ÜBER EINIGE REAKTIONEN DER DIALKYLBENZYLPHOSPHINIMIDE

Abstract

Dialkylbenzylphosphine imides C₆H₅CH₂–PRR′[dbnd]N″ (R, R′ = CH₃, C₂H₅; R″ = H, CH₃, Si(CH₃)₃ react with aliphatic and aromatic aldehydes in benzene solution on heating to 80°C directly and in high yields according to a Horner-Wittig-reaction with formation of an olefine whereas ketones like benzophenone and acetophenone only perform an O/NR″ exchange (R″ = H).

Dialkylbenzylphosphinimide C₆H₅CH₂–PRR′[dbnd]N″ mit R, R′ = CH₃, C₂H₅ und R″ = H, CH₃, Si(CH₃)₃ reagieren mit aliphatischen und aromatischen Aldehyden in benzolischer Lösung beim Erwärmen auf 80°C direkt und mit hohen Ausbeuten im Sinne einer Horner-Wittig-Reaktion unter Olefinbildung, während sich mit Ketonen wie Benzophenon oder Acetophenon nur ein O/NR″-Austausch (R″ = H) vollzieht.     

Phospha-alkynes - Useful Building Blocks in Organic Chemistry1

Abstract

The syntheses of phospholes (7, [3+2]-cycloaddition), bicyclophosphaalkenes (17, [4+2]-cycloaddition), and phosphabenzenes (15, [4+2]-cycloaddition followed by an extrusion process) starting from the phosphaalkynes (4) are described. The 2–Dewar phosphabenzene 18, obtained from the cyclobutadiene 21 and 4 (R =^tBu), is the starting material for the synthesis of the valency isomers 19, 20, 22, and 23.     

Genetic Manipulation of the Fusarium fujikuroi Fusarin Gene Cluster Yields Insight into the Complex Regulation and Fusarin Biosynthetic Pathway

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Speciation of gadolinium in surface water samples and plants by hydrophilic interaction chromatography hyphenated with inductively coupled plasma mass spectrometry

Hydrophilic interaction chromatography (HILIC) coupled with inductively coupled plasma mass spectrometry (ICP-MS) was optimized for speciation analysis of gadolinium-based contrast agents in environmental samples, in particular surface river waters and plants. Surface water samples from the Teltow channel, near Berlin, were investigated over a distance of 5 km downstream from the influx of a wastewater treatment plant. The total concentration of gadolinium increased significantly from 50 to 990 ng?L^?1 due to the influx of the contrast agents. After complete mixing with the river water, the concentration remained constant over a distance of at least 4 km. Two main substances [Dotarem® (Gd-DOTA) and Gadovist® (Gd-BT-DO3A)] have been identified in the river water using standards. A gadolinium-based contrast agent, possibly Gd-DOTA (Dotarem®), was also detected in water plant samples taken from the Teltow channel. Therefore, uptake of contrast agents [Gadovist® (Gd-BTDO3A), Magnevist® (Gd-DTPA), Omniscan® (Gd-DTPA-BMA), Dotarem® (Gd-DOTA), and Multihance® (Gd-BOPTA)] by plants was investigated in a model experiment using Lepidium sativum (cress plants). HILIC–ICP-MS was used for identification of different contrast agents, and a first approach for quantification using aqueous standard solutions was tested. For speciation analysis, all investigated contrast agents could be extracted from the plant tissues with a recovery of about 54 % for Multihance® (Gd-BOPTA) up to 106 % for Gadovist® (Gd-BT-DO3A). These experiments demonstrate that all contrast agents investigated are transported from the roots to the leaves where the highest content was measured.     

A competitive displacement assay with quantum dots as fluorescence resonance energy transfer donors

The unique optoelectronic properties of semiconductor quantum dots (QDs) make them well-suited as fluorescent bioprobes for use in various biological applications. Modification of CdSe/ZnS QDs with biologically relevant molecules provides for multipotent probes that can be used for cellular labeling, bioassays, and localized optical interrogation by means of fluorescence resonance energy transfer (FRET). Herein, we demonstrate the use of red-emitting streptavidin-coated QDs (QD₆₀₅) as donors in FRET to introduce a competitive displacement-based assay for the detection of oligonucleotides. Various QD–DNA bioconjugates featuring 25-mer probe sequences diagnostic of Hsp23 were prepared. The single-stranded oligonucleotide probes were hybridized to dye-labeled (Alexa Fluor 647) reporter sequences, which were provided for a FRET-sensitized emission signal due to proximity of the QD and dye. The dye-labeled sequence was designed to be partially complementary and include base-pair mismatches to facilitate displacement by a more energetically favorable, fully complementary recognition motif embedded within a 98-mer displacer sequence. Overall, this study demonstrates proof-of-concept at the nM level for competitive displacement hybridization assays in vitro by reduction of fluorescence intensity that directly correlates to the presence of oligonucleotides of interest. This work demonstrates an analytical method that could potentially be implemented for monitoring of intracellular gene expression in the future.     

A One‐Pot Synthesis of 3‐Amino‐1H‐isoindol‐1‐one thiazol‐2‐ylhydrazones

A reaction of phthalonitrile with thiosemicarbazide and α‐haloketones proceeded in one‐pot, giving rise to 3‐amino‐1H‐isoindol‐1‐one thiazol‐2‐ylhydrazones in high yields.     

Hamaker 2: A Toolkit for the Calculation of Particle Interactions and Suspension Stability and its Application to Mullite Synthesis by Colloidal Methods

For modern processing of ceramics at the nanoscale, the influence of interparticle interactions in the suspended state becomes increasingly important. The Hamaker 2 program has been developed for the rapid prediction of these interactions, allowing us to gain important understanding of the often delicate balance of forces in ceramic powder suspensions. This article discusses the theoretical foundation of the implemented models and shows the benefit of this predictive approach applied to mullite production by colloidal methods.