Chemical functionalization of carbon nanomaterials: Bridging the gap between simple carriers and smart (metalfree) catalysts

© 2017 Swiss Chemical Society. The last few years have witnessed a wonderful technological renaissance that boosted the development of carbon-based nanomaterials (CNMs) doped with light heteroelements and featuring hierarchical porous architectures as valuable metal-free catalysts for a number of key industrial transformations. To date, several approaches to their synthesis have been developed, although many of them lack any real control of the final doping and composition. In contrast, chemical functionalization offers a unique and powerful tool to tailor CNMs' chemical and electronic surface properties as a function of their downstream application in catalysis. Different catalytic processes (hydrolysis/esterification/transesterification reactions, C-C bond forming reactions, CO2 derivatization into products of added value and electrochemical oxygen reduction reactions (ORR)) can be conveniently promoted by these materials. In addition, selected examples from this series offer a valuable platform for the in-depth comprehension of the underlying reaction mechanisms. This perspective article offers an overview on the main examples of ad hoc chemically decorated CNMs successfully exploited as metal-free catalysts, highlighting at the same time the importance of the surface chemistry control for the design of more active, metal-free and single-phase heterogeneous catalysts

Metal-Organic Frameworks as Heterogeneous Catalysts in Hydrogen Production from Lightweight Inorganic Hydrides

© 2017 American Chemical Society. Ammonia-borane (NH 3 ·BH 3 , AB), hydrazine (NH 2 NH 2 ), lithium borohydride (Li(BH 4 )), and sodium alanate (Na(AlH 4 )) are popular chemical hydrogen storage inorganic solid materials featuring high gravimetric hydrogen contents (H wt %) and remarkable stability under ambient conditions. Ultrapure H 2 is formed from these compounds either via pyrolysis (i.e., a simple material heating) or via hydrolysis (chemical reaction with water). In both cases, a series of homogeneous and heterogeneous catalysts have been designed to assist the process. Among the latter, metal-organic frameworks (MOFs, crystalline 3D porous lattices made of metallic nodes and organic polytopic linkers) have rapidly emerged as versatile candidates for this role. The nanoconfinement of lightweight hydrides in MOFs produces a "hydride@MOF" composite material. Hydride coordination to MOF exposed metal sites or its reaction with functional groups on the organic linkers facilitates the thermal decomposition, lowering the hydrogen release temperature and increasing the hydrogen production rate. For hydrolysis, MOFs are used as templates for the preparation of metal(0) nanoparticles (NPs) uniformly distributed in their inner cavities through a preliminary impregnation with a solution containing a metal salt followed by reduction. The "NPs@MOF" are the real active species that catalyze the reaction between the hydride and water, with concomitant H 2 evolution. This perspective highlights the most representative literature examples of MOFs as heterogeneous catalysts (or catalyst supports) for H 2 production from inorganic lightweight hydrides. Future trends in the field will also be discussed. (Figure Presented)

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

How to teach an old dog new (electrochemical) tricks: Aziridine-functionalized CNTs as efficient electrocatalysts for the selective CO<inf>2</inf> reduction to CO

© 2018 The Royal Society of Chemistry. The electrocatalytic conversion of CO2 to energy-rich chemicals or energy vectors is a highly challenging approach to cope with an ever increasing demand for energy storage and valorization of renewable resources. Herein we report on the electrocatalytic reduction of CO2 to CO using covalently N-decorated carbon nanotubes as highly efficient and chemoselective metal-free electrocatalysts. At odds with more conventional synthetic methods for the production of N-doped nanocarbons, chemical functionalization warrants a unique control of "surface N-defects" available for the process, ruling out any synergistic contribution to electrocatalysis coming from other surface or bulk N-containing groups. With a CO faradaic efficiency (FECO) close to 90% and productivity as high as 48 NLCO gN-1 h-1, NH-aziridine functionalized MWCNTs have shown CO2RR performance that is among the highest reported so far for related metal-free systems. At the same time, it has offered a unique view-point for the comprehension of the underlying structure-reactivity relationship

Heterogeneity of covid-19 outbreak in italy

An outbreak of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) started in December 2019 in China and was declared a pandemic on 11.03.2020 by WHO. Italy is one of the most afflicted Country by this epidemic with 136,110 confirmed cases and 16,654 deaths on 9.4.2020 (at the same date, the Ministry of Health was reporting 143,626 cases). During these few months the National Health Service have made a great effort to cope with the increasing request of intensive care beds and all the elective activities in hospital have been suspended. Data from the different Italian regions shows different patterns of positive and dead for this syndrome. Moreover, striking differences of the observed lethality of the infections among different areas were immediately evident from the epidemic reports. It will be of critical relevance to understand the expected evolution of the first lock-down phase, driving the exhaustion of the Covid-19 outbreak

MECPerf: An Application-Level Tool for Estimating the Network Performance in Edge Computing Environments

Edge computing is an emerging architecture in 5G networks where computing power is provided at the edge of the fixed network, to be as close as possible to the end users. Computation offloading, better communication latency, and reduction of traffic in the core network are just some of the possible benefits. However, the Quality of Experience (QoE) depends significantly on the network performance of the user device towards the edge server vs. cloud server, which is not known a priori and may generally change very fast, especially in heterogeneous, dense, and mobile deployments. Building on the emergence of standard interfaces for the installation and operation of thirdparty edge applications in a mobile network, such as the MultiAccess Edge Computing (MEC) under standardization at the European Telecommunications Standards Institute (ETSI), we propose MECPerf, a tool for user-driven network performance measurements. Bandwidth and latency on different network segments are measured and stored in a central repository, from where they can be analyzed, e.g., by application and service providers without access to the underlying network management services, for run-time resource optimization

Novel yttrium and zirconium catalysts featuring reduced Ar-BIANH2 ligands for olefin hydroamination (Ar-BIANH2 = bis-arylaminoacenaphthylene)

The novel class of bis-arylaminoacenaphthylenes (Ar-BIANH(2)) was employed for the preparation of zirconium and yttrium complexes to be used as catalysts for cyclohydroamination of a number of primary and secondary aminoalkenes. The complex [(2,6-iPr(2)C(6)H(3)-BIAN)Zr(NMe2)(2)(eta(1)-NHMe2)] was isolated and completely characterized, including X-ray diffraction analysis. Despite its easy and almost quantitative isolation, it showed only moderate catalytic performance in the intramolecular hydroamination, irrespective of the cyclization precursor used. On the other hand, in situ generated Y-III complexes obtained using the same class of ligands were found to be very active, leading to the hydroamination of substrates including those normally reluctant in undergoing cyclization such as those featuring an internal non-activated C=C double bond. Electron donating substituents and especially steric hindrance on the ligand improve the performance of the catalysts, allowing us to decrease the catalyst loading to 1 mol% in the latter case

Analysis of circulating extracellular vesicle-associated microRNAs in cortisol-producing adrenocortical tumors

PURPOSE: Circulating microRNAs (miRNA) have been described in patients with adrenocortical tumors, but the expression of miRNAs in non-functioning and cortisol-producing tumors has not been yet compared. Therefore, the objective of this study was to evaluate the expression of plasma extracellular vesicle (EV)-associated microRNAs in patients with non-functioning adrenocortical adenoma (NFA), cortisol-producing adrenocortical adenoma (CPA) and cortisol-producing adrenocortical carcinoma (CP-ACC). METHODS: Preoperative plasma EV samples of 13 NFAs, 13 CPAs and 9 CP-ACCs were subjected to extracellular vesicle isolation. miRNAs were investigated by targeted quantitative real-time PCR normalized to cel-miR-39 as reference. Five miRNAs have been selected for this analysis based on the previous studies including hsa-miR-22-3p, hsa-miR-27a-3p, hsa-miR-210-3p, hsa-miR-320b and hsa-miR-375. RESULTS: We have observed significant overrepresentation of three miRNAs in both CPA and CP-ACC relative to NFA: hsa-miR-22-3p (p < 0.01 and p < 0.0001, respectively), hsa-miR-27a-3p (p < 0.05 in both comparisons) and hsa-miR-320b (p < 0.05 and p < 0.0001, respectively). Hsa-miR-320b has been significantly overrepresented in CP-ACC relative to CPA (p < 0.01). Hsa-miR-210-3p turned out to be significantly overrepresented only in CP-ACC compared to NFA (p < 0.05). Significant correlation was revealed between circulating miRNA concentrations and urinary free cortisol values for hsa-miR-22-3p, hsa-miR-27a-3p and hsa-miR-320b (p < 0.0001 for all) and cortisol after low-dose dexamethasone test for hsa-miR-22-3p and hsa-miR-320b (p < 0.05). Hsa-miR-27a-3p has been significantly stimulated by low-dose dexamethasone test (p < 0.05). CONCLUSIONS: EV-associated miRNAs are differentially expressed in different non-functioning and cortisol-producing adrenocortical tumors

Prognostic and monitoring value of circulating tumour cells in adrenocortical carcinoma: a preliminary monocentric study.

Adrenocortical carcinoma (ACC), a rare and aggressive neoplasia, presents poor prognosis when metastatic at diagnosis and limited therapies are available. Specific and sensitive markers for early diagnosis and a monitoring system of therapy and tumor evolution are urgently needed. The liquid biopsy represents a source of tumor material within a minimally invasive blood draw that allows the recovery of circulating tumor cells (CTCs). CTCs have been recently shown to be detectable in ACC. In the present paper, we evaluated the prognostic value of CTCs obtained by size-filtration in a small pilot cohort of 19 ACC patients. We found CTCs in 68% of pre-surgery and in 38% of post-surgery blood samples. In addition, CTC clusters (CTMs) and cancer associated macrophages (CAMLs) were detectable in some ACC patients. The median number of CTCs significantly decreased after the mass removal. Finally, stratifying patients in high and low pre-surgery CTC number groups, assuming the 75th percentile CTC value as cut-off, CTCs significantly predicted patients&rsquo; overall survival (log rank = 0.005), also in a multivariate analysis adjusted for age and tumor stage. In conclusion, though preliminary and performed in a small cohort of patients, our study suggests that CTC number may represent a promising marker for prognosis and disease monitoring in ACC