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1.
2.
Stephen W. Burgess Jogin R. Wu Kerry Swift Barry R. Lentz 《Journal of fluorescence》1991,1(2):105-112
Rate constants were determined for the transfer of the fluorescent lipid probe 1-palmitoyl-2-[[2-[4-(6-phenyl-trans-1,3,5-hexatrienyl)phenyl]ethyl] oxy]carbonyl]-3-sn-phosphatidylcholine (DPHpPC) between large, unilamellar extrusion vesicles composed either of dipalmitoyl phosphatidylcholine (DPPC) or of DPPC mixed with a small amount (0.5 mol%) of lyso phosphatidylcholine (Lyso PC). Transfer of the lipid probe in the presence of varying concentrations of poly(ethylene glycol) (PEG) was monitored using the SLM 48000-MHF Multi-Harmonic Fourier Transform phase and modulation spectrofluorometer to collect multifrequency phase and modulation fluorescence data sets on a subsecond time scale. The unique ability of this instrument to yield accurate fluorescence lifetime data on this time scale allowed transfer to be detected in terms of a time-dependent change in the fluorescent lifetime distribution associated with the lipid-like DPHpPC probe. This probe demonstrates two short fluoresence decay times (ca. 1.1–1.4 and 4.3–4.8 ns) in a probe-rich environment but a single long lifetime (ca. 7 ns) in a probe-poor environment. A simple two-state model for initial lipid transfer was used to analyze the multifrequency data sets collected over a 4-s time frame to obtain the time rate of change of the concentrations of donor and acceptor probe populations following rapid mixing of vesicles with PEG. The ability to measure fluorescence lifetimes on this time scale has allowed us to show that the of rate of lipid transfer increased dramatically at 35% PEG in both fusing and nonfusing vesicle systems. These results are interpreted in terms of a distinct interbilayer structure associated with intimate bilayer contact induced by high and potentially fusogenic concentrations of PEG. 相似文献
3.
Balbo-Block M Bartel C Lentz D Preugschat D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2001,7(4):881-893
The radical alkylation of tetraethylammonium pentacarbonyl(cyano)chromate 1 yielded the halogenated ethyl isocyanide complexes [(CO)5Cr(CN-CClX-CClYF)] 3 (a, X= Cl, Y= F; b, X = F, Y= F and c, X=Y= Cl). Dehalogenation of 3 using zinc in diethyl ether gave [(CO)5Cr(CN-CX=CFY)] 4. The compounds 4a, b reacted with various nucleophiles exclusively at the difluoromethylene group. The unstable phosphorane 5, which is formed on reaction of 4b with trimethylphosphane, decomposed thermally and on hydrolysis yielding pentacarbonyl(1,2-difluoroethenyl isocyanide)chromium (6). The cyano substituent can be introduced in the beta position of the isocyanide function by reaction of 4a, b with potassium cyanide, leading to the formation of [(CO)5Cr(CN-CX=CF-CN)] (7). Reactions of 4a, b with organolithium or organomagnesium compounds yielded [(CO)5Cr(CN-CX=CF-R)] (8) and [(CO)5Cr(CN-CF=CF-C...C-CF=CF-NC)Cr(CO)5] (10). The trimethylsilyl group in 8a, b, d could be removed by a solution of potassium carbonate in methanol leading to [(CO)5Cr(CN-CX=CF-Cn-H)] (11) (n=2,4). Octacarbonyldicobalt reacted with 8e under coordination of the C-C triple bond to the hexacarbonyldicobalt fragment, resulting in the cluster compound 12. The crystal and molecular structure of 8i, 11 a, b, and 12 were elucidated by X-ray crystallography. The alkenyl and alkynyl isocyanides CN-CCl=CF2 (13a), CN-CF=CF2 (13b), CN-CCl=CClF (13c), CN-CF=CFH (14), CN-CC-H (15), CN-CC-CN (16), and CN-CCl=CF-CN (17) were obtained by flash vacuum pyrolysis of 4a, 4b, 4c, 6, and 7a, respectively. 相似文献
4.
The IR- and RAMAN -spectra are reported from OP(OCH3)2Cl, OP(OCH3)Cl2, SP(OCH3)Cl, SP(OCH3)Cl2. The assignement to the fundamental vibration is given and all Valence-force-constants are calculated. With increasing number of chlorine atoms decrease f P? OCH3 and f P? Cl. In the contrary, f O? P and f S? P increase. Here the influence of decreasing electro negativity is compensated by the change from an element of the first period of eight elements to an element of the second period. 相似文献
5.
Harro Lentz Ernst Ulrich Franck 《Angewandte Chemie (International ed. in English)》1978,17(10):728-730
Liquid or dense supercritical ammonia has been suggested as an extraction fluid. It is indeed good solvent for very different classes of compounds, as can be seen from phase diagrams. Such diagrams for binary systems of ammonia and hydrocarbons are presented and discussed on the basis of their critical curves. Apparatus and methods for the measurement of phase equilibria and equation of state data of fluid mixtures at high pressure are described. 相似文献
6.
Halfsandwich Complexes of Chromium with the Trifluoromethyl Isocyanide Ligand The synthesis and properties of the halfsandwich complexes [η6-1,3,5-C6H3(CH3)3]Cr(CO)2(CNCF3), [η6-1,3,5-C6H3(CH3)3]Cr(CO)(CNCH3)(CNCF3) und [η6-1,3,5-C6H3(CH3)3]Cr(CNCF3)3 is reported. The vibrational spectroscopic data proof the strong π accepting character of the trifluoromethyl isocyanide ligand. 相似文献
7.
Barry R. Lentz 《Journal of fluorescence》1995,5(1):29-38
An important process in the life of a cell is fusion between cellular membranes. This is the process by which two cellular compartments surrounded by different membranes join to become a single compartment surrounded by a single membrane, without significant loss of compartment contents. To demonstrate fusion, the cell biophysicist must demonstrate all three critical aspects of the process: (1) mixing of membrane components, (2) mixing of compartment contents; and (3) retention of compartment contents. Most commonly, accomplishing this involves the use of fluorescence probes. The general theme to the methods described involves some form of concentration-dependent quenching. An unique method developed in our laboratory utilizes the concentration dependence of the fluorescence lifetime of a phosphatidylcholine containing carboxyethyl diphenylhexatriene at position 2 and palmitic acid at position 1 of glycerol (DPHpPC). The fluorescence lifetime of this molecule and that of its parent fluorophore diphenylhexatriene (DPH) shorten dramatically as their two-dimensional concentrations in a membrane increase. This lifetime quenching can be described by dimer formation that reduces the symmetry of the DPH excited state. This phenomenon allows one to use the fluorescence lifetime to gain insight into the local concentration of probe in microscopic regions of a membrane. One application of this is in distinguishing lipid transfer between the outer leaflets of two contacting membrane bilayers from fusion between these membranes that leads to mixing of lipids in both the inner and outer leaflets of the membrane bilayers. This allows a single measurement to demonstrate fusion between membrane pairs.Abbreviations PEG
poly(ethylene glycol)
- Na2EDTA
ethyiene-diamine-tetraacedic acid, disodium salt
- LUV
large, unilamellar vesicles made by rapid extrusion technique
- DPH
1,6-diphenyl-trans-1,3,5-hexatriene
- DPHpPC
1-palmitoyl-2-[[[2-[4- (phenyl-trans-1,3,5-hexatrienyl)phenyl]ethyl]oxy]carbonyl]-3-sn-phosphatidylcholine
- DPPC
1,2-dipalmitoyl-3-sn-phosphatidylcholine
- PA
palmitic acid
- NBD-PE
N-(7-nitro-2,1,3-benzoxadiazol-4-yl)-PE
- Rh-PE
N-(lissamine Rhodamine B sulfoyl)-PE
- R18
octadecyl Rhodamine B chloride
- ANTS
1-aminonaphthalene-3,6,8-trisulfonic acid
- DPX
N,N-p-xylylene-bis(pyradinium bromide) 相似文献
8.
The synthesis of the shape-persistent macrocycles 10a and 10b with two bipyridine units in opposing sides by Hagihara/Sonogashira cross-coupling chemistry of suitably functionalized building blocks is reported. X-ray analysis of single crystals of 10b shows a layered structure with channels filled with solvent molecules and parts of the flexible chains. with which the cycle is decorated for solubility reasons. 相似文献
9.
10.
Syntheses, Structure Determination and Reactions of Phosphine Substituted Derivatives of Fe3(CO)9(μ3-CF)2 Photolysis of Fe3(CO)9(μ3-CF)2 1 in the presence of acetonitrile 2a or benzoenitrile 2b results in the substitution of a single carbonyl ligand by a nitrile ligand yielding Fe3(CO)8(CH3CN)(μ3-CF)2 3a and Fe3(CO)8(C6H5CN)(μ3-CF)2 3b, respectively. The acetonitrile ligand in 3a can be easily replaced by trimethyl-phosphine 4a or triphenylphosphine 4b . The monosubstituted compounds Fe3(CO)8(PR3)(μ3-CF)25, R = CH3 a, R = C6H5, b are obtained as major products besides a small amount of the disubsituted products Fe3(CO)7(PR3)2(μ3-CF)2 6. The structure of 5a has been elucidated by a single crystal X-ray structure determination. Thermal ligand substitution in 1, however, results in the formation of a mixture of mono-, disubstituted, and trisubstituted products, in which 6b is the major product for diphenylphosphine. 5a reacts with ethyne 7 forming a phosphine substituted diferra-allyl-cluster Fe3(CO)7(PR3)(μ3-CF)(μ3? CF? CH? CH) 8. The structure of one isomere of 8 has been determinated by X-ray crystallography. 相似文献