Molecular structures,electronic spectra,and aromaticity of 1,6- and 1,8-dioxa analogues of pyrene and benzo[a]pyrene. Semiempirical molecular orbital calculations

The molecular structures of [1]benzopyrano[6,5,4-def][1]benzopyran, [2]benzopyrano[7,8,1,def]-1-benzopyran, 1-benzopyrano[6,5,4-mna]xanthene, and 2-benzopyrano[7,8,1-mna]xanthene have been optimized by using the PM3 semiemperical MO method. These calculated molecules have been shown to be planar. Their aromaticity has been investigated by use of the HOMA index. The molecules are found to be less aromatic than the correspolding parednt hydrocarbons, pyrene and benzo[a]pyrene. The CNDO/S MO method has been used to interpret th experimental uv-vis specrtoscopic data. The result of the PM3, CNDO/S and HOMA-index clculations are in good arteement with the experimental data.     

Selective cross-catenation of Pd(II) and Pt(II) coordination rings

The reversible cross-catenation of two different coordination rings (Pd(II)- and Pt(II)-linked rings) has been achieved by using the labile nature of the Pd-N interaction and efficient hydrophobic contact between the rings.     

Chalcogeno-Morita-Baylis-Hillman Reaction of Chalcogenide-Enones with Carbonyl Compounds

Abstract

The Chalcogeno-Morita-Baylis-Hillman reaction was achieved by the reactions of 2-(methylchalcogeno)phenyl vinyl ketones with carbonyl compounds or acetals in the presence of BF₃· Et₂O. This reaction proceeds via the intramolecular Michael addition of the chalcogenide group to an enone moiety followed by the aldol reaction of the resulting chalcogenonio-enolate with an aldehyde. The reactions were worked up with triethylamine or saturated aqueous NaHCO₃ to give the α -methylene aldols (the Morita-Baylis-Hillman adducts).     

Supramolecular nanocarrier of siRNA from PEG-based block catiomer carrying diamine side chain with distinctive pKa directed to enhance intracellular gene silencing

An siRNA nanocarrier formed through self-assembly of PEG-based block catiomer possessing two distinct amino groups with different pKa values in a side chain was developed. This design provided the carrier with a sufficient siRNA complexation and an assumed buffering capacity in the endosomes, allowing it to exhibit remarkable gene knockdown abilities as well as sufficient serum tolerability.     

Formation of Stable and Monodispersive Polyion Complex Micelles in Aqueous Medium from Poly(L-lysine) And Poly(Ethylene Glycol)-Poly(Aspartic Acid) Block Copolymer

Abstract

In this study, the formation of polyion complex micelles from a pair of poly(L-lysine) homopolymers (P(Lys)) and poly(ethylene glycol)-poly(aspartic acid) block copolymers (PEG-P(Asp)) with varying chain length was demonstrated in aqueous medium. There exists the lower critical chain length in the charged segments of both P(Lys) and PEG-P(Asp) to form stable polyion complex micelles in nanometric scale. The scaled average characteristic line width (ΓTK²) was independent on the detection angles for all combinations, suggesting that the formed polyion complex micelles may have a spherical shape. Furthermore, the transitional diffusion coefficient (D_T) had no concentration dependence, indicating the micelle system was free from secondary aggregates (the cluster of micelles). It is of interest that the micellar size was almost constant (ca. 50 nm) regardless of the change in the chain length of the charged segments. Size distribution was extremely narrow, and the values of variance μ₂/Γ ²) were always less than 0.1. Laser-Doppler electrophoresis measurements revealed that the polyion complex micelles were electrically neutral, suggesting that the PEG corona surrounding the polyion complex core may contribute to their stable dispersion in an aqueous medium through steric repulsion of the tethered hydrophilic chain, in this case, PEG. This system was considerably stable against the change in ionic strength, and it maintained a constant diameter in the region below 0.4 M NaCl. However, they dissociated under high ionic strength condition as 0.6 M NaCl. The system may have potential utility to include charged peptides and nucleotides in the core, delivering these biologically useful substances into a target site in the body.     

Headspace Solid-Phase Microextraction/Gas Chromatography–Mass Spectrometry for the Determination of 2-Nonenal and Its Application to Body Odor Analysis

The odors and emanations released from the human body can provide important information about the health status of individuals and the presence or absence of diseases. Since these components often emanate from the body surface in very small quantities, a simple sampling and sensitive analytical method is required. In this study, we developed a non-invasive analytical method for the measurement of the body odor component 2-nonenal by headspace solid-phase microextraction coupled with gas chromatography–mass spectrometry by selective ion monitoring. Using a StableFlex PDMS/DVB fiber, 2-nonenal was efficiently extracted and enriched by fiber exposition at 50 °C for 45 min and was separated within 10 min using a DB−1 capillary column. Body odor sample was easily collected by gauze wiping. The limit of detection of 2-nonenal collected in gauze was 22 pg (S/N = 3), and the linearity was obtained in the range of 1–50 ng with a correlation coefficient of 0.991. The method successfully analyzed 2-nonenal in skin emissions and secretions and was applied to the analysis of body odor changes in various lifestyles, including the use of cosmetics, food intake, cigarette smoking, and stress load.