Cathodic corrosion is an electrochemical phenomenon that etches metals at moderately negative potentials. Although cathodic corrosion probably occurs by forming a metal-containing anion, such intermediate species have not yet been observed. Here, aiming to resolve this long-standing debate, our work provides such evidence through X-ray absorption spectroscopy.
View Article and Find Full Text PDFPurpose: Rare diseases are individually uncommon yet collectively prevalent. They affect over 300,000 people in Ireland, with 50-70 % impacting children. This study explores the supportive care needs of parents caring for children with rare diseases in Ireland, utilising a validated Parental Needs Scale for Rare Diseases (PNS-RD).
View Article and Find Full Text PDFThe orphan nuclear receptor NR2E3 has emerged as a potential tumor suppressor, yet its precise mechanisms in tumorigenesis require further investigation. Here, we demonstrate that the full-length protein isoform of NR2E3 instead of its short isoform activates wild-type p53 and is capable of rescuing certain p53 mutations in various cancer cell lines. Importantly, we observe a higher frequency of NR2E3 mutations in three solid tumors compared to the reference population, highlighting its potential significance in tumorigenesis.
View Article and Find Full Text PDFAlthough sex determination is a fundamental process in vertebrate development, it is very plastic. Diverse genes became major sex determinants in teleost fishes. Deciphering how individual sex-determining genes orchestrate sex determination can reveal new actors in sexual development.
View Article and Find Full Text PDFBackground: The complex physical, cognitive, and psychological consequences of stroke can disrupt a survivor's sense of pre-stroke normality and identity. This can have a substantial impact on their individual and social lives. Individual reports about life after stroke have improved our understanding of this impact.
View Article and Find Full Text PDFIron(IV)-oxo intermediates found in iron enzymes and artificial catalysts are competent for H atom abstraction in catalytic cycles. For = 2 intermediates, both axial and equatorial approaches are well-established. The mechanism for = 1 sites is not as well understood: an equatorial approach is more energetically favorable, and an axial approach requires crossing from the = 1 to the = 2 surface.
View Article and Find Full Text PDFThe rise of atmospheric oxygen as a result of photosynthesis in cyanobacteria and chloroplasts has transformed most environmental iron into the ferric state. In contrast, cells within organisms maintain a reducing internal milieu and utilize predominantly ferrous iron. Ferric reductases are enzymes that transfer electrons to ferric ions, either extracellularly or within endocytic vesicles, enabling cellular ferrous iron uptake through Divalent Metal Transporter 1.
View Article and Find Full Text PDFIntroduction: This study aimed to i) identify the care needs of families experiencing cardiac arrest; and ii) co-identify strategies for meeting the identified care needs. Cardiac arrest survivors and family members (of survivors and non-survivors) were engaged as "experience experts," collaborators and co-researchers in this study.
Methods: A qualitative study using semi-structured interviews of cardiac arrest survivors and family members was conducted.
As a first step in preparing for the return of samples from the Moon by the Artemis Program, NASA initiated the Apollo Next Generation Sample Analysis Program (ANGSA). ANGSA was designed to function as a low-cost sample return mission and involved the curation and analysis of samples previously returned by the Apollo 17 mission that remained unopened or stored under unique conditions for 50 years. These samples include the lower portion of a double drive tube previously sealed on the lunar surface, the upper portion of that drive tube that had remained unopened, and a variety of Apollo 17 samples that had remained stored at -27 °C for approximately 50 years.
View Article and Find Full Text PDFBackground: Healthcare transition can be challenging for young people and families living with chronic kidney conditions, including those with rare renal disorders who often have multi-systemic conditions, those who have undergone kidney transplantation, and those who face intense treatments like dialysis. Comprehensive, holistic healthcare transition interventions are required, encompassing physical, psychosocial, sexual, educational and vocational support.
Aim: This manuscript presents a systematic scoping review synthesising the healthcare transition interventions to support youth and families within nephrology services.
Human manganese superoxide dismutase (MnSOD) is a crucial oxidoreductase that maintains the vitality of mitochondria by converting superoxide (O) to molecular oxygen (O) and hydrogen peroxide (HO) with proton-coupled electron transfers (PCETs). Human MnSOD has evolved to be highly product inhibited to limit the formation of HO, a freely diffusible oxidant and signaling molecule. The product-inhibited complex is thought to be composed of a peroxide (O) or hydroperoxide (HO) species bound to Mn ion and formed from an unknown PCET mechanism.
View Article and Find Full Text PDFHuman manganese superoxide dismutase (MnSOD) plays a crucial role in controlling levels of reactive oxygen species (ROS) by converting superoxide (O ) to molecular oxygen (O) and hydrogen peroxide (HO) with proton-coupled electron transfers (PCETs). The reactivity of human MnSOD is determined by the state of a key catalytic residue, Tyr34, that becomes post-translationally inactivated by nitration in various diseases associated with mitochondrial dysfunction. We previously reported that Tyr34 has an unusual pK due to its proximity to the Mn metal and undergoes cyclic deprotonation and protonation events to promote the electron transfers of MnSOD.
View Article and Find Full Text PDFBackground: Rare diseases encompass a diverse group of debilitating and sometimes life-threatening conditions that affect a small percentage of the population, posing a significant public health challenge. Despite their rarity, around 70% of these diseases afflict children, yet limited research has focused on their experiences. This study aimed to gain insights into the day-to-day challenges children living with rare diseases face.
View Article and Find Full Text PDFTo fully harness the potential of abundant metal coordination complex photosensitizers, a detailed understanding of the molecular properties that dictate and control the electronic excited-state population dynamics initiated by light absorption is critical. In the absence of detectable luminescence, optical transient absorption (TA) spectroscopy is the most widely employed method for interpreting electron redistribution in such excited states, particularly for those with a charge-transfer character. The assignment of excited-state TA spectral features often relies on spectroelectrochemical measurements, where the transient absorption spectrum generated by a metal-to-ligand charge-transfer (MLCT) electronic excited state, for instance, can be approximated using steady-state spectra generated by electrochemical ligand reduction and metal oxidation and accounting for the loss of absorptions by the electronic ground state.
View Article and Find Full Text PDFThe known I^{π}=8_{1}^{+}, E_{x}=2129-keV isomer in the semimagic nucleus ^{130}Cd_{82} was populated in the projectile fission of a ^{238}U beam at the Radioactive Isotope Beam Factory at RIKEN. The high counting statistics of the accumulated data allowed us to determine the excitation energy, E_{x}=2001.2(7) keV, and half-life, T_{1/2}=57(3) ns, of the I^{π}=6_{1}^{+} state based on γγ coincidence information.
View Article and Find Full Text PDFHuman manganese superoxide dismutase (MnSOD) plays a crucial role in controlling levels of reactive oxygen species (ROS) by converting superoxide (O ) to molecular oxygen (O ) and hydrogen peroxide (H O ) with proton-coupled electron transfers (PCETs). The reactivity of human MnSOD is determined by the state of a key catalytic residue, Tyr34, that becomes post-translationally inactivated by nitration in various diseases associated with mitochondrial dysfunction. We previously reported that Tyr34 has an unusual pK due to its proximity to the Mn metal and undergoes cyclic deprotonation and protonation events to promote the electron transfers of MnSOD.
View Article and Find Full Text PDFVesicular transport is essential for delivering cargo to intracellular destinations. Evi5 is a Rab11-GTPase-activating protein involved in endosome recycling. In humans, Evi5 is a high-risk locus for multiple sclerosis, a debilitating disease that also presents with excess iron in the CNS.
View Article and Find Full Text PDFTo prevent motion artifacts in small animal positron emission tomography (PET), animals are routinely scanned under anesthesia or physical restraint. Both may potentially alter metabolism and neurochemistry. This study investigates the feasibility of fully awake acquisition and subsequent absolute quantification of dynamic brain PET data via pharmacokinetic modelling in moving rats using the glutamate 5 receptor radioligand [C]ABP688 and point source based motion correction.
View Article and Find Full Text PDFBackground: Lifestyle changes, in addition to preventive medications, optimise stroke secondary prevention. Evidence from systematic reviews support behaviour-change interventions post-stroke to address lifestyle-related risk. However, understanding of the theory-driven mediators that affect behaviour-change post-stroke is lacking.
View Article and Find Full Text PDFIntroduction: Ensuring access for older people to Primary Health Care (PHC) is vital to achieve universal health coverage, improve health outcomes, and health-system performance. However, older people living in Low-and Middle-Income Countries (LMICs) face barriers constraining their timely access to appropriate care. This review aims to summarize the nature and breadth of literature examining older people's experiences with access to PHC in LMICs, and access barriers and enablers.
View Article and Find Full Text PDFBackground: Using digital technologies to provide services and supports remotely may improve efficiency and accessibility of healthcare, and support people with disabilities to live independently. This study aimed to explore the experience of using digital technologies to access and provide disability services and supports during the Covid-19 pandemic, from the perspective of people with disabilities, families and service providers.
Methods: Using a multiple case study design, we purposively sampled three cases based on service user characteristics and geographical reach of the service.
Human manganese superoxide dismutase (MnSOD) is a crucial oxidoreductase that maintains the vitality of mitochondria by converting to and with proton-coupled electron transfers (PCETs). Since changes in mitochondrial concentrations are capable of stimulating apoptotic signaling pathways, human MnSOD has evolutionarily gained the ability to be highly inhibited by its own product, . A separate set of PCETs is thought to regulate product inhibition, though mechanisms of PCETs are typically unknown due to difficulties in detecting the protonation states of specific residues that coincide with the electronic state of the redox center.
View Article and Find Full Text PDFKβ X-ray emission spectroscopy (XES) is widely used to fingerprint the local spin of transition-metal ions, including in pump-probe experiments, to identify excited states or in chemical and biological reactions to characterize short-lived intermediates. In this study, the spectra of ferrous and ferric complexes for various spin states were measured experimentally and described theoretically through restricted active space (RAS) calculations including dynamic correlations. Through the RAS calculations from simple atomic models to complex molecular systems, spectral effects such as the exchange interactions, crystal-field strength, and covalent orbital mixing were evaluated and discussed.
View Article and Find Full Text PDFHuman manganese superoxide dismutase (MnSOD) is a crucial oxidoreductase that maintains the vitality of mitochondria by converting O to O and H O with proton-coupled electron transfers (PCETs). Since changes in mitochondrial H O concentrations are capable of stimulating apoptotic signaling pathways, human MnSOD has evolutionarily gained the ability to be highly inhibited by its own product, H O . A separate set of PCETs is thought to regulate product inhibition, though mechanisms of PCETs are typically unknown due to difficulties in detecting the protonation states of specific residues that coincide with the electronic state of the redox center.
View Article and Find Full Text PDFX-ray free-electron lasers (XFELs) provide intense pulses that can generate stimulated X-ray emission, a phenomenon that has been observed and studied in materials ranging from neon to copper. Two schemes have been employed: amplified spontaneous emission (ASE) and seeded stimulated emission (SSE), where a second color XFEL pulse provides the seed. Both phenomena are currently explored for coherent X-ray laser sources and spectroscopy.
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