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41.
Excited state intramolecular hydrogen atom transfer of phenylethynyl-substituted 2′-hydroxychalcones
Satomi Tasaki Atsuya Momotake Yoko Kanna Tatsuo Arai 《Research on Chemical Intermediates》2013,39(1):61-72
(E)-1-[2-Hydroxy-4-(phenylethynyl)phenyl]-3-[4-(phenylethynyl)phenyl]prop-2-en-1-one (1), (E)-1-[2-hydroxy-4-(phenylethynyl)phenyl]-3-phenylprop-2-en-1-one (2), and (E)-1-(2-hydroxyphenyl)-3-[4-(phenylethynyl)phenyl]prop-2-en-1-one (3), which belong to a new class of 2′-hydroxychalcones with phenylethynyl group(s) at the para position of the phenyl ring, were synthesized, and their photochemical properties were investigated. The lowest energy absorption band of 1 peaks at a longer wavelength (383 nm) with a much larger molar extinction coefficient (5.0 × 104 M ?1 cm?1) than that of the parent 2′-hydroxychalcone (2′HC) (2.0 × 104 M ?1 cm?1 at 318 nm). Upon photoexcitation, all three compounds underwent excited-state intramolecular hydrogen atom transfer (ESIHT) to produce an excited tautomer that emitted fluorescence with a large Stokes shift in the longer wavelength region at 600–700 nm. The quantum yield of the tautomer fluorescence of 1 was not high at 298 K (Φ f = 9.1 × 10?5), but was highest among 2′HC and its analogues. The Φ f values of 1–3 increased 10–30 fold upon reducing the temperature from 298 to 77 K. 相似文献
42.
Neomacrophorins I (1), II (2), and III (3) were isolated from the culture broth of Trichoderma sp. 1212-03, which was collected at Shirakami Mountainous area in Japan. Structural analyses disclosed that these resemble known macrophorins but possess axial-hydroxy group at C3 as well as different side chains at C7′. These are diastereomeric forms of macrophorins for 5′,6′-epoxide functionality. The NMR analyses suggested their relative configurational relationship between the C1–C15 drimene and C1′–C7′ epoxyquinone moieties. ECD spectral discussions verified them particularly for C5′,C6′-epoxyquinone (1), C5′,C6′-epoxysemiquinone (2 and 3), and 2″,3″-dihydroxybutanoate moiety in 1 and 2. The configuration of C3″-stereocenter of 3 was determined by chiral GC–MS after converting into methyl (S)-3″-hydroxybutanoate by basic of 3 methanolysis. Biological assays disclosed that 1 induces hyphal branching of Cochliobolus miyabeanus as well as cytotoxicity against human colorectal cancer COLO 201. 相似文献
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We investigated the fluorescent properties, including the excited-state intermolecular proton transfer, of urea derivatives comprising a coumarin ring, which is a widely used fluorophore. We prepared two different coumarin–urea derivatives, 6CU and 7CU, which bear a urea-based substituent at the 6 and 7 positions of a coumarin ring, respectively. In the presence of the acetate ion, 7CU showed additional tautomer fluorescence emission with respect to 6CU, indicating that tautomer formation depends on the positions of the urea-based substituent on the coumarin ring. Thus, the resonance structures of urea derivatives might play an important role in the behavior of dual fluorescence, which is an important phenomenon applicable to photochemical anion sensing. Moreover, in order to further improve the fluorescence properties of the mentioned derivatives, a CF3 group was introduced in a phenyl ring opposite to a coumarin ring. The fluorescence quantum yield of 7CUCF3 thus synthesized was 65 times as large as that of 7CU, an observation that renders 7CUCF3 a suitable anion sensor candidate. The results of this study will contribute to the development of new molecular designs for highly fluorescent sensing. 相似文献
45.
Takaishi T Sagawa A Nagakura K Maeda T 《The Journal of the Acoustical Society of America》2002,111(6):2601-2608
As the maximum speed of high speed trains increases, the effect of aeroacoustic noise on the sound level on the ground becomes increasingly important. In this paper, the distribution of dipole sound sources at the bogie section of high speed trains is predicted numerically. The three-dimensional unsteady flow around a train is solved by the large eddy simulation technique. The time history of vortices shows that unstable shear layer separation at the leading edge of the bogie section sheds vortices periodically. These vortices travel downstream while growing to finally impinge upon the trailing edge of the section. The wavelength of sound produced by these vortices is large compared to the representative length of the bogie section, so that the source region can be regarded as acoustically compact. Thus a compact Green's function adapted to the shape can be used to determine the sound. By coupling the instantaneous flow properties with the compact Green's function, the distribution of dipole sources is obtained. The results reveal a strong dipole source at the trailing edge of the bogie section where the shape changes greatly and the variation of flow with time is also great. On the other hand, the bottom of the bogie section where the shape does not change, or the leading edge and boundary layer where the variation of flow with time is small, cannot generate a strong dipole source. 相似文献
46.
Utilization of a metalloligand, ([Cu(2,4-pydca)2(H2O)].2Et3NH) (1) (2,4-pydca = pyridine-2,4-dicarboxylate), as a building unit provides a novel porous coordination polymer, ([ZnCu(2,4-pydca)2(H2O)3(DMF)].DMF)n (2), in which the Zn(II) ion at the node of the network acts as a linker and the Cu(II) ion in the channel wall is available for guest-coordination. 相似文献
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The regioselective ring-opening reaction of α-methyl-β-propiolactone with 3,3-ethylene-dioxybutylmagnesium bromide in the presence of copper(I) catalyst afforded 2-methyl-6-oxoheptanoic acid, which was easily converted into (E)-3,7-dimethyl-2-2-octene-1,8-diol in good yield. 相似文献
50.
Yasuhiro Sanada Tatsuo Akiyama Yusuke Ujihira Eiji Niki 《Fresenius' Journal of Analytical Chemistry》1982,312(6):526-529
Summary Sodium ion-selective electrodes (Na+-ISE) were prepared by implanting Si+ and Li+ into alumina wafers and their characteristics were investigated. The alumina wafer had a thickness of 100 m and a diameter of 1.40 cm. The ionselective membrane was produced by ion-implanting of Li+ and Si+ on both sides of a single-crystal alumina wafer. The total doses of Li+ and Si+ were controlled to be the same, viz. 1013–1015 ions/cm2. The ion-implanted alumina wafer with 1014 or 4×1014 ions/cm2 of Li+ and Si+ showed better characteristics than the others.The response curves of the 1014 ions/cm2 implanted alumina wafer had a slope of 42 mV/pNa in a concentration range from 1–10–4mol/l. The full response achieved after about 1 min was reproducible. The proposed idea of producing Na+-ISE by ion-implantation technique was applied to functuate the gate surface of the field effect transitor to sodium ion. The sodium ion-sensitive FET (Na+-ISFET) prepared by implanting Li+ and Al+ at a dose of 5×1014 ions/cm2 showed a slope of 30 mV/pNa in a concentration range from 1–10–4mol/l.
Herstellung Na+-ionenselektiver Elektroden durch Einbau von Lithium und Silicium in Einkristall-Alumniumoxidblättchen und Anwendung zur Erzeugung von ISFET
Zusammenfassung Na+-selektive Elektroden wurden durch Einbau von Si+ und Li+ in Aluminiumoxidblättchen hergestellt und ihre Charakteristiken untersucht. Die Blättchen hatten eine Dicke von 100 m und einen Durchmesser von 1,40 cm. Ebenso wurde die Membran für einen ISFET hergestellt. Die Gesamtmenge von Li+ und Si+ wurde auf 1013–1015 Ionen/cm2 eingestellt, wobei sich bei 1014 oder 4×1014 Ionen/cm2 die beste Charakteristik ergab.Die Responsekurven der mit 1014 Ionen/cm2 versehenen Aluminiumoxidplättchen hatten eine Neigung von 42 mV/pNa in einem Konzentrationsbereich von 1–10–4mol/l. Der nach 1 min erhaltene volle Response war reproduzierbar. Die vorgeschlagene Technik wurde zur Einstellung der Gate-Oberfläche des Feldeffekt-Transistors auf Natriumion benutzt. Der Na+-sensitive FET (Na+-ISFET), der durch Einbau von Li+ und Al+ mit 5×1014 Ionen/cm2 hergestellt wurde, zeigte eine Neigung der Signalkurve von 30 mV/pNa in einem Bereich von 1–10–4mol/l.相似文献