Esterase-assisted accumulation of 3-carboxy-2,2,5,5-tetramethyl-1-pyrrolidinyloxyl into lymphocytes

The intracellular detection of hydroxyl radical (HO*) through spin trapping/electron paramagnetic resonance (EPR) spectroscopy has been one of the great challenges in studying free radicals in biology. While 5-carboxy-5-methyl-1-pyrroline N-oxide, can specifically spin trap HO* in homogeneous solutions, the ionic nature of nitrone at physiologic pH prevents its entry into cells. We hypothesized that conversion of carboxyl-bearing spin probes such as nitrone into an esterase-hydrolyzable labile ester would permit intracellular localization and accumulation of the spin probes. To test the feasibility of such an approach, we prepared the model compound, 3-acetoxymethoxycarbonyl-2,2,5,5-tetramethyl-1-pyrrolidinyloxyl. This ester enabled ready accumulation of spin label to mM levels in lymphocytes. We suggest that its retention within these cells was the result of intracellular hydrolysis to 3-carboxy-2,2,5,5-tetramethyl-1-pyrrolidinyloxyl. Moreover, our studies show that aminoxyl was stable in the intracellular environment. These model studies suggest a viable strategy for detecting intracellular HO* by using the acetoxymethyl ester of 5-carboxy-5-methyl-1-pyrroline N-oxide.     

Electrode Kinetics and Activation Energy of Uranyl-Ferron Chelate by Polarography

The uranyl chelate of ferron was investigated polarographically over the pH range 1.98–10.00 and ligand concentration 0.005–0.060.M. A reversible and diffusion controlled reduction wave was obtained, however, when ferron concentration below 0.02M and pH below 5.0, it became irreversible. The chelate species identified were UO₂(HA) ₂ at pH range 2.5–7.1 and UO₂(OH) (A) ₂^?3 over pH 7.1. The electron-transfer coefficient, rate constant, diffusion coefficient and activation energy of the reduction process were determined.     

Synthesis, crystal structure, and solid-state NMR spectroscopy of a salt-inclusion stannosilicate: [Na3F][SnSi3O9

A salt-inclusion stannosilicate, [Na3F][SnSi3O9], has been synthesized using a flux-growth method and characterized by single-crystal X-ray diffraction. The structure consists of six-membered silicate rings linked via corner sharing by SnIVO6 octahedra to form a 3-D framework that delimits two types of channels. The F atoms and Na atoms are located in the structural channels and form a dimer with the anti-Al2Cl6(g) structure. This stannosilicate adopts a new structure and is the first metal silicate that contains both Na+ and F- ions in the channels. The 19F and 29Si MAS NMR and 23Na MQMAS NMR spectra are consistent with the crystallographic results.     

A Bio‐inspired Cu4O4 Cubane: Effective Molecular Catalysts for Electrocatalytic Water Oxidation in Aqueous Solution

Inspired by the cubic Mn₄CaO₅ cluster of natural oxygen‐evolving complex in Photosystem II, tetrametallic molecular water oxidation catalysts, especially M₄O₄ cubane‐like clusters (M=transition metals), have aroused great interest in developing highly active and robust catalysts for water oxidation. Among these M₄O₄ clusters, however, copper‐based molecular catalysts are poorly understood. Now, bio‐inspired Cu₄O₄ cubanes are presented as effective molecular catalysts for electrocatalytic water oxidation in aqueous solution (pH 12). The exceptional catalytic activity is manifested with a turnover frequency (TOF) of 267 s^?1 for [(L_Gly‐Cu)₄] at 1.70 V and 105 s^?1 for [(L_Glu‐Cu)₄] at 1.56 V. Electrochemical and spectroscopic study revealed a successive two‐electron transfer process in the Cu₄O₄ cubanes to form high‐valent Cu^III and Cu^IIIO^. intermediates during the catalysis.     

Two New Saturated Sesquiterpene Diols—Cadinan-3β, 9β-Diol and Cadinan-3β, 9α-Diol from Taiwania Cryptomerioides Hayata

From the wood of Taiwania cryptomerioides Hayata, two new sesquiterpenes, cadinan-3β, 9β-diol and cadinan-3β, 9α-diol were isolated as minor components. Their structures were elucidated as (I) and (II), respectively.     

S42+ and S42− : an ab initio study

The structures of S₄²⁺ and S₄^2? have been investigated by ab initio calculations using the GAUSSIAN 70 system of programs and the 44-31G basis set. Electronic singlet states of the square form and three possible conformations of the chain structure were examined for both ions, and the singlet rectangle form of S₄^2? was also investigated. The anti chain form of S₄²⁺ was found to be 78.3 kJ mol^? more stable than the square form, in contrast to previous experimental data. S₄^2?is predicted to adopt the chain structure with the anti conformation.     

Ultrafast quenching of tryptophan fluorescence in proteins: Interresidue and intrahelical electron transfer

Quenching of tryptophan fluorescence in proteins has been critical to the understanding of protein dynamics and enzyme reactions using tryptophan as a molecular optical probe. We report here our systematic examinations of potential quenching residues with more than 40 proteins. With site-directed mutation, we placed tryptophan to desired positions or altered its neighboring residues to screen quenching groups among 20 amino acid residues and of peptide backbones. With femtosecond resolution, we observed the ultrafast quenching dynamics within 100 ps and identified two ultrafast quenching groups, the carbonyl- and sulfur-containing residues. The former is glutamine and glutamate residues and the later is disulfide bond and cysteine residue. The quenching by the peptide-bond carbonyl group as well as other potential residues mostly occurs in longer than 100 ps. These ultrafast quenching dynamics occur at van der Waals distances through intraprotein electron transfer with high directionality. Following optimal molecular orbital overlap, electron jumps from the benzene ring of the indole moiety in a vertical orientation to the LUMO of acceptor quenching residues. Molecular dynamics simulations were invoked to elucidate various correlations of quenching dynamics with separation distances, relative orientations, local fluctuations and reaction heterogeneity. These unique ultrafast quenching pairs, as recently found to extensively occur in high-resolution protein structures, may have significant biological implications.     

Synthetic Transformations of Sulfur‐Substituted 4‐Quinolizidinones

Sulfur‐substituted 4‐quinolizidinones, previously prepared by aza‐Diels‐Alder reactions and ring‐closing metathesis, are now subjected to further synthetic transformations. Formal synthesis of cermizine C and 5‐epi‐cermizine C, and some other useful reactions have been achieved.     

Distinguishing authentic and counterfeit banknotes by surface chemical composition determined using electrospray laser desorption ionization mass spectrometry

Electrospray laser desorption ionization mass spectrometry (ELDI/MS) was used to rapidly distinguish authentic banknotes from counterfeits of the US dollar and the New Taiwan dollar. The banknotes' surfaces were irradiated with a pulsed ultraviolet laser, after which the desorbed ink compounds entered an electrospray plume and formed ions via interactions with charged solvent species. Authentic banknotes were found to differ from their counterfeit equivalents in their surface chemical compositions. The detected chemical compounds included various polymers, plasticizers and inks; these results were comparable with those obtained using solvent extraction followed by electrospray ionization mass spectrometry analysis. Because of the high spatial resolution of the laser beam, ELDI/MS analysis resulted in minimal damage to the banknotes. Copyright © 2013 John Wiley & Sons, Ltd.