Surfactant-Free, Size-Controllable, and Scalable Green Synthesis of ZIF-8 Particles with Narrow Size Distribution by Tuning Key Reaction Parameters in Water Solvent.

The chemical/physical properties and reliable performance of nanoporous materials are strongly influenced by the particle size and corresponding distribution. Among many types of MOFs, ZIF-8, is still widely used and many studies have been conducted to control the particle size and uniformity of ZIF-8 using surfactants and organic solvents. However, the use of surfactants and organic solvents process is expensive and may cause environmental pollution. For the first time, in this paper, a surfactant-free, size-controllable, and scalable green synthesis method of ZIF-8 particles is reported using four reaction parameters (temperature, concentration, pouring time, and reactant ratio) that affect the formation of nuclei and growth of ZIF-8 crystals. The as-synthesized ZIF-8 nanoparticles show great uniformity and controllable particle sizes in the wide range of 147-915 nm. In addition, a 2 L large-scale synthesis of ZIF-8 with narrow size distribution is developed by finely tuned particle size in water without any additives. To demonstrate the efficient utilization of nanopores according to the particle size and size distribution, an adsorption test is conducted on the ZIF-8 nanoparticles. This study will support the synthesis of size-controlled ZIF-8 with narrow size distribution and their composites for achieving high performance in the emerging applications.

Multiporous ZIF-8 carbon/cellulose composite beads: Highly efficient and scalable adsorbents for water treatment.

Metal-organic framework (MOF) particles are one of the most promising adsorbents for removing organic contaminants from wastewater. However, powder-type MOF particles face challenges in terms of utilization and recovery. In this study, a novel bead-type adsorbent was prepared using activated carbon based on the zeolitic imidazolate framework-8 (AC-ZIF-8) and a regenerated cellulose hydrogel for dye removal. AC-ZIF-8 particles with a large surface area were obtained by carbonization and chemical activation with KOH. The AC-ZIF-8 powders were efficiently immobilized in hydrophilic cellulose hydrogel beads via cellulose dissolution/regeneration. The prepared AC-ZIF-8/cellulose hydrogel (AC-ZIF-8/CH) composite beads exhibit a large specific surface area of 1412.8 m2/g and an excellent maximum adsorption capacity of 565.13 mg/g for Rhodamine B (RhB). Moreover, the AC-ZIF-8/CH beads were effective over a wide range of pH, temperatures and for different types of dyes. These composite beads also offer economic benefits through desorption of dyes for recycling. The AC-ZIF-8/CH beads can be produced in substantial amounts and used as fillers in a fixed-bed column system, which can purify the continuous inflow of dye solutions. These findings suggest that our simple approach for preparing high-performance adsorbent beads will broaden the application of dye adsorbents, oil-water separation, and catalysts.

Effects of autophagy-inhibiting chemicals on sialylation of Fc-fusion glycoprotein in recombinant CHO cells.

The occurrence of autophagy in recombinant Chinese hamster ovary (rCHO) cell culture has attracted attention due to its effects on therapeutic protein production. Given the significance of glycosylation in therapeutic proteins, this study examined the effects of autophagy-inhibiting chemicals on sialylation of Fc-fusion glycoproteins in rCHO cells. Three chemical autophagy inhibitors known to inhibit different stages were separately treated with two rCHO cell lines that produce the same Fc-fusion glycoprotein derived from DUKX-B11 and DG44. All autophagy inhibitors significantly decreased the sialylation of Fc-fusion glycoprotein in both cell lines. The decrease in sialylation of Fc-fusion glycoprotein is unlikely to be attributed to the release of intracellular enzymes, given the high cell viability and low activity of extracellular sialidases. Interestingly, the five intracellular nucleotide sugars remained abundant in cells treated with autophagy inhibitors. In the mRNA expression profiles of 27 N-glycosylation-related genes using the NanoString nCounter system, no significant differences in gene expression were noted. With the positive effect of supplementing nucleotide sugar precursors on sialylation, attempts were made to enhance the levels of intracellular nucleotide sugars by supplying these precursors. The addition of nucleotide sugar precursors to cultures treated with inhibitors successfully enhanced the sialylation of Fc-fusion glycoproteins compared to the control culture. This was particularly evident under mild stress conditions and not under relatively severe stress conditions, which were characterized by a high decrease in sialylation. These results suggest that inhibiting autophagy in rCHO cell culture decreases sialylation of Fc-fusion glycoprotein by constraining the availability of intracellular nucleotide sugars. KEY POINTS: •  The autophagy inhibition in rCHO cell culture leads to a significant reduction in the sialylation of Fc-fusion glycoprotein. •  The pool of five intracellular nucleotide sugars remained highly abundant in cells treated with autophagy inhibitors. •  Supplementation of nucleotide sugar precursors effectively restores decreased sialylation, particularly under mild stress conditions but not in relatively severe stress conditions.

Label-Free Surface-Enhanced Raman Scattering Detection of Fire Blight Pathogen Using a Pathogen-Specific Bacteriophage.

Fire blight is one of the most devastating plant diseases, causing severe social and economic problems. Herein, we report a novel method based on label-free surface-enhanced Raman scattering (SERS) combined with an Erwinia amylovora-specific bacteriophage that allows detecting efficiently fire blight bacteria E. amylovora for the first time. To achieve the highest SERS signals for E. amylovora, we synthesized and compared plasmonic nanoparticles (PNPs) with different sizes, i.e., bimetallic gold core-silver shell nanoparticles (Au@AgNPs) and monometallic gold nanoparticles (AuNPs) and utilized the coffee-ring effect for the self-assembly of PNPs and enrichment of fire blight bacteria. Furthermore, we investigated the changes in the SERS spectra of E. amylovora after incubation with an E. amylovora-specific bacteriophage, and we found considerable differences in the SERS signals as a function of the bacteriophage incubation time. The results indicate that our bacteriophage-based label-free SERS analysis can specifically detect E. amylovora without the need for peak assignment on the SERS spectra but simply by monitoring the changes in the SERS signals over time. Therefore, our facile method holds great potential for the label-free detection of pathogenic bacteria and the investigation of viral-bacterial interactions.

Multi-Scale Engineered 2D Carbon Polyhedron Array with Enhanced Electrocatalytic Performance.

Electrocatalyst engineering from the atomic to macroscopic level of electrocatalysts is one of the most powerful routes to boost the performance of electrochemical devices. However, multi-scale structure engineering mainly focuses on the range of atomic-to-particle scale such as hierarchical porosity engineering, while catalyst engineering at the macroscopic level, such as the arrangement configuration of nanoparticles, is often overlooked. Here, a 2D carbon polyhedron array with a multi-scale engineered structure via facile chemical etching, ice-templating induced self-assembly, and high-temperature pyrolysis processes is reported. Controlled phytic acid etching of the carbon precursor introduces homogeneous atomic phosphorous and nitrogen doping, as well as a well-defined mesoporous structure. Subsequent ice-templated self-assembly triggers the formation of a 2D particle array superstructure. The atomic-level doping gives rise to high intrinsic activity, while the well-engineered porous structure and particle arrangement addresses the mass transport limitations at the microscopic particle level and macroscopic electrode level. As a result, the as-prepared electrocatalyst delivers outstanding performance toward oxygen reduction reaction in both acidic and alkaline media, which is better than recently reported state-of-the-art metal-free electrocatalysts. Molecular dynamics simulation together with extensive characterizations indicate that the performance enhancement originates from multi-scale structural synergy.

Multiscale Porous Carbon Materials by In Situ Growth of Metal-Organic Framework in the Micro-Channel of Delignified Wood for High-Performance Water Purification.

Porous carbon materials are suitable as highly efficient adsorbents for the treatment of organic pollutants in wastewater. In this study, we developed multiscale porous and heteroatom (O, N)-doped activated carbon aerogels (CAs) based on mesoporous zeolitic imidazolate framework-8 (ZIF-8) nanocrystals and wood using 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) oxidation, in situ synthesis, and carbonization/activation. The surface carboxyl groups in a TEMPO-oxidized wood (TW) can provide considerably large nucleation sites for ZIF-8. Consequently, ZIF-8, with excellent porosity, was successfully loaded into the TW via in situ growth to enhance the specific surface area and enable heteroatom doping. Thereafter, the ZIF-8-loaded TW was subjected to a direct carbonization/activation process, and the obtained activated CA, denoted as ZIF-8/TW-CA, exhibited a highly interconnected porous structure containing multiscale (micro, meso, and macro) pores. Additionally, the resultant ZIF-8/TW-CA exhibited a low density, high specific surface area, and excellent organic dye adsorption capacity of 56.0 mg cm-3, 785.8 m2 g-1, and 169.4 mg g-1, respectively. Given its sustainable, scalable, and low-cost wood platform, the proposed high-performance CA is expected to enable the substantial expansion of strategies for environmental protection, energy storage, and catalysis.

A 2D/2D heterojunction of ultrathin Pd nanosheet/MXene towards highly efficient methanol oxidation reaction: the significance of 2D material nanoarchitectonics.

Two-dimensional (2D) Pd nanosheet-based catalysts have recently garnered widespread attention due to their high atom utilization efficiency. However, their catalytic ability and structural stability still require significant enhancement before they can be widely applied. In this study, we presented the rational design and controllable fabrication of a novel 2D/2D heterojunction, which consists of ultrathin Pd nanosheets (NSs) grown on the Ti3C2Tx MXene surface (Pd NSs/MXene). This heterostructure was achieved through a robust and convenient stereo-assembly strategy. The newly developed Pd NSs/MXene heterojunction not only provides numerous exposed active Pd atoms with an optimized electronic structure but also enables an intimate Pd/MXene interfacial interaction, ensuring a stable hybrid configuration. Consequently, the resulting Pd NSs/MXene heterojunction exhibits exceptional methanol oxidation properties. It possesses a large electrochemically active surface area, high mass and specific activities, and a long operating life, which are significantly superior to those of traditional Pd nanoparticle/carbon and Pd nanosheet/carbon catalysts. Theoretical simulations further reveal strong electronic interactions between the Pd nanosheet and MXene, which dramatically enhance the adsorption energy of the Pd component and simultaneously lower its d-band center. As a result, the Pd NSs/MXene heterojunction is less susceptible to CO poisoning. This work introduces a new 2D/2D heterojunction based on MXene and noble metallic materials and holds significance for the development of other novel heterojunctions, particularly within the realm of 2D material nanoarchitectonics.

Nanoarchitectonics of Metallene Materials for Electrocatalysis.

Controlling the synthesis of metal nanostructures is one approach for catalyst engineering and performance optimization in electrocatalysis. As an emerging class of unconventional electrocatalysts, two-dimensional (2D) metallene electrocatalysts with ultrathin sheet-like morphology have gained ever-growing attention and exhibited superior performance in electrocatalysis owing to their distinctive properties originating from structural anisotropy, rich surface chemistry, and efficient mass diffusion capability. Many significant advances in synthetic methods and electrocatalytic applications for 2D metallenes have been obtained in recent years. Therefore, an in-depth review summarizing the progress in developing 2D metallenes for electrochemical applications is highly needed. Unlike most reported reviews on the 2D metallenes, this review starts by introducing the preparation of 2D metallenes based on the classification of the metals (e.g., noble metals, and non-noble metals) instead of synthetic methods. Some typical strategies for preparing each kind of metal are enumerated in detail. Then, the utilization of 2D metallenes in electrocatalytic applications, especially in the electrocatalytic conversion reactions, including the hydrogen evolution reaction, oxygen evolution reaction, oxygen reduction reaction, fuel oxidation reaction, CO2 reduction reaction, and N2 reduction reaction, are comprehensively discussed. Finally, current challenges and opportunities for future research on metallenes in electrochemical energy conversion are proposed.

Magnetic Covalent Organic Framework Composites for Wastewater Remediation.

Covalent organic frameworks (COFs) with high specific surface area, tailored structure, easy functionalization, and excellent chemical stability have been extensively exploited as fantastic materials in various fields. However, in most cases, COFs prepared in powder form suffer from the disadvantages of tedious operation, strong tendency to agglomerate, and poor recyclability, greatly limiting their practical application in environmental remediation. To tackle these issues, the fabrication of magnetic COFs (MCOFs) has attracted tremendous attention. In this review, several reliable strategies for the fabrication of MCOFs are summarized. In addition, the recent application of MCOFs as outstanding adsorbents for the removal of contaminants including toxic metal ions, dyes, pharmaceuticals and personal care products, and other organic pollutants is discussed. Moreover, in-depth discussions regarding the structural parameters affecting the practical potential of MCOFs are highlighted in detail. Finally, the current challenges and future prospects of MCOFs in this field are provided with the expectation to boost their practical application.

Hydrophobic, Sustainable, High-Barrier Regenerated Cellulose Film via a Simple One-Step Silylation Reaction.

With the increasing importance of environmental protection, high-performance biopolymer films have received considerable attention as effective alternatives to petroleum-based polymer films. In this study, we developed hydrophobic regenerated cellulose (RC) films with good barrier properties through a simple gas-solid reaction via the chemical vapor deposition of alkyltrichlorosilane. RC films were employed to construct a biodegradable, free-standing substrate matrix, and methyltrichlorosilane (MTS) was used as a hydrophobic coating material to control the wettability and improve the barrier properties of the final films. MTS readily coupled with hydroxyl groups on the RC surface through a condensation reaction. We demonstrated that the MTS-modified RC (MTS/RC) films were optically transparent, mechanically strong, and hydrophobic. In particular, the obtained MTS/RC films exhibited a low oxygen transmission rate of 3 cm3/m2 per day and a low water vapor transmission rate of 41 g/m2 per day, which are superior to those of other hydrophobic biopolymer films.

Toward millimeter thick cellulose nanofiber/epoxy laminates with good transparency and high flexural strength.

While cellulose nanofiber-based bioplastics are of great interest for replacing synthetic polymer and glass materials, the main limitation is their low thickness, which makes them difficult for various applications. In this study, we fabricated millimeter-scale thick bioplastic composites, based on 2,2,6,6-tetramethylpiperidine-1-oxy-oxidized cellulose nanofibers (TEMPO-CNF) and epoxy resin, via sequential lamination processes. The glycerol as softener was added to TEMPO-CNF dispersion to prepare a thick TEMPO-CNF layer without shrinkage. It was discovered that the total thickness of TEMPO-CNF/epoxy laminates can be easily controlled by changing the thickness and number of TEMPO-CNF layers and the total thickness can also be easily increased up to 2.4 mm. Furthermore, these TEMPO-CNF/epoxy laminates have high flexural strength (272 MPa) as well as good transmittance (85% % at 600 nm). We anticipate that our approach will significantly broaden the strategies for fabricating nanocellulose-based bioplastics for use as a replacement for transparent synthetic polymers and glass materials.

Recent progress of functional metal-organic framework materials for water treatment using sulfate radicals.

Human health is being threatened by the ever-increasing water pollution. Sulfate radical (SO4•-)-based advanced oxidation processes (SR-AOPs) are rapidly being developed and gaining considerable attention due to their high oxidation potential and selectivity as a way to purify water by degrading organic contaminants in it. Among the catalytic materials that can activate the precursor to generate SO4•-, metal-organic frameworks (MOFs) are the most promising heterogeneous catalytic material in SR-AOPs because of their various structure possibilities, large surface area, ordered porous structure, and regular activation sites. Herein, an in-depth overview of MOFs and their derivatives for water purification with SR-AOPs is provided. The latest studies on pristine MOFs, MOF composites, and MOF derivatives (metal oxides, metal-carbon hybrids, and carbon materials) are summarized. The mechanisms of decomposition of pollutants in water via radical and non-radical pathways are also discussed. This review suggests future research directions for water purification through MOF-based SR-AOP.

Anti-Counterfeiting Tags Using Flexible Substrate with Gradient Micropatterning of Silver Nanowires.

Anti-counterfeiting technologies for small products are being developed. We present an anti-counterfeiting tag, a grayscale pattern of silver nanowires (AgNWs) on a flexible substrate. The anti-counterfeiting tag that is observable with a thermal imaging camera was fabricated using the characteristics of silver nanowires with high visible light transmittance and high infrared emissivity. AgNWs were patterned at microscale via a maskless lithography method using UV dicing tape with UV patterns. By attaching and detaching an AgNW coated glass slide and UV dicing tape irradiated with multiple levels of UV, we obtained AgNW patterns with four or more grayscales. Peel tests confirmed that the adhesive strength of the UV dicing tape varied according to the amount of UV irradiation, and electrical resistance and IR image intensity measurements confirmed that the pattern obtained using this tape has multi-level AgNW concentrations. When applied for anti-counterfeiting, the gradient-concentration AgNW micropattern could contain more information than a single-concentration micropattern. In addition, the gradient AgNW micropattern could be transferred to a flexible polymer substrate using a simple method and then attached to various surfaces for use as an anti-counterfeiting tag.

Facile preparation of nanocellulose/Zn-MOF-based catalytic filter for water purification by oxidation process.

Sulfate radical (SO4•-)-based advanced oxidation processes (SR-AOPs) have recently attracted much attention due to their potential in degrading organic pollutants. Metal-organic frameworks (MOFs) have been reported as effective materials to generate SO4•-. However, it is challenging to separate and recover the dispersed MOF particles from the reaction solution when MOFs are used alone. We used cellulose nanofibers (CNFs) as a porous filter template to immobilize Zn-based MOF, zeolitic imidazolate framework-8 (ZIF-8), and obtained a catalytic composite membrane having peroxymonosulfate (PMS) activating function to produce SO4•-. The CNF was effective in holding ZIF-8 nanoparticle and making a durable porous filter. The activated PMS-produced •OH and SO4•- radicals from ZIF-8 play an important role in the catalytic reaction. More than 90% of methylene blue and rhodamine B was degraded by ZIF-8/CNFs composite membrane in the PMS environment within 60 min. The ZIF-8/CNFs catalytic filters can be used several times without performance reduction for organic dye degradation. The results show that ZIF-8/CNFs catalytic membrane can be separated from organic pollution system quickly and used for the efficient separation and recovery of MOF particle-based catalytic materials. Therefore, this study provides a new perspective for fabricating the MOFs particles-immobilized catalytic filter by biomass nanocellulose-based materials for water purification. This method can be used for facile fabrication of the cellulose-based porous functional filter and open diverse applications.

Detection of nanoplastics based on surface-enhanced Raman scattering with silver nanowire arrays on regenerated cellulose films.

Plastic pollution has steadily become a global issue due to its ubiquity and degradation into micro and nanoparticles. Herein, we report the construction of surface-enhanced Raman scattering (SERS)-active array substrates with regenerated cellulose (RC) and plasmonic nanoparticles (AuNRs and AgNWs) via a simple vacuum-assisted filtration method using a silicon mask for rapid nanoplastic detection. The AgNWs/RC film exhibited a SERS intensity of crystal violet approximately six times higher than that of the AuNRs/RC film with a high enhancement factor of 1.8 × 107. Moreover, the AgNWs/RC film exhibits a better SERS activity for polystyrene nanoplastic detection than the AuNRs/RC film because the dense AgNW network structures are well suited for nanoplastic detection. The AgNWs/RC film can detect PS nanoplastics down to 0.1 mg/mL with a good reproducibility of the SERS signal. The low-cost, flexible, and highly sensitive AgNWs/RC films could provide an efficient and rapid SERS-based method for nanoplastic detection.

Double-crosslinked cellulose nanofiber based bioplastic films for practical applications.

While green bioplastic based on carbohydrate polymers have showed considerable promise, the methods typically used to prepare them in a single material have remained a significant challenge. In this study, a simple approach is proposed to fabricate high performance cellulose films composed of chemically and physically dual-crosslinked 2,2,6,6-tetramethylpiperidine-1-oxy-oxidized cellulose nanofibers (DC TEMPO-CNFs). The hydroxyl groups of TEMPO-CNF suspensions were firstly crosslinked chemically with epichlorohydrin (ECH), and subsequently TEMPO-CNF matrices were crosslinked physically via the strong electrostatic interaction between carboxylate and Ca2+ ions. It was found that the optimized DC TEMPO-CNF films exhibit a good transmittance (90 %) and a high tensile strength (303 MPa). Furthermore, these DC TEMPO-CNF films revealed superior thermal stability and excellent water resistance compared to neat TEMPO-CNF films without crosslinked domains. We believe that these results will pave the way to preparing practical polysaccharide bioplastics with simple, environmentally-friendly manufacturing processes.

Flexible nanocellulose-based SERS substrates for fast analysis of hazardous materials by spiral scanning.

Surface-enhanced Raman scattering (SERS) has proven to be a valuable tool for assessing harmful chemicals in various substances, including water, soil, and foods. However, a fast measurement system is required for multiplexed detection to extend the range of its applications. The rotating scanning stage of the SERS substrate is considered to be a promising approach to achieving a fast measurement system. This paper reports a facile measurement system by using a flexible nanocellulose-based SERS substrate and a spiral scanning system, which rotates the cylinder sample holder and moves the stage. A flexible nanocellulose-based SERS substrate deposited with Au nanoparticles is suitable for the spiral scanning system, which requires SERS substrates to be highly flexible and durable. The well-known toxic fungicide, thiram, was tested by this system. The results revealed that the nanocellulose-based SERS substrate is well-fitted with a spiral scanning system and that the signal data from a large area substrate can be obtained within 30 s. It is noteworthy that the error of spiral scanning measurements is smaller than that of multi-spot sampling. This work provides a powerful tool for Raman spectroscopic analysis, which requires quantitative and fast testing. Furthermore, various flexible SERS substrates can be utilized in this system for toxic materials detection.

Vapor phase polymerization for electronically conductive nanopaper based on bacterial cellulose/poly(3,4-ethylenedioxythiophene).

Eco-friendly conductive polymer nanocomposites have garnered attention as an effective alternative for conventional conductive nanocomposites. Here, we report the fabrication and optimization of flexible, self-standing, and conductive bacterial cellulose/poly(3,4-ethylene dioxythiophene) (BC/PEDOT) nanocomposites using the vapor phase polymerization (VPP) method. Eco-friendly bacterial cellulose (BC) is used as a flexible matrix, and the highly conductive PEDOT polymer is introduced into the BC matrix to achieve electronic conductivity. We demonstrate that vapor phase polymerized BC/PEDOT composites exhibit more than 10 times lower sheet resistance (18 Ω/square) compared to solution polymerized BC/PEDOT (188 Ω/square). The resultant BC/PEDOT fabricated could be bent up to 100 times and completely rolled up without a notable decrease in electronic performance. Moreover, bent BC/PEDOT films enable operation of a green light-emitting diode (LED) light, indicating the flexibility and stability of conductive BC/PEDOT films. Overall, this study suggests a strategy for the development of eco-friendly, flexible, and conductive nanocomposite films.

Universal Electrochemical Synthesis of Mesoporous Chalcogenide Semiconductors: Mesoporous CdSe and CdTe Thin Films for Optoelectronic Applications.

Here we report the soft-template-assisted electrochemical deposition of mesoporous semiconductors (CdSe and CdTe). The resulting mesoporous films are stoichiometrically equivalent and contain mesopores homogeneously distributed over the entire surface. To demonstrate the versatility of the method, two block copolymers with different molecular weights are used, yielding films with pores of either 9 or 18 nm diameter. As a proof of concept, the mesoporous CdSe film-based photodetectors show a high sensitivity of 204 mW-1 cm2 at 680 nm wavelength, which is at least two orders of magnitude more sensitive than the bulk counterpart. This work presents a new synthesis route for nanostructured semiconductors with optical band gaps active in the visible spectrum.

Surface-enhanced Raman scattering-active AuNR array cellulose films for multi-hazard detection.

In this study, we report a surface-enhanced Raman scattering (SERS)-active array film, which is based on regenerated cellulose hydrogels and gold nanorods (AuNRs), by combining a silicon rubber mask with a vacuum filtration method. This strategy enables the direct AuNR array formation on hydrogel surface with a precisely controlled number density. Moreover, the control of interparticle nanogap has been realized by the spatial deformation of hydrogels. A decrease in gaps between AuNRs deposited on hydrogels can result in SERS enhancement because 3D porous hydrogel structures turned into 2D closely packed hydrogel films during drying. In our experiments, SERS sensor arrays show excellent SERS activity to detect rhodamine 6 G and thiram down to 10 pM and 100 fM with competitive enhancement factors of 3.9 × 108 and 9.5 × 109, respectively. Importantly, the resultant SERS-active arrays with nine sensor units can efficiently detect nine different analytes on a single substrates at a time. Moreover, we demonstrate that physical bending has little effect on the SERS activity of flexible AuNR array hydrogel films, which indicates the high reproducibility of SERS measurement. This SERS array film has great potential to simultaneously detect multiple hazards for the practical application of SERS analysis.