Solid State Calix[4]arene Tubular Assemblies Based on Cation–π Interactions

Infinite tubular assemblies based on calix[4]arenes can be easily constructed using cation–π interactions of silver triflate with preorganised aromatic subunits (1,3-alternate or pinched cone conformations). X-ray crystallographic analysis shows that the overall self-assembly is held together by triflate anions playing the role of the bridges between the individual complexes.     

Moisturizing emulsion systems based on the novel long-chain alkyl polyglucoside emulsifier

Mesomorphic behavior of the novel long-chain alkyl polyglucoside emulsifier comprising arachidyl alcohol (C₂₀), behenyl alcohol (C₂₂), and arachidyl glucoside was investigated in order to determine the prevalent stabilization mechanism and moisturizing capacity of emulsion systems based on it. For this to be accomplished thermoanalytical methods (differential scanning calorimetry and thermogravimetric analysis) coupled with microscopy, rheological, X-ray diffraction methods and a short-term in vivo study of skin hydration level were performed. Obtained results have proved that C₂₀/C₂₂ alkyl polyglucoside mixed emulsifier is able to provide the synergism between the two main types of lamellar phases, the liquid-crystalline (Lα), and the gel crystalline (Lβ) one, building the emulsion systems of different stability and performance. Formation of lamellar structures influenced for more than one half of water within the system to be entrapped. Conducted investigation of hydration potential in real-time conditions provided valuable information on the investigated emulsion vehicles’ moisturizing potential as well as their contribution to the skin barrier improvement. Therefore, it could be expected that emulsions based on this alkyl polyglucoside emulsifier could influence the delivery of active ingredients of both the lipophilic and hydrophilic type. The employment of thermoanalytical methods in our work suggests the possibility for thermal methods to be used more frequently in the characterization of both the novel raw materials and the belonging emulsion systems.     

Study of carbon black obtained by pyrolysis of waste scrap tyres

Waste scrap tyres were thermally decomposed under various conditions. Decompositions were followed by the TGA method. Specific heating regimes were tested to obtain optimal structural properties of resulting pyrolytic carbon black produced by pyrolysis of scrap tyres and the process was characterized in temperature interval from 380 to 1,200 °C and heating rate 10, 20 and 50 °C min^?1 under nitrogen atmosphere. The original scrap tyres and pyrolytic carbon black were characterized by Raman and Fourier transform infrared spectroscopy methods. Textural properties were also determined. Effect of temperature and heating rate on process of pyrolysis of scrap tyres was observed. Shifting of temperature of maximum pyrolysis rate to lower value and spreading of DTG peak is caused by increasing heating rate. Temperature 570 °C was sufficient for total scrap tyres pyrolysis. Graphitic and disordered structure was distinguished in the formed carbon black by Raman spectroscopy. With increasing temperature, heating rate and weight loss, the amount of the graphitic structure was reduced at the expense of disordered structure. Destruction of nonporous scrap tyres and formation of porous structure took place at higher temperature. Porous carbon black is formed above 380 °C, specific surface area increased up to 88 m² g^?1 .     

Green chromatography separation of analytes of greatly differing properties using a polyethylene glycol stationary phase and a low-toxic water-based mobile phase

A simple, rapid, and environmentally friendly HPLC method was developed and validated for the separation of four compounds (4-aminophenol, caffeine, paracetamol, and propyphenazone) with different chemical properties. A “green” mobile phase, employing water as the major eluent, was proposed and applied to the separation of analytes with different polarity on polyethylene glycol (PEG) stationary phase. The chromatography separation of all compounds and internal standard benzoic acid was performed using isocratic elution with a low-toxicity mobile phase consisting of 0.04 % (v/v) triethylamine and water. HPLC separation was carried out using a PEG reversed-phase stationary phase Supelco Discovery HS PEG column (15?×?4 mm; particle size 3 μm) at a temperature of 30 °C and flow rate at 1.0 mL min^?1. The UV detector was set at 210 nm. In this study, a PEG stationary phase was shown to be suitable for the efficient isocratic separation of compounds that differ widely in hydrophobicity and acid–base properties, particularly 4-aminophenol (log P, 0.30), caffeine (log P, ?0.25), and propyphenazone (log P, 2.27). A polar PEG stationary phase provided specific selectivity which allowed traditional chromatographic problems related to the separation of analytes with different polarities to be solved. The retention properties of the group of structurally similar substances (aromatic amines, phenolic compounds, and xanthine derivatives) were tested with different mobile phases. The proposed green chromatography method was successfully applied to the analysis of active substances and one degradation impurity (4-aminophenol) in commercial preparation. Under the optimum chromatographic conditions, standard calibration was carried out with good linearity correlation coefficients for all compounds in the range (0.99914–0.99997, n?=?6) between the peak areas and concentration of compounds. Recovery of the sample preparation was in the range 100?±?5 % for all compounds. The intraday method precision was determined as RSD, and the values were lower than 1.00 %.

Qualitative and quantitative analysis of the unsaponifiable fraction of vegetable oils by using comprehensive 2D GC with dual MS/FID detection

The present investigation is focused on the development of a comprehensive two-dimensional GC (GC?×?GC) method, with dual MS/FID detection, for the qualitative and quantitative analysis of the entire unsaponifiable fraction of vegetable oils. The unsaponifiable fraction forms a minor, highly specific part of a vegetable oil, and can be used as an indicator of genuineness. The column set used consisted of a low-polarity first dimension, and a medium-polarity secondary one, both characterized by a high thermal stability. The use of dual detection enabled the attainment of both mass spectral information and relative % FID data. The complexity of the fingerprint, generated by the unsaponifiable fraction, fully justified the employment of the two-dimensional GC technology. Furthermore, two other GC?×?GC benefits contributed greatly to the attainment of promising results, namely sensitivity enhancement and the formation of group-type patterns. The method herein proposed could potentially open a new opportunity for the more in-depth knowledge of the unsaponifiable fraction of vegetable oils.     

Self-assembly of 5,11,17,23-tetranitro-25,26,27,28-tetramethoxythiacalix[4]arene with neutral molecules and its use for anion recognition

Methylation of 5,11,17,23-tetranitrothiacalix[4]arene with diazomethane leads to the tetramethoxy derivative, which was studied using single-crystal X-ray crystallography. It revealed that this compound, albeit in the 1,3-alternate conformation, can form the inclusion complexes with various solvent molecules possessing acidic methyl groups (ethyl acetate, nitromethane, acetone, acetonitrile) and creates interesting infinite channels filled with solvent molecules. The subsequent transformation of nitro groups into the ureido moieties gave receptors capable of anion recognition even in a highly HB-competitive solvent like DMSO.     

Determination of 129I in biomonitors collected in the vicinity of a nuclear power plant by neutron activation analysis

Neutron activation analysis (NAA) was used to determine ¹²⁹I and the ¹²⁹I/¹²⁷I ratio in bovine thyroid, moss, and river sediment samples collected in the vicinity of the Temelín nuclear power plant (NPP) in south Bohemia. The NAA procedures comprised pre-irradiation separation of ¹²⁹I by combustion of the samples in the stream of oxygen at 1,000 °C and trapping the liberated iodine in a LiOH/(NH₄)₂SO₃ solution. Post-irradiation separation of ¹³⁰I produced by the reaction ¹²⁹I(n,γ)¹³⁰I was carried out by extraction of elementary iodine with chloroform followed by precipitation of PdI₂. Nondestructive, epithermal NAA was used to determine ¹²⁷I employing the ¹²⁷I(n,γ)¹²⁸I reaction. The results showed that mean values of ¹²⁹I and the ¹²⁹I/¹²⁷I ratio in the bovine thyroids varied from 22 to 61 mBq kg^?1 (dry mass) and 2.8 × 10^?9 to 5.4 × 10^?9, respectively. These values are close to the lower end of results reported from various regions non-polluted with ¹²⁹I. No significant differences were found between ¹²⁹I concentrations and the ¹²⁹I/¹²⁷I ratios in the bovine thyroids collected prior to the start and after several years of operation of the NPP. The mean value and standard deviation of ¹²⁹I in mBq kg^?1, dry mass and the ¹²⁹I/¹²⁷I ratio in moss Pleurozium schreberi were 23 ± 16 and 2.3 × 10^?9, respectively, whereas values of ¹²⁹I in the river sediments were below 8–10 mBq kg^?1 (dry mass) after several years of the NPP operation.     

Study of chemoselective asymmetric hydrogenation of (1-bromo-1-alkenyl)boronic esters with iridium–PˆN complexes

In this paper we report the first chemoselective asymmetric hydrogenation of (1-bromo-1-alkenyl)boronic esters, which constitutes a new route to (α-bromoalkyl)boronic esters. The study demonstrates that excellent chemoselectivities along with full conversions can be obtained for hydrogenation of alkyl substituted derivatives with iridium–PˆN complexes. Moreover, acyclic alkyl derivatives afford (α-bromoalkyl)boronic esters in good enantioselectivities ranging from 64 to 73% ee. A cyclic alkyl derivative was obtained only in a nearly racemic form. The (1-bromo-1-alkenyl)boronic esters appear to be less reactive towards homogenous hydrogenation conditions than their chloro analogues as demonstrated by the higher catalyst loadings required to achieve full conversions for alkyl derivatives and lower conversions observed for the aryl substituted derivatives.     

Recognition of chiral anions using calix[4]arene-based ureido receptor in the 1,3-alternate conformation

A new type of calixarene-based receptor designed for the recognition of chiral anions was prepared by the introduction of (S)-2-methylbutan-1-ol moieties into the lower rim of calixarene. The immobilization of calixarene skeleton in the 1,3-alternate conformation enabled the construction of a cavity consisting of preorganised ureido functions and chiral substituents in close proximity. This cavity is capable of chiral discrimination of selected anions as demonstrated on d- and l-phenylalaninates.