Triindolo-truxene, a C3-symmetric molecule with a large π-conjugated plane, has six methylene carbon atoms and three aromatic carbon atoms that can be facilely functionalized. Herein, butyl, carbonyl, cyano, and/or malononitrile groups were introduced at six methylene carbon atoms (6-, 14-, 22- or 8-, 16-, 24-positions) and/or three aromatic carbon atoms (2-, 10-, and 18-positions) of triindolo-truxene to produce eight derivatives. Their photophysical properties, electrochemical properties, and molecular assembly can be effectively modulated by substituents and substitution patterns. Incorporation of electron-deficient groups led to redshifts in both the absorption and emission of these derivatives and also lowered their HOMO and LUMO levels. Different substitution patterns resulted in the different intramolecular donor–acceptor interactions. Electron-deficient substituents at the methylene carbon atoms in the 6-, 14-, and 22-positions led to intramolecular charge transfer from the fluorene arms to the truxene core, whereas the corresponding substitutions at the methylene carbon atoms in the 8-, 16-, and 24-positions resulted in intramolecular charge transfer from the truxene core to the fluorene arms. The molecular packing in single crystals and molecular aggregation in solution are also influenced by the substituents and substitution patterns. This work provides a straightforward strategy to alter the properties of triindolo-truxene. 相似文献
The present paper discusses some characteristics of the molecular volumes of phosphates, arsenates and vanadates. In the salts, the volumes of per acid radical ((?)) quantitatively depend on the radii, charges, numbers of cations and anions. The functional relations between the (?) values of phosphates, arsenates, vanadates and the factors mentioned above are obtained. The molecular volumes of these salts are equal to the sum of the topological volumes of cations and anions. The authors have got a series of universally united topological volume values of cations and anions. It confirms that the topological molecular volume of the crystal water (H_2O) in the hydrates of the salts approximates to a constant, 244 (?)~3 with σ_(n-1)= 2.1. The topological volume of the hydroxide ion (OH~-) approximates to a constant too. The average value is 16.89 (?)~3 with σ_(n-1)=1.68. 相似文献
Synthetic and natural ionophores have been developed to catalyze ion transport and have been shown to exhibit a variety of biological effects. We synthesized 24 aza- and diaza-crown ethers containing adamantyl, adamantylalkyl, aminomethylbenzoyl, and ε-aminocaproyl substituents and analyzed their biological effects in vitro. Ten of the compounds (8, 10–17, and 21) increased intracellular calcium ([Ca2+]i) in human neutrophils, with the most potent being compound 15 (N,N’-bis[2-(1-adamantyl)acetyl]-4,10-diaza-15-crown-5), suggesting that these compounds could alter normal neutrophil [Ca2+]i flux. Indeed, a number of these compounds (i.e., 8, 10–17, and 21) inhibited [Ca2+]i flux in human neutrophils activated by N-formyl peptide (fMLF). Some of these compounds also inhibited chemotactic peptide-induced [Ca2+]i flux in HL60 cells transfected with N-formyl peptide receptor 1 or 2 (FPR1 or FPR2). In addition, several of the active compounds inhibited neutrophil reactive oxygen species production induced by phorbol 12-myristate 13-acetate (PMA) and neutrophil chemotaxis toward fMLF, as both of these processes are highly dependent on regulated [Ca2+]i flux. Quantum chemical calculations were performed on five structure-related diaza-crown ethers and their complexes with Ca2+, Na+, and K+ to obtain a set of molecular electronic properties and to correlate these properties with biological activity. According to density-functional theory (DFT) modeling, Ca2+ ions were more effectively bound by these compounds versus Na+ and K+. The DFT-optimized structures of the ligand-Ca2+ complexes and quantitative structure-activity relationship (QSAR) analysis showed that the carbonyl oxygen atoms of the N,N’-diacylated diaza-crown ethers participated in cation binding and could play an important role in Ca2+ transfer. Thus, our modeling experiments provide a molecular basis to explain at least part of the ionophore mechanism of biological action of aza-crown ethers. 相似文献
To improve the insulating properties of polybrominated diphenyl ethers(PBDEs), we studied the molecular structures and energy gap(Eg) values of 209 PBDEs using a three-dimensional quantitative structure-activity relationship(3D-QSAR) model, molecular docking, and molecular dynamics. We also analyzed the interaction mechanisms of PBDEs using a 2D-QSAR model, molecular substitution characteristics, and molecular docking. The 3D-QSAR model showed that the 2-, 4-, 5-, and 6-positions significantly influenced the PBDE insulating properties. Using BDE-34 as a template molecule, we designed six derivatives with 0.47%-28.44% higher insulation tlian BDE-34. Compared with BDE-34, the stability and flame retardancy of the above six derivatives were not adversely affected. These derivatives, except for 2,6-cyanomethyl-BDE, 2-cyanomethyl-BDE, and 2-aniinomethyl-BDE, were more toxic and biodegradable than BDE-34, but showed weaker bioaccumulation and migration abilities than BDE-34. Mechanism analysis showed that the highest occupied orbital energy, the most negative charge, and the dipole moment were the main quantitative parameters that aflected the PBDE insulating properties. PBDE insulation gradually decreased as the number of Br atoms increased. The level of similarity between the substitution patterns on the two benzene rings was significantly correlated with PBDE insulation, with hydrophobic groups having a more significant efiect on PBDE insulation. 相似文献
To reveal the potential fungicidal mechanism of 5-((4-((4-chlorophenoxy)methyl)-5-iodo-1 H-1,2,3-triazole-1-yl)methyl)-2-methylpyrimidin-4-amine(PA-1) against Botrytis cinerea(B. cinerea), the three-dimensional structure of B. cinerea pyruvate dehydrogenase complex E1 component(PDHc-E1) is homology modeled, as the PA-1 shows potent E. coli PDHc-E1 and B. cinerea inhibition. Subsequent molecular docking indicates the PA-1 can tightly bind to B. cinerea PDHc-E1. Molecular dynamic simulation and MM... 相似文献
Three ab initio calculations (HF/6-3IG, HF/6-3IG*, and HF/6-3IG**) on 2,4,6-trinitrotoluene were made, The results compare well with xray data, except dihedral angles of NO2 relative to the plane of the benzene ring. The deviations are attributed to packing forces and steric effects in the crystal. The most stable structure was a torsional angle 10° of the methyl top with the benzene ring, unlike toluene. The rotational barriers of the methyl top and the 4-nitro group are small. Hydrogen bonding, dipole moments and total atomic charges arc calculated. 相似文献
A theoretical study of homocyclic sulfur species S6, S7, and S8 was carried out using a molecular valence method involving stepwise approximations for orthogonality and core-valence interactions. The valence shell orbitals are described at the minimal basis level. The geometries of the molecules are predicted well as compared with other theoretical studies and the experimental values. The slight overestimation of the SS bond length is typical to the nonpolarized basis sets. The energies of the valence orbitals are well in accord with the conventional all-electron ab initio results. The trend in the stabilities of the three molecules is discussed. The present method provides an attractive possibility to study homocyclic and heterocyclic systems involving heavier chalcogens with no increase of the computing time. 相似文献
The design and elaboration of a series of macrocyclic templates that exhibit a propensity to adopt a β‐strand‐like peptide‐backbone conformation led to potent and selective inhibitors of calpain 2. Macrocycle 1 retarded calcium‐induced opacification in an ovine‐lens culture assay and is a lead compound for the development of a drug for cataract treatment. Cbz=carbobenzyloxy.