Surface bodies and p-affine surface area

The surface body is a generalization of the floating body. Its relation to p-affine surface area is studied.     

An immobiline DryStrip application method enabling high-capacity two-dimensional gel electrophoresis

In the field of proteomics the need to detect low-abundance cellular components, such as regulatory proteins, is of critical importance. Two-dimensional polyacrylamide gel electrophoresis (2-D PAGE) is one of the most commonly used separation tools for these biological investigations. In this paper we report an alternative micropreparative 2-D PAGE sample application method, called the "paper bridge loading" method. This method makes it possible to apply a larger sample volume to commercially available immobilized pH gradient (IPG) strips. The Vh products required for focusing are only marginally longer than those used in analytical experiments. The method was compared to traditional cup loading and in-gel rehydration. With 18 cm long narrow-range Immobiline DryStrip pH 4.5-5.5, the "paper bridge" method allowed the application of 10 mg human plasma proteins compared to 3 mg with traditional loading methods. The corresponding figures using Escherichia coli sample was found to be 6 mg and less than 2 mg, respectively. The paper bridge method also showed the best results in terms of spot resolution and separation of high molecular weight proteins.     

Reaction mechanism of soluble epoxide hydrolase: insights from molecular dynamics simulations

Molecular dynamics simulations have been performed to gain insights into the catalytic mechanism of the hydrolysis of epoxides to vicinal diols by soluble epoxide hydrolase (sEH). The binding of a substrate, 1S,2S-trans-methylstyrene oxide, was studied in two conformations in the active site of the enzyme. It was found that only one is likely to be found in the active enzyme. In the preferred conformation the phenyl group of the substrate is pi-sandwiched between two aromatic residues, Tyr381 and His523, whereas the other conformation is pi-stacked with only one aromatic residue, Trp334. Two simulations were carried out to 1 ns for each conformation to evaluate the protonation state of active site residue His523. It was found that a protonated histidine is essential for keeping the active site from being disrupted. Long time scale, 4 ns, molecular dynamics simulation was done for the structure with the most likely combination of binding conformation and protonation state of His523. Near Attack Conformers (NACs) are present 5.3% of the time and nucleophilic attack on either epoxide carbon atom, approximately 75% on C(1) and approximately 25% on C(2), is found. A maximum of one hydrogen bond between the epoxide oxygen and either of the active site tyrosines, Tyr465 and Tyr381, is present, in agreement with experimental mutagenesis results that reveal a slight loss in activity if one tyrosine is mutated and essential loss of all activity upon double mutation of the two tyrosines in question. It was found that a hydrogen bond from Tyr465 to the substrate oxygen is essential for controlling the regioselectivity of the reaction. Furthermore, a relationship between the presence of this hydrogen bond and the separation of reactants was found. Two groups of amino acid segments were identified each as moving collectively. Furthermore, an overall anti-correlation was found between the movements of these two individually collectively moving groups, made up by parts of the cap-region, including the two tyrosines, and the site of the catalytic triad, respectively. This overall anti-correlated collective domain motion is, perhaps, involved in the conversion of E.NAC to E.TS.     

The isotopes259106,260106, and261106

In irradiations of²⁰⁷Pb and²⁰⁸Pb, respectively, with⁵⁴Cr theα-decay of the isotopes²⁵⁹106,²⁶⁰106, and²⁶¹106 could be observed for the first time. For²⁶⁰106 a spontaneous fission branch of (50 _?20 ⁺³⁰ )% was observed. The isotopes were identified by genetic relationships of α-decay after separation in-flight with the velocity filter SHIP and implantation into a position-sensitive silicon surface-barrier detector. The measured partial fission halflife of the doubly even isotope²⁶⁰106 of (7.2 _?2.7 ^+4.8 )ms exceeds the predicted values by at least a factor of 40. This result could be explained by the high shell corrections of the ground state mass, derived from the measured α-decay energies. The experimental results show evidence for an island of purely shell stabilized nuclei in the region of deformed isotopes beyond the actinides.     

Mechanistic investigation of the 2,5-diphenylpyrrolidine-catalyzed enantioselective alpha-chlorination of aldehydes

The mechanism for the 2,5-diphenylpyrrolidine-catalyzed enantioselective alpha-chlorination of aldehydes with electrophilic halogenation reagents has been investigated by using experimental and computational methods. These studies have led us to propose a mechanism for the reaction that proceeds through an initial N-chlorination of the chiral catalyst-substrate complex, followed by a 1,3-sigmatropic shift of the chlorine atom to the enamine carbon atom. The suggested reaction course is different from previously proposed mechanisms for organocatalytic enamine reactions, in which the carbon-electrophile bond is formed directly. Furthermore, the rate-determining step in the overall reaction was determined and the presence of nonlinear effects was probed.     

On the uniqueness of symmetric bases in finite dimensional Banach spaces

Suppose{e _i} _i=1 ⁿ and{f _i} _i=1 ⁿ are symmetric bases of the Banach spacesE andF. Letd(E,F)≦C andd(E,l _n ² )≧n' for somer>0. Then there is a constantC _r=C_r(C)>0 such that for alla _i∈Ri=1,...,n $$C_r^{ - 1} \left\| {\sum\limits_{i = 1}^n {a_i e_i } } \right\| \leqq \left\| {\sum\limits_{i = 1}^n {a_i f_i } } \right\| \leqq C_r \left\| {\sum\limits_{i = 1}^n {a_i e_i } } \right\|$$ We also give a partial uniqueness of unconditional bases under more restrictive conditions.     

Extension of the self-consistent spectrophotometric basicity scale in acetonitrile to a full span of 28 pKa units: unification of different basicity scales

The earlier compiled self-consistent spectrophotometric basicity scale in acetonitrile (AN) was expanded to range from 3.8 to 32.0 pK(a) units, that is 28 orders of magnitude. Altogether 54 new relative basicity measurements (DeltapK(a) measurements) were carried out and 37 new compounds were introduced to the scale (it now includes altogether 89 bases). The relative basicity of any two bases in the scale can be obtained by combining at least two independent sets of measurements. Multiple overlapping measurements make the results more reliable. The overall consistency (as defined earlier) of the measurements is s = 0.03 pK(a) units. Thorough analysis of all of our experimental data (DeltapK(a) values of this and earlier works) and experimental pK(a) data in AN available in the literature (works from the groups of Coetzee and Padmanabhan, Kolthoff and Chantooni, Jr., the Schwesinger group, Bren' et al. and some others, altogether 19 papers) was carried out. On the basis of this analysis the anchor point of the scale-pyridine-was shifted upward by 0.20 pK(a) units thereby also revising the absolute pK(a) values of all the bases on the scale. This way very good agreement between our relative data and the absolute pK(a) values of the abovementioned authors was obtained. The revised basicity scale was interconnected with the earlier published self-consistent acidity scale by DeltapK(a) measurements between acids and bases. The rms deviation between the directly measured DeltapK(a) values and the absolute pK(a) values of the compounds was 0.10 pK(a) units.     

Light‐Driven Coordination‐Induced Spin‐State Switching: Rational Design of Photodissociable Ligands

The bistability of spin states (e.g., spin crossover) in bulk materials is well investigated and understood. We recently extended spin‐state switching to isolated molecules at room temperature (light‐driven coordination‐induced spin‐state switching, or LD‐CISSS). Whereas bistability and hysteresis in conventional spin‐crossover materials are caused by cooperative effects in the crystal lattice, spin switching in LD‐CISSS is achieved by reversibly changing the coordination number of a metal complex by means of a photochromic ligand that binds in one configuration but dissociates in the other form. We present mathematical proof that the maximum efficiency in property switching by such a photodissociable ligand (PDL) is only dependent on the ratio of the association constants of both configurations. Rational design by using DFT calculations was applied to develop a photoswitchable ligand with a high switching efficiency. The starting point was a nickel–porphyrin as the transition‐metal complex and 3‐phenylazopyridine as the photodissociable ligand. Calculations and experiments were performed in two iterative steps to find a substitution pattern at the phenylazopyridine ligand that provided optimum performance. Following this strategy, we synthesized an improved photodissociable ligand that binds to the Ni–porphyrin with an association constant that is 5.36 times higher in its trans form than in the cis form. The switching efficiency between the diamagnetic and paramagnetic state is efficient as well (72 % paramagnetic Ni–porphyrin after irradiation at 365 nm, 32 % paramagnetic species after irradiation at 440 nm). Potential applications arise from the fact that the LD‐CISSS approach for the first time allows reversible switching of the magnetic susceptibility of a homogeneous solution. Photoswitchable contrast agents for magnetic resonance imaging and light‐controlled magnetic levitation are conceivable applications.