Cancer SLC6A6-mediated taurine uptake transactivates immune checkpoint genes and induces exhaustion in CD8+ T cells.

Taurine is used to bolster immunity, but its effects on antitumor immunity are unclear. Here, we report that cancer-related taurine consumption causes T cell exhaustion and tumor progression. The taurine transporter SLC6A6 is correlated with aggressiveness and poor outcomes in multiple cancers. SLC6A6-mediated taurine uptake promotes the malignant behaviors of tumor cells but also increases the survival and effector function of CD8+ T cells. Tumor cells outcompete CD8+ T cells for taurine by overexpressing SLC6A6, which induces T cell death and malfunction, thereby fueling tumor progression. Mechanistically, taurine deficiency in CD8+ T cells increases ER stress, promoting ATF4 transcription in a PERK-JAK1-STAT3 signaling-dependent manner. Increased ATF4 transactivates multiple immune checkpoint genes and induces T cell exhaustion. In gastric cancer, we identify a chemotherapy-induced SP1-SLC6A6 regulatory axis. Our findings suggest that tumoral-SLC6A6-mediated taurine deficiency promotes immune evasion and that taurine supplementation reinvigorates exhausted CD8+ T cells and increases the efficacy of cancer therapies.

Portable smartphone platform utilizing AIE-featured carbon dots for multivariate visual detection for Cu2+, Hg2+ and BSA in real samples.

Heavy metals cause serious toxic threats to both environment and human health. The multivariate, instrument-free, portable, and rapid detection strategy is crucial for determination of heavy metals. Herein, aggregation-induced emission (AIE) featured carbon dots (SN-CDs) were fabricated hydrothermally by optimizing co-doping precursors. With bright yellow emission at 560 nm, the SN-CDs were utilized for multivariate sensing Cu2+, Hg2+ and bovine serum albumin (BSA) based on AIE behavior and static quenching effect, with detection limits of 0.46 µmol·L-1, 25.8 nmol·L-1 and 1.52 µmol·L-1. A portable smartphone platform was constructed to enable portable, prompt, and sensitive analysis for Cu2+, Hg2+, and BSA via different strategies in real water and food samples with satisfied recovery. Moreover, a logic gate circuit was designed to provide the possibilities for utilization of intelligent facility. The proposed AIE SN-CDs possessing great contribution in preferable sensing performance, present promising prospects in real-time monitoring of environment and food safety.

Molecularly imprinted electrochemical sensor based on CoNi-MOF/RGO nanocomposites for sensitive detection of the hippuric acid.

Toluene, a volatile organic compound, may have adverse effects on the nervous and digestive system when inhaled over an extended period. The assessment of environmental toluene exposure can be effectively conducted by detecting hippuric acid (HA), a toluene metabolite. In this investigation, a molecularly imprinted electrochemical sensor was developed for HA detection, utilizing the synergistic effects of reduced graphene oxide (RGO) and a bimetallic organic skeleton known as CoNi-MOF. Initially, graphene oxide (GO) was synthesized using a modified Hummers' method, and RGO with better conductivity was achieved through reduction with ascorbic acid (AA). Subsequently, CoNi-MOF was introduced to enhance the material's electron transport capabilities further. The molecularly imprinted membrane was then prepared via electropolymerization to enable selective HA recognition. Under optimal conditions, the synthesized sensor exhibited accurate HA detection within a concentration range of 2-800 nM, with a detection limit of 0.97 nM. The sensor's selectivity was assessed using a selectivity coefficient, yielding an imprinting factor of 6.53. The method was successfully applied to the quantification of HA in urine, demonstrating a favorable recovery rate of 93.4%-103.9%. In conclusion, this study presents a practical platform for the detection of human metabolite detection.

Dual-mode fluorimetric and colorimetric sensors based on iron and nitrogen co-doped carbon dots for the detection of dopamine.

Determination of dopamine (DA) is crucial for its intimate relationship with clinical trials and biological environment. Herein, Fe, N co-doped carbon dots (AFC-CDs) were fabricated by optimizing precursors and reaction conditions for fluorimetric/colorimetric dual-mode sensing of DA. With synergistic influence of Förster resonance energy transfer and static quenching effect, DA significantly quenched the blue luminescence of AFC-CDs at 442 nm, the production of recognizable tan-brown complex caused evident colorimetric response, achieved the dual-mode fluorimetric/colorimetric sensing for DA. The excellent selectivity and satisfied sensitivity can be confirmed with the limit of detection at 0.29 µM and 2.31 µM via fluorimetric/colorimetric mode respectively. The reliability and practicability were proved by recovery of 94.81-101.61% in real samples. Notably, the proposed electron transfer way between AFC-CDs and DA was hypothesized logically, indicated dual-mode probe provided a promising platform for the sensing of trace DA, and could be expanded in environment and food safety.

Exercise-induced ß-hydroxybutyrate promotes Treg cell differentiation to ameliorate colitis in mice.

Increasing attention is being paid to the mechanistic investigation of exercise-associated chronic inflammatory disease improvement. Ulcerative colitis (UC) is one type of chronic inflammatory bowel disease with increasing incidence and prevalence worldwide. It is known that regular moderate aerobic exercise (RMAE) reduces the incidence or risk of UC, and attenuates disease progression in UC patients. However, the mechanisms of this RMAE's benefit are still under investigation. Here, we revealed that ß-hydroxybutyrate (ß-HB), a metabolite upon prolonged aerobic exercise, could contribute to RMAE preconditioning in retarding dextran sulfate sodium (DSS)-induced mouse colitis. When blocking ß-HB production, RMAE preconditioning-induced colitis amelioration was compromised, whereas supplementation of ß-HB significantly rescued impaired ß-HB production-associated defects. Meanwhile, we found that RMAE preconditioning significantly caused decreased colonic Th17/Treg ratio, which is considered to be important for colitis mitigation; and the downregulated Th17/Treg ratio was associated with ß-HB. We further demonstrated that ß-HB can directly promote the differentiation of Treg cell rather than inhibit Th17 cell generation. Furthermore, ß-HB increased forkhead box protein P3 (Foxp3) expression, the core transcriptional factor for Treg cell, by enhancing histone H3 acetylation in the promoter and conserved noncoding sequences of the Foxp3 locus. In addition, fatty acid oxidation, the key metabolic pathway required for Treg cell differentiation, was enhanced by ß-HB treatment. Lastly, administration of ß-HB without exercise significantly boosted colonic Treg cell and alleviated colitis in mice. Together, we unveiled a previously unappreciated role for exercise metabolite ß-HB in the promotion of Treg cell generation and RMAE preconditioning-associated colitis attenuation.

Robust Glycoproteomics Platform Reveals a Tetra-Antennary Site-Specific Glycan Capping with Sialyl-Lewis Antigen for Early Detection of Gastric Cancer.

The lack of efficient biomarkers for the early detection of gastric cancer (GC) contributes to its high mortality rate, so it is crucial to discover novel diagnostic targets for GC. Recent studies have implicated the potential of site-specific glycans in cancer diagnosis, yet it is challenging to perform highly reproducible and sensitive glycoproteomics analysis on large cohorts of samples. Here, a highly robust N-glycoproteomics (HRN) platform comprising an automated enrichment method, a stable microflow LC-MS/MS system, and a sensitive glycopeptide-spectra-deciphering tool is developed for large-scale quantitative N-glycoproteome analysis. The HRN platform is applied to analyze serum N-glycoproteomes of 278 subjects from three cohorts to investigate glycosylation changes of GC. It identifies over 20 000 unique site-specific glycans from discovery and validation cohorts, and determines four site-specific glycans as biomarker candidates. One candidate has branched tetra-antennary structure capping with sialyl-Lewis antigen, and it significantly outperforms serum CEA with AUC values > 0.89 compared against < 0.67 for diagnosing early-stage GC. The four-marker panel can provide improved diagnostic performances. Besides, discrimination powers of four candidates are also testified with a verification cohort using PRM strategy. This findings highlight the value of this strong tool in analyzing aberrant site-specific glycans for cancer detection.

Albumin, an interesting and functionally diverse protein, varies from 'native' to 'effective' (Review).

Human serum albumins (HSAs) are synthesized in the liver and are the most abundant proteins in plasma of healthy human. They play an important role in the pathophysiological processes of the liver and even the whole organism. Previous studies have mainly focused on the regulation of HSAs' expression. However, with the progress of research in recent years, it has been found that the content of circulating albumin cannot fully reflect the biological function of albumin itself. Given the aforementioned fact, the concept of serum 'effective albumin concentration' has been proposed. It refers to the content of albumin that is structurally and functionally intact. Alterations in the molecular structure and function of albumin have been reported in a variety of diseases, including liver disease. Moreover, these changes have been verified to affect the progression of oxidative stress­related diseases. However, the link between albumin structure and function has not been fully elaborated, and the mechanisms by which different forms of albumin affect disease also need to be further investigated. In this context, the present review mainly expounded the biological characteristics and functions of albumin, summarized the different types of post­translational modification of albumin, and discussed their functional changes and possible mechanisms in non­alcoholic fatty liver disease, alcoholic hepatitis, viral hepatitis and different stages of cirrhosis. This will help to improve understanding of the role of albumin in disease development and provide a more comprehensive physiological basis for it in disease treatment.

ZIF-based boronic acid modified molecular imprinted polymers in combination with silver nanoparticles/glutathione coated graphene oxide adsorbent for the selective enrichment of ellagic acid.

This study focuses on the extraction of ellagic acid (EA), a valued phenolic compound, from agricultural waste chestnut shell samples. A novel approach is introduced using a combination of boronic acid-modified molecularly imprinted polymer (ZIF@B@MIP) and a nanocomposite of graphene oxide-coated silver nanoparticles (GO@Ag@GSH) to enhance EA enrichment. ZIF@B@MIP precisely captured EA through boronate affinity-based molecular imprinting recognition. ZIF@B@MIP employs boronate affinity-based molecular imprinting recognition to precisely capture EA, while GO@Ag@GSH provides ample adsorption sites. The synergistic effect of ZIF@B@MIP and GO@Ag@GSH demonstrates excellent enrichment capability and selectivity for EA. High-performance liquid chromatography (HPLC) is employed for sensitive EA detection, achieving a maximum adsorption capacity of 46.25 mg g-1 and an imprinting factor of 3.01. The adsorption capacity to different structural analogue was investigated, and the selectivity coefficient was used to evaluate the selectivity, and its value was 1.16-3.01. The method successfully enriches EA in chestnut shell samples with a recovery rate of 95.6 %-110.1 %. This research presents an innovative approach for effective phenolic components enrichment from natural resources for pharmaceutical and biochemical applications.

Phosphorylation of RGS16 at Tyr168 promote HBeAg-mediated macrophage activation by ERK pathway to accelerate liver injury.

Liver injury is closely associated with macrophage activation following HBV infection. Our previous study showed that only HBeAg, but not HBsAg and HBcAg, stably enhances inflammatory cytokine production in macrophages. And we also indicated that HBeAg could induce macrophage activation via TLR2 and thus aggravate the progression of liver fibrosis. However, the specific molecular mechanism of HBeAg in macrophage activation is not clear. We screened significantly overexpressed RGS16 from RNASeq results of HBeAg-stimulated macrophages and validated them with cellular assays, GSE83148 microarray dataset, and in clinical samples. Meanwhile, small interference, plasmid, and lentivirus transfection assays were used to establish cell models for knockdown and overexpression of RGS16, and q-PCR, ELISA, Transwell, and CCK-8 assays were used to analyze the role of RGS16 in HBeAg-induced macrophage activation. In addition, the upstream and downstream mechanisms of RGS16 in HBeAg-treated macrophage activation were explored using inhibitors, phostag gels, and RGS16 phosphorylation mutant plasmids. Finally, the effect of RGS16 on hepatic inflammation in murine tissues was evaluated by H&E staining, liver enzyme assay and immunofluorescence. RGS16 was significantly upregulated in HBeAg-induced macrophage activation, and its expression was enhanced with increasing HBeAg content and treatment time. Functional experiments showed that overexpression of RGS16 promoted the production of inflammatory factors TNF-α and IL-6 and boosted macrophage proliferation and migration, while knockdown of RGS16 exhibited the opposite effect. Mechanistically, we discovered that RGS16 is regulated by the TLR2/P38/STAT5 signaling pathway. Meanwhile, RGS16 enhanced ERK phosphorylation via its own Tyr168 phosphorylation to contribute to macrophage activation, thereby accelerating liver injury. Finally, in mice, overexpression of RGS16 markedly strengthened liver inflammation. HBeAg upregulates RGS16 expression through the TLR2-P38-STAT5 axis, and the upregulated expression of RGS16 enhances macrophage activation and accelerates liver injury by promoting ERK phosphorylation. In this process, phosphorylation of Tyr168 is necessary for RGS16 to function. KEY MESSAGES: RGS16 boosted HBeAg-induced macrophage inflammation, proliferation, and migration. Tyr168 phosphorylation of RGS16 affected by ERK promoted macrophage activation. HBeAg upregulated the expression of RGS16 through TLR2/P38/STAT5 signal pathway. RGS16 promoted liver injury by regulating macrophage functions in mouse model.

GhDof1.7, a Dof Transcription Factor, Plays Positive Regulatory Role under Salinity Stress in Upland Cotton.

Salt stress is a major abiotic stressor that can severely limit plant growth, distribution, and crop yield. DNA-binding with one finger (Dof) is a plant-specific transcription factor that plays a crucial role in plant growth, development, and stress response. In this study, the function of a Dof transcription factor, GhDof1.7, was investigated in upland cotton. The GhDof1.7 gene has a coding sequence length of 759 base pairs, encoding 252 amino acids, and is mainly expressed in roots, stems, leaves, and inflorescences. Salt and abscisic acid (ABA) treatments significantly induced the expression of GhDof1.7. The presence of GhDof1.7 in Arabidopsis may have resulted in potential improvements in salt tolerance, as suggested by a decrease in H2O2 content and an increase in catalase (CAT) and superoxide dismutase (SOD) activities. The GhDof1.7 protein was found to interact with GhCAR4 (C2-domain ABA-related 4), and the silencing of either GhDof1.7 or GhCAR4 resulted in reduced salt tolerance in cotton plants. These findings demonstrate that GhDof1.7 plays a crucial role in improving the salt tolerance of upland cotton and provide insight into the regulation of abiotic stress response by Dof transcription factors.

Antinociceptive and neuroprotective effect of echinacoside on peripheral neuropathic pain in mice through inhibiting P2X7R/FKN/CX3CR1 pathway.

Clinically, neuropathic pain treatment remains a challenging issue because the major therapy, centred around pharmacological intervention, is not satisfactory enough to patient by reason of low effectiveness and more adverse reaction. Therefore, it is still necessary to find more effective and safe therapy to ameliorate neuropathic pain. The purpose of this study was to explore the antinociceptive effect of Echinacoside (ECH), an active compound of Cistanche deserticola Ma, on peripheral neuropathic pain induced by chronic constriction injury (CCI) in mice, and to demonstrate its potential mechanism in vivo and vitro. In the present study, results showed that intraperitoneal administration of ECH (50, 100, and 200 mg/kg) could alleviate mechanical allodynia, cold allodynia and thermal hyperalgesia via behavioural test. Moreover, the structure and function of injured sciatic nerve by CCI were taken a turn for the better to a certain extent after ECH treatment using histopathological and electrophysiological test. Furthermore, ECH repressed the expression of the P2X7R and FKN and reduced the expression and release of the IL-1ß, IL-6 and TNF-α. Besides, ECH could decrease Ca2+ influx and Cats efflux and inhibit phosphorylation of p38MAPK. To sum up, the present study illustrated that ECH could alleviate peripheral neuropathic pain by inhibiting microglia overactivation and inflammation through P2X7R/FKN/CX3CR1 signalling pathway in spinal cord. This study would provide a new perspective and strategy for the pharmacological treatment on neuropathic pain.

8-Oxoguanine DNA glycosylase 1 selectively modulates ROS-responsive NF-κB targets through recruitment of MSK1 and phosphorylation of RelA/p65 at Ser276.

Nuclear factor kappa B (NF-κB) activity is regulated by various posttranslational modifications, of which Ser276 phosphorylation of RelA/p65 is particularly impacted by reactive oxygen species (ROS). This modification is responsible for selective upregulation of a subset of NF-κB targets; however, the precise mechanism remains elusive. ROS have the ability to modify cellular molecules including DNA. One of the most common oxidation products is 8-oxo-7,8-dihydroguanine (8-oxoGua), which is repaired by the 8-oxoguanine DNA glycosylase1 (OGG1)-initiated base excision repair pathway. Recently, a new function of OGG1 has been uncovered. OGG1 binds to 8-oxoGua, facilitating the occupancy of NF-κB at promoters and enhancing transcription of pro-inflammatory cytokines and chemokines. In the present study, we demonstrated that an interaction between DNA-bound OGG1 and mitogen-and stress-activated kinase 1 is crucial for RelA/p65 Ser276 phosphorylation. ROS scavenging or OGG1 depletion/inhibition hindered the interaction between mitogen-and stress-activated kinase 1 and RelA/p65, thereby decreasing the level of phospho-Ser276 and leading to significantly lowered expression of ROS-responsive cytokine/chemokine genes, but not that of Nfkbis. Blockade of OGG1 binding to DNA also prevented promoter recruitment of RelA/p65, Pol II, and p-RNAP II in a gene-specific manner. Collectively, the data presented offer new insights into how ROS signaling dictates NF-κB phosphorylation codes and how the promoter-situated substrate-bound OGG1 is exploited by aerobic mammalian cells for timely transcriptional activation of ROS-responsive genes.

LMP2-mRNA lipid nanoparticle sensitizes EBV-related tumors to anti-PD-1 therapy by reversing T cell exhaustion.

BACKGROUND: Targeting EBV-proteins with mRNA vaccines is a promising way to treat EBV-related tumors like nasopharyngeal carcinoma (NPC). We assume that it may sensitize tumors to immune checkpoint inhibitors. RESULTS: We developed an LMP2-mRNA lipid nanoparticle (C2@mLMP2) that can be delivered to tumor-draining lymph nodes. C2@mLMP2 exhibited high transfection efficiency and lysosomal escape ability and induced an increased proportion of CD8 + central memory T cells and CD8 + effective memory T cells in the spleen of the mice model. A strong synergistic anti-tumor effect of C2@mLMP2 in combination with αPD-1 was observed in tumor-bearing mice. The mechanism was identified to be associated with a reverse of CD8 + T cell exhaustion in the tumor microenvironment. The pathological analysis further proved the safety of the vaccine and the combined therapy. CONCLUSIONS: This is the first study proving the synergistic effect of the EBV-mRNA vaccine and PD-1 inhibitors for EBV-related tumors. This study provides theoretical evidence for further clinical trials that may expand the application scenario and efficacy of immunotherapy in NPC.

A novel fluoropolymer as a protein delivery vector with robust adjuvant effect for cancer immunotherapy.

The inefficient treatment using protein-based nanovaccines is largely attributed to their inadequate immunogenicity. Herein, we developed a novel fluoropolymer (PF) via ring-opening polymerization and constructed a fluoropolymer-based nanovaccine for tumor immunotherapy. Due to the existence of fluoroalkyl chains, PF not only played a crucial role in tumor antigen delivery but also exhibited a remarkable adjuvant effect in enhancing the immunogenicity of nanovaccines. The nanovaccines formed by mixing PF with a model antigen ovalbumin (OVA) enhanced the uptake of antigen proteins by dendritic cells (DCs) and promoted the maturation and antigen presentation of DCs. Compared with free OVA, PF/OVA showed better efficacy in both pre-cancer prevention and tumor treatment. Furthermore, the proportion of CD4+ T and CD8+ T cells was significantly increased in lymph nodes and tumors of mice immunized with PF/OVA. Additionally, there was a great enhancement in the levels of key anti-tumor cytokines (TNF-α and IFN-γ) in the serum of the PF/OVA immunized mice. Our research has shown that fluoropolymer PF applied as a protein vector and adjuvant has great potential for the development of nanovaccines with robust immunogenicity.

Shared metabolic shifts in endothelial cells in stroke and Alzheimer's disease revealed by integrated analysis.

Since metabolic dysregulation is a hallmark of both stroke and Alzheimer's disease (AD), mining shared metabolic patterns in these diseases will help to identify their possible pathogenic mechanisms and potential intervention targets. However, a systematic integration analysis of the metabolic networks of the these diseases is still lacking. In this study, we integrated single-cell RNA sequencing datasets of ischemic stroke (IS), hemorrhagic stroke (HS) and AD models to construct metabolic flux profiles at the single-cell level. We discovered that the three disorders cause shared metabolic shifts in endothelial cells. These altered metabolic modules were mainly enriched in the transporter-related pathways and were predicted to potentially lead to a decrease in metabolites such as pyruvate and fumarate. We further found that Lef1, Elk3 and Fosl1 may be upstream transcriptional regulators causing metabolic shifts and may be possible targets for interventions that halt the course of neurodegeneration.

When Coordination Polymers Meet Wood: From Molecular Design toward Sustainable Solar Desalination.

Solar-driven interfacial evaporation harnessing solar energy on a water surface provides a sustainable and economic means to efficiently capture freshwater from nontraditional water sources. Endowed with a hierarchical porous structure and mechanical stability, wood-based evaporators represent a renewable alternative to petroleum-based materials. Nonetheless, incidental inferiorities of a low evaporation rate and weak interfacial strength are challenging to overcome. Herein, we propose the usage of chemically stable coordination polymers (Ni-dithiooxamidato, Ni-DTA) as hydrophilic photothermal nanomaterials for the molecular design of robust wood-based evaporators with improved performance. In situ synthesis of Ni-DTA onto the channel wall of balsawood provides sufficient photothermal domains that localize the converted energy for facilitated interfacial evaporation. A rational control of methanol/dimethylformamide ratios enables the coexistence of 1D-nanofibers and 0D-nanoparticles, endowing Balsa-NiDTA with a high evaporation rate of 2.75 kg m-2 h-1 and an energy efficiency of 82% under one-sun illumination. Experimental and simulation results reveal that Ni-DTA polymers with strong hydration ability decrease the equivalent evaporation enthalpy induced by decreased H-bonding density of water molecules near the evaporation interface. The Balsa-NiDTA evaporator showed a high chemical stability, mainly due to the robust Ni-S/Ni-N bonds and the superior cellulose affinity of Ni-DTA. Furthermore, the Balsa-NiDTA evaporator shows an excellent antibacterial activity and low oil-fouling propensity. This work presents a facile and mild strategy to design chemically stable wood-based evaporators, contributing to highly efficient and sustainable solar desalination under harsh conditions.

Construction of the molecularly imprinted adsorbent based on shaddock peel biochar sphere for highly sensitive detection of ribavirin in food and water resources.

Ribavirin (RBV) that is not metabolically released into the environment can contaminate the environment and even make organisms resistant to it. Therefore, it is of great significance to establish a simple and effective method for adsorbing RBV in the environment. In this study, a novel biochar-based boronate affinity molecularly imprinted polymers (C@H@B-MIPs) were synthesized. This is the first time that shaddock peel biochar sphere was used as a carrier for specific recognition of RBV. The polymerization conditions were optimized and the binding properties of RBV were studied. Benefiting from the synergistic effect of boronate affinity and surface imprinting, the C@H@B-MIPs showed rapid equilibrium kinetics of 15 min, high adsorption capacity of 18.30 mg g-1, and excellent reusability for RBV. The linear range was 0.05-100 mg L-1, and the detection limit was 0.023 mg L-1. This method was triumphant applied to the selective adsorption of RBV in food and water resources with recovery rates of 81.4-97.7%. This study provides a practical platform for the manufacture of efficient biomass-based adsorbents.

Controllable synthesis of bifunctional magnetic carbon dots for rapid fluorescent detection and reversible removal of Hg2.

Mercury is one of the most toxic heavy metals, whose identification and separation are crucial for environmental remediation. Till now, it remains a significant challenge upon simultaneous detection and removal of Hg2+. Herein, bifunctional probe magnetic carbon dots were synthesized and optimized via systematic structure manipulation of the carbon and iron precursors towards fluorescence, Hg2+ adsorption and magnetic separation. The probe exhibited blue emission at 440 nm with high quantum yield of 55 % and a high paramagnetism with the saturation magnetization value of 22.70 emu/g. Furthermore, the fluorescent detection of Hg2+ with limit of 5.40 nM and high selectivity were achieved through surface structure manipulation with moderate -NH2, -SH and Fe contents. As a result, the magnetic removal of Hg2+ was consecutively effectuated with high removal efficiency of 98.30 %. The detection and recovery of Hg2+ in real samples were further verified and demonstrated the excellent environmental tolerance of probe. The reusability was viable with recycling at least three turns by external magnet. This work not only provides a promising approach for simultaneous detection and removal of heavy metal pollution, but also provides an excellent example as a versatile platform for multifunction integration via the structure manipulation for other applications.

Immobilized horseradish peroxidase on boric acid modified polyoxometalate molecularly imprinted polymer for biocatalytic degradation of phenol in wastewater: Optimized immobilization, degradation and toxicity assessment.

The degradation of phenol from wastewater is crucial for environmental protection. Biological enzymes, such as horseradish peroxidase (HRP), have shown great potential in the degradation of phenol. In this research, we prepared a hollow CuO/Cu2O octahedron adsorbent with a carambola matrix shape through the hydrothermal method. The surface of the adsorbent was modified by silane emulsion self-assembly, where 3-aminophenyl boric acid (APBA) and polyoxometalate (PW9) were combined with silanization reagents and grafted onto the surface. The adsorbent was then molecularly imprinted with dopamine to obtain boric acid modified polyoxometalate molecularly imprinted polymer (Cu@B@PW9@MIPs). This adsorbent was used to immobilize HRP, which served as a biological enzyme catalyst from horseradish. The adsorbent was characterized, and its synthetic conditions, experimental conditions, selectivity, reproducibility, and reusability were evaluated. The maximum adsorption amount of HRP under optimized conditions was 159.1 mg g-1, as determined using high-performance liquid chromatography (HPLC). At pH 7.0, the immobilized enzyme showed a high efficiency of up to 90.0% in removing phenol, after 20 min of reaction with 25 mmol L-1 H2O2 and 0.20 mg mL-1 Cu@B@PW9@HRP. Growth tests of aquatic plants confirmed that the adsorbent reduced harm. Gas chromatography-mass spectrometry (GC-MS) tests revealed that the degraded phenol solution contained about fifteen phenol derivatives intermediates. This adsorbent has the potential to become a promising biological enzyme catalyst for dephenolization.

The synthesis of gold nanoclusters with high stability and their application in fluorometric detection for Hg2+ and cell imaging.

Sensing Hg2+ is significant to protecting human health and environmental ecosystems, for its toxicity and genotoxicity. Here, highly stable fluorescent folic acid (FA)-protected Au nanoclusters (FA-AuNCs) were synthesized by optimizing the reactive parameters with high quantum yield of 34.7%. Main components of Au4L were confirmed by MALDI-TOF, and the electron-rich residues of FA shell enabled FA-AuNCs excellent photostability. FA-AuNCs exhibited sensitive response behavior to Hg2+ with a minimum detectability of 1.3 nM, and presented extreme effect to the detection of Hg2+ in real water. Notably, the cellular imaging and in-situ detection of Hg2+ in cells can be achieved visually. The high selectivity was attributed to the chemical bond formed between Au+ (4f145d10) and Hg2+ (4f145d10). And the internal filter effect and static quenching effect were proved triggering the quenching of FA-AuNCs. The ultra-stable FA-AuNCs provide a potential promising opportunity for the in-situ tracing Hg2+ from environmental and biological samples.