Stick balancing,falls and Dragon-Kings

The extent to which the occurrence of falls, the dominant feature of human attempts to balance a stick at their fingertip, can be predicted is examined in the context of the “Dragon-King” hypothesis. For skilled stick balancers, fluctuations in the controlled variable, namely the vertical displacement angle θ, exhibit power law behaviors. When stick balancing is made less stable by either decreasing the length of the stick or by requiring the subject to balance the stick on the surface of a table tennis racket, systematic departures from the power law behaviors are observed in the range of large θ. This observation raises the possibility that the presence of departures from the power law in the large length scale region, possibly Dragon-Kings, may identify situations in which the occurrence of a fall is more imminent. However, whether or not Dragon-Kings are observed, there is a Weibull-type survival function for stick falling. The possibility that increased risk of falling can, at least to some extent, be predicted from fluctuations in the controlled variable before the event occurs has important implications for the development of preventative strategies for the management of phenomena ranging from earthquakes to epileptic seizures to falls in the elderly.     

Flexible,dicationic imidazolium salts for in situ application in palladium‐catalysed Mizoroki–Heck coupling of acrylates under aerobic conditions

The synthesis, characterization and in situ catalytic performance of new unsymmetric N,N′‐disubstituted imidazolium‐based dicationic salts in Mizoroki–Heck coupling of acrylates with aryl bromides under aerobic conditions are described. A series of flexible dicationic salts with varying steric and electronic properties were synthesized in good to excellent yields. All the salts were well characterized using spectroscopic techniques. X‐ray diffraction analysis of two salts with the same dicationic backbone and different counter anions shows that the ligand adopts two different conformations which are influenced by the nature of the anion. Thus, the ligand is capable of changing its conformation according to the change in environment due to its flexible nature. All the synthesized imidazolium salts were found to be active in in situ palladium‐catalysed Mizoroki–Heck coupling under aerobic conditions. Amongst the salts, the hydroxyl‐functionalized imidazolium salt, incorporating the features of both bidentate chelating O,O ligand and carbene, shows the maximum catalytic activity. A variety of aryl and heteroaryl methyl and ethyl cinnamates were synthesized using these imidazolium salts as preligands. In addition, NMR studies confirm in situ generation of normal N‐heterocyclic carbenes from the C‐2 position of imidazol‐2‐ylidene ring. The mercury poisoning test was also performed to ascertain the nature of catalytically active palladium species. Aerobic conditions, low catalytic loading (0.5 mol%), shorter reaction times, broad functional group tolerance and good to excellent isolated yields are some of the significant features of the novel catalytic systems described here. Copyright © 2016 John Wiley & Sons, Ltd.     

New Enantioselective Routes to Cyclic and Acyclic S,O-acetals; Enzymatic Resolution of α-Acetoxy Sulfides and Enantioselective Synthesis of the Antiviral Agent Lamivudine

A new method for the synthesis of cyclic and acyclic optically active S,O-acetals is reported, along with subsequent stereocontrolled transformations, culminating in a synthesis of the important antiviral nucleoside Lamivudine.     

Analysis of polar peptides using a silica hydride column and high aqueous content mobile phases

The retention behavior of a set of polar peptides separated on a silica hydride stationary phase was examined with a capillary HPLC system coupled to ESI‐MS detection. The mobile phases consisted of formic acid or acetic acid/acetonitrile/water mixtures with the acetonitrile content ranging from 5 to 80% v/v. The effects on peptide retention of these two acidic buffer additives and their concentrations in the mobile phase were systematically investigated. Strong retention of the peptides on the silica hydride phase was observed with relatively high‐organic low‐aqueous mobile phases (i.e. under aqueous normal‐phase conditions). However, when low concentrations of acetic acid were employed as the buffer additive, strong retention of the peptides was also observed even when high aqueous content mobile phases were employed. This unique feature of the stationary phase therefore provides an opportunity for chromatographic analysis of polar peptides with water‐rich eluents, a feature usually not feasible with traditional RP sorbents, and thus under conditions more compatible with analytical green chemistry criteria. In addition, both isocratic and gradient elution procedures can be employed to optimize peptide separations with excellent reproducibility and resolution under these high aqueous mobile phase conditions with this silica hydride stationary phase.     

Simultaneous separation of hydrophobic and polar bases using a silica hydride stationary phase

In this study, the retention behavior of selected hydrophobic and polar bases on a minimally modified silica hydride phase was investigated. From these results and the associated retention plots, significant differences in the chromatographic dependencies of these two classes of basic compounds were evident. The polar bases exhibited strong retention with mobile phases of high organic solvent content, but displayed weak retention with mobile phases of high water content. In contrast, the hydrophobic bases showed “U‐shape” retention dependencies, indicative of the interplay of both RP and normal‐phase retention characteristics. These studies have demonstrated that hydrophobic and polar bases can be simultaneously separated on the same column either under typical RP‐like or aqueous normal‐phase‐like conditions, respectively, with distinctive selectivity. Finally, the effects of temperature on the RP and aqueous normal phase modality of separations with these analytes were investigated, where discrete changes in retention behavior were also observed.     

Miniaturized molecularly imprinted polymer extraction method for the gas chromatographic analysis of flavonoids

In this study, the use of monolithic molecularly imprinted polymers in a micropipette tip format allowing the simple and fast extraction of flavonoids from standard solutions and a black tea sample is demonstrated. The imprinted polymer employed quercetin, methacrylic acid or 4‐vinylpyridine, and ethylene glycol dimethacrylate as template, functional monomer, and cross‐linker, respectively. Surface morphologies of the quercetin‐imprinted polymers and the corresponding nonimprinted polymers were characterized by SEM. Extraction of flavonoid standards was performed to evaluate the selectivity and recovery with these imprinted and nonimprinted polymers. Flavonoid compositions in aliquots eluted from the tips were identified using fast GC with flame ionization detection. Maximum specific capacities of 0.2, 5.7, and 16.0 mg/g for catechin, morin, and quercetin, respectively, were obtained with the imprinted polymer prepared with methacrylic acid, with the corresponding recoveries of 99.8, 98.8, and 95.4%, respectively. Efficient extraction by the quercetin‐imprinted polymer of epicatechin, catechin, and quercetin from an apple‐flavored black tea sample was achieved, with GC–MS employed for compound identification for both the tea and extracted samples.     

High-resolution heteronuclear correlation spectroscopy in solid state NMR of aligned samples

A new two-dimensional scheme is proposed for accurate measurements of high-resolution chemical shifts and heteronuclear dipolar couplings in NMR of aligned samples. Both the (1)H chemical shifts and the (1)H-(15)N dipolar couplings are evolved in the indirect dimension while the (15)N chemical shifts are detected. This heteronuclear correlation (HETCOR) spectroscopy yields high-resolution (1)H chemical shifts split by the (1)H-(15)N dipolar couplings in the indirect dimension and the (15)N chemical shifts in the observed dimension. The advantages of the HETCOR technique are illustrated for a static (15)N-acetyl-valine crystal sample and a (15)N-labeled helical peptide sample aligned in hydrated lipid bilayers.     

Long‐Lived Spin States for Low‐Field Hyperpolarized Gas MRI

Parahydrogen induced polarization was employed to prepare a relatively long‐lived correlated nuclear spin state between methylene and methyl protons in propane gas. Conventionally, such states are converted into a strong NMR signal enhancement by transferring the reaction product to a high magnetic field in an adiabatic longitudinal transport after dissociation engenders net alignment (ALTADENA) experiment. However, the relaxation time T₁ of ～0.6 s of the resulting hyperpolarized propane is too short for potential biomedical applications. The presented alternative approach employs low‐field MRI to preserve the initial correlated state with a much longer decay time T_LLSS=(4.7±0.5) s. While the direct detection at low‐magnetic fields (e.g. 0.0475 T) is challenging, we demonstrate here that spin‐lock induced crossing (SLIC) at this low magnetic field transforms the long‐lived correlated state into an observable nuclear magnetization suitable for MRI with sub‐millimeter and sub‐second spatial and temporal resolution, respectively. Propane is a non‐toxic gas, and therefore, these results potentially enable low‐cost high‐resolution high‐speed MRI of gases for functional imaging of lungs and other applications.