Reversible Mechanical Switching of Magnetic Interactions in a Molecular Shuttle

An acid–base switchable molecular shuttle based on a [2]rotaxane, incorporating stable radical units in both the ring and dumbbell components, is reported. The [2]rotaxane comprises a dibenzo[24]crown-8 ring (DB24C8) interlocked with a dumbbell component that possesses a dialkylammonium (NH₂⁺) and a 4,4′-bipyridinium (BPY²⁺) recognition site. Deprotonation of the rotaxane NH₂⁺ centers effects a quantitative displacement of the DB24C8 macroring to the BPY²⁺ recognition site, a process that can be reversed by acid treatment. Interaction between stable 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radicals connected to the ring and dumbbell components could be switched between noncoupled (three-line electron paramagnetic resonance (EPR) spectrum) and coupled (five-line EPR spectrum) upon displacement of the spin-labelled DB24C8 macroring. The complete base- and acid-induced switching cycle of the EPR pattern was repeated six times without an appreciable loss of signal, highlighting the reversibility of the process. Hence, this molecular machine is capable of switching on/off magnetic interactions by chemically driven reversible mechanical effects. A system of this kind represents an initial step towards a new generation of nanoscale magnetic switches that may be of interest for a variety of applications.     

Absolute quantification of superoxide dismutase in cytosol and mitochondria of mice hepatic cells exposed to mercury by a novel metallomic approach

In the last years, the development of new methods for analyzing accurate and precise individual metalloproteins is of increasing importance, since numerous metalloproteins are excellent biomarkers of oxidative stress and diseases. In that way, methods based on the use of post column isotopic dilution analysis (IDA) or enriched protein standards are required to obtain a sufficient degree of accuracy, precision and high limits of detection. This paper reports the identification and absolute quantification of Cu,Zn-superoxide dismutase (Cu,Zn-SOD) in cytosol and mitochondria from mice hepatic cells using a innovative column switching analytical approach. The method consisted of orthogonal chromatographic systems coupled to inductively coupling plasma-mass spectrometry equipped with a octopole reaction systems (ICP-ORS-MS) and UV detectors: size exclusion fractionation (SEC) of the cytosolic and mitochondrial extracts followed by online anion exchange chromatographic (AEC) separation of Cu/Zn containing species. After purification, Cu,Zn-SOD was identified after tryptic digestion by molecular mass spectrometry (MS). The MS/MS spectrum of a doubly charged peptide was used to obtain the sequence of the protein using the MASCOT searching engine. This optimized methodology reduces the time of analysis and avoids the use of sample preconcentration and clean-up procedures, such as cut-off centrifuged filters, solid phase extraction (SPE), precipitation procedures, off-line fractions insolates, etc. In this sense, the method is robust, reliable and fast with typical chromatographic run time less than 20 min. Precision in terms of relative standard deviation (n = 5) is of 3–5% and detection limits is 0.21 ng Cu g⁻¹.     

Laser Ablation Molecular Isotopic Spectrometry: Parameter influence on boron isotope measurements

Laser Ablation Molecular Isotopic Spectrometry (LAMIS) was recently reported for optical isotopic analysis of condensed samples in ambient air and at ambient pressure. LAMIS utilizes molecular emissions which exhibit larger isotopic spectral shits than in atomic transitions. For boron monoxide ¹⁰BO and ¹¹BO, the isotopic shifts extend from 114 cm⁻¹ (0.74 nm) to 145–238 cm⁻¹ (5–8 nm) at the B²Σ⁺ (v = 0) → X²Σ⁺ (v = 2) and A²Π_i (v = 0) → X²Σ⁺ (v = 3) transitions, respectively. These molecular isotopic shifts are over two orders of magnitude larger than the maximum isotopic shift of approximately 0.6 cm⁻¹ in atomic boron. This paper describes how boron isotope abundance can be quantitatively determined using LAMIS and how atomic, ionic, and molecular optical emission develops in a plasma emanating from laser ablation of solid samples with various boron isotopic composition. We demonstrate that requirements for spectral resolution of the measurement system can be significantly relaxed when the isotopic abundance ratio is determined using chemometric analysis of spectra. Sensitivity can be improved by using a second slightly delayed laser pulse arriving into an expanding plume created by the first ablation pulse.     

Studies on the biodegradation of fosfomycin: synthesis of 13C-labeled intermediates, feeding experiments with Rhizobium huakuii PMY1, and isolation of labeled amino acids from cell mass by HPLC

Racemic (1R*,2R*)‐1,2‐dihydroxy‐[1‐¹³C₁]propylphosphonic acid and 1‐hydroxy‐[1‐¹³C₁]acetone were synthesized and fed to R. huakuii PMY1. Alanine and a mixture of valine and methionine were isolated as their N‐acetyl derivatives from the cell hydrolysate by reversed‐phase HPLC and analyzed by NMR spectroscopy. It was found that the carbon atoms of the respective carboxyl groups were highly ¹³C‐labeled (up to 65 %). Hydroxyacetone is therefore considered an obligatory intermediate of the biodegradation of fosfomycin by R. huakuii PMY1.     

Vibrational Spectra of [Zn(15NH3)4] (ReO4)2 and [Cd(NH3)4] (ReO4)2 With 110Cd/116Cd and H/D Isotopic Substitution

The infrared spectra of the zinc tetraammine with ¹⁵N, and cadmium tetraammine perrhenates with ¹¹⁰Cd/¹¹⁶Cd and H/D isotopic substitution, provides useful data in determining skeletal pseudo - exact force constants. An approximate set of force constants in the F₂ symmetry class for the whole complexes were obtained.     

Vibrational Spectra of 2,2′-Pyridil and 2,2′-Pyridil-18O and Assignment of Infrared and Raman Bands

Abstract

Vibrational spectra of 2,2′-pyridil and 2,2′-pyridil-¹⁸O in the solid state and in solutions have been measured in the Raman (4000–50 cm^?1) and infrared (4000–100 cm^?1). The assignment of the bands observed is performed using the group vibrational concept and isotopic shifts data of the normal modes. The presence of synand anti-phase vibrations of both pyridyl rings is discussed. The results are compared to the corresponding data for some similar molecules.     

Visualisation of biopolymer mixtures using confocal scanning laser microscopy (CSLM) and covalent labelling techniques

Confocal scanning laser microscopy (CSLM) has been used to study the behaviour of mixtures of proteins, gelatine, whey proteins and β-lactoglobulin, and polysaccharides, dextran, gellan gum, carrageenan, gum Arabic, and starch. CSLM proved to be a suitable technique to visualise the microstructure of these (phase separated) mixtures in two and three-dimensional images. Contrast through fluorescence is obtained either by covalent labelling (polysaccharides and proteins) or non-covalent labelling (proteins and starch). Double and triple labelling allows the visualisation of individual components in a complex mixture of biopolymers.     

Study of Exotic Nuclei

A high-sensitive fluorescence cell has been developed with an aim to perform laser spectroscopy of exotic nuclei. This fluorescence cell has been tested off-line for stable isotope ¹³³Cs. Also, an investigation of the nuclear root mean square (r.m.s.) charge and neutron radii, and of the binding energies of the cesium long isotopic chain has been carried out in the relativistic mean field (RMF) and relativistic Hartree–Bogoliubov (RHB) formalisms. The RMF/RHB calculations are compared with the experimental data and are found to be in good agreement.