Search Results (14)

Several series of new polymers were synthesized in this study: binary copolyesters of vanillic (VA) and 4′-hydroxybiphenyl-4-carboxylic (HBCA) acids, as well as ternary copolyesters additionally containing 4-hydroxybenzoic acid (HBA) and obtained via three different ways (in solution, in melt, and in solid state). The high values of logarithmic intrinsic viscosities and the insolubility of several samples proved their high molecular weights. It was found that the use of vanillic acid leads to the production of copolyesters with a relatively high glass transition temperature (~130 °C). Thermogravimetric analysis revealed that the onset of weight loss temperatures of ternary copolyesters occurred at 330–350 °C, and the temperature of 5% mass loss was in the range of 390–410 °C. Two-stage thermal destruction was observed for all aromatic copolyesters of vanillic acid: decomposition began with VA units at 420–480 °C, and then the decomposition of more heat-resistant units took place above 520 °C. The copolyesters were thermotropic and exhibited a typical nematic type of liquid crystalline order. The mechanical characteristics of the copolyesters were similar to those of semi-aromatic copolyesters, but they were much lower than the typical values for fully aromatic thermotropic polymers. Thus, vanillic acid is a mesogenic monomer suitable for the synthesis of thermotropic fully aromatic and semi-aromatic copolyesters, but the processing temperature must not exceed 280 °C. Full article

Monosaccharide composition analysis is essential to the structural characterization and research into the biological activity of polysaccharides. In this study, a systematic comparison was performed among commonly used monosaccharide composition analysis methods, including colorimetric and chromatographic methods. These were tested on 16 aldoses, ketoses, alditols, amino sugars, and uronic acids. Furthermore, the effect of hydrolysis methods was also investigated. The results showed that the phenol sulfuric acid method is greatly affected by the type of monosaccharide that is used as the reference substance. The determination of uronic acid using sulfuric acid carbazole is less affected by neutral sugars than that method using m-hydroxybiphenyl. The high-performance thin-layer chromatography (HPTLC) method can simultaneously analyze multiple samples and accurately determine the type of uronic acid. High-performance liquid chromatography (HPLC) can provide a good qualitative and quantitative analysis of aldose, amino sugars, and uronic acids, while gas chromatography–mass spectrometry (GC-MS) can detect aldose, ketose, and alditols. Fructose was detected in a large amount in inulin and Codonopsis pilosula after one-step hydrolysis, while it was totally destroyed in two-step hydrolysis. The release of galacturonic acid significantly increased after two-step hydrolysis in pectin and Lycium barbarum, which indicated that one-step hydrolysis is not enough for acidic polysaccharides. The results of this study are beneficial for selecting appropriate hydrolysis and analysis methods in order to accurately analyze the monosaccharide compositions of natural polysaccharides. Full article

Over the past few decades, drug-induced liver damage (DILI) has become a serious public health problem due to drug abuse. Among multifarious reactive oxygen species, mounting evidence attests that ClO⁻ has been used as a potential biomarker in DILI. In this work, a new “turn-on” fluorescent probe 1 was designed and synthesized by modifying 4′-hydroxybiphenyl-4-carbonitrile (dye 2) with N, N-dimethylthiocarbamate as a response site for detecting ClO⁻. Probe 1 displayed a low detection limit (72 nM), fast response time (30 s), wide pH operating range (6–8), great tissue penetration, large Stokes shift (125 nm) and 291-fold fluorescence enhancement at 475 nm in the mapping of ClO⁻. Probe 1 could trace amounts of exogenous and endogenous ClO⁻ with high sensitivity in MCF-7 cells and HeLa cells. Expectantly, the fluoxetine-induced liver injury model is successfully established, and probe 1 has been used for detecting the fluctuation of ClO⁻ levels in the mouse model of fluoxetine-induced liver injury. All in all, probe 1 with its high specificity, good biological compatibility and liver tissue penetration ability is expected to assist with the early diagnosis of DILI and the clinical screening of various new drugs. We expect that probe 1 could be efficiently used as a powerful molecular tool to predict clinical DILI and explore molecular mechanisms between molecules and disease. Full article

A series of new wholly aromatic (co)polyesters based on m-substituted bifunctional comonomers—4′-hydroxybiphenyl-3-carboxylic (3HBCA) and 3-hydroxybenzoic (3HBA) acids with molar ratios of 3HBCA:3HBA from 0:100 to 60:40, respectively—was synthesized. NMR and FTIR spectroscopy methods proved the full compliance of the copolymer composition with the target ratio of comonomers, as well as high compositional homogeneity (absence of block sequences). The resulting copolyesters have a sufficiently high molecular weight and their intrinsic viscosity values are in the range of 0.6–0.8 dL/g. Thermal analysis showed that all 3HBCA-3HBA copolyesters are amorphous, and with an increase in the content of biphenyl units (3HBCA), the glass transition temperature increases significantly (up to 190 °C). The onset of the intense thermal decomposition of the synthesized polyesters occurs above 450 °C. Thus, this indicates a sufficiently high thermal stability of these polyesters. Rheological measurements have shown that melts of copolyesters with a high content of 3HBCA units exhibit anisotropic properties. At the same time, the method of polarization optical microscopy did not confirm the transition to the liquid crystal state for these polyesters. These results confirm that it is possible to obtain high-performance polyesters based on 3HBCA, but not a mesogenic comonomer. Thus, 3HBCA is a promising comonomer for the synthesis of new thermotropic copolyesters with controlled anisotropic properties. Full article

The Rhodococcus erythropolis (strain IGTS8) bacterium has a tremendous industrial interest as it can remove sulfur from crude oil through its four-enzyme (DszA-D) 4S metabolic pathway. DszC is one of the rate-limiting enzymes of the pathway and the one that most suffers from feedback inhibition. We have combined molecular docking and molecular dynamics simulations to identify binding sites through which two products of the 4S pathway, 2-hydroxybiphenyl and 2′-hydroxybiphenyl-2-sulfinate, induce DszC feedback inhibition. We have identified four potential binding sites: two adjacent binding sites close to the 280–295 lid loop proposed to contribute to DszC oligomerization and proper binding of the flavin mononucleotide cofactor, and two other close to the active site of DszC and the substrate binding site. By considering (i) the occupancy of the binding sites and (ii) the similar inhibitor poses, we propose that the mechanism of feedback inhibition of DszC occurs through disturbance of the DszC oligomerization and consequent binding of the flavin mononucleotide due to the weakening of the interactions between the 280–295 lid loop, and both the 131–142 loop and the C-terminal tail. Nevertheless, inhibitor binding close to the active site or the substrate binding sites also compromises critical interactions within the active site of DszC. The disclosed molecular details provide valuable insight for future rational enzyme engineering protocols to develop DszC mutants more resistant against the observed feedback inhibition mechanism. Full article

Thirteen new liquid crystalline racemic mixtures were synthesized and investigated. For these racemic mixtures, the phase sequences and their changes were determined by polarizing optical microscopy (POM). The phase transition temperatures and transition enthalpies were checked by differential scanning calorimetry (DSC). All new racemates have an anticlinic smectic C_A phase in a broad temperature range. Three highly tilted antiferroelectric mixtures were doped with six racemates at a concentration of 20% by weight. The helical pitch of the prepared mixtures was measured by the spectrophotometry method. All doped mixtures have a longer helical pitch than the base mixtures. Full article

A health risk assessment was carried out for the residents of Łęgnowo-Wieś settlement adjacent to a former Zachem Chemical Plant, Bydgoszcz, Poland. Due to the unique Zachem site history and contamination profile, an innovative strategy for soil sampling and contaminant selection was applied. The novelty in the developed strategy consisted of selecting substances for the health risk assessment, taking into consideration the location and boundaries of the groundwater contamination plumes in relation to contamination sources. This allowed limiting the number of the analysed contaminants. The risk assessment focused on the surface soil of a residential area, which was divided into 20 sampling sectors and 6 backyards with wells from which water was used for watering edible plants. A total of 80 inorganic and organic substances were determined, including metals, phenol, aniline, BTEX, diphenyl sulphone, chloroaniline, epichlorohydrin, hydroxybiphenyl, nitrobenzene, octylphenols, toluenediamine, toluidine, 16 polycyclic aromatic hydrocarbons, tetrachloroethylene and trichloroethylene. For the health risk assessment, the United States Environmental Protection Agency’s deterministic method was applied. This applies conservative assumptions to obtain risk estimates protective for most of the potential receptors. Three exposure pathways were analysed: (1) incidental soil ingestion, (2) dermal contact with soil and (3) inhalation of fugitive soil particles and volatiles. In all sampling sectors and backyards, the total non-cancer risks (hazard index) were significantly lower than the acceptable level of 1. The acceptable cancer risk level for the single carcinogen of 1 × 10⁻⁵ was only insignificantly exceeded in the case of benzo(a)pyrene in three sectors and one backyard. The total cancer risks were lower than the acceptable level of 1 × 10⁻⁴ in all sampling sectors and all backyards. The findings show that the soil in the entire residential area is safe for the residents’ health and no remedial actions are required. However, since not all possible exposure pathways were analysed in this study, further research focused on assessing the health risk resulting from the consumption of locally grown food is strongly recommended. Full article

A combination of theoretical and experimental approaches was applied to determine the chromatographic rules of isomeric compounds’ behavior for preliminary identification. In gas chromatography-mass spectrometry (GC-MS), identification is performed by spectra matching, however, difficulties arise with isomeric compounds, which cannot be distinguished from each other without additional information. The thermodynamic characteristics of the adsorption of symmetric and asymmetric isomers of chlorophenylphenols, dimethoxybiphenyls, tri- and tetrachlorobiphenyls were determined using molecular statistical calculations. By-products in the chlorination of 4-hydroxybiphenyl were identified: 4-hydroxy-2,3′- and 3,2′-dichlorobiphenyls, 4-hydroxy-3,5,2′- and 2,3,6-trichlorobiphenyls. A developed theoretical approach was applied to predict the retention order of tri- and tetra-chlorobiphenyls. The GC-MS data and molecular statistical calculations made it possible to determine the main products of methoxybenzene dimerization as well as identify impurities. Thermodynamic parameters were received to describe the unusual retention behavior of epimers in reversed-phase high-performance liquid chromatography. Molecular descriptors were calculated to determine correlation with retention of both structural isomers and epimers. Descriptor combining surface area and partial charge information turned out to be useful in evaluating retention order for isomers. Full article

A series of novel copolyesters based on polyethylene terephthalate (PET) and 4′-hydroxy-biphenyl-4-carboxylic acid (HBCA) was obtained by melt polycondensation of bis(2-hydroxyethyl) terephthalate and 4′-acetoxybiphenyl-4-carboxylic acid (ABCA) as co-monomers with Sb₂O₃ as a catalyst. Using this synthetic procedure, a set of copolymers containing 20–80 mol% of HBCA units was prepared. According to NMR spectroscopy, the copolymers were of random composition. Copolyesters comprising 60–80 mol% of HBCA possessed increased heat resistance and formed nematic melts at 270 °C and higher. The liquid crystal (LC) phase formation was accompanied by transition to non-Newtonian characteristics of the melt flow, as well as an equalization of storage and loss moduli values. According to XRD and polarizing microscopy, the LC glassy phase of the copolyesters coexists with crystalline regions of poly-(4′-hydroxy-4-biphenylcarboxylate), non-melting up to 400 °C and above. The mechanical characteristics of these LC copolyesters showed similar or better values than those of well-known LC polymers. These novel copolyesters can be useful in obtaining heat-resistant materials with an ordered structure and, as a consequence, improved performance. Full article

Solvent evaporation is often used in the sample preparation procedure for the determination of organic pollutants such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organic pesticides. Because of the loss of analyte during this step, a high-boiling solvent, i.e., a keeper, is often added to the extract before evaporation. However, there are almost no basic studies found in the literature on the selection of keepers for the appropriate type of analytes (keepers are usually selected only on the basis of information provided by various recommendations). In this work, the effect of several keepers (isooctane, toluene, nonane, octanol, dodecane) on the recovery of various analytes (PAHs, PCBs, organic pesticides) was evaluated (during evaporation in a stream of nitrogen, at 40 °C). The analysis of the results obtained for the tested compounds shows that 1-octanol is a universal keeper for compounds with low volatility, i.e., PCBs (average recovery: 97.6%), organochlorine pesticides (average recovery: 95.0%), organophosphorus pesticides (OPPs; average recovery: 99.7%) and higher mass PAHs (average recovery: 91.9%). The use of isooctane as a keeper yields high recoveries for PAHs, regardless of their volatility (average recovery: 95.5%). When using 1-octanol or dodecane as a keeper, the reversed solvent effect (during GC analysis) was noted in relation to volatile analytes causing the distortion of their peaks. Additionally, the phenomenon of loss of some analytes (e.g., OPPs) was observed during evaporation without heating the vials. However, in the case of PCBs, organochlorine pesticides (OCPs) and o-hydroxybiphenyl, evaporation under such conditions yields recoveries greater than or equal to 90.0%. The results presented in this work can help in finding a suitable keeper for a specific group of analytes or an alternative to the commonly used one, especially in the case of recovery problems. Full article

The sewage sludge isolate Pseudomonas nitroreducens HBP-1 was the first bacterium known to completely degrade the fungicide 2-hydroxybiphenyl. PacBio and Illumina whole-genome sequencing revealed three circular DNA replicons: a chromosome and two plasmids. Plasmids were shown to code for putative adaptive functions such as heavy metal resistance, but with unclarified ability for self-transfer. About one-tenth of strain HBP-1′s chromosomal genes are likely of recent horizontal influx, being part of genomic islands, prophages and integrative and conjugative elements (ICEs). P. nitroreducens carries two large ICEs with different functional specialization, but with homologous core structures to the well-known ICEclc of Pseudomonas knackmussii B13. The variable regions of ICEPni1 (96 kb) code for, among others, heavy metal resistances and formaldehyde detoxification, whereas those of ICEPni2 (171 kb) encodes complete meta-cleavage pathways for catabolism of 2-hydroxybiphenyl and salicylate, a protocatechuate pathway and peripheral enzymes for 4-hydroxybenzoate, ferulate, vanillin and vanillate transformation. Both ICEs transferred at frequencies of 10⁻⁶–10⁻⁸ per P. nitroreducens HBP-1 donor into Pseudomonas putida, where they integrated site specifically into tRNA^Gly-gene targets, as expected. Our study highlights the underlying determinants and mechanisms driving dissemination of adaptive properties allowing bacterial strains to cope with polluted environments. Full article

Antibiotic resistance has become the main deadly factor in infections, as bacteria can protect themselves by hiding in a self-constructed biofilm. Consequently, more attention is being paid to the search for “non-antibiotic drugs” to solve this problem. Phytoanticipins, the natural antibiotics from plants, could be a suitable alternative, but few works on this aspect have been reported. In this study, a preliminary study on the synergy between sodium houttuyfonate (SH) and levofloxacin (LFX) against the biofilm formation of Pseudomonas aeruginosa was performed. The minimal inhibitory concentrations (MIC) of LFX and SH, anti-biofilm formation and synergistic effect on Pseudomonas aeruginosa, and quantification of alginate were determined by the microdilution method, crystal violet (CV) assay, checkerboard method, and hydroxybiphenyl colorimetry. The biofilm morphology of Pseudomonas aeruginosa was observed by fluorescence microscope and scanning electric microscope (SEM). The results showed that: (i) LFX and SH had an obvious synergistic effect against Pseudomonas aeruginosa with MIC values of 0.25 μg/mL and 128 μg/mL, respectively; (ii) ½ × MIC SH combined with 2 × MIC LFX could suppress the biofilm formation of Pseudomonas aeruginosa effectively, with up to 73% inhibition; (iii) the concentration of alginate decreased dramatically by a maximum of 92% after treatment with the combination of antibiotics; and (iv) more dead cells by fluorescence microscope and more removal of extracellular polymeric structure (EPS) by SEM were observed after the combined treatment of LFX and SH. Our experiments demonstrate the promising future of this potent antimicrobial agent against biofilm-associated infections. Full article

The crystal structures of four homologous series of rod-like molecules are reviewed, two of which form hydrogen bonds and two with a symmetric chemical constitution. Many of the compounds investigated turn into liquid crystalline phases upon temperature increase. It is of valuable interest to know possible conformations and possible packing arrangements as prerequisites to model liquid crystalline structures. The hydrogen bonds of homologous series of pure 4-(ω-hydroxyalkyloxy)-4′-hydroxybiphenyl (HnHBP, n the alkyloxy tail length) are realized through head to tail arrangements of the hydroxyl groups and crystallize except one compound in chiral space groups without the molecules containing any asymmetric carbon. The hydrogen bonds of the homologous series of 4-substituted benzoic acids with various lengths of the tail provide dimers through strong polar bonding of adjacent carboxyl groups and thus provide the stiff part of a mesogenic unit prerequisite for liquid crystalline phases. The homologous series of dialkanoyloxybiphenyls (BP-n, n = 1, 19), of which nine compounds could be crystallized, show liquid crystalline behavior for longer alkane chain lengths, despite the high mobility of the alkane chain ends already detectable in the crystal phase. A single molecule, half a molecule or two half molecules form the asymmetric unit in a centrosymmetric space group. The homologous series of 1,4-terephthalidene-bis-N-(4′-n-alkylaniline) (TBAA-n) exhibit a large variety of packing arrangements in the crystalline state, with or without relying on the symmetry center within the molecules. Full article