Publications by authors named "Crawley M"

Objective: This study described therapists' delivery of six child mental health evidence-based practices (EBPs) over 33 months during the sustainment phase of a system-driven implementation aimed at improving access to EBPs in community settings.

Method: Seven hundred seventy-seven therapists and 162 program leaders delivering at least one of six EBPs of interest completed surveys, and these data were matched to therapist administrative claims data. Survival analyses examined (a) therapists' discontinuation of delivery of all Los Angeles County Department of Mental Health direct client services (i.

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Article Synopsis
  • The reaction of four 1,2-dibromoxylenes with two tetra-3-pyridylporphyrins resulted in the creation of a metal-free organic nanocage (oNC) that was produced in a highly efficient 91.5% yield.
  • The synthesized oNC was subsequently metalated with cobalt(II), copper(II), and nickel(II) ions to produce dinuclear complexes, which were characterized using various analytical techniques such as mass spectrometry and X-ray diffraction.
  • The cofacial cobalt porphyrins showed significant potential as catalysts for the Oxygen Reduction Reaction, demonstrating high selectivity for producing hydroxyl during electrochemical processes, while the robust architecture of the oNC allows for potential applications with
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We report on the synthesis and characterization of Mn(III) chloride (MnCl) complexes coordinated with -oxide ylide ligands, namely trimethyl--oxide (MeNO) and pyridine--oxide (PyNO). The compounds are reactive and, while isolable in the solid-state at room temperature, readily decompose into Mn(II). For example, "[MnCl(ONMe)]" decomposes into the 2D polymeric network compound complex salt [Mn(µ-Cl)Mn(µ-ONMe)][Mn(µ-Cl)]·(MeNO·HCl) ().

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This work details the synthesis and characterization of complexes of the form [MnX(PR)] (X = Cl, Br, I), which is a rare type of coordination compound. Prior to this work, the only mode of synthesis was oxidizing mixtures of MnX and PR with dry air, but these procedures give low yields and variable outcomes. By taking advantage of the starting material [MnCl(OPPh)] () and other new strategies, we present robust synthetic protocols for both new and known Mn(III) halido phosphine complexes.

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The synthesis and characterization of a series of (TBA)[M{MoO(OMe)NO}] (M = Zr, Hf, Th, and U) sandwich complexes is reported. A preformed lacunary, Lindqvist-type, polyoxomolybdate-alkoxide cluster provides access to first examples of actinide-polyoxomolybdate sandwich complexes isolated under non-aqueous conditions. Incorporation of metal(iv) cations into this framework was found to "switch on" reversible redox chemistry at the {Mo} ligands, with the Zr and Hf containing complexes accepting up to two electrons, while the Th and U derivates accommodate as many as four additional electrons.

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A tellurorosamine dye [] undergoes aerobic photooxidation. Although Te(IV) species have been used in a number of oxidations, key Te(IV)-oxo and Te(IV)-bis(hydroxy) intermediates are challenging to study. Under aerobic irradiation with visible light, (λ = 600 nm) transforms into a Te(IV) species (λ = 669 nm).

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Macrocyclic Co(II) complexes with appended amide-glycinate groups were prepared to develop paramagnetic Co(II) chemical exchange saturation transfer (CEST) agents of reduced overall charge. Complexes with reduced charge and lowered osmolarity are important for their loading into liposomes and to provide complexes that are highly water soluble and well tolerated in animals. Co(L1) has two non-coordinating benzyl groups and two amide-glycinate pendants, whereas Co(L2) has two unsubstituted amide pendants and two amide-glycinate pendants on cyclam (1,4,8,11-tetraazacyclododecane).

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Article Synopsis
  • Researchers developed a one-pot method to create a stable molecular complex, [Mn(NO)(OPPh)], which serves as an effective reagent for selective one-electron oxidation (deelectronation).
  • The complex boasts a high reduction potential of 1.02 V versus ferrocene, making it one of the strongest readily available redox agents for chemical reactions.
  • It is easy to handle, stable in air as a solid, and soluble in common lab solvents, allowing for the synthesis of other manganese complexes with similarly high reduction potentials.
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High-spin Fe(III) complexes of 1,4,7-triazacyclononane (TACN) with mixed oxygen donor pendants including hydroxypropyl, phenolate or amide groups are prepared for study as T MRI probes. Complexes with two hydroxypropyl pendants and either amide (Fe(TOAB)) or phenolate (Fe(PTOB)) groups are compared to an analog with three hydroxypropyl groups (Fe(NOHP)), in order to study the effect of the third pendant on the coordination sphere as probed by solution chemistry, relaxivity and structural studies. Solution studies show that Fe(PTOB) has two ionizations with the phenol pendant deprotonating with a p of 1.

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Self-assembled metallacyles and cages formed via coordination chemistry have been used as catalysts to enforce 4H/4e reduction of oxygen to water with an emphasis on attenuating the formation of hydrogen peroxide. That said, the kinetically favored 2H/2e reduction to HO is critically important to industry. In this work we report the synthesis, characterization, and electrochemical benchmarking of a hexa-porphyrin cube which catalyses the electrochemical reduction of molecular oxgyen to hydrogen peroxide.

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Prussian blue (PB) and its analogues are promising materials for electrochemical energy storage, yet their use in flow-type devices is limited by their lack of redox responsiveness as colloidal suspensions. We have investigated the redox chemistry amine functionalization of PB along with its Cu analogue (CuPBA). No redox response of colloidal PB was observed and suspensions of CuPBA formed films on electrode surfaces with and without applied potentials; the films were redox-active but the material that remained suspended in solution did not participate in redox chemistry.

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The chemistry of zirconium-based metal-organic polyhedra (ZrMOPs) is often limited by their poor solubilities. Despite their attractive features-including high yielding and facile syntheses, predictable topologies, high stability, and tunability-problematic solubilities have caused ZrMOPs to be under-studied and under-applied. Although these cages have been synthesized with a wide variety of carboxylate-based bridging ligands, we explored a new method for ZrMOP functionalization node-modification, which we hypothesized could influence solubility.

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We report the electrocatalytic Oxygen Reduction Reaction on a rigid Co(II) porphyrin prism scaffold bridged by Ag(I) ions. The reactivity of this scaffold differs significantly from previous prism catalysts in that its selectivity is similar to that of monomer (∼35% HO) yet it displays sluggish kinetics, with an order of magnitude lower of ∼0.5 M s.

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Introduction: Falls are the second leading cause of trauma-related deaths worldwide. Identifying fall risk patients and initiating interventions reduces injuries and mortality, particularly in the elderly. The primary aim of this retrospective study was to identify missed opportunities for fall risk identification and intervention for geriatric trauma patients.

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Soils are subjected to multiple anthropogenic modifications, but the synergistic impacts of simultaneous environmental stressors on below-ground communities are poorly understood. We used a large-scale (1152 plots), long-term (26 years), multi-factorial grassland experiment to assess the impact of five common agricultural practises (pesticides, herbicide, liming, fertilizers and grazing exclusion) and their interactive effects on the composition and activity of soil microbial communities. We confirmed that pH strongly impacts belowground communities, but further demonstrate that pH strongly mediates the impacts of other management factors.

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Cofacial porphyrin catalysts for the Oxygen Reduction Reaction (ORR) formed via coordination-driven self-assembly have so far been limited to designs with fourfold symmetry, where four molecular clips bridge two porphyrin sites. We have synthesized six PyPh (Py = pyridyl, Ph = phenyl) metalloporphyrin prisms (Co, Zn) bridged by molecular clips containing two Rh centers. Four of these structures are lower symmetry, with the PyPh and PyPh prisms containing three and two molecular clips, respectively.

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Objective: Determine which variables impact postoperative discharge destination following head and neck microvascular free flap reconstruction.

Study Design: Retrospective review of prospectively collected databases.

Methods: Consecutive patients undergoing head and neck microvascular free flap reconstruction between January 2010 and December 2019 (n = 1972) were included.

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Background: Submandibular gland (SMG) transfer decreased radiation-associated xerostomia in the 2/3-dimensional radiotherapy era. We evaluated the dosimetric implications of SMG transfer on modern intensity modulated radiotherapy (IMRT) plans.

Methods: Eighteen oropharynx cancer patients underwent SMG transfer followed by IMRT; reoptimized plans using the baseline SMG location were generated.

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A metal-organic polyhedron (MOP) with four paramagnetic Fe(III) centers was studied as a magnetic resonance imaging (MRI) probe. The MOP was characterized in solution by using electron paramagnetic resonance (EPR), UV-visible (UV-vis) spectroscopies, Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry, and in the solid state with single-crystal X-ray diffraction. Water proton T relaxation properties were examined in solution and showed significant enhancement in the presence of human serum albumin (HSA).

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Nutrients and herbivores are well-known drivers of grassland diversity and stability in local communities. However, whether they interact to impact the stability of aboveground biomass and whether these effects depend on spatial scales remain unknown. It is also unclear whether nutrients and herbivores impact stability via different facets of plant diversity including species richness, evenness, and changes in community composition through time and space.

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Objective: Determine if age correlated with surgical or medical complications following head and neck free flap reconstruction.

Study Design: Retrospective review of prospectively collected databases.

Methods: Patients undergoing head and neck free flap reconstruction at three tertiary care institutions were included (n = 1972).

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We assembled eight cofacial porphyrin prisms using MTPyP (M = Co(II) or Zn(II), TPyP = 4-tetrapyridylporphyrin) and functionalized ruthenium-based "molecular clips" using coordination-driven self-assembly. Our approach allows for the rapid synthesis of these architectures in isolated yields as high as 98% for the assembly step. Structural and reactivity studies provided a deeper understanding of the role of the building blocks on the oxygen reduction reaction (ORR).

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Eutrophication is a widespread environmental change that usually reduces the stabilizing effect of plant diversity on productivity in local communities. Whether this effect is scale dependent remains to be elucidated. Here, we determine the relationship between plant diversity and temporal stability of productivity for 243 plant communities from 42 grasslands across the globe and quantify the effect of chronic fertilization on these relationships.

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