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1.
Molecules ; 29(17)2024 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-39275073

RESUMO

Thorium is a radionuclide used in various environmental studies such as dating, sediment movement, soil-plant transfer studies, and contamination of waste from the natural fuel cycle. The liquid-liquid extraction method using tri-n-butyl phosphate (TBP) allows for the separation of Th from the accompanying actinides. However, the separation of Th and U present in the same sample is not trivial. This separation is influenced by the starting acid (HCl or HNO3), the concentration of TBP in an organic solvent, and the concentration of the acid used for re-extracting Th, which is typically HCl. Therefore, it is necessary to study these factors to ensure that the method has sufficient chemical yield and selectivity in complex matrices. This study presents a systematic investigation of the aforementioned parameters, making the necessary variations to select an optimal method for the radiochemical separation of Th. The ideal conditions were obtained using 4 M HCl as the acid prior to extraction, a 1:4 solution of TBP in xylene, and 4 M HCl as the re-extracting agent. The accuracy and precision were studied in four intercomparison exercises conducted in quadruplicate, using the parameters Enumbers, RB(%), and RSD(%) for 232Th and 230Th. The sensitivity of the method was experimentally studied and the limit of detection (LoD) was determined according to ISO 11929:2005. Additionally, the linearity of the method showed that the experimental and theoretical activity concentrations of 232Th and 230Th had slopes of 1 with an intercept close to 0.

2.
Toxicol Appl Pharmacol ; 449: 116114, 2022 08 15.
Artigo em Inglês | MEDLINE | ID: mdl-35690110

RESUMO

Tri-n-butyl phosphate (TnBP) is a widely used organophosphate ester, but its effects on the regenerative process under damaging circumstances remain unknown. In the present study, zebrafish larvae were exposed to 0, 50, 100, 200 and 1000 µg/L TnBP, and the caudal fins were cut at 72 hours post fertilization (hpf). First, after exposure to TnBP, the number of total neutrophils decreased together with decreased neutrophils in the tail, and TnBP inhibited chemotaxis. Second, reactive oxygen species (ROS) levels in the zebrafish decreased greatly. Following exposure to TnBP, transcription levels of many genes regulating fin regeneration, such as fgf20a, fgfr1a, bmp2a and bmp4, were significantly downregulated, while inflammatory factors such as cxcl8a, cxcl18b, il-6, and tnfa were abnormally upregulated. In addition, TnBP inhibited the regenerative area after caudal fin amputation. The inflammatory state was adverse during the regenerative process. In summary, TnBP exposure is immunotoxic and decreases oxidative stress in injured zebrafish larvae.


Assuntos
Neutrófilos , Peixe-Zebra , Animais , Larva , Organofosfatos , Peixe-Zebra/genética , Proteínas de Peixe-Zebra/genética
3.
Molecules ; 27(2)2022 Jan 16.
Artigo em Inglês | MEDLINE | ID: mdl-35056872

RESUMO

The article presents data on the solvent extraction separation of rare-earth elements (REEs), such as La(III), Ce(III), Pr(III), and Nd(III), using synergic mixtures of methyltrioctylammonium nitrate (TOMANO3) with tri-n-butyl phosphate (TBP) from weakly acidic nitrate solutions. Specifically, experimental results on separation of REEs, for the pair Ce(III)/Pr(III) for quaternary mixtures of REEs (La(III), Ce(III), Pr(III), Nd(III)) and for the pair La(III)/Pr(III) for solutions containing La(III), Pr(III), and Nd(III), are presented. It was shown that effective separation for the pair Ce(III)/Pr(III) from a solution containing 219 g Ce(III)/L, 106 g La(III)/L, 20 g Pr(III)/L, 55 g Nd(III)/L, and 0.1 mol/L HNO3, was achieved using 56 steps of a multistage, counter-current solvent extraction cascade with scrubbing, at an organic-to-aqueous phase volume ratio (O/A) equal to 2/1 on the extraction section and O/A equal to 4/1 on the scrubbing section, using 3.3 mol/L solutions of the mixture TOMANO3-TBP with molar ratio 0.15:0.85 in dodecane. Separation for the pair La(III)/Pr(III) could be achieved using a solvent extraction cascade with scrubbing in 32 steps at O/A equal to 2/1 on the extraction section and O/A equal to 2.8/1 on the scrubbing section of the solvent extraction cascade from a solution containing 258 g La(III)/L, 58 g Pr(III)/L, 141 g Nd(III)/L, and 0.1 mol/L HNO3 with 3.0 mol/L solution of the mixture TOMANO3-TBP with molar ratio 0.2:0.8 in dodecane.

4.
Curr Opin Colloid Interface Sci ; 55: 101479, 2021 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-34149296

RESUMO

We provide here a general view on the interactions of surfactants with viruses, with a particular emphasis on how such interactions can be controlled and employed for inhibiting the infectivity of enveloped viruses, including coronaviruses. The aim is to provide to interested scientists from different fields, including chemistry, physics, biochemistry, and medicine, an overview of the basic properties of surfactants and (corona)viruses, which are relevant to understanding the interactions between the two. Various types of interactions between surfactant and virus are important, and they act on different components of a virus such as the lipid envelope, membrane (envelope) proteins and nucleocapsid proteins. Accordingly, this cannot be a detailed account of all relevant aspects but instead a summary that bridges between the different disciplines. We describe concepts and cover a selection of the relevant literature as an incentive for diving deeper into the relevant material. Our focus is on more recent developments around the COVID-19 pandemic caused by SARS-CoV-2, applications of surfactants against the virus, and on the potential future use of surfactants for pandemic relief. We also cover the most important aspects of the historical development of using surfactants in combatting virus infections. We conclude that surfactants are already playing very important roles in various directions of defence against viruses, either directly, as in disinfection, or as carrier components of drug delivery systems for prophylaxis or treatment. By designing tailor-made surfactants, and consequently, advanced formulations, one can expect more and more effective use of surfactants, either directly as antiviral compounds or as part of more complex formulations.

5.
Environ Toxicol ; 35(12): 1326-1333, 2020 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-32662595

RESUMO

Organophosphate flame retardants (OPFRs) have become a growing concern due to their potential environmental and health risk. However, limited studies have described the toxicity, particularly neurotoxicity of alkyl and aromatic OPFRs. This study investigated the neurotoxicity of alkyl tri-n-butyl phosphate (TnBP) and aromatic tricresyl phosphate (TCP) to rat adrenal pheochromocytoma (PC12) cells for 24 h. Viability detection showed dose-response toxicity effect of TCP and TnBP to PC12 cells. The half-maximal inhibitory concentration of 24 h (24 h-IC50 ) of TCP and TnBP were 2415.61 and 338.09 µM, respectively. Both TnBP and TCP significantly changed the acetylcholinesterase (AChE) activity, and TnBP is more likely to cause neurotoxicity to PC12 cells compared to TCP. Also, The results of LDH and caspase-3 activity detection as well as Hoechst staining suggested that cell apoptosis induced by TCP and TnBP may be the primary pathway. These findings provide a toxicity data of aromatic and alkyl-substituted OPFRs to PC12 cells, and a new insight into the toxicity of OPFRs on health risk assessment.


Assuntos
Apoptose/efeitos dos fármacos , Retardadores de Chama/toxicidade , Neurônios/efeitos dos fármacos , Organofosfatos/toxicidade , Tritolil Fosfatos/toxicidade , Acetilcolinesterase/metabolismo , Animais , Caspase 3/metabolismo , Sobrevivência Celular/efeitos dos fármacos , Relação Dose-Resposta a Droga , Neurônios/enzimologia , Neurônios/patologia , Células PC12 , Ratos
6.
Environ Res ; 172: 289-295, 2019 05.
Artigo em Inglês | MEDLINE | ID: mdl-30822562

RESUMO

This study evaluates for the first time organophosphorus flame retardant (OPFR) occurrence in the Alboran Sea delphinids (Spain). OPFRs were detected in all the individuals with concentration levels up to 24.7 µg/g lw. Twelve out of sixteen tested analytes were detected, being TBOEP which presented the highest detection frequency, and IDPP which presented the highest levels of concentration. OPFR distribution in different tissues (blubber, brain, kidney, muscle and liver) was evaluated. The pattern distribution showed the highest contribution for blubber (mean value of 68%) and the lowest contribution for liver (mean value of 2%). Seven OPFRs were detected in brain samples showing their capacity to surpass the blood-brain barrier and reach the brain. Moreover, high affinity for the brain tissue was observed. This is extremely important due to the neurotoxic effects of several compounds such as TCEP and TNBP. OPFR levels were compared with previously published PBDE concentrations, and no significant differences were observed. Taking into account the lower use and lower bioaccumulation and biomagnification capacities of OPFRs, this could indicate an additional OPFR source of pollution in addition to their use as FRs.


Assuntos
Golfinhos , Retardadores de Chama , Plastificantes , Animais , Retardadores de Chama/análise , Oceanos e Mares , Compostos Organofosforados/análise , Plastificantes/análise , Espanha , Distribuição Tecidual
7.
Chemphyschem ; 16(12): 2653-62, 2015 Aug 24.
Artigo em Inglês | MEDLINE | ID: mdl-26149535

RESUMO

We present new results on the liquid-liquid extraction of uranium (VI) from a nitric acid aqueous phase into a tri-n-butyl phosphate/1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (TBP/[C4 mim][Tf2 N]) phase. The individual solubilities of the ionic-liquid ions in the upper part of the biphasic system are measured over the whole acidic range and as a function of the TBP concentration. New insights into the extraction mechanism are obtained through the in situ characterization of the extracted uranyl complexes by coupling UV/Vis and extended X-ray absorption fine structure (EXAFS) spectroscopy. We propose a chemical model to explain uranium (VI) extraction that describes the data through a fit of the uranyl distribution ratio DU . In this model, at low acid concentrations uranium (VI) is extracted as the cationic complex [UO2 (TBP)2 ](2+) , by an exchange with one proton and one C4 mim(+) . At high acid concentrations, the extraction proceeds through a cationic exchange between [UO2 (NO3 )(HNO3 )(TBP)2 ](+) and one C4 mim(+) . As a consequence of this mechanism, the variation of DU as a function of TBP concentration depends on the C4 mim(+) concentration in the aqueous phase. This explains why noninteger values are often derived by analysis of DU versus [TBP] plots to determine the number of TBP molecules involved in the extraction of uranyl in an ionic-liquid phase.

8.
Chemosphere ; 334: 138972, 2023 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-37230301

RESUMO

Tri-n-butyl phosphate (TnBP) is commonly used as flame retardant and rubber plasticizer, and has been widely detected in aquatic organisms and natural waters. However, the potential toxicity of TnBP in fish remains unclear. In the present study, silver carp (Hypophthalmichthys molitrix) larvae were treated with environmentally relevant concentrations (100 or 1000 ng/L) of TnBP for 60 d and then they were depurated in clean water for 15 d, and the accumulation and depuration of the chemical in six tissues of silver carp were measured. Furthermore, effects on growth were evaluated and potential molecular mechanisms were explored. Results indicated that TnBP could be rapidly accumulated and depurated in silver carp tissues. In addition, the bio-accumulation of TnBP displayed tissue-specificity, where intestine contained the greatest and vertebra had the smallest level of TnBP. Furthermore, exposure to environmentally relevant concentrations of TnBP led to time- and concentration-dependent growth inhibition of silver carp, even though TnBP was completely depurated in tissues. Mechanistic studies suggested that exposure to TnBP up- and down-regulated the expression of ghr and igf1 in liver, respectively, and increased GH contents in plasma of silver carp. TnBP exposure also up-regulated the expression of ugt1ab and dio2 in liver, as well as decreased T4 contents in plasma of silver carp. Our findings provide direct evidence of health hazards of TnBP to fish in natural waters, calling for more attention of environmental risks of TnBP in aquatic environment.


Assuntos
Carpas , Animais , Bioacumulação , Organofosfatos/metabolismo , Fígado/metabolismo
9.
Environ Sci Pollut Res Int ; 30(36): 85578-85591, 2023 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-37389749

RESUMO

As an emerging flame retardant, organic phosphate flame retardants have been extensively used worldwide. The aim of this study is to determine the effects of TnBP on neurobehavior of Caenorhabditis elegans (C. elegans) and its mechanisms. L1 larvae of wild-type nematodes (N2) were exposed to TnBP of 0, 0.1, 1, 10, and 20 mg/L for 72 hours. Then, we observed that the body length and body width were inhibited, the head swings were increased, the pump contractions and chemical trend index were reduced, the production of reactive oxygen species (ROS) was increased, and the expression of mitochondrial oxidative stress related genes (mev-1 and gas-1) and P38 MAPK signal pathway-related genes (pmk-1, sek-1, and nsy-1) was altered. After reporter gene strains BZ555, DA1240, and EG1285 were exposed to TnBP of 0, 0.1, 1, 10, and 20 mg/L for 72 hours, the synthesis of dopamine, glutamate, and Gamma-Amino Butyric Acid (GABA) was increased. In addition, the pmk-1 mutants (KU25) led to the sensitivity of C. elegans to TnBP in terms of head swings. The results showed that TnBP had harmful effects on the neurobehavior of C. elegans, oxidative stress might be one of the mechanisms of its neurotoxicity, and P38 MAPK signal pathway might play an important regulatory role in this process. The results revealed the potential adverse effects of TnBP on the neurobehavior of C. elegans.


Assuntos
Proteínas de Caenorhabditis elegans , Caenorhabditis elegans , Animais , Proteínas de Caenorhabditis elegans/genética , Proteínas de Caenorhabditis elegans/metabolismo , Proteínas de Caenorhabditis elegans/farmacologia , Proteínas Quinases p38 Ativadas por Mitógeno/metabolismo , Organofosfatos/farmacologia
10.
Heliyon ; 9(3): e14302, 2023 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-36967953

RESUMO

Organophosphate esters (OPEs) are extensively manufactured and used in China. Whether exposure to OPEs during pregnancy increases the risk of gestational diabetes mellitus (GDM) is unknown. Between 2011 and 2012, a case-control study including 130 and 67 women with and without GDM, respectively, was conducted in Hangzhou, China. The levels of 10 OPEs in maternal serum samples at delivery were quantified, and the relationships between the OPE concentrations and GDM risk were investigated. The results show that in all participants, tri-n-butyl phosphate (TNBP, median: 2.02 ng/mL) was the most common OPE present in the serum, followed by tri-phenyl phosphate (TPHP, median: 1.74 ng/mL) and tri-iso-butyl phosphate (median: 1.68 ng/mL). With one-unit elevation in the tris (2-chloroethyl) phosphate, TNBP, TPHP, and tris (2-butoxy ethyl) phosphate (TBOEP) concentrations in maternal serum, 1-h glucose levels increased by 0.19 (95% confidence interval (CI): -0.01, 0.29), 0.11 (95% CI: -0.18, 0.62), 0.29 (95% CI: 0.12, 0.58), and 0.20 units (95% CI: 0.01, 0.44), respectively. In addition, a unit increase in TBOEP levels in maternal serum was associated with an increase of 0.26 units (95% CI: 0.09, 0.61) in 2-h glucose levels. After adjusting for covariate factors, serum TNBP (odds ratio (OR) = 2.07; 95% CI: 1.27, 3.41), TBOEP (OR = 2.63; 95% CI: 1.68, 4.11), and TPHP (OR = 1.03; 95% CI: 1.05, 1.51) concentrations were associated with GDM incidence in pregnant women. Overall, TNBP, TBOEP, and TPHP exposure during pregnancy is associated with GDM risk and increased glucose levels.

11.
AIChE J ; 67(7): e17219, 2021 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-34219744

RESUMO

The synergic solvent extraction system of tri-n-butyl phosphate (TBP) and FeCl3 (or ionic liquids, ILs) has been extensively studied for selective extraction of Li from Mg-containing brines. However, Cyanex 923 (C923), which extracts many metals stronger than TBP, has not yet been examined for Li/Mg separation. Here, we report on the unexpected observation that the C923/FeCl3 system has opposite Li/Mg selectivity compared to the TBP/FeCl3 system. Detailed investigations show that the opposite selectivity of the C923/FeCl3 (or IL) system is due to three factors: (1) the strong extraction of Fe by C923 leads to a low concentration of [FeCl4]- in the system, which is essential for Li extraction; (2) C923 in combination with an IL extracts Mg strongly by an ion-pair mechanism; (3) most importantly, C923 extracts Mg by solvation, resulting in an insufficient concentration of C923 for Li extraction. The unexpected poor Li/Mg selectivity of C923 highlights the irreplaceable role of TBP in the selective recovery of Li.

12.
J Colloid Interface Sci ; 587: 229-239, 2021 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-33360895

RESUMO

Alkyl phosphates were extensively used in liquid-liquid extraction of lanthanides and actinides, but to a lesser extent for alkali and alkaline earth metals. The high amount of alkyl phosphate, which is usually used in the organic layer (>40 wt%), is not favoured due to its corrosive effect and toxicity. In the present work, diluted chloroform solutions (20.0 mM) of tri-n-butyl phosphate (TBP), tris(2-ethylhexyl) phosphates (TRIS) and bis(2-ethylhexyl) phosphate (BIS) were investigated for their extraction of Li, Na, K, Mg and Ca ions. The extraction experiments were conducted on 7.0 M HNO3 aqueous solutions containing 60.0 mM of metal ions in binary (Li+ and Mg2+), ternary (Li+, Na+ and K+) and quinary (Li+, Na+, K+, Mg2+ and Ca2+) mixtures. The Li+ selectivity over Mg2+ was very high in the binary system. Remarkably, increasing HNO3 concentration in the aqueous layer had opposing effect on the extraction of Li+ (positive) and Mg2+ (negative). However, the selectivity for Li+ became less dramatic in the case of ternary and quinary system, though the selectivity varied with initial metal concentrations. The amounts of water and NO3- transferred into the organic layer demonstrated their synergistic effect on extracting metal ions. In the ternary and quinary systems, the total concentrations of metal ions in the organic layer (ranged from 49 to 85 mM) were higher than the concentration of ligand in the organic layer (20.0 mM), suggesting that metal ions may be extracted into water/ligand/NO3- aggregates in the organic layer. TBP, TRIS and BIS do not have significant difference in their extraction behaviour. The FTIR results indicated formation of P+-O-M+/M2+ in the solid TBP/metal complex.

13.
AIChE J ; 67(7): e17213, 2021 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-34219743

RESUMO

Several molecular polar solvents have been used as solvents of the more polar phase in the solvent extraction (SX) of metals. However, the use of hydrophilic ionic liquids (ILs) as solvents has seldomly been explored for this application. Here, the hydrophilic IL ethylammonium nitrate (EAN), has been utilized as a polar solvent in SX of transition metal nitrates by tri-n-butyl phosphate (TBP). It was found that the extraction from EAN is considerably stronger than that from a range of molecular polar solvents. The main species of Co(II) and Fe(III) in EAN are likely [Co(NO3)4]2- and [Fe(NO3)4]-, respectively. The extracted species are likely Fe(TBP)3(NO3)3 and a mixture of Co(TBP)2(NO3)2 and Co(TBP)3(NO3)2. The addition of H2O or LiCl to EAN reduces the extraction because the metal cations coordinate to water molecules and chloride ions stronger than to nitrate ions. This study highlights the potential of using hydrophilic ILs to enhance SX of metals.

14.
Mar Pollut Bull ; 149: 110490, 2019 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-31445349

RESUMO

Microplastics and organophosphate esters are ubiquitous pollutants in the marine environment. However, their interactions are poorly understood. In the present study, the sorptions of tri-n-butyl phosphate (TnBP) and tris(2-chloroethyl) phosphate (TCEP) on polyethylene (PE) and polyvinyl chloride (PVC) microplastics in seawater were investigated. Results indicated that the first-order kinetic model and pseudo-second-order were suitable to describe PE and PVC microparticles for the adsorption of the two organophosphate esters, respectively. The adsorption capacity increased with the decrease in particle size. The highest adsorption capacity appeared at 15 °C. The equilibrium isotherms data for the adsorption of the two organophosphate esters on PVC and PE microplastics were best fitted with Freundlich isotherm model and Langmuir isotherm model, respectively. The pore-filling mechanism involved in the adsorption of TnBP and TCEP on PVC microplastics and the monolayer coverage was the predominant mechanism for the adsorption of TnBP and TCEP on PE microplastics.


Assuntos
Microplásticos , Plásticos , Polietileno , Cloreto de Polivinila , Adsorção , Cinética , Organofosfatos , Tamanho da Partícula , Fosfatos , Água do Mar , Poluentes Químicos da Água/análise
15.
Biotechnol J ; 14(8): e1800646, 2019 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-30810288

RESUMO

Continuous virus inactivation (VI) remains one of the missing pieces while the biopharma industry moves toward continuous manufacturing. The challenges of adapting VI to the continuous operation are two-fold: 1) achieving fluid homogeneity and 2) a narrow residence time distribution (RTD) for fluid incubation. To address these challenges, a dynamic active in-line mixer and a packed-bed continuous virus inactivation reactor (CVIR) are implemented, which act as a narrow RTD incubation chamber. The developed concept is applied using solvent/detergent (S/D) treatment for inactivation of two commonly used model viruses. The in-line mixer is characterized and enables mixing of the viscous S/D chemicals to ±1.0% of the target concentration in a small dead volume. The reactor's RTD is characterized and additional control experiments confirm that the VI is due to the S/D action and not induced by system components. The CVIR setup achieves steady state rapidly before two reactor volumes and the logarithmic reduction values of the continuous inactivation process are identical to those obtained by the traditional batch operation. The packed-bed reactor for continuous VI unites fully continuous processing with very low-pressure drop and scalability.


Assuntos
Biotecnologia/instrumentação , Biotecnologia/métodos , Solventes , Inativação de Vírus , Animais , Vírus da Diarreia Viral Bovina/patogenicidade , Desenho de Equipamento , Cinética , Vírus da Leucemia Murina/patogenicidade
16.
Environ Pollut ; 234: 389-395, 2018 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-29202417

RESUMO

Tri-n-butyl phosphate (TBP) is widely used in various industrial processes and has been detected in all environmental matrices. So far, little work has been done regarding the metabolism of TBP on terrestrial invertebrates. We investigated the metabolism of TBP in the earthworm, Perionyx excavatus, after acute exposure to TBP for one and two days in filter paper contact test, as well as after chronic exposure for 28 days in soil experiment. Biotransformation products were identified by using liquid chromatography coupled with quadrupole time-of-flight mass spectrometry, and by exploiting the information dependent acquisition in tandem mass spectrometry. TBP exhibited low accumulation in earthworm-soil ecosystem at 10 mg/kg and 50 mg/kg. The presence of earthworms significantly enhanced TBP degradation at 50 mg/kg in soil. Dibutyl phosphate and hydroxylated TBP were the major phase I metabolites. Three novel phase II metabolites were identified: ethanol dibutyl phosphate and its sulfate conjugate, and the phosphate conjugate of hydroxylated TBP. Hydroxylation and further phosphorylation dominated metabolism in chronic exposure. An extensive metabolic pathway of TBP in earthworm was proposed. This is the first report of TBP metabolism in terrestrial invertebrates and highlights the necessity to identify metabolites of contaminants when evaluating their bioaccumulation and toxicity.


Assuntos
Oligoquetos/metabolismo , Organofosfatos/farmacocinética , Poluentes do Solo/farmacocinética , Animais , Biotransformação , Ecossistema , Organofosfatos/metabolismo , Solo/química , Sulfatos/metabolismo
17.
Spectrochim Acta A Mol Biomol Spectrosc ; 173: 328-334, 2017 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-27682218

RESUMO

A systematic photoluminescence based investigation was carried out to understand the complexation of Eu3+ with different ligands (TBP: tri-n-butyl phosphate, DHOA: di-n-hexyl octanamide, Cyanex 923: tri-n-alkyl phosphine oxide and Cyanex 272: Bis (2,4,4 trimethyl) pentyl phosphinic acid) used for preferential separation of lanthanides and actinides in various stages of nuclear fuel cycle. In case of TBP and DHOA complexes, 3 ligand molecules coordinated in monodentate fashion and 3 nitrate ion in bidentate fashion to Eu3+ to satisfy the 9 coordination of Eu. In case of Cyanex 923 and Cyanex 272 complexes, 3 ligand molecules, 3 nitrate ion and 3 water molecules coordinated to Eu3+ in monodentate fashion. The Eu complexes of TBP and DHOA were found to have D3h local symmetry while that for Cyanex 923 and Cyanex 272 were C3h. Judd-Ofelt analysis of these systems revealed that the covalency of EuO bond followed the trend DHOA>TBP>Cyanex 272>Cyanex 923. Different photophysical properties like radiative and non-radiative life time, branching ratio for different transitions, magnetic and electric dipole moment transition probabilities and quantum efficiency were also evaluated and compared for these systems. The magnetic dipole transition probability was found to be almost independent of ligand field perturbation while electric dipole transition probability for 5D0-7F2 transition was found to be hypersensitive with ligand field with a trend DHOA>TBP>Cyanex 272>Cyanex 923.

18.
Food Chem ; 217: 660-667, 2017 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-27664684

RESUMO

A multiresidue method for the determination of 17 emerging contaminants in vegetables was developed based on ultrasound-assisted matrix solid-phase dispersion (MSPD). The analysis was performed using isotope dilution gas chromatography tandem mass spectrometry. In the development of the MSPD procedure, different parameters such as sonication and the type of sorbent or extraction solvent were assayed. Manual and in situ derivatization was assayed and the chromatographic response was higher when the reaction takes place in the injection port. The limits of detection obtained for the studied compounds were in the range of 0.1-0.4ngg(-1) for the different vegetables analyzed. The developed method was applied to vegetables obtained from several local markets. At least one of the organophosphates was detected in the analyzed samples at levels ranging from 0.6 to 4.6ngg(-1) and bisphenol A was detected in all the samples at concentration up to 16ngg(-1).


Assuntos
Compostos Benzidrílicos/análise , Compostos Benzidrílicos/isolamento & purificação , Contaminação de Alimentos/análise , Fenóis/análise , Fenóis/isolamento & purificação , Extração em Fase Sólida/métodos , Verduras/química , Cromatografia Gasosa-Espectrometria de Massas , Extração em Fase Sólida/instrumentação , Espectrometria de Massas em Tandem/métodos
19.
Food Chem ; 196: 673-81, 2016 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-26593541

RESUMO

Organophosphate esters (OPEs) are common flame retardants that are used in a wide variety of products. These compounds might migrate into and pollute food products. An analytical method involving an improved approach called the "quick, easy, cheap, effective, rugged, and safe" (QuEChERS) method and ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) was developed to simultaneously measure trace levels of nine OPEs in milk powder. Separation of the nine OPEs was optimized on a reversed-phase column within 7 min. The stable isotope tri-n-butyl phosphate-d27 (TBP-d27) was used as an internal standard. This method was validated in terms of its linearity, sensitivity, precision, accuracy and matrix effects. Matrix-matched calibration curves were constructed with 1/x(2) as the weighting factor for all of the target compounds resulting in coefficients of regression lines between 0.9938 and 0.9999. The average accuracy was between 73.5% and 110.2%. Intra- and inter-assay precisions for six replicates ranged from 3.9% to 8.9% or below 11%, respectively. The limits of detection (LODs) were in the range of 0.1-0.25 µg/kg, and the limits of quantification (LOQs) were below 1.5 µg/kg. Significant matrix effects have been observed, but suppression or enhancement of the signal was compensated for by the use of an isotopically labeled internal standard. This validated method was successfully applied to determine the concentrations of the OPEs in milk powder.


Assuntos
Cromatografia Líquida de Alta Pressão/métodos , Ésteres/química , Retardadores de Chama/análise , Contaminação de Alimentos/análise , Leite/química , Organofosfatos/química , Espectrometria de Massas em Tandem/métodos , Animais , Limite de Detecção
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