Tunable Size Research Articles

Bound states in the continuum in circular waveguides: toward the on-chip integration of nanofiber on silicon platform.

In previously reported researches on bound state in the continuum (BIC) waveguides, almost all of them are demonstrated with top-down fabrication procedures, leading to inconvenience for post-manipulation and size tuning. Nanofibers with circular cross sections are the fundamental components to transport energy due to their intrinsic advantages of high flexibility and adjustability, which is replaceable and can be readily manipulated over size and position on the substrate. In this work, we explore the possibility of achieving on-chip integration of silica nanofiber onto a silicon-on-insulator platform. By constructing additional leakage channels in coupled nanofiber waveguides, coherently destructive interferences are successfully achieved. The heavy leakage losses from the low-index nanofiber to a high-index silicon substrate are completely eliminated with BIC, and the propagation length of the nanofiber waveguide is significantly improved.

In-situ generation of anti-fouling TpPa/PVDF membranes showing excellent photocatalytic degradation and self-cleaning for dyes in water

Covalent organic frameworks (COFs) have been widely studied in membrane separation technology due to their high porosity, high specific surface area, and tunable pore size. However, COF particles tend to aggregate in blend membranes. In this study, in-situ generation of 2,4,6-Triformylphloroglucinol p-Phenylenediamine (TpPa) was carried out in Polyvinylidene fluoride/N,N-dimethylacetamide (PVDF/DMAc), followed by nonsolvent-induced phase separation (NIPS) method to obtain TpPa/PVDF membranes. The introduction of hydrophilic TpPa resulted in improved hydrophilicity and increased roughness of the membrane. During the filtration of dyes including Methylene Blue, Congo Red, and Eriochrome Black T, the TpPa/PVDF membrane exhibited high rejection rates (>90 %) and improved permeation flux (6–8 times of the original PVDF membrane). Investigation of its photocatalytic ability revealed that the TpPa/PVDF membrane exhibited excellent photocatalytic degradation of dyes, making it suitable for self-cleaning of fouled membranes and allowing for multiple reuse (up to 8 times). In the 6-cycle filtrations of Bovine Serum Albumin (BSA) and Humic Acid (HA), the membrane showed not only high rejection and permeation but also superior flux recovery rate (FRR), indicating good anti-fouling ability. This study has achieved efficient treatment of dye wastewater through membrane separation technology and has provided a novel anti-fouling COFs-modified membrane with photocatalytic self-cleaning ability.

Thermal Enhancement of Upconversion in Sub‐10 nm Yb3+/Er3+/Na+ Tridoped Cs2ZrF6 Nanocrystals for Ratiometric Temperature Sensing

AbstractAlkaline zirconium fluorides (AxZryFx+y, A = Li, Na, and K), featuring unique crystallographic structures, have recently emerged as a class of attractive hosts for fabricating lanthanide (Ln3+)‐doped upconversion nanocrystals (UCNCs) that exhibited distinct morphology, upconversion luminescence (UCL) performance, and physicochemical property. In this paper, for the first time the controlled preparation of Yb3+/Er3+‐doped UCNCs is reported based on the trigonal Cs2ZrF6 host, leading to tunable morphology and size of the resulting UCNCs by varying the reaction temperature and time. By further incorporating Na+ ions into the Cs2ZrF6 crystal lattice, sub‐10 nm Yb3+/Er3+/Na+ tridoped UCNCs with highly improved crystallinity and thus greatly enhanced UCL intensity are obtained. Moreover, these resulting UCNCs display abnormal thermal enhancement of UCL over a temperature range from 333 to 493 K, enabling the fabrication of supersensitive luminescent nanothermometers for temperature sensing. Based on the luminescence intensity ratio of two nonthermally coupled levels (i.e., 4F9/2 and 2H11/2) of Er3+, the as‐prepared Cs2ZrF6:Yb/Er/Na UCNCs exhibit an extremely large absolute sensitivity of 177.3% K−1 and a considerably high relative sensitivity of 1.52% K−1 at 333 K. These results unambiguously demonstrate that Cs2ZrF6 is a suitable host material for preparing small‐sized Ln3+‐doped UCNCs as nanothermometer for high‐performance ratiometric temperature sensing.

Simple and flexible production of controllable emulsion droplets from open-type co-flow microfluidics

An open-type co-flow microfluidic technique that allows simple microflow manipulation with a broad operation range of flow rates for controllably producing uniform droplets with widely adjustable sizes is developed. The microfluidic device employs a co-flow geometry with relatively open shearing space to largely reduce the pressure drop in the microchannel to facilitate the flow of liquids. Such a device significantly extends the operation window of the dripping regime and eliminates the back flow, to benefit easy microflow manipulation with broadly adjustable flow rates for producing monodisperse droplets with widely tunable sizes. Typically, at Wed = 0.0028, the operation window of the dripping regime and adjustable range of flow rates for this device are both at least ∼3 times wider than those of traditional co-flow devices with confined shearing space for droplet generation. This work provides a facile microfluidic platform with simple flow manipulation and a wide operation range for the wide-scale impact of droplet microfluidics.

A chiral metal–organic polyhedron used as stationary phase for gas chromatographic separations

Metal-organic polyhedra (MOPs), as a novel class of porous materials, exhibit distinctive application potential in molecular recognition, separation, catalysis, luminescent materials, drug delivery, and biomedicine owing to their tunable geometric shape and size, well-defined cavities, and discrete characteristics. In this study, we report that a chiral MOP [Cu12(LV)12(H2O)12] (V = L-valine) coated capillary column was used for gas chromatographic separations. The MOP coated capillary column offered the efficient separation of n-alkanes, alkylbenzenes, n-alcohols, multiple types of isomers, and enantiomers with high selectivity. Various enantiomers including esters, halogenated hydrocarbons, alcohols, ethers, aldehydes, and amino acid derivatives were well resolved on this chiral column, especially for some amino acid derivatives (e.g., Rs = 5.24 for tyrosine derivative). Compared with the commercial β-DEX 120 column for separation of the tested racemates, the chiral resolution performance of the MOP coated column can be complementary to that of β-DEX 120 column. Using 1,2-dichloropropane and o, m, p-dichlorobenzene as analytes, the MOP coated column exhibited good stability and reproducibility for gas chromatographic separations. The relative standard deviations (RSDs) of the retention time and peak area for repeated separation of 1, 2-dichloropropane and o, m, p-dichlorobenzene were less than 1.15 and 0.79 %, respectively. The results show that the chiral MOP holds great potential as a novel type of CSP for application in gas chromatography.

Precise Spectral Overlap-Based Donor-Acceptor Pair for a Sensitive Traffic Light-Typed Bimodal Multiplexed Lateral Flow Immunoassay.

Bimodal-type multiplexed immunoassays with complementary mode-based correlation analysis are gaining increasing attention for enhancing the practicability of the lateral flow immunoassay (LFIA). Nonetheless, the restriction in visually indistinguishable multitargets induced by a single fluorescent color and difficulty in single acceptor ineffectual fluorescence quenching due to the various spectra of multiple different donors impede the further execution of colorimetric-fluorescence bimodal-type multiplexed LFIAs. Herein, the precise spectral overlap-based donor-acceptor pair construction strategy is proposed by regulating the size of the nanocore, coating it with an appropriate nanoshell, and selecting a suitable fluorescence donor with distinct colors. By in situ coating Prussian blue nanoparticles (PBNPs) on AuNPs with a tunable size and absorption spectrum, the resultant APNPs demonstrate efficient fluorescence quenching ability, higher colloidal stability, remarkable colorimetric intensity, and an enhanced antibody coupling efficiency, all of which facilitate highly sensitive bimodal-type LFIA analysis. Following integration with competitive-type immunoreaction, this precise spectral overlap-supported spatial separation traffic light-typed colorimetric-fluorescence dual-response assay (coined as the STCFD assay) with the limits of detection of 0.013 and 0.152 ng mL-1 for ractopamine and clenbuterol, respectively, was proposed. This work illustrates the superiority of the rational design of a precise spectral overlap-based donor-acceptor pair, hinting at the enormous potential of the STCFD assay in the point-of-care field.

Inhibiting advanced glycation end products (AGEs) of high-performance hemodialysis membranes self-assembled by gallic acid and Ti3C2Tx MXene

Current patients with chronic kidney disease (CKD) suffer from either accumulation of advanced glycation end products (AGEs) or inefficient clearance of the middle molecule uremic toxins, threatening their long-term survival rate. In particular, conventional hemodialysis membranes cannot prevent AGEs formation because of continuous oxidative stress from reactive oxygen species (ROS). Herein, a persistent ROS scavenging and efficient uremic toxin clearance of hemodialysis membrane is proposed by the in situ deposition of a gallic acid-Ti3C2Tx MXene (GA-MXene)n multilayers through a self-assembly method, where n denotes the number of deposition layers. These hemodialysis membranes have a highly interconnecting composite laminate with tunable pore size. In the dialysis experiment, the (GA-MXene)2 membrane with the vertical nano-slits shows the highest middle molecule uremic toxin clearance of 80.0% compared with state-of-the-art hemodialysis membranes, which has been approximately equal to the clearance of small molecule urea. Furthermore, GA conferring efficient ROS scavenging rate over dialysis treatment time allows anti-oxidative activities to inhibit AGEs’ formation. (GA-MXene)n multilayers enhanced the serum total antioxidant capacity and suppressed lipid peroxidation from oxidative damage. Ultimately, the (GA-MXene)n hemodialysis membranes provide excellent anticoagulant properties and cytocompatibility through the heparin-mimicking sulfonated Ti3C2Tx MXene and biological activity of GA. This work facilitates the blood purification application of MXenes and opens up an avenue for developing functional multilayers for high-performance hemodialysis membranes and beyond.

Nanomaterials for co‐immobilization of multiple enzymes

AbstractIn order to co‐immobilize multiple enzymes, a wide range of nanomaterials has been designed to achieve synergistic enzyme activity and enhance catalytic efficiency. Nanomaterials, as carriers for enzyme co‐immobilization, possess various advantages such as tunable morphology and size, high specific surface area, and abundant chemically active sites. They can significantly enhance enzyme stability, activity, and catalytic efficiency. We overview the commonly used methods and strategies of enzyme co‐immobilization. This review further summarizes the latest research advances in nanomaterials for enzyme co‐immobilization applications over the past 5 years. Meanwhile, the advantages and challenges of these nanomaterials used for enzyme co‐immobilization as well as some potential future directions are also discussed.

Energy Storage Performance of Electrode Materials Derived from Manganese Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) are porous materials assembled using metal and organic linkers, showing a high specific surface area and a tunable pore size. Large portions of metal open sites in MOFs can be exposed to electrolyte ions, meaning they have high potential to be used as electrode materials in energy storage devices such as supercapacitors. Also, they can be easily converted into porous metal oxides by heat treatment. In this study, we obtained high energy storage performance by preparing electrode materials through applying heat treatment to manganese MOFs (Mn-MOFs) under air. The chemical and structural properties of synthesized and thermally treated Mn-MOFs were measured by Fourier-transform infrared spectroscopy (FTIR), Raman spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The surface area and porosity were investigated by nitrogen adsorption/desorption isotherms. The electrochemical properties were studied by cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) using a three-electrode cell. It was found that Mn-MOF electrodes that underwent heat treatment at 400 °C under air consisted of Mn2O3 with high specific surface area and porosity. They also showed a superior specific capacitance of 214.0 F g-1 and an energy density value of 29.7 Wh kg-1 (at 0.1 A g-1) compared to non-treated Mn-MOFs.

Biodegradable Honeycomb-Mimic Scaffolds Consisting of Nanofibrous Walls.

The scaffold is a porous three-dimensional (3D) material that supports cell growth and tissue regeneration. Such 3D structures should be generated with simple techniques and nontoxic ingredients to mimic bio-environment and facilitate tissue regeneration. In this work, simple but powerful techniques are demonstrated for the fabrication of lamellar and honeycomb-mimic scaffolds with poly(L-lactic acid). The honeycomb-mimic scaffolds with tunable pore size ranging from 70 to 160µm are fabricated by crystal needle-guided thermally induced phase separation in a directional freezing apparatus. The compressive modulus of the honeycomb-mimic scaffold is ≈4 times higher than that of scaffold with randomly oriented pore structure. The fabricated honeycomb-mimic scaffold exhibits a hierarchical structure from nanofibers to micro-/macro-tubular structures. Pre-osteoblast MC3T3-E1 cells cultured on the honeycomb-mimic nanofibrous scaffolds exhibit an enhanced osteoblastic phenotype, with elevated expression levels of osteogenic marker genes, than those on either porous lamellar scaffolds or porous scaffolds with randomly oriented pores. The advanced techniques for the fabrication of the honeycomb-mimic structure may potentially be used for a wide variety of advanced functional materials.

Carrier-Free, Amorphous Verteporfin Nanodrug for Enhanced Photodynamic Cancer Therapy and Brain Drug Delivery.

Glioblastoma (GBM) is hard to treat due to cellular invasion into functioning brain tissues, limited drug delivery, and evolved treatment resistance. Recurrence is nearly universal even after surgery, chemotherapy, and radiation. Photodynamic therapy (PDT) involves photosensitizer administration followed by light activation to generate reactive oxygen species at tumor sites, thereby killing cells or inducing biological changes. PDT can ablate unresectable GBM and sensitize tumors to chemotherapy. Verteporfin (VP) is a promising photosensitizer that relies on liposomal carriers for clinical use. While lipids increase VP's solubility, they also reduce intracellular photosensitizer accumulation. Here, a pure-drug nanoformulation of VP, termed "NanoVP", eliminating the need for lipids, excipients, or stabilizers is reported. NanoVP has a tunable size (65-150nm) and 1500-fold higher photosensitizer loading capacity than liposomal VP. NanoVP shows a 2-fold increase in photosensitizer uptake and superior PDT efficacy in GBM cells compared to liposomal VP. In mouse models, NanoVP-PDT improved tumor control and extended animal survival, outperforming liposomal VP and 5-aminolevulinic acid (5-ALA). Moreover, low-dose NanoVP-PDT can safely open the blood-brain barrier, increasing drug accumulation in rat brains by 5.5-fold compared to 5-ALA. NanoVP is a new photosensitizer formulation that has the potential to facilitate PDT for the treatment of GBM.

Structural-color meta-nanoprinting embedding multi-domain spatial light field information

Abstract Recently, multifunctional metasurface has showcased its powerful functionality to integrate nanoprinting and holography, and display ultracompact meta-images in near- and far-field simultaneously. Herein, we propose a tri-channel metasurface which can further extend the meta-imaging ranges, with three independent images located at the interface, Fresnel and Fourier domains, respectively. Specifically, a structural-color nanoprinting image is decoded right at the interface of the metasurface, enabled by varying the dimensions of nanostructures; a Fresnel holographic image and another Fourier holographic image are present at the Fresnel and Fourier (far-field) domains, respectively, enabled by geometric phase. The spectral and phase manipulation capabilities of nanostructures have been maximized, and the spatial multiplexing capabilities for diffraction in metasurfaces have also been fully exploited. By leveraging the design freedom enabled through the tuning of the geometric size and orientation of nanostructures, as well as optimizing the diffraction spatial light wave transformation, the encoding of multiple images on the single-celled metasurface is achieved. More interestingly, due to the spatial separation of images across different channels, crosstalk is virtually eliminated, effectively enhancing imaging quality. The proposed metasurface offers several advantages, including a compact design, easiness of fabrication, minimal crosstalk, and high storage density. Consequently, it holds promising applications in image display, data storage, information encryption, anti-counterfeiting, and various other fields.

Aggregation-Induced Emission Luminogens: A New Possibility for Efficient Visualization of RNA in Plants.

RNAs play important roles in regulating biological growth and development. Advancements in RNA-imaging techniques are expanding our understanding of their function. Several common RNA-labeling methods in plants have pros and cons. Simultaneously, plants' spontaneously fluorescent substances interfere with the effectiveness of RNA bioimaging. New technologies need to be introduced into plant RNA luminescence. Aggregation-induced emission luminogens (AIEgens), due to their luminescent properties, tunable molecular size, high fluorescence intensity, good photostability, and low cell toxicity, have been widely applied in the animal and medical fields. The application of this technology in plants is still at an early stage. The development of AIEgens provides more options for RNA labeling. Click chemistry provides ideas for modifying AIEgens into RNA molecules. The CRISPR/Cas13a-mediated targeting system provides a guarantee of precise RNA modification. The liquid-liquid phase separation in plant cells creates conditions for the enrichment and luminescence of AIEgens. The only thing that needs to be looked for is a specific enzyme that uses AIEgens as a substrate and modifies AIEgens onto target RNA via a click chemical reaction. With the development and progress of artificial intelligence and synthetic biology, it may soon be possible to artificially synthesize or discover such an enzyme.

Bio-based flame retardant for manufacturing fire safety, strong yet tough versatile epoxy resin

Bio-based flame retardants have attracted growing attention for sustainability and comparable efficiency to petroleum-based counterparts but suffer from compatibility issues with epoxy resins and the trade-off between strength and toughness. Here, a Schiff base-derived phosphorus-based flame retardant (TV-DOPO) was developed from biobased vanillin and tyramine. In the presence of the binary curing agents, nanoscale in-situ constructive phase separation induced by hierarchical thermal curing process and strong hydrogen bonding provide the composite resin with enhanced both stiffness and toughness. The flexural and impact strengths reached 159 MPa and 55.4 kJ m−2, which were increased by 36.5% and 129.6%, respectively, compared with the pristine epoxy, meanwhile excellent flame retardance was well maintained (UL-94 V-0 rating). Remarkably, these conjugated phosphaphenanthrene-containing composite resins demonstrate excellent UV-shielding capacity and optical transmittance. In this work, in-situ construction of a crosslinked network with tunable size of phase separation domains can be simply achieved by modulating the ratio of binary curing agents, to fabricate epoxy resins with all-around enhanced performance.

Synthesis of submicron-sized LiNi0.5Co0.2Mn0.3O2 cathode particles via reverse microemulsion method: Tailoring size, interfacial properties, and enhanced electrochemical performance for lithium-ion battery

This study explores the impact of submicron-sized cathode materials on lithium-ion battery performance, an area with limited prior research due to synthetic challenges. Employing the reverse microemulsion method, LiNi0.5Co0.2Mn0.3O2 (NCM) cathode particles with tunable sizes (180 nm to 340 nm) were synthesized. Notably, NCM6.67-4.5, which prepared under the volume ratio of the oil phase to the water phase (i.e. 6.67) and applying 4.5 mL NH4OH as the complexing agent, obtained the largest particle size (340 nm). Further investigation revealed that NCM6.67-4.5 exhibited superior discharge specific capacity (177.54 mAh·g−1) and a high coulomb efficiency (99.5 %). The larger particle size in the submicron range facilitated heightened lithium-ion diffusion rates and reduced polarization. Focused Ion Beam-Scanning Electron Microscopy (FIB-SEM) confirmed that increased particle size diminishes specific surface area, mitigating interfacial side reactions during battery cycling. This research underscores the importance of controlling cathode particle size for optimizing electrochemical performance in lithium-ion batteries.

Preparation of Proline-Modified UIO−66 Nanomaterials and Investigation of Their Potential in Lipase Immobilization

Metal–organic frameworks (MOFs) are regarded as excellent carriers for immobilized enzymes due to their substantial specific surface area, high porosity, and easily tunable pore size. Nevertheless, the use of UIO−66 material is significantly limited in immobilized enzymes due to the absence of active functional groups on its surface. This study comprised the synthesis of UIO−66 and subsequent modification of the proline (Pro) on UIO−66 through post-synthetic modification. UIO−66 and UIO−66/Pro crystals were employed as matrices to immobilize Rhizopus oryzae lipase (ROL). The contact angle demonstrated that the introduction of Pro onto UIO−66 resulted in favorable conformational changes in the structure of ROL. The immobilized enzyme ROL@UIO−66/Pro, produced via the covalent-bonding method, exhibited greater activity (0.064715 U/mg (about 1.73 times that of the free enzyme)) and stability in the ester hydrolysis reaction. The immobilized enzymes ROL@UIO−66 (131.193 mM) and ROL@UIO−66/Pro (121.367 mM), which were synthesized using the covalent-bonding approach, exhibited a lower Km and higher substrate affinity compared to the immobilized enzyme ROL@UIO−66/Pro (24.033 mM) produced via the adsorption method. This lays a solid foundation for the industrialization of immobilized enzymes.

Proportional Fairness for Long-Term Evolution-Licensed Assisted Access (LTE-LAA) with Wi-Fi Coexistence in Unlicensed Spectrum

Long-Term Evaluation-Licensed Assisted Access (LTE-LAA) has good potential for fair coexistence with Wi-Fi in an unlicensed spectrum. Though the LTE-LAA utilizes the same listen before-talk technique as the distributed coordination function in IEEE 802.11, it utilizes completely different parameters and transmission durations. For this reason, a fair coexistence between LTE-LAA and Wi-Fi leaves an open question on how the LTE-LAA network should choose its parameters. To tackle this issue, an analytical framework considering the effects of varying important parameters, which are the different initial back-off window sizes, the numbers of sensing durations, the maximum back-off stages, the number of retransmissions and the transmission opportunities for LTE-LAA and Wi-Fi nodes on their performances has been developed. The node and network airtime performances are evaluated by using the current standard parameters setting to see how this setting affects the node and network airtime performances. From there, optimal settings of the initial backoff window size and number of sensing durations are applied by using the obtained node airtime equation that is derived from the Markov renewal process and evaluated as functions of system parameters. The optimum initial backoff window size and number of sensing durations of LTE-LAA are evaluated and verified by the calculation and simulation using MATLAB software. The analysis shows that LTE-LAA maintained unfair coexistence with Wi-Fi by using the current standard parameter setting as its initial back off window size or sensing duration. But in contrast, using the optimum initial backoff window size and number of sensing durations of LTE-LAA shows that they can maintain proportional fairness. It is unconcealed that the initial backoff window size tuning of LTE-LAA carries a high possibility of achieving fairness because it needs less system data and achieves a higher exactness result.

Modulator Directed Synthesis of Size-Tunable Mesoporous MOFs and Their Derived Nanocarbon-Based Electrocatalysts for Oxygen Reduction

Although MOF-derived carbon materials have been widely used for electrocatalysis, it is challenging to prepare size-tunable MOF precursors through simple modulation. In this work, a series of mesoporous MOF (PCN-224) with a wide tunable particle size from micro- to nano-scale were successfully synthesized by in-situ introduction of 3-mercaptopropionic acid as the modulator. After carbonization and acid etching, the derived carbons (MAx-NC) inherit the mesoporous structure and exhibit uniform particles ranging from 30 to 900 nm. MAx-NC were used as model catalysts to explore the size effects on electrocatalysis. Considering the similar compositional and structural properties, the electrochemical activity depends on the number of accessible surface active sites. MA3-NC with optimized particle sizes (∼300 nm) would not only provide abundant surface active sites but also consist of large secondary pores between the particles for fast mass transport. Moreover, suitable Fe atom was introduced into the optimized MAx-NC, which shows comparable half-wave potential and better stability than commercial Pt/C for the typical oxygen reduction reaction. This work provides an efficient “modulation” strategy for preparing size-tunable mesoporous MOF cubes and their carbon derivatives, paving a new way to customize nanosized MOFs for wider applications.

Determination of four phenolic endocrine-disrupting chemicals in water by dispersive solid-phase extraction-ultra performance liquid chromatography-tandem mass spectrometry based on metal-organic skeleton porous carbon materials

Phenolic endocrine-disrupting chemicals (EDCs) are exogenous substances that interfere with the endocrine system and disrupt normal cell functions upon entering a living organism, leading to reproductive and developmental toxicity. Therefore, the development of a rapid and efficient analytical method for detecting phenolic EDCs in environmental waters is crucial. Owing to the low concentration of phenolic EDCs in environmental water, appropriate sample pretreatment methods are necessary to remove interferences caused by the sample matrix and enrich the target analytes before instrumental analysis. Dispersive solid-phase extraction (DSPE) has gained considerable attention as a simple and rapid sample pretreatment method for environmental-sample analysis. In this method, an adsorbent material is uniformly dispersed in a sample solution and the target analytes are extracted through processes such as vortexing. Compared with traditional solid-phase extraction (SPE), DSPE increases the contact area between the adsorbent and sample solution, reduces the required amounts of adsorbent and organic solvents, and improves the extraction efficiency. The adsorbent material plays a critical role in DSPE because it determines the extraction efficiency of the method. Metal-organic frameworks (MOFs) are porous framework materials composed of metal clusters and multifunctional organic ligands. They possess many excellent properties such as tunable pore sizes, large surface areas, and good thermal and chemical stability, rendering them ideal adsorbent materials for sample pretreatment. MOF-derived porous carbon materials obtained through high-temperature carbonization not only increase the density of MOF materials for better separation but also retain the advantages of a large surface area, highly ordered porous structure, and high porosity. In this study, a porous carbon material derived from an MOF, named as University of Oslo-66-carbon (UiO-66-C), was synthesized using a solvothermal method and applied as an adsorbent to enrich four phenolic EDCs (bisphenol A, 4-tert-octylphenol, 4-nonylphenol, and nonylphenol) in water. A method combining DSPE with ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was established to analyze these phenolic EDCs in water. The UiO-66-C dosage, pH of water sample, adsorption time, eluent type and volume, elution time, and ion strength were optimized. Gradient elution was performed using methanol-water as the mobile phase. The target analytes were separated on an ACQUITY UPLC BEH C18 column (100 mm×2.1 mm, 1.7 μm), and multiple reaction monitoring (MRM) was conducted in negative electrospray ionization mode. The method exhibited a linear correlation within the range of 0.5-100 μg/L for the four phenolic EDCs. The limits of detection (LODs) and quantification (LOQs) of the four phenolic EDCs were 0.01-0.13 μg/L and 0.03-0.42 μg/L, respectively. The precision of the method was evaluated through intra- and inter-day relative standard deviations (RSDs), with values ranging from 1.5% to 10.6% and from 6.1% to 13.2%, respectively. When applied to the detection of phenolic EDCs in tap and surface water, the spiked recoveries of the four phenolic EDCs were 77.1%-116.6%. Trace levels of 4-nonylphenol and nonylphenol were detected in surface water at levels of 1.38 and 0.26 μg/L, respectively. The proposed method exhibits good accuracy and precision; thus, it provides a new rapid, efficient, and sensitive approach for the detection of phenolic EDCs in environmental water.

DNA polyhedrons cube, prism, and square pyramid protect the catalytic activity of catalase: A thermodynamics and kinetics study

DNA is widely used as building block material for the construction of polyhedral nanostructures. DNA polyhedrons (DNA prism, cube, and square pyramid) are small 3D wireframed nanostructures with tunable shapes and sizes. Despite substantial progress in synthesis, the study regarding cellular responses to DNA polyhedrons is limited. Herein, the molecular interaction between DNA polyhedrons and the antioxidant enzyme, catalase has been explored. The enzymatic activity of bovine liver catalase (BLC) remains unaltered in the presence of DNA polyhedrons after 1 h of incubation. However, the activity of BLC was protected after 24 h of incubation in the presence of DNA polyhedrons as compared to the natural unfolding. The kinetics study confirmed the protective role of DNA polyhedrons on BLC with lower KM and higher catalytic efficiency. Furthermore, no profound conformational changes of BLC occur in the presence of DNA polyhedrons as observed in spectroscopic studies. From fluorescence quenching data we confirmed the binding between DNA polyhedrons and BLC. The thermodynamic parameters indicate that non-covalent bonds played a major role during the interaction of BLC with DNA polyhedrons. Moreover, the hepatic catalase activity remains unaltered in the presence of DNA polyhedrons. The cytotoxicity assay revealed that DNA polyhedrons were biocompatible in the cellular environment. The protective role of DNA polyhedrons on enzyme activity and the unaltered conformational change of protein ensures the biocompatibility of DNA polyhedrons in the cellular environment.