Enthalpy/entropy driven activation of the first interquinone electron transfer in bacterial photosynthetic reaction centers embedded in vesicles of physiologically important phospholipids

The thermodynamics and kinetics of light-induced electron transfer in bacterial photosynthetic RCs are sensitive to physiologically important lipids (phosphatidylcholine, cardiolipin and phosphatidylglycerol) in the environment. The analysis of the temperature-dependence of the rate of the P(+)Q(A)(-)Q(B)-->P(+)Q(A)Q(B)(-) interquinone electron transfer revealed high enthalpy change of activation in zwitterionic or neutral micelles and vesicles and low enthalpy change of activation in vesicles constituted of negatively charged phospholipids. The entropy change of activation was compensated by the changes of enthalpy, thus the free energy change of activation ( approximately 500 meV) did not show large variation in vesicles of different lipids.     

Determination of the active and inactive metabolites of prasugrel in human plasma by liquid chromatography/tandem mass spectrometry

Two fast and sensitive liquid chromatography/tandem mass spectrometry (LC/MS/MS)-based bioanalytical assays were developed and validated to quantify the active and three inactive metabolites of prasugrel. Prasugrel is a novel thienopyridine prodrug that is metabolized to the pharmacologically active metabolite in addition to three inactive metabolites, which directly relate to the formation and elimination of the active metabolite. After extraction and separation, the analytes were detected and quantified using a triple quadrupole mass spectrometer using positive electrospray ionization. The validated concentration range for the inactive metabolites assay was from 1 to 500 ng/mL for each of the three analytes. Additionally, a 5x dilution factor was validated. The interday accuracy ranged from -10.5% to 12.5% and the precision ranged from 2.4% to 6.6% for all three analytes. All results showed accuracy and precision within +/-20% at the lower limit of quantification and +/-15% at other levels. The validated concentration range for the active metabolite assay was from 0.5 to 250 ng/mL. Additionally, a 10x dilution factor was validated. The interbatch accuracy ranged from -7.00% to 5.98%, while the precision ranged from 0.98% to 3.39%. Derivatization of the active metabolite in blood with 2-bromo-3'-methoxyacetophenone immediately after collection was essential to ensure the stability of the metabolite during sample processing and storage. These methods have been applied to determine the concentrations of the active and inactive metabolites of prasugrel in human plasma.     

Influence of the activation temperature on structural and textural properties of NiMo/Al2O3 hydrodesulfurization catalysts

Investigations of a commercial NiMo/Al₂O₃ hydrodesulfurization (HDS) catalyst are directed towards optimization of the activation procedure of HDS catalyst concerning active phase formation and thermal stability. Structural and textural data obtained with XRD, IR-FTIR, XPS and LTNA reveal that the optimal temperature for the formation of active species on the catalyst surface and an appropriate pore structure is 300°C.     

自动化质谱图解卷积和鉴定系统用于鉴定含痕量杂原子的石油馏分（英文）

Here we present a simple yet effective gas chromatography-mass spectrometry (GC-MS) identification approach for the detection of heteroatom-containing compounds (HACCs) in petroleum fractions. The MS/AMDIS (Automated Mass Spectral Deconvolution and Identification System) program was used to identify parts per million (ppm) HACC concentrations in petroleum fractions in place of traditional techniques (extraction and standard injection). Polycyclic aromatic sulfur heterocycles (S-PAHs) were used as model compounds to confirm the validity of the AMDIS identifiers, which were compared with extracted results using the off-line X-calibur software. AMDIS was able to identify ppm concentrations of S-PAHs in oil condensate. There was good agreement between experimental and AMDIS identification results for S-PAHs in oil condensate. AMDIS was also used to detect nitrogen-containing compounds (NCCs) and alkylphenols in oil condensate. Our results confirmed the presence of 2-methylbenzothiazole, carbazole, and 2,4-ditertbutyl phenol. In a crude oil sample, AMDIS identification of m/z=191 biomarkers was consistent with empirical results. Therefore, AMDIS can help to reduce the number of experimental steps in identification protocols.     

An investigation of enhanced secondary ion emission under Au n + (n=1–7) bombardment

We investigate the mechanism of the nonlinear secondary ion yield enhancement using Au(n)+ (n = 1, 2, 3, 5, 7) primary ions bombarding thin films of Irganox 1010, DL-phenylalanine and polystyrene on Si, Al, and Ag substrates. The largest differences in secondary ion yields are found using Au+, Au2+, and Au3+ primary ion beams. A smaller increase in secondary ion yield is observed using Au5+ and Au7+ primary ions. The yield enhancement is found to be larger on Si than on Al, while the ion yield is smaller using an Au+ beam on Si than on Al. Using Au(n)+ ion structures obtained from Density Functional Theory, we demonstrate that the secondary yield enhancement is not simply due to an increase in energy per area deposited into the surface (energy deposition density). Instead, based on simple mechanical arguments and molecular dynamics results from Medvedeva et al, we suggest a mechanism for nonlinear secondary ion yield enhancement wherein the action of multiple concerted Au impacts leads to efficient energy transfer to substrate atoms in the near surface region and an increase in the number of secondary ions ejected from the surface. Such concerted impacts involve one, two, or three Au atoms, which explains well the large nonlinear yield enhancements observed going from Au+ to Au2+ to Au3+ primary ions. This model is also able to explain the observed substrate effect. For an Au+ ion passing through the more open Si surface, it contacts fewer substrate atoms than in the more dense Al surface. Less energy is deposited in the Si surface region by the Au+ primary ion and the secondary ion yield will be lower for adsorbates on Si than on Al. In the case of Au(n)+ the greater density of Al leads to earlier break-up of the primary ion and a consequent reduction in energy transfer to the near-surface region when compared with Si. This results in higher secondary ion yields and yield enhancements on silicon than aluminum substrates.     

Quality Evaluation of Light- and Dark-Colored Hungarian Honeys,Focusing on Botanical Origin,Antioxidant Capacity and Mineral Content

Melissopalynology, antioxidant capacity and mineral and toxic element contents were analyzed in eight types of Hungarian honeys. Based on color, two groups were distinguished: light honeys comprised acacia, amorpha, phacelia and linden honeys; while dark honeys included sunflower, chestnut, fennel and sage honeys, with 100 to 300 and 700 to 1500 mAU, respectively. The unifloral origin of each sample was supported using pollen analysis. The absorbance of honey correlated positively with antioxidant capacity determined by three different methods (TRC, DPPH, ORAC), and also with mineral content. The exception was the light amber linden honey with significantly higher K content and antiradical activity than other light honeys. The Mn, Zn and Fe contents were the highest in chestnut, sunflower and fennel honeys, respectively. The black meadow sage honey performed best regarding the content of other elements and antioxidant activity. The concentrations of several toxic elements were below the detection limit in the samples, indicating their good quality. The principal component analysis (PCA) revealed correlations between different antioxidant assays and minerals, and furthermore, confirmed the botanical authentication of the honeys based on the studied parameters. To our best knowledge, the present study is the first to provide a complex analysis of quality parameters of eight unifloral Hungarian honeys.     

Expanding the Ligand Classes Used for Mn(II) Complexation: Oxa-aza Macrocycles Make the Difference

We report two macrocyclic ligands based on a 1,7-diaza-12-crown-4 platform functionalized with acetate (tO2DO2A²⁻) or piperidineacetamide (tO2DO2AM^Pip) pendant arms and a detailed characterization of the corresponding Mn(II) complexes. The X−ray structure of [Mn(tO2DO2A)(H₂O)]·2H₂O shows that the metal ion is coordinated by six donor atoms of the macrocyclic ligand and one water molecule, to result in seven-coordination. The Cu(II) analogue presents a distorted octahedral coordination environment. The protonation constants of the ligands and the stability constants of the complexes formed with Mn(II) and other biologically relevant metal ions (Mg(II), Ca(II), Cu(II) and Zn(II)) were determined using potentiometric titrations (I = 0.15 M NaCl, T = 25 °C). The conditional stabilities of Mn(II) complexes at pH 7.4 are comparable to those reported for the cyclen-based tDO2A²⁻ ligand. The dissociation of the Mn(II) chelates were investigated by evaluating the rate constants of metal exchange reactions with Cu(II) under acidic conditions (I = 0.15 M NaCl, T = 25 °C). Dissociation of the [Mn(tO2DO2A)(H₂O)] complex occurs through both proton− and metal−assisted pathways, while the [Mn(tO2DO2AM^Pip)(H₂O)] analogue dissociates through spontaneous and proton-assisted mechanisms. The Mn(II) complex of tO2DO2A²⁻ is remarkably inert with respect to its dissociation, while the amide analogue is significantly more labile. The presence of a water molecule coordinated to Mn(II) imparts relatively high relaxivities to the complexes. The parameters determining this key property were investigated using ¹⁷O NMR (Nuclear Magnetic Resonance) transverse relaxation rates and ¹H nuclear magnetic relaxation dispersion (NMRD) profiles.