A Strong-Acid-Resistant [Th6 ] Cluster-Based Framework for Effectively and Size-Selectively Catalyzing Reductive Amination of Aldehydes with N,N-Dimethylformamide.

Utilization of N,N-dimethylformamide (DMF) as an amine source and reductant for synthesizing tertiary amines is a promising way to replace the substrates formaldehyde and dimethylamine, and it is desirable to seek porous acid-resistant catalysts for heterogeneous catalysis of this reaction. Herein, a robust metal-organic framework (MOF) {[Th6 O4 (OH)4 (H2 O)6 (BCP)3 ]⋅10 DMF}n (1) containing stacked nanocages with a diameter of 1.55 nm was constructed. Compound 1 can maintain its single-crystal structure even kept in air at 400 °C for 3 h, and in DMF or water at 200 °C for 7 days. Density functional theory (DFT) calculations suggested that the high interaction energy between the [Th6 O4 (OH)4 (H2 O)6 ]12+ clusters and ligands was responsible for the excellent stability of 1. Catalytic investigations revealed that 1 can effectively and size-selectively catalyze the reductive amination of aldehydes with DMF, and it can be reused at least five times without obvious loss in catalytic activity.

Selectively Regulating Lewis Acid-Base Sites in Metal-Organic Frameworks for Achieving Turn-On/Off of the Catalytic Activity in Different CO2 Reactions.

Regulating Lewis acid-base sites in catalysts to investigate their influence in the chemical fixation of CO2 is significant but challenging. A metal-organic framework (MOF) with open metal Co sites, {(NH2 Me2 )[Co3 (µ3 -OH)(BTB)2 (H2 O)]⋅9 H2 O⋅5 DMF}n (1), was obtained and the results of the catalytic investigation show that 1 can catalyze cycloaddition of CO2 and aziridines to give 99 % yield. The efficiency of the cyclization of CO2 with propargyl amines is only 32 %. To improve the catalytic ability of 1, ligand XN with Lewis base sites was introduced into 1 and coordinated with the open Co sites, resulting in a decrease of the Lewis acid sites and an increase in the Lewis base sites in a related MOF 2 ({(NH2 Me2 )[Co3 (µ3 -OH)(NHMe2 )(BTB)2 (XN)]⋅8 H2 O⋅4 DMF}n ). Selective regulation of the type of active centers causes the yield of oxazolidinones to be enhanced by about 2.4 times, suggesting that this strategy can turn on/off the catalytic activity for different reactions. The catalytic results from 2 treated with acid solution support this conclusion. This work illuminates a MOF-construction strategy that produces efficient catalysts for CO2 conversion.

Efficient Cycloaddition of CO2 and Aziridines Activated by a Quadruple-Interpenetrated Indium-Organic Framework as a Recyclable Catalyst.

On the basis of the global warming effect, it is of great significance to convert CO2 into the high value-added products oxazolidinones, but investigations on main-group-based metal-organic frameworks (MOFs) as heterogeneous catalysts still have not been reported so far. In this work, a quadruple-interpenetrated porous indium-based MOF, {[NH2(CH3)2][In(CPT)2]·3CH3CN·3DMA}n (1), is constructed from the organic ligand 3,5-bis(4'-carboxyphenyl)-1,2,4-triazole through solvothermal reactions, and N2 adsorption proves that the framework has a high Brunauer-Emmett-Teller surface areas with 2024 m2/g. The catalytic research on CO2 conversion reveals that compound 1 has high reactivity for the cycloaddition of CO2 with aziridines, and the product 3-ethyl-5-phenyloxazolidin-2-one can be obtained with a yield of 99% under mild conditions. In addition, 1 exhibits excellent activity for different kinds of substrates and can be reused at least five cycles without any significant deactivation, suggesting that 1 is a potential candidate for the chemical conversion of CO2 and aziridines. Mechanistic explorations indicate that the high efficiency of 1 is attributed to the indium center in the framework as a Lewis acid site, and the large porosity can enrich substrates. Importantly, 1 behaved as the first main-group MOF-based catalyst in the reported coupling reaction of CO2 with aziridines.

Hypoxia-induced MFAP5 Promotes Tumor Migration and Invasion via AKT Pathway in Head and Neck Squamous Cell Carcinoma.

Objective: Microfibrillar-associated protein 5 (MFAP5) is highly expressed in many types of cancers. Our previous study has observed that overexpression of MFAP5 was correlated with lymph nodes metastasis and poor prognosis in head and neck squamous cell carcinoma (HNSCC), but the underlying mechanism is poorly understood. Materials and methods: The MFAP5 expression is detected under hypoxia condition. HNSCC cell lines are transfected with MFAP5-expressing lentivirus vector to establish stable overexpression model. Wound-healing, migration and invasion assay are used to determine the effect of MFAP5 on HNSCC and metastasis-related proteins are examined by Western blot. In vivo lung metastasis assays are conducted by the tail vein injection. In addition, immunohistochemistry is applied to analyze the correlation of MFAP5, hypoxia-induced factor-1 α (HIF-1α), and vimentin in 84 HNSCC patients' tissue samples. Results: Firstly, MFAP5 expression can be markedly induced under hypoxia condition in HNSCC cell lines. Cell lines with MFAP5 overexpression has a significant higher ability of migration and invasion. In addition, in vivo assay observes that overexpression of MFAP5 can promote tumor lung metastasis. Furthermore, MFAP5 facilitates this process by activating epithelial-mesenchymal transition (EMT) program via AKT pathway in HNSCC cell lines. The pro-metastatic effect of MFAP5 can be reversed by MK2206, an AKT phosphorylation inhibitor. Lastly, the positive correlation among HIF-1α, MFAP5 and vimentin from tissue samples and TCGA dataset are also observed in HNSCC. Conclusion: Our study demonstrates MFAP5 plays a critical role in hypoxia-induced EMT program via AKT pathway in HNSCC, which would be a very promising therapeutic target.

Crystal structures of hybrid completely reduced phosphomolybdates and catalytic performance applied as molecular catalysts for the reduction of chromium(VI).

The exploration of highly efficient and low-cost catalysts for the treatment of hexavalent chromium CrVI in environmental remediation is currently one of the most challenging topics. Here, three phosphomolybdate hybrid compounds have been successfully isolated by the hydrothermal method and been applied as supramolecular catalysts for the reduction of CrVI. Single-crystal X-ray diffraction revealed their formulae as (H2bpp)2[Fe(H2O)][Sr(H2O)4]2{Fe[Mo6O12(OH)3(H2PO4)(HPO4)(PO4)2]2}·5H2O (1), (H2bpp)2[Na(H2O)(OC2H5)][Fe(H2O)2][Ca(H2O)2]2{Fe[Mo6O12(OH)3(H2PO4)(HPO4)(PO4)2]2}·4H2O (2) and (H2bpe)3{Fe[Mo6O12(OH)3(HPO4)3(H2PO4)]2}·8H2O (3) [bpp is 1,3-bis(pyridin-4-yl)propane (C13H14N2) and bpe is trans-1,2-bis(pyridin-4-yl)ethylene (C12H10N2)]. The three hybrids consist of supramolecular networks built up by noncovalent interactions between {Fe[P4Mo6VO31]2}22- polyanions and protonated organic cations. This kind of hybrid polyoxometalate could be applied as heterogeneous molecular catalysts for the reduction of CrVI. It was found that the organic moiety plays a vital role in influencing the catalytic activity of the polyanions. Organic bpp-containing hybrids 1 and 2 are highly active in the catalytic reduction of heavy metal CrVI ions using HCOOH as reductant, while bpe-containing hybrid 3 is inactive to this reaction. This work is significant for the design of new catalysts, as well as the exploration of reaction mechanisms at a molecular level.

Novel fully reduced phosphomolybdates for highly efficient removal of inorganic hexavalent chromium and the organic dye methylene blue.

New Na-bridged phosphomolybdates (H2en)12[{Na0.8K0.2(H2O)}2{Na[Mo6O12(OH)3(HPO4)2(PO4)2]2}2]·7H2O (1), (H2bpp)2[{Sr2(H2O)4}{Na3(H2O)10}{Na[Mo6O12(OH)3(HPO4)3(PO4)]2}]·2H2O (2), and (H2bpp)6 [{Ca2(H2O)4}{Na2(H2O)4}{Na[Mo6O12(OH)3(HPO4)3(PO4)]2}2] (3) (en = ethylenediamine, bpp = 1,3-bi(4-pyridyl)propane), were synthesized by a hydrothermal method and characterized. Single-crystal X-ray diffraction analysis revealed that the three hybrids were composed of fully reduced 'hourglass-shaped' {Na[PV4MoV6X31]2}n- (X = O/OH) clusters and N-containing organic cations. The electrochemical measurements showed that this kind of highly negatively charged metal-oxygen cluster in crystals 1-3 has the ideal behaviour of reversible electron gain or loss, which is related to the function of electron transfer catalysts in oxidation reduction reactions. Experimental results indicated that they were active as heterogeneous crystal catalysts in the catalytic reduction of inorganic hexavalent chromium with formic acid as reductant, and also had a significant catalytic effect on the photodegradation of the organic dye methylene blue under mild conditions.

Synthesis of Hybrid Phosphomolybdates and Application as Highly Stable and Effective Catalyst for the Reduction of Cr(VI).

Three hybrid phosphomolybdates were successfully synthesized by hydrothermal method and characterized by a series of physicochemical analysis techniques. X-ray single-crystal structural analysis revealed that three compounds with the reductive polyanionic clusters (MoV) were wrapped by protonated organic component bpp cations (bpp = 1,3-bi(4-pyridyl)propane) through the complex supramolecular hydrogen bonding network. They also have similar molecular formulas: (H2bpp)3[PbM(H2O)2]2H6{M[Mo6O12(OH)3(HPO4)3(PO4)]2}2· nH2O (M = Fe in 1, Zn in 2, n = 4; or M = Mn in 3, n = 6). The oxidation states of all Mo centers in these polyanions are in the form of +5, presenting clusters with the higher negative charge. The feature showed that they were easy to be modified by transition metal and organic moieties, so as to form a high-dimensional structure and produce functional materials with specific properties. Comparison of catalytic ability of three crystals to reduce CrVI using formic acid as reductant, found that crystal 1 was effectively active to this redox reaction. The conversion of CrVI can reach 99% after 120 min of heating in 55 °C water bath, and the conversion of above 95% can still be achieved after 5 recycles of applications.

Prognostic impact of perineural invasion in early stage oral tongue squamous cell carcinoma: Results from a prospective randomized trial.

BACKGROUND: Although perineural invasion (PNI) has been recognized as a poor prognostic factor for oral cancer, few studies have focused on tongue squamous cell carcinoma (TSCC). Using a prospective randomized trial, this study investigated the role of PNI in the regional control and survival of the patients with cT1-2N0 TSCC, and clarified the benefit of neck management based on PNI status. METHODS: PNI status was reviewed under H&E staining in tumors of 221 patients with cT1-2N0 TSCC, who were randomly assigned into elective neck dissection (END) group (n = 111) and observation group (n = 110). Oncologic and survival outcomes were analyzed by multivariate regression and Kaplan-Meier analyses. RESULTS: PNI was identified in 34 patients and multivariate analyses revealed that PNI remained an independent predictor for cervical lymph node metastasis (CLNM), local relapse, neck relapse and disease-specific survival (DSS) after controlling for T stage and pathologic differentiation. END could not improve the benefit for patients. Stratified analysis revealed that END also could not improve neck control or DSS among patients with PNI. CONCLUSIONS: This study demonstrated that PNI was an invaluable pathological parameter to independently predict cervical metastasis, local relapse, neck relapse and poor survival outcomes, but END could not improve benefits compared to observation for the PNI-positive patients.

Oral peripheral ameloblastoma: A retrospective series study of 25 cases

BACKGROUND: Peripheral ameloblastoma (PA) is a rare and unusual variant of odontogenic tumor, which was described only in isolated case reports in literature. The objective of this study was to investigate the clinical profile, treatment and outcome of PA in a consecutive case series. MATERIAL AND METHODS: A total of 25 patients with histologically confirmed PA from 2001 to 2015 were retrospectively reviewed in our institution. RESULTS: Of the 25 patients, 22 males and 3 females were identified (male: female = 7.3:1). The average age was 48.3 years (range 11-81 years) with lingual or palate gingival region being the most common site (76%). The course of disease was less than 6 months in 92.0% (23/25) of all patients (mean, 3.3 months; range, 1-12 months). All patients underwent complete surgical removal of the lesions, and one lesion recurrence occurred during the follow-up period. CONCLUSIONS: The clinical profile and outcome of PA from Eastern China were elucidated in this retrospective analysis based on a case series. Our experience may provide some insights into the differential diagnosis and clinical management of PA. The first choice of treatment is surgical excision, which can result in a good prognosis

MFAP5 and TNNC1: Potential markers for predicting occult cervical lymphatic metastasis and prognosis in early stage tongue cancer.

The purpose of this study is to identify candidate genes that could predict prognosis of early-stage tongue squamous cell carcinoma (TSCC) and its occult cervical lymphatic metastasis by large-scale gene expression profiling. Tumor tissue and matched normal mucosa samples were collected from patients with TSCC and analyzed with Affymetrix HTA2.0 high-density oligonucleotide array. Differentially expressed genes in TSCC with cervical lymph node metastasis (CLNM) were further analyzed with Gene Ontology and Kyoto Encyclopedia of Genes and Genomes for their functions and related pathways. A total of 107 differentially expressed genes (p < 0.05) were identified by microarray in TSCC samples with CLNM (n = 6) compared to those without CLNM (n = 6). Genes involved in the cell-matrix adherens junction and migration function including MFAP5, TNNC1, MGP, FBFBP1 and FBXO32 were selected and validated by RT-PCR in TSCC samples (n = 32). Of the five genes, MFAP5 and TNCC1 expressions were further validated by immohistochemistry (n = 61). The significant positive correlation between MFAP5 and TNNC1 expression (p<0.001) was observed. Notably, over-expression of MFAP5 and TNNC1 were correlated with CLNM, metastasis relapse-free survival and overall survival. Our findings indicated that MFAP5 and TNNC1 may be potential markers for predicting occult cervical lymphatic metastasis and prognosis of oral tongue carcinoma.