RESUMO
The development of efficient strategies for the removal of heavy metal ions from aqueous solutions is rapidly demanded as these contaminants are very toxic and carcinogenic and show detrimental effects on the living creatures. The main focus of the current study is on the preparation and assessment of electrospun adsorptive nanofiber membranes for the removal of toxic Ni(II) and Cu(II) from wastewater in the ultrafiltration process. Hydrothermally synthesized titanate nanotubes (TNT) was modified with thiol functional groups and then directly incorporated to the polyvinyl chloride nanofiber matrices via electrospinning process to fabricate an adsorptive membrane. The as-prepared electrospun nanofiber membranes and the nanoadsorbents were characterized with respect to the physiochemical properties, surface structure and morphology, applying XPS, FTIR, FESEM, EDX and TEM analysis and then, the membranes were evaluated in terms of the removal of the heavy metal ions in a continuous ultrafiltration mode. In adsorptive filtration of the metal ions, the effective factors including nanoadsorbents loading (0.5-1.5 wt%), initial metal ion concentration (60-150 mg/L), feed temperature (~25 °C-45 °C), presence of competing ion and reusability were investigated in the UF system where the membranes containing 1.5 wt% thiol-modified TNT and virgin TNT adsorbents demonstrated excellent removal efficiency compared to the other membranes. The Cu(II) and Ni(II) removal efficiency of the membrane containing 1.5 wt% functionalized TNT was 90% and 86.7%, respectively which was the highest ones. As was expected and due to the uniform dispersion and less aggregation of the modified TNT adsorbents on the large surface area of the electrospun nanofibers, more adsorption capacity of the nanoparticles can be exploited. Moreover, the strong affinity of the thiol functional groups toward the metal cations, these membranes removed metal contaminants more efficiently. Besides, the Cu(II) removal efficiency of the fabricated membranes didn't show any drastic changes in the presence of the competing ions. Furthermore, acceptable performance was achieved for the prepared membranes even after four adsorption/regeneration cycles in the continuous UF experiments, demonstrating the feasibility and effectiveness of the prepared adsorptive nanofiber membranes for the removal of heavy metal ions.
Assuntos
Metais Pesados , Nanofibras , Nanotubos , Trinitrotolueno , Poluentes Químicos da Água , Purificação da Água , Adsorção , Íons , Cloreto de Polivinila , Compostos de Sulfidrila , Poluentes Químicos da Água/análiseRESUMO
Nanoparticles of cadmium selenide (CdSe) doped with europium, were synthesized as stabilizing agents using thioglycolic acid ligand. This method is based on the enhancing effect of CdSe quantum dots (QDs) doped with europium on chemiluminescence (CL) emission. This emission was generated by mixing CdSe QDs with manganese (II), iron (II) and chrome (II) sulfates as catalysts in the presence of hydrogen peroxide (H2 O2 ). The structural characteristics and morphology of these nanoparticles were investigated by scanning electron microscopy, Fourier transform infrared spectroscopy, ultraviolet-visible absorption spectroscopy, X-ray pattern and dynamic light scattering methods. The CdSe QDs doped with europium were used as the sensitizer in a luminol-hydrogen peroxide CL system. The sensitized CdSe QDs were analyzed for antibacterial activity against Gram-positive or Gram-negative bacteria. The results showed that the CdSe QDs are effective against all the studied bacteria, effectiveness was especially higher for Bacillus subtilis.
Assuntos
Antibacterianos/farmacologia , Compostos de Cádmio/farmacologia , Európio/farmacologia , Luminescência , Pontos Quânticos/química , Compostos de Selênio/farmacologia , Antibacterianos/síntese química , Antibacterianos/química , Bacillus subtilis/efeitos dos fármacos , Compostos de Cádmio/síntese química , Compostos de Cádmio/química , Escherichia coli/efeitos dos fármacos , Európio/química , Testes de Sensibilidade Microbiana , Pseudomonas aeruginosa/efeitos dos fármacos , Compostos de Selênio/síntese química , Compostos de Selênio/química , Staphylococcus aureus/efeitos dos fármacosRESUMO
We report herein the development of a novel chemiluminescence system based on simultaneous introducing of synthetic coumarin derivatives and chitosan-induced Au/Ag alloy NPs on the luminol CL system and suggest how it may be useful for determination of glucose. Chitosan-induced Au/Ag nanoalloys in the coumarin derivatives intensified-luminol CL system, in addition to catalyze CL reaction can make a change in the process of coumarin derivatives effect as fluorophore on the luminol CL system. This phenomenon is caused by interaction between active functional groups of coumarin derivatives and chitosan. The interaction strength depends on the coumarin derivatives' structure and their substituents. Considering the inevitable trend luminol radical and superoxide anion radical to absorption on the surface of the embedded Au/Ag nanoalloy in the chitosan matrix, it can be concluded that chitosan acts as a platform for all reagents involved in the CL reaction including coumarin derivatives, Au/Ag nanoalloy and luminol, and electron-transfer taking place on it; Placing all chemiluminescent reagents together on the chitosan network can lead to a powerful CL due to increasing rigidity of CL system. The most efficient coumarin derivative on the Au/Ag nanoalloy-fluorophore-luminol-H2O2 CL system, in relation to interaction capability with chitosan' functional groups, was selected and the CL condition in presence of it was optimized. Whereas the glucose oxidase-mediated oxidation of glucose yields gluconic acid and H2O2, under optimum condition the most efficient CL system was applied to detection of glucose due to enzymatically production of hydrogen peroxide. The linear response range of 1.5 × 10(-6)-5.0 × 10(-3) M and the detection limit (defined as the concentration that could be detected at the signal-to-noise ratio of 3) of 7.5 × 10(-7) M was found for the glucose standards. Also, the developed method was successfully applied to determination of glucose in real serum and urine samples of diabetic patients and validated against colorimetric spectroscopy method.
Assuntos
Quitosana/química , Cumarínicos/química , Glucose/análise , Ouro/química , Luminol/química , Nanopartículas Metálicas/química , Prata/química , Ligas/química , Catálise , Peróxido de Hidrogênio/química , Concentração de Íons de Hidrogênio , Limite de Detecção , Medições Luminescentes , Ácido Succínico/químicaRESUMO
A novel glucose biosensor based on the chemiluminescence (CL) detection of enzymatically generated hydrogen peroxide (H2O2) was constructed by one covalent immobilization of glucose oxidase (GOD) in glutaraldehyde-functionalized glass cell. In following, chitosan-induced Au/Ag nanoparticles dispersed in ion liquid (IL) were synthesised and immobilized on it. Herein, chitosan molecules acted as both the reducing and stabilizing agent for the preparation of NPs and also, as a coupling agent GOD and Au/Ag alloy NPs. In addition to catalyze luminol CL reaction, these NPs offered excellent catalytic activity toward hydrogen peroxide generation in enzymatic reaction between GOD and glucose. The used IL in fabrication of biosensor increased its stability. Also, IL alongside Cu(2+) accelerated enzymatic and CL reaction kinetic, and decreased luminol CL reaction optimum pH to 7.5 which would enable sensitive and precision determination of glucose. Under optimum condition, linear response range of glucose was found to be 1.0 × 10(-6)-7.5 × 10(-3)M, and detection limit was 4.0 × 10(-7)M. The CL biosensor exhibited good storage stability, i.e., 90% of its initial response was retained after 2 months storage at pH 7.0. The present CL biosensor has been applied satisfactory to analysis of glucose in real serum and urine samples.
Assuntos
Técnicas Biossensoriais , Quitosana/química , Glucose/análise , Líquidos Iônicos/química , Nanopartículas Metálicas/química , Cobre/química , Enzimas Imobilizadas/química , Enzimas Imobilizadas/metabolismo , Glucose Oxidase/química , Glucose Oxidase/metabolismo , Ouro/química , Humanos , Peróxido de Hidrogênio/química , Concentração de Íons de Hidrogênio , Medições Luminescentes , Luminol/química , Prata/químicaRESUMO
Indolizine derivatives are of great interest as fluorescent emitters for peroxyoxalate chemiluminescence. The reaction of peroxyoxalates such as bis-(2,4,6-trichlorophenyl) oxalate (TCPO) with H2O2 can transfer energy to fluorescer via the formation of dioxetanedione intermediate. Four indolizine derivatives were used as a novel fluorescer in the chemiluminescence (CL) systems in this study. The relationship between CL intensity and the concentration of fluorescer, peroxyoxalate, sodium salicylate and hydrogen peroxide was investigated. Optimum conditions were obtained for four fluorescers and it was found that the indolizine can be used as an efficient green fluorescence emitter. Vitamin B6 induces a sharp decrease in the CL intensity of the TCPO-hydrogen peroxide-sodium salicylate system. A simple, rapid and sensitive CL method for the determination of vitamin B6 has been developed. The results showed a linear relationship between vitamin B6 concentration and peroxyoxalate CL intensity in the range 7.0 × 10(-8) -1.0 × 10(-4) . A detection limit of 2.3 × 10(-8) M and relative standard deviation (RSD) of < 4.5% were obtained.
Assuntos
Indolizinas/química , Medições Luminescentes/métodos , Vitamina B 6/análise , Análise de Alimentos/métodos , Peróxido de Hidrogênio/química , Concentração de Íons de Hidrogênio , Limite de Detecção , Substâncias Luminescentes/química , Musa/química , Oxalatos/química , Sensibilidade e Especificidade , Salicilato de Sódio/química , Comprimidos/análiseRESUMO
A novel chemiluminescence (CL) reaction, Benzodiazepines-H2O2-1-Ethyl-3-Methylimidazolium Ethylsulfate/copper, for determination of clonazepam and diazepam at nanogram per milliliter level in batch-type system have been described. The method relies on the catalytic effect of 1-Ethyl-3-Methylimidazolium Ethylsulfate/copper on the chemiluminescence reaction of Benzodiazepines, the oxidation of Benzodiazepines with hydrogen peroxide in natural medium. The influences of various experimental parameters such as solution pH, the ratio of 1-Ethyl-3 Methylimidazolium ethylsulfate concentration to copper ion, the type of buffer and the concentration of CL reagents were investigated. Under the optimum condition, the proposed method was satisfactorily applied for the determination of these drugs in tablets and urine without the interference of their potential impurities.
Assuntos
Clonazepam/urina , Cobre/química , Diazepam/urina , Imidazóis/química , Medições Luminescentes/métodos , Soluções Tampão , Calibragem , Catálise , Clonazepam/química , Diazepam/química , Humanos , Peróxido de Hidrogênio/química , Concentração de Íons de HidrogênioRESUMO
Furan derivatives (synthesized and purified in organic laboratories) are a great interest as fluorescent emitters for peroxyoxalate chemiluminescence. Reaction of peroxyoxalates such as bis-(2,4,6-trichloro-phenyl) oxalate with H(2)O(2) can transfer energy to fluorophore via formation of dioxetanedione intermediate. Furan derivatives used as a novel fluorescer in this study which produces a blue light in the chemiluminescence systems. The relationship between the chemiluminescence intensity and concentrations of TCPO, sodium salicylate, hydrogen peroxide and the fluorescer has been investigated. The linear ranges for Furan derivatives were 0.25-5 × 10(-4) M and 0.1-5 × 10(-4) M (A and B compounds, respectively). Kinetic parameters for the peroxyoxalate-chemiluminescence were also calculated from the computer fitting of the corresponding chemiluminescence intensity/time profiles.
Assuntos
Corantes Fluorescentes/química , Furanos/química , Peróxido de Hidrogênio/química , Medições Luminescentes , Oxalatos/química , Catálise , Cor , Furanos/análise , Salicilato de Sódio/químicaRESUMO
The solvatochromism of dihydroxybenzene derivatives as probes in 18 solvents were investigated in the UV-vis spectra. The position, intensity and shape of absorption bands change with various solvent nature. These changes were rationalized by solvatochromic parameters such as alpha, beta, ET(30), DN and AN using multiple linear regression (MLR) method. The studied dihydroxibenzene derivatives show negative solvatochromism and the correlation coefficients of derived equations by MLR method were obtained in the range 0.974-0.996. The linear solvation energy relationship parameters of the backward regression were applied to the Kamlet and Taft equation for the interaction of these three probes and solvents. The best LSER equation for these three probes, and the LSER parameters of backward regression with their mean effects and the regression coefficient have been calculated.
Assuntos
Benzeno/química , Hidrogênio/química , Solventes/química , Espectrofotometria/métodos , Hidroquinonas/química , Estrutura Molecular , Resorcinóis/químicaRESUMO
Effect of aliphatic amines and their concentration on fluorescence intensity of 4-methyl umbelliferone (4-MU) one of coumarin derivative were investigated. This compound has blue light emission under UV lamp in methanolic solution. Spectral investigation of 4-MU solution containing amine compounds showed lower intensity at 350-410 nm (quenching region) and higher intensity at 430-500 nm (enhancing region) as compared to pure methanolic solution of 4-MU. Fluorescence intensity at isoemitting point was independent from concentration of amines. The variation of fluorescence intensity could be used for determination of aliphatic amines in both quenching and enhancing region. Linear ranges for determination of amines in the quenching region were obtained from Stern-Volmer diagram of 4-MU. Determination of amines at fluorescence enhancing region using inverse fluorescence intensity against inverse amine concentration (bireciprocal plot) were investigated and related equations was also proposed.
Assuntos
Aminas/análise , Himecromona/análogos & derivados , Butilaminas/química , Himecromona/química , Metanol/química , Propilaminas/química , Compostos de Amônio Quaternário/química , Espectrometria de FluorescênciaRESUMO
The purpose of this study is to accesses the efficiency of removal of pesticide Mancozeb (Dithiocarbamates family) using different sorbents (synthetic zeolite type A, Humic Acid (HA) extracted from soil of Noshahr jungle in the north of Iran and mixture of them). The adsorption efficiency of the adsorbents was evaluated by Freundlich isotherms to select the best sorbent. The main effective parameters such as the amount of sorbents, pH, agitating time and concentrations of Mancozeb were tested. The results for 1.6 ppm of pesticide at pH=5 shows the optimum values 2, 0.75, 0.5 g for HA, zeolite NaA and mixture of them, respectively. The adsorption capacity decreases as pH increases and the adsorption effect for 0.1 g of sorbents at pH=5 were obtained in the order: (mixture of sorbents) > (synthetic zeolite type A) > (extracted Humic Acid).
Assuntos
Fungicidas Industriais/química , Maneb/química , Resíduos de Praguicidas/química , Poluentes do Solo/química , Zineb/química , Adsorção , Relação Dose-Resposta a Droga , Substâncias Húmicas , Concentração de Íons de Hidrogênio , Temperatura , Fatores de Tempo , Nicotiana/química , Zeolitas/químicaRESUMO
Oscillating chemical reactions are complex systems, involving a large number of chemical species. In oscillating chemical reaction, some species, usually a reaction intermediate, exhibit fluctuation in its concentration. In this report, visible oscillating chemiluminescence produced by the addition of luminol (3-aminophthalhydrazide) to the oscillating system of H2O2-KSCN-CuSO4-TMAOH was investigated using spectrofluorimetry method. The effects of ingredient concentration of the oscillating system and complexing agents like citric acid and cysteine on the behavior of the oscillating system were investigated. Moreover, the influence of nonaqueous solvents such as ethanol and ethylene glycol has been studied.
RESUMO
The quenching effect of triethylamine on strong chemiluminescence of bis-(2,4,6-trichlorophenyl)oxalate-hydrogen peroxide system in the presence of 7-amino-4-trifluoromethylcumarin was studied. The system resulted in a nice Stern-Volmer plot with a kQ value of 1.07 x 10(-3) M(-1), in the quencher concentration range of 1.52 x 10(-4) - 1.36 x 10(-3) M. The linear correlation between the decay rate constant of the resulting chemiluminescence and the quencher concentration was also investigated.
Assuntos
Cumarínicos/química , Etilaminas/química , Oxalatos/química , Fluorescência , Cinética , Medições Luminescentes , Modelos Químicos , Espectrometria de FluorescênciaRESUMO
Iranian firefly larvae, Lampyris turkestanicus collected from north of Iran and their luciferin were analyzed by HPLC, TLC, MS and spectroscopic Fourier transform ([FT]-IR, FT-NMR, UV and fluorescence) methods. The results showed that luciferin in L turkestanicus lanterns was the same as in the American firefly, Photinus pyralis and synthetic D-luciferin.