The structure and absolute configuration of verticillol,a macrocyclic diterpene alcohol from the wood of sciadopitys verticillata sieb. et zucc. (taxodiaceae)

The structure of verticillol diepoxide 4 has been established by direct single crystal X-ray analysis. The structure of verticillol 5 follows from the chemical correlation to the diepoxide 4 as well as from NMR-LIS studies on verticillol which also provide evidence for the conformation of this alcohol. The absolute configuration of verticillol 5 has been assigned on the basis of CD data for the verticillol norketodiepoxide 6a.     

Effect of polymer architecture on the adsorption properties of a nonionic polymer

The adsorption of a linear- and bottle-brush poly(ethylene oxide (PEO))-based polymer, having comparable molecular weights, was studied by means of quartz crystal microbalance with dissipation monitoring ability (QCM-D) and AFM colloidal probe force measurements. The energy dissipation change monitored by QCM-D and the range of the steric forces obtained from force measurements demonstrated that linear PEO forms a more extended adsorption layer than the bottle-brush polymer, despite that the adsorbed mass is higher for the latter. Competitive adsorption studies revealed that linear PEO is readily displaced from the interface by the bottle-brush polymer. This was attributed to the higher surface affinity of the latter, which is governed by the number of contact points between the polymers and the interface, and the smaller loss of conformational entropy.     

Identification of transformation products from β‐blocking agents formed in wetland microcosms using LC‐Q‐ToF

Identification of degradation products from trace organic compounds, which may retain the biological activity of the parent compound, is an important step in understanding the long‐term effects of these compounds on the environment. Constructed wetlands have been successfully utilized to remove contaminants from wastewater effluent, including pharmacologically active compounds. However, relatively little is known about the transformation products formed during wetland treatment. In this study, three different wetland microcosm treatments were used to determine the biotransformation products of the β‐adrenoreceptor antagonists atenolol, metoprolol and propranolol. LC/ESI‐Q‐ToF run in the MS^E and MS/MS modes was used to identify and characterize the degradation products through the accurate masses of precursor and product ions. The results were compared with those of a reference standard when available. Several compounds not previously described as biotransformation products produced in wetlands were identified, including propranolol‐O‐sulfate, 1‐naphthol and the human metabolite N‐deaminated metoprolol. Transformation pathways were significantly affected by microcosm conditions and differed between compounds, despite the compounds' structural similarities. Altogether, a diverse range of transformation products in wetland microcosms were identified and elucidated using high resolving MS. This work shows that transformation products are not always easily predicted, nor formed via the same pathways even for structurally similar compounds. Copyright © 2016 John Wiley & Sons, Ltd.     

Experimental observation of different-order components of a vibrational wave packet in a bulk dielectric using high-order Raman scattering

We use high-order Raman scattering in a bulk dielectric to characterize coherent dynamics with precision typical for gas phase experiments. The experimental pump-probe approach allows for the simultaneous observation and separation in space and time of the individual contributions of different-order Raman processes to a coherent wave packet without relying on phase-matching conditions and within the same experimental geometry. We propose a novel technique to discriminate between stimulated excitation of vibronic levels in the impulsive and intermediate excitation regimes, futhermore allowing us to distinguish between different pathways contributing to the same fifth-order Raman processes.     

Synthesis,adsorption and adhesive properties of a cationic amphiphilic block copolymer for use as compatibilizer in composites

In this work, the objective was to synthesize a compatibilizer that can electrostatically adsorb onto cellulose fibers, in fiber-based composites, to enhance the interaction between the fibers and non-polar polymer matrices. This physical route to attach the compatibilizer onto and thereby modify a fiber surface is convenient since it can be performed in water under mild conditions. Polystyrene (PS) was used for the high molecular weight, non-polar, block and poly(dimethylamino)ethyl methacrylate (PDMAEMA) was used as the polar block, which was subsequently quaternized to obtain cationic charges. The block copolymer self-assembles in water into cationic micelles and the adsorption to both silicon oxide surfaces and cellulose model surfaces was studied. The micelles spread out on the surface after heat treatment and contact angle measurements showed that the contact angles against water increased significantly after this treatment. AFM force measurements were performed with a PS probe to study the adhesive properties. The adhesion increased with increasing contact time for the treated surfaces, probably due to entanglements between the polystyrene blocks at the treated surface and the probe. This demonstrates that the use of this type of amphiphilic block copolymer is a promising route to improve the compatibility between charged reinforcing materials, such as cellulose-based fibers/fibrils, and hydrophobic matrices in composite materials.     

Aklyl Chain Order Parameters and Phase Diagrams for Systems Containing Sodium n-Octanoate,Water, and Different Alcohols

Lamellar liquid crystalline phases containing sodium n-octanoate, water, and an alcohol have been studied by means of ²H NMR. Order parameters have been determined for the octanoate alkyl chain in systems containing ethanol, 1-propanol, 1-butanol, 1-pentanol, benzyl alcohol or 1, 8-octandiol. The straight chain alcohols yield decreasing octanoate order parameters with decreasing chain length. With 1, 8-octandiol the octanoate order parameters are somewhat smaller than with 1-propanol, indicating quite flexible octanoate hydrocarbon chains. Using mono-deuteriated benzyl alcohol. C₆H₅CHDOH, the S_CD as well as the S_HD (= S_HH ) order parameters were determined in the same measurement. A typical measurement yields |S _HD|-|S_CD | = 0.04 ± 0.04, where the error estimation includes the uncertainties in the quadrupole and the magnetic dipole-dipole coupling constants. It is stressed that in order to ascertain a significant difference between S_HH and S_CD , it is necessary to know the coupling constants with high accuracy. The phase diagram for the system sodium n-octanoate/water/benzyl alcohol was determined, mainly by ²H and ²³Na NMR.     

Repulsion between oppositely charged surfaces in multivalent electrolytes

In answer to recent experimental force measurements between oppositely charged surfaces we here reproduce the repulsion in the presence of multivalent salt using Monte Carlo simulations within the primitive model. Our osmotic pressure curves are in good agreement with experimental results. In contrast with Poisson-Boltzmann calculations, both repulsion and charge inversion are seen in the simulations. Repulsion is observed only for conditions under which there is charge inversion at large separations. However, in these cases, the repulsion is present also at intermediate separations, where there is no charge inversion. The charge inversion is thereby not the cause of the repulsion. Instead the repulsion appears to be an effect of the large amount of excess salt in the slit. Both phenomena, however, are closely linked and a consequence of ion-ion correlations, promoted by a strong electrostatic coupling.