Silica-Derived Nanostructured Electrode Materials for ORR, OER, HER, CO2RR Electrocatalysis, and Energy Storage Applications: A Review.

Silica-derived nanostructured catalysts (SDNCs) are a class of materials synthesized using nanocasting and templating techniques, which involve the sacrificial removal of a silica template to generate highly porous nanostructured materials. The surface of these nanostructures is functionalized with a variety of electrocatalytically active metal and non-metal atoms. SDNCs have attracted considerable attention due to their unique physicochemical properties, tunable electronic configuration, and microstructure. These properties make them highly efficient catalysts and promising electrode materials for next generation electrocatalysis, energy conversion, and energy storage technologies. The continued development of SDNCs is likely to lead to new and improved electrocatalysts and electrode materials. This review article provides a comprehensive overview of the recent advances in the development of SDNCs for electrocatalysis and energy storage applications. It analyzes 337,061 research articles published in the Web of Science (WoS) database up to December 2022 using the keywords "silica", "electrocatalysts", "ORR", "OER", "HER", "HOR", "CO2RR", "batteries", and "supercapacitors". The review discusses the application of SDNCs for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO2RR), supercapacitors, lithium-ion batteries, and thermal energy storage applications. It concludes by discussing the advantages and limitations of SDNCs for energy applications.

Enhancement of critical-sized bone defect regeneration using UiO-66 nanomaterial in rabbit femurs.

BACKGROUND: Repair of large-sized bone defects is a challengeable obstacle in orthopedics and evoked the demand for the development of biomaterials that could induce bone repair in such defects. Recently, UiO-66 has emerged as an attractive metal-organic framework (MOF) nanostructure that is incorporated in biomedical applications due to its biocompatibility, porosity, and stability. In addition, its osteogenic properties have earned a great interest as a promising field of research. Thus, the UiO-66 was prepared in this study and assessed for its potential to stimulate and support osteogenesis in vitro and in vivo in a rabbit femoral condyle defect model. The nanomaterial was fabricated and characterized using x-ray diffraction (XRD) and transmission electron microscopy (TEM). Afterward, in vitro cytotoxicity and hemolysis assays were performed to investigate UiO-66 biocompatibility. Furthermore, the material in vitro capability to upregulate osteoblast marker genes was assessed using qPCR. Next, the in vivo new bone formation potential of the UiO-66 nanomaterial was evaluated after induction of bone defects in rabbit femoral condyles. These defects were left empty or filled with UiO-66 nanomaterial and monitored at weeks 4, 8, and 12 after bone defect induction using x-ray, computed tomography (CT), histological examinations, and qPCR analysis of osteocalcin (OC) and osteopontin (OP) expressions. RESULTS: The designed UiO-66 nanomaterial showed excellent cytocompatibility and hemocompatibility and stimulated the in vitro osteoblast functions. The in vivo osteogenesis was enhanced in the UiO-66 treated group compared to the control group, whereas evidence of healing of the treated bone defects was observed grossly and histologically. Interestingly, UiO-66 implanted defects displayed a significant osteoid tissue and collagen deposition compared to control defects. Moreover, the UiO-66 nanomaterial demonstrated the potential to upregulate OC and OP in vivo. CONCLUSIONS: The UiO-66 nanomaterial implantation possesses a stimulatory impact on the healing process of critical-sized bone defects indicating that UiO-66 is a promising biomaterial for application in bone tissue engineering.

Cellulose-Based Nanomaterials Advance Biomedicine: A Review.

There are various biomaterials, but none fulfills all requirements. Cellulose biopolymers have advanced biomedicine to satisfy high market demand and circumvent many ecological concerns. This review aims to present an overview of cellulose knowledge and technical biomedical applications such as antibacterial agents, antifouling, wound healing, drug delivery, tissue engineering, and bone regeneration. It includes an extensive bibliography of recent research findings from fundamental and applied investigations. Cellulose-based materials are tailorable to obtain suitable chemical, mechanical, and physical properties required for biomedical applications. The chemical structure of cellulose allows modifications and simple conjugation with several materials, including nanoparticles, without tedious efforts. They render the applications cheap, biocompatible, biodegradable, and easy to shape and process.

Trifluoromethylated Flavonoid-Based Isoxazoles as Antidiabetic and Anti-Obesity Agents: Synthesis, In Vitro α-Amylase Inhibitory Activity, Molecular Docking and Structure-Activity Relationship Analysis.

Diabetes mellitus is a major health problem globally. The management of carbohydrate digestion provides an alternative treatment. Flavonoids constitute the largest group of polyphenolic compounds, produced by plants widely consumed as food and/or used for therapeutic purposes. As such, isoxazoles have attracted the attention of medicinal chemists by dint of their considerable bioactivity. Thus, the main goal of this work was to discover new hybrid molecules with properties of both flavonoids and isoxazoles in order to control carbohydrate digestion. Moreover, the trifluoromethyl group is a key entity in drug development, due to its strong lipophilicity and metabolic stability. Therefore, the present work describes the condensation of a previously synthesized trifluoromethylated flavonol with different aryl nitrile oxides, affording 13 hybrid molecules indicated as trifluoromethylated flavonoid-based isoxazoles. The structures of the obtained compounds were deduced from by 1H NMR, 13C NMR, and HRMS analysis. The 15 newly synthesized compounds inhibited the activity of α-amylase with an efficacy ranging from 64.5 ± 0.7% to 94.7 ± 1.2% at a concentration of 50 µM, and with IC50 values of 12.6 ± 0.2 µM-27.6 ± 1.1 µM. The most effective compounds in terms of efficacy and potency were 3b, 3h, 3j, and 3m. Among the new trifluoromethylated flavonoid-based isoxazoles, the compound 3b was the most effective inhibitor of α-amylase activity (PI = 94.7 ± 1.2% at 50 µM), with a potency (IC50 = 12.6 ± 0.2 µM) similar to that of the positive control acarbose (IC50 = 12.4 ± 0.1 µM). The study of the structure-activity relationship based on the molecular docking analysis showed a low binding energy, a correct mode of interaction in the active pocket of the target enzyme, and an ability to interact with the key residues of glycosidic cleavage (GLU-230 and ASP-206), explaining the inhibitory effects of α-amylase established by several derivatives.

Surfactant assisted synthesis of hierarchical porous metal-organic frameworks nanosheets.

Two-dimensional metal-organic frameworks show increasing research attention due to their unique properties including tunable thickness, simple packing into a film and membrane, and high surface-to-volume atom ratios. A bottom-up synthesis strategy using cetyltrimethylammonium bromide for the synthesis of copper-benzenedicarboxylate (Cu(BDC)) nanosheets is reported. The method offers the synthesis of hierarchical porous Cu(BDC) lamellae with micrometer lateral dimensions, and nanometer thickness (100-150 nm). Electron microscope (scanning and transmission), and N2 adsorption isotherms confirm the formation of lamellae Cu(BDC) with mesopore size of 5-80 nm. The material has thermal stability up to 400 °C with good chemical stability in several organic solvents. However, the material transforms to another phase (Cu(BDC)(H2O)2) when soaked in water and alcohols. The transformation reduces crystal size and offers the formation of hydrogen bond resulting in an increase in the sorption of CO2 by ∼10% compared to the pristine material Cu(BDC).

Nanoparticle-based surface assisted laser desorption ionization mass spectrometry: a review.

Great endeavors are undertaken to find effective nanoparticles to replace organic matrices for the analysis of small molecules using laser desorption ionization mass spectrometry (LDI-MS). Nanoparticles offer high sensitivity and better selectivity compared to conventional organic matrices. Surface assisted LDI-MS (SALDI-MS), and surface enhanced LDI-MS (SELDI-MS) provide clear background spectra without observable interferences peaks, and cause no fragmentation (soft ionization) of thermal and acidity labile molecules. This review article (with 460 references) summarizes the recent applications of nanoparticles including metallic, metal oxides, silicon, quantum dots, metal-organic frameworks and covalent organic frameworks, for the analysis of small molecules. Nanoparticles serve not only as surface for LDI-MS, but they can be also used as probe or pseudo-stationary phase for separation, enrichment, and microextraction. Hopefully, the knowledge and learning points gained from this review will deepen the understanding of nanoparticles applications for LDI-MS. Graphical Abstract Schematic representation of laser desorption ionization mass spectrometry using various nanoparticles (such as metallic nanoparticles, carbon nanomaterials, silicon based nanomaterials, metal oxides, quantum dots, metal-organic frameworks, and covalent organic frameworks). Advanced technologies using nanoparticles are also reviewed.

Nanoparticle assisted laser desorption/ionization mass spectrometry for small molecule analytes.

Nanoparticle assisted laser desorption/ionization mass spectrometry (NPs-ALDI-MS) shows remarkable characteristics and has a promising future in terms of real sample analysis. The incorporation of NPs can advance several methods including surface assisted LDI-MS, and surface enhanced LDI-MS. These methods have advanced the detection of many thermally labile and nonvolatile biomolecules. Nanoparticles circumvent the drawbacks of conventional organic matrices for the analysis of small molecules. In most cases, NPs offer a clear background without interfering peaks, absence of fragmentation of thermally labile molecules, and allow the ionization of species with weak noncovalent interactions. Furthermore, an enhancement in sensitivity and selectivity can be achieved. NPs enable straightforward analysis of target species in a complex sample. This review (with 239 refs.) covers the progress made in laser-based mass spectrometry in combination with the use of metallic NPs (such as AuNPs, AgNPs, PtNPs, and PdNPs), NPs consisting of oxides and chalcogenides, silicon-based NPs, carbon-based nanomaterials, quantum dots, and metal-organic frameworks. Graphical abstract An overview is given on nanomaterials for use in surface-assisted laser desorption/ionization mass spectrometry of small molecules.

Graphene oxide nanosheets in complex with cell penetrating peptides for oligonucleotides delivery.

A new strategy for gene transfection using the nanocarrier of cell penetrating peptides (CPPs; PepFect14 (PF14) or PepFect14 (PF14) (PF221)) in complex with graphene oxide (GO) is reported. GO complexed with CPPs and plasmid (pGL3), splice correction oligonucleotides (SCO) or small interfering RNA (siRNA) are performed. Data show adsorption of CPPs and oligonucleotides on the top of the graphenic lamellar without any observed change of the particle size of GO. GO mitigates the cytotoxicity of CPPs and improves the material biocompatibility. Complexes of GO-pGL3-CPPs (CPPs; PF14 or PF221) offer 2.1-2.5 fold increase of the cell transfection compared to pGL3-CPPs (CPPs; PF14 or PF221). GO-SCO-PF14 assemblies effectively transfect the cells with an increase of >10-25 fold compared to the transfection using PF14. The concentration of GO plays a significant role in the material nanotoxicity and the transfection efficiency. The results open a new horizon in the gene treatment using CPPs and offer a simple strategy for further investigations.

A Fast and Scalable Approach for Synthesis of Hierarchical Porous Zeolitic Imidazolate Frameworks and One-Pot Encapsulation of Target Molecules.

A trimethylamine (TEA)-assisted synthesis approach that combines the preparation of hierarchical porous zeolitic imidazolate framework ZIF-8 nanoparticles and one-pot encapsulation of target molecules is presented. Two dye molecules, rhodamine B (RhB) and methylene blue (MB), and one protein (bovine serum albumin, BSA) were tested as the target molecules. The addition of TEA into the solution of zinc nitrate promoted the formation of ZnO nanocrystals, which rapidly transformed to ZIF-8 nanoparticles after the addition of the linker 2-methylimidazole (Hmim). Hierarchical porous dye@ZIF-8 nanoparticles with high crystallinity, large BET surface areas (1300-2500 m2/g), and large pore volumes (0.5-1.0 cm3/g) could be synthesized. The synthesis procedure was fast (down to 2 min) and scalable. The Hmim/Zn ratio could be greatly reduced (down to 2:1) compared to previously reported ones. The surface areas, and the mesopore size, structure, and density could be modified by changing the TEA or dye concentrations, or by postsynthetic treatment using reflux in methanol. This synthesis and one-pot encapsulation approach is simple and can be readily scaled up. The photophysical properties such as lifetime and photostability of the dyes could be tuned via encapsulation. The lifetimes of the encapsulated dyes were increased by 3-27-fold for RhB@ZIF-8 and by 20-fold for MB@ZIF-8, compared to those of the corresponding free dyes. The synthesis approach is general, which was successfully applied for encapsulation of protein BSA. It could also be extended for the synthesis of hierarchical porous cobalt-based ZIF (dye@ZIF-67).

Surface tuning laser desorption/ionization mass spectrometry (STLDI-MS) for the analysis of small molecules using quantum dots.

In most applications of quantum dots (QDs) for surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS), one side of QDs is supported by a solid substrate (stainless - steel plate), whereas the other side is in contact with the target analytes. Therefore, the surface capping agent of QDs is a key parameter for laser desorption/ionization mass spectrometry (LDI-MS). Cadmium telluride quantum dots (CdTe QDs) modified with different capping agents are synthesized, characterized, and applied for surface tuning laser desorption/ionization mass spectrometry (STLDI-MS). Data shows that CdTe quantum dot modified cysteine (cys@CdTe QDs) has an absorption that matches with the wavelength of the N2 laser (337 nm). The synergistic effect of large surface area and absorption of the laser irradiation of cys@CdTe QDs enhances the LDI-MS process for small - molecule analysis, including α-, ß-, and γ-cyclodextrin, gramicidin D, perylene, pyrene, and triphenylphosphine. Cys@CdTe QDs are also applied using Al foils as substrates. Aluminum foil combined with cys@CdTe QDs enhances the ionization efficiency and is cheap compared to traditional matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) with a stainless - steel plate.

Effect of surface capping of quantum dots (CdTe) on proteomics.

RATIONALE: Investigation of nanoparticles for laser desorption/ionization mass spectrometry (LDI-MS) is routinely reported. However, the effect of surface capping of nanomaterials for LDI-MS is not well studied. METHODS: Different capping agents of quantum dots (CdTe) affect the spectra quality and sensitivity of protein analysis and protein digestion using trypsin enzyme assisted by microwave. Surface modification of CdTe quantum dots with different capping agents, namely 3-mercaptopropionic acid (3-MPA), 4-aminothiophenol (4-ATP), 4-mercaptobenzoic acid (4-MBA), 11-mercaptoundecanoic acid (11-MUA), cysteine (Cys) and thioglycolic acid (TG), were investigated for quantum dots (QDs)-assisted trypsin protease followed by analysis using mass spectrometry. RESULTS: CdTe QDs were used as a surface to assist trypsin protease and laser desorption/ionization mass spectrometry (surface-assisted laser desorption/ionization mass spectrometry, SALDI-MS). The MS profiles for the investigated analytes (bovine serum albumin (BSA), lysozyme, cytochrome c, α-casein, transferrin and myoglobin) revealed almost the absence of degradation that implies the softness of the present technique. QDs-assisted LDI-MS offered high sensitivity and high resolution. QDs showed significant enhancement of microwave-assisted trypsin digestion of the investigated proteins and these improvements boosted the identifications of fragments with a database. CONCLUSIONS: A capping agent of quantum dots affects the analysis of proteins and peptides using LDI-MS. CdTe QDs offer sensitive, high-resolution and simple analysis of proteins. QDs improved the protein digestion using the microwave-assisted trypsin digestion. Copyright © 2016 John Wiley & Sons, Ltd.

Gold nanoparticles assisted laser desorption/ionization mass spectrometry and applications: from simple molecules to intact cells.

Gold nanoparticles (AuNPs) assisted laser desorption/ionization mass spectrometry (GALDI-MS) provided new horizons and offered many functions for various applications. This review summarized AuNPs applications for analytical, biotechnology and proteomics. AuNPs efficiently absorbed the laser radiation and transferred the energy to the analyte for the desorption/ionization process. The unique features of AuNPs such as large surface area and high absorption coefficient lead not only to high resolution, low interference and low limit of detection, but also offered selective detection for certain species. AuNPs provided an excellent surface for the analysis of several species such as small molecules, biomarkers, proteins and cells (pathogenic bacteria or cancer cells). AuNPs played many roles such as surface for LDI-MS, probe and stationary phase for separation or preconcentration. AuNPs modified various surface chemistry was applied for a wide range of different wavelength. AuNPs severed as a source of Au(+) ions that were suitable for analyte cationisation. Characterization of Au nanoclusters (AuNCs) by mass spectrometry, pros and cons were also highlighted. Graphical Abstract Schematic representation of the analysis by Gold Nanoparticles Assisted Laser Desorption/Ionization Mass Spectrometry (GALDI-MS).

Synthesis of a highly dispersive sinapinic acid@graphene oxide (SA@GO) and its applications as a novel surface assisted laser desorption/ionization mass spectrometry for proteomics and pathogenic bacteria biosensing.

Graphene oxide (GO)-modified sinapinic acid (3,5-dimethoxy-4-hydroxycinnamic acid, SA) (SA@GO) was synthesized and characterized; it was then investigated as a new surface assisted laser desorption/ionization mass spectrometry (SALDI-MS) for proteomics and pathogenic bacteria biosensing. SA@GO could effectively decrease the time necessary for sweet spotting searching, reducing the amount of organic matrix and solvent and enhance the sensitivity. SA@GO shows high performance as a matrix alone without the need to add trifluoroacetic acid (TFA). However, the analysis of the intact bacteria cells shows improvement in the signal intensity (2-5 fold) and offers a low limit of detection. All these analyses could be performed with low concentrations (1-10 fmol) and tiny volumes (0.5-1 µL). This study demonstrated that the exploration of new hybrid materials is pivotal to achieve high performance and high ionization. Because of the plane of GO, it assists protein-protein interactions that make it undergo softer ionization.

Heteroatoms-doped carbon dots as dual probes for heavy metal detection.

The utilization of l-cysteine in hydrothermal synthesis allows for the manufacture of carbon dots (CDs) that are doped with heteroatoms including oxygen, nitrogen, and sulfur (N, S, O-doped CDs). CDs have a particle size ranging from 1 to 3 nm, with an average particle size of 2.5 nm. N, S, and O-doped CDs display a blue fluorescence emission at a wavelength of 425 nm. It shows a reliance on the specific excitation wavelength between 320 and 500 nm. It has a selective quenching effect specifically with copper (Cu2+) ions when exposed to interactions with heavy metal ions, as compared to other metal ions. The assay has a limit of detection (LOD) of 2 µM and exhibits a linear correlation within the concentration range of 10-33.3 µM. The fluorescence mechanism was elucidated by employing various analytical techniques, such as transmission electron microscopy (TEM), high-resolution TEM , UV-Vis spectroscopy, zeta potential analysis, and conductometry. An analysis of the data reveals that Cu2+ ions exhibit a strong attraction to the external surface of N, S, and O-doped CDs, leading to the formation of aggregates. N, S, and O-doped CDs can be also used as probes for electrochemical investigations utilizing cyclic voltammetry (CV), linear sweep voltammetry (LSV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS) to produce Nyquist and Bode plots. The electrochemical results offer substantiation for the interaction between Cu2+ ions and N, S, and O-doped CDs. Zero-dimensional carbon nanomaterials, i.e. CDs, can improve the detection of heavy metals using optical and electrochemical methods.

In situ polymerization of a melamine-based microsphere into 3D nickel foam for supercapacitors.

An in situ synthesis approach is used to directly grow a microsphere of melamine-glutaraldehyde (MAGA) polymer over three-dimensional (3D) nickel foam (NF). The materials are used to produce nitrogen-doped carbon (NC) with and without NF. These precursors undergo carbonization at various temperatures, namely 400 °C, 500 °C, and 700 °C. The electrochemical properties of the materials would be significantly improved by directly growing MAGA polymer on the surface of NF. The electrochemical performance of NC/NF-400 was excellent, with a capacitance of 297 F g-1 achieved at a current density of 1 A g-1. The in situ growing approach does not necessitate the use of additional chemical agents, such as binders or conductive compounds when preparing the electrode. In addition, the material exhibits only 10% reduction in capacitance after undergoing 5000 cycles, indicating excellent cycling performance. The outstanding electrochemical performance achieved by using the in situ method of MAGA microsphere polymer on NF may be attributed to the rapid transit of ions to the electrode surfaces, facilitating effortless redox reactions.

Boosting photocatalytic water splitting of TiO2 using metal (Ru, Co, or Ni) co-catalysts for hydrogen generation.

The photocatalytic activity of titanium dioxide (TiO2) nanoparticles toward hydrogen generation can be significantly improved via the loading of various metals e.g., Ru, Co, Ni as co-catalysts. The metal co-catalysts are loaded into TiO2 nanoparticles via different deposition methods; incipient wet impregnation (Imp), hydrothermal (HT), or photocatalytic deposition (PCD). Among all of the tested materials, 0.1 wt% Ru-TiO2 (Imp) provided the highest initial hydrogen catalytic rate of 23.9 mmol h-1 g-1, compared to 10.82 and 16.55 mmol h-1 g-1 for 0.3 wt% Ni-TiO2 (Imp) and 0.3 wt% Co-TiO2 (Imp), respectively. The loading procedures, co-catalyst metals type, and their loading play a significant role in elevating the photocatalytic activity of pristine TiO2 semiconductors toward hydrogen generation. Redox transition metals e.g., Co and Ni exhibit comparable photocatalytic performance to expensive elements such as Ru.

Dye encapsulation and one-pot synthesis of microporous-mesoporous zeolitic imidazolate frameworks for CO2 sorption and adenosine triphosphate biosensing.

One-pot co-precipitation of target molecules e.g. organic dyes and the synthesis of a crystal containing microporous-mesoporous regimes of zeolitic imidazolate frameworks-8 (ZIF-8) are reported. The synthesis method can be used for cationic (rhodamine B (RhB), methylene blue (MB)), and anionic (methyl blue (MeB)) dyes. The crystal growth of the ZIF-8 crystals takes place via an intermediate phase of zinc hydroxyl nitrate (Zn5(OH)8(NO3)2) nanosheets that enabled the adsorption of the target molecules i.e., RhB, MB, and MeB into their layers. The dye molecules play a role during crystal formation. The successful encapsulation of the dye molecules was proved via diffuse reflectance spectroscopy (DRS) and electrochemical measurements e.g., cyclic voltammetry (CV), linear sweep voltammetry (LSV), and electrochemical impedance spectroscopy (EIS). The materials were investigated for carbon dioxide (CO2) adsorption and adenosine triphosphate (ATP) biosensing. ZIF-8, RhB@ZIF-8, MB@ZIF-8, and MeB@ZIF-8 offered CO2 adsorption capacities of 0.80, 0.84, 0.85, and 0.53 mmol g-1, respectively. The encapsulated cationic molecules improved the adsorption performance compared to anionic molecules inside the crystal. The materials were also tested as a fluorescent probe for ATP biosensing. The simple synthesis procedure offered new materials with tunable surface properties and the potential for multi-functional applications.

An introductory review on advanced multifunctional materials.

This review summarizes the applications of some of the advanced materials. It included the synthesis of several nanoparticles such as metal oxide nanoparticles (e.g., Fe3O4, ZnO, ZrOSO4, MoO3-x, CuO, AgFeO2, Co3O4, CeO2, SiO2, and CuFeO2); metal hydroxide nanosheets (e.g., Zn5(OH)8(NO3)2·2H2O, Zn(OH)(NO3)·H2O, and Zn5(OH)8(NO3)2); metallic nanoparticles (Ag, Au, Pd, and Pt); carbon-based nanomaterials (graphene, graphene oxide (GO), graphitic carbon nitride (g-C3N4), and carbon dots (CDs)); biopolymers (cellulose, nanocellulose, TEMPO-oxidized cellulose nanofibers (TOCNFs), and chitosan); organic polymers (e.g. covalent-organic frameworks (COFs)); and hybrid materials (e.g. metal-organic frameworks (MOFs)). Most of these materials were applied in several fields such as environmental-based technologies (e.g., water remediation, air purification, gas storage), energy (production of hydrogen, dimethyl ether, solar cells, and supercapacitors), and biomedical sectors (sensing, biosensing, cancer therapy, and drug delivery). They can be used as efficient adsorbents and catalysts to remove emerging contaminants e.g., inorganic (i.e., heavy metals) and organic (e.g., dyes, antibiotics, pesticides, and oils in water via adsorption. They can be also used as catalysts for catalytic degradation reactions such as redox reactions of pollutants. They can be used as filters for air purification by capturing carbon dioxide (CO2) and volatile organic compounds (VOCs). They can be used for hydrogen production via water splitting, alcohol oxidation, and hydrolysis of NaBH4. Nanomedicine for some of these materials was also included being an effective agent as an antibacterial, nanocarrier for drug delivery, and probe for biosensing.

3D printing of cellulose/leaf-like zeolitic imidazolate frameworks (CelloZIF-L) for adsorption of carbon dioxide (CO2) and heavy metal ions.

Metal-organic frameworks (MOFs) have advanced several technologies. However, it is difficult to market MOFs without processing them into a commercialized structure, causing an unnecessary delay in the material's use. Herein, three-dimensional (3D) printing of cellulose/leaf-like zeolitic imidazolate frameworks (ZIF-L), denoted as CelloZIF-L, is reported via direct ink writing (DIW, robocasting). Formulating CelloZIF-L into 3D objects can dramatically affect the material's properties and, consequently, its adsorption efficiency. The 3D printing process of CelloZIF-L is simple and can be applied via direct printing into a solution of calcium chloride. The synthesis procedure enables the formation of CelloZIF-L with a ZIF content of 84%. 3D printing enables the integration of macroscopic assembly with microscopic properties, i.e., the formation of the hierarchical structure of CelloZIF-L with different shapes, such as cubes and filaments, with 84% loading of ZIF-L. The materials adsorb carbon dioxide (CO2) and heavy metals. 3D CelloZIF-L exhibited a CO2 adsorption capacity of 0.64-1.15 mmol g-1 at 1 bar (0 °C). The materials showed Cu2+ adsorption capacities of 389.8 ± 14-554.8 ± 15 mg g-1. They displayed selectivities of 86.8%, 6.7%, 2.4%, 0.93%, 0.61%, and 0.19% toward Fe3+, Al3+, Co2+, Cu2+, Na+, and Ca2+, respectively. The simple 3D printing procedure and the high adsorption efficiencies reveal the promising potential of our materials for industrial applications.

Three-Dimensional Printing of Cellulose/Covalent Organic Frameworks (CelloCOFs) for CO2 Adsorption and Water Treatment.

The development of porous organic polymers, specifically covalent organic frameworks (COFs), has facilitated the advancement of numerous applications. Nevertheless, the limited availability of COFs solely in powder form imposes constraints on their potential applications. Furthermore, it is worth noting that COFs tend to undergo aggregation, leading to a decrease in the number of active sites available within the material. This work presents a comprehensive methodology for the transformation of a COF into three-dimensional (3D) scaffolds using the technique of 3D printing. As part of the 3D printing process, a composite material called CelloCOF was created by combining cellulose nanofibrils (CNF), sodium alginate, and COF materials (i.e., COF-1 and COF-2). The intervention successfully mitigated the agglomeration of the COF nanoparticles, resulting in the creation of abundant active sites that can be effectively utilized for adsorption purposes. The method of 3D printing can be described as a simple and basic procedure that can be adapted to accommodate hierarchical porous materials with distinct micro- and macropore regimes. This technology demonstrates versatility in its use across a range of COF materials. The adsorption capacities of 3D CelloCOF materials were evaluated for three different adsorbates: carbon dioxide (CO2), heavy metal ions, and perfluorooctanesulfonic acid (PFOS). The results showed that the materials exhibited adsorption capabilities of 19.9, 7.4-34, and 118.5-410.8 mg/g for CO2, PFOS, and heavy metals, respectively. The adsorption properties of the material were found to be outstanding, exhibiting a high degree of recyclability and exceptional selectivity. Based on our research findings, it is conceivable that the utilization of custom-designed composites based on COFs could present new opportunities in the realm of water and air purification.