Abstract
Effecting the synergistic function of single metal atom sites and their supports is of great importance to achieve high-performance catalysts. Herein, we successfully fabricate ...polyoxometalates (POMs)-stabilized atomically dispersed platinum sites by employing three-dimensional metal-organic frameworks (MOFs) as the finite spatial skeleton to govern the accessible quantity, spatial dispersion, and mobility of metal precursors around each POM unit. The isolated single platinum atoms (Pt
1
) are steadily anchored in the square-planar sites on the surface of monodispersed Keggin-type phosphomolybdic acid (PMo) in the cavities of various MOFs, including MIL-101, HKUST-1, and ZIF-67. In contrast, either the absence of POMs or MOFs yielded only platinum nanoparticles. Pt
1
-PMo@MIL-101 are seven times more active than the corresponding nanoparticles in the diboration of phenylacetylene, which can be attributed to the synergistic effect of the preconcentration of organic reaction substrates by porous MOFs skeleton and the decreased desorption energy of products on isolated Pt atom sites.
Dysfunction of the circadian rhythm is one of most common nonmotor symptoms in Parkinson's disease (PD), but the molecular role of the circadian rhythm in PD is unclear. We here showed that ...inactivation of brain and muscle ARNT‐like 1 (BMAL1) in 1‐methyl‐4‐phenyl‐1,2,4,5‐tetrahydropyridine (MPTP)‐treated mice resulted in obvious motor functional deficit, loss of dopaminergic neurons (DANs) in the substantia nigra pars compacta (SNpc), decrease of dopamine (DA) transmitter, and increased activation of microglia and astrocytes in the striatum. Time on the rotarod or calorie consumption, and food and water intake were reduced in the Bmal1−/− mice after MPTP treatment, suggesting that absence of Bmal1 may exacerbate circadian and PD motor function. We observed a significant reduction of DANs (~35%) in the SNpc, the tyrosine hydroxylase protein level in the striatum (~60%), the DA (~22%), and 3,4‐dihydroxyphenylacetic acid content (~29%), respectively, in MPTP‐treated Bmal1−/− mice. Loss of Bmal1 aggravated the inflammatory reaction both in vivo and in vitro. These findings suggest that BMAL1 may play an essential role in the survival of DANs and maintain normal function of the DA signaling pathway via regulating microglia‐mediated neuroinflammation in the brain.
Besides the conventional carbon sources, acetyl-CoA has recently been shown to be generated from acetate in various types of cancers, where it promotes lipid synthesis and tumour growth. The ...underlying mechanism, however, remains largely unknown. We find that acetate induces a hyperacetylated state of histone H3 in hypoxic cells. Acetate predominately activates lipogenic genes ACACA and FASN expression by increasing H3K9, H3K27 and H3K56 acetylation levels at their promoter regions, thus enhancing de novo lipid synthesis, which combines with its function as the metabolic precursor for fatty acid synthesis. Acetyl-CoA synthetases (ACSS1, ACSS2) are involved in this acetate-mediated epigenetic regulation. More importantly, human hepatocellular carcinoma with high ACSS1/2 expression exhibit increased histone H3 acetylation and FASN expression. Taken together, this study demonstrates that acetate, in addition to its ability to induce fatty acid synthesis as an immediate metabolic precursor, also functions as an epigenetic metabolite to promote cancer cell survival under hypoxic stress.
A polyoxovanadate-based nickel–organic framework, Ni(bib)2{V2O6}({V6}-MOF, bib = 1,4-bis(1H-imidazoly-1-yl)benzene), was facilely prepared under gentle hydrothermal conditions and structurally ...characterized. Single-crystal X-ray diffraction analysis indicates that the {V6} cluster in the {V6}-MOF is constructed of two VO5 tetragonal pyramids and four VO4 tetrahedrons via the apex sharing of O atoms, presenting a hollow Linqvist-like structure, which is different from these reported hexanuclear vanadium clusters. The {V6}-MOF not only expands the structure of polyoxovanadates (POVs) but also catalyzes the rapid detoxification of mustard gas simulant (2-chloroethyl ethyl sulfide, CEES) at 25 °C. The catalytic results were determined by means of GC, GC–MS, and 1H NMR. Using {V6}-MOF as a heterogeneous catalyst, CEES underwent catalyzed oxidation to only nontoxic product 2-chloroethyl ethyl sulfoxide (CEESO) within 40 min, and the conversion and selectivity were almost 100%. In addition, {V6}-MOF exhibits high sustainability, and no obvious reductions in conversion and selectivity are observed after five runs.
Large-scale datasets possessing clean label annotations are crucial for training Convolutional Neural Networks (CNNs). However, labeling large-scale data can be very costly and error-prone, and even ...high-quality datasets are likely to contain noisy (incorrect) labels. Existing works usually employ a closed-set assumption, whereby the samples associated with noisy labels possess a true class contained within the set of known classes in the training data. However, such an assumption is too restrictive for many applications, since samples associated with noisy labels might in fact possess a true class that is not present in the training data. We refer to this more complex scenario as the open-set noisy label problem and show that it is nontrivial in order to make accurate predictions. To address this problem, we propose a novel iterative learning framework for training CNNs on datasets with open-set noisy labels. Our approach detects noisy labels and learns deep discriminative features in an iterative fashion. To benefit from the noisy label detection, we design a Siamese network to encourage clean labels and noisy labels to be dissimilar. A reweighting module is also applied to simultaneously emphasize the learning from clean labels and reduce the effect caused by noisy labels. Experiments on CIFAR-10, ImageNet and real-world noisy (web-search) datasets demonstrate that our proposed model can robustly train CNNs in the presence of a high proportion of open-set as well as closed-set noisy labels.
As a new class of multifunctional materials, photochromic materials have received much attention due to their potential applications in many fields. In order to investigate the effect of anions on ...the electron-transfer properties of photochromic coordination polymers, five bipyridinium-based complexes with different anions, namely Zn(bcbpy)(H2O)(Cl)·Cl·2H2O (1), Zn(bcbpy)(H2O)(Br)·Br·2H2O (2), Zn(bcbpy)2·2I·6H2O (3), Zn(bcbpy)2·2ClO4·6.4H2O (4), and Zn(bcbpy)(N3)2·3H2O (5) (H2bcbpy·2Cl = 1,1′-bis(3-carboxylatobenzyl)-4,4′-bipyridinium dichloride), were synthesized via self-assembly and were characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, and single-crystal X-ray diffraction. Due to different charge transfer interactions between the anions and the electron-deficient bipyridinium moiety, these complexes exhibit different electron-transfer photochromic behaviors. Specifically, complexes 1, 2, 4, and 5 were photochromic but 3 was not. This difference could be attributed to a stronger charge transfer interaction in complex 3 in comparison to complexes 1, 2, 4, and 5, as well as the heavy-atom effect of iodine. It is expected that this study will provide a new perspective for the rational design and synthesis of novel photochromic materials.
The aims of this study were to investigate the prevalence and proportion of laboratory-confirmed urethral Chlamydia trachomatis (CT) and Neisseria gonorrhoeae (NG) infections that were asymptomatic ...among individuals presenting to clinics in Shenzhen and the risk factors related to asymptomatic CT infection. In a cross-sectional study, eligible individuals were invited to participate in the questionnaire, and urine specimens were collected to identify CT and NG infections using a nucleic acid amplification test (NAAT). Considering the differences in the presentation of symptoms between men and women, this study was stratified by gender. Corresponding outcomes were analyzed by Chi-square test and multivariate logistic regression. A total of 2,871 participants were asymptomatic and included in our analyses: 1120 (39.0%) men and 1751 (61.0%) women. The prevalence of asymptomatic NG and CT infections was 0.9% and 6.2% in men, and 0.4% and 7.9% in women, respectively. The proportion of asymptomatic urethral CT among men with urethral CT was 28.3%; for women, it was 34.2%. For asymptomatic men with CT, 3 independent risk factors were identified: (1) men under the age of 30 (aOR, 1.83; 95% CI, 1.11-3.03); (2) being employed in the commercial service work (2.82; 1.36-5.84); and (3) being recruited through the urological department (2.12; 1.19-3.79). For asymptomatic women with urethral CT, age less than 30 years was a risk factor. In conclusion, a substantial prevalence of asymptomatic CT infections was found among men and women presenting to clinics in Shenzhen. The significant correlation between asymptomatic CT infection and these risk factors could help identify high-risk populations and guide screening.
A series of remarkable crystalline compounds Cu2(BTC)4/3(H2O)26H n XM12O40·(C4H12N)2 (X = Si, Ge, P, As; M = W, Mo) were obtained from the simple one-step hydrothermal reaction of copper nitrate, ...benzentricaboxylate (BTC), and different Keggin polyoxometalates (POMs). In these compounds, the catalytically active Keggin polyanions were alternately arrayed as noncoordinating guests in the cuboctahedral cages of a Cu-BTC-based metal−organic framework (MOF) host matrix. X-ray crystallographic analyses, TG, FT-IR, UV−vis, N2 adsorption studies, and acid−base titration demonstrated their high stability and toleration for thermal and acid−base conditions. No POM leaching or framework decomposition was observed in our study. The representative acid catalytic performance of a compound containing PW12 species was assessed through the hydrolysis of esters in excess water, which showed high catalytic activity and can be used repeatedly without activity loss. Moreover, catalytic selectivity, which is dependent on the molecular size of substrates, and substrate accessibility for the pore surface were observed. It is the first time that the well-defined, crystalline, MOF-supported POM compound has behaved as a true heterogeneous acid catalyst. The unique attributes of MOF and well-dispersed level of POMs prohibited the conglomeration and deactivation of POMs, which allowed for the enhancement of their catalytic properties.
Nonlinear optical switches that reversibly convert between on/off states by thermal stimuli are promising for applications in the fields of photoelectronics and photonics. Currently one main drawback ...for practical application lies in the control of their switch temperature, especially for the temperature range near room temperature. By mixed melting treatment, here we describe an alloy-like nonlinear optical switch with tunable switch temperature via a dual solid solution approach within the coordination polymer system. We initially prepare a coordination polymer (i-PrNHMe
)Cd(SCN)
, which functions as a high-contrast thermoresponsive nonlinear optical switch originating from a phase transition at around 328 K. Furthermore, by taking advantage of a synergistic dual solid solution effect, the melt mixing of it with its analogue (MeNHEt
)Cd(SCN)
, which features an unequal anionic chain templated by an isomeric ammonium, can afford coordination polymer solid solutions with switch temperatures that are tunable in a range of 273-328 K merely by varying the component ratio.
Naphthalene diimides (NDIs), a class of organic dyes with high photochemical activity and high redox activity, have attracted considerable interest attributing to their photoinduced electron transfer ...to form stable radical anions upon irradiation in the presence of electron donors. In this study, a naphthalenediimide-based ligand and different aromatic carboxylic acids self-assembled in the presence of zinc ions, forming three novel coordination polymers, Zn2 (DPMNI) (TPDC)2 (1), Zn (DPMNI) (BPC) (2), Zn (DPMNI) (HBTC) (3) (DPMNI = N,N′-bis(4-pyridylmethyl)-1,4,5,8-naphthalene diimide, H2TPDC = thiophene-2,5-dicarboxylic acid, H2BPC = 4,4′-biphenyldicarboxylic acid, H3BTC = 1,3,5-benzenetricarboxylic acid). These coordination polymers characterized by single-crystal X-ray diffraction, elemental analyses, IR spectroscopy, powder X-ray diffraction, and theromgravimetric analysis. Because of the presence of electron-deficient NDI moieties, they exhibit reversible photochromic properties. Furthermore, due to the different π–π interactions between the NDI moieties and aromatic carboxylic acid, compounds 1–3 exhibit different photosensitive properties. Moreover, the solvatochromic behaviour of compound 1 was also investigated.
Three novel NDI-based coordination polymers were prepared by solvothermal reaction, which exhibit reversible photochromic properties and solvatochromic behaviour in the presence of different solvents. Display omitted
•Three CPs based on electron-deficient naphthalene diimide dye are prepared.•Compounds 1–3 exhibit the visibly detectable photochromism.•Compound 1 exhibits solvatochromic behaviour in the presence of different solvents.•Solvatochromic effect of compound 1 arise from the intermolecular electron-transfer transition.
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