Feasibility of Raman microspectroscopic identification of biomarkers through gypsum crystals

Pioglitazone is a medicine of thiazolidinedione (TZD) class with hypoglycemic (antihyperglycemic, antidiabetic) action. Pioglitazone binding to human serum albumin (HSA) was investigated at different temperatures (290, 300 and 310 K) by fluorescence spectroscopic method. Molecular docking study was also carried out besides the experiments. Experimental results revealed that pioglitazone have an ability to quench the intrinsic fluorescence of HSA tryptophan through a static quenching procedure. The binding constant was determined using Stern-Volmer modified equation and energy transfer mechanisms of quenching were discussed. Thermodynamic parameters were also calculated according to enthalpy changes dependence on different temperatures. According to the theoretical and experimental results, hydrogen bonding was found to play a major role in the interaction of pioglitazone with HSA.     

Vibrational analysis of 1-methyl-pyridinium-2-aldoxime and 1-methyl-pyridinium-4-aldoxime cations

Pyrimidinium aldoximes are administered intravenously in cases of acute organophosphate poisoning. Since questions regarding their morphology and active conformation in the solution are still open, an effort was made to establish correspondence between their crystal state conformers and vibrational spectra, thus facilitating the future work on the assignment of bands in solution. Normal coordinate analysis including the potential energy distribution for all modes was performed for 1-methyl-pyridinium-2-aldoxime (PAM2AN) and 1-methyl-pyridinium-4-aldoxime (PAM4AN) cations (charge=+e, spin=0). Positions of infrared and Raman bands of corresponding chloride salts agree rather well with predicted values, except for modes taking part in hydrogen bonding to anions. The strength of hydrogen bonding is estimated to be of medium strength in both salts, the bonding in PAM2AN being stronger. The calculated and observed values of the characteristic stretching modes for the aldoxime moiety have been in accordance with the stronger acidity of PAM2AN structural isomer.     

Differential scanning calorimetry study of the solidification sequence of austenitic stainless steel

The solidification sequence of austenitic stainless steels can be predicted with thermodynamic calculations. Another way is to use models where the value of the Cr_eq./Ni_eq. ratio determines the relationship between the solidification mode and the composition factor. In this study the solidification of AISI 304LN stainless steel at different cooling rates was studied using differential scanning calorimetry (DSC). The samples were linearly heated above the liquidus temperature to 1550 °C at heating rates of 5, 10, and 25 K/min. The solidification (cooling) scans from 1550 °C involved the same selected ramps. After the DSC measurements the samples were metallographically analyzed to reveal the variations in the solidification microstructures. The microhardness of the solidified samples was also measured. It was found that the cooling rate critically influenced the solidification. The solidification behavior, which depends on the cooling rate, determines the evolution of the microstructure. At the slowest cooling rates a relief-cell morphology was observed, and at the fastest cooling rate the formation of dendrites was evident. With an increasing cooling rate the liquidus temperature decreased and the reaction enthalpy increased.     

Polarization induced water molecule dissociation below the first-order electronic-phase transition temperature

Hydrogen produced from the photocatalytic splitting of water is one of the reliable alternatives to replace the polluting fossil and the radioactive nuclear fuels. Here, we provide unequivocal evidence for the existence of blue- and red-shifting O-H covalent bonds within a single water molecule adsorbed on the MgO surface as a result of asymmetric displacement polarizabilities. The adsorbed H-O-H on MgO gives rise to one weaker H-O bond, while the other O-H covalent bond from the same adsorbed water molecule compensates this effect with a stronger bond. The weaker bond (nearest to the surface), the interlayer tunneling electrons and the silver substrate are shown to be the causes for the smallest dissociative activation energy on the MgO monolayer. The origin that is responsible to initiate the splitting mechanism is proven to be due to the changes in the polarizability of an adsorbed water molecule, which are further supported by the temperature-dependent static dielectric constant measurements for water below the first-order electronic-phase transition temperature.     

Dispersion interactions of carbohydrates with condensate aromatic moieties: theoretical study on the CH-π interaction additive properties

In this article we present the first systematic study of the additive properties (i.e. degree of additivity) of the carbohydrate-aromatic moiety CH-π dispersion interaction. The additive properties were studied on the β-D-glucopyranose, β-D-mannopyranose and α-L-fucopyranose complexes with the naphthalene molecule by comparing the monodentate (single CH-π) and bidentate (two CH-π) complexes. All model complexes were optimized using the DFT-D approach, at the BP/def2-TZVPP level of theory. The interaction energies were refined using single point calculations at highly correlated ab initio methods at the CCSD(T)/CBS level, calculated as E + (E(CCSD(T))-E(MP2))(Small Basis). Bidentate complexes show very strong interactions in the range from -10.79 up to -7.15 and -8.20 up to -6.14 kcal mol(-1) for the DFT-D and CCSD(T)/CBS level, respectively. These values were compared with the sum of interaction energies of the appropriate monodentate carbohydrate-naphthalene complexes. The comparison reveals that the bidentate complex interaction energy is higher (interaction is weaker) than the sum of monodentate complex interaction energies. Bidentate complex interaction energy corresponds to 2/3 of the sum of the appropriate monodentate complex interaction energies (averaging over all modeled carbohydrate complexes). The observed interaction energies were also compared with the sum of interaction energies of the corresponding previously published carbohydrate-benzene complexes. Also in this case the interaction energy of the bidentate complex was higher (i.e. weaker interaction) than the sum of interaction energies of the corresponding benzene complexes. However, the obtained difference is lower than before, while the bidentate complex interaction energy corresponds to 4/5 of the sum of interaction energy of the benzene complexes, averaged over all structures. The mentioned comparison might aid protein engineering efforts where amino acid residues phenylalanine or tyrosine are to be replaced by a tryptophan and can help to predict the changes in the interactions. The observed results also show that DFT-D correctly describes the CH-π interaction energy and their additive properties in comparison to CCSD(T)/CBS calculated interaction energies. Thus, the DFT-D approach might be used for calculation of larger complexes of biological interest, where dispersion interaction plays an important role.     

The thermodynamic dissociation constant of naphazoline by the regression analysis of potentiometric data

The mixed dissociation constant of naphazoline is determined at various ionic strengths I [mol dm⁻³] in the range of 0.01 to 0.26 and at temperatures of 25°C and 37°C using ESAB and HYPERQUAD regression analysis of the potentiometric titration data. A strategy of efficient experimentation is proposed in a protonation constant determination, followed by a computational strategy for the chemical model with a protonation constant determination. Two group parameters, L ₀ and H _T were ill-conditioned in the model and their determination is therefore uncertain. These group parameters, L ₀ and H _T, can significantly influence a systematic error in the estimated common parameter pK_a and they always should be refined together with pK _a. The thermodynamic dissociation constant pK _a^T was estimated by nonlinear regression of {pK _a, I} data at 25°C and 37°C: for naphazoline pK _al^T = 10.41(1) and 10.13(2). Goodness-of-fit tests for various regression diagnostics enabled the reliability of the parameter estimates to be found.      

The comparison of sample extraction procedures for the determination of cations in soil by IC and ICP-AES

This paper presents the extraction of cations from a soil sample, type ranker on serpentinite, in deionized water, by use of three different extraction techniques. The first extraction technique included the use of a rotary mixer, the second technique involved the use of a microwave digestion system with different extraction temperatures, and the third technique employed an ultrasonic bath with different extraction times. Ion chromatography was used for determining the concentration of Li, Na, K, Ca, Mg and ammonium ions in soil extracts with subsequent determination of concentrations for all cations, except for ammonium ion extraction, conducted by Inductively Coupled Plasma-Atomic Emission Spectrometry. The results of cation extractions showed that microwave assisted extraction was most efficient for the Li, Na, K, Ca, Mg, Co, Mn, Ni, Pb and ammonium ions. Use of a rotary mixer for extraction was most efficient for Cd and Zn ions, while use of ultrasound bath was most efficient for Cr, Cu, Fe and Al ions. Several times higher amount of cations extracted by the most efficient, compared to the second best technique, under optimal conditions, were noticed in the case of: Ca, Mg, Co, Mn, Fe, Al, and Zn ions.     

The relationship between the mercury concentration in fish muscles and scales/fins and its significance

The determination of mercury in fish typically involves analysis of muscles. For predicting the concentration of mercury in fish muscle on the basis of the analysis of fish scales or fins, the relationship between total mercury concentrations in fish muscles and in fish scales and fins was studied. Mercury content in fish muscles, scales and fins was determined by atomic absorption spectrometry with thermal decomposition of the sample in a flow of oxygen. A number of scale treatments were applied in order to remove impurities and to enhance the prediction quality. For scale treatment, 40 min of washing with DI water in an ultrasonic bath is recommended. A coefficient of determination r²= 0.93 for the relationship between Hg concentrations in muscles and scales was achieved for 40 fish among the different fish species tested (European bream, perch, roach) from the Hamry Reservoir, Czech Republic. With respect to fin sampling, the coefficient of determination r² for these fish was 0.86. The analysis of fish scales and caudal fins is a useful screening tool for assessing the relative mercury contamination of monitored fish. The method of sampling scales is not suitable for fish species with small scales such as brown trout.