Latest ArticlesN, N'-Disulfonylhydrazines have been proven to be the most reactive precursors of the sulfonyl radicals among all types of sulfonyl substituted hydrazines as early as half a century ago. However, the sulfonyl radicals generated from these compounds have not been used in organic synthesis except the simple selfdimerization synthesis of disulfones controlled by the “solvent-cage-effects”. In this article, N, N'-disulfonylhydrazines were introduced as new sulfonylating reagents and their combinations with NIS were disclosed as new iodosulfonylating reagents of alkynes. Finally, a highly efficient method for the synthesis of (E)-β-iodovinyl arenesulfones was developed by mixing an alkyne, a N, N'-disulfonylhydrazine and NIS in aqueous THF at room temperature for 5 min.
Protein-metabolite interactions (PMIs) play important roles in various biological processes, especially in disease progression. However, due to the complexity of living cells, it is very difficult to identify specific PMIs. Herein, we chose one oncogenic factor, metadherin (MTDH), as a bait to identify its in vivo interacting metabolites in cancer cells. Cholesterol is an important metabolite and essential structural component of cell membranes. It could also drive several diseases including cancer. Interestingly, we found that cholesterol robustly interacted with MTDH and downregulated the expression of MTDH in cancer cells. Furthermore, MTDH disturbed metabolite alterations under cholesterol treatment in MTDH transduced cancer cells. Collectively, our results uncover an undescribed PMI where MTDH, as an oncogenic factor, might positively regulate cancer progression by interacting with cholesterol. This study interprets the theoretical basis of PMI-oriented cancer progression and targeting therapies in clinic.
Linear carbon chains (LCCs) are a one-dimensional sp1-hybridized allotrope of carbon. LCCs are extremely unstable: The longer the LCCs, the less stable the materials. Thus, it is a big challenge to synthesize long LCCs. Although the research on the short LCCs, e.g., polyynes, can be traced back to the 18th, LCCs are still not well-known compared to other allotropes of carbon, e.g., fullerenes, carbon nanotubes and graphene. Therefore, introducing recent progress on LCCs is of great significance to draw more attention in the community of nanocarbons as well as nanomaterials in general. Theoretically, various excellent properties have been predicted. Experimentally, LCCs with different length in many kinds of forms have been successfully synthesized. In this review, we summarized recent studies of polyynic LCCs from both theoretical and experimental aspects. Also, perspectives are highlighted to point out the further investigations of the materials.
The chemical composition obviously affects the surface wettability of a three-dimensional (3D) graphene material apart from its surface energy and microstructure. In the hydrothermal preparation, the heteroatom doping changes the chemical composition and wettability of the 3D graphene material. To realize the controllable surface wettability of graphene materials, aminobenzene sulfonic acid (ABSA) was selected as a typical doping agent for the preparation of nitrogen and sulfur co-doped 3D graphene foam (SNGF) using a hydrothermal method. Different from using o-ABSA or p-ABSA as the dopant, SNGF with tunable surface wettability is obtained only when m-ABSA is used. This result indicates that the substituent position of -SO3H group in the benzene ring of ABSA is rather important for the tunable wettability. This work provides some theoretical foundations for dopant selection and some new insights in manipulating the properties of 3D graphene foams by adjusting the configuration of dopants.
A TFA promoted multi-component reaction of aryldiazonium with sodium metabisulphite and thiols to construct thiosulfonates under transition-metal free conditions is reported. The thiosulfonates were isolated in good yields with broad tolerance of functional group. Readily available inorganic Na2S2O5 was applied as the sulfur dioxide surrogate. This strategy features easily available substrates, mild reaction conditions and free transition-metal catalyst.
Extracellular vesicles (EVs) derived from cancer cells are considered as ideal biomarker for liquid biopsy in cancer diagnosis, and are stable and abundant. Electrochemical methods for the detection of EVs are preferred over conventional methods such as Western blotting and enzyme-linked immunosorbent assay for their high sensitivity and real-time detection. This article summaries studies proposing the electrochemical methods utilizing immunological and molecular methodologies for detecting EVs derived biomacromolecules such as miRNAs and transmembrane protein for cancer diagnosis. Moreover, the electrochemical detection methods are compared and future prospects for the development of electrochemical methods for EVs detection are concluded.
An efficient protocol for the synthesis of asymmetric 1, 3-diketones was reported through diacylation of 1, 1-diborylalkanes using two different acyl sources. In this transformation, an enolate boron species was initially formed by introducing an acyl group, then it was trapped by another acyl group to form 1, 3-diketone. This method not only provided the gateway to obtain a series of 1, 3-diketones, but also afforded an operationally simple and efficient access to pyrazoles and isoxazoles.
Herein, we prepared novel three-dimensional (3D) gear-shaped Co3O4@C (Co3O4 modified by amorphous carbon) and sheet-like SnO2/CC (SnO2 grow on the carbon cloth) as anode and cathode to achieve efficient removal of 4-nitrophenol (4-NP) in the presence of peroxymonosulfate (PMS) and simultaneous electrocatalytic reduction of CO2, respectively. In this process, 4-NP was mineralized into CO2 by the Co3O4@C, and the generated CO2 was reduced into HCOOH by the sheet-like SnO2/CC cathode. Compared with the pure Co0.5 (Co3O4 was prepared using 0.5 g urea) with PMS (30 mg, 0.5 g/L), the degradation efficiency of 4-NP (60 mL, 10 mg/L) increased from 74.5%-85.1% in 60 min using the Co0.5 modified by amorphous carbon (Co0.5@C). Furthermore, when the voltage of 1.0 V was added in the anodic system of Co0.5@C with PMS (30 mg, 0.5 g/L), the degradation efficiency of 4-NP increased from 85.1%-99.1% when Pt was used as cathode. In the experiments of 4-NP degradation coupled with simultaneous electrocatalytic CO2 reduction, the degradation efficiency of 4-NP was 99.0% in the anodic system of Co0.5@C with addition of PMS (30 mg, 0.5 g/L), while the Faraday efficiency (FE) of HCOOH was 24.1% at voltage of -1.3 V using the SnO2/CC as cathode. The results showed that the anode of Co3O4 modified by amorphous carbon can markedly improve the degradation efficiency of 4-NP, while the cathode of SnO2/CC can greatly improve the FE and selectivity of CO2 reduction to HCOOH and the stability of cathode. Finally, the promotion mechanism was proposed to explain the degradation of organic pollutants and reduction of CO2 into HCOOH in the process of electrocatalysis coupled with advanced oxidation processes (AOPs) and simultaneous CO2 reduction.
Manganese-catalyzed hydrogenation of unsaturated molecules has made tremendous progresses recently benefiting from non-innocent pincer or bidentate ligands for manganese. Herein, we describe the hydrogenation of quinolines and imines catalyzed by simple manganese carbonyls, Mn2(CO)10 or MnBr(CO)5, thus eliminating the prerequisite pincer-type or bidentate ligands.
Formaldehyde (HCHO) is one kind of common indoor toxic pollutant, the catalytic oxidation degradation of formaldehyde at room temperature is desired. In this work, a new single atomic catalyst (SAC), Al doped graphene, for the catalytic oxidation of HCHO molecules was proposed through density function theory (DFT) calculations. It is found that Al atoms can be adsorbed on graphene stably without aggression. Then HCHO can be effectively oxidized into CO2 and H2O in the presence of O2 molecules on Al doped graphene with a low energy barrier of 0.82 eV and releasing energy of 2.29 eV with the pathway of HCHO → HCOOH → CO → CO2. The oxidation reaction can happen promptly with reaction time τ = 56.9 s at the speed control step at room temperature. Therefore, this work proposed a high-performance catalyst Al-doped graphene without any noble metal for HCHO oxidation at ambient temperature, and corresponding oxidation pathway and mechanism are also deeply understood.
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