Transient absorption spectroscopy is used to study the excited‐state dynamics of Co3(dpa)4(NCS)2, where dpa is the ligand di(2‐pyridyl)amido. The ππ*, charge‐transfer, and d–d transition states are excited upon irradiation at wavelengths of 330, 400 and 600 nm, respectively. Similar transient spectra are observed under the experimental temporal resolution and the transient species show weak absorption. We thus propose that a low‐lying metal‐centered d–d state is accessed immediately after excitation. Analyses of the experimental kinetic traces reveal rapid conversion from the ligand‐centered ππ* and the charge‐transfer states to this metal‐centered d‐d state within 100 fs. The excited molecule then crosses to a second d–d state within the ligand‐field manifold, with a time coefficient of 0.6–1.4 ps. Because the ground‐state bleaching band recovers with a time coefficient of 10–23 ps, we propose that an excited molecule crosses from the low‐lying d–d state either directly within the same spin system or with spin crossing via the state 2B to the ground state 2A2 (symmetry group C4). In this trimetal string complex, relaxation to the ground electronic surface after excitation is thus rapid.相似文献
Dendritic poly(amidoamine)s (PAMAM)s were introduced into the side chains of disulfide‐containing poly(amidoamine)s via repetitive Michael addition and amidation. The bioreducible poly(amidoamine)s grafted with dendritic polyamidoamines showed high buffer capacity, low cytotoxicity and strong DNA binding ability at low N/P ratio. They were able to condense DNA into small sized polycation/DNA complexes, which degraded and released the incorporated DNA under reductive conditions. In comparison to the original disulfide‐containing poly(amidoamine) with aminoethyl side chain, the grafting of the bioreducible poly(amidoamine) with dendrimer greatly improved the transfection efficiencies of 293T and HeLa cells with foreign DNA at various N/P ratios. The structure–gene delivery property relations of dendrimer‐grafted polycations will provide valuable insight into the design of highly efficient and less toxic polycationic gene carriers.
Polynorbornenes appended with porphyrins containing a range of different linkers are synthesized. The use of bisamidic chiral alanine linkers between the pending porphyrins and the polymeric backbone has been shown to bring the adjacent porphyrin chromophores to more suitable orientation for exciton coupling owing to hydrogen bonding between the adjacent linkers. The hydrogen bonding between the adjacent pendants in these polymers may induce a cooperative effect and therefore render single‐handed helical structures for these polymers. Such a cooperative effect is reflected in the enhancement of FRET efficiencies between zinc–porphyrin and free base porphyrin in random copolymers. 相似文献
As part of a homologous series of novel polyfluorinated bipyridyl (bpy) ligands, the title compound, C16H14F6N2O2, contains the smallest fluorinated group, viz. CF3. The molecule resides on a crystallographic inversion centre at the mid‐point of the pyridine Cipso—Cipso bond. Therefore, the bpy skeleton lies in an anti conformation to avoid repulsion between the two pyridyl N atoms. Weak intramolecular C—H...N and C—H...O interactions are observed, similar to those in related polyfluorinated bpy–metal complexes. A π–π interaction is observed between the bpy rings of adjacent molecules and this is probably a primary driving force in crystallization. Weak intermolecular C—H...N hydrogen bonding is present between one of the CF3CH2– methylene H atoms and a pyridyl N atom related by translation along the [010] direction, in addition to weak benzyl‐type C—H...F interactions to atoms of the terminal CF3 group. It is of note that the O—CH2CF3 bond is almost perpendicular to the bpy plane. 相似文献
Acetohydroxyacid synthase (AHAS) is the target enzyme of several classes of herbicides, such as sulfonylureas and imidazolinones. Now many mutant AHASs with herbicide resistance have emerged along with extensive use of herbicides, therefore it is imperative to understand the detailed interaction mechanism and resistance mechanism so as to develop new potent inhibitors for wild-type or resistant AHAS. With the aid of available crystal structures of the Arabidopsis thaliana (At) AHAS-inhibitor complex, molecular dynamics (MD) simulations were used to investigate the interaction and resistance mechanism directly and dynamically at the atomic level. Nanosecond-level MD simulations were performed on six systems consisting of wild-type or W574L mutant AtAHAS in the complex with three sulfonylurea inhibitors, separately, and binding free energy was calculated for each system using the MM-GBSA method. Comprehensive analyses from structural and energetic aspects confirmed the importance of residue W574, and also indicated that W574L mutation might alert the structural charactersistic of the substrate access channel and decrease the binding affinity of inhibitors, which cooperatively weaken the effective channel-blocked effect and finally result in weaker inhibitory effect of inhibitor and corresponding herbicide resistance of W574L mutant. To our knowledge, it is the first report about MD simulations study on the AHAS-related system, which will pave the way to study the interactions between herbicides and wild-type or mutant AHAS dynamically, and decipher the resistance mechanism at the atomic level for better designing new potent anti-resistance herbicides. 相似文献
A series of second generation of amphiphilic dendronized homopolymers are efficiently synthesized, and their thermoresponsiveness in aqueous solutions and secondary structures in methanol solutions are described. These polymers are constructed in each repeat unit with various generations of hydrophobic 4-aminoproline and hydrophilic oligoethylene glycol (OEG)-based dendrons, and their over-all hydrophilicity is tuned by varying these dendron generations. Polymers with or without the first generation of proline dendron show good water solubility at room temperature, but exhibit typical thermoresponsive behaviors at elevated temperatures as characterized by turbidity measurements using UV-vis spectroscopy, while the polymer with the secondary generation of proline dendron is not soluble in water. All polymers show ordered secondary structures as evidenced by the optical rotation and circular dichroism experiments. Finally, assembly of these amphiphilic homopolymers into porous films via breath figure (BF) technique is described, and polymer structures are found to show significant influence on the morphology of porous film. 相似文献
Both title compounds are derivatives of salicylic acid. 5‐Formylsalicylic acid (systematic name: 5‐formyl‐2‐hydroxybenzoic acid), C8H6O4, possesses three good hydrogen‐bond donors and/or acceptors coplanar with their attached benzene ring and abides very well by Etter's hydrogen‐bond rules. Intermolecular O—H...O and some weak C—H...O hydrogen bonds link the molecules into a planar sheet. Reaction of this acid and o‐phenylenediamine in refluxing ethanol produced in high yield the new zwitterionic compound 5‐(benzimidazolium‐2‐yl)salicylate [systematic name: 5‐(1H‐benzimidazol‐3‐ium‐2‐yl)‐2‐hydroxybenzoate], C14H10N2O3. Each imidazolium N—H group and its adjacent salicyl C—H group chelate one carboxylate O atom via hydrogen bonds, forming seven‐membered rings. As a result of steric hindrance, the planes of the molecules within these pairs of hydrogen‐bonded molecules are inclined to one another by ∼74°. There are also π–π stacking interactions between the parallel planes of the imidazole ring and the benzene ring of the salicyl component of the adjacent molecule on one side and the benzimidazolium component of the molecule on the other side. 相似文献