Ion chromatographic determination of oxalate in plasma: correlation study with an enzymatic method

An ion chromatographic (IC) method for the determination of oxalate in plasma was developed. The method exploits a rapid and simple sample preparation step that substantially reduces the plasma chloride level to facilitate the oxalate determination. The chloride is removed as silver chloride by using a cation-exchange resin in the silver cation form. The dependence on chloride concentration and pH was evaluated. The oxalate recovery in plasma samples was found to be 93 ± 18% (n=4 trials) according to a standard addition study. A comparison of the IC method with an enzymatic method indicated that both methods measure the same oxalate concentration over the range examined, 5–300 μM. Furthermore, the comparison involved a correlation study that allowed cross-validation of the two methods, suggesting that neither is adversely affected by interferences. The detection limit of the IC method was 0.5 μM or 4.4 ng oxalate.     

Fast, easy, solvent-free, microwave-promoted Michael addition of anilines to α,β-unsaturated alkenes: synthesis of N-aryl functionalized β-amino esters and acids

The rapid, simple, microwave-promoted synthesis of N-aryl functionalized β-amino esters using Michael addition reactions is presented. Reactions are performed neat at 200 °C for 20 min and are catalyzed by acetic acid. The esters can be easily hydrolyzed to the corresponding N-aryl functionalized β-amino acids.     

Four-arm oligonucleotide Ni(II)-cyclam-centered complexes as precursors for the generation of supramolecular periodic assemblies

The development of a multiarm metal-centered DNA building block as a precursor for the construction of supramolecular assemblies has relied upon the preparation of a Ni(II)-1,4,8,11-tetrazacyclotetradecane ligand (cyclam) functionalized with four linkers. This complex can be incorporated into a support-bound DNA sequence and the remaining three linkers can then be elongated by DNA synthesis. The result is a Ni(II)-cyclam complex tethering four 20-mer DNA strands. This building block, designed to be tetrahedral in nature, can in principle be used to form tetrahedral assemblies. These assemblies can be designed to be of known size and composition or permitted to grow into complexes of essentially infinite size, ideally the macroscopic version of a crystal.     

Structural changes and chain radius of gyration in cold-drawn polyethylene after annealing: small- and wide-angle X-ray scattering and small-angle neutron scattering studies

Samples made from linear polyethylene were drawn at room temperature and subsequently annealed at high temperatures below the melting point. The structural changes of the crystalline lamellae and lamellar superstructures as well as the single chain radius of gyration were studied by means of combined small- and wide-angle X-ray scattering and small-angle neutron scattering (SANS). After drawing, the polymeric chain segments in the crystalline phase are preferentially oriented along the drawing direction with a high degree of orientation whereas the lamellae in the samples are found to be slightly sheared exhibiting oblique surfaces as evidenced by X-ray scattering. SANS indicates that the chains are highly elongated along the drawing direction. Annealing the deformed samples at temperatures where the mechanical alpha-process of polyethylene is active leads to a thickening of both crystalline lamellae and amorphous layers. The chains in the crystalline phase retain their high degree of orientation after annealing while the lamellae are sheared to a larger extent. In addition, there is also lateral growth of the crystalline lamellae during high-temperature annealing. Despite the structural changes of the crystalline and amorphous regions, there is no evidence for global chain relaxation. The global anisotropic shape of the chains is preserved even after prolonged annealing at high temperatures. The results indicate that the mobility of polyethylene chains-as seen, e.g., by 13C NMR-is a local phenomenon. The results also yield new insight into mechanical properties of drawn PE, especially regarding stress relaxation and creep mechanisms.     

The rotational spectrum and theoretical study of a dinuclear complex, MnRe(CO)(10)

The first rotational spectrum of a dinuclear complex, MnRe(CO)(10), has been obtained using a high-resolution pulsed beam microwave spectrometer. Sixty-four hyperfine components of the J=11-->J(')=12 and J=12-->J(')=13 rotational transitions were measured for two rhenium isotopomers. The B values obtained from the experiment are B=200.36871(18) MHz for the (187)Re isotopomer and B=200.5561(10) MHz for the (185)Re isotopomer. The measured rotational constants are in reasonably good agreement with the B values calculated from the x-ray diffraction structural data, and from theoretical calculations. The gas-phase Mn-Re bond distance is approximately 2.99 A, and the calculated value is only slightly longer. The experimental quadrupole coupling constant for the manganese atom is eQq(aa) ((55)Mn)=-16.52(5) MHz, and the corresponding quadrupole coupling constants for the two rhenium isotopomers are eQq(aa) ((187)Re)=370.4(4) MHz and eQq(aa) ((185)Re)=390.9(6) MHz. The quadrupole coupling constants were also determined from a variety of theoretical calculations, with very large Gaussian orbital bases. The best estimates, at a nonrelativistic level, are eQq(aa) ((55)Mn)=0.68 MHz and eQq(aa) ((187)Re)=327.6 MHz with a 874 GTO basis set, but the results are very basis set dependent, especially the sign of the Mn quadrupole coupling. Very slight bending of angles MnC(eq)O(eq) and ReC(eq)O(eq) angles is found in the calculations.     

Control of traveling waves in the Mammalian cortex

We experimentally confirmed predictions that modulation of the neuronal threshold with electrical fields can speed up, slow down, and even block traveling waves in neocortical slices. The predictions are based on a Wilson-Cowan-type integro-differential equation model of propagating neocortical activity. Wave propagation could be modified quickly and reversibly within targeted regions of the network. To the best of our knowledge, this is the first example of direct modulation of the threshold to control wave propagation in a neural system.     

Zur Geometrie der partiellen Differentialgleichung 2. Ordnung

Ohne Zusammenfassung     

Determination of domoic acid in seawater and phytoplankton by liquid chromatography-tandem mass spectrometry

Domoic acid (DA) is an algal neurotoxin produced by diatoms primarily of the genus Pseudo-nitzschia and is responsible for the human intoxication syndrome known as amnesic shellfish poisoning. A method has been developed to determine DA in seawater and phytoplankton matrices by liquid chromatography-tandem mass spectrometry for both quantitation and confirmation purposes. Sample extraction and clean-up was achieved on a C18 solid-phase extraction (SPE) cartridge. An acidic condition is critical for retaining hydrophilic DA on the cartridge. Direct injection of SPE eluate for analysis is recommended in order to avoid loss of DA by drying with heat prior to resuspension and injection. DA was quantified using the fragments produced from the protonated DA ion through multiple reaction monitoring (MRM). Recoveries exceeded 90% for all seawater samples spiked with DA and approximated 98% of toxin standard added to cultured phytoplankton material. Acceptable reproducibility (ca. 5% or less) was obtained for all intra-day and inter-day samples. The detection limit was 30 pg/ml level with a 20 microl injection volume, which demonstrated the value of this method for not only confirming DA production by minimally toxic phytoplankton species, but also for investigating the potentially important role of dissolved DA in marine food webs.     

ITO‐free top emitting organic light emitting diodes with enhanced light out‐coupling

Bottom emitting organic light emitting diodes (OLEDs) can suffer from lower external quantum efficiencies (EQE) due to inefficient out‐coupling of the generated light. Herein, it is demonstrated that the current efficiency and EQE of red, yellow, and blue fluorescent single layer polymer OLEDs is significantly enhanced when a MoO_x(5 nm)/Ag(10 nm)/MoO_x(40 nm) stack is used as the transparent anode in a top emitting OLED structure. A maximum current efficiency and EQE of 21.2 cd/A and 6.7%, respectively, was achieved for a yellow OLED, while a blue OLED achieved a maximum of 16.5 cd/A and 10.1%, respectively. The increase in light out‐coupling from the top‐emitting OLEDs led to increase in efficiency by a factor of up to 2.2 relative to the optimised bottom emitting devices, which is the best out‐coupling reported using solution processed polymers in a simple architecture and a significant step forward for their use in large area lighting and displays.