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1.
Sci Total Environ ; 923: 171531, 2024 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-38458449

RESUMO

A novel lanthanide metal-organic-gel (MOG)-derived material/nitrogen-doped graphdiyne (Tb-Ru-MOG/CeO2/N-GDY) composite with a dual-source signal amplification strategy was prepared and used to construct a molecularly imprinted sensor based on bifunctional monomers for the detection of imidacloprid (IMI) using electrochemiluminescence (ECL). In a green reaction environment, terbium (III) (Tb3+) can undergo multiple coordination reactions with 4'-(4-carboxyphenyl)-2,2':6',2″-terpyridine (Hcptpy) and tris(4,4'-dicarboxylicacid-2,2'-bipyridyl) ruthenium (II) dichloride (Ru(dcbpy)32+), and combine with ceria nanoparticles (CeO2 NPs) to form Tb-Ru-MOG/CeO2. Within the Tb-Ru-MOG/CeO2 framework, energy transfer from the double ligands can sensitize the central Tb3+, triggering a distinct antenna effect and energy-transfer, and its polyporous configuration offered a nanoconfined space for Ce3+/Ce4+ to effectively catalyze coreactant radicals (S2O82-), leading to in-situ endogenous activation ECL reactions. The conductive N-GDY accelerated electron movement and increased the loading on the electrode surface, enhancing the exogenous excitation of the ECL signals. Leveraging the synergistic effect of the bifunctional monomer, the synthesized molecularly imprinted polymers (MIPs) ECL sensor demonstrated a wide detection range from 10 nM to 10,000 nM for IMI, with a limit of detection (LOD) of 1.37 nM, showcasing an innovative concept for the dual-source strategy of signal amplification in integrated ECL composites to analyze food and environmental hazards.

2.
J Agric Food Chem ; 71(43): 16303-16309, 2023 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-37856445

RESUMO

The residue of chlortetracycline is potentially hazardous to human health; it is meaningful to exploit a portable, rapid, sensitive, and selective method for detection of chlortetracycline (CTC). In this study, a novel fluorescence bionic sensing probe (NH2-MIL-53&N,P-CDs@MIP) was successfully prepared based on the nitrogen and phosphorus codoped carbon dots decorated iron-based metal-organic frameworks combining with molecular imprinted polymer for the detection of CTC. A fluorescence intensity-responsive "on-off" detection of CTC on account of the inner-filter effect (IFE) was achieved by NH2-MIL-53&N,P-CDs@MIP. Under the optimal conditions, the fluorescence quenching degree of NH2-MIL-53&N,P-CDs@MIP presented a good linear relationship with the CTC concentration in the range 0.06-30 µg mL-1 and the limit of detection (LOD) was 0.019 µg mL-1. The fluorescent probe was applied to detect CTC in milk samples, and experimental results showed a good recovery rate (88.73%-96.28%). Additionally, a smartphone-integrated fluorescence sensing device based on NH2-MIL-53&N,P-CDs@MIP was exploited to replace the expensive and bulky fluorescence spectrophotometer for quantitative determination of CTC with the LOD of 0.033 µg mL-1. The sensing system showed high selectivity, strong stability, high specificity, and portability, which provide a great strategy for the quantitative detection of antibiotic residue.


Assuntos
Clortetraciclina , Estruturas Metalorgânicas , Impressão Molecular , Pontos Quânticos , Humanos , Estruturas Metalorgânicas/química , Carbono/química , Ferro , Smartphone , Espectrometria de Fluorescência/métodos , Pontos Quânticos/química , Limite de Detecção , Corantes Fluorescentes/química , Impressão Molecular/métodos
3.
J Mater Chem B ; 10(47): 9878-9886, 2022 12 07.
Artigo em Inglês | MEDLINE | ID: mdl-36437799

RESUMO

The self-assembly of a series of catalytically active polypeptides toward hydrolysis of glucoside compounds, namely, gastrodin, polydatin and esculin was investigated. These active peptides are composed of two functional fragments: one is the hydrophobic sequence LHLHLRL, which forms assembling segments in the presence of Zn ions (Zn2+); another functional sequence of active peptides are catalytic sites such as Glu (E), Asp (D) and His (H), where carboxylic acids (-COOH) or imidazole groups act like scissors to cleave glucoside bonds of the compounds (according to the acid-base coupling mechanism). The effects of the amino acid sequence of the peptide, Zn2+ concentration, pH and the size or steric hindrance of glucoside compounds on the hydrolytic activity were studied. It was found that the crystalline structure of assembled peptides was crucial to provide the peptide with catalytic hydrolytic activity. Noncovalent interaction index was used to analyse the noncovalent interaction of PEs with glucoside compounds, including hydrogen bonds, van der Waals, and steric effect in the complexes. The binding energy of complexes, the direction and site of nucleophilic attack during deglycosylation processes were also investigated by molecular docking and the electron density Laplace function. This revealed that the differences in the hydrolytic activity of peptides toward glucoside compounds with different sizes originated from different hydrogen bond interactions between the peptides and substrates. These active peptides may find application in the preparation of drugs by de-glycosylation of natural compounds.


Assuntos
Esculina , Peptídeos , Simulação de Acoplamento Molecular
4.
Analyst ; 147(11): 2477-2483, 2022 May 30.
Artigo em Inglês | MEDLINE | ID: mdl-35535597

RESUMO

Heterocyclic amines (HCA) are the main mutagenic factors in cooked meat products and are considered to be hazardous chemicals in the field of food safety. In this study, inspired by the "host-guest" interaction mechanism, a new technique for detecting 2-amino-1-methyl-6-phenylimidazo [4,5-b] pyridine (PhIP) was developed, taking advantage of the molecular cavities of cucurbit[7]uril (CB[7]) and the powerful guest recognition properties between CB[7] and PhIP. Based on this recognition mechanism, three steps were included in the detection procedure: firstly, regenerated cellulose (RC) membrane was oxidized by NaIO4 to generate aldehyde groups; secondly, the PhIP molecules to be detected were trapped by the aldehyde groups via amine-aldehyde conjugation chemistry; thirdly, the RC membrane with trapped PhIP was immersed into solutions of dansyl chloride-labelled CB[7] to allow the host-guest interaction to occur, so that PhIP could be quantified by fluorescence of the dansyl chloride dye. The limit of detection, linear range and recovery of this method were about 0.224 µg kg-1, 10-1000 nM and 89.0-96.4%, respectively. So far, most reported techniques for HCA detection are based on HPLC coupled with mass spectroscopy, and the method reported here might be the first quick measurement technique for HCA and may find wide application in food safety detection.


Assuntos
Carcinógenos , Carne , Aldeídos , Aminas , Carcinógenos/análise , Compostos Heterocíclicos com 2 Anéis , Imidazóis , Imidazolidinas , Compostos Macrocíclicos , Carne/análise
5.
ACS Chem Neurosci ; 13(6): 766-775, 2022 03 16.
Artigo em Inglês | MEDLINE | ID: mdl-35230090

RESUMO

Polyphenols are the class of naturally synthesized compounds in the secondary metabolism of plants, which are widely distributed in fruits and vegetables. Their potential health treatment strategies have attracted wide attention in the scientific community. The abnormal aggregation of Aß to form mature fibrils is pathologically related to Alzheimer's disease (AD). Therefore, inhibiting Aß40 fibrillogenesis was considered to be the major method for the intervention and therapy of AD. Glycosides, as a cluster of natural phenolic compounds, are widely distributed in Chinese herbs, fruits, and vegetables. The inhibitory effect of glycosides (phloridzin, salidroside, polydatin, geniposide, and gastrodin) and their corresponding small molecules (phloretin, 4-hydroxyphenyl ethanol, resveratrol, genipin, and 4-hydroxybenzyl alcohol) on Aß40 aggregation and fibrils prolongation, disaggregation against mature fibrils, and the resulting cytotoxicity were studied by systematical biochemical, cell biology and molecular docking techniques, respectively. As a result, all inhibitors were observed against Aß40 aggregation and fibrils prolongation and disaggregated mature Aß40 fibrils in a dose-dependent manner. Besides, the cell validity experiments also showed that all inhibitors could effectively alleviate the cytotoxicity induced by Aß40 aggregates, and the glycoside groups played important roles in this inhibiting process. Finally, molecular docking was performed to study the interactions between these inhibitors and Aß40. Docking showed that all inhibitors were bound to the similar region of Aß40, and glycoside group formed hydrogen bonds with the pivotal residues Lys16. These results indicated that the glycoside groups could increase the inhibitory effects and reduce cytotoxicity. Glycosides have tremendous potential to be developed as an innovative type of aggregation inhibitor to control and treat neurodegenerative diseases.


Assuntos
Doença de Alzheimer , Peptídeos beta-Amiloides , Doença de Alzheimer/metabolismo , Amiloide/metabolismo , Peptídeos beta-Amiloides/química , Glicosídeos/farmacologia , Humanos , Ligação de Hidrogênio , Simulação de Acoplamento Molecular , Fragmentos de Peptídeos/química
6.
J Hazard Mater ; 428: 128262, 2022 04 15.
Artigo em Inglês | MEDLINE | ID: mdl-35051771

RESUMO

Organophosphorus pesticides (OPs) detection has attracted considerable attention because of the extensive application of OPs. In this research, non-toxic and high-performance metalloenzyme mimics of Zn2+-bonding peptides were developed by obtaining inspiration from phosphotriesterase (PTE) and nanofiber formation. Furthermore, based on the electrochemical activity of p-nitrophenol (PNP), the electrochemical sensor of metalloenzyme mimics was developed. By examining the effect of the active sites of peptides and fibril formation on the degradation of OPs, the optimal metalloenzyme mimic was selected. Furthermore, optimal metalloenzyme mimics were combined with NiCo2O4 to develop an electrochemical sensor of OPs. By monitoring square wave voltammetry (SWV) signals of PNP degraded from OPs, the amounts of OPs in actual samples could be determined in 15 min. We discovered that both the active sites of α metal and ß metal were required for metalloenzyme mimics; Zn2+ promoted peptide fibrosis and especially acted as a cofactor for degrading OPs. Compared to traditional methods, the electrochemical sensor of metalloenzyme mimics was sensitive, reliable, and non-toxic; furthermore, the detection limit of methyl paraoxon was as low as 0.08 µM. The metalloenzyme mimics will be a promising material for detecting OPs in the food industry and environment fields.


Assuntos
Técnicas Biossensoriais , Metaloproteínas , Praguicidas , Compostos Organofosforados , Peptídeos
7.
Analyst ; 145(24): 8068-8076, 2021 Jan 07.
Artigo em Inglês | MEDLINE | ID: mdl-33078789

RESUMO

In this work, amino acids (AAs) including serine (S), histidine (H) and glutamic acid (E)-conjugated poly(3-thiophene acetate acid) (P3TAA) were synthesized to promote the catalytic hydrolysis and in situ electrochemical detection of organophosphorus pesticides (OPs). The hydrolysis of OPs followed the mechanism of proton transfer relay composed of AAs of S, H, E, called the "catalytic triad", found in biomimetic hydrolases. P3TAA was used as a carrier to attach S, H, E, and these AA sites have the hydrolysis activity of Ops; the polymer P3TAA-AAs behaved like biomimetic enzymes. After the hydrolysis of OPs (e.g., methyl paraoxon, ethyl paraoxon and methyl parathion), p-nitrophenol (PNP) was generated, which can be detected electrochemically. Herein, an electrochemical method using P3TAA-conjugated S, H, E-modified electrodes for the determination of OPs was developed. OPs can be quantified by the electrochemical responses of PNP. This technique was selective toward OPs with the p-nitrophenol group. The detection limit of OPs (methyl paraoxon, methyl parathion and ethyl paraoxon) reached 0.5 µM. This detection technique was successfully applied to the detection of OPs in real samples with high detection accuracy.

8.
Ecotoxicol Environ Saf ; 207: 111251, 2021 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-32905935

RESUMO

A mildly one-pot method is developed for the synthesis of quasi-networked Au1.5Pt1Co1 ternary alloy nanoparticles (TANPs) at room temperature through the co-reduction of AuCl4-, PtCl6- and Co2+ with hydrazine hydrate. Characterizations of XRD, XPS, HRTEM, EDS and SAED successfully reveal the crystal structure, composition, valence and morphology of Au1.5Pt1Co1 TANPs, respectively. The glassy carbon electrode (GCE) modified by Au1.5Pt1Co1 TANPs with good dispersion and multi-density surface defects occupies the optimal electrochemical active surface area (ECSA). After the coated poly-L-cysteine (P-L-Cys) film on the Au1.5Pt1Co1/GCE surface, the morphology, element mapping and surface roughness of the P-L-Cys/Au1.5Pt1Co1/GCE are investigated via FESEM and AFM to verify continuous electrode modification processes. The electrochemical behaviors of the composite electrode for hydroquinone (HQ) are evaluated by cyclic voltammetry (CV) with interfacial properties of adsorption and diffusion. Differential pulse voltammetry (DPV) for HQ electrochemical sensing at 0.10 V (vs. SCE) exhibits two linear response ranges from 0.1 to 30 and 30-200 µM, respectively. A low detection limit (S/N = 3) of 0.045 µM is obtained with a sensitivity of 4.247 µA µM-1·cm-2. The resulting P-L-Cys/Au1.5Pt1Co1/GCE also presents ascendant selectivity, repeatability, reproducibility and stability. In addition, the established method is applied to the assessment of the HQ level in real water samples (mineral water, tap water and lake water) with the satisfactory results of spiked recoveries. The sensor may become a promising tool for the trace analysis of the electroactive substance in food or environmental samples.


Assuntos
Cisteína , Hidroquinonas/análise , Nanopartículas Metálicas/química , Ligas , Carbono/química , Eletrodos , Reprodutibilidade dos Testes , Água/química
9.
J Mater Chem B ; 8(41): 9601-9609, 2020 10 28.
Artigo em Inglês | MEDLINE | ID: mdl-33006351

RESUMO

Enzyme mimics have been developed by imitating and incorporating specific features of native enzymes to achieve catalytic activity, and are expectedly comparable to that of native enzymes. Here, inspired by the "catalytic triad" in serine proteases, a series of peptide-based enzyme mimics were designed to follow the rational design principle of peptides via self-assembly, and were further applied in the degradation of di(2-ethylhexyl)phthalate (DEHP). The relationship of the structure of enzyme mimics with their degradation activity was analyzed by transmission electron microscopy, fluorescence spectroscopy, circular dichroism, Raman spectroscopy, X-ray diffraction spectroscopy, and computational modeling. These results show that the hydrophobic skeleton, amino acid sequence, species, and periodic distribution have important effects on the structure of the peptide sequence and the number of hydrogen bonds; in addition, pH can also affect the self-assembly characteristics of peptides and the formation of stable fibers, which are all closely linked to the catalytic activity of the enzyme mimics. The self-assembled peptides had a stable fibrous morphology and secondary structure after the DEHP degradation assay. The enzyme mimics with high catalytic activity constructed from the self-assembled peptides may provide guidance for the future degradation of DEHP in food packaging or water treatment, and also give insights into the design of enzyme mimics in other related fields.


Assuntos
Dietilexilftalato/metabolismo , Poluentes Ambientais/metabolismo , Peptídeos/metabolismo , Plastificantes/metabolismo , Animais , Materiais Biomiméticos/química , Materiais Biomiméticos/metabolismo , Domínio Catalítico , Células HeLa , Humanos , Modelos Moleculares , Células PC12 , Peptídeos/química , Ratos , Serina Proteases/química , Serina Proteases/metabolismo
10.
J Hazard Mater ; 389: 122074, 2020 05 05.
Artigo em Inglês | MEDLINE | ID: mdl-31978818

RESUMO

Extensive use of organophosphorus pesticides (OPs) in crop protection has aroused worldwidely great concern about safety and the detection of OPs is of great significance to food safety and human health. In this work, peptides attached with tetraphenylethylene (TPE) molecule were synthesized to from an aggregation-induced emission fluorescent probe (TPE-Peptide) for the determination of OPs. The working mechanism was as follows: in presence of OPs, OPs would react with active site serine in the peptide sequence via covalent bond and adducts were formed between OPs and the peptides; once formed, the adducts accelerated the aggregation of peptides, thus inducing strong emission of TPE-Peptide probe. So the adducts formation and the enhanced emission of the TPE-Peptide probe were the key factors for the OPs' sensing. Herein, the adducts formed between OPs and TPE-Peptide probe, the aggregated peptide fibrils were characterized by fluorescence, mass spectrometry, transmission electron microscopy, dynamic light scattering, atomic force microscopy, circular dichroism spectra and confocal fluorescence microscopy etc. This TPE-Peptide probe displayed highly sensitive fluorescence response where OPs' concentrations ranged from 1 to 100 µM with the limit of detection 0.6 µM and also showed selectivity.


Assuntos
Corantes Fluorescentes/química , Organofosfatos/análise , Peptídeos/química , Praguicidas/análise , Brassica/química , Carbamatos/análise , Carbamatos/química , Contaminação de Alimentos/análise , Limite de Detecção , Organofosfatos/química , Praguicidas/química , Espectrometria de Fluorescência/métodos , Estilbenos/química
11.
Bioelectrochemistry ; 132: 107398, 2020 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-31837616

RESUMO

In this paper, an advanced molecularly imprinted electrochemical sensor (MIECS) based on electropolymerized olaquindox (OLA) surface molecularly imprinted polymer thin film on a modified glassy carbon electrode (GCE) was developed for the detection of OLA. It was fabricated by coating dopamine@graphene (DGr) on GCE, then electropolymerizing pyrrole (Py) and molecularly imprinted polymers (MIPs). Graphene (Gr) was introduced for improving conductivity and sensitivity. Dopamine (DA) was used for dispersion and adhesion of Gr. Polypyrrole (PPy) could fix DGr and enhance the current response evidently. The established sensor could selectively recognize OLA but not the analogs of OLA. Some essential parameters controlling the performance of the developed sensor were investigated and optimized. Under optimal conditions, the linear relationship between the current intensity and OLA concentration was obtained from 50 nmol L-1 to 500 nmol L-1 with a limit of detection (LOD) of 7.5 nmol L-1. Analytical results of OLA based on the developed MIECS for fish and feedstuffs showed a good agreement with the results based on high performance liquid chromatography (HPLC).


Assuntos
Dopamina/química , Técnicas Eletroquímicas/instrumentação , Eletrodos , Grafite/química , Impressão Molecular , Polímeros/química , Pirróis/química , Quinoxalinas/análise , Limite de Detecção , Reprodutibilidade dos Testes , Propriedades de Superfície
12.
Mikrochim Acta ; 186(12): 746, 2019 11 06.
Artigo em Inglês | MEDLINE | ID: mdl-31691865

RESUMO

Well-dispersed and graft-crosslinked gold nanoparticles (AuNPs) were synthesized by the reduction of tetrachloroaurate with hydrazine at room temperature. The AuNPs possess a high density of surface defects which is due to grafting of n-octanoic acid to polyvinylpyrrolidone. The physical and chemical properties of the resulting AuNPs were characterized by UV-vis, XRD, TEM/HRTEM, SAED, and XPS, respectively. The modified AuNPs were placed on a glassy carbon electrode (GCE) in an electropolymerized taurine layer to obtain a sensitive, selective, stable and rapid electrochemical dopamine sensor. The peak current, typically measured at 0.17 V (vs. SCE), increases linearly in the 1.0 to 120 µM dopamine concentration range, and the limit of detection (at S/N = 3) is 0.16 µM with a sensitivity of 2.94 µA·µM-1·cm-2. The sensor was successfully applied to the determination of dopamine in injections and spiked serum samples. The recoveries from spiked serum samples range from 97.5 to 102.4%, with RSDs ranging between 2.8 and 3.4%. Graphical abstract Schematic representation of a glassy carbon electrode modified with in-situ graft-crosslinked gold nanoparticles combined with an electropolymerized polytaurine membrane. The sensor exhibits excellent features towards dopamine determination.


Assuntos
Dopamina/sangue , Nanopartículas Metálicas/química , Polímeros/química , Caprilatos/química , Carbono/química , Dopamina/química , Técnicas Eletroquímicas/instrumentação , Técnicas Eletroquímicas/métodos , Eletrodos , Ouro/química , Humanos , Limite de Detecção , Membranas Artificiais , Oxirredução , Polimerização , Polímeros/síntese química , Povidona/química , Reprodutibilidade dos Testes , Taurina/química
13.
Chem Commun (Camb) ; 55(89): 13458-13461, 2019 Nov 18.
Artigo em Inglês | MEDLINE | ID: mdl-31647069

RESUMO

Here, an enzyme mimic inspired by serine proteases was developed for the degradation of PAEs. This enzyme mimic, comprised an active site (SHD), a self-assembling polypeptide (LKLKLKL), a spacer (GGG) and a polymerizable site (DOPA) and showed high activity towards the degradation of DEHP in cells.


Assuntos
Dietilexilftalato/metabolismo , Ésteres/metabolismo , Ácidos Ftálicos/metabolismo , Serina Proteases/metabolismo , Sobrevivência Celular/efeitos dos fármacos , Dietilexilftalato/química , Dietilexilftalato/farmacologia , Ésteres/química , Ésteres/farmacologia , Células HeLa , Humanos , Concentração de Íons de Hidrogênio , Tamanho da Partícula , Ácidos Ftálicos/química , Ácidos Ftálicos/farmacologia , Serina Proteases/química , Propriedades de Superfície , Temperatura
14.
ACS Chem Neurosci ; 10(11): 4633-4642, 2019 11 20.
Artigo em Inglês | MEDLINE | ID: mdl-31637909

RESUMO

The abnormal aggregation of amyloid beta (Aß or A beta) from monomeric proteins into amyloid fibrils is an important pathological contact to Alzheimer's disease (AD). Amyloid beta 40 (Aß40), the pivotal biomarker of AD, aggregates to form amyloid plaques. For this reason, inhibition of amyloid fibrillation had become a crucial prevention and therapeutic strategy. Usually, LVFFA is the central hydrophobic fragment of Aß and can inhibit the aggregation of Aß40. In this work, in order to improve the inhibitory ability of LVFFA, hexapeptide CLVFFA were conjugated at the surface of Au clusters (AuNCs) to manufacture a nanosized inhibitor, AuNCs-CLVFFA. Thioflavin T fluorescence and transmission electron microscope results showed that AuNCs-CLVFFA inhibited Aß40 fibrillogenesis, fibrils' prolongation, and mature fibrils' disaggregation. Furthermore, AuNCs as the backbone of the inhibitor showed extraordinary inhibition ability for Aß40 aggregation at a low AuNCs-CLVFFA concentration. Free hexapeptide CLVFFA, at the same concentration, showed almost no inhibition. Additionally, the inhibitor could maintain the optical properties of nanoclusters, and the cell viability demonstrated that the inhibitor had good biocompatibility and may potentially be applied into AD therapy or treatment.


Assuntos
Peptídeos beta-Amiloides/metabolismo , Amiloide/efeitos dos fármacos , Amiloide/metabolismo , Ouro/administração & dosagem , Nanopartículas Metálicas/administração & dosagem , Fragmentos de Peptídeos/metabolismo , Agregados Proteicos/efeitos dos fármacos , Peptídeos beta-Amiloides/antagonistas & inibidores , Animais , Relação Dose-Resposta a Droga , Ouro/química , Humanos , Nanopartículas Metálicas/química , Células PC12 , Fragmentos de Peptídeos/antagonistas & inibidores , Agregados Proteicos/fisiologia , Ratos
15.
Nanoscale ; 9(45): 18066-18074, 2017 Nov 23.
Artigo em Inglês | MEDLINE | ID: mdl-29131232

RESUMO

Cellulose, an impressive potential sustainable fuel, is difficult to hydrolyze because of the protection of ß-1,4-glycosidic bonds through the tight hydrogen bonding network. In this study, homogenous graphene oxide (GO)-peptide nanofiber hybrid hydrogels (GO-PNFs) were designed as a ß-glycosyl hydrolase mimetic to achieve efficient degradation of cellobiose and cellopentaose. For comparison, free peptides, graphene oxide mixed with free peptides (GO-peptdies) and self-assembled peptide nanofibers (PNFs) were also studied for their activity as a hydrolase mimetics for degradation of cellobiose. Among these materials, GO-PNFs showed the highest hydrolysis activity. Transmission electron microscopy, atomic force microscopy, fluorescence analysis, circular dichroism spectroscopies, X-ray diffraction, Raman spectra and computational modeling were used to interpret the difference in activity mechanism in these artificially designed enzymes. These investigations suggested that high catalytic performance of GO-PNFs toward cellobiose and cellopentaose hydrolysis could be attributed to the formation of nanofiber structures of peptides, optimal molecular conformation and less steric hindrance to access the substrate. More importantly, GO not only served as a platform for attaching PNFs, but also created a hydrophobic microenvironment and facilitated proton transfer, an essential step in catalytic hydrolysis, thus enhancing catalytic activity. All these provided insights into the potential use of peptides and GO hybrid composite nanoenzymes in efficient cellulose hydrolysis.


Assuntos
Materiais Biomiméticos/química , Grafite/química , Hidrogéis/química , Hidrolases/química , Nanofibras/química , Peptídeos/química , Celobiose/química , Óxidos
16.
Anal Biochem ; 530: 50-56, 2017 08 01.
Artigo em Inglês | MEDLINE | ID: mdl-28454733

RESUMO

Alpha-fetoprotein (AFP) is widely used as a tumor marker for the serum diagnosis of primary hepatoma. Sensitive detection of AFP level plays an important role in the early diagnosis of disease and highly reliable prediction. In this study, a novel non-competitive immunoassay (IA) based on poly(guanidinium ionic liquid) monolithic material was developed for detecting ultra trace levels of AFP in capillary electrochromatography (CEC) mode. The AFP was mixed with an excess amount of fluorescently labeled antibody. After incubation, the immunocomplex was separated from the free labeled antibody and detected by CEC coupled with laser-induced fluorescence detector. Under the optimized conditions, the developed CEC-IA performed a low detection limit of 0.05 µg L-1 (S/N = 3) and a wide linearity ranging from 0.1 to 1000 µg L-1 for AFP, which can be largely attributed to the high separation and enrichment efficiency of poly(guanidinium ionic liquid) monolithic material for the targets. The application of this method was demonstrated by determining AFP in human serum.


Assuntos
Eletrocromatografia Capilar/métodos , Guanidina/química , Imunoensaio/métodos , Líquidos Iônicos/química , alfa-Fetoproteínas/análise , Anticorpos/imunologia , Humanos , Limite de Detecção
17.
Nanoscale ; 8(38): 16851-16856, 2016 Sep 29.
Artigo em Inglês | MEDLINE | ID: mdl-27714071

RESUMO

An artificial enzyme was constructed by attaching short peptides with active sites (SHELKLKLKL, WLKLKLKL) onto carbon nanotubes (CNT). It was found that the combination of SHE amino acids was essential to form a catalytic triad. W was also incorporated into this artificial enzyme and acted as a substrate binding site, thus producing an enzyme model with synergism of 67.7% catalytic groups and 32.3% binding groups, CNT-(SHE/W)2:1-LKLKLKL. When the peptide SHELKLKLKL was attached with the catalytic triad site close to the surface of CNT, the composite had higher activity than a leucine-attached system terminated with the catalytic triad site, suggesting that CNT not only served as a platform for attaching active amino acids, but also created a hydrophobic microenvironment and facilitated the proton transfer process to enhance the catalytic activity. The artificial enzyme exhibited Michaelis-Menten behaviour, indicating that it was indeed a mimic of the corresponding natural enzyme. This work showed that a well-designed combination of CNT and short peptides containing active sites can mimic a natural enzyme.


Assuntos
Hidrolases/química , Nanotubos de Carbono , Peptídeos/química , Engenharia de Proteínas , Sítios de Ligação , Domínio Catalítico
18.
Biosens Bioelectron ; 74: 313-7, 2015 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-26148676

RESUMO

A triple-dimensional sensing chip is developed based on simultaneous utilization of fluorescence (FL), electrochemical (ECL) and mass-sensitivity (MS) properties of a novel nanocomposites. The sensing nanomaterial is composed of CdSe/ZnS quantum dots (QDs) and graphene through a one-pot room-temperature reverse microemulsion polymerization. Here, full integration of QDs and graphene on one chip provides triple-dimensional sensing signals. It enables quick and accurate discrimination of eight analytes in a "lab-on-a-nanomaterial" approach and notably improves the overall sensor performance. Unknown samples randomly taken from the training set at concentrations of 0.7 µM are successfully classified by principal component analysis (PCA) with accuracies of 92.5%, compared with the high performance liquid chromatography (HPLC) method. We further apply it to discriminate eight antioxidants from real oil samples, and explore the mechanism.


Assuntos
Antioxidantes/análise , Técnicas Biossensoriais/instrumentação , Condutometria/instrumentação , Pontos Quânticos , Óleo de Soja/química , Espectrometria de Fluorescência/instrumentação , Compostos de Cádmio/química , Misturas Complexas/análise , Desenho de Equipamento , Análise de Falha de Equipamento , Análise de Alimentos/instrumentação , Grafite/química , Compostos de Selênio/química , Compostos de Zinco/química
19.
Anal Chim Acta ; 806: 136-43, 2014 Jan 02.
Artigo em Inglês | MEDLINE | ID: mdl-24331049

RESUMO

A facile and efficient molecularly imprinted polymer (MIP) recognition element of electrochemical sensor was fabricated by directly electro-polymerizing monomer o-phenylenediamine (oPD) in the presence of template quinoxaline-2-carboxylic acid (QCA), based on one-step controllable electrochemical modification of poly(pyrrole)-graphene oxide-binuclear phthalocyanine cobalt (II) sulphonate (PPY-GO-BiCoPc) functional composite on glassy carbon electrode (GCE). The MIP film coated on PPY-GO-BiCoPc functional composite decorated GCE (MIP/PPY-GO-BiCoPc/GCE) was presented for the first time. The synergistic effect and electro-catalytic activity toward QCA redox of PPY-GO-BiCoPc functional composite were discussed using various contrast tests. Also, the effect of experimental variables on the current response such as, electro-polymerization cycles, template/monomer ratio, elution condition for template removal, pH of the supporting electrolyte and accumulation time, were investigated in detail. Under the optimized conditions, the proposed MIP sensor possessed a fast rebinding dynamics and an excellent recognition capacity to QCA, while the anodic current response of square wave voltammetry (SWV) was well-proportional to the concentration of QCA in the range of 1.0×10(-8)-1.0×10(-4) and 1.0×10(-4)-5.0×10(-4) mol L(-1) with a low detection limit of 2.1 nmol L(-1). The established sensor was applied successfully to determine QCA in commercial pork and chicken muscle samples with acceptable recoveries (91.6-98.2%) and satisfactory precision (1.9-3.5% of SD), demonstrating a promising feature for applying the MIP sensor to the measurement of QCA in real samples.


Assuntos
Técnicas Eletroquímicas , Impressão Molecular , Fenilenodiaminas/química , Polímeros/química , Pirróis/química , Quinoxalinas/análise , Animais , Galinhas , Eletrodos , Grafite/química , Indóis/química , Isoindóis , Carne/análise , Polimerização , Suínos
20.
J Sep Sci ; 35(4): 534-40, 2012 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-22282414

RESUMO

A solid-phase extraction (SPE) method was developed to extract 14 pesticides simultaneously from environment samples using cigarette filter as the sorbent before gas chromatography-mass spectrometry (GC-MS) analysis. Parameters influencing the extraction efficiency, such as the sample loading flow rate, eluent and elution volume, were optimized. The optimum sample loading rate was 3 mL/min, and the retained compounds were eluted with 6 mL of eluent at 1 mL/min under vacuum. Good linearity was obtained for all the 14 pesticides (r(2) >0.99) from 0.1 to 20 µg/L for water and from 2 to 400 µg/kg for soil samples. The detection limits (signal-to-noise=3) of the proposed method ranged from 0.01 to 0.20 µg/L for water samples and from 0.42 to 6.95 µg/kg for soil samples. The developed method was successfully applied for determination of the analytes in real environmental samples, and the mean recoveries ranged from 76.4 to 103.7% for water samples and from 79.9 to 105.3% for soil samples with the precisions (relative standard deviation) between 2.0 and 13.6%.


Assuntos
Monitoramento Ambiental/métodos , Filtração/instrumentação , Hidrocarbonetos Clorados/análise , Compostos Organofosforados/análise , Resíduos de Praguicidas/análise , Extração em Fase Sólida/métodos , Monitoramento Ambiental/instrumentação , Cromatografia Gasosa-Espectrometria de Massas , Poluentes do Solo/química , Extração em Fase Sólida/instrumentação , Poluentes Químicos da Água/química
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