Heterogeneous Reaction Conditions Research Articles

The Role of Metal and Acid Sites in the Liquid‐phase Hydrodeoxygenation of Lignin‐derived Phenolic Dimers

AbstractBio‐oil obtained from the depolymerization of lignocellulosic biomass is a potential alternative source to replace fossil fuels. However, due to high oxygen content, the bio‐oil must be upgraded. In this direction, the hydrodeoxygenation reaction (HDO) is widely applied. Considering the complex chemical composition of the bio‐oil, a variety of model molecules have been used in the literature to study the mechanism of the HDO process. In this work, we discuss heterogeneous catalysts and reaction conditions (temperature, pressure, and solvent) generally used for the HDO of dimeric aryl ethers representative of the main ether linkages present in the lignin:α‐O‐4, β‐O‐4, and 4‐O‐5. The present work aims to shed light on the role of metal and acid sites and understand the influence of the reaction conditions on the reaction pathways.

Cellulose acylation in homogeneous and heterogeneous media: Optimization of reactions conditions

The dependence of the DS on the acid anhydride/anhydroglucose unit ((RCO)2O/AGU) molar ratio was correlated using second-order polynomials. The regression coefficients of the (RCO)2O/AGU terms showed that increasing the length of the RCO group of the anhydride led to lower values of DS. For acylation under heterogeneous reaction conditions, the following were employed: acid anhydrides and butyryl chloride as acylating agents; iodine as a catalyst; N,N-dimethylformamide (DMF) as a solvent, pyridine, and triethylamine as solvents and catalysts. For acylation using acetic anhydride plus iodine, the values of DS correlate with reaction time by a second-order polynomial. Due to its role as a polar solvent and a nucleophilic catalyst, pyridine was the most effective base catalyst, independent of the acylating agent (butyric anhydride and butyryl chloride).

Hydrogen peroxide disproportionation: time-resolved optical measurements of spectra, scattering and imaging combined with correlation analysis and simulations

We study how time-dependent optical measurements of spectra, scattering, and imaging can be used to add to the understanding of heterogeneous reactions, compared to work performed using tools developed for homogeneous reactions. Using hydrogen peroxide disproportionation by potassium permanganate as a model reaction, we measure the entire spectrum over reaction time, enabling a clear and useful correlation analysis and assignment of chemical species in heterogeneous conditions. We measure time-dependent dynamic light scattering to study oxygen nanobubble product formation kinetics and equilibrium. We perform macroscopic video-rate reaction imaging and information-theoretic analysis to characterize reaction and transport contributions to the observed signal. To illustrate the differences arising from measuring sample subsets vs the entire system, we integrate stochastic and macroscopic numerical simulations of reaction-diffusion to study homogeneous and heterogeneous reaction conditions. We hope the tools presented here may help understanding other chemical reactions in similar conditions.

Characterisation of reduction state of cystine linkages on wool fibre surface under heterogeneous reaction conditions

As a natural biomaterial with outstanding properties, keratin fibres hold promising potential in many application fields. The reduction of disulphides in keratin to the corresponding thiols plays a central role e.g. in modification and functionalisation of wool, in hair cosmetics, as well as in advanced applications using keratin as biomaterial. To achieve controlled conditions, the need for a quantitative determination of thiols on the solid wool fibre is evident. This work presents an advanced method of heterogeneous potentiometric back titration method for thiol detection in intact keratin fibres. First, keratin is reductively treated with NaBH4, then the thiol content in keratin is determined using K3[Fe(CN)6] and K2CrO4 as reagents and potentiometric endpoint detection. Thiol concentration in the range between 6.83 and 26.17 (±2.13) μmol/g can be detected with the heterogeneous back titration. Thus, the method is simple in execution and reliable in performance and of significant potential, both as scientific technique to quantify thiols in insoluble keratin material, as well as for process and quality control in industry.

Two fungal flavonoid-specific glucosidases/rutinosidases for rutin hydrolysis and rutinoside synthesis under homogeneous and heterogeneous reaction conditions

The glycosidases within GH5-23 cleave the glycosidic bond of β-glucosylated or rutinosylated flavonoids. Moreover, by virtue of their transglycosylation activity, glycoconjugates with glucosyl and rutinosyl moieties are accessible. Here we report the biochemical characterization and biotechnological assessment of two heterologously expressed members of GH5-23—McGlc from Mucor circinelloides and PcGlc from Penicillium chrysogenum. Both enzymes exhibited the highest hydrolytic activities with quercetin-3-β-O-glucopyranoside, whereas lower specificity constants were determined with the rutinosides narcissin, rutin and hesperidin. High stabilities against thermal, ethanol and dimethyl sulfoxide-induced inactivation, a very limited secondary hydrolysis of the formed transglycosylation products, and no detectable product inhibition were additional features appropriate for biotechnological applications. The enzymes were compared in their efficiencies to hydrolyze rutin and to synthesize 2-phenylethyl rutinoside under homogeneous and heterogeneous reaction conditions using high rutin concentrations of 100 and 300 mM. Highest transglycosylation efficiencies were achieved with fully dissolved rutin in reaction mixtures containing 25% dimethyl sulfoxide. Molecular docking and multiple sequence alignments suggest that the hydrophobic environment of aromatic residues within the + 1 subsite of GH5-23 glycosidases is very important for the binding of flavonoid glucosides and rutinosides.

Reactions of Sodium Diisopropylamide: Liquid-Phase and Solid-Liquid Phase-Transfer Catalysis by N,N,N',N″,N″-Pentamethyldiethylenetriamine.

Sodium diisopropylamide (NaDA) in N,N-dimethylethylamine (DMEA) and DMEA-hydrocarbon mixtures with added N,N,N',N″,N″-pentamethyldiethylenetriamine (PMDTA) reacts with alkyl halides, epoxides, hydrazones, arenes, alkenes, and allyl ethers. Comparisons of PMDTA with N,N,N',N'-tetramethylethylenediamine (TMEDA) accompanied by detailed rate and computational studies reveal the importance of the trifunctionality and κ2-κ3 hemilability. Rate studies show exclusively monomer-based reactions of 2-bromooctane, cyclooctene oxide, and dimethylresorcinol. Catalysis with 10 mol % PMDTA shows up to >30-fold accelerations (kcat > 300) with no evidence of inhibition over 10 turnovers. Solid-liquid phase-transfer catalysis (SLPTC) is explored as a means to optimize the catalysis as well as explore the merits of heterogeneous reaction conditions.

Reactivity of substrates with multiple competitive reactive sites toward NBS under neat reaction conditions promoted by visible light

Regioselectivity of visible-light-induced transformations of a range of (hetero)aryl alkyl-substituted ketones bearing several competitive reactive sites (α-carbonyl, benzyl and aromatic ring) with N-bromosuccinimide (NBS) was studied under solvent-free reaction conditions (SFRC) and in the absence of inert-gas atmosphere, radical initiators and catalysts. An 8-W energy-saving household lamp was used for irradiation. Heterogeneous reaction conditions were dealt with throughout the study. All substrates were mono- or dibrominated at the α-carbonyl position, and additionally, some benzylic or aromatic bromination was observed in substrates with benzylic carbon atoms or electron-donating methoxy groups, respectively. Surprisingly, ipso-substitution of the acyl group with a bromine atom took place with (4-methoxynaphthyl) alkyl ketones. While the addition of the radical scavenger TEMPO (2,2,6,6-tetramethylpiperidin-1-yloxy) decreased the extent of α- and ring bromination, it completely suppressed the benzylic bromination and α,α-dibromination with NBS under SFRC.

Harnessing Additional Capability from in Water Reaction Conditions: Aldol versus Knoevenagel Chemoselectivity

AbstractAldol reaction chemoselectivity, racemic or enantioselective, has not been previously demonstrated in the presence of Knoevenagel active functional groups. Here, we show that unhindered β‐diketones remain unreacted while a ketone moiety undergoes a highly enantioselective aldol desymmetrization resulting in three new stereogenic centers using in water reaction conditions. A mechanistic hypothesis for the chemoselective formation of either aldol or Knoevenagel products is presented. It elucidates how these amino acid catalyzed reactions completely suppress formation of the expected Knoevenagel product under in water (heterogeneous) reaction conditions, but not when water is present as a dissolved cosolvent (homogeneous). Finally, the developed hypothesis reinforces and expands the role of water at an organic‐water interface.magnified image

A convenient strategy to synthesize highly tunable gelatin methacryloyl with very low gelation temperature

Gelatin methacryloyl (GelMA) is a polymeric derivative of gelatin (Gel) widely used in tissue engineering, as well as in wound dressing and drug delivery field. This work offers an alternative and convenient method for the synthesis and characterization of GelMA. In particular, the methacrylation was carried out under homogeneous single-phase reaction conditions, which allows of obtaining a good reproducibility of the derivatization degree of the polymer in a simple and fast way. The experimental conditions were adequately optimized to have the methacrylation of only ε-amino groups of lysine and hydroxylysine, as confirmed by FT-IR and 1H NMR analysis. The degree of derivatization of GelMA was determined using an internal standard applied to 1H NMR analysis. Based on these measurements, it was found that the optimized reaction proceeds to complete functionalization of ε-amino groups of lysine and hydroxylysine. The effect of the reaction conditions on the rheological properties of GelMA was investigated through temperature sweep experiments and compared with those of the polymer obtained under traditional heterogeneous reaction conditions. A significant difference was found in the gelation temperature of GelMA synthesized following the two different procedures. In particular, the proposed single-phase synthetic protocol gave a polymer which behaves like a solution when used at 10% w/v concentration and even at temperatures as low as 5 °C, whereas the polymer obtained with the classic biphasic procedure behaves like a gel within the same range of temperatures and when used at the same concentration. These results are particularly interesting as they could open GelMA to new applications particularly in the biomedical field.

Temperature-responsive smart tracers for field-measurement of inter-well thermal evolution: Heterogeneous kinetics and field demonstration

Temperature-responsive smart tracers enable advanced warning of a “premature thermal breakthrough” and may therefore improve reservoir management and reduce financial risk. A successful calculation of inter-well fluid temperatures requires that temperature-dependent kinetics are known, which typically result from homogeneous batch reactor experiments. However, recent meso-scale field experiments at the Altona Field Laboratory involving fluid flow in a discretely-fractured reservoir suggest that silica-fluid interfaces may accelerate hydrolysis kinetics. Here, the Arrhenius parameters of phenyl acetate hydrolysis are investigated under heterogeneous reaction conditions in packed-bed column experiments. The breakthrough curve of the reaction product is compared to an inert reference tracer (carbon-cored nanoparticles). Temperatures experienced during field testing ranging from 10 to 40 ℃ were studied using a phosphate buffer solution to maintain a near-neutral pH, as found in the reservoir. The empirically-determined pre-exponential factor and activation energy values are subsequently used in a first-order kinetic model to improve calculations of effective reservoir temperatures for these meso-scale field tests. The results suggest that hydrolysis reactions can directly monitor inter-well reservoir temperatures, but only if the influence of solid-fluid interactions are carefully accounted for.

Hydrothermal intercalation for the synthesis of novel three-dimensional hierarchically superstructured carbons composed of graphene-like ultrathin nanosheets

Hierarchical superstructured carbons (HSCs) assembled by low-dimensional fibers or sheets have held a great prospect in energy applications on account of their stable intersecting carbon network, large accessible surface area and optimized ion transfer. However, the synthesis of HSCs with well-defined nanostructure is still a challenge. Herein, a novel HSC is developed on the basis of constructing sandwich-type alternate layered carbon/Zn2SiO4 composite by an intercalation growth strategy. This type of HSC is assembled by graphene-like ultrathin carbon nanosheets with a thickness less than 1 nm (2–3 carbon layers), and displays rigid and stable 3D network owing to the interconnected self-supported nanosheets. The in-depth investigation reveals that the growth of HSC complies with a unique “octopus model”, and both the homogeneous and heterogeneous reaction conditions are applicable for the synthesis system. More importantly, the as-constructed superstructure can be coated on the surface of any SiO2-containing substrates, which offers an avenue to design superstructured carbons with various morphologies. With combination of the large accessible surface area and optimized nanostructure for ion transfer and electron immigration, the as-prepared HSC demonstrates superior performance in electronic double-layer capacitor.

A green solid acid catalyst 12-tungstophosphoric acid H3[PW12O40] supported on g-C3N4 for synthesis of quinoxalines

A green Keggin-type heteropoly-12-tungstophosphoric acid, (H3[PW12O40].12H2O) supported on graphitic carbon nitride g-C3N4 (HPW/g-C3N4-40), was developed for one-pot synthesis of quinoxaline derivatives from 1,2-diketone and 1,2-diamines. Use of green solvent, heterogeneous reaction condition, simple workup procedure, short reaction time and reusability of the catalyst are the advantages of this protocol.

The Quest for the Ideal Base: Rational Design of a Nickel Precatalyst Enables Mild, Homogeneous C-N Cross-Coupling.

Palladium-catalyzed amination reactions using soluble organic bases have provided a solution to the many issues associated with heterogeneous reaction conditions. Still, homogeneous C-N cross-coupling approaches cannot yet employ bases as weak and economical as trialkylamines. Furthermore, organic base-mediated methods have not been developed for Ni(0/II) catalysis, despite some advantages of such systems over those employing Pd-based catalysts. We designed a new air-stable and easily prepared Ni(II) precatalyst bearing an electron-deficient bidentate phosphine ligand that enables the cross-coupling of aryl triflates with aryl amines using triethylamine (TEA) as base. The method is tolerant of sterically congested coupling partners, as well as those bearing base- and nucleophile-sensitive functional groups. With the aid of density functional theory (DFT) calculations, we determined that the electron-deficient auxiliary ligands decrease both the pKa of the Ni-bound amine and the barrier to reductive elimination from the resultant Ni(II)-amido complex. Moreover, we determined that the preclusion of Lewis acid-base complexation between the Ni catalyst and the base, due to steric factors, is important for avoiding catalyst inhibition.

Eco-friendly heteropoly acid supported on natural clay for the synthesis of calix[4]resorcinarene derivatives

The catalytic activity of green catalyst heteropoly-11-tungsto-1-vanadophosphoric acid, H4[PVW11O40] (HPV) supported on activated natural clay (HPVAC) has been tested towards the synthesis of calix[4]resorcinarene under solvent-free condition. It is a one-pot multi-component condensation reaction of four moles of aromatic aldehydes with four moles of resorcinol. The advantages of the protocol, solvent-free heterogeneous reaction condition, simple workup procedure, short reaction time, high yield of products and reusability of the catalyst make this method to declare as green approach for synthesis of calix[4]resorcinarene.

Nanoporous Na+-Montmorillonite Perchloric Acid as an Efficient and Recyclable Catalyst for the Chemoselective Protection of Hydroxyl Groups.

Nanoporous Na+-montmorillonite perchloric acid as a novel heterogeneous reusable solid acid catalyst was easily prepared by treatment of Na+-montmorillonite as a cheap and commercially available support with perchloric acid. The catalyst was characterized using a variety of techniques including X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), energy dispersive X-ray spectroscopy (EDX), pH analysis and determination of the Hammett acidity function. The prepared reagent showed excellent catalytic activity for the chemoselective conversion of alcohols and phenols to their corresponding trimethylsilyl ethers with 1,1,1,3,3,3-hexamethyldisilazane (HMDS) at room temperature. Deprotection of the resulting trimethylsilyl ethers can also be carried out using the same catalyst in ethanol. All reactions were performed under mild and completely heterogeneous reaction conditions in good to excellent yields. The notable advantages of this protocol are: short reaction times, high yields, availability and low cost of the reagent, easy work-up procedure and the reusability of the catalyst during a simple filtration.

Pd-Catalyzed C-N Coupling Reactions Facilitated by Organic Bases: Mechanistic Investigation Leads to Enhanced Reactivity in the Arylation of Weakly Binding Amines.

The ability to use soluble organic amine bases in Pd-catalyzed C-N cross-coupling reactions has provided a long-awaited solution to the many issues associated with employing traditional, heterogeneous reaction conditions. However, little is known about the precise function of these bases in the catalytic cycle and about the effect of variations in base structure on catalyst reactivity. We used 19F NMR to analyze the kinetic behavior of C-N coupling reactions facilitated by different organic bases. In the case of aniline coupling reactions employing DBU, the resting state was a DBU-bound oxidative addition complex, LPd(DBU)(Ar)X, and the reaction was found to be inhibited by base. In general, however, depending on the binding properties of the chosen organic base, increased concentration of the base can have a positive or negative influence on the reaction rate. Furthermore, the electronic nature of the aryl triflate employed in the reaction directly affects the reaction rate. The fastest reaction rates were observed with electronically neutral aryl triflates, while the slowest were observed with highly electron-rich and -deficient substrates. We propose a model in which the turnover-limiting step of the catalytic cycle depends on the relative nucleophilicity of the base compared to that of the amine. This hypothesis guided the discovery of new reaction conditions for the coupling of weakly binding amines, including secondary aryl amines, which were unreactive nucleophiles in our original protocol.

Potassium coordination polymer complex containing tetrazolyl ligand

A novel potassium complex, [K2L2(H2O)MeOH]n (1), was prepared by reacting KOH and a substituted tetrazolyl ligand LH (LH = 1-[5-(2-hydroxyphenyl)-2H-tetrazol-2-yl]-2-methyl-2-propanol). The prepared complex was characterized by infrared spectroscopy and mass analysis and its solid-state structure was determined to be a high dimensional coordination polymer by X-ray crystallography. The synthesized potassium coordination polymer 1 was used as a catalyst for the cycloaddition of CO2 to propylene oxide and is the first potassium coordination polymer to be used for this purpose. The prepared catalyst provided high selectivity toward cyclic propylene carbonate (>99%) and showed considerable activity despite the heterogeneous reaction condition.

One-pot multi-component synthesis of N,N′-alkylidene bisamides and imidazoles using heteropoly-11-tungsto-1-vanadophosphoric acid supported on natural clay as catalyst: A green approach

ABSTRACTOne-pot multi-component synthesis of N,N′-alkylidene bisamides, 2,4,5-trisubstituted imidazoles and 1,2,4,5-tetrasubstituted imidazoles in the presence of catalytic material heteropoly-11-tungsto-1-vanadophosphoric acid (HPV) supported on activated natural clay for about 20% (HPVAC-20) under solvent-free reaction condition have been achieved. Green heterogeneous reaction condition, simple workup procedure, short reaction time, high yield of products, and reusability of the catalyst are the advantages of this protocol.

Synthesis and Metal Ion Uptake Studies of Silica Gel-Immobilized Schiff Base Derivatives and Catalytic Behaviors of their Cu(II) Complexes

New silica supported Schiff base ligands were prepared by the condensation reaction of 4,6-diacetylresorcinol with silica-gel derivatives, which modified with 3-aminopropyltriethoxysilane and N-(2-aminoethyl) -3-aminopropyltrimethoxysilane. Metal ion uptake capacities of these compounds were studied towards of selected transition metal (Cd(II), Cu(II), Co(II), Mn(II), Pb(II) and Ni(II)) cations in an aqueous medium. In addition, Cu(II) complexes of these ligands were prepared by using heterogeneous reaction conditions. The synthesized compounds were characterized by using elemental analysis, FT-IR, DR-UV-vis., CP/MAS 13C-NMR, AAS, XRD and TGA techniques. Moreover, the morphological and chemical properties of these compounds were investigated by using a scanning electron microscope (SEM) coupled to an energy-dispersive X-ray spectrometer (EDX). The catalytic performances of the Cu(II) complexes were investigated on H2O2 decomposition. These complexes displayed good catalytic activities towards the decomposition of H2O2 as heterogeneous catalysts.

One-pot three-component synthesis of bis(indolyl)methanes under solvent-free condition using heteropoly-11-tungsto-1-vanadophosphoric acid supported on natural clay as catalyst

ABSTRACTOne-pot three-component condensation reaction of two moles of indole and one mole of aromatic aldehyde for the synthesis of bis(indolyl)methanes in the presence of new catalytic material, heteropoly-11-tungsto-1-vanadophosphoric acid, H4[PVVW11O40] (HPV) supported on activated natural clay under solvent-free reaction condition has been proposed. The catalysts were prepared by incipient wetness impregnation method. The physicochemical characterizations of the HPV (20%) supported on natural clay (HPVAC-20) have also been discussed. Solvent-free heterogeneous reaction condition, simple workup procedure, short reaction time, high yield of products, and reusability of the catalyst are the advantages of the protocol.