Ternary Rare Earth and Actinoid Transition Metal Carbides Viewed as Carbometalates.

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Polar properties of hydrothermally synthesized BiFeO3 thin films

Multiferroic bismuth ferrite (BiFeO₃) has attracted considerable attention due to applications related to the bulk photovoltaic effect in which the direction of polarization determines the direction of the photocurrent. Epitaxial thin films are produced by means of techniques that usually require high temperature processes. The hydrothermal method can be seen as an alternative route to obtain highly textured thin films in quantities compatible with batch processing; nevertheless, the structural, dielectric and electric properties are generally affected by the presence of hydrogen and other reaction by-products. In this work, functional and highly textured BiFeO₃ films were successfully produced on metallic SrTiO₃:Nb (0.5 wt.%) (100) substrates via hydrothermal synthesis. X-ray diffraction (XRD) and Atomic Force Microscopy (AFM) were used to analyze the structural properties of the films. Piezoresponse Force Microscopy (PFM) and Photoconductive Atomic Force Microscopy (Pc-AFM) were used to determine their functional properties. We show the polarization switching and confirm the presence of the bulk photovoltaic effect for the first time in hydrothermally synthesized BiFeO₃.     

HPLC in clinical chemistry: Selected topics and clinical applications

Nowadays, HPLC is a very valuable tool in the clinical laboratory. In the future more and more HPLC methods will replace old photometric assays and also immunoassays, since these methods fulfill the claims in clinical chemistry: high precision, accuracy, sensitivity and specificity.     

Angular tolerance of Shack-Hartmann wavefront sensors with microaxicons

Wavefront sensing under nonparaxial conditions was studied with Shack-Hartmann setups based on arrays of microaxicons. The robustness of the generated pseudonondiffracting subbeams against tilt and axial displacement was demonstrated for ultraflat Gaussian- and inverse-Gaussian-shaped elements in transmission and reflection. To characterize slight aberrations and to identify optimum parameter fields, spatial moments of intensity profiles were analyzed with high sensitivity. Reflective design enables for wavefront sensing at oblique incidence as necessary for low-feedback detection and phase diagnostics of ultrashort pulses.     

Viscosity destabilizes sonoluminescing bubbles

In single-bubble sonoluminescence (SBSL) microbubbles are trapped in a standing sound wave, typically in water or water-glycerol mixtures. However, in viscous liquids such as glycol, methylformamide, or sulphuric acid it is not possible to trap the bubble in a stable position. This is very peculiar as larger viscosity normally stabilizes the dynamics. Suslick and co-workers call this new mysterious state of SBSL "moving-SBSL." We identify the history force (a force nonlocal in time) as the origin of this destabilization and show that the instability is parametric. A force balance model quantitatively accounts for the observed quasiperiodic bubble trajectories.     

Hydrogel characteristics of electron-beam-immobilized poly(vinylpyrrolidone) films on poly(ethylene terephthalate) supports

A novel strategy for the preparation of thin hydrogel coatings on top of polymer bulk materials was elaborated for the example of poly(ethylene terephthalate) (PET) surfaces layered with poly(vinylpyrrolidone) (PVP). PVP layers were deposited on PET foils or SiO2 surfaces (silicon wafer or glass coverslips) precoated with PET and subsequently cross-linked by electron beam treatment. The obtained films were characterized by ellipsometry, X-ray photoelectron spectroscopy, infrared spectroscopy in attenuated total reflection, atomic force microscopy (AFM), and electrokinetic measurements. Ellipsometric experiments and AFM force-distance measurements showed that the cross-linked layers swell in aqueous solutions by a factor of about 7. Electrokinetic experiments indicated a strong hydrodynamic shielding of the charge of the underlying PET layer by the hydrogel coatings and further proved that the swollen films were stable against shear stress and variation of pH. In conclusion, electron beam cross-linking ofpreadsorbed hydrophilic polymers permits a durable fixation of swellable polymer networks on polymer supports which can be adapted to materials in a wide variety of shapes.     

1,2,5]Thiadiazolo[3,4-c][1,2,5]thiadiazolidyl: a long-lived radical anion and its stable salts

[1,2,5]Thiadiazolo[3,4-c][1,2,5]thiadiazole (1) is synthesized in 62% yield by fluoride ion-induced condensation of 3,4-difluoro-1,2,5-thiadiazole with (Me(3)SiN=)(2)S. The reversible electrochemical reduction of 1 leads to the long-lived [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazolidyl radical anion (2) and further to the dianion (3). The radical anion 2 is also obtained by the chemical reduction of the precursor 1 with t-BuOK in MeCN. The radical anion 2 is characterized by ESR spectroscopy in solution and in the crystalline state. The stable salts [K(18-crown-6)][2] and [K(18-crown-6)][2].MeCN (8 and 9, respectively) are isolated from the spontaneous decomposition of the [K(18-crown-6)][PhXNSN] (6, X = S; 7, X = Se) salts in MeCN solution followed by XRD characterization. The radical anion 2 acts as a bridging ligand in 8 and as chelating ligand in 9. The structural changes observed by XRD in going from 1 to 2 are explained by means of DFT/(U)B3LYP/6-311+G calculations.     

Dehydroaromatization of quinoxalines: one-step syntheses of trinuclear 1,6,7,12,13,18-hexaazatrinaphthylene titanium complexes

We report the spontaneous coupling of N-heterocycles, initiated by C-H bond activation reactions. The reaction of quinoxalines and the titanocene acetylene complex Cp2Ti{eta2-C2(SiMe3)2}, as an excellent titanocene source, results in the formation of trinuclear 1,6,7,12,13,18-hexaazatrinaphthylene (HATN) titanium complexes. These HATN titanium complexes are thermally stable but sensitive to air and moisture. A three-fold dehydrogenative C-C coupling is proposed as the main step in the presented synthetic procedure. Particularly using commercial starting materials, an efficient route for the dehydrogenative coupling of N-heterocycles, leading to multidentate ligands, has been established.     

Enhanced ALA-induced fluorescence in hyperparathyroidism

INTRODUCTION: Intraoperative localization of parathyroid glands can be challenging especially in minimally invasive surgery. Fluorescence diagnosis using the photosensitizer aminolevulinic acid (ALA) has been described to identify normal parathyroid glands during experimental bilateral neck exploration. The present study evaluated fluorescence differences between hyperplastic and normal parathyroid glands as a precondition for a clinical application of the technique. MATERIALS AND METHODS: Polycystic kidney disease (PKD) rats with hyperparathyroidism due to hyperplastic parathyroid glands and Wistar rats with normal parathyroid glands were photosensitized by peritoneal lavage with ALA solution. After surgical exposure of thyroid and parathyroid glands the operative site was observed under blue light conditions using the d-light system to assess fluorescence characteristics of each tissue. Fluorescence intensities of parathyroid glands and surrounding thyroid tissue were measured by spectrometry. Parathyroid hormone in serum of the rats was determined by enzyme-linked immunosorbent assay (ELISA). RESULTS: Observation of the exposed thyroid site showed a subjectively stronger red fluorescence of the parathyroid glands in the PKD rats in comparison to the Wistar rats, whereas thyroid tissue appeared equally fluorescent. In the PKD animals, spectrometric fluorescence intensity was 10 times higher in the parathyroid glands than in the thyroid gland, whereas in the Wistar rats the ratio was 3.2:1. Fluorescence intensity in the parathyroid glands was more than twice in the PKD rats than in the Wistar rats, however slightly lower in the thyroid tissue. ELISA confirmed the pathophysiological change of a hyperparathyroidism with significantly increased serum levels of parathyroid hormone in the PKD rats. DISCUSSION: Hyperparathyroidism enhances ALA-induced fluorescence of the parathyroid glands. A combined surgical fluorescence strategy may justify a unilateral, minimally invasive approach in selected patients and serve to improve the capability of the surgeon to safely and efficiently manage parathyroid diseases.     

Characterization of a cross-linked DNA-Endonuclease VIII repair complex by electrospray ionization mass spectrometry

Electrospray mass spectrometry techniques were used to characterize components of the active site in Endonuclease VIII by identifying the amino acid sequence and the binding site for a tryptic peptide derived from Endo VIII in a cross-linked DNA-peptide complex. Endo VIII, a DNA repair enzyme with both glycosylase and lyase activities, was covalently bound to a thymidine glycol-containing oligodeoxynucleotide duplex by converting a transient Schiff base formed during the course of the glycosylase activity to a stable covalent bond by chemical reduction with sodium borohydride. After tryptic digestion of the initial product, the identification of the cross-linked peptide was deduced initially from the molecular mass of the tryptic product obtained by negative ion electrospray mass analysis. Nanospray tandem mass spectrometry (MS/MS) analysis of the tryptic product corroborated the molecular mass of the peptide fragment and verified the point of attachment to the oligomer, but failed to produce sufficient fragmentation to sequence the peptide completely. Direct evidence for the amino acid sequence of the peptide was obtained after enzymatic digestion of the DNA portion of the cross-linked DNA-peptide product and analysis by negative ion nanospray MS/MS. Examination of the ions from collision induced fragmentation disclosed that this substance was the N-terminal tryptic fragment of Endo VIII cross-linked to a portion of the oligomer, and that the N-terminal proline from Endo VIII was covalently bound to the residual deoxyribose moiety at the original location of the thymine glycol in the oligomer.