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Date Presented 03/21/24 This 2021 retrospective national survey of 1,549 self-reported caregivers of children with developmental disabilities provided insight into the prevalence of reported poor physical and mental health and its impact on personal activities of daily living (ADL) function. Primary Author and Speaker: Cindy W. W. Poole Additional Authors and Speakers: David Levine, Stephanie Forbert, Tessa Baker, Sydney Baker, Sarah Tindall, Blair Shelton [ABSTRACT FROM AUTHOR]

Since the very beginning of astronomy the location of objects on the sky has been a fundamental observational quantity that has been taken for granted. While precise two dimensional positional information is easy to obtain for observations in the electromagnetic spectrum, the positional accuracy of current and near future gravitational wave detectors is limited to between tens and hundreds of square degrees, which makes it extremely challenging to identify the host galaxies of gravitational wave events or to detect any electromagnetic counterparts. Gravitational wave observations provide information on source properties that is complementary to the information in any associated electromagnetic emission. Observing systems with multiple messengers thus has scientific potential much greater than the sum of its parts. A gravitational wave detector with higher angular resolution would significantly increase the prospects for finding the hosts of gravitational wave sources and triggering a multi-messenger follow-up campaign. An observatory with arcminute precision or better could be realised within the Voyage 2050 programme by creating a large baseline interferometer array in space and would have transformative scientific potential. Precise positional information of standard sirens would enable precision measurements of cosmological parameters and offer new insights on structure formation; a high angular resolution gravitational wave observatory would allow the detection of a stochastic background and resolution of the anisotropies within it; it would also allow the study of accretion processes around black holes; and it would have tremendous potential for tests of modified gravity and the discovery of physics beyond the Standard Model. [ABSTRACT FROM AUTHOR]

The gravitational-wave astronomical revolution began in 2015 with LIGO's observation of the coalescence of two stellar-mass black holes. Over the coming decades, ground-based detectors like laser interferometer gravitational-wave observatory (LIGO), Virgo and KAGRA will extend their reach, discovering thousands of stellar-mass binaries. In the 2030s, the space-based laser interferometer space antenna (LISA) will enable gravitational-wave observations of the massive black holes in galactic centres. Between ground-based observatories and LISA lies the unexplored dHz gravitational-wave frequency band. Here, we show the potential of a decihertz observatory (DO) which could cover this band, and complement discoveries made by other gravitational-wave observatories. The dHz range is uniquely suited to observation of intermediate-mass (∼102–104M⊙) black holes, which may form the missing link between stellar-mass and massive black holes, offering an opportunity to measure their properties. DOs will be able to detect stellar-mass binaries days to years before they merge and are observed by ground-based detectors, providing early warning of nearby binary neutron star mergers, and enabling measurements of the eccentricity of binary black holes, providing revealing insights into their formation. Observing dHz gravitational-waves also opens the possibility of testing fundamental physics in a new laboratory, permitting unique tests of general relativity (GR) and the standard model of particle physics. Overall, a DO would answer outstanding questions about how black holes form and evolve across cosmic time, open new avenues for multimessenger astronomy, and advance our understanding of gravitation, particle physics and cosmology. [ABSTRACT FROM AUTHOR]

Homoleptic σ‐bonded uranium–alkyl complexes have been a synthetic target since the Manhattan Project. The current study describes the synthesis and characterization of several unprecedented uranium–methyl complexes. Amongst these complexes, the first example of a homoleptic uranium–alkyl dimer, [Li(THF)4]2[U2(CH3)10], as well as a seven‐coordinate uranium–methyl monomer, {Li(OEt2)Li(OEt2)2UMe7Li}n were both crystallographically identified. The diversity of complexes reported herein provides critical insight into the structural diversity, electronic structure and bonding in uranium–alkyl chemistry. [ABSTRACT FROM AUTHOR]

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The use of N-methylpyrrolidone (NMP) as a cosolvent in ferric salt catalyzed cross-coupling reactions is crucial for achieving the highly selective, preparative scale formation of cross-coupled product in reactions utilizing alkyl Grignard reagents. Despite the critical importance of NMP, the molecular level effect of NMP on in situ formed and reactive iron species that enables effective catalysis remains undefined. Herein, we report the isolation and characterization of a novel trimethyliron(II) ferrate species, [Mg(NMP)6][FeMe3]2 (1), which forms as the major iron species in situ in reactions of Fe(acac)3 and MeMgBr under catalytically relevant conditions where NMP is employed as a co-solvent. Importantly, combined GC analysis and 57Fe Mössbauer spectroscopic studies identified 1 as a highly reactive iron species for the selective formation generating cross-coupled product. These studies demonstrate that NMP does not directly interact with iron as a ligand in catalysis but, alternatively, interacts with the magnesium cations to preferentially stabilize the formation of 1 over [Fe8Me12]- cluster generation, which occurs in the absence of NMP. [ABSTRACT FROM AUTHOR]

The combination of simple cobalt salts and N-heterocyclic carbene (NHC) ligands has been highly effective in C–H functionalization, hydroarylation and cross-coupling catalysis, though displaying a strong dependence on the identity of the NHC ligand. In addition, reactions effective with NHC ligands are often ineffective with phosphine ligands, further motivating the evaluation of the fundamental electronic structure and bonding differences in well-defined distorted tetrahedral Co(ii) complexes. Magnetic circular dichroism (MCD) studies indicate that Co(ii)–bisphosphines have larger ligand fields than Co(ii)–NHC complexes. Theoretical density functional theory (DFT) calculations were performed on an expanded set of L2CoCl2 complexes (L2 = NHC, bisphosphine and diamine) to study the electronic structure and relative ligation properties of NHCs compared to bisphosphine and diamine ligands. Mayer bond order and charge decomposition analyses indicate that NHC ligands are slightly stronger donor ligands than bisphosphines but also result in a weakening of Co–Cl bonds in a trans-like influence. From MCD and DFT studies, changing the NHC N-substituent has a larger effect on the ligand field of Co(ii)–NHC complexes than saturating the backbone. Overall, these studies provide detailed insight into the electronic structure and bonding effects in Co(ii) complexes with ligand types commonly explored in catalysis. [ABSTRACT FROM AUTHOR]

Iron complexes containing pincer ligands that incorporate N-heterocyclic carbene (NHC) moieties are of significant interest in organometallic catalysis in order to generate more oxidatively robust complexes that may exhibit novel catalytic properties. In order to define the effect that introducing NHC moieties into pincer ligands has on electronic structure and bonding in iron(II)-pincer complexes, MCD and DFT studies of (iPrCDA)FeBr2, (iPrPDI)FeBr2, and (iPrCNC)FeBr2 were performed. These studies quantify the electronic structures and bonding interactions as a function of pincer ligand variation. They also demonstrate that the observed ligand fields (and, hence, spin states) directly correlate to the increased Fe-C bonding and pincer-donating abilities that result from introducing NHC moieties into the pincer ligand. However, the net donor abilities of the pincers and the strength of the Fe-pincer interaction do not directly correlate to the number of NHC moieties present, but instead are determined to be due to differences in Fe-C and overall Fe-pincer bonding as a result of the position of the NHC moieties in the pincer ligand and the overall geometric constraints of the pincer architecture. [ABSTRACT FROM AUTHOR]

Despite its continued observational successes, there is a persistent (and growing) interest in extending cosmology beyond the standard model, Λ CDM . This is motivated by a range of apparently serious theoretical issues, involving such questions as the cosmological constant problem, the particle nature of dark matter, the validity of general relativity on large scales, the existence of anomalies in the CMB and on small scales, and the predictivity and testability of the inflationary paradigm. In this paper, we summarize the current status of Λ CDM as a physical theory, and review investigations into possible alternatives along a number of different lines, with a particular focus on highlighting the most promising directions. While the fundamental problems are proving reluctant to yield, the study of alternative cosmologies has led to considerable progress, with much more to come if hopes about forthcoming high-precision observations and new theoretical ideas are fulfilled. [ABSTRACT FROM AUTHOR]

Euclid is a European Space Agency medium-class mission selected for launch in 2020 within the cosmic vision 2015-2025 program. The main goal of Euclid is to understand the origin of the accelerated expansion of the universe. Euclid will explore the expansion history of the universe and the evolution of cosmic structures by measuring shapes and red-shifts of galaxies as well as the distribution of clusters of galaxies over a large fraction of the sky. Although the main driver for Euclid is the nature of dark energy, Euclid science covers a vast range of topics, from cosmology to galaxy evolution to planetary research. In this review we focus on cosmology and fundamental physics, with a strong emphasis on science beyond the current standard models. We discuss five broad topics: dark energy and modified gravity, dark matter, initial conditions, basic assumptions and questions of methodology in the data analysis. This review has been planned and carried out within Euclid’s Theory Working Group and is meant to provide a guide to the scientific themes that will underlie the activity of the group during the preparation of the Euclid mission. [ABSTRACT FROM AUTHOR]

The first direct syntheses, structural characterizations, and reactivity studies of iron-phenyl species formed upon reaction of Fe(acac) 3 and PhMgBr in THF are presented. Reaction of Fe(acac) 3 with 4 equiv. PhMgBr in THF leads to the formation of [FePh 2 (μ-Ph)] 2 2- at -80 °C, which can be stabilized through the addition of N -methylpyrrolidone. Alternatively, at -30 °C this reaction leads to the formation of the tetranuclear iron-phenyl cluster, Fe 4 (μ-Ph) 6 (THF) 4 . Further synthetic studies demonstrate that analogous tetranuclear iron clusters can be formed with both 4-F-PhMgBr and p -tolylMgBr, illustrating the generality of this structural motif for reactions of simple ferric salts and aryl Grignard reagents in THF. Additional studies isolate and define key iron species involved in the synthetic pathway leading to the formation of the tetranuclear iron-aryl species. While reaction studies demonstrate that [FePh 2 (μ-Ph)] 2 2- is unreactive towards electrophile, Fe 4 (μ-Ph) 6 (THF) 4 is found to rapidly react with bromocyclohexane to selectively form phenylcyclohexane. Based on this reactivity, a new catalytic reaction protocol has been developed that enables efficient cross-couplings using Fe 4 (μ-Ph) 6 (THF) 4 , circumventing the current need for additives such as TMEDA or supporting ligands to achieve effective cross-coupling of PhMgBr and a secondary alkyl halide.

The use of N-methylpyrrolidone (NMP) as a co-solvent in ferric salt catalyzed cross-coupling reactions is crucial for achieving the highly selective, preparative scale formation of cross-coupled product in reactions utilizing alkyl Grignard reagents. Despite the critical importance of NMP, the molecular level effect of NMP on in situ formed and reactive iron species that enables effective catalysis remains undefined. Herein, we report the isolation and characterization of a novel trimethyliron(II) ferrate species, [Mg(NMP) 6 ][FeMe 3 ] 2 (1), which forms as the major iron species in situ in reactions of Fe(acac) 3 and MeMgBr under catalytically relevant conditions where NMP is employed as a co-solvent. Importantly, combined GC analysis and 57 Fe Mössbauer spectroscopic studies identified 1 as a highly reactive iron species for the selective formation generating cross-coupled product. These studies demonstrate that NMP does not directly interact with iron as a ligand in catalysis but, alternatively, interacts with the magnesium cations to preferentially stabilize the formation of 1 over [Fe 8 Me 12 ] - cluster generation, which occurs in the absence of NMP., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The combination of simple cobalt salts and N-heterocyclic carbene (NHC) ligands has been highly effective in C-H functionalization, hydroarylation and cross-coupling catalysis, though displaying a strong dependence on the identity of the NHC ligand. In addition, reactions effective with NHC ligands are often ineffective with phosphine ligands, further motivating the evaluation of the fundamental electronic structure and bonding differences in well-defined distorted tetrahedral Co(ii) complexes. Magnetic circular dichroism (MCD) studies indicate that Co(ii)-bisphosphines have larger ligand fields than Co(ii)-NHC complexes. Theoretical density functional theory (DFT) calculations were performed on an expanded set of L 2 CoCl 2 complexes (L 2 = NHC, bisphosphine and diamine) to study the electronic structure and relative ligation properties of NHCs compared to bisphosphine and diamine ligands. Mayer bond order and charge decomposition analyses indicate that NHC ligands are slightly stronger donor ligands than bisphosphines but also result in a weakening of Co-Cl bonds in a trans-like influence. From MCD and DFT studies, changing the NHC N-substituent has a larger effect on the ligand field of Co(ii)-NHC complexes than saturating the backbone. Overall, these studies provide detailed insight into the electronic structure and bonding effects in Co(ii) complexes with ligand types commonly explored in catalysis.

In the structure of the title complex, [Fe(C5H7O2)3] or Fe(acac)3, the asymmetric unit contains one mol-ecule in a general position. The coordination sphere of the Fe(III) atom is that of a slightly distorted octahedron. The crystal under investigation was a two-component pseudo-merohedral twin in the monoclinic system with a β angle close to 90°. Twin law [100/0-10/00-1] reduced the R1 residual [I > 2σ(I)] from 0.0769 to 0.0312, and the mass ratio of twin components refined to 0.8913 (5):0.1087 (5). In the crystal, mol-ecules are arranged in sheets normal to [001] via non-classical C-H⋯O hydrogen bonding. No other significant inter-molecular inter-actions are observed. The structure is a new polymorph of Fe(acac)3 and is isotypic with one polymorph of its gallium analog.