Fibronectin adsorption on gold, Ti-, and Ta-oxide investigated by QCM-D and RSA modelling

The adsorption of fibronectin on gold, Ti-, and Ta-oxide surfaces is investigated by means of the quartz crystal microbalance with dissipation (QCM-D) technique. The surface chemistry (gold, Ti-, and Ta-oxide) is found to influence the frequency shift observed during adsorption of the fibronectin layer with the magnitude being Delta f Au>Delta f Ti-oxide approximately Delta f Ta-oxide. Corresponding variations in the dissipation change normalised to frequency change (Delta D/Delta f) for the layer are observed. The QCM-D data are further analyzed by the random sequential adsorption (RSA) model, and adsorption rate parameter ka and footprint (a) determined, which supported the trend seen in the Delta f and Delta D/Delta f values. The value of ka found by the RSA modelling of the QCM-D resonance frequency data is found to match the ratio between the mass measured by QCM-D and the mass reported by optical techniques in literature. We conclude that comparison of the adsorption rate parameter (ka) obtained by RSA modelling of the QCM-D data with ka values obtained from RSA modelling of data obtained using optical techniques can be a route to determine the degree of hydration of the adsorbed protein layer.     

Oligospiroketals as novel molecular rods

A modular approach for the synthesis of molecular rods based on oligospiroketals has been developed. The strategy relies on different terminal and intermediate segments, which are joined by ketal formation between ketones and diols. For this purpose it was necessary to develop a new ketalization method to circumvent some problems related with the established methods. The terminal segments are either derived from 4-piperidinone or from 4-oxocyclohexane carboxylic acid whereas the intermediate segments rest on pentaerythritol and cyclohexane-1,4-dione. A series of trispiro (14-18), hexaspiro (19) and nonaspiro (20) compounds have been prepared and characterized. From these we realized that it is imperative to use solubility enhancing groups if more than seven rings are joined.     

The Temperature Dependence of Protoporphyrin IX Production in Cells and Tissues

The formation of protoporphyrin IX (PpIX) in human skin during topical application of 5-aminolevulinic acid (ALA) was found to be strongly temperature dependent, with an activation energy of about 17 kcal/mol. This temperature dependence is mainly related to porphyrin production and not to ALA penetration into the skin. The penetration of ALA into mouse and human skin was almost temperature independent. The activation energy of PpIX production in mouse skin was practically identical with that in human skin. The activation energy of ALA uptake by cells in vitro was about 10 kcal/mol and that for PpIX production was about 13 kcal/mol. The latter activation energy was within the error limits similar to that for the activity of the enzyme porphobilinogen deaminase, suggesting that this enzyme might represent a rate-limiting step for PpIX production in living tissue.     

Non-ionic contributions to the electric-field gradient at 111Cd/181Ta impurities in bixbyites

The electric-field-gradient (EFG) tensor at both cation sites of the bixbyite structure in ¹⁸¹Hf-implanted Lu- and Sm-sesquioxides was determined by the PAC technique. The cumulated EFG data at Ta-impurity sites in binary oxides enable us to discuss the “universal” character of the empirical correlation between local and ionic contributions to the EFG in these systems. An EFG factorization in terms of the electronic characteristics of the probe and the geometry of the cation coordination is proposed, which explains the experimental EFG results at Ta/Cd impurity sites in bixbyites and agrees with a simplified decomposition of the EFG valence contribution coming from ab-initio calculations. This revised version was published online in August 2006 with corrections to the Cover Date.     

Cover Picture

The cover picture shows two new catalytic asymmetric reactions in front of an enantiomeric pair of lurs—one of the national symbols of Denmark. Chiral bisoxazoline copper complexes catalyze the reactions. The reaction on the left is the direct enantioselective Mannich reaction of carbonyl compounds with imines to give highly functionalized 4‐oxo‐glutamic esters, while the reaction on the right is the enantioselective nitro‐Mannich reaction of nitro alkanes with imines to give optically active β‐nitro‐α‐amino esters. Why the lur in relation to the present chemistry? Lurs exist as pairs of enantiomers and they probably belong to some of the first man‐made pair of enantiomers, as they are from the Bronze Age (1000–500 BC). The lurs are the oldest musical instruments that can still be played, and are used as enantiomers. Side by side stood two lur‐players, symmetric in every detail, the soft curves of the instruments swaying upwards and outwards at each side. The sonorous notes emphasized the solemn nature of the rituals. It is conceivable that the sound of the lur also accompanied the crackle of the funeral pyre when one of the tribe was cremated and laid to rest in the burial mound of his forefathers. The lurs are made of bronze (copper) and were discovered in lakes; less than 50 are known. The most famous pair of lurs was found in Brudevælte and is the pair shown on the cover. Further information about lurs can be obtained from kaj@chem.au.dk. The picture of the lurs and the accompanying music (click here to listen to the music: www.angewandte.com) are used with permission from The National Museum. For more details about the two new catalytic asymmetric reactions, see Jørgensen et al. on p. 2992 ff. and p. 2995 ff.     

Non-Specific GH30_7 Endo-β-1,4-xylanase from Talaromyces leycettanus

This study describes the catalytic properties of a GH30_7 xylanase produced by the fungus Talaromyces leycettanus. The enzyme is an ando-β-1,4-xylanase, showing similar specific activity towards glucuronoxylan, arabinoxylan, and rhodymenan (linear β-1,3-β-1,4-xylan). The heteroxylans are hydrolyzed to a mixture of linear as well as branched β-1,4-xylooligosaccharides that are shorter than the products generated by GH10 and GH11 xylanases. In the rhodymenan hydrolyzate, the linear β-1,4-xylooligosaccharides are accompanied with a series of mixed linkage homologues. Initial hydrolysis of glucuronoxylan resembles the action of other GH30_7 and GH30_8 glucuronoxylanases, resulting in a series of aldouronic acids of a general formula MeGlcA²Xyl_n. Due to the significant non-specific endoxylanase activity of the enzyme, these acidic products are further attacked in the unbranched regions, finally yielding MeGlcA²Xyl_2-3. The accommodation of a substituted xylosyl residue in the −2 subsite also applies in arabinoxylan depolymerization. Moreover, the xylose residue may be arabinosylated at both positions 2 and 3, without negatively affecting the main chain cleavage. The catalytic properties of the enzyme, particularly the great tolerance of the side-chain substituents, make the enzyme attractive for biotechnological applications. The enzyme is also another example of extraordinarily great catalytic diversity among eukaryotic GH30_7 xylanases.     

Fluorescein thiocarbamyl amino acids as internal standards for migration time correction in capillary sieving electrophoresis

A number of algorithms have been developed to correct for migration time drift in capillary electrophoresis. Those algorithms require identification of common components in each run. However, not all components may be present or resolved in separations of complex samples, which can confound attempts for alignment. This paper reports the use of fluorescein thiocarbamyl derivatives of amino acids as internal standards for alignment of 3-(2-furoyl)quinoline-2-carboxaldehyde (FQ)-labeled proteins in capillary sieving electrophoresis. The fluorescein thiocarbamyl derivative of aspartic acid migrates before FQ-labeled proteins and the fluorescein thiocarbamyl derivative of arginine migrates after the FQ-labeled proteins. These compounds were used as internal standards to correct for variations in migration time over a two-week period in the separation of a cellular homogenate. The experimental conditions were deliberately manipulated by varying electric field and sample preparation conditions. Three components of the homogenate were used to evaluate the alignment efficiency. Before alignment, the average relative standard deviation in migration time for these components was 13.3%. After alignment, the average relative standard deviation in migration time for these components was reduced to 0.5%.     

Three points method for searching the best least absolute deviations plane

In this paper a new method for estimation of optimal parameters of a best least absolute deviations plane is proposed, which is based on the fact that there always exists a best least absolute deviations plane passing through at least three different data points. The proposed method leads to a solution in finitely many steps. Moreover, a modification of the aforementioned method is proposed that is especially adjusted to the case of a large number of data and the need to estimate parameters in real time. Both methods are illustrated by numerical examples on the basis of simulated data and by one practical example from the field of robotics.     

A general formula for the algebraic degree in semidefinite programming

In this article, we use a natural desingularization of the conormalvariety of (n x n)-symmetric matrices of rank at most r to finda general formula for the algebraic degree in semidefinite programming.