Catechol reactivity: Synthesis of dopamine derivatives substituted at the 6-position

Dopamine is a ubiquitous neurotransmitter essential in the proper functioning of the human body. In addition to this critical role, the catecholamine core has shown utility as a scaffold for numerous drugs and in other applications, like metal detection and adhesive materials. Substituents at the 6-position of dopamine’s catechol core can modulate its stereoelectronic properties, the acidity of its phenolic hydroxyl groups, and the overall hydrophobicity of the molecule. Herein, we report the synthesis of a series of four novel dopamine analogues substituted at the 6-position of catechol core. The ¹H NMR chemical shift of the aromatic proton meta to the substituent correlated strongly with the Hammett σ_m constant, confirming the electronic properties of substituents.     

Electrochemical sensing based on printable temporary transfer tattoos

The realization of epidermal chemical sensing requires a fabrication methodology compatible with the non-planarity and irregularities of the human anatomy. This communication describes the development of printed temporary transfer tattoo (T3) electrochemical sensors for physiological and security monitoring of chemical constituents leading to the demonstration of 'electronic skin'.     

Inequalities for absolutely regular sequences: application to density estimation

This paper investigates the problem of density estimation for absolutely regular observations. In a first part, we state two important results: a new variance inequality and a Rosenthal type inequality. This allows us to study the ? _p -integrated risk, p≧ 2, of a large class of density estimators including kernel or projection estimators. Under the summability condition on the mixing coefficients ∑ _{k≧ 0} (k+1) ^{p− 2} β _k <∞, the rates obtained are those known to be optimal in the independent setting. Received: 17 October 1995 / In revised form: 26 October 1996     

Recent advances in amino acid analysis by capillary electrophoresis

This paper describes a number of articles that have been published on amino acid analysis using CE during the period from June 2003 to May 2005. This review article follows the previous ones of Smith (Electrophoresis 1999, 20, 3078-3083), Prata et al. (Electrophoresis 2001, 22, 4129-4138), and Poinsot et al. (Electrophoresis 2003, 24, 4047-4062). Several new developments in amino acid analysis with CE are reported concerning UV detection, LIF, MS, and NMR. In addition, we describe articles concerning clinical and pharmaceutical studies, neuroclinical applications, and agricultural and food analysis.     

Vibrational spectroscopy and quantum chemical studies of 1,6,7,12,13,18-hexaazatrinaphthylene and related compounds

The spectral properties of 1,6,7,12,13,18-hexaazatrinaphthylene (HATN) and a number of related compounds are modeled using density functional theory, B3LYP. The calculations predict the frequencies with mean absolute deviation of 6 cm(-1) and there is little improvement on going to basis sets larger than 6-31 G(d). The substituent effects on the observed spectra are modeled effectively in both frequency shifts and relative intensities. The electronic properties may be predicted using TD-DFT and these are in very good agreement, in terms of transition energies and intensities, with the experimental data.     

Characterization of Brain Metabolism by Nuclear Magnetic Resonance

The noninvasive, quantitative ability of nuclear magnetic resonance (NMR) spectroscopy to characterize small molecule metabolites has long been recognized as a major strength of its application in biology. Numerous techniques exist for characterizing metabolism in living, excised, or extracted tissue, with a particular focus on ¹H-based methods due to the high sensitivity and natural abundance of protons. With the increasing use of high magnetic fields, the utility of in vivo ¹H magnetic resonance spectroscopy (MRS) has markedly improved for measuring specific metabolite concentrations in biological tissues. Higher fields, coupled with recent developments in hyperpolarization, also enable techniques for complimenting ¹H measurements with spectroscopy of other nuclei, such as ³¹P and ¹³C, and for combining measurements of metabolite pools with metabolic flux measurements. We compare ex vivo and in vivo methods for studying metabolism in the brain using NMR and highlight insights gained through using higher magnetic fields, the advent of dissolution dynamic nuclear polarization, and combining in vivo MRS and ex vivo NMR approaches.