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Nearly all compounds comprise numerous isotopologues ensuing from stable natural isotopes for constituent elements. The consequent isotopic envelopes in mass spectra can reveal the ion stoichiometry but not geometry. We found those envelopes to split in differential ion mobility (FAIMS) spectra in a manner dependent on the ion geometry and buffer gas composition. The resulting multidimensional matrix of isotopic shifts is specific to isomers, providing a fundamentally new approach to the characterization of chemical structure. The physical origins of the effect remain to be clarified but likely ensue from the transposition of center of mass of the ion within its geometry frame affecting the partition of energy in above-thermal collisions between the translational and rotational degrees of freedom. The additivity of shifts, holding with no exception so far, may be the key to unraveling the foundations of observed behavior. [ABSTRACT FROM AUTHOR]

Context: Sleep schedule adjustments are common requirements of modern-day athletes. Many nonpharmacologic and pharmacologic strategies exist to facilitate circadian rhythm shifts to maximize alertness and performance during competition. This review summarizes the evidence for commonly used pharmacologic agents and presents recommendations for the sports medicine provider.Evidence Acquisition: MEDLINE searches were performed using the following keywords: sleep aids, circadian rhythm adjustment, athletes and sleep, caffeine and sports, melatonin and athletes, and sleep aids and sports. Pertinent articles were extracted and discussed.Study Design: Clinical review.Level Of Evidence: Level 2.Results: There are very few available studies investigating pharmacologic sleep aids in athletes. Data from studies involving shift workers and airline personnel are more abundant and were used to formulate recommendations and conclusions.Conclusion: Melatonin, caffeine, and nonbenzodiazepine sleep aids have a role in facilitating sleep schedule changes in athletes and maximizing sports performance through sleep enhancement. [ABSTRACT FROM AUTHOR]

Histone proteins are subject to dynamic post-translational modifications (PTMs) that cooperatively modulate the chromatin structure and function. Nearly all functional PTMs are found on the N-terminal histone domains (tails) of ~50 residues protruding from the nucleosome core. Using high-definition differential ion mobility spectrometry (FAIMS) with electron transfer dissociation, we demonstrate rapid baseline gas-phase separation and identification of tails involving monomethylation, trimethylation, acetylation, or phosphorylation in biologically relevant positions. These are by far the largest variant peptides resolved by any method, some with PTM contributing just 0.25% to the mass. This opens the door to similar separations for intact proteins and in top-down proteomics. [ABSTRACT FROM AUTHOR]

This paper studies bandwidth selection for kernel estimation of derivatives of multidimensional conditional densities, a non-parametric realm unexplored in the literature. This paper extends Baird [Cross validation bandwidth selection for derivatives of multidimensional densities. RAND Working Paper series, WR-1060; 2014] in its examination of conditional multivariate densities, derives and presents criteria for arbitrary kernel order and density dimension, shows consistency of the estimators, and investigates a minimization criterion which jointly estimates numerator and denominator bandwidths. I conduct a Monte Carlo simulation study for various orders of kernels in the Gaussian family and compare the new cross validation criterion with those implied by Baird [Cross validation bandwidth selection for derivatives of multidimensional densities. RAND Working Paper series, WR-1060; 2014]. The paper finds that higher order kernels become increasingly important as the dimension of the distribution increases. I find that the cross validation criterion developed in this paper that jointly estimates the derivative of the joint density (numerator) and the marginal density (denominator) does orders of magnitude better than criteria that estimate the bandwidths separately. I further find that using the infinite order Dirichlet kernel tends to have the best results. [ABSTRACT FROM PUBLISHER]

The article presents information on the significant legal developments in nations comprising the Asia Pacific Region during 2012. It informs that Australia is taking bold preventative steps on the regulation of dark pools liquidity, automated algorithmic trading, and High Frequency Trading (HFT). It further informs that about the legal developments of other countries including Korea, Japan and Philippines in the case of telecommunication, environment and oil and gas.

The isotopic molecular envelopes due to stable isotopes for most elements were a staple of mass spectrometry since its origins, often leveraged to identify and quantify compounds. However, all isomers share one MS envelope. As the molecular motion in media also depends on the isotopic composition, separations such as liquid chromatography (LC) and ion mobility spectrometry (IMS) must also feature isotopic envelopes. These were largely not observed because of limited resolution, except for the (structurally uninformative) shifts in LC upon H/D exchange. We recently found the isotopic shifts in FAIMS for small haloanilines (∼130-170 Da) to hinge on the halogen position, opening a novel route to isomer characterization. Here, we extend the capability to heavier species: dibromoanilines (DBAs, ∼250 Da) and tribromoanilines (TBAs, ∼330 Da). The 13 C shifts for DBAs and TBAs vary across isomers, some changing sign. While 81 Br shifts are less specific, the 2-D 13 C/ 81 Br shifts unequivocally differentiate all isomers. The trends for DBAs track those for dichloroanilines, with the 13 C shift order preserved for most isomers. The peak broadening due to merged isotopomers is also isomer-specific. The absolute shifts for TBAs are smaller than those for lighter haloanilines, but differentiate isomers as well because of compressed uncertainties. These results showcase the feasibility of broadly distinguishing isomers in the more topical ∼200-300 Da range using the isotopic shifts in IMS spectra.