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These results suggest that the Chol-U-Pr-mPEG-coated PP surface with an optimized swollen layer has been established as a bioinert surface by a facile method.Bis(pyrazolyl)bipyridinylmethane iron(II) complexes show a versatile spin state switching behavior in different solvents. In the solid, the magnetic properties of the compounds have been characterized by X-ray diffraction, Mößbauer spectroscopy, and SQUID magnetometry and point toward a high spin state. For nitrilic solvents, the solvation of the complexes leads to a change of the coordination environment from N5O to N6 and results in a temperature-dependent SCO behavior. Thermodynamic properties of this transformation are obtained via UV/vis spectroscopy, SQUID measurements, and the Evans NMR method. Moreover, a coordination-induced spin state switch (CISSS) to low spin is observed by using methanol as solvent, triggered through a rearrangement of the coordination sphere. The same behavior can be observed by changing the stoichiometry of the ligand-to-metal ratio in MeCN, where the process is reversible. This transformation is monitored via UV/vis spectroscopy, and the resulting new bis-meridional coordination motif, first described for bis(pyrazolyl)methanes, is characterized in the solid state via X-ray diffraction, Mößbauer spectroscopy, and SQUID measurements. The sophisticated correlation of these switchable properties in dependence on different types of solvents reveals that the influence of the solvent on the coordination environment and magnetic properties should not be underestimated. Furthermore, careful investigation is necessary to differentiate between a thermally-induced spin crossover and a coordination-induced spin state switch.Protein misfolding and denaturation, represented by amyloid fibrillation, are associated with many diseases. However, as a general chemical biological process, the dynamic structure information on amyloid fibrillation has not been demonstrated categorically. Herein, hen egg white lysozyme (HEWL) was used as the model protein of interest to realize in situ nanoscale imaging of protein fibrillation process using the fluorophores with aggregation-induced emission (AIE) activity. The AIE-active fluorophores exhibit the reversible capability of association and dissociation with β-sheet structure and thus dynamic binding-induced emission, which causes the spontaneous switching of fluorescence. The entire HEWL denaturation process induced by sodium dodecyl sulfate (SDS) at ambient conditions was demonstrated in detail by using two AIE-active fluorophores (TPE-NaSO3 and PD-BZ-OH) through reversible electrostatic interaction and specific labeling between AIE probes and β-sheet structures of amyloid fibrils, respectively. Z57346765 The results indicate that PD-BZ-OH is more specific AIE probe for amyloid fibrils than TPE-NaSO3. In comparison, the SEM and TEM results show the same denaturation process of protein fibrillation induced by SDS at different concentrations. The static super-resolution imaging of amyloid fibrils is performed with a resolution of 35 nm using PD-BZ-OH aqueous solution without additional auxiliary conditions. The dynamic evolution process of HEWL amyloid fibrillation is in situ visualized through super-resolution fluorescent microscopy with nanoscale resolution. Both static and dynamic super-resolution imaging of amyloid fibrillation provides detailed nanoscale structure information exceeding 50 nm resolution, which is of great significance in the exploration of amyloid fibrillation and related diseases.While N-hydroxyphthalimide (NHPI) ester has emerged as a powerful reagent as an alkyl radical source for a variety of C-C bond formations, the corresponding C(sp3)-N bond formation is still in its infancy. We demonstrate herein transition-metal-free decarboxylative C(sp3)-X bond formation enabled by the photochemical activity of the NHPI ester-NaI-NHC complex, giving primary C(sp3)-(N)phth, secondary C(sp3)-I, or tertiary C(sp3)-(meta C)phth coupling products. The primary C(sp3)-(N)phth coupling offers convenient access to primary amines.Hybrid organic-inorganic perovskites (HOIPs) with the general formula ABX3 hold phenomenal research interest for their great scientific and technological potential in photovoltaic, piezoelectric, and electroluminescent devices. It is their considerable structural diversity that offers a good opportunity to build a variety of HOIP structures with various functionalities. However, no organometallic-based HOIP piezoelectrics have yet been found, despite the structural diversity and functional richness of organometallic compounds such as the ferrocene-based family. Here, for the first time, we report an organometallic-based HOIP piezoelectric, [(ferrocenylmethyl)trimethylammonium]PbI3. Benefitting from the stability of ferrocene-based cations, excellent piezoelectric performance, comparable to that of LiNbO3, can be obtained and optimized by tuning the anionic framework. The involvement of organometallic cations enables a narrow band gap of 2.37 eV, much lower than those of most HOIPs and some inorganic semiconductors. This work provides a new future direction for the study of perovskites and will inspire intriguing research on organometallic-based HOIP piezoelectrics.The installation of vicinal mesylate and silyl ether groups in a quinic acid derivative generates a system prone for stereoselective borane-catalyzed hydrosilylation through a siloxonium intermediate. The diversification of the reaction conditions allowed the construction of different defunctionalized fragments foreseen as useful synthetic fragments. The selectivity of the hydrosilylation was rationalized on the basis of deuteration experiments and computational studies.We report the reactivity of N-phosphinoguanidines of the formula (HNR)(Ph2PNR)C(NAr) (R = i Pr and Ar = 2,6- i Pr2C6H3 [Dipp] for 1a, R = i Pr and Ar = 2,4,6-Me3C6H2 [Mes] for 1b, and R = Cy and Ar = Dipp for 1c), prepared in high yields from the corresponding trisubstituted guanidines, toward main group metal alkyls AlMe3, ZnEt2, Mg n Bu2, and n BuLi to obtain novel phosphinoguanidinato and phosphinimine-amidinato compounds. Reactions of 1a-c with AlMe3 at room temperature led to the kinetic phosphinoguanidinato products [Alκ2-N,N'-(NR)C(NAr)(NRPPh2)Me2] (2a-c), whereas the mild heating (60-80 °C) of solutions of 2a-c give the thermodynamic phosphinimine-amidinato products [Alκ2-N,N'-(NR)C(NAr)(PPh2NR)Me2] (3a-c) after ligand rearrangement. The reactions of equimolar amounts of 1a-c and ZnEt2 initially give solutions containing unstable phosphinoguanidinato compounds [Znκ2-N,P-(NR)C(NAr)(NRPPh2)Et] (4a-c), which rearrange upon mild heating to the phosphinimine-amidinato derivatives [Znκ2-N,N'-(NR)C(NAr)(PPh2NR)Et] (6a-c).
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