Single dibenzoterrylene molecules in naphthalene and 2,3-dimethylnaphthalene crystals: vibronic spectra

Fluorescence excitation spectra of single dibenzoterrylene (DBT) molecules embedded in naphthalene (N) and 2,3-dimethylnaphthalene (2,3-DMN) crystals were studied at 5 K. The frequencies characterizing the vibronic structure of single DBT molecules in an N crystal agree with the theoretical prediction for the isolated DBT molecule. The 'dipolar' disorder encountered in 2,3-DMN crystals leads to a broad distribution of frequencies of the (0,0) lines of single DBT molecules. Moreover, the observed vibronic frequencies and intensities in the spectrum of DBT in 2,3-DMN crystals are slightly different to those in an N crystal. We conclude that the structure of DBT molecules in a 2,3-DMN crystal is disturbed in comparison with isolated DBT and the main change concerns its central tetracene moiety.     

Increasing the solubility characteristics of fenofibrate with cyclodextrin

The incidence of genetic lipoprotein disorders, or hyperlipoproteinaemia, is currently increasing. Examinations were carried out on the hyperlipoproteinaemic drug fenofibrate and various cyclodextrin derivatives were applied to increase the solubility of this drug. Numerous products with several compositions (drug: CD mole ratio=2:1, 1:1, 1:2 or 1:3) were studied and three preparation methods (powder mixing, kneading and precipitation) were used. In vitro drug liberation and membrane diffusion examinations revealed compositions suitable for the preparation of a capsule dosage form (1:2 and 1:3 physical mixtures).Dedicated to Dr. Béla Selmeczi, university professor, with the best wishes for his 65th birthday.     

Helical twisting power of antiferroelectric chiral terphenyls in different matrices

To determine the influence of chemical structure on the Helical Twisting Power (HTP), we tested four optically active dopants having a terphenyl rigid core and the same chiral centre but differing in the length of nonchiral terminal chain and the substitution of benzene rings with fluorine atoms. The compounds were added to different achiral liquid crystalline matrices: nematic and smectic C. It was found that HTP as well as its temperature variation depends on the kind of used matrices. It gives a conclusion that information about HTP obtained in one matrix cannot be uncritically transferred to another one.     

Polymorphic forms of bisoprolol fumarate

Bisoprolol fumarate is a beta blocker-type drug substance which has been well known for several decades. However, no relevant data can be found in the literature about its crystal polymorphism. The purpose of this paper was to present two anhydrous forms (Form I and Form II) and a hydrate of bisoprolol fumarate substance. Crystalline forms were studied by various solid-state analytical methods: Fourier transform infrared (FT-IR) spectroscopy, X-ray powder diffraction (XRPD), dynamic vapor sorption (DVS) and thermoanalytical methods (thermogravimetry and differential scanning calorimetry). Thermodynamic stability and solubility of the presented polymorphs were also investigated. Both FT-IR and XRPD methods were found to be suitable for the characterization of the different crystal structures. Thermoanalytical measurements showed that (1) Form I and Form II own clearly different melting points and (2) both Form II and hydrate forms can transform into Form I at higher temperature values. Results of the DVS measurements prove that both Form I and Form II became metastable under extremely humid conditions (>?80% RH) and converted into the hydrate. Thermodynamic stability studies showed that Form I and Form II polymorphs are in enantiotropic relationship with an enantiotropic point at about 40–45 °C. Solubility studies indicated that all of the prepared forms are highly soluble, and no difference was found between them. Considering the recommendations of the corresponding International Conference of Harmonization guideline, it can be stated that no specification is required for crystal polymorphism in case of this substance.

     

Improvement of the magnetic properties of low-neodymium magnets by minor addition of titanium

Rapidly solidified nanocomposite Nd₉Fe_77−xB₁₄Ti_x alloys, consisting of magnetic Nd₂Fe₁₄B phase and soft magnetic phases, were investigated. The effect of titanium addition on the structure and magnetic properties was studied. It was found that 2–4 at% Ti addition leads to substantial increase of the coercivity and maximum energy product, maintaining the remanence unchanged. The highest properties: J_r=0.81 T, _JH_c=907 kA/m, (BH)_max=99 kJ/m³, were achieved for the Nd₉Fe₇₃B₁₄Ti₄ alloy. This effect we attribute to the formation of fine and homogeneous grain structure and a change of the phase morphology in the Ti-containing alloys. The initial magnetization curve indicates a change of the coercivity mechanisms giving rise to pinning of domain walls, which is caused by reduction of the crystallite size.     

Time Evolution of Microbial Composition and Metabolic Profile for Biogenic Amines and Free Amino Acids in a Model Cucumber Fermentation System Brined with 0.5% to 5.0% Sodium Chloride

Salt concentrations in brine and temperature are the major environmental factors that affect activity of microorganisms and, thus may affect formation of biogenic amines (BAs) during the fermentation process. A model system to ferment cucumbers with low salt (0.5%, 1.5% or 5.0% NaCl) at two temperatures (11 or 23 °C) was used to study the ability of indigenous microbiota to produce biogenic amines and metabolize amino acid precursors. Colony counts for presumptive Enterococcus and Enterobacteriaceae increased by 4 and up to 2 log of CFU∙mL⁻¹, respectively, and remained viable for more than 10 days. 16S rRNA sequencing showed that Lactobacillus and Enterobacter were dominant in fermented cucumbers with 0.5% and 1.5% salt concentrations after storage. The initial content of BAs in raw material of 25.44 ± 4.03 mg∙kg⁻¹ fluctuated throughout experiment, but after 6 months there were no significant differences between tested variants. The most abundant BA was putrescine, that reached a maximum concentration of 158.02 ± 25.11 mg∙kg⁻¹. The Biogenic Amines Index (BAI) calculated for all samples was significantly below that needed to induce undesirable effects upon consumption. The highest value was calculated for the 23 °C/5.0% NaCl brine variant after 192 h of fermentation (223.93 ± 54.40). Results presented in this work indicate that possibilities to control spontaneous fermentation by changing salt concentration and temperature to inhibit the formation of BAs are very limited.     

Application of a New Dehydroascorbic Acid Reducing Agent in the Analysis of Vitamin C Content in Food

The analysis of total vitamin C content in food is most frequently performed by reducing dehydroascorbic acid to ascorbic acid, which is then assayed with the technique of high-performance liquid chromatography combined with spectrophotometric detection. Tris(2-carboxyethyl)phosphine is currently the only agent in use that efficiently reduces dehydroascorbic acid at pH < 2. Therefore, there is a continued need to search for new reducing agents that will display a high reactivity and stability in acidic solutions. The objective of the study was to verify the applicability of unithiol and tris(hydroxypropyl)phosphine for a reducing dehydroascorbic acid in an extraction medium with pH < 2. The conducted validation of the newly developed method of determining the total content of vitamin C using tris(hydroxypropyl)phosphine indicates its applicability for food analysis. The method allows obtaining equivalent results compared to the method based on the use of tris(2-carboxyethyl)phosphine. The low efficiency of dehydroascorbic acid reduction with the use of unithiol does not allow its application as a new reducing agent in vitamin C analysis.     

Synthesis and Reactions of a New Cyclobutanethione Derivative

The 3,3‐dichloro‐2,2,4,4‐tetramethylcyclobutanethione ( 4b ) was prepared from the parent diketone by successive reaction with PCl₅ and Lawesson reagent in pyridine. This new thioketone 4b was transformed into 1‐chlorocyclobutanesulfanyl chloride 5 and chloro 1‐chlorocyclobutyl disulfide 9 by treatment with PCl₅ and SCl₂, respectively, in chlorinated solvents (Schemes 1 and 2). These products reacted with S‐ and P‐nucleophiles by substitution of Cl⁻ at the S‐atom; e.g., the reaction with 4b yielded the di‐ and trisulfides 6b and 11 , respectively. Surprisingly, only pentasulfide 12 was formed in the reaction of 9 with thiobenzophenone (Scheme 3). In contrast to 5 and 9 , the corresponding chloro 1‐chlorocyclobutyl trisulfide 13 could not be detected, but reacted immediately with the starting thioketone 4b to give the tetrasulfide 14 (Scheme 4). Oxidation of 4b with 3‐chloroperbenzoic acid (mCPBA) yielded the corresponding thione oxides (= sulfine) 15 , which underwent 1,3‐dipolar cycloadditions with thioketones 3a and 4b (Scheme 5). Furthermore, 4b was shown to be a good dipolarophile in reactions with thiocarbonylium methanides (Scheme 6) and iminium ylides (= azomethine ylides; Scheme 7). In the case of phenyl azide, the reaction with 4b gave the symmetrical trithiolane 25 (Scheme 8).