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131.
132.
Dr. Miriam Corredor Dr. Daniel Carbajo Cecilia Domingo Dr. Yolanda Pérez Dr. Jordi Bujons Prof. Dr. Angel Messeguer Dr. Ignacio Alfonso 《Angewandte Chemie (International ed. in English)》2018,57(37):11973-11977
Despite heparin being the most widely used macromolecular drug, the design of small‐molecule ligands to modulate its effects has been hampered by the structural properties of this polyanionic polysaccharide. Now a dynamic covalent selection approach is used to identify a new ligand for heparin, assembled from extremely simple building blocks. The amplified molecule strongly binds to heparin (KD in the low μm range, ITC) by a combination of electrostatic, hydrogen bonding, and CH–π interactions as shown by NMR and molecular modeling. Moreover, this ligand reverts the inhibitory effect of heparin within an enzymatic cascade reaction related to blood coagulation. This study demonstrates the power of dynamic covalent chemistry for the discovery of new modulators of biologically relevant glycosaminoglycans. 相似文献
133.
Tatiana Yu Samgina Sergey V. Kovalev Miriam D. Tolpina Polonca Trebse Gregor Torkar Albert T. Lebedev 《Journal of the American Society for Mass Spectrometry》2018,29(5):842-852
Our scientific interests involve de novo sequencing of non-tryptic natural amphibian skin peptides including those with intramolecular S–S bond by means of exclusively mass spectrometry. Reliable discrimination of the isomeric leucine/isoleucine residues during peptide sequencing by means of mass spectrometry represents a bottleneck in the workflow for complete automation of the primary structure elucidation of these compounds. MS3 is capable of solving the problem. Earlier we demonstrated the advanced efficiency of ETD-HCD method to discriminate Leu/Ile in individual peptides by consecutive application of ETD to the polyprotonated peptides followed by HCD applied to the manually selected primary z-ions with the targeted isomeric residues at their N-termini and registration of the characteristic w-ions. Later this approach was extended to deal with several (4–7) broad band mass ranges, without special isolation of the primary z-ions. The present paper demonstrates an advanced version of this method when EThcD is applied in the whole mass range to a complex mixture of natural non-tryptic peptides without their separation and intermediate isolation of the targeted z-ions. The proposed EThcD method showed over 81% efficiency for the large natural peptides with intact disulfide ring, while the interfering process of radical site migration is suppressed. Due to higher speed and sensitivity, the proposed EThcD approach facilitates the analytical procedure and allows for the automation of the entire experiment and data processing. Moreover, in some cases it gives a chance to establish the nature of the residues in the intact intramolecular disulfide loops. 相似文献
134.
Electrochemical Hydroxylation of Arenes Catalyzed by a Keggin Polyoxometalate with a Cobalt(IV) Heteroatom 下载免费PDF全文
Dr. Alexander M. Khenkin Miriam Somekh Dr. Raanan Carmieli Prof. Dr. Ronny Neumann 《Angewandte Chemie (International ed. in English)》2018,57(19):5403-5407
The sustainable, selective direct hydroxylation of arenes, such as benzene to phenol, is an important research challenge. An electrocatalytic transformation using formic acid to oxidize benzene and its halogenated derivatives to selectively yield aryl formates, which are easily hydrolyzed by water to yield the corresponding phenols, is presented. The formylation reaction occurs on a Pt anode in the presence of [CoIIIW12O40]5? as a catalyst and lithium formate as an electrolyte via formation of a formyloxyl radical as the reactive species, which was trapped by a BMPO spin trap and identified by EPR. Hydrogen was formed at the Pt cathode. The sum transformation is ArH+H2O→ArOH+H2. Non‐optimized reaction conditions showed a Faradaic efficiency of 75 % and selective formation of the mono‐oxidized product in a 35 % yield. Decomposition of formic acid into CO2 and H2 is a side‐reaction. 相似文献
135.
Green and Rapid Hydrothermal Crystallization and Synthesis of Fully Conjugated Aromatic Compounds 下载免费PDF全文
M. Josef Taublaender Dr. Florian Glöcklhofer Prof. Martina Marchetti‐Deschmann Dr. Miriam M. Unterlass 《Angewandte Chemie (International ed. in English)》2018,57(38):12270-12274
Highly fused, fully conjugated aromatic compounds are interesting candidates for organic electronics. With higher crystallinity their electronic properties improve. It is shown here that the crystallization of three archetypes of such molecules—pentacenetetrone, indigo, and perinone—can be achieved hydrothermally. Given their molecular structure, this is a truly startling finding. In addition, it is demonstrated that perinone can also be synthesized in solely high‐temperature water from the starting compounds naphthalene bisanhydride and o‐phenylene diamine without the need for co‐solvents or catalysts. The transformation can be drastically accelerated by the application of microwave irradiation. This is the first report on the hydrothermal generation of two fused heterocycles. 相似文献
136.
Thomas J. Kistenmacher William F. Urmey Miriam Rossi 《Journal of chemical crystallography》1977,7(5):219-227
The crystal and molecular structures of the naturally occurring, N(3)-substituted purine triacanthine (6-amino-3-dimethylallylpurine) are presented. Triacanthine crystallizes, from a saturated DMSO solution, in the monoclinic system, space groupP21/c. Crystallographic data are as follows:a = 12.451(4),b = 8.508(4),c = 11.365(3) Å, = 122.74(2) °,V
c
= 1012.66 Å3,Z = 4,D
m
= 1.335(1),D
x
= 1.333 g cm–3. The structural solution was obtained by direct methods and has been refined, based on full-matrix least squares with 2124 observedF
o
data, to a finalR value of 0.075. The principal molecular features are (1) the occurrence of the substituted purine as the amino tautomer, (2) a nearly planar purine ring system, and (3) a highly planar dimethylallyl group oriented approximately orthogonally to the purine ring system. The crystal packing is dominated by intermolecular hydrogen bonds involving the exocyclic amino group and the acceptor sites N(1) and N(9). Sheets of such hydrogen-bonded molecules are stacked along [10¯1]. Two distinct types of molecular overlaps are observed within these stacks. 相似文献
137.
We study certain aspects of finite-dimensional non-semisimple symmetric Hopf algebras H and their duals H*. We focus on the set I(H) of characters of projective H-modules which is an ideal of the algebra of cocommutative elements of H*. This ideal corresponds via a symmetrizing form to the projective center (Higman ideal) of H which turns out to be ΛH, where Λ is an integral of H and
is the left adjoint action of H on itself. We describe ΛH via primitive and central primitive idempotents of H. We also show that it is stable under the quantum Fourier transform. Our best results are obtained when H is a factorizable ribbon Hopf algebra over an algebraically closed field of characteristic 0. In this case ΛH is also the image of I(H) under a “translated” Drinfel'd map. We use this fact to prove the existence of a Steinberg-like character. The above ingredients are used to prove a Verlinde-type formula for ΛH. 相似文献
138.
139.
The flux of platelet agonists into flowing blood is a critical event in thrombosis and hemostasis. However, few in vitro methods exist for examining and controlling the role of platelet agonists on clot formation and stability under hemodynamic conditions. In this paper, we describe a membrane-based method for introducing a solute into flowing blood at a defined flux. The device consisted of a track-etched polycarbonate membrane reversibly sealed between two microfluidic channels; one channel contained blood flowing at a physiologically relevant shear rate, and the other channel contained the agonist(s). An analytical model described the solute flux as a function of the membrane permeability and transmembrane pressure. The model was validated using luciferase as a model solute for transmembrane pressures of 50-400 Pa. As a proof-of-concept, the weak platelet agonist ADP was introduced into whole blood flowing at 250 s(-1) at three fluxes (1.5, 2.4, and 4.4 x 10(-18) mol microm(-2) s(-1)). Platelet aggregation was monitored by fluorescence microscopy during the experiment and the morphology of aggregates was determined by post hoc confocal and electron microscopy. At the lowest flux (1.5 x 10(-18) mol microm(-2) s(-1)), we observed little to no aggregation. At the higher fluxes, we observed monolayer (2.4 x 10(-18) mol microm(-2) s(-1)) and multilayer (4.4 x 10(-18) mol microm(-2) s(-1)) aggregates of platelets and found that the platelet density within an aggregate increased with increasing ADP flux. We expect this device to be a useful tool in unraveling the role of platelet agonists on clot formation and stability. 相似文献
140.
Marcelín-Jiménez G Morales-Martínez M Angeles-Moreno AP Mendoza-Morales L 《Biomedical chromatography : BMC》2008,22(10):1143-1148
Pharmacokinetics of diphenidol (DPN) is limited due to the lack of analytical methodology. Here, a micro-assay for DPN quantification was developed, by coupling ultra-performance liquid chromatography with tandem mass spectrometry. The procedure involved plasma precipitation and injection of supernatant into UPLC with an Acquitytrade mark C18 column. Detection was in positive electrospray, following transitions of m/z 310.3 --> 292.3 and m/z 275.3 --> 230.2 for DPN and chlorphenamine (internal standard), respectively. The method was linear with a range of 4-400 ng/mL, and a 2 min run time. This method was applied in a switchability trial, where both formulations of DPN were bioequivalent. 相似文献