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1.
Recently, oral absorption of cyclic hexapeptides was improved by N‐methylation of their backbone amides. However, the number and position of N‐methylations or of solvent exposed NHs did not correlate to intestinal permeability, measured in a Caco‐2 model. In this study, we investigate enantiomeric pairs of three polar and two lipophilic peptides to demonstrate the participation of carrier‐mediated transporters. As expected, all the enantiomeric peptides exhibited identical lipophilicity (logD7.4) and passive transcellular permeability determined by the parallel artificial membrane permeability assay (PAMPA). However, the enantiomeric polar peptides exhibited different Caco‐2 permeability (Papp) in both directions a–b and b–a. The same trend was observed for one of the lipophilic peptide, whereas the second lipophilic enantiomer pair showed identical Caco‐2 permeability (within the errors). These findings provide the first evidence for the involvement of carrier‐mediated transport for peptides, especially for those of polar nature.  相似文献   
2.
The ligand 2,2′,2″-nitrilotriphenol reacts with P(III) and P(V) compounds to form corresponding phosphorus complexes. Syntheses and NMR data of 2,2′,2″-nitrilotriphenyl phosphite ( II ), 2,2′,2″-nitrilotriphenyl phosphate ( III ) and of a hydrolysis product of II , 2,2′-[N-(2-hydroxyphenyl)imino]diphenly phosphonate ( IV ), are reported, as well as crystal structures of II and IV . Phosphite II shows a bicycloundecane framework; no N?Pinteraction is present. The phosphonate IV shows two coordinated and one dangling phenol group; the N-atom does not interact with the P-atom. Strong acids protonate II as well as III to form cations: in these, NMR evidence indicates coordination of the N-atom to the P-atom.  相似文献   
3.
4.
We give an easy general construction for uniform oriented matroids with disconnected realization space. This disproves the longstanding isotopy conjecture for simple line arrangements or order types in the plane.The research of Bernd Sturmfels and Neil White was supported in part by the Institute for Mathematics and Its Applications with funds provided by the National Science Foundation.  相似文献   
5.
For the assignment of the configuration at C(8) and C(15) of the natural oviposition-deterring pheromone 1 in Rhagoletis cerasi L., the four possible stereoisomers of 1 are synthesized. By condensing the C6 building blocks (5R)- 4 and (5S)- 4 with the boron enolates of the C10 building blocks (4S)- 13 and (4R)- 13 , followed by decarboxylative dehydration, all stereoisomers of 16 are available (Scheme 5). Glucosylation of 16 followed by formation of the taurin amide gives, after deprotection, the four stereoisomers (8R,15S)- 1 , (8R,15R)- 1 , (8R,15S) -1 , and (8S,15S)- 1 (Scheme 6).  相似文献   
6.
The synthesis of N-methyl-benz[f]isoindole ( 2 ) and N-methyl-dibenz[e,g]isoindole ( 3 ) is reported. The NMR. spectra of N-methyl-isoindole ( 1 ) and of 2 have been analysed and the implications concerning the alternation of bond lengths are discussed. The photophysical properties of 1 to 3 have been investigated by the following methods: HeI photoelectron (PE.) spectroscopy, UV./VIS. absorption (polarization measurements by the stretched-foil technique) and emission spectroscopy (fluorescence spectra, lifetimes and quantum yields, phosphorescence spectra), and flash spectroscopy (triplet-triplet absorption spectra). The discussion of the results is based on HMO. and PPP SCF CI. calculations and points to the relationship between the heterocycles 1 to 3 and the corresponding benzenoid hydrocarbons obtained by replacement of the ? NMe? subunit by ? CH?CH? . Some comments concerning the ground state properties of isoindole and related compounds are derived from the analysis of their electronic structure.  相似文献   
7.
The HeI photoelectron spectra of the title compound 1 (1,5,9-cyclododecatriene-3,7,11-triyne), 1,5-didehydro[12]annulene (1,3,5,9-cyclododecatetraene-7, 11-diyne ( 2 )), sym-tri-benzotridehydro[12]annulene (tribenzo[a,e,i]-5,6,11,12,17,18-hexadehydrocyclododecene ( 3 )), and sym-dibenzodidehydro[8]annulene (dibenzo[a,e]-5,6,11,12-tetradehydrocyclooctene ( 4 )) have been recorded and analysed on the basis of various semi-empirical model calculations. Despite the distinct bond length alternation in the parent compounds and, apparently, in the radical cations, the first ionization occurs at low energies in these compounds (7.6 ± 0.2 eV). The spectra yield little information with regard to the transannular interactions of the triple bonds.  相似文献   
8.
The ESCA spectrum of protonated 1,8-bis-(dimethylamino) naphthalene (“proton sponge”) (I) has been recorded in the region of N1s binding energies. The results indicate that IH+ possesses an unsymmetrical N? H…?N hydrogen bridge.  相似文献   
9.
The propensity of the N?N bond to undergo photo [2 + 2] cycloadditions has been further explored. In the specifically designed 1,5-azo/enes 1–3 , no [2 + 2] cycloaddition has been observed upon either direct or sensitized excitation with light of various wave lengths at temperatures down to 77 K, in line with expectations based on X-ray ( 1 : d = 2.71 Å, ω = 129°) and PE measurements ( 1 : I1 = 8.00, I2 = 9.05 eV; 2 ; I1 = 8.00, I2 = 9.25eV). The steric/stereoelectronic demands for the participation of the N?N bond in pericyclic reactions are clearly more stringent than those for the C?C bond.  相似文献   
10.
13C-only spectroscopy was used to measure multiple residual (13)C-(13)C dipolar couplings (RDCs) in uniformly deuterated and (13)C-labeled proteins. We demonstrate that (13)C-start and (13)C-observe spectra can be routinely used to measure an extensive set of the side-chain residual (13)C-(13)C dipolar couplings upon partial alignment of human ubiquitin in the presence of bacteriophages Pf1. We establish that, among different broadband polarization transfer schemes, the FLOPSY family can be used to exchange magnetization between a J coupled network of spins while largely decoupling dipolar interactions between these spins. An excellent correlation between measured RDCs and the 3D structure of the protein was observed, indicating a potential use of the (13)C-(13)C RDCs in the structure determination of perdeuterated proteins.  相似文献   
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