Calculating NMR parameters in aluminophosphates : evaluation of dispersion correction schemes

Periodic density functional theory (DFT) calculations have recently emerged as a popular tool for assigning solid-state nuclear magnetic resonance (NMR) spectra. However, in order for the calculations to yield accurate results, accurate structural models are also required. In many cases the structural model (often derived from crystallographic diffraction) must be optimised (i.e., to an energy minimum) using DFT prior to the calculation of NMR parameters. However, DFT does not reproduce weak long-range "dispersion'' interactions well, and optimisation using some functionals can expand the crystallographic unit cell, particularly when dispersion interactions are important in defining the structure. Recently, dispersion-corrected DFT (DFT-D) has been extended to periodic calculations, to compensate for these missing interactions. Here, we investigate whether dispersion corrections are important for aluminophosphate zeolites (AlPOs) by comparing the structures optimised by DFT and DFT-D (using the PBE functional). For as-made AlPOs (containing cationic structure-directing agents (SDAs) and framework-bound anions) dispersion interactions appear to be important, with significant changes between the DFT and DFT-D unit cells. However, for calcined AlPOs, where the SDA-anion pairs are removed, dispersion interactions appear much less important, and the DFT and DFT-D unit cells are similar. We show that, while the different optimisation strategies yield similar calculated NMR parameters (providing that the atomic positions are optimised), the DFT-D optimisations provide structures in better agreement with the experimental diffraction measurements. Therefore, it appears that DFT-D calculations can, and should, be used for the optimisation of calcined and as-made AlPOs, in order to provide the closest agreement with all experimental measurements.PostprintPeer reviewe

Theoretical investigation of transgastric and intraductal approaches for ultrasound-based thermal therapy of the pancreas.

BackgroundThe goal of this study was to theoretically investigate the feasibility of intraductal and transgastric approaches to ultrasound-based thermal therapy of pancreatic tumors, and to evaluate possible treatment strategies.MethodsThis study considered ultrasound applicators with 1.2 mm outer diameter tubular transducers, which are inserted into the tissue to be treated by an endoscopic approach, either via insertion through the gastric wall (transgastric) or within the pancreatic duct lumen (intraductal). 8 patient-specific, 3D, transient, biothermal and acoustic finite element models were generated to model hyperthermia (n = 2) and ablation (n = 6), using sectored (210°-270°, n = 4) and 360° (n = 4) transducers for treatment of 3.3-17.0 cm3 tumors in the head (n = 5), body (n = 2), and tail (n = 1) of the pancreas. A parametric study was performed to determine appropriate treatment parameters as a function of tissue attenuation, blood perfusion rates, and distance to sensitive anatomy.ResultsParametric studies indicated that pancreatic tumors up to 2.5 or 2.7 cm diameter can be ablated within 10 min with the transgastric and intraductal approaches, respectively. Patient-specific simulations demonstrated that 67.1-83.3% of the volumes of four sample 3.3-11.4 cm3 tumors could be ablated within 3-10 min using transgastric or intraductal approaches. 55.3-60.0% of the volume of a large 17.0 cm3 tumor could be ablated using multiple applicator positions within 20-30 min with either transgastric or intraductal approaches. 89.9-94.7% of the volume of two 4.4-11.4 cm3 tumors could be treated with intraductal hyperthermia. Sectored applicators are effective in directing acoustic output away from and preserving sensitive structures. When acoustic energy is directed towards sensitive structures, applicators should be placed at least 13.9-14.8 mm from major vessels like the aorta, 9.4-12.0 mm from other vessels, depending on the vessel size and flow rate, and 14 mm from the duodenum.ConclusionsThis study demonstrated the feasibility of generating shaped or conformal ablative or hyperthermic temperature distributions within pancreatic tumors using transgastric or intraductal ultrasound

Optical spectroscopy of radio galaxies in the 7C Redshift Survey

We present optical spectroscopy of all 49 radio galaxies in the 7C-I and 7C-II regions of the 7C Redshift Survey (7CRS). The low-frequency (151 MHz) selected 7CRS sample contains all sources with flux-densities S_151 > 0.5 Jy in three regions of the sky; 7C-I and 7C-II were chosen to overlap with the 5C6 and 5C7 surveys respectively, and cover a total sky area of 0.013 sr. The sample has been completely identified and spectroscopy of the quasars and broad-lined radio galaxies has been presented in Willott et al. (1998). Only seven of the radio galaxies do not have redshift determinations from the spectroscopy, giving a redshift completeness for the sample of >90%. The median redshift of the 7CRS is 1.1. We present a composite 0.2<z<0.8 7CRS radio galaxy spectrum and investigate the strengths of the 4000 Angstrom breaks in these radio galaxies. We find an anti-correlation between the 4000 Angstrom break strength and emission line luminosity, indicating that departures from old elliptical galaxy continuum shapes are most likely due to non-stellar emission associated with the active nucleus.Comment: 14 pages, 6 figures, MNRAS in pres

Diabetes and artificial intelligence (AI) beyond the closed loop: A review of the landscape, promise and challenges for AI-supported management and self-care for all diabetes types.

The discourse amongst diabetes specialists and academics regarding technology and artificial intelligence (AI) typically centres around the 10% of people with diabetes who have type 1 diabetes, focusing on glucose sensors, insulin pumps and, increasingly, closed-loop systems. This focus is reflected in conference topics, strategy documents, technology appraisals and funding streams. What is often overlooked is the wider application of data and AI, as demonstrated through published literature and emerging marketplace products, that offers promising avenues for enhanced clinical care, health-service efficiency and cost-effectiveness. This review provides an overview of AI techniques and explores the use and potential of AI and data-driven systems in a broad context, covering all diabetes types, encompassing: (1) patient education and self-management; (2) clinical decision support systems and predictive analytics, including diagnostic support, treatment and screening advice, complications prediction; and (3) the use of multimodal data, such as imaging or genetic data. The review provides a perspective on how data- and AI-driven systems could transform diabetes care in the coming years and how they could be integrated into daily clinical practice. We discuss evidence for benefits and potential harms, and consider existing barriers to scalable adoption, including challenges related to data availability and exchange, health inequality, clinician hesitancy and regulation. Stakeholders, including clinicians, academics, commissioners, policymakers and those with lived experience, must proactively collaborate to realise the potential benefits that AI-supported diabetes care could bring, whilst mitigating risk and navigating the challenges along the way.</p

Physiological Responses to Acute Silver Exposure in the Freshwater Crayfish (\u3cem\u3eCambarus diogenes diogenes\u3c/em\u3e)—A Model Invertebrate?

Adult crayfish (Cambarus diogenes diogenes) exposed to 8.41 ± 0.17 μg silver/L (19.4% as Ag+) in moderately hard freshwater under flow-through conditions for 96 h exhibited ionoregulatory disturbance, elevated metabolic ammonia (Tamm) production and substantial silver accumulation in the gills, hemolymph, and hepatopancreas. The ionoregulatory disturbance included both a generally reduced unidirectional Na1 influx and an increased unidirectional Na+ efflux, leading to a substantial net loss of Na+ from the silver-exposed crayfish. The Na+ uptake in silver-exposed crayfish differed overall from controls, while the increased Na+ efflux recovered to control values 48 h into the 96 h of exposure. The general inhibition of Na+ uptake could be explained by a reduced sodium/potassium-adenosine triphosphatase (Na/K-ATPase) activity in terminally obtained gill samples from the silver exposed crayfish. The silver-induced effect on Na+ uptake and loss translated to reduced hemolymph Na+ concentrations but not significantly reduced hemolymph Cl- concentrations. Hemolymph Tamm and Tamm efflux both increased in silver-exposed crayfish, indicating an increased metabolic Tamm production. The present study demonstrates that the toxic mechanism of waterborne silver exposure in freshwater crayfish resembles that of freshwater teleost fish. The crayfish might therefore be a useful model system for extending current environmental regulatory strategies, currently based on teleost fish, to invertebrates

The Lino Site: A Stratified Late Archaic Campsite in a Terrace of the San Idelfonzo Creek, Webb County, Southern Texas

Archeologists from TRC Mariah Associates Inc. of Austin conducted mitigation excavations at the Lino site (41WB437) during a six-week period in April and May 1998 under contract with the Texas Department of Transportation, Environmental Affairs Division. The prehistoric archeological site was within the right-of-way of the planned expansion of Highway 83, south of Laredo. A single 196 m2 block measuring 7m north-south by 28 m east-west was investigated following requirements of a contract that stipulated a three-pronged approach to data recovery. First, a Gradall™ was employed to carefully strip 2 to 4 cm thick layers in eight 3m wide areas within the block. Balks measuring 80 cm wide by 120 cm tall were left standing between each 3 m wide Gradall™ -stripped area. The material discovered in situ during the Gradall™ stripping was plotted using a total data station. When clusters of cultural materials were encountered during the Gradall™ stripping, these were designated as features, and a series of manual excavations in 1 by 1 m units were dug around each feature. The matrix surrounding these features was screened and in situ data recorded with the total data station. Feature matrix was collected and floated in the laboratory. A total of 124 m2 were hand excavated around 24 recognized features discovered during Gradall™ stripping. Upon reaching the target depth of 120 cm below the surface, the Gradall™ stripping ceased, having mechanically removed 187 m3 of deposits