Telehealth Movement-to-Music With Arm-Based Sprint-Intensity Interval Training to Improve Cardiometabolic Health and Cardiorespiratory Fitness in Children With Cerebral Palsy: Protocol for a Pilot Randomized Controlled Trial.

BACKGROUND: Children with mobility disabilities, including those with cerebral palsy, have limited options and limited time to exercise to manage their cardiometabolic health and cardiorespiratory fitness. Regular cardiovascular exercise during childhood is a critical health behavior for preventing health decline in adulthood. Thus, there is an urgent need for accessible, age-appropriate, convenient exercise modalities in this group. Sprint-intensity interval training (SIT), combined with telehealth procedures, may be ideal for children with disabilities. SIT includes repetitive bouts of maximal exercise effort combined with rest periods, which can be effective in eliciting comparable results to moderate-exercise training with very short training durations. OBJECTIVE: This phase 1 pilot feasibility randomized controlled trial aims to investigate the potential effects of a 12-week SIT program on indicators of cardiorespiratory fitness and cardiometabolic health among children with cerebral palsy. An ancillary aim is to evaluate the feasibility of the program through several process feasibility metrics. METHODS: This study uses a 2-armed parallel group design. A total of 50 physically inactive children with cerebral palsy (aged 6-17 years) will be randomly allocated into 1 of 2 groups: a 12-week SIT or a waitlist control group that continues habitual activity for 12 weeks. The SIT prescription includes 3 tele-supervised sessions per week with 30 repeated sequences of 4 seconds of maximal arm exercise, with active recovery, warm-up, and cooldown periods (for an approximately 20-minute total session). SIT includes guided videos with child-themed arm routines and music. The exercise sessions will be remotely supervised through a web-based videoconference application and include safety monitoring equipment. Outcomes are measured at pre- and postintervention (weeks 0 and 13, respectively). Health outcome measures include peak oxygen consumption (VO2 peak), measured by a graded exercise test; high-sensitivity C-reactive protein and blood insulin, hemoglobin A1c, triglycerides, and cholesterol using a finger stick dried blood spot test; blood pressure, using a sphygmomanometer; and body composition (total mass, total lean mass, tissue % lean, and tissue % fat) using dual x-ray absorptiometry. Feasibility will be evaluated by the following metrics: adverse events or problems experienced throughout the intervention related to participant safety; perceived enjoyment; and recruitment, enrollment, and attrition rates. RESULTS: Recruitment procedures started in November 2023. All data are anticipated to be collected by February 2025. Full trial results are anticipated to be analyzed and submitted for publication by March 2025. Secondary analyses of data will be subsequently published. CONCLUSIONS: This trial tests an accessible and low-cost exercise program that leverages principles of high-intensity exercise to provide a convenient program for children with physical disabilities. Knowledge obtained from this study will inform the development of a larger trial for improving the cardiometabolic health, cardiorespiratory fitness, and well-being of children with physical disabilities. TRIAL REGISTRATION: ClinicalTrials.gov NCT05619211; https://clinicaltrials.gov/study/NCT05619211. INTERNATIONAL REGISTERED REPORT IDENTIFIER (IRRID): DERR1-10.2196/56499.

First-Generation Students, College Majors, and Gendered Pathways.

Emerging literatures have highlighted the social- and resource-related inequalities among first-generation college students. Less attention has been devoted to the curricular pathways (i.e., college majors) these students follow and their potentially gendered character. We build on educational inequality and gender literatures in this article, and arguments surrounding habitus and class-based dispositions to address this gap. Our analyses draw on several waves of the Education Longitudinal Survey (ELS-2002) merged with national data on sex composition of fields of study. Our results suggest unique pathways in college for first-generation compared to continuing-generation students. Specifically, first-generation students are more likely to choose occupationally specific "applied" majors than their continuing-generation counterparts. Modeling by gender reveals little to moderate variation between first- and continuing-generation students' representation in female-dominated majors. These patterns generally hold for 2- and 4-year college going samples. We conclude by discussing the relevance of these findings for educational inequality, eventual job returns, and occupational mobility.

First-generation inequality and college integration.

Institutional integration has long been an important focus in literatures on inequality, education and mobility. Building on this work and drawing from multi-wave survey and records data from a large public university, the analyses we offer in this article provide unique and systematic comparative tests of first- versus continuing-generation inequalities in integration, disaggregated by academic versus social types, and with attention to other potentially influential status attributes. Our findings reveal: (1) clear overall inequalities in campus integration for first-generation students that cut across gender and race/ethnic lines; (2) a higher likelihood of employment among first-generation students-employment that tends to detract from integration opportunities; and (3) especially pronounced inequalities when it comes to forms of academic and social integration that entail bureaucratic- and resource-related barriers. We discuss the implications for understanding inequality and the first-generation experience in higher education and for more general sociological conceptions of institutional integration and mobility.

Multimodality Multisystem Imaging of Pregnancy-Related Changes: Featuring Neurologic, Cardiothoracic, Breast, Gynecologic, and Musculoskeletal Issues.

ABSTRACT: Pregnancy and the puerperium are a time of significant physiologic change, and with an average of 4 million births in the United States yearly, radiologists encounter pregnancy-related imaging findings regularly. While many of these findings represent physiologic changes, a significant number represent pathology, making it paramount for radiologists to distinguish between the two. This case-based article reviews imaging findings within the nervous, cardiovascular, pulmonary, breast, gynecologic, musculoskeletal, digestive, hematologic, and integumentary systems throughout pregnancy and the postpartum period.

Divergent Adsorption Behavior Controlled by Primary Coordination Sphere Anions in the Metal-Organic Framework Ni2X2BTDD.

CO, ethylene, and H2 demonstrate divergent adsorption enthalpies upon interaction with a series of anion-exchanged Ni2X2BTDD materials (X = OH, F, Cl, Br; H2BTDD = bis(1H-1,2,3-triazolo[4,5-b][4',5'-i])dibenzo[1,4]dioxin)). The dissimilar responses of these conventional π-acceptor gaseous ligands are in contrast with the typical behavior that may be expected for gas sorption in metal-organic frameworks (MOFs), which generally follows similar periodic trends for a given set of systematic changes to the host MOF structure. A combination of computational and spectroscopic data reveals that the divergent behavior, especially between CO and ethylene, stems from a predominantly σ-donor interaction between the former and Ni2+ and a π-acceptor interaction for the latter. These findings will facilitate further deliberate postsynthetic modifications of MOFs with open metal sites to control the equilibrium selectivity of gas sorption.

Surviving Under Pressure: The Role of Solvent, Crystal Size, and Morphology During Pelletization of Metal-Organic Frameworks.

As metal-organic frameworks (MOFs) gain traction for applications, such as hydrogen storage, it is essential to form the as-synthesized powder materials into shaped bodies with high packing densities to maximize their volumetric performance. Mechanical compaction, which involves compressing the materials at high pressure, has been reported to yield high monolith density but often results in a significant loss in accessible porosity. Herein, we sought to systematically control (1) crystal size, (2) solvation, and (3) compacting pressure in the pelletization process to achieve high packing density without compromising the porosity that makes MOFs functional. It was determined that solvation is the most critical factor among the three factors examined. Solvation that exceeds the pore volume prevents the framework from collapsing, allowing for porosity to be maintained through pelletization. Higher pelletization pressure results in higher packing density, with extensive loss of porosity being observed at a higher pressure if the solvation is below the pore volume. Lastly, we observed that the morphology and size of the MOF particles result in variation in the highest achievable packing efficiency, but these numbers (75%) are still greater than many existing techniques used to form MOFs. We concluded that the application of pressure through pelletization is a suitable and widely applicable technique for forming high-density MOF-monoliths.

Spectroscopic Evidence of Hyponitrite Radical Intermediate in NO Disproportionation at a MOF-Supported Mononuclear Copper Site.

Dianionic hyponitrite (N2 O22- ) is often proposed, based on model complexes, as the key intermediate in reductive coupling of nitric oxide to nitrous oxide at the bimetallic active sites of heme-copper oxidases and nitric oxide reductases. In this work, we examine the gas-solid reaction of nitric oxide with the metal-organic framework CuI -ZrTpmC* with a suite of in situ spectroscopies and density functional theory simulations, and identify an unusual chelating N2 O2.- intermediate. These results highlight the advantage provided by site-isolation in metal-organic frameworks (MOFs) for studying important reaction intermediates, and provide a mechanistic scenario compatible with the proposed one-electron couple in these enzymes.

Thermal Cycling of a MOF-Based NO Disproportionation Catalyst.

The metal-organic framework CuI-MFU-4l reacts with NO, initially forming a copper(I)-nitrosyl at low pressure, and subsequently generates NO disproportionation products CuII-NO2 and N2O. The thermal stability of MFU-4l allows NOx to be released from the framework at temperatures greater than 200 °C. This treatment regenerates the original CuI-MFU-4l, which can engage in subsequent cycles of NO disproportionation.

Bioinspired chemistry at MOF secondary building units.

The secondary building units (SBUs) in metal-organic frameworks (MOFs) support metal ions in well-defined and site-isolated coordination environments with ligand fields similar to those found in metalloenzymes. This burgeoning class of materials has accordingly been recognized as an attractive platform for metalloenzyme active site mimicry and biomimetic catalysis. Early progress in this area was slowed by challenges such as a limited range of hydrolytic stability and a relatively poor diversity of redox-active metals that could be incorporated into SBUs. However, recent progress with water-stable MOFs and the development of more sophisticated synthetic routes such as postsynthetic cation exchange have largely addressed these challenges. MOF SBUs are being leveraged to interrogate traditionally unstable intermediates and catalytic processes involving small gaseous molecules. This perspective describes recent advances in the use of metal centers within SBUs for biomimetic chemistry and discusses key future developments in this area.

Record-Setting Sorbents for Reversible Water Uptake by Systematic Anion Exchanges in Metal-Organic Frameworks.

The reversible capture of water vapor at low humidity can enable transformative applications such as atmospheric water harvesting and heat transfer that uses water as a refrigerant, replacing environmentally detrimental hydro- and chloro-fluorocarbons. The driving force for these applications is governed by the relative humidity at which the pores of a porous material fill with water. Here, we demonstrate modulation of the onset of pore-filling in a family of metal-organic frameworks with record water sorption capacities by employing anion exchange. Unexpectedly, the replacement of the structural bridging Cl- with the more hydrophilic anions F- and OH- does not induce pore-filling at lower relative humidity, whereas the introduction of the larger Br- results in a substantial shift toward lower relative humidity. We rationalize these results in terms of pore size modifications as well as the water hydrogen bonding structure based on detailed infrared spectroscopic measurements. Fundamentally, our data suggest that, in the presence of strong nucleation sites, the thermodynamic favorability of water pore-filling depends more strongly on the pore diameter and the interface between water in the center of the pore and water bound to the pore walls than the hydrophilicity of the pore wall itself. On the basis of these results, we report two materials that exhibit record water uptake capacities in their respective humidity regions and extended stability over 400 water adsorption-desorption cycles.

Experimental and Computational Investigation of the Aerobic Oxidation of a Late Transition Metal-Hydride.

The rational development of homogeneous catalytic systems for selective aerobic oxidations of organics has been hampered by the limited available knowledge of how oxygen reacts with important organometallic intermediates. Recently, several mechanisms for oxygen insertion into late transition metal-hydride bonds have been described. Contributing to this nascent understanding of how oxygen reacts with metal-hydrides, a detailed mechanistic study of the reaction of oxygen with the IrIII hydride complex (dmPhebox)Ir(OAc)(H) (1) in the presence of acetic acid, which proceeds to form the IrIII complex (dmPhebox)Ir(OAc)2(OH2) (2), is described. The evidence supports a multifaceted mechanism wherein a small amount of an initially formed metal hydroperoxide proceeds to generate a metal-oxyl species that then initiates a radical chain reaction to rapidly convert the remaining IrIII-H. Insight into the initiation step was gained through kinetic and mechanistic studies of the radical chain inhibition by BHT (butylated hydroxytoluene). Computational studies were employed to contribute to a further understanding of initiation and propagation in this system.

Reversible Metalation and Catalysis with a Scorpionate-like Metallo-ligand in a Metal-Organic Framework.

The installation of metallo-ligands in metal-organic frameworks (MOFs) is an effective means to create site-isolated metal centers toward single-site heterogeneous catalysis. Although trispyrazolyborate (Tp) and tripyrazolylmethane (Tpm) form one of the most iconic classes of homogeneous catalysts, neither has been used as a metallo-ligand for the generation of MOFs thus far. Here, we show that upon in situ metalation with CuI, a tricarboxylated Tpm ligand reacts with ZrOCl2 to generate a new MOF exhibiting neutral scorpionate-like chelating sites. These sites undergo for facile demetalation and remetalation with retention of crystallinity and porosity. When remetalated with CuI, the MOF exhibits spectroscopic features and catalytic activity for olefin cyclopropanation reactions that are similar to the molecular [Cu(CH3CN)Tpm*]PF6 complex (Tpm* = tris(3,5-dimethylpyrazolyl)methane). These results demonstrate the inclusion of Tp or Tpm metallo-ligands in a MOF for the first time and provide a blueprint for immobilizing Tpm* catalysts in a spatially isolated and well-defined environment.

Tunable Metal-Organic Frameworks Enable High-Efficiency Cascaded Adsorption Heat Pumps.

Rising global standards of living coupled to the recent agreement to eliminate hydrofluorocarbon refrigerants are creating intense pressure to develop more sustainable climate control systems. In this vein, the use of water as the refrigerant in adsorption heat pumps is highly attractive, but such adsorption systems are constrained to large size and poor efficiency by the characteristics of currently employed water sorbents. Here we demonstrate control of the relative humidity of water uptake by modulating the pore size in a family of isoreticular triazolate metal-organic frameworks. Using this method, we identify a pair of materials with stepped, nonoverlapping water isotherms that can function in tandem to provide continuous cooling with a record ideal coefficient of performance of 1.63. Additionally, when used in a single-stage heat pump, the microporous Ni2Cl2BBTA has the largest working capacity of any material capable of generating a 25 °C difference between ambient and chiller output.

Precise control of pore hydrophilicity enabled by post-synthetic cation exchange in metal-organic frameworks.

The ability to control the relative humidity at which water uptake occurs in a given adsorbent is advantageous, making that material applicable to a variety of different applications. Here, we show that cation exchange in a metal-organic framework allows precise control over the humidity onset of the water uptake step. Controlled incorporation of cobalt in place of zinc produces open metal sites into the cubic triazolate framework MFU-4l, and thereby provides access to materials with uptake steps over a 30% relative humidity range. Notably, the MFU-4l framework has an extremely high water adsorption capacity of 1.05 g g-1, amongst the highest known for porous materials. The total water capacity is independent of the cobalt loading, showing that cation exchange is a viable route to increase the hydrophilicity of metal-organic frameworks without sacrificing capacity.

Perspectives of Nurses, Nurse Leaders, and Women Regarding Anticipatory Rounds in the Postpartum Period.

OBJECTIVE: To obtain the perspectives of staff nurses, nurse leaders, and women with regard to the relevance and timing of nursing interactions during anticipatory rounds in the postpartum period. DESIGN: A qualitative descriptive design using focus groups. SETTING: A hospital with 405 beds that serves a Midwestern U.S. community of approximately 256,000 people. PARTICIPANTS: A purposive sample of 12 staff nurses, 6 nurse leaders, and 15 women attended a total of 10 focus groups. METHODS: We conducted 10 semistructured focus groups: 6 with staff nurses, 1 with nurse leaders, and 3 with women. Each participant attended one focus group. Sessions were recorded and transcribed. Investigators independently coded transcripts and identified themes collectively. RESULTS: Participants identified one overarching theme, Taking the Whole Picture Into Account, and five subthemes that were reflective of relevant nursing interactions: Help With Newborn Feeding, Managing Patient Comfort, Appreciating the Need for Safety, Being There, and Knowing Ahead of Time. Participants agreed that conducting rounds once every 2 to 3 hours was the most appropriate time frame. CONCLUSION: Participants identified important nursing interactions and their timing. Moreover, anticipatory rounding for women after birth includes more than completion of simple tasks or checklists. These findings indicate beginning evidence for what should occur during anticipatory rounds on the mother-baby unit. Timing of rounds can be flexible based on each woman's unique needs, thus reinforcing patient-centered care. However, interactions and timing should take place only when the whole picture is taken into account.

Probing Dative and Dihydrogen Bonding in Ammonia Borane with Electronic Structure Computations and Raman under Nitrogen Spectroscopy.

Although ammonia borane is isoelectronic with ethane and they have similar structures, BH3NH3 exhibits rather atypical bonding compared to that in CH3CH3. The central bond in ammonia borane is actually a coordinate covalent or dative bond rather than the conventional covalent C-C bond in ethane where each atom donates one electron. In addition, strong intermolecular dihydrogen bonds can form between two or more ammonia borane molecules compared to the relatively weak dispersion forces between ethane molecules. As a result, ammonia borane's physical properties are very sensitive to the environment. For example, gas-phase and solid-state ammonia borane have very different BN bond lengths and BN stretching frequencies, which led to much debate in the literature. It has been demonstrated that the use of cluster models based on experimental crystal structures led to better agreement between theory and experiment. Here, we employ a variety of cluster models to track how the interaction energies, bond lengths, and vibrational normal modes evolve with the size and structural characteristics of the clusters. The M06-2X/6-311++G(2df,2pd) level of theory was selected for this analysis on the basis of favorable comparison with CCSD(T)/aug-cc-pVTZ data for the ammonia borane monomer and dimer. Fourteen unique fully optimized molecular cluster geometries, (BH3NH3)n≤12, and nine crystal models, (BH3NH3)n≤19, were used to elucidate how the local environment impacts ammonia borane's physical properties. Computational results for the BN stretching frequencies are also compared directly to the Raman spectrum of solid ammonia borane at 77 K using Raman under liquid nitrogen spectroscopy (RUNS). A strong linear correlation was found to exist between the BN bond length and stretching frequency, from an isolated monomer to the most distorted BH3NH3 unit in a cluster or crystal structure model. Excellent agreement was seen between the frequencies computed for the largest crystal model and the RUNS experimental spectra (typically within a few wavenumbers).

ß-Hydride Elimination and C-H Activation by an Iridium Acetate Complex, Catalyzed by Lewis Acids. Alkane Dehydrogenation Cocatalyzed by Lewis Acids and [2,6-Bis(4,4-dimethyloxazolinyl)-3,5-dimethylphenyl]iridium.

NaBArF4 (sodium tetrakis[(3,5-trifluoromethyl)phenyl]borate) was found to catalyze reactions of (Phebox)IrIII(acetate) (Phebox = 2,6-bis(4,4-dimethyloxazolinyl)-3,5-dimethylphenyl) complexes, including (i) ß-H elimination of (Phebox)Ir(OAc)(n-alkyl) to give (Phebox)Ir(OAc)(H) and the microscopic reverse, alkene insertion into the Ir-H bond of (Phebox)Ir(OAc)(H), and (ii) hydrogenolysis of the Ir-alkyl bond of (Phebox)Ir(OAc)(n-alkyl) and the microscopic reverse, C-H activation by (Phebox)Ir(OAc)(H), as indicated by H/D exchange experiments. For example, ß-H elimination of (Phebox)Ir(OAc)(n-octyl) (2-Oc) proceeded on a time scale of minutes at -15 °C in the presence of (0.4 mM) NaBArF4 as compared with a very slow reaction at 125 °C in the absence of NaBArF4. In addition to NaBArF4, other Lewis acids are also effective. Density functional theory calculations capture the effect of the Na+ cation and indicate that it operates primarily by promoting κ2-κ1 dechelation of the acetate anion, which opens the coordination site needed to allow the observed reaction to proceed. In accord with the effect on these individual stoichiometric reactions, NaBArF4 was also found to cocatalyze, with (Phebox)Ir(OAc)(H), the acceptorless dehydrogenation of n-dodecane.

Competition between Hydrophilic and Argyrophilic Interactions in Surface Enhanced Raman Spectroscopy.

The competition for binding and charge-transfer (CT) from the nitrogen containing heterocycle pyrimidine to either silver or to water in surface enhanced Raman spectroscopy (SERS) is discussed. The correlation between the shifting observed for vibrational normal modes and CT is analyzed both experimentally using Raman spectroscopy and theoretically using electronic structure theory. Discrete features in the Raman spectrum correspond to the binding of either water or silver to each of pyrimidine's nitrogen atoms with comparable frequency shifts. Natural bond orbital (NBO) calculations in each chemical environment reveal that the magnitude of charge transfer from pyrimidine to adjacent silver atoms is only about twice that for water alone. These results suggest that the choice of solvent plays a role in determining the vibrational frequencies of nitrogen containing molecules in SERS experiments.

Understanding the role of hyponitrite in nitric oxide reduction.

Herein, we review the preparation and coordination chemistry of cis and trans isomers of hyponitrite, [N2O2](2-). Hyponitrite is known to bind to metals via a variety of bonding modes. In fact, at least eight different bonding modes have been observed, which is remarkable for such a simple ligand. More importantly, it is apparent that the cis isomer of hyponitrite is more reactive than the trans isomer because the barrier of N2O elimination from cis-hyponitrite is lower than that of trans-hyponitrite. This observation may have important mechanistic implications for both heterogeneous NOx reduction catalysts and NO reductase. However, our understanding of the hyponitrite ligand has been limited by the lack of a general route to this fragment, and most instances of its formation have been serendipitous.