New cyclodextrin derivatives as chiral selectors in capillary electrophoresis

The separation of three pairs of enantiomeric herbicides has been successfully achieved by capillary electrophoresis at two different pH values in the presence of cyclodextrin derivatives previously synthesized in our laboratory. Two of these derivatives constitute a new class of receptor, the hemispherodextrins, in which a trehalose capping moiety is bonded to β-cyclodextrin. Because of their peculiar structure hemispherodextrins have very promising characteristics and the low receptor concentration required to achieve separation deserves particular interest.     

Helium cosmic ray flux measurements at Mars

The helium energy spectrum in Martian orbit has been observed by the MARIE charged particle spectrometer aboard the 2001 Mars Odyssey spacecraft. The orbital data were taken from March 13, 2002 to October 28, 2003, at which time a very intense Solar Particle Event caused a loss of communication between the instrument and the spacecraft. The silicon detector stack in MARIE is optimized for the detection of protons and helium in the energy range below , which typically includes almost all of the flux during SPEs. This also makes MARIE an efficient detector for GCR helium in the energy range of 50–. We will present the first fully normalized flux results from MARIE, using helium ions in this energy range.     

Evaluating shielding effectiveness for reducing space radiation cancer risks

We discuss calculations of probability distribution functions (PDF) representing uncertainties in projecting fatal cancer risk from galactic cosmic rays (GCR) and solar particle events (SPE). The PDFs are used in significance tests for evaluating the effectiveness of potential radiation shielding approaches. Uncertainties in risk coefficients determined from epidemiology data, dose and dose–rate reduction factors, quality factors, and physics models of radiation environments are considered in models of cancer risk PDFs. Competing mortality risks and functional correlations in radiation quality factor uncertainties are included in the calculations. We show that the cancer risk uncertainty, defined as the ratio of the upper value of 95% confidence interval (CI) to the point estimate is about 4-fold for lunar and Mars mission risk projections. For short-stay lunar missions (), SPEs present the most significant risk, however one that is mitigated effectively by shielding, especially for carbon composites structures with high hydrogen content. In contrast, for long duration lunar () or Mars missions, GCR risks may exceed radiation risk limits that are based on acceptable levels of risk. For example, the upper 95% CI exceeding 10% fatal risk for males and females on a Mars mission. For reducing GCR cancer risks, shielding materials are marginally effective because of the penetrating nature of GCR and secondary radiation produced in tissue by relativistic particles. At the present time, polyethylene or carbon composite shielding cannot be shown to significantly reduce risk compared to aluminum shielding based on a significance test that accounts for radiobiology uncertainties in GCR risk projection.     

A re-investigation of copper coordination in the octa-repeats region of the prion protein

An aqueous solution spectroscopic (Vis and EPR) study of the copper(II) complexes with the Ac-HGGG-NH2 and Ac-PHGGGWGQ-NH2 polypeptides (generically designated as L) suggests square base pyramids ascribable to [Cu(L)H(-2)] complex species, which contain three nitrogen donor atoms, arising from imidazole and peptide groups, in the equatorial plane and for a pseudo-octahedral geometry in the case of [CuLH-3]- and [Cu(L)H-4]2- which have four nitrogen donor atoms in their equatorial plane. The coordination sphere of the copper complex in the [Cu(L)H(-2)] species, which is present at neutral pH values, is completed by two oxygen donor atoms. ESI-MS spectra ascertained that water molecules are not present in the coordination equatorial plane of this latter species, in comparison with other copper(II) complexes with ligands bearing nitrogen and oxygen donor atoms and surely having equatorial water molecules. This indicates the coordination of a carbonyl oxygen atom in the equatorial plane has to be invoked. However, no direct proof about the involvement of a carbonyl group oxygen donor atom apically linked to copper was obtained, due to the flexibility of these structures at room temperature. Additionally, the low A(ll) value leads one to consider another oxygen atom of a carbonyl group being involved in the apical bond to copper in a fast exchange fashion. This apical interaction, which may also involve a water molecule, is more pronounced in the Cu-Ac-HGGG-NH2 than in the analogous Cu-Ac-PHGGGWGQ-NH2 system, probably because of the presence of tryptophan and proline in the polypeptide sequence.     

Mass spectrometry detection as an innovative and advantageous tool in ligand exchange capillary electrophoresis

The copper(II) complex of a modified cyclodextrin, namely 6-mono-deoxy-6-[4-(2-aminoethyl)imidazolyl]-β-CD (CDmh), previously synthesized and characterized in our laboratory and already used as chiral selector for ligand exchange capillary electrophoresis (LECE) with optical detection, is investigated here in LECE using electrospray-mass spectrometry (ESI-MS) as the detection device. The potential of this hyphenated method is compared with the results previously obtained with optical detection by studying the chiral resolution of tryptophan racemate. Chiral separation conditions compatible with LECE-ESI-MS could be achieved based on the figures of merit obtained by LECE-UV. Interestingly, the values of LOD obtained by LECE-ESI-MS were significantly better than those obtained by LECE-UV and thus, ESI-MS detection seems to open new perspectives in chiral separations by LECE.     

Polarization splitter based on a square-lattice photonic-crystal fiber

A three-core polarization splitter based on a square-lattice photonic-crystal fiber is presented. The component separates the input field into two orthogonally polarized beams that are coupled to the horizontal and vertical output ports. The splitter has been designed through modal and beam propagation analysis by employing high-performance codes based on the finite-element method. Results obtained for a device length of 20 mm show extinction ratios as low as -23 dB with bandwidths as great as 90 nm.     

Simultaneous separation of different enantiomeric pairs in capillary electrophoresis by mixing different hemispherodextrins,a very versatile class of receptors

Six different racemates of the profen family were used as analytes in order to test the chiral selector properties of three members of a new class of cyclodextrin derivatives, hemispherodextrins (HMs), in capillary electrophoresis. In addition to experiments carried out to separate each enantiomeric pair one by one, other experiments were carried out on samples containing all six enantiomeric pairs. Electropherograms were obtained either by adding a single HM to the background electrolyte (BGE), or a binary mixture of HMs. The results obtained confirm the excellent chiral selector properties of the HMs, and furthermore show that these compounds can also be used for achiral selection. When mixing different HMs, a complementary effect in chiral selectivity is observed, which, in our opinion, deserves further study.     

Confinement loss spectral behavior in hollow-core Bragg fibers

The influence of each cross-section geometric parameter on hollow-core Bragg fiber guiding properties has been numerically investigated. Fabricated fibers have been modeled, giving insight into the spectral behavior of the confinement loss. It has been verified that, by changing the amount of silica and air in the fiber cladding, it is possible to change the reflection conditions undergone by the field within the core, thus shifting the confinement loss spectrum.