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Three multiphase metallaphotoredox catalysts M−Salen−CMP (M Zn, Cu and Co) with dual-catalytic functions were constructed by linking M−salen (M Zn, Cu and Co) and 2, 4, 6-tris(4-ethylphenyl)-1, 3, 5-triazine (TEPT) monomer via covalent bonds. The catalysts M−SATE−CMP (M Zn, Cu and Co) have different d-band centers based on different metal active centers, resulting in the difference of the optical property as well as their adsorption and activation capacities for the reactants. Therefore, they can selectively photocatalytically oxidize β-keto esters to α-hydroperoxide β-keto esters (ROOH) or α-hydroxyl β-keto esters (ROH), where ROOH is an intermediate of ROH. [Display omitted] Photocatalytic selective oxidation plays an important role in developing green chemistry. However, it is challenging to design an efficient photocatalyst for controlling the selectivity of photocatalytic oxidation reaction and exploring its detailed mechanism. Here, we synthesized three conjugated microporous polymers (CMPs) with D-A structures, named M−SATE−CMPs (M Zn, Cu and Co), with different d-band centers based on different metal centers, resulting in the discrepancy in adsorption and activation capacities for the reactants, which produces the selectivity of β-keto esters being catalyzed into α-hydroperoxide β-keto esters (ROOH) or to α-hydroxyl β-keto esters (ROH). Density functional theory (DFT) calculations also demonstrate that the adsorption and activation capacities of the metal active centers in M−SATE−CMPs (M Zn, Cu and Co) for ROOH are the key factors to influence the photocatalytic selective oxidation of β-keto ester. This study provides a promising strategy for designing a metallaphotoredox catalyst whose photocatalytic selectivity depends on the d-band center of metal site in the catalyst. [ABSTRACT FROM AUTHOR]

We have developed a one-pot synthesis of bio-carbon nanowires from the natural product sodium alginate at low temperature, without using any catalyst, for anticoagulation applications. Sodium alginate is carbonized and sulfated/sulfonated in situ by solid state heating of a mixture of sodium alginate and ammonium sulfite. By regulating the heating temperature and the ratio of ammonium sulfite to sodium alginate, we modulated the degree of sulfation/sulfonation and carbonization, as well as the morphology of the carbon nanomaterials. The core-shell sulfated/sulfonated bio-carbon nanowires (CNWs Alg@SOx) made by the reaction of a mixture of ammonium sulfite and sodium alginate with a mass ratio of 5 (ammonium sulfite to sodium alginate) at 165 °C for 3 h, exhibit strong inhibition of thrombin activity due to their ultrahigh binding affinity towards it (dissociation constant (K d) = 8.7 × 10−11 M). The possible formation mechanism of the carbon nanowires has been proposed. The thrombin-clotting time delay caused by CNWs Alg@SOx is ∼ 170 times longer than that caused by sodium alginate. Hemolysis and cytotoxicity assays demonstrated the high biocompatibility of CNWs Alg@SOx. Furthermore, the thromboelastography of whole-blood coagulation and rat-tail bleeding assays further reveal that CNWs Alg@SOx have a much stronger anticoagulation activity than sodium alginate and naturally sulfated polysaccharides (e.g., fucoidan). Our results suggest that the low-temperature prepared, cost-effective, and highly biocompatible CNWs Alg@SOx show great potential as an efficient anticoagulant for the prevention and treatment of diseases associated with thrombosis. [ABSTRACT FROM AUTHOR]

Two methodologies are proposed in this paper to reduce electromagnetic vibration and noise of permanent magnet synchronous motor. A multiphysics model is firstly established to predict the vibration and noise. Experimental tests are conducted to validate the model. Then, the source of the vibration and noise peaks from calculated and tested results is located. Two methodologies are proposed to mitigate this source. One is by reducing its amplitude through adjusting slot opening width and magnet shape. The other is by changing the phase of the specific force harmonic along the axial direction through stepwise or continuous magnet skewing. The optimum skewing angle is analytically derived. Based on the validated multiphysics model, optimizations under different methods are compared. It is found that considerable reductions of noise can be achieved by reducing low space harmonics of radial force. In particular, to reduce the noise over a wide frequency band, magnet skewing is a better solution than optimizing slot opening width and magnet shape. [ABSTRACT FROM AUTHOR]

The Hippo tumor suppressor pathway is an important regulator of cell proliferation and apoptosis, and signal transduction occurs through phosphorylation of the effector protein TAZ by the serine/threonine kinase LATS1/2. Here, we report the biophysical and computational studies to characterize the interaction between TAZ and LATS1/2 through WW domain-PPxY motif binding. We show that the TAZ WW domain exhibits a binding preference for the second of the two PPxY motifs of LATS1 in vitro . We modelled the structure of the domain in complex with LATS1 PPxY2 peptide and, through molecular dynamics simulations, show that WW domain-PPxY2 complex is stable with some flexibility in the peptide region. Next, we predict and verify that L143 and T150 of the WW domain are important for TAZ binding with the PPxY2 peptide using mutational and isothermal titration calorimetric studies. Furthermore, we suggest that the electrostatic potential of charged residues within the binding pocket may influence the ligand affinity among otherwise highly similar WW domains. [ABSTRACT FROM AUTHOR]

Two new amino acid ionic liquids (AAILs) [C n mim][Thr] ( n = 2, 4) (1-alkyl-3-methylimidazolium threonine salt) were prepared and characterized. The values of density, surface tension and refractive index of the ILs were measured at T = (288.15 to 328.15) K and the values of the molar surface Gibbs free energy, g , were calculated. Using the molar surface Gibbs free energy, the traditional Eötvös equation was improved to be a new Eötvös equation. It is found that the slope of the new Eötvös equation is the molar surface entropy of the ILs and the intercept is the molar surface enthalpy which is a temperature-independent constant. With the help of the refractive index and the molar surface Gibbs free energy, an equation to predict surface tension of the ILs was derived. Using this equation, predicted values of surface tension with the corresponding experimental ones are highly correlated and extremely similar. According to a new scale of polarity for ILs, the polarity of ionic liquids [C n mim][Thr] ( n = 2, 4) was estimated. [ABSTRACT FROM AUTHOR]

Abstract: In this paper, we are concerned with numerical methods for the solution of initial–boundary value problems of anomalous diffusion equations of order . The classical Crank–Nicholson method is used to discretize the fractional diffusion equation and then the spatial extrapolation is used to obtain temporally and spatially second-order accurate numerical estimates. Two preconditioned iterative methods, namely, the preconditioned generalized minimal residual (preconditioned GMRES) method and the preconditioned conjugate gradient for normal residual (preconditioned CGNR) method, are proposed to solve relevant linear systems. Numerical experiments are given to illustrate the efficiency of the methods. [Copyright &y& Elsevier]

Abstract: Transendothelial trafficking model mimics in vivo differentiation of monocytes into dendritic cells (DC). The serum from patients with systemic lupus erythematosus promotes the differentiation of monocytes into mature DC. We have shown that selective inhibition of NF-κB by adenoviral gene transfer of a novel mutated IκBα (AdIκBαM) in DC contributes to T cell tolerance. Here we demonstrated for the first time that asthmatic serum facilitated human monocyte-derived DC (MDDC) maturation associated with increased NF-κB activation in this model. Furthermore, selective blockade of NF-κB by AdIκBαM in MDDC led to increased apoptosis, and decreased levels of CD80, CD83, CD86, and IL-12 p70 but not IL-10 in asthmatic serum-stimulated MDDC, accompanied by reduced proliferation of T cells. These results suggest that AdIκBαM-transferred MDDC are at a more immature stage which is beneficial to augment the immune tolerance in asthma. [Copyright &y& Elsevier]

Objective: To investigate the distribution of cystathionine-beta-synthase (CBS) in the brain of the spontaneous hypertensive rat. Method: Eight adult male spontaneously hypertensive rats (SHR), and 8 pargue-Darley (SD) rats were assigned into hypertensive group and control group correspondingly. All rats were killed by over-dose anesthesia. The cerebral cortex, cerebellum, hypothalamus, hippocampus, medulla oblongata were dissociated quickly. Their mRNA of CBS was detected by RT-PCR or Real Time-PCR. Results: The transcriptional levels of CBS in brains in the SHR group were significantly decrease compared with the normal control group (0.93±0.01 vs. 1.00±0.00, P<0.05; 0.39±0.02 vs. 1.00±0.00, P<0.01; 0.07±0.01 vs. 1.00±0.00, P<0.01; 0.09±0.03 vs. 1.00±0.00, P<0.01; 0.36±0.06 vs. 1.00±0.00, P<0.01). Conclusion: The expression of CBS mRNA in brain tissue of SHR rats are down-regulated, it is likely to get through the mechanism of central, such as medulla oblongata, which probably involved in the pathogenesis of hypertension. [ABSTRACT FROM AUTHOR]

Magnaporthe oryzae seriously threatens rice production and multiple signaling pathways are involved in regulating the pathogenic mechanism of M. oryzae. In M. oryzae , the role of MoFim1 in organizing actin is already identified. The research highlighted its role in other signaling pathways. In this research, MoFIM1 null mutant was produced; resulted in disturbance of three MAPK signaling pathways, hydrophobicity development, and autophagy. The hydrophobicity of mutant Δ Mofim1 was identified to be abnormal by the hydrophobicity testing. Through infection experiments, it was also found that the appressorium-like structure of Δ Mofim1 lost the ability to infect the host cells. Moreover, through the detection of western blot, MoFim1 was involved in three MAPK signaling pathways, and MoFilm1 interacted with MoPmk1. Furthermore, disruption of the gene of MoFIM1 resulted to an influence of autophagy, which certified by fluorescence observation and western blot. Taken together, this research demonstrated that MoFim1 played a crucial role in MAPK signal pathway and autophagy, which laid a more theoretical foundation for improving the pathogenic mechanism of M. oryzae. • The growth and pathogenicity of the mutant Δ Mofim1 were inhibited. • Δ Mofim1 affected the formation and penetration of appressorium-like structure. • The hydrophobicity of aerial hyphae was disrupted in the mutant Δ Mofim1. • MoFim1 participated in three MAPK signaling pathway (including Pmk1/Mps1/Osm1 MAPK signaling pathway). • Knocking out MoFIM1 lead to an abnormal increase in autophagy levels. [ABSTRACT FROM AUTHOR]

Abstract: The lack of disease-modifying pharmacological agents for effective treatment of multiple sclerosis (MS) still represents a large and urgent unmet medical need. Our previous studies showed that ligands to type 2 imidazoline receptors (I2R) were effective in protecting spinal cord injury caused by experimental autoimmune encephalomyelitis (EAE), a mouse model of MS. In this study, we further examined the protective property of a very selective ligand of I2R, 2-(2-benzofuranyl) 2-imidazoline (2-BFI) against EAE. Importantly, a mechanism of 2-BFI-mediated protection was investigated which possibly involves an I2R binding protein, brain-creatine kinase (B-CK), as well as CaATPase and calpain. The enzymatic activity of B-CK and CaATPase was significantly reduced in EAE injured spinal cord. Reduction of B-CK activity in EAE spinal cord may lead to energy reduction and dysfunction in cellular calcium homeostasis. Increased intracellular calcium evokes elevation of calpain activity occurring in EAE spinal cord which causes further tissue damage. Indeed, EAE injured spinal cord showed significant reduction in CaATPase and increase calpain activities. Remarkably, spinal cord tissue from mice treated daily with 2-BFI during the progression of EAE significantly restored B-CK and CaATPase enzymatic activities and showed no induction in calpain activity. Moreover, EAE spinal cord from 2-BFI treated mice also demonstrated better preservation of myelin; reduced axonal injury, as evidenced by the lower level of β-APP expression, and above all, highly improved neurobehavioral scores (p <0.01; n =10). These findings suggest that 2-BFI can be further developed as a therapeutic drug for MS treatment. [Copyright &y& Elsevier]

We aimed to develop a high-throughput deep DNA sequencing assay of cerebrospinal fluid (CSF) to identify clinically relevant oncogenic mutations that contribute to the development of glioblastoma (GBM) and serve as biomarkers to predict patients' responses to surgery. For this purpose, we recruited five patients diagnosed with highly suspicious GBM according to preoperative magnet resonance imaging. Subsequently, patients were histologically diagnosed with GBM. CSF was obtained through routine lumbar puncture, and plasma from peripheral blood was collected before surgery and 7 days after. Fresh tumor samples were collected using routine surgical procedures. Targeted deep sequencing was used to characterize the genomic landscape and identify mutational profile that differed between pre-surgical and post-surgical samples. Sequence analysis was designed to detect protein-coding exons, exon-intron boundaries, and the untranslated regions of 50 genes associated with cancers of the central nervous system. Circulating tumor DNAs (ctDNAs) were prepared from the CSF and plasma from peripheral blood. For comparison, DNA was isolated from fresh tumor tissues. Non-silent coding variants were detected in CSF and plasma ctDNAs, and the overall minor allele frequency (MAF) of the former corresponded to an earlier disease stage compared with that of plasma when the tumor burden was released (surgical removal). Gene mutation loads of GBMs significantly correlated with overall survival (OS, days) (Pearson correlation = −0.95, P = 0.01). We conclude that CSF ctDNAs better reflected the sequential mutational changes of driver genes compared with those of plasma ctDNAs. Deep sequencing of the CSF of patients with GBM may therefore serve as an alternative clinical assay to improve patients' outcomes. • The comparison of CSF and plasma samples in each single patient with GBM shows that ctDNA in CSF better reflect the sequential change of those tumor drivers than in plasma, implicating a potential value of serial sampling of CSF to monitor key mutations within GBM burden and/or minimal residual tumor. [ABSTRACT FROM AUTHOR]

Autophagy is a conserved cellular process that degrades cytoplasmic constituents in vacuoles. Plant pathogenic fungi develop special infection structures and/or secrete a range of enzymes to invade their plant hosts. It has been demonstrated that monitoring autophagy processes can be extremely useful in visualizing the sequence of events leading to pathogenicity of plant pathogenic fungi. In this review, we introduce the molecular mechanisms involved in autophagy. In addition, we explore the relationship between autophagy and pathogenicity in plant pathogenic fungi. Finally, we discuss the various experimental strategies available for use in the study of autophagy in plant pathogenic fungi. [ABSTRACT FROM AUTHOR]

Abstract: Background and aims: Epithelial barrier dysfunction plays a critical role in the initiation of a number of immune diseases; the causative factors are not fully understood. The present study aimed to elucidate the mechanism by which the eosinophil-derived interferon (IFN)-lambda induced the gut epithelial barrier dysfunction. Methods: The duodenal biopsies were obtained from patients with or without food allergies. The eosinophils and IFNλ expression were observed by immune staining. Intestinal epithelial cell line, T84 cells, and a mouse model were employed to observe the effect of IFNλ on the epithelial barrier function and the initiation of skewed T helper (Th)2 polarization in the mouse intestine. Results: IFNλ expression was observed in over 80% human eosinophils of the subjects with or without food allergies. Exposure to microbial products, lipopolysaccharide or peptidoglycan, could induce eosinophils to release IFNλ. Exposure to IFNλ could induce intestinal epithelial barrier dysfunction via inducing the epithelial cell apoptosis. Concurrent exposure to microbial products and food antigens could induce aberrant antigen specific Th2 polarization and Th2 pattern inflammation in the intestine. Conclusions: Eosinophils express IFNλ that can induce intestinal epithelial barrier dysfunction and promotes the initiation of the aberrant Th2 polarization in the intestine. [Copyright &y& Elsevier]

Abstract: Mnh6, a nonhistone protein containing an HMG1 box, was isolated from the rice blast fungus, Magnaporthe grisea. In the current study, we utilized an MNH6-deletion mutant to investigate the role of Mnh6 in the disease cycle of M. grisea. The Δmnh6 mutant exhibited pleiotropic effects on fungal morphogenesis, including reduction in mycelial growth, conidiation, appressorium development, plant penetration, and infectious growth in host cells. Furthermore, Δmnh6 mutant had greatly reduced pathogenicity on barley and rice compared to the wild-type. The reintroduction of an intact copy of MNH6 into the Δmnh6 mutant restored morphological features and pathogenicity, suggesting that Mnh6 is required for fungal development, effective pathogenicity, and completion of the disease cycle of M. grisea. [Copyright &y& Elsevier]

• Further study on Sarcophyton ehrenbergi yielded eleven new cembrane diterpenes. • Absolute configurations were determined by Mosher's method and TDDFT-ECD approach. • Potent inhibition of TNF- α similar as that of positive control were observed. Eleven new cembrane diterpenes, namely, sarcoehrenins A–J (1 – 9 , 11) and (2 S ,11 S ,12 S)-isosarcophytoxide (10), along with six known compounds, gibberosene B (12), (13 S)-cembra-1,3,7,11-tetraen-13-ol (13), (+)-sarcophtol (14), cembrene-C (15), (1 R ,4 R ,2 E ,7 E ,11 E)-cembra-2,7,11-trien-4-ol (16) and (1 S ,4 R ,2 E ,7 E ,11 E)-cembratrien-4-ol (17) were isolated from the soft coral Sarcophyton ehrenbergi collected from Weizhou Island, Beibu Gulf, South China Sea. The structures of these compounds were elucidated by a combination of detailed spectroscopic analyses, chemical methods, and comparison with reported data. The absolute configuration of compound 2 was established by the modified Mosher's method in association with TDDFT ECD calculation, while the absolute configuration of compound 3 was assigned by TDDFT ECD approach. In in vitro bioassays, compounds 13 and 17 showed potent TNF- α inhibitory activities being similar to that of positive control dexamethasone. A preliminary structural-activity relationship was also described. [ABSTRACT FROM AUTHOR]

A novel lanthanide germanate, namely RbNdGe 2 O 6 , has been successfully synthesized by high-temperature solid-state reaction in open air atmosphere for the first time. Single crystal X-ray diffraction indicates a 3D framework composed of 1D neodymium oxygen chains connected with cyclogermanate Ge 3 O 9 units with Rb+ located in the internal space. X-ray powder diffraction coupled with Rietveld refinement reveals the sample's phase purity we have prepared. Thermal behavior analysis shows RbNdGe 2 O 6 is very stable, it doesn't decomposition until heated up to 998 ​°C. UV–visible absorption and diffuse reflection spectrum feature characteristic absorption bands of f -electron transition and an optical bandgap value of 4.65 ​eV. Magnetic susceptibilities measurement gives significant antiferromagnetic interactions between magnetic centers. The photodegradation experiments were performed to evaluate photocatalytic activities of RbNdGe 2 O 6. By using P25 as a reference, RbNdGe 2 O 6 features to be an effective visible-light-driven catalyst in photodegrading methylene blue. Although the BET value of RbNdGe 2 O 6 is only 3% that of P25, the photocatalytic activity reaches 0.55 times that of P25. Furthermore, the proposed photocatalytic mechanism which dominated by holes was further verified by adding ammonium oxalate as a quencher. New compound RbNdGe 2 O 6 was reported for the first time. Its structure features a 3D framework composed of 1D neodymium oxygen chains connected with cyclogermanate Ge 3 O 9 units with Rb+ located in the internal space. This material features an impressive visible-light-driven photodegradation methylene blue, and the proposed photocatalytic mechanism was also studied. Image 1 [ABSTRACT FROM AUTHOR]

• This was the first chemical study of soft coral Litophyton nigrum. • Nardosinanes and neolemnanes were firstly reported from the genus Litophyton. • Mosher's method, TDDFT-ECD and X-Ray analysis were used to determine absolute configurations. • Cytotoxic and inhibitory activities of protein kinases were evaluated. Three new nardosinane-type sesquiterpenoids linardosinenes A–C (1 – 3) and four new neolemnane-type sesquiterpenoids lineolemnenes A–D (4 – 7), together with the related known compound 4-acetoxy-2,8-neolemnadien-5-one (8), were isolated from the Xisha soft coral Litophyton nigrum. The structures of these new compounds were elucidated by comprehensive analyses of spectroscopic data, in association with modified Mosher's method and ECD calculations for configurational assignments and the absolute configuration of 8 was determined by X-ray diffraction analysis for the first time. Structurally uncommon nornardosinane and seconeolemnane skeletons for compounds 1 and 7 , respectively, are rare carbon frameworks in naturally occurring sesquiterpenoids. The absolute configurations of 1 , 7 , and 8 were determined by modified Mosher's method, TDDFT ECD approach, and X-ray diffraction analysis, respectively. This is the first chemical study of L. nigrum and the first report of nornardosinane, seconeolemnane and related sesquiterpenoids from the genus Litophyton. The isolates 1 – 7 were evaluated for their cytotoxicity against THP-1, SNU-398, HT-29, Capan-1 and A549 cell lines and inhibitory activities against PTP1B, BRD4, HDAC1 and HDAC6 protein kinases. The results indicated that compounds 2 – 5 inhibited proliferation of human cancer cells. However, none of them were potent inhibitors of protein kinases. [ABSTRACT FROM AUTHOR]

• A series of polycyclic furanobutenolide-derived norcembranoids were obtained. • TDDFT-ECD and X-Ray diffraction analysis were employed to determine absolute configurations. • ECD spectra data were in agreement with the proposed empirical ECD helicity rule. • Potent immunosuppressive activities against T and/or B lymphocytes were observed. One new polycyclic furanobutenolide-derived norcembranoid, xiguscabrolide H (1), together with eleven known related norditerpenoids 2 – 12 were isolated from South China Sea soft corals Sinularia scabra and S. polydactyla , respectively. Among them, compounds 1 , 6 , 8 , and 12 were discovered from the former species, while compounds 2 – 5 , 7 , and 9 – 11 were obtained from the latter species. The structure of new compound 1 was elucidated by extensive spectroscopic analysis and by the comparison with the reported data. With the assistance of time-dependent density functional theory electronic circular dichroism (TDDFT-ECD) calculations, its absolute configuration was determined. Moreover, the absolute stereostructures of the known compounds 3 , 4 , and 9 – 12 , of which only relative configurations were assigned, were established for the first time by X-Ray diffraction analysis and TDDFT-ECD calculations, respectively. In bioassay, several isolates exhibited potent inhibitory effects on the ConA-induced T lymphocytes and/or LPS-induced B lymphocytes proliferation. [ABSTRACT FROM AUTHOR]