Boosting the in situ encapsulation of proteins with MIL-100(Fe): the role of strong Lewis acid centers

Encapsulation of biomolecules using Metal-Organic Frameworks (MOFs) to form stable biocomposites has been demonstrated a valuable strategy for their preservation and controlled release, which has been however restricted to specific electrostatic surface conditions. We present a general in situ strategy that promotes the spontaneous MOF growth onto a broad variety of proteins, for the first time, regardless of their surface nature. We demonstrate that MOFs based on cations exhibiting considerable inherent acidity such as MIL-100(Fe) enable biomolecule encapsulation, including alkaline proteins previously inaccesible by the welldeveloped in situ encapsulation with azolate-based MOFs. In particular, MIL-100(Fe) scaffold permits effective encapsulation of proteins with very distinct surface nature, retaining their activity and allowing triggered release under biocompatible conditions. This general strategy will enable an ample use of biomolecules in desired biolotechnological applications.

Influence of thermoactivation on properties of mineral additives in dry mixtures

Information on the effect of thermal activation of silicate and aluminosilicate rocks used as a filler in dry building mixtures on their reactivity of interaction with lime binder is presented. The change in the distribution of acidic Bronsted and Lewis centers on the filler surface as a result of thermal activation is shown. It was found that the number of Bronsted and Lewis acid centers on the surface of fired clays exceeds the number of the same centers on the surface of unbaked clays. The number of adsorption centers at pKa from 0 to 7 and pKa> 13 on the surface of fired diatomite is 2.435 * 10-5 mol/g, and on the surface of unbaked diatomite -1.678 * 10−5 mol/g. The heat treatment of diatomite at low temperatures (2000C and 3000C) does not significantly affect the values of the compressive strength of the mortar. An increase in the firing temperature to 7000C leads to an increase in strength characteristics up to R = 4.38 MPa. However, the greatest effect is achieved when diatomite is fired at a temperature of t = 9000C. The value of the ultimate strength in compression was R = 5.1 MPa.

Structure-Catalytic Properties Relationship in Friedel Crafts Alkylation Reaction for MCM-36-Type Zeolites Obtained by Isopropanol-Assisted Pillaring

MWW type zeolites are characterized by the presence of zeolitic layers of 2.5 nm thickness, containing 10-member ring sinusoidal channels inside and supercavities with 12-member ring openings located on their surfaces. Expansion and pillaring of layered zeolites increase the access to active sites and can enable or facilitate catalytic activity towards larger reactant molecules. This goal is explored in this work reporting the pillaring of layered zeolite MCM-56 with MWW topology by tetraethylorthosilicate (TEOS) treatment with the assistance of isopropanol, aimed at obtaining hierarchical micro-mesoporous systems. MCM-56 (Si/Al = 12) was synthesized with hexamethyleneimine as a structure-directing and aniline as a structure-promoting agent. Hierarchical porous systems were obtained using two different pillaring methods: (1) with TEOS only and (2) with TEOS mixed with isopropanol. The MWW framework was preserved during swelling/pillaring in both methods. Pillared zeolites obtained via alcohol-assisted pillaring possessed unique intermediate micro-mesopores with the size of about 2 nm. IR study revealed a decrease in the concentration of accessible acid centers upon pillaring. However, the fraction of acid sites on the external surface, accessible for adsorption of large molecules, increased by up to 90%. Catalytic activity was evaluated in the Friedel-Crafts alkylation of mesitylene with benzyl alcohol. Pillaring resulted in reduction of the acid site concentrations, but the materials retained high catalytic activity. Pillaring in the presence of alcohol produced increased turnover frequency values based on the concentrations of the external acid sites.

n-Nonane hydroisomerization over hierarchical SAPO-11-based catalysts with sodium dodecylbenzene sulfonate as a dispersant

To enhance the gasoline octane number, low-octane linear n-alkanes should be converted into their high-octane di-branched isomers via n-alkane hydroisomerization. Therefore, hierarchical SAPO-11-based catalysts are prepared by adding different contents of sodium dodecylbenzene sulfonate (SDBS), and they are applied in n-nonane hydroisomerization. When n(SDBS)/n(SiO2) is less than or equal to 0.125, the synthesized hierarchical molecular sieves are all pure SAPO-11, and as the SDBS content increases, the submicron particle size decreases, and the external surface area (ESA) increases. Additionally, these hierarchical SAPO-11 have smaller submicron particles and higher ESA values than conventional SAPO-11. When n(SDBS)/n(SiO2) is greater than 0.125, with increasing SDBS content (n(SDBS)/n(SiO2) = 0.25), the synthesized SAPO-11 contains amorphous materials, which leads to a decline in the ESA; with the further increase in SDBS content (n(SDBS)/n(SiO2) = 0.5), the products are all amorphous materials. These results indicate that in the case of n(SDBS)/n(SiO2) = 0.125, the synthesized SAPO-11 molecular sieve (S–S3) has the most external Brønsted acid centers and the highest ESA of these SAPO-11, and these advantages favor generation of the di-branched isomers in hydrocarbon hydroisomerization. Among these Pt/SAPO-11 catalysts, Pt/S–S3 displays the highest selectivity to entire isomers (83.4%), the highest selectivity to di-branched isomers (28.1%) and the minimum hydrocracking selectivity (15.7%) in n-nonane hydroisomerization.

Development of (γ-Al2O3-Zeolite Y)/α-Al2O3-HPCM Catalyst based on Highly Porous α-Al2O3-HPCM Support for Decreasing Oil Viscosity

Highly porous cellular material (α-Al2O3-HPCM) support was synthesized by the template method. Highly porous support was used for the synthesis of the catalyst. A thin secondary layer with 25–30 μ thick γ-Al2O3 and zeolite Y was applied on the α-Al2O3-HPCM surface ((γ-Al2O3 (85%)-zeolite Y (15%))/α-Al2O3-HPCM). The catalyst based on the highly porous support was tested in a process of decreasing oil viscosity. The catalyst in the form of cylindrical granules and a thermal process of decreasing oil viscosity without the catalyst were used as the basis for comparison. α-Al2O3-HPCM in the catalyst provides low-quantity pores (d < 10 nm) and a quantity of general acid centers compared with the granular catalyst. On the other hand, it shows a more significant oil viscosity decrease (from 2500 to 41 cPs) and a low rate of gas generation (137 mL/h) for the catalyst with highly porous support. A high oil fraction was observed in the presence of the (γ-Al2O3-zeolite Y)/α-Al2O3-HPCM compared to the granular catalyst. The presence of large transport cells (pores) 1500–2000 μ for the catalyst based on highly porous support allowed a work period four times longer than that of experiment only with temperature without catalysts.

The crucial roles of guest water in a biocompatible coordination network in the catalytic ring-opening polymerization of cyclic esters: a new mechanistic perspective

A new ring-opening polymerization mechanism is unveiled based on synergistic catalysis involving Brønsted and Lewis acid centers in a coordination framework.