Macromolecular Recognition: Discrimination between Human and Bovine Serum Albumins by Cyclodextrins

The interactions of cyclodextrins (CDs) with human serum albumin (HSA) and bovine serum albumin (BSA) were investigated by two‐dimensional nuclear Overhauser effect spectroscopy (2D NOESY), steady state fluorescence, isothermal titration calorimetry, and circular dichroism spectroscopy. 2D NOESY indicates that α‐CD and β‐CD, but not γ‐CD, interact with the aromatic amino acid residues on HSA. On the other hand, the 2D NOESY signals between CDs and BSA are not significantly correlated. Hence, CDs can discriminate the subtle protein structural differences of HSA and BSA.

     

Heterogeneously Hybridized Porous Coordination Polymer Crystals: Fabrication of Heterometallic Core–Shell Single Crystals with an In‐Plane Rotational Epitaxial Relationship

MOF on MOF: Core–shell porous coordination polymer (PCP) crystals are fabricated at the single‐crystal level by epitaxial growth in solution. Synchrotron X‐ray diffraction measurements unveiled the structural relationship between the shell crystal and the core crystal, where in‐plane rotational epitaxial growth compensates the difference in lattice constant.

     

Asymmetric synthesis of 4,8-dihydroxyisochroman-1-one polyketide metabolites using chiral hypervalent iodine(III)

Stereoselective oxylactonization of ortho-alkenylbenzoate with chiral hypervalent iodine is applied to the asymmetric synthesis of 4-oxyisochroman-1-one polyketide metabolites including 4-hydroxymellein (1), a derivative of fusarentin 2, monocerin (3), and an epimer of monocerin epi-3.     

Molecular chirality and chiral capsule-type dimer formation of cyclic triamides via hydrogen-bonding interactions

Chiral properties of bowl-shaped cyclic triamides bearing functional groups with hydrogen-bonding ability were examined. Chiral induction of cyclic triamide 3a was observed by addition of chiral amine in solution, and chiral separation was achieved by simple crystallization to afford chiral capsule-type dimer structure of 4a.     

Photoreaction of Ketoprofen with Tryptophan and Tyrosine in Phosphate Buffer Solution

Reaction of excited ketoprofen (KP) with tryptophan (Trp) and tyrosine (Tyr) in a phosphate buffer solution was studied by the transient absorption spectroscopy. Both amino acids, which would interact with KP in bovine serum albumin [Monti, S. [2009] Phys. Chem. Chem. Phys., 11, 9104–9113], accelerated the proton transfer reaction to yield 3‐ethylbenzophenone ketyl biradical (EBPH) from KP carbanion, which was produced by photoexcitation of KP^? through decarboxylation. By means of the actinometry method with benzophenone, the reaction quantum yield was successfully estimated to be fairly large, and Trp, Tyr, DOPA and 4‐methylphenol were found to be a good proton donor for the carbanion. The formation rate constants of EBPH by the amino acids (k_r) were also determined to be (2.7 ± 0.1) × 10⁹ M^?1s^?1 for Trp and (7.8 ± 0.4) × 10⁸ M^?1s^?1 for Tyr, which were larger than those by basic amino acids and dipeptides reported. The reason for the highly efficient proton transfer reaction with Trp and Tyr would be explained by difference of the activation energy for the reaction. These results suggest that the proton transfer should be a key process for an initial photoreaction of KP with a protein, causing photosensitization in vivo.     

Degradation profiles in aged EPDM water seals using focused ion beam-scanning electron microscopy

The degradation of an ethylene–propylene-diene (EPDM) rubber seal used in a water supply system was investigated using focused ion beam-scanning electron microscopy (FIB-SEM). The EPDM rubber seal was used for 3 years within the temperature range 20–40 °C in a city water system. The accretions present on the surface of the EPDM seal after use were observed by SEM and were found to consist of iron and oxygen atoms based on energy dispersive X-ray spectroscopy (EDS) analysis. A cross-sectional depth image of the EPDM rubber was obtained by FIB-SEM, after slicing the EPDM rubber with a focused Gallium ion beam. Iron and oxygen atoms in the cross-section of the EPDM rubber were detected through EDS. The distribution of iron was comparable to that of oxygen derived from the carbonyl groups generated by the degradation of EPDM, suggesting that iron ions may promote the degradation of natural rubber through catalytic effects.     

Temporal variation of atmospheric polycyclic aromatic hydrocarbon concentrations in PM10 from the Kathmandu Valley and their gas-particle concentrations in winter

The concentrations of polycyclic aromatic hydrocarbons (PAHs) in particulate matter (PM) with a diameter <10 µm (PM₁₀, 50% cut off) were investigated in the Kathmandu Valley, Nepal, during 2003. In order to understand the dynamics of atmospheric PAHs in winter, the PAH concentrations in total PM and in the gaseous phase were investigated in the valley in December 2005. Total of 45 PAH compounds (∑45PAHs) were analysed by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). In 2003, the ∑45PAH concentrations in PM₁₀ ranged between 4.3 and 89 ng m^?3 (annual average; 27 ± 24 ng m^?3). The average concentrations of ∑45PAHs in December 2005 were 210 ± 33 ng m^?3 in total PM and 430 ± 90 ng m^?3 in the gaseous phase. The ∑45PAH concentration in PM accounted for more than 30% of the sum of their particulate and gaseous forms. Phenanthrene (Ph) was the most predominant compound in the gaseous phase, whereas four- to seven-ring PAHs were predominant in total PM. The highest values of ∑45PAHs occurred in the winter and spring. Estimates of emission sources based on diagnostic molecular ratios showed that atmospheric PAHs in the Kathmandu Valley mainly originated from the exhaust gas of diesel engine. In the winter and spring, PAH pollution would be accelerated by the operations of brick kilns and the frequent formation of an atmospherically stable layer in the valley.     

Dynamic molecular movements and aggregation structures of lipids in a liquid state

This paper discusses the molecular conformations and the liquid structures of triacylglycerols (TGs) and fatty acids in their melts. Three models for liquid state ordering have been proposed for TG melts to date: the smectic liquid crystal model, the nematic liquid crystal model, and the discotic model. To completely resolve the liquid structure of TGs, further research is required. However, some information on the molecular level has been obtained for fatty acids that are relatively simple compounds. The combination of various spectroscopic and thermodynamic measurements revealed that the hydrogen-bonded dimers of fatty acids are units of intermolecular and intramolecular movements in the liquids and in non-polar solvents. The dimers that construct the clusters resemble the smectic liquid crystal and determine the physicochemical properties of the liquid of the fatty acid. Cholesterol stabilizes the clusters, while ethanol destroys them. Self-diffusion and neutron diffraction measurements revealed that two kinds of fatty acids exist in their binary liquid mixture exist as the homodimers composed of same species.     

Characterization of humic acids in sediments from dam reservoirs by pyrolysis-gas chromatography/mass spectrometry using tetramethylammonium hydroxide: Influence of the structural features of humic acids on iron(II) binding capacity

The structural features of humic acids (HAs) isolated from sediments on the bottom of dam reservoirs that can affect their binding capacities for Fe(II) were investigated by pyrolysis-gas chromatography/mass spectroscopy using tetramethylammonium hydroxide (TMAH-py-GC/MS). The binding capacities for Fe(II) increased with increasing O/C molar ratio, suggesting that the oxygen-containing functional group content plays a role in the binding of Fe(II). However, it was not possible to identify specific binding-sites for Fe(II) by TMAH-py-GC/MS analysis. Although C_16:1ω7, iso-C_15:0 and anteiso-C_17:0 fatty acids, which serve as molecular markers of anaerobic microbial activity, were detected in all of the HA samples, the contents of these acids were not correlated with binding capacities for Fe(II). However, the ratio of C_16:0 to C_16:1ω7 fatty acids, which is used as an index of anaerobic bacterial activity, increased with increasing Fe(II) binding capacities of the HAs. It thus appears likely that the activities of anaerobic bacteria on the bottom of dam reservoirs contribute to alterations in the structural features for HAs, and that this process results in increased binding capacities for Fe(II).