Supramolecular Solvent-Based Microextraction of Selected Anticonvulsant and Nonsteroidal Anti-Inflammatory Drugs from Sediment Samples

The increase in the production and consumption of pharmaceuticals increases their presence in the global environment, which may result in direct threats to living organisms. For this reason, there is a need for new methods to analyze drugs in environmental samples. Here, a new procedure for separating and determining selected drugs (diclofenac, ibuprofen, and carbamazepine) from bottom sediment and water samples was developed. Drugs were determined by ultra-high performance liquid chromatography coupled with an ultraviolet detector (UHPLC-UV). In this work, a universal and single-step sample treatment, based on supramolecular solvents (SUPRAS), was proposed to isolate selected anticonvulsants and nonsteroidal anti-inflammatory drugs (NSAIDs) from sediment samples. The following parameters were experimentally selected: composition of the supramolecular solvent (composition THF:H₂O (v/v), amount of decanoic acid), volume of extractant, sample mass, extraction time, centrifugation time, and centrifugation speed. Finally, the developed procedure was validated. A Speedisk procedure was also developed to extract selected drugs from water samples. The recovery of analytes using the SUPRAS procedure was in the range of 88.8–115%, while the recoveries of the Speedisk solid-phase extraction procedure ranged from 81.0–106%. The effectiveness of the sorption of the tested drugs by sediment was also examined.     

Photophysics and photochemical studies of 1,4-dihydropyridine derivatives

The absorption and fluorescence properties of nifedipine (NPDHP), felodipine (CPDHP) and a series of structurally related 1,4-dihydropyridines were studied in aqueous solution and organic solvents of different properties. The absorption and fluorescence spectra were found to depend on the chemical nature of the substituents at the position 4 of the 1,4-dihydropyridine ring (DHP) and on solvent properties. In aqueous solution, the fluorescence spectra of 4-phenyl substituted compounds are blue-shifted with respect to the alkyl substituted compounds. The more fluorescent compound is CPDHP. Nifedipine is not fluorescent. All compounds, with the exception of CPDHP, present monoexponential fluorescence decay with very short lifetime (0.2-0.4 ns). CPDHP showed a biexponential emission decay with a long-lived component of 1.7 ns; this behavior is explained in terms of different conformers because of the hindered rotation of the phenyl group by the ortho-substitution. Analysis of the solvent effect on the maximum of the absorption spectrum by using the linear solvent-energy relation solvato-chromic equation indicates the redshifts are influenced by the polarizability, hydrogen bonding ability and the hydrogen bond acceptance of the solvent. Whereas, the fluorescence characteristics (spectra, quantum yields and lifetimes) are sensitive to the polarizabilty and hydrogen bond ability of the solvents. Photo-decomposition of nifedipine is dependent on the solvent properties. Faster decomposition rates were obtained in nonprotic solvents. The 4-carboxylic derivative goes to decarboxylation. Under similar conditions, the other DHP compounds did not show appreciable photodecomposition.     

Biopolyols obtained via crude glycerol-based liquefaction of cellulose: their structural,rheological and thermal characterization

In this work lignocellulose biomass liquefaction was used to produce biopolyols suitable for the manufacturing of rigid polyurethane foams. In order to better evaluate the mechanism of the process, pure cellulose was applied as a raw material. The effect of time and temperature on the effectiveness of liquefaction and the parameters of resulting biopolyols were characterized. The prepared materials were analyzed in terms of their chemical structure, rheology, thermal and oxidative stability, and basic physical and mechanical properties that are important from the point of view of polyurethane manufacturing. The optimal parameters for the biopolyol production with a 94 % yield were achieved at 150 °C for a 6-h reaction duration. The obtained polyols were characterized by the hydroxyl number of 643 mg KOH/g and enhanced thermal and oxidative stability compared to the polyols obtained at lower temperatures, which is associated with the altered mechanism of liquefaction. The results of rheological tests, analyzed with the use of Ostwald-de Waele and Herschel Bulkley models, revealed that the prepared biopolyols can be classified as pseudoplastic fluids with the viscosity values similar to those of commercially available products. Rigid foams obtained via partial substitution of petrochemical polyol with prepared bio-based one were characterized by slightly increased apparent density and average cell size comparing to unmodified materials. The best mechanical performance was observed for the sample containing 35 wt% of biopolyol in the polyol mixture, which indicates a synergistic effect between the applied polyols. The applied modification delayed thermal degradation of foams due to changes in thermal decomposition process. In conclusion, the presented work confirms that lignocellulose biomass liquefaction can be successfully applied as a manufacturing method of polyols later used in the production of polyurethanes.     

Co-Precipitated Ni-Mg-Al Hydrotalcite-Derived Catalyst Promoted with Vanadium for CO2 Methanation

Co-precipitated Ni-Mg-Al hydrotalcite-derived catalyst promoted with vanadium were synthesized with different V loadings (0–4 wt%) and studied in CO₂ methanation. The promotion with V significantly changes textural properties (specific surface area and mesoporosity) and improves the dispersion of nickel. Moreover, the vanadium promotion strongly influences the surface basicity by increasing the total number of basic sites. An optimal loading of 2 wt% leads to the highest activity in CO₂ methanation, which is directly correlated with specific surface area, as well as the basic properties of the studied catalysts.     

Adjusting the Structure of β-Cyclodextrin to Improve Complexation of Anthraquinone-Derived Drugs

β-Cyclodextrin (CD) derivatives containing an aromatic triazole ring were studied as potential carriers of the following drugs containing an anthraquinone moiety: anthraquinone-2-sulfonic acid (AQ2S); anthraquinone-2-carboxylic acid (AQ2CA); and a common anthracycline, daunorubicin (DNR). UV-Vis and voltammetry measurements were carried out to determine the solubilities and association constants of the complexes formed, and the results revealed the unique properties of the chosen CDs as effective pH-dependent drug complexing agents. The association constants of the drug complexes with the CDs containing a triazole and lipoic acid (βCDLip) or galactosamine (βCDGAL), were significantly larger than that of the native βCD. The AQ2CA and AQ2S drugs were poorly soluble, and their solubilities increased as a result of complex formation with βCDLip and βCDGAL ligands. AQ2CA and AQ2S are negatively charged at pH 7.4. Therefore, they were less prone to form an inclusion complex with the hydrophobic CD cavity than at pH 3 (characteristic of gastric juices) when protonated. The βCDTriazole and βCDGAL ligands were found to form weaker inclusion complexes with the positively charged drug DNR at an acidic pH (pH 5.5) than in a neutral medium (pH 7.4) in which the drug dissociates to its neutral, uncharged form. This pH dependence is favorable for antitumor applications.     

Preparation of polymeric nanoparticles using a new polymerizable surfactant

A novel polymerizable surfactant (so-called surfmer) was synthesized and characterized according to its structure, surface activity and polymerization ability. Polymeric micelles (size of 6 and 130 nm) appeared in the polyreaction initiated by free radicals from VA-044. In the presence of the monomer (i.e., methyl methacrylate) microemulsion systems were formed that in turn were transformed into latex entities (size — 40 nm). Additionally, an emulsion polymerization was performed with the use of n-hexadecane as an oil phase resulting in the production of nanocapsules (size in the range — 165–220 nm). The shape and morphologies of the nanoobjects were confirmed using Atomic Force Microscopy (AFM).     

Quantifying nonclassicality of one-mode Gaussian states of the radiation field

We define the degree of nonclassicality of a one-mode Gaussian state of the quantum electromagnetic field in terms of the Bures distance between the state and the set of all classical one-mode Gaussian states. We find the closest classical Gaussian state and the degree of nonclassicality using a recently established expression for the Uhlmann fidelity of two single-mode Gaussian states. The decrease of nonclassicality under thermal mapping is carefully analyzed. Along the same lines, we finally present the evolution of nonclassicality during linear amplification.     

Kinetics and mechanism of the benzenethiolysis of O-ethylS-(2,4-dinitrophenyl) and O-ethyl S-(2,4,6-trinitrophenyl) dithiocarbonates and O-methyl O-(2,4-dinitrophenyl) thiocarbonate

Reactions of O-ethyl 2,4-dinitrophenyl dithiocarbonate (EDNPDTC), O-ethyl 2,4,6-trinitrophenyl dithiocarbonate (ETNPDTC), and O-methyl O-(2,4-dinitrophenyl) thiocarbonate (MDNPTOC) with a series of benzenethiolate anions in aqueous solution, at 25.0 degrees C and an ionic strength of 0.2 M (KCl), are subjected to a kinetic investigation. Under excess benzenethiolate, these reactions obey pseudo-first-order kinetics and are first order in benzenethiolate. Nonetheless, similar reactant concentrations were used in the reactions of 4-nitrobenzenethiolate anion with the ethyl trinitrophenyl ester (ETNPDTC), which showed overall second-order kinetics. The nucleophilic rate constants (k(N)) are pH independent, except those for the reactions of ETNPDTC with the X-benzenethiolates with X = H, 4-Cl, and 3-Cl, which increase as pH decreases. The Br?nsted-type plots (log k(N) vs pK(a) of benzenethiols) are linear with slopes beta = 0.66 for the reactions of both ethyl dinitrophenyl ester (EDNPDTC) and ethyl trinitrophenyl ester (ETNPDTC) and beta = 0.58 for those of the thiocarbonate ester (MDNPTOC). For the benzenethiolysis of MDNPTOC and EDNPDTC, no breaks were found in the Br?nsted-type plots at pK(a) 4.1 and 3.4, respectively, consistent with concerted mechanisms. Benzenethiolysis of the ethyl trinitrophenyl ester (ETNPDTC) should also be concerted in view of the even more unstable tetrahedral "intermediate" that would have been formed had this reaction been stepwise. ETNPDTC is more reactive toward benzenethiolate anions than EDNPDTC due to the better leaving group involved in the former substrate. The k(N) values found for the reactions of EDNPDTC with benzenethiolates are larger than those obtained for the concerted reactions of the same substrate with isobasic phenoxide anions. This is explained by Pearson's "hard and soft acids and bases" principle. The concerted mechanism for the benzenethiolysis of MDNPTOC, in contrast to the stepwise mechanism found for the phenolysis of this substrate, is attributed to the greater kinetic instability of the hypothetical tetrahedral "intermediate" formed in the former reaction, due to the greater nucleofugality of ArS(-) compared with an isobasic ArO(-). Benzenethiolates are more reactive toward MDNPTOC and EDNPDTC than the corresponding carbonate and thiolcarbonate, respectively. This is also in accordance with the HSAB principle, since benzenthiolates are relatively soft bases that prefer to bind to a relatively soft thiocarbonyl center rather than a relatively hard carbonyl center.     

Plans for correlation studies for BES program at RHIC

We present an overview of the main concepts concerning correlation studies for the Beam Energy Scan Program at STAR. QGP signatures at higher RHIC energies are the most obvious example of the creation of a new state of matter. In order to learn more about the transition to this state and to find a possible location of a critical point between a first-order transition and cross-over area, a new program dedicated to such analyses is formulated. Correlation studies are one of the most important obervables of the scanning of unknown region of the phase diagram. Measurements of elliptic flow, local parity violation in strong interactions, azimuthally-sensitive correlations as well as two-proton femtoscopy and nonidentical particle correlations are discussed in this paper.