Photocatalyzed C3-H Nitrosylation of Imidazo[1,2-a]pyridine under Continuous Flow and External Photocatalyst-, Oxidant-, and Additive-Free Conditions.

This study reports a protocol for the highly regioselective photocatalyzed C-H nitrosylation of imidazo[1,2-a]pyridine scaffolds at the C3 position under a combination of visible-light irradiation and continuous flow without any external photocatalyst. This protocol involves mild and safe conditions and shows good tolerance to air and water along with excellent functional group compatibility and site selectivity, generating various 3-nitrosoimidazo[1,2-a]pyridines in excellent yields under photocatalyst-, oxidant-, and additive-free conditions.Notably, the proposed nitrosylation reaction, which introduces the chromophore NO into imidazo[1,2-a]pyridine scaffolds, occurs efficiently under visible-light irradiation without any additional photocatalyst owing to the intense light-absorption characteristics of the nitrosylation products. This study could guide future studies on the development of green organic-synthesis strategies with a wide variety of potential applications.

Multi-F-Structured MOF Materials Enhance Nanogenerator Output Performance for Corrosion Protection of Metallic Materials.

MOF (metal organic framework) materials have been used as functional materials in a number of fields due to their diverse spatial tunability, which produces rich porous structures with stable and continuous pores and a high specific surface area. A triboelectric nanogenerator can convert trace mechanical energy into electrical energy, and the application of MOF materials to triboelectric nanogenerators has been intensively studied. In this work, we report on two MOFs with similar spatial structures, and the modulation of the end microstructures was achieved using the difference in F content. The output performance of friction power generation increases with the increase in F content, and the obtained polyacidic ligand materials can be used to construct self-powered corrosion protection systems, which can effectively protect metallic materials from corrosion.

A novel AIE-active imidazolium macrocyclic ratiometric fluorescence sensor for pyrophosphate anion.

An imidazolium bridged macrocyclophane was synthesized as a ratiometric fluorescence sensor with aggregation-induced emission (AIE) characteristic to detect pyrophosphate anion with high selectivity among various anions. In the presence of zinc ion, macrocyclophane can form aggregates through complexation with pyrophosphate anion and emit ratiometric fluorescence, resulting from an enhancement in its aggregate-state emission and a reduction in its monomer emission. This AIE-active macrocycle showed great potential as a ratiometric fluorescence receptor.

Fluorescent porous organic polymers for detection and adsorption of nitroaromatic compounds.

A fluorescent porous organic polymer (FPOP) with strong fluorescence and tunable emission colors, was synthesized through a simple cost-effective method via Scholl coupling reaction. Experiments proved the stability and excellent detection and adsorption ability, and microporous nature of the material. Luminescence of FPOP was quenched when addition of nitroaromatic compounds. The properties along with large-scale and low-cost preparation make these FPOP potential candidates for fluorescence detection of nitroaromatic compounds. Additionally, FPOP shows higher adsorption capacity and rate than other reported adsorbents, and has the possibility of being an effective adsorbent for industrial usage. Moreover, a fluorescent test paper was further developed and is found to be sensitive to 10-8 M level, complete with a rapid response time and visual detection. This newly developed strategy may open up an avenue for exploring porous polymers, particularly those with a strong fluorescence, for the large-scale fabrication of FPOP for various advanced applications.

Identification of Hub Genes and MicroRNAs Associated With Idiopathic Pulmonary Arterial Hypertension by Integrated Bioinformatics Analyses.

OBJECTIVE: The aim of this study is the identification of hub genes associated with idiopathic pulmonary arterial hypertension (IPAH). MATERIALS AND METHODS: GSE15197 gene expression data was downloaded from the Gene Expression Omnibus (GEO) database. Differentially expressed genes (DEGs) were identified by screening IPAH patients and controls. The 5,000 genes with the greatest variances were analyzed using a weighted gene co-expression network analysis (WGCNA). Modules with the strongest correlation with IPAH were chosen, followed by a functional enrichment analysis. Protein-protein interaction (PPI) networks were constructed to identify hub gene candidates using calculated degrees. Real hub genes were found from the overlap of DEGs and candidate hub genes. microRNAs (miRNAs) targeting real hub genes were found by screening miRNet 2.0. The most important IPAH miRNAs were identified. RESULTS: There were 4,395 DEGs identified. WGCNA indicated that green and brown modules associated most strongly with IPAH. Functional enrichment analysis showed that green and brown module genes were mainly involved in protein digestion and absorption and proteoglycans in cancer, respectively. The top ten candidate hub genes in green and brown modules were identified, respectively. After overlapping with DEGs, 11 real hub genes were identified: EP300, MMP2, CDH2, CDK2, GNG10, ALB, SMC2, DHX15, CUL3, BTBD1, and LTN1. These genes were expressed with significant differences in IPAH versus controls, indicating a high diagnostic ability. The miRNA-gene network showed that hsa-mir-1-3p could associate with IPAH. CONCLUSION: EP300, MMP2, CDH2, CDK2, GNG10, ALB, SMC2, DHX15, CUL3, BTBD1, and LTN1 may play essential roles in IPAH. Predicted miRNA hsa-mir-1-3p could regulate gene expression in IPAH. Such hub genes may contribute to the pathology and progression in IPAH, providing potential diagnostic and therapeutic opportunities for IPAH patients.

The Cd phytoextraction potential of hyperaccumulator Sedum alfredii-oilseed rape intercropping system under different soil types and comprehensive benefits evaluation under field conditions.

Soil trace elements (TEs) contamination has become a worldwide problem in arable lands and poses great risk to human health via food chain. Intercropping of hyperaccumulator and cash crops is now proposed as a promising alternative phytoremediation technique to address the issue. However, the effect of intercropping in different soil types and field-scale benefits evaluation are rarely reported. A greenhouse pot experiment and a field trial were therefore designed to explore the effects of intercropping Sedum alfredii (hyperaccumulative population) and oilseed rape on Cd phytoextraction potential, Cd transport and crop production, as well as establishing a feasible assessment framework on the basis of benefits evaluation in contaminated soils. Compared with oilseed rape monoculture, intercropping with S. alfredii significantly and consistently increased biomass, seed yield and Cd accumulation in oilseed rape in five typical soil types. Accumulations of Cd varied with soil types, ranging from 22.8 to 4000 µg pot-1. Stepwise multiple linear regression analysis (SMLRA) showed Cd concentrations in plants were related to available phosphorus (AP), pH, soil organic matter (OM), available potassium (AK), silt and sand; R2 values varied from 0.834 to 0.994 (P < 0.05). A field trial also verified that intercropping could significantly enhance Cd phytoextraction. The highest index for comprehensive benefits evaluation was 0.61 observed in the S. alfredii and oilseed rape intercropping system. This system presented higher Cd phytoextraction potential and comprehensive benefits index whilst allowing ongoing agricultural activities in slightly and moderately Cd-contaminated soils. These results provide a possible technical approach for phytoremediation practice and give new insights into theoretical reference for development of Cd phytoextraction and benefits evaluation.

Responses of soil bacterial community and Cd phytoextraction to a Sedum alfredii-oilseed rape (Brassica napus L. and Brassica juncea L.) intercropping system.

Soil pollution with heavy metals has become a common problem in agricultural ecosystems and poses a threat to food safety and human health. Intercropping is now considered a promising alternative to address this issue. However, our understandings about the influences of intercropping systems on rhizosphere microbiota composition and their association with plant performance are still limited. In this study, rhizobox microcosm experiments were conducted to investigate the influence of cropping regimes (i.e. monoculture and intercropping) on the rhizosphere bacterial microbiota and their linkages with the phytoextraction of cadmium (Cd) by Zhongyouza 19 (Brassica napus L.), Xikou Huazi (Brassica juncea L.) and Sedum alfredii using 16S rRNA gene sequencing. Cadmium accumulation in shoots of B. napus and B. juncea grown under intercropping were enhanced by 370% and 27.8% respectively, as compared to monoculture. Soil compartmentation as a major determinant explained 57.6% of the rhizosphere bacterial microbiota variation, whereas plant species and cropping regime accounted for 26.4% of the variation. The overall abundance of the taxa was Proteobacteria, Acidobacteria, Bacteroidetes, Chloroflexi, Verrucomicrobia, and Actinobacteria. Intercropping significantly enriched amplicon sequence variants (ASVs) abundance belonging to Actinobacteria, Bacilli, Deltaproteobacteria while depleting that of Acidobacteria in rhizosphere. Intercropping with S. alfredii influenced more on microbial composition of B. napus rhizosphere. The change in rhizosphere bacterial communities was related to metal availability, soil properties, and plant parameters. The enriched families of Pedosphaeraceae, Ruminococcaceae, Chitinophagaceae, Gemmatimonadaceae, Nitrosomonadaceae, and Parachlamydiaceae were positively correlated with metal concentration in plants. These results indicate that S. alfredii and oilseed rape intercropping could be a promising approach for enhancing the remediation of Cd contaminated soil. Understanding the complex plant-microbe-metal interactions of intercropping system could facilitate the development of remediation strategy for phytoremediation of contaminated soils and sustainable agricultural production.

Theoretical acquirement of the red shift of nu(FH) upon complexation with Ne.

Counterpoise (CP)-corrected geometry optimization and frequency calculation have been performed at MP2(FC) level of theory for the linear van der Waals complex FH...Ne. With the basis set 6-311++(2df, 3pd), CP-corrected frequency shift of nu(FH) is -0.4504 cm(-1), which agrees well with the experimental red shift of 0.4722 cm(-1).

C-H...O hydrogen bond in chloroform-triformylmethane complex: blue-shifted or red-shifted?

B3LYP/6-311+G** level of theory is used to investigate the C-H...O hydrogen bond formed by chloroform and two conformers of triformylmethane (TFM), i.e. cis-TFM (concerned with C1 configuration) and trans-TFM (concerned with C2 and C3 configurations). Polarized continuum model (PCM) is used to study the solvent (chloroform) effect on this hydrogen bond. The C3 configuration is more stable than the C1 configuration whether the absolute energy or the stabilization energy is concerned. For the C1 and C2 configurations this hydrogen bond is of blue-shifted type both in gas phase and in chloroform solution. For the C3 configuration this hydrogen bond is of red-shifted type in gas phase but turns into blue-shifted type in chloroform solution instead. It's inappropriate to simply designate this hydrogen bond as blue-shifted type or red-shifted type.

Vibration assignment of carbon-sulfur bond in 2-thione-1,3-dithiole-4,5-dithiolate derivatives.

The higher frequency peak near 1050 cm(-1) of the doublet in the infrared and Raman spectra of 2-thione-1,3-dithiole-4,5-dithiolate (DMIT) derivatives corresponds mainly to the stretching vibration of carbon-sulfur double bond in the terminal S=CS2 fragments of DMIT skeletons while the lower one corresponds mainly to the Fermi resonance peak between overtones of symmetric stretching vibration of two carbon-sulfur single bond in the S=CS2 fragment of DMIT skeletons and the higher frequency. On the other hand, the higher frequency near 500 cm(-1) corresponds mainly to the symmetric stretching vibration of two carbon-sulfur single bond in the S=CS2 fragments of DMIT skeletons while the lower one corresponds mainly to the symmetric stretching vibration of the four carbon-sulfur single bond in the S2C=CS2 fragments of DMIT skeletons.

Molecular structure and infrared spectra of (HXeCN)n (n=2, 3 or 4).

The structure, energetics, and vibrational spectra of the (HXeCN)2 dimer were investigated at the CCSD(T), MP2 and B3LYP levels. Such properties of the (HXeCN)3 trimer and (HXeCN)4 tetramer were investigated at the B3LYP level. The dimer, trimer, and tetramer were predicted to have a C2h, C2v, and D2d structure, respectively. In all of these oligomers, the N⋯Xe intermonomeric interaction is the most important one for holding the monomers together. Included with the ZPVE and BSSE, the stabilization energy of the dimer is 12.36 kcal/mol at the CCSD(T) level, while those of the dimer, trimer, and tetramer are 10.42, 18.23, and 31.34 kcal/mol, respectively, at the B3LYP level. At the B3LYP level, with respect to those of the isolated monomer, the C-Xe and Xe-H asymmetric stretching frequencies are shifted by -11.2 and +128.0 cm(-1) for the dimer, -51.6, +220.7 and -11.5, +96.6 cm(-1) for the trimer, and -14.1 and +201.8 cm(-1) for the tetramer.

Molecule design and screening of novel unsymmetrical zinc phthalocyanine sensitizers for dye-sensitized solar cells.

The molecular orbital and optical properties of the dyes PCH001 and TT1 reported previously were studied using the density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations. The results show that the electronic spectra simulated for PCH001 and TT1 in ethanol were in good agreement with the experimental data. The molecular orbital spatial orientation was used to interpret the discrepancy of the photovoltaic performances of the PCH001 and TT1 sensitized solar cells. The conjugation between the carboxyl group and the phthalocyanine ring in TT1 was found to be better than that through the C-C single bond in PCH001, which may contribute to TT1's improved performance. Four new unsymmetrical phthalocyanine molecules with the peripheral substituents as donors and anchoring groups as acceptors, namely CZ1, CZ2, trans- and cis-CZ3, were designed and compared to PCH001 and TT1. The new molecules CZ2 and cis-CZ3 were promising and may challenge the current record of PCH001 and TT1 in phthalocyanine-sensitized solar cells.

Tetra-n-butylammonium bis(2-thioxo-1,3-dithiole-4,5-dithiolato-kappa2S4,S5)nickelate(III).

The crystal structure of the title compound, (C(16)H(36)N)[Ni(C(3)S(5))(2)], is isomorphous with that of the corresponding Pt complex but different from the structures reported for compounds of the same chemical composition, and so provides a new crystalline phase of this complex. The nickel complex anion has good planarity and lies on a crystallographic inversion centre. There is disorder in the two terminal C atoms of two of the butyl chains of the tetra-n-butylammonium cation, the N atom of which is located on a twofold axis.