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1.
Sci Rep ; 9(1): 15273, 2019 Oct 24.
Artigo em Inglês | MEDLINE | ID: mdl-31649341

RESUMO

In direct methanol fuel cell technology, highly stable electrochemical catalysts are critically important for their practical utilization at the commercial scale. In this study, sub ~10 nm hollow Pt-Ni (1:1 at. ratio) nanoboxes supported on functionalized Vulcan carbon (Pt-Ni/C-R2) were synthesized through a facile method for the efficient electrooxidation of methanol. Two reaction procedures, namely, a simultaneous reduction and a modified sequential reduction method using a reverse microemulsion (RME) method, were adopted to synthesize solid Pt-Ni NPs and hollow nanoboxes, respectively. To correlate the alloy composition and surface structure with the enhanced catalytic activity, the results were compared with the nanocatalyst synthesized using a conventional NaBH4 reduction method. The calculated electroactive surface area for the Pt-Ni/C-R2 nanoboxes was 190.8 m2.g-1, which is significantly higher compared to that of the Pt-Ni nanocatalyst (96.4 m2.g-1) synthesized by a conventional reduction method. Hollow nanoboxes showed 34% and 44% increases in mass activity and rate of methanol oxidation reaction, respectively, compared to solid NPs. These results support the nanoreactor confinement effect of the hollow nanoboxes. The experimental results were supported by Density Functional Theory (DFT) studies, which revealed that the lowest CO poisoning of the Pt1Ni1 catalyst among all Ptm-Nin mixing ratios may account for the enhanced methanol oxidation. The synthesized hollow Pt-Ni/C (R2) nanoboxes may prove to be a valuable and highly efficient catalysts for the electrochemical oxidation of methanol due to their low cost, numerous catalytically active sites, low carbon monoxide poisoning, large electroactive surface area and long-term stability.

2.
ACS Omega ; 4(9): 13645-13657, 2019 Aug 27.
Artigo em Inglês | MEDLINE | ID: mdl-31497682

RESUMO

Arsenic is considered as a toxic heavy metal which is highly detrimental to ecological systems, and long-term exposure to it is highly dangerous to life as it can cause serious health effects. Timely detection of traces of active arsenic (As3+) is very crucial, and the development of simple, cost-effective methods is imperative to address the presence of arsenic in water and food chain. Herein, we present an extensive study on chemical-free electrogenerated nanotextured gold assemblage for the detection of ultralow levels of As3+ in water up to 0.08 ppb concentration. The gold nanotextured electrode (Au/GNE) is developed on simple Au foil via electrochemical oxidation-reduction sweeps in a metal-ion-free electrolyte solution. The ultrafine nanoscale morphological attributes of Au/GNE substrate are studied by scanning electron microscopy. Square wave anodic stripping voltammetry (ASV) response for different concentrations of arsenites is determined and directly correlated with As3+ detection regarding the type of electrolyte solution, deposition potential, and deposition time. The average of three standard curves are linear from 0.1 ppb up to 9 ppb (n = 15) with a linear regression coefficient R 2 = 0.9932. Under optimized conditions, a superior sensitivity of 39.54 µA ppb-1 cm-2 is observed with a lower detection limit of 0.1 ppb (1.3 nM) (based on the visual analysis of calibration curve) and 0.08 ppb (1.06 nM) (based on the standard deviation of linear regression). Furthermore, the electrochemical Au/GNE is also applicable for arsenic detection in a complex system containing Cu2+, Ni2+, Fe2+, Pb2+, Hg2+, and other ions for the selective and sensitive analysis. Au/GNE substrate also possesses remarkable reproducibility and high stability for arsenic detection during repeated analysis and thus can be employed for prolonged applications and reiterating analyses. This electrochemically generated nanotextured electrode is also applicable for As3+ detection and analysis in a real water sample under optimized conditions. Therefore, fabrication conditions and analytical and electroanalytical performances justify that because of its low cost, easy preparation method and assembly, high reproducibility, and robustness, nanosensor Au/GNE can be scaled up for further applications.

3.
Dalton Trans ; 48(11): 3714-3722, 2019 Mar 12.
Artigo em Inglês | MEDLINE | ID: mdl-30806439

RESUMO

In this study, a facile and potentially scalable synthesis of AgBiS2 (schapbachite) using melts of metal xanthates is presented; AgBiS2 is both a significant mineral and a technologically important material. This ternary material was synthesized by a novel and low-cost solventless route using simple ethyl xanthate complexes of silver and bismuth. p-XRD analysis indicates that the synthesized ternary material is highly crystalline and belongs to the cubic phase (schapbachite). The electrochemical properties of the material were tested; the potential of the synthesized material for application in charge storage shows a high specific capacitance of 460 F g-1 at 2 mV s-1. A capacitance retention of 83% with a 100% coulombic efficiency was observed after 3000 cycles. The charge storage potential, analysed by fabricating actual symmetrical devices, shows a specific capacitance of 14 F g-1 at 2 mV s-1. An energy density of 26 W h kg-1 and a power density of 3.6 kW kg-1 were observed. Besides, the potential for the oxygen evolution reaction was also studied. An overpotential of 414 mV and a Tafel slope of 134 mV dec-1 were obtained for water oxidation. The fabrication of an electrolyzer cell using the synthesized material as the cathode indicates that a current of 10 mA cm-2 can be achieved at a potential of 1.63 V.

4.
Chem Sci ; 9(45): 8553-8560, 2018 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-30568779

RESUMO

The development of efficient and selective nanostructured catalysts for industrially relevant hydrogenation reactions continues to be an actual goal of chemical research. In particular, the hydrogenation of nitriles and nitroarenes is of importance for the production of primary amines, which constitute essential feedstocks and key intermediates for advanced chemicals, life science molecules and materials. Herein, we report the preparation of graphene shell encapsulated Co3O4- and Co-nanoparticles supported on carbon by the template synthesis of cobalt-terephthalic acid MOF on carbon and subsequent pyrolysis. The resulting nanoparticles create stable and reusable catalysts for selective hydrogenation of functionalized and structurally diverse aromatic, heterocyclic and aliphatic nitriles, and as well as nitro compounds to primary amines (>65 examples). The synthetic and practical utility of this novel non-noble metal-based hydrogenation protocol is demonstrated by upscaling several reactions to multigram-scale and recycling of the catalyst.

5.
Dalton Trans ; 47(15): 5465-5473, 2018 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-29595861

RESUMO

A new organo-tin complex has been synthesized and used as a single source precursor for the synthesis of SnSe nanosheets by the hot injection method and thin films by the aerosol assisted chemical vapor deposition (AACVD) method. The films were deposited on glass substrates at three different temperatures. The textural quality and preferential growth were found to be significantly altered by changes in the deposition temperature. Oleylamine capped nanosheets and the as-deposited thin films by AACVD were characterized by powder X-ray diffraction (p-XRD) and microscopic techniques. The thin films were also studied by Raman spectroscopy. The stoichiometry is marginally affected by temperature, and all films were slightly selenium deficient. The synthesized material was also evaluated for the photoelectrochemical (PEC) splitting of water. The PEC study revealed the bifunctional nature of the material, which can be applied for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER), by switching the applied potential.

6.
ChemSusChem ; 11(3): 542-546, 2018 02 09.
Artigo em Inglês | MEDLINE | ID: mdl-29250932

RESUMO

Metal-organic frameworks (MOFs) are class of porous materials that can be assembled in a modular manner by using different metal ions and organic linkers. Owing to their tunable structural properties, these materials are found to be useful for gas storage and separation technologies, as well as for catalytic applications. A cost-effective zinc-based MOF ([Zn(bpcda)(bdc)]n ) is prepared by using N,N'-bis(pyridin-4-ylmethylene)cyclohexane-1,4-diamine [N,N'-bis(pyridin-4-ylmethylene)cyclohexane-1,4-diamine] and benzenedicarboxylic acid (bdc) linkers. This new material exhibits remarkable photoelectrochemical (PEC) catalytic activity in water splitting for the evolution of oxygen. Notably, this non-noble metal-based MOF, without requiring immobilization on other supports or containing metal particles, produced a highest photocurrent density of 31 µA cm-2 at 0.9 V, with appreciable stability and negligible photocorrosion. Advantageously for the oxygen evolution process, no external reagents or sacrificial agents are required in the aqueous electrolyte solution.


Assuntos
Técnicas Eletroquímicas/métodos , Estruturas Metalorgânicas/química , Compostos Orgânicos/química , Processos Fotoquímicos , Compostos de Zinco/química , Catálise , Análise Custo-Benefício , Ácidos Dicarboxílicos/química , Porosidade , Piridinas/química , Água/química
7.
Ultrason Sonochem ; 37: 669-675, 2017 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-28427681

RESUMO

This article presented the synthesis of a hybrid nanoarchitecture material composed of reduced graphene oxide (RGO) multiple sheets and ZnO nanowire arrays (NWAs) formed on an arbitrary ZnO coated fluorine doped tin oxide (FTO) substrates via pulse sonication and hydrothermal approach. The NWAs have high aspect-ratio, high density, apt positioning and well-ordered formation. FESEM images demonstrated that RGO layers have been effectively intercalated between and on the accessible surfaces of the ZnO NWAs. The diameter of ZnO nanowires is 80-150nm and length about 1-2µm. Raman spectrum of hybrid material exhibited characteristic D and suppressed G peaks for graphene and E2 mode at 437cm-1 for ZnO NWAs. UV-visible spectrum indicated slight red shift towards visible range after formation of RGO/ZnO NWAs heterostructure. The Photoelectrochemical results indicated higher current densities for RGO/ZnO NWAs heterostructure due to water oxidation reaction at the working electrode compared to pristine ZnO NWAs.

8.
Dalton Trans ; 45(38): 14928-39, 2016 Oct 14.
Artigo em Inglês | MEDLINE | ID: mdl-27549401

RESUMO

Pristine Mn2O3 and Ag-Mn2O3 composite thin films have been developed on fluorine doped tin oxide (FTO) coated glass substrates at 450 °C by aerosol assisted chemical vapor deposition (AACVD) using a methanol solution of a 1 : 2 mixture of acetatoargentate(i), Ag(CH3COO), and a newly synthesized manganese complex, [Mn(dmae)2(TFA)4] (1) (dmae = N,N-dimethylaminoethanolate, TFA = trifluoroacetate). The phase purity and stoichiometric composition of the films were investigated by X-ray diffraction (XRD) and Raman spectroscopy techniques. Energy dispersive X-ray (EDX) and X-ray photoelectron spectroscopy (XPS) analyses revealed a Ag to Mn ratio of 1 : 2 and further confirmed the uniform dispersion of Ag nanoparticles into the Mn2O3 structure. Optical studies showed a direct band gap of 2.0 eV for the pristine Mn2O3 film that was lowered to 1.8 eV for Ag-Mn2O3 due to the plasmonic interaction of Ag with Mn2O3. The Ag-Mn2O3 composite film displayed enhanced photocatalytic activity in photoelectrochemical (PEC) water splitting and yielded a photocurrent of 3 mA cm(-2) at 0.7 V versus Ag/AgCl which was 1.6 times higher than a pristine Mn2O3 film alone, under AM 1.5 G illumination (100 mW cm(-2)). The high PEC efficiency is mainly due to the plasmonic effect of Ag nanoparticles, which enhances the visible light absorption, efficient electron-hole separation and high carrier mobility of the Ag-Mn2O3 photoelectrode. The charge carrier density of Ag-Mn2O3 is two times higher than the pristine Mn2O3 as calculated by the Mott-Schottky plot. Based on the PEC studies a mechanism is proposed to elucidate the high activity of Ag-Mn2O3 in PEC water splitting.

9.
Talanta ; 153: 83-98, 2016 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-27130094

RESUMO

The inorganic nitrate (NO3‾) anion is present under a variety of both natural and artificial environmental conditions. Nitrate is ubiquitous within the environment, food, industrial and physiological systems and is mostly present as hydrated anion of a corresponding dissolved salt. Due to the significant environmental and toxicological effects of nitrate, its determination and monitoring in environmental and industrial waters are often necessary. A wide range of analytical techniques are available for nitrate determination in various sample matrices. This review discusses biosensors available for nitrate determination using the enzyme nitrate reductase (NaR). We conclude that nitrate determination using biosensors is an excellent non-toxic alternative to all other available analytical methods. Over the last fifteen years biosensing technology for nitrate analysis has progressed very well, however, there is a need to expedite the development of nitrate biosensors as a suitable alternative to non-enzymatic techniques through the use of different polymers, nanostructures, mediators and strategies to overcome oxygen interference.


Assuntos
Técnicas Biossensoriais , Humanos , Nitrato Redutase , Nitratos , Óxidos de Nitrogênio , Oxigênio
10.
Dalton Trans ; 45(25): 10222-32, 2016 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-27230711

RESUMO

Cobalt titanate-titania composite oxide films have been grown on FTO-coated glass substrates using a single-source heterometallic complex [Co2Ti4(µ-O)6(TFA)8(THF)6]·THF () which was obtained in quantitative yield from the reaction of diacetatocobalt(ii) tetrahydrate, tetraisopropoxytitanium(iv), and trifluoroacetic acid from a tetrahydrofuran solution. Physicochemical investigations of complex have been carried out by melting point, FT-IR, thermogravimetric and single-crystal X-ray diffraction analyses. CoTiO3-TiO2 films composed of spherical objects of various sizes have been grown from by aerosol-assisted chemical vapor deposition at different temperatures of 500, 550 and 600 °C. Thin films characterized by XRD, Raman and X-ray photoelectron spectroscopy, scanning electron microscopy, energy-dispersive X-ray analysis have been explored for electrochemical detection of dopamine (DA). The cyclic voltammetry with the CoTiO3-TiO2 electrode showed a DA oxidation peak at +0.215 V while linear sweep voltammetry displayed a detection limit (LoD) of 0.083 µM and a linear concentration range of 20-300 µM for DA. Thus, the CoTiO3-TiO2 electrode is a potential candidate for the sensitive and selective detection of DA.


Assuntos
Cobalto/química , Dopamina/análise , Titânio/química , Técnicas Eletroquímicas , Eletrodos , Vidro/química , Temperatura Alta , Limite de Detecção , Microscopia Eletrônica de Varredura , Espectroscopia Fotoeletrônica , Análise Espectral Raman , Temperatura de Transição , Difração de Raios X
11.
Langmuir ; 31(38): 10599-609, 2015 Sep 29.
Artigo em Inglês | MEDLINE | ID: mdl-26327251

RESUMO

The transportation and accumulation of redox active species at the buried interface between glassy carbon electrodes and plasticized polymeric membranes have been studied using synchrotron radiation X-ray photoelectron spectroscopy (SR-XPS), near edge X-ray absorption fine structure (NEXAFS), in situ electrochemical Fourier transform infrared-attenuated total reflectance (FTIR-ATR) spectroscopy, cyclic voltammetry (CV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS). Ferrocene tagged poly(vinyl chloride) [FcPVC], ferrocene (Fc), and its derivatives together with tetracyanoquinodimethane (TCNQ) doped plasticized polymeric membrane electrodes have been investigated, so as to extend the study of the mechanism of this reaction chemistry to different time scales (both small and large molecules with variable diffusion coefficients) using a range of complementary electrochemical and surface analysis techniques. This study also provides direct spectroscopic evidence for the transportation and electrochemical reactivity of redox active species, regardless of the size of the electrochemically reactive molecule, at the buried interface of the substrate electrode. With all redox dopants, when CA electrolysis was performed, redox active species were undetectable (<1 wt % of signature elements or below the detection limit of SR-XPS and NEXAFS) in the outermost surface layers of the membrane, while a high concentration of redox species was located at the electrode substrate as a consequence of the deposition of the reaction product (Fc(+)-anion complex) at the buried interface between the electrode and the membrane. This reaction chemistry for redox active species within plasticized polymeric membranes may be useful in the fashioning of multilayered polymeric devices (e.g., chemical sensors, organic electronic devices, protective laminates, etc.) based on an electrochemical tunable deposition of redox molecules at the buried substrate electrode beneath the membrane.


Assuntos
Carbono/química , Plastificantes/química , Polímeros/química , Eletrodos , Oxirredução , Propriedades de Superfície
12.
Eur J Med Chem ; 95: 464-72, 2015 May 05.
Artigo em Inglês | MEDLINE | ID: mdl-25841201

RESUMO

Two new gold(I) complexes that contain tri-ter-butylphosphine and dialkyl dithiocarbamate ligands were synthesized and characterized by FTIR, NMR spectroscopy, Cyclic voltammetry, elemental analysis and X-ray diffraction. The in vitro cytotoxicity of both complexes was examined against A549 (lung cancer), MCF7 (breast cancer), and HeLa (cervical cancer) human cancer cell lines. Both complexes exhibit very strong in vitro cytotoxic effects against A549, MCF7 and HeLa cell lines. The screening of the cytotoxic activity based on IC50 data against the A549, MCF7, and HeLa lines shows that the synthesized gold(I) complexes are highly effective, particularly against HeLa cancer cell line. Based on IC50 data, the cytotoxic activity of both complexes is better than well-known commercial anticancer drug cisplatin against all the three cancer lines tested.


Assuntos
Antineoplásicos/síntese química , Antineoplásicos/farmacologia , Ouro/química , Compostos Organometálicos/síntese química , Compostos Organometálicos/farmacologia , Fosfinas/química , Tiocarbamatos/química , Antineoplásicos/química , Linhagem Celular Tumoral , Técnicas de Química Sintética , Desenho de Fármacos , Ensaios de Seleção de Medicamentos Antitumorais , Eletroquímica , Humanos , Ligantes , Compostos Organometálicos/química
13.
Anal Chim Acta ; 851: 78-86, 2014 Dec 03.
Artigo em Inglês | MEDLINE | ID: mdl-25440668

RESUMO

Three new calixarene Tl(+) ionophores have been utilized in Tl(+) ion-selective electrodes (ISEs) yielding Nernstian response in the concentration range of 10(-2)-10(-6)M TlNO3 with a non-optimized filling solution in a conventional liquid contact ISE configuration. The complex formation constants (logßIL) for two of the calixarene derivatives with thallium(I) (i.e. 6.44 and 5.85) were measured using the sandwich membrane technique, with the other ionophore immeasurable due to eventual precipitation of the ionophore during these long-term experiments. Furthermore, the unbiased selectivity coefficients for these ionophores displayed excellent selectivity against Zn(2+), Ca(2+), Ba(2+), Cu(2+), Cd(2+) and Al(3+) with moderate selectivity against Pb(2+), Li(+), Na(+), H(+), K(+), NH4(+) and Cs(+), noting that silver was the only significant interferent with these calixarene-based ionophores. When optimizing the filling solution in a liquid contact ISE, it was possible to achieve a lower limit of detection of approximately 8nM according to the IUPAC definition. Last, the new ionophores were also evaluated in four solid-contact (SC) designs leading to Nernstian response, with the best response noted with a SC electrode utilizing a gold substrate, a poly(3-octylthiophene) (POT) ion-to-electron transducer and a poly(methyl methacrylate)-poly(decyl methacrylate) (PMMA-PDMA) co-polymer membrane. This electrode exhibited a slope of 58.4mVdecade(-1) and a lower detection limit of 30.2nM. Due to the presence of an undesirable water layer and/or leaching of redox mediator from the graphite redox buffered SC, a coated wire electrode on gold and graphite redox buffered SC yielded grossly inferior detection limits against the polypyrrole/PVC SC and POT/PMMA-PDMA SC ISEs that did not display signs of a water layer or leaching of SC ingredients into the membrane.


Assuntos
Calixarenos/química , Eletrodos Íon-Seletivos , Tálio/análise , Acrilamidas/química , Interações Hidrofóbicas e Hidrofílicas , Ionóforos/química , Limite de Detecção , Membranas Artificiais , Polimetil Metacrilato/química , Tálio/química
14.
BMC Genomics ; 15: 840, 2014 Oct 02.
Artigo em Inglês | MEDLINE | ID: mdl-25277059

RESUMO

BACKGROUND: Oysters impart significant socio-ecological benefits from primary production of food supply, to estuarine ecosystems via reduction of water column nutrients, plankton and seston biomass. Little though is known at the molecular level of what genes are responsible for how oysters reproduce, filter nutrients, survive stressful physiological events and form reef communities. Neuropeptides represent a diverse class of chemical messengers, instrumental in orchestrating these complex physiological events in other species. RESULTS: By a combination of in silico data mining and peptide analysis of ganglia, 74 putative neuropeptide genes were identified from genome and transcriptome databases of the Akoya pearl oyster, Pinctata fucata and the Pacific oyster, Crassostrea gigas, encoding precursors for over 300 predicted bioactive peptide products, including three newly identified neuropeptide precursors PFGx8amide, RxIamide and Wx3Yamide. Our findings also include a gene for the gonadotropin-releasing hormone (GnRH) and two egg-laying hormones (ELH) which were identified from both oysters. Multiple sequence alignments and phylogenetic analysis supports similar global organization of these mature peptides. Computer-based peptide modeling of the molecular tertiary structures of ELH highlights the structural homologies within ELH family, which may facilitate ELH activity leading to the release of gametes. CONCLUSION: Our analysis demonstrates that oysters possess conserved molluscan neuropeptide domains and overall precursor organization whilst highlighting many previously unrecognized bivalve idiosyncrasies. This genomic analysis provides a solid foundation from which further studies aimed at the functional characterization of these molluscan neuropeptides can be conducted to further stimulate advances in understanding the ecology and cultivation of oysters.


Assuntos
Crassostrea/genética , Neuropeptídeos/genética , Pinctada/genética , Proteômica , Sequência de Aminoácidos , Animais , Mineração de Dados , Genoma/genética , Dados de Sequência Molecular , Neuropeptídeos/química , Pinctada/metabolismo
15.
Eur J Med Chem ; 84: 343-63, 2014 Sep 12.
Artigo em Inglês | MEDLINE | ID: mdl-25036793

RESUMO

Fourteen new organotin(IV) complexes with general formula R2SnL2 or R3SnL where R = CH3, C2H5, C4H9, C6H5, C6H11, CH2-C6H5, C(CH3)3, C8H17 and L = N-[(2-methoxyphenyl)]-4-oxo-4-[oxy]butanamide were synthesized and characterized by elemental analyses, FT-IR, NMR ((1)H, (13)C and (119)Sn), mass spectrometry and single crystal X-ray structural analysis. Crystallographic data for four triorganotin(IV) complexes (R3SnL, R = CH3, C2H5, C4H9, CH2-C6H5) showed the tin has approximate trigonal bipyramidal geometry with the R groups in the trigonal plane. The carboxylate groups of ligands L bridge adjacent tin atoms, resulting in polymeric chains. In case of the diorganotin(IV) derivatives a six-coordinate geometry at the tin atom is proposed from spectroscopic evidence. The Me-Sn-Me bond angle in complex 7 was determined from the (2)J[(119)Sn-(1)H] value as 166.3° that falls in the range of six-coordinate geometry. The ligand and its complexes (1-14) were screened for their antimicrobial, antitumor, cytotoxic and antileishmanial activities and found to be biologically active. The ligand and its complexes bind to DNA via intercalative interactions resulting in hypochromism and minor bathochromic shifts as confirmed by UV-visible spectroscopy. Based on in vitro studies such as the potato disc method, the synthesized compounds were found to possess significant antitumor activity. Also, from cytotoxicity and DNA interaction studies, these compounds can also be used for the prevention and treatment of cancer. Gel electrophoresis assay was used to investigate the damage to double stranded super coiled plasmid pBR322 DNA by the synthesized compounds and compounds 1 and 7 were found to cause the maximum damage. All the synthesized compounds exhibit strong antileishmanial activity that was even higher than that of Amphotericin B, with significant cytotoxicity. This study, therefore, demonstrated the potential use of these compounds as source of novel agents for the treatment of leishmaniasis.


Assuntos
Antibacterianos/farmacologia , Antifúngicos/farmacologia , Antiprotozoários/farmacologia , DNA de Cadeia Simples/efeitos dos fármacos , Compostos Orgânicos de Estanho/síntese química , Compostos Orgânicos de Estanho/farmacologia , Animais , Antibacterianos/síntese química , Antibacterianos/química , Antifúngicos/síntese química , Antifúngicos/química , Antiprotozoários/síntese química , Antiprotozoários/química , Artemia/efeitos dos fármacos , Bactérias/efeitos dos fármacos , Cristalografia por Raios X , DNA de Cadeia Simples/química , Relação Dose-Resposta a Droga , Fungos/efeitos dos fármacos , Humanos , Leishmania/efeitos dos fármacos , Ligantes , Testes de Sensibilidade Microbiana , Modelos Moleculares , Estrutura Molecular , Compostos Orgânicos de Estanho/química , Testes de Sensibilidade Parasitária , Tumores de Planta/microbiologia , Plasmídeos , Solanum tuberosum/efeitos dos fármacos , Solanum tuberosum/microbiologia , Relação Estrutura-Atividade
16.
Anal Chem ; 85(21): 10495-502, 2013 Nov 05.
Artigo em Inglês | MEDLINE | ID: mdl-24080025

RESUMO

The ion-to-electron transduction reaction mechanism at the buried interface of the electrosynthesized poly(3-octylthiophene) (POT) solid-contact (SC) ion-selective electrode (ISE) polymeric membrane has been studied using synchrotron radiation-X-ray photoelectron spectroscopy (SR-XPS), near edge X-ray absorption fine structure (NEXAFS), and electrochemical impedance spectroscopy (EIS)/neutron reflectometry (NR). The tetrakis[3,5-bis(triflouromethyl)phenyl]borate (TFPB(-)) membrane dopant in the polymer ISE was transferred from the polymeric membrane to the outer surface layer of the SC on oxidation of POT but did not migrate further into the oxidized POT SC. The TFPB(-) and oxidized POT species could only be detected at the outer surface layer (≤14 Ǻ) of the SC material, even after oxidation of the electropolymerized POT SC for an hour at high anodic potential demonstrating that the ion-to-electron transduction reaction is a surface confined process. Accordingly, this study provides the first direct structural evidence of ion-to-electron transduction in the electropolymerized POT SC ISE by proving TFPB(-) transport from the polymeric ISE membrane to the oxidized POT SC at the buried interface of the SC ISE. It is inferred that the performance of the POT SC ISE is independent of the thickness of the POT SC but is instead contingent on the POT SC surface reactivity and/or electrical capacitance of the POT SC. In particular, the results suggest that the electropolymerized POT conducting polymer may spontaneously form a mixed surface/bulk oxidation state, which may explain the unusually high potential stability of the resulting ISE. It is anticipated that this new understanding of ion-to-electron transduction with electropolymerized POT SC ISEs will enable the development of new and improved devices with enhanced analytical performance attributes.


Assuntos
Elétrons , Eletrodos Íon-Seletivos , Polímeros/química , Tiofenos/química , Propriedades de Superfície
17.
Analyst ; 138(15): 4266-9, 2013 Aug 07.
Artigo em Inglês | MEDLINE | ID: mdl-23714844

RESUMO

Cyclic voltammetry (CV), synchrotron radiation-X-ray photoelectron spectroscopy (SR-XPS) and near edge X-ray absorption fine structure (NEXAFS) show that oxidation of ferrocene tagged PVC induces an accumulation of high molecular weight polymer at the buried interface between the substrate electrode and the plasticized membrane.


Assuntos
Compostos Ferrosos/metabolismo , Plastificantes/química , Cloreto de Polivinila/metabolismo , Transporte Biológico/fisiologia , Eletrodos , Compostos Ferrosos/análise , Metalocenos , Espectroscopia Fotoeletrônica/métodos , Cloreto de Polivinila/análise
18.
Anal Chim Acta ; 744: 39-44, 2012 Sep 26.
Artigo em Inglês | MEDLINE | ID: mdl-22935372

RESUMO

A nitrate ion-selective electrode (ISE) employing a permeable tubular membrane impregnated with a conventional ISE cocktail has been used successfully in the coulometric analysis of nitrate in fresh waters. The liquid ISE membrane comprising a nitrate ionophore [tridodecylmethylammonium nitrate (TDMAN)], lipophilic electrolyte [tetradodecyl-ammoniumtetrakis(4-chlorophenyl)borate (ETH 500)] and plasticizer [bis(3-ethyl-hexyl)sebacate (DOS)] was supported on a porous polypropylene tube. Coulometric analysis with the tubular membrane ISE showed that nitrate could be detected in the range 10-100 µM with a precision of 2.3% relative standard deviation (RSD), limit of detection of 1.1 µM and relative accuracy of 4.4% compared to a certified reference material (CRM) Lake sample.

19.
Anal Chem ; 84(14): 6158-65, 2012 Jul 17.
Artigo em Inglês | MEDLINE | ID: mdl-22703479

RESUMO

Seawater analysis is one of the most challenging in the field of environmental monitoring, mainly due to disparate concentration levels between the analyte and the salt matrix causing interferences in a variety of analytical techniques. We propose here a miniature electrochemical sample pretreatment system for a rapid removal of NaCl utilizing the coaxial arrangement of an electrode and a tubular Nafion membrane. Upon electrolysis, chloride is deposited at the Ag electrode as AgCl and the sodium counterions are transported across the membrane. This cell was found to work efficiently at potentials higher than 400 mV in both stationary and flow injection mode. Substantial residual currents observed during electrolysis were found to be a result of NaCl back diffusion from the outer side of the membrane due to insufficient permselectivity of the Nafion membrane. It was demonstrated that the residual current can be significantly reduced by adjusting the concentration of the outer solution. On the basis of ion chromatography results, it was found that the designed cell used in flow injection electrolysis mode reduced the NaCl concentration from 0.6 M to 3 mM. This attempt is very important in view of nutrient analysis in seawater where NaCl is a major interfering agent. We demonstrate that the pretreatment of artificial seawater samples does not reduce the content of nitrite or nitrate ions upon electrolysis. A simple diffusion/extraction steady state model is proposed for the optimization of the electrolysis cell characteristics.

20.
Biosens Bioelectron ; 26(11): 4270-5, 2011 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-21592768

RESUMO

A bilayer amperometric nitrate biosensor with an integrated permselective layer has been developed for exclusion of inorganic anion and cation interferences. The inner PPy(polypyrrole)-NaR-NADH layer of the biosensor is formed by galvanostatic polymerization of pyrrole (Py) in presence of nitrate reductase (NaR) and nicotinamide adenine dinucleotide (NADH), followed by formation of the outer permselective poly-ortho-phenylenediamine (P-o-PDA) layer by potentiodynamic polymerization of ortho-phenylenediamine (o-PDA). The exclusion efficiency (E(eff)) of the outer layer in rejecting inorganic cation and anion interferences is evaluated by a new proposed relationship. 73-87% and 47-84% of anion and cation interferences, respectively, were efficiently rejected with the permselective layer. Further improvement in the exclusion efficiency for cations was accomplished by combining the use of the outer layer with the addition of 1mM EDTA into the measurement solution. The addition of EDTA improved the E(eff) achieved for cation rejection by 10-40% to give net E(eff) of 89-94%. The inclusion of the outer layer also aided the retention of NaR and NADH in the inner PPy-NaR-NADH layer and, hence, enabled improved amperometric detection of nitrate, achieving a detection limit of 0.20 µM and a linear concentration range of 10-500 µM with a 3.4%rsd (n=10).


Assuntos
Técnicas Biossensoriais/métodos , Nitratos/análise , Técnicas Biossensoriais/estatística & dados numéricos , Cátions/análise , Eletroquímica , Limite de Detecção , Fenilenodiaminas , Polímeros , Pirróis
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