Apolar 2‐alkoxyalkoxy‐substituted nematic liquid crystals

The synthesis is reported of a series of apolar nematic liquid crystals incorporating an alkoxyalkoxy chain attached in a terminal position to the molecular core. The dependence of the mesomorphism and phase transition temperatures on the nature of the terminal chain with one, two or three oxygen atoms was studied. Some compounds with a completely alicyclic molecular core and a terminal 2‐methoxyethoxy chain exhibit a nematic phase with a low melting point, birefringence and viscosity and a relatively high clearing point in the absence of smectic phases. They do not to absorb light in the near UV and may be useful as components of UV‐stable nematic mixtures for use in photoluminescent liquid crystal displays. The presence of the methoxyethoxy chain leads to a relatively large dipole moment perpendicular to the molecular long axis.     

Preparation and characterization of a set of IAEA reference air filters for quality control in air-pollution studies

Several sets of reference air filters were prepared as part of an IAEA evaluation of the performance of laboratories involved in air-pollution studies. Each set comprised three polycarbonate membrane filters, two of which were loaded with urban air particulate matter (APM) obtained in Vienna or Prague, and one unloaded filter. The filters were loaded by filtration of a suspension of the APM materials in water. The homogeneity both of bulk APM materials and of the loaded filters was evaluated and found suitable by determining several elements by instrumental neutron-activation analysis (INAA), proton-induced X-ray emission (PIXE), and micro-X-ray energy-dispersive fluorescence analysis (micro-EDXRF). After evaluation of the homogeneity, INAA, PIXE, EDXRF, atomic absorption spectrometry (AAS), inductively coupled plasma optical emission spectrometry (ICP-OES), and ICP mass spectrometry (ICP-MS) were used to characterize the filter materials and establish "target values" and their associated standard deviations for 15 elements. Problems encountered during the preparation of these unique, simulated air filters and the criteria for setting both the target values and standard deviations are presented.     

Further studies on the application of vinylogous amides and β-halovinylaldehydes to the regiospecific synthesis of unsymmetrical,polyfunctionalized 2,3,4- and 1,2,3,4- substituted pyrroles

Highly functionalized pyrroles with appropriate regiochemical functionality represent an important class of marine natural products and potential drug candidates. We describe herein a detailed study of the reaction of α-aminoacid esters with vinylogous amides and also β-halovinylaldehydes for the regiospecific synthesis of 2,3,4-trisubstituted and 1,2,3,4-tetrasubstituted pyrroles. Since the vinylogous amides and β-halovinylaldehydes are readily available precursors, rapid access to a wide variety of unsymmetrically substituted pyrroles is accomplished via this methodology.     

Alignment and orientation effects in resonant charge exchange from laser excited Na*(3p)

A collisional alignment and orientation study with planar symmetry is described, determining the complete density matrix for resonant charge transfer from laser excited atoms. Results are reported for the Na⁺+Na*(3p) system over the collision energy rangeE _c.m.=50?100 eV. We communicate the optimal alignment angle γ and linear polarisationP _l ⁺ of the charge cloud as well as its relative height ρ₀₀ and the angular momentumL _⊥ ⁺ transferred in the collision as a function of the scattering angle. For preparation of the sodium 3p orbital in the scattering plane (positive reflection symmetry) we observe that at small reduced scattering angles (<20 eV°) the preparation of apσ at large internuclear distances contributes most to the scattering intensity whereas at larger reduced scattering angles (>60 eV°) apπ⁺ preparation is more important. In contrast, preparation of thepπ^? orbital (perpendicular to the scattering plane) is large at small and vanishes at larger scattering angles. We conclude that orbital following cannot be assumed in this resonant charge transfer process. The angular momentum transfer is observed to be small, indicating only little coherence in the process, but shows nevertheless an interesting behaviour as a function of scattering angle.     

Locked vs. unlocked nucleic acids (LNA vs. UNA): contrasting structures work towards common therapeutic goals

Oligonucleotide chemistry has been developed greatly over the past three decades, with many advances in increasing nuclease resistance, enhancing duplex stability and assisting with cellular uptake. Locked nucleic acid (LNA) is a structurally rigid modification that increases the binding affinity of a modified-oligonucleotide. In contrast, unlocked nucleic acid (UNA) is a highly flexible modification, which can be used to modulate duplex characteristics. In this tutorial review, we will compare the synthetic routes to both of these modifications, contrast the structural features, examine the hybridization properties of LNA and UNA modified duplexes, and discuss how they have been applied within biotechnology and drug research. LNA has found widespread use in antisense oligonucleotide technology, where it can stabilize interactions with target RNA and protect from cellular nucleases. The newly emerging field of siRNAs has made use of LNA and, recently, also UNA. These modifications are able to increase double-stranded RNA stability in serum and decrease off-target effects seen with conventional siRNAs. LNA and UNA are also emerging as versatile modifications for aptamers. Their application to known aptamer structures has opened up the possibility of future selection of LNA-modified aptamers. Each of these oligonucleotide technologies has the potential to become a new type of therapy to treat a wide variety of diseases, and LNA and UNA will no doubt play a part in future developments of therapeutic and diagnostic oligonucleotides.     

Photoelectrochemical study of Zn cytochrome-c immobilised on a nanoporous metal oxide electrode

Transient optical spectroscopies and photocurrent action spectra are used to demonstrate photoinduced charge separation between zinc-substituted cytochrome c and a nanocrystalline TiO2 electrode.     

Aqueous partial molar heat capacities and volumes for NaTcO4 and NaReO4

A flow microcalorimeter/densimeter system has been commissioned to measure heat capacities and densities of solutions containing radioactive species as a function of temperature. Measurements were made for NaTcO₄(aq) at six temperatures (189.15 K to 373.15 K for the heat capacities, 287.43 K to 396.67 K for the densities) over the molality range 0.01 to 0.29 mol-kg^–1. Measurements for NaReO₄(aq) (NaReO₄ is a common nonradioactive analogue for NaTcO₄) were made under similar conditions, but for eight temperatures and a more extensive range of molalities, 0.05 to 0.65 mol-kg^–1. Heat capacities of NaCl(aq) reference solutions were also measured from 293.15 K to 398.15 K.The heat capacity and density data are analysed using Pitzer's ioninteraction model. Equations for the apparent molar heat capacities and volumes are reported. Values of the NaReO₄(aq) partial molar heat capacities are compared to literature values based on integral heats of solution. The agreement between the two sets of NaReO₄ results is good below 330 K, but only fair at the higher temperatures. Values of the partial molar volumes have also been derived. Using literature values and the results of our experiments, it is calculated that the disproportionation of hydrated TcO₂(s) to form TcO ₄ ^– (aq) and Tc(cr) occurs more readily at high temperatures. The uncertainties introduced by using thermodynamic values for ReO ₄ ^– (aq), in the absence of values for TcO ₄ ^– (aq), are discussed.