Camera orientation and 3D-deformation measurement by use of cross gratings

The orientation of stereo cameras in a close range environment is derived by a modified bundle block adjustment, using the cross coordinates of a shifted high quality grating. By means of the HOUGH-transform, approximate grating coordinates are determined, which are used to calculate the final coordinates fully automatically with a correlation filter technique. The stereo setup is applied to measure the 3D-deformation on the surface of a cold welded Cu---Al tension specimen supplied with a titanium dioxide cross grating.     

Single-pulse collision-insensitive picosecond planar laser-induced fluorescence of OHA 2 Σ + (v′ = 2) in atmospheric-pressure flames

Single-pulse two-dimensional picosecond Laser-Induced Fluorescence (LIF) imaging of the OH density in a single quantum state was performed for the first time, using a premixed methane-oxygen flame at atmospheric pressure. A picosecond, excimer-Raman-laser system (268 nm, 470 ps FWHM) was used for excitation of OH. The fluorescence from the laser sheet was imaged onto a fast gated intensified camera with a 400 ps gate width. The short laser pulse minimizes the collisional redistribution of population in the ground state during excitation, while the short camera gate avoids significant quenching of the excited-state fluorescence. The fluorescence signal obtained in this way is a direct measure of the population in a selected quantum state. In contrast to common nanosecond LIF signals no corrections on variations of the collisional environment are necessary. This collision-insensitive approach to two-dimensional LIF yields an OH detection limit of 10 ppm in a cube of 330 µm per side with a single 1 mJ laser pulse. A rate-equation model is used to estimate the effects on the observed signal of fluctuations in pulse energy and duration, laser-camera timing jitter, and spatial variations in the collisional environment.     

Dispersion in phase separators for flow-injection extraction systems

Cylindrical phase separators with various volumes, incorporating a supported teflon membrane, are evaluated with respect to phase separation efficiency and dispersion, and are compared with grooved separators. At the flow rates normally used in analytical flow-extraction systems, the separation efficiency is better than 99% for a large range of phase-volume ratios (Q_aq/Q_org = 0.05–30), with some exceptions for the smallest separator, which had a total volume of only 5.6 μl. The dispersion is very low when the injection volumes are those common in f.i.a. (dispersion coefficient 1.0–1.3 for 47 μl) provided that the separation of organic phase is complete. Under these conditions, the volume of the unsegmented cavity is most important for the dispersion in the separator. The cylindrical separators are similar to the grooved type with respect to dispersion. Pulssation in the flows give lower dispersion in the unsegmented parts of the system.     

Synthesis of anti-tumour phosphatidylinositol analogues from glucose by the use of ring-closing olefin metathesis

A divergent strategy is described for synthesis of the novel phosphatidylinositols 1-3. The synthetic approach commences from benzyl-protected methyl 6-iodo-6-deoxy-alpha-D-glucopyranoside, which undergoes zinc-mediated reductive fragmentation followed by vinyl Grignard addition and ring-closing metathesis to afford the key conduritol B intermediate 7. This can trifurcate to form three different benzyl-protected myo-inositol headgroups 4-6, which after phosphorylation and attachment of the glycerolipid part give phosphatidylinositols 1-3. Preliminary biological testing against human colon adenocarcinoma cells reveals that analogues 1-3 are significant anti-tumour agents.     

Novel chiral pyromellitdiimide (1,2,4,5-benzenetetracarboxydiimide) dimers and trimers: exploring their structure,electronic transitions,and exciton coupling

The chiral but highly symmetrical acyclic and cyclic pyromellitic diimide dimers and trimers 2-5 have been obtained and characterized for the first time. The pyromellitdiimide chromophores in these molecules are linked by a rigid diequatorially 1,2-disubstituted cyclohexane skeleton. The structures of the compounds have been determined in detail by molecular modeling and, in the case of cyclic dimer 4 and trimer 5, by means of X-ray diffraction analysis. The electronically excited states of the pyromellitdiimide chromophore (1a) have been studied in these and other model compounds by means of linear dichroism (LD), magnetic circular dichroism (MCD), and circular dichroism (CD) spectroscopy. CD spectra of the rigid cyclic trimer 5 have provided the most detailed information on the excited states of the pyromellitdiimide chromophore. The low-energy tail (340-360 nm) of the absorption envelope can be assigned to out-of-plane polarized n-pi* transitions (I, II). The higher energy bands are due to contributions from up to six pi-pi* transitions, these being polarized either along the long (IV-VI, VIII) or short axis (III, VII). The results of ab initio CIS/cc-pVDZ and semiempirical INDO/S-CI calculations have been compared with the experimental data. CD Cotton effects in the region 200-260 nm, which result from exciton interactions between electric dipole allowed transitions of two pyromellitdiimide chromophores in compounds 2-5, provide reliable and useful information concerning the conformation and absolute configuration of these molecules, which may be extrapolated to other oligoimide systems.     

Design and evaluation of a new phase separator for liquid-liquid extraction in flow systems

A modified phase separator incorporating a supported teflon membrane is described. The separator has very high phase-separation efficiency even under extreme conditions of phase-volume ratio and total flow rate. The use of appropriate support is shown to give much better endurance to the membrane. Even pressures high enough to make water penetrate the membrane did not cause any damage, which makes the system much easier to handle. The long-term stability of the separator was found to be good and very little of the aqueous phase penetrated the membrane.     

Sample preconcentration by continuous flow extraction with a flow injection atomic absorption detection system

The flow manifold described allows automatic extraction of metal ions in aqueous samples into 4-methyl-2-penthanone with ammonium pyrrolidinedithiocarbamate as an extracting agent. The organic extract is led into the loop of an injector situated in an integrated feed system of an atomic absorption spectrometer. No dispersion of the injected organic extract plug, 110 μl, occurs in the aqueous feed stream and the resulting signal from the spectrometer is a peak. An increase in sensitivity of 15–20 is achieved for copper, nickel, lead and zinc in comparison with direct aspiration of the aqueous samples. The sampling frequency is 40 h^?1 and the consumption of 4-methyl-2-pentanone is typically 0.3 ml min^?1. The detection limit for copper is about 1 μ l^?1.     

Ambivalent intercalators for DNA: L-shaped platinum(II) complexes

Novel platinum(II) square planar coordination complexes, in which two heteroaromatic ligands are held by the metal in an unusual L-shaped geometry orthogonal to each other, have been synthesized, and their interaction with DNA was investigated with absorption and linear dichroism spectroscopy. As a rule, the ligand that is coplanar with the coordination square of Pt is found to be oriented perpendicular relative to the DNA helix axis when bound, suggestive of its intercalation between the base pairs of DNA. However, when this coplanar ligand is replaced by two pyridines, the opposite ligand, orthogonal to the coordination square, is instead preferentially intercalated. This behavior shows that these new complexes do indeed show some properties of true ambintercalators, i.e., compounds that can bind by intercalation of either of two distinct aromatic moieties.     

Proteolytic cleavage reveals interaction patterns between silica nanoparticles and two variants of human carbonic anhydrase

To characterize the sites on the protein surface that are involved in the adsorption to silica nanoparticles and the subsequent rearrangements of the protein/nanoparticle interaction, a novel approach has been used. After incubation of protein with silica nanoparticles for 2 or 16 h, the protein was cleaved with trypsin and the peptide fragments were analyzed with mass spectrometry. The nanoparticle surface area was in 16-fold excess over available protein surface to minimize the probability that the initial binding would be affected by other protein molecules. When the fragment patterns obtained in the presence and absence of silica nanoparticles were compared, we were able to characterize the protein fragments that interact with the surface. This approach has allowed us to identify the initial binding sites on the protein structure and the rearrangement of the binding sites that occur upon prolonged incubation with the surface.