Developing nurse and midwife centred rostering principles using co-design: a mixed-methods study.

Background: Current nursing and midwifery rosters are based on guidelines which may no longer adequately meet the needs of health services or staff and often result in decreased job satisfaction, poor health and wellbeing, and high turnover. Little is known about the rostering needs and preferences of contemporary nurses and midwives in Australia. The aim of this study was to identify the rostering concerns, needs and preferences of nurses and midwives, and co-design acceptable, equitable and feasible rostering principles.

Alkali cation-π interactions in aqueous systems, modulating supramolecular stereoisomerism of nanoscopic metal-organic capsules.

Contrary to common chemical intuition, cation-π interactions can persist in polar, aqueous reaction solutions, rather than in dry non-coordinative solvent systems. This account highlights how alkali ion-π interactions impart distinctive structure-influencing supramolecular forces that can be exploited in the preparation of nanoscopic metal-organic capsules. The incorporation of alkali ions from polar solutions into molecular pockets promotes the assembly of otherwise inaccessible capsular entities whose structures are distinctive to those of common polyoxovanadate clusters in which {V=O} moieties usually point radially to the outside, shielding the molecular entities.

Immunogenicity of BNT162b2 COVID-19 vaccine in New Zealand adults.

Background: There is very little known about SARS-CoV-2 vaccine immune responses in New Zealand populations at greatest risk for serious COVID-19 disease.

Methods: This prospective cohort study assessed immunogenicity in BNT162b2 mRNA vaccine recipients in New Zealand without previous COVID-19, with enrichment for Māori, Pacific peoples, older adults ≥ 65 years of age, and those with co-morbidities. Serum samples were analysed at baseline and 28 days after second dose for presence of quantitative anti-S IgG by chemiluminescent microparticle immunoassay and for neutralizing capacity against Wuhan, Beta, Delta, and Omicron BA.

The context, contribution and consequences of addressing the COVID-19 pandemic: A qualitative exploration of executive nurses' perspectives.

Aims: To explore (1) the context in which nursing executives were working, (2) nursing's contribution to the healthcare response and (3) the impact from delivering healthcare in response to the pandemic.

Design: Retrospective, constructivist qualitative study.

Methods: Individual interviews using a semi-structured interview guide were conducted between 12 February and 29 March 2021.

Defining Expertise in Cancer Nursing Practice.

Background: Thirty-five years ago, Benner defined an expert nurse as one who applies deep knowledge and experience across different contexts and clinical situations. Since that time, there has been little exploration of expertise in cancer nursing.

Objectives: To explore and describe characteristics of expert cancer nurses and to consider whether Benner's typology of an expert nurse remains relevant in today's complex oncology settings.

Australian Indigenous Communities: Efforts to Improve Cancer Care.

Aboriginal and Torres Strait Islander people are the Indigenous inhabitants of Australia who face many inequities regarding cancer care and outcomes. They are more likely to be diagnosed with cancer than non-Indigenous Australians and have not experienced the improvement in survival that non-Indigenous Australians have.

Retrospective evaluation of a clinical decision support tool for effective computed tomography angiography utilization in urgent brain imaging of suspected TIA/minor stroke in the emergency department.

Objectives: The Canadian Stroke Best Practice Recommendations suggests that patients suspected of transient ischemic attack (TIA)/minor stroke receive urgent brain imaging, preferably computed tomography angiography (CTA). Yet, high requisition rates for non-cerebrovascular patients overburden limited radiological resources, putting patients at risk. We hypothesize that our clinical decision support tool (CDST) developed for risk stratification of TIA in the emergency department (ED), and which incorporates Canadian guidelines, could improve CTA utilization.

Investigating the Formation of Giant {Pd} and {Pd} Macrocycles Using NMR, HPLC, and Mass Spectrometry.

The formation of giant polyoxometalate (POM) species is relatively underexplored, as their self-assembly process is complex due to the rapid kinetics. Polyoxopalladates (POPds) are a class of POMs based on Pd, the largest of which is the {Pd} wheel, and its slower kinetics mean the system is more amenable to systematic study. Here, we show that it is possible to follow the assembly of two types of Pd wheels, {Pd} and the smaller {Pd}, formed using glycolate and propionate ligands, respectively.

Self-Sorting of Heteroanions in the Assembly of Cross-Shaped Polyoxometalate Clusters.

Heteroanion (HA) moieties have a key role in templating of heteropolyoxometalate (HPA) architectures, but clusters templated by two different templates are rarely reported. Herein, we show how a cross-shaped HPA-based architecture can self-sort the HA templates by pairing two different guests into a divacant {XYWO} building block, with four of these building block units being linked together to complete the cross-shaped architecture. We exploited this observation to incorporate HA templates into well-defined positions within the clusters, leading to the isolation of a collection of mixed-HA templated cross-shaped polyanions [(XYWO)(WO)] (X = H-P, Y = Se, Te, As).

Digitization of multistep organic synthesis in reactionware for on-demand pharmaceuticals.

Chemical manufacturing is often done at large facilities that require a sizable capital investment and then produce key compounds for a finite period. We present an approach to the manufacturing of fine chemicals and pharmaceuticals in a self-contained plastic reactionware device. The device was designed and constructed by using a chemical to computer-automated design (ChemCAD) approach that enables the translation of traditional bench-scale synthesis into a platform-independent digital code.

Long-Term Motor Recovery After Severe Traumatic Brain Injury: Beyond Established Limits.

Objective: To report neural plasticity changes after severe traumatic brain injury.

Setting: Case-control study.

Participants: Canadian soldier, Captain Trevor Greene survived a severe open-traumatic brain injury during a 2006 combat tour in Afghanistan.

ACR Select Identifies Inappropriate Underutilization of Magnetic Resonance Imaging in British Columbia.

Purpose: A study was performed to evaluate the ACR Select software in determining the level of appropriateness of computed tomography (CT) and magnetic resonance imaging (MRI) in Island Health in British Columbia.

Methods: A total of 1228 consecutive CT and MRI studies performed in a 3-day period were entered into a software program provided by the National Decision Support Company based on the ACR Appropriateness Criteria. The program was able to analyze 93% (1141) of these studies.

Following the Reaction of Heteroanions inside a {W18O56} Polyoxometalate Nanocage by NMR Spectroscopy and Mass Spectrometry.

By incorporating phosphorus(III)-based anions into a polyoxometalate cage, a new type of tungsten-based unconventional Dawson-like cluster, [W18O56(HP(III)O3)2(H2O)2](8-), was isolated, in which the reaction of the two phosphite anions [HPO3](2-) within the {W18O56} cage could be followed spectroscopically. As well as full X-ray crystallographic analysis, we studied the reactivity of the cluster using both solution-state NMR spectroscopy and mass spectrometry. These techniques show that the cluster undergoes a structural rearrangement in solution whereby the {HPO3} moieties dimerize to form a weakly interacting (O3PH⋅⋅⋅HPO3) moiety.

The effect of the spacer of bis(biurea) ligands on the structure of A2 L3 -type (A=anion) phosphate complexes.

By tuning the length and rigidity of the spacer of bis(biurea) ligands L, three structural motifs of the A2 L3 complexes (A represents anion, here orthophosphate PO4 (3-) ), namely helicate, mesocate, and mono-bridged motif, have been assembled by coordination of the ligand to phosphate anion. Crystal structure analysis indicated that in the three complexes, each of the phosphate ions is coordinated by twelve hydrogen bonds from six surrounding urea groups. The anion coordination properties in solution have also been studied.

Exploring the symmetry, structure, and self-assembly mechanism of a gigantic seven-fold symmetric {Pd₈₄} wheel.

The symmetry, structure and formation mechanism of the structurally self-complementary {Pd84} = [Pd84O42(PO4)42(CH3CO2)28](70-) wheel is explored. Not only does the symmetry give rise to a non-closest packed structure, the mechanism of the wheel formation is proposed to depend on the delicate balance between reaction conditions. We achieve the resolution of gigantic polyoxopalladate species through electrophoresis and size-exclusion chromatography, the latter has been used in conjunction with electrospray mass spectrometry to probe the formation of the ring, which was found to proceed by the stepwise aggregation of {Pd6}(-) = [Pd6O4(CH3CO2)2(PO4)3Na(6-n)H(n)](-) building blocks.

A versatile tripodal Cu(I) reagent for C-N bond construction via nitrene-transfer chemistry: catalytic perspectives and mechanistic insights on C-H aminations/amidinations and olefin aziridinations.

A Cu(I) catalyst (1), supported by a framework of strongly basic guanidinato moieties, mediates nitrene-transfer from PhI═NR sources to a wide variety of aliphatic hydrocarbons (C-H amination or amidination in the presence of nitriles) and olefins (aziridination). Product profiles are consistent with a stepwise rather than concerted C-N bond formation. Mechanistic investigations with the aid of Hammett plots, kinetic isotope effects, labeled stereochemical probes, and radical traps and clocks allow us to conclude that carboradical intermediates play a major role and are generated by hydrogen-atom abstraction from substrate C-H bonds or initial nitrene-addition to one of the olefinic carbons.

Continuous parallel ESI-MS analysis of reactions carried out in a bespoke 3D printed device.

Herein, we present an approach for the rapid, straightforward and economical preparation of a tailored reactor device using three-dimensional (3D) printing, which can be directly linked to a high-resolution electrospray ionisation mass spectrometer (ESI-MS) for real-time, in-line observations. To highlight the potential of the setup, supramolecular coordination chemistry was carried out in the device, with the product of the reactions being recorded continuously and in parallel by ESI-MS. Utilising in-house-programmed computer control, the reactant flow rates and order were carefully controlled and varied, with the changes in the pump inlets being mirrored by the recorded ESI-MS spectra.

Nanoscale control of polyoxometalate assembly: a {Mn8W4} cluster within a {W36Si4Mn10} cluster showing a new type of isomerism.

Two near isomeric clusters containing a novel {Mn(8)W(4)} Keggin cluster within a [W(36)Mn(10)Si(4)O(136)(OH)(4)(H(2)O)8](24-) cluster are reported: K(10)Li(14)[W(36)Si(4)O(136)Mn(II)(10)(OH)(4)(H(2)O)(8)] (1) and K(10)Li1(3.5)Mn(0.25)[W(36)Si(4)O(136)Mn(II)(10)(OH)(4)(H(2)O)(8) ] (1').

A classification of spin frustration in molecular magnets from a physical study of large odd-numbered-metal, odd electron rings.

The term "frustration" in the context of magnetism was originally used by P. W. Anderson and quickly adopted for application to the description of spin glasses and later to very special lattice types, such as the kagomé.

Anion-dependent formation of helicates versus mesocates of triple-stranded M2L3 (M = Fe2+, Cu2+) complexes.

A series of dinuclear triple-stranded complexes, [Fe(2)L(3)⊃X]X(6) [X = BF(4)(-) (1), ClO(4)(-) (2)], [Fe(2)L(3)⊃SO(4)](2)(SO(4))(5) (3), [Fe(2)L(3)⊃Br](BPh(4))(6) (4), Fe(2)L(3)(NO(3))Br(6) (5), and [Cu(2)L(3)⊃NO(3)](NO(3))(6) (6), which incorporate a central cavity to encapsulate different anions, have been synthesized via the self-assembly of iron(II) or copper(II) salts with the N,N'-bis[5-(2,2'-bipyridyl)methyl]imidazolium bromide (LBr) ligand. X-ray crystallographic studies (for 1-4 and 6) and elemental analyses confirmed the cagelike triple-stranded structure. The anionic guest is bound in the cage and shows remarkable influence on the outcome of the self-assembly process with regard to the configuration at the metal centers.

Observation of Fe(V)=O using variable-temperature mass spectrometry and its enzyme-like C-H and C=C oxidation reactions.

Oxo-transfer chemistry mediated by iron underpins many biological processes and today is emerging as synthetically very important for the catalytic oxidation of C-H and C=C moieties that are hard to activate conventionally. Despite the vast amount of research in this area, experimental characterization of the reactive species under catalytic conditions is very limited, although a Fe(V)=O moiety was postulated. Here we show, using variable-temperature mass spectrometry, the generation of a Fe(V)=O species within a synthetic non-haem complex at -40 °C and its reaction with an olefin.

Cubic assembly of a geometrically frustrated {Fe12} spin cluster.

We describe an S(4)-symmetric {Fe(12)} spin cluster [Fe(12)O(4)(OH)(2)(L)(4)(OAc)(8)][Cl](2) {H(4)L = (HOCH(2)CH(2))(2)NCH(2)CH(2)N(CH(2)CH(2)OH)(2)} where the iron(III) centres describe a squashed hexagonal antiprism. The clusters pack into a large cubic cell with circular cavities, lined by weak C-H···O interactions, and a unit cell volume of over 60,000 Å(3) containing large solvent accessible voids. The core of the cluster is stable in solution, as confirmed by electrospray mass spectrometry.

Ferromagnetically coupled chiral cyanide-bridged {Ni₆Fe₄} cages.

Enantiomeric, ferromagnetically coupled decanuclear {Ni₆Fe₄} cages with adamantane-like cores were synthesized around templating tetraethylammonium cations, as shown by crystallographic analysis and CSI-MS, and their homochiral nature was confirmed by circular dichroism measurements.