Anodic hydroxylation of 1-carbomethoxy-1,2,3,4-tetrahydrocarbazoles

1-Carbomethoxy-1,2,3,4-tetrahydrocarbazole (1) and its 7-methoxy derivative (2) were oxidized at carbon felt anodes in acetonitrile containing 0.2 M LiClO₄ and 2-17 M water at potentials on the rising portion of the primary oxidation peak to yield products formed by formal substitution of the C-1 H atom with hydroxide. The resulting 1-hydroxy-l-carbomethoxy-1,2,3,4-tetrahydrocarbazole and its 7-methoxy derivative were isolated in 44 and 22% yields, respectively, when sodium bicarbonate was used to control acidity of the medium. Structures were elucidated by NMR, IR, elemental analysis, and mass spectrometry. Voltammetry at carbon-paste and glassy carbon electrodes showed that the oxidations proceed by an ECE or DISPI pathway. The rate-determining step is the reaction of water with a cation radical electrochemically generated from 1 or 2, involving either proton abstraction or nucleophilic addition.     

Bioluminescent detection of insect pheromones using an enzyme-based flow injection analysis system

The combination of flow injection analysis with chemiluminescent detection is shown to provide extremely selective and sensitive detection of insect pheromones which possess an aldehyde moiety. The flow injection analysis system provides reproducible control of both the reaction chemistry and the sample introduction process. Microliter volume samples can be precisely handled and analyzed with this experimental configuration. The detection system is based on the luciferase-catalyzed oxidation of reduced flavin mononucleotide which occurs in the presence of aldehydes with carbon backbones of between 14 and 16 carbons. A limit of detection of 3 fmol of tetradecyl aldehyde is demonstrated and the system is shown to be insensitive to the presence of various organic solvents up to concentrations of approximately 10%. The key experimental variables which control sensitive detection of pheromone at the femtomole level with be investigated and discussed.     

Hapten immobilization for antibody sensing using a dynamic modification protocol

Optical fiber (OF) sensors are often limited by the immobilization technique used to associate a specific sensing ligand with the OF surface. This is particularly true when the ligand is biologically active as, for example, in the case of immobilized haptens or antibodies. The dynamic modification protocol is a regenerable and experimentally simple way to immobilize a variety of sensing molecules on an OF surface. Furthermore, the protocol is immune to hydrolysis and not limited by diffusion through a membrane or sol–gel. In this publication the approach is extended by immobilizing the hydrophobic hapten (octadecyl 6-(2,4 dinitrophenyl)aminohexanoic acid) as a means to prepare an OF sensor for antibodies specific for 2,4 dinitrophenyl (DNP). The LOD for anti-DNP is 0.5 nanomolar and the K_apparent is 1.0±0.2×10⁶. Nonspecific antibody adsorption is problematic in this sensing approach and was found to limit the quantitative capabilities of the sensor. However, time discrimination can be used to allow the nonspecific antibody to desorb prior to measurement thus minimizing the influence of nonspecific binding on sensor performance.     

High angular-resolution automated visible-wavelength scanning angle Raman microscopy

A scanning angle (SA) Raman microscope with 532-nm excitation is reported for probing chemical content perpendicular to a sample interface. The instrument is fully automated to collect Raman spectra across a range of incident angles from 20.50 to 79.50° with an angular spread of 0.4 ± 0.2° and an angular uncertainty of 0.09°. Instrumental controls drive a rotational stage with a fixed axis of rotation relative to a prism-based sample interface mounted on an inverted microscope stage. Three benefits of SA Raman microscopy using visible wavelengths, compared to near infrared wavelengths are: (i) better surface sensitivity; (ii) increased signal due to the frequency to the fourth power dependence of the Raman signal, and the possibility for resonant enhancement; (iii) the need to scan a reduced angular range to shorten data collection times. These benefits were demonstrated with SA Raman measurements of thin polymer films of polystyrene or a diblock copolymer of polystyrene and poly(3-hexylthiophene-2,5-diyl). Thin film spectra were collected with a signal-to-noise ratio of 30 using a 0.25 s acquisition time.     

新开花粉蛋白的盐酸胍去折叠过程

本文利用荧光光谱和园二色光谱了新开花粉蛋白的盐酸胍去折叠过程。结果显示：新开花粉蛋白的盐酸胍去折叠是一个只包含天然蛋白和变性终态的二态过程,与已经报道的天花粉蛋白的盐酸胍去折叠的过程不同。