the optimum condition, the change of fluorescence intensity was proportion to the concentration of ALP in the range from 0.05 U L-1 to 5 U L-1 with an ultralow limit of detection of 2.07 × 10-3 U L-1 was achieved, which is superior to other reported methods. Furthermore, the proposed method also successfully applied for the spiked milk sample assay with satisfactory recovery in the range of 98.83%-103.00%. This work proposed a new strategy for the application of entropy-driven DNA machine in the field of rapid and ultrasensitive detection.
Assuntos
Técnicas Biossensoriais , Nanopartículas Metálicas , Fosfatase Alcalina , Butanóis , Entropia , Ouro , DNA , 1-Butanol , Limite de DetecçãoRESUMO
In this study, a novel eco-friendly porous double-network keratin/polyacrylic acid (keratin-PAA) hydrogel was prepared using the one-pot method to improve the adsorption performance of the hydrogel toward Pb(II). The obtained porous keratin-PAA hydrogel was then characterized using nitrogen adsorption-desorption isotherms, thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). The interaction mechanism of Pb(II) and the keratin-PAA hydrogel was further investigated using X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). The results showed that keratin-PAA hydrogel was successfully synthesized, with a specific surface area of 49.35 m2/g and a uniform pore distribution of 6.20 nm. The synthesized keratin-PAA hydrogel only took 6 min to adsorb nearly 70% of Pb(II) from the solution because of the interconnected porous network. The keratin-PAA hydrogel also showed a maximal adsorption amount of 234.6 mg/g, and satisfactory selectivity toward Pb(II). The adsorption kinetics of the keratin-PAA hydrogel binding to Pb(II) could be better described by the pseudo-second-order model, whereas the adsorption isotherms could be fitted using the Langmuir equation; this suggested that chemisorption was the main rate-limiting step. The XPS and FT-IR analysis results indicated that the sulfur-, nitrogen- and oxygen-containing groups in the keratin-PAA hydrogel were the main binding sites for Pb(II). In real aqueous samples, the keratin-PAA hydrogel could remove 93-104% of Pb(II). It is clear that the keratin-PAA hydrogel is an outstanding adsorbent material for the removal of Pb(II) from aqueous samples.
Assuntos
Chumbo , Poluentes Químicos da Água , Adsorção , Hidrogéis , Concentração de Íons de Hidrogênio , Queratinas , Cinética , Porosidade , Espectroscopia de Infravermelho com Transformada de Fourier , Poluentes Químicos da Água/análiseRESUMO
Ochratoxin A (OTA) contamination of corn has received significant attention due to the wide distribution and high toxicity of OTA. The maximum residue limit standard of OTA in corn has been established by the Chinese Government and other unions. Nanoparticle-based fluorescence resonance energy transfer (FRET) assays are promising methods for the sensitive and fast detection of OTA. However, satisfactory detection sensitivity is commonly achieved with complicated signal amplification processes or specific nanoparticle morphologies, which means that these assays are not conducive to fast detection. This study proposes a simple and novel strategy to improve the sensitivity of FRET aptasensors. In this strategy, a DNA tetrahedron was first used in gold nanorod-based FRET aptasensors. DNA tetrahedron-modified gold nanorods are used as fluorescent acceptors, and Cy5-modified complementary sequences of the OTA aptamer are used as fluorescent donors. The aptamers of OTA are embedded in the DNA tetrahedrons, and FRET occurs when the aptamers hybridize with the Cy5-modified complementary sequences. The aptamer-integrated DNA tetrahedron modified on the surface of gold nanorods acts as an anchor, thus avoiding the crowding and entanglement of aptamers. Due to the competitive combination between the OTA aptamers and complementary sequences, the greater the amount of OTA, the less the amount of Cy5-modified complementary sequences that bind with the aptamers and the less the amount of Cy5 that is quenched. Thus, the fluorescence intensity is positively related to the OTA concentration. In this study, in the concentration range of 0.01-10 ng/mL, the fluorescence intensity was found to be linearly related to the logarithmic concentration of OTA. The limit of detection was calculated to be 0.005 ng/mL. The specificity of the developed biosensor was demonstrated to be efficient. The accuracy and stability of the developed aptasensor were also tested, and the method exhibited good performance in real samples.
Assuntos
Aptâmeros de Nucleotídeos , Técnicas Biossensoriais , Nanotubos , Ocratoxinas , Aptâmeros de Nucleotídeos/química , Técnicas Biossensoriais/métodos , DNA , Transferência Ressonante de Energia de Fluorescência/métodos , Ouro/química , Limite de Detecção , Ocratoxinas/análiseRESUMO
Thiourea derivatives are expected to be potential monomers of As(Ш) molecular imprinted polymers (MIPs) which are used to specifically recognize As(Ш). However, the specific recognition and binding mechanisms between template and monomers are unclear, which limits the practical applications of MIPs in As(Ш)detection. In this work, density functional theory (DFT) calculations, molecular dynamics (MD) simulations and experimental methods were jointly applied to explore the binding interactions between H3AsO3 and thiourea derivatives and environmental factors influences, aiming to find out the best monomer and optimal preparation conditions for H3AsO3 MIPs. Among five monomer candidates, (2, 6-difluorophenyl) thiourea (FT) was calculated to be the most potential one, while allyl thiourea (AT) was the second choice. Configurations of the most stable binding complexes were found out. The optimal solvent was found to be toluene and the bindings were more favorable at pH 7.5 in aqueous solution. Besides, EGDMA was proved as the best cross-linker with the optimal ratio of template: monomer: cross-linker= 2:3:20. Moreover, the binding interactions were identified to be hydrogen bonds, and the non-covalent nature was revealed. These findings provide references for efficient design and preparation of good-performance H3AsO3 MIPs, which can be used to detect and remove As(Ш) from environment.
Assuntos
Impressão Molecular , Polímeros , Ligação de Hidrogênio , Impressão Molecular/métodos , Polímeros/química , Solventes , Tioureia , ÁguaRESUMO
A novel monodispersed Cd(II) ion-imprinted polymer (IIP) was synthesized inside core-shell mesoporous silica (C-SMS) particles to improve the diffusion kinetics of the polymer. The synthesized IIP@C-SMS was characterized and subsequently used in solid-phase extraction (SPE) for the selective adsorption of Cd(II) in aquatic samples. The results indicated that IIP had been successfully assembled inside the C-SMS particles with a high specific surface area (546.3 m2 g-1) and uniform mesoporous size (2.07 nm). The obtained IIP@C-SMS takes only 15 min to reach the adsorption equilibrium due to the highly developed mesoporous structure. IIP@C-SMS also presented a maximal adsorption capacity (201.9 µmol g-1) for Cd(II), which was much higher than that of NIP@C-SMS (80.3 µmol g-1). The relative selectivity coefficient of IIP@C-SMS for Cd(II)/M(II) (M = Cu(II), Pb(II), Cr(II), and Ni(II)) were 7.15, 8.70, 7.18, and 7.36, respectively, further confirming the satisfactory selectivity of IIP@C-SMS. The adsorption isotherms of IIP@C-SMS toward Cd(II) could be described by Langmuir model; whereas the adsorption kinetics could be fitted by the pseudo-second-order model, indicating chemisorption was the rate-limiting step. The FT-IR, ITC and XPS analysis further confirmed that the Cd(II)-induced cavities during the ion-imprinting process and the coordination between Cd(II) and -SH groups were the main adsorption mechanism. Furthermore, in real samples, IIP@C-SMS-SPE adsorbed approximately 93-104% of Cd(II). This work provides new insights for the design of novel macroporous sorbents for Cd(II).
Assuntos
Cádmio , Polímeros , Adsorção , Extração em Fase Sólida , Espectroscopia de Infravermelho com Transformada de FourierRESUMO
The double-mesoporous-layer imprinted polymer of mesoporous silica/mesoporous molecularly imprinted nanoparticles (MIP), with high specific surface area, rich porosity, excellent mass transfer rate and selectivity, were synthesized using imidacloprid (IDP) as a template. Under the optimal conditions of pH, contact time, concentration and temperature, MIP showed high adsorption capacity of 13.86 µg·mg-1 toward IDP and the imprinting factor reached 3.5. The adsorption process model including binding isotherm and kinetics was investigated. MIP exhibited excellent regeneration and its adsorption and selectivity were outstanding among its structurally pesticide analogues. The recovery of spiked IDP for MIP in fortified real samples can reach 96.0 ± 8.5% for cabbage and 105.0 ± 9.9% for apple. The limit of detection of the enrichment method can be as low as 0.037 µg·mL-1 with a good linear relationship (R2 = 0.996) from 0.30 to 10.0 µg·mL-1. The results indicated that the proposed method allowed class-specific detection of IDP in food samples.
Assuntos
Impressão Molecular , Nanopartículas , Adsorção , Neonicotinoides , Nitrocompostos , Dióxido de SilícioRESUMO
A novel dual-frequency ultrasound-assisted enzymatic digestion (DUED) technique was used to extract Pb(II) from certified reference materials (CRMs) of wheat flour. Following this, the interactions of Pb(II) with wheat proteins were investigated to provide evidence for the selection of enzyme species. The results showed that the simultaneous use of α-amylase and flavourzyme resulted in the recovery of 97.9% of Pb(II) in 6 min under a 40 kHz ultrasonic bath combined with a 20 kHz ultrasonic probe. The exopeptidase activity of the flavourzyme was found to be the main contributor to the extraction of Pb(II) from the CRMs. Additionally, the proposed method exhibited a low detection limit (8.2 ng/g) and high recoveries of real samples (93.4%-112.2%) with RSD less than 7.33%. Furthermore, the oxygen-containing groups of wheat proteins, the nitrogen-containing groups of albumins and globulins, and the sulfur-containing groups of gliadins and glutenins were found to offer coordination sites for Pb(II).
Assuntos
Farinha , Chumbo/isolamento & purificação , Triticum , Gliadina , Ultrassom , alfa-AmilasesRESUMO
Edible vegetable oils are easily contaminated by heavy metals, resulting in the oxidative degradation of oils and various health effects on humans. Therefore, it is very important to develop a rapid and efficient method to extract trace heavy metals from vegetable oils. In this work, a highly hydrophobic ion-imprinted polymer (IIP) was synthesized on a novel raspberry (RS)-like particle surface. The synthesized IIP@RS was characterized and used in solid-phase extraction (SPE) for the selective and fast adsorption of Cd(ii) from vegetable oils. The results showed that IIP was successfully coated onto RS particles with a high specific surface area (458.7 m2 g-1) and uniform porous structure. The contact angle (θ) value (141.8°) of IIP@RS was close to the critical value of super-hydrophobic materials, which is beneficial to their adsorption in hydrophobic vegetable oils. The IIP@RS also exhibited excellent adsorption ability and selectivity to Cd(ii) with a maximum adsorption capacity of 36.62 mg g-1, imprinting factor of 4.31 and equilibrium adsorption rate of 30 min. According to isothermal titration calorimetry results, the recognition behavior of IIP@RS for Cd(ii) was mainly contributed by Cd(ii)-induced cavities during gel formation and coordination between Cd(ii) and -SH groups in imprinted cavities. Furthermore, the adsorption process driven by entropy and enthalpy was spontaneous at all temperatures. In real vegetable oil samples, IIP@RS-SPE adsorbed approximately 96.5-115.8% of Cd(ii) with a detection limit of 0.62 µg L-1. Therefore, IIP@RS has wide application prospects in enriching and detecting Cd(ii) from vegetable oil.