Antineutrophil cytoplasmic antibody (ANCA)-associated vasculitis (AAV) is a group of systemic autoimmune diseases, which is typified by inflammatory necrosis predominantly affecting the small vessels and often accompanied by positive ANCA. Clinically, AAV primarily includes microscopic polyangiitis (MPA), granulomatosis with polyangiitis (GPA), and eosinophilic granulomatosis with polyangiitis (EGPA). It has been found that in AAV pathogenesis, both innate and adaptive immunity are related to neutrophil function mutually. Many proteins, such as myeloperoxidase (MPO) and proteinase 3 (PR3), in neutrophil cytoplasm lead to the production of proteins such as MPO-ANCA and PR3-ANCA by activating adaptive immunity. In addition, through the process of neutrophil extracellular trap (NET) formation, activation of an alternative complement pathway and the respiratory burst can stimulate the neutrophils close to vascular endothelial cells and will participate the vessel inflammation. This review aims to reveal the potential mechanisms regulating the association between the neutrophils and various types of AAVs and to emphasize the results of recent findings on these interactions. Moreover, multiple underlying signaling pathways involved in the regulation of neutrophils during AAV processes have also been discussed. The ultimate goal of this review is to identify novel biomarkers and therapeutic targets for AAV management in the future.
to desorb from the surface [1a,3a] (a rather general problem of on-surface synthesis) and in addition side reactions, namely hydroalkynylation leading to enynes and trimerization, [1b,3b,4,5a] can occur. To overcome these critical issues, different strategies have been followed in the coupling of two alkynes. Along with the variation of the surface [3] thereby also selecting different surface orientations, [5] monomer design was found as a key tool for reaction optimization. Especially the installation of sterically demanding groups next to the alkyne moiety has been found to enhance the selectivity of the Glaser coupling (Scheme 1a). [1b,5b] If o-coordinating groups are introduced, the monomers can be located at the step edges of the surface to enable the selective formation of the Glaser-coupling product by preorganization (Scheme 1a). [6] Moreover, the effect of surface coverage was investigated and it was found that at high surface loadings in the reaction of alkynyl aryl carboxylic acids, trimerization could be suppressed (Scheme 1b). [7] Further, a photochemical version [8] and a protecting group strategy [9] were developed to increase efficiency and selectivity in Glaser-couplings. Notably, along with the parent CH alkynes, silylated [10] and brominated [11] congeners have been selected as coupling partners that engage in "cleaner" Glaser coupling reactions. However, in these cases, high annealing temperatures were required either for the coupling [10] or to remove the liberated bromine atoms [11a] from the surface. Of note, cleavage of bromine atoms or carbon monoxide from disubstituted alkynes in cyclic enynes was achieved for the preparation of cyclic polyynes. [12] Besides the well-known Glaser coupling, a variety of other on-surface reactions have been successfully established, such as the Ullmann coupling, [13] imine bond formation, [14] decarboxylative coupling, [15] dehydrofluorination reaction, [16] dehydrogenative SiSi coupling [17] and disilabenzene framework formation. [18] Despite these achievements, it is still of high interest to evaluate new chemical functionalities as reactive entities in on-surface chemistry. As compared to homocoupling reactions, the intermolecular coupling of two differently functionalized monomers is far more challenging. The underlying reason is that both monomers are required to constitute a perfectly mixed self-assembly on the surface in order to enable the targeted cross-reaction. Consequently, there Aryl propiolic acids are introduced as a new class of monomers in the field of on-surface chemistry to build up poly(arylenebutadiynylenes) through decarboxylative Glaser coupling. As compared to aryl alkynes that are routinely used in the on-surface Glaser coupling, it is found that the decarboxylative coupling occurs at slightly lower temperature and with excellent selectivity. Activation occurs through decarboxylation for the propiolic acids, whereas the classical Glaser coupling is achieved through alkyne CH activation, and this process shows poor se...
The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/smll.202008036.Advanced fabrication of surface metal-organic complexes with specific coordination configuration and metal centers will facilitate to exploit novel nanomaterials with attractive electronic/magnetic properties. The precise on-surface synthesis provides an appealing strategy for in situ construction of complex organic ligands from simple precursors autonomously. In this paper, distinct organic ligands with stereo-specific conformation are separately synthesized through the well-known dehalogenative coupling. More interestingly, the exo-bent ligands promote the mono-iron chelated complexes with the Fe center significantly decoupled from the surface and of high spin, while the endo-bent ligands lead to bi-iron chelated ones instead with ferromagnetic properties.
Advanced fabrication of specific graphene analogs on surfaces will facilitate the exploitation of unexplored physical properties that may enrich their potential applications in the future, and the quest for graphene analogs has expanded from covalent graphene analogs to non-covalent ones. Previously, artificial non-covalent molecular graphene has been assembled by atomic manipulation, which, however, is a technical challenge and extremely limits the creation of non-covalent graphene analogs over a large area. Herein, we achieve the fabrication of a chlorine(Cl)-based non-covalent graphene analog stabilized by copper(Cu) adatoms on Cu(111) through an easy-to-facilitate self-assembly approach, as demonstrated by the combination of scanning tunneling microscopy imaging and density functional theory calculations. Moreover, the Cu adatoms are found to uniformly distribute within such a non-covalent graphene analog, which is inaccessible for covalent ones and shows potential for stabilizing the non-covalent graphene analog as well as modulating its overall electronic properties. Such findings exemplify the construction of non-covalent graphene analogs with a large area by a more effective self-assembled approach in contrast to the previous atomic manipulation method.
Delicate control over structural phase transition provides advanced approaches for the fabrication of the desired well-ordered nanoarchitectures on surfaces. The participation of intrinsic metal adatoms in pure organic systems can facilitate the structural phase transition by direct capture of surface metal adatoms and forming metal–organic bonds. However, most of the situations occur at low coverage; such structural phase transition at a higher molecular concentration is limited to some extent due to the poor migration ability. Thus, high-concentration phase transition needs to be explored, which might be significant for the design and exploitation of large-scale ordered metal–organic-related nanomaterials. Herein, we report the phase transition of pyrene-4,5,9,10-tetraone (PT) molecules at high coverage (∼1 monolayer (ML)) on Au(111) from hydrogen-bonded row-like nanostructures to metal–organic honeycomb networks by coordinating with surface Au adatoms as demonstrated by scanning tunneling microscopy (STM). Combined with density functional theory (DFT) calculations, we demonstrate that identical molecular density (or unit cells) of two nanostructures should be the key, which makes it possible to realize phase transition possibly by in situ rotation and coordinating with the gold adatoms. Also, the phase transition causes the modulation of electronic properties from semiconductive ones to metallic ones.
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