Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 50
Filtrar
Mais filtros










Base de dados
Intervalo de ano de publicação
1.
RSC Adv ; 13(47): 33028-33037, 2023 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-38025876

RESUMO

A gold nanourchin (AuNU) probe with a novel sensing mechanism for monitoring H2S was developed as a feasible colorimetric sensor. In this study, AuNUs that are selectively responsive to H2S were fabricated in the presence of trisodium citrate and 1,4-hydroquinone using a seed-mediated approach. Upon exposure of the AuNU solution to H2S, the hydrosulfide ions (HS-) in the solution are converted into oligomeric sulfides by 1,4-hydroquinone used as a reducing agent during the synthesis of AuNUs. The oligomeric sulfides formed in the AuNU solution upon the addition of H2S were found to coat the surface of the AuNUs, introducing a blue shift in absorption accompanied by a color change in the solution from sky blue to light green. This colorimetric alteration by the capping of oligomeric sulfides on the surface of AuNUs is unique compared to well-known color change mechanisms, such as aggregation, etching, or growth of nanoparticles. The novel H2S sensing mechanism of the AuNUs was characterized using UV-Vis spectroscopy, high-resolution transmission microscopy, X-ray photoelectron spectroscopy, surface-enhanced Raman spectroscopy, secondary ion mass spectroscopy, liquid chromatography-tandem mass spectrometry, and atom probe tomography. H2S was reliably monitored with two calibration curves comprising two sections with different slopes according to the low (0.3-15 µM) and high (15.0-300 µM) concentration range using the optimized AuNU probe, and a detection limit of 0.29 µM was obtained in tap water.

2.
Molecules ; 28(14)2023 Jul 17.
Artigo em Inglês | MEDLINE | ID: mdl-37513326

RESUMO

Azapeptides have gained much attention due to their ability to enhance the stability and bioavailability of peptide drugs. Their structural preferences, essential to understanding their function and potential application in the peptide drug design, remain largely unknown. In this work, we systematically investigated the conformational preferences of three azaamino acid residues in tripeptide models, Ac-azaXaa-Pro-NHMe [Xaa = Asn (4), Asp (5), Ala (6)], using the popular DFT functionals, B3LYP and B3LYP-D3. A solvation model density (SMD) was used to mimic the solvation effect on the conformational behaviors of azapeptides in water. During the calculation, we considered the impact of the amide bond in the azapeptide models on the conformational preferences of models 4-6. We analyzed the effect of the HB between the side-chain main chain and main-chain main-chain on the conformational behaviors of azapeptides 4-6. We found that the predicted lowest energy conformation for the three models differs depending on the calculation methods. In the gas phase, B3LYP functional indicates that the conformers tttANP-1 and tttADP-1 of azapeptides 4 and 5 correspond to the type I of ß-turn, the lowest energy conformation with all-trans amide bonds. Considering the dispersion correction, B3LYP-D3 functional predicts the conformers tctANP-2 and tctADP-3 of azapeptide 4 and 5, which contain the cis amide bond preceding the Pro residue, as the lowest energy conformation in the gas phase. The results imply that azaAsx and Pro residues may involve cis-trans isomerization in the gas phase. In water, the predicted lowest energy conformer of azapeptides 4 and 5 differs from the gas phase results and depends on the calculational method. For azapeptide 6, regardless of calculation methods and phases, tttAAP-1 (ß-I turn) is predicted as the lowest energy conformer. The results imply that the effect of the side chain that can form HBs on the conformational preferences of azapeptides 4 and 5 may not be negligible. We compared the theoretical results of azaXaa-Pro models with those of Pro-azaXaa models, showing that incorporating azaamino acid residue in peptides at different positions can significantly impact the folding patterns and stability of azapeptides.


Assuntos
Amidas , Peptídeos , Conformação Proteica , Peptídeos/química , Água/química
3.
Mikrochim Acta ; 190(4): 134, 2023 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-36920558

RESUMO

A highly sensitive and selective NH3 gas sensor was developed based on single-layer pristine graphene doped with copper(II) oxide (CuO) nanoparticles of a specific size. High-quality single-layer graphene was grown using chemical vapor deposition. Approximately 15 nm-sized CuO colloidal nanoparticles were fabricated by a microwave-assisted thermal method using copper acetate as the precursor, and dimethylformamide as the reducing and stabilizing agent. Pristine graphene was doped with an aqueous suspension of CuO nanoparticles at a coating speed of 1500 rpm using a simple spin coater. CuO nanoparticle doping induces changes in the electronic properties of graphene; in particular, p-type doping significantly altered graphene resistivity in the presence of NH3 gas. Upon exposure of the pristine graphene surface to NH3 gas, NH3 reacted with O2-/ O-/ O2- species on the graphene surface and released electrons into graphene. This caused a change in the concentration of charge carriers in the valence channel of graphene and an increase in graphene resistivity, facilitating real-time NH3 monitoring with quick response and rapid recovery at 25 ℃ and ~ 55% relative humidity. Our results indicated that graphene doped with ~ 15 nm-sized CuO nanoparticles can sense NH3 gas selectively with a resistivity response of ~ 83%. Moreover, the sensor exhibited good reusability, fast response (~ 19 s), and rapid recovery (~ 277 s) with a detection limit of 0.041 ppm and a relative standard deviation of 0.76%.

4.
Molecules ; 29(1)2023 Dec 26.
Artigo em Inglês | MEDLINE | ID: mdl-38202732

RESUMO

Lacquer sap has been traditionally used in coatings and artwork. Suitable types of lacquer are required to preserve and restore artifacts. Recently, unsuitable cashew nut shell liquid (CNSL) has often been mixed with lacquer sap, so it is necessary to identify the characteristics of lacquer sap by the production area. However, research is still focused on urushiol and laccol. In this study, Myanmarese lacquer sap collected from Gluta usitata, which contains thitsiol as the main component, was analyzed by HPLC to quantify thitsiol using the standards 3-(10-phenyldecyl) benzene-1,2-diol (thitsiol 16) and 3-(8Z,11Z-pentadecadienyl)-benzenediol (urushiol 15:2) as markers, and calibration curves were plotted. The coefficients of determination (R2) for thitsiol 16 and urushiol 15:2 were 0.9985 and 0.9983, respectively. In addition, a blind test was conducted to confirm that accurate quantitative analysis was possible even when Myanmarese lacquer was mixed with lacquer from another production area, which contained urushiol as the main component, and CNSL, which contained cardol, a completely different catechol. Quantitative analysis of thitsiol 16 and urushiol 15:2 in Myanmarese lacquer using HPLC can be used to evaluate the quality of lacquer sap and for more sophisticated activities such as restoration by classifying differences in lacquer sap by the production area.

5.
Materials (Basel) ; 15(6)2022 Mar 08.
Artigo em Inglês | MEDLINE | ID: mdl-35329454

RESUMO

Wheat and rice starches, traditionally used to stiffen fabric, become less contaminated and more antiseptic after fermentation for several years, thus enhancing their functional activity. In the present study, analytical techniques using particle size analysis, a gloss meter and a colorimeter were used to measure the physical properties of wheat and rice starches that had been fermented for 5 and 7 years, respectively. Their chemical contents and composition were determined by nutrient measurements and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The ToF-SIMS spectra and ion images showed that fermented starch contained more carbohydrate and less lipid than fresh starch. The surface morphologies of the fermented starch granules and starch-coated textiles were examined by scanning electron microscopy and compared with the surface morphologies of fresh starch granules. The fermented wheat and rice starch granules were smaller and more rounded with a lower level of N-containing compounds (proteins) and exhibited more antiseptic properties than fresh starch granules. The results showed that physical measurements and chemical analysis were simple and complementary techniques for investigating traditional Korean starch materials and textiles.

6.
Spectrochim Acta A Mol Biomol Spectrosc ; 267(Pt 1): 120457, 2022 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-34653848

RESUMO

Developing new reaction based recognizing units can enhance the specificity of target analyte molecules in practical applications of real samples and biosystems. Therefore, introducing a recognizing moiety diphenylborinate was encountered for the detection of pyruvate biomolecule through Lewis acid-base reaction based sensing strategy. The construction of the Schiff-base back bone between quinoline and N-(diethylamino)salicylaldehyde-diphenylborinate (QSB) were expressed the red shift from blue emission of quinoline in to green as that of dative bond developed between Schiff base nitrogen and boron atoms. The new sensing approach was involved such a way that fluorophore QSB is a Lewis acid while pyruvate acts as Lewis base, where the elimination of Lewis pair produced a weak green fluorescence including the formation of quinoline, N-(diethylamino)salicylaldehyde (QS). The switching products were witnessed through 1H NMR titration, HR-MS and FT-IR studies. The good selectivity and interference ability were achieved in presence of 1000-fold excess of possible interferences with LOD of 16 nM. Moreover, the tracking ability of the probe was employed towards pyruvate in live HeLa cell imaging for evaluating an exogenous and endogenous signals producing ability and its mitochondria targeting property was investigated successfully. Further, the practical utility of the probe was tested with milk samples and obtained good recovery results.


Assuntos
Ácidos de Lewis , Bases de Lewis , Corantes Fluorescentes , Células HeLa , Humanos , Ácido Pirúvico , Espectrometria de Fluorescência , Espectroscopia de Infravermelho com Transformada de Fourier
7.
Spectrochim Acta A Mol Biomol Spectrosc ; 268: 120622, 2022 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-34865974

RESUMO

Citrate is a tricarboxylate, plays vital role in prostate cancer (PC) and the level of citrate is an indicator for PC identification. Herein, triaminoguanidine carbon dots (TAG-CDs) prepared by one step hydrothermal method and used as a citrate receptor. Notably the TAG-CDs without alkaline treatment were highly fluorescent at pH 7 with high quantum yield (11.3%). TAG-CDs were characterized through TEM, XRD, FT-IR, UV-vis and spectrofluorimetry. It is noted that the average size was of 2.8 nm, the presence of highly disordered carbon, retain the functionality of TAG. The absorbance maxima obtained at 294 nm and good emitting response observed at 396 nm. The Y-aromaticity of receptor guanidinium moiety acts as Lewis acid and have peculiar interaction with Lewis base citrate via electrostatic interaction and also protons in the TAG participate hydrogen bonds with citrate, which causes quenching of TAG-CDs. From the obtained linear quenching equation the LOD was found to be 4 nM. The probe expressed high selectivity, high interference tolerance (500 - fold), fast response in 15 mins and good biocompatible. Finally, TAG-CDs utilized for the intracellular imaging of citrate in live MCF-7 cells, it showed good cytotoxicity and delivered contrast images in presence, absence of citrate. TAG-CDs detected the citrate level in human urine samples, the obtained results are validated with HPLC method.


Assuntos
Neoplasias da Próstata , Pontos Quânticos , Biomarcadores Tumorais , Carbono , Ácido Cítrico , Corantes Fluorescentes , Humanos , Masculino , Próstata , Neoplasias da Próstata/tratamento farmacológico , Espectroscopia de Infravermelho com Transformada de Fourier
8.
Talanta ; 236: 122884, 2022 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-34635264

RESUMO

This work describes (Z)-N-((Z)-2-(1,3,3-trimethylindolin-2ylidene)ethylidene)quinoline-8-amine (LYSO-QF), a high-performing and biocompatible dye comprised of quinoline and Fisher aldehyde moieties linked via an imine vinyl backbone with lysosome targeting ability that can be used to quantitatively detect the mercury ion (Hg2+) in biosystems and the natural environment. This is achieved by forming three different tetrameric, trimeric and dimeric complexes between Hg2+ and LYSO-QF with the limit of detection (LOD) of 11 nm. The complexes formed were analyzed with the aid of time-dependent density functional theory (TD-DFT) calculations. The concentration dependence of the Hg2+ complex fluorescence emission changes from grey-green to jade green and then to red as the different types of complex are formed. The favorable sensor properties of the LYSO-QF probe are demonstrated by monitoring different Hg2+ concentrations in buffer solutions, HeLa cells, zebrafish model samples and several different types of water sample. Experiments with Whatman paper strips demonstrate that the cost-effective LYSO-QF also has considerable potential for use in on-site Hg2+ detection with the naked eye.


Assuntos
Complexos de Coordenação , Mercúrio , Quinolinas , Aldeídos , Animais , Células HeLa , Humanos , Lisossomos , Peixe-Zebra
9.
Polymers (Basel) ; 13(9)2021 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-33925850

RESUMO

Researchers have widely investigated Oriental lacquers to identify the chemical composition and have elucidated corresponding polymerization mechanisms using rigorous analytical techniques. However, researchers generally test the physical properties of Oriental lacquers by conventional methods that are perhaps overly simplistic. Here, we propose accurate and quantitative methods for evaluating the physical properties of Korean, Vietnamese, and Myanmarese lacquer films using atomic force microscopy (AFM), a nanoindenter, and a 90° peel tester. We obtained surface images of the lacquers in accordance with drying time using scanning electron microscopy and AFM. The Korean lacquer film exhibited fast hardening speed, enhanced hardness, and strong adhesion strength compared with the other lacquers, although the Myanmarese lacquer film had a smoother surface than the Korean lacquer film. We used our characterization approach for evaluating a mixed Korean/Myanmarese (50/50 w/w) lacquer. Our proposed measurement techniques for Oriental lacquer films provided results that agreed with qualitative results from conventional tests. Force-distance curves in AFM and force-displacement with nanoindenter for Oriental lacquer films showed more accurate and quantitative data on the mechanical properties. Thus, researchers will find our approach useful when they optimize the chemical compositions and improve the physical properties of Oriental lacquer films for industrial applications.

10.
Mikrochim Acta ; 188(4): 132, 2021 03 20.
Artigo em Inglês | MEDLINE | ID: mdl-33745002

RESUMO

Concave gold nanocubes are viable optical nanoprobes for the determination of nitrite ions. Herein, a novel approach was developed, based on the measurement of localized surface plasmon resonance absorption. The addition of nitrite ions selectively induced the etching of concave gold nanocubes, abrading the sharp vertices to spherical corners, which resulted in blue-shifted absorption accompanied by a color change from sapphire blue to light violet. The mechanism of selective etching of concave gold nanocube tips was elucidated by using X-ray photoelectron spectroscopy and atom probe tomography. The optimized detection of NO2- via the concave gold nanocube-based probe occurred at pH 3.0 and in 20 mM NaCl concentration at 40 °C. The absorption ratios (A550 nm/A640 nm) were proportional to the NO2- concentrations in the range 0.0-30 µM, with a detection limit of 38 nM (limit of quantitation of 0.12 µM and precision of 2.7%) in tap water. The highly selective and sensitive colorimetric assay has been successfully applied to monitor the nitrite ion concentrations in spiked tap water, pond water, commercial ham, and sausage samples.


Assuntos
Colorimetria/métodos , Nanopartículas Metálicas/química , Nitritos/análise , Animais , Água Potável/análise , Contaminação de Alimentos/análise , Ouro/química , Limite de Detecção , Lagoas/análise , Carne de Porco/análise , Ressonância de Plasmônio de Superfície , Suínos , Poluentes Químicos da Água/análise
11.
Anal Chim Acta ; 1148: 238178, 2021 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-33516382

RESUMO

A tetraphenylethene (TPE) derivative was designed and synthesized upon conjugation with bis(thiophen-2-ylmethyl) amine (BTA) containing a mercury-binding moiety and further characterized by using Nuclear magnetic resonance (NMR), LC-MS, UV-Vis, and fluorescence spectroscopic methods. The resulting TPE-BTA exhibited comprehensive aggregation-induced emission while expressing a high quantum yield and emission intensity at 70% water fraction. The probe exhibited a good photochromic effect with a Stokes shift of 178 nm, and the emission intensity at 550 nm increased considerably with the color turning from dark green to bright green under a UV lamp upon the addition of 5 µM Hg2+. The lowest-energy conformation of the probe showed that two thiophene rings were perpendicular to the phenyl ring, while two BTA molecules were situated in a staggered form to each other. The sulfur and nitrogen atoms present in TPE-BTA were coordinated to the Hg2+ ion, and these binding sites were confirmed by the NMR parameters, X-ray photoelectron spectroscopy signals, and structural calculations. The binding of Hg2+ to TPE-BTA was believed to restrict the intramolecular motion of TPE-BTA, thus inducing it to shine brighter according to the unique aggregation-induced emission effect. The concentration of Hg2+ was determined based on the enhancement of the emission intensity, and the present probe showed an extremely high sensitivity with a limit of detection of 10.5 nM. Furthermore, TPE-BTA enabled selective detection of Hg2+ even in the presence of a 1000-fold excess of other interfering metal ions. The proposed method was successfully employed to determine Hg2+ in living HeLa cells and real water samples.


Assuntos
Corantes Fluorescentes , Mercúrio , Células HeLa , Humanos , Espectrometria de Fluorescência , Água
12.
RSC Adv ; 11(10): 5456-5465, 2021 Jan 28.
Artigo em Inglês | MEDLINE | ID: mdl-35423097

RESUMO

A highly sensitive and selective colorimetric assay for the dual detection of Hg2+ and As3+ using gold nanoparticles (AuNPs) conjugated with d-penicillamine (DPL) was developed. When Hg2+ and As3+ ions coordinate with AuNP-bound DPLs, the interparticle distance decreases, inducing aggregation; this results in a significant color change from wine red to dark midnight blue. The Hg4f and As3d signals in the X-ray photoelectron spectra of Hg2+ (As3+)-DPL-AuNPs presented binding energies indicative of Hg2+-N(O) and As3+-N(O) bonds, and the molecular fragment observed in time-of-flight secondary ion mass spectra confirmed that Hg2+ and As3+ coordinated with two oxygen and two nitrogen atoms in DPL. The detection of Hg2+ and As3+ can be accomplished by observing the color change with the naked eye or by photometric methods, and this was optimized to provide optimal probe sensitivity. The assay method can be applied for environmental monitoring by first selectively quantifying Hg2+ in water samples at pH 6, then estimating the As3+ concentration at pH 4.5. The efficiency of the DPL-AuNP probe was evaluated for the sequential quantification of Hg2+ and As3+ in tap, pond, waste, and river water samples, and absorbance ratios (A 730/A 525) were correlated with Hg2+ and As3+ concentrations in the linear range of 0-1.4 µM. The limits of detection in water samples were found to be 0.5 and 0.7 nM for Hg2+ and As3+, respectively. This novel probe can be utilized for the dual determination of Hg2+ and As3+, even in the presence of interfering substances in environmental samples.

13.
ACS Appl Bio Mater ; 4(2): 1932-1941, 2021 02 15.
Artigo em Inglês | MEDLINE | ID: mdl-35014462

RESUMO

Sensitive and quantitative detection of prostate cancer (PC) requires a chemosensor with an applicable sensing strategy. A star-shaped Schiff base triaminoguanidine-integrated thiophene fluorophore TAT was rationally designed with nitrogen and sulfur atoms to coordinate with Zn2+ as the initial step and to chelate with citrate as the following step. Formation of the complex TAT-Zn2+ induced an intramolecular charge transfer and caused a red-shifted, Zn2+ concentration-dependent fluorescence at 507 nm. Chelation of TAT-Zn2+ with citrate led to an emission band at 692 nm upon an aggregation-induced emission mechanism. The distinctive fluorescence emissions of Zn2+ and citrate biomarkers were demonstrated first in on-site paper-based test strips showing gradually enhanced colors at yellow and red channels and second in both in vitro and in vivo by using PC3 cells and BALB/c nude mouse animal models, respectively. The in vitro test confirmed the mitochondria organelle-targeting property of TAT, and the in vivo performance manifested the successful application of the probe in recognizing the prostate cancer. This is the first applicable chemosensor that could be in continuous recognition of dual PC biomarkers Zn2+ and citrate in cancer diagnosis with a mitochondria organelle-targeting ability.


Assuntos
Materiais Biocompatíveis/química , Biomarcadores Tumorais/análise , Ácido Cítrico/análise , Guanidinas/química , Neoplasias da Próstata/diagnóstico por imagem , Tiofenos/química , Zinco/análise , Materiais Biocompatíveis/síntese química , Humanos , Íons/análise , Masculino , Teste de Materiais , Microscopia Confocal , Estrutura Molecular , Imagem Óptica , Células PC-3 , Bases de Schiff/química , Células Tumorais Cultivadas
14.
J Anal Methods Chem ; 2020: 6134627, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-32399310

RESUMO

Over the years, soft contact lenses for vision correction and cosmetic and therapeutic purposes have been greatly improved. For cosmetic contact lenses, the pigments need to be nontoxic, and the position of the pigment layer is particularly important because of the risks posed by pigment elution and the roughness of the lens surface. In this paper, we characterized the properties of brown cosmetic contact lenses made by three different manufacturers using surface analytical techniques. The surface topographies of the noncolored and colored parts were obtained by atomic force microscopy (AFM), and the position and composition of the pigment layer were determined by analyzing the cross section of the contact lenses using scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX). The influence of pigment location on surface roughness was also examined. In addition, to find the method of the evaluation for the risk of surface elution of the pigments in the colored parts, the mass spectra and ion images of the surfaces were obtained by time-of-flight secondary ion mass spectrometry (ToF-SIMS) with a new sample preparation. From the ToF-SIMS spectra, we observed specific fragment ions of the poly(hydroxyethyl methacrylate) (PHEMA) polymer and found differences in the composition of the pigment layer depending on the manufacturers. The cross-sectioned image and 3D chemical characterizations of metallic and specific ions in the brown cosmetic contact lenses clearly indicated the spatial distribution and location of the pigment layer that can be used for the evaluation of pigment elution.

15.
J Hazard Mater ; 393: 122381, 2020 07 05.
Artigo em Inglês | MEDLINE | ID: mdl-32155520

RESUMO

Building materials have been developed mainly for thermal performance, strength, low energy consumption, and aesthetics. Consequently, large amounts of chemicals have been added to building products, resulting in the release of abundant pollutants that adversely affect human health. In particular, pollutants from the materials used to build modern dwellings can cause sick house syndrome, which leads to health resilience problems and diseases. In this study, more than 100 investigations were conducted annually from 2004 to 2017 by using the 20 L small chamber method to analyze the contents of formaldehyde (HCHO) and total volatile organic compounds (TVOC) released from 2780 building products in total. High emissions were released by some building components with raw materials containing hazardous chemicals. However, since the 2004 enactment of a legal standard for the regulation of emissions of harmful substances in building products, the pollutant emissions have tended to decrease over the years. As a result of the experiment, all 2780 building materials met the legal standard on average. Therefore, legal restrictions on the release of hazardous materials from building products have achieved reductions in pollutant emissions.

16.
Polymers (Basel) ; 13(1)2020 Dec 29.
Artigo em Inglês | MEDLINE | ID: mdl-33383703

RESUMO

Asian lacquer is a special polymeric material tapped from lacquer trees. The tree's sap is a complex mixture of compounds, such as catechol lipids, polysaccharides, glycoproteins, enzymes, and water. Researchers have not yet quantitatively analyzed blended lacquers. We evaluated the compositions of Japanese and Vietnamese lacquers, and blends of the two, using time-of-flight secondary ion mass spectrometry (ToF-SIMS), pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), and high-performance liquid chromatography (HPLC). ToF-SIMS provided quantitative results for blended lacquers; provided structural information on polymeric lacquer films; and indicated the presence of dimers of urushiol-urushiol, urushiol-laccol, and laccol-laccol derivatives. We used Py-GC/MS and HPLC to obtain linear calibration curves. The specific peak intensity was a linear function of the ratio of Japanese to Vietnamese lacquer in the blends. For an unknown mixture, all three techniques gave essentially the same results. These quantitative methods will be useful for improving the physical properties of polymeric lacquer films, and evaluating the lacquer quality in industry and historic conservation.

17.
J Anal Methods Chem ; 2019: 5174764, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31192020

RESUMO

Intracellular H2O2 monitoring is important and has driven researchers to pursue advancements for the rapid identification of H2O2, since H2O2 is short-lived in cell lines. An arylboronate derivative has been investigated as a chemospecific fluorescence recognition agent for H2O2. Triphenylimidazoleoxadiazolephenyl (TPIOP) boronate was contrived as a novel candidate for the rapid and sensitive recognition of H2O2. The probe was conjugated using the TPIOP functional group acting as an excellent fluorescent enhancer. The TPIOP group stimulated the polarization of C-B bond due to its extended π-conjugation, which included heteroatoms, and induced the production of rapid signal because of the highly polar C-B bond along with the corresponding boronate unit. While H2O2 reacts with TPIOP boronate, its nucleophilic addition to the boron generates a charged tetrahedral boronate complex, and then the C-B bond migrates toward one of the electrophilic peroxide oxygen atoms. The resulting boronate ester is then hydrolyzed by water into a phenol, which significantly enhances fluorescence through aggregation-induced emission. The TPIOP boronate probe responded to H2O2 rapidly, within 2 min, and exhibited high sensitivity with a limit of detection of 8 nM and a 1000-fold selectivity in the presence of other reactive oxygen species. Therefore, the developed TPIOP boronate chemodosimeter was successfully utilized to visualize and quantify intracellular H2O2 from human breast cancer (MCF-7) cells, as well as gaseous and aqueous H2O2 from environmental samples using Whatman paper strips coated with TPIOP boronate.

18.
Anal Chim Acta ; 1066: 112-120, 2019 Aug 20.
Artigo em Inglês | MEDLINE | ID: mdl-31027525

RESUMO

A new boronic acid derivative functionalized with a 4-(3-(4-(4,5-diphenyl-1H-imidazole-2-yl)phenyl)-1,2,4-oxadiazol-5-yl)phenyl (IOP) moiety was synthesized for use as a sequential "on-off-on"-type relay fluorescence probe for Fe3+ ions and F- ions with high selectivity and sensitivity under physiological conditions. The introduction of Fe3+ to IOP boronic acid (IOPBA) formed an Fe3+IOPBA complex, which led to quenching of the blue fluorescence intensity at 458 nm. The lowest-energy conformation of IOPBA was theoretically predicted to adopt an extended structure, and the Fe3+ ion in the Fe3+IOPBA complex was coordinated to two phenyl groups to form a π-complex. Upon addition of F- to the Fe3+IOPBA complex, the original fluorescence was recovered due to formation of [FeF6]3‒, resulting in "on-off-on"-type sensor behavior. IOPBA showed high selectivity towards Fe3+ among other cations. Moreover, the Fe3+IOPBA complex showed specific selectivity towards F-, with other cations and anions not interfering with detection. Both sensing processes showed 1:1 stoichiometry with binding constants of 6.87 × 106 and 4.49 × 106 mol-1 L for Fe3+ with IOPBA and F- with Fe3+IOPBA, respectively. The limits of detection for Fe3+ and F- were 10 and 1 nM, respectively. The proposed method was successfully applied in real water samples. Furthermore, the probe had low cytotoxicity and was successfully used as a bioimaging reagent to detect intracellular Fe3+ and F- in living HeLa cells.


Assuntos
Compostos Férricos/análise , Fluorescência , Fluoretos/análise , Sobrevivência Celular , Células HeLa , Humanos , Íons/análise , Estrutura Molecular , Imagem Óptica
19.
J Anal Methods Chem ; 2018: 6751964, 2018.
Artigo em Inglês | MEDLINE | ID: mdl-30420936

RESUMO

Recently, Cu(In X Ga(1-X))Se2 (CIGS) absorber layers have been extensively studied by many research groups for thin-film solar cell technology. CIGS material is particularly promising due to its exceptionally high absorption coefficient and large band gap range, which is adjustable as a function of alloy stoichiometry. To enhance the conversion performance of CIGS solar cells, understanding the CIGS structure and composition is a crucial challenge. We conducted a quantitative study to determine the bulk composition of the major elements such as Cu, In, Ga, and Se of four different CIGS photovoltaic cells. The compositional information was obtained by X-ray fluorescence (XRF), inductively coupled plasma atomic emission spectroscopy (ICP-AES), and femtosecond laser ablation inductively coupled plasma mass spectrometry (fs-LA-ICP-MS). Then, the XRF concentration ratio was compared with the intensity ratio of fs-LA-ICP-MS to investigate the potential of accurate and rapid analysis using the fs-LA-ICP-MS technique. In contrast to the bulk information, the surface techniques can supply detailed information about the chemical composition across the depth profile. Here, elemental depth distributions of CIGS thin films were investigated using magnetic sector secondary ion mass spectrometry (SIMS) and Auger electron spectroscopy (AES). The atomic distributions of four different CIGS absorber layers exhibited a good agreement although they were obtained using two different surface instruments, AES and SIMS. Comparative analysis results of different CIGS absorber layers using SIMS, AES, and fs-LA-ICP-MS provide us with the appropriate technique for the information of accurate composition in a rapid analysis time. Thanks to a simple approach using the Ga/(In + Ga) ratio, the optical band gap energy of the Cu(In X Ga(1-X))Se2 quaternary layer was monitored in the entire CIGS layer. The elemental distribution and the band gap determination were then used to elucidate their relationship to the corresponding CIGS cell efficiency result.

20.
J Anal Methods Chem ; 2018: 1206913, 2018.
Artigo em Inglês | MEDLINE | ID: mdl-29629208

RESUMO

A highly sensitive and selective colorimetric assay for the detection of Hg2+ ions was developed using gold nanoparticles (AuNPs) conjugated with polyethyleneimine (PEI). The Hg2+ ion coordinates with PEI, decreasing the interparticle distance and inducing aggregation. Time-of-flight secondary ion mass spectrometry showed that the Hg2+ ion was bound to the nitrogen atoms of the PEI in a bidentate manner (N-Hg2+-N), which resulted in a significant color change from light red to violet due to aggregation. Using this PEI-AuNP probe, determination of Hg2+ ion can be achieved by the naked eye and spectrophotometric methods. Pronounced color change of the PEI-AuNPs in the presence of Hg2+ was optimized at pH 7.0, 50°C, and 300 mM·NaCl concentration. The absorption intensity ratio (A700/A514) was correlated with the Hg2+ concentration in the linear range of 0.003-5.0 µM. The limits of detection were measured to be 1.72, 1.80, 2.00, and 1.95 nM for tap water, pond water, tuna fish, and bovine serum, respectively. Owing to its facile and sensitive nature, this assay method for Hg2+ ions can be applied to the analysis of water and biological samples.

SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA
...