Synthesis of Robust MOFs@COFs Porous Hybrid Materials via an Aza-Diels–Alder Reaction: Towards High-Performance Supercapacitor Materials

Metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) have attracted enormous attention in recent years. Recently, MOF@COF are emerging as hybrid architectures combining the unique features of the individual components to enable the generation of materials displaying novel physicochemical properties. Herein we report an unprecedented use of aza-Diels–Alder cycloaddition reaction as post-synthetic modification of MOF@COF-LZU1, to generate aza-MOFs@COFs hybrid porous materials with extended π-delocalization. A a proof-of-concept, the obtained aza-MOFs@COFs is used as electrode in supercapacitors displaying specific capacitance of 20.35 μF cm⁻² and high volumetric energy density of 1.16 F cm⁻³. Our approach of post-synthetic modification of MOFs@COFs hybrids implement rational design for the synthesis of functional porous materials and expands the plethora of promising application of MOFs@COFs hybrid porous materials in energy storage applications.     

Monitoring soybean seed germination by calorimetry

A method to monitor seed germination that combines isothermal calorimetry and imbibition measurements is reported. Individual seeds of three cultivars of soybean seeds (A7636RG, Munasqa and DM5.8RR) and one of radish were used. Imbibition curves were performed on individual seeds in a germination chamber at 25 °C. Calorimetric specific thermal power (p)–time (t) curves of germination were also obtained at 25 °C for 10 or more individual seeds after 30 min of equilibration of the system. Calorimetric experiments of germination in 5 mM KCN were performed to estimate specific imbibitions enthalpies (Δ_i h). The p–t curves could be extrapolated to t = 0 by relating the rate of water uptake as determined from imbibitions curves with p values. Then, p–t curves were integrated to determine the specific metabolic enthalpies Δh which in turn were related to the water content (WC) of seeds at the corresponding times. The method allows determination of specific enthalpy change due to germination, Δ_g h, which apparently is species related. Besides, the standard deviation (SD) of the Δ_g h value gives an indication of seed quality. On the other hand, the water content that seeds need to germinate and the moment at which seeds are fully imbibed can also be determined. This is very important when breeding new cultivars for water stress tolerance. The water content needed for each cultivar to germinate was 74, 57, 35 and 64% for soybean seeds cvs. A7636RG, Munasqa, DM5.8RR and radish, respectively.     

Synthesis of organophosphorus ligands with a central oxygen atom and their applications in solvent extraction

Various structurally related glycolamide compounds were synthesised and evaluated by solvent extraction experiments for the separation of rare earth elements (REEs) from aqueous acid solutions using dodecane as the diluent. We describe herein the full synthesis of a family of bifunctional ligands with a central oxygen and focus our investigation on the effects of structural modification on the extraction efficiencies. The combination of an amide, a PO donor site, and a central oxygen in such a glycolamide ligand showed interesting extraction properties for heavy rare earth elements from phosphoric acid solutions.     

A Joint Experimental/Theoretical Investigation of the Statistical Olefin/Conjugated Diene Copolymerization Catalyzed by a Hemi‐Lanthanidocene [(Cp*)(BH4)LnR]

Statistical copolymerization of ethylene and isoprene was achieved by using a borohydrido half‐lanthanidocene complex. Under copolymerization conditions, activation of [(Cp*)(BH₄)₂Nd(thf)₂] (Cp*=η⁵‐C₅Me₅) by an appropriate alkylating agent affords trans‐1,4‐poly‐isoprene‐co‐ethylene. Analysis of the microstructure of the copolymer revealed the presence of successive short sequences of ethylene/ethylene, trans‐1,4‐isoprene/ethylene, and trans‐1,4‐isoprene/trans‐1,4‐isoprene. A small amount of 1,2‐insertion of isoprene was observed, and no cyclic structures within the chain were characterized. Test runs showed that these catalysts are unable to copolymerize α‐olefins (such as hex‐1‐ene) with isoprene. The probable initial steps in the copolymerization have been computed at the DFT level of theory. Analysis of the energy profile provides insight into the catalyst’s activity and selectivity. Our theoretical results highlight the key role played by the allyl intermediate, in which diene insertion, and to a lesser extent olefin insertion, is the rate‐determining step of the process. These results also illustrate the coordination behavior of the allyl ligand during the insertion of an incoming monomer, which directly inserts, after pre‐coordination to the metal center, into the η³‐allyl ligand without inducing an η³ to η¹ haptotropic shift. Finally, the inactivity of this family of catalysts towards the copolymerization of hex‐1‐ene was rationalized on the basis of the free‐energy profile of the copolymerization.     

Carbon nanotube-functionalized silicon surfaces with efficient redox communication

Sidewall functionalized multi-walled carbon nanotubes can be covalently bound parallel to a silicon surface via a self-assembled acid-terminated monolayer used as an organic molecular glue.     

Application of the precolumn back‐flush technology in pesticide residue analysis: A practical view

Precolumn back‐flushing is a matrix minimization technique in GC in which the carrier gas flow of the precolumn is reversed after the transfer of the highest boiling analyte to the analytical column. Practical details concerning this technology have rarely been published although it is widely used. This paper now focuses on the practical implementation of precolumn back‐flushing for pesticide residue analysis of complex food matrices. Fitting the analytical column into the precolumn was found to be essential for comparable analyte responses with and without back‐flushing. The effectiveness of the reverse column flow technique is mainly affected by the transfer time after which back‐flushing starts. The transfer time was found to depend on which kind of injected matrix is used and the state of the precolumn. For the regular adaptation of the transfer time in routine analysis, a simple test was introduced in which 13‐C‐labeled deltamethrin and indeno[1,2,3‐c,d]pyrene were added to the prepared extract. Chromatograms, LOQ and RSD of up to 99 pesticides in citrus oil and liver extracts proved a clearer identification and enhanced quantification using precolumn back‐flushing compared to measurements without this technology. Furthermore, reduced system maintenance could be achieved through back‐flushing.     

Isolation of Functionalized Phenolic Monomers through Selective Oxidation and C?O Bond Cleavage of the β‐O‐4 Linkages in Lignin

Functionalized phenolic monomers have been generated and isolated from an organosolv lignin through a two‐step depolymerization process. Chemoselective catalytic oxidation of β‐O‐4 linkages promoted by the DDQ/tBuONO/O₂ system was achieved in model compounds, including polymeric models and in real lignin. The oxidized β‐O‐4 linkages were then cleaved on reaction with zinc. Compared to many existing methods, this protocol, which can be achieved in one pot, is highly selective, giving rise to a simple mixture of products that can be readily purified to give pure compounds. The functionality present in these products makes them potentially valuable building blocks.     

Elemental analyses of soil and sediment fused with lithium borate using isotope dilution laser ablation-inductively coupled plasma-mass spectrometry

Quantitative analysis using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) remains challenging primarily due to the lack of appropriate reference materials available for the wide variety of samples of interest and to elemental fractionation effects. Isotopic dilution mass spectrometry (IDMS) is becoming the methodology of choice to address these issues because the different isotopes of an element represent near-perfect internal standards. In this work, we investigated the lithium borate fusion of powdered solid samples, including soils, sediments, rock mine waste and a meteorite, as a strategy to homogenously distribute, i.e. equilibrate the elements and the added isotopically enriched standards. A comparison of this methodology using two pulsed laser ablation systems (ArF* excimer and Nd:YAG) with different wavelengths as well as two ICP-MS instruments (quadrupole and double-focusing sector field) was performed. Emphasis was put on using standard equipment to show the potential of the proposed strategy for its application in routine laboratories. Cr, Zn, Ba, Sr and Pb were successfully determined by LA-ICP-IDMS in six Standard Reference Materials (SRMs) representing different matrices of environmental interest. Experimental results showed the SRM fused glasses exhibited a low level of heterogeneity (intra- and inter-sample) for both natural abundance and isotopically enriched samples (RSD <3%, n = 3, 1σ). A good agreement between experimental results and the certified values was also observed.