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81.
Tetz Yoshimura 《International Journal of Theoretical Physics》1976,15(5):339-348
Green's function equations are considered for interacting spinor and (pseudo) scalar fields with interactions
. These equations do not determine higher many-point functions if two-point functions are given as “input.” If vertex parts
are given as input, two-point functions are determined but higher many-point functions are not determined. 相似文献
82.
Dr. Yuichi Kobayashi Yuji Takashima Yuuya Motoyama Yukari Isogawa Kyosuke Katagiri Atsuki Tsuboi Dr. Narihito Ogawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(11):3779-3785
The regioselectivity (r.s.) and enantiospecificity (e.s.) of the substitution reactions of secondary propargylic alcohol derivatives using reagents derived from ArMgBr and Cu salts were studied. First, the picolinate, 3-methylpicolinate, and diethylphosphonate derivatives of Ph(CH2)2CH(OH)C≡CTMS were reacted with PhMgBr/CuCN in ratios of 2.5:2.7–2.5:0.25. The use of 2.5:0.25 ratio in THF/DME (6:1) at 0 °C for 1 h afforded the α-substitution product from the phosphate with ≥98 % r.s. and 99 % e.s. CuBr⋅Me2S gave similar selectivity. The reaction system was then applied to phosphates derived from R1CH(OH)C≡CR2 and ArMgBr to obtain synthetically sufficient r.s. and e.s. values with R2=TMS, Ph, whereas iPr was borderline in terms of size as an R1 substituent. The presence of a substituent at the o-position of Ar marginally affected the selectivity. We also found that the use of PhMgBr/Cu(acac)2 in a 2:1 ratio in THF produced the γ-substitution products (allenes) with high r.s. and e.s. 相似文献
83.
Prof. Dr. Tomoaki Tanase Dr. Kanako Nakamae Haruka Miyano Prof. Dr. Yasuyuki Ura Prof. Dr. Yasutaka Kitagawa Dr. Shiho Yada Prof. Dr. Tomokazu Yoshimura Prof. Dr. Takayuki Nakajima 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(47):12078-12103
A series of the octapalladium chains supported by meso-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 (meso-dpmppm) ligands, [Pd8(meso-dpmppm)4(L)2](BF4)4 (L=none ( 1 ), solvents: CH3CN ( 2 a ), dmf ( 2 b ), dmso ( 2 c ), RN≡C: R=Xyl ( 3 a ), Mes ( 3 b ), Dip ( 3 c ), tBu ( 3 d ), Cy ( 3 e ), CH3(CH2)7 ( 3 f ), CH3(CH2)11 ( 3 g ), CH3(CH2)17 ( 3 h )) and [Pd8(meso-dpmppm)4(X)2](BF4)2 (X=Cl ( 4 a ), N3 ( 4 b ), CN ( 4 c ), SCN ( 4 d )), were synthesized by using 2 a as a stable good precursor, and characterized by spectroscopic (IR, 1H and 31P NMR, UV-vis-NIR, ESI-MS) measurements and X-ray crystallographic analyses (for 1 , 2 a , b , 3 a , b , e , f , 4 a – d ). On the basis of DFT calculations on the X-ray determined structure of 2 b ( [2b-Pd8]4+ ) and the optimized models [Pd8(meso-Ph2PCH2P(H)CH2P(H)CH2PH2)4(CH3CN)2]4+ ( [Pd8Ph8]4+ ) and [Pd8(meso-H2PCH2P(H)CH2P(H)CH2PH2)4(CH3CN)2]4+ ( [Pd8H8]4+ ), with and without empirically calculating dispersion force stabilization energy (B3LYP-D3, B3LYP), the formation energy between the two Pd4 fragments is assumed to involve mainly noncovalent interactions (ca. −70 kcal/mol) with four sets of interligand C−H/π interactions and Pd⋅⋅⋅Pd metallophilic one, while electron shared covalent interactions are almost canceled out within the Pd8 chain. All the compounds isolated are stable in solution and exhibit characteristic absorption at ∼900 nm, which is assignable to a spin allowed HOMO to LUMO transition, and shows temperature dependent intensity change with variable absorption coefficients presumably due to coupling with some thermal vibrations. The structures and electronic states of the Pd8 chains are found finely tunable by varying the terminal capping ligands. In particular, theoretical calculations elucidated that the HOMO-LUMO energy gap is systematically related to the central Pd−Pd distance (2.7319(6)–2.7575(6) Å) by two ways with neutral ligands L ( 1 , 2 , 3 ) and with anionic ligands X ( 4 ), which are reflected on the NIR absorption energy of 867–954 nm. The isocyanide terminated Pd8 complexes ( 3 ) further reacted with excess of RNC (6 eq) to afford the Pd4 complexes, [Pd4(meso-dpmppm)2(RNC)2](BF4)2 ( 13 ), and the cyclic voltammograms of 2 a (L=CH3CN), 3 , and 13 (R=Xyl, Mes, tBu, Cy) demonstrated wide range redox behaviors from 2{Pd4}4+ to 2{Pd4}0 through 2{Pd4}2+↔{Pd8}4+, {Pd8}3+, and {Pd8}2+ strings. The oxidized complexes, [Pd4(meso-dpmppm)2(RNC)3](BF4)4 ( 16 ), were characterized by X-ray analyses, and the two-electron reduced chain of [Pd8(meso-dpmppm)4](BF4)2 ( 7 ) was analyzed by spectroscopic and electrochemical techniques and DFT calculations. Reactions of 2 a with 1 equiv. of aromatic linear bisisocyanide (BI) in CH2Cl2 deposited insoluble coordination polymers, {[Pd8(meso-dpmppm)4(BI)](BF4)4}n ( 5 ), and interestingly, they were soluble in acetonitrile, 31P{1H} and 1H DOSY NMR spectra as well as SAXS curves suggesting that the coordination polymers may exist in acetonitrile as dynamically 1D self-assembled coordination polymers comprising ca. 50 units of the Pd8 rod averaged within the timescale. 相似文献
84.
Yusuke Yoshimura Ryuichiro Hibi Akiho Nakata Moeka Togashi Shoujiro Ogawa Takayuki Ishige Mamoru Satoh Fumio Nomura Tatsuya Higashi 《Biomedical chromatography : BMC》2019,33(7)
A liquid chromatography/electrospray ionization–tandem mass spectrometry‐based method was developed for the identification of the conjugation positions of the monoglucuronides of 25‐hydroxyvitamin D3 [25(OH)D3] and 24,25‐dihydroxyvitamin D3 [24,25(OH)2D3] in human urine. The method employed derivatization with 4‐(4‐dimethylaminophenyl)‐1,2,4‐triazoline‐3,5‐dione to convert the glucuronides into fragmentable derivatives, which provided useful product ions for identifying the conjugation positions during the MS/MS. The derivatization also enhanced the assay sensitivity and specificity for urine sample analysis. The positional isomeric monoglucuronides, 25(OH)D3‐3‐ and ‐25‐glucuronides, or 24,25(OH)2D3‐3‐, ‐24‐ and ‐25‐glucuronides, were completely separated from each other under the optimized LC conditions. Using this method, the conjugation positions were successfully determined to be the C3 and C24 positions for the glucuronidated 25(OH)D3 and 24,25(OH)2D3, respectively. The 3‐glucuronide was not present for 24,25(OH)2D3, unlike 25(OH)D3, thus we found that selective glucuronidation occurs at the C24‐hydroxy group for 24,25(OH)2D3. 相似文献
85.
Dr. Teng Zhang Dr. Yuichi Kitagawa Ryoma Moriake Pedro Paulo Ferreira da Rosa Dr. Md. Jahidul Islam Dr. Tomoki Yoneda Prof. Yasuhide Inokuma Dr. Koji Fushimi Prof. Yasuchika Hasegawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(58):14438-14443
In this study, we have demonstrated a two-legged, upright molecular design method for monochromatic and bright red luminescent LnIII-silica nanomaterials. A novel EuIII-silica hybrid nanoparticle was developed by using a doubly binding TPPO−Si(OEt)3 (TPPO: triphenyl phosphine oxide) linker. The TPPO−Si(OEt)3 was confirmed by 1H, 31P, 29Si NMR spectroscopy and single-crystal X-ray analysis. Luminescent Eu(hfa)3 and Eu(tfc)3 moieties (hfa: hexafluoroacetylacetonate, tfc: 3-(trifluoromethylhydroxymethylene)camphorate) were fixed onto TPPO−Si(OEt)3-modified silica nanoparticles, producing Eu(hfa)3(TPPO−Si)2-SiO2 and Eu(tfc)3(TPPO−Si)2-SiO2, respectively. Eu(hfa)3(TPPO−Si)2−SiO2 exhibited the higher intrinsic luminescence quantum yield (93 %) and longer emission lifetime (0.98 ms), which is much larger than those of previously reported EuIII-based hybrid materials. Eu(tfc)3(TPPO−Si)2−SiO2 showed an extra-large intrinsic emission quantum yield (54 %), although the emission quantum yield for the precursor Eu(tfc)3(TPPO−Si(OEt)3)2 was found to be 39 %. These results confirmed that the TPPO−Si(OEt)3 linker is a promising candidate for development of EuIII-based luminescent materials. 相似文献
86.
Yuichi Mori Kosei Nakaya Xianqing Piao Kazuhiro Yamamoto Akira Otomo Shiyoshi Yokoyama 《Journal of polymer science. Part A, Polymer chemistry》2012,50(7):1254-1260
A methacrylate‐based crosslinking hyperbranced polymers have been synthesized through initiator‐fragment incorporation radical polymerization and used for the temperature stable electro‐optic (EO) polymer application. This polymer consists of methyl methacrylate, 2‐metacryloxyethyl isocyanate, and ethylene glycol dimethacrylate (EGDMA) monomers. The use of EGDMA as a bifunctional unit resulted in the solvent‐soluble crosslinking hyperbranched chain, so that the EO polymer enhanced glass transition temperatures. A phenyl vinylene thiophene vinylene bridge nonlinear optical chromophore was attached to the polymer backbone as the side‐chain by a post‐functionalization reaction. The loading concentration of the chromophore was varied between 30 and 50 wt % by simply changing the mixing ratio of the precursor polymer to the chromophore. The synthesized EO polymers produced optical quality films with a light propagation loss of 0.61 dB/cm in a slab waveguide at 1.31 μm. The electrically poled film had an EO coefficient (r33) of 139 pm/V at 1.31 μm. The EO crosslinking hyperbranced polymer had a high‐glass transition temperature of 170 °C, and exhibited excellent temporal stability of the EO activity at 85 °C for 500 h. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
87.
88.
Yuichi Tominaga Takuya Kubo Kenji Sueyoshi Ken Hosoya Koji Otsuka 《Journal of polymer science. Part A, Polymer chemistry》2013,51(15):3153-3158
To synthesize the novel molecular‐ and pH‐stimulus‐responsive hydrogel, we prepared poly(ethylene glycol)‐based hydrogel containing ionic groups. We evaluated the fundamental swelling/shrinking properties of the hydrogels synthesized by various conditions. Decreasing the molecular weight of a crosslinker provided the increasing of the equilibrium swelling ratio. Also, the equilibrium swelling ratio was changed by the introduction of functional ionic monomers and its compositions. Furthermore, the swelling/shrinking behaviors of the hydrogels were affected by the environmental condition of aqueous solution, in fact the hydrogels were considerably shrunk (to one‐fifth volume) using a di‐ionic solute in the aqueous solution through the ionic interactions between the hydrogel and the solutes. Additionally, the specific shrinking to diamine compounds was also observed in response to pH change. These results clearly show the swelling/shrinking responsibility of the hydrogels toward the molecular recognitions and its pH conditions. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3153–3158 相似文献
89.
Dr. Chunlin Chen Prof. Zhongchang Wang Dr. Mitsuhiro Saito Dr. Tetsuya Tohei Prof. Yoshiro Takano Prof. Yuichi Ikuhara 《Angewandte Chemie (International ed. in English)》2014,53(6):1543-1547
Atomic‐resolution imaging of beam‐sensitive biominerals is extremely challenging, owing to their fairly complex structures and the damage caused by electron irradiation. Herein, we overcome these difficulties by performing aberration‐corrected electron microscopy with low‐dose imaging techniques, and report the successful direct atomic‐resolution imaging of every individual atomic column in the complex fluorapatite structure of shark tooth enameloid, which can be of paramount importance for teeth in general. We demonstrate that every individual atomic column in shark tooth enameloid can be spatially resolved, and has a complex fluorapatite structure. Furthermore, ab initio calculations show that fluorine atoms can be covalently bound to the surrounding calcium atoms, which improves understanding of their caries‐reducing effects in shark teeth. 相似文献
90.
Nobutaka Yoshimura Dr. Atsushi Kobayashi Dr. Masaki Yoshida Prof. Masako Kato 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(70):16939-16946
To investigate the effect of the surface structure of dye-sensitized photocatalyst nanoparticles, we prepared three types of RuII-photosensitizer (PS)-double-layered Pt-cocatalyst-loaded TiO2 nanoparticles with different surface structures, Zr- RuCP6 -Zr- RuP6 @N wt %Pt-TiO2, RuCP6 -Zr- RuP6 @N wt %Pt-TiO2, and RuCP2 -Zr- RuP6 @N wt %Pt-TiO2 (N=0.2, 1, and 5), and evaluated their photocatalytic H2 evolution activity in the presence of redox-reversible iodide as the electron donor. Although the driving force of the electron injection from I− to the photo-oxidized RuIII PS is comparable, the activity increased in the following order: RuCP2 -Zr- RuP6 @1 wt %Pt-TiO2 < RuCP6 -Zr- RuP6 @1 wt %Pt-TiO2 < Zr- RuCP6 -Zr- RuP6 @1 wt %Pt-TiO2. The apparent quantum yield of Zr- RuCP6 -Zr- RuP6 @1 wt %Pt-TiO2 in the first hour reached 1 %. Zeta-potential measurements suggest that the surface Zr4+-phosphate groups attracted I− anions to the nanoparticle–solution interface. Our results indicate that the surface modification of dye-sensitized photocatalysts is a promising approach to enhance photocatalytic activity with various redox mediators. 相似文献