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Intraepithelial lymphocytes (IELs) expressing the TCRγδ survey the intestinal epithelium to limit the invasion of microbial pathogens. The production of type I IFN is a central component of an antiviral immune response, yet how these proinflammatory cytokines contribute to γδ IEL effector function remains unclear. Based on the unique activation status of IELs and their ability to bridge innate and adaptive immunity, we investigated the extent to which type I IFN signaling modulates γδ IEL function. Using an ex vivo culture model, we find that type I IFN alone is unable to drive IFN-γ production, yet low-level TCR activation synergizes with type I IFN to induce IFN-γ production in murine γδ IELs. Further investigation into the underlying molecular mechanisms of costimulation revealed that TCRγδ-mediated activation of NFAT and JNK is required for type I IFN to promote IFN-γ expression in a STAT4-dependent manner. Whereas type I IFN rapidly upregulates antiviral gene expression independent of a basal TCRγδ signal, neither tonic TCR triggering nor the presence of a TCR agonist was sufficient to elicit type I IFN-induced IFN-γ production in vivo. However, bypassing proximal TCR signaling events synergized with IFNAR/STAT4 activation to induce γδ IEL IFN-γ production. These findings indicate that γδ IELs contribute to host defense in response to type I IFN by mounting a rapid antimicrobial response independent of TCRγδ signaling, and may produce IFN-γ in a TCR-dependent manner under permissive conditions., (Copyright © 2024 by The American Association of Immunologists, Inc.)

Background: Liver disease caused by Fasciola is a significant zoonotic and parasitic disease with substantial economic impacts on humans and animals. Many studies have looked at the prevalence of fasciolis worldwide, yet the overall prevalence and risk factors in cattle, ruminants, and humans remains unknown., Methods: We conducted a systematic review and meta-analysis to estimate the global prevalence and risk factors of fascioliasis in humans and domestic ruminants. With this aim, we searched PubMed, ScienceDirect, Web of Science, and Scopus from inception to 8 December 2022 for studies reporting the prevalence of fascioliasis in humans or domestic ruminants post-2000. We then used random effects models to describe the prevalence of fascioliasis; trim-and-fill analysis and Egger's test to assess publication bias; and meta-regression and sensitivity analyses to examine the risk factors for prevalence and heterogeneity., Results: We retrieved 4422 articles, with 371 being included in the analysis, as they concerned fascioliasis in humans and ruminants globally. The pooled prevalence of bovine fasciolosis was 17%, while ovine fasciolosis and human fascioliasis had pooled prevalences of 13% and 5%, respectively. We also conducted subgroup analyses by continents, countries, Fasciola species, sampling years, altitude, rainfall, temperature, humidity, age, sex, feeding mode, and residence. Here, altitude and age emerged as risk factors associated with an increased prevalence of fascioliasis. Both the trim-and-fill analysis and Egger's test confirmed the presence of publication bias, while the sensitivity analysis showed that the omission of any single study did not significantly influence the combined pooled prevalence., Conclusions: Fascioliasis is a widely prevalent zoonosis among humans and livestock worldwide. Strategies targeting risk factors such as altitude and age are urgently needed for prevention and control of this disease, which will consequently reduce Fasciola infection. Additionally, given the inadequacy or absence of data in some countries, greater attention should be paid to Fasciola infection, with further epidemiological studies focussing on improving data quality., Competing Interests: Disclosure of interest: The authors completed the ICMJE Disclosure of Interest Form (available upon request from the corresponding author) and disclose no relevant interests., (Copyright © 2024 by the Journal of Global Health. All rights reserved.)

Fleas, one of the most significant ectoparasites, play a crucial role as vectors in spreading zoonotic diseases globally. The Qinghai Province, as part of the Qinghai-Tibet Plateau, is one of the provinces in China with the largest number of flea species. In this study, we characterized the microbial communities of eighty-five adult fleas, belonging to nineteen species within four families (Ceratophyllidae, Ctenophthalmidae, Leptopsyllidae, and Pulicidae). We identified a total of 1162 unique operational taxonomic units at the genus level, with flea-borne pathogens such as Wolbachia, Bartonella, Rickettsia being the members of top abundant taxa. Except for comparison between Ctenophthalmidae and Leptopsyllidae families, the analyses of both alpha- and beta- diversity indicators suggested that bacterial diversity varied among flea families. This could be attributed to flea phylogeny, which also influenced by their geographical sites and animal hosts. Results of Linear discriminant analysis effect size (LEfSe) indicated that 29 genera in Ceratophylloidea, 11 genera in Ctenophthalmidae, 15 genera in Leptopsyllidae, and 22 genera in Pulicidae were significantly responsible for explaining the differences among the four flea families (linear discriminant analysis score > 2, P < 0.05). Phylogenetic Investigation of Communities by Reconstruction of Unobserved States (PICRUSt2) analyses showed that the functional pathways varied significantly across flea families, which was supported by the significant correlation between the functional pathways and the microbial communities., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Background: Metabolic disorders (MetDs) have been demonstrated to be closely linked to numerous diseases. However, the precise association between MetDs and pulmonary tuberculosis (PTB) remains poorly understood., Method: Summary statistics for exposure and outcomes from genome-wide association studies (GWASs) for exposures and outcomes were obtained from the BioBank Japan Project (BBJ) Gene-exposure dataset. The 14 clinical factors were categorized into three groups: metabolic laboratory markers, blood pressure, and the MetS diagnostic factors. The causal relationship between metabolic factors and PTB were analyzed using two-sample Mendelian Randomization (MR). Additionally, the direct effects on the risk of PTB were investigated through multivariable MR. The primary method employed was the inverse variance-weighted (IVW) model. The sensitivity of this MR analysis was evaluated using MR-Egger regression and the MR-PRESSO global test., Results: According to the two-sample MR, HDL-C, HbA1c, TP, and DM were positively correlated with the incidence of active TB. According to the multivariable MR, HDL-C (IVW: OR 2.798, 95% CI 1.484-5.274, P = 0.001), LDL (IVW: OR 4.027, 95% CI 1.140-14.219, P = 0.03) and TG (IVW: OR 2.548, 95% CI 1.269-5.115, P = 0.009) were positively correlated with the occurrence of PTB. TC (OR 0.131, 95% CI 0.028-0.607, P = 0.009) was negatively correlated with the occurrence of PTB. We selected BMI, DM, HDL-C, SBP, and TG as the diagnostic factors for metabolic syndrome. DM (IVW, OR 1.219, 95% CI 1.040-1.429 P = 0.014) and HDL-C (IVW, OR 1.380, 95% CI 1.035-1.841, P = 0.028) were directly correlated with the occurrence of PTB., Conclusions: This MR study demonstrated that metabolic disorders, mainly hyperglycemia, and dyslipidemia, are associated with the incidence of active pulmonary tuberculosis., (© 2024. The Author(s).)

The electrochemical reduction of CO 2 to CO is a powerful approach to achieving carbon neutrality. Herein, we report a five-nuclear copper cluster-based metal-azolate framework CuTz-1 as an electrocatalyst for the electrochemical CO 2 reduction reaction. It achieved a faradaic efficiency (FE) of 62.7% for yielding CO with a partial current density of -35.1 mA cm -2 in flow cell device, which can be preserved for more than ten hours with negligible changes of the current density and FE(CO). Studies of electrocatalytic mechanism studies revealed that the distance of Cu-N was increased, and the coordination number of the Cu ion was reduced, while the oxidation state of Cu was decreased after the electrocatalysis. These findings offer valuable insights into structural changes that influence the performance of the catalyst during the process of the electrochemical reduction of CO 2 process.

The photoluminescent properties of lanthanide complexes have been thoroughly investigated; however, there have been much fewer studies showcasing their potential use in ionizing radiation detection. In this work, we delve into the photo- and radio-induced luminescence of a series of lanthanide-bearing organic-inorganic hybrids and their potential as a platform for X-ray scintillation and imaging. The judicious synergy between lanthanide cations and 2,6-di(1H-pyrazol-1-yl)isonicotinate (bppCOO - ) ligands affords six new materials with three distinct structures. Notably, Eu-bppCOO-1 and Tb-bppCOO-2 display sharp fingerprint X-ray-excited luminescence (XEL), the intensities of which can be linearly correlated with the X-ray dose rates over a broad dynamic range (0.007-4.55 mGy s -1 ). Moreover, the X-ray sensing efficacies of Eu-bppCOO-1 and Tb-bppCOO-2 were evaluated, showing that Tb-bppCOO-2 features a lower detection limit of 4.06 μGy s -1 compared to 14.55 μGy s -1 of Eu-bppCOO-1. Given the higher X-ray sensitivity and excellent radiation stability of Tb-bppCOO-2, we fabricated a flexible scintillator film for X-ray imaging by embedding finely ground Tb-bppCOO-2 in the polydimethylsiloxane (PDMS) polymer. The resulting scintillator film can be utilized for high-resolution X-ray imaging with a spatial resolution of approximately 7 lp mm -1 ., (© 2023 Wiley‐VCH GmbH.)

Background: Surgery combined with radiotherapy substantially escalates the likelihood of encountering complications in early-stage cervical squamous cell carcinoma(ESCSCC). We aimed to investigate the feasibility of Deep-learning-based radiomics of intratumoral and peritumoral MRI images to predict the pathological features of adjuvant radiotherapy in ESCSCC and minimize the occurrence of adverse events associated with the treatment., Methods: A dataset comprising MR images was obtained from 289 patients who underwent radical hysterectomy and pelvic lymph node dissection between January 2019 and April 2022. The dataset was randomly divided into two cohorts in a 4:1 ratio.The postoperative radiotherapy options were evaluated according to the Peter/Sedlis standard. We extracted clinical features, as well as intratumoral and peritumoral radiomic features, using the least absolute shrinkage and selection operator (LASSO) regression. We constructed the Clinical Signature (Clinic&#95;Sig), Radiomics Signature (Rad&#95;Sig) and the Deep Transformer Learning Signature (DTL&#95;Sig). Additionally, we fused the Rad&#95;Sig with the DTL&#95;Sig to create the Deep Learning Radiomic Signature (DLR&#95;Sig). We evaluated the prediction performance of the models using the Area Under the Curve (AUC), calibration curve, and Decision Curve Analysis (DCA)., Results: The DLR&#95;Sig showed a high level of accuracy and predictive capability, as demonstrated by the area under the curve (AUC) of 0.98(95% CI: 0.97-0.99) for the training cohort and 0.79(95% CI: 0.67-0.90) for the test cohort. In addition, the Hosmer-Lemeshow test, which provided p-values of 0.87 for the training cohort and 0.15 for the test cohort, respectively, indicated a good fit. DeLong test showed that the predictive effectiveness of DLR&#95;Sig was significantly better than that of the Clinic&#95;Sig(P < 0.05 both the training and test cohorts). The calibration plot of DLR&#95;Sig indicated excellent consistency between the actual and predicted probabilities, while the DCA curve demonstrating greater clinical utility for predicting the pathological features for adjuvant radiotherapy., Conclusion: DLR&#95;Sig based on intratumoral and peritumoral MRI images has the potential to preoperatively predict the pathological features of adjuvant radiotherapy in early-stage cervical squamous cell carcinoma (ESCSCC)., (© 2024. The Author(s).)

Crystalline organic-inorganic hybrids, which exhibit colorimetric responses to ionizing radiation, have recently been recognized as promising alternatives to conventional X-ray dosimeters. However, X-ray-responsive organic-inorganic hybrids are scarce and the strategy to fine-tune their detection sensitivity remains elusive. Herein, an unprecedented mixed-ligand strategy is reported to modulate the X-ray detection efficacy of organic-inorganic hybrids. Deliberately blending the stimuli-responsive terpyridine carboxylate ligand (tpc - ) and the auxiliary pba - group with different ratios gives rise to two OD thorium-bearing clusters (Th-102 and Th-103) and a 1D coordination polymer (Th-104). Notably, distinct X-ray sensitivity is evident as a function of molar ratio of the tpc - ligand, following the trend of Th-102 > Th-103 > Th-104. Moreover, Th-102, which is exclusively built from the tpc - ligands with the highest degree of π-π interactions, exhibits the most sensitive radiochromic and fluorochromic responses toward X-ray with the lowest detection limit of 1.5 mGy. The study anticipates that this mixed-ligand strategy will be a versatile approach to tune the X-ray sensing efficacy of organic-inorganic hybrids., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Nuclear transporter importin- β 1 is emerging as an attractive target by virtue of its prevalence in many cancers. However, the lack of druggable inhibitors restricts its therapeutic proof of concept. In the present work, we optimized a natural importin- β 1 inhibitor DD1 to afford an improved analog DD1 -Br with better tolerability (>25 folds) and oral bioavailability. DD1 -Br inhibited the survival of castration-resistant prostate cancer (CRPC) cells with sub-nanomolar potency and completely prevented tumor growth in resistant CRPC models both in monotherapy (0.5 mg/kg) and in enzalutamide-combination therapy. Mechanistic study revealed that by targeting importin- β 1, DD1 -Br markedly inhibited the nuclear accumulation of multiple CRPC drivers, particularly AR-V7, a main contributor to enzalutamide resistance, leading to the integral suppression of downstream oncogenic signaling. This study provides a promising lead for CRPC and demonstrates the potential of overcoming drug resistance in advanced CRPC via targeting importin- β 1., Competing Interests: The authors declare no conflicts of interest., (© 2023 Chinese Pharmaceutical Association and Institute of Materia Medica, Chinese Academy of Medical Sciences. Production and hosting by Elsevier B.V.)

A novel radio-photoluminescence material featuring fluorochromic responses toward UV or X-ray irradiation has been obtained. Such a unique monomer- to excimer-based luminescence transition allows for dosimetry of ionizing radiation in a ratiometric manner. Rather than quenching the luminescence, the radiation-induced radical species of Th-105 boost the excimer emission, rendering it as a rare material possessing radical-excimers.

Three new halimane furanoditerpenoids (1-3) and three new clerodane furanoditerpenoids (4-6), along with seven known terpenoids including four pimarane diterpenoids (7-10) and three norisoprenoids (11-13) were isolated from the 95% EtOH extracts of the plants of Croton cnidophyllus. The 2D structures including absolute configuration of new furanoditerpenoids (1-6) were elucidated by analysis of their HRMS and NMR data as well as comparison of experimental and calculated ECD curves. Bioassay revealed that two compounds (8 and 9) possessed certain inhibitory effects against NO production stimulated by LPS, with IC 50 values of 19.00 ± 1.76 and 21.61 ± 1.11 μM, respectively., (© 2023. The Author(s).)

Actinide-bearing metal-organic frameworks (MOFs) encompass intriguing structures and properties, but the radioactivity of actinide cripples their applications. Herein, we have constructed a new thorium-based MOF ( Th-BDAT ) as a bifunctional platform for the adsorption and detection of radioiodine, a more radioactive fission product that can readily spread through the atmosphere in its molecular form or via solution as anionic species. The iodine capture within the framework of Th-BDAT from both the vapor phase and the cyclohexane solution has been verified, showing that Th-BDAT features maximum I 2 adsorption capacities ( Q max ) of 959 and 1046 mg/g, respectively. Notably, the Q max of Th-BDAT toward I 2 from cyclohexane solution ranks among the highest value for Th-MOFs reported to date. Furthermore, incorporating highly extended and π-electron-rich BDAT 4- ligands renders Th-BDAT as a luminescent chemosensor whose emission can be selectively quenched by iodate with a detection limit of 1.367 μM. Our findings thus foreshadow promising directions that might unlock the full potential of actinide-based MOFs from the point of view of practical application.

Developing ultraviolet (UV) radiation sensors featuring high sensitivity, ease of operation, and rapid readout is highly desired in diverse fields. However, the strategies to enhance sensitivity of UV detection remain limited particularly for photochromic materials, which show colorimetric response toward UV irradiation. Guided by our initial goal of facilitating easier handling, we formulated a viologen derivative ( [H 2 L]-SC ) incorporating hydrogel-based UV sensor which not only inherits the photochromism of [H 2 L]-SC but also engenders an unprecedented reversible photoelectrochromic response that is absent in either [H 2 L]-SC or hydrogel alone. Judicious synergy between photochromic [H 2 L]-SC and polyacrylamide (PAM) converts the colorimetric response of [H 2 L]-SC into the electrical resistance change of [H 2 L]-SC @PAM, which amplifies the UV sensitivity of [H 2 L]-SC by 2 orders of magnitude. Explicitly, the limit of detection (LOD) for UV decreases from 296.3 mJ/cm 2 based on the UV-vis absorption spectra of [H 2 L]-SC to 2.83 mJ/cm 2 derived from the resistance variation of [H 2 L]-SC @PAM. Moreover, linear correlation between the resistance reduction rate of [H 2 L]-SC @PAM and UV dose rate can be established, rendering it as a dual platform for quantifying both the accumulated UV dose and the instant dose rate. In addition, the proposed strategy based on constructing photoelectrochromic hybrids offers a new pathway to boost the UV sensitivity that could be universal for other photochromic materials.

Raptor, a regulatory-associated protein of mTOR, has been genetically proved to be an important regulator in lipogenesis. However, its druggable potential is rarely investigated, largely due to the lack of an inhibitor. In this study, the antiadipogenic screening of a daphnane diterpenoid library followed by target fishing led to the identification of a Raptor inhibitor, 1c (5/7/6 carbon ring with orthoester and chlorine functionalities). Pharmacodynamic studies verified that 1c is a potent and tolerable antiadipogenic agent in vitro and in vivo. Mechanistic studies revealed that the targeting of Raptor by 1c could block the formation of mTORC1 and then downregulate the downstream S6K1- and 4E-BP1-mediated C/EBPs/PPARγ signaling, eventually retarding adipocyte cell differentiation at the early stage. These findings suggest that Raptor can be explored as a novel therapeutic target for obesity and its related complications, and 1c as the first Raptor inhibitor may provide a new therapeutic option for these conditions.

Post-synthetic linker installation in a single-crystal-to-single-crystal manner was crystallographically demonstrated in thorium-based metal-organic frameworks (Th-MOFs), not only leading to the discovery of an extremely rare framework de-interpenetration, but also representing an unprecedented strategy for boosting iodine adsorption capacity.

Chromatographic fractionation of the 95% EtOH extract of the roots of Stellera chamaejasme yielded 20 sesquiterpenoids of four different types, guaiane-, carotane-, sesquicarane-, and alpiniane-types. Among them, sesquistrachanoids A-F were previously undescribed ones, whose structures including absolute configurations were elucidated by spectroscopic methods, the Mo 2 (OAc) 4 -induced ECD experiment, and analysis of experimental and calculated 1D NMR and ECD data. Sesquistrachanoid A is a 2,3-seco-guaiane-type sesquiterpenoid with a α-pyrone core and sesquistrachanoid B is the first example of 8,9-seco-guaiane-type sesquiterpenoid featured with an 1,8-δ-lactone core. Sesquistrachanoid C is a guaiane sesquiterpenoid characterized by a peroxide bridge between C-8 and C-10. All sesquiterpenoids were evaluated for their neuroprotective effects on cell damage induced by sodium nitroprusside in PC-12 cells. The bioassay results showed that six compounds at 10 μM could restore the cell viability, being comparable to that of the positive control edaravone. The mechanistic study on the most pronounced activity compound, stelleraguaianone B, demonstrated that it played a neuroprotective role by promoting the mRNA expression of antioxidant enzymes to reduce oxidative stress., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

On the base of the zwiterionic dibenzothiazole squaraine SQ, five cationic aromatics sulfonamide substituted dibenzothiazole squaraines SQ-D1 ∼ 5 have been designed and synthesized. Through the formation of the cationic compound, a higher rigid structure and the addition of the strong electron-withdrawing group (-CN), an ideal photosensitizer SQ-D2 has been gotten. In all the sulfonaminosquaraines, compound SQ-D2 exhibited the highest ROS generation efficacy and photostability. It also showed the highest photo-cytotoxicity (IC 50  = 0.25 ± 0.08 μM), very low dark-cytotoxicity and the excellent cell uptake. In animal study, it not only showed the effective tumor retention and the easy removal from the body, but also exhibited the effective PDT efficacy at low drug dose (0.15 mg/kg) and the good biocompatibility. Furthermore, photosensitizer SQ-D2 as a single component exhibited greater potential than clinically approved photosensitizer m-THPC and some nanomaterials with photosensitizers in PDT therapy towards human breast cancer. This work provides a new perspective to develop the ideal photosensitizer of the squaraine dyes., Competing Interests: Declaration of Competing Interest The authors declare no competing financial interest., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Monitoring and shielding of X-ray radiation are of paramount importance across diverse fields. However, they are frequently realized in separate protocols and a single material integrating both functions remained elusive. Herein, a hexanuclear cluster [Th 6 (µ 3 -OH) 4 (µ 3 -O) 4 (H 2 O) 6 ](pba) 6 (HCOO) 6 (Th-pba-0D) incorporating high-Z thorium cations and 3-(pyridin-4-yl)benzoate ligands that can function as a brand-new dual-module platform for visible detection and efficient shielding of ionizing radiation is demonstrated. Th-pba-0D exhibits rather unique reversible radiochromism upon alternating X-ray and UV irradiation. Moreover, the millimeter scale crystal size of Th-pba-0D renders the penetration depth of X-ray visible to naked eye and leads to the unearthing of its high X-ray attenuation efficiency. Indeed, the shielding efficacy of Th-pba-0D is comparable to that of lead glass containing 40% PbO, and a Th-pba-0D pellet with a thickness of merely 1.2 mm can shield 99.73% X-ray (16 keV). These studies portend the possible utilization of thorium-bearing materials as a bifunctional platform for radiation detection and shielding., (© 2022 Wiley-VCH GmbH.)

Based on transcriptome sequencing technology, the mouse model of prediabetes treated with Huangjing Qianshi Decoction was sequenced to explore the possible mechanism of treating prediabetes. First of all, transcriptome sequencing was performed on the normal BKS-DB mouse group, the prediabetic model group, and the Huangjing Qianshi Decoction treatment group(treatment group) to obtain differentially expressed genes in the skeletal muscle samples of mice. The serum biochemical indexes were detected in each group to screen out the core genes of Huangjing Qianshi Decoction in prediabetes. Gene Ontology(GO) database and Kyoto Encyclopedia of Genes and Genomes(KEGG) database were used to conduct signaling pathway enrichment analysis of differentially expressed genes, and real-time quantitative polymerase chain reaction(RT-qPCR) was used to verify them. The results showed that the levels of fasting blood glucose(FBG), fasting insulin(FINS), insulin resistance index(HOMA-IR), total cholesterol(TC), triglycerides(TG), and low-density lipoprotein cholesterol(LDL-C) in the mouse model were significantly decreased after treatment with Huangjing Qianshi Decoction. In the results of differential gene screening, there were 1 666 differentially expressed genes in the model group as compared with the normal group, and there were 971 differentially expressed genes in the treatment group as compared with the model group. Among them, interleukin-6(IL-6) and NR3C2 genes, which were closely related to the regulation of insulin resis-tance function, were significantly up-regulated between the model group and the normal group, and vascular endothelial growth factor A(VEGFA) genes were significantly down-regulated between the model group and the normal group. However, the expression results of IL-6, NR3C2, and VEGFA genes were adverse between the treatment group and the model group. GO functional enrichment analysis found that the biological process annotation mainly focused on cell synthesis, cycle, and metabolism; cell component annotation mainly focused on organelles and internal components; and molecular function annotation mainly focused on binding molecular functions. KEGG pathway enrichment analysis found that it involved the protein tyrosine kinase 6(PTK6) pathway, CD28-dependent phosphoinositide 3-kinase/protein kinase B(PI3K/AKT) pathway, p53 pathway, etc. Therefore, Huangjing Qianshi Decoction can improve the state of prediabetes, and the mechanism may be related to cell cycle and apoptosis, PI3K/AKT pathway, p53 pathway, and other biological pathways regulated by IL-6, NR3C2, and VEGFA.

Simple synthetic modulation based on thorium nitrate and tris((4-carboxyl)phenylduryl)amine (H 3 TCBPA) gives rise to a new thorium-based metal-organic framework, Th-TCBPA, which features excellent hydrolytic and thermal stabilities. Incorporating electron-rich TCBPA 3- linkers not only endows Th-TCBPA with high adsorption capacity toward radioiodine vapor, but also makes it a luminescence sensor for the highly sensitive and selective detection of Cr(VI) anions.

Sensitization of Cr(VI) oxyanions in environmentally or industrially relevant aquatic media is highly desired owning to their biological toxicity and essential role in nuclear fuel cycle. However, many chemosensors of CrO 4 2- and Cr 2 O 7 2- suffer from critical drawbacks, including insufficient sensitivity, selectivity, and/or hydrolytic stability. In this work, we prepared a hydrolytically stable metal-organic framework, namely Hf-BITD, which can retain its crystallinity and structural integrity in solutions over a wide pH range (0-12) and in 3 M HCl. The strong emission via rigidifying fluorescent linkers allows for sensing of CrO 4 2- and Cr 2 O 7 2- in a luminescence quenching manner, with excellent linear correlations (I 0 /I = 1+ K sv [Q]) in the ranges of 0-80 μM and 0-50 μM for CrO 4 2- and Cr 2 O 7 2- , respectively. The adsorption of Cr(VI) oxyanions and the concomitant resonance energy transfer between framework and analysts efficiently turn the emission of Hf-BITD off, which allows for selective recognition of CrO 4 2- and Cr 2 O 7 2- with detection limits of 0.38 nM and 0.33 nM, respectively. Furthermore, fabrication of Hf-BITD incorporating PVDF membrane makes Hf-BITD@PVDF a promising candidate for facile and effective sensitization of Cr(VI) oxyanions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Tigliane and rhamnofolane diterpenoids bearing glycosyl substituents are rarely found in nature. In the current study, seven new tigliane glycosides, euphorwallsides A - G (1-7), and five new rhamnofolane glycosides, euphorwallsides H - L (8-12), were isolated from the whole plants of Euphorbia wallichii. Their structures were elucidated by a combination of spectroscopic, computational, and chemical means. The aglycones of 1-5 represent a rare class of 13-deoxygenated tiglianes, while those of 8-12 represent the first examples of 4-deoxygenated rhamnofolanes. 2, 3, 5, 7, 8, and 12 showed significant neuroprotective effects on sodium nitroprusside (SNP)-induced neuronal death in pheochromocytoma cell line PC-12 at 10 μM, being more active than the clinical drug, edaravone. Mechanistic study revealed that the most active compound, 3, could inhibit reactive oxygen species (ROS) accumulation and restore the mitochondrial membrane potential via modulating the Nrf2 signaling pathway in PC-12 cells., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Five tigliane ( 1 - 5 ) and one ingenane ( 6 ) diterpenoids were isolated from the ethanol extract of Euphorbia tirucalli . The structures of these compounds were identified based on analysis of their spectroscopic data. Among them, compound 12- O -(2 E ,4 E ,6 E ,8 E -tetradecatetraenoyl)-13- O -isobutyroyl-4 β -deoxyphorbol ( 1 ) was a new tigliane. The Rho123 effluxion assay showed that tiglianes with a trans -fused 5/7 ring system such as compounds 1 , 2 , and 4 had potent inhibitory activity against P-glycoprotein in HepG2/ADR cells.

Importins are overexpressed in many cancers and mediate the abnormal nuclear transport of oncogenic factors. The druggable potential of importins still remains unclear, largely because of the lack of potent inhibitors. Herein, the anti-castration-resistant prostate cancer (CRPC) screening of a Euphorbiaceae diterpenoid library followed by target fishing led to the identification of a highly potent importin-β1 inhibitor, daphnane diterpenoid DD1 . DD1 selectively inhibited the growth and survival of CRPC cells at subnanomolar concentrations and completely blocked tumor growth in preclinical models at an extremely low dosage. Mechanistic studies revealed that targeting of importin-β1 by DD1 significantly reduced the nuclear accumulation of key CRPC drivers, shutting down their downstream oncogenic signaling. Disruption of the predicted binding sites of DD1 on importin-β1 abolished this anti-CRPC effect. These findings suggest that importin-β1 is an effective therapeutic target in CRPC and that DD1 as the most potent importin-β1 inhibitor to date can be developed as therapeutics for treatment of this disease.

Synergistic assembly of uranyl centres and luminescent 2,6-bis(pyrazol-1-yl)pyridine-4-carboxylates (bppCOOH) gives rise to a uranyl coordination polymer, namely U-bppCOO, which exhibits a luminescence quenching response toward UV or X-ray irradiation doses. Notably, the photosensitivity of U-bppCOO has been significantly enhanced via metal-ligand assembly compared with that of the naked bppCOOH ligand.

Crotonianoids A-C ( 1 - 3 ), three unusual tigliane diterpenoids, were isolated from the seeds of Croton tiglium . Compound 1 is a 13,14:13,15- diseco -tigliane featuring a unique spiro[bicyclo[5.3.0]decane-2,5'-2'(3' H ,4' H )-furanone] core; 2 is a 13,15- seco -tigliane incorporating a rare peroxide bridge between C-13 and C-15; and 3 is the first example of a phorbol ester with a 10 R -configuration. Their structures were determined by spectroscopic, computational, and X-ray diffraction methods. Compounds 1 and 2 markedly inhibited the growth and survival of prostate cancer cell C4-2B at micromolar concentrations and induced cell apoptosis. Mechanistic study revealed that 1 and 2 could suppress androgen receptor (AR) signaling pathway by promoting the degradation of AR protein.

This perspective highlights the recent advances in the structural and practical aspects of thorium-based metal-organic frameworks (Th-MOFs) and molecular clusters. Thorium, as an underexplored actinide, features surprisingly rich coordination geometries and accessibility of the 5f orbital. These features lead to a myriad of topologies and electronic structures, many of which are undocumented for other tetravalent metal-containing MOFs or clusters. Moreover, Th-MOFs inherit the modularity, structural tunability, porosity, and versatile functionality of the state-of-the-art MOFs. Recognizing the radioactive nature of these thorium-bearing materials that may limit their practical uses, Th-MOFs and Th-clusters still have great potential for various applications, including radionuclide sequestration, hydrocarbon storage/separation, radiation detection, photoswitch, CO 2 conversion, photocatalysis, and electrocatalysis. The objective of this updated perspective is to propose pathways for the renaissance of interest in thorium-based materials.

Effective detections of radionuclides including uranium and its predominant fission products, for example, iodine, are highly desired owing to their radiotoxicity and potential threat to human health. However, traditional analytical techniques of radionuclides are instrument-demanding, and chemosensors targeted for sensitization of radionuclides remain limited. In this regard, we report a sensitive and selective sensor of UO 2 2+ and I - based on the unique quenching behavior of a luminescent Zr-based metal-organic framework, Zr 6 O 4 (OH) 4 (OH) 6 (H 2 O) 6 (TCPE) 1.5 ·(H 2 O) 24 (C 3 H 7 NO) 9 ( Zr-TCPE ). Immobilization of the luminescent tetrakis(4-carboxyphenyl)ethylene (TCPE 4- ) linkers by Zr 6 nodes enhances the photoluminescence quantum yield of Zr-TCPE , which facilitates the effective sensing of radionuclides in a "turn-off" manner. Moreover, Zr-TCPE can sensitively and selectively recognize UO 2 2+ and I - ions with the lowest limits of detection of 0.67 and 0.87 μg/kg, respectively, of which the former one is much lower than the permissible value (30 μg/L) defined by the U.S. EPA. In addition, Zr-TCPE features excellent hydrolytic stability and can withstand pH conditions ranging from 3 to 11. To facilitate real-world applications, we have further fabricated polyvinylidene fluoride-integrating Zr-TCPE as luminescence-based sensor membranes for on-site sensing of UO 2 2+ and I - .

A novel X-ray dosimeter based on a uranium coordination polymer U-Cbdcp was obtained by the judicious synergy between the luminescent uranyl centres and zwitterionic tritopic ligands. Notably, U-Cbdcp exhibits luminescence quenching upon increasing X-ray dose, which in combination with its excellent radiolytic stability, makes it suitable for X-ray dosimetry., Competing Interests: The authors declare no competing financial interest., (This journal is © The Royal Society of Chemistry.)

Intraepithelial lymphocytes expressing the γδ T cell receptor (γδ IELs) serve as a first line of defense against luminal microbes. Although the presence of an intact microbiota is dispensable for γδ IEL development, several microbial factors contribute to the maintenance of this sentinel population. However, whether specific commensals influence population of the γδ IEL compartment under homeostatic conditions has yet to be determined. We identified a novel γδ IEL hyperproliferative phenotype that arises early in life and is characterized by expansion of multiple Vγ subsets. Horizontal transfer of this hyperproliferative phenotype to mice harboring a phenotypically normal γδ IEL compartment was prevented following antibiotic treatment, thus demonstrating that the microbiota is both necessary and sufficient for the observed increase in γδ IELs. Further, we identified two guilds of small intestinal or fecal bacteria represented by 12 amplicon sequence variants (ASV) that are strongly associated with γδ IEL expansion. Using intravital microscopy, we find that hyperproliferative γδ IELs also exhibit increased migratory behavior leading to enhanced protection against bacterial infection. These findings reveal that transfer of a specific group of commensals can regulate γδ IEL homeostasis and immune surveillance, which may provide a novel means to reinforce the epithelial barrier., (© 2022. The Author(s), under exclusive licence to Society for Mucosal Immunology.)

Here, we report a universal single-atom coating (SAC) strategy by taking advantage of the rich chemistry of tannic acid (TA). TA units not only self-assemble into a cross-linked porous polyphenolic framework, but also can grip on different substates via multiple binding modes. Benefiting from the diverse chelating ability of TA, a series of mono-, and bi-metallic SACs can be formed on substrates of different materials (e. g., carbon, SiO 2 , TiO 2 , MoS 2 ), dimensions (0D-3D) and sizes (50 nm-5 cm). By contrast, uniform SAC cannot be achieved using common approaches such as pyrolysis of metal-dopamine complexes or metal-organic frameworks. As a proof-of-concept demonstration, two Co SACs immobilized on graphene and TiO 2 were prepared. The former one shows six-fold higher mass activity than Pt/C toward oxygen reduction. The latter one displays outstanding photocatalytic activity owing to the high activity of the single atoms and the formation of the single-atom coating-TiO 2 heterojunction., (© 2022 Wiley-VCH GmbH.)

Developing materials that possess colorimetric responses to external stimuli is a promising strategy for addressing the current challenges in radiation dosimetry. Currently, colorimetric ionizing-radiation-responsive materials remain underexplored, and those with multistimuli response are rare. Herein, the integration of thorium cation and photoresponsive terpyridine carboxylate ligand gives rise to a thorium nanocluster, Th-101 , which displays the second case of fluorochromic response and unprecedented piezochromic behavior among all actinide materials. The emission color of Th-101 exhibits a gradual transition from blue to cyan to green upon irradiation with accumulated dose, which renders colorimetric dosimetry of ionizing radiation based on a red-green-blue (RGB) concept. Further fabricating Th-101 into a custom-built optoelectronic device allows for on-site quantification of radiation dose with merits of ease of operation, rapid readout, and cost-effectiveness.

Simple synthetic modulation based on uranyl acetate and phenanthroline has resulted in two uranyl clusters (1 and 2) with different topologies and nuclearities. Notably, the dimeric complex exhibits distinct luminescence quenching upon UV and X-ray irradiation with detection limits of 4.30 × 10 -6 J and 0.32 Gy, respectively. To advance the practical application, 1 was further fabricated with polyvinylidene fluoride into a flexible strip as a UV and X-ray indicator.

The monotherapy of mTOR inhibitors (mTORi) in cancer clinical practice has achieved limited success due to the concomitant activation of compensatory pathways, such as Akt signaling and cytoprotective autophagy. Thus, the combination of mTORi and the inhibitors of these pro-survival pathways has been considered a promising therapeutic strategy. Herein, we report the synergistic effects of a natural anti-cancer agent Jolkinolide B (JB) and mTORi (temsirolimus, rapamycin, and everolimus) for the effective treatment of bladder cancer. A mechanistic study revealed that JB induced a dual inhibition of Akt feedback activation and cytoprotective autophagy, potentiating the anti-proliferative efficacy of mTORi in both PTEN-deficient and cisplatin-resistant bladder cancer cells. Meanwhile, mTORi augmented the pro-apoptotic and pro-paraptotic effects of JB by reinforcing JB-activated endoplasmic reticulum stress and MAPK pathways. These synergistic mechanisms were related to cellular reactive oxygen species accumulation. Our study suggests that dual inhibition of Akt feedback activation and cytoprotective autophagy is an effective strategy in mTORi-based therapy, and JB + mTORi combination associated with multiple anti-cancer mechanisms and good tolerance in mouse models may serve as a promising treatment for bladder cancer., (Copyright © 2021 Elsevier B.V. All rights reserved.)

This study analyzed the molecular mechanism of Huangjing Qianshi Decoction(HQD) in the treatment of prediabetes based on network pharmacology and molecular docking. The active components of HQD were identified and screened based on Traditional Chinese Medicine Systems Pharmacology Database and Analysis Platform(TCMSP, http://Lsp.nwu.edu.cn/tcmsp.php) and then the targets of the components and the genes related to prediabetes were retrieved, followed by identifying the common targets of the decoction and the disease. The medicinal component-target network was constructed by Cytoscape to screen key components. The protein-protein interaction(PPI) network was established by STRING and hub genes were identified by Cytoscape-CytoNCA, followed by Gene Ontology(GO) term enrichment and Kyoto Encyclopedia of Genes and Genomes(KEGG) of the hub genes with R-clusterProfi-ler. Thereby, the possible signaling pathways were predicted and the molecular mechanism was deduced. A total of 79 active components of HQD and 785 diabetes-related targets of the components were screened out. The hub genes mainly involved the GO terms of tricarboxylic acid cycle, peptide binding, amide binding, hydrolase activity, and kinase activity regulation, and the KEGG pathways of AGE-RAGE signaling pathway, TNF signaling pathway, AMPK signaling pathway, IL-17 signaling pathway, and insulin signaling pathway. Western blot result showed that HQD-containing serum significantly reduced the expression of AKT1, AGE, and RAGE proteins in insulin resistance model cells. HQD's treatment of prediabetes is characterized by multiple pathways, multiple targets, and multiple levels. The main mechanism is that the components zhonghualiaoine, baicalein, kaempferol, and luteolin act on AKT1 and inhibit the AGE-RAGE axis.

Three new diterpenoids, euphopanes A-C ( 1 - 3 ), including one ent -isopimarane ( 1 ), one ent -abietane ( 2 ) and one cembrane ( 3 ), along with five known compounds ( 4 - 8 ) were isolated from the roots of Euphorbia pekinensis . Their structures were elucidated by extensive spectroscopic analysis, and the absolute configurations of compounds 1 - 3 were determined by ECD calculations. All the isolates were screened for the cytotoxicity against three cancer cell lines (C4-2B, C42B/ENZR, and MDA-MB-231), and compounds 1 , 2 , and 4 showed significant cytotoxicity against human prostate cancer cells C4-2B with IC 50 values of 14.3, 16.9, and 15.3 μM, respectively.

A brand-new application of thorium-bearing clusters in the field of ionizing radiation detection is exemplified by two novel hexanuclear thorium clusters, Th-bppCOO-1 and Th-bppCOO-2 , which incorporate carboxylate-functionalized 2,6-di(pyrazol-1-yl)pyridine ligands. Notably, Th-bppCOO-1 is composed of an unprecedented [Th 6 (OH) 4 O 4 (H 2 O) 5 ] 12+ secondary building unit, the Th 6 core of which is decorated by five H 2 O molecules. Furthermore, selective photoluminescence quenching responses of Th-bppCOO-1 and Th-bppCOO-2 toward X-ray over UV radiation have been demonstrated for the first time.

Polymorphism control of metal-organic frameworks is highly desired for elucidating structure-property relationships, but remains an empirical process and is usually done in a trial-and-error approach. We adopted the rarely used actinide cation Th 4+ and a ditopic linker to construct a series of thorium-organic frameworks (TOFs) with a range of polymorphs. The extraordinary coordination versatility of Th 4+ cations and clusters, coupled with synthetic modulation, gives five distinct phases, wherein the highest degree of interpenetration (threefold) and porosity (75.9 %) of TOFs have been achieved. Notably, the O atom on the capping site of the nine-coordinated Th 4+ cation can function as a bridging unit to interconnect neighboring secondary building units (SBUs), affording topologies that are undocumented for other tetravalent-metal-containing MOFs. Furthermore, for the first time HCOOH has been demonstrated as a bridging unit of SBUs to further induce structural complexity. The resulting TOFs exhibit considerably different adsorption behaviors toward organic dyes, thus suggesting that TOFs represent an exceptional and promising platform for structure-property relationship study., (© 2021 Wiley-VCH GmbH.)

Polygonatum sibiricum polysaccharides (PSP) can decrease the levels of fasting blood glucose, total cholesterol, and triglyceride (TG) in hyperlipidemic and diabetic animals. It can also reduce inflammatory cytokines and promote glucose uptake in adipocytes. However, the underlying molecular mechanisms of PSP in improving insulin resistance (IR) in skeletal muscle remain unclear. In this study, palmitic acid (PA) induced an IR model in L6 myotubes. After treatment, cell proliferation was measured using the CCK8. miR-340-3p, glucose transporter 4 (GLUT-4), and interleukin-1 receptor-associated kinase 3 (IRAK3) expression was measured by qRT-PCR. IRAK3 protein levels were measured by Western blotting. Glucose in the cell supernatant, TG concentration in L6 myotubes, and the levels of IL-1β, IL-6, and TNF-α were measured by an ELISA. We found that cell survival, glucose uptake, and GLUT-4 expression in L6 myotubes were significantly suppressed, while lipid accumulation and inflammatory factor levels were enhanced by PA stimulation. Furthermore, PSP treatment markedly alleviated these effects. Interestingly, PSP also significantly reduced the upregulated expression of miR-340-3p in the L6 myotube model of IR. Furthermore, overexpression of miR-340-3p reversed the beneficial effects of PSP in the same IR model. miR-340-3p can bind to the 3'-untranslated regions of IRAK3 . Additionally, PA treatment inhibited IRAK3 expression, whereas PSP treatment enhanced IRAK3 expression in L6 myotubes. Additionally, miR-340-3p also inhibited IRAK3 expression in L6 myotubes. Taken together, PSP improved inflammation and glucose uptake in PA-treated L6 myotubes by regulating miR-340-3p/IRAK3, suggesting that PSP may be suitable as a novel therapeutic agent for IR.

Expanding the family of lanthanide terpyridine coordination polymers has yielded eighteen new complexes with two different phases, Ln(TPC) 2 (HCOO)(H 2 O) ( Ln-1 ) and Ln(TPC)(HCOO) 2 ( Ln-2 ) (Ln = Sm-Lu, except Tm). Both structures are composed of lanthanide cations interconnected by 2,2':6',2''-terpyridine-4'-carboxylate ligands to yield one-dimensional chain topologies. However, the incorporation of an additional crystallographically unique decorative TPC ligand into Ln-1 gives rises to a distinct phase. The encapsulation of both metal- and ligand-based phosphors within single coordination polymers leads to dual-emission of the afforded materials. Furthermore, judicious lanthanide doping in heterometallic Ln-1 and Ln-2 allows for fine-tuning the photoluminescent colours over a wide range of gamut. Such a combination showcases the capability to fine-tune the emission colours from deep green, to red, and to blue. In addition, direct white-light emission upon UV excitation can be achieved in the Sm x Gd 1- x -1 system.

Aim: We retrospectively analyzed the distribution of distant lymph node metastasis and its impact on prognosis in patients with metastatic NPC after treatment., Methods: From 2010 to 2016, 219 NPC patients out of 1,601 (182 from the Affiliated Cancer Hospital and Institute of Guangzhou Medical University, and 37 from the Affiliated Dongguan Hospital, Southern Medical University) developed distant metastasis after primary radiation therapy. Metastatic lesions were divided into groups according to location: bones above the diaphragm (supraphrenic bone, SUP-B); bones below the diaphragm (subphrenic bone, SUB-B); distant lymph nodes above the diaphragm (supraphrenic distant lymph nodes, SUP-DLN); distant lymph nodes below the diaphragm (subphrenic distant lymph nodes, SUB-DLN), liver, lung, and other lesions beyond bone/lung/distant lymph node above the diaphragm (supraphrenic other lesions, SUP-OL); other lesions beyond bone/liver/distant lymph node below the diaphragm (subphrenic other lesions, SUB-OL); the subtotal above the diaphragm (supraphrenic total lesions, SUP-TL); and the subtotal below the diaphragm (subphrenic total lesions, SUB-TL). Kaplan-Meier methods were used to estimate the probability of patients' overall survival (OS). Univariate and multivariate analyses were applied using the Cox proportional hazard model to explore prediction factors of OS., Results: The most frequent metastatic locations were bone (45.2%), lung (40.6%), liver (32.0%), and distant lymph nodes (20.1%). The total number of distant lymph node metastasis was 44, of which 22 (10.0%) were above the diaphragm, 18 (8.2%) were below the diaphragm, and 4 (1.8%) were both above and below the diaphragm. Age (HR: 1.02, 95% CI: 1.00, 1.03, p = 0.012), N stage (HR: 1.26, 95% CI: 1.04, 1.54, p = 0.019), number of metastatic locations (HR: 1.39, 95% CI: 1.12, 1.73, p = 0.003), bone (HR: 1.65, 95% CI: 1.20, 2.25, p = 0.002), SUB-B (HR: 1.51, 95% CI: 1.07, 2.12, p = 0.019), SUB-DLN (HR: 1.72, 95% CI: 1.03, 2.86, p = 0.038), and SUB-O L(HR: 4.46, 95% CI: 1.39, 14.3, p = 0.012) were associated with OS. Multivariate analyses revealed that a higher N stage (HR: 1.23, 95% CI: 1.00, 1.50, p = 0.048), SUB-DLN (HR: 1.72, 95% CI: 1.02, 2.90, p = 0.043), and SUB-OL (HR: 3.72, 95% CI: 1.14, 12.16, p = 0.029) were associated with worse OS., Conclusion: Subphrenic lymph node metastasis predicts poorer prognosis for NPC patients with metachronous metastasis; however, this needs validation by large prospective studies., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Zhang, Zhang, Liang, Chen, Zhi, Yin, Wang, Dong and Chen.)

By first applying a thorium-organic framework (Th-SINAP-2) as a radiation attenuator and by incorporating a terpyridine derivative (Htpbz) as a photo-responsive guest, selective photochromism in response to X-rays was achieved in the host-guest assembly of Htpbz@Th-SINAP-2. Such a combination endows the afforded material with the lowest detection limit of X-ray dose among all photochromic sensors and a brand-new function of X-ray dosimetry for thorium containing materials.

Triple-negative breast cancer (TNBC) is a lethal malignancy without safe and effective therapeutic drugs. In this study, the anti-TNBC bioassay-guided isolation of the medicinal plant Croton kongensis followed by the structural modification led to the construction of a small ent -kaurane diterpenoid library ( 1 - 25 ). With subsequent biological screening, 20 highly potent compounds (IC 50 s < 3 μM) were identified. Among them, 8,9-seco- ent -kaurane 6 displayed comparable activity (IC 50 s ∼ 80 nM) to doxorubicin but with better selectivity. The analysis of structure-activity relationships suggested that the cleavage of the C8-C9 bond and the presence of α,β-unsaturated ketone moiety were essential for the activity. The mechanistic study revealed that 6 induced apoptosis, autophagy, and metastasis suppression in TNBC cells via inhibition of Akt. In vivo , 6 significantly suppressed the TNBC tumor growth without causing side effects. All these results suggested that 6 may serve as a promising lead for the development of novel anti-TNBC agents in the future.

Bladder cancer is a clinically heterogeneous disease with a poor prognosis. In the current study, anti-proliferation assay of a Euphorbiaceae diterpenoid library led to the identification of an anti-bladder cancer agent Jolkinolide B (JB). JB showed significant cytotoxicity against a panel of bladder cancer cell lines and suppressed the growth of cisplatin (CDDP)-resistant bladder cancer xenografts in single or combination treatments. Mechanistic study revealed that, besides inducing mitogen-activated protein kinase (MAPK)-related apoptosis, JB could trigger the paraptosis via activation of reactive oxygen species (ROS)-mediated endoplasmic reticulum (ER) stress and extracellular signal-regulated kinase (ERK) pathway. The excessive production of ROS could be induced by JB via inhibition of thioredoxin reductase 1 (TrxR1) and depletion of glutathione (GSH). Collectively, JB that targets thioredoxin and GSH systems to induce two distinct cell death modes may serve as a promising candidate in future anti-bladder cancer drug development., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The field of metal-organic framework (MOF)-based biomimetic catalysts has achieved great progress but is still in its infancy. The systematic investigation of the tailored construction of MOF-based biomimetic catalysts is required for further development. Herein, two iron-based MOFs, namely, [(Fe 3 O) 2 (H 2 O) 4 (HCOO)(L) 2 ] n (HUST-5: H 6 L = hexakis(4-formylphenoxy) cyclotriphosphazene; HUST = Huazhong University of Science and Technology) and [(Fe 3 O)(H 2 O) 3 (L)] n (HUST-7) have been fabricated through the assembly of different iron clusters and hexa-carboxylate ligand under the control of the added acid species. The two MOFs exhibit distinct secondary building units (SBUs) and topological structures, which could be used as biomimetic catalysts for the systematic comparisons of structural characteristics and the catalytic activity. Both MOFs possess catalytic activity similar to that of natural peroxidases towards the catalysis of the oxidation of a variety of substrates. Significantly, HUST-5 and HUST-7 can effectively catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by H 2 O 2 accompanied by significant colorimetric biosensing. With same compositions, different catalytic performances were obtained due to differences in the porous structures and characteristics of SBUs in two Fe-MOFs, which was also validated by theoretical calculation results. Furthermore, the phenomenon of colorimetric biosensing could be significantly suppressed by the addition of ascorbic acid (AA) during the oxidation process of TMB. It was observed from these findings that a facile colorimetric biosensing platform for detecting H 2 O 2 and ascorbic acid has been successfully explored. Therefore, this work provides another unique perspective for the tailor-made preparation of stable MOF-based peroxidase mimics with excellent catalytic performance and colorimetric biosensing.

Acute lung injury (ALI) involves series of inflammatory pathologies and cause high morbidity. Salviplenoid A (SA) was a new sesquiterpenoid from the traditional inflammatory herb Salvia plebeia. In our previous study, SA exhibited antiinflammatory activity in RAW264.7 cells. However, the extensive effects of SA in human cells and in vivo and the active mechanisms are unclear. Thus, in this study, we sought to access its effects in vitro and in vivo and to investigate its mechanisms. SA was proved to inhibit the induction of proinflammatory cytokines in human cell types, including pulmonary epithelial cells and endothetial cells. It also depressed monocyte adhesion. Moreover, SA potently attenuated the acute lung inflammation in the LPS-induced mouse model shown by down-regulation of proinflammatory mediators, inhibition of polymorphonuclear neutrophil infiltration, and alleviation of related symptoms like alveolar congestion and mucus secretion. Further evaluation confirmed that SA regulated NF-κB pathway by inhibiting the IκB-α phosphorylation. And it markedly mediated Nrf2/HO-1 pathway by activating the Nrf2/HO-1 expression and promoting Nrf2 nuclear translocation. Therefore, SA could attenuate acute lung inflammation via suppressing NF-κB and activating Nrf2, which provide a theoretical basis for the potential application of SA in clinic., (© 2020 John Wiley & Sons Ltd.)

Targeted synthesis, through a heteroleptic methodology, has resulted in three types of lanthanide (Ln) coordination polymers (CPs) with tailored dimensionality, tunable photoluminescent colors, and distinct luminescence quenching upon UV and X-ray irradiation. The homoleptic Ln(tpbz)(NO 3 ) 2 [ CP-1 ; tpbz = 4-(2,2':6',2″-terpyridin-4'-yl)benzoate] is assembled from Ln cations and bridging tpbz ligands, accompanied by the decoration of NO 3 - anions, forming a one-dimensional (1D) chain structure. The presence of ancillary dicarboxylate linkers, 1,4-benzenedicarboxylate (bdc) and 2,5-thiophenedicarboxylate (tdc), promotes additional bridging between 1D chains to form a two-dimensional layer and a three-dimensional framework for Ln(tpbz)(bdc) ( CP-2 ) and Ln(tpbz)(tdc) ( CP-3 ), respectively. The multicolor and luminescence properties of the obtained CPs were investigated, displaying typical red Eu III -based and green Tb III -based emissions. The Sm III -bearing CP-1 - CP-3 , however, exhibit diverse ratiometric Ln III - and ligand-based emissions, with the photoluminescent colors varying from pink to orange to cyan. Notably, the Tb III -containing CP-1 - CP-3 display distinct luminescence quenching upon continuous exposure to UV and X-ray irradiation. To our best knowledge, CP-2-Tb represents one of the most sensitive UV dosage probes (3.2 × 10 -7 J) among all CPs.

Krypton (Kr) and xenon (Xe) are nowadays widely applied in technical and industrial fields. Separating and collecting highly pure Xe from nuclear facilities are necessary and urgent. However, the technology is limited due to the inert nature of Xe and other interferential factors. In this work, a calcium-based metal-organic framework, Ca-SINAP-1 , which comprises a three-dimensional microporous framework with a suitable pore width, was researched for xenon and krypton separation through both experimental and theoretical methods. Ca-SINAP-1 , synthesized in solvothermal and gamma ray conditions, features accessible open-metal sites, exhibits a high Xe/Kr selectivity of 10.32, and owns a Xe adsorption capacity of 2.87 mmol/g at room temperature (1.0 bar). Particularly, its excellent chemical stability (from pH 2 to 13) and thermal stability (up to 550 °C), as well as radiation-resistance (up to 400 kGy β irradiations), render this material a promising candidate for radioactive inert gases treatment.

Rational design and synthesis of new photochromic sensors have been active research areas of inquiry, particularly on how to predict and tailor their properties and functionalities. Herein, two thulium 2,2':6',2''-terpyridine-4'-carboxylate (TPC)-functionalized metal-organic hybrids, Tm(TPC) 2 (HCOO)(H 2 O) ( TmTPC-1 ) and Tm(TPC)(HCOO) 2 ( TmTPC-2 ) with different photochromic response behaviors, have been successfully prepared, allowing for straightforward investigations of the structure-property correlation. Single-crystal X-ray diffraction and electron paramagnetic resonance analyses revealed that the incorporation of a unique dangling decorating TPC unit in TmTPC-1 offers a shorter and more accessible π-π interaction pathway between the adjacent TPC moieties than that in TmTPC-2 . Such a structural feature leads to the production of radical species via a photoinduced intermolecular electron-transfer (IeMCT) process upon UV or X-ray irradiation, which ultimately endows TmTPC-1 with a rather unusual UV and X-ray dual photochromism. A linear relationship between the change of UV-vis absorbance intensity and X-ray dose was established, making TmTPC-1 a promising dosimeter for X-ray radiation with an extremely high energy threshold (30 kGy). To advance the development for real-world application, we have fabricated polyvinylidene fluoride (PVDF) membranes incorporating TmTPC-1 for functioning either as a UV imager or as an X-ray radiation indicator. Lastly, TmTPC-1 exhibits high thermal stability (up to 400 °C) and radioresistance (at least 900 kGy), and also excellent reversibility of photochromic transformation (at least 5 cycles).