Top Varieties of Generalized MV-Algebras and Unital Lattice-Ordered Groups

In spite of the well-know fact that the system of ?-groups with strong unit (unital ?-groups) does not form a variety, there is a categorical connection between the category of unital ?-groups and the variety of generalized MV-algebras which enables us to naturally export equational machinery and terminology like “variety” from the latter category to the former.

Using this categorical equivalence, we study varieties, or equationally defined classes, and top varieties, varieties above the normal valued variety, of both structures. We generalize Chang's Completeness Theorem for generalized MV-algebras, and formulate some open questions for both structures.     

Determining NMR flow propagator moments in porous rocks without the influence of relaxation

Flow propagators, used for the study of advective motion of brine solution in porous carbonate and sandstone rocks, have been obtained without the influence of Nuclear Magnetic Resonance (NMR) relaxation times, T₁ and T₂. These spin relaxation mechanisms normally result in a loss of signal that varies depending on the displacement ζ of the flowing spins, thereby preventing the acquisition of quantitative propagator data. The full relaxation behaviour of the system under flow needs to be characterised to enable the implementation of a true quantitative measurement. Two-dimensional NMR correlations of ζ − T₂ and T₁ − T₂ are used in combination to provide the flow propagators without relaxation weighting. T₁ − ζ correlations cannot be used due to the loss of T₁ information during the displacement observation time Δ. Here the moments of the propagators are extracted by statistical analysis of the full propagator shape. The measured displacements (first moments) are seen to correlate with the expected mean displacements for long observation times Δ. The higher order moments of the propagators determined by this method indicate those obtained previously using a correction were overestimated.     

CyClick Chemistry for the Synthesis of Cyclic Peptides

Here, we report a novel “CyClick” strategy for the macrocyclization of peptides that works in an exclusively intramolecular fashion thereby precluding the formation of dimers and oligomers via intermolecular reactions. The CyClick chemistry is highly chemoselective for the N‐terminus of the peptide with a C‐terminal aldehyde. In this protocol, the peptide conformation internally directs activation of the backbone amide bond and thereby facilitates formation of a stable 4‐imidazolidinone‐fused cyclic peptide with high diastereoselectivity (>99 %). This method is tolerant to a variety of peptide aldehydes and has been applied for the synthesis of 12‐ to 23‐membered rings with varying amino acid compositions in one pot under mild reaction conditions. The reaction generated peptide macrocycles featuring a 4‐imidazolidinone in their scaffolds, which acts as an endocyclic control element that promotes intramolecular hydrogen bonding and leads to macrocycles with conformationally rigid turn structures.     

Photochemical Conjugation and One‐Pot Radiolabelling of Antibodies for Immuno‐PET

Monoclonal antibodies (mAbs), immunoglobulin fragments, and other proteins are important scaffolds in the development of radiopharmaceuticals for diagnostic immuno‐positron emission tomography (immuno‐PET) and targeted radioimmunotherapy (RIT). Conventional methods for radiolabelling proteins with metal ions such as ⁶⁸Ga, ⁶⁴Cu, ⁸⁹Zr, and ⁹⁰Y require multi‐step procedures involving pre‐purification, functionalisation with a chelate, and subsequent radiolabelling. Standard coupling chemistries are time‐consuming, difficult to automate, and involve synthesis, isolation, and storage of an intermediate, new molecular entity (the conjugated mAb) whose biochemical properties can differ from those of the parent protein. To circumvent these issues, we developed a photoradiochemical approach that uses fast, chemoselective, light‐induced protein modification under mild conditions with novel metal‐ion‐binding chelates derivatised with aryl azide (ArN₃) groups. Experiments show that one‐pot photochemical conjugation and radiolabelling of formulated mAbs can be achieved in <20 min.     

A magnetic resonance imaging-based articulatory and acoustic study of "retroflex" and "bunched" American English /r/

Speakers of rhotic dialects of North American English show a range of different tongue configurations for /r/. These variants produce acoustic profiles that are indistinguishable for the first three formants [Delattre, P., and Freeman, D. C., (1968). "A dialect study of American English r's by x-ray motion picture," Linguistics 44, 28-69; Westbury, J. R. et al. (1998), "Differences among speakers in lingual articulation for American English /r/," Speech Commun. 26, 203-206]. It is puzzling why this should be so, given the very different vocal tract configurations involved. In this paper, two subjects whose productions of "retroflex" /r/ and "bunched" /r/ show similar patterns of F1-F3 but very different spacing between F4 and F5 are contrasted. Using finite element analysis and area functions based on magnetic resonance images of the vocal tract for sustained productions, the results of computer vocal tract models are compared to actual speech recordings. In particular, formant-cavity affiliations are explored using formant sensitivity functions and vocal tract simple-tube models. The difference in F4/F5 patterns between the subjects is confirmed for several additional subjects with retroflex and bunched vocal tract configurations. The results suggest that the F4/F5 differences between the variants can be largely explained by differences in whether the long cavity behind the palatal constriction acts as a half- or a quarter-wavelength resonator.     

Characterisation of sol-gel prepared (HfO2)x(SiO2)1-x (x=0.1, 0.2 and 0.4) by 1H, 13C, 17 O and 29Si MAS NMR, FTIR and TGA

The HfO2-SiO2 system is attracting interest as a possible new dielectric material in semiconductor devices. Knowledge of the location of hafnium within the silica network and the effect hafnium has on the structure will be central to the successful use of this material system in this application. Here, sol-gel techniques have been used to manufacture (HfO2)x(SiO2)1-x samples (x=0.1, 0.2 and 0.4, each heat treated at 250, 500 and 750 degrees C) and these have been characterised by magic angle spinning (MAS) NMR (1H, 13C, 17 O, 29Si), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis. 29Si MAS NMR showed that increasing the hafnia content decreases the connectivity of the silicate network, i.e. increases the range of differently connected SiO4 (Qn) units with more having increased numbers of non-bridging oxygens (i.e. lower n). FTIR and 17 O MAS NMR showed unequivocally that the x=0.4 sample phase-separated at higher temperatures, while in the x=0.1 sample the hafnium was homogeneously mixed into the SiO2 phase without any phase separation.     

Photochemical Reactions in the Synthesis of Protein–Drug Conjugates

The ability to modify biologically active molecules such as antibodies with drug molecules, fluorophores or radionuclides is crucial in drug discovery and target identification. Classic chemistry used for protein functionalisation relies almost exclusively on thermochemically mediated reactions. Our recent experiments have begun to explore the use of photochemistry to effect rapid and efficient protein functionalisation. This article introduces some of the principles and objectives of using photochemically activated reagents for protein ligation. The concept of simultaneous photoradiosynthesis of radiolabelled antibodies for use in molecular imaging is introduced as a working example. Notably, the goal of producing functionalised proteins in the absence of pre-association (non-covalent ligand-protein binding) introduces requirements that are distinct from the more regular use of photoactive groups in photoaffinity labelling. With this in mind, the chemistry of thirteen different classes of photoactivatable reagents that react through the formation of intermediate carbenes, electrophiles, dienes, or radicals, is assessed.     

High‐Frequency Fe–H Vibrations in a Bridging Hydride Complex Characterized by NRVS and DFT

High‐spin iron species with bridging hydrides have been detected in species trapped during nitrogenase catalysis, but there are few general methods of evaluating Fe?H bonds in high‐spin multinuclear iron systems. An ⁵⁷Fe nuclear resonance vibrational spectroscopy (NRVS) study on an Fe(μ‐H)₂Fe model complex reveals Fe?H stretching vibrations for bridging hydrides at frequencies greater than 1200 cm^?1. These isotope‐sensitive vibrational bands are not evident in infrared (IR) spectra, showing the power of NRVS for identifying hydrides in this high‐spin iron system. Complementary density functional theory (DFT) calculations elucidate the normal modes of the rhomboidal iron hydride core.