Selectively protected galactose derivatives for the synthesis of branched oligosaccharides

Synthesis and characterization of several new anomerically pure galactose derivatives, based on simple and effective protective group manipulations of benzyl β-d-galactopyranoside, are reported. The monosaccharides described contain selectively protected/deprotected hydroxyl functionalities at their 1,2,3,4- and 6-positions rendering them useful as building blocks for construction of branched oligosaccharides.     

Structural characterisation of tyrosine-nitrated peptides by ultraviolet and infrared matrix-assisted laser desorption/ionisation Fourier transform ion cyclotron resonance mass spectrometry

Nitration of tyrosine residues in proteins may occur in cells upon oxidative stress and inflammation processes mediated through generation of reactive nitroxyl from peroxynitrite. Tyrosine nitration from oxidative pathways may generate cytotoxic species that cause protein dysfunction and pathogenesis. A number of protein nitrations in vivo have been reported and some specific Tyrosine nitration sites have been recently identified using mass spectrometric methods. High-resolution Fourier transform ion cyclotron resonance mass spectrometry (MALDI) FT-ICR-MS) is shown here to be a highly efficient method in the determination of protein nitrations. Following the identification of nitration of the catalytic site Tyr-430 residue of bovine prostacyclin synthase, we synthesised several model peptides containing both unmodified tyrosine and 3-nitro-tyrosine residues, using solid-phase peptide synthesis (SPPS). The structures of the nitrotyrosine peptides were characterised both by ESI- and by matrix-assisted laser desorption/ionisation (MALDI)-FT-ICR-MS, using a standard ultraviolet (UV) nitrogen nitrogen laser and a 2.97 microm Nd-YAG infrared laser. Using UV-MALDI-MS, 3-nitrotyrosyl-peptides were found to undergo extensive photochemical fragmentation at the nitrophenyl group, which may hamper or prevent the unequivocal identification of Tyr-nitrations in cellular proteins. In contrast, infrared-MALDI-FT-ICR-MS did not produce fragmentation of molecular ions of Tyr-nitrated peptides.     

An unexpected allomer of chlorophyll: 13(S)-hydroxy-10-methoxychlorophyll b

The allomerization of chlorophyll b in methanol produced 13²(S)-hydroxy-10-methoxychlorophyll b in a yield of ca. 8%. The formation of this allomer was totally unexpected, as 10-substituted chlorophylls have never been reported before. The structure of the new chlorophyll b derivative was determined on the basis of UV/Vis, FAB-MS, ¹H NMR and 2D ROESY NMR spectra. This letter focuses on the NMR analysis.     

Hydrophobic modification of nanocellulose and all-cellulose composite films using deep eutectic solvent as a reaction medium

Cellulose - In this work, deep eutectic solvent (DES) based on imidazole and triethylmethylammonium chloride was used as a reaction medium for the esterification of cellulose nanofiber (CNF) and...     

A Selenium‐Nitrogen Chain with Selenium in Different Oxidation States

The reaction of tBuNH₂ with a mixture of SeCl₂ and SeOCl₂ in a 6:2:1 molar ratio produces the novel selenium‐nitrogen chain ClSeN(tBu)Se(O)Cl ( 4 ), in which the selenium atoms are in two different oxidation states, Se^II and Se^IV. The crystal structure of 4 is compared with that of the related Se^II/Se^II system ClSeN(tBu)SeCl ( 1 ) and differences are attributed to hyperconjugative effects. The energetics of the formation of 4 via two different routes are elucidated by PBE0/def2‐TZVPP calculations.     

Avoiding eddy-current problems in ultra-low-field MRI with self-shielded polarizing coils

In ultra-low-field magnetic resonance imaging (ULF MRI), superconductive sensors are used to detect MRI signals typically in fields on the order of 10-100 μT. Despite the highly sensitive detectors, it is necessary to prepolarize the sample in a stronger magnetic field on the order of 10-100 mT, which has to be switched off rapidly in a few milliseconds before signal acquisition. In addition, external magnetic interference is commonly reduced by situating the ULF-MRI system inside a magnetically shielded room (MSR). With typical dipolar polarizing coil designs, the stray field induces strong eddy currents in the conductive layers of the MSR. These eddy currents cause significant secondary magnetic fields that may distort the spin dynamics of the sample, exceed the dynamic range of the sensors, and prevent simultaneous magnetoencephalography and MRI acquisitions. In this paper, we describe a method to design self-shielded polarizing coils for ULF MRI. The experimental results show that with a simple self-shielded polarizing coil, the magnetic fields caused by the eddy currents are largely reduced. With the presented shielding technique, ULF-MRI devices can utilize stronger and spatially broader polarizing fields than achievable with unshielded polarizing coils.     

Effect of hydrogen doping in ZnO thin films by pulsed DC magnetron sputtering

This study examined the role of hydrogen impurities in highly oriented ZnO thin films. Hydrogen intentionally incorporated was found to play an important role as a donor in n-type conduction, improving the free carrier concentration. The increase in the conductivity of ZnO thin films was attributed to the two centers assigned to isolated hydrogen atoms in the anti-bonding sites as well as bond-centered interstitial hydrogen located between the Zn–O bonds and Zn vacancy passivated by one or two hydrogen atoms. Micro Raman spectroscopy showed two additional modes at approximately 501 and 573 cm⁻¹. These two peaks were attributed to damage to the crystal lattice, which could be explained by the optical-phonon branch at the zone boundary and host lattice defects, such as vacancy clusters, respectively.     

Phase diagram of the uniaxial and biaxial soft-core Gay-Berne model

Classical molecular dynamics simulations have been used to explore the phase diagrams for a family of attractive-repulsive soft-core Gay-Berne models [R. Berardi, C. Zannoni, J. S. Lintuvuori, and M. R. Wilson, J. Chem. Phys. 131, 174107 (2009)] and determine the effect of particle softness, i.e., of a moderately repulsive short-range interaction, on the order parameters and phase behaviour of model systems of uniaxial and biaxial ellipsoidal particles. We have found that isotropic, uniaxial, and biaxial nematic and smectic phases are obtained for the model. Extensive calculations of the nematic region of the phase diagram show that endowing mesogenic particles with such soft repulsive interactions affect the stability range of the nematic phases, and in the case of phase biaxiality it also shifts it to lower temperatures. For colloidal particles, stabilised by surface functionalisation, (e.g., with polymer chains), we suggest that it should be possible to tune liquid crystal behaviour to increase the range of stability of uniaxial and biaxial phases (by varying solvent quality). We calculate second virial coefficients and show that they are a useful means of characterising the change in effective softness for such systems. For thermotropic liquid crystals, the introduction of softness in the interactions between mesogens with overall biaxial shape (e.g., through appropriate conformational flexibility) could provide a pathway for the actual chemical synthesis of stable room-temperature biaxial nematics.     

Exploring hurdles to transfer : student experiences of applying knowledge across disciplines

This paper explores the ways students perceive the transfer of learned knowledge to new situations – often a surprisingly difficult prospect. The novel aspect compared to the traditional transfer studies is that the learning phase is not a part of the experiment itself. The intention was only to activate acquired knowledge relevant to the transfer target using a short primer immediately prior to the situation where the knowledge was to be applied. Eight volunteer students from either mathematics or computer science curricula were given a task of designing an adder circuit using logic gates: a new context in which to apply knowledge of binary arithmetic and Boolean algebra. The results of a phenomenographic classification of the views presented by the students in their post-experiment interviews are reported. The degree to which the students were conscious of the acquired knowledge they employed and how they applied it in a new context emerged as the differentiating factors.