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.

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.

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.

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.

Structure of AQEE-30 of VGF Neuropeptide in Membrane-Mimicking Environments.

AQEE-30 is one of the VGF peptides, which are derived from the VGF polypeptide precursor, and related to various physiological phenomena including neuroprotective effects in Huntington's disease and amyotrophic lateral sclerosis (ALS). Although various functions of AQEE-30 have been reported so far, the structure of this peptide has not been reported yet. In this study, the structure of human AQEE-30 was investigated in hexafluoroisopropanol (HFIP) and dodecyl phosphocholine (DPC) micelle solutions, using circular dichroism (CD) and nuclear magnetic resonance (NMR) spectroscopy. CD results showed that AQEE-30 had a partial helical structure in aqueous buffer, and the helical structure was stabilized in the HFIP and DPC micelle solutions. The 3D structures determined by NMR spectroscopy showed that AQEE-30 adopted mainly α-helical structure in both the HFIP and DPC micelle solutions. The surface of AQEE-30 showed that it was predominantly negatively charged. The residues from 601 to 611 in both the HFIP and DPC micelle solutions showed amphiphilicity with four negatively charged residues, glutamate. The C-terminal consecutive arginine residues formed a partial positively charged surface. These results suggest an α-helical active structure of AQEE-30 in the cell-membrane environment.

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.

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.

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.

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.

Development of a Polo-like Kinase-1 Polo-Box Domain Inhibitor as a Tumor Growth Suppressor in Mice Models.

Polo-like kinase-1 (Plk1) plays a key role in mitosis and has been identified as an attractive anticancer drug target. Plk1 consists of two drug-targeting sites, namely, N-terminal kinase domain (KD) and C-terminal polo-box domain (PBD). As KD-targeting inhibitors are associated with severe side effects, here we report on the pyrazole-based Plk1 PBD inhibitor, KBJK557, which showed a remarkable in vitro anticancer effect by inducing Plk1 delocalization, mitotic arrest, and apoptosis in HeLa cells. Further, in vivo optical imaging analysis and antitumorigenic activities in mouse xenograft models demonstrate that KBJK557 preferentially accumulates in cancer cells and selectively inhibits cancer cell proliferation. Pharmacokinetic profiles and partition coefficients suggest that KBJK557 was exposed in the blood and circulated through the organs with an intermediate level of clearance (t1/2, 7.73 h). The present investigation offers a strategy for specifically targeting cancer using a newly identified small-molecule inhibitor that targets the Plk1 PBD.

Cellulose nanocrystal-coated TEMPO-oxidized cellulose nanofiber films for high performance all-cellulose nanocomposites.

High performance biopolymer films are of great interest as effective alternatives to non-biodegradable and petroleum-based polymer films. However, most natural biopolymer films possess weak mechanical and poor gas barrier properties, limiting their applicability. In this work, we developed all-cellulose nanocomposite films through a simple vacuum filtration process, using cellulose nanocrystals (CNCs) and 2,2,6,6-tetramethylpiperidine-1-oxy-oxidized cellulose nanofibers (TEMPO-CNFs). The TEMPO-CNFs were employed to construct a transparent, free-standing substrate matrix and the CNCs were used as a coating material to improve the mechanical and water vapor barrier properties of the final material. We have demonstrated that the top and bottom CNCs-coated TEMPO-CNF substrates (CNC/TEMPO-CNF/CNC) have excellent mechanical and good water vapor barrier properties. The resulting CNC/TEMPO-CNF/CNC films revealed a high tensile strength of 114 MPa and a low specific water vapor transmission rate (SWVTR) of 19 g∙mm/m2∙day. In addition, the CNC/TEMPO-CNF/CNC films were resistant to various solvents including water, ethanol, tetrahydrofuran (THF), and acetone. This type of high performance cellulose nanocomposite can be used as a renewable material for a broad range of potential applications.

Secreted tryptophanyl-tRNA synthetase as a primary defence system against infection.

The N-terminal truncated form of a protein synthesis enzyme, tryptophanyl-tRNA synthetase (mini-WRS), is secreted as an angiostatic ligand. However, the secretion and function of the full-length WRS (FL-WRS) remain unknown. Here, we report that the FL-WRS, but not mini-WRS, is rapidly secreted upon pathogen infection to prime innate immunity. Blood levels of FL-WRS were increased in sepsis patients, but not in those with sterile inflammation. FL-WRS was secreted from monocytes and directly bound to macrophages via a toll-like receptor 4 (TLR4)-myeloid differentiation factor 2 (MD2) complex to induce phagocytosis and chemokine production. Administration of FL-WRS into Salmonella typhimurium-infected mice reduced the levels of bacteria and improved mouse survival, whereas its titration with the specific antibody aggravated the infection. The N-terminal 154-amino-acid eukaryote-specific peptide of WRS was sufficient to recapitulate FL-WRS activity and its interaction mode with TLR4-MD2 is now suggested. Based on these results, secretion of FL-WRS appears to work as a primary defence system against infection, acting before full activation of innate immunity.

Estrogenic endocrine-disrupting chemicals modulate the production of inflammatory mediators and cell viability of lipopolysaccharide-stimulated macrophages.

Estrogenic endocrine-disrupting chemicals (EDCs) are exogenous substances that act as competitive inhibitors of estrogen in the endocrine system. By disrupting the endocrine system, EDCs can cause severe disabilities and diseases, including cancers and altered sexual development. Although the influence of these molecules in the endocrine system is evident, the effects of EDCs on the immune system as well as their cytotoxicity have been poorly examined. Therefore, we selected 21 EDCs that are commonly found in Korean ecosystems, such as surface waters and effluents, and studied their immunologic effects by comparing nitric oxide (NO) production and cytotoxicity in lipopolysaccharide (LPS)-stimulated RAW 264.7 cells (RAW cells), a macrophage cell line. Among the EDCs tested, fenitrothion (FTH) inhibited the messenger RNA (mRNA) expression of inducible NO synthase (iNOS), resulting in reduced NO production, while treatment with andostenedione (AD), diethyl phthalate, di-n-butyl phthalate (DBP), estriol, or molinate decreased production of NO in an iNOS-independent fashion. In contrast, benzo(a)pyrene (B(a)P) increased the production of NO in RAW cells. In addition, AD, DBP, or FTH inhibited the mRNA expression of tumor necrosis factor alpha or interleukin-1 beta. Treatment with 17-α-ethynylestradiol, 17-ß-estradiol, 4-n-butyl phenol, or alachlor induced apoptosis of RAW cells, while dicyclohexyl phthalate and B(a)P caused cell death in an apoptosis-independent manner. These data suggest that EDCs can influence the immune response to pathogens by modulating the functions of macrophages.

Expression, purification and biochemical characterization of the N-terminal regions of human TIG3 and HRASLS3 proteins.

Tarzarotene-induced gene 3 (TIG3) and HRAS-like suppressor (HRASLS3) are members of the HREV107 family of class II tumor suppressors, which are down-regulated in various cancer cells. TIG3 and HRASLS3 also exhibit phospholipase activities. Both proteins share a common domain architecture with hydrophilic N-terminal and hydrophobic C-terminal regions. The hydrophobic C-terminal region is important for tumor suppression. However, the function of the hydrophilic N-terminal region remains elusive. To facilitate biochemical characterizations of TIG3 and HRASLS3, we expressed and purified the N-terminal regions of TIG3 and HRASLS3, designated TIG3 (1-134) and HRASLS3 (1-133), in a bacterial system. We found that the N-terminal regions of TIG3 and HRASLS3 have calcium-independent phospholipase A(2) activities. Limited proteolysis revealed that TIG3 (1-132) is a structural domain in the N-terminal region of TIG3. Our data suggest that the hydrophobic C-terminal regions might be crucial for cellular localization, while the hydrophilic N-terminal regions are sufficient for the enzymatic activity of both TIG3 and HRASLS3.

Structure and interaction of ubiquitin-associated domain of human Fas-associated factor 1.

Fas-associated factor (FAF)-1 is a multidomain protein that was first identified as a member of the Fas death-inducing signaling complex, but later found to be involved in various biological processes. Although the exact mechanisms are not clear, FAF1 seems to play an important role in cancer, asbestos-induced mesotheliomas, and Parkinson's disease. It interacts with polyubiquitinated proteins, Hsp70, and p97/VCP (valosin-containing protein), in addition to the proteins of the Fas-signaling pathway. We have determined the crystal structure of the ubiquitin-associated domain of human FAF1 (hFAF1-UBA) and examined its interaction with ubiquitin and ubiquitin-like proteins using nuclear magnetic resonance. hFAF1-UBA revealed a canonical three-helical bundle that selectively binds to mono- and di-ubiquitin (Lys48-linked), but not to SUMO-1 (small ubiquitin-related modifier 1) or NEDD8 (neural precursor cell expressed, developmentally down-regulated 8). The interaction between hFAF1-UBA and di-ubiquitin involves hydrophobic interaction accompanied by a transition in the di-ubiquitin conformation. These results provide structural insight into the mechanism of polyubiquitin recognition by hFAF1-UBA.