[3 + 2]-Cycloaddition of azomethine ylide at 1,3-dimethyl-6-(2-oxo-1,2-dihydro-3H-indol-3-ylidene)-3a,9a-diphenyl-3,3a,9,9a-tetrahydroimidazo[4,5-e][1,3]thiazolo[3,2-b][1,2,4]triazine-2,7(1H,6H)-diones

[3 + 2]-Cycloaddition of azomethine ylide generated from formaldehyde and sarcosine at the double bond of 1,3-dimethyl-6-(2-oxo-1,2-dihydro-3H-indol-3-ylidene)-3a,9a-diphenyl-3,3a,9,9a-tetrahydroimidazo[4,5e][1,3]thiazolo[3,2-b][1,2,4]triazine-2,7(1H,6H)-diones occurs stereospecifically at the face opposite to the phenyl substituents. Product 3a crystallizes as a conglomerate.     

Adsorption of lead(II), cadmium(II) and dysprosium(III) from aqueous solutions using mesoporous silica modified with phosphonic acid groups

The mesoporous silica samples with different concentrations of phosphonic acid groups on the surface were obtained by direct template synthesis. The block-copolymer Pluronic P123 was used as a template, and sodium meta-silicate with diethylphosphatoethyltriethoxysilane as precursors. According to the SAXS diffractograms, mesoporous silica samples have a p6mm hexagonal symmetry. In addition, we used sol–gel method to synthesize xerogel with the same groups for comparison. All samples possess high values of specific surface area 615–730?m²/g and sorption pore volume. FTIR and potentiometric titration methods were used to investigate the surface layer of these samples. Sorption properties of the samples with phosphonic acid groups were studied in respect to a row of metal cations, among which we focused on lead(II), cadmium(II), and dysprosium(III) cations.

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Synthesis and structure of bis(tetraphenyl-λ5-stibanyl)-1,7-carborane-1,7-dicarboxylate

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Synthesis of chiral nopinane annelated 3-methyl-1-aryl-1H-pyrazolo[3,4-b]pyridines by condensation of pinocarvone oxime with 1-aryl-1H-pyrazol-5-amines

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One-pot two-step stannylation/Stille homocoupling of aryl bromides and iodides under solvent-free conditions

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Chiral recognition capabilities of melamine and cyanuric acid supramolecular structures

Currently, there are numerous papers that discuss local chiral domains in supramolecular structures of achiral molecules established using the STM method, and by using DFT calculations. However, there are no data regarding the obtainment of macroscopically chiral 2D-supramolecular structures from achiral molecules. In this study, melamine and cyanuric acid supramolecular structures were self-assembled on a graphitized carbon black surface, which had a surface structure that was identical to HOPG, and also on the surface of an inert solid support for chromatography. Chirality induction according to the Kondepudi effect was used. For the supramolecular structures, MD calculations showed the possibility of obtaining a chiral structure. To establish macroscopic chirality, we proposed the use of the difference in enantiomer adsorption on the modified adsorbents. For this, two indirect methods were used: static adsorption with a polarimetric control and gas chromatography. Both methods indicated the chiral recognition ability of the adsorbents used.     

Lignins Isolated via Catalyst-Free Organosolv Pulping from Miscanthus x giganteus,M. sinensis,M. robustus and M. nagara: A Comparative Study

As a low-input crop, Miscanthus offers numerous advantages that, in addition to agricultural applications, permits its exploitation for energy, fuel, and material production. Depending on the Miscanthus genotype, season, and harvest time as well as plant component (leaf versus stem), correlations between structure and properties of the corresponding isolated lignins differ. Here, a comparative study is presented between lignins isolated from M. x giganteus, M. sinensis, M. robustus and M. nagara using a catalyst-free organosolv pulping process. The lignins from different plant constituents are also compared regarding their similarities and differences regarding monolignol ratio and important linkages. Results showed that the plant genotype has the weakest influence on monolignol content and interunit linkages. In contrast, structural differences are more significant among lignins of different harvest time and/or season. Analyses were performed using fast and simple methods such as nuclear magnetic resonance (NMR) spectroscopy. Data was assigned to four different linkages (A: β-O-4 linkage, B: phenylcoumaran, C: resinol, D: β-unsaturated ester). In conclusion, A content is particularly high in leaf-derived lignins at just under 70% and significantly lower in stem and mixture lignins at around 60% and almost 65%. The second most common linkage pattern is D in all isolated lignins, the proportion of which is also strongly dependent on the crop portion. Both stem and mixture lignins, have a relatively high share of approximately 20% or more (maximum is M. sinensis Sin2 with over 30%). In the leaf-derived lignins, the proportions are significantly lower on average. Stem samples should be chosen if the highest possible lignin content is desired, specifically from the M. x giganteus genotype, which revealed lignin contents up to 27%. Due to the better frost resistance and higher stem stability, M. nagara offers some advantages compared to M. x giganteus. Miscanthus crops are shown to be very attractive lignocellulose feedstock (LCF) for second generation biorefineries and lignin generation in Europe.     

Cationic amphiphilic polyelectrolytes and oppositely charged surfactants at the silica-aqueous interface

The influence of sodium dodecyl sulfate (SDS) on the interfacial behavior of two amphiphilic polyelectrolytes, which are copolymers of the cationic monomers triethyl(vinylbenzyl)ammonium chloride and dimethyldodecyl(vinylbenzyl)ammonium chloride, at the silica-aqueous interface was studied. The fraction of amphiphilic monomers was varied, where 0DT, 40DT, and 80DT contained 0, 40, and 80 mol % monomers with dodecyl side chains, respectively. We used in situ ellipsometry to follow the kinetics of adsorption, in terms of adsorbed amount and adsorbed layer thickness, as well as the response of the adsorbed layers to changes in ionic strength and surfactant concentration. Different results were obtained when surfactant was added to the preadsorbed layers compared to the cases when complexes were preformed in the solution prior to the adsorption. In the whole range of concentrations studied, SDS interacts with 40DT and 80DT noncooperatively, whereas for 0DT cooperativity of binding is observed. The amount adsorbed increased significantly as the SDS concentration was close to the cmc. At high SDS concentrations, a lowering of the layer density was observed. For the amphiphilic polyelectrolytes, 40 DT and 80DT, no desorption from the interface was detected for the range of SDS concentrations studied, while 0DT features a maximum in adsorbed amount at concentrations close to the cmc of SDS. Adsorption of 40DT and 80DT from their mixtures with SDS is found to be path dependent with respect to the variation in SDS concentration, where the reversibility decreases with increasing SDS concentration above the expected charge neutralization point. The coadsorption of 80DT and SDS is highly irreversible with respect to changes in the ionic strength within the time scale of the experiment. In this study, we attempt to illustrate both general mechanisms and specific effects. With regard to the general behavior, it is important to note the charge regulation of both the silica surfaces and the polyion/surfactant complexes; an interplay between the two charge-regulating effects is the key to understanding our observations.     

Tuning of optical properties of CdS nanoparticles synthesized in a glass matrix

Attempts were made to provide the data concerning directed synthesis of semiconductor nanoparticles in a dielectric silica-based glass matrix. These attempts involve finding out the connections between the structure, size of CdS nanoparticles, and optical properties of the nanocomposites produced. High-resolution focused ion beam scanning electron microscopy images of CdS nanoparticles incorporated in glass and SAXS results confirm the formation of uniformly distributed spherical CdS nanoparticles with an average diameter of about 6.2 nm. UV–Vis measurements show that CdS composites possess a direct bandgap wider than 2.45 eV depending on the heat treatment conditions; thus, heat treatment can be used to control nanoparticle size in each selected composite. The emission spectra showed a maximum at about 603 nm and a red shift of about 100 nm with increasing annealing temperature that is associated with the presence of defect states in the nanoparticles. In addition, semiconductor phase concentration in the glass matrix was found by using optical absorption data for the first time, which allows understanding the effect of nanocomposite structure on luminescence properties.