Bistriazoles Connected Through a B−B Bridge,Synthesized by Highly Selective Dipolar Cycloaddition Reactions of a Diazido-diborane(4)

In this work we report the first cycloaddition reactions between a diazido diborane(4) and terminal alkynes, providing unique access to bis-1,2,3-triazoles connected by a B−B bridge. The catalyst-free reactions are highly selective, yielding exclusively the thermodynamically disfavored bis-1,4-triazoles. The reactions are enabled by the high thermal stability of the diazido-diborane [B(hpp)(N₃)]₂ (hpp=1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-α]pyrimidinate). Due to the tetra-coordinate boron atoms in this reagent, the reactions are tolerant with respect to the introduction of Lewis-basic groups at the alkyne. The scope and limitations of the new reactions are discussed.     

Acetylene Derivatives of Cationic Diazaoxatriangulenes and Diaza [4]Helicenes - Access to Red Emitters and Planar Chiral Stereochemical Traits

Cationic triangulenes, and related helicenes, constitute a rich class of dyes and fluorophores, usually absorbing and emitting light at low energy, in the orange to red domains. Recently, to broaden the scope of applications, regioselective late-stage functionalizations on these core moieties have been developed. For instance, with the introduction of electron-donating groups (EDGs), important bathochromic shifts are observed pushing absorptions towards or in the near-infrared (NIR) spectral domain while emissive properties disappear essentially completely. Herein, to upset this drawback, acetylene derivatives of cationic diazaoxa triangulenes (DAOTA) and [4]helicenes are prepared (16 examples). Contrary to other EDG-functionalized derivatives, C≡C− functionalized products remain broadly fluorescent, with red-shifted absorptions (Δλ_abs up to 25 nm) and emissions (Δλ_em up to 73 nm, Φ_PL up to 51 %). Quite interestingly, a general dynamic stereoisomerism phenomenon is evidenced for the compounds derived from achiral DAOTA cores. At low temperature in ¹H NMR spectroscopy (218 K), N−CH₂ protons become diastereotopic with chemical shifts differences (Δδ) as high as +1.64 ppm. The signal coalescence occurs around 273 K with a barrier of ∼12 kcal mol⁻¹. This phenomenon is due to planar chiral conformations (S_p and R_p configurations), induced by the geometry of the alkyl (n-propyl) side-chains next to the acetylenic substituents. Ion pairing studies with Δ-TRISPHAT anion not only confirm the occurrence of the chiral conformations but evidence a moderate but definite asymmetric induction from the chiral anion onto the cations. Finally, DFT calculations offer a valuable insight on the geometries, the corresponding stereodynamics and also on the very large difference in NMR for some of the diastereotopic protons.     

Comprehensive Characterization of Shredded Lithium-Ion Battery Recycling Material

Herein we report on an analytical study of dry-shredded lithium-ion battery (LIB) materials with unknown composition. Samples from an industrial recycling process were analyzed concerning the elemental composition and (organic) compound speciation. Deep understanding of the base material for LIB recycling was obtained by identification and analysis of transition metal stoichiometry, current collector metals, base electrolyte and electrolyte additive residues, aging marker molecules and polymer binder fingerprints. For reversed engineering purposes, the main electrode and electrolyte chemistries were traced back to pristine materials. Furthermore, possible lifetime application and accompanied aging was evaluated based on target analysis on characteristic molecules described in literature. With this, the reported analytics provided precious information for value estimation of the undefined spent batteries and enabled tailored recycling process deliberations. The comprehensive feedstock characterization shown in this work paves the way for targeted process control in LIB recycling processes.     

Radical Reactivity of the Biradical [⋅P(μ-NTer)2P⋅] and Isolation of a Persistent Phosphorus-Cantered Monoradical [⋅P(μ-NTer)2P-Et]

The activation of C−Br bonds in various bromoalkanes by the biradical [⋅P(μ-NTer)₂P⋅] ( 1 ) (Ter=2,6-bis-(2,4,6-trimethylphenyl)-phenyl) is reported, yielding trans-addition products of the type [Br−P(μ-NTer)₂P−R] ( 2 ), so-called 1,3-substituted cyclo-1,3-diphospha-2,4-diazanes. This addition reaction, which represents a new easy approach to asymmetrically substituted cyclo-1,3-diphospha-2,4-diazanes, was investigated mechanistically by different spectroscopic methods (NMR, EPR, IR, Raman); the results suggested a stepwise radical reaction mechanism, as evidenced by the in-situ detection of the phosphorus-centered monoradical [⋅P(μ-NTer)₂P-R].< To provide further evidence for the radical mechanism, [⋅P(μ-NTer)₂P-Et] ( 3Et ⋅) was synthesized directly by reduction of the bromoethane addition product [Br-P(μ-NTer)₂P-Et] ( 2 a ) with magnesium, resulting in the formation of the persistent phosphorus-centered monoradical [⋅P(μ-NTer)₂P-Et], which could be isolated and fully characterized, including single-crystal X-ray diffraction. Comparison of the EPR spectrum of the radical intermediate in the addition reaction with that of the synthesized new [⋅P(μ-NTer)₂P-Et] radical clearly proves the existence of radicals over the course of the reaction of biradical [⋅P(μ-NTer)₂P⋅] ( 1 ) with bromoethane. Extensive DFT and coupled cluster calculations corroborate the experimental data for a radical mechanism in the reaction of biradical [⋅P(μ-NTer)₂P⋅] with EtBr. In the field of hetero-cyclobutane-1,3-diyls, the demonstration of a stepwise radical reaction represents a new aspect and closes the gap between P-centered biradicals and P-centered monoradicals in terms of radical reactivity.     

Einige Bemerkungen zu einer allgemeinen Klasse von Stoffgesetzen für große elasto-plastische Formänderungen

Übersicht Unter den üblichen Voraussetzungen der phänomenologischen Plastizitätstheorie großer Formänderungen werden die Formulierungsbedingungen und einige spezielle Formulierungsmöglichkeiten für Fließbedingungen einer ziemlich allgemeinen Klasse erörtert, die isotrope und anisotrope Verfestigung umfaßt. Es schließen sich einige Bemerkungen zur Belastungsbedingung und zum zugehörigen Formänderungsgesetz an.

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Summary The restrictions for the formulation of yield conditions belonging to a rather general class comprehending isotropic and anisotropic hardening and some special cases are discussed under the usual assumptions of the phenomenological theory of plasticity at large deformations. Connected with this some remarks are following on the loading condition and the related stress-strain relations.

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Herrn Professor Dr. Dr. h. c. U. Wegner zum 70. Geburtstag.     

Mikroskopische Untersuchung der Tropfenkondensation

The heat transfer during dropwise condensation can be calculated from the distribution function of the drop sizes and the growth function of single drops. Both functions are obtained from motion pictures with high magnification. The motion pictures are taken during condensation of steam of about 25 °C on vertical copper and brass surfaces. A simple approximation for the growth function is given which agrees with the exact solution ofUmur andGriffith [8] within the limits of about 1%.     

Deformation und Stabilität windbeanspruchter Kühlturmschalen

Übersicht Nach der Formulierung des Deformations- und des Stabilitätsproblems auf der Grundlage ursprünglich nicht-konformer, dreiecksförmiger, gekrümmter finiter Elemente wird zunächst das Deformationsproblem für eine ausgeführte Kühlturmschale numerisch gelöst. Die nachfolgende Stabilitätsanalyse dieser Kühlturmschale zeigt gute Übereinstimmung der mittels der Methode der finiten Elemente errechneten Beulsicherheit mit dem aufgrund des Munganschen Beulkriteriums erhaltenen Kleinstwert der Beulsicherheit.

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Summary Following the formulation of the deformation and stability problem on the basis of originally non-conforming triangular curved finite elements with the help of a variational principle with subsidiary conditions, the deformation problem is solved numerically for an existing cooling tower shell. The subsequent stability analysis of this cooling tower shell shows relatively good agreement of the buckling safety computed by means of the finite element method and the minimum of buckling safety obtained with the help of Mungan's stability criterion.

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Diese Arbeit wurde mit Unterstützung der Cooling Tower Division von Zurn Industries, Tampa, Florida, USA, begonnen und mit Unterstützung Seitens des Fonds zur Förderung der wissenschaftlichen Forschung, Wien, zu Ende geführt. Beiden Sponsoren Sei an dieser Stelle aufrichtig gedankt. Der erstgenannte Autor ist darüber hinaus der Max Kade Foundation, New York, N. Y., für die Finanzierung Seines Studienaufenthaltes an der Cornell University, Ithaca, N. Y., im Rahmen dessen er mit der Thematik dieses Aufsatzes konfrontiert wurde, zu Dank verpflichtet. Aus demselben Grund sagt der dritte Autor für ein NATO Fellowship Dank.     

The die swell phenomenon

Summary A polymer melt or solution undergoes an increase in its cross-section when it is forced out of an orifice into air. The normal stress effects and elastic effects shown by these materials are frequently invoked to explain this die swell phenomenon. These explanations are here discussed and criticised. The analogous situation for a Newtonian jet is also discussed and the solution to a related problem of two-dimensional lowReynolds number flow is given.

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Zusammenfassung Kunststoffschmelzen oder -lösungen zeigen nach dem Austritt aus einer Mündung in Luft eine Aufweitung des Querschnitts. Häufig wird dieses Schwell-Phänomen als Folge von Normalspannungen und Elastizität erklärt. Erklärungen dieser Art werden hier kritisch untersucht.Ebenso wird der entsprechende Fall einer Newtonschen Düsenströmung diskutiert. Für das verwandte Problem einer zweidimensionalen Strömung bei niedrigerReynolds-Zahl wird die Lösung gegeben.

     

Untersuchung der verdickung von latex-dispersionen durch ethylacrylat-methacrylsäure-copolymere

Zusammenfassung Es wurden dynamische and stationdre Scherversuche durchgeführt, um den Verdickungseinfluß von Copolymeren aus Ethylacrylat and 15, 40 bzw. 65 Gew. % Methacrylsdure auf Latex-Dispersionen aus Ethylacrylat mit 0 bzw. 1 Gew. % Acrylsaure zu untersuchen. Nach Überschreiten eines Schwellwertes der Verdickungsmittelkonzentration, welche mit dem Sauregehalt im Verdickungsmittel und im Latex abnahm, wurde ein starker Anstieg des Speicher-und Verlust-Moduls (G and G) sowie der Fließgrenze und der Thixotropie beobachtet. Gleichzeitig wurde ein Überwiegen der viskosen Eigenschaften sowie eine zunehmende Flockulationsfähigkeit des Verdickungsmittels festgestellt. Bei größerem Säuregehalt im Latex überwogen die elastischen Eigenschaften, gleichzeitig erhöhte sich die Bestandigkeit gegen Flockulation. Die Verdickungswirkung der unterschiedlich zusammengesetzen Systeme wird durch die Ausbildung einer Raumnetzstruktur erklärt. Das Flockulationsverhalten wird auf Änderungen der Ladung und des freien Volumens zurückgeführt.

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The thickening effect of latices of ethylacrylate-methacrylic acid copolymers (15, 40, and 65 wt. % of the acid) on latices of ethylacrylate-acrylic acid copolymers (0 and 1 wt. % of the acid) was studied by using dynamic and steady shear flow measurement. It was found that beyond a certain concentration of the thickener the storage modulus G, the loss modulus G, the yield stress values, and thixotropic behavior rapidly increased. At the same time, viscous properties and the flocculation ability of the thickeners prevailed. On the contrary, an increase in acid content in the latex made the elastic properties and flocculation resistance of the system more pronounced. The thickening effect is explained by the formation of an ordered structure. The flocculation behavior is explained by changes of the electrical charge and the free volume.

Teilweise vorgetragen an der Jahrestagung der Deutschen Rheologischen Gesellschaft, 13.–15. Mai 1991, Berlin.     

Zum Randwertproblem der schwingenden schubelastischen Platte

Übersicht Über das Prinzip von Hamilton werden mittels verschiedener Ritzansätze für die Verschiebungen bzw. Spannungen Bewegungsgleichungen für die schwingende Platte hergeleitet. Abhängig von der Phasengeschwindigkeit ebener Biegewellen wird ein Schubbeiwert definiert, der im Vergleich mit der exakten Lösung der unendlichen Platte als Gütekriterium dient.

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On the boundary value problem of vibrating plates

Summary Following Hamilton's principle the equations of motion of a vibrating plate are derived by means of an expansion of the displacements respectively stresses using Ritz method. Depending upon the wave velocity of straight-crested flexural waves a shear coefficient is defined to check the above solutions with the known exact solution for the infinite plate.