Gradient high-performance liquid chromatography of statistical and block copolymers of styrene and t-butyl methacrylate

Copolymers of styrene (S) and tert-butyl methacrylate (TBMA) containing 24–92 mass % of the latter monomer were investigated using a silica column with isooctane/tetrahydrofuran (THF) gradients and on a phenyl bonded-phase column by methanol (MeOH)/THF gradients using UV detection. In both cases, retention decreased with increasing TBMA content of the sample. This is in contrast to the behavior of copolymers of S and methyl methacrylate (MMA) whose retention in gradient elution on silica columns increases with MMA content due to the polarity of this unit. The inversion of elution order is a result of the bulky TBMA residues shielding the polar groups of the ester units. For copolymers of varying composition, the gradation in retention on retention on silica is quite sufficient for separating S/MMA but not for S/TBMA mixtures. The latter could be separated by composition on phenyl packings through MeOH/THF gradient elution. Block copolymers containing 80 or 92% TBMA could be baseline-separated. It was also possible to separate these samples from admixed PTBMA or PS homopolymers. Under the conditions used, the retention of a given block copolymer was somewhat higher than that of a statistical copolymer having the same composition. A block copolymer containing 80% TBMA was converted by transesterification into a S/MMA block copolymer. The elution of the latter fitted well in the sequence of S/MMA copolymers on silica column.     

Adsorption mode of ethyl pyruvate on platinum: an in situ XANES study

The adsorption of ethyl pyruvate on Pt(111) has been studied by in situ XANES measurements in the presence and absence of hydrogen. Depending on the hydrogen and ethyl pyruvate pressure, the C and O K‐edge spectra exhibit distinctly different angular dependence. Without hydrogen ethyl pyruvate is oriented preferentially perpendicular to the surface, indicating bonding via the O lone pairs. In the presence of hydrogen the mean orientation is more tilted towards the surface. Likely, ethyl pyruvate also interacts with Pt via its π system under these conditions. The observed angle‐dependent shift of the energy of the π* and σ* resonances indicates the coexistence of differently adsorbed ethyl pyruvate species. The experimental findings demonstrate the importance of the in situ approach for unraveling the adsorption mode of ethyl pyruvate in the enantioselective hydrogenation over cinchona‐alkaloid‐modified Pt. This revised version was published online in July 2006 with corrections to the Cover Date.     

Ultraviolet lithography on sloped surfaces utilizing diamond turned holograms

A lithography method by means of a diamond turned hologram (DTH) is presented, that allows patterning of sloped surfaces. The DTH is manufactured by a modified diamond turning process, using a piezoelectric actuator, the nano fast tool servo, which modulates the depth of cut within submicrometer range at a frequency up to 10 kHz. In order to machine a DTH to be applied as phase masks for ultraviolet lithography, workpiece materials have to feature a sufficient reflectivity and excellent machinability. Ultra-fine grained aluminium was identified as most suitable workpiece material, since its reflectivity measures around 80 % and a homogenous structure can be machined. The employed DTH is used in a lithography setup in conjunction with a helium cadmium laser emitting at a wavelength of λ = 325 nm. Patterns up to a linewidth of 30 μm were successfully and consistently transferred on a photoresist coated planar substrate with a tilt angle of 30° with respect to the optical axis.     

Modelling of the disulphide-swapped isomer of human insulin-like growth factor-1: implications for receptor binding

Insulin-like growth factor-1 (IGF-1) is a serum protein whichunexpectedly folds to yield two stable tertiary structures withdifferent disulphide connectivities; native IGF-1 [18–61,6–48,47–52]and IGF-1 swap [18–61,6–47, 48–52]. Here we demonstratein detail the biological properties of recombinant human nativeIGF-1 and IGF-1 swap secreted from Saccharomyces cerevisiae.IGF-1 swap had a ~30 fold loss in affinity for the IGF-1 receptoroverexpressed on BHK cells compared with native IGF-1.The parallelincrease in dose required to induce negative cooperativity togetherwith the parallel loss in mitogenicity in NIH 3T3 cells impliesthat disruption of the IGF-1 receptor binding interaction ratherthan restriction of a post-binding conformational change isresponsible for the reduction in biological activity of IGF-1swap. Interestingly, the affinity of IGF-1 swap for the insulinreceptor was ~200 fold lower than that of native IGF-1 indicatingthat the binding surface complementary to the insulin receptor(or the ability to attain it) is disturbed to a greater extentthan that to the IGF-1 receptor. A 1.0 ns high-temperature moleculardynamics study of the local energy landscape of IGF-1 swap resultedin uncoiling of the first A-region -helix and a rearrangementin the relative orientation of the A- and B-regions. The modelof IGF-1 swap is structurally homologous to the NMR structureof insulin swap and CD spectra consistent with the model arepresented. However, in the model of IGF-1 swap the C-regionhas filled the space where the first A-region -helix has uncoiledand this may be hindering interaction of Val44 with the secondinsulin receptor binding pocket.     

Controllable Broadband Absorption in the Mixed Phase of Metamagnets

Materials with broad absorption bands are highly desirable for electromagnetic filtering and processing applications, especially if the absorption can be externally controlled. Here, a new class of broadband‐absorption materials is introduced. Namely, layered metamagnets exhibit an electromagnetic excitation continuum in the magnetic‐field‐induced mixed ferro‐ and anti­ferromagnetic phase. Employing a series of complementary experimental techniques involving neutron scattering, muon spin relaxation, specific heat, ac and dc magnetization measurements, and electron magnetic resonance, a detailed magnetic phase diagram of Cu₃Bi(SeO₃)₂O₂Br is determined and it is found that the excitations in the mixed phase extend over at least ten decades of frequency. The results, which reveal a new dynamical aspect of the mixed phase in metamagnets, open up a novel approach to controllable microwave filtering.     

CDM potential of solar water heating systems in India

The Clean Development Mechanism (CDM) provides industrialized countries with an incentive to invest in emission reduction projects in developing countries to achieve a reduction in CO₂ emissions at lowest cost that also promotes sustainable development in the host country. Solar water heating systems (SWHs) could be of interest under the CDM because they directly displace greenhouse gas emissions while contributing to sustainable development by reducing local pollutants. However, there are only three solar water heating projects under the CDM so far. An attempt has been made to estimate the CDM potential of SWHs in India in this study. Our estimates indicate that there is a vast theoretical potential of CO₂ mitigation by the use of SWHs in India. The annual CER potential of SWHs in India could theoretically reach 27 million tonnes. Under more realistic assumptions about diffusion of SWHs based on past experiences with the government-run programmes, annual CER volumes by 2012 could reach 4–9 million and 15–22 million by 2020. This would require that the government sets the subsidy level for SWHs at a level that allows them to become viable with the CER revenue. From a macro-economic point of view this makes sense if the sustainability benefits are deemed sufficiently high to warrant promotion of this project type.     

The statistics of the thermal motion of the atoms during imaging process in transmission electron microscopy and related techniques

The concern of this work is the influence of the thermal motion of the atoms on electron scattering simulations, used for quantitative interpretation of results in high-resolution electron microscopy. We distinguish between the influence of inelastic phonon excitation and the effect of a moving lattice on images generated by elastically scattered electrons. It is shown that, analog to aberrations, the impact of a moving lattice differs substantially with respect to different imaging conditions and cannot be described by the Debye–Waller damping applicable in XRD. We derive a new formalism, based on the frozen lattice and multislice approach, to incorporate the statistics of the thermal motion into elastic TEM imaging simulations, taking into account different imaging conditions. The averaging over different atom positions is generally performed within a density matrix framework, which can be linearized in the special case of off-axis electron holography. All findings are supported by explicit numerical simulations: molecular dynamics simulations are performed to get a realistic thermal motion and the electron scattering simulations are performed within the new multislice algorithm.     

用空气建造——有感于200首尔设计奥林匹克气膜建筑

气膜建筑的外围结构采用了柔软的薄膜。想象一下未来建筑外围结构在这方面将如何发展？那真是其乐无穷！就目前来看,当今建筑的发展越来越强调提高能源、材料方面的利用效率。