10/14/2024


Ferrocenes are versatile ligand scaffolds, complexes of which have found numerous applications in catalysis. Structurally similar but of higher redox stabilites are sandwich complexes of the [Re(η6-arene)2]+ type. We report herein routes for conjugating potential ligands to a single or to both arenes in this scaffold. Since the arene rings can freely rotate, the [Re(η6-arene)2]+ has a high degree of structural flexibility. Polypyridyl ligands were successfully introduced. The coordination of Co(ii) to such a model tetrapyridyl-Re(i)-bis-benzene complex produced a bimetallic Re(i)-Co(ii) complex. To show the stability of the resulting architecture, a selected complex was subjected to photocatalytic reactions. It showed good activity in proton reduction over a long time and did not decompose, corroborating its extraordinary stability even under light irradiation. Its activity compares well with the parent catalyst in turn over numbers and frequencies. The supply of electrons limits catalytic turnover frequency at concentrations below ∼10 μM. We also show that other ligands can be introduced along these strategies. The great diversity offered by [Re(η6-arene)2]+ sandwich complexes from a synthetic point allows this concept to be extended to other catalytic processes, comparable to ferrocenes.MAX and MXene phases possess unique physical properties, encompassing the realms of both ceramics and metals. Their nanolaminated layered configuration, high anisotropic electrical conductivity, and ability to scatter electromagnetic radiation are beneficial in multiple applications. Herein, detailed applications of MAX and MXene are studied in the fields of microwave absorption and Li ion batteries (LIB). In particular, coatings based on MAX, MXene, ball-milled NanoMAX, and NanoMAX-derived-MXene (MXene-N) and their composites are examined in terms of their comparative efficacy for the aforesaid applications. NanoMAX and MXene-N based composites with graphite exhibit superior performance with specific reflection loss values (representing absorbance when measured with metal-backing) of -21.4 and -19 dB cm3 g-1, respectively, as compared to their bulk counterparts, that too with a low density (0.63 g cm-3) and very small thickness (0.03 mm). These performance improvements in absorbance in only 30 μm coatings can be attributed to reflective losses compounded with multiple internal reflections within the nanocomposite intensified by dielectric losses, arising from high interface density. The pristine samples were also studied for their performance as Li ion battery anodes. Herein, MXene-N exhibits the best performance with a specific capacity of 330 mA h g-1 at 100 mA g-1 and excellent cycling stability tested up to 1000 cycles.We report on the shear rheology of liquid crystalline solutions composed of charged, rodlike polymers that form supramolecular assemblies dispersed in water. Under steady shear, we observe shear thickening behavior, followed by a hesitation in the viscosity accompanied by an extremely narrow range of negative first normal stress difference. The Peclet number (Pe, shear rate normalized by rod rotational diffusivity) for the onset of shear thickening is in agreement with previous, high-resolution numerical simulations of the Doi-Edwards-Hess kinetic theory. We interrogate these dynamic responses through shear step-down experiments, revealing a complex evolution of transient responses. Detailed analysis of the stress transients provides compelling evidence that the principal axis of the rod orientational distribution, the nematic director, undergoes a cascade of transitions and coexistence of periodic states known as kayaking, tumbling, and wagging, before transitioning to steady flow alignment above a critical shear rate.Dissection of a cervical artery is a well-known cause of stroke, especially in younger patients. We describe the case of a 39-year-old male, who presented to our emergency department after a one-day history of headache and vomiting, with associated sudden onset posterior neck pain and cerebellar signs following a massage. Computed tomography angiogram and brain demonstrated bilateral vertebral artery dissection and cerebellar stroke. He was admitted to hospital for monitoring and conservative management with antiplatelet therapy, resulting in a good outcome. This is the first reported case of bilateral vertebral artery dissection and stroke to be associated with massage. This case also suggests, unlike many reports in the literature, that significant vascular pathology can result from massage even without cervical spine manipulation.There has been a lot of speculation that patients with coronavirus disease 2019 (COVID-19) who are receiving angiotensin-converting enzyme (ACE) inhibitors or angiotensin receptor blockers (ARBs) may be at increased risk for adverse outcomes. We reviewed the available evidence, and have not found this to be the case. We recommend that patients on such medications should continue on them unless there is a clinical indication to stop their use.Since the 1970s, neoliberalism has been the dominant economic and political philosophy among global institutions and some Western governments. Its three main strategies are privatisation and competitive markets; reduced public expenditure on social services and infrastructure; and deregulation to enhance economic activity and ensure freedom of 'choice'. Generally, these measures have negatively affected the health and wellbeing of communities. In New Zealand, privatisation and competition led to income inequality and an unequal distribution of the 'determinants of health', a burden borne disproportionately by children, the poor, and by Māori and Pacific people. https://www.selleckchem.com/products/fti-277-hcl.html Limiting health expenditure led to inequalities in access to services with restructuring in the 1990s, subverting the service culture of the health system. Failure to regulate for the protection of citizens has undermined health and safety systems, the security of work and collective approaches to health improvement. There has been some retreat from neoliberalism in New Zealand, but we can do more to focus on 'upstream' health initiatives, to recognise that social investment, including adequate funding of services, returns benefits far in excess of any costs, and to make sure that social and cultural equity goals are achieved.