Host-guest interactions template: the synthesis of a [3]catenane

Formation of a [3]catenane containing dibenzo-24-crown ether wheels and a large dipyridiniumethane ring is templated by formation of a host-guest adduct between the [3]catenane and the external crown ether.     

Direct detection of membrane channels from gels using water-in-oil droplet bilayers

We form planar lipid bilayers between an aqueous droplet and a hydrogel support immersed in a lipid-oil solution. By scanning the bilayer over the surface of an SDS-PAGE gel, we are able to directly detect membrane proteins from gels using single-channel recording. Using this technique, we are able to examine low levels of endogenous protein from cell extracts without the need for over-expression. We also use droplet bilayers to detect small molecules from hydrogels. The bilayers show enhanced stability compared to conventional planar lipid bilayers, and both bilayer size and position can be controlled during an experiment. Hydrogel scanning with droplet bilayers provides a new method for the discovery and characterization of ion channels with the potential for high-throughput screening.     

Straightforward synthesis of sphinganines via a serine-derived Weinreb amide

Sphinganines can be synthesized in just three steps from easily prepared serine-derived Weinreb amide 4. Pre-deprotonation of the acidic (N-H and O-H) protons of 4 allows for its efficient conversion to amino ketones 5. Such ketones can be selectively reduced to either erythro- or threo-sphinganines. Partially protected sphinganines 11 are also readily accessible in five steps from 4. Thus, Weinreb amide 4 represents one of the most versatile templates described to date for sphinganine synthesis.     

Crossed beams and theoretical studies of the dynamics of hyperthermal collisions between Ar and ethane

Crossed molecular beams experiments and classical trajectory calculations have been used to study the dynamics of Ar+ethane collisions at hyperthermal collision energies. Experimental time-of-flight and angular distributions of ethane molecules that scatter into the backward hemisphere (with respect to their original direction in the center-of-mass frame) have been collected. Translational energy distributions, derived from the time-of-flight distributions, reveal that a substantial fraction of the collisions transfer abnormally large amounts of energy to internal excitation of ethane. The flux of the scattered ethane molecules increased only slightly from directly backward scattering to sideways scattering. Theoretical calculations show angular and translational energy distributions which are in reasonable agreement with the experimental results. These calculations have been used to examine the microscopic mechanism for large energy transfer collisions ("supercollisions"). Collinear ("head-on") or perpendicular ("side-on") approaches of Ar to the C-C axis of ethane do not promote energy transfer as much as bent approaches, and collisions in which the H atom is "sandwiched" in a bent Ar...H-C configuration lead to the largest energy transfer. The sensitivity of collisional energy transfer to the intramolecular potential energy of ethane has also been examined.     

Assessment of the UVR protection provided by different tree species

In recent years, SunSmart campaigns have emphasized the importance of the use of shade as a strategy in the reduction of human exposure to solar UV radiation (UVR), particularly in early life with the provision of shade in schools. Trees can play an important role in shade provision, either as the main shade provider or to augment shade structures and increase UVR protection provided to the general population. A study to measure the protection provided by a range of trees common in Australian urban environments was undertaken during the summers of 2004/2005 and 2005/2006. Solar UVR beneath the trees was measured using UVR sensitive polysulphone badges positioned horizontally within the shaded area and were compared with those in full sunshine to give an indication of the protection provided. Measurements made on sunny days during the months of October to April indicated that the shade cover provided by the trees depended upon the tree species and changed with season as a result of changing foliage and sun angles. Measured protection factors ranged from 5 to 10 and were generally a maximum in the height of summer when the sun was highest in the sky and the foliage was densest.     

The caffeine contents of dietary supplements commonly purchased in the US: analysis of 53 products with caffeine-containing ingredients

As part of a study initiating the development of an analytically validated Dietary Supplement Ingredient Database (DSID) in the United States (US), a selection of dietary supplement products were analyzed for their caffeine content. Products sold as tablets, caplets, or capsules and listing at least one caffeine-containing ingredient (including botanicals such as guarana, yerba mate, kola nut, and green tea extract) on the label were selected for analysis based on market share information. Two or three lots of each product were purchased and analyzed using high-pressure liquid chromatography (HPLC). Each analytical run included one or two National Institute of Standards and Technology (NIST) Standard Reference Materials (SRMs) and two products in duplicate. Caffeine intake per serving and per day was calculated using the maximum recommendations on each product label. Laboratory analysis for 53 products showed product means ranging from 1 to 829 mg caffeine/day. For products with a label amount for comparison (n = 28), 89% (n = 25) of the products had analytically based caffeine levels/day of between −16% and +16% of the claimed levels. Lot-to-lot variability (n = 2 or 3) for caffeine in most products (72%) was less than 10%.     

Synthesis, ionisation potentials and electron affinities of hexaazatrinaphthylene derivatives

Several hexaazatrinaphthylene derivatives and a tris(thieno)hexaazatriphenylene derivative have been synthesised by reaction of the appropriate diamines with hexaketocyclohexane. The crystal structure of 2,3,8,9,14,15-hexachloro-5,6,11,12,17,18-hexaazatrinaphthylene has been determined by X-ray diffraction; this reveals a molecular structure in good agreement with that predicted by density functional theory (DFT) calculations and pi-stacking with an average spacing between adjacent molecular planes of 3.18 A. Solid-state ionisation potentials have been measured by using UV photoelectron spectroscopy and fall in the range of 5.99 to 7.76 eV, whereas solid-state electron affinities, measured using inverse photoelectron spectroscopy, vary in the range -2.65 to -4.59 eV. The most easily reduced example is a tris(thieno)hexaazatriphenylene substituted with bis(trifluoromethyl)phenyl groups; DFT calculations suggest that the highly exothermic electron affinity is due both to the replacement of the outermost phenylene rings of hexaazatrinaphthylene with thieno groups and to the presence of electron-withdrawing bis(trifluoromethyl)phenyl groups. The rather exothermic electron affinities, the potential for adopting pi-stacked structures and the low intramolecular reorganisation energies obtained by DFT calculations suggest that some of these molecules may be useful electron-transport materials.     

Influence of promoters on the performance of Au/MnOx and Pt/SnOx/SiO2 low-temperature CO oxidation catalysts

The influence of promoters on Pt/SnO_x/SiO₂ and Au/MnO_x low-temperature CO oxidation catalysts has been investigated under stoichiometric reaction conditions with no CO₂ added to the feed gas. The performance of Pt/SnO_x/SiO₂ catalysts is improved significantly by the addition of 1 wt.% Fe but reduced by the addition of 5 wt.%Fe, 1 wt.% Sb, 5 wt.% Sb, 1 wt.% As, 5 wt.%As and 1.8 wt.% P. The performance of Au/MnO_x is improved significantly by the addition of 1 at.% Ce but reduced by the addition of 1 at.% Co. For the catalysts and conditions examined, the Au/MnO_x catalysts are superior to the Pt/SnO_x/SiO₂ catalysts with respect to both activity and decay characteristics.     

Phytotherapy in Integrative Oncology—An Update of Promising Treatment Options

Modern phytotherapy is part of today’s conventional evidence-based medicine and the use of phytopharmaceuticals in integrative oncology is becoming increasingly popular. Approximately 40% of users of such phytopharmaceuticals are tumour patients. The present review provides an overview of the most important plants and nature-based compounds used in integrative oncology and illustrates their pharmacological potential in preclinical and clinical settings. A selection of promising anti-tumour plants and ingredients was made on the basis of scientific evidence and therapeutic practical relevance and included Boswellia, gingko, ginseng, ginger, and curcumin. In addition to these nominees, there is a large number of other interesting plants and plant ingredients that can be considered for the treatment of cancer diseases or for the treatment of tumour or tumour therapy-associated symptoms. Side effects and interactions are included in the discussion. However, with the regular and intended use of phytopharmaceuticals, the occurrence of adverse side effects is rather rare. Overall, the use of defined phytopharmaceuticals is recommended in the context of a rational integrative oncology approach.     

Dewetting of unreacted epoxy/amine mixtures on silica

We employ a direct method, time-of-flight secondary ion mass spectroscopy (ToF-SIMS), to determine experimentally the chemical compositions of the wetted and dewetted regions of an uncured epoxy thin film. Determining the composition of the dewetted region indicated the presence of a very thin sublayer of resin in what was thought to be a region devoid of resin. The capability of ToF-SIMS to probe small 65 x 65 microm(2) areas of the surface has permitted us to directly compare the SIMS spectra of the wetted and dewetted regions to the survey spectra of the reactants. This may indicate the strength of resin/silica interactions, which determine interface formation and properties.