Fast-atom bombardment and tandem mass spectrometry of macrolide antibiotics

Molecular weights of macrolide antibiotics can be determined from either (M + H)⁺ or (M + Met)⁺, the latter desorbed from alkali metal salt-saturated matrices. The ion chemistry of macrolides, as determined by tandem mass spectrometry (MS/MS), is different for ions produced as metallated than those formed as (M + H)⁺ species. An explanation for these differences is the location of the charge. For protonated species, the charge is most likely situated on a functional group with high proton affinity, such as the dimethylamino group of the ammo sugar. The alkali metal ion, however, is bonded to the highly oxygenated aglycone. As a result, the collision-activated dissociation spectra of protonated macrolides are simple with readily identifiable fragment ions in both the high and low mass regions but no fragments in the middle mass range. In contrast, the cationized species give complex spectra with many abundant ions, most of which are located in the high mass range. The complementary nature of the fragmentation of these two species recommends the study of both by MS/MS when determining the structure or confirming the identity of these biomaterials.     

Ligand–protein recognition studies as determined by nuclear relaxation analysis

The ligand–macromolecule interaction is analysed in terms of selective (R₁^SE) and non-selective (R₁^NS) spin–lattice relaxation rates, considering the contribution arising from all possible specific and non-specific receptor sites. A linear relation between ΔR₁^SE and macromolecule concentration is demonstrated to exist under any coordination conditions. The slope of the straight line obtained is defined as the ‘affinity index' which is proposed as a general criterion for assessing the total ability of a ligand to interact with a macromolecule.     

Chaotic motions of a rigid rotor in short journal bearings

In the present paper the conditions that give rise to chaotic motions in a rigid rotor on short journal bearings are investigated and determined. A suitable symmetry was given to the rotor, to the supporting system, to the acting system of forces and to the system of initial conditions, in order to restrict the motions of the rotor to translatory whirl. For an assigned distance between the supports, the ratio between the transverse and the polar mass moments of the rotor was selected conveniently small, with the aim of avoiding conical instability. Since the theoretical analysis of a system's chaotic motions can only be carried out by means of numerical investigation, the procedure here adopted by the authors consists of numerical integration of the rotor's equations of motion, with trial and error regarding the three parameters that characterise the theoretical model of the system: m, the half non-dimensional mass of the rotor, , the modified Sommerfeld number relating to the lubricated bearings, and , the dimensionless value of rotor unbalance. In the rotor's equations of motion, the forces due to the lubricating film are written under the assumption of isothermal and laminar flow in short bearings. The number of numerical trials needed to find the system's chaotic responses has been greatly reduced by recognition of the fact that chaotic motions become possible when the value of the dimensionless static eccentricity % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbnL2yY9% 2CVzgDGmvyUnhitvMCPzgarmWu51MyVXgaruWqVvNCPvMCG4uz3bqe% fqvATv2CG4uz3bIuV1wyUbqee0evGueE0jxyaibaieYlf9irVeeu0d% Xdh9vqqj-hEeeu0xXdbba9frFf0-OqFfea0dXdd9vqaq-JfrVkFHe9% pgea0dXdar-Jb9hs0dXdbPYxe9vr0-vr0-vqpWqaaeaabiGaciaaca% qabeaadaabauaaaOqaaiabew7aLnaaBaaaleaacaWGZbaabeaaaaa!4046!\[\varepsilon _s \] is greater than 0.4. In these conditions, non-periodic motions can be obtained even when rotor unbalance values are not particularly high (=0.05), whereas higher values (>0.4) make the rotor motion periodic and synchronous with the driving rotation. The present investigation has also identified the route that leads an assigned rotor to chaos when its angular speed is varied with prefixed values of the dimensionless unbalance . The theoretical results obtained have then been compared with experimental data. Both the theoretical and the experimental data have pointed out that in the circumstances investigated chaotic motions deserve more attention, from a technical point of view, than is normally ascribed to behaviours of this sort. This is mainly because such behaviours are usually considered of scarce practical significance owing to the typically bounded nature of chaotic evolution. The present analysis has shown that when the rotor exhibits chaotic motions, the centres of the journals describe orbits that alternate between small and large in an unpredictable and disordered manner. In these conditions the thickness of the lubricating film can assume values that are extremely low and such as to compromise the efficiency of the bearings, whereas the rotor is affected by inertia forces that are so high as to determine severe vibrations of the supports.Nomenclature C radial clearance of bearing (m) - D diameter of bearing (m) - e dimensional eccentricity of journal (m) - e _s value of e corresponding to the static position of the journal - E dimensional static unbalance of rotor (m) - f _x, f _y =F _x/(P), F _y/(P): non-dimensional components of fluid film force - F _x, F _y dimensional components of fluid film force (N) - g acceleration of gravity (m/s²) - L axial length of bearing (m) - m % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbnL2yY9% 2CVzgDGmvyUnhitvMCPzgarmWu51MyVXgaruWqVvNCPvMCG4uz3bqe% fqvATv2CG4uz3bIuV1wyUbqee0evGueE0jxyaibaieYlf9irVeeu0d% Xdh9vqqj-hEeeu0xXdbba9frFf0-OqFfea0dXdd9vqaq-JfrVkFHe9% pgea0dXdar-Jb9hs0dXdbPYxe9vr0-vr0-vqpWqaaeaabiGaciaaca% qabeaadaabauaaaOqaaiabg2da9maalaaabaGaeqyYdC3aaWbaaSqa% beaacaaIYaaaaaGcbaGaeqyYdC3aa0baaSqaaGabciaa-bdaaeaaca% WFYaaaaaaakiabg2da9maalaaabaGaeqyYdC3aaWbaaSqabeaacaaI% YaaaaOGaam4qaaqaaiabeo8aZjaadEgaaaaaaa!4C14!\[ = \frac{{\omega ^2 }}{{\omega _0^2 }} = \frac{{\omega ^2 C}}{{\sigma g}}\]: half non-dimensional mass of rotor - M half mass of rotor (kg) - n angular speed of rotor (in r.p.m.=60/2) - t time     

Pulsed Nd:YAG laser welding of AISI 304 to AISI 420 stainless steels

The technique to weld AISI 304 stainless steel to AISI 420 stainless steel with a pulsed Nd:YAG laser has been investigated. The main objective of this study was to determine the influence of the laser beam position, with respect to the joint, on weld characteristics. Specimens were welded with the laser beam incident on the joint and moved 0.1 and 0.2 mm on either side of the joint. The joints were examined in an optical microscope for cracks, pores and to determine the weld geometry. The microstructure of the weld and the heat affected zones were observed in a scanning electron microscope. An energy dispersive spectrometer, coupled to the scanning electron microscope, was used to determine variations in (weight %) the main chemical elements across the fillet weld. Vickers microhardness testing and tensile testing were carried out to determine the mechanical properties of the weld. The results of the various tests and examinations enabled definition of the best position for the incident laser beam with respect to the joint, for welding together the two stainless steels.     

Modulating the Enantiodiscrimination Features of Inherently Chiral Selectors by Molecular Design: A HPLC and Voltammetry Study Case with Atropisomeric 2,2’-Biindole-Based Monomers and Oligomer Films

A family of inherently chiral electroactive selectors based on the 2,2’-biindole atropisomeric scaffold, of easy synthesis and modulable functional properties, is studied in cascade in two enantioselection contexts. They are at first investigated as probes in enantioselective HPLC, studying molecular structure and temperature effects, and achieving very efficient semipreparative enantioseparation. The enantiomers thus obtained, of remarkable chiroptical features (optical rotation as well as circular dichroism), are successfully applied as selectors in chiral voltammetry in different media for discrimination of the enantiomers of chiral electroactive probes, either by conversion into enantiopure electroactive electrode surfaces by electrooligomerization on glassy carbon substrate (the two monomers with shorter alkyl chains), or as chiral additive in achiral ionic liquid (the monomer with longest alkyl chains). Discrimination is conveniently and reproducibly achieved in terms of significant potential differences for the two enantiomers, specularly inverting either probe or selector configuration. In one case successful discrimination is also observed with the two probe enantiomers concurrently present, either as racemate or with enantiomeric excesses, neatly accounted for by the peak current ratios.     

Environment induced quantum Zeno effect in coupled microwave cavities

We model a feasible experiment involving two interacting microwave cavities with very different quality factors. An excitation is initially present in the high Q cavity. Modeling the environment as linearly coupled oscillators, we find a Zeno-like behavior which should occur when the dissipation constant is large enough as compared to the unitary coupling.     

L‐lysine and EDTA polymer mimics as resins for the quantitative and reversible removal of heavy metal ion water pollutants

Traditional precipitation methods for inorganic micropollutant removal from waters are increasingly being replaced by sorption methods based on both natural and synthetic materials. In this context, two novel effective heavy metal ions absorbers are presented. These resins, LYMA and LMT85, were crosslinked poly(amidoamine)s carrying amine and carboxyl groups in their repeating units. In particular, the LYMA‐repeating unit contains one carboxyl and two amine groups and is a mimic of L ‐lysine, whereas LMT85 contains two amine and five carboxyl groups and is a mimic of EDTA. Both resins were prepared at moderate cost by simple eco‐friendly procedures. The heavy metal ion set adopted as benchmark was Cu²⁺, Cd²⁺, Pb²⁺, Zn²⁺, Ni²⁺, and Co²⁺. LYMA proved selective for Cu²⁺ and Ni²⁺, the other ions tested being negligibly absorbed, whereas LMT85 proved capable of rapidly and quantitatively absorbing all the ions tested either singly or in mixed solution. The absorption process was reversible, and the resins were easily regenerated by acidification. The absorption of several metal ions imparted intense coloring to the resins, a feature possibly exploitable for analytical purposes. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

CW laser-induced photothermal conversion and shape transformation of gold nanodogbones in hydrated chitosan films

We investigate the photothermal conversion and transformation of gold nanoparticles with an initial dogbone shape after dispersion in hydrated chitosan films, which is a representative model of biological tissue, and excitation by a CW diode laser for 1 min. Gold nanodogbones are observed to undergo a distinct modification above a sharp threshold of ~11 W cm⁻² and 110 °C. Surprisingly, the very same modification is achieved up to at least 36 W cm⁻² and 250 °C. We use an analytical model derived from Gans theory to associate the change in color of the films with the change in shape statistics of these gold nanoparticles. This model proves both convenient and dependable. We interpret the photothermal transformation as a rearrangement of particles with a dogbone shape and an aspect ratio of 4.1 into rods with an aspect ratio of 2.5, where material from the end lobes of the dogbones may relocate to the waists of the rods. In turn, additional transitions to stable gold nanospheres may exhibit fairly slower kinetics.