Misuse and Artifact in Factor Analytic Research

The theory of factor analysis has been developed for incorporating mathematical　statistical theories such as the maximum likelihood method and asymptotic methods. However, there have been several instances of misuse while employing procedures for factor analysis studies. In several studies, factor analysis has been performed by deleting items exhibiting the ceiling effect or floor effect. The number of samples required for factor analysis is not well known. Kaiser-Guttman criterion cannot be applied for determining the number of factors. Furthermore, various studies have employed Scree Graphs and Parallel Analysis for the said purpose, but no definitive method exists for the same. Orthogonal rotation methods such as Varimax cannot be considered as a conclusive solution. However, Geomin has been considered as a better rotation method not only for simple structure but also for more complex factor configuration. Simple structure and bifactor structure are discussed in connection to factor rotation problem. Although there are various artifacts associated with the usage of factor analysis, this issue can be addressed by verifying factorial invariance through multi-group simultaneous analysis incorporated by SEM programs such as Mplus and R Package.因子分析の理論は、最尤法と漸近的方法のような数理統計学的理論を組み込んだ形で発展してきた。しかしながら、因子分析研究の手順にはまだ誤用がみられる。いくつかの研究において、天井効果や床効果を示す項目を削除して因子分析が行われている。因子分析に必要なサンプル数は明確ではない。因子の数を決定するためにKaiser-Guttman 基準は使うことはできない。そして、この目的でScree Graph とParallel Analysis を使用している研究は数多くあるが、そのための決定的な方法はない。Varimax のような直交回転は最終的な解と考えることはできない。しかしながら、Geomin は単純構造だけでなくより複雑な因子の布置に対しても優れた回転方法と考えられている。因子回転問題を考慮した単純構造とbifactor 構造について議論した。因子分析の使い方には多くのartifacts があるが、この問題は、Mplus やR Package などのSEMプログラムによって組み込まれた複数集団の同時分析によって因子的不変性を検証することによって対処することができる

Tuning Carbon Dioxide Adsorption Affinity of Zinc(II) MOFs by Mixing Bis(pyrazolate) Ligands with N-Containing Tags

The four zinc(II) mixed-ligand metal-organic frameworks (MIXMOFs) Zn(BPZ)x(BPZNO2)1-x, Zn(BPZ)x(BPZNH2)1-x, Zn(BPZNO2)x(BPZNH2)1-x, and Zn(BPZ)x(BPZNO2)y(BPZNH2)1-x-y (H2BPZ = 4,4′-bipyrazole; H2BPZNO2 = 3-nitro-4,4′-bipyrazole; H2BPZNH2 = 3-amino-4,4′-bipyrazole) were prepared through solvothermal routes and fully investigated in the solid state. Isoreticular to the end members Zn(BPZ) and Zn(BPZX) (X = NO2, NH2), they are the first examples ever reported of (pyr)azolate MIXMOFs. Their crystal structure is characterized by a three-dimensional open framework with one-dimensional square or rhombic channels decorated by the functional groups. Accurate information about ligand stoichiometric ratio was determined (for the first time on MIXMOFs) through integration of selected ligands skeleton resonances from 13C cross polarized magic angle spinning solid-state NMR spectra collected on the as-synthesized materials. Like other poly(pyrazolate) MOFs, the four MIXMOFs are thermally stable, with decomposition temperatures between 708 and 726 K. As disclosed by N2 adsorption at 77 K, they are micro-mesoporous materials with Brunauer-Emmett-Teller specific surface areas in the range 400-600 m2/g. A comparative study (involving also the single-ligand analogues) of CO2 adsorption capacity, CO2 isosteric heat of adsorption (Qst), and CO2/N2 selectivity in equimolar mixtures at p = 1 bar and T = 298 K cast light on interesting trends, depending on ligand tag nature or ligand stoichiometric ratio. In particular, the amino-decorated compounds show higher Qst values and CO2/N2 selectivity vs the nitro-functionalized analogues; in addition, tag "dilution" [upon passing from Zn(BPZX) to Zn(BPZ)x(BPZX)1-x] increases CO2 adsorption selectivity over N2. The simultaneous presence of amino and nitro groups is not beneficial for CO2 uptake. Among the compounds studied, the best compromise among uptake capacity, Qst, and CO2/N2 selectivity is represented by Zn(BPZ)x(BPZNH2)1-x

Lattice expansion of graphite oxide by pressure induced insertion of liquid ammonia

© 2015 Elsevier Ltd. All rights reserved. A pressure induced lattice expansion of Graphite Oxide (GO) in presence of NH3 was observed by X-ray diffraction during room temperature compression and decompression up to 7 GPa in a diamond anvil cell (DAC). A remarkable increase (∼11%) of the interlayer d-spacing of GO was observed between 0.2 and 1.1 GPa in the liquid phase of NH3, indicating the occurrence of molecular insertion between the GO layers. The expansion is reversible with the release of pressure, thus leading to a pressure induced breathing of the GO lattice. The presence of high density NH3 between the GO layers opens new perspectives for N-doping and chemical functionalization of GO and for designing new advanced carbon based nanostructured materials

High-Pressure Chemistry of Graphene Oxide in the Presence of Ar, N<inf>2</inf>, and NH<inf>3</inf>

© 2016 American Chemical Society.The high pressure structural and reactive beahvior of graphene oxide (GO) in the presence of Ar, N2, and NH3 was studied in diamond anvil cells (DAC) by X-ray diffraction (XRD) and vibrational spectroscopy (FTIR and Raman), with the purpose of investigating the use of pressure for N-doping and functionalization of GO in high-density conditions. The pressure evolution of the interlayer d-spacing of GO during room temperature compression and decompression indicates the pressure-induced insertion of the selected systems between the GO layers and the stability of the GO layered structure at high pressure. Thermal and photoinduced reactivity was studied in GO with N2 and in GO with NH3 in different pressure conditions. The comparison of the infrared spectra of the recovered samples at ambient conditions with respect to the starting GO provides evidence for the occurrence of chemical reactivity of N2 and NH3 with GO, leading to N incorporation and GO functionalization, as also confirmed by the Raman spectra. The observed reactivity opens new perspectives for the high-pressure chemistry of GO and carbon-based nanostructured systems

Cobalt(II) Bipyrazolate Metal-Organic Frameworks as Heterogeneous Catalysts in Cumene Aerobic Oxidation: A Tag-Dependent Selectivity

"This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c00481"[EN] Three metal-organic frameworks with the general formula Co(BPZX) (BPZX(2-) = 3-X-4,4'-bipyrazolate, X = H, NH2, NO2) constructed with ligands having different functional groups on the same skeleton have been employed as heterogeneous catalysts for aerobic liquid-phase oxidation of cumene with O-2 as oxidant. O-2 adsorption isotherms collected at p(O2) = 1 atm and T = 195 and 273 K have cast light on the relative affinity of these catalysts for dioxygen. The highest gas uptake at 195 K is found for Co(BPZ) (3.2 mmol/g (10.1 wt % O-2)), in line with its highest BET specific surface area (926 m(2)/g) in comparison with those of Co(BPZNH(2)) (317 m(2)/g) and Co(BPZNO(2)) (645 m(2)/g). The O-2 isosteric heat of adsorption (Q(2)) trend follows the order Co(BPZ) > Co(BPZNH(2)) > Co(BPZNO(2)). Interestingly, the selectivity in the cumene oxidation products was found to be dependent on the tag present in the catalyst linker: while cumene hydroperoxide (CHP) is the main product obtained with Co(BPZ) (84% selectivity to CHP after 7 h, p(O2) = 4 bar, and T = 363 K), further oxidation to 2-phenyl-2-propanol (PP) is observed in the presence of Co(BPZNH(2)) as the catalyst (69% selectivity to PP under the same experimental conditions).S.G., R.V., and M.M. acknowledge Universita dell'Insubria for partial funding. G.G. thanks the Italian MIUR through the PRIN 2017 Project Multi-e: Multielectron Transfer for the Conversion of Small Molecules: an Enabling Technology for the Chemical Use of Renewable Energy (20179337R7) for financial support. G.G. thanks the TRAINER project (Catalysts for Transition to Renewable Energy Future) ref. ANR-17-MPGA-0017 for support. C.P. thanks the University of Camerino and the Italian MIUR throughout the PRIN 2015 Project Towards a Sustainable Chemistry (20154 x 9ATP_002). This project has also received funding from the European Union's Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant agreement No. 641887 (project acronym: DEFNET) and the Spanish Government through projects MAT2017-82288-C2-1-P and Severo Ochoa (SEV-2016-0683). Professor Norberto Masciocchi (University of Insubria, Como, Italy) is acknowledged for fruitful discussions. 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Unraveling Surface Basicity and Bulk Morphology Relationship on Covalent Triazine Frameworks with Unique Catalytic and Gas Adsorption Properties

© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, WeinheimActivity and selectivity are key features at the basis of an efficient catalytic system for promoting the steam- and oxygen-free dehydrogenation (DDH) of ethylbenzene to styrene. The catalyst stability under severe reaction conditions, the reduction of leaching of its active sites, and their resistance to deactivation phenomena on stream are other fundamental aspects to keep in mind while synthesizing new catalytic materials for the process. Although the recent use of single-phase (doped or undoped) carbon nanomaterials has significantly contributed to improving this catalysis, the relationship between materials morphology and their chemical surface properties still remains to be addressed. Here, a class of highly microporous, N-doped covalent triazine frameworks (CTFs) with superior activity and stability in the DDH compared to the benchmark systems of the state-of-the-art is reported. Notably, a comparative analysis of their chemico-physical properties has unveiled the role of the “chemically accessible” surface basicity on the catalyst passivation on stream. Finally, the unique properties of the synthesized CTFs are demonstrated by their excellent H2 storage capability and CO2 absorption that rank among the highest reported so far for related systems

Pyrazole-Based PCN Pincer Complexes of Palladium(II): Mono- and Dinuclear Hydroxide Complexes and Ligand Rollover C-H Activation

© 2015 American Chemical Society. Palladium complexes of the novel unsymmetrical phosphine pyrazole-containing pincer ligands PCNH (PCNH = 1-[3-[(di-tert-butylphosphino)methyl]phenyl]-1H-pyrazole) and PCNMe (PCNMe = 1-[3-[(di-tert-butylphosphino)methyl]phenyl]-5-methyl-1H-pyrazole) have been prepared and characterized through single-crystal X-ray diffraction and multinuclear 1H, 13C{1H}, and 31P{1H} NMR spectroscopy. In preparations of the monomeric hydroxide species (PCNH)Pd(OH), an unexpected N detachment followed by C-H activation on the heterocycle 5-position took place resulting in conversion of the monoanionic {P,C-,N} framework into a dianionic {P,C-,C-} ligand set. The dinuclear hydroxide-bridged species (PCNH)Pd(μ-OH)Pd(PCC) was the final product obtained under ambient conditions. The "rollover" activation was followed via 31P{1H} NMR spectroscopy, and dinuclear cationic μ-OH and monomeric PdII hydroxide intermediates were identified. DFT computational analysis of the process (M06//6-31G∗, THF) showed that the energy barriers for the pyrazolyl rollover and for C-H activation through a σ-bond metathesis reaction are low enough to be overcome under ambient-temperature conditions, in line with the experimental findings. In contrast to the PCNH system, no "rollover" reactivity was observed in the PCNMe system, and the terminal hydroxide complex (PCNMe)Pd(OH) could be readily isolated and fully characterized. (Chemical Equation Presented)

Ideas and perspectives : Tracing terrestrial ecosystem water fluxes using hydrogen and oxygen stable isotopes – challenges and opportunities from an interdisciplinary perspective

The authors thank Marialaura Bancheri, Michele Bottazzi, Roman Cibulka, Massimo Esposito, Alba Gallo, Cesar D. Jimenez-Rodriguez, Angelika Kuebert, Ruth Magh, Stefania Mambelli, Alessia Nannoni, Paolo Nasta, Vladimir Rosko, Andrea Rücker, Noelia Saavedra Berlanga, Martin Šanda, and Anna Scaini for their contributions during the discussion at the workshop “Isotope-based studies of water partitioning and plant–soil interactions in forested and agricultural environments”. The authors also thank “Villa Montepaldi” and the University of Florence for the access to the workshop location, and the municipality of San Casciano in Val di Pesa for logistical support. The authors thank the Department of Innovation, Research and University of the Autonomous Province of Bozen/Bolzano for covering the Open Access publication costs. Last, but not least, the authors wish to thank Matthias Sprenger, Stephen Good, and J. Renée Brooks, as well as the Editor David R. Bowling, whose constructive reviews greatly improved this manuscript.Peer reviewedPublisher PD

Nitro-functionalized Bis(pyrazolate) Metal–Organic Frameworks as Carbon Dioxide Capture Materials under Ambient Conditions

© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim The metal–organic frameworks (MOFs) M(BPZNO2) (M=Co, Cu, Zn; H2BPZNO2=3-nitro-4,4′-bipyrazole) were prepared through solvothermal routes and were fully investigated in the solid state. They showed good thermal stability both under a N2 atmosphere and in air, with decomposition temperatures peaking up to 663 K for Zn(BPZNO2). Their crystal structure is characterized by 3D networks with square (M=Co, Zn) or rhombic (M=Cu) channels decorated by polar NO2 groups. As revealed by N2 adsorption at 77 K, they are micro-mesoporous materials with BET specific surface areas ranging from 400 to 900 m2 g−1. Remarkably, under the mild conditions of 298 K and 1.2 bar, Zn(BPZNO2) adsorbs 21.8 wt % CO2 (4.95 mmol g−1). It shows a Henry CO2/N2 selectivity of 15 and an ideal adsorbed solution theory (IAST) selectivity of 12 at p=1 bar. As a CO2 adsorbent, this compound is the best-performing MOF to date among those bearing a nitro group as a unique chemical tag. High-resolution powder X-ray diffraction at 298 K and different CO2 loadings revealed, for the first time in a NO2-functionalized MOF, the insurgence of primary host–guest interactions involving the C(3)–NO2 moiety of the framework and the oxygen atoms of carbon dioxide, as confirmed by Grand Canonical Monte Carlo simulations. This interaction mode is markedly different from that observed in NH2-functionalized MOFs, for which the carbon atom of CO2 is involved