Carboxymethyl ß-Cyclodextrin Assistance for the 4-Nitrophenol Reduction Using Cobalt-Based Layered Double Hydroxides.

Cobalt-aluminum-layered double hydroxides containing carboxymethyl ß-cyclodextrin (CMßCD) were synthesized by coprecipitation and evaluated as a cobalt source for the 4-nitrophenol reduction in an aqueous medium. Several physicochemical techniques (XRD, FTIR, TGA) indicated the intercalation of the anionic cyclodextrin without damages to the hydrotalcite-type structure. These lamellar cobalt-aluminum hybrid materials (CoAl_CMßCD) were evaluated in the 4-nitrophenol reduction and showed higher activities in comparison with the CMßCD-free standard material (CoAl_CO3). To rationalize these results, a set of experimental controls going from physical mixtures of CoAl_CO3 with different cyclodextrins to other cobalt-based materials were investigated, highlighting the beneficial effects of both the layered double hydroxide and CMßCD-based hybrid structures. CMßCD also showed a beneficial effect as an additive during the 4-nitrophenol reduction. CoAl_CO3, dispersed in a fresh CMßCD solution could be re-used for five successive cycles without the loss of activity.

Hollow NiCo2O4-ZnO-Co3O4-/N-C Micro-Cage for Synergistic Bisphenol A Degradation by Activating Persulfate.

The NiCo2O4-ZnO-Co3O4-/N-C micro-cage was successfully synthesized by calcination of the precursor obtained from a hollow ZIF-8/ZIF-67 with nickel nitrate. The preparation process concerning ion exchange and leaching was illustrated by the investigation of the composition and structure of the composites. As a catalyst for the activation of persulfate (PDS) to degrade bisphenol A (BPA), it was discovered that the BPA degradation in the presence of NiCo2O4-Co3O4-ZnO/N-C was more efficient than the solids obtained by ZIF-67 with nickel nitrate, indicated by the sevenfold increase of the apparent reaction rate. The further electrochemical analysis evidenced that the electron transfer was more easily accomplished in the system of BPA-PDS-NiCo2O4-Co3O4-ZnO/N-C. This enhanced activity of NiCo2O4-Co3O4-ZnO/N-C was mainly due to the hollow structure, the synergistic effect of NiCo2O4, as well as the smaller size of the active species, which facilitated the transportation of molecules and ions as well as the activation of PDS.

First Steps to Rationalize Host-Guest Interaction between α-, ß-, and γ-Cyclodextrin and Divalent First-Row Transition and Post-transition Metals (Subgroups VIIB, VIIIB, and IIB).

Cyclodextrins (CDs) are cyclic oligosaccharides mainly composed of six, seven, and eight glucose units, so-called α-, ß-, and γ-CDs, respectively. They own a very particular molecular structure exhibiting hydrophilic features thanks to primary and secondary rims and delimiting a hydrophobic internal cavity. The latter can encapsulate organic compounds, but the former can form supramolecular complexes by hydrogen-bonding or electrostatic interactions. CDs have been used in catalytic processes to increase mass transfer in aqueous-organic two-phase systems or to prepare catalysts. In the last case, interaction between CDs and metal salts was considered to be a key point in obtaining highly active catalysts. Up to now, no work was reported on the investigation of factors affecting the binding of metal to CD. In the study herein, we present the favorable combination of electrospray ionization coupled to mass spectrometry [ESI-MS(/MS)] and density functional theory molecular modeling [B3LYP/Def2-SV(P)] to delineate some determinants governing the coordination of first-row divalent transition metals (Mn2+, Co2+, Ni2+, Cu2+, and Fe2+) and one post-transition metal (Zn2+) with α-, ß-, and γ-CDs. A large set of features concerning the metal itself (ionic radius, electron configuration, and spin state) as well as the complexes formed (the most stable conformer, relative abundance in MS, CE50 value in MS/MS, binding energy, effective coordination number, average bond lengths, binding site localization, bond dissociation energies, and natural bond orbital distribution) were screened. Taking into account all of these properties, various selectivity rankings have been delineated, portraying differential association/dissociation behaviors. Nonetheless, unique 3D topologies for each CD-metal complex were emphasized. The combination of these approaches brings a stone for building a compendium of molecular features to serve as a suitable descriptor or predictor for a better first round rationalization of catalytic activities.

Robust Ruthenium Catalysts Supported on Mesoporous Cyclodextrin-Templated TiO2-SiO2 Mixed Oxides for the Hydrogenation of Levulinic Acid to γ-Valerolactone.

In this paper, we present a versatile template-directed colloidal self-assembly method for the fabrication in aqueous phase of composition-tuned mesoporous RuO2@TiO2-SiO2 catalysts. Randomly methylated ß-cyclodextrin/Pluronic F127 supramolecular assemblies were used as soft templates, TiO2 colloids as building blocks, and tetraethyl orthosilicate as a silica source. Catalysts were characterized at different stages of their synthesis using dynamic light scattering, N2-adsorption analysis, powder X-ray diffraction, temperature programmed reduction, high-resolution transmission electron microscopy, high-angle annular bright-field and dark-field scanning transmission electron microscopy, together with EDS elemental mapping. Results revealed that both the supramolecular template and the silica loading had a strong impact on the pore characteristics and crystalline structure of the mixed oxides, as well as on the morphology of the RuO2 nanocrystals. Their catalytic performance was then evaluated in the aqueous phase hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) under mild conditions (50 °C, 50 bar H2). Results showed that the cyclodextrin-derived catalyst displayed almost quantitative LA conversion and 99% GVL yield in less than one hour. Moreover, this catalyst could be reused at least five times without loss of activity. This work offers an effective approach to the utilization of cyclodextrins for engineering the surface morphology of Ru nanocrystals and pore characteristics of TiO2-based materials for catalytic applications in hydrogenation reactions.

Polyoxometalate, Cationic Cluster, and γ-Cyclodextrin: From Primary Interactions to Supramolecular Hybrid Materials.

Herein, we report on a three-component supramolecular hybrid system built from specific recognition processes involving a Dawson-type polyoxometalate (POM), [P2W18O62]6-, a cationic electron-rich cluster [Ta6Br12(H2O)6]2+, and γ-cyclodextrin (γ-CD). Such materials have been investigated using a bottom-up approach by studying the specific interactions between γ-CD and both types of inorganic units. Their ability to interact has been investigated in the solid state by single-crystal X-ray diffraction (XRD) and in solution using multinuclear NMR methods (including DOSY, EXSY, and COSY), electrospray ionization mass and UV-vis spectroscopies, electrochemistry, and isothermal titration calorimetry experiments. Single-crystal XRD analysis reveals that POM:γ-CD constitutes a highly versatile system which gives aggregates with 1:1, 1:2, and 1:3 stoichiometry. Surprisingly, these arrangements exhibit a common feature wherein the γ-CD moiety interacts with the Dawson-type POMs through its primary face. We present also the first structural model involving an octahedral-type metallic cluster with γ-CD. XRD study reveals that the cationic [Ta6Br12(H2O)6]2+ ion is closely embedded within two γ-CD units to give a supramolecular ditopic cation, suitable to be used as a linker within extended structure. Solution study demonstrates clearly that pre-associations exist in solution, for which binding constants and thermodynamic parameters have been determined, giving preliminary arguments about the chaotropic nature of the inorganic ions. Finally, both building blocks, i.e., the ditopic supramolecular cation {[Ta6Br12(H2O)6]@2CD}2+ and the Dawson-type anion, react together to give a three-component, well-ordered hybrid material derived either as a supramolecular hydrogel or single crystals. The solid-state structure shows an unprecedented helicoidal tubular chain resulting from the periodic alternation of POM and supramolecular cation, featuring short hydrogen-bonding contacts between the electron-poor POM and electron-rich cluster. The 1D tubular ionic polymer observed in the single crystals should make it possible to understand the long-range ordering observed within the hydrogel hybrid material. The supramolecular chemical complementarities between the γ-CD-based ditopic cation and POM open a wide scope for the design of hybrid materials that accumulate synergistic functionalities.

Nonconventional Three-Component Hierarchical Host-Guest Assembly Based on Mo-Blue Ring-Shaped Giant Anion, γ-Cyclodextrin, and Dawson-type Polyoxometalate.

In this communication, we report on a noteworthy hybrid supramolecular assembly built from three functional components hierarchically organized through noncovalent interactions. The one-pot synthesis procedure leads to the formation of large Mo-blue ring-shaped anion {Mo154}, which contains the supramolecular adduct based on the symmetric encapsulation of the Dawson-type [P2W18O62]6- anion by two γ-cyclodextrin units. Such a nanoscopic onion-like structure, noted [P2W18O62]@2γ-CD@{Mo154} has been characterized by single-crystal X-ray diffraction, thus demonstrating the capability of the giant inorganic torus to develop relevant supramolecular chemistry, probing the strong affinity of the inner and outer faces of the γ-CD for the polyoxometalate surfaces. Furthermore, interactions and behavior in solution have been studied by multinuclear NMR spectroscopy, which supports specific interactions between γ-CD and POM units. Finally, the formation of this three-component hybrid assembly from one-pot procedure, in water and using nearly stoichiometric conditions, is discussed in terms of the driving forces orchestrating this highly efficient multilevel recognition process.

Selective Secondary Face Modification of Cyclodextrins by Mechanosynthesis.

α-, ß-, and γ-cyclodextrins (CDs) were modified on their secondary face by mechanosynthesis at room temperature using a laboratory-scale ball-mill. Mono-2-tosylated α-, ß-, and γ-CDs were obtained in good yield from mixtures of native α-, ß-, and γ-CDs, respectively, N-tosylimidazole, and an inorganic base, with each of them being in the solid state. The yields appeared to be dependent upon the nature of the base and the reaction time. A kinetic monitoring by (1)H NMR spectroscopy demonstrated that the highest yields in mono-2-tosyl-CDs were measured using KOH as a base in very short reaction times (up to 65% in 80 s). Mono-(2,3-manno-epoxide) α-, ß-, and γ-CDs were subsequently synthesized by ball-milling a mixture of monotosylated α-, ß-, and γ-CDs, respectively, and KOH. The characterization of the modified CDs was carried out by X-ray diffraction, mass spectrometry, solid-state NMR, and diffuse reflectance UV-vis (DR UV-vis) spectroscopies. Clues to the supramolecular arrangement of the molecules in the solid state provide information on the reaction mechanism.

Understanding the role of cyclodextrins in the self-assembly, crystallinity, and porosity of titania nanostructures.

A series of mesoporous titania photocatalysts with tailorable structural and textural characteristics was prepared in aqueous phase via a colloidal self-assembly approach using various cyclodextrins (CDs) as structure-directing agents. The photocatalysts and the structure-directing agents were characterized at different stages of the synthesis by combining X-ray diffraction, N2-adsorption, field emission scanning electron microscopy, transmission electron microscopy, UV-visible spectroscopy, dynamic light scattering, and surface tension measurements. The results demonstrate that the cyclic macromolecules efficiently direct the self-assembly of titania colloids, resulting in a fine-tuning of the crystal phase composition, crystallite size, surface area, particle morphology, pore volume, and pore size. Depending on the chemical nature of the substituents in the cyclodextrin ring, synergistic or competitive effects arising from the adsorption capacity of these cyclic oligosaccharides onto titania surface, surface-active properties, and ability to aggregate in water by intermolecular interactions were found to substantially impact the characteristics of the final material. We propose that, in contrast to the native cyclodextrins, which tend to favor the local agglomeration of titania nanoparticles due to the strong intermolecular interactions, the substitution of hydroxyl groups by a relatively large number of methoxyl or 2-hydropropoxyl ones in the ß-CD derivatives allows for creating smoother interfaces, thus facilitating the self-assembly of the colloids in a more homogeneous network. The photocatalytic activity of those titania materials was evaluated in the photodegradation of a toxic herbicide, phenoxyacetic acid, and was correlated to the structural and textural characteristics of the photocatalysts.

Effect of Functional Group on the Catalytic Activity of Lipase B from Candida antarctica Immobilized in a Silica-Reinforced Pluronic F127/α-Cyclodextrin Hydrogel.

Surface modification plays a key role in the fabrication of highly active and stable enzymatic nanoreactors. In this study, we report for the first time the effect of various functional groups (epoxy, amine, trimethyl, and hexadecyl) on the catalytic performance of lipase B from Candida antarctica (CALB) incorporated within a monolithic supramolecular hydrogel with multiscale pore architecture. The supramolecular hydrogel formed by host-guest interactions between α-cyclodextrin (α-CD) and Pluronic F127 was first silicified to provide a hierarchically porous material whose surface was further modified with different organosilanes permitting both covalent anchoring and interfacial activation of CALB. The catalytic activity of nanoreactors was evaluated in the liquid phase cascade oxidation of 2,5-diformylfuran (DFF) to 2,5-furandicarboxylic acid (FDCA) under mild conditions. Results showed that high FDCA yields and high efficiency conversion of DFF could be correlated with the ability of epoxy and amine moieties to keep CALB attached to the carrier, while the trimethyl and hexadecyl groups could provide a suitable hydrophobic-hydrophilic interface for the interfacial activation of lipase. Cationic cross-linked ß-CD was also evaluated as an enzyme-stabilizing agent and was found to provide beneficial effects in the operational stability of the biocatalyst. These supramolecular silicified hydrogel monoliths with hierarchical porosity may be used as promising nanoreactors to provide easier enzyme recovery in other biocatalytic continuous flow processes.

Oxidation of 2,5-diformfylfuran to 2,5-furandicarboxylic acid catalyzed by Candida antarctica Lipase B immobilized in a cyclodextrin-templated mesoporous silica. The critical role of pore characteristics on the catalytic performance.

HYPOTHESIS: Porous silica has been extensively used as suitable carrier for the immobilization of various enzymes. Randomly Methylated ß-Cyclodextrin (RaMeßCD) has surface active properties and very high solubility in water and could therefore be used as template in the fabrication of silica particles with tunable pore size. EXPERIMENTS: Silica particles were prepared by sol-gel process in alkaline medium with and without use of RaMeßCD. Lipase Bfrom Candida antarctica (CALB) was either incorporated within the pores of RaMeßCD-derived support or covalently attached on the surface of CD-free silica particles and its catalytic performance was assayed in the oxidation of 2,5-diformylfuran (DFF) to 2,5-furandicarboxylic acid (FDCA). Enzymatic reactors were characterized by N2-adsorption analysis, small angle XRD, TG/DSC experiments, ATR-FTIR spectroscopy, HR-TEM and LSCM, while reaction products were determined based on 1H NMR spectroscopy combined with HPLC. FINDINGS: Results showed that the use of RaMeßCD as structure directing agent led to mesoporous silica composed of uniform 8 nm-sized particles with 11 nm-sized mesopores compatible with the dimensions of CALB (3.0 nm × 4.0 nm × 5.0 nm). Incorporation of CALB within the pores of RaMeßCD-derived silica caused almost a two-fold increase in specific activity after 7 h at 40 °C when compared to lipase immobilized on the surface of CD-free silica particles (33.2 µmol g-1 min-1vs. 14.4 µmol g-1 min-1). Moreover, the RaMeßCD-derived biocatalyst demonstrated enhanced operational stability during the recycling experiments, retaining more than 90% of its initial activity after five 24 h-reaction cycles. These findings open up new avenues for future research on the use of cyclodextrins in the development of enzyme-based nanoreactors.

Confinement of Candida Antarctica Lipase B in a Multifunctional Cyclodextrin-Derived Silicified Hydrogel and Its Application as Enzymatic Nanoreactor.

Supramolecular hydrogels with a three-dimensional cross-linked macromolecular network have attracted growing scientific interest in recent years because of their ability to incorporate high loadings of bioactive molecules such as drugs, proteins, antibodies, peptides, and genes. Herein, we report a versatile approach for the confinement of Candida antarctica lipase B (CALB) within a silica-strengthened cyclodextrin-derived supramolecular hydrogel and demonstrate its potential application in the selective oxidation of 2,5-diformylfuran (DFF) to 2,5-furandicarboxylic acid (FDCA) under mild conditions. The enzymatic nanoreactor was deeply characterized using thermogravimetric analysis, Fourier transform infrared spectroscopy, N2-adsorption, dynamic light scattering, UV-visible spectroscopy, transmission electron microscopy, scanning electron microscopy, and confocal laser scanning microscopy, while the reaction products were established on the basis of 1H nuclear magnetic resonance spectroscopy combined with high-performance liquid chromatography. Our results revealed that while CALB immobilized in conventional sol-gel silica yielded exclusively 5-formylfuran-2-carboxylic acid (FFCA), confinement of the enzyme in the silicified hydrogel imparted a 5-fold increase in DFF conversion and afforded 67% FDCA yield in 7 h and almost quantitative yields in less than 24 h. The hierarchically interconnected pore structure of the host matrix was found to provide a readily accessible diffusion path for reactants and products, while its flexible hydrophilic-hydrophobic interface was extremely beneficial for the interfacial activation of the immobilized lipase.

Robust Mesoporous CoMo/γ-Al2O3 Catalysts from Cyclodextrin-Based Supramolecular Assemblies for Hydrothermal Processing of Microalgae: Effect of the Preparation Method.

Hydrothermal liquefaction (HTL) is a promising technology for the production of biocrude oil from microalgae. Although this catalyst-free technology is efficient under high-temperature and high-pressure conditions, the biocrude yield and quality can be further improved by using heterogeneous catalysts. The design of robust catalysts that preserve their performance under hydrothermal conditions will be therefore very important in the development of biorefinery technologies. In this work, we describe two different synthetic routes (i.e., impregnation and cyclodextrin-assisted one-pot colloidal approach), for the preparation in aqueous phase of six high surface area CoMo/γ-Al2O3 catalysts. Catalytic tests performed on the HTL of Nannochloropsis gaditana microalga indicate that solids prepared by the one-pot colloidal approach show higher hydrothermal stability and enhanced biocrude yield with respect to the catalyst-free test. The positive effect of the substitution of the block copolymer Tetronic T90R4 for Pluronic F127 in the preparation procedure was evidenced by diffuse reflectance UV-visible spectroscopy, X-ray diffraction, N2-adsorption-desorption, and H2-temperature-programmed reduction measurements and confirmed by the higher quality of the obtained biocrude, which exhibited lower oxygen content and higher-energy recovery equal to 62.5% of the initial biomass.

Unexpected multifunctional effects of methylated cyclodextrins in a palladium charcoal-catalyzed Suzuki-Miyaura reaction.

[reaction: see text] Native and modified cyclodextrins (CDs) have shown polyvalent properties in a biphasic Pd/C-catalyzed Suzuki-Miyaura reaction. In addition to their mass transfer ability, the CDs favored the dispersion of the catalyst in water. With the randomly methylated CDs (RaMe-beta-CD), the gains of initial activities were multiplied by factors between 3.8 and 343 depending on the nature of the substrates. The reusability of the system was also demonstrated.

Photocatalysis of Volatile Organic Compounds in water: Towards a deeper understanding of the role of cyclodextrins in the photodegradation of toluene over titanium dioxide.

HYPOTHESIS: Cyclodextrin-assisted photodegradation of toluene was investigated in water in the presence of a photo-irradiated commercial titanium dioxide photocatalyst. It was expected that cyclodextrins could form water-soluble supramolecular host/guest complexes with the toluene and thus promote the approach of the pollutant on the TiO2 surface and enhance the phototocatalytic oxidation efficiency. EXPERIMENTS: Photodegradation kinetics of toluene were investigated under UV-C and near-visible light radiation in aqueous suspensions of TiO2. Impact of cyclodextrin (CD) on the photocatalytic efficiency of TiO2 was evaluated with different cyclodextrins: α-CD, ß-CD, γ-CD and RAME-ß-CD. Host-guest association constants were determined by static headspace gas chromatography and affinity of cyclodextrins for the TiO2 surface by isothermal adsorption studies. Issue of the cyclodextrin stability during the degradation process was examined using Total Organic Carbon, NMR and MALDI-TOF analyses. FINDINGS: Toluene could be fully mineralized by TiO2 in water within hours, even if the presence of cyclodextrin caused a delay in the photodegradation process. The chemical nature of cyclodextrins was found to exert a significant influence on the extent of inhibitory effect, which was discussed in terms of balance between solubilization efficiency, substrate protection and coverage of active sites of TiO2 by competitive adsorption. The cyclodextrin degradation was also studied and discussed.

Biphasic Palladium-Catalyzed Hydroesterification in a Polyol Phase: Selective Synthesis of Derived Monoesters.

The palladium-catalyzed hydroesterification reaction was performed with polyols and olefins in a liquid/liquid biphasic system composed of unreacted polyol on the one hand and apolar reaction products/organic solvents on the other hand. The palladium-based catalyst was immobilized in the polyol phase thanks to the use of cationic triarylphosphines possessing pendent protonated amino groups in the acidic reaction medium or to the sulfonated phosphine TPPTS (trisodium triphenylphosphine-3,3',3''-trisulfonate). Owing to the insolubility of the products in the catalytic phase, this approach allowed the synthesis of monoesters of polyols with high selectivities as well as the easy separation of the catalyst through simple decantation.

Self-assembled metastable γ-Ga2O3 nanoflowers with hexagonal nanopetals for solar-blind photodetection.

Metastable γ-Ga2O3 nanoflowers assembled from hexagonal nanopetals are successfully constructed by the oxidation of metallic Ga in acetone solution. The nanoflowers with a hollow interior structure exhibit a short response time and a large light-current-dark-current ratio under a relatively low bias voltage, suggesting an especially important potential application in solar-blind photodetection.

Synthesis of 1,4:3,6-dianhydrohexitols diesters from the palladium-catalyzed hydroesterification reaction.

The hydroesterification of alpha olefins has been used to synthesize diesters from bio-based secondary diols: isosorbide, isomannide, and isoidide. The reaction was promoted by 0.2% palladium catalyst generated in situ from palladium acetate/triphenylphosphine/para-toluene sulfonic acid. Optimized reaction conditions allowed the selective synthesis of the diesters with high yields and the reaction conditions could be scaled up to the synthesis of hundred grams of diesters from isosorbide and 1-octene with solvent-free conditions.

Cyclodextrins adsorbed onto activated carbons: preparation, characterization, and effect on the dispersibility of the particles in water.

We have investigated the adsorption equilibrium of selected cyclodextrins onto activated carbons. A number of parameters were examined including the type of carbon material, the size of macrocyclic cavity, and the chemical nature of the oligosaccharide (e.g., neutral, anionic, or cationic cyclodextrin). Adsorption isotherm studies revealed that the maximum amount of cyclodextrin immobilized on the carbon surface is obtained for the native ß-CD, while the adsorption capacity of the ionic cyclodextrins derivatives strongly depends on the net surface charge of the activated carbon. The affinity of cyclodextrins for activated carbons was further utilized to prepare modified activated carbons containing controlled amounts of cyclodextrins through an adsorption process. The resulting materials were characterized by N(2) adsorption-desorption volumetric measurements, FTIR and Raman spectroscopy, while the quantitative determination of the oligosaccharide content on activated carbons was performed by gravimetric measurements. On the basis of the Turbiscan results, it was found that the chemical structure of cyclodextrins, which are incorporated in the carbon framework, had significant influence on the dispersibility and stabilization of the solid particles in water. Agglomeration and precipitation of the carbon particles were markedly suppressed with substituted cyclodextrins whose hydroxyl groups were partially substituted by methyl or alkylammonium groups.