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771.
A Cell‐Targeted Non‐Cytotoxic Fluorescent Nanogel Thermometer Created with an Imidazolium‐Containing Cationic Radical Initiator 下载免费PDF全文
Dr. Seiichi Uchiyama Dr. Toshikazu Tsuji Kyoko Kawamoto Dr. Kentaro Okano Eiko Fukatsu Takahiro Noro Kumiko Ikado Sayuri Yamada Yuka Shibata Dr. Teruyuki Hayashi Dr. Noriko Inada Dr. Masaru Kato Dr. Hideki Koizumi Prof. Hidetoshi Tokuyama 《Angewandte Chemie (International ed. in English)》2018,57(19):5413-5417
A cationic fluorescent nanogel thermometer based on thermo‐responsive N‐isopropylacrylamide and environment‐sensitive benzothiadiazole was developed with a new azo compound bearing imidazolium rings as the first cationic radical initiator. This cationic fluorescent nanogel thermometer showed an excellent ability to enter live mammalian cells in a short incubation period (10 min), a high sensitivity to temperature variations in live cells (temperature resolution of 0.02–0.84 °C in the range 20–40 °C), and remarkable non‐cytotoxicity, which permitted ordinary cell proliferation and even differentiation of primary cultured cells. 相似文献
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The analytic expression for the weight‐average molecular weight development in free‐radical polymerization that involves a polyfunctional chain‐transfer agent is proposed. Free‐radical polymerization is kinetically controlled; therefore, the probability of chain connection with a polyfunctional chain‐transfer agent as well as the primary chain‐length distribution changes during the course of polymerization. We consider the primary chains formed at different times as different types of chains, and the heterochain branching model is used to obtain the weight‐average chain length at a given conversion level in a matrix formula, described as Pw = W { D w + ( I + T ) SP ( I – TSP )–1 Df }. Because the primary chains are formed consecutively, the number of chain types N is extrapolated to infinity, but such extrapolation can be conducted with the calculated values for only three different N values. The criterion for the onset of gelation is simply described as a point at which the largest eigenvalue of the product of matrixes, TSP reaches unity, i. e., det ( I – TSP ) = 0. The present model can readily be extended for the star‐shaped polyfunctional initiators, and the relationships between the model parameters and kinetic rate expression for such reaction systems are also shown. 相似文献
776.
Aimin Huang Guanguang Xia Franz-Josef Spiess Xiao Chen Jeffery Rozak Steven L. Suib Tomonori Takahashi Yuji Hayashi Hiroshige Matsumoto 《Research on Chemical Intermediates》2001,27(9):957-974
Decomposition of CF4 by glow-discharge and arc plasmas was studied using a tubular quartz reactor, a disk type, and a T-type quartz reactor. The effects of different metal electrodes, input voltage, and reactor type on the efficiency of CF4 total destruction (DRE) were studied. The T-shape reactor was more efficient in CF4 destruction than either the disk or tubular type due to a combined effect of glow discharge and arc plasmas. Several hydrogen and oxygen sources, such as H2O, H2, O2, and CH4, were used to convert CF4. Using H2 and O2 as the hydrogen and oxygen sources presented better DRE than using H2O. The effect of different hydrogen and oxygen sources on the conversion of CF4 followed the trend: (H2 + O2) > (CH4 + O2) > H2O. The maximum DRE of 95% was observed with 0.5% CF4 using H2 and O2. A mass spectrometer and an emission spectroscope equipped with a charge-coupled detector (CCD) were used to characterize the products and intermediates. Mass spectrometric studies indicated that the reaction products were HF, CO2, and trace amounts of NO. N2 first negative and second positive emission lines were observed in the glow discharge plasmas as well as in the arc plasmas of N2. However, C and F intermediates were observed only in arc plasmas of CF4. Reactions occurring in the glow discharge plasmas and arcs seem to follow different mechanisms. 相似文献
777.
Mikata Y Mizukami K Hayashi K Matsumoto S Yano S Yamazaki N Ohno A 《The Journal of organic chemistry》2001,66(5):1590-1599
Precursors of NAD model compounds 1c and 3a,b were successfully resolved into their atropisomers with respect to carbamoyl rotation. Atropisomers of quinoline derivatives are much more stable than pyridine derivatives as determined by cyclic voltammetry and X-ray crystallography. The 1,4-reduction of NAD model compound 4 was successfully achieved, affording novel NADH model compound 5. The rotational properties of the side chain of 5 were investigated by means of dynamic NMR. The rotational rate and syn/anti ratio, which indicate the orientation between carbonyl oxygen and hydrogen at the 4-position, are significantly affected by addition of magnesium ion. In the rotational transition state, the double-bond character of the C(carbonyl)-N(amide) bond is disrupted judging from the activation parameters. The oxidation of chiral 5 with p-benzoquinone in the presence of magnesium ion catalyst gave predominantly one enantiomer of 4. On the other hand, oxidation of 5 with p-chloranil (tetrachloro-p-benzoquinone) in the absence of magnesium ions affords the opposite enantiomer of 4 as the major product. The product enantiomer ratio is parallel to the syn/anti ratio in the starting material, indicating the importance of ground state conformation to stereochemistry of the reaction. 相似文献
778.
Bagasse, corn husk, and switchgrass were pretreated with ammonia water to enhance enzymatic hydrolysis. The sample (2 g) was
mixed with 1–6 mL ammonia water (25–28% ammonia) and autoclaved at 120°C for 20 min. After treatment, the product was vacuum-dried
to remove ammonia gas. The dried solid could be used immediately in the enzymatic hydrolysis without washing. The enzymatic
hydrolysis was effectively improved with more than 0.5 and 1 mL ammonia water/g for corn husk and bagasse, respectively. In
bagasse, glucose, xylose, and xylobiose were the main products. The adsorption of CMCase and xylanase was related to the initial
rate of enzymatic hydrolysis. In corn husks, arabinoxylan extracted by pretreatment was substantially unhydrolyzed because
of the high ratio of arabinose to xylose (0.6). The carbohydrate yields from cellulose and hemicellulose were 72.9% and 82.4%
in bagasse, and 86.2% and 91.9% in corn husk, respectively. The ammonia/water pretreatment also benefited from switchgrass
(Miscanthus sinensis and Solidago altissima L.) hydrolysis. 相似文献
779.
Ryosuke Matsubara Yuki Katsuragi Takaya Sakaguchi Shuhei Eguchi Masahiko Hayashi Akihiro Ando 《Tetrahedron》2018,74(27):3642-3651
Furoxans are distinctive heteroaromatic compounds in that they are potentially capable of releasing nitric oxide under physiological conditions. In order to utilize the furoxan scaffold for the development of functional molecules, synthetically relevant functional groups are required for access to diverse furoxans. In this report, a facile route to furoxans with sulfonyloxy groups, which are halide surrogates, has been developed. The key features of this strategy include the synthesis and utilization of bench-stable hydroxyfuroxan salts, the use of sulfonyl anhydrides in the sulfonylation step instead of sulfonyl chlorides, and the photochemical isomerization of one regioisomer to another in order to gain access to both. 相似文献
780.
Catalytic asymmetric 1,4-addition (conjugate addition; Michael addition) is one of the most powerful methods for carbon-carbon bond formation. Following the first efficient catalyst system developed by Feringa, which is composed of Cu(OTf)2 and phosphoramidite with dialkylzincs, a variety of chiral catalysts have been reported for the catalytic asymmetric conjugate addition. In this digest review, we will first summarize novel chiral ligands that work efficiently for cyclic and acyclic enones and demonstrate the wide applicability of Michael acceptors. We will also introduce unique phenomena that include the nonlinear effect and reversal of enantioselectivity. Organomagnesium reagents have also been used instead of organozincs. Finally, we introduce the recent examples of the synthesis of natural products based on the catalytic asymmetric reaction. The rare experimental studies into the mechanism of copper-catalyzed 1,4-addition reported by Kitamura and Noyori’s group are also introduced. 相似文献