Synthesis of (pentacarbonyl)tungstate(−1) and (pentacarbonyl)molybdate(−1) dinucleotides

New methods for preparation of metallo dinucleotides with transition metals directly bonded to phosphorus are presented. (Pentacarbonyl)tungstate(−1) and (pentacarbonyl)molybdate(−1) dimers are prepared by the reaction of dinucleotide-H-phosphonate with M(CO)₅(THF) (M = W, Mo). These syntheses can be completed in solution or on solid-phase.     

On Toeplitz-type Operators Related to Wavelets

Let G be the “ax + b”-group with the left invariant Haar measure dν and ψ be a fixed real-valued admissible wavelet on . The structure of the space of Calderón (wavelet) transforms inside is described. Using this result some representations, properties and the Wick calculus of the Calderón-Toeplitz operators T _α acting on whose symbols a = a(ζ) depend on for are investigated. This paper was supported by Grant VEGA 2/0097/08.     

On crossing numbers of hypercubes and cube connected cycles

We prove tight bounds for crossing numbers of hypercube and cube connected cycles (CCC) graphs.The research of both authors was supported by Alexander von Humboldt Foundation, Bonn, Germany.     

Dichroic, dinuclear mu2-(eta2-NO)-nitrosoaniline-bridged complexes of rhenium of the type [[(CO)3Re(mu-X)]2ONC6H4NR2] (X = Cl, Br, I; R = Me, Et)

A series of unusual dinuclear mu2-(eta2-NO)-nitrosoaniline-bridged complexes [[(CO)3Re(mu-X)]2ONC6H4NR2] (X = Cl, Br, I; R = Me, Et) with dichroic properties have been synthesised by reaction of pentacarbonylhalogenorhenium(I) [(CO)5ReX] (X = Cl, Br, I) with the corresponding nitrosoaniline derivatives R2NC6H4NO (R = Me, Et). The deeply coloured solutions in CH2Cl2 show broad UV/Vis absorptions from 595 to 620 nm depending on the halogen bridges and N substituents. Single crystals of all six compounds exhibit a pronounced linear dichroism. The molecular structures have been determined by single-crystal X-ray analyses. All the compounds contain two face-shared octahedra, with two halogens and one NO ligand as bridges. The NO ligand coordinates in a nonsymmetrical eta2-like fashion with N or O coordination to each Re centre. Therefore, the C-nitroso group and the planar NC2 moiety of NR2 both lie almost exactly within the symmetry plane of the dinuclear complexes. These complexes belong to the novel and simple class of neutral dinuclear C-nitroso complexes that include the rare, non-assisted mu2-(eta2-NO) ligand function and have only single halogen atoms in bridging positions.     

Polymerization of styrene in presence of masticated rubber

The influence of the concentration of hydroperoxide (peroxide) groups in rubber (formed during mastication) and the influence of concentration of rubber on the polymerization of styrene were studied at 95, 105, 115 and 130°. The retardation effect of rubber (or non-rubber ingredients) is also due to the participation of less reactive (allylic) radicals from rubber on the termination. The derived kinetic relations allows calculation of a complex constant B* and the rate constant of decomposition of -OOH groups of rubber (k_d) at various temperatures; the latter are essentially smaller than those in masticated rubber. From kinetic analysis of experimental results, it follows that, during the polymerization of styrene in the presence of rubber, two types of rubber radicals can be formed, viz. a less reactive allylic radical and a more reactive alkyl radical.     

Composition of <Emphasis Type="Italic">α</Emphasis>−<Emphasis Type="Italic">F</Emphasis><Emphasis Type="Italic">e</Emphasis> nanoparticles precipitated from CuFe alloy studied by hyperfine interactions

Iron-based nanoparticles prepared by precipitation from solid solution of saturated binary Cu-Fe alloy were studied by transmission electron microscopy, high-energy X-ray diffraction and Mössbauer spectroscopy. The results showed that the investigated as-prepared nanoparticles contained two phases. The major phase was determined as α?F e and the minor phase as γ?F e ₂ O ₃. Furthermore, additionally annealed samples in Ar protective atmosphere were investigated. Results showed clear decrease in contribution of α?F e phase and also revealed the presence of various iron oxides (maghemite, magnetite, hematite and w?stite).     

Rapid analysis of multiple pesticide residues in fruit-based baby food using programmed temperature vaporiser injection-low-pressure gas chromatography-high-resolution time-of-flight mass spectrometry

A rapid method using programmed temperature vaporiser injection-low-pressure gas chromatography-high-resolution time-of-flight mass spectrometry (PTV-LP-GC-HR-TOF-MS) for the analysis of multiple pesticide residues in fruit-based baby food was developed. The fast and inexpensive buffered QuEChERS (quick, easy, cheap, effective, rugged, and safe) extraction method and "conventional" approach that employs ethyl acetate extraction followed by gel permeation chromatography (GPC) cleanup were employed for sample preparation. A PTV injector in solvent venting mode was used to reduce volume of acetonitrile and acetic acid (from the buffered QuEChERS extracts) that caused higher column bleed without their elimination. Otherwise, the time-to-digital converter would become saturated in HR-TOF-MS. For fast GC separation allowing analysis of 100 analytes within a 7 min runtime, both a high temperature programming rate and vacuum conditions in a megabore GC column were employed. The use of HR-TOF-MS allowed the unbiased identification and reliable quantification of target analytes through the application of a narrow mass window (0.02 Da) for extracting analyte ions and the availability of full spectral information even at very low levels. With only a few exceptions, the lowest calibration levels for the pesticides tested were 相似文献   

Biplanar crossing numbers. II. Comparing crossing numbers and biplanar crossing numbers using the probabilistic method

The biplanar crossing number cr₂(G) of a graph G is min{cr(G₁) + cr(G₂)}, where cr is the planar crossing number. We show that cr₂(G) ≤ (3/8)cr(G). Using this result recursively, we bound the thickness by Θ(G) ‐ 2 ≤ Kcr₂(G)^0.4057 log₂n with some constant K. A partition realizing this bound for the thickness can be obtained by a polynomial time randomized algorithm. We show that for any size exceeding a certain threshold, there exists a graph G of this size, which simultaneously has the following properties: cr(G) is roughly as large as it can be for any graph of that size, and cr₂(G) is as small as it can be for any graph of that size. The existence is shown using the probabilistic method. © 2008 Wiley Periodicals, Inc. Random Struct. Alg., 2008     

Fast and Tunable Phosphorescence from Organic Ionic Crystals

Crystalline diphosphonium iodides [MeR₂P-spacer-R₂Me]I with phenylene ( 1 , 2 ), naphthalene ( 3 , 4 ), biphenyl ( 5 ) and anthracene ( 6 ) as aromatic spacers, are photoemissive under ambient conditions. The emission colors (λ_em values from 550 to 880 nm) and intensities (Φ_em reaching 0.75) are defined by the composition and substitution geometry of the central conjugated chromophore motif, and the anion-π interactions. Time-resolved and variable-temperature luminescence studies suggest phosphorescence for all the titled compounds, which demonstrate observed lifetimes of 0.46–92.23 μs at 297 K. Radiative rate constants k_r as high as 2.8×10⁵ s⁻¹ deduced for salts 1 – 3 were assigned to strong spin-orbit coupling enhanced by an external heavy atom effect arising from the anion-π charge-transfer character of the triplet excited state. These rates of anomalously fast metal-free phosphorescence are comparable to those of transition metal complexes and organic luminophores that utilize triplet excitons via a thermally activated delayed fluorescence mechanism, making such ionic luminophores a new paradigm for the design of photofunctional and responsive molecular materials.     

Deep Membrane Proteome Profiling Reveals Overexpression of Prostate-Specific Membrane Antigen (PSMA) in High-Risk Human Paraganglioma and Pheochromocytoma,Suggesting New Theranostic Opportunity

Pheochromocytomas and paragangliomas (PPGLs) are rare neuroendocrine tumors arising from chromaffin cells of adrenal medulla or sympathetic or parasympathetic paraganglia, respectively. To identify new therapeutic targets, we performed a detailed membrane-focused proteomic analysis of five human paraganglioma (PGL) samples. Using the Pitchfork strategy, which combines specific enrichments of glycopeptides, hydrophobic transmembrane segments, and non-glycosylated extra-membrane peptides, we identified over 1800 integral membrane proteins (IMPs). We found 45 “tumor enriched” proteins, i.e., proteins identified in all five PGLs but not found in control chromaffin tissue. Among them, 18 IMPs were predicted to be localized on the cell surface, a preferred drug targeting site, including prostate-specific membrane antigen (PSMA), a well-established target for nuclear imaging and therapy of advanced prostate cancer. Using specific antibodies, we verified PSMA expression in 22 well-characterized human PPGL samples. Compared to control chromaffin tissue, PSMA was markedly overexpressed in high-risk PPGLs belonging to the established Cluster 1, which is characterized by worse clinical outcomes, pseudohypoxia, multiplicity, recurrence, and metastasis, specifically including SDHB, VHL, and EPAS1 mutations. Using immunohistochemistry, we localized PSMA expression to tumor vasculature. Our study provides the first direct evidence of PSMA overexpression in PPGLs which could translate to therapeutic and diagnostic applications of anti-PSMA radio-conjugates in high-risk PPGLs.