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821.
Dr. Filipa Marcelo Catarina Dias Dr. Alice Martins Dr. Paulo J. Madeira Tiago Jorge Prof. M. Helena Florêncio Prof. F. Javier Cañada Prof. Eurico J. Cabrita Prof. Jesús Jiménez‐Barbero Prof. Amélia P. Rauter 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(21):6641-6649
Acetylcholinesterase (AChE) inhibition is one of the most currently available therapies for the management of Alzheimer’s disease (AD) symptoms. In this context, NMR spectroscopy binding studies were accomplished to explain the inhibition of AChE activity by Salvia sclareoides extracts. HPLC‐MS analyses of the acetone, butanol and water extracts eluted with methanol and acidified water showed that rosmarinic acid is present in all the studied samples and is a major constituent of butanol and water extracts. Moreover, luteolin 4′‐O‐glucoside, luteolin 3′,7‐di‐O‐glucoside and luteolin 7‐O‐(6′′‐O‐acetylglucoside) were identified by MS2 and MS3 data acquired during the LC‐MSn runs. Quantification of rosmarinic acid by HPLC with diode‐array detection (DAD) showed that the butanol extract is the richest one in this component (134 μg mg?1 extract). Saturation transfer difference (STD) NMR spectroscopy binding experiments of S. sclareoides crude extracts in the presence of AChE in buffer solution determined rosmarinic acid as the only explicit binder for AChE. Furthermore, the binding epitope and the AChE‐bound conformation of rosmarinic acid were further elucidated by STD and transferred NOE effect (trNOESY) experiments. As a control, NMR spectroscopy binding experiments were also carried out with pure rosmarinic acid, thus confirming the specific interaction and inhibition of this compound against AChE. The binding site of AChE for rosmarinic acid was also investigated by STD‐based competition binding experiments using Donepezil, a drug currently used to treat AD, as a reference. These competition experiments demonstrated that rosmarinic acid does not compete with Donepezil for the same binding site. A 3D model of the molecular complex has been proposed. Therefore, the combination of the NMR spectroscopy based data with molecular modelling has permitted us to detect a new binding site in AChE, which could be used for future drug development. 相似文献
822.
Giorgio Marrubini Alice Pedrali Petrus Hemström Tobias Jonsson Patrik Appelblad Gabriella Massolini 《Journal of separation science》2013,36(21-22):3493-3502
Short‐chain carboxylic acids are relevant in pharmaceutical, food quality control, and biomedical analysis. In this study, 11 acids commonly found in drugs and in food products were selected. Wine was chosen as matrix for testing the method. The test compounds were used for comparing the selectivity of four 150 × 2.1 mm zwitterionic hydrophilic interaction LC (HILIC) columns (ZIC‐HILIC 5 μm, 200 Å, and 3.5 μm, 100 Å, ZIC‐pHILIC 5 μm, ZIC‐cHILIC 3 μm, 100 Å) while varying the conditions to optimize for low UV wavelength detection and achieve high sensitivity. Retention using potassium phosphate and ammonium carbonate as mobile‐phase components at pH 6.0, 7.5, and 8.5–8.9 was studied considering recent hypotheses on HILIC mechanism‐related with the Hofmeister series effect and ion hydration. An isocratic method with UV detection at 200 nm and mobile phase consisting of 75% acetonitrile and 10 mM potassium phosphate at pH 6.0 applied to a ZIC‐cHILIC column was found provisionally optimal and partially validated for the 11 analytes. Satisfactory results (R2 from 0.9940 to >0.9999), and recoveries from 93–106% for all analytes evidenced the method as suitable for wine analysis. To the best of our knowledge, no previous study has reported on the direct ZIC‐HILIC separation and UV detection of the acids considered here in wine. 相似文献
823.
Amer Al Abdel Hamid Carl P. Tripp Alice E. Bruce Mitchell R. M. Bruce 《Research on Chemical Intermediates》2011,37(7):791-810
In order to gain additional insight into mercury selectivity with nano-sized DMSA-[silica], we investigated a series of ligands related to DMSA, these are: monomercaptosuccinic acid; MMSA, 2-mercapto-4-methyl-5-thiazoleacetic acid; MCT, ortho-thiosalicylic acid; o-TSA and para-thiosalicylic acid; p-TSA. The MMSA chelate is structurally similar to DMSA except that it has only one thiol group. The chelates o-TSA and p-TSA each have one thiol and one carboxylic acid group. MCT includes neutral S and N atoms in close proximity to the thiolate binding site. MCT, o-TSA and p-TSA resemble each other in having equal numbers of carboxylic acid and thiol groups and formation of amide bonds with the linker on silica is expected to eliminate the carboxylate binding sites, making thiolates the only binding sites for Hg(II), Cd(II), and Pb(II) metals ions in the nano-sized; MMSA-[silica], MCT-[silica], o-TSA-[silica], and p-TSA-[silica]. Each of the nano-sized MMSA-[silica], MCT-[silica], o-TSA-[silica], and p-TSA-[silica], show a higher preference for Hg(II) over Cd(II) and Pb(II) compared to the same free chelates in solution, respectively. In addition, there are differences in the level of metal ion chelation for each functionalized silica nanoparticle. These differences in the degree of metal chelation for each functionalized silica nanoparticles surface are explained by the difference in thiolate/carboxylate ratio upon attachment to the surface and on steric reasons based on the orientation of the thiol groups on the surface. When attached via amide bond formation, the thiolate site in o-TSA-[silica] will face towards the silica surface, while for p-TSA-[silica], the thiolate site is expected to be pointed outwards and away from the silica surface. In comparing MMSA-[silica] to DMSA-[silica], the thiolate/carboxylate ratio decreases from 2/1 in DMSA-[silica] to 1/1 in MMSA-[silica] (assuming attachment via one amide bond in each case). This effect of increasing the ratio of thiolate to carboxylate upon attachment to the surface is believed to play a role in the selectivity enhancement towards Hg(II) over Cd(II) and Pb(II). 相似文献
824.
Background
Karns and Knight (2009) [1] demonstrated by using ERP and gamma band oscillatory responses that intermodal attention modulates visual processing at the latency of the early phase of the C1 response (62-72 ms) thought to be generated in the primary visual cortex. However, the timing of attentional modulation of visual cortex during object-based attention remains a controversial issue. 相似文献825.
Francesco A. Bottino Elena Fabbri Ignazio L. Fragal Graziella Malandrino Alice Orestano Francesco Pilati Antonino Pollicino 《Macromolecular rapid communications》2003,24(18):1079-1084
Polystyrene/montmorillonite nanocomposites were prepared via in situ bulk polymerization. New imidazolium salts were used to modify montmorillonite obtaining an improvement in thermal stability in comparison with a montmorillonite modified with a standard alkylammonium cation. The synthesized cations facilitate the formation of partially exfoliated structures because of the presence in their structure of a polymerizable group. The polystyrene/montmorillonite nanocomposites were characterized by X‐ray diffraction, thermogravimetric analysis, scanning electron microscopy (SEM), and transmission electron microscopy (TEM).
826.
Luisa Affatigato Alice Sciortino Giuseppe Sancataldo Alessio Incocciati Roberta Piacentini Alessandra Bonamore Marco Cannas Fabrizio Messina Mariano Licciardi Valeria Militello 《Photochemistry and photobiology》2023,99(5):1218-1224
Ferritin nanoparticles play many important roles in theranostic and bioengineering applications and have been successfully used as nanovectors for the targeted delivery of drugs due to their ability to specifically bind the transferrin receptor (TfR1, or CD71). They can be either genetically or chemically modified for encapsulating therapeutics or probes in their inner cavity. Here, we analyzed a new engineered ferritin nanoparticle, made of the H chain mouse ferritin (HFt) fused with a specific lanthanide binding tag (LBT). The HFt-LBT has one high affinity lanthanide binding site per each of the 24 subunits and a tryptophane residue within the tag that acts as an antenna able to transfer the energy to the lanthanide ions via a LRET process. In this study, among lanthanides, we selected europium for its red emission that allows to reduce overlap with tissue auto-fluorescence. Steady state emission measurements and time-resolved emission spectroscopy have been employed to investigate the interaction between the HFt-LBT and the Eu3+ ions. This allowed us to identify the Eu3+ energy states involved in the process and to pave the way for the future use of HFt-LBT Eu3+ complex in theranostics. 相似文献
827.
In this paper we show a new inequality that generalizes to the unit sphere the Lebedev-Milin inequality of the exponentiation of functions on the unit circle. It may also be regarded as the counterpart on the sphere of the second inequality in the Szegö limit theorem on the Toeplitz determinants on the circle. On the other hand, this inequality is also a variant of several classical inequalities of Moser-Trudinger type on the sphere. The inequality incorporates the deviation of the center of mass from the origin into the optimal inequality of Aubin for functions with mass centered at the origin, and improves Onofri's inequality with the contribution of the shifting of the mass center explicitly expressed. © 2021 Wiley Periodicals LLC. 相似文献
828.
Andrew J. Devine Dr. Alice E. Parnell Dr. Catherine R. Back Dr. Nicholas R. Lees Dr. Samuel T. Johns Ainul Z. Zulkepli Rob Barringer Dr. Katja Zorn Dr. James E. M. Stach Prof. Matthew P. Crump Prof. Martin A. Hayes Dr. Marc W. van der Kamp Prof. Paul R. Race Prof. Christine L. Willis 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2023,135(3):e202213053
Abyssomicin C and its atropisomer are potent inhibitors of bacterial folate metabolism. They possess complex polycyclic structures, and their biosynthesis has been shown to involve several unusual enzymatic transformations. Using a combination of synthesis and in vitro assays we reveal that AbyV, a cytochrome P450 enzyme from the aby gene cluster, catalyses a key late-stage epoxidation required for the installation of the characteristic ether-bridged core of abyssomicin C. The X-ray crystal structure of AbyV has been determined, which in combination with molecular dynamics simulations provides a structural framework for our functional data. This work demonstrates the power of combining selective carbon-13 labelling with NMR spectroscopy as a sensitive tool to interrogate enzyme-catalysed reactions in vitro with no need for purification. 相似文献
829.
Shu Hui Wang Luiziana F. Silva Juliana Kloss Marilda Munaro Gabriel Pinto de Souza M. Alice Wada J. Gregório C. Gomez S. Zawadzki L. Akcelrud 《Macromolecular Symposia》2003,197(1):255-264
Two series of segmented polyurethanes were prepared with systematic variation in soft and hard segment length. The soft segment was constituted by polycaprolactone (PCL) blocks of molecular masses 530 or 2000 and the hard segment (HS) by urethane blocks, in a concentration that varied from 12% to 44% in weight of the whole polyurethane. Morphological analyses indicated that the amount of crystallinity of copolymers was strongly dependent on the PCL molar mass and hard segment content. The copolymers with longer PCL soft segments (Mn=2000) were semicrystalline, but those with shorter PCL segment (Mn=530) were unable to crystallize. The primary factor affectingthe biodegradability of copolymers as evaluated by Sturm tests was the extent of the phase separation, and that the segmental blending of the less biodegradable polyurethane (HS) blocks with PCL in the amorphous phase had a critical unfavorable consequence, which may be attributed to the size of the accessible area by microorganisms. 相似文献