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91.
Dr. Camino Bartolomé Dr. Fernando Villafañe Dr. Jose M. Martín‐Alvarez Dr. Jesús M. Martínez‐Ilarduya Prof. Dr. Pablo Espinet 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(11):3702-3709
The X‐ray structure of the title compound [Pd(Fmes)2(tmeda)] (Fmes=2,4,6‐tris(trifluoromethyl)phenyl; tmeda=N,N,N′,N′‐tetramethylethylenediamine) shows the existence of uncommon C? H???F? C hydrogen‐bond interactions between methyl groups of the TMEDA ligand and ortho‐CF3 groups of the Fmes ligand. The 19F NMR spectra in CD2Cl2 at very low temperature (157 K) detect restricted rotation for the two ortho‐CF3 groups involved in hydrogen bonding, which might suggest that the hydrogen bond is responsible for this hindrance to rotation. However, a theoretical study of the hydrogen‐bond energy shows that it is too weak (about 7 kJ mol?1) to account for the rotational barrier observed (ΔH≠=26.8 kJ mol?1), and it is the steric hindrance associated with the puckering of the TMEDA ligand that should be held responsible for most of the rotational barrier. At higher temperatures the rotation becomes fast, which requires that the hydrogen bond is continuously being split up and restored and exists only intermittently, following the pulse of the conformational changes of TMEDA. 相似文献
92.
Canales A Angulo J Ojeda R Bruix M Fayos R Lozano R Giménez-Gallego G Martín-Lomas M Nieto PM Jiménez-Barbero J 《Journal of the American Chemical Society》2005,127(16):5778-5779
The first direct NMR determination of the conformation of a conformationally flexible heparin-like hexasaccharide bound to a key receptor, FGF-1, is described. The determination has been based on the use of a 13C-labeled protein and a regular 12C sugar. FGF-1 recognizes several conformations of the iduronic moieties of the hexasaccharide. Therefore, this case is different than that described for the controversial recognition of heparin-like saccharides by AT-III, which seems to recognize just one conformation of the iduronic acid residues. 相似文献
93.
González-Núñez ME Mello R Royo J Asensio G Monzó I Tomás F López JG Ortiz FL 《The Journal of organic chemistry》2005,70(9):3450-3457
[reaction: see text] Data on the apparent dipole moment of thianthrene-5-oxide (1) and (1)H NMR spectra in different solvents support the conformational mobility of 1, which flaps between two limit boat conformations with the sulfinyl group in pseudoequatorial and pseudoaxial positions, respectively. The conformational equilibrium of 1 occurs too fast for the (1)H NMR (500 MHz) time-scale even at -130 degrees C, and the equilibrium constant has not been determined. The apparent dipole moments of 1 in n-hexane and 1,4-dioxane and the (1)H NMR spectra of 1 and the model compounds cis- and trans-thianthrene-5,10-dioxides (2) and thianthrene (5) in different solvents and at various temperatures confirm that the relative position of the conformational equilibrium of 1 is solvent-dependent, and more polar solvents favor the conformation with the sulfoxide group in the pseudoaxial position (1(')(ax)). Variable-temperature (1)H NMR spectra have established the interconversion barrier of trans-2 and confirmed that the conformational equilibrium of cis-2 is strongly displaced toward the conformation with both sulfinyl groups in the pseudoequatorial position. The (1)H NMR data support the transannular interaction of the functional groups in 1 and trans-2. 相似文献
94.
Garbiñe Álvarez Francisco Alcaide Oscar Miguel Laura Calvillo María Jesús Lázaro Jacob J. Quintana Juan Carlos Calderón Elena Pastor 《Journal of Solid State Electrochemistry》2010,14(6):1027-1034
This paper presents the behavior of ordered mesoporous carbon (OMC)-supported catalysts as anodes for direct methanol fuel
cells (DMFC), fed with an aqueous methanol solution. OMC samples were prepared by the nanocasting method from a polymerized
furan resin using mesoporous silica as a template. Pt and PtRu nanoparticles were supported on OMC with high dispersion, the
particle size being 2.4 nm at PtRu loading of 15 wt.%. The resulting catalysts were analyzed using carbon monoxide stripping
voltammetry, cyclic voltammetry, and chronoamperometry in three-electrode experiments and recording cell voltage vs. current
density curves in practical DMFC. It was found that PtRu-catalyzed technical electrodes exhibited good activity towards methanol
electrooxidation in half-cell experiments under fuel-cell-relevant conditions. Specifically, Pt85Ru15/OMC catalyst showed the highest catalytic enhancement compared to Pt/OMC for the steady-state electrooxidation of methanol
at 60 °C and 0.5 V, by a factor of 22 in 2-M MeOH solution. DMFC single cells yielded an open-circuit voltage of 0.625 V at
60 °C. Polarization curves indicate that DMFC with OMC-supported Pt85Ru15 catalyst at the anode exhibited the best performance. 相似文献
95.
Estefanía Gioria Dr. Juan del Pozo Dr. Jesús M. Martínez‐Ilarduya Prof. Dr. Pablo Espinet 《Angewandte Chemie (International ed. in English)》2016,55(42):13276-13280
A Pd complex, cis‐[Pd(C6F5)2(THF)2] ( 1 ), is proposed as a useful touchstone for direct and simple experimental measurement of the relative ability of ancillary ligands to induce C?C coupling. Interestingly, 1 is also a good alternative to other precatalysts used to produce Pd0L. Complex 1 ranks the coupling ability of some popular ligands in the order PtBu3>o‐TolPEWO‐F≈tBuXPhos>P(C6F5)3≈PhPEWO‐F>P(o‐Tol)3≈THF≈tBuBrettPhos?Xantphos≈PhPEWO‐H?PPh3 according to their initial coupling rates, whereas their efficiency, depending on competitive hydrolysis, is ranked tBuXPhos≈PtBu3≈o‐TolPEWO‐F>PhPEWO‐F>P(C6F5)3?tBuBrettPhos>THF≈P(o‐Tol)3>Xantphos>PhPEWO‐H?PPh3. This “meter” also detects some other possible virtues or complications of ligands such as tBuXPhos or tBuBrettPhos. 相似文献
96.
Dr. José A. González-Delgado Dr. Miguel A. Romero Dr. Francisco Boscá Dr. Jesús F. Arteaga Prof. Dr. Uwe Pischel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(62):14229-14235
The light-gated organocatalysis via the release of 4-N,N-dimethylaminopyridine (DMAP) by irradiation of the [Ru(bpy)2(DMAP)2]2+ complex with visible light was investigated. As model reaction the acetylation of benzyl alcohols with acetic anhydride was chosen. The pre-catalyst releases one DMAP molecule on irradiation at wavelengths longer than 455 nm. The photochemical process was characterized by steady-state irradiation and ultrafast transient absorption spectroscopy. The latter enabled the observation of the 3MLCT state and the spectral features of the penta-coordinated intermediate [Ru(bpy)2(DMAP)]2+. The released DMAP catalyzes the acetylation of a wide range of benzyl alcohols with chemical yields of up to 99 %. Control experiments revealed unequivocally that it is the released DMAP which takes the role of the catalyst. 相似文献
97.
Apoorva D. Srivastava Dr. Luca Unione Dr. Margreet A. Wolfert Dr. Pablo Valverde Dr. Ana Ardá Prof. Dr. Jesús Jiménez-Barbero Prof. Dr. Geert-Jan Boons 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(67):15605-15612
The parasitic worm, Schistosoma mansoni, expresses unusual fucosylated glycans in a stage-dependent manner that can be recognized by the human innate immune receptor DC-SIGN, thereby shaping host immune responses. We have developed a synthetic approach for mono- and bis-fucosylated LacdiNAc (LDN-F and LDN-DF, respectively), which are epitopes expressed on glycolipids and glycoproteins of S. mansoni. It is based on the use of monosaccharide building blocks having carefully selected amino-protecting groups, facilitating high yielding and stereoselective glycosylations. The molecular interaction between the synthetic glycans and DC-SIGN was studied by NMR and molecular modeling, which demonstrated that the α1,3-fucoside of LDN-F can coordinate with the Ca2+-ion of the canonical binding site of DC-SIGN allowing for additional interactions with the underlying LDN backbone. The 1,2-fucoside of LDN-DF can be complexed in a similar manner, however, in this binding mode GlcNAc and GalNAc of the LDN backbone are placed away from the protein surface resulting in a substantially lower binding affinity. Glycan microarray binding studies showed that the avidity and selectivity of binding is greatly enhanced when the glycans are presented multivalently, and in this format Lex and LDN-F gave strong responsiveness, whereas no binding was detected for LDN-DF. The data indicates that S. mansoni has developed a strategy to avoid detection by DC-SIGN in a stage-dependent manner by the addition of a fucoside to a number of its ligands. 相似文献
98.
Yeray Dorca Roberto Sánchez-Naya Jesús Cerdá Dr. Joaquín Calbo Dr. Juan Aragó Dr. Rafael Gómez Prof. Dr. Enrique Ortí Prof. Dr. Luis Sánchez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(64):14700-14707
A comparative investigation of the chiral amplification features of a series of three families of C3-symmetric tricarboxamides, 1,3,5-triphenylbenzenetricarboxamides (TPBAs), benzenetricarboxamides (BTAs) and oligo(phenylene ethynylene) tricarboxamides (OPE-TAs), is here reported. As previously observed for BTAs and OPE-TAs, a similar dichroic response is obtained for TPBAs decorated with one, two or three chiral side chains bearing stereogenic centers, thus confirming the efficient transfer of point chirality to the supramolecular helical aggregates. Unlike BTAs and OPE-TAs, the chiral amplification ability of TPBAs in majority rules experiments shows a negligible dependence on the number of chiral centers per monomeric unit, and stands the largest among the series of tricarboxamides. Detailed experimental and theoretical studies demonstrate that the rotation angle between the TPBA units in the helical stack is intermediate to that observed for BTAs and OPE-TAs. This feature strongly conditions the steric interactions between vicinal molecules in the stack and the final chiral amplification outcome. Furthermore, theoretical calculations show that achiral side chains favor the interdigitation of the helical aggregates and thereby the formation of bundle superstructures. 相似文献
99.
Puerta A Díez-Masa JC Martín-Álvarez PJ Martín-Ventura JL Barbas C Tuñón J Egido J de Frutos M 《The Analyst》2011,136(4):816-822
α-1-Acid glycoprotein (AGP) is a serum glycoprotein that presents several isoforms. Changes in the isoforms of AGP have been related to different pathological states including cardiovascular diseases (CVDs) such as acute myocardial infarction. However, to our knowledge, the role of variations of AGP isoforms as a potential biomarker of atherothrombosis has not been addressed. In this work, a preliminary study about differences in the capillary zone electrophoresis (CZE) profile of intact (non-hydrolyzed) AGP isoforms between healthy individuals and patients with atherothrombosis, specifically abdominal aortic aneurysm (AAA) and carotid atherosclerosis (CTA), has been performed. Biological samples (plasmas and sera) were analyzed by CZE after immunoaffinity chromatography purification. Up to 13 peaks corresponding to groups of isoforms of intact AGP from plasma samples were detected by CZE-UV. Electrophoretic profiles were aligned, peaks assigned, and linear discriminant analysis (LDA) of percentage of the corrected areas of AGP peaks was employed to discriminate and classify the CZE profiles of AGP samples. LDA enabled to accomplish 92.9% of correct classification of the AGP samples when the three groups of samples were considered. Besides, the LDA model showed high predictive power in the groups healthy vs. sick, healthy vs. AAA, and healthy vs. CTA. The described method was a successful approach to study the potential of AGP isoforms profile as a biomarker of atherothrombosis. To the best of our knowledge this has been the first time that a possible role of the CZE profile of intact AGP isoforms as a biomarker of vascular diseases has been demonstrated. 相似文献
100.
Determination of tocopherols in vegetable oils by CEC using methacrylate ester-based monolithic columns 总被引:1,自引:0,他引:1
Lerma-García MJ Simó-Alfonso EF Ramis-Ramos G Herrero-Martínez JM 《Electrophoresis》2007,28(22):4128-4135
The separation and determination of tocopherols (Ts) in vegetable oils by CEC using methacrylate ester-based monolithic columns has been developed. The effects of pore size of the monolithic columns were studied, and the composition of mobile phase was optimized. The optimal pore size of the monolith was obtained with 12 wt% 1,4-butanediol in the polymerization mixture. Excellent resolution between tocopherols was achieved within 10 min analysis time with a 99:1 v/v MeOH-aqueous buffer containing 5 mM tris(hydroxymethyl)aminomethane at pH 8.0. The LODs were lower than 2.3 microg/mL, and interday and column-to-column reproducibilities at 25 microg/mL were better than 5.6%. Using a 93:7 v/v MeOH-aqueous buffer, both tocopherols and tocotrienols (T(3)s) of grapeseed and palm oils were resolved. Application to the detection of olive oil adulteration with low-cost edible oils was demonstrated. 相似文献