Synthesis, Crystal Structures and Photoluminescent Properties of One-Dimensional Europium(III)- and Terbium(III)-Glutarate Coordination Polymers, and Their Applications for the Sensing of Fe3+ and Nitroaromatics

Acknowledgements X.C. thanks the National Natural Science Foundation of China (Grants No. 1771057 and U1804253). S.H. is grateful to Henan Normal University for a postdoctoral fellowship. Supplementary data CCDC numbers 1919755 and 1919756 for 1 and 2 respectively, contain the crystal data of this article. These data are available from Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/datarequest/cif. The supporting material of this article can be download from the journal webpage.Peer reviewedPublisher PD

Synthesis, crystal structures and photoluminescent properties of one-dimensional Europium(III)- and Terbium(III)-glutarate coordination polymers, and their applications for the sensing of Fe3+ and nitroaromatics

Two lanthanide–glutarate coordination polymers, viz.: {[Eu(C5H6O4)(H2O)4]Cl}n, (1) and [Tb(C5H7O4)(C5H6O4)(H2O)2]n, (2) have been synthesized and characterized by IR spectroscopy, thermogravimetric analysis and X-ray crystallography. In 1, the Eu(III) ions are coordinated by four O atoms from two bidentate chelating carboxylates, one O atom from a bridging carboxylate and four O atoms from water molecules adopting an EuO9 muffin shaped coordination geometry. In 2, the Tb(III) ions are coordinated by six O atoms from three bidentate chelating carboxylates, one O atom from a bridging carboxylate and two O atoms from water molecules to generate muffin like TbO9 polyhedron. In both compounds, the metal polyhedra share edges, producing centrosymmetric Ln2O2 diamonds, and are linked into [001] chains by bridging glutarate di-anions. The crystal structures are stabilized by O–HO and O–HCl hydrogen bonds in 1, and O–HO hydrogen bonds in 2. Compound 1 exhibits a red emission attributed to the 5D0 → 7FJ (J = 1–4) transitions of the Eu(III) ion, whereas 2 displays green emission corresponding to the 5D4 → 7FJ (J = 0–6) transitions of the Tb(III) ion. Both the compounds exhibit high sensitivity and selectivity for Fe3+ ions due to luminescence quenching compared to other metal ions, which include; Na+, Mg2+, Al3+, Cr3+, Mn2+, Fe2+, Co2+, Ni2+, Zn2+ and Cd2+. Compounds 1 and 2 also show high luminescence quenching sensitivity for 4-nitrophenol over the other aromatic and nitroaromatic compounds, namely; bromobenzene, 1,3-dimethylbenzene, nitrobenzene, 4-nitrotolune, 4-nitrophenol, 2,6-dinitrophenol and 2,4,6-trinitrophenol

Table_2_Identifying a lactic acid metabolism-related gene signature contributes to predicting prognosis, immunotherapy efficacy, and tumor microenvironment of lung adenocarcinoma.docx

Lactic acid, once considered as an endpoint or a waste metabolite of glycolysis, has emerged as a major regulator of cancer development, maintenance, and progression. However, studies about lactic acid metabolism-related genes (LRGs) in lung adenocarcinoma (LUAD) remain unclear. Two distinct molecular subtypes were identified on basis of 24 LRGs and found the significant enrichment of subtype A in metabolism-related pathways and had better overall survival (OS). Subsequently, a prognostic signature based on 5 OS-related LRGs was generated using Lasso Cox hazards regression analysis in TCGA dataset and was validated in two external cohorts. Then, a highly accurate nomogram was cosntructed to improve the clinical application of the LRG_score. By further analyzing the LRG_score, higher immune score and lower stromal score were found in the low LRG_score group, which presented a better prognosis. Patients with low LRG_score also exhibited lower somatic mutation rate, tumor mutation burden (TMB), and cancer stem cell (CSC) index. Three more independent cohorts (GSE126044: anti-PD-1, GSE135222: anti-PD-1, and IMvigor210: anti-PD-L1) were analyzed, and the results showed that patients in the low LRG_score category were more responsive to anti-PD-1/PD-L1 medication and had longer survival times. It was also determined that gefitinib, etoposide, erlotinib, and gemcitabine were more sensitive to the low LRG_score group. Finally, we validated the stability and reliability of LRG_score in cell lines, clinical tissue samples and HPA databases. Overall, the LRG_score may improve prognostic information and provide directions for current research on drug treatment strategies for LUAD patients.</p

Table_2_A stratification system of ferroptosis and iron-metabolism related LncRNAs guides the prediction of the survival of patients with esophageal squamous cell carcinoma.docx

Ferroptosis and iron-metabolism have been widely reported to play an important role in cancer. Long non-coding RNAs (lncRNAs) are increasingly recognized as the crucial mediators in the regulation of ferroptosis and iron metabolism. A systematic understanding of ferroptosis and iron-metabolism related lncRNAs (FIRLs) in esophageal squamous cell carcinoma (ESCC) is essential for prognosis prediction. Herein, Pearson’s correlation analysis was carried out between ferroptosis and iron-metabolism-related genes (FIRGs) and all lncRNAs to derive the FIRLs. Based on weighted gene co-expression network exploration (WCGNA), least absolute shrinkage and selection operator (LASSO) regression and Cox regression analysis, a risk stratification system, including 3 FIRLs (LINC01068, TMEM92-AS1, AC243967.2), was established. According to Kaplan-Meier analysis, receiver operating characteristic (ROC) curve analysis, and univariate and multivariate Cox regression analyses, the risk stratification system had excellent predictive ability and clinical relevance. The validity of the established prognostic signature was further examined in TCGA (training set) and GEO (validation set) cohorts. A nomogram with enhanced precision for forecasting OS was set up on basis of the independent prognostic elements. Functional enrichment analysis revealed that three FIRLs took part in various cellular functions and signaling pathways, and the immune status was varied in the high-risk and low-risk groups. In the end, the oncogenic effects of LINC01068 was explored using in vitro researches. Overall, a risk stratification system of three FIRLs was found to have significant prognostic value for ESCC and may serve as a ferroptosis-associated therapeutic target in the clinic.</p

Table_1_Identifying a lactic acid metabolism-related gene signature contributes to predicting prognosis, immunotherapy efficacy, and tumor microenvironment of lung adenocarcinoma.docx

Lactic acid, once considered as an endpoint or a waste metabolite of glycolysis, has emerged as a major regulator of cancer development, maintenance, and progression. However, studies about lactic acid metabolism-related genes (LRGs) in lung adenocarcinoma (LUAD) remain unclear. Two distinct molecular subtypes were identified on basis of 24 LRGs and found the significant enrichment of subtype A in metabolism-related pathways and had better overall survival (OS). Subsequently, a prognostic signature based on 5 OS-related LRGs was generated using Lasso Cox hazards regression analysis in TCGA dataset and was validated in two external cohorts. Then, a highly accurate nomogram was cosntructed to improve the clinical application of the LRG_score. By further analyzing the LRG_score, higher immune score and lower stromal score were found in the low LRG_score group, which presented a better prognosis. Patients with low LRG_score also exhibited lower somatic mutation rate, tumor mutation burden (TMB), and cancer stem cell (CSC) index. Three more independent cohorts (GSE126044: anti-PD-1, GSE135222: anti-PD-1, and IMvigor210: anti-PD-L1) were analyzed, and the results showed that patients in the low LRG_score category were more responsive to anti-PD-1/PD-L1 medication and had longer survival times. It was also determined that gefitinib, etoposide, erlotinib, and gemcitabine were more sensitive to the low LRG_score group. Finally, we validated the stability and reliability of LRG_score in cell lines, clinical tissue samples and HPA databases. Overall, the LRG_score may improve prognostic information and provide directions for current research on drug treatment strategies for LUAD patients.</p

Table_1_A stratification system of ferroptosis and iron-metabolism related LncRNAs guides the prediction of the survival of patients with esophageal squamous cell carcinoma.docx

Ferroptosis and iron-metabolism have been widely reported to play an important role in cancer. Long non-coding RNAs (lncRNAs) are increasingly recognized as the crucial mediators in the regulation of ferroptosis and iron metabolism. A systematic understanding of ferroptosis and iron-metabolism related lncRNAs (FIRLs) in esophageal squamous cell carcinoma (ESCC) is essential for prognosis prediction. Herein, Pearson’s correlation analysis was carried out between ferroptosis and iron-metabolism-related genes (FIRGs) and all lncRNAs to derive the FIRLs. Based on weighted gene co-expression network exploration (WCGNA), least absolute shrinkage and selection operator (LASSO) regression and Cox regression analysis, a risk stratification system, including 3 FIRLs (LINC01068, TMEM92-AS1, AC243967.2), was established. According to Kaplan-Meier analysis, receiver operating characteristic (ROC) curve analysis, and univariate and multivariate Cox regression analyses, the risk stratification system had excellent predictive ability and clinical relevance. The validity of the established prognostic signature was further examined in TCGA (training set) and GEO (validation set) cohorts. A nomogram with enhanced precision for forecasting OS was set up on basis of the independent prognostic elements. Functional enrichment analysis revealed that three FIRLs took part in various cellular functions and signaling pathways, and the immune status was varied in the high-risk and low-risk groups. In the end, the oncogenic effects of LINC01068 was explored using in vitro researches. Overall, a risk stratification system of three FIRLs was found to have significant prognostic value for ESCC and may serve as a ferroptosis-associated therapeutic target in the clinic.</p

Preparation of a Smart and Portable Film for in Situ Sensing of Iron Microcorrosion

Corrosion of iron-containing materials, which presents serious economic and safety problems, normally begins with microcorrosion, which refers to the early stages of corrosion before visible changes appear on the surface. If microcorrosion could be detected and repaired immediately, corrosion damage could be greatly reduced. Current technology and materials, however, are not able to detect microcorrosion of iron in a cheap and convenient manner. Here, we have used a natural product, ellagic acid (EA), to fabricate an EA-functionalized poly­(vinyl alcohol) (PVA) film (EAF) for in situ sensing of the initial stage of microcorrosion. EAF was able to effectively sense iron microcorrosion via an obvious color change. The film also had good long-term stability and mechanical strength. Since EAF can be easily prepared from inexpensive and green raw materials, the film opens up a new opportunity for the detection of iron microcorrosion

Theoretical Insight into the Mechanism of Cu(I)-Catalyzed [2 + 2 + 1] Cycloaddition to β‑Pyrrolinones: Azaheterocycle Formation and Assisted Dehydrogenation with Solvent MeNO₂

The construction of multisubstituted β-pyrrolinones from simple starting materials remains a great challenge. Recently, a novel Cu(I)-catalyzed [2 + 2 + 1] cycloaddition reaction was developed for rapid access to fully substituted β-pyrrolinones, which are difficult to synthesize through traditional methods as this approach may involve unusual C-nucleophilic addition of enamines and umpolung of imines. Elucidating the reaction mechanism may inspire the development of new methodologies via the unusual C-nucleophilic addition of enamines and imines. However, the reaction mechanism is still unclear because none of the intermediates was observed during the reaction process. In this work, we employed theoretical and computational chemistry to investigate the possible pathway. Finally, the calculated results indicate that ketene formed by the Wolff rearrangement of α-diazo-β-ketoester reacts with enamine formed by the addition of alkynes and amine, affording the five-membered azaheterocycle, and this process involves the formation of a six-membered ring intermediate and sequential isomerization, and the further dehydrogenation needs to be assisted with solvent MeNO2

Additional file 1: Table S1. of Stimulatory effect of icariin on the proliferation of neural stem cells from rat hippocampus

Raw data for Fig. 3. (DOCX 18 kb

Synergistic Amelioration of Osseointegration and Osteoimmunomodulation with a Microarc Oxidation-Treated Three-Dimensionally Printed Ti-24Nb-4Zr-8Sn Scaffold via Surface Activity and Low Elastic Modulus

Biomaterial scaffolds, including bone substitutes, have evolved from being primarily a biologically passive structural element to one in which material properties such as surface topography and chemistry actively direct bone regeneration by influencing stem cells and the immune microenvironment. Ti-6Al-4V(Ti6Al4V) implants, with a significantly higher elastic modulus than human bone, may lead to stress shielding, necessitating improved stability at the bone–titanium alloy implant interface. Ti-24Nb-4Zr-8Sn (Ti2448), a low elastic modulus β-type titanium alloy devoid of potentially toxic elements, was utilized in this study. We employed 3D printing technology to fabricate a porous scaffold structure to further decrease the structural stiffness of the implant to approximate that of cancellous bone. Microarc oxidation (MAO) surface modification technology is then employed to create a microporous structure and a hydrophilic oxide ceramic layer on the surface and interior of the scaffold. In vitro studies demonstrated that MAO treatment enhances the proliferation, adhesion, and osteogenesis capabilities on the scaffold surface. The chemical composition of the MAO-Ti2448 oxide layer is found to enhance the transcription and expression of osteogenic genes in bone mesenchymal stem cells (BMSCs), potentially related to the enrichment of Nb2O5 and SnO2 in the oxide layer. The MAO-Ti2448 scaffold, with its synergistic surface activity and low stiffness, significantly activates the anti-inflammatory macrophage phenotype, creating an immune microenvironment that promotes the osteogenic differentiation of BMSCs. In vivo experiments in a rabbit model demonstrated a significant improvement in the quantity and quality of the newly formed bone trabeculae within the scaffold under the contact osteogenesis pattern with a matched elastic modulus. These trabeculae exhibit robust connections to the external structure of the scaffold, accelerating the formation of an interlocking structure between the bone and implant and providing higher implantation stability. These findings suggest that the MAO-Ti2448 scaffold has significant potential as a bone defect repair material by regulating osteoimmunomodulation and osteogenesis to enhance osseointegration. This study demonstrates an optional strategy that combines the mechanism of reducing the elastic modulus with surface modification treatment, thereby extending the application scope of β-type titanium alloy