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In this study, new monolithic poly(9-anthracenylmethyl methacrylate-co-trimethylolpropane trimethacrylate (TRIM) columns, referred as ANM monoliths were prepared, for the first time, and were used for the separation media for biomolecules and proteomics analysis by nano-liquid chromatography (nano-LC). Monolithic columns were prepared by in situ polymerization of 9-anthracenylmethyl methacrylate (ANM) and trimethylolpropane trimethacrylate (TRIM) in a fused silica capillary column of 100 µm ID. Polymerization solution was optimized in relation to monomer and porogenic solvent. Scanning electron microscopy (SEM) and chromatographic analyses were performed for the characterization studies of ANM monoliths. The ANM monolith produced more than 46.220 plates/m, and the chromatographic evaluation of the optimized ANM monolith was carried out using homologous alkylbenzenes (ABs) and polyaromatic hydrocarbons (PAHs), allowing both strong hydrophobic and π-π interactions. Run-to-run and column-to-column reproducibility values were found as <2.91% and 2.9–3.2%, respectively. The final monolith was used for biomolecule separation, including both three dipeptides, including Alanine-Tyrosine (Ala-Tyr), Glycine-Phenylalanine (Gly-Phe), and L-carnosine and five standard proteins, including ribonuclease A (RNase A), α-chymotrypsinogen (α-chym), lysozyme (Lys), cytochrome C (Cyt C), and myoglobin (Mb) in order to evaluate its potential. Both peptides and proteins were baseline separated using the developed ANM monolith in nano-LC. The ANM monolith was then applied to the protein and peptide profiling of MCF-7 cell line, which allowed a high-resolution analysis of peptides, providing a high peak capacity. [ABSTRACT FROM AUTHOR]

ABSTRACT Islands are fundamental model systems in ecology, biogeography, and evolutionary biology. However, terrestrial islands, unlike their aquatic counterparts, have received comparatively less attention. Among these land islands, inselbergs (i.e. isolated rock outcrops with diverse lithologies and a modest topographical prominence) stand out as iconic examples distributed worldwide across global biomes. Due to their durable lithology, inselbergs change slowly, persisting for tens of millions of years. In this review, we propose a biological definition for inselbergs that captures three fundamental characteristics of inselbergs from the perspective of biota. These are old age, isolation and the presence of unique microhabitats that are rare or absent in the surrounding matrix, fostering distinct communities often with unique and endemic biota. We synthesise the state of the art and formulate a set of testable hypotheses to deepen our understanding of the origins and maintenance of diversity on inselbergs, which are increasingly exposed to anthropogenic threats. By offering different habitats compared to the surrounding habitat matrix (e.g. moist microhabitats in dryland landscapes and xeric environments in humid tropical landscapes), inselbergs may allow specific lineages to thrive beyond their typical geographical limits. Particularly in drylands and degraded landscapes, inselbergs may not just provide different habitats but also act as ecological refuges or evolutionary refugia by providing a wider range of potential microhabitats than the surrounding matrix, enhancing resilience and promoting regional biodiversity. The central role of the matrix ensures that the ecological and evolutionary dynamics of inselbergs differ from those of true islands such as oceanic islands. Given that inselberg biota coexist within a terrestrial matrix, interactions between inselberg and matrix populations impact each other significantly. Over evolutionary timescales, matrix species may contract to inselberg refugia, preserving lineages while cycles of isolation and reconnection may drive speciation via a species pump. Although inselberg biodiversity has been studied predominantly from an island biogeography perspective, we argue that depending on the spatial scale, habitat specificity and mobility of the organisms considered, a range of different theories and paradigms can help explain the biogeography and local distribution patterns of different taxonomic and functional groups of inselberg species. [ABSTRACT FROM AUTHOR]

Practical aspects of the successful preparation of monolithic poly(methylsilsesquioxane) (PMSQ) aerogels with glasslike transparency via ambient pressure drying (APD) are discussed in detail. Two-step acid-base process starting from methyltrimethoxysilane (MTMS) in the presence of nonionic poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) surfactant and the use of strong base as polycondensation catalyst resulted in fine mesoporous structure, showing low bulk density (0.148 g cm−3) and glasslike transparency (95% at 10 mm thickness). Cracking and irreversible shrinkage during APD have been prevented by optimized aging and drying processes. In particular, aging in an aqueous alcohol solution containing a low concentration of MTMS under controlled temperature has been found to be crucial in obtaining PMSQ aerogels with crack-free, low-density, glasslike transparency, and monolithic nature. A large-area APD aerogel in 93 × 93 × 6 mm3, with thermal conductivity of 15.6 mW m−1 K−1, has successfully been obtained due to optimizations of aging and drying conditions. Similar APD aerogels have also been obtained when alkali metal hydroxides, especially lithium hydroxide, are employed as base catalysts. These findings are expected to play important roles in designing industrial productions of monolithic aerogels for thermal superinsulation and other applications. Highlights: Poly(methylsilsesquioxane) aerogels with glasslike transparency were prepared from methyltrimethoxysilane. Aerogels were obtained also by ambient pressure drying in addition to supercritical drying. A large-area aerogel monolith with low thermal conductivity was successfully obtained. [ABSTRACT FROM AUTHOR]

Poly(butyl methacrylate‐co‐ethylene dimethacrylate) monolith was in situ prepared in a liquid chromatography capillary column with a 75 μm internal diameter. This monolith offered high permeability (5.3 ± 10−14 m2) and good peak capacity (140 for a 15 cm column length at 300 nl/min with a 20 min gradient time). This is exemplified by its separation ability in reversed mode for subunit analysis of monoclonal antibodies after IdeS digestion (middle‐up analysis). The potential of this column was also illustrated for the fast analytical control of therapeutic monoclonal antibodies in standardized infusion bags prepared in advance in a pharmacy department. Linearity analysis revealed the column's capability for accurate quantification analysis of the different dose bandings (in mg) of monoclonal antibodies in <2 min. In addition, lifetime analysis data indicated that the column can be highly reproducible and has a long lifetime with stable and low back pressure. The variations observed on the peak shape and area between unstressed (intact) and stressed monoclonal antibodies indicated that our nano liquid chromatographic method was stability indicating. In addition, using a gradient elution mode, the presence of minor components in the infusion bags was visualized. [ABSTRACT FROM AUTHOR]

This study demonstrated the production of activated carbon monoliths from biomass waste (Delonix regia pods) using a facile method. This was achieved using solvated polystyrene as the binder, which has never been achieved in the past, and KOH as the activating agent. The monolith's pore structures, functional group, morphology, and elemental composition were all investigated. According to the results, the monolith was found to have mesoporous properties, with a surface area of 314.9 m2/g and a pore size of 2.45 nm. Several functional groups, including nitro, carboxyl, and carbonyl groups, were identified, which confirms the potential applications of the monolith. Meanwhile, the KOH activator causes the production of particles with various clusters. The results demonstrated that solvated polystyrene has the ability to function as a binder in monolithic formation and are comparable to those of earlier investigations. [ABSTRACT FROM AUTHOR]

Drying shrinkage during ambient pressure drying of silica gels is made reversible by preventing condensation reactions of surface silanol groups via surface modification. This partial recovery of the gel volume and structure is referred to as the spring-back effect (SBE) and enables the production of monolithic silica aerogels by evaporative drying. The SBE is sometimes completed by annealing at mild temperatures. Similarities between drying-related deformations and deformations induced by mechanical stimuli suggest analogous underlying mechanisms. While the causes of drying shrinkage are relatively well-known, it remains unclear how the relaxation of the structure by drying and annealing occurs across the different length scales. Here we show a complete structural recovery of silica aerogels at the macro- and nano-scale enabled by annealing. We propose that residual deformations after drying and mechanical compression are caused by the entanglement of silica clusters that can be unraveled by annealing at 230 °C. The deformation under loading is interpreted as two different re-arrangement mechanisms for dry and annealed gels, by the sliding of the silica clusters along the loading direction and by the compression of large pores beyond the fractal structure, respectively. Our results demonstrate how the shape and structure of silica aerogels can be restored and controlled by thermal activation, broadening the various applications of these materials. We also emphasize how tuning silica gels to promote a two-step SBE by annealing can pave the way toward the production of larger monolithic aerogels by APD. Highlights: Two-step spring-back of silica aerogels upon annealing at 230 °C. Residual solvent and silica cluster entanglement hinder full re-expansion. Annealed aerogels show a near-zero Poisson's ratio during compression. Interpretation of fractal dimension evolution during deformation of mesoporous materials. Annealing allows full recovery of macro- and nano-structure, highlighting programmable nature. [ABSTRACT FROM AUTHOR]

Solvothermal synthesis is the predominant method for creating new structured covalent organic frameworks (COFs), yet it grapples with challenges in controlling shape and morphology. This issue is attributed to the unregulated solvent‐feeding process, which results in rapid polymerization and uncontrolled phase separation. Consequently, a two‐step solvent‐feeding process is reported for the solvothermal shaping of imine‐linked COF monoliths with hierarchical porosity. The synthesis conditions for COF powders reported in existing literature are directly utilized without extensive optimization; however, solvents are divided into two segments prior to feeding. A minor segment of solvents is employed to dissolve monomers, which polymerize in situ to form amorphous monoliths. Subsequently, the remaining organic solvent, along with an acetic acid aqueous solution, is added for crystallization. The versatility of this two‐step feeding process in producing COF monoliths is illustrated. The high‐quality COF monoliths demonstrate benzene uptakes ranging from 6.0 to 16.8 mmol g−1 at 298 K. This study confirms that the two‐step solvent feeding process can be effectively integrated with the conventional solvothermal method to enhance the solution‐processability of COFs. It is anticipated that this modified solvothermal approach can readily shape COFs to meet practical application requirements. [ABSTRACT FROM AUTHOR]

Staphylococcus aureus Protein A was immobilized on an in‐house made neutravidin poly (glycidyl methacrylate‐co‐ethylene dimethacrylate) capillary column with a 25 µm internal diameter, a length of 30 mm and a mass loadability of 60 ng. The immobilized quantity of protein A on the organic monolith was very low, in the pico mole range (1.80 pmol). This was of significance importance when working with less available or expensive purified enzyme. This capillary column was integrated into a nano liquid chromatographic system and used for the fast determination without dilution of the doses of therapeutic monoclonal antibodies (mAbs) in standardized infusion bags prepared in advance in a pharmacy department. This chromatographic method was linear in the studied concentration range with good precision and accuracy. Heat stressed studies indicated that the protein A affinity capillary column was able to monitor degraded mAbs. As well, the high specificity of this column to capture immunoglobulin G2 in cell culture supernatant was visualized. As the mAbs are produced through genetic engineering of animal cells this last result demonstrated that this novel protein A column could be used in the feature for rapid screening of immunoglobulin G concentration in cell culture. [ABSTRACT FROM AUTHOR]

Cylindrical column with packed stationary phase is the workhorse of liquid chromatography systems. These stationary phases are commonly classified on the basis of different form factors namely, beads and monoliths for protein chromatography. Monolithic rods are one of the important geometries derived from polymers through complex polymerization schemes with additional requirements such as cross-linkers and specific reaction conditions. To address these practical difficulties and enable ease of fabrication at laboratory scale, acrylic copolymers are hypothesized to perform as a monolithic stationary phase suitable for protein chromatography. The present work proposes a rapid fabrication technique to obtain monolithic rods that could be reconditioned without any of the above additional steps. It is characterized with monolith diameter that could be controlled using acrylic copolymer concentration. Formation of the copolymeric stationary phase inside microchannel led to annular geometry and in turn, demonstrated fabrication of moon-shaped channels (MSCs) for the first time in literature. An online monitoring system facilitated tracer breakthrough analysis with MSCs to report sharp peak front and an estimate of channel void volume. Breakthrough curves with single protein validated the selection of blue dextran as tracer and indicated retention of proteins due to electrostatic interactions on the functional copolymer surface. [ABSTRACT FROM AUTHOR]

Cloud computing has become a popular choice for deploying web applications, but the selection of the appropriate architecture for different application types remains a challenge for businesses. In this study, we conducted performance and cost analyses of three architectures: Monolith, Microservice, and Serverless (specifically Lambda and Fargate) to provide businesses with valuable insights for decision-making. To ensure the relevance of our findings, we conducted tests on an application designed for static, database, and batch job services, deployed on AWS. Using JMeter, we simulated traffic with varying levels of high, medium, and low intensity, distributing 500 requests across six test scenarios. The results and subsequent analysis revealed that Lambda outperformed the other architectures significantly, while Fargate and Microservice architectures exhibited lower performance in comparison. However, cost played a crucial role in architecture selection. Fargate proved to be exceptionally expensive, with costs escalating further when batch jobs were involved. On the other hand, Lambda demonstrated lower overall costs compared to the other architectures, especially when batch jobs were running under low traffic conditions. However, the cost advantage diminished when running batch jobs in higher traffic scenarios, surpassing the expenses of Monolith and Microservice architectures. The findings highlight the superior performance of Lambda, but also emphasize the importance of considering costs and specific workload requirements when selecting an architecture. Lambda outperformed other architectures by reducing average response time by 25% and cost by 15% under low-traffic scenarios compared to Monolithic and Microservice architectures.

A new design strategy for ZK-friendly hash functions has emerged since the proposal of Reinforced Concrete at CCS 2022, which is based on the hybrid use of two types of nonlinear transforms: the composition of some small-scale lookup tables (e.g., 7-bit or 8-bit permutations) and simple power maps over Fp. Following such a design strategy, some new ZK-friendly hash functions have been recently proposed, e.g., Tip5, Tip4, Tip4’, and the Monolith family. All these hash functions have a small number of rounds, i.e., 5 rounds for Tip5, Tip4, and Tip4’, and 6 rounds for Monolith (recently published at ToSC 2024/3). Using the composition of some small-scale lookup tables to build a large-scale permutation over Fp – which we call S-box – is a main feature in such designs, which can somehow enhance the resistance against the Gröbner basis attack because this large-scale permutation will correspond to a complex and high-degree polynomial representation over Fp. As the first technical contribution, we propose a novel and efficient algorithm to study the differential property of this S-box and to find a conforming input pair for a randomly given input and output difference. For comparison, a trivial method based on the use of the differential distribution table (DDT) for solving this problem will require time complexity O(p2). For the second contribution, we also propose new frameworks to devise efficient collision attacks on such hash functions. Based on the differential properties of these S-boxes and the new attack frameworks, we propose the first collision attacks on 3-round Tip5, Tip4, and Tip4’, as well as 2-round Monolith-31 and Monolith-64, where the 2-round attacks on Monolith are practical. In the semi-free-start (SFS) collision attack setting, we achieve practical SFS collision attacks on 3-round Tip5, Tip4, and Tip4’. Moreover, the SFS collision attacks can reach up to 4-round Tip4 and 3-round Monolith-64. As far as we know, this is the first third-party cryptanalysis of these hash functions, which improves the initial analysis given by the designers.

Continuous-flow reactions using immobilized chiral catalysts are attracting much attention in the field of fine chemical productions. Porous materials can mitigate the mass transfer limitation and undesired steric effects from support materials owing to their large surface area and high porosity. Among them, porous monoliths, which are self-standing materials with interconnected pores with narrow diameters offer high permeability during the continuous-flow operation. Supporting the chiral catalyst on the monolith, asymmetric reaction can be achieved under continuous-flow condition. To date, the continuous-flow reactors with porous monoliths have been developed for chiral catalysis. Herein, we first developed porous organogel monoliths as support for chiral catalyst in continuous-flow reaction. The monolith showed higher catalytic durability than those of batch in asymmetric aldol additions. Detailed studies on continuous-flow conditions and physical properties of the monolith revealed the importance of increasing the gel porosity of the monolith.

In this study, we successfully fabricated biocomposite monoliths using a facile, cost-effective, and friendly method via the thermally induced phase separation method using Polystyrene, Lignin, and OV-POSS. The properties of the prepared composites were estimated using Fourier transform infrared measurement (FTIR), scanning electron microscopy (SEM), and thermogravimetric analyzer (TGA). Furthermore, wettability properties were studied using water and oil. FTIR analysis indicates Polyester, Lignin, and OV-POSS were physically blended. The investigation by SEM showed the successful merging of components. Moreover, it revealed that OV-POSS nanoparticles acted as a support for reduced surface roughness. TGA measurements revealed that thermal stability was much better with increased OV-POSS loading. OV-POSS modified monolith exhibited hydrophobic with water contact angles of more than 130°. Results indicate that the produced monolith has a good sorption behavior to oils and organic liquids, whereas PL10L-0.3P showed higher sorption capacities followed by PL10L-0.1P, PL10L, and PL, respectively. The performance of the monoliths on oil/water separation was investigated through the selective removal of oil or organic solvent from water. Hence, the monoliths showed high separation efficiency above 90% and good reusability. The analysis showed that the adsorption for the oil and solvent process followed the pseudo-second-order model with a linear regression coefficient (R2) of > 0.999. The equilibrium data fit well with the Langmuir model. Besides, thermodynamic parameter analysis results showed that the adsorption was spontaneous and endothermic. An economic study examining the obtained resulted in a rate of investment (ROI) of 38.12%, a breakeven point (BEP) of 44.70%; this research is expected to be useful for the monolith industry that has attractive potential in practical industrial water treatment. [ABSTRACT FROM AUTHOR]

In the evolving landscape of software architecture, the shift from monolithic structures to agile, scalable microservices has revolutionized cloud-native application development. However, the inherent dynamism of microservices can lead to the inadvertent creation of unnecessary microservices, introducing complexity and inefficiency. Moreover, with a lack of control mechanisms in evolution, systems can lead to what is known as architecture degradation. This research ventures into the emerging domain of microservice-to-microservice transformation, a concept focused on optimizing existing cloud-native systems. We experiment with a machine learning methodology initially designed for monolith-to-microservices migration, adapting it to the complex microservices landscape, with a specific focus on the train-ticket application (Zhou in Association for Computing Machinery, https://doi.org/10.1145/3183440.3194991), which is an established system benchmark in the community. To identify the optimal microservice distribution, we employ a combination of the Variational Autoencoder and fuzzy c-means clustering. Our results demonstrate a close resemblance to the original application in terms of structural modularity. Though they fall short of achieving the ideal interface number exhibited by the original microservices, our findings highlight the potential of automated microservice composition, effectively narrowing the gap between human-designed and machine-generated microservices and advancing the field of software architecture. [ABSTRACT FROM AUTHOR]

Cloud computing has become a popular choice for deploying web applications, but the selection of the appropriate architecture for different application types remains a challenge for businesses. In this study, we conducted performance and cost analyses of three architectures: Monolith, Microservice, and Serverless (specifically Lambda and Fargate) to provide businesses with valuable insights for decisionmaking. To ensure the relevance of our findings, we conducted tests on an application designed for static, database, and batch job services, deployed on AWS. Using JMeter, we simulated traffic with varying levels of high, medium, and low intensity, distributing 500 requests across six test scenarios. The results and subsequent analysis revealed that Lambda outperformed the other architectures significantly, while Fargate and Microservice architectures exhibited lower performance in comparison. However, cost played a crucial role in architecture selection. Fargate proved to be exceptionally expensive, with costs escalating further when batch jobs were involved. On the other hand, Lambda demonstrated lower overall costs compared to the other architectures, especially when batch jobs were running under low traffic conditions. However, the cost advantage diminished when running batch jobs in higher traffic scenarios, surpassing the expenses of Monolith and Microservice architectures. The findings highlight the superior performance of Lambda, but also emphasize the importance of considering costs and specific workload requirements when selecting an architecture. Lambda outperformed other architectures by reducing average response time by 25% and cost by 15% under low-traffic scenarios compared to Monolithic and Microservice architectures. [ABSTRACT FROM AUTHOR]

The climate crisis, driven by increasing CO2 levels in the atmosphere, has heightened the need for new, environmentally friendly energy sources. Hydrogen gas, which can meet our energy needs, has become a particularly intriguing topic. This study investigated the partial oxidation reaction of methane with cordierite monolith catalysts. The Ni-coated catalysts were supported with γ-Al2O3, CeO2, ZrO2, and CeO2-ZrO2. The catalysts were tested at temperatures of 750, 800, and 850 °C with different flow rates and methane feed concentrations (2%, 5%, and 10%). It was demonstrated that catalyst activity varies depending on these parameters. It has been found that high gas hourly space velocity (GHSV) and CH4 feed rates decrease catalyst activity. The obtained reaction results indicated that the optimal reaction parameters were 800 °C, a GHSV of 1 × 104 h−1, and a CH4 feed concentration of 2%. By optimizing these parameters, catalysts with high CH4 conversion and selectivity for H2 and CO were achieved. The prepared catalysts were characterized using scanning electron microscopy with energy dispersive X-ray analysis (SEM-EDX), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), and temperature-programmed reduction (TPR). [ABSTRACT FROM AUTHOR]

Materials with monolithic structures, such as epoxy monoliths, are used for a variety of applications, such as for column fillers in gas chromatography and HPLC, for separators in lithium-ion batteries, and for precursor polymers for monolith adhesion. In this study, we investigated the fabrication of epoxy monoliths using 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (TETRAD-C) as the tetrafunctional epoxy and 4,4′-methylenebis(cyclohexylamine) (BACM) as the amine curing agent to control pore diameters using polyethylene glycols (PEGs) of differing molecular weights as the porogenic agents. We fabricated an epoxy monolith with micron-order pores and high strength levels, and which is suitable for the precursors of composite materials in cases where smaller PEGs are used. We discussed the effects of the porous structures of monoliths on their physical properties, such as tensile strength, elongation, elastic modulus, and glass transition temperatures. For example, epoxy monoliths prepared in the presence of PEGs exhibited an elastic modulus less than 1 GPa at room temperature and Tg values of 175–187 °C, while the epoxy bulk thermoset produced without any porogenic solvent showed a high elastic modulus as 1.8 GPa, which was maintained at high temperatures, and a high Tg of 223 °C. In addition, the unique adhesion characteristics of epoxy monolith sheets are revealed as a result of the combinations made with commercial epoxy and acrylic adhesives. Epoxy monoliths that are combined with conventional adhesives can function as sheet-type adhesives purposed with avoiding problems when only liquid-type adhesives are used. [ABSTRACT FROM AUTHOR]

The objective was to discuss the research on zirconia published in the past 15 years to help the dental materials community understand the key properties of the types of zirconia and their clinical applications. A literature search was performed in May/2023 using Web of Science Core Collection with the term "dental zirconia". The search returned 5102 articles, which were categorized into 31 groups according to the research topic. The current approach to improving the translucency of zirconia is to decrease the alumina content while increasing the yttria content. The resulting materials (4Y-, 5Y-, and above 5 mol% PSZs) may contain more than 50% of cubic phase, with a decrease in mechanical properties. The market trend for zirconia is the production of CAD/CAM disks containing more fracture resistant 3Y-TZP at the bottom layers and more translucent 5Y-PSZ at the top. Although flaws located between layers in multilayered blocks might represent a problem, newer generations of zirconia layered blocks appear to have solved this problem with novel powder compaction technology. Significant advancements in zirconia processing technologies have been made, but there is still plenty of room for improvement, especially in the fields of high-speed sintering and additive manufacturing. The wide range of zirconia materials currently available in the market may cause confusion in materials selection. It is therefore imperative for dental clinicians and laboratory technicians to get the needed knowledge on zirconia material science, to follow manufacturers' instructions, and to optimize the design of the prosthetic restoration with a good understanding where to reinforce the structure with a tough and strong zirconia. [Display omitted] • The trend for dental zirconia is the production of composition-gradient materials. • More translucent dental zirconia results from low alumina and high yttria contents. • Flaws between layers in multilayered blocks decrease the mechanical properties. • Improvements regarding high-speed sintering and additive manufacturing are needed. [ABSTRACT FROM AUTHOR]

Hash functions are a crucial component in incrementally verifiable computation (IVC) protocols and applications. Among those, recursive SNARKs and folding schemes require hash functions to be both fast in native CPU computations and compact in algebraic descriptions (constraints). However, neither SHA-2/3 nor newer algebraic constructions, such as Poseidon, achieve both requirements. In this work we overcome this problem in several steps. First, for certain prime field domains we propose a new design strategy called Kintsugi, which explains how to construct nonlinear layers of high algebraic degree which allow fast native implementations and at the same time also an efficient circuit description for zeroknowledge applications. Then we suggest another layer, based on the Feistel Type-3 scheme, and prove wide trail bounds for its combination with an MDS matrix. We propose a new permutation design named Monolith to be used as a sponge or compression function. It is the first arithmetization-oriented function with a native performance comparable to SHA3-256. At the same time, it outperforms Poseidon in a circuit using the Merkle tree prover in the Plonky2 framework. Contrary to previously proposed designs, Monolith also allows for efficient constant-time native implementations which mitigates the risk of side-channel attacks.

Nano-scale separation techniques (NSTs) offer significant advantages in relation to drug analysis in a wide range of samples. NSTs, including low flow rate LC systems or capillary or chip based electrophoresis/electrochromatography systems, have become the primary tool for advanced drug analysis, and indispensable technology for sensitive and selective drug analysis. In recent decades, significant advances have been achieved using NSTs for drug analysis. In this review, sample preparation strategies, new advances and applications in NSTs and the contribution toward forensic science applications were reported. In addition, some recent and selected applications with or without mass spectrometry (e.g., low resolution/high resolution -MS) are summarized.

Highlights A comprehensive investigation on the research states of 3D-printed metal/covalent organic frameworks (M/COFs) is conducted with the discussion on the M/COF-mixed monolith and M/COF-covered monolith separately. Recent advances in design strategies regarding both the paste/scaffold formation and the 3D-printing/covering process for preserving the better structural features of M/COFs (surface area, porosity, and micromorphology) in their 3D printed monolith are overviewed and discussed.

Recently, the phenomenon of switching back from microservice to monolith has increased in frequency, leading to intense debate in the industry. In this paper, we conduct a multivocal literature review to investigate reasoning and key aspects to pay attention to when switching back and analyze other practitioners' opinions. The results show four cases of switching back from microservice to monolith: Istio control plane, Amazon Prime Video monitoring service, Segment, and InVision. The five main reasons that led to switching back are cost, complexity, scalability, performance, and organization. During the switching back process, six key aspects need to be addressed: (1) stopping the development of more services, (2) consolidating and testing paths, (3) unifying data storage, (4) implementing the message bus principle, (5) giving up diverse techniques, and (6) learning to use modular design principles. As to the practitioners' opinions, they had mixed views about the switching back phenomenon. However, most thought that switching back required consideration of the actual system situation and principles. These results pave the way for further research and guide researchers and companies through the process of switching back from microservice to monolith. [ABSTRACT FROM AUTHOR]

Κ-Carrageenan (ΚC) is a widely used food hydrogel, but its use as an environmental adsorption separation material still needs to be further developed. Herein, a novel macroporous anionic monolith was synthesized by the oil-in-water high internal phase emulsion template method. The monolith was obtained by the continuous phase polymerization of sodium styrenesulfonate (NaSS) and acrylic acid (AA), in which ΚC was introduced to form a semi-interpenetrating network structure to improve its overall performance. The results showed that the mechanical strength of the monolith increased with ΚC content. Because of the use of two strong hydrophilic monomers, NaSS and AA, the porous monolith proved to be superoleophobic underwater. In addition, the porous materials had a strong cationic dye adsorption capacity (2455 mg/g for malachite green, 1180 mg/g for methylene blue) and a fast removal rate, good reusability, and oil-water separation. This work highlights their potential application value in the purification of complex water environments. [ABSTRACT FROM AUTHOR]

Powdered Ni-based catalysts exhibit good performance in the dry reforming of methane (DRM); however, they suffer from limited industrial applicability. Structured monolithic catalysts can overcome these limitations. In this sense, we present the synthesis of Ni–Ce mixed oxide-type catalysts immobilized in cordierite monoliths using a simple coprecipitation method and slurry coating without additives using hydrotalcite precursors for catalyst preparation. Our research explores the role of Ce (0–7 % w/w) as a promoter and the impact of immobilizing mixed oxides (MO) within cordierite monoliths on the physicochemical properties and catalytic performance of non-previously H 2 -reduced materials in DRM at 700 °C. Our findings reveal the favorable impact of Ce on the physicochemical properties of the catalyst in both the powder and monoliths, including smaller crystallite sizes, enhanced CO 2 adsorption, and reducibility with higher Ce loading. The immobilized mixed oxide (MO) maintained its crystalline structure and formed stable, uniform layers with thicknesses below 10 μm in the monoliths. The powders exhibited stable conversions of 70–80% for CH 4 and 66–75% for CO 2 , whereas the monoliths showed conversions of 85–90% for CH 4 and 80–90% for CO 2 at 700 °C and 94,680 mL·g cat −1·h−1. A higher catalyst loading in the monoliths did not result in detrimental catalytic conversion. On average, the monoliths had a higher H 2 /CO ratio (1.25–1.5) compared to the powders (1–1.25), which may explain the increased coke formation rate in the monoliths from methane cracking. Ce improved the stability and reduced coke formation, particularly when the space velocity was lower. This research highlights the significant advantages of immobilizing mixed oxides (MO) in monolithic structures, making them highly promising for potential industrial scale-up. Their stability, recoverability, elimination of high-cost H 2 reduction, and reusability in subsequent catalytic tests contributed to their favorable characteristics. [Display omitted] • Coprecipitation simplifies slurry coatings for monolith immobilization. • Monoliths were prepared without additives. • The monoliths exhibited high stability and consistent performance upon reuse. • Ce improved stability and reduced coke formation at lower space velocities. • Immobilized catalysts produced more carbon, but no pressure drops were observed. [ABSTRACT FROM AUTHOR]

Highlights: A comprehensive investigation on the research states of 3D-printed metal/covalent organic frameworks (M/COFs) is conducted with the discussion on the M/COF-mixed monolith and M/COF-covered monolith separately. Recent advances in design strategies regarding both the paste/scaffold formation and the 3D-printing/covering process for preserving the better structural features of M/COFs (surface area, porosity, and micromorphology) in their 3D printed monolith are overviewed and discussed. Metal–organic framework (MOF) and covalent organic framework (COF) are a huge group of advanced porous materials exhibiting attractive and tunable microstructural features, such as large surface area, tunable pore size, and functional surfaces, which have significant values in various application areas. The emerging 3D printing technology further provides MOF and COFs (M/COFs) with higher designability of their macrostructure and demonstrates large achievements in their performance by shaping them into advanced 3D monoliths. However, the currently available 3D printing M/COFs strategy faces a major challenge of severe destruction of M/COFs' microstructural features, both during and after 3D printing. It is envisioned that preserving the microstructure of M/COFs in the 3D-printed monolith will bring a great improvement to the related applications. In this overview, the 3D-printed M/COFs are categorized into M/COF-mixed monoliths and M/COF-covered monoliths. Their differences in the properties, applications, and current research states are discussed. The up-to-date advancements in paste/scaffold composition and printing/covering methods to preserve the superior M/COF microstructure during 3D printing are further discussed for the two types of 3D-printed M/COF. Throughout the analysis of the current states of 3D-printed M/COFs, the expected future research direction to achieve a highly preserved microstructure in the 3D monolith is proposed. [ABSTRACT FROM AUTHOR]

A novel chiral monolithic nano-column was developed for the enantioseparation of chiral drugs by nano-liquid chromatography (nano-LC). The monolithic capillary with 50 µm i.d. was first prepared by an in-situ polymerization using butyl methacrylate (BuMA), ethylene dimethacrylate (EDMA) and NFMoc-Lysine modified GO nanoparticles. The final monolithic stationary phase was characterized by using FT-IR spectra of synthesized structures, scanning electron microscopy (SEM) and chromatographic analyses. After characterization, the prepared chiral monolithic column was investigated for the chiral separation of pharmaceutical racemates, including anti-inflammatory drugs (e.g., ketoprofen, ibuprofen, naproxen, etodolac and flurbiprofen) and β-blockers (e.g. propranolol, metoprolol and atenolol). It was demonstrated that NFMoc-Lysine modified GO nanoparticles incorporated chiral monolith could be successfully developed while this chiral monolith allowed sensitive chiral separation of chiral drugs. The chiral separation could be mostly achieved via the formation of π-π interactions as well as hydrophilic interactions between chiral stationary phase and enantiomers

3D-printed high-surface carbon monoliths have been fabricated and tested as catalyst supports of CO2 methanation active phases (NiO-CeO2, 12 wt% Ni). The carbon carriers show a developed microporosity and good adherence to the catalytic phases of NiO-CeO2, showing great stability and cyclability. Two monolith designs were used: a conventional parallel-channeled structure (honeycomb) and a complex 3D network of non-linear channels built upon interconnected circular sections (circles), where flow turbulences along the reactant gas path are spurred. The effect of the active phases particle size on the catalyst distribution and the overall performance has been assessed by comparing NiO-CeO2 nanoparticles of 7 nm average (Np), with a reference counterpart of uncontrolled structure (Ref). The improved radial gases diffusion in the circles monolith design is confirmed, and nanoparticles show enhanced CO2 methanation activity than the uncontrolled-size active phase at low temperatures (< 300 ºC). On the contrary, the Ref catalysts achieve higher CH4 production at higher temperatures, where the reaction kinetics is controlled by mass transfer limitations (T > 300 ºC). SEM and Hg porosimetry evidence that nanoparticles are deposited at deeper penetration through the narrow micropores of the carbon matrix of the monolithic supports, which tend to accumulate on the channels surface remaining more accessible to the reactant molecules. Altogether, this study examines the impact of the channel tortuosity and the active phase sizing on the CO2 methanation activity, serving as ground knowledge for the further rational and scalable fabrication of carbon monolith for catalytic applications.

Renewable hydrogen accelerates market use as costs reduce. Bioethanol is a well-established energy carrier to blend then burn with fossil fuels and is now ready as a convenient cost-effective feedstock for distributed or centralized renewable hydrogen production. Structured monolith catalysts coated with noble metal-based catalysts were demonstrated for renewable hydrogen generation. Key process steps include bioethanol autothermal reforming, water-gas shift and CO preferential oxidation. Each component was individually tested for 4000 h at laboratory scale. Pilot scale reactors were designed, constructed, and validated to produce high purity hydrogen. The bioethanol processor was designed based on simulation studies and validation experiments. A compact bioethanol processing system with capacity to produce up to 1.6 kg/h H 2 was built and operated for more than 1000 h without significant loss of performance. A hydrogen rich stream with CO concentration lower than 15 ppm was obtained, which could be supplied to a PEM fuel cell system or further purified. • A bioethanol processor with capacity to produce 1.6 kg/h H 2 was operated for 1000 h. • Noble metal-based structured catalysts were proved for H 2 generation. • Bioethanol processor was designed based on CFD studies and validation experiments. • H 2 yield of 4.3 mol H 2 /mol EtOH was achieved in reforming gas with 100% conversion. • The processor can be used for stationary or mobile applications at different scales. [ABSTRACT FROM AUTHOR]

Arsenic pollution of water is one of the severest environmental challenges threatening human health. Iron-based nanomaterials have been demonstrated effective in arsenic removal. However, they generally suffer from low removal efficiency towards highly toxic As(III), loss of active sites owing to agglomeration, and poor reusability. Herein, we report a carbonized melamine foam supported Mn(IV)-doped β-FeOOH nanospindles(CF@Mn-FeOOH NSp) for tackling the technical hurdles. The designed CF@Mn-FeOOH NSp appears as a free-standing monolith through a low-cost and straightforward hydrothermal method. The atomic-scale integration of Mn(IV) into β-FeOOH enables an oxidation-adsorption bifunctionality, where Mn(IV) serves as oxidizer for As(III) and Fe(III) acts as adsorber for As(V). The maximal adsorption capacity for As(V) and As(III) can reach 152 and 107 mg g-1, respectively. Meanwhile, As in simulated high arsenic groundwater can be decreased to below 10 μg L-1 within 24 h. By simple "filtrating-washing", 85% and 82% of its initial adsorption capacity for As(V) and As(III) can be easily recovered even after 5-cycles reuse. Kinetics and isotherm adsorption study indicate that the arsenic adsorption behavior is mainly through chemical bonding during single-layer adsorbing process. The as-prepared CF@Mn-FeOOH offers a scalable, efficient, and recyclable solution for arsenic removal in groundwater and wastewater from mines and industry.

The pollution caused by mercury (Hg) is a matter of concern regarding worldwide ecosystems and public health. It is dangerous as it is highly poisonous and has more ways to get exposed than other heavy metal ions. Recently, the application of biomaterials with varying structures and designs for mercury adsorption has grown. In this research, clay monoliths (CM) and clay-manganese monoliths (CMM) were synthesized, investigated, and compared regarding their ability to adsorb mercury ions from water to determine the most effective adsorbents. CM and CMM were extruded through a stainless-steel molder with dimensions of 7 holes, 9 mm in radius, and 20 mm in height. The surface morphologies of both adsorbents were characterized using infrared (IR) spectroscopy and scanning electron microscopy (SEM). The effects of contact time (40, 80, 120, 160, 200, and 240 minutes) and initial concentrations (3–5 mg/L) were applied to evaluate both adsorption processes. The experiment was conducted in a batch reactor using a monolithic adsorbent that operated for 240 minutes. The experimental equilibrium data of the adsorption were examined with Langmuir and Freundlich models to find the best-fit isotherm. In the kinetic study, the pseudo-first-order was investigated in both linear and nonlinear models. The adsorption results showed that CMM had the highest adsorption efficiency (42.7%). The equilibrium study concluded that the Langmuir was the most significant isotherm model. The highest monolayer capacity and Langmuir constants (KL and aL) were 0.396, 1.329, and 0.396, respectively. The adsorption of both adsorbents was well displayed in the pseudo-first-order non-linear model. Experiments and processed data compromise the finding that CMM is more effective than CM at adsorbing mercury ions.

Several supported liquid-phase (SLP) catalysts with immobilized Rh-biphephos complexes on monolithic supports were prepared and applied for continuous gas-phase hydroformylation (HyFo) of 1-butene. The support comprised macroporous monolithic silicon carbide (SiC) with deposited silica nanoparticles (NPs) in order to provide mesopores with enhanced capillary forces to retain the liquid-phase. Variable parameters were examined for the monolithic SiC supports, including size and loading of deposited silica NPs and intermediate calcination between silica deposition steps to obtain the most efficient support configuration for the SLP system. The SLP catalysts with larger deposited silica NPs gave higher catalytic activity (i.e. 1-butene conversion and turnover frequency) compared to the supports with smaller sized silica NPs. However, the selectivity towards the preferred linear aldehyde was higher in the SLP catalysts with supports containing less silica with small silica NPs. Importantly, the prepared SLP catalyst systems showed long-term stability in HyFo with negligible formation of high boiling aldol condensation products. [ABSTRACT FROM AUTHOR]

The microservices architecture (MSA) style has been gaining interest in recent years because of its high scalability, ability to be deployed in the cloud, and suitability for DevOps practices. While new applications can adopt MSA from their inception, many legacy monolithic systems must be migrated to an MSA to benefit from the advantages of this architectural style. To support the migration process, we propose MicroMiner, a microservices identification approach that is based on static‐relationship analyses between code elements as well as semantic analyses of the source code. Our approach relies on machine learning (ML) techniques and uses service types to guide the identification of microservices from legacy monolithic systems. We evaluate the efficiency of our approach on four systems and compare our results to ground‐truths and to those of two state‐of‐the‐art approaches. We perform a qualitative evaluation of the resulted microservices by analyzing the business capabilities of the identified microservices. Also a quantitative analysis using the state‐of‐the‐art metrics on independence of functionality and modularity of services was conducted. Our results show the effectiveness of our approach to automate one of the most time‐consuming steps in the migration of legacy systems to microservices. The proposed approach identifies architecturally significant microservices with a 68.15% precision and 77% recall. [ABSTRACT FROM AUTHOR]

Herein, we report the preparation of lipase immobilised on single-walled carbon nanotubes (SWCNTs) as an enantioselector for capillary monolithic columns and their application in the chiral separation of racemic pharmaceuticals. The columns were prepared through the encapsulation of functionalised SWCNTs (c-SWCNTs) within an organic monolithic polymer, followed by the immobilisation of lipase over the obtained monolith, over a three-day (L1) and five-day (L2) period. The prepared columns were tested for the enantioselective nano-HPLC separation of 50 racemic drugs. A suitable resolution was achieved for 25 drugs using nano-RP-HPLC conditions for both the L1 and L2 capillaries, while no specific resolution was detected under normal-phase HPLC conditions. The developed c-SWCNT-lipase-based polymeric monolithic capillaries are a promising expansion for separating pharmaceutical enantiomers' using nano-HPLC. [ABSTRACT FROM AUTHOR]

Ultralow flow LC employs ultra‐narrow bore columns and mid‐range pL/min to low nL/min flow rates (i.e., ≤20 nL/min). The separation columns that are used under these conditions are typically 2–30 μm in inner diameter. Ultralow flow LC systems allow for exceptionally high sensitivity and frequently high resolution. There has been an increasing interest in the analysis of scarce biological samples, for example, circulating tumor cells, extracellular vesicles, organelles, and single cells, and ultralow flow LC was efficiently applied to such samples. Hence, advances towards dedicated ultralow flow LC instrumentation, technical approaches, and higher throughput (e.g., tens‐to‐hundreds of single cells analyzed per day) were recently made. Here, we review the types of ultralow flow LC technology, followed by a discussion of selected representative ultralow flow LC applications, focusing on the progress made in bioanalysis of amount‐limited samples during the last 10 years. We also discuss several recently reported high‐sensitivity applications utilizing flow rates up to 100 nL/min, which are below commonly used nanoLC flow rates. Finally, we discuss the path forward for future developments of ultralow flow LC. [ABSTRACT FROM AUTHOR]

Herein, a green, carbon dioxide-in-water high-internal-phase emulsion (C/W HIPEs) was developed and stabilized with polyvinyl alcohol (PVA) for the formation of chitosan oligosaccharide/poly(acrylamide-co-sodium 4-styrene sulfonate) [COS/P(AM-co-SSS)] monolithic porous hydrogel. The obtained monolith was characterized via FT-IR and SEM. The SEM patterns depicted that the monoliths were interconnected, the void sizes were 78.5 µm, and the interconnected pore throats were 28 μm approximately. Mechanical measurement results indicated that the maximum compress stress of the monolith could reach 334.4 kPa at 90% strain, and it exhibited good mechanical stability. After 200 cycles of compression, it could still recover its original shape without cracking. The obtained COS-based monolith was selected to remove tetracycline (TC) for evaluating the adsorptive features of the interpenetrating pore-containing monolith. The monolithic COS/P(AM-co-SSS) hydrogel behaved with strong antibiotic adsorption capacity (1600.4 mg/g for TC). The adsorption process agreed well with the pseudo-second-order kinetic and Langmuir isothermal models. In addition, the porous monolith had a strong electrostatic force on TC according to the thermodynamic study. This work provides a green route for the development of novel monolithic hydrogels and highlights its potential application in the treatment of antibiotic-containing wastewater. [ABSTRACT FROM AUTHOR]

In miniaturized affinity chromatography, the development of hydrophilic organic monoliths with reduced non-specific interactions and high-protein grafting capacity remains a hot topic. In this work, we propose the one-step synthesis of a diol organic monolith to replace the gold-standard epoxy-based organic monoliths (which require post-modification, namely hydrolysis, prior to use). The synthesis of this new monolith builds upon the use of N-N'-Methylenebis(acrylamide) (MBA), as a hydrophilic crosslinker, and 2,3-dihydroxypropyl methacrylate (DHPMA), a diol monomer that eliminates the time-consuming epoxy ring opening step and its associated side reactions. The optimization of one-step synthesis parameters led to a monolith with a satisfactory permeability ((4.8 ± 0.5) × 10−14 m2), high efficiency (117,600 plates/m at optimum flow velocity (uopt = 0.09 cm s−1)) and reduced non-specific interactions. It is exemplified by its separation ability in the HILIC mode (separation of nucleosides), and by the retention data set of 41 test solutes, which were used to evaluate the non-specific interactions. This new poly(DHPMA-co-MBA) monolith has not only hydrophilic surface properties, but also improved protein grafting capacity compared to the glycidyl-based monolith (13 ± 0.7 pmol cm−1). The potential of this monolith is illustrated in affinity chromatography, where the concanavalin ligands are ranked according to their Kd values. [ABSTRACT FROM AUTHOR]