Latest ArticlesThiolate-bridged hetero-bimetallic complexes [Cp*M(MeCN)N2S2FeCl][PF6] (2, M = Ru; 3, M = Co, Cp* = η5-C5Me5, N2S2 = N, N'-dimethyl-3, 6-diazanonane-1, 8-dithiolate) were prepared by self-assembly of dimer [N2S2Fe]2 with mononuclear precursor [Cp*Ru(MeCN)3][PF6] or [Cp*Co(MeCN)3][PF6]2 in the presence of CHCl3 as a chloride donor. Complexes 2 and 3 exhibit obviously different redox behaviors investigated by cyclic voltammetry and spin density distributions supported by DFT calculations. Notably, iron-cobalt complex 3 possesses versatile reactivities that cannot be achieved for complex 2. In the presence of CoCp2, complex 3 can undergo one-electron reduction to generate a stable formally CoIIFeII complex [Cp*CoN2S2FeCl] (4). Besides, the terminal chloride on the iron center in 3 can be removed by dehalogenation agent AgPF6 or exchanged with azide to afford the corresponding complexes [Cp*Co(MeCN)N2S2Fe(MeCN)][PF6]2 (5) and [Cp*Co(MeCN)N2S2Fe(N3)][PF6] (6). In addition, complexes 2, 3 and 4 show distinct catalytic reactivity toward the disproportionation of hydrazine into ammonia. These results may be helpful to understand the vital role of the heterometal in some catalytic transformations promoted by heteromultinuclear complexes.
Over the last decade, numerous research efforts have been devoted to pillar [n]arenes since their debut. The popularity of pillararenes is a reflection of current research trend in supramolecular and macrocyclic chemistry in general. Among the vast applications (such as chemosensors, drug delivery, transmembrance channels, and separation) of pillararenes, their utilization in catalysis is a relatively less explored area. However, soaring attention has been paid by researchers in recent years and this field has seen gradual increasing publications. Therefore, in this review we will discuss progress in the emerging applications of pillararene architectures in catalysis based on various reaction genre including reduction, oxidation, coupling, decomposition and others. Furthermore, this review not only focuses on the pillararenes based current progress in catalysis, but also provides the signs for future development in this research field.
Detection of point mutations in driver genes is of great significance for the early diagnosis, treatment, and prognostic evaluation of cancer. However, current detection methods do not offer versatility, specificity, and rapid performance simultaneously. Thus, multiple mutation detection processes are necessary, which results in long processing times and high costs. In this study, we developed a thermodynamics-guided two-way interlocking DNA cascade system for universal multiplexed mutation detection (TTI-CS). This strategy is based on the DNA probe, which changes the thermodynamic balance of the DNA cascade by the designed bubble structure, thereby achieving a good distinction between mutant and wild-type DNA. The designed method greatly shortens the detection time through two-way intrusion. In addition, this method only changes two inexpensive trigger and bridge sequences, which replace the specific and expensive nucleic acid probes used in analyses based on traditional DNA probe methods, thereby enabling multiple detections. We performed the detection of synthetic single-stranded DNA for the five mutation points and successfully detected in endometrial cancer specimens. The detection limit of this method is 0.1%, which better meets the needs of clinical low-abundance multiple mutation detection. Overall, TTI-CS is currently one of the best methods for detecting multiple mutation detections.
As a kind of microplasma sustained in air, solution electrode glow discharge (SEGD) ignited between the liquid electrode and metal electrode is attractive to the fields of optical emission spectrometry and mass spectrometry due to its unique advantages, such as low power consumption and low carrier gas consumption. Moreover, the complex and efficient reactions in the liquid phase and plasma phase of SEGD make it considerable research potential in the fields of biology and medicine, material synthesis, electrochemistry. Considering the close relationship between the various fields on SEGD, here we are devoted to provide an overview of the development of SEGD in various fields. More importantly, a systematic discussion on the discharge mechanism is conducted based on the research process in various fields for getting deeper insight into the SEGD.
Two-dimensional (2D) materials have received extensive attention in the fields of electronics, optoelectronics, and magnetic devices attributed to their unique electronic structures and physical properties. The application of strain is a simple and effective strategy to change the lattice structure of 2D materials thus modulating their physical properties, which further facilitate their applications in carrier mobility transistor, magnetic sensor, single-photon emitter etc. In this short review, we focus on the strain applied via substrate engineering. Firstly, the relationship between the strain and physical properties has been summarized. Secondly, the methods for achieving substrate engineering-induced strain have been demonstrated. Finally, the latest applications of strained 2D materials have been introduced. In addition, the future challenges and development prospects of strain-modulated 2D materials have also been proposed.
A visible-light-induced spirocyclizative hydroarylation via reductive dearomatization of a series of non-activated arenes including 2-phenyl indoles and naphthalene derivatives under mild conditions is described. An intriguing chemoselective dearomative hydroarylation of 2-phenyl indoles is presented. This dearomative hydroarylation protocol rapidly delivers valuable spirocycles with carbon−carbon double bonds from readily accessible aromatic precursors in a single step.
MoS2 nanosheets (NSs) are novel 2D nanomaterials (NMs) with potential uses in many areas, and therefore oral exposure route to MoS2 NSs is plausible. Currently, MoS2 NSs are considered as biocompatible NMs, but there is lacking of systemic investigations to study the interactions of MoS2 NSs with intestinal cells. In this study, we exposed the 3D Caco-2 spheroids to MoS2 NSs or MoS2 powders (denoted as MoS2-bulk), and investigated the potential adverse effects of MoS2-materials based on transcriptomics and lipidomics analysis. As expected, both MoS2 NSs and MoS2-bulk were dose-dependently internalized into 3D Caco-2 spheroids but did not induce cytotoxicity, membrane disruption or decrease of thiols. However, the Gene Ontology (GO) and Kyoto Encyclopedia of Gene and Genomes (KEGG) analysis indicated that nutrient absorption and metabolism was decreased. One of the most significantly decreased KEGG pathways is fat digestion and absorption (map04975), and Western blotting analysis further showed that fatty acid binding protein 1 and apolipoprotein A1, key proteins involved in fat digestion and absorption, were down-regulated by MoS2 NSs or MoS2-bulk. In addition, BODIPY 493/503 staining suggested that exposure to MoS2 NSs and MoS2-bulk decreased lipid levels in the spheroids. However, lipidomics data indicated that MoS2 materials only decreased 8 lipid classes, including lysophosphatidylcholine, lysodimethylphosphatidylethanolamine, N-acylethanolamine, ceramide phosphoethanolamines, gangliosides, lysosphingomyelin and sulfatide, whereas most of the lipid classes were indeed increased. In addition, MoS2 NSs was more potent to decrease the lipid classes compared with MoS2-bulk. Combined, the results from this study showed that MoS2 NSs and bulk materials were non-cytotoxic but altered lipid profiles in 3D Caco-2 spheroids.
Semiconductor-noble metal composite has become a research focus due to its superior performance compared with its respectⅳe component. Although various methods have been developed to synthesize semiconductor-noble metal heterostructures, most of them are relatⅳely complex multistep and use toxic reactants of high cost and risk. In this work, a series of Cu2O/Ag heterojunctions were quickly prepared in one step via simple microwave-assisted green route. XRD, SEM, TEM, EDS, XPS, etc. were used to characterize obtained products, and the results indicate a Cu2O/Ag metal-semiconductor heterojunction in micro-nano size was fabricated successfully. In addition, antibacterial behavior of Cu2O/Ag heterojunctions against E. coli and S. aureus were investigated. Owing to the synergistic effect of Cu2O and Ag, the heterojunction exhibits much better antibacterial performance than the pristine Cu2O does. This work provides new insights into the green design and fabrication of surface-modified Cu2O hybrid multifunctional materials for antibacterial applications.
Numerous strategies for linking desired chemical probes with target peptides and proteins have been developed and applied in the field of biological chemistry. Approaches for site-specific modification of native amino acid residues in test tubes and biological contexts represent novel biological tools for understanding the role of peptides and proteins. Selective N-terminal modification strategies have been broadly studied especially in the last 10 years, as N-terminal positions are typically solvent exposed and provide chemically distinct sites for many peptide and protein targets, making N terminus distinct from other functional groups. A growing number of chemical and enzymatic techniques have been developed to modify N-terminal amino acids, and those techniques have the potential in the fields of medicine, basic research and applied materials science. This review focuses on appraising modification methodologies with the potential for biological applications from the past 10 years.
A sulfonium ylide participated alkylation and arylation under transition-metal free conditions is described. The disparate reaction pattern allowed the separate activation of non-ylidic S-alkyl and S-aryl bond. Under acidic conditions, sulfonium ylides serve as alkyl cation precursors which facilitate the alkylations. While under alkaline conditions, cleavage of non-ylidic S-aryl bond produces O-arylated compounds efficiently. The robustness of the protocols were established by the excellent compatibility of wide variety of substrates including carbohydrates.
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