Fabrication of Two-Dimensional Homo-Bimetallic Porphyrin Framework Thin Films for Optimizing Nonlinear Optical Limiting.

Developing efficient metal-organic framework (MOF) optical devices with tunable third-order nonlinear optical (NLO) properties is an important challenge for scientific research and practical application. Herein, 2D monometallic and hetero/homo-bimetallic porphyrin MOF thin films (ZnTCPP(M) M = H2, Fe, Zn) were fabricated using the liquid-phase epitaxial (LPE) layer-by-layer (LBL) method to investigate the metal substitution dependent third-order NLO behavior. The prepared homo-bimetallic ZnTCPP(Zn) thin film exhibited enhanced third-order NLO performance with a higher third-order nonlinear susceptibility of ∼4.21 × 10-7 esu compared to monometallic and hetero-bimetallic counterparts. Additionally, theoretical calculations were performed to complement the experimental findings and revealed that the enhanced NLO effect of the ZnTCPP(Zn) thin film is mainly attributed to the enhanced local excitation. These findings not only provide a comprehensive understanding of the relationship between metal types and the NLO behavior of porphyrin MOF thin films but also offer valuable insights into the design and optimization of NLO devices.

Fluoroether Double-Chain Phosphate Surfactants: An Exploration of Alternatives to Fluorotelomer Surfactants.

While legacy fluorosurfactants have already been categorized as persistent organic pollutants, there appeared to be many strategies to develop alternatives. In this work, fluoroether double-chain phosphate surfactants (C72 diPAP-Na and C72 diPAP-NH4) were designed and synthesized with the initial intention of exploring the creation of new fluorosurfactants containing oxygen heteroatoms in the fluorocarbon chain segments to provide an alternative to the legacy long-chain fluorosurfactants. Furthermore, it was expected that they would even exceed the existing 6:2 fluorotelomer surfactants (6:2 diPAP-Na and 6:2 diPAP-NH4). Compared with characterizations of surface activity, foam performance, and wettability, the results showed that each of them has its own distinctive performance. Although the C72 series as new fluoroether surfactants cannot fully replace the 6:2 series of fluorosurfactants in terms of performance, there is a possibility of substitution in some aspects, which is of positive significance for further exploration to improve alternatives to legacy fluorosurfactants.

Synthesis, Surface Activity, and Foamability of Two Short-Chain Fluorinated Sulfonate Surfactants with Ether Bonds.

Fluorinated surfactants are widely used in many fields because of their excellent surface active properties, but their high stability has caused many environmental problems. With the ban and restriction of classical long-chain fluorinated surfactants such as perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) worldwide, the development and replacement of their alternatives is now a major challenge. How to reduce environmental persistence, bioaccumulation, and biotoxicity while maintaining high surface activity has become an important issue in the development of fluorinated surfactants. Using short-chain fluorinated surfactants is one of the important solutions to resolve the pollution of organic fluorinated compounds. In this article, we synthesized two short-chain fluorinated surfactants with ether bonds. One of them 6:2 FTESNa (2) used the perfluoroalkyl chain (n-C6F13-) and the other C72 FEESNa (4) used the fluoroether segment with six fluorinated carbons and two oxygens (CF3OCF(CF3)CF2OCF(CF3)). The surface activity, foam performance, and wettability of the two molecules were measured. The surface tensions at critical micelle concentration (γcmc) and the critical micelle concentration (cmc) of 2 and 4 were 17.6 mN/m (2.2 g/L) and 20.2 mN/m (4.6 g/L), respectively. Both of them were significantly superior to the surface activity of 6:2 FTSNa (7) which is one of the current alternatives for PFOS. Additionally, the foamability and foam stability of both 2 and 4 were better than that of 7. In the aspect of wettability on PTFE, that of 4 was greater than those of 2 and 7. In summary, this work provided a new choice for alternatives of PFOS and PFOA.

Deoxygenation of ClSO2CF2COOMe with Triphenylphosphine for the Metal-Free Direct Electrophilic Difluoroalkylthiolation of Various Heterocycles.

A direct electrophilic difluoroalkylthiolation reaction of indole derivatives and other electron-rich heterocycles using methyl 2,2-difluoro-2-(chlorsulfonyl)acetate (ClSO2CF2COOMe) derived from Chen's reagent (FSO2CF2COOMe) is described. The ester group in the product can be further utilized in subsequent versatile transformations. The reactions provide good yields of the corresponding difluoroalkylthiolation products and exhibit high functional group compatibility. It is expected to serve as an alternative and practical protocol for difluoroalkylthiolation of various heterocycles.

TFA-Promoted Intermolecular Friedel-Crafts Alkylation of Arenes with 2,2,2-Trifluoroethylaryl Sulfoxides.

The classical Pummerer rearrangement of 2,2,2-trifluoroethylaryl sulfoxide with trifluoracetic anhydride (TFAA) affords the S,O-acetal efficiently. In the presence of trifluoracetic acid (TFA) as the co-solvent, the S,O-acetal can regenerate reactive thionium intermediate of Pummerer rearrangement. When employing arenes as nucleophiles, this strategy produces corresponding 1-thiyl-2,2,2-trifluoroethyl arenes with excellent yields under metal-free conditions.

Porphyriynes: 18-π-Conjugated Macrocycles Incorporating a Triple Bond.

Tetraphenylporphyriyne (Pyne1), a novel porphyrin analogue with a C≡C bond incorporated into an 18-π-conjugated system, has been created via cleavage of the N-confused pyrrolic ring in Ag(III) N-confused tetraphenylporphyrin. The structure of Pyne1 was confirmed by X-ray crystallography and 1H NMR, IR, and UV-vis spectroscopy. The mechanism of cleavage of the N-confused pyrrolic ring was investigated by theoretical calculations. The successful synthesis of other Pynes indicated the generality of this protocol.

The promoter hypermethylation of SULT2B1 accelerates esophagus tumorigenesis via downregulated PER1.

BACKGROUND: Esophageal cancer is currently the eighth most common tumor in the world and a leading cause of cancer death. SULT2B1 plays crucial roles in tumorigenesis. The purpose of this study is to explore the role of SULT2B1 in esophageal squamous cell carcinoma (ESCC). METHODS: The expression of SULT2B1 and its clinicopathological characteristics were evaluated in ESCC cohorts. Bisulfite genomic sequencing and methylation specific PCR were used to detect the promoter hypermethylation of the SULT2B1 gene. The effects of SULT2B1 on the biological characters of ESCC cells were identified on functional assays. Subcutaneous xenograft models revealed the role of SULT2B1 in vivo with tumor growth. RNA-Seq analysis and qRT-PCR were performed to recognize the targeted effect of SULT2B1 on PER1. RESULTS: SULT2B1 was not expressed or at a low level in most patients with ESCC or in ESCC cell lines, and this was accompanied by poor clinical prognosis. Furthermore, the downregulation of SULT2B1 occurred in promoter hypermethylation. According to the functional results, overexpression of SULT2B1 could inhibit tumoral proliferation in vitro and retard tumor growth in vivo, whereas SULT2B1 knockdown could accelerate ESCC progression. Mechanistically, SULT2B1 targeted PER1 at the mRNA level during post-transcriptional regulation. Finally, PER1 was verified as a suppressor and poor-prognosis factor in ESCC. CONCLUSIONS: SULT2B1 loss is a consequence owing to its ability to promote hypermethylation. In addition, it serves as a suppressor and poor-prognosis factor because of the post-transcriptional regulation of PER1 in ESCC.

Copper-catalyzed three-component reaction of arylhydrazine hydrochloride, DABSO, and NFSI for the synthesis of arenesulfonyl fluorides.

This paper reports a convenient copper-catalyzed three-component conversion of arylhydrazine hydrochlorides to arenesulfonyl fluorides in good yields under mild conditions, using 1,4-diazabicyclo [2.2.2]octane bis(sulfur dioxide) (DABSO) as a sulfonyl source and N-fluorobenzenesulfonimide (NFSI) as a fluorine source based on a radical sulfur dioxide insertion and fluorination strategy. Notably, arylhydrazine hydrochloride is used as a safe precursor of aryl radicals.

Rapid Access to N-Protected Sulfonimidoyl Fluorides: Divergent Synthesis of Sulfonamides and Sulfonimidamides.

Herein we report a practical and efficient copper-catalyzed approach for the conversion of various arenediazonium salts to the corresponding N-protected sulfonimidoyl fluorides. This operationally simple protocol tolerates a wide range of functional groups and can be applied to the late-stage modification of complex bioactive molecules. Furthermore, pharmaceutically important primary sulfonamides and sulfonimidamides derived from these valuable N-protected sulfonimidoyl fluoride units were prepared in minimal synthetic steps.

Bronchoscopy for diagnosis of COVID-19 with respiratory failure: A case report.

BACKGROUND: Although the imaging features of coronavirus disease 2019 (COVID-19) are starting to be well determined, what actually occurs within the bronchi is poorly known. Here, we report the processes and findings of bronchoscopy in a patient with COVID-19 accompanied by respiratory failure. CASE SUMMARY: A 65-year-old male patient was admitted to the Hainan General Hospital on February 3, 2020 for fever and shortness of breath for 13 d that worsened for the last 2 d. The severe acute respiratory syndrome coronavirus 2 nucleic acid test was positive. Routine blood examination on February 28 showed a white blood cell count of 11.02 × 109/L, 86.9% of neutrophils, 6.4% of lymphocytes, absolute lymphocyte count of 0.71 × 109/L, procalcitonin of 2.260 ng/mL, and C-reactive protein of 142.61 mg/L. Oxygen saturation was 46% at baseline and turned to 94% after ventilation. The patient underwent video bronchoscopy. The tracheal cartilage ring was clear, and no deformity was found in the lumen. The trachea and bilateral bronchi were patent, while the mucosa was with slight hyperemia; no neoplasm or ulcer was found. Moderate amounts of white gelatinous secretions were found in the dorsal segment of the left inferior lobe, and the bronchial lumen was patent after sputum aspiration. The right inferior lobe was found with hyperemia and mucosal erosion, with white gelatinous secretion attachment. The patient's condition did not improve after the application of therapeutic bronchoscopy. CONCLUSION: For patients with COVID-19 and respiratory failure, bronchoscopy can be performed under mechanical ventilation to clarify the airway conditions. Protection should be worn during the process. Considering the risk of infection, it is not necessary to perform bronchoscopy in the mild to moderate COVID-19 patients.

Laminin γ2-mediating T cell exclusion attenuates response to anti-PD-1 therapy.

PD-1/PD-L1 blockade therapies provide notable clinical benefits for patients with advanced cancers, but the factors influencing the effectiveness of the treatment remain incompletely cataloged. Here, the up-regulation of laminin γ2 (Ln-γ2) predicted the attenuated efficacy of anti-PD-1 drugs and was associated with unfavorable outcomes in patients with lung cancer or esophageal cancer. Furthermore, Ln-γ2 was transcriptionally activated by transforming growth factor-ß1 (TGF-ß1) secreted from cancer-associated fibroblasts via JNK/AP1 signaling, which blocked T cell infiltration into the tumor nests by altering the expression of T cell receptors. Coadministration of the TGF-ß receptor inhibitor galunisertib and chemotherapy drugs provoked vigorous antitumor activity of anti-PD-1 therapy in mouse tumor models. Therefore, Ln-γ2 may represent a useful biomarker to optimize clinical decisions and predict the response of cancer patients to treatment with anti-PD-1 drugs.

DNase1L3 suppresses hepatocellular carcinoma growth via inhibiting complement autocrine effect.

Hepatocellular carcinoma (HCC) is one of the most aggressive types of cancer and currently lacks effective treatment strategies. The present study revealed that deoxyribonuclease 1 like 3 (DNase1L3) expression levels were significantly downregulated in numerous types of gastrointestinal cancer, and especially in HCC. Tissue microarrays were further used to illustrate that DNase1L3 expression levels were frequently downregulated in HCC tissues compared with normal liver tissues. In addition, DNase1L3 expression levels were identified to be significantly associated with tumor size (p=0.0028), tumor thrombus formation (p<0.01), and a poorer overall survival (p=0.005) and disease-free survival (p=0.006) of HCC. Gene Ontology functional term enrichment analysis of biological processes discovered that DNase1L3 was significantly associated with complement activation. Further studies demonstrated that the ectopic expression of DNase1L3 suppressed cell growth and inhibited the PI3K/AKT signaling pathway activation following C3a receptor agonist treatment. In conclusion, the findings of the present study suggested, for the first time, that DNase1L3 may serve as a biomarker for the prognosis of patients with HCC, and may suppress HCC growth via inhibiting the PI3K/AKT signaling pathway.

Tumor Fibroblast-Derived FGF2 Regulates Expression of SPRY1 in Esophageal Tumor-Infiltrating T Cells and Plays a Role in T-cell Exhaustion.

T-cell exhaustion was initially identified in chronic infection in mice and was subsequently described in humans with cancer. Although the distinct signature of exhausted T (TEX) cells in cancer has been well investigated, the molecular mechanism of T-cell exhaustion in cancer is not fully understood. Using single-cell RNA sequencing, we report here that TEX cells in esophageal cancer are more heterogeneous than previously clarified. Sprouty RTK signaling antagonist 1 (SPRY1) was notably enriched in two subsets of exhausted CD8+ T cells. When overexpressed, SPRY1 impaired T-cell activation by interacting with CBL, a negative regulator of ZAP-70 tyrosine phosphorylation. Data from the Tumor Immune Estimation Resource revealed a strong correlation between FGF2 and SPRY1 expression in esophageal cancer. High expression of FGF2 was evident in fibroblasts from esophageal cancer tissue and correlated with poor overall survival. In vitro administration of FGF2 significantly upregulated expression of SPRY1 in CD8+ T cells and attenuated T-cell receptor-triggered CD8+ T-cell activation. A mouse tumor model confirmed that overexpression of FGF2 in fibroblasts significantly upregulated SPRY1 expression in TEX cells, impaired T-cell cytotoxic activity, and promoted tumor growth. Thus, these findings identify FGF2 as an important regulator of SPRY1 expression involved in establishing the dysfunctional state of CD8+ T cells in esophageal cancer. SIGNIFICANCE: These findings reveal FGF2 as an important regulator of SPRY1 expression involved in establishing the dysfunctional state of CD8+ T cells and suggest that inhibition of FGF2 has potential clinical value in ESCC. GRAPHICAL ABSTRACT: http://cancerres.aacrjournals.org/content/canres/80/24/5583/F1.large.jpg.

A Series of Deoxyfluorination Reagents Featuring OCF2 Functional Groups.

Research on perfluoroalkyl ether carboxylic acids (PFECAs) as alternatives for perfluoroalkyl substances continues with the goal of protecting the environment. However, very little is known about the utilization of decomposition products of PFECAs. We report herein a new series of deoxyfluorination reagents featuring OCF2 functional groups derived from certain PFECAs. Alkyl fluorides were generated from various alcohols in ≤97% yield by these novel reagents. The mechanistic experiment verified in situ generation of carbonic difluoride (COF2).

Cobalt-Catalyzed Radical Hydrotrifluoroethylation of Styrenes with Trifluoroethyl Iodide.

The cobalt-catalyzed radical trifluoroethylation of styrenes with CF3CH2I under mild conditions is described. By controlling the reaction conditions, we realized both radical trifluoroethylation self-coupling and hydrotrifluoroethylation of styrenes. The standard conditions are also suitable for other fluoroalkyl halides, generating the corresponding hydrofluoroalkylation products in good yields.

Arenesulfonyl Fluoride Synthesis via Copper-Catalyzed Fluorosulfonylation of Arenediazonium Salts.

We report herein a general and practical copper-catalyzed fluorosulfonylation reaction of a wide range of abundant arenediazonium salts to smoothly prepare various arenesulfonyl fluorides using the 1,4-diazabicyclo[2.2.2]octane-bis(sulfur dioxide) adduct as a convenient sulfonyl source in combination with KHF2 as an ideal fluorine source and without the need for additional oxidants. Interestingly, the electronic character of the arene ring in the starting arenediazonium salts has a significant impact on the reaction mechanistic pathway.

Insights into Charge Transfer at an Atomically Precise Nanocluster/Semiconductor Interface.

The deposition of an atomically precise nanocluster, for example, Ag44 (SR)30 , onto a large-band-gap semiconductor such as TiO2 allows a clear interface to be obtained to study charge transfer at the interface. Changing the light source from visible light to simulated sunlight led to a three orders of magnitude enhancement in the photocatalytic H2 generation, with the H2 production rate reaching 7.4 mmol h-1 gcatalyst -1 . This is five times higher than that of TiO2 modified with Ag nanoparticles and even comparable to that of TiO2 modified with Pt nanoparticles under similar conditions. Energy band alignment and transient absorption spectroscopy reveal that the role of the metal clusters is different from that of both organometallic complexes and plasmonic nanoparticles: A type II heterojunction charge-transfer route is achieved under UV/Vis irradiation, with the cluster serving as a small-band-gap semiconductor. This results in the clusters acting as co-catalysts rather than merely photosensitizers.

In situ synthesis of polypyrrole on graphite felt as bio-anode to enhance the start-up performance of microbial fuel cells.

This study introduces an effective method to deposit polypyrrole (PPy) on graphite felt (GF) as anode to improve the start-up performance of microbial fuel cells (MFCs). The results of scanning electron microscope (SEM) and electrochemical testing reveal that polypyrrole is able to improve the electrical conductivity and surface roughness, which is beneficial to the microorganism attachment and growth. It shows that microorganisms grow faster on polypyrrole-modified anode than on unmodified anode. It takes ca. 5 days for polypyrrole-modified anode to reach a reproducible voltage platform, while it takes 11 days for unmodified anode. Moreover, the maximum power density of microbial fuel cells with polypyrrole-modified anode was 919 mW m-2, which were 2.3 times of that with unmodified anode. This research revealed that polypyrrole modification can improve the start-up performance of microbial fuel cells. It is considered as a feasible, economical and sustainable anode.

Facile Synthesis of a Porous ZnO Nanorod Array with Enhanced Photocatalysis for Photoelectrochemical Water Splitting Application.

Highly efficient and effective porous ZnO nanorod arrays were fabricated by annealing ZnO nanorod arrays grown on a substrate using a simple hydrothermal method. The annealing had a positive effect on the nanorod morphology, structure and optical properties. The porosity was closely related to the annealing temperature. After heating at 450 °C, pores appeared on the nanorods. It was demonstrated that the porosity could be exploited to improve the visible light absorption of ZnO and reduce the bandgap from 3.11 eV to 2.99 eV. A combination of improved charge separation and transport of the heat-treated ZnO thus led to an increase in the photoelectrochemical properties. At an irradiation intensity of 100 mW/cm-2, the photocurrent density of the porous nanorod array was approximately 1.3 mA cm-2 at 1.2 V versus Ag/AgCl, which was five times higher than that of the ZnO nanorods. These results revealed the synthesis of promising porous ZnO nanorods for photoelectrochemical applications.

Multi-functional photocatalytic fuel cell for simultaneous removal of organic pollutant and chromium (VI) accompanied with electricity production.

It is of significant importance to realize the efficient wastewater treatment and energy recovery. This study presents a multi-functional photocatalytic fuel cell (PFC), which could reductively treat Cr(VI) contaminant and oxidatively degrade organic pollutant simultaneously along with electricity production in an economical strategy. TiO2 nanotube arrays (TNA) and graphite were used as photoanode and cathode in two separated chambers, respectively. The optimized PFC with open circuit voltage of 1.06 V, maximum power density of 1 W m-2 and short circuit current density of 3.7 A m-2 can be obtained by increasing Cr(VI) concentration and decreasing pH values in catholyte. Under optimized PFC conditions, more photogenerated electrons will be transferred to cathode for Cr(VI) reduction, and accelerating electron-hole separation in the photoanode, then facilitating the oxidation of organic pollutants on anode. More than 96.8% removal efficiency for 6.8 mM Cr(VI) with a cathodic efficiency of 95.1% can be achieved within 6 h. Methylene blue (MB), an organic model pollutant, is totally decolorized on photoanode, which is significantly improved compare to photocatalysis (61.5% removal efficiency). The stable cycle operation of this economical PFC has obtained owing to the stable and low cost materials of both photoanode and cathode. This work may provide an efficient and economical method to simultaneously remove two types of pollutants with electricity harvested in one cell.