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1.
Methods ; 222: 10-18, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38154527

RESUMO

ß-Galactosidase serves as a pivotal biomarker for both cancer and cellular aging. The advancement of fluorescent sensors for tracking ß-galactosidase activity is imperative in the realm of cancer diagnosis. We have designed a near-infrared fluorescent probe (PTA-gal) for the detection of ß-galactosidase in living systems with large Stokes shifts. PTA-gal exhibits remarkable sensitivity and selectivity in detecting ß-galactosidase, producing near-infrared fluorescent signals with a remarkably low detection limit (2.2 × 10-5 U/mL) and a high quantum yield (0.30). Moreover, PTA-gal demonstrates biocompatibility and can effectively detect ß-galactosidase in cancer cells as well as within living animals.


Assuntos
Corantes Fluorescentes , Imagem Óptica , Animais , beta-Galactosidase
2.
Chem Res Toxicol ; 36(12): 2010-2018, 2023 12 18.
Artigo em Inglês | MEDLINE | ID: mdl-37994028

RESUMO

Phosgene, an exceptionally hazardous gas, poses a grave concern for the health and safety of the general public. The present study describes a fluorescent ratiometric probe for phosgene employing 2-(naphthalen-2-yl) benzo[d]oxazol-5-amine (NOA) with an amino group as the recognition site. NOA detects phosgene through the intramolecular charge transfer mechanism. The electron-rich amine group of NOA attacks the electrophilic carbonyl group of phosgene, resulting in a quick response within 20 s. NOA demonstrates a low detection limit of 60 nM while maintaining high selectivity and sensitivity toward phosgene. The final product was isolated and verified by nuclear magnetic resonance spectroscopy. The probe can detect phosgene not just quickly in a solution environment but also in its solid state. The probe's applications in fingerprint imaging and bioimaging are also demonstrated.


Assuntos
Gases , Fosgênio , Gases/química , Fosgênio/química , Corantes Fluorescentes/química , Aminas
3.
Anal Methods ; 15(33): 4159-4167, 2023 Aug 24.
Artigo em Inglês | MEDLINE | ID: mdl-37577757

RESUMO

Only a few probes are suited for highly acidic environments and sensitive to pH values below 4. Thus, finding a solution for detecting strong acidic (pH value below 2) conditions is still challenging. Herein, we constructed and created a pH-switched fluorescent probe based on pyrene and a heteroatom containing pyridine unit. When exposed to acidic environments (pH 2.0), the probe's fluorescence redshifted with distinct colour and fluorescence changes owing to protonation on the nitrogen atom containing pyridine moiety, which could be deprotonated by HS- selectively compared to other competing analytes. Pyr can detect HS- with a rapid response within 5 s and showed very good quantum yield under acidic environments. The sensing mechanism was confirmed by Density Functional Theory (DFT) studies using the B3LYP and 6-31G+ (d) basis sets. Furthermore, the probe was utilized to monitor HS- in actual water samples and identify H2S gas by a simple paper strip test.

4.
Anal Chim Acta ; 1252: 341028, 2023 Apr 29.
Artigo em Inglês | MEDLINE | ID: mdl-36935144

RESUMO

A facile and rapid skin metabolomics protocol is proposed. The liquid microjunction-surface sampling probe system has been partly automated, and used in conjunction with hydrogel probes for skin metabolite analysis. A control device was built to precisely control the segmented solvent flow and analyte re-extraction into the liquid microjunction. This mode provides rapid online re-extraction of the analytes from hydrogel probes. Humectant was added to the hydrogel, and moist heat treatment was used to make the hydrogel probes rugged for sampling in the clinical setting. The developed method was validated for the analysis of choline - a putative biomarker of psoriasis. A linear relationship over six calibration levels from 3.18 × 10-5 to 3.18 × 10-4 mol m-2 has been obtained. The limit of detection was 6.6 × 10-6 mol m-2, while the recoveries range from 92 to 109%. The within-run and between-run precision were evaluated and the coefficients of variation range from 1.84 to 7.13%. Furthermore, the developed method has been used to screen patients (n = 10) and healthy participants (control group; n = 10) for psoriasis-related skin metabolites. Metabolomic profiling of the skin excretion-related signals identified potential biomarkers of psoriasis: choline, pipecolic acid, ornithine, urocanic acid, and methionine.


Assuntos
Hidrogéis , Psoríase , Humanos , Espectrometria de Massas/métodos , Pele , Psoríase/diagnóstico , Biomarcadores , Cromatografia Líquida de Alta Pressão/métodos
5.
J Agric Food Chem ; 71(2): 1190-1200, 2023 Jan 18.
Artigo em Inglês | MEDLINE | ID: mdl-36602329

RESUMO

Colorimetric and fluorescent probes have received a lot of attention for detecting lethal analytes in realistic systems and in living things. Herein, a dual-approachable Benzo-hemicyaninebased red-emitting fluorescent probe PBiSMe, for distinct and instantaneous detection of CN- and HS- was synthesized. The PBiSMe emitted red fluorescence (570 nm) can switch to turn-off (570 nm) and blue fluorescence (465 nm) in response to CN- and HS-, respectively. Other nucleophilic reagents, such as reactive sulfur species (RSS) and anions, have no contact or interference with the probe; instead, a unique approach is undertaken to exclusively interact with CN- and HS- over a wide pH range. The measured detection limits for CN- (0.43 µM) and HS- (0.22 µM) ions are lower than the World Health Organization's (WHO) recommended levels in drinking water. We confirmed 1:1 stoichiometry ratio using Job's plot and observed good quantum yield for both analytes. The probe-coated paper strips were used to detect the H2S gas produced by food spoilage (such as eggs, raw meat, and fish) via an eye-catching visual response. Moreover, fluorescence bioimaging studies of living cells was done to confirm the probe's potential by monitoring the presence of CN- and HS- in a living system.


Assuntos
Corantes Fluorescentes , Sulfeto de Hidrogênio , Espectrometria de Fluorescência/métodos , Cianetos
6.
Spectrochim Acta A Mol Biomol Spectrosc ; 273: 121043, 2022 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-35189492

RESUMO

Hydrogen sulfide (H2S), one of redox-active sulfur species, is known as a signaling molecule and an antioxidant in biological tissues to maintain cellular functions. The development of selective and sensitive H2S detection is important to understand the role of H2S in vivo. Herein, a new two-photon probe NNE was developed to detect hydrogen sulfide using 6-acetyl-N-methyl-2-naphthylamine with an attachment of 7-nitrobenzo-oxadiazole. The probe NNE exhibits high selectivity towards hydrogen sulfide over other anions. Nucleophilic substitution of H2S leads to a turn-on response with 28-fold enhancement in quantum yield (from 0.004 to 0.117). NNE shows a high sensitivity towards hydrogen sulfide with an extremely low detection limit at 6.8 nM. Furthermore, the probe NNE exhibits two-photon excited fluorescence, making it a suitable probe for monitoring H2S distribution in live cells and tissues without background fluorescence interference.


Assuntos
Sulfeto de Hidrogênio , Diagnóstico por Imagem , Corantes Fluorescentes , Células HeLa , Humanos , Imagem Óptica , Oxirredução , Fótons
7.
J Anal Toxicol ; 46(3): 246-256, 2022 Mar 21.
Artigo em Inglês | MEDLINE | ID: mdl-33575738

RESUMO

Abuse of new psychoactive substances (NPS) has become a health and social issue of global concern. p-Methoxyamphetamine (PMA)/p-methoxymethamphetamine (PMMA) with fluoro- or chloro-derivatives of amphetamine and methamphetamine were among the most common drugs found in specimens from fatal cases in Taiwan during the January 2011 to December 2018 period. A liquid-liquid extraction sample preparation protocol with highly sensitive ultra-high performance liquid chromatography-tandem mass spectrometry approach was developed for the simultaneous analysis of seven phenethylamine-type drugs-PMA, PMMA, p-methoxyethylamphetamine, 4-fluoroamphetamine (4-FA), 4-fluoromethamphetamine (4-FMA), 4-chloroamphetamine (4-CA) and 4-chloromethamphetamine (4-CMA)-in postmortem blood and urine specimens. Separation by liquid chromatography was performed by Agilent Zorbax SB-Aq column. Tandem mass spectrometry was operated in Agilent Jet Stream Technology electrospray ionization in positive-ion multiple reaction monitoring mode. An analytical methodology was evaluated using drug-free blood and urine after fortification with 100-2,000 ng/mL of the seven target analytes. Average extraction recoveries were >80%; slightly higher ion suppression was observed for PMA and 4-CA; intra-/inter-day precision (% coefficient of variation) and accuracy were in the ranges of 0.52-12.3% and 85-110%, respectively. Limit of detection and lower limit of quantitation for these seven analytes were both in the 0.5-5 ng/mL range. Interference and carryover were not significant. This relatively simple methodology was found effective and reliable for routine identification and quantitation of these seven analytes in postmortem and antemortem blood and urine specimens received in 2018. Analytical data obtained from these actual cases indicated the following: (i) compared to findings reported during the 2007-2011 period, the use of substituted phenethylamine-type drugs decreased in 2018; (ii) ketamine and 7-aminonimetazepam (the main metabolite of nimetazepam) were the most common co-ingested substances in specimens containing PMA/PMMA, 4-FA/4-FMA, or 4-CA/4-CMA; and (iii) in drug fatalities, the concentration of PMA was significantly higher than the concentration of PMMA in both urine and blood, while the reverse was true in urine specimens from antemortem cases.


Assuntos
Drogas Desenhadas , Ketamina , Cromatografia Líquida de Alta Pressão/métodos , Cromatografia Líquida , Ketamina/urina , Limite de Detecção , Reprodutibilidade dos Testes , Espectrometria de Massas em Tandem/métodos
8.
Spectrochim Acta A Mol Biomol Spectrosc ; 267(Pt 2): 120521, 2022 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-34717199

RESUMO

Cysteine (Cys), an essential amino acid, plays several crucial functions in numerous biological processes. Notably, the detection of Cys is critical to disease diagnosis. Fluorescent probes that can quickly detect Cys will help to study the mechanism of certain diseases. Herein, a new fluorescent probe, ANP, which is based on 6-acetyl-N-methyl-2-naphthyl amine, has been developed for Cys detection over Hcy and GSH in vivo. The addition of thiol on α,ß-unsaturated ketone promotes 87-fold fluorescence turn-on response with a 65 nM limit of detection. The high two-photon efficiency of the probe ANP (cross-section = 22.3) makes it a suitable probe for evaluating Cys in living cells without background fluorescence interference. Its application was extended to monitor the Cys distribution in live cells and tissues.


Assuntos
Cisteína , Corantes Fluorescentes , Glutationa , Células HeLa , Homocisteína , Humanos , Fótons , Espectrometria de Fluorescência , Compostos de Sulfidrila
9.
ACS Omega ; 6(42): 28194-28202, 2021 Oct 26.
Artigo em Inglês | MEDLINE | ID: mdl-34723017

RESUMO

Photochemical redox reactions of Cu(II) complexes of eight amino acid ligands (L) with nonpolar side chains have been systematically investigated in deaerated aqueous solutions. Under irradiation at 313 nm, the intramolecular carboxylate-to-Cu(II) charge transfer within Cu(II)-amino acid complexes leads to Cu(I) formation and the concomitant decomposition of amino acids. All amino acid systems studied here can produce ammonia and aldehydes except proline. For the 1:1 Cu(II) complex species (CuL), the Cu(I) quantum yields at 313 nm (ΦCu(I),CuL) vary by fivefold and in the sequence (0.10 M ionic strength at 25 °C) alanine (0.094) > valine (0.059), leucine (0.059), isoleucine (0.056), phenylalanine (0.057) > glycine (0.052) > methionine (0.032) > proline (0.019). This trend can be rationalized by considering the stability of the carbon-centered radicals and the efficient depopulation of the photoexcited state, both of which are dependent on the side-chain structure. For the 1:2 Cu(II) complex species (CuL2), the Cu(I) quantum yields exhibit a similar trend and are always less than those for CuL. The photoformation rates of ammonia, Cu(I), and aldehydes are in the ratio of 1:2.0 ± 0.2:0.7 ± 0.2, which supports the proposed mechanism. This study suggests that the direct phototransformation of Cu(II)-amino acid complexes may contribute to the bioavailable nitrogen for aquatic microorganisms and cause biological damage on cell surfaces in sunlit waters.

10.
ACS Appl Mater Interfaces ; 13(24): 28610-28626, 2021 Jun 23.
Artigo em Inglês | MEDLINE | ID: mdl-34110776

RESUMO

The development of aggregation-induced emission enhancement (AIEE) active nanoprobes without any synthetic complication for solution-state and organic thin-film transistor (OTFT)-based sensory applications is still a challenging task. In this study, the novel pyrene-incorporated Schiff base (5-phenyl-4-((pyren-1-ylmethylene)amino)-4H-1,2,4-triazole-3-thiol; PT2) with an AIEE property was synthesized via a one-pot reaction and was reported for detecting Zn2+ and tyrosine in the solution state and OTFT. In the AIEE studies of PT2 (in CH3CN) at various water fractions (fw: 0-97.5%), the existence of J-aggregation, crystalline changes, and nanofibers formation was confirmed by ultraviolet absorption/photoluminescence (UV/PL) spectroscopy, powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), and dynamic-light scattering (DLS) techniques. Similarly, PT2-based Zn2+ detection and sensory reversibility with tyrosine were demonstrated by UV/PL studies with evidence related to crystalline/nanolevel changes in PXRD, SEM, TEM, AFM, and DLS data. Distinct decay profiles associated with the AIEE and sensory responses of PT2 were observed in time-resolved photoluminescence spectra. From the standard deviation and linear fittings of PL titrations, detection limits (LODs) of the Zn2+ with PT2 and the tyrosine with PT2-Zn2+ were estimated as 0.79 and 45 nM, respectively. High-resolution mass and 1H NMR results confirmed 2:1 and 1:1 stoichiometry and binding sites of PT2-Zn2+-PT2* and tyrosine-Zn2+ complexes. Moreover, the values of association constants determined by linear fittings were 4.205 × 10-7 and 1.73 × 10-8 M-2, correspondingly. Optimization via the density functional theory disclosed the binding sites and suppression of twisted intramolecular charge transfer/photoinduced electron transfer (TICT/PET) as well as the involvement of restricted intramolecular rotation in the AIEE and PET "ON-OFF-ON" mechanisms in the Zn2+ and tyrosine sensors. Results from the B16-F10 cellular and zebrafish imaging of AIEE, Zn2+, and tyrosine sensors further attested the applicability of PT2 in biological samples. Finally, the PT2 and pentacene-incorporated OTFT devices were fabricated. The devices displayed more than 90% change in drain-source current when reacted with Zn2+ with an LOD of 5.46 µM but showed no response to tyrosine, thereby confirming the reversibility. Moreover, the OTFT devices also demonstrated Zn2+ ion detection in tap water and lake water samples.


Assuntos
Corantes Fluorescentes/química , Pirenos/química , Tirosina/análise , Zinco/análise , Animais , Teoria da Densidade Funcional , Água Potável/análise , Técnicas Eletroquímicas/métodos , Corantes Fluorescentes/síntese química , Lagos/análise , Limite de Detecção , Modelos Químicos , Pirenos/síntese química , Bases de Schiff/síntese química , Bases de Schiff/química , Transistores Eletrônicos , Peixe-Zebra
11.
Int J Mol Sci ; 22(3)2021 Jan 25.
Artigo em Inglês | MEDLINE | ID: mdl-33503808

RESUMO

Neutrophils produce hypochlorous acid (HOCl) as well as other reactive oxygen species as part of a natural innate immune response in the human body; however, excessive levels of HOCl can ultimately be detrimental to health. Recent reports suggest that betacyanin plant pigments can act as potent scavengers of inflammatory factors and are notably effective against HOCl. Comparison of the in vitro anti-hypochlorite activities of a novel betalain-rich red beetroot (Beta vulgaris L.) extract with its pure betalainic pigments revealed that the extract had the highest anti-hypochlorite activity, far exceeding the activity of all of the betalainic derivatives and selected reference antioxidants. This suggests that it may be an important food-based candidate for management of inflammatory conditions induced by excessive HOCl production. Among all pigments studied, betanidin exhibited the highest activity across the pH range.


Assuntos
Beta vulgaris/química , Betacianinas/química , Betalaínas/química , Corantes/química , Ácido Hipocloroso/química , Pigmentos Biológicos/química , Extratos Vegetais/química , Cromatografia Líquida , Humanos , Estrutura Molecular , Oxirredução , Hipoclorito de Sódio/química , Espectrometria de Massas por Ionização por Electrospray , Análise Espectral , Espectrometria de Massas em Tandem
12.
Trends Endocrinol Metab ; 32(2): 66-75, 2021 02.
Artigo em Inglês | MEDLINE | ID: mdl-33353809

RESUMO

Skin retains numerous low-molecular-weight compounds (metabolites). Some of these compounds fulfill specific physiological roles, while others are by-products of metabolism. The skin surface can be sampled to detect and quantify skin metabolites related to diseases. Miniature probes have been developed to detect selected high-abundance metabolites secreted with sweat. To characterize a broad spectrum of skin metabolites, specimens are collected with one of several available methods, and the processed specimens are analyzed by chromatography, mass spectrometry (MS), or other techniques. Diseases for which skin-related biomarkers have been found include cystic fibrosis (CF), psoriasis, Parkinson's disease (PD), and lung cancer. To increase the clinical significance of skin metabolomics, it is desirable to verify correlations between metabolite levels in skin and other biological tissues/matrices.


Assuntos
Metabolômica/métodos , Pele/metabolismo , Homeostase/fisiologia , Humanos , Macrófagos/metabolismo
13.
ACS Appl Bio Mater ; 4(9): 7007-7015, 2021 09 20.
Artigo em Inglês | MEDLINE | ID: mdl-35006933

RESUMO

Detection of chemical warfare agents (CWA) by simple and rapid methods with real-sample applications are quite inevitable in order to ease the threats to living systems caused by uncertain terror attacks and wars. Herein we have developed the first far-red to near infra-red (NIR) probe based on a covalent assembly approach for the detection of trace amounts of nerve agent mimic diethyl chloro phosphate (DCP) in soil and their fluorescent bio imaging in live cells. The probe features abrupt fluorescence turn on sensing of DCP with fluorescence quantum yield Φ = 0.622. It senses DCP selectively over other analytes in excellent sensitivity with a detection limit of 6.9 nM. In real time, the probe treated strips were employed to detect the DCP vapor effectively with eye catching fluorescence response. The presence of trace amounts of these acute warfare agents in the environment were monitored by soil analysis. Further fluorescent bio imaging was carried out to monitor trace level DCP in living cells using the HeLa cell line.


Assuntos
Agentes Neurotóxicos , Corantes Fluorescentes/análise , Células HeLa , Humanos , Agentes Neurotóxicos/análise , Compostos Organofosforados/análise , Solo
14.
J Pharm Biomed Anal ; 190: 113545, 2020 Oct 25.
Artigo em Inglês | MEDLINE | ID: mdl-32846402

RESUMO

Hypochlorous acid (HOCl) is involved in numerous cellular processes, such as pathogen response, immune regulation, and anti-inflammation. Consequently, the development of HOCl detection at the cellular level has been an important issue in investigating the dynamic distributions of HOCl. Herein, a fluorescent probe, Lyso-NA, containing a HOCl-reactive aminophenol group and a lysosomal-targeting morpholine group, has been effectively designed for detecting lysosomal HOCl. The reaction of Lyso-NA with HOCl induces the oxidation of aminophenol and accompanied by a 136-fold fluorescence enhancement. The detection limit is found at 13 nM. The fluorescence enhancement is accomplished through the suppression of twisted intramolecular charge transfer (TICT). With morpholine, the probe Lyso-NA shows the great lysosomal targetable ability for imaging endogenous lysosomal HOCl in living cells and tissues by two-photon microscopy, providing an opportunity to monitor HOCl in the lysosomes for understanding its biological functions.


Assuntos
Corantes Fluorescentes , Ácido Hipocloroso , Animais , Lisossomos , Camundongos , Imagem Óptica , Células RAW 264.7
15.
ACS Omega ; 5(31): 19896-19904, 2020 Aug 11.
Artigo em Inglês | MEDLINE | ID: mdl-32803086

RESUMO

The homeostasis of short-lived reactive species such as hydrogen sulfide/hypochlorous acid (H2S/HOCl) in biological systems is essential for maintaining intercellular balance. An unchecked increase in biological H2S concentrations impedes homeostasis. In this report, we present a molecular probe pyrene-based sulfonyl hydrazone derived from pyrene for the selective detection of H2S endogenously as well as exogenously through a "turn-off" response in water. The structure of the receptor is confirmed by Fourier-transform infrared spectroscopy, 1H and 13C nuclear magnetic resonance spectroscopy, electrospray ionization mass spectrometry, and single-crystal X-ray diffraction studies. The receptor shows excellent green emission in both the aqueous phase and solid state. Quenching of green emission of the receptor is observed only when H2S is present in water with a detection limit of 18 nM. Other competing anions and cations do not have any influence on the receptor's optical properties. The efficiency of H2S detection is not negatively impacted by other reactive sulfur species too. The sensing mechanism of H2S follows a chemodosimetric reductive elimination of sulfur dioxide, which is supported by product isolation. The receptor is found to be biocompatible, as evident by the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay, and its utility is extended to endogenous and exogenous fluorescence imaging of HeLa cells and zebrafish.

16.
Spectrochim Acta A Mol Biomol Spectrosc ; 242: 118757, 2020 Dec 05.
Artigo em Inglês | MEDLINE | ID: mdl-32791389

RESUMO

A novel rhodamine-pyridine conjugated spectroscopic probe RhP was synthesized and its X-ray single crystalline properties were revealed with tabulation. The RhP displayed a distinct pale-pink colorimetric and "turn-on" fluorescent response to Fe3+ in aqueous media [H2O:DMSO (95:5, v/v)] than that of other interfering ions. During the Fe3+ recognition, the absorption (UV-Vis) and photoluminescence (PL) spectral studies revealed new peaks at 561 and 592 nm, respectively. The 1:1 stoichiometry and binding sites were verified by Job's plot, ESI-mass, and 1H NMR titrations. Subsequently, LOD and binding constant for RhP + Fe3+ complex were estimated as 102.3 nM and 6.265 × 104 M-1 from linear fitting and Benesi-Hildebrand plots, correspondingly. Sensor reversibility of RhP + Fe3+ by EDTA was demonstrated by UV/PL and TRPL investigations. Moreover, the photoinduced energy transfer mechanism and band gap changes were established from the DFT interrogations. Lastly, cellular imaging studies were carried out to authenticate the real applicability of RhP in Fe3+ detection.


Assuntos
Colorimetria , Corantes Fluorescentes , Íons , Rodaminas , Água
17.
Spectrochim Acta A Mol Biomol Spectrosc ; 233: 118234, 2020 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-32163873

RESUMO

Hypochlorous acid has played several functions in the biological system. However, excess HOCl can cause damage to biomolecules and result in some diseases. Accordingly, a new fluorescent probe, BSP, has been developed for fast recognition of HOCl through the HOCl-induced oxidation of methyl phenyl sulfide to sulfoxide. The reaction of BSP with HOCl caused a 22-fold fluorescence enhancement (quantum yield increase from 0.006 to 0.133). The detection limit of HOCl is found to be 30 nM (S/N = 3). The fluorescence enhancement is due to the suppression of the photo-induced electron transfer from the methyl phenyl sulfide moiety to BODIPY. Eventually, the cellular fluorescence imaging experiment showed that BSP could be effectively used for monitoring HOCl in living cells.


Assuntos
Corantes Fluorescentes/química , Ácido Hipocloroso , Animais , Ácido Hipocloroso/análise , Ácido Hipocloroso/metabolismo , Camundongos , Microscopia de Fluorescência , Oxirredução , Células RAW 264.7 , Safrol/análogos & derivados , Safrol/química , Sulfetos/química
18.
ACS Appl Mater Interfaces ; 12(9): 10959-10972, 2020 Mar 04.
Artigo em Inglês | MEDLINE | ID: mdl-32026696

RESUMO

A novel amphiphilic aggregation-induced emission (AIE) copolymer, that is, poly(NIPAM-co-TPE-SP), consisting of N-isopropylacrylamide (NIPAM) as a hydrophilic unit and a tetraphenylethylene-spiropyran monomer (TPE-SP) as a bifluorophoric unit is reported. Upon UV exposure, the close form of non-emissive spiropyran (SP) in poly(NIPAM-co-TPE-SP) can be photo-switched to the open form of emissive merocyanine (MC) in poly(NIPAM-co-TPE-MC) in an aqueous solution, leading to ratiometric fluorescence of AIEgens between green TPE and red MC emissions at 517 and 627 nm, respectively, via Förster resonance energy transfer (FRET). Distinct FRET processes of poly(NIPAM-co-TPE-MC) can be observed under various UV and visible light irradiations, acid-base conditions, thermal treatments, and cyanide ion interactions, which are also confirmed by theoretical studies. The subtle perturbations of environmental factors, such as UV exposure, pH value, temperature, and cyanide ion, can be detected in aqueous media by distinct ratiometric fluorescence changes of the FRET behavior in the amphiphilic poly(NIPAM-co-TPE-MC). Moreover, the first FRET sensor polymer poly(NIPAM-co-TPE-MC) based on dual AIEgens of TPE and MC units is developed to show a very high selectivity and sensitivity with a low detection limit (LOD = 0.26 µM) toward the cyanide ion in water, which only contain an approximately 1% molar ratio of the bifluorophoric content and can be utilized in cellular bioimaging applications for cyanide detections.


Assuntos
Cianetos/análise , Transferência Ressonante de Energia de Fluorescência/métodos , Polímeros/química , Poluentes da Água/análise , Acrilamidas/química , Fluorescência , Transferência Ressonante de Energia de Fluorescência/instrumentação , Água Doce/análise , Interações Hidrofóbicas e Hidrofílicas , Limite de Detecção
19.
Anal Chem ; 92(3): 2756-2763, 2020 02 04.
Artigo em Inglês | MEDLINE | ID: mdl-31902204

RESUMO

Extraction of volatile compounds from complex liquid matrices is a critical step in volatile compound analysis workflows. Recently, green chemistry principles are increasingly implemented in extraction processes. Some of the available approaches are solvent-free but still require concentration or trapping of analytes. Here, we propose effervescent tablet-induced extraction (ETIE) as a method of transferring volatile/semivolatile compounds from liquid matrices to the gas phase for analysis. This technique relies on the release of carbon dioxide produced in situ during a neutralization reaction, which occurs when a tablet is inserted into an aqueous sample matrix. In this process, many bubbles of carbon dioxide are instantly formed in the sample matrix. The bubbles rapidly extract and liberate volatile compounds from the sample. The gaseous effluent is then immediately transferred to a detector (atmospheric pressure chemical ionization mass spectrometry (MS) or gas chromatography (GC) hyphenated with MS). ETIE-GC-MS can be used for analysis of volatile compounds present in real samples. The method was validated for analysis of selected ethyl esters present in a yogurt drink. The calibration data set was linear over a range from 5 × 10-7 to 1 × 10-5 M. The limits of detection ranged from 1.51 × 10-7 to 6.82 × 10-7 M, while the recoveries ranged from 71 to 118%. Inter- and intraday precision of selected ethyl esters in aqueous solution was satisfactory (relative standard deviation, 3.6-18.3%). Furthermore, it is shown that ETIE improves the performance of headspace solid-phase microextraction while eliminating the need for heating and shaking samples.

20.
ACS Appl Bio Mater ; 3(9): 6439-6446, 2020 Sep 21.
Artigo em Inglês | MEDLINE | ID: mdl-35021775

RESUMO

Luminescent carbon dots (CDs) have become attractive materials because of their superior photophysical properties and various potential applications. However, most of the formerly developed CDs only have strong blue emission, which limits their further applications, particularly in bioimaging. Herein luminescent CDs have been successfully synthesized via a one-pot solvothermal process using 4-bromoaniline and ethylenediamine as starting materials. The luminescent CDs emit strong green fluorescence with high quantum yield as well as excellent biocompatibility and biolabeling potentials. At first, the luminescent CDs exhibited high selectivity for phosgene with a turn-off fluorescence detection. The limit of detection was 81 nM, which is sensitive for the determination of phosgene over other competing toxic pollutants. In addition, the luminescent CDs have shown a three-state "on-off-on" emission with the stepwise addition of Ag+ and cysteine (Cys). Luminescent CDs show fluorescence quenching by Ag+ and fluorescence regaining with further addition of Cys, with lower detection limits of 3.9 µM (Ag+) and 3.4 µM (Cys), respectively. The luminescent CDs were utilized to obtain a clear fingerprint. During the drying process, the coffee ring effect and electrostatic interaction between the positive surface charge of amine-functionalized CDs and negatively charged fingerprint residues facilitate the formation of clear fingerprints on different platforms.

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