Enhanced Low-Density Silicone Foams Blown by Water-Hydroxyl Blends.

Water, alcohols, diols, and glycerol are low-cost blowing agents that can be used to create the desired silicone foam structures. Although their combined use can be beneficial, it remains unclear how it affects the physical properties of the resulting materials. We conducted a comparative study of these hydroxyl-bearing blowing agents in fumed silica- and mica-filled polymer composite systems for simultaneous blowing and crosslinking to obtain a low-density, uniform porosity and superior mechanical properties. The foams were optimized for a uniform open-pore structure with densities ranging from 75 to 150 kg‧m-3. Varying the diol chain length (Cn) from one to seven carbons can alter the foam density and structure, thereby enhancing the foam tensile strength while maintaining a low density. Replacing 10 mol% of water with 1,4-butanediol decreased the density by 26%, while increasing the specific strength by 5%. By combining glycerol and water blowing, the resulting foams exhibited a 30% lower apparent density than their water-blown analogs. The results further showed that Cn > 4 alkane chain diols had an odd-even effect on the apparent density and cell wall thickness. All foamable compositions had viscosities of approximately 7000 cSt and curing times below 2 min, allowing for quick dispensing and sufficient time for the foam to cure in semi-industrial volumes.

Microbial growth and adhesion of Escherichia coli in elastomeric silicone foams with commonly used additives.

Silicone is often used in environments where water repellency is an advantage. Contact with water promotes the adhesion of microorganisms and biofilm formation. Depending on the application, this may increase the possibility of food poisoning and infections, the material's degrading appearance, and the likelihood of manufacturing defects. The prevention of microbial adhesion and biofilm formation is also essential for silicone-based elastomeric foams, which are used in direct contact with human bodies but are often difficult to clean. In this study, the microbial attachment in and the retention from the pores of silicone foams of different compositions is described and compared to those of commonly used polyurethane foams. The growth of the gram-negative Escherichia coli in the pores and their leaching during wash cycles is characterised by bacterial growth/inhibition, adhesion assay, and SEM imaging. The structural and surface properties of the materials are compared. Despite using common antibacterial additives, we have found that non-soluble particles stay isolated in the silicone elastomer layer, thus affecting surface microroughness. Water-soluble tannic acid dissolves into the medium and seems to aid in inhibiting planktonic bacterial growth, with a clear indication of the availability of tannic acid on the surfaces of SIFs.

Comparison of Toxicity and Cellular Uptake of CdSe/ZnS and Carbon Quantum Dots for Molecular Tracking Using Saccharomyces cerevisiae as a Fungal Model.

Plant resource sharing mediated by mycorrhizal fungi has been a subject of recent debate, largely owing to the limitations of previously used isotopic tracking methods. Although CdSe/ZnS quantum dots (QDs) have been successfully used for in situ tracking of essential nutrients in plant-fungal systems, the Cd-containing QDs, due to the intrinsic toxic nature of Cd, are not a viable system for larger-scale in situ studies. We synthesized amino acid-based carbon quantum dots (CQDs; average hydrodynamic size 6 ± 3 nm, zeta potential -19 ± 12 mV) and compared their toxicity and uptake with commercial CdSe/ZnS QDs that we conjugated with the amino acid cysteine (Cys) (average hydrodynamic size 308 ± 150 nm, zeta potential -65 ± 4 mV) using yeast Saccharomyces cerevisiae as a proxy for mycorrhizal fungi. We showed that the CQDs readily entered yeast cells and were non-toxic up to 100 mg/L. While the Cys-conjugated CdSe/ZnS QDs were also not toxic to yeast cells up to 100 mg/L, they were not taken up into the cells but remained on the cell surfaces. These findings suggest that CQDs may be a suitable tool for molecular tracking in fungi (incl. mychorrhizal fungi) due to their ability to enter fungal cells.

Fluorescent nanoparticles as tools in ecology and physiology.

Fluorescent nanoparticles (FNPs) have been widely used in chemistry and medicine for decades, but their employment in biology is relatively recent. Past reviews on FNPs have focused on chemical, physical or medical uses, making the extrapolation to biological applications difficult. In biology, FNPs have largely been used for biosensing and molecular tracking. However, concerns over toxicity in early types of FNPs, such as cadmium-containing quantum dots (QDs), may have prevented wide adoption. Recent developments, especially in non-Cd-containing FNPs, have alleviated toxicity problems, facilitating the use of FNPs for addressing ecological, physiological and molecule-level processes in biological research. Standardised protocols from synthesis to application and interdisciplinary approaches are critical for establishing FNPs in the biologists' tool kit. Here, we present an introduction to FNPs, summarise their use in biological applications, and discuss technical issues such as data reliability and biocompatibility. We assess whether biological research can benefit from FNPs and suggest ways in which FNPs can be applied to answer questions in biology. We conclude that FNPs have a great potential for studying various biological processes, especially tracking, sensing and imaging in physiology and ecology.

Antibacterial activity of the nitrovinylfuran G1 (Furvina) and its conversion products.

2-Bromo-5-(2-bromo-2-nitrovinyl)furan (G1 or Furvina) is an antimicrobial with a direct reactivity against thiol groups. It is active against Gram-positive and Gram-negative bacteria, yeasts and filamentous fungi. By reacting with thiol groups it causes direct damage to proteins but, as a result, is very short-living and interconverts into an array of reaction products. Our aim was to characterize thiol reactivity of G1 and its conversion products and establish how much of antimicrobial and cytotoxic effects are due to the primary activity of G1 and how much can be attributed to its reaction products. Stability of G1 in growth media as well as its conversion in the presence of thiols was characterized. The structures of G1 decomposition products were determined using NMR and mass-spectroscopy. Concentration- and time-dependent killing curves showed that G1 is bacteriostatic for Escherichia coli at the concentration of 16 µg/ml and bactericidal at 32 µg/ml. However, G1 is inefficient against non-growing E. coli. Addition of cysteine to medium reduces the antimicrobial potency of G1. Nevertheless, the reaction products of G1 and cysteine enabled prolonged antimicrobial action of the drug. Therefore, the activity of 2-bromo-5-(2-bromo-2-nitrovinyl)furan is a sum of its immediate reactivity and the antibacterial effects of the conversion products.

The Functional Role of eL19 and eB12 Intersubunit Bridge in the Eukaryotic Ribosome.

During translation, the two eukaryotic ribosomal subunits remain associated through 17 intersubunit bridges, five of which are eukaryote specific. These are mainly localized to the peripheral regions and are believed to stabilize the structure of the ribosome. The functional importance of these bridges remains largely unknown. Here, the essentiality of the eukaryote-specific bridge eB12 has been investigated. The main component of this bridge is ribosomal protein eL19 that is composed of an N-terminal globular domain, a middle region, and a long C-terminal α-helix. The analysis of deletion mutants demonstrated that the globular domain and middle region of eL19 are essential for cell viability, most likely functioning in ribosome assembly. The eB12 bridge, formed by contacts between the C-terminal α-helix of eL19 and 18S rRNA in concert with additional stabilizing interactions involving either eS7 or uS17, is dispensable for viability. Nevertheless, eL19 mutants impaired in eB12 bridge formation displayed slow growth phenotypes, altered sensitivity/resistance to translational inhibitors, and enhanced hyperosmotic stress tolerance. Biochemical analyses determined that the eB12 bridge contributes to the stability of ribosome subunit interactions in vitro. 60S subunits containing eL19 variants defective in eB12 bridge formation failed to form 80S ribosomes regardless of Mg(2+) concentration. The reassociation of 40S and mutant 60S subunits was markedly improved in the presence of deacetylated tRNA, emphasizing the importance of tRNAs during the subunit association. We propose that the eB12 bridge plays an important role in subunit joining and in optimizing ribosome functionality.

Functionalization of Titanium Alloy Surface by Graphene Nanoplatelets and Metal Oxides: Corrosion Inhibition.

Corrosion inhibition of metallic substrates is an important and crucial step for great economical as well as environmental savings. In this paper, we introduce an extra thin effective corrosion inhibitive material having layered structure designed for protection and functionalization of Ti Grade 5 alloy substrates. The coating consists of a first layer made of thin graphene nanoplatelets, on top of which a multilayer Al2O3 and TiO2 films is applied by low-temperature atomic layer deposition. The amorphous structure of the metal oxide films was confirmed by micro-Raman and X-ray diffraction analysis. Corrosion inhibition ability of the prepared coatings was analyzed by open circuit potential, potentiodynamic plot and by voltammetric analysis, in aqueous potassium bromide solution. The open circuit potential of the graphene-metal oxide coated substrate showed much passive nature than bare substrate or graphene coated or only metal oxide coated substrates. The localized corrosion potential of the graphene-metal oxide coated, only metal oxide coated, and bare substrates were found 5.5, 3.0, and 1.1 V, respectively. In addition, corrosion current density values of the graphene-metal oxide and only metal oxide coated substrates showed much more passive nature than the bare and graphene coated substrates. Long immersion test in the salt solution further clarified the effective corrosion inhibition of the graphene-metal oxide coated substrate. The analyzed results reflect that the graphene-metal oxide films can be used to prepare better and effective corrosion inhibition coatings for the Ti Grade 5 alloy to increase their lifetime.

An energy transfer kinetic probe for OH-quenchers in the Nd(3+):YPO4 nanocrystals suitable for imaging in the biological tissue transparency window.

Tetragonal xenotime-type yttrium orthophosphate (YPO4) Nd(3+) doped nanoparticles suitable for biomedical applications were prepared by microwave-hydrothermal treatment. We applied the energy transfer probing based on the analysis of kinetics of impurity quenching to determine the presence and spatial position of -OH fluorescence quenching acceptors in the impurity-containing nanoparticles. We show that the impurity quenching kinetics of the 0.1 at% Nd(3+) doped YPO4 nanoparticles is a two stage (ordered and disordered) static kinetics, determined by a direct energy transfer to the -OH acceptors. Analyzing the ordered stage, we assume that the origin of the -OH groups is the protonation of the phosphate groups, while analyzing the disordered stage, we assume the presence of water molecules in the mesopores. We determine the dimension of the space of the -OH acceptors as d = 3 and quantify their absolute concentration using the disordered Förster stage of kinetics. We use the late stage of kinetics of fluorescence hopping (CDD ≫ CDA) quenching (the fluctuation asymptotics) at 1 at% Nd(3+) concentration as an energy transfer probe to quantify the relative concentration of -OH molecular groups compared to an optically active rare-earth dopant in the volume of NPs, when energy migration over Nd(3+) donors to the -OH acceptors accelerates fluorescence quenching. In doing so we use just one parameter α = γ(A)/γ(D) = n(A)√[C(DA)]/n(D)√[C(DD)], defined by the relation of concentration of the -OH acceptors to the concentration of an optically active dopant. The higher is the α, the higher is the relative concentration of -OH acceptors in the volume of nanoparticles. We find α = 2.95 for the 1 at% Nd(3+):YPO4 NPs that, according to the equation for α, and the results obtained for the values of the microparameters CDD(Nd-Nd) = 24.6 nm(6) ms(-1) and CDA(Nd-OH) = 0.6 nm(6) ms(-1), suggests twenty times higher concentration for acceptors other than donors. As the main result we have established that the majority of -OH acceptors is located not on the surface of the Nd(3+):YPO4 nanoparticles, as many researchers assumed, but in their volume, and can be either associated with crystal structure defects or located in the mesopores.

Effect of glucose content on thermally cross-linked fibrous gelatin scaffolds for tissue engineering.

Thermally cross-linked glucose-containing electrospun gelatin meshes were studied as possible cell substrate materials. FTIR analysis was used to study the effect of glucose on cross-linking reactions. It was found that the presence of glucose increases the extent of cross-linking of fibrous gelatin scaffolds, which in return determines scaffold properties and their usability in tissue engineering applications. Easy to handle fabric-like scaffolds were obtained from blends containing up to 15% glucose. Maximum extent of cross-linking was reached at nearly 20% glucose content. Cross-linking effectively resulted in decreased solubility and increased resistance to enzymatic degradation. Preliminary short-term cell culture experiments indicate that such thermally cross-linked gelatin-glucose scaffolds are suitable for tissue engineering applications.

Pd-catalyzed regioselective allylation of mono- and disubstituted hydrazines.

Palladium-catalyzed allylation of hydrazines using allyl alcohols is reported. This highly efficient protocol furnishes monoallylated hydrazines selectively, in 27-99% yields. Following an optimization of the reaction conditions and of the Pd-ligands, the allylations of both mono- and disubstituted hydrazines were investigated, as well as the effects of C2-substitution on the allylating agent. Of particular interest, a novel method for the selective monoallylation of monosubstituted hydrazines is demonstrated.

Evaluation of carbohydrates and lignocellulosic biomass from different wood species as raw material for the synthesis of 5-bromomethyfurfural.

The influence of different parameters on the conversion of carbohydrates and biomass into the potential biofuel intermediate 5-bromomethylfurfural (BMF) has been studied. Our optimized conditions avoid the use of lithium salt additives, making this method cheaper and environmentally more benign compared to previously reported methods. Different wood species and their potential as a raw material in BMF and furfural production have also been evaluated. In addition, we report a very simple and efficient procedure for conversion of 5-hydroxymethylfurfural (HMF) into BMF or 5-chloromethylfurfural (CMF).

Electrochemical modification of gold electrodes with azobenzene derivatives by diazonium reduction.

An electrochemical study of Au electrodes electrografted with azobenzene (AB), Fast Garnet GBC (GBC) and Fast Black K (FBK) diazonium compounds is presented. Electrochemical quartz crystal microbalance, ellipsometry and atomic force microscopy investigations reveal the formation of multilayer films. The elemental composition of the aryl layers is examined by X-ray photoelectron spectroscopy. The electrochemical measurements reveal a quasi-reversible voltammogram of the Fe(CN)6 (3-/4-) redox couple on bare Au and a sigmoidal shape for the GBC- and FBK-modified Au electrodes, thus demonstrating that electron transfer is blocked due to the surface modification. The electrografted AB layer results in strongest inhibition of the Fe(CN)6 (3-/4-) response compared with other aryl layers. The same tendencies are observed for oxygen reduction; however, the blocking effect is not as strong as in the Fe(CN)6 (3-/4-) redox system. The electrochemical impedance spectroscopy measurements allowed the calculation of low charge-transfer rates to the Fe(CN)6 (3-) probe for the GBC- and FBK-modified Au electrodes in relation to bare Au. From these measurements it can be concluded that the FBK film is less compact or presents more pinholes than the electrografted GBC layer.

Alkoxide-based precursors for direct drawing of metal oxide micro- and nanofibres.

The invention of electrospinning has solved the problem of producing micro- and nanoscaled metal oxide fibres in bulk quantities. However, until now no methods have been available for preparing a single nanofibre of a metal oxide. In this work, the direct drawing method was successfully applied to produce metal oxide (SnO2, TiO2, ZrO2, HfO2 and CeO2) fibres with a high aspect ratio (up to 10 000) and a diameter as small as 200 nm. The sol-gel processing includes consumption of precursors obtained from alkoxides by aqueous or non-aqueous polymerization. Shear thinning of the precursors enables pulling a material into a fibre. This rheological behaviour can be explained by sliding of particles owing to external forces. Transmission (propagation) of light along microscaled fibres and their excellent surface morphology suggest that metal oxide nanofibres can be directly drawn from sol precursors for use in integrated photonic systems.

Proteins in the insulin-secreting cell line MIN6 bind the imidazoline compound BL11282.

The imidazoline BL11282 stimulates insulin release and alters islet proteomes. Subcellular fractions of MIN6 cells showed that the membrane fraction exhibited binding to BL11282 on a Biacore chip and to BL11282-labelled magnetic beads. Bound material extracted from the beads showed a approximately 50 kDa differential band upon SDS-PAGE and a weaker 100 kDa band. The former was sensitive to competitive removal by preincubation of the fraction with BL11282, then highlighting the approximately 100 kDa band. Masspectrometric analysis revealed the approximately 50 kDa band to be EF1A and the approximately 100 kDa band to be glucose regulated P94, both of interest in insulin synthesis and secretion.

Phytochemical analysis of the essential oil of Thymus serpyllum L. growing wild in Estonia.

Variations in the essential oil composition of Thymus serpyllum L., growing wild in Estonia (33 samples) and in some other countries (Russia, Latvia and Armenia, seven samples) were determined. The oil were obtained from Estonia (46 samples) in yields 0.6-4.4 and 1.9-8.2 mL kg(-1) in other countries. The T. serpyllum herb grown in Estonia usually did not confirmed to the EP standard in the aspect of the essential oil contents (3.0 mL kg(-1)). Variations in the essential oil composition of wild thyme were studied using capillary gas chromatographic methods. A total of 94 components were identified. Thymol and carvacrol, mentioned in literature as principial components, are not the main components of the essential oil of wild thyme growing in Estonia. (E)-nerolidol, caryophyllene oxide, myrcene and borneol chemotypes of wild thyme drug are distinguishable. The chemical composition of samples from Russia, Latvia and Armenia is very variable.

Use of polyanions for alkylation of hydrazine derivatives.

Alkylation of hydrazine and its derivatives still remains a quite complicated task. The novel method utilizing the polyanion strategy is reported. Formation and use of trianion for alkylation of hydrazine derivatives is first reported. Described method provides fast and convenient access to multialkylated derivatives. Scope and limitations of new method are also investigated.

Efficient methodology for selective alkylation of hydrazine derivatives.

Formation and use of a nitrogen dianion for selective hydrazine alkylation is reported. The scope and limitations of a new method were demonstrated. The novel method provides fast and easy access to substituted hydrazines, which are widely used as drugs, pesticides, and precursors for a variety of compounds in organic synthesis. [reaction: see text]

Determination of thiopurine S-methyltransferase (TPMT) activity by comparing various normalization factors: reference values for Estonian population using HPLC-UV assay.

Thiopurine S-methyltransferase (TPMT; EC 2.1.1.67) is the key enzyme in the metabolism of thiopurine drugs. Determination of TPMT activity has been used for the individualization of thiopurine dose. We developed HPLC-UV assay for the determination of TPMT activity in human erythrocytes using 6-mercaptopurine as a substrate. Various extraction and chromatographic conditions were compared. In-house developed extraction with acetonitrile provided the lowest limit of quantification. TPMT activity was determined in 99 previously genotyped healthy Estonians. TPMT activity was expressed as the formation of 6-methylmercaptopurine ng/ml/h and normalized either to haemoglobin, haematocrit, erythrocyte count or protein content. The receiver-operating characteristic curve analysis revealed similar accuracy values for TPMT activity in predicting heterozygous and wild type individuals for each method of calculation. In healthy Estonians, TPMT activity varied from 21.5 to 129.6 ng/ml/h. For heterozygous individuals (n = 18), TPMT activity was 48.1 +/- 11.7 ng/ml/h. Wild type individuals (n = 81) revealed significantly higher TPMT activity 79.3 +/- 20.7 ng/ml/h (P < 0.001). This sensitive HPLC assay for quantitative determination of TPMT activity could easily be used in clinical settings. Under constant experimental conditions for haemolysate preparation no normalization is required.

Addition of arylboronic acids to symmetrical and unsymmetrical azo compounds.

[reaction: see text] The addition of aryl- and heteroarylboronic acids to azo compounds is described. Copper salt catalysis was necessary to perform the reaction under mild conditions and high yields. Excellent regioselectivity was observed in addition to unsymmetrical azo compounds.

Acidity of di- and triprotected hydrazine derivatives in dimethyl sulfoxide and aspects of their alkylation.

The pK(a) values in DMSO for 22 di- and triprotected hydrazine NH acids and two monosubstituted hydrazines have been determined using potentiometric titration. The results of density functional theory calculations at the B3LYP/6-311+G level of gas-phase acidities of a representative selection of mono-, di-, and trisubstituted hydrazines are compared with both the relevant published and novel experimental titration data. In the course of this work, a rough estimation of the pK(a) value of hydrazine in DMSO (ca. 38.0) has been deduced. For typical triprotected compounds of this kind containing moderately electron-withdrawing carbamate and imidodicarbonate or arenesulfonylcarbamate functions the pK(a) values fall in the range 15.1-17.3, whereas for N,N'-diprotected hydrazines with a carbamate and an aromatic sulfonyl group the corresponding values are 12.7-14.5. Several of these triprotected derivatives have recently been applied preparatively in stepwise synthesis of substituted hydrazines using alkyl halides as electrophiles in the presence of a phase transfer catalyst, and a few of them, with varying success, have been examined in model experiments with benzyl alcohol, triphenylphosphine, and diethyl azodicarboxylate in the Mitsunobu reaction. The dependence of the reactivity on the intrinsic acidity of the hydrazines in this reaction is highlighted. Furthermore, the regioselective alkylation of an N,N'-diprotected hydrazine can be rationalized on the basis of the presented data.