Catastrophic Cognition Is a Stronger Predictor Than Emotional Factors of Acute Postoperative Pain in Patients With Traumatic Orthopedic Injuries.

BACKGROUND: Both cognitive (pain catastrophizing [PC]) and emotional factors (anxiety, depression, and optimism) play vital roles in acute postoperative pain (APOP) management among patients with traumatic orthopedic injuries (TOIs). It remains uncertain if these psychological factors independently or collectively impact APOP in patients with TOIs, and the underlying mechanisms by which various psychological factors impact APOP in patients with TOIs are also ambiguous. PURPOSE: The aims of the current research were to analyze the effects of PC and emotional factors (anxiety, depression, and optimism) on APOP in patients with TOIs and explore the potential mechanisms by which PC and emotional factors influence APOP based on a hypothetical moderated mediation pathway mediated by pain-related fear. METHODS: This was an observational cross-sectional study. RESULTS: PC was a significantly positive predictor of APOP regardless of coexistence with emotional factors. TOI patients who had higher PC had more severe APOP (ß = 0.57, standard error [SE] = 0.005, p < .01, adjusted R2 = 0.78; ß = 0.84, SE = 0.003, p < .01, adjusted R2 = 0.77, respectively). Furthermore, when positive and negative emotions coexisted (adjusted R2 = 0.74), anxiety levels were a significant positive predictor of APOP (ß = 0.71, SE = 0.009, p < .01) and optimism was a significant negative predictor of APOP (ß = -0.24, SE = 0.008, p < .01). Pain-related fear played a mediating role in the association between the level of PC (effect = 0.044, 95% confidence interval [CI] = 0.027 to 0.062), anxiety (effect = 0.102, 95% CI = 0.075 to 0.137), and APOP in patients with TOIs. Optimism moderated the strength of the relationship between PC (95% CI = -0.020 to -0.010), anxiety (95% CI = -0.045 to -0.003), and APOP mediated by pain-related fear. CONCLUSIONS: Clinical staff should assess the level of PC and emotional factors to identify TOI patients at high risk for APOP, subsequently facilitating the optimization of pain management and efficient utilization of nursing resources through early discussion.

LTßR Agonism Promotes Anti-Tumor Immune Responses via Modulation of the Tumor Microenvironment.

The presence of high endothelial venules (HEV) and tertiary lymphoid structures (TLS) in solid tumors is correlated with favorable prognosis and better responses to immune-checkpoint blockade (ICB) in many cancer types. Elucidation of the molecular mechanisms underlying intratumoral HEV and TLS formation and their contribution to anti-tumor responses may facilitate development of improved treatment strategies. Lymphotoxin beta receptor (LTßR) signaling is a critical regulator of lymph node organogenesis and can cooperate with antiangiogenic and ICB treatment to augment tumor-associated HEV formation. Here, we demonstrated that LTßR signaling modulates the tumor microenvironment via multiple mechanisms to promote anti-tumor T cell responses. Systemic activation of the LTßR pathway via agonistic antibody treatment induced tumor-specific HEV formation, upregulated the expression of TLS-related chemokines, and enhanced dendritic cell (DC) and T cell infiltration and activation in syngeneic tumor models. In vitro studies confirmed direct effects of LTßR agonism on DC activation and maturation and associated DC-mediated T cell activation. Single agent LTßR agonist treatment inhibited syngeneic tumor growth in a CD8+ T cell- and HEV-dependent manner, and the LTßR agonist enhanced anti-tumor effects of anti-PD-1 and CAR T cell therapies. An in vivo tumor screen for TLS-inducing cytokines revealed that the combination of LTßR agonism and lymphotoxin alpha (LT⍺) expression promoted robust intratumoral TLS induction and enhanced tumor responses to anti-CTLA-4 treatment. Collectively, this study highlights crucial functions of LTßR signaling in modulating the tumor microenvironment and could inform future HEV/TLS-based strategies for cancer treatments.

Association between stigma and quality of life among chronic refractory wounds patients and informal caregivers: an actor-partner interdependence model analysis.

PURPOSE: The co-occurrence of health impairments in patients and their informal caregivers may be particularly common in intimate care settings in China. Patients with Chronic Refractory Wounds (CRWs) and their informal caregivers constitute a dyad and exhibit dyadic effects during the caring process. Unfortunately, no study has yet explored the dyadic effects of stigma on the QoL of patients with CRWs and their caregivers. METHODS: We used a convenience sampling method and recruited CRWs patient-caregiver dyads (N = 207) in China between April 2022 and October 2023. RESULTS: We found that: (i) dyadic members experience varying degrees of stigma; (ii) the actor-partner effect of CRWs patients' stigma on their own and their informal caregivers' QoL was significant (Path A1: ß = - 1.27, Path A2: ß = - 0.37, Path P1: ß = - 0.08, Path P2: ß = - 0.18); (iii) informal caregivers' stigma adversely affects both their own and their patients' psychological QoL((Path A4: ß = - 0.65, Path P4: ß = - 0.52)). Informal caregivers' stigma can negatively impact patients' physical QoL (Path P3: ß = - 0.17), whereas it does not significantly affect their own physical QoL. CONCLUSION: There is a notable actor-partner effect of the CRWs patients' stigma on their own and their informal caregivers' QoL. CRWs patients' stigma should become a priority for the government to improve CRWs patients' and informal caregivers' QoL. Besides, health professionals should be addressing several assessments and interventions to decrease informal caregivers' affiliate stigma symptoms and improve CRWs patients' and informal caregivers' QoL.

Applications of Nanozymes in Chiral-Molecule Recognition through Electrochemical and Ultraviolet-Visible Analysis.

Chiral molecules have similar physicochemical properties, which are different in terms of physiological activities and toxicities, rendering their differentiation and recognition highly significant. Nanozymes, which are nanomaterials with inherent enzyme-like activities, have garnered significant interest owing to their high cost-effectiveness, enhanced stability, and straightforward synthesis. However, constructing nanozymes with high activity and enantioselectivity remains a significant challenge. This review briefly introduces the synthesis methods of chiral nanozymes and systematically summarizes the latest research progress in enantioselective recognition of chiral molecules based on electrochemical methods and ultraviolet-visible absorption spectroscopy. Moreover, the challenges and development trends in developing enantioselective nanozymes are discussed. It is expected that this review will provide new ideas for the design of multifunctional chiral nanozymes and broaden the application field of nanozymes.

Selective fluorescence detection of acetylsalicylic acid, succinic acid and ascorbic acid based on a responsive lanthanide metal fluorescent coordination polymer.

A fluorescent sensor for highly selective and ultrasensitive detection of acetylsalicylic acid (ASA), succinic acid (SA), and ascorbic acid (AA) was reported. The water-soluble fluorescent ligand salicylic acid (Sal) was generated through catalyzing ASA by the hydrolase activity of zeolitic-imidazolate framework-8 (ZIF-8) or natural esterase (Est). The Sal can coordinate with 2-methylimidazole (2-MIm) and Ln(III) to form a fluorescent lanthanide coordination polymer (LCP), which has a fluorescence emission peak with the maximum wavelength at 412 nm (the excitation wavelength at 300 nm). Therefore, the detection of ASA can be achieved through the fluorescence intensity changes of LCPs in the system, which has comparable sensitivity and good selectivity (linear range of 0.031-1.00 mM and LODs of 11.72 and 3.22 µM) as compared to a direct reaction between Est/ZIF-8 and ASA for detecting ASA (linear range of 0.05-1.20 mM and limits of detection (LODs) of 4.43 and 4.58 µM). Furthermore, upon the addition of SA and AA, the fluorescence intensity of the reaction system can be enhanced and weakened through changing the energy resonance transfer pathways and affecting the enzymatic reaction process, respectively, realizing their sensitive and selective fluorescence detection. The established fluorescent sensors can work well in a wide linear range of SA concentrations from 0 to 2.50 mM (Est-based reaction system) and 0 to 1.50 mM (ZIF-8-based reaction system) with the LODs of 0.032 and 0.028 mM, respectively. The linear ranges of AA concentrations are from 0.0078 to 0.25 mM (Est-based reaction system) and 0.0078 to 0.13 mM (ZIF-8-based reaction system) with the LODs of 2.54 and 3.80 µM, respectively. The established sensors were successfully used in the detection of SA in rabbit plasma, with a recovery of 84.0%-98.7%. Additionally, the contents of ASA in Aspirin Enteric-Coated tablets and AA in vitamin C tablets were also determined by the developed methods.

Matrix overcompensation calibration: A new strategy to correct matrix effects of carbon origin in multielement analysis by inductively coupled plasma mass spectrometry.

BACKGROUND: Elemental analysis by inductively coupled plasma mass spectrometry (ICP-MS) may suffer from matrix effects; those caused by organic matrices cannot be corrected by internal standardization. A new strategy, matrix overcompensation calibration (MOC), was developed to correct such matrix effects. RESULTS: Clear fruit juices were diluted 1:50 in 1 % HNO3 (v/v)- 0.5 % HCl (v/v)- 5 % ethanol (v/v). A standard series was treated likewise to construct an external calibration curve. As, Se, Cd, and Pb in juices were determined by dilute-and-shoot ICP-MS based on this MOC strategy. The results agreed with those obtained by standard addition calibration and microwave-aided digestion; data accuracy was validated by spike-recovery studies. SIGNIFICANCE: Unlike standard addition calibration, a single external calibration curve established by MOC can be applicable to juices of diversified fruit, geographical, and manufacturer origins enhancing productivity.

Halide Superionic Conductors for All-Solid-State Batteries: Effects of Synthesis and Composition on Lithium-Ion Conductivity.

Owing to their high-voltage stabilities, halide superionic conductors such as Li3YCl6 recently emerged as promising solid electrolyte (SE) materials for all-solid-state batteries (ASSBs). It has been shown that by either introducing off-stoichiometry in solid-state (SS) synthesis or using a mechanochemical (MC) synthesis method the ionic conductivities of Li3-3xY1+xCl6 can increase up to an order of magnitude. The underlying mechanism, however, is unclear. In the present study, we adopt a hopping frequency analysis method of impedance spectra to reveal the correlations in stoichiometry, crystal structure, synthesis conditions, Li+ carrier concentrations, hopping migration barriers, and ionic conductivity. We show that unlike the conventional Li3YCl6 made by SS synthesis, mobile Li+ carriers in the defect-containing SS-Li3-3xY1+xCl6 (0 < x < 0.17) and MC-Li3-3xY1+xCl6 are generated with an activation energy and their concentration is dependent on temperature. Higher ionic conductivities in these samples arise from a combination of a higher Li+ carrier concentration and lower migration energy barriers. A new off-stoichiometric halide (Li2.61Y1.13Cl6) with the highest ionic conductivity (0.47 mS cm-1) in the series is discovered, which delivers exceptional cycling performance (∼90% capacity retention after 1000 cycles) in ASSB cells equipped with an uncoated high-energy LiNi0.8Mn0.1Co0.1O2 (NMC811) cathode. This work sheds light on the thermal activation process that releases trapped Li+ ions in defect-containing halides and provides guidance for the future development of superionic conductors for all-solid-state batteries.

Facet-Dependent Ni Segregation in a Micron-Sized Single-Crystal Li1.2Ni0.2Mn0.6O2 Cathode.

Elemental surface segregation in cathode materials is critical for determining the phase and interfacial reaction between the electrode and electrolyte, which consequently affects the electrochemical properties. Single-crystal cathodes of Li1.2Ni0.2Mn0.6O2 and Li1.2Ni0.2Mn0.6O1.95F0.05 with octahedral morphologies of (102)- and (003)-dominated facets have been manifested to show enhanced electrochemical properties. However, the surface structural features of such single crystals have not been investigated. Herein, using scanning transmission electron microscopy, energy dispersive X-ray spectroscopy, and electron energy loss spectroscopy, we probe the elemental surface segregation characteristics in these single-crystal cathodes. We reveal that Ni surface segregation shows dependence on the crystal facet such that it occurs on crystal facets with a mix of cations and anions but not on the facets with only cations or anions. Furthermore, facet-dependent surface reconstructions are observed, featuring a spinel-like structure at the Ni-rich facet but a rock-salt structure at the facet without Ni segregation. The commonly known Mn reduction appears at the single-crystal surfaces and is more pronounced at the facet without Ni segregation. We further reveal that fluorination leads to stabilization of surface oxygens. This study provides detailed structural and chemical information about the facet-dependent Ni surface segregation and the resulting phase formation in the rather less explored micron-sized octahedral Li1.2Ni0.2Mn0.6O2 and Li1.2Ni0.2Mn0.6O1.95F0.05 single crystals, which is key to further exploration of the electrochemical properties of the cathodes in the form of microsized single crystals.

Fluorination Effect on Lithium- and Manganese-Rich Layered Oxide Cathodes.

Lithium- and manganese-rich (LMR) layered oxides are promising high-energy cathodes for next-generation lithium-ion batteries, yet their commercialization has been hindered by a number of performance issues. While fluorination has been explored as a mitigating approach, results from polycrystalline-particle-based studies are inconsistent and the mechanism for improvement in some reports remains unclear. In the present study, we develop an in situ fluorination method that leads to fluorinated LMR with no apparent impurities. Using well-defined single-crystal Li1.2Ni0.2Mn0.6O2 (LNMO) as a platform, we show that a high fluorination level leads to decreased oxygen activities, reduced side reactions at high voltages, and a broadly improved cathode performance. Detailed characterization reveals a particle-level Mn3+ concentration gradient from the surface to the bulk of fluorinated-LNMO crystals, ascribed to the formation of a Ni-rich LizNixMn2-xO4-yFy (x > 0.5) spinel phase on the surface and a "spinel-layered" coherent structure in the bulk where domains of a LiNi0.5Mn1.5O4 high-voltage spinel phase are integrated into the native layered framework. This work provides fundamental understanding of the fluorination effect on LMR and key insights for future development of high-energy Mn-based cathodes with an intergrown/composite crystal structure.

Detection of Arsenic(V) by Fluorescence Sensing Based on Chlorin e6-Copper Ion.

The high toxicity of arsenic (As) can cause irreversible harm to the environment and human health. In this study, the chlorin e6 (Ce6), which emits fluorescence in the infrared region, was introduced as the luminescence center, and the addition of copper ion (Cu2+) and As(V) provoked a regular change in fluorescence at 652 nm, whereas that of As(III) was 665 nm, which was used to optionally detect Cu2+, arsenic (As(III), and As(V)). The limit of detection (LOD) values were 0.212 µM, 0.089 ppm, and 1.375 ppb for Cu2+, As(III), and As(V), respectively. The developed method can be used to determine Cu2+ and arsenic in water and soil with good sensitivity and selectivity. The 1:1 stoichiometry of Ce6 with Cu2+ was obtained from the Job plot that was developed from UV-visible spectra. The binding constants for Cu2+ and As(V) were established to be 1.248 × 105 M-1 and 2.35 × 1012 M-2, respectively, using B-H (Benesi-Hildebrand) plots. Fluorescence lifetimes, B-H plots, FT-IR, and 1H-NMR were used to postulate the mechanism of Cu2+ fluorescence quenching and As(V) fluorescence restoration and the interactions of the two ions with the Ce6 molecule.

Construction of Mn-decorated zeolitic imidazolate framework-90 nanostructure as superior oxidase-like mimic for colorimetric detection of glucose and choline.

A Mn decorated zeolitic imidazolate framework-90 (ZIF-90) nanozyme (Mn/ZIF-90) was constructed through an effective and rapid post-synthetic strategy for the first time. The Mn in Mn/ZIF-90 exists in mixed valence states, which is doped to the ZIF-90 through the formation of Mn-O bond. The Zn-N coordination structure of ZIF-90 may change the electronic arrangement of oxygen atoms in the free carbonyl groups (-CHO), allowing the coordination of Mn with O. The prepared Mn/ZIF-90 possesses outstanding oxidase-like activity and remarkable stability. Besides, the catalytic activity of Mn/ZIF-90 can be inhibited in the presence of H2O2. Therefore, using the Mn/ZIF-90-triggered chromogenic reaction of 3,3',5,5'-tetramethylbenzidine (TMB) as an amplifier, a versatile enzyme cascade-based colorimetric method for the detection of glucose and choline with good sensitivity and selectivity was developed. The linear ranges for glucose and choline are 6.25-500 µM and 5-1000 µM, respectively. Furthermore, the developed method was applied in the detection of glucose and choline in rabbit plasma samples, and the recoveries are 89.5-107.3 % and 96.0-109.3 %, respectively. In short, the simple and efficient post-synthetic doping method may provide a new thought for the rational designs of enzyme mimics with improved catalytic performance. Moreover, the colorimetric method based on the excellent catalytic activity of Mn/ZIF-90 may be extended to detect other H2O2-generating or consuming molecules and evaluate the activity of bio-enzymes that can catalyze the generation of glucose or choline.

Dilute-and-shoot ICPMS quantification of V, Ni, Co, Cu, Zn, As, Se, Ag, Cd, Ba, and Pb in fruit juices based on matrix overcompensation calibration.

Analysis of V, Co, Ni, Cu, Zn, As, Se, Ag, Cd, Ba, and Pb in fruit juices was performed by inductively coupled plasma mass spectrometry (ICPMS) after simple 50-fold dilution in 1% (v/v) HNO3-0.5% (v/v) HCl-5% (v/v) ethanol. Ethanol was added to overwhelm native organic components and dominate matrix effects. A universal calibration curve was built based on a likewise treated reagent standard series. This new matrix overcompensation calibration (MOC) strategy was developed to effectively compensated for matrix effects of carbon origin and achieved quantitative (92.5-118.8%) recoveries comparable to those by standard addition calibration (92.1-117.8%) and microwave-aided digestion (99.3-116.8%). The LODs were 0.528, 0.204, 0.195, and 2.07 ng mL-1 for toxic elements As, Cd, Pb, and Ni, respectively, adequate for their regulatory monitoring. Ge, Rh, Tb, and Ir were used as internal standards. MOC renders a calibration curve universally applicable to any clear fruit juices of diversified crop, geographic, and manufacturer origins resulting in cost saving and enhanced productivity.

Anion Engineering for Stabilizing Li Interstitial Sites in Halide Solid Electrolytes for All-Solid-State Li Batteries.

Halide solid electrolytes (SEs) have been highlighted for their high-voltage stability. Among the halide SEs, the ionic conductivity has been improved by aliovalent metal substitutions or choosing a ccp-like anion-arranged monoclinic structure (C2/m) over hcp- or bcc-like anion-arranged structures. Here, we present a new approach, hard-base substitution, and its underlying mechanism to increase the ionic conductivity of halide SEs. The oxygen substitution to Li2ZrCl6 (trigonal, hcp) increased the ionic conductivity from 0.33 to 1.3 mS cm-1 at Li3.1ZrCl4.9O1.1 (monoclinic, ccp), while the sulfur and fluorine substitutions were not effective. A systematic comparison study revealed that the energetic stabilization of interstitial sites for Li migration plays a key role in improving the ionic conductivity, and the ccp-like anion sublattice is not sufficient to achieve high ionic conductivity. We further examined the feasibility of the oxyhalide SE for practical and all-solid-state battery applications.

Atomic-scale probing of short-range order and its impact on electrochemical properties in cation-disordered oxide cathodes.

Chemical short-range-order has been widely noticed to dictate the electrochemical properties of Li-excess cation-disordered rocksalt oxides, a class of cathode based on earth abundant elements for next-generation high-energy-density batteries. Existence of short-range-order is normally evidenced by a diffused intensity pattern in reciprocal space, however, derivation of local atomic arrangements of short-range-order in real space is hardly possible. Here, by a combination of aberration-corrected scanning transmission electron microscopy, electron diffraction, and cluster-expansion Monte Carlo simulations, we reveal the short-range-order is a convolution of three basic types: tetrahedron, octahedron, and cube. We discover that short-range-order directly correlates with Li percolation channels, which correspondingly affects Li transport behavior. We further demonstrate that short-range-order can be effectively manipulated by anion doping or post-synthesis thermal treatment, creating new avenues for tailoring the electrochemical properties. Our results provide fundamental insights for decoding the complex relationship between local chemical ordering and properties of crystalline compounds.

A Novel Molecularly Imprinted Sensor Based on CuO Nanoparticles with Peroxidase-like Activity for the Selective Determination of Astragaloside-IV.

In this work, dopamine (DA) was polymerized on the surface of CuO nanoparticles (CuO NPs) to form a molecularly imprinted polymer (MIP@PDA/CuO NPs) for the colorimetric detection of astragaloside-IV (AS-IV). The synthesis process of MIP is simple and easy to operate, without adding other monomers or initiators. CuO NPs has high peroxidase (POD)-like activity that can catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) to generate oxidized TMB (OxTMB) in the presence of H2O2, having a maximum ultraviolet-visible (UV-Vis) absorption peak at 652 nm. The AS-IV can specifically bind to the surface imprinted cavities and prevent the entry of TMB and H2O2, which will lead to the inhibition of the catalytic reaction. Therefore, a new approach based on the POD-like activity of MIP@PDA/CuO NPs for AS-IV detection was developed with a linear range from 0.000341 to 1.024 mg/mL. The LOD and LOQ are 0.000991 and 0.000341 mg/mL, respectively. The developed method can accurately determine AS-IV in Huangqi Granules and different batches of Ganweikang Tablets, which are similar to the results measured by HPLC-ELSD and meet the requirements of Chinese Pharmacopoeia (2020 edition) for the amount of AS-IV in Huangqi Granules. The combination of MIP with CuO NPs not only endows the detection of AS-IV with high selectivity and reliability, but also expands the application of nanozymes in the detection of small-molecule compounds that have weak UV absorption, and do not have reducibility or oxidation properties.

Tris-Copper Nanozyme as a Novel Laccase Mimic for the Detection and Degradation of Phenolic Compounds.

Phenolic compounds are one of the main organic pollutants in the environment that can seriously affect ecosystems, even at very low concentrations. Due to the resistance of phenolic compounds to microorganisms, conventional biological treatment methods face challenges in effectively addressing this pollution problem. In this study, a novel laccase mimic (Tris-Cu nanozyme) is prepared using a simple and rapid synthesis strategy based on the coordination of copper ions and amino groups in Tris(hydroxymethyl)aminomethane (Tris). It is found that the Tris-Cu nanozyme exhibits good catalytic activity against a variety of phenolic compounds, the Km, Vmax and Kcat are determined to be 0.18 mM, 15.62 µM·min-1 and 1.57 × 107 min-1 using 2,4-dichlorophenol (2,4-DP) as the substrate, respectively. Then, based on the laccase-like activity of the Tris-Cu nanozyme, a novel colorimetric method for 2,4-DP (the limit of detection (LOD) = 2.4 µM, S/N = 3) detection in the range of 10-400 µM was established, and its accuracy was verified by analyzing tap and lake water samples. In addition, the Tris-Cu nanozyme shows excellent removal abilities for six phenolic compounds in experiments. The removal percentages for 2,4-DP, 2-chlorophenol (2-CP), phenol, resorcinol, 2,6-dimethoxyphenol (2,6-DOP), and bisphenol A (BPA) are 100%, 100%, 100%, 100%, 87%, and 81% at 1 h, respectively. In the simulated effluent, the Tris-Cu nanozyme maintains its efficient catalytic activity towards 2,4-DP, with a degradation percentage of 76.36% at 7 min and a reaction rate constant (k0) of 0.2304 min-1. Therefore, this metal-organic complex shows promise for applications in the monitoring and degrading of environmental pollutants.

Adenine phosphate-Cu nanozyme with multienzyme mimicking activity for efficient degrading phenolic compounds and detection of hydrogen peroxide, epinephrine and glutathione.

BACKGROUND: With the development of nanotechnology, various nanomaterials with enzyme-like activity (nanozymes) have been reported. Due to their superior properties, nanozymes have shown important application potential in the fields of bioanalysis, disease detection, and environmental remediation. However, only a few nanomaterials with multi-enzyme mimicry activity have been reported. In this study, a novel multienzyme mimic was synthesized through a simple and rapid preparation protocol by coordinating copper ions with N3, N6 (amino), N7, and N9 on adenine phosphate. RESULTS: The prepared adenine phosphate-Cu complex exhibits significant peroxidase, laccase, and oxidase mimicking activities. The Michaelis-Menten constant (Km) and the maximal velocity (Vmax) values of the peroxidase, laccase, and oxidase mimicking activities of AP-Cu nanozyme are 0.052 mM, 0.14 mM, and 2.49 mM; and 0.552 µM min-1, 6.70 µM min-1, and 2.24 µM min-1, respectively. Then, based on its laccase mimicking activity, the nanozyme was applied in the degradation of phenolic compounds. The calculated kinetic constant for the degradation of 2,4-dichlorophenol is 0.468 min-1 and the degradation efficiency of 2,4-dichlorophenol (0.1 mM) reaches 96.14% at 7 min. Finally, based on the multienzyme mimicking activity of adenine phosphate-Cu nanozyme, simple colorimetric sensing methods with high sensitivity and good selectivity were developed for the detection of hydrogen peroxide, epinephrine, and glutathione in the ranges of 20.0-200.0 µM (R2 = 0.9951), 5.0-100.0 µM (R2 = 0.9970), and 5.0-200.0 µM (R2 = 0.9924) with the limits of quantitation of 20.0 µM, 5.0 µM, and 5.0 µM, respectively. SIGNIFICANCE: In short, the synthesis of nanozymes with multi-enzyme mimicry activity through coordination between copper ions and small molecule mimicry enzymes provides new ideas for the design and research of multi-enzyme mimics.

Microenvironment-dependent growth of Sezary cells in humanized IL-15 mice.

Sezary syndrome (SS) is a rare, aggressive leukemic variant of cutaneous T-cell lymphoma (CTCL) that lacks adequate therapeutic options and representative small-animal models. Here, we demonstrate that IL-15 is a critical CTCL growth factor. Importantly, an immunodeficient knock-in mouse model genetically engineered to express human IL-15 uniquely supported the growth of SS patient samples relative to conventional immunodeficient mouse strains. SS patient-derived xenograft (PDX) models recapacitated key pathological features of the human disease, including skin infiltration and spread of leukemic cells to the periphery, and maintained the dependence on human IL-15 upon serial in vivo passaging. Detailed molecular characterization of the engrafted cells by single-cell transcriptomic analysis revealed congruent neoplastic gene expression signatures but distinct clonal engraftment patterns. Overall, we document an important dependence of Sezary cell survival and proliferation on IL-15 signaling and the utility of immunodeficient humanized IL-15 mice as hosts for SS - and potentially other T and NK cell-derived hematologic malignancies - PDX model generation. Furthermore, these studies advocate the thorough molecular understanding of the resultant PDX models to maximize their translational impact.

Recent advances in the colorimetric and fluorescence analysis of bioactive small-molecule compounds based on the enzyme-like activity of nanomaterials.

Nanomaterials with enzyme-like activity have been widely used in the construction of colorimetric and fluorescence sensors due to their advantages of cost-effectiveness, high stability, good biocompatibility, and ease of modification. Furthermore, the colorimetric and fluorescence sensors, which are effective approaches for detecting bioactive small-molecule compounds, have been extensively explored due to their simple operation and high sensitivity. Recent significant researches have focused on designing various sensors based on nanozymes with peroxidase- and oxidase-like activity for the colorimetric and fluorescence analysis of different analytes. In this review, recent developments (from 2018 to present) in the colorimetric and fluorescent analysis of bioactive small-molecule compounds based on the enzyme-like activity of nanomaterials were summarized. In addition, the challenges and design strategies in developing colorimetric and fluorescent assays with high performance and specific sensing were discussed.

Rapid and sensitive detection of alkaline phosphatase and glucose oxidase activity through fluorescence and colorimetric dual-mode analysis based on CuO NPs@ZIF-8 mediated enzyme-cascade reactions.

The combined application of nanozymes and natural enzymes has received widespread attention in recent years. In this work, a simple and efficient method was used to synthesize a composite material of CuO nanoparticle-modified zeolitic imidazolate framework-8 (CuO NPs@ZIF-8) with multiple enzyme activities (glucose oxidase-like and hydrolase-like activities) to detect the activity of natural enzymes through fluorescence and colorimetric (UV-vis) dual-mode detection. The hydrolase- and oxidase-like activities of CuO NPs@ZIF-8 show an acceptable affinity with l-ascorbic acid 2-phosphate trisodium (AAP) and o-phenylenediamine (OPD). Using the developed sensor, highly sensitive detection of natural enzymes glucose oxidase (GOX) and alkaline phosphatase (ALP) was achieved through both fluorescent and colorimetric analyses with a wide linear range (fluorescence for GOX: 0.86-1.23 × 105 mU mL-1, UV-vis for GOX: 0.081-1.62 × 105 mU mL-1; fluorescence for ALP: 0.042-1.20 × 104 mU mL-1, UV-vis for ALP: 0.0046-1.23 × 104 mU mL-1) and low LOQs (fluorescence for GOX: 0.86 mU mL-1, UV-vis for GOX: 0.081 mU mL-1; fluorescence for ALP: 0.042 mU mL-1, UV-vis for ALP: 0.0046 mU mL-1). Compared to the other fluorescent and colorimetric sensors, this sensor has better catalytic activity due to the addition of GOX and ALP, which can amplify the detection signal and improve the sensitivity. This is the first time that composite material CuO NPs@ZIF-8 with "tandem enzyme" activity was synthesized and applied in the detection of enzyme activity. Additionally, the proposed fluorescent and UV-vis platforms exhibit the capability to detect GOX and ALP in serum samples with satisfactory recovery, indicating potential application prospects in biochemical analysis.