RESUMEN
In the aqueous solution, l-CySS-OMe induced pS-WP5 from racemic WP5. Upon the addition of dithiothreitol as a reducing reagent to the above system, pS-WP5 was then converted to pR-WP5 for the reason that l-CySS-OMe was reduced to l-Cys-OMe. Followed by the addition of H2O2 as an oxidation reagent, pR-WP5 was converted back to pS-WP5. The chiral conformational transferring process between pR-WP5 and pS-WP5 can be easily and visually observed by reading the CD signal.
RESUMEN
Chirality at different levels is widely observed in nature, but the clue to connect it all together, and the way chirality transfers among different levels are still obscure. Herein, a l-/d-lysine-based self-assembly system was constructed, in which two-step chirality transfer among three different levels was observed in aqueous solution. The chirality originated from the point chirality of amino acid derivatives l-/d-PyLys hydrochloride, and was transferred to the planar conformational chirality of water-soluble pillar[5]arene pR-/pS-WP5. Then, with the aid of pR-/pS-WP5, nanoparticles were formed that exhibited L-/R-handed circularly polarized luminescence with a dissymmetry factor of up to ±0.001, arising from pyrene chiral excimers. This multilevel chirality transfer not only provides a perspective to trace potential clues, and to pursue certain ways by which the chirality transfers, but also offers a strategy to create controllable CPL emission in aqueous media.
Asunto(s)
Luminiscencia , Nanopartículas , Aminoácidos , Estereoisomerismo , AguaRESUMEN
A stoichiometry-controlled chirality induction was successfully achieved through coassemblies of amphiphilic tetraphenylethylene derivative TPEA, γ-cyclodextrin (γ-CD), and water-soluble pillar[5]arene WP5 in aqueous solution. Stoichiometric variation of WP5 was found to be an effective strategy to induce topological transition between the pseudo[4]rotaxane and the vesicular form. Interestingly, the formation of pseudo[4]rotaxane triggered dual chirality induction from chiral γ-CD to TPEA (negative ICD1), and then, to dynamically racemic WP5 (positive ICD2), whereas both ICD1 and ICD2 were silent in the vesicular form.
Asunto(s)
Materiales Biocompatibles/química , Calixarenos/química , Compuestos de Amonio Cuaternario/química , Estilbenos/química , gamma-Ciclodextrinas/química , Ensayo de Materiales , Estructura Molecular , Tamaño de la Partícula , Solubilidad , Estereoisomerismo , Agua/químicaRESUMEN
Chiral α-amino acids play critical roles in the metabolic process in nearly all life forms. So far, chiral recognition of α-amino acids has mainly focused on the determination of l/d enantiomers. Herein, selection of planar chiral conformations between water-soluble pillar[5]arene WP5 and pillar[6]arene WP6 was observed due to α-side chain or ethyl ester moieties of l-α-amino acid ethyl ester hydrochlorides binding with WP5 and WP6, respectively. Therefore, α-side chain and ethyl ester moieties of l-α-amino acid ethyl ester hydrochlorides were recognized by observing the induced CD signal and its inversion. This is a rare example of being able to detect the chiral region around α-carbon of a chiral α-amino acid molecule.
RESUMEN
A crown-shaped cyclotriveratrylene (CTV) analogue with persubstituted arene units-namely, cyclotrixylohydroquinoylene (CTX)-was synthesized from tetrasubstituted o-xylohydroquinone. Importantly, a series of CTX derivatives were prepared by introducing second bridged methylene, phenylphosphine oxide, and dimethylsilyl at the middle rim, referred to as CTX[CH2], CTX[P(O)Ph], and CTX[SiMe2], respectively, with the completely locked crown conformation, leading to the formation of unique C3-symmetric Chinese censer-shaped pocket structures. In addition, the water-soluble CTX[CH2] derivative (WCTX[CH2]) was synthesized from CTX[CH2] by simple oxidation reaction with the modification at the upper rim, and its host-guest interaction with methyl viologen in water was investigated.
RESUMEN
The competitive conformation chirality of dynamically racemic water-soluble pillar[5]arene WP5 can be induced by 19 different l-amino acid ethyl ester hydrochlorides. Among them, l-Arg-OEt and 18 other l-amino acid ethyl ester hydrochlorides can induce the opposite-handedness conformation of WP5. This was ascribed to the different binding models with a side-chain moiety or ethyl ester moiety of amino acids toward the cavity of WP5.
Asunto(s)
Calixarenos/química , Aminoácidos , Dicroismo Circular , Modelos Moleculares , Conformación Molecular , Solubilidad , Estereoisomerismo , Agua/químicaRESUMEN
MyD88 and IRAK4 are important components of TLR signaling pathways. However, information about MyD88 and IRAK4 is vacant in golden pompano (Trachinotus ovatus), a marine teleost with great commercial value. Thus, in this study the full lengths of trMyD88 and trIRAK4 were cloned from golden pompano using RT-PCR and RACE-PCR methods. trMyD88 was 1213 bp in length, encoding a putative protein of 288 amino acids (aa), consisting of a 99 aa of death domain at its N-terminal and a 137 aa of the TIR domain at its C-terminal. trIRAK4 was 1606 bp in length, encoding a putative protein of 469 aa, including an N-terminal death domain and a central kinase domain, connected by a ProST domain. Other domains or aa residues needed for their functions were also identified in trMyD88 and trIRAK4. Physicochemical features and 3-D structures of trMyD88 and trIRAK4 were also analyzed. Quantitative real-time PCR revealed that the 2 genes were ubiquitously expressed in tissues from healthy pompano, especially highly in the spleen and head kidney, indicating their roles in the immune response. Further, trMyD88 and trIRAK4 were up-regulated at 12 h after the Vibrio alginilyticus and polyI:C challenge and continued to 48 h post challenge. Our results demonstrated that MyD88 and IRAK4 played important roles in the golden pompano innate immune system, providing the basis for further study of the signaling pathways that these 2 genes are involved in.
Asunto(s)
Proteínas de Peces/genética , Quinasas Asociadas a Receptores de Interleucina-1/genética , Factor 88 de Diferenciación Mieloide/genética , Perciformes/genética , Vibriosis/inmunología , Vibrio alginolyticus/inmunología , Animales , Clonación Molecular , Proteínas de Peces/metabolismo , Riñón Cefálico/metabolismo , Inmunidad Innata , Quinasas Asociadas a Receptores de Interleucina-1/metabolismo , Factor 88 de Diferenciación Mieloide/metabolismo , Perciformes/inmunología , Poli I-C/inmunología , Conformación Proteica , Análisis de Secuencia de ADN , Bazo/metabolismoRESUMEN
Toll like receptor (TLR) 7, 8 and 9 are intracellular TLRs which play important roles in host immune defense against bacterial or virus pathogens. In this study, TLR7, 8 and 9 were identified from golden pompano (Trachinotus ovatus), a marine teleost with great economic values. Sequence analysis revealed that the three TLRs contained several conserved characteristic features, including signal peptides, 25 leucine-rich repeat (LRR) motifs, a transmembrane domain and a TIR motif. These three TLRs shared high sequence identity and similarity with their counterparts from other teleosts. The phylogenetic tree analysis showed the three TLRs were clustered well with their piscine counterparts, confirming the correctness of their nomenclatures and closed relationships during evolution. Quantitative real-time PCR revealed that the three TLRs were ubiquitously expressed in all the tested tissues from normal pompano, with high expression in spleen and head kidney, indicating their role in immune reaction. Further, pompano TLR7 and TLR8 was up-regulated in spleen and head kidney from 12 h to 48 h following polyI:C challenge, but remained no changes to Vibrio alginilyticus infection. In contrast, pompano TLR9 could be induced by V. alginilyticus infection but remained apathetic to polyI:C challenge. These results indicated that pompano TLR7, 8 and 9 might have distinct roles in response to bacterial or virus pathogens. Our results provided the basis for further study on ligand specificity and signaling pathways of fish TLRs which are required for elucidating the immune functions of fish TLRs.