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Ammonia (NH3) is a carbon-free, hydrogen-rich chemical related to global food safety, clean energy, and environmental protection. As an essential technology for meeting the requirements raised by such issues, NH3 capture has been intensively explored by researchers in both fundamental and applied fields. The four typical methods used are (1) solvent absorption by ionic liquids and their derivatives, (2) adsorption by porous solids, (3) ab-adsorption by porous liquids, and (4) membrane separation. Rooted in the development of advanced materials for NH3 capture, we conducted a coherent review of the design of different materials, mainly in the past 5 years, their interactions with NH3 molecules and construction of transport pathways, as well as the structure-property relationship, with specific examples discussed. Finally, the challenges in current research and future worthwhile directions for NH3 capture materials are proposed.
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Owing to their high porosity and tunability, porous solids such as metal-organic frameworks (MOFs), zeolites, or activated carbons (ACs) are of great interest in the fields of air purification, gas separation, and catalysis, among others. Nonetheless, these materials are usually synthetized as powders and need to be shaped in a more practical way that does not modify their intrinsic property (i.e., porosity). Elaborating porous, freestanding and flexible sheets is a relevant shaping strategy. However, when high loadings (>70 wt.%) are achieved the mechanical properties are challenged. A new straightforward and green method involving the combination softwood bleached kraft pulp fibers (S) and nano-fibrillated cellulose (NFC) is reported, where S provides flexibility while NFC acts as a micro-structuring and mechanical reinforcement agent to form high loadings porous solids paper sheets (>70 wt.%). The composite has unobstructed porosity and good mechanical strength. The sheets prepared with various fillers (MOFs, ACs, and zeolites) can be rolled, handled, and adapted to different uses, such as air purification. As an example of potential application, a MOF paper composite has been considered for the capture of polar volatile organic compounds exhibiting better performance than beads and granules.
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A new photopyroelectric detection configuration is proposed in order to measure the thermal effusivity of porous solids. Compared with the previously reported detection scheme this configuration makes use of a transparent window in front of the pyroelectric sensor. In such a way, the heat losses by convection at the sensor's irradiated surface are eliminated, and consequently, the conduction remains the only process responsible for the heat propagation in the whole detection cell. In the paper, the mathematical model for this new configuration is developed, with the main conclusion that the sample's thermal effusivity can be finally obtained via a fitting procedure with only two fitting parameters (instead of three as previously reported); in such a way, the possible degeneracy of the results is eliminated. The suitability of the method is demonstrated with application on some porous building materials and cellulose-based pressed powders.
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The reliable self-assembly of microporous metal-phosphonate materials remains a longstanding challenge. This stems from, generally, more coordination modes for the functional group allowing more dense structures, and stronger bonding driving less crystalline products. Here, a novel orthogonalized aryl-phosphonate linker, 1,3,5-tris(4'-phosphono-2',6'-dimethylphenyl) benzene (H6 L3) has been used to direct formation of open frameworks. The peripheral aryl rings of H6 L3 are orthogonalized relative to the central aromatic ring giving a tri-cleft conformation of the linker in which small aromatic molecules can readily associate. When coordinated to magnesium ions, a series of porous crystalline metal-organic, and hydrogen-bonded metal-organic frameworks (MOFs, HMOFs) are formed (CALF-41 (Mg), HCALF-42 (Mg), -43 (Mg)). While most metal-organic frameworks are tailored based on choice of metal and linker, here, the network structures are highly dependent on the inclusion and structure of the guest aromatic compounds. Larger guests, and a higher stoichiometry of metal, result in increased solvation of the metal ion, resulting in networks with connectivities increasingly involving hydrogen-bonds rather than direct phosphonate coordination. Upon thermal activation and aromatic template removal, the materials exhibit surface areas ranging from 400-600â m2 /g. Self-assembly in the absence of aromatic guests yields mixtures of phases, frequently co-producing a dense 3-fold interpenetrated structure (1). Interestingly, a series of both more porous (530-900â m2 /g), and more robust solids is formed by complexing with trivalent metal ions (Al, Ga, In) with aromatic guest; however, these are only attainable as microcrystalline powders. The polyprotic nature of phosphonate linkers enables structural analogy to the divalent analogues and these are identified as CALF-41 analogues. Finally, insights to the structural transformations during metal ion desolvation in this family are gained by considering a pair of structurally related Co materials, whose hydrogen-bonded (HCALF-44 (Co)) and desolvated (CALF-44 (Co)) coordination bonded networks were fully structurally characterized.
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Alterations of fluid phase transitions in porous materials are conventionally employed for the characterization of mesoporous solids. In the first approximation, this may be based on the application of the Kelvin equation for gas-liquid and the Gibbs-Thomson equation for solid-liquid phase equilibria for obtaining pore size distributions. Herein, we provide a comparative analysis of different phase coexistences measured in mesoporous silica solids with different pore sizes and morphology. Instead of comparing the resulting pore size distributions, we rather compare the transitions directly by using a common coordinate for varying the experiment's thermodynamic parameters based on the two equations mentioned. Both phase transitions in these coordinates produce comparable results for mesoporous solids of relatively large pore sizes. In contrast, marked differences are found for materials with smaller pore sizes. This illuminates the fact that, with reducing confinement sizes, thermodynamic fluctuations become increasingly important and different for different equilibria considered. In addition, we show that in the coordinate used for analysis, mercury intrusion matches perfectly with desorption and freezing transitions.
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The coordinative pliancy of the phosphonate functional group means that metal-phosphonate materials often self-assemble as well-packed structures with minimal porosity, as efficient inter-ligand packing is enabled. Here, we report a multistep synthesis of a novel aryl-phosphonate linker with an orthogonalized ligand core, 1,3,5-tris(4'-phosphonophenyl)-2,4,6-trimethylbenzene (H6 L2) designed to form more open structures. A series of crystalline metal-phosphonate frameworks (CALF-35 to -39) have been assembled by coordinating to divalent metals (Ba, Sr, Ca, Mg, Zn). H6 L2 is unable to pack efficiently and, as a consequence, yields several distinct microporous structures. The resulting structures are discussed in detail, with a focus on the solid-state packing of the sterically rigidified linker. Combined with larger cations (Sr, and Ba), H6 L2 packs in a parallel-offset manner, yielding isomorphous and microporous metal-organic frameworks (CALF-35 (Sr), and (Ba)). When coordinated to smaller metals (Ca, Mg, Zn), H6 L2 forms four new structures. Two Ca MOFs of different stoichiometry, (CALF-36 and 37) and a Mg MOF CALF-38 show narrow pores and have high selectivities for CO2 over N2 and CH4 . Finally, in CALF-39 (Zn), H6 L2 linkers pack in a herringbone fashion, resulting in a material with 10.9×10.1â Å2 square channels. The stability of all structures was tested, and the most porous structure, CALF-39 (Zn), was found to retain its structure and gas adsorption after immersion in water over pHâ 3-11.
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Estructuras Metalorgánicas , Organofosfonatos , Ligandos , Estructuras Metalorgánicas/química , Metales/química , PorosidadRESUMEN
PURPOSE: To develop a new direct granule fed 3D printing method for manufacturing pharmaceutical solid dosage forms with porous structures using a thermal droplet deposition technology. METHODS: Eudragit® E PO was used as the model polymer, which is well-known to be not FDM printable without additives. Wet granulation was used to produce drug loaded granules as the feedstock. The flow and feedability of the granules were evaluated. The physicochemical properties and in vitro drug release performance of the granules and the printed tablets were fully characterised. RESULTS: Using the method developed by this study, Eudragit E PO was printed with a model drug into tablets with infills ranging from 30-100%, without additives. The drug was confirmed to be molecularly dispersed in the printed tablets. The printing quality and performances of the porous tablets were confirmed to be highly compliant with the pharmacopeia requirement. The level of infill density of the porous tablets had a significant effect on their in vitro drug release performance. CONCLUSION: This is the first report of thermal droplet deposition printing via direct granule feeding. The results of this study demonstrated that this new printing method can be used as a potentially valuable alternative for decentralised pharmaceutical solid dosage form manufacturing.
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Impresión Tridimensional , Tecnología Farmacéutica , Formas de Dosificación , Liberación de Fármacos , Porosidad , Comprimidos/química , Tecnología Farmacéutica/métodosRESUMEN
Stationary phases (SPs) based on silica matrices functionalized with amino groups linked to their surface through alkyl chains of various length have found remarkable success in performing HILIC separations, showing really effective resolution towards a wide typology of compounds of biological interest, such as carbohydrates, nucleosides, purine and pyrimidine bases. Recently, we developed an operationally simple procedure, named DNBA-M, non-destructive for the analysed SP, designed to quantify the density of basic groups (typically amino groups) chemically bonded to the surface of porous solids. In the present study the DNBA-M procedure has been suitably modified to allow the quantification of any typology of amino groups present on silica matrices packed into HPLC columns. The new approach, named OC-DNBA-M, has been successfully validated through analysis of two HPLC columns packed with aminopropyl-silica matrices. Afterwards, it was also demonstrated as the OC-DNBA-M procedure may allow the effective and in-depth analysis of the structural composition characterizing SPs packed inside HPLC columns, in which amino-groups have been differently and only partially involved in following ureidic functionalizations. It was also proved how the analysed columns can be readily re-employed for the chromatographic applications for which they have been designed, without appreciable deterioration of the respective discrimination abilities.
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Cromatografía Líquida de Alta Presión/métodos , Porosidad , Dióxido de Silicio/química , EstereoisomerismoRESUMEN
3D printing has the unique ability to produce porous pharmaceutical solid dosage forms on-demand. Although using porosity to alter drug release kinetics has been proposed in the literature, the effects of porosity on the swellable and erodible porous solid dosage forms have not been explored. This study used a model formulation containing hypromellose acetate succinate (HPMCAS), polyethylene oxide (PEO) and paracetamol and a newly developed hot melt droplet deposition 3D printing method, Arburg plastic free-forming (APF), to examine the porosity effects on in vitro drug release. This is the first study reporting the use of APF on 3D printing porous pharmaceutical tablets. With the unique pellet feeding mechanism of APF, it is important to explore its potential applications in pharmaceutical additive manufacturing. The pores were created by altering the infill percentages (%) of the APF printing between 20 and 100% to generate porous tablets. The printing quality of these porous tablets was examined. The APF printed formulation swelled in pH 1.2 HCl and eroded in pH 6.8 PBS. During the dissolution at pH 1.2, the swelling of the printing pathway led to the gradual decreases in the open pore area and complete closure of pores for the tablets with high infills. In pH 6.8 buffer media, the direct correlation between drug release rate and infills was observed for the tablets printed with infill at and less than 60%. The results revealed that drug release kinetics were controlled by the complex interplay of the porosity and dynamic changes of the tablets caused by swelling and erosion. It also implied the potential impact of fluid hydrodynamics on the in vitro data collection and interpretation of porous solids.
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Impresión Tridimensional , Tecnología Farmacéutica , Liberación de Fármacos , Cinética , Porosidad , ComprimidosRESUMEN
Bone defects are treated with bone grafts, replacing damaged or diseased bone tissue with either natural bone or bone substitutes. This study investigates the structure, mechanical properties, and in vitro response of an all-ceramic composite designed for use as a bone 'spackling' paste: a formable synthetic bone graft paste used to repair bone defects in place, reacting with CO2 gas in ambient conditions to become a void-filling, rigid scaffold. The composite is comprised of bioactive glass frit and a soluble liquid silicate precursor combined to form an air-setting, open porous scaffold with compressive strength within the low range for trabecular bone (1.3-4.4 MPa). Characterization of scaffolds, with varying amounts of binder, was executed in accordance with established design criteria of porosity, load-bearing capacity, and bioactivity. Bioactivity was assessed via morphological, structural, and chemical changes in surface mineralization that occurred during in vitro immersion in simulated body fluid. All phases of composite specimens were observed to form calcium phosphate minerals, indicating that a chemical change occurred between the bioactive glass and sodium silicate binder phase. Ion exchange between the two phases was likely, as sodium silicate (control) was not found to produce calcium phosphate in the absence of bioactive glass. Of the selected compositions, composites with 7.4 vol% sodium silicate binder were observed to possess the highest open porosity (44 vol%), highest rate of calcium phosphate mineralization, most uniform surface mineral distribution, and largest amount of hydroxycarbonate apatite formation. The structure, mechanical properties, and in vitro response of the composite scaffolds analyzed in this research signify their potential success as bone tissue scaffolds.
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Cementos para Huesos , Andamios del Tejido , Huesos , Cerámica , Vidrio , Porosidad , Ingeniería de TejidosRESUMEN
Iron(III) aminoterephthalate Metal-Organic Frameworks (Fe-BDC-NH2 MOFs) have been demonstrated to show potential for relevant industrial and societal applications (i.e., catalysis, drug delivery, gas sorption). Nevertheless, further analysis is required in order to achieve their commercial production. In this work, a systematic synthetic strategy has been followed, carrying out microwave (MW) assisted hydro/solvothermal reactions to rapidly evaluate the influence of different reaction parameters (e.g., time, temperature, concentration, reaction media) on the formation of the benchmarked MIL-101-NH2, MIL-88B-NH2, MIL-53-NH2 and MIL-68-NH2 solids. Characterization of the obtained solids by powder X-ray diffraction, dynamic light scattering and transmission electron microscopy allowed us to identify trends to the contribution of the evaluated parameters, such as the relevance of the concentration of precursors and the impact of the reaction medium on phase crystallization. Furthermore, we presented here for the first time the MW assisted synthesis of MIL-53-NH2 in water. In addition, pure MIL-101-NH2 was also produced in water while MIL-88-NH2 was the predominant phase obtained in ethanol. Pure phases were produced with high space-time yields, unveiling the potential of MW synthesis for MOF industrialization.
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Han et al. [(2020), IUCrJ, 7, 228-237] using advanced electron microscopy and crystallographic modelling rationalise the microstructure of twinning defects in order to visualize mesophase transitions and surface properties of G and D bicontinuous cubic mesostructured silica. This work furthers our understanding of how these phases originate in many natural and synthetic systems.
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Bicontinuous cubic structures in soft matter consist of two intertwining labyrinths separated by a partitioning layer. Combining experiments, numerical modelling and techniques in differential geometry, we investigate twinning defects in bicontinuous cubic structures. We first demonstrate that a twin boundary is most likely to occur at a plane that cuts the partitioning layer almost perpendicularly, so that the perturbation caused by twinning remains minimal. This principle can be used as a criterion to identify potential twin boundaries, as demonstrated through detailed investigations of mesoporous silica crystals characterized by diamond and gyroid surfaces. We then discuss that a twin boundary can result from a stacking fault in the arrangement of inter-lamellar attachments at an early stage of structure formation. It is further shown that enhanced curvature fluctuations near the twin boundary would cost energy because of geometrical frustration, which would be eased by a crystal distortion that is experimentally observed.
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The development of well ordered nanonetwork materials (in particular gyroid-structured materials) has been investigated using a block-copolymer template for templated electroless plating as an example system for the examination of network formation using X-ray scattering. By taking advantage of the nucleation and growth mechanism of templated electroless plating, gyroid-structured Au was successfully fabricated through the development of Au nanoparticles, then tripods and branched tripods, and finally an ordered network. Each stage in the development of the network phase could then be examined by combining real-space transmission electron microscopy observations with reciprocal-space small-angle X-ray scattering results. The fingerprint scattering profile of the building block for the network (i.e. the tripod of the gyroid) could be well fitted with the form factor of an effective sphere, and the diffraction results from the ordered network could thus be reasonably addressed. As a result, the examination of well ordered network materials can be simplified as the scattering from the form factor of a sphere convoluted with the nodes of its structure factor, providing a facile method of identifying the network phases from X-ray scattering data.
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During screening of the phase space using KOH and 1-methyl-4-aza-1-azoniabicyclo-[2.2.2]octane hydroxide (1-methyl-DABCO) under hydrothermal zeolite synthesis conditions, K-paracelsian was synthesized. Scanning electron microscopy, energy dispersive X-ray spectroscopy and ex situ powder X-ray diffraction analysis revealed a material that is compositionally closely related to the mineral microcline and structurally closely related to the mineral paracelsian, both of which are feldspars. In contrast to the feldspars, K-paracelsian contains intrazeolitic water corresponding to one molecule per cage. In the case of K-paracelsian it might be useful to consider it a link between feldspars and zeolites. It was also shown that K-paracelsian can be described as the simplest endmember of a family of dense double-crankshaft zeolite topologies. By applying the identified building principle, a number of known zeolite topologies can be constructed. Furthermore, it facilitates the construction of a range of hypothetical small-pore structures that are crystallo-chemically healthy, but which have not yet been realized experimentally.
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Functionalization of isophthalic acid ligands with linear alkoxide groups from ethoxy through pentoxy is shown to have a pronounced effect on both the synthesis of porous paddlewheel-based molecular assemblies and their resulting surface areas and gas adsorption properties. Shorter chain length is compatible with either tetragonal or hexagonal two-dimensional materials, with the hexagonal phase favored with longer chain length. Precise tuning of reaction conditions affords discrete molecular species that are soluble in a variety of organic solvents. The isolated porous molecules display BET surface areas ranging from 125 m2/g to 545 m2/g. The pentoxide-based molecular assembly shows considerable promise for the separation of hydrocarbons with average isosteric heats of adsorption of -48 and -31 kJ/mol for ethylene and ethane, respectively.
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In this paper, we review and illustrate applications, reported in the literature or used in our group, of 27Al-27Al double-quantum single-quantum (DQ-SQ) MAS NMR experiments for the structural characterization of Al-containing microporous solids, namely zeolites, aluminophosphates and metal-organic frameworks. Information regarding the periodic frameworks or the localization of the various aluminum species in the materials are obtained from the analysis of the two-dimensional NMR spectra, which allows getting local structural details sometimes inaccessible from other characterization technique. An application of 27Al-27Al of the DQ-SQ experiment for the detection of aluminum pairing in zeolite is shown.
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A crystalline and permanently porous copper phosphonate monoester framework has been synthesized from a tetraaryl trigonal phosphonate monoester linker. This material has a surface area over 1000â m2 g-1 , as measured by N2 sorption, the highest reported for a phosphonate-based metal-organic framework (MOF). The monoesters result in hydrophobic pore surfaces that give a low heat of adsorption for CO2 and low calculated selectivity for CO2 over N2 and CH4 in binary mixtures. By careful manipulation of synthetic conditions, it is possible to selectively remove some of the monoesters lining the pore to form a hydrogen phosphonate while giving an isomorphous structure. This increases the affinity of the framework for CO2 giving higher ambient uptake, higher heat of adsorption, and much higher calculated selectivity for CO2 over both N2 and CH4 . Formation of the acid groups is noteworthy as complexation with the parent acid gives a different structure.
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The mechanical properties of colloidal nanocrystal superlattices can be tailored through exposure to low-pressure plasma. The elastic modulus and hardness of the ligand-free 3.7 nm ZrO2 superlattice are found to be similar to bulk yttria-stabilized tetragonal polycrystals of the same relative density but without any doping.
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The impact of selected cellulose solvent systems based on the principal constituents tetrabutylammonium fluoride (TBAF), 1-ethyl-3-methyl-1H-imidazolium-acetate, N-methylmorpholine-N-oxide, or calcium thiocyanate octahydrate (CTO) on the properties of cellulose II aerogels prepared from these solvent systems has been investigated as a means towards tailoring cellulose aerogel properties with respect to specific applications. Cotton linters were used as representative plant cellulose. Cellulose was coagulated from solutions with comparable cellulose content, and dried with supercritical carbon dioxide after solvent exchange. The resulting bulk aerogels were comprehensively morphologically and mechanically tested to relate structure and mechanical properties. Different solvent systems caused considerable differences in the properties of the bulk samples, such as internal surface area (nitrogen sorption), morphology, porosity (He pycnometry, thermoporosimetry), and mechanical stability (compression testing). The results of SAXS, WAXS, and solid-state 13C NMR spectroscopy suggest that this is due to different mechanisms of cellulose self-assembling on the supramolecular and nanostructural level, respectively, as reflected by the broad ranges of cellulose crystallinity, fibril diameter, fractal dimension and skeletal density. Both solid state NMR and WAXS experiments confirmed the sole existence of the cellulose II allomorph for all aerogels, with crystallinity reaching a maximum of 46-50 % for CTO-derived aerogels. Generally, higher fibril diameter, degree of crystallinity, hence increased skeletal density were associated with good preservation of shape and dimension throughout conversion of lyogels to aerogels, and enhanced mechanical stability, but somewhat reduced specific surface area. Amorphous, yet highly rigid aerogels derived from TBAF/DMSO mixtures deviated from this trend, most likely due to their particular homogeneous and nanostructured morphology.