Synthese und Charakterisierung neuer intramolekular stickstoffstabilisierter Organoaluminium‐ und Organogalliumalkoxide

Synthesis and Characterization of New Intramolecularly Nitrogen‐stabilized Organoaluminium‐ and Organogallium Alkoxides The intramolecularly nitrogen stabilized organoaluminium alkoxides [Me₂Al{μ‐O(CH₂)₃NMe₂}]₂ ( 1a ), Me₂AlOC₆H₂(CH₂NMe₂)₃‐2,4,6 ( 2a ), [(S)‐Me₂Al{μ‐OCH₂CH(i‐Pr)NH‐i‐Pr}]₂ ( 3a ) and [(S)‐Me₂Al{μ‐OCH₂CH(i‐Pr)NHCH₂Ph}]₂ ( 4 ) are formed by reacting equimolar amounts of AlMe₃ and Me₂N(CH₂)₃OH, C₆H₂[(CH₂NMe₂)₃‐2,4,6]OH, (S)‐i‐PrNHCH(i‐Pr)CH₂OH, or (S)‐PhCH₂NHCH(i‐Pr)CH₂OH, respectively. An excess of AlMe₃ reacts with Me₂N(CH₂)₂OH, Me₂N(CH₂)₃OH, C₆H₂[(CH₂NMe₂)₃‐2,4,6]OH, and (S)‐i‐PrNHCH(i‐Pr)CH₂OH producing the “pick‐a‐back” complexes [Me₂AlO(CH₂)₂NMe₂](AlMe₃) ( 5 ), [Me₂AlO(CH₂)₃NMe₂](AlMe₃) ( 1b ), [Me₂AlOC₆H₂(CH₂NMe₂)₃‐2,4,6](AlMe₃)₂ ( 2b ), and [(S)‐Me₂AlOCH₂CH(i‐Pr)NH‐i‐Pr](AlMe₃) ( 3b ), respectively. The mixed alkyl‐ or alkenylchloroaluminium alkoxides [Me(Cl)Al{μ‐O(CH₂)₂NMe₂}]₂ ( 6 ) and [{CH₂=C(CH₃)}(Cl)Al{μ‐O(CH₂)₂NMe₂}]₂ ( 8 ) are to obtain from Me₂AlCl and Me₂N(CH₂)₂OH and from [Cl₂Al{μ‐O(CH₂)₂NMe₂}]₂ ( 7 ) and CH₂=C(CH₃)MgBr, respectively. The analogous dimethylgallium alkoxides [Me₂Ga{μ‐O(CH₂)₃NMe₂}]₂ ( 9 ), [(S)‐Me₂Ga{μ‐OCH₂CH(i‐Pr)NH‐i‐Pr}]_n ( 10 ), [(S)‐Me₂Ga{μ‐OCH₂CH(i‐Pr)NHCH₂Ph}]_n ( 11 ), [(S)‐Me₂Ga{μ‐OCH₂CH(i‐Pr)N(Me)CH₂Ph}]_n ( 12 ) and [(S)‐Me₂Ga{μ‐OCH₂(C₄H₇NHCH₂Ph)}]_n ( 13 ) result from the equimolar reactions of GaMe₃ with the corresponding alcohols. The new compounds were characterized by elemental analyses, ¹H‐, ¹³C‐ and ²⁷Al‐NMR spectroscopy, and mass spectrometry. Additionally, the structures of 1a , 1b , 2a , 2b , 3a , 5 , 6 and 8 were determined by single crystal X‐ray diffraction.     

Backbone-controlled LUMO energy induces intramolecular C–H activation in ortho-bis-9-borafluorene-substituted phenyl and o-carboranyl compounds leading to novel 9,10-diboraanthracene derivatives

The choice of backbone linker for two ortho-bis-(9-borafluorene)s has a great influence on the LUMO located at the boron centers and, therefore, the reactivity of the respective compounds. Herein, we report the room temperature rearrangement of 1,2-bis-(9-borafluorenyl)-ortho-carborane, C₂B₁₀H₁₀-1,2-[B(C₁₂H₈)]₂ ([2a]) featuring o-carborane as the inorganic three-dimensional backbone and the synthesis of 1,2-bis-(9-borafluorenyl)benzene, C₆H₄-1,2-[B(C₁₂H₈)]₂ (2b), its phenylene analog. DFT calculations on the transition state for the rearrangement support an intramolecular C–H bond activation process via an S_EAr-like mechanism in [2a], and predicted that the same rearrangement would take place in 2b, but at elevated temperatures, which indeed proved to be the case. The rearrangement gives access to 3a and 3b as dibora-benzo[a]fluoroanthene isomers, a form of diboron polycyclic aromatic hydrocarbon (PAH) that had yet to be explored. The isolated compounds 2b, 3a, and 3b were fully characterized by NMR, HRMS, cyclic voltammetry (CV), single-crystal X-ray diffraction analysis, and photophysical measurements, supported by DFT and TD-DFT calculations.

The backbone linker for two ortho-bis-(9-borafluorene)s influences the LUMO at the boron centers and the reactivity of the respective compounds.     

Untersuchungen über Radium- und Bariumfällungen unter Anwendung von Thorium X als Indikator

Zusammenfassung Zunächst wird im Zusammenhang mit Messungen der Fällungsgeschwindigkeit von Thorium X in sulfathaltigen Lösungen eine Methode beschrieben, die es gestattet, während der Fällung, und zwar ohne Störung des Fällungsvorganges, diejenigen Mengen von Thorium X zu bestimmen, die sich jeweils zu bestimmten Zeitpunkten noch in Lösung befinden; dabei konnte der Gehalt an Th X mit Hilfe einer Emanationsmethode genau ermittelt werden.Die Versuchsergebnisse, die in Kurven wiedergegeben sind, lassen deutlich erkennen, daß die Fällung von Th X nicht momentan erfolgt, sondern eine gewisse Zeit beansprucht, die von der Konzentration der zugesetzten Sulfat- und Bariumchloridlösung sowie vom Zusatz anderer Fremdionen abhängig ist; es wird jedoch schließlich immer der gleiche Endzustand vollständiger Ausfällung erreicht, wenn mit äquivalenten Mengen gearbeitet wird.Die Annahme, daß die Fällung momentan erfolgt, daß aber das Fällungsprodukt sich im Laufe der Zeit von einem feinkristallinischen Zustand mit großer Emanierfähigkeit in einen grobkristallinen mit geringer Emanationsabgabe umwandelt, konnte durch besondere Experimente widerlegt werden.Schließlich wird noch eine Apparatur zur Messung des Thorongehalts angegeben, die auch für Untersuchungen des Thoriumgehalts von Quellwässern Anwendung finden kann.

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Summary A method has been worked out which makes it possible to determine the rate of precipitation of thorium X in solutions containing sulphate ion. The amount of thorium X is determined rapidly and accurately by the thorium emanation—thoron—evolved under fixed conditions. Determinations have been made every 5 minute during the time following precipitation, and the results are given graphically.They bring forward, very clearly, that the precipitation of thorium X requires a certain length of time, depending on the concentration of the sulphate and barium-chloride solutions used and on the presence of other ions. However, if equivalent quantities of barium- and sulphate ions are used, the same final result is always reached.It might have been supposed that the precipitation takes place instantaneously but that in course of time, the precipitate undergoes changes through recrystallisations and that the emanating power changes accordingly. That hypothesis, however, could be disproved by special experiments.At last an apparatus for measuring the thoron content is given which can also be applied for investigations of the thorium content of source waters.

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Résumé Les auteurs décrivent une méthode qui leur a permis de déterminer la vitesse de précipitation du thorium X en solutions contenant de l'ion sulfurique. Le thorium X est dosé par son émanation — le thoron — sous des conditions fixées, et les dosages peuvent se faire à intervalles régulières pendant le temps que demande la précipitation.Les résultats montrent que la précipitation du thorium X ne se fait point à l'instant, mais demande un certain temps, dépendant de la concentration des solutions de sulfate et de chlorure de baryum ajoutées et aussi de la présence d'ions étrangers.Les auteurs réfutent par leurs expériences la théorie que la précipitation se fait momentanément et que le précipité change peu à peu son état cristallin et par cela même, sa faculté de dégager l'émanation.Enfin les auteurs décrivent un appareil pour les dosages de thoron, qui pourra servir de même pour déterminer la teneur en thorium dans les eaux vives.

     

A new method for the automated selection of the number of components for deconvolving overlapping chromatographic peaks

Mathematical deconvolution methods can separate co-eluting peaks in samples for which (chromatographic) separation fail. However, these methods often heavily rely on manual user-input and interpretation. This is not only time-consuming but also error-prone and automation is needed if such methods are to be applied in a routine manner.     

Differential geometric analysis of alterations in MH α‐helices

Antigen presenting cells present processed peptides via their major histocompatibility (MH) complex to the T cell receptors (TRs) of T cells. If a peptide is immunogenic, a signaling cascade can be triggered within the T cell. However, the binding of different peptides and/or different TRs to MH is also known to influence the spatial arrangement of the MH α‐helices which could itself be an additional level of T cell regulation. In this study, we introduce a new methodology based on differential geometric parameters to describe MH deformations in a detailed and comparable way. For this purpose, we represent MH α‐helices by curves. On the basis of these curves, we calculate in a first step the curvature and torsion to describe each α‐helix independently. In a second step, we calculate the distribution parameter and the conical curvature of the ruled surface to describe the relative orientation of the two α‐helices. On the basis of four different test sets, we show how these differential geometric parameters can be used to describe changes in the spatial arrangement of the MH α‐helices for different biological challenges. In the first test set, we illustrate on the basis of all available crystal structures for (TR)/pMH complexes how the binding of TRs influences the MH helices. In the second test set, we show a cross evaluation of different MH alleles with the same peptide and the same MH allele with different peptides. In the third test set, we present the spatial effects of different TRs on the same peptide/MH complex. In the fourth test set, we illustrate how a severe conformational change in an α‐helix can be described quantitatively. Taken together, we provide a novel structural methodology to numerically describe subtle and severe alterations in MH α‐helices for a broad range of applications. © 2013 Wiley Periodicals, Inc.     

Qualitative interpretation of physico-chemical and isotopic parameters in the Krka River (Croatia) assessed by multivariate statistical analysis

Multivariate statistical analyses were applied on the measured physico-chemical (Cd, Pb, Cu, Zn, Mg, Ca, O₂, alkalinity, temperature, pH, SAS, DOC and DIC) and isotopic parameters (δ¹³C and δ¹⁸O) to estimate and distinguish anthropogenic from natural influences to the water system of the Krka River. Analyses were conducted on the data collected during six years from twelve sampling sites. On the basis of orientation, positioning and grouping of parameters arranged by biplots, four main hypotheses were defined and finally statistically confirmed. Thereof, two main and distinct processes occurring in the Krka River could be highlighted: (i) upstream pollution, caused by the inflow of untreated waste-waters of city of Knin and (ii) downstream self-purification, caused by the sedimentation and/or co-precipitation of pollutants coupled by the inflow of clean subterranean water (groundwater recharge). Grouping of (i) hydrological and carbon cycle connected parameters, and (ii) anthropogenically influenced correlated parameters were proposed as a result of statistical analysis. Regarding the pH, it is shown that a stream section influenced by the subterranean inflow of Zrmanja River is statistically significantly different for all sampling campaigns during six years, being lower for about 0.5 pH unit.     

Investigating microcrystalline cellulose crystallinity using Raman spectroscopy

Cellulose - Microcrystalline cellulose (MCC) is a semi-crystalline material with inherent variable crystallinity due to raw material source and variable manufacturing conditions. MCC crystallinity...     

Capillary Atmospheric Pressure Electron Capture Ionization (cAPECI): A Highly Efficient Ionization Method for Nitroaromatic Compounds

We report on a novel method for atmospheric pressure ionization of compounds with elevated electron affinity (e.g., nitroaromatic compounds) or gas phase acidity (e.g., phenols), respectively. The method is based on the generation of thermal electrons by the photo-electric effect, followed by electron capture of oxygen when air is the gas matrix yielding O₂ ^– or of the analyte directly with nitrogen as matrix. Charge transfer or proton abstraction by O₂ ^– leads to the ionization of the analytes. The interaction of UV-light with metals is a clean method for the generation of thermal electrons at atmospheric pressure. Furthermore, only negative ions are generated and neutral radical formation is minimized, in contrast to discharge- or dopant assisted methods. Ionization takes place inside the transfer capillary of the mass spectrometer leading to comparably short transfer times of ions to the high vacuum region of the mass spectrometer. This strongly reduces ion transformation processes, resulting in mass spectra that more closely relate to the neutral analyte distribution. cAPECI is thus a soft and selective ionization method with detection limits in the pptV range. In comparison to standard ionization methods (e.g., PTR), cAPECI is superior with respect to both selectivity and achievable detection limits. cAPECI demonstrates to be a promising ionization method for applications in relevant fields as, for example, explosives detection and atmospheric chemistry.