The development of novel diagnostic tools is a primary goal in bioanalytical chemistry. Here we report the synthesis of Tröger's base functionalized with amino- and coumarin-units designed as a monomeric unit for the development of an electrochemical cancer sensor. The synthesized receptor was deposited onto a conducting support using electrochemical polymerization, characterized spectroscopically and tested potentiometrically towards metabolites used as tumor markers of neuroblastoma.
- Publikační typ
- časopisecké články MeSH
Repeated depositions of polyaniline (PANI) have been used to control the thickness of the polymeric film deposited on poly(vinyl chloride) (PVC) membrane surface. The oxidation of aniline was carried out in a dispersion mode, i.e. in the presence of poly(N-vinylpyrrolidone) (PVP). Two kinds of PVC were used for this purpose: a non-plasticized PVC for the study of PANI deposition and PVC, plasticized with nitrophenyl octyl ether (NPOE), as a prototype of a liquid membrane electrode. The results of UV-visible and FTIR spectroscopies and electron microscopy showed that (1) the film thickness increased by about equal increments of approximately 40 nm after each polymerization, and (2) the interface with PVC was constituted by PANI film and adhering PANI-PVP colloidal particles. The various thicknesses of the deposited PANI films affected the potentiometric response of the NPOE/PVC membrane with and without an anion-exchanger. The potentiometric anionic response was observed with a minimal thickness of PANI film on the blank NPOE/PVC membrane. Sensitivity of the PANI film to pH occurred only with a blank NPOE/PVC membrane coated with a thick polymeric film, while it was strongly suppressed by the presence of a lipophilic anion-exchanger, tridodecylmethylammonium chloride (TDDMACl), in the membrane, regardless of the thickness of the polymer film. The thickness of the PANI film did not affect the anionic selectivity pattern of TDDMACl-based membranes to any great extent, but its presence improved and stabilized their potentiometric characteristics (sensitivity, linear-response range).
- Publikační typ
- časopisecké články MeSH
A novel application of a single stranded (ss) oligonucleotide as an active component of polymeric membrane in an ion-selective electrode (ISE) is described. The original oligonucleotides, oligo(dA)(15), modified by cholesterol, triphenylmethyl and hexadecyl derivatives, were immobilized into poly(vinyl chloride) (PVC) membrane using extraction protocol. In parallel, the adsorption protocol was used to immobilize unmodified oligo(dA)(15) on the PVC membrane based on tridodecylmethyammonium chloride (TDDMA(+)Cl(-)). Immobilization of ss oligonucleotide probe through spacer was more effective for the potentiometric detection of the hybridization between complementary oligonucleotides. It was found that cholesterol-oligo(dA)(15) modified membranes were sensitive toward complementary oligo(dT)(15) in the concentration range 2-80 nM at pH 7. An explanation for the detection mechanism is proposed.
- MeSH
- analýza selhání vybavení MeSH
- biokompatibilní potahované materiály chemie MeSH
- biosenzitivní techniky přístrojové vybavení metody MeSH
- design vybavení MeSH
- DNA sondy chemie genetika MeSH
- elektrochemie přístrojové vybavení metody MeSH
- hybridizace in situ přístrojové vybavení metody MeSH
- oligonukleotidy analýza chemie genetika MeSH
- polyvinylchlorid chemie MeSH
- reprodukovatelnost výsledků MeSH
- senzitivita a specificita MeSH
- Publikační typ
- časopisecké články MeSH
- hodnotící studie MeSH
- práce podpořená grantem MeSH
- Názvy látek
- biokompatibilní potahované materiály MeSH
- DNA sondy MeSH
- oligonukleotidy MeSH
- polyvinylchlorid MeSH
The ion selective electrode (ISE)-based potentiometric approach is shown to be an effective means of characterizing the anion recognition sites in the molecular receptor calix[2]pyridino[2]pyrrole (CPP). In particular, potentiometric pH-measurements involving the use of experimental PVC-membranes based on CPP revealed the existence of both mono- and diprotonated forms of the receptor under readily accessible conditions. Based on these analyses, apparent surface protonation constants for this heterocalixarene were found to lie between 8.5-8.9 (pK(B1)) and 3.3-3.8 (pK(B2)). CPP was found to interact with targeted anionic analytes based on both coulombic and hydrogen bond interactions, as inferred from varying the kinds of ionic sites present within the membrane phase. Potentiometric selectivity studies revealed that CPP preferred "Y-shaped" anions (e.g. acetate, lactate, benzoate) over spherical anions (e.g. fluoride and chloride), fluoride over chloride within the set of spherical anions, and the ortho-isomer over the corresponding meta- and para-isomers in the case of hydroxybenzoate (salicylate and congeners). In the context of this study, the advantages of potentiometric determinations of acetylsalicylic acid using optimized PVC-membranes based on CPP relative to more conventional PVC-membrane ISEs based on traditional anion exchanger were also demonstrated.
- MeSH
- anionty chemie MeSH
- Aspirin analýza MeSH
- chemické modely MeSH
- chemické techniky analytické metody MeSH
- iontově selektivní elektrody * MeSH
- ionty MeSH
- kalixareny chemie MeSH
- koncentrace vodíkových iontů MeSH
- kyselina salicylová chemie MeSH
- polymery chemie MeSH
- potenciometrie metody MeSH
- vazebná místa MeSH
- vodíková vazba MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Research Support, N.I.H., Extramural MeSH
- Názvy látek
- anionty MeSH
- Aspirin MeSH
- ionty MeSH
- kalixareny MeSH
- kyselina salicylová MeSH
- polymery MeSH
Monomeric and polymeric 5-nitroquinoxaline derivatives disubstituted in the 2 and 3 positions with 2-pyrrolyl (A), 2-furyl (B) and 2-thienyl (C) groups were prepared and characterized. The substituted 5-nitroquinoxalines were used as active components in poly(vinyl chloride)-membrane and electropolymerized electrodes that were then tested as possible sensors for various cationic species. In contrast to the difurylnitroquinoxaline-based systems, the monomeric and polymeric dipyrrolyl- and dithienylquinoxaline electrodes displayed a good selectivity for Ag(+) ions, providing a near-Nernstian response in the 10(-5) to 10(-2) mol L(-1) concentration range. The similar potentiometric behavior displayed by the monomeric and polymeric forms of systems A and C supports the contention that the main binding modes displayed by the monomeric forms are retained in the corresponding polymeric structures.
- Publikační typ
- časopisecké články MeSH
