Showing papers by "Francis Verpoort published in 2016"
TL;DR: This review has portrayed the structure, synthesis and applications of a variety of biomimetic MOFs from an unprecedented angle and demonstrated critically each of the five discrete situations by assimilating available benchmark researches in an attempt to provide a concise literature source on the ingenious design strategies and versatile biomimetics applications of this domain of materials.
Abstract: In this review, we have portrayed the structure, synthesis and applications of a variety of biomimetic MOFs from an unprecedented angle. Synthetic MOF analogues of five distinct enzymes: phosphotriesterase, hydrogenase, cytochrome P450, chymotrypsin and carbonic anhydrase, have been discussed with their skeletal comparison to actual enzymatic active sites as reference, and an explanation of catalytic pathways from the mechanistic cycle of the corresponding enzymes is depicted. We demonstrated critically each of the five discrete situations by assimilating available benchmark researches in an attempt to provide a concise literature source on the ingenious design strategies and versatile biomimetic applications of this domain of materials.
332 citations
TL;DR: A review of metal-organic polyhedra self-assembly can be found in this article, where the authors focus on each and every application with various unprecedented examples and highlight few challenges still need to be addressed.
179 citations
TL;DR: This chapter describes the use of different plant and vegetable food residues asNutraceuticals and functional foods and their uses are well addressed along with their disease management and their action as nutraceutical delivery vehicles.
Abstract: This chapter describes the use of different plant and vegetable food residues as nutraceuticals and functional foods. Different nutraceuticals are mentioned and explained. Their uses are well addressed along with their disease management and their action as nutraceutical delivery vehicles.
130 citations
TL;DR: In this paper, a simple and straightforward method at room temperature was used to synthesize a ZIF-67 catalyst for the cycloaddition of carbon dioxide to epoxides to afford cyclic carbonates.
Abstract: Zeolitic imidazole framework (ZIF)-67 is an efficient heterogeneous catalyst for the cycloaddition of carbon dioxide to epoxides to afford cyclic carbonates. In this work, ZIF-67 was synthesized by a simple and straightforward method at room temperature. The coupling reaction in the presence of ZIF-67 without any co-catalyst or solvent was studied under different conditions. The reaction conversion was more than 99% and the selectivity toward chloropropene carbonate was considerably higher (>99%) than the previously reported ZIF-8. Moreover, the ZIF-67 catalyst could be recycled at least four times without noticeable loss of catalytic activity.
100 citations
TL;DR: A survey and discussion of N-heterocyclic carbene precursor-containing MOFs and their various applications are provided in this paper, where the carbenic carbon in Nhetercycleclic carbenes enhances the potential of MOFs synthesized from azolium-containing linkers.
100 citations
TL;DR: In this article, a new heterogeneous NHC catalyst (1-Pd) was obtained by the post-synthetic modification of an azolium-containing metal-organic framework (1) which was synthesized by solvothermal reaction of 1,3-bis(4-carboxyphenyl)imidazolium chloride (H2L+Cl−) and Zn(NO3)2·6H2O.
85 citations
TL;DR: A plethora of strategies for immobilizing well-defined metathesis catalysts on solid supports have been developed over the past decades as mentioned in this paper, and the main focus was set on the immobilization of ruthenium alkylidenes or so-called Grubbs complexes, as these catalysts are known for their high activity, stability and commercial viability.
Abstract: A plethora of strategies for immobilizing well-defined metathesis catalysts on solid supports have been developed over the past decades. Whereas most reviews on classical heterogeneous metathesis catalyst designs mainly discuss covalent binding approaches, we here extended this topic with non-covalent surface science methods, a research area that gained interest recently. Within this context, the main focus was set on the immobilization of ruthenium alkylidenes or so-called Grubbs complexes, as these catalysts are known for their high activity, stability and commercial viability. Besides giving an overview of different immobilization strategies, the wide diversity of supported Grubbs catalysts also allows for discussing implications of attaching Grubbs catalysts that go beyond the traditional benefits of heterogeneous catalysis, such as easy catalyst separation. More specifically, this Review will summarize several unique opportunities of immobilized homogeneous catalysts in liquid-phase metathesis transformations in terms of impact on activity, stability, and product selectivity, as to highlight the economic potential, but without ignoring possible shortcomings and limitations.
45 citations
TL;DR: In this article, a class of dehydrogenative transformations for amide bond formation have been developed, which are atom-economic and environmentally-benign processes with their respective starting materials of alcohols and amines.
Abstract: Recently, a class of dehydrogenative transformations for amide bond formation have been developed. These transformations are atom-economic and environmentally-benign processes with their respective starting materials of alcohols and amines, aldehydes and amines, as well as symmetrical esters and amines, showing a promising prospect for applications. These unique protocols have been reported using various ruthenium-based catalytic systems. However, challenges still exist in this area. For example, existing catalytic systems usually suffer from low efficiency, high catalyst loading, and lack of structural diversity.
45 citations
TL;DR: In this article, the authors explored the catalytic performance of these heterogeneous Mo, W, and Re oxides systems and found that high dispersion of metal oxide on the support surface and the oxidation state of the metal oxide in the surface of catalyst play crucial factors on the catalysts efficiency.
Abstract: For several decades olefin metathesis reactions over supported Mo, W, and Re oxides catalysts have attracted remarkable interest owning to their growing industrial applications. Therefore, particular attention was devoted to improve the catalytic activity of these catalysts. In the way of exploration of the catalytic performances of these heterogeneous Mo, W, and Re oxides systems, it was found that high dispersion of metal oxide on the support surface and the oxidation state of the metal oxide on the surface of catalyst play crucial factors on the catalysts efficiency. Importantly, these factors have an origin in the preparation methods and the properties of the used supports. In this regard, we have tried to address the various preparation methods of immobilized Mo, W, and Re oxide catalysts as well as properties of supporting material to better understand their impacts on the catalytic performances of these catalysts.
37 citations
TL;DR: The post-synthetic modification of azolium containing MOFs generated a new heterogeneous N-heterocyclic carbene catalyst (1-Pd), which is very active for Sonogashira cross coupling reaction as mentioned in this paper.
35 citations
01 Dec 2016
TL;DR: In this article, a brief discussion of materials applied in technologies with a particular emphasis on biogas cleaning is presented, followed by the alternative properties and possibilities of liquid and solid adsorbents as well as chemical reactions used for biOGas cleaning to produce biomethane suitable as fuel source to replace or reduce fossil fuel consumption.
Abstract: Biomethane is one of the biofuel sources produced from biogas which is an important source of renewable energy. Since it is an alternative and clean energy source, its implementation as fuel source applying established energy infrastructure is an attractive opportunity. However, biogas as a source of biomethane contains undesirable compounds, e.g., H2S, NH3, siloxanes, water, etc. and needs to be decontaminated before usage. Biogas cleaning technologies are presented from a material point of view along with their property modifications. A brief discussion of materials applied in technologies with a particular emphasis on biogas cleaning is followed by the alternative properties and possibilities of liquid and solid adsorbents as well as chemical reactions used for biogas cleaning to produce biomethane suitable as fuel source to replace or reduce fossil fuel consumption.
TL;DR: In this paper, the authors demonstrate the photochemical water oxidation catalysed by three cobalt salophen complexes with different axial ligands in the presence of [Ru(bpy)3]2+ as a photosensitizer and Na2S2O8 as an electron acceptor in phosphate buffer of pH 9 and 7.
TL;DR: Literature sources on metal-organic materials encapsulating versatile porphyrinoids and heme enzymes have been discussed in this article, where general fundamentals and structural and chemical requisites of these architectures are discussed in introduction followed by historical perspectives of the initial composites.
TL;DR: In this paper, the behavior of xLi-MOF-5 was evaluated via phase identification based on XRD, functional group coordination using FTIR and adsorption measurements.
Abstract: Lithium incorporation in metal–organic frameworks during solvothermal synthesis demonstrates a significant modification of the structure chemistry and surface properties of MOFs towards the adsorption selectivity of gas mixtures (CO2 and CH4) at ambient conditions. Variation of the lithium loading (xLi-MOF-5) led to tunability of the interpenetration resulting in materials with substantial differences in their properties. The behavior of xLi-MOF-5 was evaluated via phase identification based on XRD, functional group coordination using FTIR and adsorption measurements applying N2, CO2 and CH4 gas adsorption/desorption analysis. These efforts give rise to a new strategy to tailor MOFs for high efficiency CO2 adsorption and separation.
TL;DR: This work has presented a new lead scaffold for further development of bc1 complex inhibitors, implying the essential role of a 4-substituted phenyl group for the high potency of this promising target of numerous antibiotics and fungicides.
Abstract: The cytochrome bc1 complex (cyt bc1 or complex III) is a promising target of numerous antibiotics and fungicides. With an aim to indentify new lead structures for the bc1 complex, a series of novel inhibitors were discovered from the natural product karrikinolide for the first time. Extensive screening results suggested variable inhibitory activities of these compounds against succinate-cytochrome reductase [SCR, a mixture of respiratory complex II (SQR) and complex III (the bc1 complex)], implying the essential role of a 4-substituted phenyl group for the high potency. Exceptionally, compound 12g showed excellent inhibition potency having an IC50 value in the sub-micromolar range, demonstrating its higher potency than the commercial control amisulbrom by over two orders of magnitude. Further experiments inferred that these newly prepared compounds mainly target the bc1 complex. Seemingly, this work has presented a new lead scaffold for further development of bc1 complex inhibitors.
TL;DR: In this paper, the general formula [Ru 4 (p -cymene) 4 ( N, N ', N '-L) 2 (ox) 2 ][CF 3 SO 3 ] 4 ( 1 -4 ) and [Ru 6 (p-cymenes) 6 ( N, N '', N'', N ″-L] 2(ox) 3 ] 6 ( 5 ) in methanol in the presence of AgO 3 SCF 3 (1 − 4 ) were fully characterized by analytical techniques including elemental analysis, IR spectrosc
TL;DR: In this paper, the authors demonstrate a high yield preparation of large macrocyclic oligo(butadiene)s, preferably the C16 to C44 fraction, from commercial 1,4-polybutadienes by exploring intramolecular backbiting using a series of commercially available Ru catalysts.
TL;DR: TDDFT has been used to investigate the excited state intramolecular proton transfer (ESIPT) mechanism of a new chromophore II and it is demonstrated that the ESIPT reaction can be facilitated based on the photo-excitation.
TL;DR: It was demonstrated that the elongation of the aliphatic chain does not significantly affect the reactivity of the ester, but has a high impact on the activation parameters of the reaction.
Abstract: The reactivity and activation parameters for the ring-opening metathesis polymerization of eight norbornene esters in the presence of a N-chelating Hoveyda–Grubbs II type catalyst were determined using in situ 1H-NMR. The ester molecules differ in the structure of substituent and the location of ester groups. Kinetic studies have shown that effective polymerization constants and activation parameters highly depend on the monomer structures. It was demonstrated that the elongation of the aliphatic chain does not significantly affect the reactivity of the ester, but has a high impact on the activation parameters of the reaction. Branching of the aliphatic substituent has a significant influence on the reactivity and activation parameters. Furthermore, the orientation of the ester substituents in the norbornene ring substantially affects the activation parameters.
TL;DR: In this paper, a second generation of ruthenium catalysts bearing different sized indenylidene ligands, denoted as RuCl2(3-(2,6-xylyl)-1-indenylidsene)(SIMes)(PCy3) 5a, 5b, 5c and 5d, were characterized by NMR, IR, HRMS and elemental analysis.
TL;DR: In this paper, the structure, synthesis and applications of a variety of biomimetic MOFs from an unprecedented angle have been portrayed, and an explanation of catalytic pathways from the mechanistic cycle of the corresponding enzymes is depicted.
Abstract: In this review, we have portrayed the structure, synthesis and applications of a variety of biomimetic MOFs from an unprecedented angle. Synthetic MOF analogues of five distinct enzymes: phosphotriesterase, hydrogenase, cytochrome P450, chymotrypsin and carbonic anhydrase, have been discussed with their skeletal comparison to actual enzymatic active sites as reference, and an explanation of catalytic pathways from the mechanistic cycle of the corresponding enzymes is depicted. We demonstrated critically each of the five discrete situations by assimilating available benchmark researches in an attempt to provide a concise literature source on the ingenious design strategies and versatile biomimetic applications of this domain of materials.
TL;DR: An efficient, easy-to-handle, and mild substitution reaction approach has been developed for the synthesis of phosphonate derivatives, which are very important in the field of industrial, agricultu....
Abstract: An efficient, easy-to-handle, and mild substitution reaction approach has been developed for the synthesis of phosphonate derivatives, which are very important in the field of industrial, agricultu...
TL;DR: A plethora of strategies for immobilizing well-defined metathesis catalysts on solid supports have been developed over the past decades as discussed by the authors, and the main focus was set on the immobilization of ruthenium alkylidenes or so-called Grubbs complexes, as these catalysts are known for their high activity, stability and commercial viability.
Abstract: A plethora of strategies for immobilizing well-defined metathesis catalysts on solid supports have been developed over the past decades. Whereas most reviews on classical heterogeneous metathesis catalyst designs mainly discuss covalent binding approaches, we here extended this topic with non-covalent surface science methods, a research area that gained interest recently. Within this context, the main focus was set on the immobilization of ruthenium alkylidenes or so-called Grubbs complexes, as these catalysts are known for their high activity, stability and commercial viability. Besides giving an overview of different immobilization strategies, the wide diversity of supported Grubbs catalysts also allows for discussing implications of attaching Grubbs catalysts that go beyond the traditional benefits of heterogeneous catalysis, such as easy catalyst separation. More specifically, this Review will summarize several unique opportunities of immobilized homogeneous catalysts in liquid-phase metathesis transformations in terms of impact on activity, stability, and product selectivity, as to highlight the economic potential, but without ignoring possible shortcomings and limitations.
TL;DR: A review of metal-organic polyhedra self-assembly can be found in this article, where the authors focus on each and every application with various unprecedented examples and highlight few challenges still need to be addressed.
Abstract: Self-assembly is a potent synthetic tool that allowed chemists to design numerous complex structures, supramolecules of various shapes from relatively simple starting materials. Metal–organic polyhedra are a rising and promising member of the self-assembled supramolecule family possessing fascinating structures and functionalities directly deriving from the precursor units. During the last two decades, research in this field has been briskly progressed and it is now objective to exemplify various applications such as biomedical, catalysis, molecular sensing, gas adsorption and separation, and synthesis of metal–organic frameworks from polyhedra. This review will be focus on each and every application with various unprecedented examples and highlight few challenges still need to be address.
TL;DR: In this paper, a class of dehydrogenative transformations for amide bond formation have been developed, which are atom-economic and environmentally-benign processes with their respective starting materials of alcohols and amines.
Abstract: Recently, a class of dehydrogenative transformations for amide bond formation have been developed. These transformations are atom-economic and environmentally-benign processes with their respective starting materials of alcohols and amines, aldehydes and amines, as well as symmetrical esters and amines, showing a promising prospect for applications. These unique protocols have been reported using various ruthenium-based catalytic systems. However, challenges still exist in this area. For example, existing catalytic systems usually suffer from low efficiency, high catalyst loading, and lack of structural diversity.