RESUMO
Dynamic poly(phenylacetylene)s (PPAs) adopt helical structures with different elongation or helical senses depending on the types of pendants. Hence, a good knowledge of the parameters that define their structures becomes a key factor in the understanding of their properties and functions. Herein, the techniques used for the study of the secondary structure of PPAs using atomic-force microscopy (AFM) are presented, with special attention directed towards the methods used for the preparation of monolayers, and their consequences in the quality of the AFM images. Thus, monolayers formed by drop casting, spin coating followed by crystallization or annealing, Langmuir-Blodgett and Langmuir-Schaefer methods, onto highly oriented pyrolytic graphite (HOPG) or mica, are described, together with the AFM images and the resulting helical structure obtained for different PPAs. Furthermore, some conclusions are drawn both on the adequacy of the different techniques for the formation of monolayers and on the solid supports utilized to elucidate the secondary structure of different PPAs.
Assuntos
Acetileno/análogos & derivados , Nanoestruturas/química , Acetileno/química , Microscopia de Força Atômica , Modelos Moleculares , Nanoestruturas/ultraestrutura , EstereoisomerismoRESUMO
The chiral polymer poly-(R)-1 behaves in solution, despite its chiral pendants, as a dynamic axially racemic (i.e., 1 : 1) mixture of left- and right-handed helices, but its deposition on graphite by a Langmuir-Schaefer (LS) technique leads to a helical sense-selective packing that forms separate enantiomeric domains of left- and right-handed helical chains observed by high resolution atomic force microscopy (AFM). The polymer structure within these domains is very uniform, seldom altered by the presence of reversals, grouped always in contiguous pairs maintaining a single helical sense along the polymer chain. The LS deposition technique has been shown to be crucial to obtain good quality monolayers from poly-(R)-1 and other poly(phenylacetylene)s (PPAs: poly-2, poly-3 and poly-4) with short pendants, where spin coating, drop casting and Langmuir-Blodgett (LB) failed, and suggests that this technique could be the method of choice for the preparation of 2D monolayers for high resolution AFM studies of PPAs with short pendants. Key helical parameters (i.e., sense, pitch, packing angle) are easily measured in this way.
RESUMO
We have previously reported the ability of chitosan nanocapsules to enhance and prolong the oral absorption of peptides. In the present work, our goal was to design a new type of nanocapsules, using chitosan chemically modified with poly(ethylene glycol) (PEG) (0.5% and 1% pegylation degree) and to investigate the consequences of this modification on the in vitro and in vivo behaviour of the nanocapsules. Chitosan-PEG nanocapsules and the control PEG-coated nanoemulsions were obtained by the solvent displacement technique. Their size was in the range of 160-250 nm. Their zeta potential was greatly affected by the nature of the coating, being positive for chitosan-PEG nanocapsules and negative in the case of PEG-coated nanoemulsions. The presence of PEG, whether alone or grafted to chitosan, improved the stability of the nanocapsules in the gastrointestinal fluids. Using the Caco-2 model cell line it was observed that the pegylation of chitosan reduced the cytotoxicity of the nanocapsules. In addition, these nanocapsules did not cause a significant change in the transepithelial resistance of the monolayer. Finally, the results of the in vivo studies showed the capacity of chitosan-PEG nanocapsules to enhance and prolong the intestinal absorption of salmon calcitonin. Additionally, they indicated that the pegylation degree affected the in vivo performance of the nanocapsules. Therefore, by modulating the pegylation degree of chitosan, it was possible to obtain nanocapsules with a good stability, a low cytotoxicity and with absorption enhancing properties.
Assuntos
Quitosana/química , Portadores de Fármacos/química , Nanopartículas , Polietilenoglicóis/química , Administração Oral , Animais , Células CACO-2 , Calcitonina/administração & dosagem , Calcitonina/metabolismo , Cálcio/sangue , Cápsulas , Sobrevivência Celular/efeitos dos fármacos , Humanos , Absorção Intestinal , Masculino , Ratos , Ratos Sprague-Dawley , SolubilidadeRESUMO
The absolute configuration of a 1,n-diol can be assigned from the (1)H NMR spectra of its (R)- and (S)-AMAA diesters if the chemical shifts are interpreted as the result of the joint action of the two chiral auxiliaries.
RESUMO
[structure: see text] The C-glycoconjugate C(2)-alpha-D-mannosylpyranosyl-L-tryptophan (1), a metabolite known to be generated in humans through a novel posttranslational process, has been isolated from marine ascidians Leptoclinides dubius and Pharyngodictyon cauliflos and its N(alpha)-methyl derivative (2) from Ritterella rete.
Assuntos
Triptofano/análogos & derivados , Triptofano/isolamento & purificação , Urocordados/química , Animais , Cromatografia Líquida de Alta Pressão , Humanos , Ressonância Magnética Nuclear Biomolecular , Triptofano/química , Urocordados/metabolismoRESUMO
The photooxidation of thebaine (3) with a sun lamp affords two main products: hydrodibenzofuran 10 (major) and benzofuran 11 (minor). The latter compound becomes predominant if a Hg lamp is used instead of a sun lamp. The formation of 10 proceeds via an endoperoxide intermediate that undergoes oxidation at the nitrogen atom. Protection of the nitrogen either by protonation or quaternization prevents its oxidation and thus the photooxidation of 3 in acid media constitutes a one-pot procedure for the preparation of 14-hydroxycodeinone 35. Photooxidation of the thebaine ammonium salt 31 allows the isolation in good yields of the corresponding to thebaine endoperoxide 32. The selective protection and reduction of the keto, aldehyde, and olefinic groups of hydrodibenzofuran 10 allowed the preparation of several diol and keto alcohol derivatives. This is the first report on the use of photooxidation to functionalize thebaine at C(6) and C(14) and also the first on the isolation of opioid endoperoxides.
Assuntos
Derivados da Morfina/síntese química , Entorpecentes/química , Oxigênio/química , Peróxidos/química , Tebaína/química , Benzofuranos/síntese química , Benzofuranos/química , Benzofuranos/metabolismo , Codeína/análogos & derivados , Codeína/síntese química , Codeína/química , Luz , Espectroscopia de Ressonância Magnética , Mercúrio , Derivados da Morfina/química , Entorpecentes/metabolismo , Oxidantes/química , Oxidantes/metabolismo , Oxicodona/análogos & derivados , Oxicodona/síntese química , Oxicodona/química , Oxigênio/metabolismo , Peróxidos/metabolismo , Fotoquímica , Oxigênio Singlete , Tebaína/metabolismoRESUMO
The prediction of the absolute configuration of alpha-chiral carboxylic acids from the 1H NMR spectra of their esters with (R)- and (S)-ethyl 2-hydroxy-2-(9-anthryl) acetate [(R)- and (S)-9-AHA, 5] is discussed. Low-temperature NMR experiments, MM, semiempirical, and aromatic shielding effect calculations allowed the identification of the main conformers and showed that, in all esters studied, conformer ap is the most stable. A simple model for the assignment of the absolute configuration from NMR data is presented, and its reliability is corroborated with acids 6-31 of known absolute configuration. In addition to 5, other auxiliary reagents with open (32-38) and cyclic (39-42) structures have also been studied. trans-(+)- and (-)-2-phenyl-1-cyclohexanol (41) was found to be particularly efficient and produced delta delta RS values similar to those of 5.
RESUMO
Two new cytotoxic tetronic acid derivatives with a rearranged drimane skeleton [1a and 1b], were isolated from the sponge Dactylospongia elegans, along with smenospongic acid [3], illimaquinone [4], dactylospongenones A, B, C, and D [5], and dictyoceratin C [6]. The structures of 1a and 1b were elucidated by spectroscopic and chemical methods. Treatment of 1 with base gave smenospongic acid [3], suggesting that this latter compound is an end-product of D. elegans metabolism. A biogenetic route from furoterpenes to the tetronic acids [1a and b] and smenospongic acid [3] is proposed.