Supramolecular Catalysis of the oxa-Pictet–Spengler Reaction with an Endohedrally Functionalized Self-Assembled Cage Complex

An endohedrally functionalized self-assembled Fe₄L₆ cage complex can catalyze oxa-Pictet—Spengler cyclizations of tryptophols and various aldehyde derivatives, showing strong rate accelerations and size-selectivity. Selective molecular recognition of substrates controls the reactivity, and the cage is capable of binding and activating multiple different species along the multistep reaction pathway. The combination of a functionalized active site, size-selective reactivity, and multistep activation, all from a single host molecule, illustrates the biomimetic nature of the catalysis.     

新的氨基酸受体的合成和分子识别性质研究

从双氨基甲基手性双环胍出发,经三步反应合成了由稳定的共价键桥联双环胍、氮杂冠醚和萘环的氨基酸受体1.液-液竞争萃取和^1HNMR实验表明受体对氨基酸两性离子具有较好的侧链选择性和对映选择性,能够选择性地将L-芳香族氨基酸从水相转移到二氯甲烷有机相。     

A conformationally constrained fused tricyclic nisin AB-ring system mimic toward an improved pyrophosphate binder of lipid II

The bacteria-specific membrane component lipid II is essential for bacterial cell wall synthesis. A tricyclic nisin mimic was designed and synthesized in which both thioether moieties were mimicked by an alkane-bridge, as well as the introduction of a third conformational constraint consisting of a macrocyclic lactam-bridge between the N-terminus and the B-ring. The newly designed tricyclic AB-ring mimic was found to bind lipid II since it was able to inhibit nisin-induced membrane leakage in a dose-dependent manner. These results imply that the tricyclic AB-ring mimic may form a novel class of lead structures for the development of nisin-based peptide antibiotics.     

Carboxylic acid recognition of diamidine having a fluorescent 1,8-diphenylanthracene unit and its detection of amidinium-carboxylate and amidinium formation

A diphenylanthracene-based diamidine (1a) fluorescent probe for the detection of dicarboxylic acids has been designed and synthesized, which has an extended π-conjugation rather than a simple anthracene ring, in order to observe highly different fluorescence wavelengths after complex formation with dicarboxylic acids. The fluorescence spectra of the mixed solution of the diamidine 1a and carboxylic acids showed two different fluorescence bands, which corresponded to the complex formation (amidinium-carboxylate formation, λ_em?=?450?nm, light blue color) and dissociated amidinium formation (λ_em?=?510?nm as a broad band, green color). The complexed and dissociated states were confirmed by DOSY NMR and TD-DFT calculations. These different fluorescence wavelengths may come from the differences in the dihedral angles between the phenyl rings at the 1,8-position and anthracene ring (difference in π-conjugation) of 1a under complex formation and dissociated amidinium formation. The proposed mechanism for the observation of the different fluorescence wavelengths (complex formation and amidinium formation) was also confirmed by the fluorescence study of diamidine 1b which causes restricted rotation of the phenyl rings by substitution of the steric methyl groups, and observed the same fluorescence spectra for the complex formation and amidinium formation (400, 420, 450?nm as a vibrational structure of anthracene ring). These fluorescence characteristics of the diamidine 1a are also applicable for the detection of α,ω?dicarboxylic acids.     

Orientational Recognition and Low-Resistance Passing (LRP) Regulation of Segmental Re-innervation by Central Neurons in Leeches

Re-innervation of sensory and motor neurons on a defined area of the body wall was studied in two species of leeches, Whitmania pigra and Hirudo medicinalis, as a model of segmental animals. Following isolation and rotation of a tube of body wall, the mechanical sensory and annular erection (AE) motor neurons re-innervated the body wall, at a rate of approximately 3. 8 -8. 4 μm/h. The patterns of re-innerva-tion by pairs of neurons on each side of a ganglion were bilaterally symmetric. The repairs are synchronous for the sensory and motor neurons which are of different functions but in a same ganglion. The gap junctions are widely spread in leech between neurons and glia cells, as well as among the neurons and glia cells themselves. Therefore, it is proposed that the nervous system repair is regulated by a low-resistance pathway. In the xenotransplantation experiments, neurons recognized target tissues before the immuno-recognition and rejection.     

Potentiometric response and mechanism of anionic recognition of heterocalixarene-based ion selective electrodes

The ion selective electrode (ISE)-based potentiometric approach is shown to be an effective means of characterizing the anion recognition sites in the molecular receptor calix[2]pyridino[2]pyrrole (CPP). In particular, potentiometric pH-measurements involving the use of experimental PVC-membranes based on CPP revealed the existence of both mono- and diprotonated forms of the receptor under readily accessible conditions. Based on these analyses, apparent surface protonation constants for this heterocalixarene were found to lie between 8.5-8.9 (pK_B1) and 3.3-3.8 (pK_B2). CPP was found to interact with targeted anionic analytes based on both coulombic and hydrogen bond interactions, as inferred from varying the kinds of ionic sites present within the membrane phase. Potentiometric selectivity studies revealed that CPP preferred “Y-shaped” anions (e.g. acetate, lactate, benzoate) over spherical anions (e.g. fluoride and chloride), fluoride over chloride within the set of spherical anions, and the ortho-isomer over the corresponding meta- and para-isomers in the case of hydroxybenzoate (salicylate and congeners). In the context of this study, the advantages of potentiometric determinations of acetylsalicylic acid using optimized PVC-membranes based on CPP relative to more conventional PVC-membrane ISEs based on traditional anion exchanger were also demonstrated.     

A Study of the Probe Effect on the Apparent Image of Biological Atomic Force Microscopy

The atomic force microscopy (AFM) possesses high spatial resolution and it is compatible with liquid environments. AFM can provide possibility to study a wide range of biological problems at the molecular level and acquire topological information at nanometre resolution under physiological conditions1,2. However, a major problem for image reconstruction of biological specimens is that structures of most biological molecules are very soft and delicate, which could be easily deformed and dama…     

对DNA具有识别和断裂功能的金属插入剂的研究

本文详尽介绍了国际上对金属配合物与DNA 以插入方式进行识别和反应的前瞻性的工作,为设计能够与特定序列的DNA 进行识别和反应的金属配合物提供了多种策略。     

Applications of Pattern Recognition in Drug Discovery

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