Inherent Porosity Research Articles

Synergistic antibacterial and wound-healing applications of an imidazole-based porous organic polymer encapsulated silver nanoparticles composite

Here, a novel antibacterial agent (IM-POP-Ag) through encapsulation of Ag nanoparticles (AgNPs) into an imidazole-based porous organic polymer (IM-POP) was developed for synergistic antibacterial and wound healing. IM-POP with an ultrahigh N content of 38.42 at% was synthesized via the copolymerization of cheap and industrially mass-produced imidazole-2-carbaldehyde and melamine, via catalyst-free Schiff base chemistry, which could realize the effectively anchor of Ag on the porous skeleton (with an Ag loading of 26.01 wt%), avoiding the aggregation and reducing the toxicity of AgNPs greatly. The inherent porosity of POP realizes the effectively control on the size of AgNPs and the coordination of Ag+ changed imidazole into imidazolium, gifting the antibacterial activity to the carriers. As a result, IM-POP-Ag presented a synergistic antibacterial activity against both Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli.). For example, at the same Ag content, the survival rates of E. coli and S. aureus in response to 200 μg mL−1 IM-POP-Ag (equivalent to 50 μg mL−1 AgNPs) were 3.44 ± 0.21% and 6.34 ± 0.40%, respectively, far outperforming that of bare AgNPs (12.19 ± 0.54% and 20.20 ± 0.19%). In vivo experiments on mice testified IM-POP-Ag could significantly promote the healing rate of infected wounds which could facilitate the growth of vessel and hair follicle, accelerating epithelialization. Hence, this novel and mass-produced antibacterial agent provides a new strategy and theoretical basis for the application of AgNPs with higher efficacy and biocompatibility in the near future.

A numerical study of the effects of temperature and injection velocity on oil-water relative permeability for enhanced oil recovery

The paper quantitatively explore the influence of injection rate and temperature on oil-water relative permeability curves during hot water flooding operations in a porous medium flow. ANSYS-CFD was used to construct a numerical model of hot-water injection into an oil saturated sandstone core sample. The modelling technique is based on the Eulerian-Mixture model, using a 3D cylindrical core sample with known inherent permeability and porosity. Injection water at 20 °C was injected into a core sample that was kept at 63 °C and had 14-mD permeability and 26% porosity. For the investigation, three distinct injection rates of 2.9410–6 m/s, 4.41 × 10−6 m/s, and 5.88 × 10−6 m/s were utilised. Furthermore, same injection procedures were repeated under the same conditions, but the core temperature was changed to 90 °C, allowing us to quantify the influence of temperature on the relative permeability curves of oil-water immiscible flow.The results of this study show that the relative permeability of oil is strongly influenced by flow, while the effect of the relative permeability of water is negligible. In addition, the flow rate influences the residual oil and water saturation, as well as the associated effective permeability. From 20 to 90 °C there is little sensitivity to relative permeability or temperature. This study does not provide proof that temperature effects do not exist with genuine reservoir fluids, rocks, and temperature ranges. However, this study has demonstrated the feasibility of utilising CFD approaches to estimate fluid relative permeability, as well as the combined influence of temperature change and flow rate on relative permeability, with the potential for considerable cost-time advantages.

Methods to Characterize Granular Hydrogel Rheological Properties, Porosity, and Cell Invasion

Granular hydrogels are formed through the packing of hydrogel microparticles and are emerging for various biomedical applications, including as inks for 3D printing, substrates to study cell-matrix interactions, and injectable scaffolds for tissue repair. Granular hydrogels are suited for these applications because of their unique properties including inherent porosity, shear-thinning and self-healing behavior, and tunable design. The characterization of their material properties and biological response involves technical considerations that are unique to modular systems like granular hydrogels. Here, we describe detailed methods that can be used to quantitatively characterize the rheological behavior and porosity of granular hydrogels using reagents, tools, and equipment that are typically available in biomedical engineering laboratories. In addition, we detail methods for 3D cell invasion assays using multicellular spheroids embedded within granular hydrogels and describe steps to quantify features of cell outgrowth (e.g., endothelial cell sprouting) using standard image processing software. To illustrate these methods, we provide examples where features of granular hydrogels such as the size of hydrogel microparticles and their extent of packing during granular hydrogel formation are modulated. Our intent with this resource is to increase accessibility to granular hydrogel technology and to facilitate the investigation of granular hydrogels for biomedical applications.

Characterization and modeling of the temperature-dependent thermal conductivity in sintered porous silicon-aluminum nanomaterials

Nanostructured silicon and silicon-aluminum compounds are synthesized by a novel synthesis strategy based on spark plasma sintering (SPS) of silicon nanopowder, mesoporous silicon (pSi), and aluminum nanopowder. The interplay of metal-assisted crystallization and inherent porosity is exploited to largely suppress thermal conductivity. Morphology and temperature-dependent thermal conductivity studies allow us to elucidate the impact of porosity and nanostructure on the macroscopic heat transport. Analytic electron microscopy along with quantitative image analysis is applied to characterize the sample morphology in terms of domain size and interpore distance distributions. We demonstrate that nanostructured domains and high porosity can be maintained in densified mesoporous silicon samples. In contrast, strong grain growth is observed for sintered nanopowders under similar sintering conditions. We observe that aluminum agglomerations induce local grain growth, while aluminum diffusion is observed in porous silicon and dispersed nanoparticles. A detailed analysis of the measured thermal conductivity between 300 and 773 K allows us to distinguish the effect of reduced thermal conductivity caused by porosity from the reduction induced by phonon scattering at nanosized domains. With a modified Landauer/Lundstrom approach the relative thermal conductivity and the scattering length are extracted. The relative thermal conductivity confirms the applicability of Kirkpatrick’s effective medium theory. The extracted scattering lengths are in excellent agreement with the harmonic mean of log-normal distributed domain sizes and the interpore distances combined by Matthiessen’s rule.

Preliminary Study on Machining of Additively Manufactured Ti-6Al-4V

Additively manufactured metals differ from their conventionally produced counterparts due to the inherent material inhomogeneity, porosity, and thermal stress induced by the process. These differences make the machining of additively manufactured metals more difficult and cause premature tool failure or unexpected surface finish at certain conditions. This study takes the first step to investigate and identify the causes of these issues, particularly for Ti-6Al-4V. Printed and wrought samples, as well as heat treatment effect, are compared in a dry cutting condition at a cutting speed of 90 m/min in terms of cutting power, vibration, temperature, and produced surface finish. The results show a lower cutting power and more vibration for as-printed Ti samples, indicating a less ductile microstructure and inclusion of pores. Heat treatment can eliminate these phenomena. No significant difference is found in the produced surface finish at the current cutting condition.

Phenothiazine-based covalent organic frameworks with low exciton binding energies for photocatalysis.

Designing delocalized excitons with low binding energy (Eb) in organic semiconductors is urgently required for efficient photochemistry because the excitons in most organic materials are localized with a high Eb of >300 meV. In this work, we report the achievement of a low Eb of ∼50 meV by constructing phenothiazine-based covalent organic frameworks (COFs) with inherent crystallinity, porosity, chemical robustness, and feasibility of bandgap engineering. The low Eb facilitates effective exciton dissociation and thus promotes photocatalysis by using these COFs. As a demonstration, we subject these COFs to photocatalytic polymerization to synthesize polymers with remarkably high molecular weight without any requirement of the metal catalyst. Our results can facilitate the rational design of porous materials with low Eb for efficient photocatalysis.

Behavior of steel clamp confined brick aggregate concrete circular columns subjected to axial compression

Re-use of recycled aggregates in concrete has become a very sustainable solution owing to its environment-friendly and cost-effective nature. Clay bricks are most widely used in construction all over the world. Subsequently, waste generated from the demolition of clay-brick structures is most troublesome. Inherent porosity of bricks compromises the compressive strength of concrete with clay brick aggregates (C-CBA) that has rendered its use in structural concrete for quite some time. With some external clamping pressures, this deficiency can be countered. This study presents an experimental investigation into the use of steel clamps as a strengthening material for C-CBA. Steel clamps are cost-effective, readily available, and very easy to use. C-CBA were tested in two groups depending upon compressive strength: 15 & 35 MPa. Further, 3, 5, and 11 steel clamps were used in each group. Results suggested that steel clamps can effectively be used in enhancing the compressive strength of C-CBA to a level that is acceptable to be used in structural concrete. Increase in peak compressive strength of C-CBA was found to be proportional with the number of steel clamps employed. Three analytical concrete models were used to predict the compressive strength of C-CBA after strengthening. It was concluded that all three analytical models predicted well C-CBA compressive strength for 3-clamp specimens. However, their pre-diction accuracy was highly compromised as the number of steel clamps were increased.

The Emerging Role of Decellularized Plant-Based Scaffolds as a New Biomaterial.

The decellularization of plant-based biomaterials to generate tissue-engineered substitutes or in vitro cellular models has significantly increased in recent years. These vegetal tissues can be sourced from plant leaves and stems or fruits and vegetables, making them a low-cost, accessible, and sustainable resource from which to generate three-dimensional scaffolds. Each construct is distinct, representing a wide range of architectural and mechanical properties as well as innate vasculature networks. Based on the rapid rise in interest, this review aims to detail the current state of the art and presents the future challenges and perspectives of these unique biomaterials. First, we consider the different existing decellularization techniques, including chemical, detergent-free, enzymatic, and supercritical fluid approaches that are used to generate such scaffolds and examine how these protocols can be selected based on plant cellularity. We next examine strategies for cell seeding onto the plant-derived constructs and the importance of the different functionalization methods used to assist in cell adhesion and promote cell viability. Finally, we discuss how their structural features, such as inherent vasculature, porosity, morphology, and mechanical properties (i.e., stiffness, elasticity, etc.) position plant-based scaffolds as a unique biomaterial and drive their use for specific downstream applications. The main challenges in the field are presented throughout the discussion, and future directions are proposed to help improve the development and use of vegetal constructs in biomedical research.

Thiosemicarbazide‐Linked Covalent Organic Framework: Preparation, Properties and Applications

AbstractWith the unique advantages in structure and property, covalent organic frameworks have been widely employed for separation and enrichment. In this work, the thiosemicarbazide‐linked covalent organic framework (TpTc) was prepared by using 1,3,5‐triformylphloroglucinol and non‐rigid thiosemicarbazide as building blocks for the first time. The as‐prepared TpTc COF was fully characterized, presenting an agaric‐like structure, large specific surface area (63.5 m2 g−1), uniform pore size distribution (1.36 nm), inherent porosity and ordered crystallinity. The potential of TpTc as adsorbent for metal ions capture was investigated by static batch adsorption experiment using the one‐factor procedure. The maximum adsorption capacities of 73.50, 56.53 and 94.13 mg g−1 were obtained for Cu (II), Pb (II) and Cd (II) at natural pH, respectively. The anchoring of three metal ions onto TpTc is a multi‐layer sorption involving chemical adsorption, and obeys the Freundlich and pseudo‐second‐order model. According to XPS analysis, the adsorption mechanism may be attributed to the coordination and electrostatic interaction between metal ions and N, O and S atoms on TpTc COF. This work not only provides a candidate for the application of COFs in metal ions capture, but also a reference for exploring functional design of COFs.

Isomeric sp2-C-conjugated porous organic polymer-mediated photo- and sono-catalytic detoxification of sulfur mustard simulant under ambient conditions

Isomeric sp2-C-conjugated porous organic polymer-mediated photo- and sono-catalytic detoxification of sulfur mustard simulant under ambient conditions

Thirty-minute synthesis of hierarchically ordered sulfur particles enables high-energy, flexible lithium-sulfur batteries

An innovative lithium-sulfur (Li-S) battery technology is proposed that provides high energy density, fast charging, and mechanical flexibility. Via the rapid (30 min) one-pot reaction of elemental sulfur and vinyl phosphonic acid (VPA), SVPA microparticles containing dissimilar sulfur allotropes were developed. The spontaneous formation of wrinkles and pores on the particles facilitates electrolyte access and alleviates mechanical stress during battery cycling. The large surface area created by the ordered sulfur domains enhances lithium diffusion coefficients and facilitates polysulfide conversion kinetics in the Li-S cells, leading to a high discharge capacity of 1529 mAh·g −1 at 0.05 C and excellent rate performance (721 mAh·g −1 at 7 C). Additionally, owing to the inherent electrode porosity imparted by SVPA microparticles, a high areal capacity of ~5 mAh·cm −2 is obtained at increased cathode loadings. Abundant phosphonate moieties at the surfaces and interfaces of particles act as effective chemical anchors for lithium polysulfides, thereby mitigating the shuttle effects, which can prolong cycle lives at various C rates. The impressive properties of the SVPA microparticles are demonstrated for Li-S pouch cells, which exhibit stable operation under various deformations and highlight the SVPA microparticles as a promising candidate for next-generation Li-S batteries for wearable electronics A simple but radical approach is proposed to advance sulfur electrodes with smart nanostructures via the rapid one-pot reaction between elemental sulfur and vinyl phosphonic acid. This study serves as a platform for the development of next-generation Li-S batteries with high energy density, rate capability, and mechanical flexibility. • Hierarchically ordered sulfur electrodes were developed via rapid, solvent-free synthesis of SVPA microparticles. • The ordered sulfur domains and abundant phosphonate moieties at wrinkled surfaces of SVPA improved redox kinetics and cathode integrity. • Li-S batteries based on SVPA microparticles empowered one of the highest areal capacity, excellent rate capability and flexible characteristics

FeCo alloy encased in nitrogen-doped carbon for efficient formaldehyde removal: Preparation, electronic structure, and d-band center tailoring

Formaldehyde is a typical indoor air pollutant that has posed severely adverse effects on human health. Herein, a novel FeCo alloy nanoparticle-embedded nitrogen-doped carbon (FeCo@NC) was synthesized with the aim of tailoring the transition-metal d-band structure toward an improved formaldehyde oxidation activity for the first time. A unique core@shell metal–organic frameworks (MOFs) architecture with a Fe-based Prussian blue analogue core and Co-containing zeolite imidazole framework shell was firstly fabricated. Then, Fe and Co ion alloying was readily achieved owing to the inherent MOF porosity and interionic nonequilibrium diffusion occurring during pyrolysis. High-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure spectra confirm that small FeCo alloys in situ form in FeCo@NC, which exhibits a higher formaldehyde removal efficiency (93%) than the monometallic Fe-based catalyst and a remarkable CO2 selectivity (85%) at room temperature. Density functional theory calculations indicate the number of electrons transferred from the metal core to the outer carbon layer is altered by alloying Fe and Co. More importantly, a downshift in the d-band center relative to the Fermi level occurs from − 0.93 to − 1.04 eV after introducing Co, which could alleviate the adsorption of reaction intermediates and greatly improve the catalytic performance.

Wooden‐based materials: Eco‐friendly materials for direct mass spectrometric analysis and microextraction

Lignocellulosic materials have arisen as a sustainable alternative in microextraction techniques during the last 10 years. As they are natural materials, their use fits into some of the principles of Green Analytical Chemistry. Their inherent porosity, narrow shape, and rigidity permit their use in ambient ionization mass spectrometry techniques. In particular, the combination of wooden-based materials and direct analysis gives birth to the so-called wooden-tip electrospray ionization mass spectrometry technique. This approach has been used for the direct analysis of complex samples, and as a streamlined tool for fingerprint quality analysis. Also, wooden-based materials can be superficially modified to boost the interaction with target compounds, allowing their isolation from complex samples. This review describes the potential and applicability of direct analysis using lignocellulosic materials, as well as other alternatives related to their use in microextraction.

Precise Construction of Stable Bimetallic Metal–Organic Frameworks with Single-Site Ti(IV) Incorporation in Nodes for Efficient Photocatalytic Oxygen Evolution

Precise Construction of Stable Bimetallic Metal–Organic Frameworks with Single-Site Ti(IV) Incorporation in Nodes for Efficient Photocatalytic Oxygen Evolution

Facile preparation of Porous aromatic frameworks PAF-56 membranes for nanofiltration of dyes solutions

Porous aromatic frameworks (PAFs), possessing a high specific surface area, inherent porosity, nanosized channels and diverse structure, exhibit extraordinary potential in various fields. Herein, PAF-56 membranes were in situ fabricated on modified polyvinylidene fluoride (PVDF) membranes by a mild and facile refluxing method (62 ℃) and applied in nanofiltration. The influence of reaction time, reactant concentrations and catalyst concentration on the PAF-56/PVDF membranes were explored. The PAF-56/PVDF membranes showed a remarkable rejection (>95.08 %) and permeability (>40 L m-2h−1 bar−1) for dyes (Mw > 319) solutions. The membrane also exhibited excellent reusability and chemical stability, indicating great potential for actual separations.

Salt-tolerant and low-cost flame-treated aerogel for continuously efficient solar steam generation

Interface solar-driven evaporation is a very promising technology used in solar energy harvesting, seawater desalination and water purification. However, salt accumulation is still a serious problem that hinders the long-term stable operation of the evaporator. Herein, we use natural wood with inherent porosity to develop a flexible cellulose aerogel, which can be used as efficient and stable solar evaporator for desalination after simple surface carbonization. This aerogel evaporator achieves a solar steam efficiency of 83.4% and an evaporation rate of 1.40 kg m−2 h−1 under the sunlight intensity of 1 kW m−2. In the simulated evaporation experiment for 7 days, the evaporator shows a stable evaporation rate (about 1.39 kg m−2 h−1), indicating the potential for long-term operation. In addition, the evaporator has the ability to resist salt accumulation and self-cleaning. The low cost, simple preparation and multiple functions make the evaporator promising to be a continuous and stable installation for solar desalination.

The Use of Collagen with High Concentration in Cartilage Tissue Engineering by Means of 3D-Bioprinting

3D-bioprinting is a promising technology for a tissue scaffold fabrication in the case of damaged tissue/organ replacement. Collagen is one of the most appropriate hydrogel for the purpose, due to its exceptional biocompatibility. However, the use of collagen with conventionally low concentration makes bioprinting process difficult and does not provide its high accuracy. The purpose of the study was evaluation of suitability of collagen with high concentration in case of chondrocyte-laden scaffold fabrication via 3D-bioprinting for cartilage regeneration in vitro and in vivo. The results of the study showed that inherent porosity of 4% collagen was not enough for cell survival in the case of long-term incubation in vitro. With the beginning of the scaffold incubation, cell migration to the surface and out of the scaffold was observed. The residual cells died mostly within 4 weeks. As for in vivo study, in 2 weeks after implantation of the scaffold, a weak granulomatous inflammation was observed. In 6 weeks, a connective tissue was formed in the area of implantation. In the tissue, macrophages and groups of small cells with round nuclei were found. In accordance with morphological criteria, these cells could be considered as young chondrocytes. However, its amount was not enough to initiate the formation of cartilage.

Electrochemical and photoluminescence response of laser-induced graphene/electrodeposited ZnO composites

The inherent scalability, low production cost and mechanical flexibility of laser-induced graphene (LIG) combined with its high electrical conductivity, hierarchical porosity and large surface area are appealing characteristics for many applications. Still, other materials can be combined with LIG to provide added functionalities and enhanced performance. This work exploits the most adequate electrodeposition parameters to produce LIG/ZnO nanocomposites. Low-temperature pulsed electrodeposition allowed the conformal and controlled deposition of ZnO rods deep inside the LIG pores whilst maintaining its inherent porosity, which constitute fundamental advances regarding other methods for LIG/ZnO composite production. Compared to bare LIG, the composites more than doubled electrode capacitance up to 1.41 mF cm−2 in 1 M KCl, while maintaining long-term cycle stability, low ohmic losses and swift electron transfer. The composites also display a luminescence band peaked at the orange/red spectral region, with the main excitation maxima at ~ 3.33 eV matching the expected for the ZnO bandgap at room temperature. A pronounced sub-bandgap tail of states with an onset absorption near 3.07 eV indicates a high amount of defect states, namely surface-related defects. This work shows that these environmentally sustainable multifunctional nanocomposites are valid alternatives for supercapacitors, electrochemical/optical biosensors and photocatalytic/photoelectrochemical devices.

RGD-pectin microfiber patches for guiding muscle tissue regeneration.

Opportunely arranged microscaled fibers offer an attractive 3D architecture for tissue regeneration as they may enhance and stimulate specific tissue regrowth. Among different scaffolding options, encapsulating cells in degradable hydrogel microfibers appears as particularly attractive strategy. Hydrogel patches, in fact, offer a highly hydrated environment, allow easy incorporation of biologically active molecules, and can easily adapt to implantation site. In addition, microfiber architecture is intrinsically porous and can improve mass transport, vascularization, and cell survival after grafting. Anionic polysaccharides, as pectin or the more popular alginate, represent a particularly promising choice for the fabrication of cell-laden patches, due to their extremely mild gelation in the presence of divalent ions and widely accepted biocompatibility. In this study, to combine the favorable properties of hydrogel and fibrous architecture, a simple coaxial flow wet-spinning system was used to prepare cell-laden, 3D fibrous patches using RGD-modified pectin. Rapid fabrication of coherent self-standing patches, with diameter in the range of 100-200 μm and high cell density, was possible by accurate choice of pectin and calcium ions concentrations. Cells were homogeneously dispersed throughout the microfibers and remained highly viable for up to 2 weeks, when the initial stage of myotubes formation was observed. Modified-pectin microfibers appear as promising scaffold to support muscle tissue regeneration, due to their inherent porosity, the favorable cell-material interaction, and the possibility to guide cell alignment toward a functional tissue.

3D Printing of Microgel Scaffolds with Tunable Void Fraction to Promote Cell Infiltration.

Granular, microgel-based materials have garnered interest as promising tissue engineering scaffolds due to their inherent porosity, which can promote cell infiltration. Adapting these materials for 3D bioprinting, while maintaining sufficient void space to enable cell migration, can be challenging, since the rheological properties that determine printability are strongly influenced by microgel packing and void fraction. In this work, a strategy is proposed to decouple printability and void fraction by blending UV-crosslinkable gelatin methacryloyl (GelMA) microgels with sacrificial gelatin microgels to form composite inks. It is observed that inks with an apparent viscosity greater than ≈100 Pa s (corresponding to microgel concentrations ≥5 wt%) have rheological properties that enable extrusion-based printing of multilayered structures in air. By altering the ratio of GelMA to sacrificial gelatin microgels, while holding total concentration constant at 6 wt%, a family of GelMA:gelatin microgel inks is created that allows for tuning of void fraction from 0.20 to 0.57. Furthermore, human umbilical vein endothelial cells (HUVEC) seeded onto printed constructs are observed to migrate into granular inks in a void fraction-dependent manner. Thus, the family of microgel inks holds promise for use in 3D printing and tissue engineering applications that rely upon cell infiltration.