Metal-Free White Light-Emitting Fluorescent Material Based on Simple Pillar[5]arene-tripodal Amide System and Theoretical Insights on Its Assembly and Fluorescent Properties.

The booming of host-guest assembly-based supramolecular chemistry provides abundant ways to construct functional systems and materials. Attracted by the important application prospect of white light emission and aggregation-induced emission (AIE) materials, herein, we report an efficient way for fabricating metal-free white light-emitting AIE materials through the supramolecular assembly of simple organic compounds: methoxyl pillar[5]arene (MP5) and tri-(pyridine-4-ylamido)benzene (TAP). By host-guest assembly, MP5 and TAP formed a supramolecular polymer (MP5-T); meanwhile, the MP5-T xerogel powder emitted white light at CIE coordinates (0.29 and 0.29). The supramolecular assembly and white light-emitting mechanisms were carefully investigated by experiments as well as quantum chemical calculations including density functional theory (DFT), reduced density gradient, electrostatic surface potential, independent gradient model, and frontier molecular orbital (highest-occupied molecular orbital-lowest-unoccupied molecular orbital) analyses. Interestingly, according to the experiments and calculations, the supramolecular assembly is critical in the white light-emitting phenomenon. Moreover, in this work, the quantum chemical calculations could not only support experimental phenomena but also provide deep understanding and visualized presentation of the assembly and emission mechanism. In addition, the obtained MP5-T solid powder could serve as a novel and easy means to make material for white light-emitting devices.

Transparency and AIE tunable supramolecular polymer hydrogel acts as TEA-HCl vapor controlled smart optical material.

Stimuli-responsive optical materials attract lots of attention due to their broad applications. Herein, a novel smart stimuli-responsive supramolecular polymer was successfully constructed using a simple tripodal quaternary ammonium-based gelator (TH). The TH self-assembles into a supramolecular polymer hydrogel (TH-G) and shows aggregation-induced emission (AIE) properties. Interestingly, the transparency and fluorescence of the TH-G xerogel film (TH-GF) could be reversibly regulated by use of triethylamine (TEA) and hydrochloric acid (HCl) vapor. When alternately fumed with TEA and HCl vapor, the optical transmittance of the TH-GF was changed from 8.9% to 92.7%. Meanwhile, the fluorescence of the TH-G shows an "ON/OFF" switch. The reversible switching of the transparency and the fluorescence of the TH-GF is attributed to the assembly and disassembly of the supramolecular polymer TH-G. Based on these stimuli-response properties, the TH-GF could act as an optical material and shows potential applications as smart windows or fluorescent display material controlled by TEA and HCl vapor.

A bi-component supramolecular gel for selective fluorescence detection and removal of Hg2+ in water.

A bi-component supramolecular gel (RQ) was successfully constructed by the assembly of the gelators 4-aminophenyl functionalized naphthalimide derivative (R) and tri-(pyridine-4-yl)-functionalized trimesic amide (Q) in DMSO-H2O (6.1 : 3.9, v/v) binary solution. The gel RQ exhibits excellent self-healing capacity. Interestingly, the RQ could fluorescently detect and reversibly remove Hg2+ from water through cation-π interactions with high selectivity, efficient adsorption and quick response. The limit of lowest detection (LOD) of the RQ for Hg2+ is 4.52 × 10-8 M and the separation ratio is 91.14%. Moreover, the RQ could be efficiently recycled and regenerated with little loss via a simple treatment by I-. Notably, thin films based on RQ and RQ + Hg2+ were prepared, which could serve as convenient and efficient test tools for the detection of Hg2+ and I-, respectively. This work provided an efficient method and novel supramolecular gel material for the separation and detection of Hg2+.

Plasminogen activator inhibitor-1 regulates LPS induced inflammation in rat macrophages through autophagy activation.

BACKGROUND: The mechanisms by which plasminogen activator inhibitor-1 (PAI-1) regulates inflammation, especially in acute respiratory distress syndrome (ARDS), are largely unknown. OBJECTIVE: To assess the relationship between PAI-1 and autophagy in inflammatory reactions induced by LPS in rat NR8383 cells. METHODS: ELISA was used to assess the amounts of TNF-α, IL-1ß, and PAI-1 in cell culture supernatants; TLR4, MyD88, PAI-1, LC3, Beclin1, and mTOR protein and mRNA levels were determined by western blot and quantitative RT-PCR, respectively; western blot was used to determine NF-κB protein levels. To further evaluate the role of PAI-1, the PAI-1 gene was downregulated and overexpressed using the siRNA transfection technology and the pCDH-PAI-1, respectively. Finally, the GFP Positive Expression Rate Method was used to determine the rate of GFP-LC3 positive NR8383 cells. RESULTS: In LPS-induced NR8383 cells, TNF-α, IL-1ß, and PAI-1 expression levels increased remarkably. Upon PAI-1 knockdown, TNF-α, IL-1ß, PAI-1, TLR4, MyD88, NF-κB, LC3, and Beclin1 levels were decreased, while mTOR increased. Conversely, overexpression of PAI-1 resulted in increased amounts of TNF-α, IL-1ß, PAI-1, TLR4, MyD88, NF-κB, LC3, and Beclin1. However, no significant change was observed in mTOR expression. CONCLUSIONS: In NR8383 cells, PAI-1 contributes in the regulation of LPS-induced inflammation, likely by promoting autophagy.

Targeted small molecule therapy and inhibitors for lymphoma.

Lymphoma, a blood tumor, has become the ninth most common cancer in the world in 2020. Targeted inhibition is one of the important treatments for lymphoma. At present, there are many kinds of targeted drugs for the treatment of lymphoma. Studies have shown that Histone deacetylase, Bruton's tyrosine kinase and phosphoinositide 3-kinase all play an important role in the occurrence and development of tumors and become important and promising inhibitory targets. This article mainly expounds the important role of these target protein in tumors, and introduces the mechanism of action, structure-activity relationship and clinical research of listed small molecule inhibitors of these targets, hoping to provide new ideas for the treatment of lymphoma.

[Box: see text].

Ru(II)-catalyzed P(III)-assisted C8-alkylation of naphthphosphines.

We report a phosphine-directed ruthenium-catalyzed C8-selective alkylation of naphthalenes with alkenes. This protocol provides straightforward access to a large library of electron-rich C8-alkyl substituent 1-naphthphosphines, which outperformed common commercial phosphines and their precursors in the Pd-catalyzed Suzuki-Miyaura coupling of aryl bromides with alkylboronic acid.

HuD regulates the cpg15 expression via the 3'-UTR and AU-rich element.

The candidate plasticity related gene 15 (cpg15) plays important roles in neural development and plasticity. In the present study, we studied the role of the cpg15 3'-untranslated region (UTR) in regulating the expression of the gene. The results showed that the presence of the 3'-UTR significantly decreases, while loss of a putative AU-rich element (ARE) in the 3'-UTR increases the cpg15 expression, indicating that the 3'-UTR and ARE may be essential for regulation of cpg15 expression. In addition, HuD, a neural-specific RNA binding protein, increased the cpg15 expression, which depends on the presence of the 3'-UTR and ARE. RNA-binding protein immunoprecipitation (RIP) assay demonstrated that HuD forms a complex with cpg15 mRNA in the cells of rat hippocampus. Deletion of HuD domains RRM1 plus RRM2 or Hinge region plus RRM3 attenuates the function of HuD in enhancing the cpg15 expression. The results suggest that HuD regulates the cpg15 expression via the 3'-UTR-mediated mechanism, which requires the presence of the ARE.

[Effects of Vegetation Restoration on the Structure and Function of the Rhizosphere Soil Bacterial Community of Solanum rostratum].

Invasive plants can change soil microbial communities and therefore promote invasion. While vegetation restoration has been adopted in certain infested lands to curb the invasion of Solanum rostratum, changes in the composition and function of rhizosphere soil bacterial communities of the species before and after the restoration has not yet been reported. In this study, two vegetation combinations used in previous studies were selected as candidates:Astragalus adsurgens+Elymus dahuricus+Bromus inermis (T1) and A. adsurgens+Festuca arundinacea+Agropyron cristatum+Leymus chinensis (T2). Rhizosphere soil samples were collected from each combination (T1 and T2), a S. rostratum invaded area (SR), and the native plant (NP) control to analyze the bacterial community structure and diversity using 16S rDNA gene sequencing on the Illumina MiSeq platform. PICRUSt was further used to predict the functional abilities of soil bacterial communities. Results of 16S rDNA gene sequencing showed that both the Simpson and Chao1 indices were higher in the SR treatment than in the NP treatment, but neither reached a significant level, although both indices decreased significantly after vegetation restoration (T1 and T2; P<0.05). The relative abundance of Microvirga, Skermanella, and Sphingomonas from phylum Proteobacteria and Bryobacter from the phylum Acidobacteria were significantly lower in the SR treatment (P<0.05) when compared with the NP treatment and higher in restoration treatments (T1 and T2). The RDA analysis showed that soil organic matter (OM), total nitrogen (TN), total phosphorus (TP), total potassium (TK), and available potassium (AK) were important factors affecting the composition of the bacterial community. Based on the PICRUSt analysis of soil bacterial community functions, the relative abundance of gene families related to biosynthesis of amino acids, purine metabolism, pyrimidine metabolism, ribosome, and aminoacyl-tRNA biosynthesis were higher in the rhizosphere samples of the SR treatment than those of the NP treatment and reduced significantly after vegetation restoration (T1 and T2; P<0.05). The structure and function of rhizosphere soil bacterial community of S. rostratum and vegetation restoration were analyzed and provided a theoretical basis for the invasion mechanism and ecological restoration of S. rostratum.

Hydrogen Bonds in Bis(1H-benzimidazole-κN3)cadmium(II) Dibenzoate: Hirshfeld Surface Analysis and AIM Perspective.

The coordination complex bis(1H-benzimidazole-κN3)cadmium(II) dibenzoate has been synthesized and characterized by single crystal diffraction analysis. Cadmium center is six coordinated and formed a distorted octahedron coordinated geometry. The Hirshfeld analysis shows that in the dnorm-surface of the compound, there are dark red spots near the hydrogen-bonds acceptor and donor atoms, while intermolecular interactions result in faint-red spots. The AIM analysis was performed, there exist a BCP in each N(C)-H∙∙∙O hydrogen bond, the bond paths also can be seen, the |V(b)|/G(b) < 1 and the H(b) > 0, the interaction is indicative of being a closed shell. The TG results are consistent with the X-ray diffraction structure.

Linear tri-pillar[5]arene-based acceptor for efficiently separate paraquat from water through collaboration effect.

Paraquat, one of non-selective herbicides, is widely used in agricultural production. However, it can cause death of people or animals quickly owing to its fatal toxicity. In the present work, for efficient separation and removal of the paraquat, a concept "employ collaboration effect to enhance the Host-Guest interactions" was rationally introduced into the design of paraquat adsorbent material. According to this concept, a novel linear tri-pillar[5]arene-based acceptor molecule was synthesized. Interestingly, the acceptor shows outstanding adsorption properties for paraquat through the collaboration effect of the adjacent pillar[5]arene moieties in the linear tri-pillar[5]arene acceptor. Compared with other adsorbents such as activated carbon and single-pillar[5]arene-based adsorbent materials, the linear tri-pillar[5]arene acceptor shows higher adsorption rate for paraquat. Additionally, the linear tri-pillar[5]arene acceptor was applied to adsorb the commercial pesticide paraquat sample in water with adsorption rate of 98%. Therefore, the linear tri-pillar[5]arene acceptor could serve as a paraquat adsorbent material and convey greatly potential application in the field of removal of paraquat. The concept "employ collaboration effect to enhance the Host-Guest interactions" is a useful way for the development of adsorption materials.

Assessment of the Clinical Usefulness of Preoperative Computed Tomography in Colorectal Cancer Patients Who Received Unplanned Reoperation.

BACKGROUND: In the unplanned reoperation of colorectal cancer patients, computed tomography (CT) is increasingly utilized to locate postoperative complications and previously unlocalized lesions. The purpose of this study is to explore the application of CT in the mortality and complications of the reoperation of colorectal cancer. Patients and Methods. We performed a retrospective review of collected data from the colorectal surgeries of 90 identified colorectal cancer patients who received an unplanned reoperation from 2010 to 2018. Patients were stratified according to those with preoperative CT imaging (CT group, n = 36) and those without preoperative CT imaging (NCT group, n = 54). Twenty-four statistical indicators of each patient were studied, including their preoperative risk, surgical characteristics, and postoperative outcomes, and satisfaction was evaluated. All data were statistically analysed for predicting postoperative complications by univariate and multivariate logistic regression analyses. RESULTS: Ninety patients received an unplanned reoperation in the study, and 40% (36/90) of these patients underwent preoperative CT examination. Patients' risk factors were similar between CT and NCT groups. Preoperative imaging was more commonly performed for reoperative new anastomosis + ileostomy but less common for reoperative Dixon's procedure. The operative duration of the NCT group was longer (139 vs. 104 min, respectively, P = 0.01). Preoperative NCT examination (OR 1.24; 95% CI = 1.09-1.42; P = 0.01) was an independent predictor of postoperative complications. Importantly, three patients died after an unplanned reoperation for colorectal cancer, which occurred only in the NCT group (5.6% vs. 0.0%, P = 0.01). CONCLUSION: The use of conventional preoperative CT optimizes the choice of the surgical site and the strategy of laparotomy, so as to reduce the length of operation. Preoperative imaging evaluation should be performed for patients undergoing repeat abdominal surgery.

APOC3 promotes TNF-α-induced expression of JAM-1 in endothelial cell via PI3K-IKK2-p65 pathway.

Atherosclerosis is a chronic inflammatory disease with lipid accumulation. Apolipoprotein C3 (APOC3), which is an important regulator of human lipid metabolism, is associated with multiple vascular mechanisms in atherosclerosis and proinflammatory responses. We have previously reported that the expression of inflammatory cytokine TNF-α is elevated in human endothelial cells (HUVECs) after APOC3 treatment. This study investigates the APOC3 signaling pathway involved in TNF-α-mediated expression of JAM-1 in HUVECs. Cultured HUVECs were exposed to APOC3 (50 µg/ml) for 16 h. Mechanistic studies were carried out by silencing TNF-α gene with lentiviral TNF-α-shRNA. Our study was based on the eight signaling pathway inhibitors to block the effect of APOC3 in HUVECs. The expression of JAM-1 was determined by qRT-PCR, Western blotting, and flow cytometry. IKK2 degradation and NF-κB p65 phosphorylation were determined by Western blotting. Our results showed that APOC3 significantly promoted the TNF-α-induced expression of JAM-1 in HUVECs. Inhibiting APOC3 reversed the TNF-α-induced overexpression of JAM-1. Moreover, APOC3 induced the expression of NF-κB p65 and degraded IκB. In conclusion, APOC3 promoted the expression of JAM-1 via the NF-κB, IKK2, and PI3K signaling pathway.

Five monocyclic pyridinium derivative based halo-argentate/cuprate hybrids or iodide salts: influence of composition on photochromic behaviors.

The rational choice of an electron acceptor was proved to be an effective strategy for the development of novel electron transfer (ET) photochromic iodides, but the types and amounts of reported electron acceptors are relatively limited so far, especially for monocyclic aromatic molecules. Herein, using monocyclic pyridinium derivatives (N-protonation-4-carboxypyridinium/N-protonation-4-carbamoylpyridinium/1-methyl-4-(carbomethoxy)pyridinium) as structural directing agents and electron acceptors, five new electron donor-acceptor-based halo-argentate/cuprate hybrids or iodide salts have been synthesized, including [HINA][Ag4I5] (1), [HINAM]I (2), [HINAM]I·0.5(I2) (3), [MCMP][Ag2Br3] (4) and [MCMP][Cu2I3] (5). Noteworthily, compounds 1-3 exhibit interesting photochromic behaviours, while compounds 4 and 5 are non-photochromic. Finally, the possible chromic mechanisms and influencing factors for the title compounds were also discussed.

[Influence of impurities on waste plastics pyrolysis: products and emissions].

The study is aimed to evaluate the impact of impurities like food waste, paper, textile and especially soil on the pyrolysis of waste plastics. For this purpose, emissions, gas and liquid products from pyrolysis of waste plastics and impurities were studied, as well as the transfer of element N, Cl, S from the substrates to the pyrolysis products. It was found that the presence of food waste would reduce the heat value of pyrolysis oil to 27 MJ/kg and increase the moisture in the liquid products, therefore the food residue should be removed from waste plastics; and the soil, enhance the waste plastics' pyrolysis by improving the quality of gas and oil products. The presence of food residue, textile and paper leaded to higher gas emissions.

[Analysis on the target product from sewage sludge pyrolysis and experiments on using the char for enhancing plant cultivation].

Characteristics of sewage sludge pyrolysis under low temperatures were studied and the influences of reaction temperature and moisture content on products distribution and their properties were also investigated with a purpose to select a proper target product. After a dissective comparison, char produced from the pyrolysis process was chosen as the target product and then its effect on plant cultivation was checked by using it to plant garlic when blended into normal soil; also its heavy metals contents and their transfer to the garlic were investigated. The primary research results showed that with the moisture content reduced to a certain level, char production was above 40% of sewage sludge when the pyrolysis process took place under 550 degrees C; ash content of the char is around 60% - 65%, but it is rich with nitrogen, phosphorus and potassium contents. The heavy metal contents in the char meet up with the limitations for land use, and the garlic stems planted in the soil blended with the char grew much faster than those planted in normal soil with their averaged height being 3-4 cm higher; however the heavy metal contents in the fast-growing garlic stems were a little higher than that in the normal ones, which was not suitable for edible plants. The results obtained suggested that char produced from sewage sludge pyrolysis process could be a target product arranged for land use especially for non-edible plant cultivation.

Development of a melanoma-specific adenovirus.

Concerns regarding the hepatotoxicity of adenovirus for cancer gene therapy have led to attempts to engineer viruses for tissue-specific gene expression and tissue-specific replication. The Tyrex2 (a tandem murine melanocyte-specific enhancer) system was used to express luciferase, purine nucleoside phosphorylase (PNP), and the essential adenoviral gene E1A. In nonmelanoma cell lines, the CMV promoter/enhancer (CMV p/e) was 969 times stronger than the Tyrex2 construct, whereas in melanoma cells it was only 2.6 times stronger. An adenovirus with Tyrex2 regulating PNP (Ad2Tyr2-PNP) was tested for cytotoxicity. In melanoma cells, treatment with Ad2Tyr2-PNP plus the prodrug 6-methylpurine deoxyriboside (6-MPDR) resulted in 90% cytotoxicity by day 4. In non-melanoma cell lines, only the CMV p/e resulted in significant cytotoxicity. We compared the intrinsic E1A promoter/enhancer (E1A p/e) system with the melanoma-specific constructs and found that the Tyrex2 system achieved higher levels of luciferase than the E1A p/e in all melanoma lines tested. In non-melanoma cell lines, the E1A p/e is 12.4 times stronger than the Tyrex2 construct. Tyrex2 was then used to regulate adenoviral E1A expression to construct a melanoma-specific replicating adenovirus. We were unable to achieve selective replication. As E1A is a known transactivator of the adenovirus major late promoter (MLP), we studied the ability of the MLP to express a transgene in the context of tissue-selective E1A expression. We were able to demonstrate high levels of luciferase activity with this construct; however, selectivity was lost. Melanoma-specific adenovirus expression was achieved with the Tyrex2 construct, and this led to melanoma-specific cytotoxicity by the potent PNP suicide gene. Selective melanoma-specific replication was not successful. The MLP may be a useful promoter in the context of a tissue-specific replicating adenovirus.