FRET pumping of rhodamine-based probe in light-harvesting nanoparticles for highly sensitive detection of Cu2.

In this work we presented novel strategy for increasing the performance of popular fluorescent probes on the basis of rhodamine-lactam platform. This strategy is based on the incorporation of probe molecules into the light-harvesting nanoparticles to pump modulated optical signal by Förster resonant energy transfer. Using the commercially available Cu2+ probe as a reference chemical, we have developed an efficient approach to significantly improve its sensing performance. Within obtained nanoparticles coumarin-30 nanoantenna absorbs excitation light and pumps incorporated sensing molecules providing bright fluorescence to a small number of emitters, while changing the probe-analyte equilibrium from liquid-liquid to solid-liquid significantly increased the apparent association constant, which together provided a ∼100-fold decrease in the detection limit. The developed nanoprobe allows highly sensitive detection of Cu2+ ions in aqueous media without organic co-solvents usually required for dissolution of the probe, and demonstrate compatibility with inexpensive fluorometers and the ability to detect low concentrations with the naked eye.

Application of chitosan and its N-heterocyclic derivatives for preconcentration of noble metal ions and their determination using atomic absorption spectrometry.

Chitosan and its N-heterocyclic derivatives N-2-(2-pyridyl)ethylchitosan (2-PEC), N-2-(4-pyridyl) ethylchitosan (4-PEC), and N-(5-methyl-4-imidazolyl) methylchitosan (IMC) have been applied in group preconcentration of gold, platinum, and palladium for subsequent determination by atomic absorption spectroscopy (AAS) in solutions with high background concentrations of iron and sodium ions. It has been shown that the sorption mechanism, which was elucidated by XPS, significantly influences the sorption capacity of materials, the efficiency of metal ions elution after preconcentration, and, as a result, the accuracy of metal determination by AAS. We have shown that native chitosan was not suitable for preconcentration of Au(III), if the elution step was used as a part of the analysis scheme. The group preconcentration of Au(III), Pd(II), and Pt(IV) with subsequent quantitative elution using 0.1M HCl/1M thiourea solution was possible only on IMC and 4-PEC. Application of IMC for analysis of the national standard quartz ore sample proved that gold could be accurately determined after preconcentration/elution with the recovery above 80%.

Synthesis and properties of isomeric pyridyl-containing chitosan derivatives.

Here we report on the method of synthesis in gel of a new heterocyclic aminopolymer-N-2-(4-pyridyl)ethylchitosan (4-PEC) via direct addition of 4-vinylpyridine to chitosan that yields a derivative with the substitution degree (DS) up to 0.8. The comparison of reactivity, thermal, spectroscopic, and sorption properties of a new derivative and its isomer N-2-(2-pyridyl)ethylchitosan (2-PEC) is presented. 2-PEC has higher sorption capacity and forms more stable chelates with [PdCl4](2-) and [PtCl6](2-) ions than 4-PEC, but the latter shows higher selectivity to noble metals ions in the presence of Cl(-) ions. A gradual increase of the sorption capacities and the affinity coefficient for Cu(2+) and Ni(2+) in the row chitosan<4-PEC<2-PEC was related to the increase of electron donor nitrogen atoms content and chelating properties of 2-PEC. A nearly negligible increase of the 4-PEC sorption capacity for Ag(+), as compared to plain chitosan, was suggested to be dependent on the difference in complexation models for 2-PEC and 4-PEC derivatives. The density functional theory (DFT) calculations have shown that the "pendant" model of the complex with Ag(I) is energetically favorable only for 2-PEC derivative, while in cases of chitosan and 4-PEC only "bridge" complexes can be formed that results in lower sorption capacity.

Interaction of N-acylated and N-alkylated chitosans included in liposomes with lipopolysaccharide of gram-negative bacteria.

The interactions of lipopolysaccharide (LPS) with the polycation chitosan and its derivatives - high molecular weight chitosans (300 kDa) with different degree of N-alkylation, its quaternized derivatives, N-monoacylated low molecular weight chitosans (5.5 kDa) - entrapped in anionic liposomes were studied. It was found that the addition of chitosans changes the surface potential and size of negatively charged liposomes, the magnitudes of which depend on the chitosan concentration. Acylated low molecular weight chitosan interacts with liposomes most effectively. The binding of alkylated high molecular weight chitosan with liposomes increases with the degree of its alkylation. The analysis of interaction of LPS with chitoliposomes has shown that LPS-binding activity decreased in the following order: liposomes coated with a hydrophobic chitosan derivatives > coated with chitosan > free liposomes. Liposomes with N-acylated low molecular weight chitosan bind LPS more effectively than liposomes coated with N-alkylated high molecular weight chitosans. The increase in positive charge on the molecules of N-alkylated high molecular weight chitosans at the cost of quaternization does not lead to useful increase in efficiency of binding chitosan with LPS. It was found that increase in LPS concentration leads to a change in surface ζ-potential of liposomes, an increase in average hydrodynamic diameter, and polydispersity of liposomes coated with N-acylated low molecular weight chitosan. The affinity of the interaction of LPS with a liposomal form of N-acylated chitosan increases in comparison with free liposomes. Computer simulation showed that the modification of the lipid bilayer of liposomes with N-acylated low molecular weight chitosan increases the binding of lipopolysaccharide without an O-specific polysaccharide with liposomes due to the formation of additional hydrogen and ionic bonds between the molecules of chitosan and LPS.

pH-indicators doped polysaccharide LbL coatings for hazardous gases optical sensing.

Sensitive layer-by-layer (LbL) coatings for optical detection of gaseous NH(3) and HCl were prepared by self-assembly of oppositely charged polysaccharides (chitosan and λ-carrageenan) followed by doping LbLs with pH-sensitive dyes - bromothymol blue (BTB) and Congo red (CR). It has been shown that CR, being an amphoteric dye, diffuses into LbL films regardless of the charge of the outermost polyelectrolyte layer, and the dye loading increases linearly with the LbL film thickness, whereas BTB diffuses into LbL films only when the outermost layer is positively charged, and linearity between dye loading and film thickness holds only up to 8-12 double layers (DLs) deposited. Formation of dye-doped LbL coatings at the surface of K(+)/Na(+) ion-exchanged glass has allowed fabrication of composite optical waveguide (OWG) gas sensor for detection of ammonia and hydrochloric acid vapors. The response time of BTB-doped composite OWG for ammonia detection was below 1s, and the detection limit was below 1 ppm. CR-doped OWG sensors have shown high sensitivity to HCl vapor but slow relaxation time (up to several hours for 12 DL LbL films).

N-(2-(2-pyridyl)ethyl)chitosan: Synthesis, characterization and sorption properties.

The method of producing N-2-(2-pyridyl)ethylchitosan (PE-chitosan) with substitution degrees (DS) up to 1.2 has been developed using the "synthesis in gel" approach for direct addition reaction between 2-vynilpyridine and chitosan. Investigation of sorption properties has revealed significantly higher affinity of pyridylethyl fragments to Pt(IV)) and Pd(II) ions compared to the unsubstituted amino groups of chitosan. The maximum sorption capacities of PE-chitosan in 0.1M HCl solution were estimated as 5.56mmol/g for Au(III), 3.67mmol/g for Pd(II), and 2.75mmol/g for Pt(IV). Sorption capacities of PE-chitosan for transition metal ions at pH 4-8 were 1.5-2.6 higher than those of chitosan with the highest values attained for Cu(II) and Ag(I) ions - 1.50mmol/g and 1.53mmol/g, respectively. The PE-chitosan application for preconcentration of Au(III) with subsequent elution with HCl/thiourea mixtures was proved to be efficient for atomic absorption spectroscopy analysis of multi-component solutions with low gold content.

Comparative study of electrokinetic potentials and binding affinity of lipopolysaccharides-chitosan complexes.

Electrokinetic properties of complexes of chitosan (Ch) with lipopolysaccharides (LPSs) from Escherichia coli O55:B5, Yersinia pseudotuberculosis 1B 598, and Proteus vulgaris O25 (48/57) and their size distribution were investigated using zeta-potential distribution assay and quasi-elastic light scattering. The interaction of LPS from different microorganisms with chitosan at the same w/w ratio of components (1:1) resulted in the formation of complexes in which the negative charge of LPS was neutralized (LPS from E. coli) or overcompensated (Y. pseudotuberculosis and P. vulgaris). The changing in size of the endotoxin aggregates during binding with chitosan was observed. The binding constants of chitosan with LPSs were determined by a method with using the anionic dye Orange II. The LPS from E. coli possess higher affinity to chitosan in comparison with the two others samples of endotoxin.

Interaction of carboxylic acids with chitosan: effect of pK and hydrocarbon chain length.

Sorption of acetic, propionic, butyric, valeric, and isovaleric acid on chitosan and cross-linked chitosan was studied in aqueous solutions and water/ethanol mixtures. Langmuir, Freundlich, and Redlich-Peterson equations were used to fit experimental isotherms of sorption. Correlation between maximum sorption and the pK value of every carboxylic acid was found for sorption on chitosan in aqueous solutions, while sorption in water/ethanol mixtures was mainly determined by structure and the hydrocarbon chain length of the carboxylic acid. Slight molecular-sieves effect was found for carboxylic acids sorption on cross-linked chitosan.