Die Struktur des Pentaphenyldisilans

Structure of Pentaphenyldisilane For the first time Pentaphenyldisilane was prepared by Gilman and Goodman. It is produced by the reaction of Ph₃SiLi with Ph₂ClSiH. The crystal structure presents an ideally staggered conformation. The distance d(Si? Si) = 235.7 pm corresponds to a normal single bond length. This emphasizes the complete relief of the central Si? Si bond by the insertion of only one hydrogen atom.     

Metabolic Tumor Imaging with Rapidly Signal-Enhanced 1-13C-Pyruvate-d3

The metabolism of malignant cells differs significantly from that of healthy cells and thus, it is possible to perform metabolic imaging to reveal not only the exact location of a tumor, but also intratumoral areas of high metabolic activity. Herein, we demonstrate the feasibility of metabolic tumor imaging using signal-enhanced 1-¹³C-pyruvate-d₃, which is rapidly enhanced via para-hydrogen, and thus, the signal is amplified by several orders of magnitudes in less than a minute. Using as a model, human melanoma xenografts injected with signal-enhanced 1-¹³C-pyruvate-d3, we show that the conversion of pyruvate into lactate can be monitored along with its kinetics, which could pave the way for rapidly detecting and monitoring changes in tumor metabolism.     

Bead cellulose derivatives as supports for immobilization and chromatographic purification of proteins

Characteristic data are presented for Divicell, a macroporous bead cellulose with excellent flow parameters. The preparation of Divicell derivatives and their properties are described with respect to their application as chromatographic supports. The ion exchangers Divicell DEAE and Divicell CM were manufactured in two types with different exclusion limits and an available capacity for proteins of up to 100 mg/ml gel. Divicell Blue is a bead cellulose with covalently bound Cibacron Blue F3G-A and was found to be a very suitable adsorbent for the selective separation and purification of human serum albumin. Activation of Divicell with sodium periodate, epichlorohydrin and 5-norbornene-2,3-dicarboximido carbonochloridate provided activated supports used for immobilization of ligands in organic solvents and in aqueous solutions. Coupling of amines, diamines, amino acids, carbohydrates and proteins is described. The immobilized ligands retained their biological activity as determined by their specific adsorption of proteins. Divicell alkyl derivatives were tested in hydrophobic interaction chromatography with bovine serum albumin as a model. Examples are presented of the application of Divicell derivatives to the purification of biomacromolecules such as immunoglobulins and lectins by affinity chromatography. The results were comparable to those obtained using the corresponding Sepharose-derived absorbents.     

Cluster isobars for high-precision mass spectrometry

Doublet mass measurements of the isobars²⁸Si₃ and¹²C₇ are performed by use of a Penning trap mass spectrometer and the Fourier transform ion cyclotron resonance (FT-ICR). The carbon and silicon cluster ions are produced by laser ablation. Results of these preliminary measurements are presented.     

Ultrafast Delamination of Graphite into High-Quality Graphene Using Alternating Currents

To bridge the gap between laboratory-scale studies and commercial applications, mass production of high quality graphene is essential. A scalable exfoliation strategy towards the production of graphene sheets is presented that has excellent yield (ca. 75 %, 1–3 layers), low defect density (a C/O ratio of 21.2), great solution-processability, and outstanding electronic properties (a hole mobility of 430 cm² V⁻¹ s⁻¹). By applying alternating currents, dual exfoliation at both graphite electrodes enables a high production rate exceeding 20 g h⁻¹ in laboratory tests. As a cathode material for lithium storage, graphene-wrapped LiFePO₄ particles deliver a high capacity of 167 mAh g⁻¹ at 1 C rate after 500 cycles.     

Nonlinear Optical Switching in Regioregular Porphyrin Covalent Organic Frameworks

Covalent organic frameworks (COFs) have garnered immense scientific interest among porous materials because of their structural tunability and diverse properties. However, the response of such materials toward laser‐induced nonlinear optical (NLO) applications is hardly understood and demands prompt attention. Three novel regioregular porphyrin (Por)‐based porous COFs—Por‐COF‐HH and its dual metalated congeners Por‐COF‐ZnCu and Por‐COF‐ZnNi—have been prepared and present excellent NLO properties. Notably, intensity‐dependent NLO switching behavior was observed for these Por‐COFs, which is highly desirable for optical switching and optical limiting devices. Moreover, the efficient π‐conjugation and charge‐transfer transition in ZnCu‐Por‐COF enabled a high nonlinear absorption coefficient (β=4470 cm/GW) and figure of merit (FOM=σ₁/σ_o, 3565) value compared to other state‐of‐the‐art materials, including molecular porphyrins (β≈100–400 cm/GW), metal–organic frameworks (MOFs; β≈0.3–0.5 cm/GW), and graphene (β=900 cm/GW).     

Acyl- und Alkylidenphosphane. XXVIII. Synthese und Struktur von 1,3-Dibenzyl- und 1,3-Diethyl-2,4-bis(phenylimino)-1,3-diphosphetan

Acyl- and Alkylidenephosphines. XXVIII. Synthesis and Structure of 1,3-Dibenzyl- and 1,3-Diethyl-2,4-bis(phenylimino)-1,3-diphosphetane Catalyzed by small amounts of solid sodium hydroxide, the adducts 1a and 1b formed from benzyl- or ethylbis(trimethylsilyl)phosphine and phenylisocyanate, react at +20°C slowly to give hexamethldisiloxane and oligomeric [(phenylimino)methylidene]phosphines. In different solvents the benzyl compound was found to exist only as a mixture of [N,N′-(E)/(Z)]-isomeric 2,4-bis-(phenylimino)-1,3-diphosphetanes 2a with their alkyl groups at the phosphorus atoms in trans position, whereas in case of the ethyl derivative 2b a second pair of [N,N′-(E)/(Z)]-isomeric dimers with their substituents in cis position and two trimeric forms ( 3b and 4b ) could be detected in cyclopentane. [N,N′-(E)]-1r,3t-dibenzyl- ( 2a ) and [N,N′-(E)]-1r,3t-diethyl-2,4-bis(phenylimino)-1,3-diphosphetane 2b isolated from 1,2-dimethoxyethane or cyclopentane, crystallize in the monoclinic space group P2₁/c or P2₁/n, resp., with following dimensions of the unit cell determined at temperatures of measurement of +20 ± 3°C/?130 ± 3°C: a = 2145.4(1)/569.3(1); b = 568.1(2)/719.1(2); c = 1960.2(2)/2042.6(4) pm; β 99.43(1)°/95.03(2)°; Z = (2+2) and 2, resp. X-ray structure determinations (R_w = 0.034/0.041) show both molecules to be centrosymmetric. Characteristic rounded bond lengths (pm) and angles (°) are: endocyclic P? C 185/184; C? P? C 82/81; P? C? P 98/99; exocyclic P? C 186/184; C?N l27/127; C?N? C 121/11.     

Trace and surface analysis of ceramic layers of solid oxide fuel cells by mass spectrometry

For the trace analysis of impurities in thick ceramic layers of a solid oxide fuel cell (SOFC) sensitive solid-state mass spectrometric methods, such as laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and radiofrequency glow discharge mass spectrometry (rf-GDMS) have been developed and used. In order to quantify the analytical results of LA-ICP-MS, the relative sensitivity coefficients of elements in a La(0.6)Sr(0.35)MnO(3) matrix have been determined using synthetic standards. Secondary ion mass spectrometry (SIMS) - as a surface analytical method - has been used to characterize the element distribution and diffusion profiles of matrix elements on the interface of a perovskite/Y-stabilized ZrO(2) layer. The application of different mass spectrometric methods for process control in the preparation of ceramic layers for the SOFC is described.     

Characterization of tri-o-methylcellulose by one- and two-dimensional NMR methods

Tri-O-methylcellulose was prepared from partially O-methylated cellulose and its chemical shifts (¹H and ¹³C), and proton coupling constants were assigned using the following NMR methods: (1) One-dimensional ¹H and ¹³C spectra of the title compound were used to assign functional groups and to compare with literature data; (2) double quantum filtered proton–proton correlation spectroscopy (¹H, ¹H DQF-COSY) was used to assign the chemical shifts of the network of 7 protons in the anhydroglucose portion of the repeat unit; (3) the heteronuclear single-quantum coherence (HSQC) spectrum was used to establish connectivities between the bonded protons and carbons; (4) the heteronuclear multiple-bond correlation (HMBC) spectrum was used to connect the hydrogens of the methyl ethers to their respective sugar carbons; (5) the combination of HSQC and HMBC spectra was used to assign the ¹³C shifts of the methyl ethers; (6) all spectra were used in combination to verify the assigned chemical shifts; (7) first-order proton coupling constants data (J_H,H in Hz) were obtained from the resolution-enhanced proton spectra. The NMR spectra of tri-O-methylcellulose and other cellulose ethers do not resemble the spectra of similarly substituted cellobioses. Although the ¹H and ¹³C shifts and coupling constants of 2,3,6-tri-O-methylcellulose closely resemble those of methyl tetra-O-methyl-β-D -glucoside, there are differences with regard to the chemical shifts and the order of appearances of the resonating nuclei of the methyl ether appendages and the proton at position 4 in the pyranose ring. H4 in tri-O-methylcellulose is deshielded by the acetal system comprising the β-1→4 linkage, and it resonates downfield. H4 in the permethylated glucoside is not as deshielded by the equitorial O-methyl group at C4, and it resonates upfield. The order of appearance of the ¹H and ¹³C resonances in the spectra of the tri-O-methylcellulose repeat unit (from upfield to downfield) are H2 < H3 < H5 < H6a < H3a < H2a < pro R H6B < H4 < pro S H6A ≪ H1 and C6a < C3a < C2a < C6 < C5 < C4 < C2 < C3 ≪ C1, respectively. Close examination of the pyranose ring coupling constants of the repeat unit in tri-O-methylcellulose supports the ⁴C₁ arrangement of the glucopyranose ring. Examination of the proton coupling constants about the C5-C6 bond (J_5,6A and J_5,6B) in the nuclear Overhauser effect difference spectra revealed that the C6 O-methyl group is predominantly in the gauche gauche conformation about the C5-C6 bond for the polymer in solution. © 1999 John Wiley & Sons, Inc.* J Polym Sci A: Polym Chem 37: 4019–4032, 1999