Search

Interleukin 10 (IL-10) is a synthetic inhibitor of human cytokines with immunomodulatory and anti-inflammatory effects. This study was designed to investigate the expression variation of IL-10 in the multiple sites including cortex, hippocampus, and lung tissues of neonatal hypoxic-ischemic (HI) rats and explore the crucial role of IL-10 in alleviating HI brain damage. In this study, neonatal Sprague-Dawley rats were subjected to the right common carotid artery ligation, followed by 2 h of hypoxia. The expression of IL-10 in the cortex, hippocampus, and lung tissues was measured with immunohistochemistry, real-time quantitative polymerase chain reaction (RT-qPCR), and western blot (WB). Immunofluorescence double staining was performed to observe the localization of IL-10 in neurons and astrocytes. Moreover, not-targeting and targeting IL-10 siRNA lentivirus vectors were injected into the rats of the negative control (NC) and IL-10 group, respectively, and the mRNA levels of B-cell lymphoma 2 (Bcl-2) and endoplasmic reticulum protein 29 (ERp29) were detected by RT-qPCR following IL-10 silence. The results demonstrated that the IL-10 expression was markedly increased after HI and IL-10 were colocalized with neurons and astrocytes which were badly injured by HI insult. In addition, Bcl-2 and ERp29 were remarkably decreased following IL-10 mRNA interference compared with the NC group. Our findings revealed that IL-10 exerted its antiapoptotic and neuroprotective effects by regulating the expression of Bcl-2 and ERp29, indicating that IL-10 may be a promising molecule target for HIE treatment. Refereed/Peer-reviewed

Objective Label-free quantitative proteomics was applied to analyze differentially expressed proteins (DEPs) in the cerebrospinal fluid (CSF) of patients with encephalitis. The database was used to screen for possible biomarkers in encephalitis, followed by validation and preliminary investigation of the role of some DEPs in the pathogenesis of encephalitis using enzyme-linked immunosorbent assay (ELISA). Methods We performed label-free quantitative proteomics on 16 cerebrospinal fluid samples (EM group, encephalitis with mental and behavioral disorders patients, n = 5; NED group, encephalitis without mental and behavioral disorders patients, n = 6; N group, healthy individuals, n = 5). The extracted CSF proteins were examined by mass spectrometry and enzymatic digestion and detected using protein profiling and data analysis. Interproscan was used to perform Gene Ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway enrichment analysis of the DEPs. ELISA was used to verify the changes in the levels of some DEPs in the CSF. Results A total of 941 proteins were found to be significantly differentially expressed, including 250 upregulated DEPs and 691 downregulated DEPs. GO analysis suggested that there were six enriched functions that intersect among the EM, NED, and N groups, including synapse organization, membrane, integral component of membrane, membrane part, G-protein-coupled receptor signaling pathway, and transmembrane signaling receptor activity. KEGG analysis revealed that there were three signaling pathways that intersect among the EM, NED, and N groups, including fructose and mannose metabolism, inositol phosphate metabolism, and Jak-STAT signaling pathway. Furthermore, four downregulated encephalitis-related neurological synapse proteins were identified after screening for differentially expressed proteins, including NRXN3, NFASC, LRRC4B, and NLGN2. The result of ELISA further verified that the expression of NLGN2 and LRRC4B was obviously higher in the NED group than in the N group. Conclusions These findings demonstrated that NLGN2 and LRRC4B proteins were upregulated in the NED group and could be potential biomarkers for the diagnosis of encephalitis, but still needs a lot of multiomics studies to be used in clinical.

We report the first homoleptic alkynyl-protected AgCu superatomic nanocluster [Ag9Cu6(tBuCC)12]+ (NC 1, also Ag9Cu6 in short), which has a body-centered-cubic structure with a Ag1@Ag8@Cu6 metal core. Such a configuration is reminiscent of the reported AuAg bimetallic nanocluster [Au1@Ag8@Au6(tBuCC)12]+ (NC 2, also Au7Ag8 in short), which is also synthesized by an anti-galvanic reaction (AGR) approach with a very high yield for the first time in this study. Despite a similar Ag8 cube for both NCs, structural anatomy reveals that there are some subtle differences between NCs 1 and 2. Such differences, plus the different M1 kernel and M6 octahedron, lead to significantly different optical absorbance features for NCs 1 and 2. Density functional theory calculations revealed the LUMO and HOMO energy levels of NCs 1 and 2, where the characteristic absorbance peaks can be correlated with the discrete molecular orbital transitions. Finally, the stability of NCs 1 and 2 at different temperatures, in the presence of an oxidant or Lewis base, was investigated. This study not only enriches the M15+ series, but also sets an example for correlating the structure–property relationship in alkynyl-protected bimetallic superatomic clusters.

To investigate the therapeutic efficacy of Scutellarin (SCU) on neurite growth and neurological functional recovery in neonatal hypoxic-ischemic (HI) rats. Primary cortical neurons were cultured to detect the effect of SCU on cell viability of neurons under oxygen-glucose deprivation (OGD). Double immunofluorescence staining of Tuj1 and TUNEL then observed the neurite growth and cell apoptosis in vitro,and double immunofluorescence staining of NEUN and TUNEL was performed to examine the neuronal apoptosis and cell apoptosis in brain tissues after HI in vivo. Pharmacological efficacy of SCU was also evaluated in HI rats by neurobehavioral tests, triphenyl tetrazolium chloride staining, Hematoxylin and eosin staining and Nissl staining. Astrocytes and microglia expression in damaged brain tissues were detected by immunostaining of GFAP and Iba1. A quantitative real-time polymerase chain reaction and western blot were applied to investigate the genetic expression changes and the protein levels of autophagy-related proteins in the injured cortex and hippocampus after HI. We found that SCU administration preserved cell viability, promoted neurite outgrowth and suppressed apoptosis of neurons subjected to OGD both in vitroand in vivo. Meanwhile, 20 mg/kg SCU treatment improved neurological functions and decreased the expression of astrocytes and microglia in the cortex and hippocampus of HI rats. Additionally, SCU treatment depressed the elevated levels of autophagy-related proteins and the p75 neurotrophin receptor (p75NTR) in both cortex and hippocampus. This study demonstrated the potential therapeutic efficacy of SCU by enhancing neurogenesis and restoring long-term neurological dysfunctions, which might be associated with p75NTR depletion in HI rats. Refereed/Peer-reviewed

Differentiation therapies with all-trans retinoic acid (ATRA) have been successful in treating acute promyelocytic leukemia, a rare subtype of acute myeloid leukemia (AML). However, their efficacy is limited in the case of other AML subtypes. Here, we show that the combination of ATRA with salt-inducible kinase (SIK) inhibition significantly enhances ATRA-mediated AML differentiation. SIK inhibition augmented the ability of ATRA to induce growth inhibition and G1 cell cycle arrest of AML cells. Moreover, combining ATRA and SIK inhibition synergistically activated the Akt signaling pathway but not the MAPK pathway. Pharmacological blockade of Akt activity suppressed the combination-induced differentiation, indicating an essential role for Akt in the action of the combination treatment. Taken together, our study reveals a novel role for SIK in the regulation of ATRA-mediated AML differentiation, implicating the combination of ATRA and SIK inhibition as a promising approach for future differentiation therapy.

Objective: In order to investigate the effects of LMP1-Fab antibody on Nasopharyngeal carcinoma (NPC) cancer stem cells (CSCs). Methods/ Results: Methods were performed to study the effects of LMP1-Fab antibody on NPC CSCs in vivo and in vitro, for example, transwell chamber assay, wound healing assay, western blot assay, quantitative real-time PCR assay animal experiments, animal fluorescence imaging, H&E staining, immunohistochemistry. We identified that LMP1 activated the migration and invasion of NPC. Whereas the LMP1-Fab antibody inhibited cell invasion, epithelial-mesenchymal transition (EMT) and migration of NPC CSCs in LMP1+ HNE2 cells. Furthermore, LMP1-Fab antibody significantly increased the expression of E-cadherin, and reduced the expressions of vimentin,N -cadherin and Slug in LMP1+ HNE2 CSCs cells. Mechanistically, LMP1-Fab antibody inhibited lung and liver metastasis by regulating the wnt/ -catenin pathway in the nude mice. Conclusion: These results suggested that the novel antibody-targeting LMP1 is likely to be a potential strategy for the treatment of NPC.

To assess the serum iron and ferritin levels in relation to the prevalence of hyperuricemia (HU) and the serum uric acid (SUA) level.Serum iron and ferritin concentrations were detected by Ferene method and chemiluminescence method, respectively. SUA level was detected by uricase-PAP method. HU was defined as SUA ≥ 416 μmol/L for male and ≥ 357 μmol/L for female. Multivariable-adjusted logistic regressions were constructed to investigate the associations between serum iron/ferritin levels and prevalence of HU. Pearson correlation analysis and multivariable linear regression were performed to examine the correlations between serum iron/ferritin levels and SUA level.A total of 2824 subjects (mean age 52.2 ± 7.2) were included. The overall prevalence of HU was 17.3%. Compared with the lowest quartile, the multivariable-adjusted odds ratios (OR) and its 95% confidence interval (CI) of HU were 1.33 (95%CI 0.97-1.82), 1.17 (95%CI 0.85-1.60), and 1.56 (95%CI 1.14-2.13) in the second, third, and fourth quartiles of serum iron, respectively (P for trend = 0.012), and were 1.29 (95%CI 0.89-1.88) in the second, 2.13 (95%CI 1.47-3.07) in the third, and 2.25 (95%CI 1.54-3.29) in the fourth quartile of serum ferritin (P for trend 0.001). Pearson correlation coefficient indicated a weak positive correlation between serum iron (r = 0.2, P 0.001) and ferritin (r = 0.3, P 0.001) levels and SUA. Such positive correlations were further confirmed by multiple linear regression (serum iron: standardized β = 0.059, P 0.001; serum ferritin: standardized β = 0.061, P = 0.001).Both serum iron and ferritin showed a positive correlation with the prevalence of HU, and a weak positive correlation with SUA level. Key Points • Subjects with higher levels of serum iron or ferritin had higher prevalence of HU. • There was a weak positive correlation between serum iron/ferritin levels and SUA level.

Interest on the nonlinear optical (NLO) switches that turn on/off the second-harmonic generation (SHG) triggered by the external stimulus (such as heat) have continuously grown, especially on the solid-state NLO switches showing superior stability, reversibility, and reproducibility. Herein, we discover (NH4)2PO3F, as an entirely new solid-state NLO switch showing outstanding switch contrast and reversibility as well as strong SHG intensity (1.1 × KH2PO4 (KDP)) and high laser-induced damage threshold (2.0 × KDP), undergoes a unique first-order phase transition that originates from a reversible hydrogen-bond rearrangement and needs to overcome an energy barrier. Accordingly, we put forward a strategy to continuously modify such an energy barrier by reducing the number of hydrogen bonds per unit cell via an isoelectronic replacement of NH4+ by K+ with a similar size yet incapability of providing any hydrogen bond. Consequently, Kx(NH4)2-xPO3F (x = 0-0.3) exhibiting excellent switching performance are obtained. Remarkably, Kx(NH4)2-xPO3F not only realizes a continuously tunable Tc spanning from 270 to 150 K, representing the widest NLO switching temperature range ever known but also indicates the first solid-state NLO switch example with continuous Tc. Intrinsically, such a Tc decline depends on the weakening degree of the hydrogen-bonding interactions in the unit cell. These new insights will shed useful light on the future material design and open new application possibilities.

An ultraviolet (UV) filter is the core component of sunscreen and protects skin from various photo damages. Current UV filters are hampered by skin penetration, poor photostability, photocatalytic generation of harmful reactive oxygen species (ROS), and potential environmental risks. In this work, manganese dioxide nanoclusters were developed as an eco-friendly UV filter by a facile two-step synthesis, using colloid silica as support under ambient conditions. These nanoclusters show a better UV-shielding profile than commercial titanium dioxide nanoparticles and capability to scavenge various ROS. They can be easily incorporated by a sunscreen formula and demonstrate an excellent skin photoprotection performance both in vitro and in vivo.

The biosynthesis of flavonoids and anthocyanidins has been exclusively investigated in angiosperms but largely unknown in ferns. This study integrated metabolomics and transcriptome to analyze the fronds from different development stages (S1 without spores and S2 with brown spores) of Cyclosorus parasiticus. About 221 flavonoid and anthocyanin metabolites were identified between S1 and S2. Transcriptome analysis revealed several genes encoding the key enzymes involved in the biosynthesis of flavonoids, and anthocyanins were upregulated in S2, which were validated by qRT-PCR. Functional characterization of two chalcone synthases (CpCHS1 and CpCHS2) indicated that CpCHS1 can catalyze the formation of pinocembrin, naringenin, and eriodictyol, respectively; however, CpCHS2 was inactive. The crystallization investigation of CpCHS1 indicated that it has a highly similar conformation and shares a similar general catalytic mechanism to other plants CHSs. And by site-directed mutagenesis, we found seven residues, especially Leu199 and Thr203 that are critical to the catalytic activity for CpCHS1.

The malfunction of ABCD1 causes X-linked adrenoleukodystrophy (X-ALD), a rare neurodegenerative disease that affect all tissues in human. Residing in the peroxisome membrane, ABCD1 plays a role in the translocation of very long chain fatty acids (VLCFA) for their damage by β-oxidation. Here, we present five Cryo-Electron microscopy structures of ABCD1 in four conformational states. Combined with functional analysis, we found that substrate and ATP trigger the closing of two nucleotide binding domains (NBDs) over a distance of 40 Å and the rearrangement of the transmembrane domains. Each of the three inward-facing structure of ABCD1 has a vestibule opens to cytosol with variable size. Furthermore, the structure of ABCD1 in the outward-facing state supports that ATP molecules pull the two NBDs together and open the transmembrane domain to the peroxisomal lumen for substrate release. The five structures provide a snapshot of substrate transporting cycle and mechanistic implications for disease-causing mutations.

Chemoresistance remains as a major hindrance in the treatment of hepatocellular carcinoma (HCC). High mobility group box protein 1 (HMGB1) enhances autophagic flux and protects tumor cells from apoptosis, which results in acquired drug resistance. However, the exact mechanisms underlying HMGB1-modulated autophagy in HCC chemoresistance remain to be defined. In the present study, we found that administration of doxorubicin (DOX) significantly promoted HMGB1 expression and induced HMGB1 cytoplasmic translocation in human HCC cell lines BEL7402 and SMMC7721, which enhanced autophagy that contributes to protecting HCC cells from apoptosis and increasing drug resistance. Moreover, we observed HMGB1 translocation and elevation of autophagy in DOX-resistant BEL7402 and SMMC7721 cells. Additionally, inhibition of HMGB1 and autophagy increased the sensitivities of BEL-7402 and SMMC-7721 cells to DOX and re-sensitized their DOX-resistant cells. Subsequently, we confirmed with HMGB1 regulated autophagy by activating the 5ʹ adenosine monophosphate-activated protein kinase (AMPK)/mTOR pathway. In summary, our results indicate that HMGB1 promotes acquired DOX resistance in DOX-treated BEL7402 and SMMC7721 cells by enhancing autophagy through the AMPK/mTOR signaling pathway. These findings provide the proof-of-concept that HMGB1 inhibitors might be an important targeted treatment strategy for HCC.

Background Neonatal hypoxic-ischemic encephalopathy (HIE) refers to the perinatal asphyxia caused by the cerebral hypoxic-ischemic injury. The current study was aimed at investigating the therapeutic efficacy of Scutellarin (Scu) administration on neurological impairments induced by hypoxic-ischemic injury and exploring the underlying mechanisms. Methods Primary cortical neurons were cultured and subjected to oxygen–glucose deprivation (OGD), and then treated with Scu administration. The growth status of neurons was observed by immunofluorescence staining of TUJ1 and TUNEL. Besides, the mRNA level of growth-associated protein 43 (GAP43) in OGD neurons with Scu treatment was detected by quantitative real-time polymerase chain reaction (qRT-PCR). To further verify the role of GAP43 in Scu treatment, GAP43 siRNA and knockout were applied in vitro and in vivo. Moreover, behavioral evaluations were performed to elucidate the function of GAP43 in the Scu-ameliorated long-term neurological impairments caused by HI insult. The underlying biological mechanism of Scu treatment was further elucidated via network pharmacological analysis. Finally, the interactive genes with GAP43 were identified by Gene MANIA and further validated by qRT-PCR. Results Our data demonstrated that Scu treatment increased the number of neurons and axon growth, and suppressed cell apoptosis in vitro. And the expression of GAP43 was downregulated after OGD, but reversed by Scu administration. Besides, GAP43 silencing aggravated the Scu-ameliorated neuronal death and axonal damage. Meanwhile, GAP43 knockout enlarged brain infarct area and deteriorated the cognitive and motor dysfunctions of HI rats. Further, network pharmacological analysis revealed the drug targets of Scu participated in such biological processes as neuronal death and regulation of neuronal death, and apoptosis-related pathways. GAP43 exhibited close relationship with PTN, JAK2 and STAT3, and GAP43 silencing upregulated the levels of PTN, JAK2 and STAT3. Conclusions Collectively, our findings revealed Scu treatment attenuated long-term neurological impairments after HI by suppressing neuronal death and enhancing neurite elongation through GAP43-dependent pathway. The crucial role of Scutellarin in neuroprotection provided a novel possible therapeutic agent for the treatment of neonatal HIE. Graphic abstract

Lipopolysaccharide (LPS)-stimulated macrophages express an aconitate decarboxylase (IRG1, also called ACOD1), leading to accumulation of the endogenous metabolite itaconate. However, the precise mechanisms by which elevated itaconate levels alter macrophage function are not clear. Our hypothesis is itaconate affects macrophage function through some uncertain mechanism. Based on this, we established a transcriptional and proteomic signature of macrophages stimulated by itaconate and identified the pathways of IL-1s secretion and altered iron metabolism. Consistently, the effect of IRG1 deficiency on IL-1s secretion and iron metabolism was confirmed in IRG1 knockout THP-1 cell lines. Several common inhibitors and other compounds were used to examine the molecular mechanisms involved. Only cysteine and antioxidants (catechin hydrate) could inhibit caspase-1 activation and IL-1s secretion in itaconate-stimulated macrophages. We further found that aconitase activity was decreased by itaconate stimulation. Our results demonstrate the counteracting effects of overexpression of mitochondrial aconitase (ACO2, a tricarboxylic acid cycle enzyme) or cytosolic aconitase (ACO1, an iron regulatory protein) on IL-1s secretion and altered iron metabolism. Both enzyme activities were inhibited by itaconate because of iron-sulfur (Fe-S) cluster destruction. Our findings indicate that the immunoregulatory functions of IRG1 and itaconate in macrophages are stressful Fe-S cluster of aconitases disrupting and iron metabolism rebalancing.

Background: The effect of interleukin-6 (IL-6) knockdown on hypoxia-ischemia (HI) of neonatal rat models was investigated to explore the underlying molecular regulation mechanism. Methods: To establish the HI model, we treated 7days postnatal Sprague-Dawley (SD) rats with the right carotid artery ligation and had them exposed to the environment of 8% oxygen and 92% nitrogen for 2 h, respectively. Then, the neurologic function and morphology changes were assessed. Subsequently, IL-6 siRNA lentivirus was injected into cerebral cortex motor area 2 days before HI; meanwhile, the interference efficiency was detected by quantitative real-time polymerase chain reaction (QRT-PCR) and Western blot. Immunofluorescence staining of Glial fibrillary acidic protein (GFAP), Hexaribonucleotide Binding Protein-3 (NeuN) and IL-6 were used to identify the location and interference effect of IL-6. In order to further research the underlying mechanisms, the expressions of downstream molecular including Bcl-2-associated X protein (BAX) and Casp3 were examined following IL-6 up-regulation by QRT-PCR.Results: It was found that both the growth of cortical neurons and the length of axon were promoted after IL-6 interference, and the cell apoptosis was decreased. In addition, the expression of BAX and Casp3 were closely associated with IL-6. Conclusions: The present findings confirmed that the decreased IL-6 improves the deficiencies in neurologic function and morphology induced by HI, and the potential mechanism may be closely related with the regulation of Casp3 and BAX.

Fat deposition in yaks plays an important part in survival, multiplication, and meat quality. In this work, the characteristic of fat deposition in male yaks (MYs) and female yaks (FYs) and the regulations of gender to yak fat deposition were explored by mRNA-Seq and non-targeted metabolomics analyses. FYs possessed a higher body fat rate (BFR) of visceral fat, fat content in longissimus dorsi (LD) and liver, and subcutaneous fat thickness (p < 0.05). The fat and cholesterol synthesis in liver and the fat transport in FY blood increased. The fat metabolism in yaks is the combined effect of carbohydrate, fatty acid, and amino acid metabolism by tricarboxylic acid (TCA) cycle, and an increase of triglyceride (TG) synthesis was accompanied by an increase of steroid synthesis. The high levels of myo-inositol and cortisol (COR) (p < 0.01) activated the calcium signaling in FY subcutaneous fat, followed by the increase of adipocyte secretion, and resulted in more leptin (LEP) secretion (p < 0.01). Then peroxisome proliferator-activated receptor (PPAR) signaling was activated by the focal adhesions and ECM–receptor interaction. Finally, the TG and steroid synthesis increased by the expression regulation of ME1, SCD, ELOVL6, DGAT2, DBI, LPL, CPT1, PLIN1, LIPA, DHCR24, and SQLE gene. The above genes can be considered as the candidate genes for yak with higher fat amount in molecular breeding in the future. This study can provide a theoretical basis for improving the meat quality and breeding of yaks.

We report the first homoleptic alkynyl-protected AgCu superatomic nanocluster [Ag9Cu6(tBuCC)12]+ (NC 1, also Ag9Cu6 in short), which has a body-centered-cubic structure with a Ag1@Ag8@Cu6 metal core. Such a configuration is reminiscent of the reported AuAg bimetallic nanocluster [Au1@Ag8@Au6(tBuCC)12]+ (NC 2, also Au7Ag8 in short), which is also synthesized by an anti-galvanic reaction (AGR) approach with a very high yield for the first time in this study. Despite a similar Ag8 cube for both NCs, structural anatomy reveals that there are some subtle differences between NCs 1 and 2. Such differences, plus the different M1 kernel and M6 octahedron, lead to significantly different optical absorbance features for NCs 1 and 2. Density functional theory calculations revealed the LUMO and HOMO energy levels of NCs 1 and 2, where the characteristic absorbance peaks can be correlated with the discrete molecular orbital transitions. Finally, the stability of NCs 1 and 2 at different temperatures, in the presence of an oxidant or Lewis base, was investigated. This study not only enriches the M15+ series, but also sets an example for correlating the structure–property relationship in alkynyl-protected bimetallic superatomic clusters., We report the first homoleptic alkynyl-protected Ag9Cu6 superatom, and its structural differences from Au7Ag8 cluster lead to different optical features and stability, where the structure–property correlation is revealed by DFT calculations.

The thermal phonon transport is a key matter for heat managing in materials science which is crucial for device miniaturization and power density increase. Herein, we report the synthesis, structure and characterization of a new compound, Cs2Ge3Ga6Se14, with a unique anisotropic structure simultaneously containing Ge3+ and Ge2+ that adopt (Ge1)3+2Se6 dimer or (Ge2)2+Se6 octahedron, respectively. The thermal conductivity was measured to be 0.57–0.48 W m−1 K−1 from 323 to 773 K, the lowest value among all the known Ge containing compounds, approaching its glass limit according to the Cahill’s formulation. More importantly, we discover for the first time that the vibration uncoupling of Ge with different valence states hinders the effective thermal energy transport between the (Ge1)3+2Se6 dimer and (Ge2)2+Se6 octahedron, and consequently lowers the thermal conductivity. In addition, we propose a structure factor fi = sin(180 − β) × dGe−Q/li (i = A, B), with which a structure map of the Cs2Ge3M6Q14 family is given.

Materials with large birefringence (Δn) are highly needed by fiber-optic isolators, whereas crystals showing strong second-order harmonic generation (SHG) are the key component for all-solid-state laser devices. Cyanurate constructed by the planar π-conjugated ring (C3N3O3, CY) is a class of fascinating materials exhibiting not only very large Δn (larger than that of calcite) but also strong SHG (2 times that of β-BaB2O4, BBO). Here, we report five new cyanurates (I-V) and their single-crystal structures; among them, II realizes a Δn = 0.4, the maximum in the cyanurate family, and IV realizes a d33 = 6.69 pm/V, one of the highest values in the cyanurate family. We discover a dependence between Δn and the coplanarity of the CY rings that is explicitly described by a Boltzmann function, in which the coplanarity is defined by the dihedral angle (γ) between the CY plane and the principal optical axes XY plane. II realizes the maximum Δn due to its zero γ that indicates perfect coplanarity. Such a Δn-γ dependence also allows the Δn prediction of cyanurates. Furthermore, we uncover that the SHG intensity of cyanurates increases monotonically as the angle (θ) between the maximum hyperpolarizability (βmax) vector and the crystal 21 polar axis decreases. We predict the dij to extend well beyond such a value and to maximize at θ = 0°. Our results have significant implications for the future rational design and discovery of high-performance materials of π-conjugated and other related systems.

The precision of array of laser applications and manipulation on smaller scales are limited by the so-called 200 nm wall, and breakthroughs rely on the discovery of new materials with transparency and phase matchability in the ultraviolet and deep ultraviolet region. Herein, we discover an unprecedented alignment of the asymmetric non-π-conjugated species [PO

Background. Glioma is the most common malignant brain tumor and the patients are prone to poor prognosis. Due to limited treatments, new drug exploration has become a general trend. Therefore, the objective of this study is to investigate the effect of the new drugs C18H17NO6and its combination with Scutellarin on glioma cells and the underlying mechanism.Method. U251 and LN229 cells were administrated with C18H17NO6and its combination with Scutellarin. The proliferation ability of glioma cells was determined by cell counting kit-8, plate clone formation assay, and EdU incorporation assay. The cell cycle and apoptosis detection were detected by flow cytometry. Moreover, TUNEL assay was also used for cell apoptosis analysis. Then, the transfer ability of cells was achieved through wound healing assay. Furthermore, polymerase chain reaction (PCR) test and western bolt analysis were used to detect the mRNA expression and protein expression, respectively. Lastly, immunofluorescence was for the purity identification of astrocyte.Result. The results showed that, with the increasing dose of C18H17NO6, the cell inhibition rate, the cells in G1 phase, and the apoptosis rate were gradually increased, but the clone number, proliferation rate, and the cells in G2 and S phases were gradually decreased in comparison with control group. However, with the increase of C18H17NO6, the transferred rate of U251 and LN229 was not significantly augmented, expect that on U251 in C18H17NO65μM group. In addition, Scutellarin 200μM has little effect on proliferation, with the inhibition rate 10-20% and proliferation rate except U251 in Scutellarin 200μM group similar to that in control group. Moreover, compared to control group, Scutellarin 300μM increased the U251 cells in G2 and S phases and the apoptosis rate of LN229 but decreased the LN229 cells in G2 and S phases. Besides, in Scutellarin 200μM group, the transfer ability of LN229 was inhibited, but not in U251. Furthermore, if C18H17NO6was combined with Scutellarin 200/300μM, the proliferation and transferred ability were suppressed and the apoptosis was elevated in LN229 cell in comparison with C18H17NO6alone. Dramatically, the combined effect on U251 was the exact opposite. Importantly, there was little toxicity on astrocyte under the dose of C18H17NO6and Scutellarin in the study. In molecular level, the mRNA and protein expression of Fas-associated factor 1 (FAF1) expression in U251 and LN229 were upregulated by C18H17NO6and its combination with Scutellarin, especially the protein expression.Conclusion. C18H17NO6could efficiently suppress cell proliferation and induce cell apoptosis in glioma cells, and its combination with Scutellarin had a promoting effect, in which the underlying mechanism referred to the upregulation of Fas-associated factor 1.

Cu2S, featuring low cost, nontoxicity, and earth abundance, has been recently recognized as a high efficiency thermoelectric (TE) material. However, before reaching the maximum of the figure of merit (ZT), Cu2S undergoes three phase transformations starting at 370 K, which give rise to severe problems, such as possible decomposition and low reliability. Herein, we discover CsCu5S3 with phase transformation at 823 K, which is significantly higher than the 370 K value of Cu2S. Single crystal diffraction data reveal that its two phases are constructed by the same Cu4S4 columnar building unit via propagating either at the opposite sides into a layered o-CsCu5S3, or at the four apexes into a 3D t-CsCu5S3, respectively. Interestingly, the o-to-t transformation is quick, but the reverse one is relatively slow. Theoretical studies reveal that the Cu4S4 column exhibits not only the most condensed atomic aggregation (Dcolumn) but also the lightest effective mass (m*), along which higher σ is realized. More interest...

This paper investigated the combustion behavior of coke breeze granulated with other raw materials for iron ore sintering in a broad temperature range up to 1350 °C in air and sintering flue gas atmosphere, based on the exploration of the physiochemical characteristics of the coke breeze granules in industry. It was shown that after granulation the −0.25 mm coke breeze particles adhered to nuclei constituted by other sintering raw materials or served as a component of granules composed of mixed fine particles with homogeneous composition. Conversely, +0.5 mm coke breeze particles acted as nuclei to which fine particles of other materials adhered. The coke breeze particles with size of 0.25–0.5 mm, on the other hand, had dual roles as either adhering fines or nuclei. According to the combustion tests of typical granules consisted of −0.25 or 2–3 mm coke breeze particles, the structure and size of the granules as well as atmosphere strongly affected the combustion behavior of coke breeze. The adhering fines on the surface of coke breeze caused a decrease in its combustion rate in air (e.g., up to 26% at 950 °C and 1050 °C). Compared with the adhering fines, the sintering flue gas atmosphere played a more pronounced role in reducing the combustion rate. In this atmosphere, the combustion rate was in close association with the reaction between coke breeze and iron oxide in adjacent iron ore particles. The granules composed of −0.25 mm mixed particles could exhibit lower reduction reaction temperature (approximately a 100 °C difference) and stronger reduction reaction intensity than those consisted of coarse coke breeze in the size of 2–3 mm, leading to a higher heat loss. Minimizing the addition of −0.25 mm coke breeze, maintaining the highest combustion temperature at around 1300 °C, and keeping relatively high oxygen content in atmosphere are expected to promote combustion efficiency of coke breeze and thus energy utilization in iron ore sintering.

Flavonoid glycosides are important plant secondary metabolites with broad pharmacological activities. Flavonoid glycosides are generated from aglycones, in reactions catalyzed by typical uridine diphosphate-dependent glycosyltransferases (UGTs). Liverworts produce various types of flavonoid glycosides; however, only two UGTs have been characterized from liverworts to date. Here, we isolated three genes encoding UGTs (MeUGT1, MeUGT2, and MpalUGT1) from the liverwort species Marchantia emarginata and Marchantia paleacea through transcriptome sequencing. Recombinant MeUGT1, MeUGT2, and MpalUGT1 proteins heterologously produced in Escherichia coli exhibited catalytic activity towards multiple flavonoids. MeUGT1 and MpalUGT1 catalyzed the glycosylation of flavonols into the corresponding 3-O-glucosides with UDP-glucose as the sugar donor, while MeUGT2 exhibited a wider substrate specificity that included flavonols, flavones, and flavanones. When MeUGT2 was expressed in E. coli, the yield of flavonol 3-O-glucosides reached to 40-60% with feeding of the substrates kaempferol or quercetin under optimal conditions. Furthermore, heterologous expression of MeUGT1 in Arabidopsis thaliana increased the flavonol glycoside contents in the plants. Therefore, the UGTs characterized in this study could provide new data that will be useful for examining flavonoid biosynthesis in liverworts.

The objective of this study was to investigate the effects of intensive fattening with total mixed rations (TMR) on carcass characteristics, meat quality, and chemical composition of the yak meat. Theoretical data has been provided for evaluating the quality of yak meat during natural grazing and short-term fattening. Based on the analysis, we found that in fattening yak, the carcass weight (CWT) was increased by 106.43%, whereas the cooking loss, tenderness, and drop loss were significantly improved due to higher intramuscular fat content and lower moisture (P < 0.05). Protein, fat, calcium, and amino acids were also much higher (P < 0.01) in fattening yak compared with the grazing yak. The levels of albumin (ALB), lactate dehydrogenase (LDH), triglyceride (TRIG), and amylase (AMYL) in serum indicated better nutritional status for fattening yaks. The transcriptomics analysis showed that the high expression of ACSL1 and ACACB genes improved the synthesis and deposition of fat in fattening yak, whereas the regulation of SLC7A8, ATP1A4, ATP1A1, SLC3A2, and CPA3 gene expression weakened the proteolysis. These results indicated that fattening with TMR improves the yield and quality of the yak meat.

Purpose: To explore the main active ingredients and mechanism of Yangyin Yiqi Huoxue (YYYQHX) Recipe in treating Sjogren’s syndrome.Methods: The main active ingredients of Yangyin Yiqi Huoxue(YYYQHX) Recipe were obtained through UPLC-LTQ-Orbitrap-MSn research technical analysis. Subsequently, the main active ingredients were analyzed by network pharmacology to explore their important targets and biological processes. Finally, the important target M3 muscarinic acetylcholine receptor (CHRM3) gene was verified by cytological experiments.Results: We identified 41 active ingredients in the YYYQHX Recipe, and identified 26 potential targets through network pharmacology methods. According to the network analysis and literature research, CHRM3 is one of the main targets of YYYQHX in the treatment of Sjogren’s syndrome. We observed the effect of YYYQHX on the CHRM3 and aquaporin 5(AQP5) genes using cytological experiments. The results showed that YYYQHX significantly increased the expression of CHRM3 and AQP5 in submandibular gland cells. This may be the mechanism of YYYQHX Recipe in improving symptoms such as dry mouth in Sjogren’s syndrome.Conclusions: This study provides a strategy for understanding the mechanism of action of YYYQHX in treating Sjogren’s syndrome by combining UPLC-LTQ-Orbitrap-MS research, network pharmacology, and experimental validation.

Long-term energy stress (ES) during the cold season is a serious problem for the breeding of yaks. In this paper, the response of fat metabolism in yaks to long-term ES during the cold season was studied. Gas chromatography (GC) analysis showed that the percentage of saturated fatty acids (SFAs) in the subcutaneous fat of the yaks in the ES group was 42.7%, which was less than the 56.6% in the CO group (p &lt, 0.01) and the percentage of polyunsaturated unsaturated fatty acids (PUFAs) in the subcutaneous fat of the yaks in the ES group was 38.3%, which was more than the 26.0% in the CO group (p &lt, 0.01). The serum analysis showed that fatty acid oxidation in yaks was increased under long-term ES. In the subcutaneous fat of yaks under long-term ES, the gene expression levels of glycerol-3-phosphate acyltransferase 4 (GPAT4), hormone-sensitive lipase (HSL), patatin-like phospholipase domain-containing protein 2 (PNPLA2), acyl-CoA dehydrogenase (ACAD), acyl-coenzyme A thioesterase 8 (ACOT8), facilitated glucose transporter (GLUT4), 3-oxoacyl-[acyl-carrier-protein] synthase (OXSM), oestradiol 17-beta-dehydrogenase 8 (HSD17B8) and malonate-Co-A ligase ACSF3 (ACSF3) were downregulated (q &lt, 0.05), whereas the gene expression levels of aquaporin-7 (AQP7), long-chain-fatty-acid-CoA ligase (ACSL), elongation of very long chain fatty acids protein (ELOVL) and fatty acid desaturase 1 (FADS1) were upregulated (q &lt, 0.05), indicating the inhibition of fat catabolism, fat anabolism, fatty acid oxidation, glucose (GLU) intake and SFA synthesis and the promotion of glycerinum (GLY) transportation and PUFA synthesis. Additional findings showed that the gene expression levels of leptin (LEP), adenosine 5&prime, monophosphate-activated protein kinase (AMPK) and phosphatidylinositol 3-kinase (PI3K) were upregulated (q &lt, 0.05), whereas the gene expression levels of malonyl-CoA decarboxylase (MCD), sterol regulatory element-binding protein 1 (SREBF1), mammalian target of rapamycin (mTOR) and serine/threonine-protein kinase (AKT) were downregulated (q &lt, 0.05), indicating that fat metabolism in the subcutaneous fat of yaks under ES was mainly regulated by AMPK signaling and mTOR and PI3K-AKT signaling were also involved. Energy consumption was inhibited in the subcutaneous fat itself. This study can provide a theoretical basis for the healthy breeding and genetic breeding of yaks.

Background Lactoferricin (Lfcin) is an antimicrobial activity center of lactoferrin, produced by hydrolysis from the N-terminal of lactoferrin. It was hypothesized that the intramolecular disulfide bond in Lfcin could affect its antibacterial function through influencing its molecular structure. To prove this hypothesis, bovine Lfcin (bLfcin) and its two derivatives, bLfcin with an intramolecular disulfate bond (bLfcin DB) and bLfcin with a mutation C36G (bLfcin C36G), were synthesized, purified, and identified. The circular dichroism spectra of the peptides were detected in solutions with different ionic and hydrophobic strength. The antibacterial activity of the peptides against Trueperella pyogenes, separated from cow milk with mastitis, were determined. Results The secondary structure of bLfcin DB showed more β-turn and less random coil than the other peptides in H2O, similar ratios of secondary structures with bLfcin and bLfcin C36G under ionic conditions, and close percentages of secondary structure with bLfcin under hydrophobic conditions. The synthetic peptides exhibited strong antimicrobial activity against T. pyogenes isolates, T. pyogenes ATCC 19,411, and E. coli ATCC 25,922. The antimicrobial activities of the three peptides were greater against T. pyogenes than against E. coli, and bLfcin DB exhibited higher antibacterial activity compared with its derivatives. Conclusions The intramolecular disulfide bond could change the molecular structure of bLfcin under alternative ionic strengths and hydrophobic effects, and the formation of the disulfide bond is beneficial to executing the antibacterial function of bLfcin.

Background Colorectal cancer, one of the most common digestive tumors with high mortality and morbidity worldwide, currently lacks effective therapies available to improve the prognosis. This study was aimed to investigate the potency of Scutellarin against colorectal cancers, and explore the related mechanism via genomic and proteomic analysis. Methods Cell counting kit-8 assay was employed to detect the viability of HCT-116 and RKO cell lines treated with Scutellarin. The apoptosis of HCT-116 and RKO cells after Scutellarin administration was determined by TUNEL staining and Caspase 3/7 activity. Cell cycle was detected by flow cytometry analysis. The wound healing and transwell invasion test detected the role of Scutellarin in migration and invasion of HCT-116 and RKO cells. Meanwhile, the energy metabolism and growth of tumor tissues in vivo at day 28 were observed by PET-CT after Scutellarin administration with 50 mg/kg, 100 mg/kg and 300 mg/kg into 4-week-old nude mice. Blood routine and liver functions were also detected to evaluate the side effect of Scutellarin. Furthermore, the disease and function classifications which the differentially expressed genes and proteins involved after Scutellarin treatment were determined by genomic and proteomic analysis respectively. Results The Scutellarin inhibited the migration and increased apoptosis of HCT-116 and RKO cell lines. Besides, Scutellarin treatment substantially decreased the growth and volume of colorectal tumors in nude mice without side effects on the blood routine and liver function. The differentially expressed genes in RKO cells after Scutellarin administration were mainly enriched in cell death and survival, organismal injury and abnormalities, and cancer. In addition, forty-seven upregulated and twenty-nine downregulated proteins were identified. Functional clustering analysis exhibited enriched biological processes, cellular components, molecular functions and related pathways of these proteins in cellular metabolic. Then protein–protein interactions analysis showed the regulatory relationship among these differentially expressed proteins. Conclusions Taken together, the present findings revealed that Scutellarin exerted significant antitumor effect with no side effects in the blood and liver by regulating various important molecules in tumor proliferation, apoptosis and metastasis.

Ethnopharmacological relevance The Qing' E Formula (QEF) is a compound preparation that was originally recorded in the ‘Prescriptions of the Bureau of Taiping People's Welfare Pharmacy’ during the Song Dynasty (10th century CE). It consists of four Chinese medicinal herbs, Eucommiae Cortex (Eucommia ulmoides), Psoraleae Fructus (Psoralea corylifolium), Juglandis Semen (Juglans regia), and Garlic Rhizoma. According to traditional Chinese medicine (TCM), QEF has the ability to tonify the kidney and strengthen muscle and bone. According to the ‘kidney governing bone’ theory in TCM, QEF is also used to treat the symptoms of climacteric syndrome, especially osteoporosis caused by reduced production of estrogen during the perimenopausal period; however, the therapeutic roles of the individual components of the QEF and their compatibility within the formula has not been investigated. Aim of the study In this study, the compatibility mechanism and estrogen-like action properties of the four herbal components in the QEF was elucidated according to the organizing principle of Chinese medicine formulas using both in vitro and in vivo models. Materials and methods The estrogen-like effects of QEF and its herbal components were investigated in MCF7 and HEK293 cells as well as ovariectomized (OVX) rats. The estrogen-like effects of the QEF and its components were analyzed in vitro using Cell Counting Kit-8 and Luciferase reporter gene assays. In the in vivo studies, the blood plasma levels of hormones, lipids, neurotransmitters, aromatase, superoxide dismutase (SOD), and malondialdehyde (MDA) were measured through enzyme-linked immunosorbent assays (ELISAs). The histological morphologies of the target organs after exposure to QEF were investigated by HE staining and immunohistochemical methods. The expression levels of estrogen pathway-related proteins and genes in the OVX rats were measured by Western blotting and real time quantitative PCR (RT-qPCR), respectively. Results The in vitro results showed that the QEF, Eucommia (EC) and Psoralea (PF) promoted the proliferation of MCF-7 cells and upregulated the expression of ERα, ERβ and pS2 genes in the MCF-7 cells. Notably, the QEF demonstrated the most active estrogen-like effects compared to the individual ingredients. The in vivo results showed that the QEF, EC, and PF increased the uterine coefficient, upregulated the expression of both ERs (ERα and ERβ) in the uterus, and increased blood serum hormone levels. QEF and its individual components ameliorated menopausal-derived lipid metabolism dysfunction, increased neurotransmitter production by stimulating the adrenal glands, enhanced the antioxidant activity in the serum by increasing the concentration of SOD, reversed ovariectomy-derived atrophy in the uterus, and reduced the weight gain associated with estrogen reduction in the OVX rats. The QEF also antagonize the loss of appetite of OVX animals caused by feeding Psoralea alone, which could explain the compatibility mechanism of Qing' E Formula with reducing toxicity and increasing efficiency. Conclusions The estrogen-like effects of Eucommia and Psoralea were mainly mediated through activation of ERα and ERβ. The phytoestrogen components regulated hormone production and the expression of related proteins and genes, which indicated that these components exhibited estrogen-like therapeutic effects. However, the QEF showed the greatest estrogen-like effects compared to the individual components. Overall, this corroborated the therapeutic prowess of the QEF and clarified the pharmacodynamic interactions between the different components extracts in the QEF.

To combine noncentrosymmetry, large second order nonlinear optical (NLO) susceptibility, deep UV transparency, and phase matchability simultaneously into a single structure is a great challenge. Especially, the relationship between the macrophase matchability and microstructure has been less investigated. Herein, we report a unique Ba2NaClP2O7 representing the first phase-matchable example of the fresnoite family, which exhibits excellent NLO properties, including short absorption edge (

Ultrasmall nanoclusters (e.g., Au15(SR)13) are crucial in not only real applications such as bioapplication but also in understanding the structure transition from gold complexes to gold nanoclusters. However, the determination of these transition-sized gold nanoclusters has long been a major challenge. In this work, two new nanoclusters in the transition regime, including the thus far smallest thiolated alloy nanocluster Cd1Au14(StBu)12 and the homogold nanocluster Au16(S-Adm)12, are obtained and their atomic structures are fully determined by single crystal X-ray diffraction. Moreover, based on the structures of Cd1Au14(SR)12 and Au16(SR)12, we perform DFT calculations to predict the structure of the “transformation” nanocluster, Au15 (Au15(SR)12– and Au15(SR)13). Overall, this work bridges the gaps between gold complexes and nanoclusters.

Differentiation therapies have been proposed to overcome the impaired cell differentiation in acute myeloid leukemia (AML). However, thus far the all-trans retinoic acid-based differentiation therapy has been the only successful modality in treating acute promyelocytic leukemia. Here, we showed that vibsanin A, a novel protein kinase C (PKC) activator, sensitized AML cells to tyrosine kinase inhibitor (TKI)-induced differentiation. Vibsanin A augmented the ability of TKIs to induce growth inhibition and G1 cell cycle arrest of AML cells. Mechanistically, PKC activation was involved in the differentiation-inducing effects of combining vibsanin A with TKIs. Moreover, we found that vibsanin A enhanced TKI-induced Lyn expression and suppression of Lyn interfered with AML cell differentiation, indicating an essential role for Lyn expression in the combination-induced differentiation. Finally, combining vibsanin A and TKIs enhanced the activation of the Raf/MEK/ERK cascade. Together, this is the first study to evaluate the synergy of vibsanin A and TKIs in AML cell differentiation. Our study lays the foundation in assessing new opportunities for the combination of vibsanin A and TKIs as a promising approach for future differentiation therapy.

The A2MIIMIV3Q8 family (A = alkali metal; MII = divalent metal; MIV = tetravalent metal; Q = chalcogenide) has attracted much attention because of its diverse structures and properties. Herein, we have successfully synthesized six new compounds as the first Mn-containing members of this family, Cs2MnGe3S8 (1), Cs2MnGe3Se8 (2), Cs2MnSn3Se8 (3), Rb2MnGe3S8 (4), Rb2MnGe3Se8 (5), and Rb2MnSn3Se8 (6). Compounds 1 and 6 crystallize in the monoclinic space group P21/n (No. 14) and P21 (No. 4), respectively, whereas compounds 2–5 crystallize in the non-centrosymmetric orthorhombic P212121 (No. 19). According to our theoretical calculations, their energy gaps are mainly dominated by s states of MIV and p states of Q and minor Mn 3d. Plate-like crystals with sizes about 20 × 5 × 1 mm3 of 2 and 3 are obtained by the Bridgeman method. In addition, we propose a structure mismatch factor that is defined as F = rMII+ rMIV + 2rQ2– – 2rA+ to provide a clear description of how three different structure types distribute amo...

The new selenide Cs2Ge3In6Se14, featuring its own structure type with germanium in mixed-valence states, is discovered via a solid-state reaction at 1173 K. The compound crystallizes in the R3m sp...

Obtaining cognate single-heteroatom doping is highly desirable but least feasible in the research of nanoclusters (NCs). In this work, we reported a new Au16Ag1(S-Adm)13 NC, which is synthesized by the combination of single-atom engineering and ligand-exchange strategies. This new NC is so far the smallest crystallographically characterized Au-based NC protected by thiolate. The Au16Ag1(S-Adm)13 exhibited a tristratified Au3–Au2Ag1–Au1 kernel capped by staple-like motifs including one dimer and two tetramers. In stark contrast to the size-growth from Au18(S–C6H11)14 to Au21(S-Adm)15 via just the ligand-exchange method, combining single Ag doping on Au18(S–C6H11)14 resulted in the size-decrease from Au17Ag1(S–C6H11)14 to Au16Ag1(S-Adm)13. DFT calculations were performed to both homogold Au18 and single-heteroatom-doped Au17Ag1 to explain the opposite results under the same ligand-exchange reaction. Our work is expected to inspire the synthesis of new cognate single-atom-doped NCs by combining single-atom e...

Ethnopharmacological relevance Fructus Psoraleae (FP), dry mature fruits of Cullen corylifolium (L.) Medik., has been used clinically to treat kidney yang deficiency-induced impotence, asthma and cold pain in waist and knee caused by kidney deficiency. A study of the source of the significant kidney-enhancing effect of FP revealed that it may be due to its strong estrogen-like activity. Aim of the study This study aimed to investigate the estrogen-like activity of the FP extract and 13 bioactive compounds in it, as well as the mechanisms underlying their estrogen-like and anti-osteoporosis activities. Materials and methods The estrogen-like activities of the 75% ethanol-only FP extract, and 75% ethanol plus petroleum ether, ethyl acetate, n-butanol or water FP extracts were each measured using Cell Counting Kit-8 (CCK-8) and luciferase reporter gene assays. The compounds were identified by high-performance liquid chromatography analysis. The activation of estrogen receptor signaling by the compounds was compared with that by estradiol (E2) using the molecular docking software MOE-Dock 2008.10. The activation of the ER-Wnt-β-catenin signaling pathway was investigated using an alkaline phosphatase (ALP) assay, qPCR analysis and Western blot analysis. Results The results revealed that the 75% ethanol plus ethyl acetate extract showed the highest estrogen-like activity among the four 75% ethanol extract fractions (further extracted with petroleum ether, ethyl acetate, n-butanol or water). Some compounds in FP showed strong estrogenic effect and anti-osteoporosis activity, and activated the Wnt-β-catenin pathway. The isoflavone compound was the most active. Conclusions This study demonstrated that FP has a strong estrogen-like activity and some of its component compounds have anti-osteoporosis activity by activating the ER-Wnt-β-catenin signaling pathway. Our detections provide a new insight into the mechanisms underlying the estrogen-like and anti-osteoporosis activities of FP, as well as a better understanding of structure effects.

Two novel tetradentate bis-cyclometalated platinum (IV) complexes of TPA-2q-PtCl2 and 3TPA-2q-PtCl2 with CˆN*NˆC cyclometalated ligands and two coordinated chlorine atoms were synthesized and characterized. The crystal structure of TPA-2q-PtCl2 shows a trans-form irregular octahedral geometry by measurement of single-crystal X-ray diffraction, where two CˆN coordination moieties are twisted and two chlorine atoms are located on both sides of platinum atom. A medium absorption band in a range of 450–474 nm is observed, which is assigned to the metal-to-ligand charge-transfer (MLCT) and intramolecular charge transfer (ILCT). And two obvious emission peaks at about 635 and 750 nm are displayed for both platinum (IV) complexes in 2-methyltetrahydrofuran solutions, which originate from the ILCT and MLCT characters to the lowest excited state. Using one of platinum (IV) complexes as a single dopant and a blend of poly(vinylcarbazole) as a host matrix, their single-emissive-layer polymer light-emitting diodes (PLEDs) exhibit an outstanding near-infrared emission with an electroluminescent (EL) peak of 750 nm. The better electroluminescent properties are obtained in the 3TPA-2q-PtCl2 doped devices with an external quantum efficiency of 0.85% and a radiance of 164 μW/cm−2. This is the first reported sample about tetradentate biscyclometalated platinum (IV) complexes used as organic NIR electroluminescent materials for promising application in PLEDs.

As an important intermediate link between the smaller and larger size thiolate-protected gold nanoparticles (RS-AuNPs), the molecular formula and atomic structure of the ∼14 kDa core-mass RS-AuNP species (containing around 70 core gold atoms) have not been determined unambiguously. In this work, we theoretically predict an unprecedented ∼14 kDa core-mass AuNP species, denoted as Au68(SR)36, which is composed a symmetric, face-centered-cubic (fcc) 68-gold atom framework. The fcc gold kernel in the Au68(SR)36 is made of eight 13-atom Au-cubotahedrons sharing 12 square faces, showing a standard 2 × 2 × 2 magic cube formula. The Au68(SR)36 is thought to be a key intermediate NP bridging the evolution of Au44(SR)28 and Au92(SR)44. The DFT calculations indicate the Au68(SR)36 has a sizable HOMO–LUMO gap of 0.98 eV and relative high thermodynamic stability. The fcc 68-atom gold framework in the Au68(SR)36 also presents a new candidate to address the atomic structure of recently reported water-soluble mercaptoben...

A large thiolate/phosphine coprotected Ag50(Dppm)6(SR)30 nanocluster was synthesized through the further growth of Ag44(SR)30 nanocluster and characterized by X-ray photoelectron spectroscopy (XPS), electrospray ionization mass spectrometry (ESI-MS), and single-crystal X-ray analysis. This new nanocluster comprised a 32-metal-atom dodecahedral kernel and two symmetrical Ag9(SR)15P6 ring motifs. The 20 valence electrons correspond to shell closure in the Jellium model. Moreover, this nanocluster could be alloyed by templated/galvanic metal exchange to the homologue AuxAg50–x(Dppm)6(SR)30 nanocluster; the latter showed much higher thermal stability than the Ag50(Dppm)6(SR)30 nanocluster. Further experiments were conducted to study the optical, electrical, and photoluminescence properties of both nanoclusters. Our work not only reports two new larger size nanoclusters but also reveals a new way to synthesize larger size silver and alloy nanoclusters, that is, controlled growth/alloying.

The atomic structure of a ten-electron (10e) thiolate-protected gold cluster, denoted as Au29(SR)19, was theoretically predicted. Based on the prediction of the atomic structure of the 10e Au29(SR)19 cluster, we proposed a novel 'gold-atom insertion, thiolate-group elimination' mechanism to understand the structural evolution of the face-centered-cubic (fcc) thiolate-protected gold clusters. The key step of structural evolution from Au28(SR)20 to Au29(SR)19 and then to the Au30(SR)18 cluster, i.e. the growth of triangle-Au3 units in the gold cores, is understood from the first insertion of an exterior Au(0) atom into the ligand shell and then cleavage of μ3-SR groups.

The concept of “graft-onto” has been exploited to facilitate nanocluster growth from Pt1Ag28 to Pt1Ag31., Atomically precise engineering on the nanocluster surface remains highly desirable for the fundamental understanding of how surface structures of a nanocluster contribute to its overall properties. In this paper, the concept of “graft-onto” has been exploited to facilitate nanocluster growth on surface structures. Specifically, the Ag2(DPPM)Cl2 complex is used for re-constructing the surface structure of Pt1Ag28(SR)18(PPh3)4 (Pt1Ag28, SR = 1-adamantanethiolate) and producing a size-growth nanocluster – Pt1Ag31(SR)16(DPPM)3Cl3 (Pt1Ag31). The grafting effect of Ag2(DPPM)Cl2 induces both direct changes on the surface structure (e.g., size growth, structural transformation, and surface rotation) and indirect changes on the kernel structure (from a fcc configuration to an icosahedral configuration). Remarkable differences have been observed by comparing optical properties between Pt1Ag28 and Pt1Ag31. Significantly, Pt1Ag31 exhibits high photo-luminescent intensity with a quantum yield of 29.3%, which is six times that of the Pt1Ag28. Overall, this work presents a new approach (i.e., graft-onto) for the precise dictation of nanocluster surface structures at the atomic level.