Biocide physically cross-linked hydrogels based on carrageenan and guanidinium polyampholytes for wound healing applications.

Over last years, hydrogels based on natural polymers have attracted considerable interest as materials for wound healing. Herein, hydrogel films based on kappa-carrageenan and guanidinium polyampholytes were prepared by the in situ physical cross-linking with potassium chloride and borax, respectively. The polyampholytes were obtained by a free radical copolymerization of 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride and unsaturated acids. To characterize the composite films, NMR, FTIR, SEM, TGA, XRD, element analysis and tensile test were used. Ampicillin was incorporated into the hydrogels to enhance wound healing potential. The healing-related characteristics, including swelling ratio, drug release and antimicrobial activity, were assessed. The equilibrium swelling ratios were in the range of 3.9-6.5 depending on the polyampholyte composition. According to the in vitro ampicillin release studies, 30-43 % of ampicillin was released from the hydrogels after 5 h at 37 °C and pH 7.4, with drug release being temperature and pH dependent. The ampicillin-loaded films showed a remarkable antimicrobial effect. The inhibition sizes for Escherichia coli and Staphylococcus aureus were 1.10-1.85 and 1.95-2.60 cm, respectively. Although the bi-polymeric hydrogels were thoroughly characterized, with the in vitro study of their biocidal effects carried out in this work, the in vivo drug release assessment needs to be further explored.

Preparation of Reactive Indicator Papers Based on Silver-Containing Nanocomposites for the Analysis of Chloride Ions.

In recent decades, metal-containing nanocomposites have attracted considerable attention from researchers. In this work, for the first time, a detailed analysis of the preparation of reactive indicator papers (RIPs) based on silver-containing nanocomposites derived from silver fumarate was carried out. Thermolysis products are silver-containing nanocomposites containing silver nanoparticles uniformly distributed in a stabilizing carbon matrix. The study of the optical properties of silver-containing nanocomposites made it possible to outline the prospects for their application in chemical analysis. RIPs were made by impregnating a cellulose carrier with synthesized silver fumarate-derived nanocomposites, which change their color when interacting with chlorine vapor. This made it possible to propose a method for the determination of chloride ions with preliminary oxidation to molecular chlorine, which is then separated from the solution by gas extraction. The subsequent detection of the active zone of RIPs using colorimetry makes it possible to identify mathematical dependences of color coordinates on the concentration of chloride ions. The red (R) color coordinate in the RGB (red-green-blue) system was chosen as the most sensitive and promising analytical signal. Calibration plots of exponential and linear form and their equations are presented. The limit of detection is 0.036 mg/L, the limits of quantification are 0.15-2.4 mg/L, and the time of a single determination is 25 min. The prospects of the developed technique have been successfully shown in the example of the analysis of the natural waters of the Don River, pharmaceuticals, and food products.

The Influence of Long-Time Storage on the Structure and Properties of Multi-Block Thermoplastic Polyurethanes Based on Poly(butylene adipate) Diol and Polycaprolactone Diol.

A series of semi-crystalline multi-block thermoplastic polyurethanes (TPU), containing poly(butylene adipate) (PBA), polycaprolactone (PCL) and their equimolar mixture (PBA/PCL) as a soft segment was synthesized. The changes in the physical-mechanical and thermal properties of the materials observed in the course of a 36-month storage at room temperature were related to the corresponding structural evolution. The latter was monitored using Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXS) and mechanical tests (tensile strength test). The effects of the composition of the soft segment on the phase separation and crystallization of the soft segment were analyzed in detail. It was found that the melting temperature of the crystalline phase increases with storage time, which is associated with hindering of the phase separation of the hard and soft segments of the TPU samples as it was detected by FTIR.

Silver Itaconate as Single-Source Precursor of Nanocomposites for the Analysis of Chloride Ions.

At present, conjugated thermolysis of metal-containing monomers is widely used as single-source precursors to obtain new metal- and metal oxide-containing nanocomposites. In this study, a detailed analysis of the main stages of conjugated thermolysis of silver itaconate was carried out. The obtained nanocomposites containing silver nanoparticles are evenly distributed in a stabilizing carbon matrix. The structural characteristics and properties of the resulting nanomaterials were studied using X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy (EDS). We have developed a method of test analysis of chlorides using paper modified with the obtained silver-containing nanocomposites. The analysis technique is based on the in situ conversion of chlorides to molecular chlorine, its dynamic release, and colorimetric detection using NP-modified paper test strips. A simple installation device is described that allows this combination to be realized. The proposed approach seems promising for nanoparticle-based determinations of other analytes that can be converted into volatile derivatives.

A combined use of silver pretreatment and impregnation with consequent Nissl staining for cortex and striatum architectonics study.

Despite a rapid growth in the application of modern techniques for visualization studies in life sciences, the classical methods of histological examination are yet to be outdated. Herein, we introduce a new approach that involves combining silver nitrate pretreatment and impregnation with consequent Nissl (cresyl violet) staining for cortex and striatum architectonics study on the same microscopy slide. The developed approach of hybrid staining provides a high-quality visualization of cellular and subcellular structures, including impregnated neurons (about 10%), Nissl-stained neurons (all the remaining ones), and astrocytes, as well as chromatophilic substances, nucleoli, and neuropil in paraffin sections. We provide a comparative study of the neuronal architectonics in both the motor cortex and striatum based on the differences in their tinctorial properties. In addition to a comparative study of the neuronal architectonics in both the motor cortex and striatum, the traditional methods to stain the cortex (motor and piriform) and the striatum are considered. The proposed staining approach compiles the routine conventional methods for thin sections, expanding avenues for more advanced examination of neurons, blood-brain barrier components, and fibers both under normal and pathological conditions. One of the main hallmarks of our method is the ability to detect changes in the number of glial cells. The results of astrocyte visualization in the motor cortex obtained by the developed technique agree well with the alternative studies by glial fibrillary acidic protein (GFAP) immunohistochemical reaction. The presented approach of combined staining has great potential in current histological practice, in particular for the evaluation of several neurological disorders in clinical, pre-clinical, or neurobiological animal studies.

The effect of separation of blocks on the crystallization kinetics and phase composition of poly(butylene adipate) in multi-block thermoplastic polyurethanes.

The influence of the hard segment nature on the crystallization kinetics of multi-block thermoplastic polyurethanes containing poly(butylene adipate) (PBA) as a soft segment was investigated. Using a combination of FTIR spectroscopy, time-domain 1H nuclear magnetic resonance (TD-NMR), differential scanning calorimetry (DSC), fast-scanning calorimetry (FSC) and wide-angle X-ray diffraction (WAXS), it was shown that aliphatic, cycloaliphatic and aromatic diisocyanates affect the phase separation efficiency of soft and hard segments. The best phase separation efficiency was observed for a sample containing aliphatic diisocyanate due to the development of a hydrogen bond network. The thermal history, phase separation and the degree of ordering of the polyurethane determine the polymorphic behavior of melt-crystallized PBA. The formation of a partially-ordered mesophase of linear aliphatic polyurethane leads to an increase in the crystallization rate of PBA at room temperature and the formation of thermodynamically stable α-crystals. The presence of bulk cycloaliphatic and aromatic diol-urethane fragments prevents the phase separation of PBA, which crystallizes after slow cooling in a mixture of α- and ß-crystalline forms. The new nanocalorimetry technique allows the identification of a direct correlation between the phase separation and crystallization kinetics of the melt-crystallized PBA in a wide range of cooling rates - from 2 to 30 000 K s-1. Particularly, ultra-fast cooling suppresses the nucleation of the ß-phase of PBA resulting in slow crystallization of only α-modification at room temperature. The role of the polyurethane mesophase in the crystallization of the soft segment was discussed for the first time.

Multiblock Thermoplastic Polyurethanes: In Situ Studies of Structural and Morphological Evolution under Strain.

The structural evolution of multiblock thermoplastic polyurethane ureas based on two polydiols, poly(1,4-butylene adipate (PBA) and poly-ε-caprolactone (PCL), as soft blocks and two diisocyanites, 2,4-toluylene diisocyanate (TDI) and 1,6-hexamethylene diisocyanate (HMDI), as hard blocks is monitored during in situ deformation by small- and wide-angle X-ray scattering. It was shown that the urethane environment determines the crystal structure of the soft block. Consequently, two populations of crystalline domains of polydiols are formed. Aromatic TDI forms rigid domains and imposes constrains on the crystallization of bounded polydiol. During stretching, the TDI-polydiol domains reveal limited elastic deformation without reorganization of the crystalline phase. The constrained lamellae of polydiol form an additional physical network that contributes to the elastic modulus and strength of the material. In contrast, polydiols connected to the linear semi-flexible HMDI have a higher crystallization rate and exhibit a more regular lamellar morphology. During deformation, the HMDI-PBA domains show a typical thermoplastic behavior with plastic flow and necking because of the high degree of crystallinity of PBA at room temperature. Materials with HMDI-PCL bonding exhibit elastic deformation due to the low degree of crystallinity of the PCL block in the isotropic state. At higher strain, hardening of the material is observed due to the stress-induced crystallization of PCL.

"Flora of Russia" on iNaturalist: a dataset.

BACKGROUND: The "Flora of Russia" project on iNaturalist brought together professional scientists and amateur naturalists from all over the country. Over 10,000 people were involved in the data collection. NEW INFORMATION: Within 20 months, the participants accumulated 750,143 photo observations of 6,857 species of the Russian flora. This constitutes the largest dataset of open spatial data on the country's biodiversity and a leading source of data on the current state of the national flora. About 87% of all project data, i.e. 652,285 observations, are available under free licences (CC0, CC-BY, CC-BY-NC) and can be freely used in scientific, educational and environmental activities.

An improved step-by-step airflow/paper-based colorimetric method for highly selective determination of halides in complex matrices.

An improved step-by-step colorimetric method for determination of halides has been developed. The method is based on successive selective oxidation of iodide, bromide and chloride into corresponding free halogens, their extraction by airflow and colorimetric detection with different paper test-strips. This procedure can be performed in a single analyzed solution and possesses high selectivity and good sensitivity due to the extraction step. Three types of paper test-strips were examined: paper modified with tetramethylammonium iodide and starch, paper modified with methyl orange and paper modified with silver triangular nanoplates. Limits of detection for iodide, bromide and chloride are 0.01, 0.02, and 0.04 mg L-1 respectively in case of the last mentioned paper. The method was applied to the analysis of samples having complex matrices, such as various seafood, preserves, bread, and natural waters, showing good accuracy of the analysis with recoveries of 95-105% and relative standard deviations not higher than 6%.

A novel paper-based sensor for determination of halogens and halides by dynamic gas extraction.

A new chemosensor in the form of indicator paper, which is sensitive to chlorine and bromine concentrations, is proposed. A simple technique of sensor preparation in a laboratory without expensive reagents is described. The method provides uniform and reproducible distribution of the reagent. A possibility to use the sensor for chemical analysis when combining with dynamic gas extraction with the application of scanner technologies and color image processing is demonstrated. Sensitive and selective techniques of chlorine, bromine, chloride, and bromide determination have been developed. The limits of detection of bromine, chlorine, bromide, and chloride have been found to be 0.06, 0.28, 0.5 and 1.4 µmol L-1 respectively. A scheme of successive determination of these analytes in the same sample including selective halides oxidation is proposed. In the simple and available set-up used for dynamic gas extraction, sample decomposition, oxidation of halide-ions and extraction of the formed halogen take place simultaneously while the color reaction of halogen interaction with the sensor is conducted out of the analyzed solution with reagents. This approach provides high selectivity and good analytical characteristics of analysis of such complex samples as foods, pharmaceutical formulations, and different water objects. The method is easy-to-use, cost-effective, time-efficient and promising for determination of other volatile compounds.

Dynamic gas extraction of iodine in combination with a silver triangular nanoplate-modified paper strip for colorimetric determination of iodine and of iodine-interacting compounds.

A method is described for sensitive and selective detection of iodine by using a paper strip modified with silver triangular nanoplates (AgTNPs). It is based on the extraction of iodine from a solution into a flow of air via dynamic gas extraction and transferring it through a reactive paper modified with AgTNPs. The interaction of AgTNPs with iodine results in a color change from blue to white. This can be visually detected and monitored by digital colorimetry. The dynamic gas extraction is highly selective for volatile compounds so that a sample pretreatment is minimal. Due to the sensitivity of AgTNPs for iodine, the limit of its detection is as low as 7 µg L-1, and the analytical range is of 20-200 µg L-1. The method also was applied in a new approach for determination of organic compounds that can interact with iodine. The organic compound is exposed to an excess of iodine, and this is followed by detection of residual iodine as described above. The method was applied to the determination of ascorbic acid, caffeine and the drug metamizole. Graphical abstract Schematic representation of a procedure of organic iodine-interacting compounds (Org.) determination. It is based on their iodination followed by gas extraction of the residual iodine, its interaction with silver triangular nanoplates and colorimetric detection with a scanner.

Towards highly selective detection using metal nanoparticles: A case of silver triangular nanoplates and chlorine.

The article describes a novel approach towards improving selectivity of volatile compounds detection using metal nanoparticles. It is based on combination of sensitive optical detection using convenient nanoparticle-modified paper test strips and dynamic gas extraction improving selectivity to volatile compounds. A simple and inexpensive setup allowing for realization of this combination is described. Analytical prospects of the approach are shown by the example of chlorine determination in highly salted aqueous solutions using silver triangular nanoplates and digital colorimetry. The limit of detection is equal to 0.03mgL-1 and the determination range is 0.1-2mgL-1. This determination can be successfully carried out in solutions containing at least 2·105 greater molar amounts of Na+, K+, Zn2+, Cl-, SO42-, and H2PO4- with no sample pretreatment. The approach seems to be compatible with different types of nanoparticles with respect to detection of various analytes, thus having good opportunities for further development.

Synthesis and potential applications of silver-porous aluminium oxide nanocomposites as prospective antiseptics and bactericides.

Alumina micro-spheres with mesoporous structure called porous aluminium oxide (POA) were prepared through a hydrothermal method using Al2(SO4)3·18H2O followed by a thermal decomposition process. Silver nanocomposites of POA (Ag/POAs) with high biochemical activity were synthesized by sorption of silver nanoparticles in the matrix of POA. Synthesis of Ag/POAs using photochemical reduction enables the producing silver nanoparticles preventing their aggregation. Ag/POAs demonstrated a stronger bactericidal activity than POA. The colony-forming ability of Escherichia coli was completely lost in 1 day on Ag/POAs at silver nanoparticles concentration of 0.241 ppm. Staphylococcus epidermidis displayed higher tolerance to Ag/POAs at all silver nanoparticles concentrations, the growth of Staphylococcus epidermidis was stopped at concentration of 0.374 ppm. The bactericidal activity of Ag/POAs against bacteria in drinking water was found to be highly effective, the growth of bacteria was completely lost in 1 day at silver nanoparticles concentration of 0.108 ppm.

New guanidine-containing nanocomposites impeding the growth of Staphylococcus epidermidis 33 and the biofilm formation.

New water-soluble nanocomposites (AgNCs) based on Ag and copolymers of 2,2-diallyl-1,1,3,3-tetraethylguanidiniumchloride with N-vinylpyrrolidone [poly(AGC-VP)] and vinylacetate [poly(AGC-VA)] have been developed. Antibacterial action of new silver nanocomposites on S. epidermidis 33 (planctonic cells and biofilms) is reported in this study. AgNCs strongly inhibited biofilms formation of S. epidermidis 33. The viability of S. epidermidis 33 cells in biofilms was considerably reduced by new AgNCs. It has been shown that S. epidermidis 33 inactivation in biofilms occurs at AgNC concentrations > 5 times higher as compared to those inhibiting completely the planktonic cells. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 630-638, 2016.

Polysulfones of new structural types as perspective antioxidant agents.

A series of polysulfones of new structural types on the basis of azanorbornenes, 2,2-diallyl-1,1,3,3-tetraethylguanidiniumchloride and tris(diethylamino)diallylaminophosphonium salts were obtained by free radical polymerization reaction. Their antioxidant properties in lipid peroxidation induced by iron/ascorbate and in erythrocyte hemolysis by H2O2 were evaluated. The polysulfone of 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride showed protection of erythrocytes against hydrogen peroxide and thermal shock, protected epithelial cells against UV irradiation, was not toxic for erythrocytes, epithelial cells SPEV and 3T3 fibroblasts. The polysulfone of N-benzyl-2-azanorbornene-5 inhibited lipid peroxidation in liver homogenate, did not exhibit cytotoxicity in SPEV and 3T3 cells, protected these against UV irradiation. Both compounds had low bioavailability and may be recommended for further investigations as excipients to be externally applied.