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471.
Frieder Mitzel Corinne Boudon Jean‐Paul Gisselbrecht Paul Seiler Maurice Gross Franois Diederich 《Helvetica chimica acta》2004,87(5):1130-1157
In this article, we report the preparation of unprecedented π‐conjugated macrocycles (Fig. 1) by acetylenic scaffolding using modular tetraethynylethene (TEE, 3,4‐diethynylhex‐3‐ene‐1,5‐diyne) building blocks. A novel photochemical access to (Z)‐bisdeprotected TEEs (Scheme 1) enabled the synthesis of the anilino‐substituted perethynylated octadehydro[12]‐ ( 5 ) and dodecadehydro[18]annulenes ( 6 ) (Scheme 2). Following the serendipitous discovery of perethynylated radiaannulenes (Scheme 3) that can be viewed as hybrids between perethynylated dehydroannulenes and expanded radialenes, two series of monocyclic ( 7 – 9 ; Scheme 6) and bicyclic ( 10 and 11 ; Scheme 7) representatives were prepared. Substantial strain in the macrocyclic perimeter of radiaannulene 7 was revealed by X‐ray crystal‐structure analysis (Fig. 2). Nevertheless, mono‐ and bicyclic radiaannulenes are stable at room temperature in air for months. The opto‐electronic properties of both dehydroannulenes and radiaannulenes are substantially enhanced by the introduction of the peripheral anilino donor groups that undergo strong intramolecular charge‐transfer interactions with the electron‐accepting all‐C cores. As a result, the UV/VIS spectra feature intense, bathochromically shifted charge‐transfer bands that disappear upon protonation of the anilino moieties and are fully recovered upon neutralization (Figs. 4–9). A comparison between anilino‐substituted perethynylated dehydroannulenes, expanded radialenes, and radiaannulenes revealed that the efficiency of the intramolecular charge‐transfer interaction strongly depends on the structure of the electron‐accepting all‐C perimeter. Electrochemical investigations (Table) demonstrated that the radiaannulenes are particularly powerful electron acceptors. Thus, bicyclic radiaannulene 11 , which possesses eight peripheral 3,5‐di(tert‐butyl)phenyl substituents, is reversibly reduced at ?0.83 V in THF (vs. Fc+/Fc), making it a better electron acceptor than buckminsterfullerene C60 under comparable conditions. 相似文献
472.
We have designed more potent inhibitors from the previously reported LF 05-0038, a 6-isoquinolinol based inhibitor of 2,3-oxidosqualene cyclase (IC50: 1.1 microM). Replacement of the 3-OH group by various 3-substituted amino groups, and modification of the alkyl chain borne by the endocyclic nitrogen led to inhibitors with IC50 in the range of 0.15 to 1 microM. In a second step, opening of the bicyclic ring system afforded the corresponding aminoalkylpiperidines which were slightly more potent. Finally, introduction of suitable aromatic containing moieties on the piperidine nitrogen yielded very potent inhibitors such as 20x (IC50 = 18 nM) easy to synthesize and achiral. The recent availability of the crystal structure of squalene-hopene cyclase allowed us to construct a three-dimensional (3D) model of the related 2,3-oxidosqualene cyclase (OSC) which was tentatively used to describe the possible mode of binding of our compounds and which can be useful for designing new inhibitors. 相似文献
473.
The synthesis of a new linear benzo[3]phenylene-[60]fullerene dyad 1 is achieved over 10 steps in 15% overall yield by using an efficient sequence combining a double cobalt(I)-mediated cyclotrimerization with a Bingel reaction. 相似文献
474.
The fragmentation of peptide acetals and peptide diols, corresponding to the hydrated form of the peptide aldehyde, is dominated by the successive losses of two molecules of MeOH and water, respectively. Using model peptides, the fragmentation mechanism, with respect to the loss of methanol and water, was elucidated. The first loss was certainly charge-directed whereas the second probably occurred via the nucleophilic attack of the nitrogen of an amine on the C-terminal carbon leading to a cyclic ion. 相似文献
475.
Fran?oise Vuadens David Crettaz Corinne Scelatta Catherine Servis Manfredo Quadroni Willy-Vincent Bienvenut Philippe Schneider Patrick Hohlfeld Lee A Applegate Jean-Daniel Tissot 《Electrophoresis》2003,24(7-8):1281-1291
In order to gain insight into the biology of fetal skin during culture, cellular proteins were studied during four culture passages (P00, P01, P04 as well as P10) using high-resolution two-dimensional (2-D) gel electrophoresis and mass spectrometry (MS). Bioinformatic analyses were focused on a region of each gel corresponding to pI between 4 and 8 and M(r) from 8000 to 35 000. In this area, 373 +/- 42 spots were detected (N = 18). Twenty-six spots presented an integrated intensity that increased in the higher passages, whereas five spots showed a progressively lower intensity in subsequent passaging. MS analysis was performed on spots that were unambiguously identified on preparative 2-D gels. Among the 26 spots showing an increased size between P00 and P10, 9 were identified, and corresponded to 3 proteins: (i) peptidyl-prolyl cis-trans isomerase A (P05092; cyclophilin A or cyclosporin A-binding protein), (ii) triosephosphate isomerase (P00938), and (iii) enoyl-CoA hydratase (P30084). Among these nine identified spots, three were absent at P00, but were present at P10. They corresponded to isoforms of peptidyl-prolyl cis-trans isomerase and triosephosphate isomerase, respectively. Liquid chromatography-tandem mass spectrometry (LC-MS/MS) analyses of the acidic isoforms of triosephosphate isomerase showed modifications of cysteine residues to cysteic acid. All these isoforms were clearly present in the skin cells of a 4-year-old child, as well as in skin cells from a 80-year-old man, at P00. These observations probably reflect either an oxidative stress related to cell culture, or, alternatively, maturation, differentiation and the aging of the cells. 相似文献
476.
W. M. Jarman Glenn W. Johnson Corinne E. Bacon Jay A. Davis Robert W. Risebrough Robert Ramer 《Analytical and bioanalytical chemistry》1997,359(3):254-260
Levels of polychlorinated biphenyls (PCBs) were measured in water (particulate and dissolved fractions) from various locations in the San Francisco Estuary over the years 1993–1995 during six cruises. Geometric mean levels of ΣPCBs (sum of 58 congeners) in the combined dissolved and particulate fractions for the six cruises ranged from 340?ng/L to 1600?ng/L. Comparing this data to previous data from 1975 and 1980 does not reveal any significant temporal trends. The partitioning of PCBs into the dissolved/particulate fraction were correlated with total suspended solids. Using the novel chemometric technique of polytopic vector analysis (PVA) on the data from cruise 8 (April 1995), five separate PCB congener fingerprints were identified in the data. Fingerprint 1 (or end-member 1) represents a slightly degraded source of Aroclor® 1260 in the northern part of the South Bay; the end-member (EM) 2 fingerprint is related to a predominantly Aroclor® 1260 source that has been moderately-severely degraded present in the highest proportions in the Pacific Ocean sample; EM-3 is interpreted as a slightly degraded Aroclor® 1242:1254:1260 mixture in southern San Pablo Bay; end-member 4 is interpreted as a moderately degraded source of multiple Aroclors® and is present in the river samples; EM-5 is interpreted as a slightly degraded Aroclor® 1254/1260 mixture present in northern San Pablo Bay and the South Bay. 相似文献
477.
478.
[reaction: see text] The first examples of totally chemo- and regioselective formal intermolecular cobalt(I)-catalyzed [2 + 2 + 2] cyclizations of three different alkynes are reported. The use of disposable silylated tethers in the sequence cyclization followed by the displacement of the silicon group led to polysubstituted arenes as a unique cycloadduct in high yields. 相似文献
479.
A series of copper(II) and copper(I) complexes have been synthesized with ligands combining 6-methyl-2,2'-bipyridines with cyclotriveratrylene (CTV) (1) and with catechol (2). The electrochemical, (1)H NMR, and mass spectrometry characterizations of these complexes are described and discussed. The six pendant bipyridines of ligand 1 allow for the formation of two trinuclear copper(I) complexes [(1)Cu(3)](BF(4))(3) differing only in the conformation "vic" or "int" adopted by the ligand to fit the tetrahedral cuprous ions. Similarly, 1 generates two trinuclear copper(II) complexes in which the conformation of the ligand fits the square planar geometry of cupric ions. In both the cuprous and cupric complexes, a conformational equilibrium exists. Ligand 2 bearing two methylbipyridines has proven to be a useful model of the coordinating sites of ligand 1. In this case, two homologous copper(I) complexes are obtained, [(2)Cu]BF(4) and [(2)(2)Cu(2)](BF(4))(2), modeling respectively two possible coordination conformations of ligand 1. With copper(II), ligand 2 yields only one complex [(2)Cu](CF(3)SO(3))(2), which allows for the unambiguous identification of the conformations observed for ligand 1 complexes. The different coordinating modes of ligand 1 in the complexes mentioned are in exchange but exhibit different physical properties, thus representing a new bistable system based on conformational isomerism which exhibits an electrochemical potential hysteresis. An equilibrium constant and thermodynamic data were obtained for this system by variable-temperature cyclic voltammetry. The influence of coordinating vs noncoordinating solvents was also studied. 相似文献
480.
Corinne Chaimbault Jean Michel Leger Jean‐Jacques Bosc Christian Jarry 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(1):e29-e30
The condensation reaction of 2‐amino‐5‐tert‐butyloxymethyl‐2‐oxazoline with ethyl cyano(ethoxymethylene)acetate led to the title cycloadduct. The structure indicates a delocalization in the pyrimidine ring. 相似文献