Coinage Metal Bis(amidinate) Complexes as Building Blocks for Self‐Assembled One‐Dimensional Coordination Polymers

The pyridyl functionalized amidinate [{PyC≡CC(NDipp)$_{2}$}Li(thf)$_{2}$]n was used to synthesize a series of bis-amidinate complexes [{PyC≡CC(NDipp)$_{2}$}$_{2}$M$_{2}$] (M=Cu, Ag, Au) with fully supported metallophilic interactions. These metalloligands were then used as building blocks for the synthesis of one-dimensional heterobimetallic coordination polymers using Zn(hfac)$_{2}$ (hfac=hexaflouroacetylacetonate) for self-assembly. Interestingly, the three coordination polymers [{PyC≡CC(NDipp)$_{2}$}$_{2}$M$_{2}$][Zn(hfac)$_{2}$] (M=Cu, Ag, Au), exhibit a zig zag shape in the solid state. To achieve linear coordination geometry other connectors such as M’(acac) (M’=Ni, Co) (acac=acetylacetonate) were investigated. The thus obtained compounds [{PyC≡CC(NDipp)$_{2}$}$_{2}$Cu$_{2}$][M’(acac)$_{2}$] (M’=Ni, Co) are indeed linear heterobimetallic coordination polymers featuring a metalloligand backbone with fully supported metallophilic interactions

Molecular gold strings: aurophilicity, luminescence and structure–property correlations

This review covers the compound class of one-dimensional gold strings. These compounds feature a formally infinite repetition of gold complexes as monomers/repeating units that are held together by aurophilic interactions, i.e. direct gold–gold contacts. Their molecular structures are primarily determined in the solid state using single crystal X-ray diffraction. The chemical composition of the employed gold complexes is diverse and furthermore plays a key role in terms of structure characteristics and the resulting properties. One of the most common features of gold strings is their photoluminescence upon UV excitation. The emission energy is often dependent on the distance of adjacent gold ions and the electronic structure of the whole string. In terms of gold strings, these parameters can be fine-tuned by external stimuli such as solvent, pH value, pressure or mechanical stress. This leads to direct structure–property correlations, not only with regard to the photophysical properties, but also electric conductivity for potential application in nanoelectronics. Concerning these correlations, gold strings, consisting of self-assembled individual complexes as building blocks, are the ideal compound class to look at, as perturbations by an inhomogeneity in the ligand sphere (such as the end of a molecule) can be neglected. Therefore, the aim of this review is to shed light on the past achievements and current developments in this area

Efficient Blue Phosphorescence in Gold(I)‐Acetylide Functionalized Coinage Metal Bis(amidinate) Complexes

The synthesis of linear symmetric ethynyl‐ and acetylide‐amidinates of the coinage metals is presented. Starting with the desilylation of the complexes [{Me$_{3}$SiC≡CC(NDipp)$_{2}$}$_{2}$M$_{2}$] (Dipp=2,6‐diisopropylphenyl) (M=Cu, Au) it is demonstrated that this compound class is suitable to serve as a versatile metalloligand. Deprotonation with n‐butyllithium and subsequent salt metathesis reactions yield symmetric tetranuclear gold(I) acetylide complexes of the form [{(PPh$_{3}$)AuC≡CC(NDipp)$_{2}$}$_{2}$M$_{2}$] (M=Cu, Au). The corresponding Ag complex [{(PPh$_{3}$)AuC≡CC(NDipp)$_{2}$}$_{2}$Ag$_{2}$] was obtained by a different route via metal rearrangement. All compounds show bright blue or blue‐green microsecond long phosphorescence in the solid state, hence their photophysical properties were thoroughly investigated in a temperature range of 20–295 K. Emission quantum yields of up to 41 % at room temperature were determined. Furthermore, similar emissions with quantum yields of 15 % were observed for the two most brightly luminescent complexes in thf solution

Modulation of electrically evoked acetylcholine release in cultured rat septal neurones

The electrically evoked release of acetylcholine and its modulation via auto- and heteroreceptors were studied in primary cell cultures prepared from embryonic rat septum (ED 17). Cultures were grown for 1, 2 or 3 weeks on circular, poly D-lysine-coated glass coverslips. They developed a dense network of non-neuronal and neuronal cells, only some of which were immunopositive for choline acetyltransferase. To measure acetylcholine release, the cells on the coverslips were pre-incubated with [3H]choline (0.1 micromol/L), superfused with modified Krebs-Henseleit buffer at 25 degrees C and electrically stimulated twice for 2 min (S1, S2; 3 Hz, 0.5 ms, 90-100 mA). The electrically evoked overflow of [3H] from the cells consisted of approximately 80% of authentic [3H]Ach, was largely Ca2+-dependent and tetrodotoxin sensitive, and hence represents an action potential-evoked, exocytotic release of acetylcholine. Using pairs of selective agonists and antagonist added before S2, muscarinic autoreceptors, as well as inhibitory adenosine A1- and opioid mu-receptors, could be detected, whereas delta-opioid receptors were not found. Evoked [3H] overflow from cultures grown for 1 week, although Ca2+ dependent and tetrodotoxin sensitive, was insensitive to the muscarinic agonist oxotremorine, whereas the effect of oxotremorine on cells grown for 3 weeks was even more pronounced than that in 2-week-old cultures. In conclusion, similar to observations on rat septal tissue in vivo, acetylcholine release from septal cholinergic neurones grown in vitro is inhibited via muscarinic, adenosine A1 and mu-opioid receptors. This in vitro model may prove useful in the exploration of regulatory mechanisms underlying the expression of release modulating receptors on septal cholinergic neurones

Nucleotide Binding Switches the Information Flow in Ras GTPases

The Ras superfamily comprises many guanine nucleotide-binding proteins (G proteins) that are essential to intracellular signal transduction. The guanine nucleotide-dependent intrinsic flexibility patterns of five G proteins were investigated in atomic detail through Molecular Dynamics simulations of the GDP- and GTP-bound states (SGDP and SGTP, respectively). For all the considered systems, the intrinsic flexibility of SGDP was higher than that of SGTP, suggesting that Guanine Exchange Factor (GEF) recognition and nucleotide switch require higher amplitude motions than effector recognition or GTP hydrolysis. Functional mode, dynamic domain, and interaction energy correlation analyses highlighted significant differences in the dynamics of small G proteins and Gα proteins, especially in the inactive state. Indeed, SGDP of Gαt, is characterized by a more extensive energy coupling between nucleotide binding site and distal regions involved in GEF recognition compared to small G proteins, which attenuates in the active state. Moreover, mechanically distinct domains implicated in nucleotide switch could be detected in the presence of GDP but not in the presence of GTP. Finally, in small G proteins, functional modes are more detectable in the inactive state than in the active one and involve changes in solvent exposure of two highly conserved amino acids in switches I and II involved in GEF recognition. The average solvent exposure of these amino acids correlates in turn with the rate of GDP release, suggesting for them either direct or indirect roles in the process of nucleotide switch. Collectively, nucleotide binding changes the information flow through the conserved Ras-like domain, where GDP enhances the flexibility of mechanically distinct portions involved in nucleotide switch, and favors long distance allosteric communication (in Gα proteins), compared to GTP

Half a century of amyloids: past, present and future

Amyloid diseases are global epidemics with profound health, social and economic implications and yet remain without a cure. This dire situation calls for research into the origin and pathological manifestations of amyloidosis to stimulate continued development of new therapeutics. In basic science and engineering, the cross-ß architecture has been a constant thread underlying the structural characteristics of pathological and functional amyloids, and realizing that amyloid structures can be both pathological and functional in nature has fuelled innovations in artificial amyloids, whose use today ranges from water purification to 3D printing. At the conclusion of a half century since Eanes and Glenner's seminal study of amyloids in humans, this review commemorates the occasion by documenting the major milestones in amyloid research to date, from the perspectives of structural biology, biophysics, medicine, microbiology, engineering and nanotechnology. We also discuss new challenges and opportunities to drive this interdisciplinary field moving forward. This journal i