Preparation of macrocyclic 15N-labelled oligoaminodeoxysaccharides as probes for RNA-binding

Two macrocyclic aminoglycosides were prepared from a 1,4-butanediol linked 2-deoxy-L-rhamnal which was O-allylated at the 4- and 4'-positions via the precursor allyl 3,4-di-O-acetyl-2,6-dideoxy-alpha-L-arabino-hexoside employing olefin metathesis and ring closing metathesis in a sequential manner. The macrocycles were 15N-labelled at all four amino groups in order to study interactions with regulatory RNA structures in solution by NMR spectroscopy. A key step for the introduction of the 15N-label was a reductive amination step using commercially available 15NH4OAc. The reductive amination proceeds with excellent stereocontrol. As a by-product the unusual acyclic amino nitrile was isolated which originated from intramolecular imine formation followed by cyanide addition to the intermediate C=N double bond.     

Application of an acoustic backscatter technique for characterizing the roughness of porous soil

An acoustic backscatter technique proposed by Oelze et al. [J. Acoust. Soc. Am. 109, 1826-1832 (2001)] was used to characterize the roughness of porous soil surfaces. Roughness estimation errors are minimized when the effective flow resistivity of the porous soil is high, e.g., above 300,000 mks Rayls/m. Four soil plots were constructed by roughening soil with farming implements. Three plots were sealed using Saran powder dissolved in methyl ethyl ketone (MEK) and then covered to prevent further weathering. A fourth plot was left in the open and exposed to rainfall, which also acted to seal the surface and further change the roughness. In sealing the surface the effective flow resistivity of the surface was increased above 300,000 mks Rayls/m, which is typical for weathered agricultural surfaces. The roughness power spectra of the soil surfaces were measured by acoustic backscatter and alternatively by a laser profiler. Regression analysis was used to approximate each roughness power spectrum versus roughness wave number with a best-fit line. The best-fit line was used to calculate the rms height and the correlation length of the rough surface by integrating the approximate roughness power spectrum over a range of roughness wave number values. The range of roughness wave number values defines the roughness length scales used in the statistical calculations. High-roughness wave numbers correspond to smaller length scales of roughness and low-roughness wave numbers correspond to larger length scales of roughness. Over certain ranges of roughness wave number values the statistics from the acoustic backscatter and laser profiler measurements is in good agreement. However, as the low-cutoff roughness wave number is decreased and the high-cutoff roughness wave number is increased, agreement between the laser and acoustic techniques diminishes.     

In vivo ultrasonic attenuation slope estimates for detecting cervical ripening in rats: Preliminary results

To effectively postpone preterm birth, cervical ripening needs to be detected and delayed. As the cervix ripens, the spacing between the collagen fibers increases and fills with water, hyaluronan, decorin, and enzymes suggesting that the ultrasonic attenuation of the cervix should decrease. The decrease in ultrasonic attenuation may be detectable, leading to an effective means of detecting cervical ripening. Herein, the traditional attenuation slope-estimation algorithm based on measuring the downshift in center frequency of the ultrasonic backscattered signal with propagation depth was modified and applied to the cervix of rats. The modified algorithm was verified using computer simulations and an ex vivo tissue sample before being evaluated in in vivo animal studies. Spherically-focused f/3 transducers with 33-MHz center frequencies and with 9-mm focal lengths were used in both the simulations and experiments. The accuracy was better than 15% in the simulations, and the attenuation slope of the cervix in the ex vivo experiment was 2.6+/-0.6 dB/cm-MHz, which is comparable to 2.5+/-0.4 dB/cm-MHz measured using a through-transmission insertion loss technique. For the in vivo experiments, a statistically significant effect of ultrasonic attenuation with gestational age was not observed. The large variances in the in vivo results were most likely due to the natural variation in attenuation for biological tissue between animals.     

Copper and iron interactions with angiotensin-converting enzyme inhibitors. A study by fast-atom bombardment tandem mass spectrometry

Fast atom bombardment, combined with high-energy collision-induced tandem mass spectrometry, has been used to investigate gas-phase metal-ion interactions with captopril, enalaprilat and lisinopril, all angiotensin-converting enzyme inhibitors.Suggestions for the location of metal-binding sites are presented. For captopril, metal binding occurs most likely at both the sulphur and the nitrogen atom. For enalaprilat and lisinopril, binding preferably occurs at the amine nitrogen. Copyright 1999 John Wiley & Sons, Ltd.     

ESI‐MS/MS of expanded porphyrins: a look into their structure and aromaticity

Electrospray mass spectrometry/mass spectrometry was used to investigate the gas‐phase properties of protonated expanded porphyrins, in order to correlate those with their structure and conformation. We have selected five expanded meso‐pentafluorophenyl porphyrins, respectively, a pair of oxidized/reduced fused pentaphyrins (22 and 24 π electrons), a pair of oxidized/reduced regular hexaphyrins (26 and 28 π electrons) and a regular doubly N‐fused hexaphyrin (28 π electrons). The gas‐phase behavior of the protonated species of oxidized and reduced expanded porphyrins is different. The oxidized species (aromatic Hückel systems) fragment more extensively, mainly by the loss of two HF molecules. The reduced species (Möbius aromatic or Möbius‐like aromatic systems) fragment less than their oxidized counterparts because of their increased flexibility. The protonated regular doubly fused hexaphyrin (non‐aromatic Hückel system) shows the least fragmentation even at higher collision energies. In general, cyclization through losses of HF molecules decreases from the aromatic Hückel systems to Möbius aromatic or Möbius‐like aromatic systems to non‐aromatic Hückel systems and is related to an increase in conformational distortion. Copyright © 2016 John Wiley & Sons, Ltd.     

Estimating concentration of ultrasound contrast agents with backscatter coefficients: experimental and theoretical aspects

Ultrasound contrast agents (UCAs) have been explored as a means to enhance therapeutic techniques. Because the effectiveness of these techniques relies on the UCA concentration at a target site, it would be beneficial to estimate UCA concentration noninvasively. In this study, a noninvasive method for estimating UCA concentration was developed in vitro. Backscatter coefficients (BSCs) estimated from measurements of Definity(?) UCAs were fitted to a theoretical scattering model in the 15-25 MHz range using a Levenberg-Marquardt regression technique. The model was defined by the UCA size distribution and concentration, and therefore concentration estimates were extracted directly from the fit. Calculation of the BSC was accomplished using planar reference measurements from the back wall of a Plexiglas(?) chamber and an average of 500 snapshots of ultrasonic backscatter from UCAs flowing through the chamber. In order to verify the ultrasonically derived UCA concentration estimates, a sample of the UCAs was extracted from the flow path and the concentration was estimated with a hemacytometer. UCA concentrations of 1, 2, and 5 times the dose recommended by the manufacturer were used in experiments. All BSC-based estimates were within one standard deviation of hemacytometer based estimates for peak rarefactional pressures of 100-400 kPa.     

Investigating the vortex melting phenomenon in BSCCO crystals using magneto-optical imaging technique

Using a novel differential magneto-optical imaging technique we investigate the phenomenon of vortex lattice melting in crystals of Bi₂Sr₂CaCu₂O₈ (BSCCO). The images of melting reveal complex patterns in the formation and evolution of the vortex solid-liquid interface with varying field (H)/temperature (T). We believe that the complex melting patterns are due to a random distribution of material disorder/inhomogeneities across the sample, which create fluctuations in the local melting temperature or field value. To study the fluctuations in the local melting temperature/field, we have constructed maps of the melting landscape T _m(H, r), viz., the melting temperature (T _m) at a given location (r) in the sample at a given field (H). A study of these melting landscapes reveals an unexpected feature: the melting landscape is not fixed, but changes rather dramatically with varying field and temperature along the melting line. It is concluded that the changes in both the scale and shape of the landscape result from the competing contributions of different types of quenched disorder which have opposite effects on the local melting transition.     

Energy dependence of multiplicity in proton-nucleus collisions and models of multiparticle production

This is a continuation of our earlier investigation (Gurtuet al 1974Phys. Lett. 50 B 391) on multiparticle production in proton-nucleus collisions based on an exposure of emulsion stack to 200 GeV/c beam at the NAL. It is found that the ratioR _em = 〈n _s〉/〈n _ch〉, where 〈n _ch〉 is the charged particle multiplicity in pp-collisions, increases slowly from about 1 at 10 GeV/c to 1·6 at 68 GeV/c and attains a constant value of 1·71 ± 0·04 in the region 200 to 8000 GeV/c. Furthermore,R _em = 1·71 implies an effectiveA-dependence ofR _A =A ^0.18,i.e., a very weak dependence. Predictions ofR _em on various models are discussed and compared with the emulsion data. Data seem to favour models of hadron-nucleon collisions in which production of particles takes place through adouble step mechanism,e.g., diffractive excitation, hydrodynamical and energy flux cascade as opposed to models which envisage instantaneous production.