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101.
Synthesis, π‐Face‐Selective Aggregation,and π‐Face Chiral Recognition of Configurationally Stable C3‐Symmetric Propeller‐Chiral Molecules with a π‐Core 下载免费PDF全文
Dr. Nozomi Saito Dr. Ryo Terakawa Prof. Dr. Masahiko Yamaguchi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(19):5601-5607
The C3‐symmetric propeller‐chiral compounds (P,P,P)‐ 1 and (M,M,M)‐ 1 with planar π‐cores perpendicular to the C3‐axis were synthesized in optically pure states. (P,P,P)‐ 1 possesses two distinguishable propeller‐chiral π‐faces with rims of different heights named the (P/L)‐face and (P/H)‐face. Each face is configurationally stable because of the rigid structure of the helicenes contained in the π‐core. (P,P,P)‐ 1 formed dimeric aggregates in organic solutions as indicated by the results of 1H NMR, CD, and UV/Vis spectroscopy and vapor pressure osmometry analyses. The (P/L)/(P/L) interactions were observed in the solid state by single‐crystal X‐ray analysis, and they were also predominant over the (P/H)/(P/H) and (P/L)/(P/H) interactions in solution, as indicated by the results of 1H and 2D NMR spectroscopy analyses. The dimerization constant was obtained for a racemic mixture, which showed that the heterochiral (P,P,P)‐ 1 /(M,M,M)‐ 1 interactions were much weaker than the homochiral (P,P,P)‐ 1 /(P,P,P)‐ 1 interactions. The results indicated that the propeller‐chiral (P/L)‐face interacts with the (P/L)‐face more strongly than with the (P/H)‐face, (M/L)‐face, and (M/H)‐face. The study showed the π‐face‐selective aggregation and π‐face chiral recognition of the configurationally stable propeller‐chiral molecules. 相似文献
102.
Design of Ratiometric Fluorescent Probes Based on Arene–Metal‐Ion Interactions and Their Application to CdII and Hydrogen Sulfide Imaging in Living Cells 下载免费PDF全文
Ippei Takashima Miyuki Kinoshita Ryosuke Kawagoe Saika Nakagawa Prof. Dr. Manabu Sugimoto Prof. Dr. Itaru Hamachi Prof. Dr. Akio Ojida 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(8):2184-2192
Non‐coordinative interactions between a metal ion and the aromatic ring of a fluorophore can act as a versatile sensing mechanism for the detection of metal ions with a large emission change of fluorophores. We report the design of fluorescent probes based on arene–metal‐ion interactions and their biological applications. This study found that various probes having different fluorophores and metal binding units displayed significant emission redshift upon complexation with metal ions, such as AgI, CdII, HgII, and PbII. X‐ray crystallography of the complexes confirmed that the metal ions were held in close proximity to the fluorophore to form an arene–metal‐ion interaction. Electronic structure calculations based on TDDFT offered a theoretical basis for the sensing mechanism, thus showing that metal ions electrostatically modulate the energy levels of the molecular orbitals of the fluorophore. A fluorescent probe was successfully applied to the ratiometric detection of the uptake of CdII ions and hydrogen sulfide (H2S) in living cells. These results highlight the utility of interactions between arene groups and metal ions in biological analyses. 相似文献
103.
Nobuyasu Hanari Taichi Yamazaki Nobuyasu Itoh Takashi Yarita Naomi Fujiki Ryoko Iwasawa Yoshie Aoyagi Masahiko Numata 《Accreditation and quality assurance》2014,19(5):391-396
A certified reference material (CRM) for the determination of perfluorooctanoic acid (PFOA) has been issued as NMIJ CRM 4056-a by the National Metrology Institute of Japan, National Institute of Advanced Industrial Science and Technology (NMIJ/AIST). Purity (kg kg?1) based on a titration method was determined by subtracting the mass fractions of impurities measured using liquid chromatography/mass spectrometry (LC/MS) from those of acids expressed as PFOA measured by a neutralization potentiometric titration. To validate an obtained result, purity based on a mass balance method was determined by subtracting the mass fractions of impurities, measured using LC/MS, Karl-Fischer titration (KFT), and vacuum evaporation, from 1 kg kg?1. Results from both titration and mass balance methods were in agreement within the accepted limits of uncertainty. The certified purity of NMIJ CRM 4056-a was determined to be 0.959 kg kg?1, calculated as the mean of the results obtained with the two methods. The standard uncertainty of the certified purity was evaluated from purity evaluations as well as from sample homogeneity and stability obtained from LC/MS and KFT analyses. Consequently, the expanded uncertainty was estimated to be 0.005 kg kg?1 with a coverage factor of k = 2. 相似文献
104.
Dr. Ming-Shui Yao Prof. Jia-Jia Zheng Ai-Qian Wu Prof. Gang Xu Sanjog S. Nagarkar Gen Zhang Masahiko Tsujimoto Prof. Shigeyoshi Sakaki Prof. Satoshi Horike Prof. Kenichi Otake Prof. Susumu Kitagawa 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(1):178-182
Single-ligand-based electronically conductive porous coordination polymers/metal–organic frameworks (EC-PCPs/MOFs) fail to meet the requirements of numerous electronic applications owing to their limited tunability in terms of both conductivity and topology. In this study, a new 2D π-conjugated EC-MOF containing copper units with mixed trigonal ligands was developed: Cu3(HHTP)(THQ) (HHTP=2,3,6,7,10,11-hexahydrotriphenylene, THQ=tetrahydroxy-1,4-quinone). The modulated conductivity (σ≈2.53×10−5 S cm−1 with an activation energy of 0.30 eV) and high porosity (ca. 441.2 m2 g−1) of the Cu3(HHTP)(THQ) semiconductive nanowires provided an appropriate resistance baseline and highly accessible areas for the development of an excellent chemiresistive gas sensor. 相似文献
105.
Dirk Schlüter Florian Kleemiss Dr. Malte Fugel Dr. Enno Lork Prof. Dr. Kunihisa Sugimoto PD Dr. Simon Grabowsky Prof. Dr. Jeffrey R. Harmer Dr. Matthias Vogt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(6):1335-1343
Derivatives of 1,2-dithienylethene (DTE) have superb photochromic properties due to an efficient reversible photocyclization reaction of their hexatriene structure and, thus, have application potential in materials for optoelectronics and (multi-responsive) molecular switches. Transition-metal complexes bearing switchable DTE motifs commonly incorporate their coordination site rather distant from the hexatriene system. In this work the redox active ligand 1,2-bis(2,5-dimethylthiophen-3-yl)ethane-1,2-dione is described, which reacts with [V(TMEDA)2Cl2] to give a rare non-oxido vanadium(IV) species 3(M,M/P,P) . This blue complex has two bidentate en-diolato ligands which chelate the VIV center and give rise to two five-membered metallacycles with the adjacent hexatriene DTE backbone bearing axial chirality. Upon irradiation with UVA light or prolonged heating in solution, the blue compound 3(M,M/P,P) converts into the purple atropisomer 4(para,M/para,P) . Both complexes were isolated and structurally characterized by single-crystal X-ray diffraction analysis (using lab source and synchrotron radiation). The antiparallel configuration (M or P helicity) present in both 3(M,M/P,P) and 4(para,M/para,P) is a prerequisite for (reversible) 6π cyclization reactions. A CW EPR spectroscopic study reveals the metalloradical character for 3(M,M/P,P) and 4(para,M/para,P) and indicates dynamic reversible cyclization of the DTE backbone in complex 3(M,M/P,P) at ambient temperature in solution. 相似文献
106.
Ming‐Shui Yao Jia‐Jia Zheng Ai‐Qian Wu Gang Xu Sanjog S. Nagarkar Gen Zhang Masahiko Tsujimoto Shigeyoshi Sakaki Satoshi Horike Kenichi Otake Susumu Kitagawa 《Angewandte Chemie (International ed. in English)》2020,59(1):172-176
Single‐ligand‐based electronically conductive porous coordination polymers/metal–organic frameworks (EC‐PCPs/MOFs) fail to meet the requirements of numerous electronic applications owing to their limited tunability in terms of both conductivity and topology. In this study, a new 2D π‐conjugated EC‐MOF containing copper units with mixed trigonal ligands was developed: Cu3(HHTP)(THQ) (HHTP=2,3,6,7,10,11‐hexahydrotriphenylene, THQ=tetrahydroxy‐1,4‐quinone). The modulated conductivity (σ≈2.53×10?5 S cm?1 with an activation energy of 0.30 eV) and high porosity (ca. 441.2 m2 g?1) of the Cu3(HHTP)(THQ) semiconductive nanowires provided an appropriate resistance baseline and highly accessible areas for the development of an excellent chemiresistive gas sensor. 相似文献
107.
108.
109.
The anthracene–9, 10–bisketene compound 9, 10-dicarbonyl-9, 10–dihydroanthracene (1) was found to react spontaneously with a variety of benzoquinones and benzoquinone diimines to give aromatic polyesters and polyamides, respectively. These addition reactions are regarded as a novel preparative route to polyarylate and polyaramide. 相似文献
110.
The living polymerization of methyl methacrylate with aluminium porphyrin ( 1 ) proceeded dramatically rapidly at room temperature in the presence of sterically crowded organoaluminium compounds such as methylaluminium ortho-substituted diphenolates ( 3a − 3g ), bis(triphenylmethanolate) ( 4a ), and triphenylaluminium, where undesired reaction between the growing species and the Lewis acids was sterically suppressed. On the basis of this Lewis acid - assisted high-speed living polymerization, various monomers such as ethyl, propyl, butyl, and dodecyl methacrylates, methacrylonitrile, and 1,2-epoxypropane were polymerized very rapidly with the aluminium porphyrin - Lewis acid systems. 相似文献