Diagonal Relationship Research Articles

Exploiting the Mixed Entropy Strategy for the Design of Fast Ion Conductors

AbstractThe inorganic solid‐state electrolytes play a crucial role in all‐solid‐state batteries. The entropy of solid‐state electrolytes has a significant impact on ion transport. It has been reported that ionic conductivity can be enhanced by increasing the entropy by adding multiple atoms to the materials. However, there is a lack of understanding regarding the potential mechanism between entropy and ion transport in the atomic‐level microstructure of materials. Herein, a new point of view is brought up to understand the influence of entropy on lithium ionic conductivity at an atomic level only by adding one element at a time inspired by the diagonal relationship. A series of materials is designed, including Li1.75Zr0.75Ta0.25Cl6, Li1.75Zr0.75Nb0.25Cl6, Li1.75Zr0.75Mo0.25Cl6, and Li1.75Zr0.75W0.25Cl6, with various mixed entropy, directed by diagonal relationship. It reveals that the substitution increases the mixed entropy, alters the disorder degree of cations around lithium ions, and improves ionic conductivity. Highlighting the importance of mixed entropy in ion migration and establishing the close connection between mixed entropy and ion conduction could provide new insights into the design and development of solid‐state electrolytes.

Is Mn(I) More Promising Than Fe(II)-A Comparison of Mn vs Fe Complexes for Olefin Metathesis.

Olefin metathesis is one of the most significant transformations in organic chemistry and is an excellent example for efficient homogeneous catalysis. Although most currently used catalysts are primarily based on 4d and 5d metals, cycloaddition and cycloreversion reactions can also be attributed to first-row transition metals, such as Fe. Surprisingly, the potential of Mn(I)-based catalysts for olefin metathesis has been unexplored despite their prominence in homogeneous catalysis and their diagonal relationship to Ru(II). In the present study, we have investigated the prospective capabilities of Mn complexes for cycloaddition and reversion reactions using density functional theory. Therefore, we have initially compared the literature known iron model systems and their isoelectronic Mn counterparts regarding their reactivity and electronic structure. Next, we constructed potential Mn complexes derived from synthetically accessible species, including carbonyl ligands and obeying octahedral geometry. Based on thermodynamic parameters and the calculation of electronic descriptors, we were able to validate the isodiagonal relationship. Our study serves as guidance for the experimental chemist.

Evaluating the linear accelerator accuracy: Integrating Winston-Lutz measurement method and mathematical calculations

The Electronic Portal Image Device (EPID) is commonly used to evaluate the difference between the mechanical and radiation centers of a linear accelerator; however, the gantry and EPID are limited in some non-coplanar angles due to collisions with the treatment couch. This study aimed to compare the results of mathematical calculations and actual measurements to evaluate the feasibility of assessing the differences in the mechanical and radiation field isocenters. A 20 mm Stereotactic Circular Collimator was mounted on the head of the linear accelerator (LINAC), and an Elekta 8 mm ball-bearing (BB) was placed on the couch, following the Winston-Lutz (WL) measurement method. Measurements were taken with varying gantry and couch positions, and Image J software was used to analyze the images. Two regions with a difference of more than 0.1 mm were identified. The first region was between T270 and T330, with gantry angles ranging from G120 to G160. The second region was between T280 and T340, with gantry angles ranging from G290 to G330, and the two regions showed a symmetric diagonal relationship in terms of the gantry angles. The paired sample t-test showed no significant difference between the actual measurements and the calculated results (p-value = 0.11). The study concluded that mathematical calculations can complement the limitations imposed by equipment collisions, providing valuable insights for treatment planning.

Development of a support programme that connects schools and homes using Good Behaviour tickets

It is known that a pupil’s environment can influence and affect their behaviour and researchers are working to create good environments at both school and home in order that schoolchildren have the support they need to navigate life inside and outside of education. In his latest work, licensed psychologist and a certified clinical psychologist Associate Professor Kazunori Edahiro, Faculty of Human Culture and Sciences, Fukuyama University, Japan, is applying behavioural science to the creation of an environment that is easy for all youth to live in, with a key focus on using positive behaviour support and ‘good behaviour tickets’. Edahiro is interested in the influence of diagonal relationships on the development of youths and, in previous work, used the ethnography method and the Trajectory Equifinality Approach (TEA). Currently, he is working to develop a support programme that can clarify the effects and changes on the mental and behavioural aspects of teachers and caregivers and connect schools and homes through the use of good behaviour tickets. Instances of good behaviour are described by tickets that are sent home, establishing a more positive relationship between school and home. In addition to immediate benefits for individual students, the programme has the potential to be applied more widely in the education system in Japan and other countries.

Studying the impact of diagonal-doping on thermal stability of main-group metal clusters via Born Oppenheimer molecular dynamics

Doping with a heteroatom is considered to be an effective tool in tuning the physico-chemical properties of metal clusters. Over a period of time, several experimental and theoretical investigations have been carried out to understand the effect of doping on structure, electronic properties and reactivity of main group clusters. However, issues pertaining to thermal stabilities of metal clusters, particularly in the context of heteroatom doping remain unexplored. Filling this lacuna, this report focuses on evaluating the finite temperature behaviour of the main group metal clusters which are doped with diagonally adjacent dopant atoms. Born-Oppenheimer Molecular Dynamical (BOMD) simulations are performed on diagonally doped LiMg, BeAl and BSi () clusters (doped diagonal pairs). The thermal response of these doped diagonal pairs is also compared with the corresponding pristine clusters such as Li, Mg, Be, Al, B and Si () clusters. The simulation trajectories and ionic motions are analysed and root mean square bond length fluctuations are calculated as a function of temperature. The results indicate that the diagonally doped BSi () clusters are thermally more stable (1200 K) as compared to the other two doped clusters (LiMg, BeAl). The enhanced thermal stability is attributed to the higher binding energies noted for BSi () clusters. Moreover, it is found that for the B-Si cluster systems, diagonal doping always enhances the thermal stability, whereas both diagonal doping and the size of the cluster affect the thermal stabilities of the LiMg, and BeAl cluster systems. An in-depth analysis of thermal-structural-electronic (frontier molecular orbitals) properties revealed that the strength of dopant-to-parent cluster interactions are playing a significant role in influencing the thermal stabilities of diagonally doped clusters. Overall this study also highlights how the heuristic chemical principle of ‘diagonal relationship’ widely used in main-group chemistry may be extended to cluster science to draw new insights regarding thermal stabilities of metal clusters.

Side-on coordination of diphosphorus to a mononuclear iron center.

The diagonal relationship in the periodic table between phosphorus and carbon has set an expectation that the triple-bonded diatomic diphosphorus molecule (P2) should more closely mimic the attributes of acetylene (HC≡CH) rather than its group 15 congener dinitrogen (N2). Although acetylene has well-documented coordination chemistry with mononuclear transition metals, coordination complexes that feature P2 bound to a single metal center have remained elusive. We report the isolation and x-ray crystallographic characterization of a mononuclear iron complex featuring P2 coordination in a side-on, η2-binding mode. An analogous η2-bound bis-timethylsilylacetylene iron complex is reported for comparison. Nuclear magnetic resonance, infrared, and Mössbauer spectroscopic analysis-in conjunction with density functional theory calculations-demonstrate that η2-P2 and η2-acetylene ligands exert a similar electronic demand on mononuclear iron centers but exhibit different reactivity profiles.

Understanding experience complexity in a smart learning journey

This paper contributes to a pedagogical model for smart learning by establishing a framework of some considerations based on learner experience of smart learning journeys. Phenomenography is used to investigate variation of learner experience in smart learning journeys. Learners participate in ‘Literary London’, situated in London, UK, and 'Malta Democracy’, situated in Valletta, Malta. An inclusive relational hierarchy of experience complexity is demonstrated with vertical, horizontal and diagonal relationships between four categories of experience variation for a smart learning journey. A pedagogical relevance structure for smart learning is discussed, supporting connectivist-inspired participatory pedagogies for smart learning environments. Sample participants consist of Education degree university students, with one other discipline represented (English Literature and Creative Writing). Various levels of study, cultural and international backgrounds are represented. Understanding learner experience of these kinds of activities may help to support today’s growing culture of learning cities, to "promote lifelong learning opportunities for all" (Unesco SDG4), within a context of the European Commission 2018 Digital Competence Framework for Citizens.

Nature of Science

Since time immemorial, science has been evolving, playing an immense role from being a philosophy to a discipline and career. Its nature and categorization into many dimensions render it unique amongst all disciplines. Though the tenets, philosophy, and scientific methods of searching for the truth of the physical world make science stand apart within its realm, it encounters heaps of debates. The article focuses on the nature of science while navigating through its evolutionary journey until the present, and the way it emerged as a versatile enterprise holding hierarchical and diagonal relationships among its distinctions. Capturing the veiled philosophical and psychological realities in an exploratory fashion, the article thus tries to bring out the real nature of science concealed within the debates of science.

Two Light‐Metal Dihydrogenisocyanurate Hydrates Linked by Diagonal Relationship: Syntheses, Crystal Structures, and Vibrational Spectra of Li[H2N3C3O3]·1.75 H2O and Mg[H2N3C3O3]2·8 H2O

Single‐crystalline materials of Li[H2N3C3O3]·1.75 H2O and Mg[H2N3C3O3]2·8 H2O were obtained by dissolving stoichiometric amounts of the respective carbonates with cyanuric acid in boiling water followed by gentle evaporation of excess water after cooling to room temperature. Even though both of these compounds crystallize in the triclinic space group P1 according to X‐ray structure analyses of their colorless and transparent single crystals, they adopt two new different structure types. Li[H2N3C3O3]·1.75 H2O exhibits the unit‐cell parameters a = 884.71(6) pm, b = 905.12(7) pm, c = 964.38(7) pm, α = 67.847(2)°, β = 62.904(2)° and γ = 68.565(2)° (Z = 4), whereas the lattice parameters for Mg[H2N3C3O3]2·8 H2O are a = 691.95(5) pm, b = 1055.06(8) pm, c = 1183.87(9) pm, α = 85.652(2)°, β = 83.439(2)° and γ = 79.814(2)° (Z = 2). In both cases, the singly deprotonated isocyanuric acid forms monovalent anions consisting of cyclic [H2N3C3O3]– units, which are arranged in ribbons typical for most hitherto known monobasic isocyanurate hydrates. The structures are governed by the oxophilic strength of the respective cation which means that they fulfil their oxophilic coordination requirements either solely with water molecules ([Mg(OH2)6]2+ for Mg2+) or with crystal water and one or two direct coordinative contacts to carbonyl oxygen atoms (O(cy)) of [H2N3C3O3]– anions ([(Li(OH2)2–3(O(cy)1–2]+ for Li+). In both structures occur dominant hydrogen bonds N–H···O within the anionic [H2N3C3O3]– ribbons as well as hydrogen bonds O–H···O between these ribbons and the hydrated Li+ and Mg2+ cations.

DOA Estimation Algorithm for Strictly Noncircular Sources With Unknown Mutual Coupling

In this letter, an ESPRIT-based algorithm is proposed to handle the direction of arrival (DOA) estimation problem for strictly noncircular sources with unknown mutual coupling. At the cost of auxiliary elements, the structure of original mutual coupling matrix is compensated, and the unknown mutual coupling coefficients are separated from the distorted steering vector to obtain the ideal steering vector. Based on noncircularity, an extended received data is constructed by combining the received data and its conjugate counterpart. After that, ESPRIT framework is applied to the extended received data, and its key point is to utilize the diagonal relationship between the transformed manifold and the ideal manifold. Simulation results show that the proposed algorithm achieves larger virtual array aperture and comparable accuracy.

Knowledge Diffusion in a Global Supply Network: A Network of Practice View

This study investigates how knowledge diffusion occurs in a globally dispersed supply network, wherein buying firms and suppliers often do not have strong relationships and competitive tensions prevail. We elaborate the Network of Practice (NoP) view by examining a global supply network in the food sector that is as an exemplar of high global dispersion. This paper provides several novel insights into global knowledge diffusion. We introduce the NoP concept of homophily into the field of supply chain management to explain knowledge diffusion within global supply networks. We take a longitudinal perspective to show that although prior contractual ties (relational homophily) and co‐location (location homophily) initially drive knowledge diffusion, in the long‐term, shared practices (practice homophily) are the principal driver of knowledge diffusion. We demonstrate that buying firms’ assurance of procedural justice, together with the predominance of geographically dispersed suppliers and the emergence of nexus members, can help dampen supplier resistance to knowledge diffusion. The study shows that knowledge diffusion in a global supply NoP occurs in two complementary forms—broadcasting forums and action groups—which vary in breadth, depth, and tie diversity. Ultimately, we present vertical (buyer‐supplier), horizontal (suppliersupplier), and diagonal (non‐competitive) relationships as important refinements of the NoP view that characterize a global supply NoP. Overall, our findings offer a path for buying firms to establish adequate online infrastructure to support the emergence of decentralized and self‐organized knowledge diffusion in a globally dispersed supply network.

Hydrostibination

AbstractA rigid naphthalenediamine framework has been used to prepare antimony hydrides that feature LUMO shapes and energies similar to those found in secondary boranes. By exploiting this feature, we introduce the first examples of uncatalyzed hydrostibination reactions of robust C≡C, C=C, C=O, and N=N bonds as new elementary hydrometalation reactions analogous to hydroboration. These results endorse the notion of a diagonal relationship between the lightest p‐block element and the heaviest Group 15 elements and may lead to the conception of novel reaction chemistry.

Hydrostibination.

A rigid naphthalenediamine framework has been used to prepare antimony hydrides that feature LUMO shapes and energies similar to those found in secondary boranes. By exploiting this feature, we introduce the first examples of uncatalyzed hydrostibination reactions of robust C≡C, C=C, C=O, and N=N bonds as new elementary hydrometalation reactions analogous to hydroboration. These results endorse the notion of a diagonal relationship between the lightest p-block element and the heaviest Group 15 elements and may lead to the conception of novel reaction chemistry.

Young children’s representation of geometric relationships between locations in location coding

From an early age, children are able to use surface layout geometry and landmarks to search for a hidden toy when disoriented. Theoretical debate remains regarding whether children represent locations based on the global environment or on local cues. Exploring whether children construct and use the relationships between discrete locations of the global environment can provide direct evidence regarding this issue. We investigated young children’s representation of two geometric relationships: diagonal relationships (Experiment 1) and same-side relationships (Experiment 2). Children (4- and 5-year-olds) were tested in a square room with a distinctively colored wall. Children completed two tasks. In a two-location task, children watched two toys hidden in two corners that formed one of the two relationships. After disorientating children, the experimenter uncovered one toy and children searched for the other one (target). In a one-location task, only one toy was hidden. In both experiments, children’s performance was better in the two-location task than in the one-location task. Furthermore, accuracy in the two-location task of Experiment 1, in which the two corners formed a diagonal relationship, was higher than that of Experiment 2, in which the two corners formed a same-side relationship and a correct location required the combination of this relationship and landmark. These findings suggest that at least by 4 years of age, children can construct geometric relationships between individual corners in their spatial representation and support the global accounts of young children's location coding.

Synthesis, structure and reactivity of acyclic and heterocyclic α-phosphino amino acids

Acyclic α-phosphino amino acids can be conveniently synthesized by a one-pot three-component reaction, but are limited to N-secondary derivatives with N-alkyl, aryl or heterocyclic substituents, provided these are not too bulky or electron-withdrawing. Phosphino-bis(amino acids), stable with a P-aryl group, undergo spontaneous lactamization in the case of a P-alkyl group to five-membered heterocyclic α-P amino acids. Closely related compounds without C(O)-group, by the diagonal relationship to proline named “(phenyl)phosphaprolines”, were obtained by cyclocondensation of 2-aminoethylphosphines with glyoxylic or α-keto carboxylic acids, in this case also furnishing N-tertiary derivatives. N-Tertiary 1,3-benzazaphospholine-2-carboxylic acids are available analogously. However, the reactivity and the ability to form active nickel catalysts for ethylene oligomerization differ for the various types of α-amino phosphino acids and depends on structural aspects. Acyclic and cyclic N-aryl derivatives, in the latter case particularly those with P-tert-butyl group and sufficiently bulky N-substituents to suppress interfering amine-Ni interactions, gave the highest activities.

Forbidden Love in the Andes: Murúa and Guaman Poma Retell the Myth of Chuquillanto and Acoytapra

Forbidden Love in the Andes: Murúa and Guaman Poma Retell the Myth of Chuquillanto and Acoytapra

Comparison of molybdenum and rhenium oxo bis-pyrazine-dithiolene complexes - in search of an alternative metal centre for molybdenum cofactor models.

A pair of structurally precise analogues of molybdenum and rhenium complexes, [Et4N]/K2[MoO(prdt)2] and K[ReO(prdt)2] (prdt = pyrazine-2,3-dithiolene), were synthesized. These complexes serve as structural models for the active sites of bacterial molybdenum cofactor containing enzymes. They were comprehensively characterized and investigated by NMR, computationally supported IR and resonance Raman spectroscopy, cyclic voltammetry, mass spectrometry, elemental analysis and single-crystal X-ray diffraction. All compiled data are discussed in the context of comparing chemical and electronic structures and consequences thereof. This study constitutes the first investigation of a potential alternative Moco model system bearing rhenium as the central metal in an identical coordination environment to its molybdenum analogue. Structural evaluation revealed a slightly stronger M[double bond, length as m-dash]O bond in the rhenium complex in accordance with spectroscopic results, i.e. observed bond strengths. Thermodynamic parameters for the redox processes MoIV ↔ MoV and ReIV ↔ ReV were obtained by temperature dependent cyclic voltammetry. In contrast to molybdenum, rhenium loses entropy upon reduction and its redox potential is more temperature sensitive, indicating more significant differences than the respective diagonal relationship between the two metals in the periodic table might suggest and questioning rhenium's suitability as a functional artificial active site metal.

High-pressure properties of dense metallic zirconium hydrides studied by ab initio calculations

Zirconium-hydrogen compounds under pressure are investigated by using ab initio density functional calculations. In addition to the high-pressure phases so far predicted, other new metallic phases of ${\mathrm{ZrH}}_{3}$, ${\mathrm{ZrH}}_{4}$, and ${\mathrm{ZrH}}_{6}$ are found above about 170, 110, and 150 GPa, respectively. The estimated superconducting transition temperatures of the ${\mathrm{ZrH}}_{4}$ and ${\mathrm{ZrH}}_{6}$ phases are as follows: 78 K in the $Fddd\phantom{\rule{4pt}{0ex}}{\mathrm{ZrH}}_{4}$ (140 GPa), 47 K in the $I4/mmm\phantom{\rule{4pt}{0ex}}{\mathrm{ZrH}}_{4}$ (230 GPa), 55 K in the $Cmc{2}_{1}\phantom{\rule{4pt}{0ex}}{\mathrm{ZrH}}_{6}$ (160 GPa), 153 K in the $P{2}_{1}/c\phantom{\rule{4pt}{0ex}}{\mathrm{ZrH}}_{6}$ (295 GPa), and 114 K in the $I4/mmm\phantom{\rule{4pt}{0ex}}{\mathrm{ZrH}}_{6}$ (295 GPa). The $I4/mmm$ structure of ${\mathrm{ZrH}}_{4}$ is actually the structure similarly predicted for ${\mathrm{MgH}}_{4}$ and ${\mathrm{ScH}}_{4}$. Also, the $I4/mmm$ structure of ${\mathrm{ZrH}}_{6}$ is a close modification of the $Im\overline{3}m$ structure proposed for ${\mathrm{MgH}}_{6}$ and ${\mathrm{ScH}}_{6}$. The structural resemblances observed in these magnesium, scandium, and zirconium hydrides suggest that diagonally adjacent elements tend to have similar chemical trends, namely, diagonal relationships, which are expected to serve as a helpful guide to searching for new metallic hydrides.

Youth Disclosure of Sexual Orientation to Siblings and Extended Family.

To explore the processes and experiences associated with disclosing sexual orientation to siblings and extended family. Few studies prioritize the experience of disclosing to siblings and extended family, despite its frequency and potential impact on the family unit. Extended family members often act as sources of support for youth; it is therefore worthwhile to consider whether this remains true during and after disclosure of sexual orientation. Interview and questionnaire data were gathered from 22 lesbian, gay, bisexual, and queer (LGBQ) youth, 14 to 21 years of age, from a large Midwestern city. Constructivist grounded theory informed the qualitative methodology and data analysis. We build on concepts of horizontal and vertical family relationships by also introducing the concept of diagonal relationships. Participants described their relationships with aunts as possessing characteristics of horizontal and vertical relationships, allowing them to act as moderators and mediators of the parent-child relationship. The concepts of vertical, horizontal, and diagonal relationships take into consideration how the structure (e.g., hierarchy, egalitarianism, boundaries) and nature (e.g., closeness, reciprocity, mentorship) of various relationships shape the coming-out process for LGBQ youth, without dismissing the importance of either immediate or extended family members. The emerging conceptualization can guide services and interventions as well as illuminate further research on the family systems of LGBQ youth.

A DFT Survey of the Effects of d‐Electron Count and Metal Identity on the Activation and Functionalization of C−H Bonds for Mid to Late Transition Metals

AbstractThe contribution of metal identity to the activation and functionalization of methane by a series of three‐coordinate imide complexes is evaluated in silico for a 3‐by‐3 block of metals from Fe to Pt. Three mechanisms were studied: oxidative addition (OA) to the metal; hydrogen atom abstraction (HAA) by the imide nitrogen; and, [2+2] addition across the metal‐imide bond. In no studied case, was a [2+2] mechanism preferred, perhaps suggesting this mechanism is largely (entirely?) the domain of d0 imides. There is a diagonal relationship within the nonet of metals studied in that OA is preferred for earlier, heavier (5d) members of the series, transitioning to an HAA mechanism for later, lighter (3d) imides. DFT indicates that important parameters in partitioning between HAA and OA mechanisms include the strength of the metal‐imide π‐bond, the ability of larger metals to accommodate increases in formal oxidation state and coordination number, and the soft acid/base compatibility of larger transition metals with soft hydride and methyl ligands