Enzymes in organic synthesis. 2. Synthesis of enantiomerically pure prostaglandin intermediates by Enzymatic Hydrolysis of (1SR, 5RS, 6RS, 7RS)-7-acetoxy-6-acetoxymethyl-2-oxabicyclo[3.3.0]octan-3-one

Subtilisin DY as well as alkaline protease from Bacillus licheniformis 41 p catalyze the hydrolysis of (1SR, 5RS, 6RS, 7RS)-7-acetoxy-6-acetoxymethyl-2-oxabicyclo[3.3.0]octan-3-one ( rac-1 ) with practically useful enantio- and regioselectivity. Under the hitherto found optimal conditions (1S, 5R, 6R, 7R)-7-hydroxy-6-hydroxymethyl-2-oxabicyclo[3.3.0]octan-3-one ( 4 ), an important intermediate in prostaglandin syntheses, could be prepared in a yield of 16% with an enantiomeric excess of 99%. The enantiomer ( ent-4 ) was obtained with the same enantiomeric excess in 20% yield. The chemical yields are related to the racemic starting material rac-1 .     

2‐(1‐Ethynylpyrene)‐Adenosine as a Folding Probe for RNA—Pyrene in or out

A series of short RNA duplexes containing one or two 1‐ethynylpyrene‐modified adenine bases was synthesised. The melting behaviour of these duplexes was examined by monitoring temperature‐dependent pyrene fluorescence. In the singly modified RNA duplexes, the bases flanking the ethynylpyrene‐rA were varied to examine the sequence specificity of the fluorescence change of pyrene upon RNA hybridisation. Because an increase in pyrene fluorescence upon melting of the duplex can be correlated with intercalation of pyrene, and a decrease is usually associated with the position of pyrene outside the strand, a relationship between the flanking bases and the tendency of the dye to intercalate has been established. It was found that pyrene intercalation is less likely to take place if the modified base is flanked only by A–U base pairs. Flanking G–C base pairs, even only in the 5′‐direction of the modified base, will favour intercalation. In addition, we examined a doubly modified compound that had a pyrene located on each strand. The spectra indicated that the two pyrenes were close enough for interaction. Upon melting of the strand, a fluorescence blue shift corresponding to the dissociation of the pyrene–pyrene complex could be observed in addition to the intensity effect already known from the singly modified compounds. Two melting curves based on the different properties of the fluorophore could be extracted, leading to different melting points corresponding to the global duplex melting and to the change of local pyrene environment, respectively.     

Injection molding of products with functional surfaces by micro-structured, PVD coated injection molds

Molding of micro structures by injection molding leads to special requirements for the molds e.g. regarding wear resistance and low release forces of the molded components. At the same time it is not allowed to affect the replication precision. Physical vapor deposition (PVD) is one of the promising technologies for applying coatings with adapted properties like high hardness, low roughness, low Young’s modulus and less adhesion to the melt of polymers. Physical vapor deposition technology allows the deposition of thin films on micro structures. Therefore, the influence of these PVD layers on the contour accuracy of the replicated micro structures has to be investigated. For this purpose injection mold inserts were laser structured with micro structures of different sizes and afterwards coated with two different coatings, which were deposited by a magnetron sputter ion plating PVD technology. After deposition, the coatings were analyzed by techniques regarding hardness, Young’s modulus and morphology. The geometries of the micro structures were analyzed by scanning electron microscopy before and after coating. Afterwards, the coated mold inserts were used for injection molding experiments. During the injection molding process, a conventional and a variothermal temperature control of the molds were used. The molded parts were analyzed regarding roughness, structure height and structure width by means of laser microscopy.     

Motormouth: Mere exposure depends on stimulus-specific motor simulations.

The authors apply an embodied account to mere exposure, arguing that through the repeated exposure of a particular stimulus, motor responses specifically associated to that stimulus are repeatedly simulated, thus trained, and become increasingly fluent. This increased fluency drives preferences for repeated stimuli. This hypothesis was tested by blocking stimulus-specific motor simulations during repeated exposure. In Experiment 1, chewing gum while evaluating stimuli destroyed mere exposure effects (MEEs) for words but not for visual characters. However, concurrently kneading a ball left both MEEs unaffected. In Experiment 2, concurrently whispering an unrelated word destroyed MEEs for words but not for characters, even when implemented either exclusively during the initial presentation or during the test phase and when the first presentation involved an evaluation or a mere study of the stimuli. In Experiment 3, a double dissociation between 2 classes of stimuli was demonstrated, namely, words (oral) and tunes (vocal). A concurrent oral task (tongue movements) destroyed MEEs for words but not for tone sequences. A concurrent vocal task (humming “mm-hm”) destroyed MEEs for tone sequences but not for words. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Modification of CaCO3 precipitation rates by water-soluble nacre proteins

Mineral growth in nacre and other CaCO₃-containing biominerals is controlled by biopolymers. Water-soluble proteins were extracted from nacre of the sea snail Haliotis laevigata by dissolving the mineral phase with 6% acetic acid. The influence of this protein mixture on CaCO₃ precipitation rates was investigated at different concentrations. A well-established assay for measuring the pH-value during CaCO₃ precipitation with and without protein additives was extended by calculating maximum precipitation rates from the pH-values. It could be shown that precipitation rates are greatly influenced by the mixtures of water-soluble nacre proteins. At very low protein concentrations (0.02 μg/ml) a rate enhancement in comparison to the pure supersaturated calcium carbonate solution by a factor of 1.4 was observed. At higher protein concentrations, a strong inhibitory effect occurred, with total inhibition at concentrations of 1.0 μg/ml and higher. Two unspecific proteins (bovine serum albumin and lysozyme) showed little or no modification of precipitation rates. In vivo, the function of the strong inhibition of CaCO₃ precipitation by nacre proteins at higher concentrations is presumably to prevent uncontrolled crystallization in the extrapallial fluid. The rate-enhancing capability of proteins at low concentrations may be explained by the presence of acidic and/or hydrophilic moieties.     

Finite element methods for the Stokes problem on complicated domains

It is a standard assumption in the error analysis of finite element methods that the underlying finite element mesh has to resolve the physical domain of the modeled process. In case of complicated domains which appear in many applications such as ground water flows this requirement sometimes becomes a bottleneck. The resolution condition links the computational complexity to the number (and size) of geometric details although the accuracy requirements, possibly, are moderate and would allow a (locally) coarse mesh width. Therefore even the coarsest available discretization can lead to a huge number of unknowns. The composite mini element is a remedy to this dilemma because the degrees of freedom are not linked to the number of geometric details. The basic concept for the Stokes problem with uniform no-slip boundary conditions has been introduced and analyzed in [D. Peterseim, S. Sauter, The composite mini element – coarse mesh computation of Stokes flows on complicated domains, SINUM, 46(6) (2008) 3181–3206]. Here, we generalize the composite mini element to slip, leak and Neumann boundary conditions so that it becomes applicable to this much larger and more important problem class. The main results are (a) the algorithmic concept remains unchanged and the new boundary conditions can be implemented as a weighted quadrature rule, (b) the stability and convergence can be proved under very mild assumption on the domain geometries, (c) the analysis is far from trivial and requires the development of substantially new tools compared to the simple case of uniform no-slip boundary conditions.     

Computer-algebra calculations and measurements on AB spin systems for double-spin-echo sequences

The time evolution of the density operator of an AB spin system during a double-spin-echo pulse sequence is evaluated analytically by a computer-algebra system. The computer-algebra system allows one to generate the extensive formulas describing the density operator and yields an expression for the integral of the spectral signals. The simulation of spectra for arbitrary sequence timings can be easily performed by this new tool without risking errors that might occur in conventional calculations. The computer-algebra method can be extended straightforward to other pulse angles and types of sequences. The double-spin-echo pulse sequence is used in the point-resolved spectroscopy (PRESS) method which is often applied for volume selective examinationsin vivo. For verification of the results generated by the computer-algebra system,¹H spectra from a half-liter spherical sample with an aqueous solution that was 0.1 M in sodium citrate and 0.1 M in sodium acetate were recorded after 90°-180°-180° double-spin-echo pulse sequences on a 1.5-T whole-body unit. The measured behavior of the citrate AB spin system corresponds very well with the theoretical predictions. Thus, the theory provides the basis for the optimization of sequence timings for double-spin-echo measurements with high signal gain from AB systems as, for example, citrate. In addition, the theoretically predicted signal modulations could be fitted to the experimental data, providing the transverse relaxation time of the AB-coupled protons.