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Hierarchical porous hypercrosslinked monoliths (PolyHIPE‐HCP) with ultrahigh specific surface areas are prepared via a solvent knitting strategy. Compared to previous work, the solvent knitting strategy is carried out in a relatively low air‐controlled atmosphere with gradient heating starting from low temperature while using DCM (Dichloromethane) as both a solvent and a cross‐linker, allowing for a slow and controlled cross‐linking process, thereby achieving a BET surface area ranging from 514 to 728 m2 g−1. Scanning electron microscopy (SEM) shows that the knitting process does not affect the presence of macroporous structure in the PolyHIPE. With the introduction of mesopores and micropores, these hierarchical porous monoliths exhibit significant potential for applications in gas adsorption and water treatment. Hence, a universal, simple and low‐cost method to synthesize polymeric monoliths with hierarchically porous structure and higher surface area is proposed, which has fascinating prospects in industrialization. [ABSTRACT FROM AUTHOR]

Highlights Challenges and future directions for 3D-printed metal-organic frameworks (MOFs) monoliths in environmental applications are discussed. Various strategies for fabrication of 3D-printed MOF monoliths are summarized. Advancements in 3D printing enable customizable and high-performance MOF monoliths. 3D orienting of MOFs opens avenues for applications in water treatment and gas adsorption.

Highlights: Challenges and future directions for 3D-printed metal-organic frameworks (MOFs) monoliths in environmental applications are discussed. Various strategies for fabrication of 3D-printed MOF monoliths are summarized. Advancements in 3D printing enable customizable and high-performance MOF monoliths. 3D orienting of MOFs opens avenues for applications in water treatment and gas adsorption. Metal–organic frameworks (MOFs) have been extensively considered as one of the most promising types of porous and crystalline organic–inorganic materials, thanks to their large specific surface area, high porosity, tailorable structures and compositions, diverse functionalities, and well-controlled pore/size distribution. However, most developed MOFs are in powder forms, which still have some technical challenges, including abrasion, dustiness, low packing densities, clogging, mass/heat transfer limitation, environmental pollution, and mechanical instability during the packing process, that restrict their applicability in industrial applications. Therefore, in recent years, attention has focused on techniques to convert MOF powders into macroscopic materials like beads, membranes, monoliths, gel/sponges, and nanofibers to overcome these challenges.Three-dimensional (3D) printing technology has achieved much interest because it can produce many high-resolution macroscopic frameworks with complex shapes and geometries from digital models. Therefore, this review summarizes the combination of different 3D printing strategies with MOFs and MOF-based materials for fabricating 3D-printed MOF monoliths and their environmental applications, emphasizing water treatment and gas adsorption/separation applications. Herein, the various strategies for the fabrication of 3D-printed MOF monoliths, such as direct ink writing, seed-assisted in-situ growth, coordination replication from solid precursors, matrix incorporation, selective laser sintering, and digital light processing, are described with the relevant examples. Finally, future directions and challenges of 3D-printed MOF monoliths are also presented to better plan future trajectories in the shaping of MOF materials with improved control over the structure, composition, and textural properties of 3D-printed MOF monoliths. [ABSTRACT FROM AUTHOR]

The increasing emissions of gaseous pollutants of anthropogenic origin, such as carbon dioxide (CO2), which causes global warming, have raised great interest in developing and improving processes that allow their mitigation. Among them, adsorption on porous materials has been proposed as a sustainable alternative. This work presents a study of CO2 equilibrium adsorption at low temperatures (0, 10, and 20 °C) over a wide range of low pressures, on activated carbon derived from Eucalyptus (ES) and Patula pine (PP) forest waste, and carbonaceous material derived from waste tires (WT). The precursors of these materials were previously prepared, and their physicochemical properties were characterized. ES and PP were thermochemically treated with phosphoric acid, and WT was oxidized with nitric acid. Additionally, these materials were used to obtain monoliths using uniaxial compaction techniques and different binding agents, with better results obtained with montmorillonite. A total of six adsorbent solids had their textural and chemical properties characterized and were tested for CO2 adsorption. The highest specific surface area (1405 m2 g−1), and micropore properties were found for activated carbon derived from Eucalyptus whose highest adsorption capacity ranged from 2.27 mmol g−1 (at 0 °C and 100 kPa) to 1.60 mmol g−1 (at 20 °C and 100 kPa). The activated carbon monoliths presented the lowest CO2 adsorption capacities; however, the studied materials showed high potential for CO2 capture and storage applications at high pressures. The isosteric heats of adsorption were also estimated for all the materials and ranged from 16 to 45 kJ mol−1 at very low coverage explained by the energetic heterogeneity and weak repulsive interactions among adsorbed CO2 molecules. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks (MOFs) can efficiently purify hydrocarbons from CO2, but their rapid saturation, driven by preferential hydrocarbon adsorption, requires energy‐intensive adsorption–desorption processes. To address these challenges, an innovative approach is developed, enabling control over MOF flexibility through densification and defect engineering, resulting in an intriguing inverse CO2/C2 hydrocarbon selectivity. In this study, the densification process induces the shearing of the crystal lattice and contraction of pores in a defective CuBTC MOF. These changes have led to a remarkable transformation in selectivity, where the originally hydrocarbon‐selective CuBTC MOF becomes CO2‐selective. The selectivity values for densified CuBTC are significantly reversed when compared to its powder form, with notable improvements observed in CO2/C2H6 (4416 vs 0.61), CO2/C2H4 (15 vs 0.28), and CO2/C2H2 (4 vs 0.2). The densified material shows impressive separation, regeneration, and recyclability during dynamic breakthrough experiments with complex quinary gas mixtures. Simulation studies indicate faster CO2 passage through the tetragonal structure of densified CuBTC compared to C2H2. Experimental kinetic diffusion studies confirm accelerated CO2 diffusion over hydrocarbons in the densified MOF, attributed to its small pore window and minimal interparticle voids. This research introduces a promising strategy for refining existing and future MOF materials, enhancing their separation performance. [ABSTRACT FROM AUTHOR]

Monuments made of natural stones represent an important part of our world's cultural heritage but deteriorate by the direct or indirect interaction of mineral and stone weathering. Application of damage indices improves stone damage diagnosis and is very appropriate for the determination of necessary preservation procedures as well as the long-term survey and maintenance of stone monuments. The sandstones used at El Infiernito in Villa de Leyva, Colombia, today show weathering damages of partly extreme intensity. In-situ surveys allowed damage mapping which help to identify major causes of damage and to understand their relationship with stone and environment characteristics. In this research, the state of deterioration of the pre-Hispanic phallic monoliths in the Archaeological Park of Monquira "El Infiernito", is presented in the form of monument visual posters. Based on the visualizing of weathering forms at representative monoliths, the state of deterioration is precisely characterized and evaluated. The monument mapping and photographic documentation method can also be useful for reassessing weather damage in the framework of long-term monitoring and maintenance of monuments. This article presents the methodology of mapping weathering forms of stone monuments by using a visual classification system developed over the years with various applications. [ABSTRACT FROM AUTHOR]

Abstract\nCULMINATIONSThe ureter typically experiences a frequency of one to five peristaltic contractions per minute. However, it is important to note that these contractions can be disrupted by various physical and mechanical irritants. Ionic contents in the urine make it electrically conducting and responsive to electromagnetic body forces. MHD can be deployed in bio magnetic therapy to control or mitigate symptoms associated with peristaltic pumping in the urinary system.  This article therefore focuses on the hydromagnetic effects on flow patterns of urine with debris (monoliths). The mechanism of urine flow is largely coordinated by the kidneys. The flow inside the ureter is interrupted by microliths, which are generated by the sedimentation of excretory products. To simulate this, a two-phase formulation is adopted, comprising the electromagnetic urological viscous fluid phase and the particulate phase for solid grains. The peristaltic propulsion of two-phase liquid in the ureter is simulated as a sinusoidal wave propagation of incompressible non-Newtonian fluid. The Williamson viscoelastic model is deployed for the rheology. Heat transfer is also included with Soret thermo-diffusion and viscous heating effects. Long wave and low Reynolds number approximations are employed based on lubrication theory. The mass, momentum, energy and concentration conservation equations with associated boundary conditions are rendered non-dimensional via appropriate scaling transformations. A numerical solution is achieved via BVP4C MATLAB quadrature.  Graphical visualizations of the velocity, temperature and concentration (solid grains) are given for the influence of suspension parameter (ζ), Hartmann number (M), Prandtl number (Pr), Weissenburg number (We), particle volume fraction (C), Eckert number (Ec), Soret number (Sr), Schmidt number (Sc). The novelty of the present work is therefore the simultaneous consideration of a generalized two-phase model, wall slip, non-Newtonian characteristics, cross diffusion, viscous dissipation, mass diffusion, magnetic body force and curvature effects in peristaltic urological transport, which has not been undertaken previously. The detailed simulations reveal that the flow velocity is reduced due to the presence of solid particles and the channel curvature, in comparison to the flow in an unobstructed channel devoid of solid particles. Enhancing the hydrodynamic slip parameter speeds up the movement of particles and fluid near the channel walls, boosts wall skin friction, raises pressure difference in the pumping area, and amplifies bolus magnitudes.The rise in peristaltic pumping results in a reduction in solid particle concentration, which is significant phenomena.This theoretical approach may aid in treating conditions such as Urinary Tract Infections (UTIs). The computations effectively demonstrate that significant manipulation of urological pumping characteristics can be achieved with an electromagnetic field. Some new features of two-phase ureteral dynamics are highlighted as relevant to magnetic therapy techniques, which may be beneficial to clinicians.A detailed new formulation is given for magnetohydrodynamic (MHD) two-phase Williamson non-Newtonian ureteral transport with mass diffusion, Soret cross diffusion, viscous heating and peristaltic wave propulsion.We compute numerically the pressure gradient, skin friction, Nusselt number, and wall shear stress in a planar channel with flexible walls, which serves as a model for the ureter under a transverse magnetic field.We also investigate the impact of Hartmann number and Weissenberg non-Newtonian number on fluid and particle phase velocities.The present work reveals some interesting insights into electromagnetic ureteral peristaltic multi-phase non-Newtonian thermo-solutal transport phenomena via extensive visualization.There is a strong suppression in the ureteral fluid phase velocity for greater magnetic field confirming the excellent flow control abilities of Magnetic Ureteral Therapy (MUT).A detailed new formulation is given for magnetohydrodynamic (MHD) two-phase Williamson non-Newtonian ureteral transport with mass diffusion, Soret cross diffusion, viscous heating and peristaltic wave propulsion.We compute numerically the pressure gradient, skin friction, Nusselt number, and wall shear stress in a planar channel with flexible walls, which serves as a model for the ureter under a transverse magnetic field.We also investigate the impact of Hartmann number and Weissenberg non-Newtonian number on fluid and particle phase velocities.The present work reveals some interesting insights into electromagnetic ureteral peristaltic multi-phase non-Newtonian thermo-solutal transport phenomena via extensive visualization.There is a strong suppression in the ureteral fluid phase velocity for greater magnetic field confirming the excellent flow control abilities of Magnetic Ureteral Therapy (MUT). [ABSTRACT FROM AUTHOR]

The increasing demand for highly pure biopharmaceuticals has put significant pressure on the biotechnological industry to innovate in production and purification processes. Nucleic acid purification, crucial for gene therapy and vaccine production, presents challenges due to the unique physical and chemical properties of these molecules. Meeting regulatory standards necessitates large quantities of biotherapeutic agents of high purity. While conventional chromatography offers versatility and efficiency, it suffers from drawbacks like low flow rates and binding capacity, as well as high mass transfer resistance. Recent advancements in continuous beds, including monoliths and cryogel-based systems, have emerged as promising solutions to overcome these limitations. This review explores and evaluates the latest progress in chromatography utilizing monolithic and cryogenic supports for nucleic acid purification. [ABSTRACT FROM AUTHOR]

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The increasing demand for highly pure biopharmaceuticals has put significant pressure on the biotechnological industry to innovate in production and purification processes. Nucleic acid purification, crucial for gene therapy and vaccine production, presents challenges due to the unique physical and chemical properties of these molecules. Meeting regulatory standards necessitates large quantities of biotherapeutic agents of high purity. While conventional chromatography offers versatility and efficiency, it suffers from drawbacks like low flow rates and binding capacity, as well as high mass transfer resistance. Recent advancements in continuous beds, including monoliths and cryogel-based systems, have emerged as promising solutions to overcome these limitations. This review explores and evaluates the latest progress in chromatography utilizing monolithic and cryogenic supports for nucleic acid purification.

In this work, a 3D printing method, robocasting was utilized to manufacture zeolite ZSM-5-based woodpile monolith catalysts of approximately 10-mm diameter, using bentonite clay as binding matrix. The effect of three different binder concentrations, in the 40–60 wt.% range, on the rheological, physicochemical, and mechanical properties was examined. The rheometer measurements showed that the printing pastes have identical shear thinning behavior and demonstrate sufficient storage modulus, irrespective of the binder concentration. The printed monoliths had high BET surface areas and porosity. The results showed that the ZSM-5 crystals retained their porous structure, textural characteristics, and crystalline structure during the additive manufacturing process. Pyridine FTIR measurements demonstrated reduced total acidity and number of Brønsted acid sites in the final specimens due to the dilution with the bentonite powder. However, the acidity reduction was roughly proportional to the binder concentration, signifying that the ZSM-5 crystallites also retain their acidity during the robocasting printing. Finally, the mechanical reliability of the thermally treated monoliths was determined by calculating the Weibull modulus values through linear regression of the Weibull equation. The increase in the binder concentration increased the compression strength by a factor of 4.5 and achieved superior mechanical reliability. [ABSTRACT FROM AUTHOR]

Over millennia, and right across the globe, people have invested time and energy to create cultural landscapes that revolve around or incorporate powerful stones. Questions about the structured nature, distribution, source, or placement of stones (both within physical and meta‐physical worlds), pose intriguing theoretical and methodological challenges. Emic and etic perspectives may provide additional insights into the complex (often animate) nature of the stone, the purpose of which varied radically between communities. In this special number of Archaeology in Oceania we explore some of the ways in which First Nations and non‐Indigenous archaeologists address these potent features and objects, across widely varying chrono‐cultural contexts in the Australia–Pacific region. [ABSTRACT FROM AUTHOR]

MOFs are a class of porous crystalline materials whose unique properties have led to applicability in several fields ranging from gas adsorption to drug delivery. Despite their high potential, MOFs are usually found as fine powders, a property that can limit their use in industrial applications. Here, a novel approach is proposed to form densified Cu-MOF (Cu-BTC) powders and monoliths using 1,2-ethanedisulfonic acid (EDSA) as a densification agent. A MOF/EDSA mixture was heated to ∼150 °C; the molten EDSA not only promotes the growth of larger MOF crystallites, but also stimulates condensation reactions between the carboxylate-based MOF ligands, further binding the particles together. When this reaction was done in a stainless-steel die under pressure MOF-based monoliths could also be formed. Notably, using this approach, the MOF had a higher density, significantly improving the volumetric CO _2 adsorption capacity. We believe this contribution provides the basis for future work wherein the intrinsic MOF particle surfaces can be selectively engineered to improve their properties towards shaping for industrial applications.

Ethyl α‐cyanocinnamate was synthesized in the Knoevenagel condensation of benzaldehyde and ethyl cyanoacetate in flow monolithic microreactor of 0.63 cm3 volume. The catalytically active core was made of silica monolith modified with various amine group precursors. Structural properties of the support, surface density of NHx groups, and catalytic activity were investigated. It was found that the poly‐ or di‐amine groups attached to the silica surface appeared to be more effective than the aminopropyl groups. Microreactors grafted with diamine functional groups, accompanied by hydrophobic methyl groups, showed the highest activity and stability. It was proved that the decisive role on the activity of catalysts was exerted by the presence of primary amines in diamine chain. The reaction conditions were optimized and it was found that almost full substrate conversion could be achieved in 6 min at 50 °C in the microreactor with low concentration of diamine groups equal to 0.33 mmol g−1. [ABSTRACT FROM AUTHOR]

The water–gas shift (WGS) activity of Pt/TiO2-based powdered and structured catalysts was investigated using realistic feed compositions that are relevant to the high-temperature shift (HTS) and low-temperature shift (LTS) reaction conditions. The promotion of the TiO2 support with small amounts of alkali- or alkaline earth-metals resulted in the enhancement of the WGS activity of 0.5%Pt/TiO2(X) catalysts (X = Na, Cs, Ca, Sr). The use of bimetallic (Pt–M)/TiO2 catalysts (M = Ru, Cr, Fe, Cu) can also shift the CO conversion curve toward lower temperatures, but this is accompanied by the production of relatively large amounts of unwanted CH4 at temperatures above ca. 300 °C. Among the powdered catalysts investigated, Pt/TiO2(Ca) exhibited the best performance under both HTS and LTS conditions. Therefore, this material was selected for the preparation of structured catalysts in the form of pellets as well as ceramic and metallic catalyst monoliths. The 0.5%Pt/TiO2(Ca) pellet catalyst exhibited comparable activity with that of a commercial WGS pellet catalyst, and its performance was further improved when the Pt loading was increased to 1.0 wt.%. Among the structured catalysts investigated, the best results were obtained for the sample coated on the metallic monolith, which exhibited excellent WGS performance in the 300–350 °C temperature range. In conclusion, proper selection of the catalyst structure and reaction parameters can shift the CO conversion curves toward sufficiently low temperatures, rendering the Pt/TiO2(Ca) catalyst suitable for practical applications. [ABSTRACT FROM AUTHOR]

Haptoglobin (Hp) is a positive acute phase protein, synthesized in the liver, with four N‐glycosylation sites carrying mainly complex type N‐glycans. Its glycosylation is altered in different types of diseases but still has not been extensively studied mainly due to analytical challenges, especially the lack of a fast, efficient, and robust high‐throughput Hp isolation procedure. Here, we describe the development of a high‐throughput method for Hp enrichment from human plasma, based on monolithic chromatographic support in immunoaffinity mode and downstream Hp N‐glycome analysis by hydrophilic interaction ultrahigh‐performance liquid chromatography with fluorescent detection (HILIC–UHPLC–FLR). Chromatographic monolithic supports in a 96‐well format enable fast, efficient, and robust Hp enrichment directly from diluted plasma samples. The N‐glycome analysis demonstrated that a degree of Hp deglycosylation differs depending on the conditions used for N‐glycan release and on the specific glycosylation site, with Asn 241 being the most resistant to deglycosylation under tested conditions. HILIC–UHPLC–FLR analysis enables robust quantification of 28 individual chromatographic peaks, in which N‐glycan compositions were determined by UHPLC coupled to electrospray ionization quadrupole time of flight mass spectrometry. The developed analytical approach enables fast evaluation of total Hp N‐glycosylation and is applicable in large‐scale studies. [ABSTRACT FROM AUTHOR]

This study presents a new model to predict the additional pressure drop for series-arranged misaligned monoliths, relevant for high-flow industrial applications. Long reactor tubes often contain multiple short monoliths, leading to extra pressure drops as the flow enters and leaves multiple monoliths. Existing models address aligned monoliths, but this research considers misalignment, where extra pressure drop is higher. Channel Reynolds from 50 to 320, spacings from 0.1 to 20 channel diameters, and several void fractions are investigated using a discrete channel model. Results indicate a significant impact of misalignment on extra pressure drops in closely spaced monoliths due to flow collisions. A correction factor model that adapts to misalignment is proposed, starting from large values for closely spaced channels and decreasing as spacing increases. The proposed model aligns with discrete channel data and phenomenological behavior of aligned channels both in trend and magnitude, showing an R2 above 0.93. • Innovative model for pressure drop correction in misaligned monoliths. • Accounts for a wide range of Reynolds numbers and gap lengths. • Demonstrates a significant impact of misalignment on pressure drop. • Validated against discrete channel CFD data and real-world behavior. [ABSTRACT FROM AUTHOR]

Highly crosslinked monolithic capillary columns with inner diameters in the range of 50–530 μm were prepared by radical polymerization of pentaerythritol tetraacrylate, polyhedral oligomeric silsesquioxane‐methacrylate, and n‐octadecyl methacrylate in the presence of methanol, dodecyl alcohol, and polyethylene glycol lauryl ether. Columns were evaluated by inverse size‐exclusion chromatography employing a set of polystyrene standards of narrow molecular‐size distribution and by scanning electron microscopy. Chromatographic performance under reversed‐phase conditions was also evaluated. The combination of two effective crosslinkers as pentaerythritol tetraacrylate and polyhedral oligomeric silsesquioxane‐methacrylate in the polymerization mixture allows for the preparation of robust and efficient monolithic capillary columns within a fairly wide range of internal diameters. [ABSTRACT FROM AUTHOR]

Cylindrical, cm‐sized monolithic Al2O3 xerogels with hierarchical meso‐/macropore system were prepared by sol‐gel synthesis. The influence of both solvent exchange and drying on monolith stability and the resulting pore system was studied following mass and volume of the monolith as well as by porosimetry and electron microscopy. Crack‐free drying of the monoliths requires a proper management of drying stress. This is achieved by adjusting the drying rate and solvent exchange procedure applied to the intermediate lyogels. Moreover, mainly through differences in capillary pressure, changing the pore fluid allows an adjustment of the mesopore width from 7.6 nm to 10.5 nm. Neither solvent exchange nor drying affect the macropores, the width of which stays at 1.5 μm. Finally, CO2 methanation over Ni‐impregnated Al2O3 monoliths reveals CO2 conversion and CH4 selectivity comparable to an industrial Ni/Al2O3 benchmark catalyst. [ABSTRACT FROM AUTHOR]

Cylindrical, cm‐sized monolithic Al2O3 xerogels with hierarchical meso‐/macropore system were prepared by sol‐gel synthesis. The influence of both solvent exchange and drying on monolith stability and the resulting pore system was studied following mass and volume of the monolith as well as by porosimetry and electron microscopy. Crack‐free drying of the monoliths requires a proper management of drying stress. This is achieved by adjusting the drying rate and solvent exchange procedure applied to the intermediate lyogels. Moreover, mainly through differences in capillary pressure, changing the pore fluid allows an adjustment of the mesopore width from 7.6 nm to 10.5 nm. Neither solvent exchange nor drying affect the macropores, the width of which stays at 1.5 μm. Finally, CO2 methanation over Ni‐impregnated Al2O3 monoliths reveals CO2 conversion and CH4 selectivity comparable to an industrial Ni/Al2O3 benchmark catalyst. [ABSTRACT FROM AUTHOR]

The question of how easy the transition is between design and manufacturing by the 3D printing of periodic open cellular structures occurs from the analysis of cases in which additive manufacturing and heterogeneous catalysis merge. The synergy between these two fields suggests that one of the great advantages that the catalysis of this manufacturing methodology can take advantage of is the obtaining of advanced designs that would allow improving the processes from the geometry of the reactors. However, not all 3D-printing techniques offer the same degree of resolution, and this uncertainty grows when using more complex materials to work with, such as ceramics or metals. Therefore, the present work seeks to answer this question by finding experimentation strategies, starting with a simple case study inspired by the additive manufacturing–catalysis combination, in which a ceramic polymer resin of high thermal resistance is used to obtain POCSs that are potentially useful in thermochemical or adsorption processes. This exploration concludes on the need to define limits for what we have called an "effective work zone" that combines both design criteria and the real possibility of printing and manipulating the pieces, making sweeps in structural parameters such as cell size and the diameter of struts in the POCS. Similarly, the possibility of coating these systems with inorganic oxides is explored, using a generic oxide (Al2O3) to analyse this scenario. Finally, a cartridge-type assembly of these systems is proposed so that they can be explored in future processes by other researchers. [ABSTRACT FROM AUTHOR]

This work aims at understanding the attachment mechanisms and stability of proteins on a chromatography medium to develop more efficient functionalization methodologies, which can be exploited in affinity chromatography. In particular, the study was focused on the understanding of the attachment mechanisms of bovine serum albumin (BSA), used as a ligand model, and protein G on novel amine-modified alumina monoliths as a stationary phase. Protein G was used to develop a column for antibody purification. The results showed that, at lower protein concentrations (i.e., 0.5 to 1.0 mg·mL−1), protein attachment follows a 1st-order kinetics compatible with the presence of covalent binding between the monolith and the protein. At higher protein concentrations (i.e., up to 10 mg·mL−1), the data preferably fit a 2nd-order kinetics. Such a change reflects a different mechanism in the protein attachment which, at higher concentrations, seems to be governed by physical adsorption resulting in a multilayered protein formation, due to the presence of ligand aggregates. The threshold condition for the prevalence of physical adsorption of BSA was found at a concentration higher than 1.0 mg·mL−1. Based on this result, protein concentrations of 0.7 and 1.0 mg·mL−1 were used for the functionalization of monoliths with protein G, allowing a maximum attachment of 1.43 mg of protein G/g of monolith. This column was then used for IgG binding–elution experiments, which resulted in an antibody attachment of 73.5% and, subsequently, elution of 86%, in acidic conditions. This proved the potential of the amine-functionalized monoliths for application in affinity chromatography. [ABSTRACT FROM AUTHOR]

Aerogels are a unique class of nanoporous ultralight materials exhibiting wide range of textural characteristic properties and tunable porosities. Due to their remarkable features such as low density, high surface area, low refractive index, small thermal conductivity, low dielectric constant and low sound velocity, they exhibit a wide range of applications in different areas such as electronics, thermal and acoustic insulation, chemistry, biomedicine and optics. The special advantages of these materials are that they can be produced in different forms such as monoliths/granular, bead/microspheres, thin films or sheets and as blankets. Aerogels are found to be potential materials for the removal of CO2 through adsorption or electrochemical reduction. There is a plethora of research on different kinds of aerogels used for CO2 adsorption process. Research has been going on toward the development of aerogel-based electrocatalyst, which can be used for valorization of CO2 through electrochemical reduction methods. Although most of the review papers have covered applications of aerogels in CO2 capture, very few discuss the processing of aerogels, more so on their applications in CO2 valorization. In this review, we have collated literature of different forms of aerogels currently available and the steps involved in their fabrication process. In addition, we have covered applications of aerogels in CO2 capture. Furthermore, we focussed on the basic principles involved in the development of an aerogel electrocatalyst as well as recent developments of aerogels in electrochemical CO2 reduction. [ABSTRACT FROM AUTHOR]

A novel acetylcholinesterase Nano liquid chromatography capillary column (75 μm i.d. × 50 mm length) was developed for the fast screening of acetylcholinesterase inhibitors and the evaluation of their molecular recognition mechanism. Biotinylated acetylcholinesterase was immobilized on a streptavidin Nano liquid chromatography capillary column. Because of the very strong streptavidin‐biotin interaction, the acetylcholinesterase immobilization step performed by frontal analysis is very fast (required less than 10 min), and the amount of immobilized acetylcholinesterase was in the microgram range (1 μg). The yellow anion obtained from the enzymatic reaction detected at 412 nm was achieved within 60 s, and the immobilized acetylcholinesterase retained 96% of the initial activity beyond 90 days. This column was successfully applied for the discrimination of weak affinity ligands to acetylcholinesterase from nonbinders, which is the heart of fragment‐based drug design. This column was used for the determination of the IC50 values of a series of inhibitor molecules. In addition, it was demonstrated that competitive experiments could be performed with our miniaturized system to confirm the existence and binding pocket of a ligand to acetylcholinesterase contained in a methanol plant extract. The results revealed that our acetylcholinesterase Nano liquid chromatography capillary column developed in this work represents a useful tool for the rapid screening of inhibitor candidates and evaluation of the action mechanism. [ABSTRACT FROM AUTHOR]

Service‐oriented architecture (SOA) has been widely used to design enterprise applications in the past two decades. The services in SOA are becoming complex with the increase in changing user requirements and SOA is still seen as monolithic from a deployment perspective. Monolithic services make the application complex, and it becomes difficult to maintain. With the evolution of microservices architecture, software architects started migrating legacy applications to microservices. However, existing migration approaches in the literature mostly focus on migrating monolithic applications to microservices. To the best of our knowledge, very few works have been done in migrating SOA applications to microservices. One of the major challenges in the migration process is the extraction of microservices from the existing legacy applications. To address this, we propose an approach to extract the candidate microservices using graph based algorithms. In particular, four algorithms are defined: (i) construction of service graph (SG), (ii) construction of task graph (TG) for each service of the a SOA application, (iii) extraction of candidate microservices using the SG of SOA application, and (iv) construction of a SG for a microservices application to retain the dependencies between the generated microservices. We chose a SOA‐based web application to demonstrate the proposed microservices extraction approach and extracted the microservices. Additionally, we have evaluated the extracted microservices and compared them with SOA based services. [ABSTRACT FROM AUTHOR]

An efficient multiple fibers solid‐phase microextraction method based on porous monolith was established for Se(IV) and Se(VI) analysis. Poly(4‐vinylphenylboronic acid/styrene‐co‐ethylene dimethacrylate/divinylbenzene) monolith was fabricated and employed as the extraction phase for efficient entrapment of Se(IV) complexed with o‐phenylenediamine, followed by elution with a methanol/formic acid (99/1.0, v/v) mixture and quantification by high‐performance liquid chromatography with diode array detector. The Se(VI) species was measured by the difference between total inorganic Se and Se(IV) after pre‐reduction. Different characterization techniques were employed to inspect the structure and morphology of prepared adsorbent. A series of key extraction factors were optimized so as to achieve the expected extraction performance. Under the optimized separation and capture parameters, the linear range and limit of detection for Se(IV) in water sample were 0.050–200 and 0.013 μg/L, respectively. For beer sample, the corresponding values were 0.010–300 and 0.032 μg/L. The developed microextraction approach was successfully utilized to detect trace Se(IV) and Se(VI) in environmental water and beer samples with satisfactory fortified recovery and repeatability. Results well reveal the attractive merits of the established method in the analysis of Se species, including simple preparation of adsorbent, convenient extraction procedure, good sensitivity, high cost‐effectiveness, and eco‐friendliness. [ABSTRACT FROM AUTHOR]

Photocatalysis has the potential to make a major technological contribution to solving pressing environmental and energy problems. There are many strategies for improving photocatalysts, such as tuning the composition to optimize visible light absorption, charge separation, and surface chemistry, ensuring high crystallinity, and controlling particle size and shape to increase overall surface area and exploit the reactivity of individual crystal facets. These processes mainly affect the nanoscale and are therefore summarized as nanostructuring. In comparison, microstructuring is performed on a larger size scale and is mainly concerned with particle assembly and thin film preparation. Interestingly, most structuring efforts stop at this point, and there are very few examples of geometry optimization on a millimeter or even centimeter scale. However, the recent work on nanoparticle‐based aerogel monoliths has shown that this size range also offers great potential for improving the photocatalytic performance of materials, especially when the macroscopic geometry of the monolith is matched to the design of the photoreactor. This review article is dedicated to this aspect and addresses some issues and open questions that arise when working with macroscopically large photocatalysts. Guidelines are provided that could help develop novel and efficient photocatalysts with a truly 3D architecture. [ABSTRACT FROM AUTHOR]

Advances in the development of column‐based analytical separations are strongly linked to the development of novel materials. Stationary phases for chromatographic separation are usually based on silica and polymer materials. Nevertheless, recent advances have been made using porous crystalline reticular materials, such as metal‐organic frameworks and covalent organic frameworks. However, the direct packing of these materials is often limited due to their small crystal size and nonspherical shape. In this review, recent strategies to incorporate porous crystalline materials as stationary phases for liquid‐phase separations are covered. Moreover, we discuss the potential future directions in their development and integration into suitable supports for analytical applications. Finally, we discuss the main challenges to be solved to take full advantage of these materials as stationary phases for analytical separations. [ABSTRACT FROM AUTHOR]

Herein, it has been developed a method to prepare metallic foams starting from Zamak5 (ZnAlCu alloy) with different pore sizes. The Zamak5 metallic foam is designed to serve as a support and metallic precursor of ZIF-8. In this way, composite materials MOF-metal can be prepared, these composites have a large number of application in energy exchange processe such as: adsorption or chemical reactions. Additionally, this method of sythesizing MOFs is environmentally friendly thanks to absence of solvents. Hanerssing the low melting point of the linker, the linker is infiltrated into the foam where the foam and the linker react to form the ZIF-8. In this way we have managed to transform part of the foam into ZIF-8 crystals that remain adhered to the foam. The foams have been characterized and modeled studying the mechanical and electrical properties, finding that both can be predected by various models. Among these, Ashby and Mortensen models for mechanical properties and Ashby and Percolation model for electrical properties stand. [ABSTRACT FROM AUTHOR]

Abstract Photocatalysis has the potential to make a major technological contribution to solving pressing environmental and energy problems. There are many strategies for improving photocatalysts, such as tuning the composition to optimize visible light absorption, charge separation, and surface chemistry, ensuring high crystallinity, and controlling particle size and shape to increase overall surface area and exploit the reactivity of individual crystal facets. These processes mainly affect the nanoscale and are therefore summarized as nanostructuring. In comparison, microstructuring is performed on a larger size scale and is mainly concerned with particle assembly and thin film preparation. Interestingly, most structuring efforts stop at this point, and there are very few examples of geometry optimization on a millimeter or even centimeter scale. However, the recent work on nanoparticle‐based aerogel monoliths has shown that this size range also offers great potential for improving the photocatalytic performance of materials, especially when the macroscopic geometry of the monolith is matched to the design of the photoreactor. This review article is dedicated to this aspect and addresses some issues and open questions that arise when working with macroscopically large photocatalysts. Guidelines are provided that could help develop novel and efficient photocatalysts with a truly 3D architecture.

[Display omitted] • Brief overview of past developments, current status. • The potential for process intensification, energy and materials efficiency. • Exciting new developments towards dedicated reactor designs, away from one-fits-all. • R&D directions for a future sustainable chemical industry. • Handling highly exothermal catalytic reactions in chemicals production. In this perspective paper a brief overview is given of the past developments in the field of structured catalysts and reactors, the potential for process intensification, energy and materials efficiency. Current exciting new developments for demanding processes are highlighted and directions indicated that contribute to a future sustainable chemical industry. [ABSTRACT FROM AUTHOR]

The evidence of Cross River State in Nigeria as a global visual cultural, biodiversity and wildlife tourism distinction located in West Africa is presented using photo-inventory. A socioscientific photo-sourcing and explanation was carried out. The ancient city of Calabar that received early Christian missionaries to Nigeria is the capital of Cross River State in Nigeria, West Africa now host the Africa's annual biggest street party (Calabar carnival). The ancient house of Mary Mitchell Slessor a Scottish missionary to Nigeria who stopped the ancient practice of killing of twins and multiple births built in 1848, stands in Calabar as a monument that attracts tourists from all parts of the world. The international Ekpe masquerade, boat and canoe race in Calabar, lebuko new yam festival in Ugep, Central Cross River are tourists attracted festivals. Being home of tropical forest with rare biodiversity added with wildlife, some mammals as endangered Gorilla, drill, chimpanzee and African black elephants, including different species of African Primates are seen in the protected zones of the National Park and Afi Wildlife Sanctuary. Photos of numerous huge ancient carved and engraved standing stones (Monoliths) dating back to 1200 BC are found in about 30 communities in Ikom, the Central part of Cross River State of Nigeria. Spectacular natural waterfalls for relaxation are in existence. The Obudu mountain Resort city exhibit the four weather type witness in Europe and America. The Resort is located on a mountain 1600 m high in the Northern Cross River State. Photos of the winding road from the bottom of the mountain to the top and nature dug swimming pools are places to visit. [ABSTRACT FROM AUTHOR]

In this study, a new adsorbent based on monolith/aminated carbon nanotubes composite was facilely prepared and employed as the extraction phase of multiple monolithic fibers solid‐phase microextraction for the capture of phenoxycarboxylic acids herbicides. The adsorbent was fabricated by mingling aminated carbon nanotubes in the poly (allylthiourea‐co‐ethylene glycol dimethacrylate) monolith. Various techniques were employed to characterize the morphology, structure, and pore size of the prepared adsorbent. The proposed microextraction method displayed satisfactory capture performance towards studied analytes through multi‐interactions such as hydrogen‐bonding, hydrophobic and π‐π interactions. Under the optimized conditions, a sensitive and reliable method to quantify trace analytes in water and soil samples was developed. The limits of detection were in the ranges of 0.13–0.25 μg/L and 0.20–0.61 μg/kg for water and soil samples, respectively. The practicality of the introduced method was demonstrated by applying it to monitor the contents of studied analytes in environmental water and soil samples. Satisfactory fortified recoveries (76.4–119%) and reproducibility were obtained. The achieved results well demonstrated that the suggested microextraction technique can efficiently extract phenoxycarboxylic acids and the developed method exhibits a promising potential for reliable and sensitive quantification of trace analytes in complex samples. [ABSTRACT FROM AUTHOR]

Monoliths of TiO2-SiO2 were synthesized by the Evaporation-Induced Self-Assembly (EISA) method and tested in the photocatalytic degradation of 4-chlorophenol. The way of adding the titanium precursor and the calcination conditions (temperature and air flow) were studied and were found to be key parameters in determining the physical, morphological, structural and photocatalytic properties. Opaque monoliths with crystalline anatase and rutile structures were obtained after calcination when the titanium precursor was directly added during the Si sol synhesis. Under another approach, adding the titanium precursor as a Ti sol to the Si sol, transparent materials with amorphous or small crystal size structures were produced. All monoliths presented mesoporous structures with specific surface areas in the value range of 528–813 m2g−1. The highest values corresponded to those materials calcined under air flow. The materials were tested in the 4-chlorophenol photocatalytic activity. After testing, a significant decrease in the concentration of 4-chlorophenol after 10 min of reaction was observed. The material in which the Ti precursor was added as sol (labeled as TSINS), presented the highest 4-chlorophenol degradation, reducing 86% of the initial concentration (2.33 × 10–4 mmol/cm3). Liquid chromatography shows the formation of intermediate compounds resulting from the decomposition of 4-chlorophenol and their subsequent partial mineralization. [ABSTRACT FROM AUTHOR]

Herein, we report the preparation and application of a new nano‐structured monolithic nanocolumn based on modified graphene oxide using narrow fused silica capillary column (e.g., 50 μm internal diameter). The nanocolumn was prepared by an in situ polymerization using butyl methacrylate, ethylene dimethacrylate, and methacryloyl graphene oxide nanoparticles. Dimethyl formamide and water were used as the porogenic solvent. After polymerization, the obtained nanocolumn was coated with dimethyloctadecylchlorosilane in order to enhance the hydrophobicity. Both isocratic and gradient nano‐liquid chromatographic separations for small molecules (e.g., alkylbenzenes) and macromolecules (e.g., intact proteins) were performed. Theoretical plates number up to 3600 plates/m in isocratic mode for propylbenzene were achieved. It was demonstrated that the feasibility of graphene oxide modified monolithic nanocolumn for high‐efficiency and high‐throughput nanoscale proteomics analysis. The high resolving power of monolithic nanocolumn yielded sensitive protein separation with narrower peak width while a high‐resolution analysis of peptides from trypsin‐digested cytochrome C could be obtained. Graphene oxide based monolithic nanocolumns are promising and can allow to powerful tools for trace proteom sample analysis. [ABSTRACT FROM AUTHOR]

Additive manufacturing of complex porous polymer geometries is a new field of advanced materials processing. Such new geometries can be used to fabricate porous polymer monoliths serving as a support for other material functions. Here, a novel fabrication technology to manufacture tailored 3D porous monoliths via additive manufacturing and templating is presented. The method is based on replicating a 3D‐printed mold with a polymer solution of polyvinylidenfluorid‐triethyl phosphate (PVDF‐TEP) and induce phase separation of the polymer solution subsequently. In a second step, the mold is removed without affecting the porous PVDF phase. As a result, porous monoliths with a templated 3D architecture are successfully fabricated. The manufacturing process is successfully applied to complex structures and can be applied to any conceivable geometry. Coating the porous 3D monoliths with another PVDF solution allows applying a skin layer yielding an asymmetric membrane monolith. As a showcase, a polydimethylsiloxane coating even leads to a smooth and dense layer of micrometer size. The methodology enables a new generation of complex porous polymer monoliths with tailored surface coatings. For the combination of poly(dimethylsiloxane) on a porous support, gas/liquid mass transfer is used in blood oxygenation with reduced diffusion limitation is within reach. [ABSTRACT FROM AUTHOR]

A hard‐templating method is presented for the synthesis of functional ring‐opening metathesis polymerization (ROMP) derived, poly(norborn‐2‐ene)‐based monolithic supports prepared under solvent‐induced phase separation conditions using the first‐generation Grubbs initiator RuCl2(PCy3)2(CHPh) (1, Cy = cyclohexyl). Norborn‐2‐ene (NBE), 1,4,4a,5,8,8a‐hexahydro‐1,4,5,8‐exo,endo‐dimethanonaphthalene (DMN‐H6) and trimethylolpropane‐tris‐(5‐norbornene‐2‐yl‐carboxylate (TMPTNC) are used as monomers and crosslinkers, respectively. 2‐Propanol and toluene are used as macro‐ and microporogen. Silica (SiO2) nanowires (SNWs) surface‐modified with NBE are used as hard templates. exo,endo‐Norborn‐5‐ene‐2‐ylmethanol (NBE‐CH2OH) is used as functional comonomer. The tailored porogenic system together with the surface‐functionalized SNWs allows for a full dispersion of the SNWs in the polymerization mixture and their incorporation into the monolithic structure during the phase separation process. This way, ROMP‐derived monoliths with pore dimensions of 10–15 nm, specific surface areas up to 3.7 m2 g−1, and pore porosities up to 33% are obtained after removal of the SNWs by chemical etching at room temperature. [ABSTRACT FROM AUTHOR]

Catalysis, a driving force of the chemical industry is increasingly being influenced by additive manufacturing. The link between them is based on the need to intensify catalytic processes in order to make them more efficient and sustainable. Additive manufacturing can satisfy such a need, generating devices with an advanced design, easy production, and great adaptation, in addition to their catalytic functionality. The exponential growth of examples reported on the application of 3D-printing in catalysis has led to the need to compile and analyse these cases and thus establish, through this review, the most in-depth analysis done to date.The manuscript includes a brief background of the history of additive manufacturing and the classification of the different printing techniques. Subsequently, it identifies the intensification of processes, among other aspects, as the key for understanding the union of additive manufacturing and catalysis. Then, it explores in detail how such a combination occurs, establishing the most comprehensive classification to date between the two large groups of printable devices with catalytic properties. Finally, a series of perspectives are proposed in which the most probable courses of new advances in this field of research are identified.

[Display omitted] • A one-dimensional model (1D) to predict the effective reaction rates in monoliths with non-uniform coating was introduced. • Linear and nonlinear isothermal kinetic expressions were studied. • A remarkable agreement between numerical solution and predictions from the 1D model was achieved. A two-zone model (1D-2Z) for the estimation of the effective reaction rates in monoliths with non-uniform coating is presented in this contribution. The model relies on the idea of splitting the cross section of the coating in two zones that can be modelled as independent zones with diffusion (and simultaneous reaction) in a single direction (1D). One of the zones is considered a slab, while the variable diffusivity model (1D-VD), whose predictive capabilities has been largely tested in previous works for a great variety of kinetic expressions and catalyst geometries, is applied to the other. The performance of the 1D-2Z model, as well as the results from approximate methods from literature are assessed for three kinetic expressions: a first order reaction, as an elementary kinetics, and two more challenging cases defined by Langmuir-Hinshelwood-Hougen-Watson expressions: one of them with a moderate inhibition effect, and the other with such an effect on the verge of the onset of multiple steady states. Square and triangular channel cross-sections presenting different degrees of non-uniform coating are considered. It was found that the 1D-2Z model is highly accurate, leading to errors in the estimation of the effectiveness factors below 8.5 % in all the cases analysed, for the entire range of Thiele modulus. Simultaneously, a noticeable decrease in computational demand can be achieved from the use of the 1D-2Z model, in comparison to the previous simplifying approaches. [ABSTRACT FROM AUTHOR]

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We report the first of its kind synthesis of CeO2/La2O3 nanocomposites that are with integrated mesoporous TiO2 monoliths, with well-defined structural and surface properties, to act as visible-light responsive photocatalysts. The structural features of the photocatalyst materials are defined using HR-TEM, p-XRD, FE-SEM, SAED, EDAX, XPS, PLS, TGA, IR, UV–Vis–DRS and BET/BJH analyses. The stoichiometric infusion of CeO2/La2O3 nanocomposites with the monolithic TiO2 network reduces the bandgap energy from 3.26 to 2.52 eV, thus promoting excellent visible-light photocatalysis. To evaluate the photocatalytic efficiency of the proposed photoactive materials, two antimicrobial drugs namely, moxifloxacin and ciprofloxacin are selected as target pollutants. It is observed that the uniform and continuous porous monolithic network ensures easy transport of pollutant molecules to the photoactive sites, thereby felicitating their faster dissipation. The influence of various physico-chemical parameters has been studied by photolysis and photocatalysis procedures, and the extent of drug degradation is quantitatively analysed by using a robust HPLC-DAD method. The photocatalysis results reveal that the monolithic photocatalyst can serve efficiently for environmental remediation applications, with excellent reusability character. [ABSTRACT FROM AUTHOR]