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81.
Dennis J. McCormac Christopher A. Marwood Doug Bruce Bruce M. Greenberg† 《Photochemistry and photobiology》1996,63(6):837-845
The aquatic higher plant Spirodela oligorrhiza , which contains proplastids when grown in the dark, was used to study light-dependent chloroplast development. Low-temperature (77 K) and room temperature fluorescence were utilized in situ on whole plants to examine plastid development. The dark-grown plants contain two 77 K fluorescence peaks, at 633 nm (F633) and at 657 nm (F657), with F633 dominating. The F657 species represents protochlorophyllide that is bound to protochloro-phyllide oxidoreductase. It was rapidly phototrans-formed to chlorophyllide (within 5 s) via a monomolec-ular reaction. Free protochlorophyllide (F633) was converted to chlorophyllide during a 3 h exposure to light. Photosystem (PS) assembly in Spirodela could be detected 2 h after the plants were first exposed to light, with the PSII reaction center (77 K fluorescence at 684 nm) appearing slightly before the PSI reaction center (77 K fluorescence at 725 nm). After the first reaction centers were formed the antenna complexes were added; the light-harvesting complex (LHC) I of PSI appeared after 8 h, and 47 kDa chlorophyll protein of PSII appeared between 12 h and 24 h. After 30 h of exposure to light, the plants acquired the ability to perform a light state transition, marking the appearance of functional LHCII complexes in the developing chloroplast. Finally, it was found that photosynthetic activity, as measured by room temperature chlorophyll fluorescence, accelerated con-comitantly with detection of the antenna complexes. Therefore, although reaction centers are detected very early during the proplastid to chloroplast conversion, they may have little activity or be unstable until the antennae are present. 相似文献
82.
Bruce JE Anderson GA Lin CY Gorshkov M Rockwood AL Smith RD 《Journal of mass spectrometry : JMS》2000,35(1):85-94
A new trapped ion cell design for use with Fourier transform ion cyclotron resonance mass spectrometry is described. The design employs 15 cylindrical ring electrodes to generate trapping potential wells and 32 separately assignable rod electrodes for excitation and detection. The rod electrodes are positioned internal to the ring electrodes and provide excitation fields that are thereby linearized along the magnetic field over the entire trapped ion volume. The new design also affords flexibility in the shaping of the trapping field using the 15 ring electrodes. Many different trapping well shapes can be generated by applying different voltages to the individual ring electrodes, ranging from quadratic to linearly ramped along the magnetic field axis, to a shape that is nearly flat over the entire trap volume, but rises very steeply near the ends of the trap. This feature should be useful for trapping larger ion populations and extension of the useful range of ion manipulation and dissociation experiments since the number of stages of ion manipulation or dissociation is limited in practice by the initial trapped ion population size. Predicted trapping well shapes for two different ring electrode configurations are presented, and these and several other possible configurations are discussed, as are the predicted excitation fields based on the use of rod electrodes internal to the trapping ring electrodes. Initial results are presented from an implementation of the design using a 3.5 T superconducting magnet. It was found that ions can be successfully trapped and detected with this cell design and that selected ion accumulation can be performed with the utilization of four rods for quadrupolar excitation. The initial results presented here illustrate the feasibility of this cell design and demonstrate differences in observed performance based upon different trapping well shapes. 相似文献
83.
On Heterocvclic Systems Containing Lead. II. Diphenyl Substituted Thiaplumbocanes, Examples for Expanding Coordination Tetrahedra around PbIV 5, 5-Diphenyl-1, 4, 6, 5-oxadithiaplumbocane (PbO8Ph2) and 2, 2-diphenyl-1, 3, 6, 2-trithiaplumbocane (PbS8Ph2) have been synthesized from diphenyl lead diacetate and the respective disodium dithiolates. The mass spectra point to rearrangements induced by reduction of PbIV to PbII in addition to fragments containing PbIV. 13C and 207Pb NMR spectra exhibit a weaker 1, 5-transannular interaction S …? Pb than O …? Pb. The crystal structures of two modifications of PbO8Ph2 (orthorhombic and triclinic) have been determined at ? 160°C and refined to R = 0.027 and 0.071. The two modifications contain four 8-membered rings crystallographical independent, three times chair-chair, once boat-chair conformation. Eight independent PbIV? S single bond distances range from 248.2(3) to 251.9(6) pm. The tetrahedral C2PbS2 configuration is expanded by one 1,5-transannular O …? Pb interaction (285,5(5) to 308(1) pm, monocapped) and further in the triclinic case by one intermolecular S …? Pb interaction (411(1) and 375(1) pm, bicapped). The crystal structure of the orthorhombic modification contains layers (8-membered ring) (phenyl)2 analogous to the structure of CdI2. In the triclinic case there are dimers arranged in analogy to the cubic closest packing. 相似文献
84.
Two new sesquiterpenoids of the unprecedented neoiemnane ring system, and one eremophflane-derived sesquiterpene diol have been isolated from the pacific soft-coral Lemnalia africana. The structure of the novel neolemnane compounds, 4 and 5, were confirmed by X-ray crystallography, and the diol, 6, has been described based upon spectral analysis and chemical modification. 相似文献
85.
Abdel-Magid AF Carson KG Harris BD Maryanoff CA Shah RD 《The Journal of organic chemistry》1996,61(11):3849-3862
Sodium triacetoxyborohydride is presented as a general reducing agent for the reductive amination of aldehydes and ketones. Procedures for using this mild and selective reagent have been developed for a wide variety of substrates. The scope of the reaction includes aliphatic acyclic and cyclic ketones, aliphatic and aromatic aldehydes, and primary and secondary amines including a variety of weakly basic and nonbasic amines. Limitations include reactions with aromatic and unsaturated ketones and some sterically hindered ketones and amines. 1,2-Dichloroethane (DCE) is the preferred reaction solvent, but reactions can also be carried out in tetrahydrofuran (THF) and occasionally in acetonitrile. Acetic acid may be used as catalyst with ketone reactions, but it is generally not needed with aldehydes. The procedure is carried out effectively in the presence of acid sensitive functional groups such as acetals and ketals; it can also be carried out in the presence of reducible functional groups such as C-C multiple bonds and cyano and nitro groups. Reactions are generally faster in DCE than in THF, and in both solvents, reactions are faster in the presence of AcOH. In comparison with other reductive amination procedures such as NaBH(3)CN/MeOH, borane-pyridine, and catalytic hydrogenation, NaBH(OAc)(3) gave consistently higher yields and fewer side products. In the reductive amination of some aldehydes with primary amines where dialkylation is a problem we adopted a stepwise procedure involving imine formation in MeOH followed by reduction with NaBH(4). 相似文献
86.
The crystal structures of the high-temperature modifications of sodium and silver orthophosphates have been determined using powder neutron diffraction (PND) data. II-Na3PO4 adopts the space group Fm3m with
at 400°C. The PO3−4 group is centered around the origin, but it shows high orientational disorder. The sodium ions occupy the
and
sites. II-Ag3PO4, at 650°C, is similar with
. The structure of I-Ag3PO4 at room temperature
has been re-examined by single-crystal X-ray diffraction. The derived model, with R=0.019 for 116 independent reflections, is in agreement with the latest work reported in the literature. The structure of I-Ag3PO4 at 375°C, as determined by PND, has
, and displays no gross modifications from that observed at 25°C, although the anisotropic nature of the silver sites is markedly more pronounced at this higher temperature. The cation mobility is discussed in relation to the high-temperatures structures. 相似文献
Full-size image (<1K)
87.
We have synthesized a 22 residue alanine-based peptide with a tris(bipyridyl)ruthenium(II) amino acid near the middle of the peptide which can act as a photoinducible electron donor. Two histidines spaced i, i + 4 near the C-terminus of the peptide were then cross-linked with a tetraammineruthenium(III) moiety to prenucleate the helix and provide an electron acceptor site. Introduction of the cross-link enhances the average helix content from 67% to 84% at 0 degrees C, as judged by circular dichroism spectroscopy. The temperature dependence of the mean molar residue ellipticity at 222 nm, [THETAV;](222), for the bimetalated peptide was fit to a modified Lifson-Roig helix-coil model to permit extraction of the population of helical conformation at each residue separating the electron donor and acceptor. On average, the residues between the donor and acceptor are 92% helical. Photoinduced electron transfer with a driving force of -1.0 eV and an estimated reorganization energy of 0.82 eV was measured by fluorescence quenching methods in H(2)O and D(2)O, yielding rate constants, k(ET), of 7 +/- 3 x 10(6) s(-)(1) and 5 +/- 1 x 10(6) s(-)(1) at 0 degrees C. Calculation of the electronic coupling matrix element, H(ab), with the Marcus equation yields a value of 0.19 +/- 0.4 cm(-)(1). Analysis in terms of the pathway model for electronic coupling indicates that this magnitude of H(ab) is consistent with the participation of hydrogen bonds in electronic coupling for an isolated alpha-helix. 相似文献
88.
The interaction of aspartic acid with kaolinite was studied by potentiometric titrations and by adsorption measurements both at constant aspartate concentration (but varying pH) and at a constant pH of 5.5. The temperature was 25 degrees C, and the ionic medium 5 mM KNO3. Aspartic acid dissociation constants estimated from titrations agreed with those from the literature. The adsorption of aspartic acid to kaolinite was weak and varied only slightly with pH; 10-18% of 100 microM aspartic acid adsorbed to kaolinite at 100 m(2)L(-1) between pH 3 and 10. Data from the titrations and adsorption experiments were fitted closely by an extended constant-capacitance surface complexation model, in which monodentate outer-sphere complexes formed between deprotonated aspartic acid molecules and protonated sites on the variable-charge edges of the kaolinite crystals. There appeared to be no adsorption to the permanently charged crystal faces. 相似文献
89.
Graham A. Bowmaker Prof. Dr. Michael I. Bruce Brian W. Skelton Neil Somers Allan H. White 《无机化学与普通化学杂志》2007,633(7):1024-1030
The complexes [Cu2Br4]2?, [Cu2I4]2?, [Cu2I2Br2]2?, [Cu2I3Cl]2?, [Ag2Cl4]2? have been characterized as their isomorphous bis(triphenylphosphoranylidene)ammonium ([Ph3PNPPh3]+ = PNP+) salts by single crystal structural determinations. All anions show the centrosymmetric doubly halogen‐bridged forms [XM(μ‐X)2MX]2? with three‐coordinate metal atoms that have been observed in [M2X4]2? complexes with other large organic cations. In [Cu2I2Br2]2? the iodide ligands occupy the bridging positions and the bromide the terminal positions, while in [Cu2I3Cl]2?, obtained in an attempt to prepare [Cu2I2Cl2]2?, two of the iodide ligands occupy the bridging positions with the third iodide and the chloride ligand occupying two statistically disordered terminal positions. In [Ag2Cl4]2? the distortion from ideal trigonal coordination of the metal atom is greater than in the copper complexes, but less than in other previously reported [Ag2Cl4]2? complexes with organic cations. The ν(MX) bands have been assigned in the far‐IR spectra, and confirm previous observations regarding the unexpectedly simple IR spectra of [Cu2X4]2? complexes. 相似文献
90.
William Vidaver Radovan Popovic Douglas Bruce Konrad Colbow 《Photochemistry and photobiology》1981,34(5):633-636
Abstract— Three phases of chlorophyll a fluorescence quenching by O2 are observed in green plants. The effects of various inhibitors on photosynthetic partial processes in chloroplasts were investigated in attempts to (1) localize the O2 -quenching sites and (2) assess possible physiological significance of O2 -quenching. Our results localize the most sensitive (and presumably functionally important) phase to a site between plastoquinone and the photosystem I acceptor, chlorophyll (P700 ), possibly plastocyanin. It is suggested that PC may transfer electrons to oxygen in addition to P700 . 相似文献