Creating a digital approach for promoting physical activity in pediatric pulmonary hypertension: A framework for future interventions.

Children with pulmonary hypertension (PH) often demonstrate limited exercise capacity. Data support exercise as an effective nonpharmacologic intervention among adults with PH. However, data on exercise training in children and adolescents are limited, and characteristics of the optimal exercise program in pediatric PH have not been identified. Exercise programs may have multiple targets, including muscle deficits which are associated with exercise limitations in both adult and pediatric PH. Wearable accelerometer sensors measure physical activity volume and intensity in the naturalistic setting and can facilitate near continuous data transfer and bidirectional communication between patients and the study team when paired with informatics tools during exercise interventions. To address the knowledge gaps in exercise training in pediatric PH, we designed a prospective, single arm, nonrandomized pilot study to determine feasibility and preliminary estimates of efficacy of a 16-week home exercise intervention, targeting lower extremity muscle mass and enriched by wearable mobile health technology. The exercIse Training in pulmONary hypertEnsion (iTONE) trial includes (1) semistructured exercise prescriptions tailored to the participant's baseline level of activity and access to resources; (2) interval goal setting fostering self-efficacy; (3) real time monitoring of activity via wearable devices; (4) a digital platform enabling communication and feedback between participant and study team; (5) multiple avenues to assess participant safety. This pilot intervention will provide information on the digital infrastructure needed to conduct home-based exercise interventions in PH and will generate important preliminary data on the effect of exercise interventions in youth with chronic cardiorespiratory conditions to power larger studies in the future.

A New Numerical Approach for the Analysis of Variable Fractal and Fractional Order Differential Equations.

The variable fractional dimensions differential and integral operator overrides the phenomenon of the constant fractional order. This leads to exploring some new ideas in the proposed direction due to its varied applications in the recent era of science and engineering. The present papers deal with the replacement of the constant fractional order by variable fractional order in various fractal-fractional differential equations. An advanced numerical scheme is developed with the help of Lagrange three-point interpolation and further, it is employed for the solution of the proposed differential equations. However, the properties of these new operators are presented in detail. Finally, the error analysis is also conducted for the numerical scheme deployed. The results are validated by the suitable choice of applications to real-life problems. The well- known multi-step-Adams-Bashforth numerical scheme for classical differential equations is recovered when the non-integer order is one.

Reply to the 'Comment on "Realization of the Zn3+ oxidation state"' by Y. Shang, N. Shu, Z. Zhang, P. Yang and J. Xu, Nanoscale, 2022, 14, DOI: 10.1039/D1NR07031B.

In a recent paper (https://doi.org/10.1039/D1NR02816B), we suggested that Zn can assume a +3-oxidation state when interacting with super-electrophilic clusters, BeB11(CN)12 and BeB23(CN)22. In a comment to our paper (https://doi.org/10.1039/D1NR07031B), Shang et al. have questioned this suggestion. Using density functional theory with the TPSSh functional and def2-SVP basis sets in the Gaussian16 software and semiempirical localized orbital bonding analysis (LOBA), the authors have made three major claims: (1) the oxidation state of Zn in Zn[BeB11(CN)12] and Zn[BeB23(CN)22] is +2; (2) electron affinities are not reliable to probe the oxidation states; and (3) our results are "misleading" because these are based on the VASP code. According to these authors, VASP is not suitable for small clusters because it uses projected augmented wave (PAW) pseudopotentials. In the following, we show that these claims are invalid, caused by both misunderstanding and the authors' use of a lower-level theory.

Relative contribution of different members of OsDREB gene family to osmotic stress tolerance in indica and japonica ecotypes of rice.

Drought/osmotic stress is the single largest production constraint in rain-fed rice cultivation. Different members of the DREB gene family are known to contribute to osmotic stress tolerance. In this study, an attempt was made to understand their relative contribution towards osmotic stress tolerance in indica and japonica ecotypes of rice. Two genotypes (one tolerant and one susceptible) from each ecotype were grown hydroponically, and 21-day-old seedlings were subjected to polyethylene glycol-induced osmotic stress (15% PEG-6000, equivalent to -3.0 bars osmotic potential). The tolerant genotypes CR143 and Moroberekan were found to have superior root traits (total root length, surface area and volume), better plant water status and increased total dry biomass as compared to their susceptible counterparts after 10 days of osmotic stress. Different members of the DREB gene family were differentially induced in response to osmotic shock (1 h after stress) and osmotic stress (24 h after stress), which also differed between the two rice ecotypes. From the gene expression profiles of 10 DREB genes (both DREB1 and DREB2 families), in indica two DREB genes, DREB1B and DREB1G, were significantly correlated with stress tolerance indices, whereas in japonica significant correlations with five DREB genes (DREB1A, DREB1B, DREB1D, DREB1E and DREB2B) were observed. We found that only one member, i.e. DREB1B, showed a significant correlation with drought tolerance indices in both indica and japonica ecotypes. This study provides an overview of the relative contribution of different members of the DREB gene family and their association with drought/osmotic stress tolerance in rice.

Rational Design of Porous Nodal-Line Semimetallic Carbon for K-Ion Battery Anode Materials.

The potassium-ion battery (KIB), as one of the most promising alternatives to the lithium-ion battery (LIB), has recently received considerable attention. One of the challenges in KIBs is the design and synthesis of high-performance anode materials with high capacity, high rate performance, and good cycling stability. Here, on the basis of first-principles calculations, we propose a three-dimensional (3D) porous nodal-line semimetal carbon allotrope, named BDL-14, consisting of benzene rings incorporated into the diamond lattice, as a potential candidate. With low mass density (1.41 g/cm3), ordered channels, high carrier velocity (0.83 × 106 m/s), high specific capacity (478.23 mAh/g), very low energy barriers (0.05-0.08 eV) for K-ion diffusion, and a small volume expansion (7.03%) during charging and discharging processes, BDL-14 can surpass the properties of anodes currently being considered.

Collective Superexchange and Exchange Coupling Constants in the Hydrogenated Iron Oxide Particle Fe8O12H8.

Motivated by the fact that Fe2O3 nanoparticles are used in the treatment of cancer, we have examined the role of ligands on the magnetic properties of these particles by focusing on (Fe2O3)4 as a prototype system with H as ligands. Using the Broken-Symmetry Density Functional Theory, we observed a strong collective superexchange in the hydrogenated Fe8O12H8 cluster. The average antiferromagnetic exchange coupling constant between the four iron-iron oxo-bridged pairs was found to be -178 cm-1, whereas coupling constants between hydroxo-bridged pairs were much smaller. We found that despite the apparent symmetry of the iron atom framework, it is not reasonable to assume this symmetry when fitting the exchange coupling constants. We also analyzed the geometrical and magnetic properties of Fe8O12H n for n = 0-12 and found that hydrogenating oxo-bridges would generally inhibit the Fe-O-Fe antiferromagnetic superexchange interactions. Antiferromagnetic lowest total energy states become favorable only when specific distributions of hydrogen atoms are realized. The (HO)4-Fe4(all spin-up)-O4-Fe4(all spin-down)-(OH)4 configuration in Fe8O12H8 presents such an example. This symmetric configuration can be considered a superdiatomic system.

Effect of hydrogenation on the structure and magnetic properties of an iron oxide cluster.

The structure and properties of the Fe8O12Hn clusters (n = 0-18) are computed using the all-electron density functional theory with the generalized gradient approximation for the exchange-correlation potential. The ground state of Fe8O12 is found to be a singlet state having a bi-capped octahedron geometry. Upon hydrogenation, the octahedral framework of Fe is retained in Fe8O12Hn up to n < 7, beyond which point the iron octahedron transforms into a cube. Hydrogen atoms are bound to oxygen atoms up to n = 12, but they bind to the faces of the Fe8 cube when n > 12. The total spin magnetic moment of a Fe8O12Hn cluster is larger than 6 µB for 1 ≤ n ≤ 18, except for n = 8 and 10, where the lowest total energy states are antiferromagnetic singlets. The reason for this deviation from the general behavior in the Fe8O12Hn series is attributed to the collective superexchange phenomenon. Surprisingly, the total spin magnetic moment of a Fe8O12Hn cluster is found to be substantially larger than the total spin magnetic moment of the bare Fe8 cluster when n = 12-18. All of the Fe8O12Hn clusters are stable with respect to an abstraction of a single hydrogen atom but are unstable toward the abstraction of an H2 dimer when n =10 and n = 14-18.

A Theoretical and Mass Spectrometry Study of Dimethyl Methylphosphonate: New Isomers and Cation Decay Channels in an Intense Femtosecond Laser Field.

Using both mass spectrometry with intense femtosecond laser ionization and high-level computational methods, we have explored the structure and fragmentation patterns of dimethyl methylphosphonate (DMMP) cation. Extensive search of the geometries of both neutral and positively charged DMMP yields new isomers that are appreciably lower in total energy than those commonly synthesized using the Michaelis-Arbuzov reaction. The stability of the standard isomer with CH3PO(OCH3)2 topology is found to be due to the presence of high barriers to isomer interconversion that involves several transition states. Our femtosecond laser ionization experiments show that the relative yields of the major dissociation products as a function of peak laser intensity correlate well with the theoretical estimates for the energies of the DMMP+ decay via various channels. In contrast, the peak laser intensities required for observation of minor dissociation products exhibit no correlation with the computed decay energies, which suggests that barrier heights and/or excited electronic states of DMMP+ determine its preferred fragmentation pathways in an intense femtosecond laser field.

Exploiting Le Chatelier's principle for a one-pot synthesis of nontoxic HHogGNPs with the sharpest nanoscopic features suitable for tunable plasmon spectroscopy and high throughput SERS sensing.

Applying Le Chatelier's principle, a one-pot synthesis method is reported that generates highly anisotropic hedgehog gold nanoparticles (HHogGNPs), undemanding of a preformed seed or surfactant. These non-toxic HHogGNPs are potent candidates for nanomedicinal applications owing to their broad-band plasmon tunability, gigantic Raman enhancement and remarkable retention in a highly salted physiological environment.

Investigation of hydrogen induced fluorescence in C60 and its potential use in luminescence down shifting applications.

Herein the photophysical properties of hydrogenated fullerenes (fulleranes) synthesized by direct hydrogenation utilizing hydrogen pressure (100 bar) and elevated temperatures (350 °C) are compared to the fulleranes C60H18 and C60H36 synthesized by amine reduction and the Birch reduction, respectively. Through spectroscopic measurements and density functional theory (DFT) calculations of the HOMO-LUMO gaps of C60Hx (0 ≤ x ≤ 60), we show that hydrogenation significantly affects the electronic structure of C60 by decreasing conjugation and increasing sp3 hybridization. This results in a blue shift of the emission maximum as the number of hydrogen atoms attached to C60 increases. Correlations in the emission spectra of C60Hx produced by direct hydrogenation and by chemical methods also support the hypothesis of the formation of C60H18 and C60H36 during direct hydrogenation with emission maxima of 435 and 550 nm respectively. We also demonstrate that photophysical tunability, stability, and solubility of C60Hx in a variety of organic solvents make them easily adaptable for application as luminescent down-shifters in heads-up displays, light-emitting diodes, and luminescent solar concentrators. The utilizization of carbon based materials in these applications can potentially offer advantages over commonly utilized transition metal based quantum dot chromophores. We therefore propose that the controlled modification of C60 provides an excellent platform for evaluating how individual chemical and structural changes affect the photophysical properties of a well-defined carbon nanostructure.

Superhalogens beget superhalogens: a case study of (BO2)n oligomers.

Superhalogens belong to a class of molecules that not only mimic the chemistry of halogen atoms but also possess electron affinities that are much larger than that of chlorine, the element with the highest electron affinity in the periodic table. Using BO2 as an example and the synergy between density functional theory-based calculations and photoelectron spectroscopy experiments we demonstrate another unusual property of superhalogens. Unlike halogens, whose ability to accept an electron falls upon dimerization, B2O4, the dimer of BO2, has an electron affinity larger than that of the BO2 building block. This ability of (BO2)2 and subsequent, higher oligomers (BO2)n (n = 3 and 4), to retain their superhalogen characteristics can be traced to the enhanced bonding interactions between oxygen and boron atoms and due to the delocalization of the charge of the extra-electron over the terminal oxygen atoms. These results open the door to the design and synthesis of a new class of metal-free highly negative ions with potential for novel applications.

Structure and Properties of Polyfluoride Fn(-) Clusters (n = 3-29).

The electronic and geometrical structures of the neutral Fn and singly negatively charged Fn(-) polyfluorides (n = 3-29) are studied using three levels of theory: density functional theory (DFT) with generalized gradient approximation, hybrid Hartree-Fock-DFT, and hybrid HF-DFT with long-range corrections. For n > 4, each polyfluoride possesses a number of states with different geometries that are closely spaced in total energy. The geometrical structures of the lowest total energy states follow different patterns for the even-n and odd-n Fn(-) anion branches with a preference for higher symmetry geometries. The largest F29(-) anion considered is found to possess Oh symmetry. All the anions beginning with F3(-) are found to possess adiabatic and vertical electron detachment energies exceeding the electron affinities of halogen atoms and are therefore superhalogen anions. Electron affinities, energies of formation, and binding energies show oscillatory behavior as functions of the number n of fluorine atoms. The neutral Fn species are found to be barely stable and are bound by polarization forces. The Fn(-) anions, on the contrary, are quite stable toward the loss of F, F(-), and F2(-), but not to the loss of F2.

Aluminum Zintl anion moieties within sodium aluminum clusters.

Through a synergetic combination of anion photoelectron spectroscopy and density functional theory based calculations, we have established that aluminum moieties within selected sodium-aluminum clusters are Zintl anions. Sodium-aluminum cluster anions, Na(m)Al(n)(-), were generated in a pulsed arc discharge source. After mass selection, their photoelectron spectra were measured by a magnetic bottle, electron energy analyzer. Calculations on a select sub-set of stoichiometries provided geometric structures and full charge analyses for both cluster anions and their neutral cluster counterparts, as well as photodetachment transition energies (stick spectra), and fragment molecular orbital based correlation diagrams.

Alanate anion, AlH4(-): photoelectron spectrum and computations.

The alanate anion, AlH4(-), was generated in the gas phase using a pulsed arc cluster ionization source. Its photoelectron spectrum was then measured with 193 nm photons. The spectrum consists of a broad feature, spanning electron binding energies from 3.8 eV to over 5.3 eV. This band reflects the photodetachment transitions between the ground state of the AlH4(-) anion and the ground state of its thermodynamically unstable neutral counterpart, AlH4. The vertical detachment energy (VDE) of AlH4(-) was measured to be 4.4 eV. Additionally, VDE values were also computed in a comprehensive theoretical study and compared both with the previously computed value and with our experimentally determined value.

An all-electron density functional theory study of the structure and properties of the neutral and singly charged M12 and M13 clusters: M = Sc-Zn.

The electronic and geometrical structures of the M12 and M13 clusters where M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn along with their singly negatively and positively charged ions are studied using all-electron density functional theory within the generalized gradient approximation. The geometries corresponding to the lowest total energy states of singly and negatively charged ions of V13, Mn12, Co12, Ni13, Cu13, Zn12, and Zn13 are found to be different from the geometries of the corresponding neutral parents. The computed ionization energies of the neutrals, vertical electron detachment energies from the anions, and energies required to remove a single atom from the M13 and M13(+) clusters are in good agreement with experiment. The change in a total spin magnetic moment of the cation or anion with respect to a total spin magnetic moment of the corresponding neutral is consistent with the one-electron model in most cases, i.e., they differ by ±1.0 µ(B). Exceptions are found only for Sc12(-), Ti12(+), Mn12(-), Mn12(+), Fe12(-), Fe13(+), and Co12(+).

Electronic and magnetic properties of manganese and iron atoms decorated with BO2 superhalogens.

Using density functional theory based calculations, we have systematically studied the equilibrium geometries, relative stabilities, and electronic and magnetic properties of Fe and Mn atoms interacting with a varying number of BO(2) moieties. These clusters are found to exhibit hyperhalogen behavior with electron affinities as high as 6.9 eV once the number of BO(2) moieties exceed the nominal valences of these transition metals toms, namely 2 for both Fe and Mn. In all cases the transition metal atoms retain a sizable spin magnetic moment, even exceeding their free atom values at certain compositions. We also note that when more than two BO(2) moieties are bound to neutral Fe and Mn atoms, they tend to dimerize. In the case of negative ions, this process occurs at n ≥ 3, thus leading to different neutral and anionic ground state geometries. The effect of these structural changes in the interpretation of photoelectron spectroscopy experiments is discussed.

The Intrinsic Ferromagnetism in a MnO2 Monolayer.

The Mn atom, because of its special electronic configuration of 3d(5)4s(2), has been widely used as a dopant in various two-dimensional (2D) monolayers such as graphene, BN, silicene and transition metal dichalcogenides (TMDs). The distributions of doped Mn atoms in these systems are highly sensitive to the synthesis process and conditions, thus suffering from problems of low solubility and surface clustering. Here we show for the first time that the MnO2 monolayer, synthetized 10 years ago, where Mn ions are individually held at specific sites, exhibits intrinsic ferromagnetism with a Curie temperature of 140 K, comparable to the highest TC value achieved experimentally for Mn-doped GaAs. The well-defined atomic configuration and the intrinsic ferromagnetism of the MnO2 monolayer suggest that it is superior to other magnetic monolayer materials.

Structure and properties of Fe(n), Fe(n)-, and Fe(n)+ clusters, n = 7-20.

The electronic and geometrical structures of the Fe(n), Fe(n)(­), and Fe(n)(+) series (n = 7­20) are studied using all-electron density functional theory with the generalized gradient approximation. Equilibria of the geometrical configurations of the lowest total energy states in all three series are found to be similar except for Fe(9)(­), Fe(9)(+), Fe(10)(­), Fe(10)(+), Fe(15)(­), and Fe(19)(+). Our computed ionization energies of the neutrals, vertical electron detachment energies, and energies of Fe atom abstraction are in good agreement with experiment. It is found that the one-electron model corresponding to the change in the total magnetic moment of ±1.0µ(B) due to either attachment or detachment of an electron is valid in most cases. The exceptions are Fe(4)(+), Fe(10)(­), Fe(10)(+), Fe(12)(­), Fe(13)(+), and Fe(14)(+), where the change in the total magnetic moment is +3µ(B) (Fe(10)(­) and Fe(12)(­)), −3µ(B) (Fe(4)(+), Fe(11)(+), and Fe(14)(+)), and −9µ(B) (Fe(13)(+)). The reason for an anomalously large quenching of the total spin magnetic moment in Fe(13)(+) is explained. Our computed total spin magnetic moments per atom match the recent experimental values within the experimental uncertainty bars.

A recipe for designing molecules with ever-increasing electron affinities.

Halogens possess among the highest electron affinities of elements in the periodic table. Superhalogen molecules with electron affinities higher than those of halogen atoms have been known to form when a metal atom is surrounded with halogen atoms. Recently, it was discovered that a new class of molecules called hyperhalogens with electron affinities higher than those of superhalogens can form when the latter serve as the building block. By use of density functional theory and B3LYP hybrid exchange-correlation functional we show that molecules with electron affinities even higher can be formed by using hyperhalogens as building blocks. We demonstrate this by using Na and Li as metal atoms and F, BF(4), and Na(BF(4))(2) as halogen, superhalogen, and hyperhalogen building blocks. The predicted electron affinities of Na[Na(BF(4))(2)](2) and Li[Li(BF(4))(2)](2) are 9.18 and 9.01 eV, which are, respectively, 0.85 and 0.5 eV higher than those of their hyperhalogen [Na(BF(4))(2) and Li(BF(4))(2)] counterparts.

Theoretical study of the stability and electronic structure of Al(BH4)n=1→4 and Al(BF4)n=1→4 and their hyperhalogen behavior.

Using density functional theory (DFT), we have systematically calculated the equilibrium geometries, electronic structure, and electron detachment energies of Al(BH(4))(n=1→4) and Al(BF(4))(n=1→4) at the B3LYP/6-311+G(2d,p) level of theory. The electron affinities of Al(BH(4))(n) not only exhibit odd-even alternation, just as seen in (BH(4))(n), but also, for n = 3 and 4, show a remarkable behavior: whereas the electron affinities of BH(3) and BH(4) are, respectively, 0.06 and 3.17 eV, those of Al(BH(4))(3) and Al(BH(4))(4) are 0.71 and 5.56 eV. Results where H is replaced by F are also very different. The electron affinities of BF(3) and BF(4) are, respectively, -0.44 and +6.86 eV, and those of Al(BF(4))(3) and Al(BF(4))(4) are 1.82 and 8.86 eV. The results demonstrate not only marked difference when H is replaced by F but also substantially enhanced electron affinities by almost 2 eV when BH(4) and BF(4) units are allowed decorate a metal atom, confirming the recently observed hyperhalogen behavior of superhalogen building blocks.