The ultrafast dynamics of subnanometer neutral cuprite clusters (CuO), < 13, are examined with pump probe spectroscopy. Upon absorption of an ultraviolet (400 nm) photon, all clusters exhibit a subpicosecond lifetime that we attribute to carrier recombination. Density functional theory (DFT) shows a change in the structural motif between small planar clusters and three-dimensional structures at = 4.
View Article and Find Full Text PDFPhys Chem Chem Phys
August 2024
The ultrafast dynamics of neutral copper oxide clusters (CuO, < 5) are reported using femtosecond pump probe spectroscopy in the gas phase. The transient spectra recorded for each cluster demonstrate they relax on a 100s of fs timescale followed by a long-lived (>50 ps) response. Density functional theory calculations are performed to determine the lowest energy structures and spin states.
View Article and Find Full Text PDFThe excited state lifetimes of neutral (Al) clusters up to ∼1 nm in diameter in size, where ≤ 43, are systematically measured with femtosecond time-resolved mass spectrometry. The onset of metallic behavior is identified as a distinct change in the relaxation behavior initiated with single ultraviolet (400 nm) photon excitation. The experimentally measured excited state lifetimes gradually decrease with size for small molecular scale clusters ( < 10) before becoming indistinguishable for larger clusters ( > 9), where the measurements are comparable to electron-lattice relaxation time of bulk Al (∼300 fs).
View Article and Find Full Text PDFThe ultrafast proton transfer dynamics of homogeneous formic acid clusters (FA), < 10, are investigated with femtosecond time-resolved mass spectrometry. We monitor the proton transfer pathway following Rydberg state electronic relaxation and find that successful ion pair formation increases logarithmically with cluster size. Ab initio calculations demonstrate similar excitation/relaxation behavior for each cluster, revealing a contact ion pair forms between two molecules composing the cluster before finally a formate anion (HCOO) is dissociated by the probe pulse.
View Article and Find Full Text PDFFemtosecond time-resolved mass spectrometry, correlation mapping, and density functional theory calculations are employed to reveal the mechanism of C═C and C≡C formation (and related H production) following excitation to the p-Rydberg states of -butyl bromide. Ultrafast pump-probe mass spectrometry shows that nonadiabatic relaxation operates as a multistep process reaching an intermediate state within ∼500 fs followed by relaxation to a final state within 10 ps of photoexcitation. Absorption of three ultraviolet photons accesses the dense p-Rydberg state manifold, which is further excited by the probe beam for C─C bond dissociation and dehydrogenation reactions.
View Article and Find Full Text PDFReaction-based fluorescent-probes have proven successful for the visualisation of biological species in various cellular processes. Unfortunately, in order to tailor the design of a fluorescent probe to a specific application ( organelle targeting, material and theranostic applications) often requires extensive synthetic efforts and the synthetic screening of a range of fluorophores to match the required synthetic needs. In this work, we have identified as a unique "plug-and-play" synthetic platform that can be used to develop a range of ONOO responsive fluorescent probes for a variety of applications.
View Article and Find Full Text PDFBackground: Rhinovirus (RV) is the main cause of asthma exacerbations in children. Some studies reported that persons with asthma have attenuated interferon (IFN) responses to experimental RV infection compared with healthy individuals. However, responses to community-acquired RV infections in controls and children with asthma have not been compared.
View Article and Find Full Text PDFBackground: Early-life wheezing-associated respiratory infection with human rhinovirus (RV) is associated with asthma development. RV infection of 6-day-old immature mice causes mucous metaplasia and airway hyperresponsiveness which is associated with the expansion of IL-13-producing type 2 innate lymphoid cells (ILC2s) and dependent on IL-25 and IL-33. We examined regulation of this asthma-like phenotype by IL-1β.
View Article and Find Full Text PDFActivation of the inflammasome is a key function of the innate immune response that regulates inflammation in response to microbial substances. Inflammasome activation by human rhinovirus (RV), a major cause of asthma exacerbations, has not been well studied. We examined whether RV induces inflammasome activation in vivo, molecular mechanisms underlying RV-stimulated inflammasome priming and activation, and the contribution of inflammasome activation to RV-induced airway inflammation and exacerbation.
View Article and Find Full Text PDFRespiratory viral infections are strongly associated with asthma exacerbations. Rhinovirus is most frequently-detected pathogen; followed by respiratory syncytial virus; metapneumovirus; parainfluenza virus; enterovirus and coronavirus. In addition; viral infection; in combination with genetics; allergen exposure; microbiome and other pathogens; may play a role in asthma development.
View Article and Find Full Text PDFThe origins and lifeways of the inhabitants of Rapa Nui (Easter Island), a remote island in the southeast Pacific Ocean, have been debated for generations. Archaeological evidence substantiates the widely accepted view that the island was first settled by people of Polynesian origin, as late as 1200 CE [1-4]. What remains controversial, however, is the nature of events in the island's population history prior to the first historic contact with Europeans in 1722 CE.
View Article and Find Full Text PDFObjectives: The Rapa Nui "ecocide" narrative questions whether the prehistoric population caused an avoidable ecological disaster through rapid deforestation and over-exploitation of natural resources. The objective of this study was to characterize prehistoric human diets to shed light on human adaptability and land use in an island environment with limited resources.
Materials And Methods: Materials for this study included human, faunal, and botanical remains from the archaeological sites Anakena and Ahu Tepeu on Rapa Nui, dating from c.
Background: We compared percent excess body mass index loss (%EBMIL) and resolution of dyslipidaemia, hypertension, and type 2 diabetes mellitus in the 4 years following laparoscopic sleeve gastrectomy (LSG) between patients calibrated with a 40-French (40F) or a 50-French (50F) bougie.
Methods: We conducted a longitudinal retrospective descriptive study of routinely collected pre- and post-surgical data from 294 patients who underwent LSG at a single surgical centre (50F--n = 106, 40F--n = 185). Obesity measurements were taken prior to surgery and at regular intervals until 48 months post-surgery.
This study examined the prevalence and characteristics of adults with an alcohol use-related problem who receive clergy services. Data come from the National Epidemiologic Survey on Alcohol and Related Conditions. Among persons who sought any services for alcohol-related problems (n = 1,910), 14.
View Article and Find Full Text PDFObjectives: Recent research shows a high rate of complementary and alternative medicine (CAM) use among persons with mental disorders, although correlates and patterns of CAM use are relatively unknown. This study tested whether CAM use is associated with perceived effectiveness of conventional treatment (i.e.
View Article and Find Full Text PDFInhalant use is the intentional inhalation of vapors from commercial products or specific chemical agents for the purpose of achieving intoxication. Inhalants are among the most common and pernicious forms of substance use and the least studied of the major drugs. Diagnosis of inhalant dependence, according to the DSM-IV [Weintraub E, Gandhi D, Robinson C.
View Article and Find Full Text PDFThis research examined the role of perceived barriers to treatment as a potential contributor to the increasing use of complementary and alternative medicine (CAM) among mentally ill populations. The study examined a sample of 435 patients receiving care through the Veterans Administration Health System and having a current diagnosis of bipolar disorder (I, II, NOS), cyclothymia, or schizoaffective disorder-bipolar subtype. Access to care and use of any of 14 CAM therapies within the past year were studied.
View Article and Find Full Text PDFWe have conducted a multistage genomewide association study, using 1,620,742 single-nucleotide polymorphisms to systematically investigate the genetic factors influencing intrinsic skin pigmentation in a population of South Asian descent. Polymorphisms in three genes--SLC24A5, TYR, and SLC45A2--yielded highly significant replicated associations with skin-reflectance measurements, an indirect measure of melanin content in the skin. The associations detected in these three genes, in an additive manner, collectively account for a large fraction of the natural variation of skin pigmentation in a South Asian population.
View Article and Find Full Text PDFPrimary Objective: The aims of this preliminary study were to explore the suitability for and benefits of commencing dysarthria treatment for people with traumatic brain injury (TBI) while in post-traumatic amnesia (PTA). It was hypothesized that behaviours in PTA don't preclude participation and dysarthria characteristics would improve post-treatment.
Research Design: A series of comprehensive case analyses.
Immunomodulation involves the use of antibodies to alter the function of molecules and is an emerging tool for manipulating both plant and animal systems. To realize the full potential of this technology, two major obstacles must be overcome. First, most antibodies do not function well intracellularly because critical disulfide bonds cannot form in the reducing environment of the cytoplasm or because of difficulties in targeting to subcellular organelles.
View Article and Find Full Text PDFWe report the isolation, sequencing and analysis of the cDNA corresponding to an alpha-D-xylosidase involved in the mobilisation of xyloglucan from the cotyledons of germinated nasturtium (Tropaeolum majus L.) seeds. The translated open reading frame (2,808 bp including the stop codon), gave a polypeptide of 935 amino acids.
View Article and Find Full Text PDFMedium chain hydrolase (MCH) is an enzyme which regulates the chain length of fatty acid synthesis specifically in the mammary gland of the rat. During lactation, MCH interacts with fatty acid synthase (FAS) to cause premature release of acyl chains, thus providing medium chain fatty acids for synthesis of milk fat. In this study we have investigated the ability of rat MCH to interact with the phylogenetically more distant FAS structure present in plant systems and to cause a perturbation of fatty acid synthesis.
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