"Pure shift" 1H NMR, a robust method for revealing heteronuclear couplings in complex spectra

We investigate the utility of “pure shift” techniques in revealing heteronuclear couplings in complex 1H NMR spectra. The results show the technique to be a robust and valuable complement to the standard 1H spectrum, and an attractive alternative to heteronuclear decoupling since the technique is independent of the size of the heteronuclear couplings and the chemical shift range(s) of the heteronuclei involved. We highlight some possible artefacts, and the subtle effects due to the presence of 13C nuclei in otherwise symmetric molecules when bilinear rotational decoupling (BIRD) elements are present in the pulse sequence

Improving the Interpretation of Small Molecule Diffusion Coefficients

Diffusion-ordered NMR spectroscopy (DOSY) is increasingly widely used for the analysis of mixtures by NMR spectroscopy, dispersing the signals of different species according to their diffusion coefficients. DOSY is used primarily to distinguish between the signals of different species, with the interpretation of the diffusion coefficients observed usually being purely qualitative, for example to deduce whether one species is bigger or smaller than another. In principle the actual values of diffusion coefficient obtained carry important information about the sizes of different species and on interactions between species, but the relationship between diffusion coefficient and molecular mass is in general a very complex one. Here a recently-proposed analytical relationship between diffusion coefficient and molecular mass for the restricted case of small organic molecules is tested against a wide range of data from the scientific literature, and generalised to cover a range of solvents and temperatures

Natural history of asymptomatic pancreatic cystic neoplasms

AbstractBackgroundThe management of asymptomatic pancreatic cysts is controversial and indications for excision are based on pathology and natural history.ObjectivesThis study aimed to examine outcomes of asymptomatic lesions using a protocol based on size and cyst fluid analysis.MethodsAsymptomatic cysts were identified from a prospectively maintained database. Sequential cross‐sectional imaging studies were assessed, and results of endoscopic ultrasound‐guided aspiration were co‐analysed.ResultsA total of 338 asymptomatic patients underwent evaluation. Overall, 84 cysts were <1.5 cm and 254 were ≥1.5 cm in diameter. Median patient follow‐up was 5.1 years [interquartile range (IQR): 4.1–6.9 years]. In the group in which cysts measured <1.5 cm in diameter, median cyst size was 1.0 cm (IQR: 0.6–1.2 cm) at presentation and increased to 1.2 cm (IQR: 0.7–1.6 cm) during follow‐up. Five (6.0%) patients underwent resection, all within 2 months of presentation. In the group in which cysts measured ≥1.5 cm in diameter, median cyst size was 2.5 cm (IQR: 2.0–3.4 cm) at presentation and increased to 2.7 cm (IQR: 3.0–4.2 cm). A total of 63 (24.8%) patients underwent resection. Surgery was performed with 2 months in 53 (84.1%) patients, within 12 months in four (6.3%) patients and at >12 months post‐presentation in six (9.5%) patients. A total of 70.6% of resected specimens were identified as malignancies or mucinous lesions.conclusionsAsymptomatic cysts of <1.5 cm in diameter can safely be followed by imaging and are expected to undergo little change. A quarter of all asymptomatic cysts measuring ≥1.5 cm are appropriately resected based on imaging and cyst fluid analysis

Selenium Deficiency and Chronic Pancreatitis: Disease Mechanism and Potential for Therapy

Background: It has been suggested that antioxidant deficiency may play a role in the pathogenesis of chronic pancreatitis. The aim of this review was to analyse the evidence for this relationship and to consider the role of antioxidant supplementation in the treatment of chronic pancreatitis

Controls on the fate and speciation of Np(V) during iron (oxyhydr)oxide crystallization

The speciation and fate of neptunium as Np(V)O2+ during the crystallization of ferrihydrite to hematite and goethite was explored in a range of systems. Adsorption of NpO2+ to iron(III) (oxyhydr)oxide phases was reversible and, for ferrihydrite, occurred through the formation of mononuclear bidentate surface complexes. By contrast, chemical extractions and X-ray absorption spectroscopy (XAS) analyses showed the incorporation of Np(V) into the structure of hematite during its crystallization from ferrihydrite (pH 10.5). This occurred through direct replacement of octahedrally coordinated Fe(III) by Np(V) in neptunate-like coordination. Subsequent analyses on mixed goethite and hematite crystallization products (pH 9.5 and 11) showed that Np(V) was incorporated during crystallization. Conversely, there was limited evidence for Np(V) incorporation during goethite crystallization at the extreme pH of 13.3. This is likely due to the formation of a Np(V) hydroxide precipitate preventing incorporation into the goethite particles. Overall these data highlight the complex behavior of Np(V) during the crystallization of iron(III) (oxyhydr)oxides, and demonstrate clear evidence for neptunium incorporation into environmentally important mineral phases. This extends our knowledge of the range of geochemical conditions under which there is potential for long-term immobilization of radiotoxic Np in natural and engineered environments

Incorporation and retention of 99-Tc(IV) in magnetite under high pH conditions

Technetium incorporation into magnetite and its behavior during subsequent oxidation has been investigated at high pH to determine the technetium retention mechanism(s) on formation and oxidative perturbation of magnetite in systems relevant to radioactive waste disposal. Ferrihydrite was exposed to Tc(VII)(aq) containing cement leachates (pH 10.5-13.1), and crystallization of magnetite was induced via addition of Fe(II)aq. A combination of X-ray diffraction (XRD), chemical extraction, and X-ray absorption spectroscopy (XAS) techniques provided direct evidence that Tc(VII) was reduced and incorporated into the magnetite structure. Subsequent air oxidation of the magnetite particles for up to 152 days resulted in only limited remobilization of the incorporated Tc(IV). Analysis of both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data indicated that the Tc(IV) was predominantly incorporated into the magnetite octahedral site in all systems studied. On reoxidation in air, the incorporated Tc(IV) was recalcitrant to oxidative dissolution with less than 40% remobilization to solution despite significant oxidation of the magnetite to maghemite/goethite: All solid associated Tc remained as Tc(IV). The results of this study provide the first direct evidence for significant Tc(IV) incorporation into the magnetite structure and confirm that magnetite incorporated Tc(IV) is recalcitrant to oxidative dissolution. Immobilization of Tc(VII) by reduction and incorporation into magnetite at high pH and with significant stability upon reoxidation has clear and important implications for limiting technetium migration under conditions where magnetite is formed including in geological disposal of radioactive wastes

Uranium fate during crystallization of magnetite from ferrihydrite in conditions relevant to the disposal of radioactive waste

Uranium incorporation into magnetite and its behaviour during subsequent oxidation has been investigated at high pH to determine the uranium retention mechanism(s) on formation and oxidative perturbation of magnetite in systems relevant to radioactive waste disposal. Ferrihydrite was exposed to U(VI)aq containing cement leachates (pH 10.5-13.1) and crystallization of magnetite was induced via addition of Fe(II)aq. A combination of XRD, chemical extraction and XAS techniques provided direct evidence that U(VI) was reduced and incorporated into the magnetite structure, possibly as U(V), with a significant fraction recalcitrant to oxidative remobilization. Immobilization of U(VI) by reduction and incorporation into magnetite at high pH, and with significant stability upon reoxidation, has clear and important implications for limiting uranium migration in geological disposal of radioactive wastes. © 2016 by Walter de Gruyter Berlin/Boston

Long-lived metal complexes open up microsecond lifetime imaging microscopy under multiphoton excitation: from FLIM to PLIM and beyond

Lifetime imaging microscopy with sub-micron resolution provides essential understanding of living systems by allowing both the visualisation of their structure, and the sensing of bio-relevant analytes in vivo using external probes. Chemistry is pivotal for the development of the next generation of bio-tools, where contrast, sensitivity, and molecular specificity facilitate observation of processes fundamental to life. A fundamental limitation at present is the nanosecond lifetime of conventional fluorescent probes which typically confines the sensitivity to sub-nanosecond changes, whilst nanosecond background autofluorescence compromises the contrast. High-resolution visualization with complete background rejection and simultaneous mapping of bio-relevant analytes including oxygen – with sensitivity orders of magnitude higher than that currently attainable – can be achieved using time-resolved emission imaging microscopy (TREM) in conjunction with probes with microsecond (or longer) lifetimes. Yet the microsecond timescale has so far been incompatible with available multiphoton excitation/detection technologies. Here we realize for the first time microsecond-imaging with multiphoton excitation whilst maintaining the essential sub-micron spatial resolution. The new method is background-free and expands available imaging and sensing timescales 1000-fold. Exploiting the first engineered water-soluble member of a family of remarkably emissive platinum-based, microsecond-lived probes amongst others, we demonstrate (i) the first instance of background-free multiphoton-excited microsecond depth imaging of live cells and histological tissues, (ii) over an order-of-magnitude variation in the probe lifetime in vivo in response to the local microenvironment. The concept of two-photon TREM can be seen as “FLIM + PLIM” as it can be used on any timescale, from ultrafast fluorescence of organic molecules to slower emission of transition metal complexes or lanthanides/actinides, and combinations thereof. It brings together transition metal complexes as versatile emissive probes with the new multiphoton-excitation/microsecond-detection approach to create a transformative framework for multiphoton imaging and sensing across biological, medicinal and material sciences