Highlighting the possible secondary interactions in the role of balhimycin and its analogues for enantiorecognition in capillary electrophoresis

It is believed that the enantiorecognition mechanism based on macrocyclic antibiotics involves multimodal interactions via hydrogen bonding, π–π interaction, steric hindrance, hydrophobic interaction and so on. A variety of enantiomeric N-benzoylated amino acids were separated using balhimycin (A) or its analogues bromobalhimycin (B) and dechlorobalhimycin (C) as chiral mobile phase additive using a CE method, which combined the partial filling technique with the dynamic coating technique and the co-EOF electrophoresis technique. The enantioresolution and the migration time were highly relevant to the structure of analytes, especially to the substitutions on the N-tagged benzoyl moiety of the amino acids. A steric effect and π–π interaction based mechanism is proposed in order to explain some observed enantioresolution differences between positional isomers. Notably dechlorobalhimycin exhibited the best enantioresolution for several N-benzoylated derivatives of leucine, which was rarely observed for N-dansylated amino acid derivatives. The hydrophobicity difference of the aglycone pocket among three chiral selectors was assumed to account for this behaviour.     

Hydrogen Bonding in the Water Stabilized Structure of the Modified Unsymmetrically Substituted Viologen Chromophore, <Emphasis Type="Italic">N</Emphasis>-ethyl-<Emphasis Type="Italic">N</Emphasis>′-(2-phosphonoethyl)-4,4′-bipyridylium Dichloride

Abstract  

The crystal structure of the modified unsymmetrically N,N′-substituted viologen chromophore, N-ethyl-N′-(2-phosphonoethyl)-4,4′-bipyridinium dichloride 0.75 hydrate (1) has been determined. Crystals are triclinic, space group P−1 with Z = 2 in a cell with a = 7.2550(1), b = 13.2038(5), c = 18.5752(7) Å, α = 86.495(3), β = 83.527(2), γ = 88.921(2)°. The two independent but pseudo-symmetrically related cations in the asymmetric unit form one-dimensional hydrogen-bonded chains through short homomeric phosphonic acid O–H···O links [2.455(4), 2.464(4) Å] while two of the chloride anions are similarly strongly linked to phosphonic acid groups [O–H···Cl, 2.889(4), 2.896(4) Å]. The other two chloride anions together with the two water molecules of solvation (one with partial occupancy) form unusual cyclic hydrogen-bonded bis(Cl···water) dianion units which lie between the layers of bipyridylium rings of the cation chain structures with which they are weakly associated.     

Classification of behavior using vocalizations of Pacific white-sided dolphins (Lagenorhynchus obliquidens)

Surface behavior and concurrent underwater vocalizations were recorded for Pacific white-sided dolphins in the Southern California Bight (SCB) over multiple field seasons spanning 3 years. Clicks, click trains, and pulsed calls were counted and classified based on acoustic measurements, leading to the identification of 19 key call features used for analysis. Kruskal-Wallis tests indicated that call features differ significantly across behavioral categories. Previous work had discovered two distinctive click Types (A and B), which may correspond to known subpopulations of Pacific white-side dolphins in the Southern California Bight; this study revealed that animals producing these different click types also differ in both their behavior and vocalization patterns. Click Type A groups were predominantly observed slow traveling and milling, with little daytime foraging, while click Type B groups were observed traveling and foraging. These behavioral differences may be characteristic of niche partitioning by overlapping populations; coupled with differences in vocalization patterns, they may signify that these subpopulations are cryptic species. Finally, random forest decision trees were used to classify behavior based on vocalization data, with rates of correct classification up to 86%, demonstrating the potential for the use of vocalization patterns to predict behavior.     

Saxophonists tune vocal tract resonances in advanced performance techniques

The acoustical impedance spectrum was measured in the mouths of saxophonists while they played. During bugling and while playing in the very high or altissimo range, experienced players tune a strong, but relatively broad, peak in the tract impedance to select which peak in the bore impedance will determine the note. Less experienced players are unable to produce resonances with impedance peaks comparable in magnitude to those of the bore and consequently are unable to play these notes. Experienced players can also tune their tracts to select which combinations of notes are played simultaneously in multiphonics or chords, and to produce pitch bending, a technique in which notes are produced at frequencies far from those of the peak of impedance of the instrument bore. However, in normal playing in the standard range, there is no consistent tuning of the tract resonances. The playing frequency, in all cases, lies close to the peak in the impedance of the reed in parallel with the series combination of the impedances measured in the mouth and the instrument bore on either side of the reed (ZMouth+ZBore)∥ZReed.     

A characterization of the scattered acoustic intensity field in the resonance region for simple spheres

The properties of the scattered acoustic vector fields generated by simple spheres illuminated by monotonic continuous wave (CW) plane waves are investigated. Analytical solutions are derived from general acoustic pressure scattering models and analyzed for wave numbers in the resonance region. Of particular interest is the understanding of the characteristics of the scattered acoustic vector field in the near-to-far-field transition region. The separable active and reactive components of the acoustic intensity are used to investigate the structural features of the scattered field components. Numerical results are presented for the near and transition regions for a rigid sphere. A method of mapping nulls in the scattered intensity field components is described. The analysis is then extended to include a simple fluid-filled boundary and finally the evacuated thin-walled shell. Near field acoustic intensity field structures are compared against mechanical material properties of vacuous shells. The ability to extract scattered field features is illustrated with measurements obtained from a recent in-air experiment using an anechoic chamber and acoustic vector sensor probes to measure the scattered acoustic vector field from rigid spheres.     

A comparison of stochastic and effective medium approaches to the backscattered signal from a porous layer in a solid matrix

This paper reports a study of the backscattering behavior of a solid layer containing randomly spaced spherical cavities in the long wavelength limit. The motivation for the work arises from a need to model the responses of porous composite materials in ultrasonic NDE procedures. A comparison is made between models based on a summation over discrete scatterers, which show interesting emergent properties, and an integral formulation based on an ensemble average, and with a simple slab effective medium approximation. The similarities and differences between these three models are demonstrated. A simple quantitative criterion is established which sets the maximum frequency at which ensemble average or equivalent homogeneous medium models can represent echo signal generation in a porous layer for given interpore spacing, or equivalently, given pore size and concentration.     

Compressibility measurements of quasi-one-dimensional quantum wires

We report measurements of the compressibility of a one-dimensional quantum wire, defined in the upper well of a GaAs/AlGaAs double quantum well heterostructure. A wire defined simultaneously in the lower well probes the ability of the upper wire to screen the electric field from a biased surface gate. The technique is sensitive enough to resolve spin splitting of the subbands in the presence of an in-plane magnetic field. We measure a compressibility signal due to the 0.7 structure and study its evolution with increasing temperature and magnetic field. We see no evidence of the formation of the quasibound state predicted by the Kondo model, instead our data are consistent with theories which predict that the 0.7 structure arises as a result of spontaneous spin polarization.     

Generalization of Carré equation

The present work offers new equations for phase evaluation in measurements. Several phase shifting equations with an arbitrary but constant phase shift between captured intensity signs are proposed. The equations are similarly derived as the so-called Carré equation. The idea is to develop a generalization of Carré equation that is not restricted to four images. Errors and random noise in the images cannot be eliminated, but the uncertainty due to their effects can be reduced by increasing the number of observations. An experimental analysis of the mistakes of the technique was made, as well as a detailed analysis of mistakes of the measurement. The advantages of the proposed equation are its precision in the measures taken, speed of processing and the immunity to noise in signs and images.     

Increase of both order and disorder in the first hydration shell with increasing solute polarity

Monte?Carlo simulations of a small model solute in an aqueous solution are used to examine the effects of solute polarity on hydration structure. A judicious definition of the orientational order parameter leads to reinterpretation of the conventional picture of hydration. As the solute varies from hydrophobic to hydrophilic the ordered first shell water simultaneously fractionates into a more highly ordered and a more disordered component. The hydrogen-bond network rearranges such that the more ordered component relaxes to configurations of optimal intermolecular angles, the other fraction being released from the network.