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1.
Bruno Voigt Twinkle Bhatia Julia Hesselbarth Dr. Monika Baumann Prof. Dr. Carla Schmidt Dr. Maria Ott Prof. Dr. Jochen Balbach 《Chemphyschem》2023,24(19):e202300439
Nucleation and growth of amyloid fibrils were found to only occur in supersaturated solutions above a critical concentration (ccrit). The biophysical meaning of ccrit remained mostly obscure, since typical low values of ccrit in the sub-μM range hamper investigations of potential oligomeric states and their structure. Here, we investigate the parathyroid hormone PTH84 as an example of a functional amyloid fibril forming peptide with a comparably high ccrit of 67±21 μM. We describe a complex concentration dependent prenucleation ensemble of oligomers of different sizes and secondary structure compositions and highlight the occurrence of a trimer and tetramer at ccrit as possible precursors for primary fibril nucleation. Furthermore, the soluble state found in equilibrium with fibrils adopts to the prenucleation state present at ccrit. Our study sheds light onto early events of amyloid formation directly related to the critical concentration and underlines oligomer formation as a key feature of fibril nucleation. Our results contribute to a deeper understanding of the determinants of supersaturated peptide solutions. In the current study we present a biophysical approach to investigate ccrit of amyloid fibril formation of PTH84 in terms of secondary structure, cluster size and residue resolved intermolecular interactions during oligomer formation. Throughout the investigated range of concentrations (1 μM to 500 μM) we found different states of oligomerization with varying ability to contribute to primary fibril nucleation and with a concentration dependent equilibrium. In this context, we identified the previously described ccrit of PTH84 to mark a minimum concentration for the formation of homo-trimers/tetramers. These investigations allowed us to characterize molecular interactions of various oligomeric states that are further converted into elongation competent fibril nuclei during the lag phase of a functional amyloid forming peptide. 相似文献
2.
Dr. Nicolas D'Imperio Dr. Valentina Pelliccioli Dr. Sara Grecchi Dr. Alberto Bossi Prof. Francesca Vasile Prof. Silvia Cauteruccio Dr. Anna I. Arkhypchuk Dr. Arvind Kumar Gupta Prof. Dr. Andreas Orthaber Prof. Dr. Sascha Ott Prof. Emanuela Licandro 《European journal of organic chemistry》2023,26(4):e202201209
The first examples of a π-conjugated benzo[b]phosphole P-oxide in which two phosphole P-oxide units are connected by a carbon-carbon double bond are described. The molecules are synthesized as E isomers with respect to the carbon-carbon double bond and exist as stable cis and trans isomers (chiral and meso one respectively) relatively to the two stereogenic P atoms. The optical and electrochemical properties of both isomers have been investigated by experiment and computations. 相似文献
3.
Hua-Hua Wang Yi-Yu Jiang Mian HR Mahmood Hai-Yang Liu Herman H.Y. Sung Ian D. Williams Chi K. Chang 《中国化学快报》2015,26(5):529-533
Tetrakis(alloxycarbonyl)porphyrin and its β-octafluoro-substituted derivatives were synthesized via Lindsey method and transformed to their zinc complexes.Single crystal X-ray structures of corresponding Zn(Ⅱ) porphyrins revealed that β-octafluorination will give more compactness of porphyrin moieties in the crystal structure owing to the hydrogen bonding interactions involving β-fluorine atoms.An unusual six-coordinated Zn(Ⅱ) was found via intramolecular coordination of oxygen atom of meso-substituents with central Zn(Ⅱ). 相似文献
4.
5.
Ferrocenyl‐Coupled N‐Heterocyclic Carbene Complexes of Gold(I): A Successful Approach to Multinuclear Anticancer Drugs 下载免费PDF全文
Dr. Julienne K. Muenzner Dr. Bernhard Biersack Alexander Albrecht Tobias Rehm Dr. Ulrike Lacher Dr. Wolfgang Milius Prof. Dr. Angela Casini Dr. Jing‐Jing Zhang Prof. Dr. Ingo Ott Prof. Dr. Viktor Brabec Olga Stuchlikova Dr. Ion C. Andronache Leonard Kaps Prof. Dr. Dr. Detlef Schuppan Prof. Dr. Rainer Schobert 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(52):18953-18962
Four gold(I) carbene complexes featuring 4‐ferrocenyl‐substituted imidazol‐2‐ylidene ligands were investigated for antiproliferative and antivascular properties. They were active against a panel of seven cancer cell lines, including multidrug‐resistant ones, with low micromolar or nanomolar IC50 (72 h) values, according to their lipophilicity and cellular uptake. The delocalized lipophilic cationic complexes 8 and 10 acted by increasing the reactive oxygen species in two ways: through a genuine ferrocene effect and by inhibiting the thioredoxin reductase. Both complexes gave rise to a reorganization of the F‐actin cytoskeleton in endothelial and melanoma cells, associated with a G1 phase cell cycle arrest and a retarded cell migration. They proved antiangiogenic in tube formation assays with endothelial cells and vascular‐disruptive on real blood vessels in the chorioallantoic membrane of chicken eggs. Biscarbene complex 10 was also tolerated well by mice where it led to a volume reduction of xenograft tumors by up to 80 %. 相似文献
6.
Lan Yu Qi Wang Lu Dai Wei-Ying Li Rong Chen Mian HR Mahmood Hai-Yang Liu Chi-Kwong Chang 《中国化学快报》2013,24(6):447-449
Pseudo-first order reaction rate constants of 5,10,15-tris(pentafluorophenyl)corrole Mn(V)-oxo (F15CMn(V)-oxo),5,15-bis(pentafluorophenyl)-10-(phenyl)corrole Mn(V)-oxo(F10CMn(V)-oxo),5,15- bis(phenyl)-10-(pentafluorophenyl)corrole Mn(V)-oxo(F5CMn(V)-oxo) and 5,10,15-tris(phenyl)corrole Mn(V)-oxo(F0CMn(V)-oxo) with a series of alkene substrates in different solvents were determined by UV-vis spectroscopy.The results indicated that the oxygen atom transfer pathway between Mn(V)-oxo corrole and alkene is solvent-dependent. 相似文献
7.
The Green function for the mixed problem for the linear Stokes system in domains in the plane 下载免费PDF全文
We construct the Green function for the mixed boundary value problem for the linear Stokes system in a two‐dimensional Lipschitz domain. 相似文献
8.
S.V. Kozhevnikov A. RühmF. Ott N.K. PleshanovJ. Major 《Physica B: Condensed Matter》2011,406(12):2463-2466
A neutron waveguide is a three-layer structure in which a guiding layer with low optical potential is placed between two cladding layers with high optical potential. Under proper operation conditions, the neutron density is resonantly enhanced inside the guiding layer. In our experimental scheme, the neutron beam enters through the surface of the top layer at glancing angle and goes out from the edge of the guiding layer, with an angular distribution corresponding to Fraunhofer diffraction from a narrow slit. The incident neutron beam is relatively wide (0.1 mm) and highly collimated (0.01°). The outgoing sub-micron beam is extremely narrow at the outlet (0.1 μm) and more divergent (0.1°). So far only the production of unpolarized sub-micron neutron beams has been reported. Here we present first experiments on polarized sub-micron neutron beams. For these studies a polarized incident beam was used and two types of magnetic waveguides were investigated: a polarizing magnetic waveguide Fe(20 nm)/Cu(140 nm)/Fe(50 nm)//glass and a non-polarizing magnetic waveguide Py(10 nm)/Al(140 nm)/Py(50 nm)//glass (Py is permalloy). The waveguide samples were characterized by polarized neutron reflectometry. 相似文献
9.
10.
Elisabet Öberg Andreas Orthaber Marie-Pierre Santoni Fredrick Howard Sascha Ott 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-3):152-158
Abstract Attempts to utilize C-ethylenic phosphaalkenes in metathesis reactions are discussed. Unprecedented reactivity is observed where the vinylphosphaalkene undergoes the first step of the catalytic cycle and cross-metathesis with the phenylmethylene moiety of Grubbs 2nd generation catalyst. However, homo-metathesis reaction to form 1,6-diphosphahexa-1,3,5-triene is not observed, presumably due to steric constraints. 相似文献