Hydrogen Bonding in Aprotic Solvents,a New Strategy for Gelation of Bioinspired Catecholic Copolymers with N‐Isopropylamide

Copolymers of N‐isopropylacrylamide (NIPAM) and dopamine methacrylate can establish a reversible, self‐healing 3D network in aprotic solvents based on hydrogen bonding. The reactivity and hydrogen bonding formation of catechol groups in copolymer chains are studied by UV–vis and ¹H NMR spectroscopy, while reversibility from sol to gel and inverse as well as self‐healing properties are tested rheologically. The produced reversible organogel can self‐encapsulate physically interacting or chemically bonded solutes such as drugs due to thermosensitivity of the used copolymer. This system offers dual‐targeted and controlled drug delivery and release—by slowing down release kinetics by supramolecular bonding of the drug and by reducing diffusion rates due to modulus increase.

     

Synthesis and Conformation of 3,6‐Connected Cyclohexadiene Chains

3,6‐Connected cyclohexadienes as precursors for polyphenylenes are synthesized and characterized by mass spectrometry and NMR spectroscopy. Pure fractions of trimers, hexamers, and nonamers are collected after separation of the product mixture by recycling GPC. The anticipated formation of rigid linear structures, due to the trans‐configuration of the monomeric units, is supported by density functional theory and experimentally confirmed by dynamic light scattering from dilute solution at low scattering angles. The obtained translational diffusion coefficients are represented by rigid rod‐like or prolate ellipsoid‐like molecular shapes. The measurements of diffusion coefficients reveal a length‐dependent ratio of 1:2:3 between the three oligomers, which directly correlates to the expected length extension from trimer to nonamer.

     

Determination of a Constitutive Friction Law Using an Elastic-Plastic Half-Space Model

Friction influences metal forming processes both in economic and technical terms. A precise understanding of friction is inevitable as friction restricts the potential of the product design. Friction depends on the occurring contact loads which is especially true for sheet-bulk metal forming (SBMF) as the incorporated contact loads appear in a very broad range. Numerical simulations, which are verified experimentally, are carried out to analyse contact interactions which typically appear in SBMF. On the one hand the multi-scale character of rough surfaces requires a very fine resolution of the contact area, on the other hand a large contact area is necessary to be representative. A half-space model is chosen for the contact analysis, because it only depends on the two-dimensional surface boundary which consumes less computing capacity than the finite element method (FEM) with its three-dimensional volume approach for the same surface resolution and area. The outcome is a constitutive friction law (CFL) consisting of two equations. The law is implemented into the framework of FEM to see the impact in a typical SBMF-process which aims to form metal sheet into cups with integrated gearing teeth. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Characterisation of filled rubber with a pronounced non-linear viscoelasticity

This contribution presents the characterisation of an incompressible carbon black-filled elastomer as one characteristical example for highly filled rubber. It shows a strongly pronounced non-linear viscoelastic behaviour and the most important characteristic is the extremely long relaxation time which has to be taken into account. The material model is developed with respect to uniaxial tension data. The basis in the development of a phenomenological model is given by the basic elasticity. For this evaluation the long term relaxation behaviour results in a complex experimental procedure. Therefore, special attention has to be paid according to an optimised experimental process in order to get the necessary reference data in an adequate and reproduceable way [1]. With this model basis further investigations are taken into account concerning the time-dependent viscoelasticity. Therefore, cyclic deformations from zero up to a maximum of deformation are considered for different strain rates. Furthermore, the relaxation behaviour is investigated for multiple strain levels. The phenomena which are observed in the experimental results yield in a purely viscoelastic model, based on a rheological analogous model consisting of an equilibrium spring and several Maxwell-elements which contain nonlinear relations for the relaxation times of the dashpot elements [1,2]. The material model's numerical realisation is accomplished in two ways. Because of its numerical simplicity especially according to the parameter identification the model is restricted only to the simple case of uniaxial tension. A second, alternative implementation is executed providing the benefit that more complex deformation conditions can also be taken into account. Therefore, the general, three-dimensional finite model is implemented in an open-source Finite Element library [3]. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Photochemical Sandmeyer-type Halogenation of Arenediazonium Salts

Trihalide salts were found to efficiently promote photochemical dediazotizing halogenations of diazonium salts. In contrast to classical Sandmeyer reactions, no metal catalysts are required to achieve high yields and outstanding selectivities for halogenation over competing hydridodediazotization. Convenient protocols are disclosed for synthetically meaningful brominations, iodinations, and chlorinations of diversely functionalized derivatives.     

Revealing Phosphorus Nitrides up to the Megabar Regime: Synthesis of α′-P3N5, δ-P3N5 and PN2

Non-metal nitrides are an exciting field of chemistry, featuring a significant number of compounds that can possess outstanding material properties. These properties mainly rely on maximizing the number of strong covalent bonds, with crosslinked XN₆ octahedra frameworks being particularly attractive. In this study, the phosphorus–nitrogen system was studied up to 137 GPa in laser-heated diamond anvil cells, and three previously unobserved phases were synthesized and characterized by single-crystal X-ray diffraction, Raman spectroscopy measurements and density functional theory calculations. δ-P₃N₅ and PN₂ were found to form at 72 and 134 GPa, respectively, and both feature dense 3D networks of the so far elusive PN₆ units. The two compounds are ultra-incompressible, having a bulk modulus of K₀=322 GPa for δ-P₃N₅ and 339 GPa for PN₂. Upon decompression below 7 GPa, δ-P₃N₅ undergoes a transformation into a novel α′-P₃N₅ solid, stable at ambient conditions, that has a unique structure type based on PN₄ tetrahedra. The formation of α′-P₃N₅ underlines that a phase space otherwise inaccessible can be explored through materials formed under high pressure.     

Planar Iron Hydride Nanoclusters: Combined Spectroscopic and Theoretical Insights into Structures and Building Principles

The controlled assembly of well-defined planar nanoclusters from molecular precursors is synthetically challenging and often plagued by the predominant formation of 3D-structures and nanoparticles. Herein, we report planar iron hydride nanoclusters from reactions of main group element hydrides with iron(II) bis(hexamethyldisilazide). The structures and properties of isolated Fe₄, Fe₆, and Fe₇ nanoplatelets and calculated intermediates enable an unprecedented insight into the underlying building principle and growth mechanism of iron clusters, metal monolayers, and nanoparticles.     

Characterization of Functional Groups in Estuarine Dissolved Organic Matter by DNP-enhanced 15N and 13C Solid-State NMR

Estuaries are key ecosystems with unique biodiversity and are of high economic importance. Along the estuaries, variations in environmental parameters, such as salinity and light penetration, can modify the characteristics of dissolved organic matter (DOM). Nevertheless, there is still limited information about the atomic-level transformations of DOM in this ecosystem. Solid-state NMR spectroscopy provides unique insights into the nature of functional groups in DOM. A major limitation of this technique is its lack of sensivity, which results in experimental time of tens of hours for the acquisition of ¹³C NMR spectra and generally precludes the observation of ¹⁵N nuclei for DOM. We show here how the sensitivity of solid-state NMR experiments on DOM of Seine estuary can be enhanced using dynamic nuclear polarization (DNP) under magic-angle spinning. This technique allows the acquisition of ¹³C NMR spectra of these samples in few minutes, instead of hours for conventional solid-state NMR. Both conventional and DNP-enhanced ¹³C NMR spectra indicate that the ¹³C local environments in DOM are not strongly modified along the Seine estuary. Furthermore, the sensitivity gain provided by the DNP allows the detection of ¹⁵N NMR signal of DOM, in spite of the low nitrogen content. These spectra reveal that the majority of nitrogen is in the amide form in these DOM samples and show an increased disorder around these amide groups near the mouth of the Seine.     

Quantum theory of cavity-assisted sideband cooling of mechanical motion

We present a quantum-mechanical theory of the cooling of a cantilever coupled via radiation pressure to an illuminated optical cavity. Applying the quantum noise approach to the fluctuations of the radiation pressure force, we derive the optomechanical cooling rate and the minimum achievable phonon number. We find that reaching the quantum limit of arbitrarily small phonon numbers requires going into the good-cavity (resolved phonon sideband) regime where the cavity linewidth is much smaller than the mechanical frequency and the corresponding cavity detuning. This is in contrast to the common assumption that the mechanical frequency and the cavity detuning should be comparable to the cavity damping.