Caring for Indigenous Data to Evaluate the Benefits of Indigenous Environmental Programs.

Advances in open data, big data and data linkage allow us to analyse more data and on a larger scale than ever before. However, this brings with it the challenge of ensuring that Indigenous data sets are used in a way that protects Indigenous rights to that data and maximises benefits for Indigenous peoples. The CARE principles for Indigenous data governance-Collective Benefit, Authority to Control, Responsibility and Ethics-were developed to protect Indigenous data sovereignty, but there are few examples of how to translate these principles into practice. In this paper, we show how these CARE principles can be applied to data collection, integration, analysis and translation practices. Our case study is a project that used data reported by Indigenous ranger groups to capture the multiple benefits of Indigenous land and water management activities. Through this case study, we offer a framework for the design and use of CARE-informed data practices, which can be embedded into project design to enable the ethical and responsible use of Indigenous data to improve Indigenous policies and services. Such practices are critical in the context of ongoing demand for Indigenous data for bureaucratic purposes, and Indigenous interest in using that data to influence management and policy decisions affecting their estates and resources.

Experimental and Theoretical Investigations of Infrared Multiple Photon Dissociation Spectra of Aspartic Acid Complexes with Zn2+ and Cd2.

Complexes of aspartic acid (Asp) cationized with Zn2+: Zn(Asp-H)+, Zn(Asp-H)+(ACN) where ACN = acetonitrile, and Zn(Asp-H)+(Asp); as well as with Cd2+, CdCl+(Asp), were examined by infrared multiple photon dissociation (IRMPD) action spectroscopy using light generated from a free electron laser. A series of low-energy conformers for each complex was found using quantum chemical calculations to identify the structures formed experimentally. The main binding motif observed for the heavy-metal complex, CdCl+(Asp)[N,CO,COs], is a charge-solvated, tridentate structure, where the metal center binds to the backbone amino group and carbonyl oxygens of the backbone and side-chain carboxylic acids. Likewise, the deprotonated Zn(Asp-H)+(ACN) and Zn(Asp-H)+(Asp) complexes show comparable [N,CO-,COs](ACN) and [N,CO-,COs][N,CO,COs] coordinations, respectively. Interestingly, there was only minor spectral evidence for the analogous Zn(Asp-H)+[N,CO-,COs] binding motif, even though this species is predicted to be the lowest-energy conformer. Instead, rearrangement and partial dissociation of the amino acid are observed, as spectral features most consistent with the experimental spectrum are exhibited by a four-coordinate Zn(Asp-NH4)+[CO2-,COs](NH3) complex. Analysis of the mechanistic pathway leading from the predicted lowest-energy conformer to the isobaric deaminated complex is explored theoretically. Further, comparison of the current work to that of Zn2+ and Cd2+ complexes of asparagine (Asn) allows additional conclusions regarding populated conformers and effects of carboxamide versus carboxylic acid binding to be drawn.

Binding energies of hydrated cobalt(ii) by collision-induced dissociation and theoretical studies: evidence for a new critical size.

The experimental sequential bond energies for loss of water from Co2+(H2O)x complexes, x = 5-11, are determined by threshold collision-induced dissociation (TCID) using a guided ion beam tandem mass spectrometer with a thermal electrospray ionization source. Kinetic energy dependent TCID cross sections are analyzed to yield 0 K thresholds for sequential loss of neutral water molecules. The thresholds are converted from 0 to 298 K values to give hydration enthalpies and free energies. Theoretical geometry optimizations and single point energy calculations at several levels of theory are performed for the reactant and product ion complexes. Theoretical bond energies for ground structures are used for direct comparison with experimental values to obtain structural information on these complexes. In addition, the dissociative charge separation process, Co2+(H2O)x → CoOH+(H2O)m + H+(H2O)x-m-1, is observed at x = 4, 6, and 7 in competition with primary water loss products. Energies for the charge separation rate-limiting transition states are calculated and compared to experimental threshold measurements. Results suggest that the critical size for which charge separation is energetically favored over water loss is xcrit = 6, in contrast to lower values in previous literature reports.

Binding energies of hydrated cobalt hydroxide ion complexes: A guided ion beam and theoretical investigation.

The sequential bond energies of CoOH+(H2O)x complexes, where x = 1-4, are measured by threshold collision-induced dissociation using a guided ion beam tandem mass spectrometer. The primary dissociation pathway for all reactants consists of loss of a single water molecule. This is followed by the sequential loss of additional water molecules at higher collision energies for the x = 2-4 complexes, whereas the x = 1 reactant loses the OH ligand competitively with the H2O ligand. The kinetic energy dependent cross sections for dissociation of CoOH+(H2O)x complexes are modeled to obtain 0 and 298 K binding energies. Our experimental results agree well with theoretically determined bond dissociation energies (BDEs) at the B3LYP, B3LYP-GD3BJ, B3P86, and MP2(full) levels of theory with a 6-311+G(2d,2p) basis set using geometries and vibrational frequencies determined at the B3LYP/6-311+G(d,p) level. Thermochemical information for the loss of OH from CoOH+(H2O)x where x = 0-4 is also derived by combining the present experimental HO-Co+(H2O) and water loss BDEs from CoOH+(H2O)x with those for Co+(H2O)y from the literature. These BDEs are also compared to theory with mixed results.

Correction: Structural characterization of gas-phase cysteine and cysteine methyl ester complexes with zinc and cadmium dications by infrared multiple photon dissociation spectroscopy.

Correction for 'Structural characterization of gas-phase cysteine and cysteine methyl ester complexes with zinc and cadmium dications by infrared multiple photon dissociation spectroscopy' by Rebecca A. Coates et al., Phys. Chem. Chem. Phys., 2015, 17, 25799-25808.

Correction: Zn2+ and Cd2+ cationized serine complexes: infrared multiple photon dissociation spectroscopy and density functional theory investigations.

Correction for 'Zn2+ and Cd2+ cationized serine complexes: infrared multiple photon dissociation spectroscopy and density functional theory investigations' by Rebecca A. Coates et al., Phys. Chem. Chem. Phys., 2016, 18, 22434-22445.

Thermochemical Investigations of Hydrated Nickel Dication Complexes by Threshold Collision-Induced Dissociation and Theory.

The experimental bond energies of Ni2+(H2O)x complexes, where x = 4-11, are determined by threshold collision-induced dissociation using a guided ion beam tandem mass spectrometer with an electrospray ionization source. The electrospray ionization source produces a distribution of Ni2+(H2O)x complexes, where an in-source fragmentation technique is employed to access the x = 4-6 complexes and control the population of excited isomers. The kinetic energy-dependent cross sections are modeled to yield 0 K bond energies for sequential loss of neutral water molecules, which are converted to 298 K binding energies. Analysis of the primary and secondary water losses from the Ni2+(H2O)x reactant ion complexes, x = 4-11, provide accurate thermochemistry for the hydration energies of Ni2+ and yield the first experimental values for x = 4 and 5 binding energies. Speculative thermochemistry for excited isomers of the x = 4-6 complexes is also obtained. Quantum chemical calculations explore the relative energies of possible geometries. Theoretical bond energies for ground structures are used for direct comparison with experimental values. Our experimental results agree well with previously calculated and experimentally obtained binding enthalpies as well as with the more extensive quantum chemical calculations performed here.

Experimental and Theoretical Investigations of Infrared Multiple Photon Dissociation Spectra of Asparagine Complexes with Zn2+ and Cd2+ and Their Deamidation Processes.

Complexes of asparagine (Asn) cationized with Zn2+ and Cd2+ were examined by infrared multiple photon dissociation (IRMPD) action spectroscopy using light generated from a free electron laser. Electrospray ionization yielded complexes of deprotonated Asn with Zn2+, [Zn(Asn-H)]+, and intact Asn with CdCl+, CdCl+(Asn). Series of low energy conformers for each complex were found using quantum chemical calculations in order to identify the structures formed experimentally. The experimentally obtained spectra were compared to those calculated from optimized structures at the B3LYP/6-311+G(d,p) level for [Zn(Asn-H)]+ and the B3LYP/def2-TZVP level with an SDD effective core potential on cadmium for the CdCl+(Asn) system. The main binding motif observed for the CdCl+ complex is a charge solvated, tridentate [N, CO, COs] structure where the metal binds to the backbone amino group and carbonyl oxygens of the carboxylic acid and side-chain amide groups. The Zn2+ system deprotonates at the backbone carboxylic acid and prefers a [N, CO-, COs] binding motif, where binding was observed at the carboxylate site along with the backbone amino group and side-chain carbonyl groups. In both cases, the theoretically determined lowest-energy conformers explain the experimental [Zn(Asn-H)]+ and CdCl+(Asn) spectra well. Additionally, complete mechanistic pathways were found for each of the major dissociation reactions of [Zn(Asn-H)]+ (primary loss of CO2, followed by the sequential loss of NH3) and CdCl+(Asn) (concomitant loss of NH3 + CO).

Zn(2+) and Cd(2+) cationized serine complexes: infrared multiple photon dissociation spectroscopy and density functional theory investigations.

The gas-phase structures of zinc and cadmium dications bound to serine (Ser) are investigated by infrared multiple photon dissociation (IRMPD) action spectroscopy using the free electron laser FELIX, in combination with ab initio calculations. To identify the structures of the experimentally observed species, [Zn(Ser-H)CH3CN](+) and CdCl(+)(Ser), the measured action spectra are compared to linear absorption spectra calculated at the B3LYP/6-311+G(d,p) level for Zn(2+) containing complexes and B3LYP/def2-TZVP levels for Cd(2+) containing complexes. Good agreement between the observed IRMPD spectra and the predicted spectra allows identification of the isomers present. The intact amino acid interacting with cadmium chloride adopts a tridentate chelation involving the amino acid backbone amine and carbonyl groups as well as the hydroxyl group of the side-chain, [N,CO,OH]. The presence of two low-energy conformers is observed for the deprotonated serine-zinc complex, with the same tridentate coordination as for the cadmium complex but proton loss occurs at both the hydroxyl side-chain, [N,CO,O(-)], and the carboxylic acid of the amino acid backbone, [N,CO(-),OH]. These results are profitably compared with the analogous results previously obtained for comparable complexes with cysteine.

Four-Stage Audit Demonstrating Increased Uptake of HIV Testing in Acute Neurology Admissions Using Staged Practical Interventions.

BACKGROUND: UK National Guidelines (UKNG) advise HIV testing in clinically indicated neurological presentations. We audited the impact of our practical strategies to increase uptake of HIV testing at a regional acute neurology admissions unit. METHODS: We audited HIV testing in 4 periods over 2 years: before we designed a UKNG-based "HIV testing in Neurology" protocol ("pre-protocol"); after dissemination of the protocol alone ("post-protocol"); post-protocol dissemination combined with both a tailored departmental admissions clerking proforma to prompt for HIV testing & consenting, and regular focussed tutorials to doctors on HIV testing in neurological patients ("post-proforma"); and finally one year after the post-proforma period ("+1 year"). We also looked at the total number of HIV tests sent from the unit during the two-year period. We assessed significance using Fisher's exact test. RESULTS: 47.8% of all acute neurology non-stroke admissions were eligible for HIV testing during all the audit periods. Testing rates were as follows: pre-protocol 21.9%; post-protocol 36.6%; post-proforma 83.3%; and at +1 year 65.4% (p<0.05 for both post-protocol and +1 year when compared to pre-protocol). Documentation of consent for HIV testing improved from 25% to 67.6% with the HIV-tailored clerking proforma. The total number of HIV tests requested from the unit doubled in the post-proforma period compared to pre-protocol (p<0.05). IN CONCLUSION: the combination of an HIV testing protocol, a tailored departmental clerking proforma and regular focussed teaching to doctors on indications for HIV testing led to a sustained increase in HIV testing uptake in our regional acute neurology admissions unit.

Experimental and Theoretical Investigations of Infrared Multiple Photon Dissociation Spectra of Glutamine Complexes with Zn(2+) and Cd(2.).

Complexes of glutamine (Gln) cationized with Zn(2+) and Cd(2+) were examined by infrared multiple photon dissociation (IRMPD) action spectroscopy using light generated from a free-electron laser. Electrospray ionization yielded complexes of deprotonated Gln with Zn(2+), [Zn(Gln-H)](+), and intact Gln with CdCl(+), CdCl(+)(Gln). For each complex, the spectra obtained were compared with those for low-energy conformers found using quantum chemical calculations to identify the structures present experimentally. Calculations were performed at the B3LYP/6-311+G(d,p) level for [Zn(Gln-H)](+) and at the B3LYP/def2-TZVP level with an SDD effective core potential on cadmium for CdCl(+)(Gln). The main binding motif observed for the Cd(2+) complex was a charge-solvated, tridentate [N,CO,COsc] structure in which the metal binds to the backbone amino group and the carbonyl oxygens of the carboxylic acid and side-chain amide groups. The Zn(2+) system similarly preferred a [N,CO(-),COsc] binding motif, where binding was observed at the carboxylate site along with the backbone amino and side-chain carbonyl groups. In both cases, the theoretically determined lowest-energy conformers explain the experimental [Zn(Gln-H)](+) and CdCl(+)(Gln) spectra well.

Patient satisfaction with radioiodine treatment and telephone follow-up for the management of thyrotoxicosis.

BACKGROUND AND OBJECTIVE: Patient satisfaction is of paramount importance when delivering a patient-centered service. Our hospital has been a center for the use of radioiodine to treat thyrotoxicosis for several years, but we began carrying out patient satisfaction surveys and implementing changes after 2008. The aim of the project reported here was to assess patient satisfaction with our radioiodine treatment and telephone follow-up service, and to compare results with our previous surveys. PATIENTS AND METHODS: Anonymous patient satisfaction questionnaires were sent to all patients who received radioiodine treatment for thyrotoxicosis between January 2012 and December 2013. Patients were asked to answer four questions concerning informed consenting, treatment, and telephone follow-up using a four-point Likert scale, and post back the questionnaires. A suggestion box was included for comments and suggestions for improvement. RESULTS: A total of 56 questionnaires were posted out (to 44 females and 12 males) and 34 questionnaires were returned (60.8% response rate). Between 94% and 100% of the responders, depending on the question asked, were satisfied with the service they received. Patients also put useful comments and suggestions in the suggestion box provided. CONCLUSION: Patients with thyrotoxicosis were satisfied with our radioiodine treatment and telephone follow-up service. This survey has revealed areas for service improvement, and highlights the importance of patient satisfaction when assessing a patient-centered service.

Structural characterization of gas-phase cysteine and cysteine methyl ester complexes with zinc and cadmium dications by infrared multiple photon dissociation spectroscopy.

Structural characterization of gas-phase ions of cysteine (Cys) and cysteine methyl ester (CysOMe) complexed to zinc and cadmium is investigated by infrared multiple photon dissociation (IRMPD) action spectroscopy using a free electron laser in combination with density functional theory calculations. IRMPD spectra are measured for [Zn(Cys-H)](+), [Cd(Cys-H)](+), [Zn(CysOMe-H)](+), [Cd(CysOMe-H)](+) and CdCl(+)(CysOMe) and are accompanied by quantum mechanical calculations of the predicted linear absorption spectra at the B3LYP/6-311+G(d,p) (Zn(2+) complexes) and B3LYP/def2TZVP levels (Cd(2+) complexes). On the basis of these experiments and calculations, the conformation that best reproduces the IRMPD spectra for the complexes of the deprotonated amino acids, [M(Cys-H)](+) and [M(CysOMe-H)](+), is a charge-solvated (CS) tridentate structure where the metal dication binds to the amine and carbonyl groups of the amino acid backbone and the deprotonated sulfur atom of the side chain, [N,CO,S(-)]. The intact amino acid complex, CdCl(+)(CysOMe) binds in the equivalent motif [N,CO,S]. These binding motifs are in agreement with the predicted ground structures of these complexes at the B3LYP, B3LYP-GD3BJ (with empirical dispersion corrections), B3P86, and MP2(full) levels.