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11.
Ren QX Douglass V Xu W Sabat M Periasamy A Demas JN DeGraff BA 《Journal of fluorescence》2007,17(3):249-255
Luminescence properties and the x-ray structures of the fluorescent crown ether, 16-anthracen-ylmethyl-1,4,7,10,13-pentaoxa-16-aza-cyclooctadecane
(CEA) and its complex with potassium hexafluorophosphate (CEAK) have been obtained. In the solid state CEAK gives a structured
blue emission and CEA gives a broad structureless green emission. The differences in luminescence behavior are explained on
the basis of crystal packing. X-ray analysis shows that every two adjacent anthracene moieties in CEA form a sandwich-like
anti-parallel dimer; the green-structureless emission then arises from the π-π stack of the aromatic rings. In CEAK, disruption
of the π-π stacking structure forces a large separation between the anthracene rings, which yields an anthracene monomer emission.
Luminescence lifetime data support the assignments. 相似文献
12.
Dixon EN Snow MZ Bon JL Whitehurst AM DeGraff BA Trindle C Demas JN 《Inorganic chemistry》2012,51(6):3355-3365
A suite of Ru(II) complexes in which one ligand is pH responsive and the other two are varied in an effort to achieve improved photophysics has been synthesized and their potential as pH reporters assessed. The more general purpose of the study was to examine the role of the accessory ligands in heteroleptic reporter complexes and the degree to which such ligands can affect the performance of luminescent reporters. For this suite of complexes, judicious choice of the accessory ligand can alter both the pK(a)* and the dynamic range of response. It was found that the emission color and brightness were influenced by pH, but the lifetimes were only weakly affected. Surprisingly, some accessory ligands which should have improved luminescent properties essentially turned off the pH response. Several possible reasons for this observation are explored. It is suggested, and density functional theory (DFT) calculations support, that the relative π* levels of the pH sensitive and the accessory ligands are critical. 相似文献
13.
Leavens BB Trindle CO Sabat M Altun Z Demas JN DeGraff BA 《Journal of fluorescence》2012,22(1):163-174
The synthesis of some heteroleptic, cyclometalated iridium(III) complexes is described. The utility of these [Ir(ppy)2(N-N)]Cl (ppy = 2-phenylpyridine and N-N = substituted bipyridine, biquinoline, or phenanthroline) complexes as luminescence-based
sensors is assessed. The emission intensity of an Ir(III) complex featuring the 3,3′-Hndcbpy ligand (Hndcbpy = dicarboxylic acid-2,2′-bipyridine; n = 0,1,2 to indicate deprotonated, mono- and diprotonated species, respectively) is seen to increase in the presence of Pb(II).
Insight into the structure and analyte-sensing capability is achieved by X-ray crystallography in conjunction with computational
modeling. Complexes incorporating carboxylic acid-functionalized bipyridine and biquinoline as the polypyridyl ligand show
pH sensitivity while similar phenanthroline complexes do not. 相似文献
14.
Guoqing Zhang Shin Han Kim Ruffin E. Evans Byeong Hyo Kim J. N. Demas Cassandra L. Fraser 《Journal of fluorescence》2009,19(5):881-889
A class of aryl trifluoromethyl-containing β-diketones were synthesized via one step Claisen condensation. These π-conjugated
diketones exhibit strong solvatochromism from intramolecular donor-acceptor charge transfer (CT). In addition, fluorescence
quantum yields (ϕf) and lifetimes (τf) were measured in different solvents. Diketones exhibit bathochromic shifts in emission spectra with increasing solvent polarity.
Fluorescence changes upon Group II metal binding were also studied. Despite the relatively simple structure, the anthracene-CF3 diketone, atm, has strong binding affinity for Mg2+. A 70 nm blue shift and sixfold increase in intensity were observed upon addition of only one equivalent MgCl2 in ethanol solution. It also shows selectivity for Mg2+ binding even in the presence of excess Ca2+. Association constant (Ka) calculations suggest atm has two orders of magnitude stronger chelation for divalent magnesium than for calcium. These findings
make atm an attractive starting point for molecular probe and light emitting material design. 相似文献
15.
Vasiliki Demas Anthony Bernhardt Vince Malba Kristl L. Adams Lee Evans Christopher Harvey Robert S. Maxwell Julie L. Herberg 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2009,200(1):56-63
Nuclear magnetic resonance (NMR) offers a non-destructive, powerful, structure-specific analytical method for the identification of chemical and biological systems. The use of radio frequency (RF) microcoils has been shown to increase the sensitivity in mass-limited samples. Recent advances in micro-receiver technology have further demonstrated a substantial increase in mass sensitivity [D.L. Olson, T.L. Peck, A.G. Webb, R.L. Magin, J.V. Sweedler, High-resolution microcoil H-1-NMR for mass-limited, nanoliter-volume samples, Science 270 (5244) (1995) 1967–1970]. Lithographic methods for producing solenoid microcoils possess a level of flexibility and reproducibility that exceeds previous production methods, such as hand winding microcoils. This paper presents electrical characterizations of RF microcoils produced by a unique laser lithography system that can pattern three dimensional surfaces and compares calculated and experimental results to those for wire wound RF microcoils. We show that existing optimization conditions for RF coil design still hold true for RF microcoils produced by lithography. Current lithographic microcoils show somewhat inferior performance to wire wound RF microcoils due to limitations in the existing electroplating technique. In principle, however, when the pitch of the RF microcoil is less than 100 μm lithographic coils should show comparable performance to wire wound coils. In the cases of larger pitch, wire cross sections can be significantly larger and resistances lower than microfabricated conductors. 相似文献
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Cao W Ferrance JP Demas J Landers JP 《Journal of the American Chemical Society》2006,128(23):7572-7578
Efficient and stable quenching of electrochemiluminescence (ECL) of tris(2,2'-bipyridine)ruthenium(II) by oxidizing ferrocene methanol (FcMeOH) at the electrode is reported. Bimolecular energy or electron transfer between Ru(bpy)(3)(2+*) and ferrocenium (Fc(+)), the oxidized species of Fc, along with suppression of radical reactions is suggested as the mechanism for quenching ECL. Fc shows more efficient quenching of ECL compared with the known quenchers phenol and 1,1-dimethyl-4,4'-bipyridine dication (MV(2+)). The ECL quenching rate constant was 5.6 x 10(10) M(-)(1) s(-)(1). Using Fc as a quencher label on a complementary DNA sequence, an intramolecular ECL quenching in hybridized oligonucleotide strands has been realized. With essentially complete quenching efficiency, this system has the potential for application to sequence-specific DNA detection. 相似文献
19.
Srinu Bodige Parameshwar Ravula Kali Charan Gulipalli Srinivas Endoori Purna Koteswara Rao Cherukumalli Narendra Sharath Chandra JN 《合成通讯》2013,43(17):2219-2234
AbstractA novel series pyrrolo[3,2-b]pyridine-3-carboxamide linked 2-methoxypyridine derivatives have been designed, synthesized and confirmed by FT-IR, 1H NMR, 13C NMR, 19F NMR, MS, and elemental analysis. The synthesized compounds were screened for their antitubercular activity using microplate alamar blue assay method and antibacterial activity. Among the tested compounds, 4- fluorophenyl (8m), 4- chlorophenyl (8n) and 4-methoxyphenyl (8i) showed potent anti-TB activity (3.12?µg/mL) in comparison with reference drug, Pyrazinamide ((3.12?µg/mL). In addition, all compounds were docked into DprE1 (PDB code: 4KW5) to explore their binding interactions at the active site. The compounds exhibited essential key interactions as that of reported DprE1 inhibitors and hence, the synthesized compounds may be considered as molecular scaffolds for antitubercular activity. Compounds, 4-chlorophenyl (8n) and 4-flurophenyl (8m) showed significant antibacterial activity against Escherichia coli and Staphylococcus aureus strains. In silico prediction of toxicities, druglikeness and drug score profiles of the tested compounds are promising. 相似文献
20.
We compare the bimolecular quenching rate constant (k2) of luminescent tris(2,2′-bipyridine)ruthenium(II) by oxygen in water, ethylene glycol and glycerol as a function of temperature and viscosity to several theoretical models. The Smoluchowski equation with experimentally determined diffusion coefficients produced calculated values that were in the best agreement with experiment. For the less viscous solvent, water, this equation produced a value that was approximately an order of magnitude larger than the experimental value. With an increase in solvent viscosity, the Smoluchowski value approached the experimental value. Using the Smoluchowski equation with calculated diffusion coefficients based on the known radii of the reacting species produced deviations an order of magnitude larger in water and a factor of two or three lower in ethylene glycol and glycerol. If an assumption is made that the radii of both molecules are equal, we have the Stokes Einstein equation, and the only parameters become temperature and viscosity. Using this relationship, the calculated values for water are about a factor of two larger and with ethylene glycol and glycerol about a factor of 6 smaller than experimental data. These results show that bimolecular quenching is a more complex process affected by many parameters such as solvent cage effects in addition to viscosity and temperature. 相似文献