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941.
Ishigami N Ago H Imamoto K Tsuji M Iakoubovskii K Minami N 《Journal of the American Chemical Society》2008,130(30):9918-9924
On single-crystal substrates, such as sapphire (alpha-Al 2O 3) and quartz (SiO 2), single-walled carbon nanotubes (SWNTs) align along specific crystallographic axes of the crystal, indicating that the SWNT growth is influenced by the crystal surface. Here, we show that not only the orientation, but also the diameter and chirality of SWNTs are affected by the crystal plane of the sapphire substrate. The aligned SWNTs grown on the A- and R-planes of sapphire have narrower diameter distributions than randomly oriented tubes produced on the C-plane sapphire and amorphous SiO 2. Photoluminescence measurements reveal a striking difference between the aligned SWNTs: near-zigzag tubes are observed on the A-plane and near-armchair tubes on the R-plane. This study shows the route for the diameter and chirality control of SWNTs by surface atomic arrangements of a single-crystal substrate. 相似文献
942.
Yang J Park M Yoon ZS Hori T Peng X Aratani N Dedecker P Hotta J Uji-i H Sliwa M Hofkens J Osuka A Kim D 《Journal of the American Chemical Society》2008,130(6):1879-1884
By using single molecule fluorescence spectroscopy we have investigated the excitation energy migration processes occurring in a series of cyclic porphyrin arrays bearing a close proximity in overall architectures to the LH2 complexes in purple bacterial photosynthetic systems. We have revealed that the conformational heterogeneity induced by the structural flexibility in large cyclic porphyrin arrays, which provides the nonradiative deactivation channels as an energy sink or trap, reduces significantly the energy migration efficiency. Our study provides detailed information on the energy migration efficiency of the artificial light-harvesting arrays at the single molecule level, which will be a guideline for future applications in single molecular photonic devices in the solid state. 相似文献
943.
Nishioka Y Yamaguchi T Kawano M Fujita M 《Journal of the American Chemical Society》2008,130(26):8160-8161
Remote chirality at the periphery of a self-assembled cage brings about the slight twist of aromatic rings, which is yet sufficient to induce considerable asymmetric induction (up to 50% ee) in the hitherto unknown [2 + 2] cross photoadditions of fluoranthenes. 相似文献
944.
Nguyen Ngoc Thanh Luan Dr. Takuya Okada Dr. Naoki Toyooka 《European journal of organic chemistry》2023,26(12):e202300047
Betuphenone F ( 6 ) is a natural product isolated from the bark of Betula alnoides Ham. ex D. Don (Betulaceae) and structurally determined by S. Awale et al. in 2021. Betuphenone F ( 6 ) has the potential to be a new-generation anti-cancer agents based on anti-austerity, as it showed preferential cytotoxicity against PANC-1 human pancreatic cancer cells under nutrient-deprived conditions (PC50 value of 4.9 μM). We succeeded in constructing the 2-oxabicyclo[3.3.1]nonane skeleton, which is a structural feature of betuphenone F ( 6 ), by exposing intermediate 9 to acid, and achieved the first total synthesis of rac-bethuphenone F ( 6 ) from phloroglucinol ( 7 ) in only three steps. 相似文献
945.
946.
947.
Shimizu M Katsuda N Katsurada T Mitani M Yoshioka Y 《The journal of physical chemistry. B》2008,112(47):15116-15126
The molecular and electronic structures of the Rieske iron-sulfur [2Fe-2S] cluster with an imidazolate and imidazole were investigated by using usual unrestricted and broken symmetry B3LYP methods for the highest and lowest spin states, respectively. The electronic structures of the lowest spin states were determined by the spin contaminations and natural orbital analyses. It was shown that the spin contamination presents the number of pairs of the antiferromagnetic spin couplings. The oxidation mechanism of the ubquinol at the Q(p) site of the cytochrome bc(1) complex was also examined by the broken symmetry B3LYP methods. In the [2Fe-2S] clusters with an imidazolate, the oxidized and lowest spin state, [(Imz(-))FeS](ox)LS, was lowest in energy among four possible states, consistent with experimental observations. In the examination of the mechanism of the ubquinol oxidation, it was confirmed that the ubiquinol docks between the imidazolate of [2Fe-2S] clusters and Glu272(-) of cytochrome b by the hydrogen bonds before the oxidation proceeds, consistent with the experimental proposals. Our results support a "Glu272-first" mechanism that Glu272 serves as an acceptor of the first proton from the ubiquinol and subsequently the proton-coupled electron transfer (PCET) occurs from the ubisemiquinone anion to the Rieske iron-sulfur [2Fe-2S] cluster. 相似文献
948.
Masahiko Ochiai Eiichi Akiyama Toshiyuki Ueno Kazuhisa Kawano Teppei Hayakawa Noriaki Oshima 《Silicon Chemistry》2008,3(6):307-312
1,3,5-Trimethoxy-1,3,5-triisopropylcyclotrisiloxane (2) was prepared from 1,3,5-triisopropyl-1,3,5-tri-o-tolylcyclotrisiloxane—(1) according to three kinds of methods as follows: the dearylchlorination of 1 using HCl/AlCl3, which led to prepare 2 includes a very slight amount of aluminum species as impurities, the dearylbromination using Br2, which simultaneously brought unnecessary bromination without isolated 2, and the dearylation using TfOH, which efficiently gave 2 of a high purity without metals of contamination. 相似文献
949.
We propose a new method to analyze and efficiently represent data recorded on a domain of general shape in by computing the eigenfunctions of Laplacian defined over there and expanding the data into these eigenfunctions. Instead of directly solving the eigenvalue problem on such a domain via the Helmholtz equation (which can be quite complicated and costly), we find the integral operator commuting with the Laplacian and diagonalize that operator. Although our eigenfunctions satisfy neither the Dirichlet nor the Neumann boundary condition, computing our eigenfunctions via the integral operator is simple and has a potential to utilize modern fast algorithms to accelerate the computation. We also show that our method is better suited for small sample data than the Karhunen–Loève transform/principal component analysis. In fact, our eigenfunctions depend only on the shape of the domain, not the statistics of the data. As a further application, we demonstrate the use of our Laplacian eigenfunctions for solving the heat equation on a complicated domain. 相似文献
950.
Dina N. Yamaleyeva Naoki Makita Duhyeong Hwang Matthew J. Haney Rainer Jordan Alexander V. Kabanov 《Macromolecular bioscience》2023,23(11):2300177
The present study expands the versatility of cationic poly(2-oxazoline) (POx) copolymers as a polyethylene glycol (PEG)-free platform for gene delivery to immune cells, such as monocytes and macrophages. Several block copolymers are developed by varying nonionic hydrophilic blocks (poly(2-methyl-2-oxazoline) (pMeOx) or poly(2-ethyl-2-oxazoline) (pEtOx), cationic blocks, and an optional hydrophobic block (poly(2-isopropyl-2-oxazoline) (iPrOx). The cationic blocks are produced by side chain modification of 2-methoxy-carboxyethyl-2-oxazoline (MestOx) block precursor with diethylenetriamine (DET) or tris(2-aminoethyl)amine (TREN). For the attachment of a targeting ligand, mannose, azide-alkyne cycloaddition click chemistry methods are employed. Of the two cationic side chains, polyplexes made with DET-containing copolymers transfect macrophages significantly better than those made with TREN-based copolymer. Likewise, nontargeted pEtOx-based diblock copolymer is more active in cell transfection than pMeOx-based copolymer. The triblock copolymer with hydrophobic block iPrOx performs poorly compared to the diblock copolymer which lacks this additional block. Surprisingly, attachment of a mannose ligand to either copolymer is inhibitory for transfection. Despite similarities in size and design, mannosylated polyplexes result in lower cell internalization compared to nonmannosylated polyplexes. Thus, PEG-free, nontargeted DET-, and pEtOx-based diblock copolymer outperforms other studied structures in the transfection of macrophages and displays transfection levels comparable to GeneJuice, a commercial nonlipid transfection reagent. 相似文献