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101.
Yanyan Zhao Ole Tietz Wei-Li Kuan Abdul K. Haji-Dheere Stephen Thompson Benjamin Vallin Elisabetta Ronchi Gergely Tth David Klenerman Franklin I. Aigbirhio 《Chemical science》2020,11(18):4773
Soluble forms of aggregated tau misfolded protein, generally termed oligomers, are considered to be the most toxic species of the different assembly states that are the pathological components of neurodegenerative disorders. Therefore, a critical biomedical need exists for imaging probes that can identify and quantify them. We have designed and synthesized a novel fluorescent probe, pTP-TFE for which binding and selectivity profiles towards aggregated tau and Aβ proteins were assessed. Our results have shown pTP-TFE to be selective for early forms of soluble tau aggregates, with high affinity of dissociation constants (Kd) = 66 nM, and tenfold selectivity over mature tau fibrils. Furthermore, we found that pTP-TFE is selective for tau over Aβ aggregates and had good cell permeability. This selectivity of pTP-TFE towards early forms of aggregated tau protein ex vivo was also supported with studies on human brain tissue containing tau and Aβ pathology. To the best of our knowledge, this is the first fluorescent molecule to be reported to have this form of selectivity profile, which suggests that pTP-TFE is a unique probe candidate for imaging-based detection of early stages of Alzheimer''s disease and other tauopathies. pTP-TFE imaging probe can distinguish soluble tau aggregated proteins from other aggregated proteins enabling earlier detection of neurodegenerative diseases. 相似文献
102.
Zusammenfassung Durch Hinzunahme von Magnesiumoxid zur Verbrennungsrohrfüllung wird der Anwendungsbereich des CHN-Automaten auf fluor- und phosphorhaltige Proben erweitert. Diese beiden Elemente werden im wesentlichen in der Magnesiumoxidzone der Füllung gebunden. Bei manchen phosphorhaltigen Verbindungen macht die geringe Pyrolysegeschwindigkeit einen längeren Analysezyklus notwendig. Die längere Verbrennungszeit wird durch eine Reduzierung des Gasstromes ermöglicht. Bei metallhaltigen Proben geben alle Verbindungen, deren Metalle unter den herrschenden Bedingungen definierte Rückstände bilden, ohne besondere Maßnahmen gute Werte. Die Bildung carbonathaltiger Rückstände bei Alkali und Erdalkali wird meistens von der Apparatur als solche registriert.
Die Firma Technicon hat uns für diese Untersuchungen dankenswerterweise einen CHN-Analyzer zur Verfügung gestellt. 相似文献
Summary The field of application of the CHN-automatic combustion devices is extended to samples containing fluorine and phosphorus by including magnesium oxide in the filling of the combustion tube. These two elements are essentially bound in the magnesium oxide zone. Many compounds containing phosphorus make it necessary to reduce the speed of the gas stream because of the low pyrolysis velocity. When samples containing metals are being analyzed, excellent results are obtained with all compounds whose metals yield definite residues under the prevailing conditions. The formation of residues containing carbonate in the case of alkali and alkaline earths is usually registered as such by the apparatus.
Die Firma Technicon hat uns für diese Untersuchungen dankenswerterweise einen CHN-Analyzer zur Verfügung gestellt. 相似文献
103.
Mechanism of Thermal Dehydration of Sodium Dihydrogenphosphate The thermal dehydration of sodium dihydrogenphosphate (P1) to sodium cyclotriphosphate (CP3) and sodium polyphosphate, the so-called Maddrell's salt (MS), is controlled by nucleation and crystallization of CP3 and MS, respectively. The wellknown influence of various formation conditions on the CP3:MS product ratio is caused by amorphous and crystalline intermediate phases and their ability to form CP3 or MS nuclei. On seeding P1 with CP3 or MS the dehydration proceeds structure-controlled via dihydrogendiphosphate to pure CP3 or pure MS. The particularities of thermal dehydration of crystalline sodium dihydrogendiphosphate, and also the dehydration and reorganization of sodium phosphate glasses (Na:P = 1:1) with different mean chain lengths, under formation of CP3 or MS are described. 相似文献
104.
The varying -bonding contributions in the title compounds caused by the different electronic and molecular structure of the chelate rings are used for explaining the large band splittings in the absorption spectra by trigonal symmetry. It is shown that usual ligand field theory and the angular overlap model are not able to account for the trigonal level splitting of Cr(acac)3 for which the coordination sphere of oxygen atoms is nearly octahedrally arranged. The experimental finding can, however, be rationalized by an extended angular overlap model which considers the phase coupling of -orbitals in the ligands leading to non-additive contributions to the metal-ligand bond energy.On leave of absence from the Bulgarian Academy of Sciences, Sofia, Bulgaria 相似文献
105.
Rahimipour S Litichever-Coslovsky N Alaluf M Freeman D Ehrenberg B Weiner L Mazur Y Fridkin M Koch Y 《Photochemistry and photobiology》2005,81(2):250-258
A combination of light, oxygen and a photosensitizer is used to induce death of cancer cells by photodynamic therapy. In this study, we have synthesized several new methyl helianthrone derivatives and compared their phototoxicity with that of hypericin. In contrast to hypericin, methyl helianthrones are soluble in aqueous solutions and have a broad range of light absorbance, which allows the use of polychromatic light. Structural modifications of methyl helianthrone demonstrated that substitution of hydrogen atoms of methyl helianthrone at Positions 2 and 5 with Br atoms or methylation of its phenolic hydroxyls, significantly increases the corresponding singlet oxygen quantum yield and their phototoxicity toward alphaT3-1, M2R and LNCaP cells. The phototoxicity of some of these compounds was similar to that of hypericin. Methyl helianthrones, like hypericin, accumulated mainly in the perinuclear region as evident by confocal microscopy. Irradiation of cells pretreated with methyl helianthrone derivatives generates intracellular reactive oxygen species and lipid free radicals, as shown by a fluorescentic probe and electron paramagnetic resonance methods, respectively. The phototoxicity of these methyl helianthrones as well as their ability to oxidize membrane lipids were significantly decreased on addition of specific Type-II inhibitors, suggesting the involvement of singlet oxygen as the main oxidant. 相似文献
106.
Abstract— Photofrin II (PF-II) is the commercial name of the active photosensitizer which is used in photodynamic therapy of cancer. The effect of the composition of lipid membranes on the binding of PF-II was studied and compared to hematoporphyrin derivative (Hpd), which is a complex mixture of porphyrins and from which PF-II is separated. We find that increasing the content of cholesterol in the bilayer decreases the partitioning of PF-II into the bilayer, similar to what we have found earlier with Hpd. However, inserting DMPC or DPPC into the membrane, which was shown to decrease the binding of Hpd, causes the opposite trend with PF-H. A membrane fluidizer such as benzyl alcohol also has different effects on the membrane binding of Hpd and PF-II. The rate of binding of PF-II to a lipid membrane is about 10 times lower than that of Hpd. These results as well as I- quenching of the fluorescence of the two porphyrins indicate that PF-II is immersed less homogeneously and deeper in the bilayer than Hpd. The unique additive-dependent binding of PF-II to lipid membranes calls for care in using Hpd as a model photosensitizer. 相似文献
107.
[reaction: see text] Metalation of oxazoles at the 4 and 5 position was achieved after regioselective C-2 silyl protection. Removal of the protecting group was then accomplished under mild conditions allowing for a straightforward preparation of C-5 monosubstituted and C-4,5 disubstituted oxazoles. The first practical C-2 protecting group of oxazoles has been demonstrated. 相似文献
108.
Cappa CD Smith JD Wilson KR Messer BM Gilles MK Cohen RC Saykally RJ 《The journal of physical chemistry. B》2005,109(15):7046-7052
Measurements of the oxygen K-edge X-ray absorption spectrum (XAS) of aqueous sodium halide solutions demonstrate that ions significantly perturb the electronic structure of adjacent water molecules. The addition of halide salts to water engenders an increase in the preedge intensity and a decrease in the postedge intensity of the XAS, analogous to those observed when increasing the temperature of pure water. The main-edge feature exhibits unique behavior and becomes more intense when salt is added. Density functional theory calculations of the XAS indicate that the observed red shift of the water transitions as a function of salt concentration arises from a strong, direct perturbation of the unoccupied molecular orbitals on water by anions, and does not require significant distortion of the hydrogen bond network beyond the first solvation shell. This contrasts the temperature-dependent spectral variations, which result primarily from intensity changes of specific transitions due to geometric rearrangement of the hydrogen bond network. 相似文献
109.
Matsumoto K Davis BG Jones JB 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(18):4129-4137
A significant enhancement of the applicability of the serine protease subtilisin Bacillus lentus (SBL) in peptide synthesis was achieved by using the strategy of combined site-directed mutagenesis and chemical modification to create chemically modified mutant (CMM) enzymes. The introduction of polar and/or homochiral auxiliary substituents, such as X=oxazolidinones, alkylammonium groups, and carbohydrates at position 166 at the base of the primary specificity S(1) pocket created SBL CMMs S166C-S-X with strikingly broad structural substrate specificities. These CMMs are capable of catalyzing the coupling reactions of not only L-amino acid esters but also D-amino acid esters as acyl donors with glycinamide to give the corresponding dipeptides in good yields. These powerful enzymes are also applicable to the coupling of L-amino acid acyl donors with alpha-branched acyl acceptor, L-alaninamide. Typical increases in isolated yields of dipeptides of 60-80 % over SBL-WT (e.g. 0 % yield of Z-D-Glu-GlyNH(2) using SBL-WT-->74 % using S166C-S-(CH(2))(2) NMe(3) (+)) demonstrate the remarkable synthetic utility of this "polar patch" strategy. Such wide-ranging systems displaying broadened and therefore similarly high, balanced yields of products (e.g. 91 % Z-L-Ala-GlyNH(2) and 86 % yield of Z-D-Ala-GlyNH(2) using S166C-S-(3R,4S)-indenooxazolidinone) may now allow the use of biocatalysts in parallel library synthesis. 相似文献
110.
Excited state lifetime and amplitude measurements were made on thiazole orange dimer (TOTO), a dimeric DNA-intercalating fluorophore, at single-molecule concentrations. As expected from previous study, the excited state lifetime of TOTO intercalated in DNA is dependent on the sequence of the double-stranded DNA, having values of 2.2 ns in poly-GC DNA and 1.8 ns in poly-AT DNA. The distribution of excited state lifetimes of single molecules of TOTO intercalated into oligonucleotides having varying proportions of poly-GC sequences relative to poly-AT sequences were analyzed as a function of the fraction of poly-GC. By using excited state lifetime distributions from the purely GC and purely AT oligonucleotides as a basis set, it was possible to estimate the GC content of oligonucleotides with intermediate GC composition to within a few percent error. This serves as a model for the analysis of equilibrium binding distributions in DNA using single-molecule methods. 相似文献