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1.
2.
Enantiomeric Cyclic Peptides with Different Caco‐2 Permeability Suggest Carrier‐Mediated Transport
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B. Sc. Eduard Puig Prof. Dr. Beat Ernst Prof. Dr. Horst Kessler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(22):8023-8027
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
3.
Amphiphilic block copolymer self‐assemblies of poly(NVP)‐b‐poly(MDO‐co‐vinyl esters): Tunable dimensions and functionalities
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Guillaume G. Hedir A. Pitto‐Barry Andrew P. Dove Rachel K. O'Reilly 《Journal of polymer science. Part A, Polymer chemistry》2015,53(23):2699-2710
Functional, degradable polymers were synthesized via the copolymerization of vinyl acetate (VAc) and 2‐methylene‐1,3‐dioxepane (MDO) using a macro‐xanthate CTA, poly(N‐vinylpyrrolidone), resulting in the formation of amphiphilic block copolymers of poly(NVP)‐b‐poly(MDO‐co‐VAc). The behavior of the block copolymers in water was investigated and resulted in the formation of self‐assembled nanoparticles containing a hydrophobic core and a hydrophilic corona. The size of the resultant nanoparticles was able to be tuned with variation of the hydrophilic and hydrophobic segments of the core and corona by changing the incorporation of the macro‐CTA as well as the monomer composition in the copolymers, as observed by Dynamic Light Scattering, Static Light Scattering, and Transmission Electron Microscopy analyses. The concept was further applied to a VAc derivative monomer, vinyl bromobutanoate, to incorporate further functionalities such as fluorescent dithiomaleimide groups throughout the polymer backbone using azidation and “click” chemistry as postpolymerization tools to create fluorescently labeled nanoparticles. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2699–2710 相似文献
4.
Beyond Stereoselectivity,Switchable Catalysis: Some of the Last Frontier Challenges in Ring‐Opening Polymerization of Cyclic Esters
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Dr. Sophie M. Guillaume Dr. Evgueni Kirillov Dr. Yann Sarazin Prof. Dr. Jean‐François Carpentier 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(22):7988-8003
Metal‐based catalysts and initiators have played a pivotal role in the ring‐opening polymerization (ROP) of cyclic esters, thanks to their high activity and remarkable ability to control precisely the architectures of the resulting polyesters in terms of molar mass, dispersity, microstructure, or tacticity. Today, after two decades of extensive research, the field is slowly reaching maturity. However, several challenges remain, while original concepts have emerged around new types or new applications of catalysis. This Review is not intended to comprehensively cover all of these aspects. Rather, it provides a personal overview of the very recent progress achieved in some selected, important aspects of ROP catalysis—stereocontrol and switchable catalysis. Hence, the first part addresses the development of new metal‐based catalysts for the isoselective ROP of racemic lactide towards stereoblock copolymers, and the use of syndioselective ROP metal catalysts to control the monomer sequence in copolymers. A second part covers the development of ROP catalysts—primarily metal‐based catalysts, but also organocatalysts—that can be externally regulated by the use of chemical or photo stimuli to switch them between two states with different catalytic abilities. Current challenges and opportunities are highlighted. 相似文献
5.
Here, we report a new strategy for rapid synthesis of branched peptide by side-chain hydrazide ligation at Asn. The hydrazide was converted to thioester at Asn side chain by NaNO2 and thiol reagent, and sequential ligation with an N-terminus Cys-peptide efficiently afforded the branched peptide. A branched cyclic peptide was successfully synthesized by side-chain ligation with a two-Cys-peptide and formation of a disulfide bond. This approach provides a new way for expeditious synthesis of branched peptides and facilitates the design of neopeptides as functional bio-mimics. 相似文献
6.
We examine two criteria for balance of a gain graph, one based on binary cycles and one on circles. The graphs for which each criterion is valid depend on the set of allowed gain groups. The binary cycle test is invalid, except for forests, if any possible gain group has an element of odd order. Assuming all groups are allowed, or all abelian groups, or merely the cyclic group of order 3, we characterize, both constructively and by forbidden minors, the graphs for which the circle test is valid. It turns out that these three classes of groups have the same set of forbidden minors. The exact reason for the importance of the ternary cyclic group is not clear. © 2005 Wiley Periodicals, Inc. J Graph Theory 相似文献
7.
Hans R. Kricheldorf Lali Vakhtangishvili Gert Schwarz 《Journal of polymer science. Part A, Polymer chemistry》2004,42(22):5725-5735
Poly(pyridine ether)s were prepared in two ways: the polycondensation of silylated 1,1,1‐tris(4‐hydroxyphenyl)ethane (THPE) with 2,6‐difluoropyridine (method A) and the polycondensation of free THPE with 2,6‐dichloropyridine (method B). With method A, the THPE/difluoropyridine feed ratio was varied from 1.0:1.0 to 1.0:1.6. Cycles, bicycles, and multicycles were the main reaction products, and crosslinking was never observed. When ideal stoichiometry was used exclusively, multicycles free of functional groups were obtained. These multicycles were detectable in matrix‐assisted laser desorption/ionization time‐of‐flight (MALDI‐TOF) mass spectra up to B38C76 with a mass of approximately 32,000 Da. With method B, the reaction conditions were varied at a fixed feed ratio to achieve an optimum for the preparation of multicyclic polyethers, but because of the lower reactivity of 2,6‐dichloropyridine, a quantitative conversion was not achieved. The reaction products were characterized with MALDI‐TOF mass spectrometry, viscosity measurements, and size exclusion chromatography. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5725–5735, 2004 相似文献
8.
Introduction In the previous studies on the oxidation reaction,peroxydisulfate was widely used as an oxidizingagent.1-5 One of the advantages of this oxidant lies in itsstability in a wide range of pH values. The reaction be-tween Fe(CN)5L3- (L=N-aromatic heterocyclic li-gands) and S2O8 2- has been proved to proceed throughan outer-sphere electron transfer mechanism.5 For a re-action [(Eq. (1)] to be under an outer-sphere mechanismthe steps involved are the formation of a reactant … 相似文献
9.
Jérôme Le NôtreAna Acosta Martinez Pierre H DixneufChristian Bruneau 《Tetrahedron》2003,59(47):9425-9432
Enyne rearrangement of silylated modified terpenoids has been used as the key step for the synthesis of new terpenes and terpenoids. The catalytic system generated in situ from [RuCl2(p-cymene]2, 1,3-bis(mesityl)imidazolinium chloride and cesium carbonate is able to perform the transformation of silylated 1,7-enynes into cyclic siloxanes. Selective cleavage of the silicon-carbon and silicon-oxygen bonds by simple reactions has been performed to afford new terpenes and terpenoids by formal addition of a C5 unit. 相似文献
10.
Tsonka Stefanova Baicheva 《Designs, Codes and Cryptography》1998,13(3):223-227
The covering radius of all ternary cyclic codes of length up to 25 is given. Some of the results were obtained by computer
and for others mathematical reasonings were applied. The minimal distances of all codes were recalculated. 相似文献