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11.
W N Li C Sotiriou-Leventis S Abdel-Baky D H Fisher R W Giese 《Journal of chromatography. A》1991,588(1-2):273-280
Benzo[a]pyrene-r-7,t-8,9,c-10-tetrahydrotetrol (100 pg, 342 fmol) was measured using the following sequence of steps: (1) chemical transformation with potassium superoxide to 2,3-pyrenedicarboxylic acid; (2) electrophore derivatization with pentafluorobenzyl bromide; (3) sample clean-up by high-performance liquid chromatography and (4) measurement by gas chromatography with electron-capture detection and by gas chromatography with electron-capture negative-ion mass spectrometry. The overall, absolute yields obtained by the two procedures were 69% and 60%, respectively. This work completes the first stage towards the establishment of a general method for detecting diolepoxide polyaromatic hydrocarbon DNA adducts by gas chromatography. 相似文献
12.
Leventis N Yang J Fabrizio EF Rawashdeh AM Oh WS Sotiriou-Leventis C 《Journal of the American Chemical Society》2004,126(13):4094-4095
We report the redox properties of four star systems incorporating the 4-benzoyl-N-alkylpyridinium cation; the redox potential varies along the branches but remains constant at fixed radii. Bulk electrolysis shows that at a semi-infinite time scale all redox centers are electrochemically accessible. However, voltammetric analysis (cyclic voltammetry and differential pulse voltammetry) shows that only two of the three redox-active centers in the perimeter are electrochemically accessible during potential sweeps as slow as 20 mV s-1 and as fast as 10 V s-1. On the contrary, both redox centers along branches are accessible electrochemically within the same time frame. These results are explained in terms of slow through-space charge transfer and the globular 3-D folding of the molecules and are discussed in terms of their implications on the design of efficient redox functional dendrimers. 相似文献
13.
Costopoulos B Benaki D Pelecanou M Mikros E Stassinopoulou CI Varvarigou AD Archimandritis SC 《Inorganic chemistry》2004,43(18):5598-5602
The decapeptide Arg-Gly-Asp-Ser-Cys-Arg-Gly-Asp-Ser-Tyr, which contains two Arg-Gly-Asp (RGD) moieties in its sequence, has been successfully labeled with radioactive rhenium (Re-188) yielding a single, stable oxorhenium complex. This complex is being evaluated for possible application in oncology as a target-specific radiotherapeutic agent, because its radioactive technetium-99m analogue has already been applied for the scintigraphic detection of malignant melanoma in humans. For structural characterization purposes, the complex of the decapeptide was synthesized at the macroscopic level using nonradioactive rhenium (Re-185/Re-187). NMR and mass spectral analysis of the nonradioactive oxorhenium complex revealed that the decapeptide coordinates to the oxorhenium core through the N(amide) of Asp3, the N(amide) of Ser4, and the N(amide) and S(thiolate) atoms of Cys5 to form a complex of the ReO[N(3)S] type. 相似文献
14.
Thangavel A Sotiriou-Leventis C Dawes R Leventis N 《The Journal of organic chemistry》2012,77(5):2263-2271
According to recent reports, supramolecular complexes of the pyrylium cation with cucurbit[x]urils (CB[x], x = 7, 8) show promising photoluminescence suitable for electroluminescent devices. In turn, photoluminescence seems to be related to the stereochemistry of the complexes; however, that has been controversial. Here, we report that in H(2)O, 2,6-disubsituted-4-phenyl pyryliums (Pylm) form dimers quantitatively (equilibrium constants >10(4) M(-1)), but they enter as such only in the larger CB[8]. In terms of orientation, (1)H NMR shows that Me-Pylm, Ph-Pylm, and t-Bu-Pylm insert their 4-phenyl groups in either the CB[7] or CB[8] cavity. The orientation of iPr-Pylm in the iPr-Pylm@CB[7] complex is similar. Experimental conclusions are supported by DFT calculations using the M062X functional and the 6-31G(d) basis set. In the case of (iPr-Pylm)(2)@CB[8], (1)H NMR of both the guest and the host indicates that both guests might enter CB[8] from the same side with their iPr groups in the cavity, but DFT calculations leave room for ambiguity. In addition to the size and hydrophobicity of the 2,6-substituents of the guests, as well as the size and flexibility of the hosts, theory reveals the importance of explicit solvation (H(2)O) and finite temperature effects (particularly for (1)H NMR shielding calculations) in the determination of the stereochemistry of those complexes. 相似文献
15.
Surfactant-templated mesoporous silica aerogels (or nanofoams) with their entire skeletal framework nanoencapsulated conformally by a thin polyurea layer are emerging as materials with high specific strength and high energy absorption. In this paper a modified split Hopkinson pressure bar was used to investigate their mechanical behavior under dynamic compression at high strain rates. The evolution of the mesoporous structure under such dynamic impact conditions was simulated using the Material Point Method (MPM). The material point model was generated from X-ray micro-computed tomography whereas each voxel was converted to a material point corresponding to the local skeletal density of the material. Simulation results agree well with the experimental data, indicating that the MPM can effectively model the compression of complex mesoporous structures. Simulations indicate a nearly uniform deformation at all three stages of compression: the elastic region, compaction and the final densification due to the low ratio of pore size to wall thickness and random distribution of the pores. Simulations have also indentified the function of the conformal polymer coating as a reinforcing factor, showing that different porosities, obtained by varying the skeletal wall thickness, affect the local stress distribution. Eventually, simulations confirm that the stress-strain behavior of aerogels under compression follows a power-law relationship with the initial bulk density, consistent with experimental results. 相似文献
16.
Ioannis T. Papadas Chariklia Kosma Yiannis Deligiannakis 《Journal of colloid and interface science》2009,339(1):19-30
Cu2+ binding on γ-Al2O3 is modulated by common electrolyte ions such as Mg2+, , and in a complex manner: (a) At high concentrations of electrolyte ions, Cu2+ uptake by γ-Al2O3 is inhibited. This is partially due to bulk ionic strength effects and, mostly, due to direct competition between Mg2+ and Cu2+ ions for the SO− surface sites of γ-Al2O3. (b) At low concentrations of electrolyte ions, Cu2+ uptake by γ-Al2O3 can be enhanced. This is due to synergistic coadsorption of Cu2+ and electrolyte anions, and . This results in the formation of ternary surface species (SOH2SO4Cu)+, (SOH2PO4Cu), and (SOH2HPO4Cu)+ which enhance Cu2+ uptake at pH < 6. The effect of phosphate ions may be particularly strong resulting in a 100% Cu uptake by the oxide surface. (c) EPR spectroscopy shows that at pH pHPZC, Cu2+ coordinates to one SO− group. Phosphate anions form stronger, binary or ternary, surface species than sulfate anions. At pH pHPZC Cu2+ may coordinate to two SO− groups. At pH pHPZC electrolyte ions and are bridging one O-atom from the γ-Al2O3 surface and one Cu2+ ion forming ternary [γ-Al2O3/elecrolyte/Cu2+] species. 相似文献
17.
When vic-dihydroxychlorins undergo a pinacol-pinacolone rearrangement, the migratory aptitudes of common porphyrin substituents follow the order: alkyl groups, propionate side chain, H > methyl group > acetate side chain. C-Alkylchlorins can be made by extremely short syntheses utilizing such rearrangement. 相似文献
18.
Chryssou K Pelecanou M Pirmettis IC Papadopoulos MS Raptopoulou C Terzis A Chiotellis E Stassinopoulou CI 《Inorganic chemistry》2002,41(18):4653-4663
Synthesis of the 2,9-dimethyl-4,7-diaza-4-alkyl-2,9-decanedithiol (1, alkyl = morpholinylethyl in a, and alkyl = pyrrolidinylethyl in b), following a widely used synthetic scheme for diaminedithiol (DADT) ligands, led to the isolation of 1-alkyl-2-(1'-methyl-1'-sulfanylethyl)-3-(2' '-methyl-2' '-sulfanylpropyl)diazolidine (3) as the major product. Both ligands 1 and 2 gave complexes with the oxorhenium ReO(V) core. Ligand 1 gave the expected ReO[SNNS] complex (2) with the side chain on nitrogen in the syn configuration. Ligand 3 gave, in the presence of a monodentate aromatic thiol, complexes of the ReO[SNN][S][S] (4) and ReO[SNN][S] type (5), respectively, in which the diazolidine ring has rearranged to a thiazolidine ring. Crystallographic analysis showed that in 4 the coordination geometry about the metal is distorted octahedral where the equatorial plane is defined by the sulfur and one of the nitrogen atoms of the ligand and the two sulfurs of the aromatic thiols, while the axial positions are occupied by the oxygen of the ReO core and the second nitrogen of the ligand. Specifically, complex 4a crystallizes in space group P2(1)/c, a = 15.63(1) A, b = 15.28(2) A, c = 16.07(1) A, beta = 113.78(2) degrees, V = 3512(5) A(3), Z = 4. Complex 4b crystallizes in space group P2(1)/n, a = 14.560(9) A, b = 14.804(9) A, c = 19.85(1) A, beta = 90.94(2) degrees, V = 4278(1) A(3), Z = 4. In 5b, the coordination geometry is distorted square pyramidal with the SNN donor atom of the ligand and the aromatic thiol defining the equatorial plane and the doubly bonded oxygen occupying the apex of the pyramid. Complex 5b crystallizes in space group P(-)1, a = 9.387(5) A, b = 11.306(5) A, c = 14.040(6) A, alpha = 84.51(1) degrees, beta = 84.45(2) degrees, gamma = 87.17(1) degrees, V = 1475(1) A(3), Z = 2. All isolated complexes are neutral and lipophilic. Complete assignments of (1)H and (13)C NMR resonances are reported. 相似文献
19.
An effective synthesis of 1-(6-hydroxyindol-1-yl)-2,2-dimethylpropan-1-one (4) was developed starting from 1H-indole (2). The key step involved suitable utilization of 4-(1-pyrrolidino)pyridine for the removal of the chloroacetyl moiety from chloroacetic acid 1-(2,2-dimethylpropionyl)-1H-indol-6-yl ester (3); a possible mechanism is, also, presented. Compound 4 might lead to selectively substituted derivatives, either on the phenolic-OH or the indolyl-NH, with putative biological interest. In this respect, we found that the core structure of 1H-indol-6-ol (1) possesses a degree of aldose reductase inhibitory potential, at a concentration of 100 microM. 相似文献
20.
In water, N-methyl-4-(p-substituted benzoyl)pyridinium cations, BP-X, exist in equilibrium with their hydrated forms (gem-diols), whose concentrations depend on the para substituent (-X). In the presence of cucurbit[7]uril (CB[7]), the benzoyl group shows a preference for the CB[7] cavity, and the ketone to gem-diol equilibrium is shifted toward the keto form, meaning that the stabilization realized through hydrophobic interactions of the benzoyl group in the CB[7] cavity exceeds the hydrogen-bonding stabilization of the gem-diols in the aqueous environment. 相似文献