Pore Surface Modification Research Articles

Engineering designed functional covalent organic frameworks via pore surface modifications for effectively reducing the dielectric constant of polyimide-based electronic packaging materials

Polyimide (PI) is considered one of the most promising candidate materials for the microelectronics and wireless communication industries. Nevertheless, the relatively high dielectric constant of PI has become a significant obstacle, constraining its utilization in the realm of microelectronics. Herein, novel PI nanocomposite films were fabricated by incorporating covalent organic frameworks (COFs) and their functionalized counterparts (COF@POSS and COF@DTF) through post-synthetic modification. Among all PI nanocomposites films, PI/COF@POSS nanocomposite film including 2 wt% COF@POSS achieved the lowest dielectric constant (2.41) and dielectric loss (0.0076). These values represented a reduction of 22.5 % and 24 % compared to pure PI, respectively. The decrease in dielectric constant is ascribed to the combined influence of the porous structure of COF and the augmentation in free volume fraction caused by the steric hindrance of POSS. Additionally, the tensile strength of the PI/COF@POSS and PI/COF@DTF nanocomposite films increased up to 121.1 MPa and 112.0 MPa, representing a 95 % and 80 % improvement over pure PI, respectively. Furthermore, the introduction of COFs functionalized with POSS and DTF significantly enhanced the hydrophobicity of PI nanocomposite films. The combination of porous organic nanofillers with surface functionalization offers a feasible route to create low-k PI nanocomposite films with improved mechanical properties and hydrophobicity.

Effects of Pore Size and Surface Modification on the Alumina Microfiltration Membrane Fouling in MBR with Backwashing

Effects of Pore Size and Surface Modification on the Alumina Microfiltration Membrane Fouling in MBR with Backwashing

Mechanism of one-step hydrothermal nitric acid treatment for producing high adsorption capacity porous materials from coal gasification fine slag

The increasing amount of coal gasification fine slag (CGFS) necessitates its resource utilization. CGFS, mainly composed of porous carbonaceous particles and partially fused spherical or agglomerated ash particles, is an inexpensive and high-quality raw material for preparing adsorbent materials. However, the challenge remains in developing a simple, low-cost, and environmentally friendly method to produce high-performance porous materials from CGFS. In this study, a one-step treatment method using 2 mol/L nitric acid under hydrothermal conditions was proposed for CGFS. The adsorbent material (CGFS-2 M) prepared under a solid–liquid ratio of 2:5 and an initial concentration of 200 mg/L methylene blue (MB) exhibited an equilibrium adsorption capacity as high as 210.20 mg/g. The excellent adsorption performance of CGFS-2 M can be attributed to several factors: acid leaching for mineral removal and pore formation, resulting in a specific surface area and total pore volume 2.2 and 1.6 times that of untreated CGFS, respectively, and an optimized mesoporous pore size distribution favorable for MB adsorption; optimal mineral removal and a well-defined carbon microcrystal structure providing more space for MB adsorption; nitric acid treatment increasing the surface oxygen content and hydrophilicity, enhancing its ability to remove MB. The synergistic effect of pore structure improvement and surface modification indicates a feasible research direction for enhancing the performance of CGFS-based adsorbent materials. These results provide theoretical support for the development of efficient CGFS-based adsorbents.

Molecularly Imprinted Macroporous Hydrogel Promotes Bone Regeneration via Osteogenic Induction and Osteoclastic Inhibition.

Macroporous hydrogels offer physical supportive spaces and bio-instructive environment for the seeded cells, where cell-scaffold interactions directly influence cell fates and subsequently affect tissue regeneration post-implantation. Effectively modifying bioactive motifs at the inner pore surface provides appropriate niches for cell-scaffold interactions. A molecular imprinting method and sacrificial templates are introduced to prepare inner pore surface modification in the macroporous hydrogels. In detail, acrylated bisphosphonates (Ac-BPs) chelating to templates (CaCO3 particles) are anchored on the inner pore surface of the methacrylated gelatin (GelMA)-methacrylated hyaluronic acid (HAMA)-poly (ethylene glycol) diacrylate (PEGDA) macroporous hydrogel (GHP) to form a functional hydrogel scaffold (GHP-int-BP). GHP-int-BP, but not GHP, effectively crafts artificial cell niches to substantially alter cell fates, including osteogenic induction and osteoclastic inhibition, and promote in situ bone regeneration. These findings highlight that molecular imprinting on the inner pore surface in the hydrogel efficiently creates orthogonally additive bio-instructive scaffolds for bone regeneration.

New advances in gated materials of mesoporous silica for drug controlled release

Drug delivery systems (DDS) are used to deliver therapeutic drugs to improve selectivity and reduce side effects. With the development of nanotechnology, many nanocarriers have been developed and applied to drug delivery, including mesoporous silica. Mesoporous silica nanoparticles (MSNs) have attracted a lot of attention for simple synthesis, biocompatibility, high surface area and pore volume. Based on the pore system and surface modification, gated mesoporous silica nanoparticles can be designed to realize on-command drug release, which provides a new approach for selective delivery of antitumor drugs. Herein, this review mainly focuses on the “gate keepers” of mesoporous silica for drug controlled release in nearly few years (2017–2020). We summarize the mechanism of drug controlled release in gated MSNs and different gated materials: inorganic gated materials, organic gated materials, self-gated drug molecules, and biological membranes. The facing challenges and future prospects of gated MSNs are discussed rationally in the end.

Regulation of hydrophobicity and water adsorption of MIL-101(Cr) through post-synthetic modification

Hydrophobic property of metal–organic frameworks (MOFs) is not only important for their stability improvement but also has a profound effect on the performance of many applications. The essence of coordination bonds led to most of the MOFs are hydrophilic and hydrophobic MOFs are generally achieved by hydrophobic modification of pore surface. Here, we report the systematic regulation of water adsorption and hydrophobic property of a classical MOF MIL-101(Cr) through post-synthetic modification. The contact angle (CA) of modified MIL-101 could vary from 17.9° to 146.5° by changing the alkyl chain length of primary amines. The water adsorption capacity and step pressure can also be tuned correspondingly.

Pore-Surface Modification as a Method of Controlling the Relaxation of a Nonwetting Liquid Dispersed in a Nanoporous Medium

Pore-Surface Modification as a Method of Controlling the Relaxation of a Nonwetting Liquid Dispersed in a Nanoporous Medium

Progress in Mesoporous Silica Nanoparticles as Drug Delivery Agents for Cancer Treatment.

Cancer treatment and therapy have made significant leaps and bounds in these past decades. However, there are still cases where surgical removal is impossible, metastases are challenging, and chemotherapy and radiotherapy pose severe side effects. Therefore, a need to find more effective and specific treatments still exists. One way is through the utilization of drug delivery agents (DDA) based on nanomaterials. In 2001, mesoporous silica nanoparticles (MSNs) were first used as DDA and have gained considerable attention in this field. The popularity of MSNs is due to their unique properties such as tunable particle and pore size, high surface area and pore volume, easy functionalization and surface modification, high stability and their capability to efficiently entrap cargo molecules. This review describes the latest advancement of MSNs as DDA for cancer treatment. We focus on the fabrication of MSNs, the challenges in DDA development and how MSNs address the problems through the development of smart DDA using MSNs. Besides that, MSNs have also been applied as a multifunctional DDA where they can serve in both the diagnostic and treatment of cancer. Overall, we argue MSNs provide a bright future for both the diagnosis and treatment of cancer.

The Application of Prussian Blue Nanoparticles in Tumor Diagnosis and Treatment.

Prussian blue nanoparticles (PBNPs) have attracted increasing research interest in immunosensors, bioimaging, drug delivery, and application as therapeutic agents due to their large internal pore volume, tunable size, easy synthesis and surface modification, good thermal stability, and favorable biocompatibility. This review first outlines the effect of tumor markers using PBNPs-based immunosensors which have a sandwich-type architecture and competitive-type structure. Metal ion doped PBNPs which were used as T1-weight magnetic resonance and photoacoustic imaging agents to improve image quality and surface modified PBNPs which were used as drug carriers to decrease side effects via passive or active targeting to tumor sites are also summarized. Moreover, the PBNPs with high photothermal efficiency and excellent catalase-like activity were promising for photothermal therapy and O2 self-supplied photodynamic therapy of tumors. Hence, PBNPs-based multimodal imaging-guided combinational tumor therapies (such as chemo, photothermal, and photodynamic therapies) were finally reviewed. This review aims to inspire broad interest in the rational design and application of PBNPs for detecting and treating tumors in clinical research.

Studies of proliferation and chondrogenic differentiation of rat adipose stem cells using an anti-oxidative polyurethane scaffold combined with cyclic compression culture.

The adipose stem cell is a potential candidate for the autologous chondrocytes repairing approach because of the abundance of fat in the animal body and its versatile differentiation capability. In this study, rat adipose stem cells (rASCs) were seeded into anti-oxidative N-acetylcysteine (NAC) grafted polyurethane (PU) scaffold and then combined with short dynamic compressive stimulation (24h) to induce rASCs chondrogenesis differentiation in vitro. The inner pore surface of the PU scaffold was first modified via alginate and type I collagen to promote rASCs adherence. The modified layers crosslinked by genipin showed outstanding stability after ultrasonic treatment, indicating the modified layers were stable and can keep the cells adhesion well during dynamic compressive stimulation. After inner pore surface modification and 10mM NAC grafting, the PU scaffold-A-C-G (graft 10mM NAC) has shown the best proliferation efficiency with homogeneous cell distribution after 72hr static culture. After short term dynamic compressive stimulation, significant gene expression in chondrogenic markers, Sox-9, and Aggrecan, were noted in both PU scaffold-A-C-G and PU scaffold-A-C-G (graft 10mM NAC). Considering the cell proliferation efficiency and gene expression, the anti-oxidative NAC grafted PU scaffold combined with short term dynamic compressive stimulation could be useful for cell culturing in stem cell therapy.

Superhydrophobic Covalent Organic Frameworks Prepared via Pore Surface Modifications for Functional Coatings under Harsh Conditions.

Covalent organic frameworks (COFs) have been widely used in catalysis, energy storage, environmental protection, and separation. However, they require a long assembly period (∼3 days) and complex synthesis conditions; differences in water resistance have restricted their overall versatility. In this paper, the preparation of COF-DhaTab was optimized, and this process can be easily performed in air. Thus, it is feasible for the scale-up of COF-DhaTab in the near future. The superhydrophobic properties of COF-DhaTab (water contact angle, >150°) can be created by regulating the wettability of COF-DhaTab by grafting fluoride. When the grafting degree of fluoride increased to 4.32%, the water contact angle of COFs increased from 0° to more than 150°. The grafted COFs are termed COF-DhaTab fluoride (COF-DTF). The chemically modified COF-DhaTab maintains its original porosity and crystallinity. The superhydrophobic COF-DTF can be applied to various substrates, for example, foam, fabric, and glass. These all exhibit outstanding water repellency, self-healing, and excellent self-cleaning. Importantly, the coating maintains its original superhydrophobicity even under extremely acidic/basic conditions (pH = 1-14) and toward boiling water (100 °C). Furthermore, COF-DTF displays long-term stability and is easily scaled. It is a promising and practical candidate for hydrophobic modifications to various substrates.

Three-dimensional microscale simulation of colloidal particle transport and deposition in chemically heterogeneous capillary tubes

The effect of surface chemical heterogeneity and hydrodynamics on particle transport and deposition in porous media was investigated by microscale simulations using a colloidal particle tracking model, called 3D-PTPO (Three-dimensional particle tracking model by Python® and OpenFOAM®) code. This work is aimed as a step toward modeling of transport and deposition in porous media idealized as a bundle of straight capillary tubes. Therefore, our focus is put upon a three-dimensional capillary with periodically repeating chemically heterogeneous surfaces namely crosswise strips patterned and chess board patterned. The main feature of this recent model is to renew the flow field by reconstructing the pore structure, to take the pore surface modification induced by the volume of the deposited particles into account. The dependency of the deposition probability and the dimensionless surface coverage (Γ/ΓRSA) on the frequency of the pitches (λ), the Péclet number (Pe) and the favorable area fraction (θ), as well as the distribution of the spatial density of deposited particles along the capillary tube were studied. The results indicate that particles tend to deposit at the leading and trailing edges of the favorable strips, and the deposition is more uniform along the patterned capillary compared to the homogeneous one. In addition, for the chemically heterogeneous capillary, in a similar manner as for the homogeneous one, a definite plateau exists for the Γ/ΓRSA at low Péclet values. For high Pe values, the declining trend for Γ/ΓRSA versus Pe is in good agreement with the derived power law dependence already observed in the literature for fully adsorbing surfaces. Moreover, for fixed θ the deposition probability is linearly correlated with λ and for given λ, such a deposition probability is also a linear function of θ.

Synthesis of NaX zeolite-graphite amine fiber composite membrane: Role of graphite amine in membrane formation for H2/CO2 separation

Pore surface modification of zeolite membrane is a challenging area to combat the trade-off between the high flux and high selectivity of the gas separation membrane. Herein we report facile method of pore along with defects modification of NaX zeolite membrane by incorporating graphite amine (Ga) into the membrane structure. Permeation properties of different membranes were evaluated by single gas permeance of H2, CO2 and separation factors for mixed gas H2-CO2 with different mixture ratio. These studies were done at room temperature and 100–300 kPa feed pressure. The results show that Ga is not only active for defect removal of NaX membrane but also enhanced the formation of NaX zeolite from mother sol. In addition, presence of graphite amine into NaX zeolite membrane increase the permeance of H2 from 5.1 × 10−7 mol m−2 s−1 kPa−1 to 36.5 × 10−7 moll m−2 s−1 kPa−1 with increase of feed pressure 100–300 kPa feed pressure due to its hydrophobic properties and separation factor of H2-CO2 enhanced up to 31 for H2-CO2 mixture gas compared to literature reported value 6.5 for FAU membrane over 3-aminopropyltriethoxysilane functionalized alumina. Herein for the first time we report that graphite amine catalyzes for the formation of NaX zeolite in addition to pore modification in zeolite membrane.

Structural and textural influences of surfactant-modified zeolitic materials over the methamidophos adsorption behavior

ABSTRACTIn this work, a natural zeolite previously conditioned with NaCl solution was modified with different hexadecyltrimethylammonium-bromide concentrations for methamidophos removal. All materials were characterized by diverse analytical techniques. Methamidophos adsorption behavior was studied by using batch experiments. Main structural and textural differences of surfactant-modified zeolitic materials were correlated with methamidophos adsorption capacity. Methamidophos adsorption was enhanced when zeolitic materials were modified with HDTMA and, more significantly, when a 25 mmol/L surfactant concentration was used, achieving a maximum adsorption capacity of 1.13 mg/g due to its pore surface modification. In this way, methamidophos adsorption present in aqueous solution was improved.

Selection of the optimum 3D-printed pore and the surface modification techniques for tissue engineering tracheal scaffold in vivo reconstruction.

The influences of pore sizes and surface modifications on biomechanical properties and biocompatibility (BC) of porous tracheal scaffolds (PTSs) fabricated by polycaprolactone (PCL) using 3D printing technology. The porous grafts were surface-modified through hydrolysis, amination, and nanocrystallization treatment. The surface properties of the modified grafts were characterized by energy dispersive spectroscopy (EDS) and scanning electron microscopy (SEM). The materials were cocultured with bone marrow mesenchymal stem cells (BMSCs). The effect of different pore sizes and surface modifications on the cell proliferation behavior was evaluated by the cell counting kit-8 (CCK-8). Compared to native tracheas, the PTS has good biomechanical properties. A pore diameter of 200 μm is the optimum for cell adhesion, and the surface modifications successfully improved the cytotropism of the PTS. Allogeneic implantation confirmed that it largely retains its structural integrity in the host, and the immune rejection reaction of the PTS decreased significantly after the acute phase. Nano-silicon dioxide (NSD)-modified PTS is a promising material for tissue engineering tracheal reconstruction. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 107A: 360-370, 2019.

Integrating Superwettability within Covalent Organic Frameworks for Functional Coating

Summary Despite the availability of a variety of skeletons for covalent organic frameworks (COFs), control of pore-surface wettability remains undeveloped, which could immensely expand their overall versatility. Herein, we contribute an effective strategy for imparting superwettability on COFs by chemically coating the pore surface with perfluoroalkyl groups to confer them with superhydrophobicity. Taking advantage of controllable modification, the resultant COFs retain the porosity and crystallinity of the pristine COFs. Benefiting from the bulk superhydrophobicity of the COF crystals and the feasibility of COF synthesis, they can be used as a coat or in situ integrated within various substrates; once applied, this renders them superhydrophobic. Given the modular nature, this protocol is compatible with the development of various specific wettabilities in COFs, which thereby constitutes a step for expanding the scope of COF applications and provides many opportunities for the processing of advanced materials and devices.

Influence of controlled functionalization of mesoporous silica nanoparticles as tailored fillers for thin-film nanocomposite membranes on desalination performance

Thin film nanocomposite (TFN) membranes comprising of controlled functionalized mesoporous silica nanoparticles (MSN) blended in the polyamide (PA) barrier layer were prepared via interfacial polymerization of m-phenylenediamine and trimesoyl chloride on a porous polyethersulfone support membrane. MSN were synthesized by sol-gel process and then functionalized with octadecyltrichlorosilane (OTS) using post-grafting method. The nitrogen adsorption measurements demonstrated that the hydrophobic alkyl chains of OTS can be grafted onto the internal pores of MSN or just be located on the external particle surface, depending on the functionalization procedure and the OTS concentration. The functionalized nanoparticles with a diameter of about 80 nm were thereafter easily dispersed in the organic phase during the interfacial polymerization. Evaluation of membranes’ performance was based on water and ethanol permeability measurements, in addition to salt rejection from aqueous solutions. The results indicated that the functionalization of the external surface of MSN only, without extension to the interior pores surface, significantly increased both water and ethanol permeabilities. Contrarily, the surface modification of the MSN internal pores only increased the permeability of ethanol and reduced the water permeability, mainly due to the hydrophobicity of OTS. The influence of nanoparticles loading, as well as the concentration of OTS and thus the extent of MSN functionalization on the separation performance of TFN membranes were also investigated. TFN membranes prepared using the optimized MSN functionalization and loading yielded up to 63% higher water permeability compared to the reference thin film composite membrane without sacrificing the membrane selectivity. This work clearly emphasizes the direct relationship between the internal pores of MSN as functional nanofiller in the PA barrier layer and increasing or decreasing the water permeability of resulting TFN membranes.

Effect of the pore size and surface modification of porous glass membranes on vanadium redox-flow battery performance

Porous glass (PG) offers the ability to vary pore sizes and modify surfaces, allowing membranes to be tailored for a given electrochemical application. In this contribution, the application of PG in all-vanadium redox-flow batteries (VFB) and the effect of surface modification with sulfonic acid groups were investigated, and the results were compared with those from well-known polymeric membranes. The performance of native and surface-modified PG membranes with pore sizes ranging from 2 to 20 nm and thicknesses of 300 and 500 µm was investigated by examining their self-discharge behavior, polarization curves and area resistance. A maximum power density of 77 mW cm−2 at a current density of 110 mA cm−2 was observed with the modified membrane 505FDS, and this density is approximately half the power density achieved with Nafion™ 117. The results can be related to the small vanadium crossover, high conductivity and chemical stability. Therefore, the great potential of PG membranes as separators in VFBs was shown.

Functionalization of MOFs via a mixed-ligand strategy: enhanced CO2 uptake by pore surface modification

A new Zn(ii) metal-organic framework (MOF) [Me2NH2][Zn2(BDPP)(HTZ)]·4DMF (1) (H4BDPP = 3,5-bis(3,5-dicarboxylphenyl)pyridine, HTZ = 1H-tetrazole) has been constructed under solvothermal conditions by using a mixed-ligand strategy. Structural analysis demonstrates that 1 is a 3D framework based on four kinds of secondary building units (SBUs), which presents a rare structure constructed from quaternary SBUs and shows an uncommon (3,3,4,6)-connected topology. In particular, 1 contains two shapes of 1D open channels with suitable pore sizes, high porosity, and a highly polar pore system decorated with uncoordinated N atoms and carboxylic O atoms, providing a good environment for selective adsorption of CO2. Inspired by the structure of 1 and reticular chemistry, 5-amino-1H-tetrazole (ATZ) was used to replace 1H-tetrazole to enhance CO2 sorption capacity by pore surface modification; as a result, an amino-functionalized MOF, [Me2NH2][Zn2(BDPP)(ATZ)]·4DMF (1-NH2) was successfully built. 1-NH2 exhibits multipoint interactions between the CO2 molecules and the framework, resulting in better CO2 uptake and selectivity for CO2 over CH4 than 1.

Development of Dual-Pore Coexisting Branched Silica Nanoparticles for Efficient Gene-Chemo Cancer Therapy.

Various strategies for combination therapy to overcome current limitations in cancer therapy have been actively investigated. Among them, simultaneous delivery of multiple drugs is a subject of high interest due to anticipated synergistic effect, but there have been difficulties in designing and developing effective nanomaterials for this purpose. In this work, dual-pore coexisting hybrid porous silica nanoparticles are developed through Volmer-Weber growth pathway for efficient co-delivery of gene and anticancer drug. Based on the different pore sizes (2-3 and 40-45 nm) and surface modifications of the core and branch domains, loading and controlled release of gene and drug are achieved by appropriate strategies for each environment. With excellent loading capacity and low cytotoxicity of the present platform, the combinational cancer therapy is successfully demonstrated against human cervical cancer cell line. Through a series of quantitative analyses, the excellent gene-chemo combinational therapeutic efficiency is successfully demonstrated. It is expected that the present nanoparticle will be applicable to various biomedical fields that require co-delivery of small molecule and nucleic acid.