Host–guest chemistry of mesoporous silicas: precise design of location,density and orientation of molecular guests in mesopores

Abstract

Mesoporous solids, which were prepared from inorganic-surfactant mesostructured materials, have been investigated due to their very large surface area and high porosity, pore size uniformity and variation, periodic pore arrangement and possible pore surface modification. Morphosyntheses from macroscopic morphologies such as bulk monolith and films, to nanoscopic ones, nanoparticles and their stable suspension, make mesoporous materials more attractive for applications and detailed characterization. This class of materials has been studied for such applications as adsorbents and catalysts, and later on, for optical, electronic, environmental and bio-related ones. This review summarizes the studies on the chemistry of mesoporous silica and functional guest species (host–guest chemistry) to highlight the present status and future applications of the host–guest hybrids.     

Synthesis and characterization of Co–Fe nanoparticles supported on mesoporous silicas

Co–Fe bimetallic samples containing 25 wt% total of metal content were prepared by incipient wetness impregnation of cobalt nitrate and iron nitrate salts over hexagonal mesoporous silica (HMS) and SBA-15 supports. Changes in the textural properties and reduction behavior were compared with monometallic cobalt/iron-based samples. The samples were characterized by N₂ physisorption, X-ray diffraction (XRD), H₂-temperature programmed reduction (TPR), transmission electron microscopy (TEM) and H₂ chemisorption. The amount of incorporated metal was estimated by atomic absorption spectroscopy (AAS). Morphological properties revealed that after introduction of the metal to the SBA-15 support, the specific area, pore volume and pore diameter decreased to a lesser extent for bimetallic samples. XRD measurements detected the formation of Co₃O₄ and CoFe₂O₄ phases for both bimetallic samples. TPR profiles indicated similar behavior for both the bimetallic and monometallic samples. Higher temperatures were observed for the reducibility of Co–Fe/HMS as compared to Co–Fe/SBA-15. Dispersion values of the bimetallic samples were higher than Fe monometallic samples and lower than Co monometallic samples according to hydrogen chemisorption. The particle size distribution of the bimetallic samples estimated by TEM microphotographs showed a smaller fraction of larger size particles for Co–Fe/SBA-15.     

Host–guest inclusion system of mangiferin with β-cyclodextrin and its derivatives

The characterization, inclusion complexation behavior and binding ability of the inclusion complexes of mangiferin (MGF) with β-cyclodextrin and its derivatives (hydroxypropyl-β-cyclodextrin (HPβCD), sulfobutyl ether β-cyclodextrin (SBEβCD) and mono (6-ethylene-diamino-6-deoxy)-β-cyclodextrin (ENβCD)) were investigated in both solution and solid state by means of PL spectroscopy, ¹H and 2D NMR, XRD, TG and DSC. The results showed that the water solubility and thermal stability of MGF were significantly increased in the inclusion complex with cyclodextrins. The MGF/CDs complexes will be potentially useful for the design of a novel formulation of mangiferin for herbal medicine.     

Tailored morphology and controlled structure of bimodal mesopores silicas via additive ammonia amount in the TEOS–CTAB–H2O system

Bimodal mesopores silicas (designated as BMMs) with tailored morphology and controlled structure have been synthesized via varying additive ammonia amount in the TEOS–CTAB–H₂O system based on hydrolysis–condensation behaviors of silicate species (TEOS) and coefficient principles of cetyltrimethylammonium bromide template (CTAB). The spherical BMMs with an average diameter of 25–150 nm were prepared in a relative low ammonia concentration solution, while the rod-like BMMs with an average size of 2 μm in length were obtained under a high ammonia concentration aqueous solution. Meanwhile, their corresponding morphologies and textural properties were characterized by various techniques, such as X-ray diffraction, SEM, TEM, FT-IR, TG, and N₂ sorption, and then, the related cooperative mechanism including sol–gel chemistry and self-assembly process was put forward.     

Structure and orientation relationship of new precipitates in a Cu–Cr–Zr alloy

The crystallography and morphology of the nano-sized precipitate particles in a ternary Cu–Cr–Zr alloy were studied by transmission electron microscopy. A new type of face-centred-cubic (f.c.c) Cr-rich precipitate was observed. This precipitate is ordered and solute enriched on alternate {110} f.c.c planes, with an ellipsoid-shaped morphology. The new orientation relationship (OR) between the precipitate and Cu matrix satisfies [211]M//[011]p and [100]M//[111]p, {-111}M//{200}p and {02-2}M//{02-2}p. The difference between this new OR and the Nishiyama–Wasserman OR between body-centred-cubic (b.c.c) Cr and the Cu matrix can be detailed by Δg vectors in the diffraction patterns. Furthermore, the precipitation strengthening effect is increased greatly with the formation of these new precipitate particles when compared to binary Cu–Cr alloys.     

Towards an ontology of design: lessons from C–K design theory and Forcing

In this paper we present new propositions about the ontology of design and a clarification of its position in the general context of rationality and knowledge. We derive such ontology from a comparison between formal design theories developed in two different scientific fields: Engineering and Set theory. We first build on the evolution of design theories in engineering, where the quest for domain independence and “generativity” has led to formal approaches, likewise C–K theory, that are independent of what has to be designed. Then we interpret Forcing, a technique in Set theory developed for the controlled invention of new sets, as a general design theory. Studying similarities and differences between C–K theory and Forcing, we find a series of common notions like “d-ontologies”, “generic expansion”, “object revision”, “preservation of meaning” and “K-reordering”. They form altogether an “ontology of design” which is consistent with unique aspects of design.     

Lipid nanoparticles of zaleplon for improved oral delivery by Box–Behnken design: optimization,in vitro and in vivo evaluation

Purpose: Zaleplon (ZL) is a hypnotic drug prescribed for the management of insomnia and convulsions. The oral bioavailability of ZL was low (～30%) owing to poor water solubility and hepatic first-pass metabolism. The cornerstone of this investigation is to develop and optimize solid lipid nanoparticles (SLNs) of ZL with the aid of Box–Behnken design (BBD) to improve the oral bioavailability.

Methods: A design space with three formulation variables at three levels were evaluated in BBD. Amount of lipid (A₁), amount of surfactant (A₂) and concentration of co-surfactant (%) (A₃) were selected as independent variables, whereas, particle size (B₁), entrapment efficiency (B₂) and zeta potential (ZP, B₃) as responses. ZL-SLNs were prepared by hot homogenization with ultrasonication method and evaluated for responses to obtain optimized formulation. Morphology of nanoparticles was observed under SEM. DSC and XRD studies were examined to understand the native crystalline behavior of drug in SLN formulations. Further, in vivo studies were performed in Wistar rats.

Results: The optimized formulation with 132.89?mg of lipid, 106.7?mg of surfactant and 0.2% w/v of co-surfactant ensued in the nanoparticles with 219.9?±?3.7?nm of size, ?25.66?±?2.83?mV surface charge and 86.83?±?2.65% of entrapment efficiency. SEM studies confirmed the spherical shape of SLN formulations. The DSC and XRD studies revealed the transformation of crystalline drug to amorphous form in SLN formulation. In conclusion, in vivo studies in male Wistar rats demonstrated an improvement in the oral bioavailability of ZL from SLN over control ZL suspension.

Conclusions: The enhancement in the oral bioavailability of ZL from SLNs, developed with the aid of BBD, explicated the potential of lipid-based nanoparticles as a potential carrier in improving the oral delivery of this poorly soluble drug.     

Synthesis and characterization of V,Mo and Nb incorporated micro–mesoporous MCM-41 materials

Highly microporous metal-MCM-41 ordered mesoporous structure catalysts having different metal/Si (V, Mo, Nb) atomic ratios and combinations of metal sources were hydrothermally synthesized. The structural properties estimated using different techniques were found to be in agreement with each other. Metals were successfully incorporated into MCM-41 without deteriorating the ordered hexagonal structure. The metal ions in the synthesis solutions probably settled on the hydrophilic end of the template hence the metal incorporation resulted improvements in the micropore structure. Low loading of metals caused an increase in the surface area and pore volume values of the catalysts. The highest total (1310 m² g^?1) and micropore surface area values (1083 m² g^?1) were obtained by Nb incorporation. The micro- and mesopore dimensions of MCM-41 increased from 0.5 to 1.1 nm and from 2.5 to 2.8 nm, respectively, with metal incorporation. Low V/Si ratios and presence of Nb in the starting solution enhanced narrow mesopore size distribution. The pore dimension and wall thickness values estimated from nitrogen adsorption and X-ray diffraction methods were consistent with the corresponding values obtained using transmission electron microscopy.     

Strength and failure modes in resistance welded thermoplastic composite joints: Effect of fibre–matrix adhesion and fibre orientation

The strength and failure modes of resistance welded thermoplastic composites were investigated. Special attention was paid to the effect of basic characteristics of the adherends such as fibre–matrix adhesion and fibre orientation. 8HS woven GF/PEI composites were resistance welded. Intralaminar failure was found to be the major failure mechanism for the well welded joints, consisting of either fibre–matrix debonding or laminate tearing. An improved fibre–matrix adhesion was found to result in significantly higher lap shear strength. Besides, the main apparent orientation of the fibres on the welding surfaces was found to have an effect on the strength of the joints.     

Development of zolmitriptan transfersomes by Box–Behnken design for nasal delivery: in vitro and in vivo evaluation

The aim was to prepare an optimized zolmitriptan (ZT)-loaded transfersome formulation using Box–Behnken design for improving the bioavailability by nasal route for quick relief of migraine and further to compare with a marketed nasal spray. Here, three factors were evaluated at three levels. Independent variables include: amount of soya lecithin (X₁), amount of drug (X₂) and amount of tween 80 (X₃). The dependent responses were vesicle size (Y₁), flexibility index (Y₂) and regression coefficient of drug release kinetics (Y₃). Prepared formulations were evaluated for physical characters and an optimal system was identified. Further, in vivo pharmacokinetic study was performed in male wistar rats to compare the amount of drug in systemic circulation after intranasal administration. Optimized ZT-transfersome formulation containing 82.74?mg of lecithin (X₁), 98.37?mg of zolmitriptan (X₂) and 32.2?mg of Tween 80 (X₃) and had vesicle size of 93.3?nm, flexibility index of 20.25 and drug release regression coefficient of 0.992. SEM picture analysis revealed that the vesicles were spherical in morphology and had a size more than 1?µm. The formulations were found to be physically stable upon storage at room temperature up to 2?months period, as there were no significant changes noticed in size and ZP. The nasal bioavailability of optimized transfersome formulation was found to be increased by 1.72 times than that of marketed nasal spray (Zolmist^®). The design and development of zolmitriptan as transfersome provided improved nasal delivery over a conventional nasal spray for a better therapeutic effect.     

Sugar microarray via click chemistry: molecular recognition with lectins and amyloid β (1–42)

Abstract

Sugar microarrays were fabricated on various substrates via click chemistry. Acetylene-terminated substrates were prepared by forming self-assembled monolayers (SAMs) on a gold substrate with alkyl-disulfide and on silicon, quartz and glass substrates with a silane-coupling reagent. The gold substrates were subjected to surface plasmon resonance measurements, and the quartz and glass substrates were subjected to spectroscopy measurements and optical microscopy observation. The saccharide-immobilized substrate on the gold substrate showed specific interaction with the corresponding lectin, and the saccharides showed inert surface properties to other proteins with a high signal-to-noise ratio. We also focused on the saccharide–protein interaction on protein amyloidosis of Alzheimer amyloid β. Amyloid β peptide showed conformation transition on the saccharide-immobilization substrate into a β-sheet, and fibril formation and amyloid aggregates were found on the specific saccharides.     

Texture evolution and probability distribution of Goss orientation in magnetostrictive Fe–Ga alloy sheets

Texture evolution and the distribution of Goss orientation in polycrystalline Fe–Ga alloy were investigated as a series of rolling and subsequent annealing processes were used to develop highly textured rolled sheet. A dramatic change from the random nature of the as-rolled and primary recrystallized texture is observed when careful control of atmosphere and temperature during anneal leads to development of a sharp Goss orientation over up to 98 % of the surface of a sample during secondary recrystallization. In this work, grain boundary properties in local areas surrounding Goss grains are investigated and the evolution of Goss orientation is traced through the different stages of alloy processing using electron backscatter diffraction analysis. To evaluate the evolution of grains with Goss orientation, {011} grains are selected and separated from other texture components at each processing step and statistical analysis used to correlate the structural inheritance chain of Goss-oriented grains. The four processing stages considered are the alloy after hot rolling, the as-rolled alloy (i.e., after subsequent warm and cold rolling), the alloy after an initial anneal during which primary recrystallization occurs, and the alloy after final anneals in which secondary recrystallization with abnormal grain growth occurs. Analysis of Goss grain orientation probability distribution functions after primary and secondary recrystallization convincingly demonstrates that the orientation of the abnormally grown Goss texture that develops during secondary recrystallization is determined by the orientation of Goss components that develop during the primary recrystallization stage of alloy processing.     

Evaluation of performance and design of GFRP dowels in jointed plain concrete pavement – part 2: numerical simulation and design considerations

The article presents a numerical investigation using three-dimensional finite element analysis (FEA) to compare the performance of glass fibre reinforced polymer (GFRP) and steel dowel bars as load transfer devices across the transverse joints of jointed plain concrete pavements (JPCP). The FEA model used concrete damaged plasticity formulation to characterise the concrete pavement; elastic, transversely isotropic material characteristics were assumed for the GFRP dowels and classical metal plasticity formulation was used for the steel dowels. The numerical results were validated with the experimental results, and a good agreement was achieved. The results showed less stress concentration in the concrete underneath the GFRP dowels (38 mm diameter) compared with the steel dowels (25 mm diameter) of similar flexural rigidity. Finally, on the basis of a detailed parametric study, design considerations for the GFRP dowels in JPCP are suggested.     

X-ray and thermochemical studies of phase transitions in crystalline host–guest compounds of 1,1′–binaphthyl–2,2′–dicarboxylic acid with ethanol and acetone

The crystal structures of two 1:2 and 1:1 host–guest compounds between BNDA and acetone have been determined by single crystal X-ray diffraction and are comparatively discussed with reference to recently reported BNDA/ethanol clathrates of different composition. Simultaneous thermogravimetry and differential scanning calorimetry (TG–DSC) in combination with the X-ray powder diffraction (XRD) method reveal that the thermal degradation of the BNDA/ethanol 1:2 α–form clathrate takes place in two steps with the intermediate formation of the 2:1 β–form clathrate. On the other hand, desolvation of the BNDA/acetone 1:2 α–form clathrate gives no indication for the formation of any intermediate phase in the TG–DSC traces unlike the XRD studies showing the existence of the β–form during desolvation. A possible explanation of this latter property is the very similar thermal decomposition temperature of both phases. The TG–DSC results for the isothermal inclusion of vaporous ethanol and acetone indicate that this process takes place in a single step with the formation of the 1:2 BNDA/ethanol and 1:1 BNDA/acetone clathrates, respectively.     

Liquid–liquid phase equilibria,density difference,and interfacial tension in the Al–Bi–Si monotectic system

We have performed thermodynamic calculation of the phase equilibria in the ternary monotectic system Al–Bi–Si. The liquid–liquid miscibility gap in the Al–Bi–Si system extends over almost the entire concentration triangle. The thermal analysis data for (Al_0.345Bi_0.655)_100−x Si _x alloys (x = 2.5, 5, 7.5, and 10 wt%) excellently agree with the calculated phase diagram. The experimental density difference of the coexisting liquid phases shows a good agreement with the density difference calculated in the approximation of ideal solution using the densities of pure elements and the compositions of L′ and L′′ from the thermodynamic calculation. The liquid–liquid interfacial tension in the (Al_0.345Bi_0.655)_100−x Si _x liquid alloys increases with Si content. The experimental temperature dependence of the interfacial tension is well described by the power low in reduced temperature (T _C–T) at approach of the critical temperature with the exponent μ = 1.3, which is close to the value predicted by the renormalization group theory of critical behavior.     

Synthesis,characterization and photocatalytic behavior of TiO2–SiO2 mesoporous composites in hydrogen generation from water splitting

TiO₂–SiO₂ mesoporous composite photocatalysts with different proportions (in wt%) of TiO₂ and SiO₂ (TiO₂–SiO₂ = 20:80, 40:60, 60:40, 80:20 and 100:0) were prepared by loading TiO₂ on as-synthesized Si–MCM-41 using sol–gel method. The physicochemical properties of composites were investigated by powder X-ray diffraction, N₂ adsorption–desorption measurements, transmission electron microscopy and UV–Vis diffuse reflectance spectroscopy. It is revealed that the titanium species are dispersed as TiO₂ having interaction with the surface of the support. Even at high TiO₂ loading, the mesostructural feature of MCM-41 was found to be intact without pore blockages. The change in morphology of TiO₂ particle was observed with increase in TiO₂ loading which may be due to different environment for the growth of TiO₂. The photocatalytic evaluation of composites was carried out in production of hydrogen by water splitting. Among the prepared samples, mesoporous composite containing 60 % TiO₂ (MTi60) has shown the best results (0.08805 mmol of H₂/h/g of TiO₂) compared to other composite photocatalysts. The catalytic performance of this sample was further enhanced (~8 times) after loading 1 % Pt in water splitting (0.70161 mmol of H₂/h/g of TiO₂). 1 % Pt loaded on pure TiO₂ (MTi100) showed hydrogen evolution of the magnitude 0.26 mmol of H₂/h/g of TiO₂. TiO₂–SiO₂ mesoporous composite photocatalyst showed much higher activity (~1.9 times) than amorphous silica-embedded titania catalyst having same composition.     

Effects of ECAE temperature and billet orientation on the microstructure,texture evolution and mechanical properties of a Mg–Zn–Y–Zr alloy

Single-pass equal channel angular extrusion (ECAE) experiments of an extruded Mg–Zn–Y–Zr alloy with an intense initial basal texture were performed in two inter-perpendicular billet orientations and at 473 and 623 K. The study was aimed to determine the effects of ECAE temperature and billet orientation on the microstructure, texture evolution and mechanical properties of the ECAEed alloy. It was found that the grain refinement achieved through the single-pass ECAE in the Orient-I billet orientation (the normal direction (ND) of the extruded plate parallel with the ECAE exit direction) was more effective than that in the Orient-II billet orientation (the ND of the extruded plate perpendicular to the ECAE exit direction). The average grain sizes after ECAE at 473 K were much smaller than those after ECAE at 623 K. The pole figures of the alloy ECAEed at 473 K showed that most of the basal planes in the Orient-I and Orient-II samples were inclined about 40° and 35°, respectively, with respect to the longitudinal direction of the ECAE extrudate. However, for the alloy ECAEed at 623 K, most of the basal planes were parallel with the longitudinal direction of the ECAE extrudate. It was remarkable that the yield strengths of the alloy ECAEed at 473 K were lower than those at 623 K. The peculiar relationship between ECAE temperature and the mechanical properties of the alloy was ascribed to the texture evolution during ECAE.     

Pseudo-Jahn–Teller effects in two-dimensional silicene,germanene and stanene: a crystal orbital vibronic coupling density analysis

The presence of the pseudo-Jahn–Teller (PJT) effect has been investigated in the heavier analogues of graphene, namely silicene, germanene and stanene, by applying the orbital vibronic coupling density theory. In order to do so, we have made a vis-a-vis analogy with their respective planar, honeycomb molecular cluster models, namely hexasilabenzene \((\hbox {Si}_{6}\hbox {H}_{6}\)), hexagermabenzene \((\hbox {Ge}_{6}\hbox {H}_{6}\)) and hexastannabenzene \((\hbox {Sn}_{6}\hbox {H}_{6})\). One-to-one mapping of the occupied crystal orbitals and unoccupied crystal orbitals in two-dimensional (2D) Si, Ge and Sn systems to the occupied molecular orbitals and unoccupied molecular orbitals of the corresponding molecular units are used to identify PJT-active bands and compute the crystal orbital vibronic coupling density (c-OVCD) and crystal orbital vibronic coupling constants (c-OVCCs). c-OVCD and c-OVCC show the local picture of the PJT coupling in these 2D systems. This article exemplifies the fruitfulness of deciphering the structural aspects in materials based on orbitals of their corresponding simple molecular units—a reductionist quantum chemical approach to materials.     

Extruder scale-up assessment in the process of extrusion–spheronization: comparison of radial and axial systems by a design of experiments approach

Scaling-up the extrusion–spheronization process involves the separate scale-up of each of the five process steps: dry mixing, granulation, extrusion, spheronization, and drying. The aim of the study was to compare two screw extrusion systems regarding their suitability for scaling-up. Two drug substances of high- and low-solubility in water were retained at different concentrations as formulation variables. Different spheronization times were tested. The productivity of the process was followed up using the extrusion rate and yield. Pellets were characterized by their size and shape, and by their structural and mechanical properties. A response surface design of experiments was built to evaluate the influence of the different variables and their interactions on each response, and to select the type of extrusion which provides the best results in terms of product quality, the one which shows less influence on the product after scale-up (“scalability”) and when the formula used changes (“robustness”), and the one which allows the possibility to adjust pellet properties with spheronization variables (“flexibility”). Axial system showed the best characteristics in terms of product quality at lab and industrial scales, the best robustness at industrial scale, and the best scalability, by comparison with radial system. Axial system thus appeared as the easiest scaled-up system. Compared to lab scale, the conclusions observed at industrial scale were the same in terms of product quality, but different for robustness and flexibility, which confirmed the importance to test the systems at industrial scale before acquiring the equipment.