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1.
The three new lignanoids 1 – 3 and the five new phyllocladane diterpenoids 7 – 11 were isolated from the leaves of Callicarpa furfuraceae, together with two known lignanoids, lariciresinol ( 4 ) and (+)‐sesamin ( 5 ), and five known diterpenoids, 17‐norphyllocladane‐3,16‐dion ( 6 ), calliterpenone ( 12 ), calliterpenone 17‐acetate ( 13 ), (3β,16α)‐phyllocladane‐3,16,17‐triol ( 14 ), and (3β,16α)‐phyllocladane‐3,16,17‐triol 17‐acetate ( 15 ). Their structures were established by spectral‐data interpretation. 相似文献
2.
3.
A concept of fluorescent metal ion sensing with an easily tunable emission wavelength is presented and its principle demonstrated by detection of Cu(2+). A fluorescein dye was chemically modified with a metal chelating group and then attached to the terminus of ss-DNA. This was combined with a complementary ss-DNA modified with another fluorescent dye (ATTO 590), emitting at a longer wavelength. In the assembled duplex, fluorescence resonance energy transfer (FRET) between the fluorescein donor (excited at 470 nm) and the ATTO 590 acceptor (emitting at 624 nm) is observed. Proper positioning within the rigid DNA double helix prevents intramolecular contact quenching of the two dyes. Coordination of paramagnetic Cu(2+) ions by the chelating unit of the sensor results in direct fluorescence quenching of the fluorescein dye and indirect (by loss of FRET) quenching of the ATTO 590 emission at 624 nm. As a result, emission of the acceptor dye can be used for monitoring of the concentration of Cu(2+), with a 20 nM detection limit. The emission wavelength is readily tuned by replacement of ATTO-DNA by other commercially available DNA-acceptor dye conjugates. Fluorescent metal ion sensors emitting at >600 nm are very rare. The possibility of tuning the emission wavelength is important with respect to the optimization of this sensor type for application to biological samples, which usually show broad autofluorescence at <550 nm. 相似文献
4.
The structure of [(CF3N2NMe)Mo(CH2SiMe3)2] (in which (CF3N2NMe)2? is [(3‐CF3C6H4NCH2CH2)2NMe]2?) is approximately trigonal bipyramidal with one axial and one equatorial alkyl ligand. Heating of solutions of [(CF3N2NMe)Mo(CH2SiMe3)2] in [D6]benzene in the presence of five equivalents of 2‐butyne led to diamagnetic [(CF3N2NMe)Mo(CHSiMe3)(η2‐MeC?CMe)], whose structure is approximately square pyramidal with the alkyne occupying the axial site. Addition of one equivalent of cyclohexene sulfide to [(CF3N2NMe)Mo(CH2SiMe3)2] at room temperature produced the diamagnetic, dimeric molybdenum(IV) sulfido complex, [{(CF3N2NMe)MoS}2]. This complex is composed of two approximately trigonal bipyramidal centers, each containing one axial and one equatorial sulfur atom. Oxidation of [(CF3N2NMe)Mo(CH2SiMe3)2] with hexachloroethane resulted in formation of tetramethylsilane, HCl, and the sparingly soluble, red alkylidyne complex, [{(CF3N2NMe)Mo(CSiMe3)Cl}2]. This complex forms a dimer through bridging chlorides. The oxidation reactions of [(CF3N2NMe)Mo(CH2SiMe3)2] with 2‐butyne, cyclohexene sulfide, or C2Cl6 are all proposed to proceed by α‐hydrogen abstraction in the MoVI species to yield (initially) the Mo?CHSiMe3 species and tetramethylsilane. 相似文献
5.
Shuhui Yu Kui Yao Francis Eng Hock Tay 《Journal of Sol-Gel Science and Technology》2007,42(3):357-364
The preferential formation of a pyrochlore structure is a knotty problem in the preparation of Pb(Zn1/3Nb2/3)O3 (PZN)-based thin film materials and its presence is significantly detrimental to the dielectric and piezoelectric properties.
In this study, 40 mol% of PZN was replaced with Pb(Mg1/3Nb2/3)O3 (PMN) for obtaining a perovskite composition around a morphotropic phase boundary (MPB), (1−x)(0.6PZN-0.4PMN)-xPT ((1−x)PZMN-xPT, PT: PbTiO3) where x = 0.23. The thin films with this composition were prepared with a polyethylene glycol (PEG) modi-fied sol-gel method on LaAlO3 substrates. The microstructural evolution of the films on heat treatment was examined with X-ray diffraction. With the aid
of PEG, the formation of the pyrochlore phase was suppressed and the perovskite phase formed directly from the amorphous gel
film. The multilayer films with a thickness around 0.25 μm showed a single perovskite phase without any detectable pyrochlore
structure. Microscopic images showed uniform grain size of a few tens of nanometers. The role of the polymer dramatically
promoting the perovskite phase was investigated with the aid of X-ray photoelectron spectroscopy and thermal analysis. The
dielectric constant of the obtained film was 4160 at 1 kHz. The film demonstrated typical ferroelectric hysteresis loops and
exhibited excellent piezoelectric performance. 相似文献
6.
The shift operator matrix (SOM) method is discussed. We show that in the thermodynamic limit, the largest eigenvalue of the SOM determines the grand canonical partition function for situations when simple, nearest-neighbor and next-nearest neighbor interacting particles are distributed on anM ×N lattice space. In addition, we present a method for calculating the appropriate shift operator matrices. 相似文献
7.
Ritleng V Yandulov DV Weare WW Schrock RR Hock AS Davis WM 《Journal of the American Chemical Society》2004,126(19):6150-6163
Three new tetramines, (ArNHCH(2)CH(2))(3)N, have been synthesized in which Ar = 3,5-(2,4,6-t-Bu(3)C(6)H(2))(2)C(6)H(3) (H(3)[HTBTN(3)N]), 3,5-(2,4,6-Me(3)C(6)H(2))(2)C(6)H(3) (H(3)[HMTN(3)N]), or 4-Br-3,5-(2,4,6-i-Pr(3)C(6)H(2))(2)C(6)H(2) (H(3)[pBrHIPTN(3)N]). The diarylated tetramine, [3,5-(2,4,6-t-Bu(3)C(6)H(2))(2)C(6)H(3)NHCH(2)CH(2)](2)NCH(2)CH(2)NH(2), has also been isolated, and the "hybrid" tetramine [3,5-(2,4,6-t-Bu(3)C(6)H(2))(2)C(6)H(3)NHCH(2)CH(2)](2)NCH(2)CH(2)NH(4-t-BuC(6)H(4)) has been prepared from it. Monochloride complexes, [(TerNCH(2)CH(2))(3)N]MoCl, have been prepared, as well as a selection of intermediates that would be expected in a catalytic dinitrogen reduction such as [(TerNCH(2)CH(2))(3)N]Mo[triple bond]N and [[(TerNCH(2)CH(2))(3)N]Mo(NH(3))][BAr'(4)] (Ter = HTBT, HMT, or pBrHIPT and Ar' = 3,5-(CF(3))(2)C(6)H(3))). Intermediates that contain the new terphenyl-substituted ligands are then evaluated for their efficiency for the catalytic reduction of dinitrogen under conditions where analogous [HIPTN(3)N]Mo species give four turnovers to ammonia under "standard" conditions with an efficiency of approximately 65%. Only [pBrHIPTN(3)N]Mo compounds are efficient catalysts for dinitrogen reduction. The reasons are explored and discussed. 相似文献
8.
9.
On Chalcogenolates. 163. Reactions of Hydrazine with Carbon Disulfide. 2. Crystal Structure of Dipotassium 1,2-Hydrazine-bis (dithioformate) The title compound K2[S2C? NH? NH? CS2] ( 1 ) crystallizes with Z = 4 in the orthorhombic space group Pbna with cell dimensions a = 6.635(1), b = 10.825(2), c = 12.866(2) Å. The crystal structure has been determined from single crystal X-ray data measured at ?85 °C and refined to a conventional R of 0.034 for 969 independent reflections (Rw = 0.042). The [S2C? NH? NH? CS2]2? ions are linked together by hydrogen bridges N? H…?S. The K+ ions are surrounded by seven sulfur atoms in irregular coordination. 相似文献
10.
On Chalcogenolates. 148. Reaction of Formamide with Carbon Disulfide. 2. Crystal Structure of Potassium N-Formyl Dithiocarbamate K[S2C? NH? CO? H] crystallizes with Z = 16 in the monoclinic space group Cc with cell dimensions a = 13.187(13) Å, b = 12.928(3) Å, c = 13.962(6) Å, and β = 101.75 (3)°. The crystal structure has been determined from single crystal X-ray data measured at 20°C and refined to a conventional R of 0.034 for 1857 independent reflections (Rw = 0.038). The compound crystallizes by building a super-structure, which is based on an H-bridged 16-membered ring-system, formed by four[S2C? NH? CO? H]? anions. Two different binuclear K+ coordination polyhedra are formed with two oxygen and two sulfur atoms in common. 相似文献