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1.
The cyclic hexapeptides (Gly-L-Pro-L-Pro-Gly-L-Pro-L-Pro) in the (peptide—Mg—peptide)2+ complex have nearly identical asymmetric conformations. Each has two cis Pro-Pro linkages and lacks any intraring hydrogen bonds. The Mg2+ ion forms six ligands in a regular octahedral array with the carbonyl oxygen atoms of the two Gly residues and one Pro residue of each peptide. The “sandwich” complex has an approximate 2-fold rotation axis through the Mg2+ relating the two peptide moieties. Cyclo(Gly-Pro-Pro-Gly-Pro-Pro)2Mg(ClO4)2· 4C2H3CN crystallizes in space group P31 with a = b = 15.744(4) Å, c = 24.002(6) Å, γ = 120°, and Z = 3. A highlight of the structure determination is the ready location of the Mg self-vector in a Harker section and the development of the entire structure by use of the tangent formula starting with the known position of the Mg atom.  相似文献   

2.
Biocompatible β-Ca3(PO4)2 and mechanically stable t-ZrO2 composites are currently being combined to overcome the demerits of the individual components. A series of five composites were synthesized using an aqueous precipitation technique. Their structural and mechanical stability was examined through X-ray diffraction, Rietveld refinement, FTIR, Raman spectroscopy, high-resolution scanning electron microscopy, and nanoindentation. The characterization results confirmed the formation of β-Ca3(PO4)2t-ZrO2 composites at 1100 °C. Heat treatment above 900 °C resulted in the degradation of the composites because of cationic interdiffusion between Ca2+ ions and O−2 vacancy in Zr4+ ions. Sequential thermal treatments correspond to four different fractional phases: calcium-deficient apatite, β-Ca3(PO4)2, t-ZrO2, and m-ZrO2. The morphological features confirm in situ synthesis, which reveals abnormal grain growth with voids caused by the upsurge in ZrO2 content. The mechanical stability data indicate significant variation in Young’s modulus and hardness throughout the composite.  相似文献   

3.
Xishi Tai  Jinhe Jiang 《Materials》2012,5(9):1626-1634
A new trinuclear Cd (II) complex [Cd3(L)6(2,2-bipyridine)3] [L = N-phenylsulfonyl-L-leucinato] has been synthesized and characterized by elemental analysis, IR and X-ray single crystal diffraction analysis. The results show that the complex belongs to the orthorhombic, space group P212121 with a = 16.877(3) Å, b = 22.875(5) Å, c = 29.495(6) Å, α = β = γ = 90°, V = 11387(4) Å3, Z = 4, Dc= 1.416 μg·m−3, μ = 0.737 mm−1, F (000) = 4992, and final R1 = 0.0390, ωR2 = 0.0989. The complex comprises two seven-coordinated Cd (II) atoms, with a N2O5 distorted pengonal bipyramidal coordination environment and a six-coordinated Cd (II) atom, with a N2O4 distorted octahedral coordination environment. The molecules form one dimensional chain structure by the interaction of bridged carboxylato groups, hydrogen bonds and π-π interaction of 2,2-bipyridine. The luminescent properties of the Cd (II) complex and N-Benzenesulphonyl-L-leucine in solid and in CH3OH solution also have been investigated.  相似文献   

4.
Fluorescent lipid and phospholipid probes were incorporated at 4°C into soybean protoplasts prepared from cultured soybean (SB-1) cells. Fluorescence microscopy showed that the plasma membrane as well as the nucleus were labeled. Fluorescence redistribution after photobleaching (FRAP) analysis was performed on these cells at 18°C to monitor the lateral mobility of the incorporated probes. After labeling at low concentrations (40 μg/ml) of phosphatidyl-N-(4-nitrobenzo-2-oxa-1,3-diazolyl)ethanolamine (NBD-PtdEtn), a single mobile component was observed with a diffusion coefficient (D) of ≈3 × 10-9 cm2/sec. After labeling at higher probe concentrations (≥100 μg/ml), two diffusing species were observed, with diffusion coefficients of ≈3 × 10-9 cm2/sec (“fast”) and ≈5 × 10-10 cm2/sec (“slow”). Similar results were observed with fluorescent derivatives of phosphatidylcholine and fatty acids. In contrast to these results, parallel analysis of 3T3 fibroblasts, using the same probes and conditions, yielded only a single diffusion component. These results suggest that the soybean plasma membrane may contain two distinct lipid domains in terms of lipid mobility. Consistent with this idea, experiments with soybean protoplasts yielded a single diffusion component under the following conditions: (i) labeling with NBD-PtdEtn (100 μg/ml), FRAP analysis at 37°C (D = 1.1 × 10-8 cm2/sec); (ii) labeling with NBD-PtdEtn (100 μg/ml), FRAP analysis at 18°C in the presence of 2 mM EGTA (D = 4.2 × 10-9 cm2/sec); (iii) labeling with 5-(N-dodecanoyl)aminofluorescein (a short-chain lipid probe), FRAP analysis at 18°C or 37°C (D = 2.5 × 10-8 cm2/sec). These results suggest that the plasma membrane of soybean cells may contain stable immiscible domains of fluid and gel-like lipids.  相似文献   

5.
The crystal structure and the photoluminescence properties of novel green Ba4-yEuySi6O16-3x/2Nx phosphors were investigated. The electronic structures of the Ba4Si6O16 host were calculated by first principles pseudopotential method based on density functional theory. The results reveal that the top of the valence bands are dominated by O-2p states hybridized with Ba-6s and Si-3p states, while the conduction bands are mainly determined by Ba-6s states for the host, which is an insulator with a direct energy gap of 4.6 eV at Γ. A small amount of nitrogen can be incorporated into the host to replace oxygen and forms Ba4-yEuySi6O16-3x/2Nx solid solutions crystallized in a monoclinic (space group P21/c, Z = 2) having the lattice parameters a = 12.4663(5) Å, b = 4.6829(2) Å, c = 13.9236(6) Å, and β = 93.61(1)°, with a maximum solubility of nitrogen at about x = 0.1. Ba4Si6O16-3x/2Nx:Eu2+ exhibits efficient green emission centered at 515–525 nm varying with the Eu2+ concentration when excited under UV to 400 nm. Furthermore, the incorporation of nitrogen can slightly enhance the photoluminescence intensity. Excitation in the UV-blue spectral range (λexc = 375 nm), the absorption and quantum efficiency of Ba4-yEuySi6O16-3x/2Nx (x = 0.1, y = 0.2) reach about 80% and 46%, respectively. Through further improvement of the thermal stability, novel green phosphor of Ba4-yEuySi6O16-3x/2Nx is promising for application in white UV-LEDs.  相似文献   

6.
High-resolution optical spectroscopy of an individual trapped ion is hampered by lack of sharp lasers. This suggests the use of a second metastable excited ion as an ultrasharp light source. To this end, laser-cool two barium ions to an equilibrium distance of ≈8 μm on the z (symmetry) axis of the trap and, in this (earth)(Ba+)2-molecule, visually or photoelectrically identify them as A and B by their location. Briefly turn on a 455-nm spectral lamp until one of the ions, say the A ion, is pumped into the metastable D5/2 level and turns invisible. Focus on the visible, spatially well-resolved B ion and turn off the blue and red illumination lasers for ≈15 s. Then turn them back on again and check on whether the excitation by chance has been transferred to the B ion and is now in the D5/2 level and dark while the A ion is bright. The cross section for absorption of the λ(D5/2S1/2) λ0 = 1.76 μm radiation by a stationary ion can be >λ02/2π. Thus, by pushing the two ions together to ≈λ0/4 by turning on a much stronger trapping field during the excitation exchange period, one might be able to detect excitation transfer in >10% of the attempts. The ions are tuned relative to each other by a 0- to 10-mV/cm variable dc field in the z direction, which displaces them axially and causes them to see different rf fields, which Stark-shifts their frequencies. In this way, a resonant transfer response as sharp as twice the natural width of the D5/2 level, 11 mHz or a Q ≈ 0.4 × 1017, might be demonstrated.  相似文献   

7.
The diffusivity of CH4 in a mixture of CCl4 and c-C6F11C2F5 of the critical composition in the region of temperature close to that of unmixing, decreases as in a homogeneous liquid from 36° to about 32°. It then passes through a minimum of 105D ≈ 4.15 cm2/sec at about 27.5°, then rises to 105D = 4.61 at 25.00°, then steeply to 6.36 cm2/sec in the further drop of only 0.3° to 24.71°.  相似文献   

8.
Natural antamanide, a cyclic decapeptide from Amanita phalloides, has been shown to have the same conformation for the backbone and comparable side groups as the biologically active synthetic [Phe4, Val6]antamanide. Packing in the crystal is quite different for the two compounds. Large channels with a polar lining are formed in the crystals of [Phe4, Val6]antamanide, whereas in natural antamanide large channels in the crystal are completely surrounded by the lipophilic side groups of the Pro, Phe, and Ala residues. Antamanide, C64H78N10O10·8H2O·X, crystallizes in space group P212121 with a = 15.88 Å, b = 34.88 Å, and c = 13.61 Å.  相似文献   

9.
Photoreduction of the intermediary electron acceptor, pheophytin (Pheo), in photosystem II reaction centers of spinach chloroplasts or subchloroplast particles (TSF-II and TSF-IIa) at 220 K and redox potential Eh = -450 mV produces an EPR doublet centered at g = 2.00 with a splitting of 52 G at 7 K in addition to a narrow signal attributed to Pheo[unk] (g = 2.0033, ΔH ≈ 13 G). The doublet is eliminated after extraction of lyophilized TSF-II with hexane containing 0.13-0.16% methanol but is restored by reconstitution with plastoquinone A (alone or with β-carotene) although not with vitamin K1. TSF-II and TSF-IIa are found to contain ≈2 nonheme Fe atoms per reaction center. Incubation with 0.55 M LiClO4 plus 2.5 mM o-phenanthroline (but not with 0.55 M LiClO4 alone) decreases this value to ≈0.6 and completely eliminates the EPR doublet, but photoreduction of Pheo is not significantly affected. Partial restoration of the doublet (about 25%) was achieved by subsequent incubation with 0.2 mM Fe2+, but not with either Mn2+ or Mg2+. The Fe removal results in the development of a photoinduced EPR signal (g = 2.0044 ± 0.0003, ΔH = 9.2 ± 0.5 G) at Eh = 50 mV, which is not observed after extraction with 0.16% methanol in hexane. It is ascribed to plastosemiquinone no longer coupled to Fe in photosystem II reaction centers. The results show that a complex of plastoquinone and Fe can act as the stable “primary” electron acceptor in photosystem II reaction centers and that the interaction of its singly reduced form with the reduced intermediary acceptor, Pheo[unk], is responsible for the EPR doublet.  相似文献   

10.
N,N′-diphenyl-N,N′-diethylurea (C17H20N2O) crystallizes in the space group P21/c. The unit cell constants are: a = 10.42 ± 0.01 Å, b = 16.86 ± 0.02 Å, c = 10.66 ± 0.001 Å, β = 125°16′ ± 5′; Z = 4, Dx = 1.16 g·cm-3, Dmeas = 1.16 ± 0.01 g·cm-3. Data for 1392 reflections were collected at room temperature on a Picker automated diffractometer. The crystal structure was solved by direct methods and refined by bloc-diagonalized matrix least-squares calculations. The molecule is characterized by a pseudo C2 symmetry; both phenyl groups are trans with respect to the oxygen atom. The hybridization of the two nitrogen atoms is intermediate between trigonal and tetrahedral; the nonplanar distortion of the amide groups is about 30°. The amide C-N bond lengths are 1.37 Å.  相似文献   

11.
We report the observation of high-resolution solid-state NMR spectra of 23Na (I = [unk]), 27Al (I = [unk]) and 51V (I = [unk]) in various inorganic systems. We show that, contrary to popular belief, relatively high-resolution (≈10 ppm linewidth) spectra may be obtained from quadrupolar systems, in which electric quadrupole coupling constants (e2qQ/h) are in the range ≈1-5 MHz, by means of observation of the (½, -½) spin transition. The (½, -½) transition for all nonintegral spin quadrupolar nuclei (I = [unk], [unk], [unk], or [unk]) is only normally broadened by dipolar, chemical shift (or Knight shift) anisotropy or second-order quadrupolar effects, all of which are to a greater or lesser extent averaged under fast magic-angle sample rotation. In the case of 23Na and 27Al, high-resolution spectra of 23NaNO3 (e2qQ/h ≈300 kHz) and α-27Al2O3 (e2qQ/h ≈2-3 MHz) are presented; in the case of 51V2O5 (e2qQ/h ≈800 kHz), rotational echo decays are observed due to the presence of a ≈103-ppm chemical shift anisotropy. The observation of high-resolution solid-state spectra of systems having spins I = [unk], [unk], and [unk] in asymmetric environments opens up the possibility of examining about two out of three nuclei by solid-state NMR that were previously thought of as “inaccessible” due to the presence of large (a few megahertz) quadrupole coupling constants. Preliminary results for an I = [unk] system, 93Nb, having e2qQ/h ≈19.5 MHz, are also reported.  相似文献   

12.
Visible light excitation of the ligand-bridged assembly [(bpy)2RuaII(L)RubII(bpy)(OH2)4+] (bpy is 2,2′-bipyridine; L is the bridging ligand, 4-phen-tpy) results in emission from the lowest energy, bridge-based metal-to-ligand charge transfer excited state (L−•)RubIII-OH2 with an excited-state lifetime of 13 ± 1 ns. Near–diffusion-controlled quenching of the emission occurs with added HPO42− and partial quenching by added acetate anion (OAc) in buffered solutions with pH control. A Stern–Volmer analysis of quenching by OAc gave a quenching rate constant of kq = 4.1 × 108 M−1⋅s−1 and an estimated pKa* value of ∼5 ± 1 for the [(bpy)2RuaII(L•−)RubIII(bpy)(OH2)4+]* excited state. Following proton loss and rapid excited-state decay to give [(bpy)2RuaII(L)RubII(bpy)(OH)3+] in a H2PO4/HPO42− buffer, back proton transfer occurs from H2PO4 to give [(bpy)2RuaII(L)Rub(bpy)(OH2)4+] with kPT,2 = 4.4 × 108 M−1⋅s−1. From the intercept of a plot of kobs vs. [H2PO4], k = 2.1 × 106 s−1 for reprotonation by water providing a dramatic illustration of kinetically limiting, slow proton transfer for acids and bases with pKa values intermediate between pKa(H3O+) = −1.74 and pKa(H2O) = 15.7.  相似文献   

13.
Analysis of electron diffraction photographs of grains of Mn2Al7, Fe2Al7, and (Mn0.7Fe0.3)2Al7 leads to the conclusion that they are 5-fold twins of a 1664-atom orthorhombic crystal with a = 32.86 Å, b = 31.23 Å, and c = 24.80 Å and with 16 icosahedral clusters of 104 atoms in positions shifted by small amounts from those of the cubic β-tungsten structure.  相似文献   

14.
A new crystal form (III) of tobacco leaf ribulosebisphosphate carboxylase [3-phospho-D-glycerate carboxy-lyase (dimerizing), EC 4.1.1.39] has been grown by dialysis procedures, and is suitable for structural studies at near atomic resolution. The crystals exhibit birefringence, grow as pseudo-regular rhombic dodecahedrons, and belong to the tetragonal space group P42212 with a = b = 149 Å, c = 138 Å, and V = 3.04 × 106 A3. Each unit cell contains two molecules, with two large and two small subunits per asymmetric unit. At low resolution (>10 Å) the crystal structure is body centered belonging to space group 1422 with one large/small pair in the asymmetric unit. Thus, at low resolution the molecular symmetry is D4, the highest possible symmetry for an oligomer of stoichiometry large8small8. Form III crystals may be identical to crystalline inclusions found in chloroplasts.  相似文献   

15.
Comparison of picosecond kinetic and spectroscopic data for Zn octaethylporphine and Fe(III)Cl octaethylporphine with that for Zn—Fe(III)Cl, a cofacial diporphyrin composed of a Zn porphyrin covalently bound to an Fe(III)Cl porphyrin with two chains of five atoms each, supports the assignment of a light-driven electron transfer (k > 1011s-1) within Zn—Fe(III)Cl to form [Zn+·—Fe(II)]Cl. The kinetics (k ≈ 1010s-1) and thermodynamics of the reverse electron transfer are compared to those of a similar electron transfer in bacterial photosynthesis, the reduction of an oxidized bacteriochlorophyll dimer, (BChl)2+·, by Fe(II) cytochrome c.  相似文献   

16.
Novel copper phosphate chloride has been obtained under middle-temperature hydrothermal conditions. Its crystal structure was established based on the low-temperature X-ray diffraction data: Na2Li0.75(Cs,K)0.5[Cu5(PO4)4Cl]·3.5(H2O,OH), sp. gr. C2/m, a = 19.3951(8) Å, b = 9.7627(3) Å, c = 9.7383(4) Å, β = 99.329(4)°, T = 150 K, MoKα (λ = 0.71073 Å), R = 0.049. The crystal structure includes tetrameric copper clusters as the main building blocks, which are built of four CuO4Cl pyramids sharing apical Cl vertices. The clusters are combined through phosphate groups and additional copper-centered polyhedra to form two mostly ordered periodic layers. Between the layers and inside the framework channels, alkali ions, H2O molecules, or OH groups are statistically distributed. Na2Li0.75(Cs,K)0.5[Cu5(PO4)4Cl]·3.5(H2O,OH) is a synthetic modification of a sampleite-polymorph of the lavendulan mineral group and represents a new member in a mero-plesiotype series of copper phosphates and arsenates, for which the crystal structures contain two-periodic [Cu4X(TO4)4] modules (T = As, P; X = Cl, O). Magnetically, this phase exhibits the phase transition at TC = 6.5 K, below which it possesses a weak ferromagnetic moment.  相似文献   

17.
Fluorescence energy transfer in the rapid-diffusion limit   总被引:8,自引:3,他引:8       下载免费PDF全文
Energy transfer is enhanced by translational diffusion of the donor and acceptor [Steinberg, I. Z. & Katchalski, E. (1968) J. Chem. Phys. 48, 2404-2410]. The effect of diffusion on energy transfer depends on Dτ0/s2, in which D is the sum of the diffusion coefficients of the donor and acceptor, τ0 is the lifetime of the donor in the absence of transfer, and s is the mean distance between donors and acceptors. In most previous studies, Dτ0/s2 1, corresponding to the static limit. We report here steady-state and kinetic fluorescence experiments showing that Dτ0/s2 1, the rapid-diffusion limit, can be attained by using Tb3+ chelated to dipicolinate as a long-lived energy donor (τ0 = 2.2 msec). The concentration of rhodamine B, the energy acceptor, resulting in 50% transfer was 0.67 μM, which is three orders of magnitude less than the concentration giving 50% transfer in the static limit. The dependence of the transfer efficiency on diffusion coefficients varying from 5 × 10-11 to 1.5 × 10-4 cm2/sec, spanning the range from the static limit to the rapid-diffusion limit, is in excellent agreement with theory. It is evident that energy donors with millisecond or longer excited state lifetimes can be used to probe translational motions in membranes and other assemblies. Energy transfer in the rapid diffusion limit is sensitive to the distance of closest approach (a) of the donor and acceptor. For a Tb·(DPA)3 chelate trapped inside the aqueous space of a membrane vesicle containing eosin phosphatidylethanolamine, a = 10 Å. The transverse location of chromophores in model membranes and biological membranes can be determined by this technique.  相似文献   

18.
Chlorophyllide a and the apoprotein of myoglobin (Mb) spontaneously form three types of complex. The M (Mr ≈ 3 × 105) and H (Mr ≥ 4 × 106) complexes, but not the L (Mr ≈ 1.7 × 104), display a circular dichroism (CD) spectrum that is highly red-shifted, nonconservative, and very intense—characteristics shared by the CD spectra of reaction center complexes from purple photosynthetic bacteria. At its 710-nm peak, the H complex CD spectrum has a larger magnitude, 0.06 differential absorbance per unit total absorbance, than has been reported for chlorophyll in any medium.  相似文献   

19.
Metal-containing polymer networks are widespread in biology, particularly for load-bearing exoskeletal biomaterials. Mytilus byssal cuticle is an especially interesting case containing moderate levels of Fe3+ and cuticle protein—mussel foot protein-1 (mfp-1), which has a peculiar combination of high hardness and high extensibility. Mfp-1, containing 13 mol % of dopa (3, 4-dihydroxyphenylalanine) side-chains, is highly positively charged polyelectrolyte (pI ∼ 10) and didn’t show any cohesive tendencies in previous surface forces apparatus (SFA) studies. Here, we show that Fe3+ ions can mediate unusually strong interactions between the positively charged proteins. Using an SFA, Fe3+ was observed to impart robust bridging (Wad ≈ 4.3 mJ/m2) between two noninteracting mfp-1 films in aqueous buffer approaching the ionic strength of seawater. The Fe3+ bridging between the mfp-1-coated surfaces is fully reversible in water, increasing with contact time and iron concentration up to 10 μM; at 100 μM, Fe3+ bridging adhesion is abolished. Bridging is apparently due to the formation of multivalent dopa-iron complexes. Similar Fe-mediated bridging (Wad ≈ 5.7 mJ/m2) by a smaller recombinant dopa-containing analogue indicates that bridging is largely independent of molecular weight and posttranslational modifications other than dopa. The results suggest that dopa-metal interactions may provide an energetic new paradigm for engineering strong, self-healing interactions between polymers under water.  相似文献   

20.
Xishi Tai  Na Wei  Donghao Wang 《Materials》2012,5(4):558-565
A new complex [Mg(L)2(phen)(H2O)2](phen)(H2O)2 [L= N-benzenesulphonyl-L-leucine] was synthesized by the reaction of magnesium chloride hexahydrate with N-benzenesulphonyl-L-leucine and 1,10-phenanthroline in the CH3CH2OH/H2O (v:v = 5:1). It was characterized by elemental analysis, IR and X-ray single crystal diffraction analysis. The crystal of the title complex [Mg(L)2(phen)(H2O)2](phen)(H2O)2 belongs to triclinic, space group P-1 with a = 0.72772(15) nm, b = 1.4279(3) nm, c = 1.4418(3) nm, α = 63.53(3)°, β = 79.75(3)°, γ = 81.83(3)°, V = 1.3163(5) nm3, Z =1, Dc= 1.258 μg·m−3, μ = 0.177 mm−1, F(000) = 526, and final R1 = 0.0506, ωR2 = 0.1328. The complex comprises a six-coordinated magnesium(II) center, with a N2O4 distorted octahedron coordination environment. The molecules are connected by hydrogen bonds and π-π stacking to form one dimensional chain structure. The luminescent property of the Mg(II) complex has been investigated in solid.  相似文献   

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