Boronic acids that change fluorescence properties upon sugar binding are very useful for the synthesis of carbohydrate sensors. Along this line, boronic acids that fluoresce beyond 500 nm are especially useful. A series of boronic acid fluorescent reporter compounds based on the 4-amino-1,8-naphthalimide structure have been synthesized (1a-d) and evaluated under near physiological conditions. These compounds showed good water solubility and significant changes in fluorescence properties after binding with sugars, with the emission wavelength being at around 570 nm. Analogues in this series with different substitutions showed similar properties. We have also examined the mechanism of the observed fluorescence changes for these compounds. 相似文献
Glucose oxidase is a flavoprotein that is relatively well-studied as a physico-chemical model system. The flavin cofactor is surrounded by several aromatic acid residues that can act as direct and indirect electron donors to photoexcited flavin. Yet, the identity of the photochemical product states is not well established. We present a detailed full spectral reinvestigation of this issue using femtosecond fluorescence and absorption spectroscopy. Based on a recent characterization of the unstable tyrosine cation radical TyrOH•+, we now propose that the primary photoproduct involves this species, which was previously not considered. Formation of this product is followed by competing charge recombination and radical pair stabilization reactions that involve proton transfer and radical transfer to tryptophan. A minimal kinetic model is proposed, including a fraction of TyrOH.+ that is stabilized up to the tens of picoseconds timescale, suggesting a potential role of this species as intermediate in biochemical electron transfer reactions. 相似文献
We successfully synthesized eight meso-aryl BODIPYs with 2,6-diethyl- or 1,2,6,7-tetraethyl substituents and characterized their photophysical properties. The steric hindrance resulting from the phenolic group in the meso-aryl moiety and the ethyl groups on the BODIPY core affected the synthesis of dipyrromethanes as an intermediate as well as the UV–Vis absorption and fluorescence emission of the BODIPYs due to the constrained rotation of the aryl ring. The potential use of the meso-hydroxyphenyl BODIPY as a pH sensor was also shown by the pH-dependent fluorescence emissions. 相似文献
Three tripodal ligands H3L1–3 containing imidazole rings were synthesized by the reaction of 1,10‐phenanthroline‐5,6‐dione with 1,3,5‐tris[(3‐formylphenoxy)methyl]benzene, 1,3,5‐tris[(3‐formylphenoxy)methyl]‐2,4,6‐trimethylbenzene, and 2,2′,2\"‐tris[(3‐formylphenoxy)ethyl]amine, respectively. Trinuclear RuII polypyridyl complexes [(bpy)6Ru3H3L1–3](PF6)6 were prepared by the condensation of Ru(bpy)2Cl2 · 2H2O with ligands H3L1–3. The pH effects on the UV/Vis absorption and fluorescence spectra of the three complexes were studied, and ground‐ and excited‐state ionization constants of the three complexes were derived. The three complexes act as “off‐on‐off” fluorescence pH switch through protonation and deprotonation of imidazole ring with a maximum on‐off ratio of 5 in buffer solution at room temperature. 相似文献
Nanoplasmonic sensors based on the localized surface plasmon resonance (LSPR) of noble metal nanoparticles have many advantages, such as real‐time detection, no need for reagent labelling, and no use of complicated equipment. However, the nanoplasmonic sensors with two dimensional structures usually suffer from a low LSPR signal and thus low sensitivity due to the low density of the nanoparticles. In addition, complicated surface functionalization is always required to suppress the non‐specific binding of the analyst to the substrate of the sensor, because the two types of surface, that is, metal and substrate surfaces, are simultaneously exposed to the reaction medium. To overcome these problems, an innovative thermal‐induced method has been proposed in the present work, to construct three dimensional (3D) nanostructure of Ag nanocubes on both surfaces of the substrate by using the unique amphiphilic property of 2‐diethylaminoethanethiol. The prepared nanoplasmonic sensor is highly sensitive due to the high density of 3D structure of the nanoparticles and the low non‐specific binding since only one type of surface is exposed. To enhance the stability of the sensor, a thin SiO2 overlayer was formed on the surface without using an additional coupling agent. Furthermore, the NiII‐nitriloacetic acid (NiII‐NTA) complex was covalently bound on the surface, so that the regeneration and reuse of the sensor becomes easy. Therefore, the easy fabrication, high stability, and good reusability of this 3D LSPR sensor makes our method competitive for the development of nanoplasmonic sensors. 相似文献
Not the Ag clusters, but rather the O atoms are responsible for the yellow color of silver-containing zeolite A. The reason for this has remained unclear since 1962. It is now shown that a charge-transfer transition from the lattice oxygen atoms to the empty 5s orbital of the silver ions (shown schematically on the right) is responsible for the yellow coloring. 相似文献
We report on the reflectance, transmittance and fluorescence spectra (λ=200–1200 nm) of four types of chicken eggshells (white, brown, light green, dark green) measured in situ without pretreatment and after ablation of 20–100 μm of the outer shell regions. The color pigment protoporphyrin IX (PPIX) is embedded in the protein phase of all four shell types as highly fluorescent monomers, in the white and light green shells additionally as non-fluorescent dimers, and in the brown and dark green shells mainly as non-fluorescent poly-aggregates. The green shell colors are formed from an approximately equimolar mixture of PPIX and biliverdin. The axial distribution of protein and colorpigments were evaluated from the combined reflectances of both the outer and inner shell surfaces, as well as from the transmittances. For the data generation we used the radiative transfer model in the random walk and Kubelka-Munk approaches. 相似文献
A versatile amphiphilic pyrano[2,3-b]indole for halochromic turn-ON luminescence in acidic or basic media is accessed by an insertion-coupling-cycloisomerization and adjusting solubilizing and phenolic functionalities. While almost non-emissive in neutral solutions, treatment with acids or bases like trifluoroacetic acid (TFA) or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) reveals distinct luminescence at wavelengths of 540 nm or 630 nm in propan-2-ol, respectively. Turn-ON emission can be detected at pH values as mild as pH = 5.31 or 8.70. Quantum yields in propan-2-ol are substantial for protonated (Φf = 0.058) and deprotonated (Φf = 0.059) species. Photometrically, pKa1 of 3.5 and pKa2 of 10.5 were determined in propan-2-ol. With lipophilic polyether sidechains and hydrophilic protonation and deprotonation sites the molecule can be regarded as amphipolar, which results in good solubility properties for different organic solvents. In aqueous media, an organic co-solvent like propan-2-ol (35%) or tetrahydrofuran (25%) is needed, and the solution can be diluted with pure water without precipitation of the compound. At higher concentrations of water, a turbid solution is formed, which indicates the formation of micellar structures or clusters. With dynamic light scattering we could show that these clusters increase in size with increasing water content. 相似文献
CT or not CT : Three imidazole‐annulated TTF derivatives 1 – 3 have been prepared and fully characterized. The influence of the TTF unit on the pKa values of the acceptor units as determined by photometric titration has been discussed. The results reported here are part of an initial exploratory study to generate a range of well‐defined coordination networks.
A series of new photo‐responsive amino acid‐derived azobenzenedicarboxylic acid derivatives (S)‐ 1 a – e were synthesized. Compound (S)‐ 1 a in the trans form exhibited no circular dichroism (CD) signal in DMF under ambient conditions, whereas intense Cotton effects were observed upon UV irradiation, indicating the formation of a chiral supramolecular structure in the cis form. The CD signals disappeared when trifluoroacetic acid (TFA) was added to the solution. The ester counterpart [(S)‐ 1 a′ ] showed no CD signal. Hydrogen bonding between the carboxy groups seemed necessary for constructing the supramolecular structure. The kinetic studies of cis to trans isomerization of (S)‐ 1 a demonstrated that the formation of a chiral supramolecule enhances the stability of the cis‐azobenzene structure. The ESI mass spectrum of stilbenedicarboxylic acid (S)‐ 4 , an analogue of (S)‐ 1 b , confirmed the formation of a dimer. A theoretical CD study revealed that (S)‐ 1 a in the cis form should be present as a cyclic chiral dimer. 相似文献
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