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1.
Mar Pollut Bull ; 195: 115582, 2023 Oct.
Article in English | MEDLINE | ID: mdl-37748418

ABSTRACT

Natural radioactive isotopes serve as a useful proxy of geological and geochemical processes in marine environment, while radiocesium serves as an indicator of man-made contamination. Monitoring of natural and anthropogenic radioactivity under conditions of the climate changes in the Arctic region is of high importance in investigations of this natural system. For the first time, we report the data on spatial distribution of natural (232Th, 226Ra, 40K) and anthropogenic (137Cs) radionuclide activities in the marine sediments from Chaun Bay (East Siberian Sea). The measured activity concentrations varied in the range 23.7-77.9 (mean 39.2) Bq kg-1 for 232Th, 16.5-39.3 (mean 26.6) Bq kg-1 for 226Ra, 535-991 (mean 726) Bq kg-1 for 40K, and 0.5-4.7 (mean 2.0) Bq kg-1 for 137Cs. The radiocesium level in the sediments showed no local sources of anthropogenic pollution in the Chaun Bay, while the average activity concentration of 40K was 1.8 times higher than worldwide.

2.
Int J Mol Sci ; 24(15)2023 Aug 03.
Article in English | MEDLINE | ID: mdl-37569760

ABSTRACT

Here, we report a new version of the extended Rate Constants Distribution (RCD) model for metal ion sorption, which includes complex-formation equilibria. With the RCD-complex model, one can predict sorbent performance in the presence of complexing agents using data on metal ion sorption from ligand-free solutions and a set of coefficients for sorption rate constants of different ionic species. The RCD-complex model was applied to breakthrough curves of Cu(II) sorption from acetate and tartrate solutions on polyethyleneimine (PEI) monolith cryogel at different flow rates and ionic speciation. We have shown that, despite the lower stability of Cu(II)-acetate complex, at high flow rates, acetate has a more pronounced negative effect on sorption kinetics than tartrate. The RCD model was successfully used to predict the shape of the breakthrough curves at an arbitrary acetate concentration but failed to predict Cu(II) sorption from tartrate solutions in a broad range of ligand concentrations. Since a twofold increase in sorption capacity was observed at low tartrate concentrations, the latter fact was related to an alteration in the sorption mechanism of Cu(II)-ions, which depended on Cu(II) ionic speciation. The obtained results emphasize the importance of information about sorption kinetics of different ionic forms for the optimization of sorption filter performance in the presence of complexing agents.


Subject(s)
Cryogels , Polyethyleneimine , Kinetics , Tartrates , Hydrogen-Ion Concentration , Metals , Ions , Acetates , Adsorption , Copper , Solutions
3.
Phys Chem Chem Phys ; 25(28): 18679-18690, 2023 Jul 19.
Article in English | MEDLINE | ID: mdl-37403572

ABSTRACT

Combined experimental 57Fe Mössbauer and theoretical DFT study of a series of iron(II)-centered (pseudo)macrobicyclic analogs and homologs was performed. The field strength of the corresponding (pseudo)encapsulating ligand was found to affect both the spin state of a caged iron(II) ion and the electron density at its nucleus. In a row of the iron(II) tris-dioximates, passing from the non-macrocyclic complex to its monocapped pseudomacrobicyclic analog caused an increase both in the ligand field strength and in the electron density at the Fe2+ ion, and, therefore, a decrease in the isomer shift (IS) value (so-called "semiclathrochelate effect"). Its macrobicyclization, giving the quasiaromatic cage complex, caused a further increase in the two former parameters and a decrease in IS (so-called "macrobicyclic effect"). The trend of their IS values was successfully predicted using the performed quantum-chemical calculations and the corresponding linear correlation with the electron density at their 57Fe nuclei was plotted. A variety of different functionals can be successfully used for such excellent prediction. The slope of this correlation was found to be unaffected by the used functional. In contrast, the predictions of both the sign and the values of quadrupole splitting (QS) for them, based on the theoretical calculations of EFG tensors, were found to be a real great challenge, which could not be solved at the moment even in the case of these C3-pseudosymmetric iron(II) complexes with known XRD structures. The latter experimental data allowed us to deduce a sign of the QSs for them. The straightforwarded molecular design of a (pseudo)encapsulating ligand is proposed to control both the spin state and the redox characteristics of an encapsulated metal ion.

4.
Biomimetics (Basel) ; 8(2)2023 May 29.
Article in English | MEDLINE | ID: mdl-37366823

ABSTRACT

Here, we have presented a new method of 1,1,3-triglycidyloxypropane (TGP) synthesis and investigated how cross-linker branching affects mechanical properties and cytotoxicity of chitosan scaffolds in comparison with those cross-linked using diglycidyl ethers of 1,4-butandiol (BDDGE) and poly(ethylene glycol) (PEGDGE). We have demonstrated that TGP is an efficient cross-linker for chitosan at a subzero temperature at TGP:chitosan molar ratios from 1:1 to 1:20. Although the elasticity of chitosan scaffolds increased in the following order of the cross-linkers PEGDGE > TGP > BDDGE, TGP provided cryogels with the highest compressive strength. Chitosan-TGP cryogels have shown low cytotoxicity for colorectal cancer HCT 116 cell line and supported the formation of 3D multicellular structures of the spherical shape and size up to 200 µm, while in more brittle chitosan-BDDGE cryogel this cell culture formed epithelia-like sheets. Hence, the selection of the cross-linker type and concentration for chitosan scaffold fabrication can be used to mimic the solid tumor microenvironment of certain human tissue, control matrix-driven changes in the morphology of cancer cell aggregates, and facilitate long-term experiments with 3D tumor cell cultures.

5.
Molecules ; 28(4)2023 Feb 08.
Article in English | MEDLINE | ID: mdl-36838620

ABSTRACT

The continuously increasing flow of toxic heavy metals to the environment due to intensive industrial activity and tightening requirements with regard to the content of metal ions in drinking and discharged waters urges the development of affordable and sensitive devices to the field control of pollutants. Here, we report a new thiated Rhodamine-lactam probe for Hg2+ detection and demonstrate how its sensitivity can be increased via the incorporation of the probe molecules into the optically transparent siloxane-acrylate coatings on polymethyl methacrylate and, alternatively, into the water-dispersible light-harvesting FRET nanoparticles (NPs), in which dye cations are separated by fluorinated tetraphenylborate anions. We have shown that the optimization of the FRET NPs composition had allowed it to reach the antenna effect of ~300 and fabricate "off/on" sensor for Hg2+ ion determination in aqueous solutions with the detection limit of ~100 pM, which is far below the maximum permissible concentration (MPC) of mercury in drinking water recommended by the World Health Organization. Although this work is more proof-of-concept than a ready-to-use analytical procedure, the suggested approaches to fabrication of the FRET NPs based on the popular rhodamine-lactam platform can be used as a background for the development of low-cost portable sensing devices for the extra-laboratory determination of hazardous metal ions.


Subject(s)
Drinking Water , Mercury , Nanoparticles , Water , Rhodamines , Cations , Mercury/analysis
6.
Molecules ; 27(23)2022 Dec 02.
Article in English | MEDLINE | ID: mdl-36500581

ABSTRACT

To understand how polyethyleneimine (PEI), as a ligand, affects structure and properties of the transition metals hexacyanoferrates (HCFs) immobilized in cross-linked PEI matrix, we have synthesized Cu(II), Zn(II), and Fe(III) HCFs via successive ion-exchange reactions with metal salts and K4[FeII(CN)6] or K3[FeIII(CN)6]. The structure and properties of the obtained materials in comparison with the crystalline HCF analogs were investigated with FT-IR, Mössbauer, and UV-Vis spectroscopy. Complete reduction of Fe(III) to Fe(II) by PEI in HCF(III) was confirmed. When synthesis was performed at pH favoring binding of precursor metal ions by PEI, cyano-bridged hybrids rather than polymer-HCFs composites were formed. Although the obtained hybrids did not demonstrate sorption activity toward cesium ions, known for crystalline HCFs, they are of interest for the other applications. SQUID measurements revealed a significant difference in magnetic properties of PEI-HCFs hybrids in comparison with crystalline HCFs. Due to the Fe(III) to Fe(II) reduction in HCF ions, Cu(II) and Fe(III) HCFs(III) lost the molecular magnets properties in PEI matrix, but magnetic ordering, including ferromagnet-antiferromagnet interactions, was observed in all hybrids over the broad temperature range.


Subject(s)
Ferric Compounds , Polyethyleneimine , Ligands , Models, Molecular , Spectroscopy, Fourier Transform Infrared , Metals/chemistry , Ions , Ferrocyanides
7.
Molecules ; 27(24)2022 Dec 15.
Article in English | MEDLINE | ID: mdl-36558066

ABSTRACT

The efficiency of the removal of Cs-137 radionuclides with porous and non-porous resorcinol−formaldehyde resins from alkaline solutions simulating the composition of real liquid radioactive waste (LRW) streams has been evaluated. Resins were synthesized through the polycondensation of resorcinol and formaldehyde in an alkaline medium at a molar ratio of 1.8/2.2 and a temperature of 210 °C. The Cs-137 distribution coefficients on RFRs in alkaline solutions simulating LRW were above 103 mL/g under static sorption conditions. In a model solution with pH 11, the full dynamic sorption capacity of non-porous RFR was 0.178 mmol/g. The values of the full dynamic sorption capacities of porous RFRs were 0.274 and 1.035 mmol/g for resins obtained with calcium carbonate and toluene as templates, respectively. When the sizes of RFR beads increased two-fold, the volume until 5% cesium breakthrough decreased by 20−40%. The most pronounced beneficial effect of the RFR's porosity was observed at flow rates from 25 to 50 BV/h. It was shown that the negative effect of metal cations on Cs-137 uptake increases in the following order: Na+ < Mg2+ < Ca2+ < K+. The number of bed volumes of LRW-simulating solution decontaminated with RFRs until 5% cesium breakthrough was above 450; that is higher than the value of known commercially available analogs. The latter shows that the developed RFRs are promising for application in technological schemes of alkaline LRW processing.

8.
Int J Mol Sci ; 23(20)2022 Oct 14.
Article in English | MEDLINE | ID: mdl-36293131

ABSTRACT

The potential of chitosan and carboxymethyl chitosan (CMC) cryogels cross-linked with diglycidyl ether of 1,4-butandiol (BDDGE) and poly(ethylene glycol) (PEGDGE) have been compared in terms of 3D culturing HEK-293T cell line and preventing the bacterial colonization of the scaffolds. The first attempts to apply cryogels for the 3D co-culturing of bacteria and human cells have been undertaken toward the development of new models of host-pathogen interactions and bioimplant-associated infections. Using a combination of scanning electron microscopy, confocal laser scanning microscopy, and flow cytometry, we have demonstrated that CMC cryogels provided microenvironment stimulating cell-cell interactions and the growth of tightly packed multicellular spheroids, while cell-substrate interactions dominated in both chitosan cryogels, despite a significant difference in swelling capacities and Young's modulus of BDDGE- and PEGDGE-cross-linked scaffolds. Chitosan cryogels demonstrated only mild antimicrobial properties against Pseudomonas fluorescence, and could not prevent the formation of Staphylococcus aureus biofilm in DMEM media. CMC cryogels were more efficient in preventing the adhesion and colonization of both P. fluorescence and S. aureus on the surface, demonstrating antifouling properties rather than the ability to kill bacteria. The application of CMC cryogels to 3D co-culture HEK-293T spheroids with P. fluorescence revealed a higher resistance of human cells to bacterial toxins than in the 2D co-culture.


Subject(s)
Chitosan , Cryogels , Humans , Cryogels/pharmacology , Cryogels/chemistry , Chitosan/pharmacology , Chitosan/chemistry , Coculture Techniques , HEK293 Cells , Staphylococcus aureus , Polyethylene Glycols , Kidney , Ethers
9.
Biomimetics (Basel) ; 7(2)2022 May 05.
Article in English | MEDLINE | ID: mdl-35645183

ABSTRACT

Macroporous scaffolds (cryogels) for the 3D cell culturing of colorectal cancer micro-tumors have been fabricated by cross-linking chitosan and carboxymethyl chitosan (CMC) with 1,4-butandiol diglycidyl ether (BDDGE) under subzero temperature. Due to the different intrinsic properties and reactivity of CMC and chitosan under the same cross-linking conditions, Young's moduli and swelling of the permeable for HCT 116 cells cryogels varied in the broad range 3-41 kPa and 3500-6000%, respectively. We have demonstrated that the morphology of micro-tumors can be controlled via selection of the polymer for the scaffold fabrication. Although both types of the cryogels had low cytotoxicity and supported fast cell proliferation, round-shaped tightly packed HCT 116 spheroids with an average size of 104 ± 30 µm were formed in CMC cryogels (Young's moduli 3-6 kPa), while epithelia-like continuous sheets with thickness up to 150 µm grew in chitosan cryogel (Young's modulus 41 kPa). There was an explicit similarity between HCT 116 micro-tumor morphology in soft (CMC cryogel) or stiff (chitosan cryogel) and in ultra-low attachment or adhesive culture plates, respectively, but cryogels provided the better control of the micro-tumor's size distribution and the possibility to perform long-term investigations of drug-response, cell-cell and cell-matrix interactions in vitro.

10.
Biomimetics (Basel) ; 7(1)2022 Jan 06.
Article in English | MEDLINE | ID: mdl-35076473

ABSTRACT

Here we demonstrate the possibility of using acyclic diethylacetal of acetaldehyde (ADA) with low cytotoxicity for the fabrication of hydrogels via Schiff bases formation between chitosan and acetaldehyde generated in situ from acetals in chitosan acetate solution. This approach is more convenient than a direct reaction between chitosan and acetaldehyde due to the better commercial availability and higher boiling point of the acetals. Rheological data confirmed the formation of intermolecular bonds in chitosan solution after the addition of acetaldehyde diethyl acetal at an equimolar NH2: acetal ratio. The chemical structure of the reaction products was determined using elemental analysis and 13C NMR and FT-IR spectroscopy. The formed chitosan-acetylimine underwent further irreversible redox transformations yielding a mechanically stable hydrogel insoluble in a broad pH range. The reported reaction is an example of when an inappropriate selection of acid type for chitosan dissolution prevents hydrogel formation.

11.
Gels ; 7(4)2021 Oct 29.
Article in English | MEDLINE | ID: mdl-34842662

ABSTRACT

Here, we discuss the applicability of (methylenebis(salicylaldehyde)-MbSA) for the fabrication of the stimuli-responsive N-carboxyethylchitosan (CEC) hydrogels with a tunable dissolution rate under physiological conditions. In comparison with non-covalent salicylimine hydrogels, MbSA cross-linking via covalent bis('imine clip') and non-covalent hydrophobic interactions allowed the fabrication of hydrogels with storage moduli > 1 kPa at ten-fold lower aldehyde/CEC molar ratio with the preservation of pH- and amino-acid responsive behavior. Although MbSA-cross-linked CEC hydrogels were stable at neutral and weakly alkaline pH, their disassembly in cell growth medium (Dulbecco's modified Eagle's medium, DMEM) under physiological conditions was feasible due to transimination reaction with amino acids contained in DMEM. Depending on the cross-linking density, the complete dissolution time of the fabricated hydrogels varied from 28 h to 11 days. The cytotoxicity of MbSA cross-linked CEC hydrogels toward a human colon carcinoma cell line (HCT 116) and primary human dermal fibroblasts (HDF) was remarkably lower in comparison with CEC-salicylimine hydrogels. Fast gelation, relatively low cytotoxicity, and tunable stimuli-induced disassembly under physiological conditions make MbSA cross-linked CEC hydrogels promising for drug encapsulation and release, 3D printing, cell culturing, and other biomedical applications.

12.
Data Brief ; 39: 107580, 2021 Dec.
Article in English | MEDLINE | ID: mdl-34841022

ABSTRACT

The article presents a dataset on ionic composition of pore water and grain size properties of 105 samples of bottom sediments and subsea permafrost from three sediment cores obtained during polar expeditions in the Buor-Khaya Bay in 2014-2015. Collection sites are located southeast of the Lena Delta near the Bykovsky Peninsula at the Buor-Khaya Bay. In this data article, the concentration of sodium, potassium, calcium, and magnesium cations, chlorides and sulphates in water extracts from sediments, as well as grain size characteristics, are presented. Based on these measurements a difference in salinisation dynamics of thawed strata within the Buor-Khaya Bay is shown.

13.
Carbohydr Polym ; 274: 118618, 2021 Nov 15.
Article in English | MEDLINE | ID: mdl-34702449

ABSTRACT

Here we report on the properties of hydrogels of carboxyalkylchitosans-salicylimines depending on the salicylaldehyde (SA) grafting density, type of carboxyalkyl substitution, pH, and presence of amino acids. The mechanism of SA grafting has been investigated using 13C NMR and FT-IR spectroscopy and elemental analysis. We have found that, despite lower SA grafting density to carboxyalkylchitosans, gelation in these solutions occurred at much lower SA:polymer molar ratios than for chitosan-salicylimines, being the highest for a N-carboxyethylchitosan with a medium substitution degree. Controlled disassembly of supramolecular architecture of hydrogel of N-carboxyethylchitosan-salicylimine at physiological pH was achieved via the transimination reaction in the presence of amino acids with the efficiency decreased in the order: lysine > arginine ≥ serine. Application of carboxyalkylchitosans opens a new window for development of salicylimine-based hydrogels with lower SA grafting density, better mechanical properties, and reversibility in a broader pH range than it was earlier known for chitosan-based biodynamers.


Subject(s)
Chitosan/analogs & derivatives , Hydrogels/chemistry , Chitosan/chemistry , Rheology
14.
J Hazard Mater ; 416: 125880, 2021 Aug 15.
Article in English | MEDLINE | ID: mdl-34492820

ABSTRACT

Here we report a new approach to predisposal processing of spent resorcinol-formaldehyde resins (RFR) selective to cesium radionuclides via dissolution and hydrothermal oxidation (HTO) with the mineralization efficiency above 85%. Using a combination of potentiometric and colloid titration, we have shown that dissolution of RFR by consecutive treatment with nitric acid and sodium hydroxide solutions at optimal concentrations of 3-5 mol/L and 1 mol/L, respectively, yields colloid solutions of partially depolymerized and oxidized RFR. The efficiency of HTO of resorcinol and RFR solutions with hydrogen peroxide was investigated in a flow-type stainless steel reactor in the temperature range 165-250 °Ð¡ and at linear flow rates of 1-3 cm/min. It was demonstrated that HTO allowed efficient resorcinol mineralization using hydrogen peroxide at H2O2: resorcinol molar ratios above 10 at 195 °Ð¡ and a linear flow rate of 2 cm/min. Due to the colloidal nature of organics in RFR solution, its efficient decomposition occurred at higher temperature or molar excess of the oxidizer as compared to resorcinol, but in both cases HTO was the most efficient in acidic media yielding acetic acid as the main oxidation resistant product.

15.
Molecules ; 26(15)2021 Jul 29.
Article in English | MEDLINE | ID: mdl-34361764

ABSTRACT

The feasibility of several approaches to the fabrication of monolith composite cryogels containing transition-metal ferrocyanides for Cs+ ion uptake has been evaluated. Although in the series of investigated metal ion precursors (Cu(II), Zn(II), Ni(II), and Co(II)), in situ formation of the sorption active phase in polyethyleneimine (PEI) cryogel was feasible only in the case of Zn(II) ferrocyanide, this approach has shown significant advantages over the immobilization of ex situ synthesized ferrocyanide nanoparticles. Nanoparticles of the mixed ferrocyanide Zn1.85K0.33[Fe(CN)6] formed in situ had an average size of 516 ± 146 nm and were homogeneously distributed in the monolith located at the polymer surface rather than embedded in the matrix. The Young modulus of the PEI cryogel increased after modification from 25 to 57 kPa, but composites maintained high permeability to the flow. Sorption of Cs+ ions has been investigated at superficial velocity up to 8 m/h. Steep breakthrough profiles and uptake efficiency of >99.5% until breakthrough point confirmed that a supermacroporous structure of the monolith composite assured good mass transfer, so that intraparticle diffusion was not the limiting stage of sorption kinetics. Application of the rate-constant distribution model (RCD model) to analyze the breakthrough curves of Cs+ sorption allowed the identification of two types of sorption sites with a difference in sorption rate constants of ~1 log unit. Most likely, sorption on "fast" sorption sites was governed by ion exchange between Cs+ ions in solution and K+ ions in the ferrocyanide lattice. Cs-137 radionuclide removal was investigated using the monolith composite columns of various geometries at superficial velocity up to the 6.6 m/h; specific gamma activity was reduced from 265 kBq/L to the background level, showing high potential of these materials for POU application.

16.
Molecules ; 25(20)2020 Oct 19.
Article in English | MEDLINE | ID: mdl-33086660

ABSTRACT

Here we report the method of fabrication of supermacroporous monolith sorbents (cryogels) via covalent cross-linking of polyallylamine (PAA) with diglycidyl ether of 1,4-butandiol. Using comparative analysis of the permeability and sorption performance of the obtained PAA cryogels and earlier developed polyethyleneimine (PEI) cryogels, we have demonstrated the advantages and disadvantages of these polymers as sorbents of heavy metal ions (Cu(II), Zn(II), Cd(II), and Ni(II)) in fixed-bed applications and as supermacroporous matrices for the fabrication of composite cryogels containing copper ferrocyanide (CuFCN) for cesium ion sorption. Applying the rate constant distribution (RCD) model to the kinetic curves of Cu(II) ion sorption on PAA and PEI cryogels, we have elucidated the difference in sorption/desorption rates and affinity constants of these materials and showed that physical sorption contributed to the Cu(II) uptake by PAA, but not to that by PEI cryogels. It was shown that PAA cryogels had significantly higher selectivity for Cu(II) sorption in the presence of Zn(II) and Cd(II) ions in comparison with that of PEI cryogels, while irreversible sorption of Co(II) ions by PEI can be used for the separation of Ni(II) and Co(II) ions. Using IR and Mössbauer spectroscopy, we have demonstrated that strong complexation of Cu(II) ions with PEI significantly affects the in situ formation of Cu(II) ferrocyanide nanosorbents leading to their inefficiency for Cs+ ions selective uptake, whereas PAA cryogel was applicable for the fabrication of efficient monolith composites via the in situ formation of CuFCN or loading of ex situ formed CuFCN colloids.


Subject(s)
Adsorption/drug effects , Chelating Agents/chemistry , Cryogels/chemistry , Metals, Heavy/isolation & purification , Hydrogen-Ion Concentration , Ions/chemistry , Ions/isolation & purification , Metals, Heavy/chemistry , Polyamines/chemistry , Polyhydroxyethyl Methacrylate/chemistry , Sorption Detoxification
17.
Gels ; 6(2)2020 May 14.
Article in English | MEDLINE | ID: mdl-32423004

ABSTRACT

Here we address the problem of what we can expect from investigations of sorption kinetics on cryogel beads in batch. Does macroporosity of beads indeed help eliminate diffusion limitations under static sorption conditions? Are sorption rate constants calculated using phenomenological kinetic models helpful for predicting sorption properties under dynamic conditions? Applying the rate constants distribution (RCD) model to kinetic curves of Cu(II) ions sorption on polyethyleneimine (PEI) cryogel and gel beads and fines, we have shown that diffusion limitations in highly swollen beads are very important and result in at least ten-fold underestimation of the sorption rate constants. To account for intraparticle diffusion, we have developed the RCD-diffusion model, which yields "intrinsic" kinetic parameters for the sorbents, even if diffusion limitations were important in kinetic experiments. We have shown that introduction of a new variable-characteristic diffusion time-to the RCD model significantly improved the reliability of sorption kinetic parameters and allowed prediction of the minimal residence time in column required for efficient uptake of the adsorbate under dynamic conditions. The minimal residence time determined from kinetic curves simulated using the RCD-diffusion model was in good agreement with experimental data on breakthrough curves of Cu(II) ion sorption on monolith PEI cryogel at different flow rates.

18.
Nanomaterials (Basel) ; 10(1)2019 Dec 24.
Article in English | MEDLINE | ID: mdl-31878209

ABSTRACT

We report an easy-to-implement device for surface-enhanced Raman scattering (SERS)-based detection of various analytes dissolved in water droplets at trace concentrations. The device combines an analyte-enrichment system and SERS-active sensor site, both produced via inexpensive and high-performance direct femtosecond (fs)-laser printing. Fabricated on a surface of water-repellent polytetrafluoroethylene substrate as an arrangement of micropillars, the analyte-enrichment system supports evaporating water droplet in the Cassie-Baxter superhydrophobic state, thus ensuring delivery of the dissolved analyte molecules towards the hydrophilic SERS-active site. The efficient pre-concentration of the analyte onto the sensor site based on densely arranged spiky plasmonic nanotextures results in its subsequent label-free identification by means of SERS spectroscopy. Using the proposed device, we demonstrate reliable SERS-based fingerprinting of various analytes, including common organic dyes and medical drugs at ppb concentrations. The proposed device is believed to find applications in various areas, including label-free environmental monitoring, medical diagnostics, and forensics.

19.
ACS Sens ; 4(11): 2879-2884, 2019 11 22.
Article in English | MEDLINE | ID: mdl-31601106

ABSTRACT

Detection of nitroaromatic compounds (NACs) is an important applied task for environmental monitoring, medical diagnostics, and forensic analysis. However, detection of NAC vapors is challenging owing to their low vapor pressure and relatively weak sensitivity of the existing detection techniques. Here, we propose a novel concept to design fluorescence (FL) detection platforms based on chemical functionalization of nanotextured dielectric surfaces exhibiting resonant light absorption, trapping, and localization effects. We demonstrate highly-efficient NAC vapor sensor with selective FL-quenching response from monolayers of carbazole moieties covalently bonded to a spiky silicon surface, "black" silicon, produced over the centimeter-scale area using simple reactive ion etching. The sensor is shown to provide unprecedented ppt (10-12) range limits of detection for several NAC vapors. Easy-to-implement scalable fabrication procedure combined with simple and versatile functionalization techniques applicable to all-dielectric surfaces make the suggested concept promising for realization of various gas sensing systems for social and environmental safety applications.


Subject(s)
Carbazoles/chemistry , Fluorescence , Nitrobenzenes/analysis , Silicon/chemistry , Microscopy, Electron, Scanning , Molecular Structure , Particle Size , Surface Properties , Volatilization
20.
Colloids Surf B Biointerfaces ; 182: 110342, 2019 Oct 01.
Article in English | MEDLINE | ID: mdl-31299538

ABSTRACT

Here we report a green synthesis of ZnSe quantum dots (QDs) in aqueous solution of polyampholyte chitosan derivative - N-(2-carboxyethyl)chitosan (CEC) with substitution degrees (DS) from 0.7 to 1.3 and molecular weight (MW) of 40 kDa and 150 kDa. We have shown that the maximum intensity of photoluminescence (PL) is exhibited by ZnSe QDs synthesized in solutions of CEC with DS 1 at Se:Zn molar ratio 1:2.5. The defect-related band was predominant in the PL spectra of ZnSe QDs obtained at room temperature; however, hydrothermal treatment at 80-150 °C during 1-2 h significantly increased contribution of exciton emission to the spectra. Cytotoxicity of ZnSe QDs was investigated by MTT assay using cancer cell lines SKOV-3; SkBr-3; PANC-1; Colon-26 and human embryonic kidney cell line HEK293. Cytotoxicity of ZnSe QDs did not depend on MW or DS of CEC but significantly depended on the cell line, being the lowest for normal human cells HEK293 and breast cancer cell line SKOV-3. The hydrothermally treated ZnSe QDs showed higher toxicity toward both normal and cancer cell lines. Since ZnSe QDs were toxic for most of the investigated cancer cell lines, they cannot be used as inert tracers for bioimaging, but can be promising for further investigation for anticancer therapy.


Subject(s)
Chitosan/analogs & derivatives , Quantum Dots/chemistry , Selenium Compounds/chemical synthesis , Zinc Compounds/chemical synthesis , Cell Line, Tumor , Cell Survival/drug effects , Chitosan/chemistry , Dose-Response Relationship, Drug , HEK293 Cells , Hot Temperature , Humans , Ligands , Luminescence , Molecular Weight , Organ Specificity , Oxidation-Reduction , Quantum Dots/toxicity , Selenium Compounds/toxicity , Solutions , Water/chemistry , Zinc Compounds/toxicity
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