The fragmentation of protonated molecules (MH(+)) in mass spectrometry usually results in even-electron product ions, but the MH(+) ions of sulfonamides are different as they often produce dominant radical cations of the constituent amines. For a series of benzenesulfonamides of anilines that bear various substituents, we found that the sulfonamides are preferentially protonated at the nitrogen, which is different from the carboxylic amides. Upon N-protonation, the S-N bond dissociates spontaneously to produce an intermediate [sulfonyl cation/aniline] complex. Within the ion-neutral complex, charge transfer between the two partners occurs in the gas phase to give rise to the ionized anilines. A substantial energy barrier was found to govern the reaction, which is consistent with the outer-sphere electron transfer mechanism. This energy barrier prevents the charge transfer when a strong electron-withdrawing substituent is attached to the aniline moiety. In contrast, when the aniline bears an electron-donating group, charge transfer is still more favorable than the dissociation of the intermediate ion-neutral complex, in spite of the existence of the energy barrier, and therefore dominates. A correlation was observed between the intensities of the ionized anilines and the ionization energies of these anilines.

This study was designed to test the effects of angiotensin-converting enzyme (ACE) inhibition on body composition and physical performance in aged rats. Male Brown Norway 3 F344 rats were randomized to receive daily injections of enalapril (40 mg/kg or 80 mg/kg) or saline from 24 to 30 months of age. Body composition was determined using dual-energy X-ray absorptiometry (DXA), and physical performance was assessed using the grip strength and inclined plane procedures. Performance measures were assessed at baseline and monthly thereafter. DXA was performed at baseline, 3 months, and 6 months of follow-up. Compared with the enalapril groups, the saline group experienced a greater 6-month decline in the physical performance measures. Lean body mass declined in both groups; however, the enalapril groups also experienced a significant loss of fat mass. These results suggest that ACE inhibition may prevent age-related declines in physical performance, which may be mediated by a reduction in body fat mass.O BSERVATIONAL studies suggest that angiotensinconverting enzyme (ACE) inhibition may help to prevent age-related declines in physical performance. We previously reported a positive association between use of ACE inhibitors and muscle strength and walking speed in a subpopulation of individuals from the Women's Health and Aging Study (WHAS) (1). Our results suggest that ACE inhibitor treatment could decrease long-term decline in physical function in elderly women. Other evidence from a recent cross-sectional study using a sample of healthy elderly men and women from the Health and Aging Body Composition Study (Health ABC) demonstrated a significant positive association between use of ACE inhibitors and skeletal muscle mass (2). However, it remains to be determined in prospective randomized controlled trials whether ACE inhibitors may prevent the progression of disability in older persons and whether this effect is mediated by remodeling body composition.Several genetic studies suggest that the renin-angiotensin system (RAS) modulates the function of skeletal muscle tissue and is a determinant of visceral adiposity. Enhanced responsiveness to exercise, mediated by an increase in muscle strength, is associated with the insertion (I) rather than the deletion (D) allele of the ACE gene, which, in turn, results in higher levels of ACE (3). There is also a higher prevalence of the ACE I/I allele among elite endurance athletes relative to the general population (4,5). Results from the Olivetti Prospective Heart Study reported that, in men aged 25-75 years, over a 20-year follow-up, the D/D genotype was a significant predictor of becoming overweight and increased abdominal adiposity (6). Although no functional outcomes were measured in this study, several studies have demonstrated that increased obesity is positively associated with declining physical performance and disability (7-10).We have recently reported on the validity of an assessment method for evaluating declining physical performance in adult rats that is conceptua...

In mass spectrometry of the alpha,beta-unsaturated aromatic ketones, Ph-CO-CH=CH-Ph', losses of a benzene from the two ends and elimination of a styrene are the three major fragmentation reactions of the protonated molecules. When the ketones are substituted on the right phenyl ring, the electron-donating groups are in favor of losing a styrene to form the benzoyl cation, PhCO(+), whereas the electron-withdrawing groups strongly favor loss of benzene of the left side to form a cinnamoyl cation, Ph'CH=CHCO(+). When the ketones are substituted on the left phenyl ring, the substituent effects on the reactions are reversed. In both cases, the ratios of the two competitive product ions are well-correlated with the sigma p(+) substituent constants. Theoretical calculations indicate that the carbonyl oxygen is the most favorable site for protonation, and the olefinic carbon adjacent to the carbonyl is also favorable especially when a strong electron-releasing group is present on the right phenyl ring. The energy barrier to the interconversion between the ions formed from protonation at these two sites regulates the overall reactions. Transfer of a proton from the carbonyl oxygen to the ipso position on either phenyl ring, which is dissociative, triggers loss of benzene.

Electrolyte engineering advances Li metal batteries (LMBs) with high Coulombic efficiency (CE) by constructing LiF-rich solid electrolyte interphase (SEI). However, the low conductivity of LiF disturbs Li+ diffusion across SEI, thus inducing Li+ transfer-driven dendritic deposition. In this work, we establish a mechanistic model to decipher how the SEI affects Li plating in high-fluorine electrolytes. The presented theory depicts a linear correlation between the capacity loss and current density to identify the slope k (determined by Li+ mobility of SEI components) as an indicator for describing the homogeneity of Li+ flux across SEI, while the intercept dictates the maximum CE that electrolytes can achieve. This model inspires the design of an efficient electrolyte that generates dual-halide SEI to homogenize Li+ distribution and Li deposition. The model-driven protocol offers a promising energetic analysis to evaluate the compatibility of electrolytes to Li anode, thus guiding the design of promising electrolytes for LMBs.

For p-(dimethylamino)chalcone (p-DMAC), the N atom is the most basic site in the liquid phase, whereas the O atom possesses the highest proton affinity in the gas phase. A novel and interesting observation is reported that the N- and O-protonated p-DMAC can be competitively produced in atmospheric pressure chemical ionization (APCI) with the change of solvents and ionization conditions. In neat methanol or acetonitrile, the protonation is always under thermodynamic control to form the O-protonated ion. When methanol/water or acetonitrile/water was used as the solvent, the protonation is kinetically controlled to form the N-protonated ion under conditions of relatively high infusion rate and high concentration of water in the mixed solvent. The regioselectivity of protonation of p-DMAC in APCI is probably attributed to the bulky solvent cluster reagent ions (S(n)H(+)) and the analyte having different preferred protonation sites in the liquid phase and gas phase.

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The elimination of SO2 from deprotonated sulfonamides in the negative ion mode was confirmed by Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) experiments. For a set of N-arylbenzenesulfonamides substituted at the para position of the arylamine, the ln([M-H-SO2](-)/[M-H]-) values were correlated with the sigmap(-) substituent constants but, instead of a linear relationship, a bent line was obtained. Analyses of the complex curve led to the identification of two competing routes, which were further investigated by Hartree-Fock theoretical calculations. Furthermore, collision-induced dissociation (CID) of deprotonated N-alkylbenzenesulfonamides containing the -CHCHNHSO2- structure yielded a [M-H-66](-) product ion This characteristic ion could help to distinguish the side-chain isomers.

A novel hexa-peri-hexabenzocoronene/oligothiophene hybrid is shown to self-assemble into a hexagonal columnar liquid crystalline phase, and respond to applied electric fields resulting in uniform homeotropic or parallel alignment depending upon the electrode structure. Furthermore, the columnar orientation can be maintained even after removal of the electric field unless the material is heated above the clearing temperature.