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1.
Mar Pollut Bull ; 155: 111170, 2020 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-32469780

RESUMO

Microplastic occurrence and composition were investigated along the Polish coast (southern Baltic Sea) on 12 beaches differing in terms of intensity of their touristic exploitation, urbanisation and sediment characteristics. Their mean concentrations varied between 76 and 295 items per kg dry sediment. Fibres and plastic fragments were the dominant microplastic types. Overall, no relationship was found between their concentrations and sediment characteristics. Fine sediments were not identified as microplastic pollution traps. The highest microplastic concentrations were recorded at some urban beaches indicating that population density and the level of coastal infrastructure development are important factors affecting microplastic pollution level on beaches. On the other hand, microplastic concentrations in national parks did not differ substantially from the other beaches. Our results suggest that sediment accumulation processes may exceed microplastic accumulation, and overcome the effect of tourism and/or urbanisation, highlighting the role of the beach hydrodynamic status in structuring beach microplastic pollution.

2.
J Pharm Biomed Anal ; 169: 49-59, 2019 May 30.
Artigo em Inglês | MEDLINE | ID: mdl-30836246

RESUMO

A method for the enantioseparation of sutezolid, the next analogue after linezolid and tedizolid, belonging to the truly new class of antibacterial agents, the oxazolidinones, was developed based on non-aqueous capillary electrophoresis (NACE), using a single isomer of cyclodextrins as a chiral pseudophase. During the experiment, the enantioseparation of sutezolid together with its predecessor, linezolid, both weak base antibacterial agents, was evaluated using anionic single-isomers of cyclodextrins from hydrophilic, up to hydrophobic: heptakis-(2,3-dihydroxy-6-sulfo)-ß-cyclodextrin, heptakis-(2,3-diacetyl-6-sulfo)-ß-cyclodextrin (HDAS-ß-CD), as well as heptakis-(2,3-dimethyl-6-sulfo)-ß-cyclodextrin (HDMS-ß-CD), respectively. Based on the observed results, the cyclodextrins, HDAS-ß-CD and HDMS-ß-CD which carry the acetyl and methyl groups at the C2 and C3 positions, respectively, provided the baseline separation of sutezolid enantiomers. However, HDMS-ß-CD led to a reversal of enantiomer migration order (EMO) in comparison to HDAS-ß-CD. Instead, enantiomers of linezolid were separated only by HDMS-ß-CD. During the experiments, different organic solvents and their mixtures in various ratios were tested. The selectivity and separation efficiency were critically affected by the nature of the buffer system, the type of organic solvent, and the concentrations of trifluoroacetic acid (TFA) in the NACE buffer system. Focusing on the desired EMO in which the eutomers (S)-sutezolid and (S)-linezolid migrated last, the highest enantioresolution using the NACE method was achieved at normal polarity mode with 45 mM HDMS-ß-CD dissolved in MeOH/ACN (85:15, v/v) containing 200 mM TFA/20 mM ammonium formate. Moreover, infrared spectroscopy, NMR and molecular modelling were investigated to provide information about complex formation.


Assuntos
Ciclodextrinas/química , Oxazolidinonas/química , Eletroforese Capilar/métodos , Linezolida/química , Espectroscopia de Ressonância Magnética/métodos , Modelos Moleculares , Espectrofotometria Infravermelho/métodos , Estereoisomerismo , Tetrazóis/química , beta-Ciclodextrinas/química
3.
Curr Med Chem ; 26(38): 6878-6895, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-30289065

RESUMO

Surface Enhanced Raman Spectroscopy (SERS) has a long history as an ultrasensitive platform for the detection of biological species from small aromatic molecules to complex biological systems as circulating tumor cells. Thanks to unique properties of graphene, the range of SERS applications has largely expanded. Graphene is efficient fluorescence quencher improving quality of Raman spectra. It contributes also to the SERS enhancement factor through the chemical mechanism. In turn, the chemical flexibility of Reduced Graphene Oxide (RGO) enables tunable adsorption of molecules or cells on SERS active surfaces. Graphene oxide composites with SERS active nanoparticles have been also applied for Raman imaging of cells. This review presents a survey of SERS assays employing graphene or RGO emphasizing the improvement of SERS enhancement brought by graphene or RGO. The structure and physical properties of graphene and RGO will be discussed too.


Assuntos
Grafite/química , Análise Espectral Raman/métodos , Técnicas Biossensoriais/métodos , Diagnóstico , Humanos , Oxirredução , Nanomedicina Teranóstica
4.
Artigo em Inglês | MEDLINE | ID: mdl-29857258

RESUMO

Adsorption of molecules of DNA (deoxyribonucleic acid) or modified DNA on gold surfaces is often the first step in construction of many various biosensors, including biosensors for detection of DNA with a particular sequence. In this work we study the influence of amine and thiol modifications at the 3' ends of single stranded DNA (ssDNA) molecules on their adsorption on the surface of gold substrates and on the efficiency of hybridization of immobilized DNA with the complementary single stranded DNA. The characterization of formed layers has been carried out using infrared spectroscopy and atomic force microscopy. As model single stranded DNA we used DNA containing 20 adenine bases, whereas the complementary DNA contained 20 thymine bases. We found that the bands in polarization modulation-infrared reflection-adsorption spectroscopy (PM-IRRAS) spectra of layers formed from thiol-modified DNA are significantly narrower and sharper, indicating their higher regularity in the orientation of DNA on gold surface when using thiol linker. Also, hybridization of the layer of thiol-modified DNA containing 20 adenine bases with the respective DNA containing thymine bases leads to formation of much more organized structures than in the case of unmodified DNA or DNA with the amine linker. We conclude that the thiol-modified ssDNA is more promising for the preparation of biosensors, in comparison with the amine-modified or unmodified ssDNA. We have also found that the above-mentioned modifications at the 3' end of ssDNA significantly influence the IR spectrum (and hence the structure) of polycrystalline films formed from such compounds, even though adsorbed fragments contain less than 5% of the DNA chain. This effect should be taken into account when comparing IR spectra of various polycrystalline films formed from modified and unmodified DNA.


Assuntos
Aminas/química , DNA de Cadeia Simples/química , Ouro/química , Hibridização de Ácido Nucleico , Compostos de Sulfidrila/química , Adenina/química , Adsorção , Microscopia de Força Atômica , Oligonucleotídeos/química , Espectrofotometria Infravermelho , Timina/química
5.
Bioconjug Chem ; 27(12): 2900-2910, 2016 Dec 21.
Artigo em Inglês | MEDLINE | ID: mdl-27748604

RESUMO

With the advent of nanotechnology, carbon nanomaterials such as carbon nanofibers (CNF) have aroused substantial interest in various research fields, including energy storage and sensing. Further improvement of their properties might be achieved via the application of viral particles such as bacteriophages. In this report, we present a filamentous M13 bacteriophage with a point mutation in gene VII (pVII-mutant-M13) that selectively binds to the carbon nanofibers to form 3D structures. The phage-display technique was utilized for the selection of the pVII-mutant-M13 phage from the phage display peptide library. The properties of this phage make it a prospective candidate for a scaffold material for CNFs. The results for binding of CNF by mutant phage were compared with those for maternal bacteriophage (pVII-M13). The efficiency of binding between pVII-mutant-M13 and CNF is about 2 orders of magnitude higher compared to that of the pVII-M13. Binding affinity between pVII-mutant-M13 and CNF was also characterized using atomic force microscopy, scanning electron microscopy, and transmission electron microscopy, which confirmed the specificity of the interaction of the phage pVII-mutant-M13 and the CNF; the binding occurs via the phage's ending, where the mutated pVII protein is located. No similar behavior has been observed for other carbon nanomaterials such as graphite, reduced graphene oxide, single-walled carbon nanotubes, and multiwalled carbon nanotubes. Infrared spectra confirmed differences in the interaction with CNF between the pVII-mutant-M13 and the pVII-M13. Basing on conducted research, we hypothesize that the interactions are noncovalent in nature, with π-π interactions playing the dominant role. Herein, the new bioconjugate material is introduced.


Assuntos
Bacteriófago M13/química , Bacteriófago M13/metabolismo , Nanofibras/química , Bacteriófago M13/genética , Grafite/química , Microscopia de Força Atômica , Microscopia Eletrônica de Varredura , Microscopia Eletrônica de Transmissão , Espectroscopia Fotoeletrônica , Mutação Puntual , Espectrofotometria Infravermelho
6.
Langmuir ; 30(38): 11329-39, 2014 Sep 30.
Artigo em Inglês | MEDLINE | ID: mdl-25229461

RESUMO

Combination of surface analytical techniques was employed to investigate the interfacial behavior of the two designed lipids-N-stearoylglycine (1) and its bulky neutral headgroup-containing derivative N-stearoylvaline ethyl ester (2)-at the air-solution interface and as transferred layers on different substrates. Formation of monolayers at the air-water interface was monitored on pure water and on aqueous solutions of different pH. Crystallization effects were visualized at pure water by recording the hystereses in the Langmuir-Blodgett (LB) isotherms and by transferring the layers onto mica, gold (111), and ITO (indium-tin oxide on glass) electrodes. Subphase pH affects the morphology and patch formation in monolayers of 1, as evidenced by BAM measurements. At pH 8.2, formation of well-ordered crystallites is observed, which upon compression elongate according to predominantly 1-D growth mechanism to form a dense layer of crystallites. This effect is not observed in monolayers of 2, whose headgroup is not protonated. The orientation of layers of 1 transferred to the solid supports is also pH dependent, and their stability can be related to formation of a hydrogen-bonded networks. AFM images of 1 exhibited platelets of multilayer phase. The IR spectra of the ITO substrates covered by 1 indicated formation of hydrogen bonds between the amide groups. The nature of the adsorption layer and its organization as a function of potential were studied in-depth by EC STM using Au(111) as the substrate. A model showing the arrangement of hydrogen bonds between adsorbed molecules is presented and related to the observed organization of the layer.

7.
Chemphyschem ; 14(1): 116-24, 2013 Jan 14.
Artigo em Inglês | MEDLINE | ID: mdl-23203943

RESUMO

Interactions between the π bonds in the aromatic rings of polyaniline (PANI) with carbon nanostructures (CNs) facilitate charge transfer between the two components. Different types of phenyleneamine-terminated CNs, including carbon nano-onions (CNOs) and single-walled and multi-walled carbon nanotubes (SWNTs and MWNTs, respectively), were prepared as templates, and the CN/PANI nanocomposites were easily prepared with uniform core-shell structures. By varying the ratio of the aniline monomers relative to the CNs in the in situ chemical polymerization process, the thickness of the PANI layers was effectively controlled. The morphological and electrical properties of the nanocomposite were determined and compared. The thickness and structure of the PANI films on the CNs were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and infrared spectroscopy. TEM and SEM revealed that the composite films consisted of nanoporous networks of CNs coated with polymeric aniline. The electrochemical properties of the composites were investigated by cyclic voltammetry and electrochemical impedance spectroscopy. These studies showed that the CN/PANI composite films had lower resistance than pure polymeric films of PANI, and the presence of CNs much improved the mechanical stability. The specific electrochemical capacitance of the CNO/PANI composite films was significantly larger than for pure PANI.

8.
Phys Chem Chem Phys ; 14(29): 10332-44, 2012 Aug 07.
Artigo em Inglês | MEDLINE | ID: mdl-22735160

RESUMO

The helical peptide Cys-Ala-Lys-(Glu-Ala-Ala-Ala-Lys)(2)-Ala-NH-(CH(2))(2)-SH has been organized forming a self-assembled monolayer on gold (0.602 peptides per nm(2)), its conductance behavior under stretching conditions being studied using scanning tunnelling microscopy and current sensing atomic force microscopy. The helical conformation of the peptide has been found to play a fundamental role in the conductance. Moreover, variation of the current upon molecular stretching indicates that peptides can be significantly elongated before the conductance drops to zero, the critical elongation being 1.22 ± 0.47 nm. Molecular dynamics simulations of a single peptide in the free state and of a variable number of peptides tethered to a gold surface (i.e. densities ranging from 0.026 to 1.295 peptides per nm(2)) have indicated that the helical conformation is intrinsically favored in solvated environments while in desolvated environments it is retained because of the fundamental role played by peptide-peptide intermolecular interactions. The structure obtained for the system with 24 tethered peptides, with a density of 0.634 peptides per nm(2) closest to the experimental one, is in excellent agreement with experimental observations. On the other hand, simulations in which a single molecule is submitted to different compression and stretching processes while the rest remain in the equilibrium have been used to mimic the variation of the tip-substrate distance in experimental measures. Results allowed us to identify the existence, and in some cases coexistence, of intermolecular and intramolecular ionic ladders, suggesting that peptide-mediated electron transfer occurs through the hopping mechanism. Finally, quantum mechanical calculations have been used to investigate the variation of the electronic structure upon compression and stretching deformations.


Assuntos
Fenômenos Mecânicos , Oligopeptídeos/química , Fenômenos Biomecânicos , Transporte de Elétrons , Elétrons , Simulação de Dinâmica Molecular , Estrutura Secundária de Proteína , Teoria Quântica , Água/química
9.
Chemistry ; 18(9): 2600-8, 2012 Feb 27.
Artigo em Inglês | MEDLINE | ID: mdl-22262451

RESUMO

Small multilayer fullerenes, also known as carbon nano-onions (CNOs; 5-6 nm in diameter, 6-8 shells), show higher reactivity than other larger carbon nanostructures. Here we report the first example of an in situ polymerization of aniline on phenyleneamine-terminated CNO surfaces. The green, protonated, conducting emeraldine polyaniline (PANI) was directly synthesized on the surface of the CNO. The functionalized and soluble CNO/PANI composites were characterized by TEM, SEM, DSC, Raman, and infrared spectroscopy. The electrochemical properties of the conducting CNO/PANI films were also investigated. In comparison with pristine CNOs, functionalized carbon nanostructures show dramatically improved solubility in protic solvents, thus enabling their easy processing for coatings, nanocomposites, and biomedical applications.


Assuntos
Compostos de Anilina/química , Carbono/química , Fulerenos/química , Nanocompostos/química , Nanoestruturas/química , Nanotecnologia , Solubilidade
10.
Bioelectrochemistry ; 80(1): 43-8, 2010 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-20630809

RESUMO

Applicability of poly-o-aminophenol (POAP) as a redox mediator for fungal laccase is investigated. Laccase has been entrapped by means of electrochemical polymerization. The obtained layers have been characterized by cyclic voltammetry, as well as by spectroscopic methods. The enzyme activity has been verified by the standard test using syringaldazine. Laccase immobilized in the POAP matrix catalyses oxygen reduction without any additional mediators. POAP is able to mediate the electron transfer between the enzyme active site and the electrode surface similarly to poly-o-phenylenediamine which has been studied previously, but its redox potential is shifted significantly towards positive values. The role of laccase in electrodeposition of POAP has been studied. It has been found that the presence of the enzyme influences the structure of electrodeposited films. Furthermore, laccase facilitates the electrodeposition. The monomer-o-aminophenol (OAP) belongs to typical laccase substrates. The polymer can be precipitated from the solution containing the monomer and laccase. The morphology of POAP formed by laccase differs from typical polymer samples synthesized chemically or electrochemically. It contains round microstructures composed of nano-needles. Laccase is therefore a promising polymerization initiator for synthesis of nanostructured conducting polymers.


Assuntos
Galvanoplastia/métodos , Lacase/química , Polímeros/química , Eletrodos , Galvanoplastia/instrumentação , Enzimas Imobilizadas , Lacase/metabolismo , Microscopia Eletrônica de Varredura , Prata/química , Compostos de Prata/química , Espectrofotometria Ultravioleta
11.
Dalton Trans ; 39(3): 730-5, 2010 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-20066218

RESUMO

Self-assembled monolayers of dithiolated neutral monotetraazamacrocyclic complexes of copper(II) and nickel(II) can provide molecularly defined platforms for the formation of a pseudorotaxane-like nanostructures on the gold electrode surface. We propose these complexes as pi-donor building blocks for the construction of new molecular devices. We show that these perpendicularly oriented macrocyclic complexes anchored to the electrode surface act as pi-electron rich species interacting with pi-electron deficient compounds dissolved in solution, such as fluorine derivatives of tetracyanoquinodimethane (F(4)TCNQ) or a charged bismacrocyclic tetraaza complex of copper(II). The interactions of the surface immobilized macrocyclic complexes with F(4)TCNQ and with ring-shaped acceptor molecules are monitored and characterized by linear scan voltammetry. The interactions with the bismacrocyclic compound lead to a new pseudorotaxane array supported on the electrode surface and switched on and off by the application of appropriate potentials.

12.
Anal Chim Acta ; 625(2): 137-44, 2008 Sep 12.
Artigo em Inglês | MEDLINE | ID: mdl-18724987

RESUMO

In this work, a new concept of the solid-state sensors free from EMF instabilities is proposed. In order to prevent the formation of an aqueous layer underneath the ion-selective membrane, instead of improving the hydrophobicity of the monolayer, the moieties terminated with acrylate groups were incorporated within the redox-active monolayer structure. It allowed to "sew" all phases of the sensor (i.e., the transducer, the intermediate layer and the ion-selective membrane) and to obtain a stable and durable ion-selective sensor. It is shown that newly designed monolayer containing both the ferrocene- and the acrylate-terminated molecules does not affect the working parameters of the electrode, such as selectivity or the slope of the calibration curve, although the EMF drift of the sensor is significantly reduced to 0.2 mV per day.


Assuntos
Acrilatos/química , Compostos Ferrosos/química , Eletrodos Íon-Seletivos , Membranas Artificiais , Sítios de Ligação , Calibragem , Eletroquímica , Ouro/química , Interações Hidrofóbicas e Hidrofílicas , Íons/química , Microscopia de Força Atômica/instrumentação , Microscopia de Força Atômica/métodos , Estrutura Molecular , Oxirredução , Potenciometria/instrumentação , Potenciometria/métodos , Reprodutibilidade dos Testes , Sensibilidade e Especificidade , Espectroscopia de Luz Próxima ao Infravermelho/instrumentação , Espectroscopia de Luz Próxima ao Infravermelho/métodos , Propriedades de Superfície , Fatores de Tempo
13.
Bioelectrochemistry ; 71(1): 99-106, 2007 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-17081808

RESUMO

The crown ethers with electro- and photoactive azo moieties containing substituents with mobile protons such as in the -COOH groups of histidine, show unique effect of pH switched on/off presence of the azo form. The differences observed for the electrochemical behavior of azocrown ethers with N-acetylhistidine and imidazole moieties reveal the interference of a chemical reduction pathway in strongly acidified solutions. This chemical reduction process leads to the formation of a hydrazine derivative which can be detected by its further electroreduction on the electrode surface. The involvement of chemical reduction is seen clearly in the presence of mobile protons of the -COOH group and mercury as the electrode substrate. The behaviour of the N-acetylhistidine azomacrocyle is similar to that of compounds known to exist in quinone-hydrazone tautomeric equilibria.


Assuntos
Compostos Azo/química , Éteres de Coroa/química , Histidina/química , Hidrazinas/análise , Benzoquinonas/química , Ácidos Carboxílicos/química , Eletroquímica , Eletrodos , Histidina/análogos & derivados , Hidrazonas/química , Concentração de Íons de Hidrogênio , Imidazóis/química , Espectroscopia de Ressonância Magnética , Mercúrio/química , Oxirredução , Prótons , Soluções/química , Espectrofotometria Ultravioleta , Análise Espectral Raman , Propriedades de Superfície
14.
Bioelectrochemistry ; 66(1-2): 79-87, 2005 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-15833706

RESUMO

We develop a concept of fabrication of the multilayer network films on electrodes by exploring the ability of a Keggin-type polyoxometallate, phosphododecamolybdate (PMo(12)O(40)(3-)), to form stable anionic monolayers (templates) on carbon and metals including platinum. By repeated alternate treatments in the solution of PMo(12)O(40)(3-) (or in the colloidal suspension of polyoxometallate-protected Pt-nanoparticles) and in the solution of monomer (e.g. anilinium) cations, the amount of the material can be increased systematically (layer-by-layer) to form stable three-dimensional assemblies on electrode (e.g. glassy carbon) surfaces. In the resulting hybrid (organic-inorganic) films, the layers of negatively charged polyoxometallate, or polyoxometallate-protected (stabilized) Pt-nanoparticles, are linked or electrostatically attracted by ultra-thin layers of such positively charged conducting polymers as polyaniline (PANI), polypyrrole (PPy) or poly(3,4-ethylenedioxythiophene), PEDOT. Consequently, the attractive physicochemical properties of polymers and reactivity of polyoxometallate or noble metal particles are combined. The films are functionalized and show electrocatalytic properties towards reduction of nitrite, bromate, hydrogen peroxide or oxygen. They are of importance to the chemical and biochemical sensing as well as to the biochemical and medical applications.


Assuntos
Eletrodos , Membranas Artificiais , Molibdênio/química , Nanoestruturas/química , Ácidos Fosfóricos/química , Platina/química , Compostos de Anilina/química , Técnicas Biossensoriais , Compostos Bicíclicos Heterocíclicos com Pontes/química , Bromatos/química , Catálise , Eletroquímica , Nitratos/química , Oxirredução , Óxidos , Compostos de Fósforo , Polímeros/química , Pirróis/química
15.
J Phys Chem B ; 109(39): 18433-8, 2005 Oct 06.
Artigo em Inglês | MEDLINE | ID: mdl-16853373

RESUMO

Polyalanine derivatives containing cysteamine linker R-(Ala)14NH-(CH2)2-SH, where R is ferrocenecarbonyl or hydrogen, were synthesized and then used to form self-assembled monolayers on gold. The tilt angles and the packing density of the molecules within monolayer assemblies were determined by FTIR spectroscopy and scanning tunneling microscopy, respectively. Electrochemical properties of monolayer-modified electrodes were studied using cyclic voltammetry and impedance spectroscopy. Measurements of electron-transfer rates using electrochemical techniques and scanning tunneling spectroscopy revealed asymmetry dependent on the applied voltage. It is suggested that the observed electron-transfer behavior is connected with the electric field generated by the molecular dipole of the polyalanine helix.


Assuntos
Elétrons , Ouro/química , Peptídeos/química , Adsorção , Propriedades de Superfície
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