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341.
Catalytic hydrogenations of olefins took place effectively in supercritical CO2 with Pd0 nanoparticles dispersed in the fluid phase using a water-in-CO2 microemulsion consisting of water, sodium bis(2-ethylhexyl) sulfosuccinate (AOT) as a surfactant, and 1-octanol as a cosolvent. The hydrogenated products dissolved in supercritical CO2 can be separated from the octanol solution containing AOT microemulsions with Pd0 nanoparticles by phase separation (upper phase, supercritical CO2 with hydrogenated products; lower phase, 1-octanol containing AOT microemulsions with Pd0 nanoparticles) accompanied by reduction of CO2 pressure. After collecting the hydrogenated products by flowing the upper CO2 phase to a collection vessel, the Pd0 nanoparticles remaining in the lower phase can be redispersed into supercritical CO2 by pressurizing the system to a pressure where a homogeneous phase is attained. The redispersed nanoparticles can be reused as catalysts for the next runs of the hydrogenations. Triphenylethylene was hydrogenated to 1,1,2-triphenylethane at conversions of 100% (1st-3rd runs), >99% (4th run), and >96% (5th run) using the recycled Pd0 nanoparticles. The feasibility of using other organic solvents as cosolvents is also studied in the present paper. 相似文献
342.
343.
The first total synthesis of (+/-)-psychotrimine, a novel trimeric indole alkaloid isolated from Psychotria rostrata, was achieved. In the total synthesis, the copper-mediated intramolecular and intermolecular aminations of halobenzenes, which respectively contributed to the construction of a pyrrolidinoindoline core and the installation of a third tryptamine unit, were used as key steps. 相似文献
344.
Protonation and ion exchange equilibria of weak base anion-exchange resins, in which tertiary amine moieties were introduced as a functional group, were investigated by applying NMR spectroscopy to species adsorbed into the resins. 31P NMR signals of the phosphinate ion in the resin phases shifted to a lower field due to the influence of protonation of the tertiary amine groups of the resins in the pH range of 4-10. Protonation constants of the tertiary amine groups in styrene-divinylbenzene (DVB)-based resins were estimated to be KH = 106.4 for Amberlite IRA96 and 106.5 for DIAION WA30 by the 31P NMR method using the phosphinate ion as a probe species. In addition to the low field shift caused by the protonation of the tertiary amine moieties, another low field shift was observed for the phosphinate ion in acrylic acid-DVB-based resins at a rather high pH. This shift should be due to an unexpected deprotonation in the acrylic resin: a tautomerism accompanying the proton release from the amide form to the imide one in the functional group, thus, the resin could exhibit a cation exchange property at the high pH. Protonation constants of the tertiary amine moieties in the acrylic resins were estimated to be 108.8 for DIAION WA10, 109.0 for Amberlite IRA67 and 109.3 for Bio-Rad AG 4-X4 on the basis of the Henderson-Hasselbalch equation using the resin phase pH estimated by the 133Cs and 1H NMR signal intensities. 相似文献
345.
Nakatake H Ekimoto H Aso M Ogawa A Yamaguchi A Suemune H 《Chemical & pharmaceutical bulletin》2011,59(6):710-713
Bisphosphonates have high affinity for hydroxyapatite (HA), which is abundantly present in bone. Also, platinum complexes are known that have a wide spectrum of antitumor activities. The conjugate of bisphosphonate and a platinum complex might have HA affinity and antitumor activity, and become a drug for metastatic bone tumor. In this study, the authors synthesized platinum complexes that had dialkyl bisphosphonic acid as a ligand, and evaluated the possibility of the synthesized complexes as a drug for metastatic bone tumor. The synthesized dialkyl bisphosphonate platinum(II) complex was characterized, and its stability in an aqueous solution was also confirmed. The synthesized platinum complex showed higher HA affinity than other platinum complexes such as cisplatin and carboplatin in an experiment of adsorption to HA. In vitro, the platinum complex showed tumor growth inhibitory effect stronger than or equal to cisplatin, which is the most commonly used antitumor agent. Moreover, the platinum complex showed a bone absorption inhibitory effect on the osteoclast. These results suggest potential of dialkyl bisphosphonate platinum(II) complexes as a drug for metastatic bone tumor. 相似文献
346.
In order to determine the effect of functional structure of ester groups on the stereoregularity of polymers, polymerization of N-[btilde]-methacryloyloxyethyl type monomers containing nucleic acid bases was made by using a free-radical initiator. From the NMR spectrometric determination of the stereoregularity of the polymers obtained, it was found that for polymerization of the monomer with adenine as the side group in dimethyl sulfoxide solution, syndiotactic placement appears to be favored by the additional enthalpy of activation required for isotactic placement. 相似文献
347.
Tran Hang Thi Michiya Matsusaki Hiroshi Hirano Hiroaki Kawano Yasuyuki Agari Mitsuru Akashi 《Journal of polymer science. Part A, Polymer chemistry》2011,49(14):3152-3162
In previous report, we discovered that a novel improvement technique to enhance the thermal properties of poly(L ‐lactide)s (PLLAs) by terminal conjugation with 3,4‐diacetoxycinnamic acid (DACA). In this study, we clarified the mechanism of the enhancement of thermal stability by using commercial polyesters and polyethers. The effect of thermal improvement by the terminal conjugation of DACA on poly(DL ‐lactide), poly(ε‐caprolactone), and poly(ethylene glycol) was almost the same as about 100 °C increase. The amount of residual tin catalyst, which enhances the thermal degradation of polyesters, was reduced at undetected level after the terminal conjugation of DACA probably due to the removal of tin during DACA conjugation process. Furthermore, the π‐π stacking interactions of DACA units and the chemical protection of terminal hydroxyl groups, which enhances intramolecular scission, were also important for the high thermal stability. We clarified that the extreme high thermal stability by DACA conjugation was induced by these above mechanisms. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
348.
Kentaro Wada Noriyuki Kogure Mariko Kitajima Hiromitsu Takayama 《Tetrahedron letters》2019,60(2):187-190
The shortest asymmetric total synthesis of lycopodine (3) and the first asymmetric total synthesis of flabelliformine (4) were accomplished by a strategy that features a cascade cyclization of linear substrate (5) to construct tetracyclic structure (6). 相似文献
349.
Masahiro Suzuki Mariko Yumoto Mutsumi Kimura Hirofusa Shirai Kenji Hanabusa 《Helvetica chimica acta》2003,86(6):2228-2238
Low‐molecular‐weight compounds based on L ‐lysine with alkylpyridinium or ‐imidazolium groups have been synthesized and studied for their gelation behavior in H2O. Most compounds formed gels below a concentration of 2.5 weight‐%, the pyridinium bromide 2a and the 1‐methyl‐1H‐imidazolium bromide 3 even at 0.1 weight‐%. The minimum gel concentration (MGC) necessary for hydrogelation increased with increasing length of the Lys Nα‐alkanoyl chain, but the gelation ability concomitantly decreased. Electron‐microscopic images demonstrated that these hydrogelators create a three‐dimensional network in H2O by entanglement of self‐assembled nanofibers. A fluorescence study with 8‐anilinonaphthalene‐1‐sulfonic acid (ANS) proved that some hydrophobic aggregates are formed at hydrogelator concentrations below an MGC of less than 50 μM (0.004%). FT‐IR, 1H‐NMR, and Fluorescence studies indicated that the driving forces for the self‐assembly into nanofibers are mainly hydrophobic interactions and H‐bonding between amide groups. 相似文献
350.
Mariko F. Matsuura Hyo-Joong Kim Daisuke Takahashi Khalil A. Abboud Steven A. Benner 《Acta Crystallographica. Section C, Structural Chemistry》2016,72(12):952-959
Reported here is the crystal structure of a heterocycle that implements a donor–donor–acceptor hydrogen‐bonding pattern, as found in the Z component [6‐amino‐5‐nitropyridin‐2(1H)‐one] of an artificially expanded genetic information system (AEGIS). AEGIS is a new form of DNA from synthetic biology that has six replicable nucleotides, rather than the four found in natural DNA. Remarkably, Z crystallizes from water as a 1:1 complex of its neutral and deprotonated forms, and forms a `skinny' pyrimidine–pyrimidine pair in this structure. The pair resembles the known intercalated cytosine pair. The formation of the same pair in two different salts, namely poly[[aqua(μ6‐2‐amino‐6‐oxo‐3‐nitro‐1,6‐dihydropyridin‐1‐ido)sodium]–6‐amino‐5‐nitropyridin‐2(1H)‐one–water (1/1/1)], denoted Z‐Sod, {[Na(C5H4N3O3)(H2O)]·C5H5N3O3·H2O}n, and ammonium 2‐amino‐6‐oxo‐3‐nitro‐1,6‐dihydropyridin‐1‐ide–6‐amino‐5‐nitropyridin‐2(1H)‐one–water (1/1/1), denoted Z‐Am, NH4+·C5H4N3O3−·C5H5N3O3·H2O, under two different crystallization conditions suggests that the pair is especially stable. Implications of this structure for the use of this heterocycle in artificial DNA are discussed. 相似文献