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Due to the high–efficiency and stable solar–to–hydrogen conversion efficiency, dye–sensitized photocatalytic hydrogen evolution is considered to be one of the ideal ways to solve today's energy and environmental problems. The coupling interaction between sensitization matrix and light–absorbing dye play an important role for the activity of the dye–sensitized photocatalytic hydrogen evolution. In this work, amide–functionalized carbon nanospheres as a new–style sensitization matrix is prepared by a low–cost and uncomplicated two–step liquid phase reactions. Because amide groups on the surface of carbon nanospheres add additional adsorption sites by introducing H–bonding and enhancing coupling interaction between the sensitization matrix and dye molecules, the adsorption capacity of amide–functionalized carbon nanospheres increase 6.7 times compared with bare carbon nanospheres. Based on the material excellent adsorption performance, the Eosin Y dye–sensitized amide–functionalized carbon nanospheres with Pt co–catalyst exhibits high–efficiency activity for H2 generation (607.4 μmol for testing 2 h), which is 14.3 and 6.4 times higher photocatalytic hydrogen evolution activity than Pt and carbon nanospheres with Pt assist. Moreover, the highest apparent quantum efficiency of photocatalyst can reach to 32.9% at 430 nm. The significantly improved photocatalytic hydrogen evolution performance of catalyst could be mainly ascribed to enhance amino groups adsorption active sites, which can fix the light–absorbing dyes on the surface of sensitization matrix and shorten the transmission distance of photogenerated charges.

A simple and effective method of high performance liquid chromatography (HPLC) with diode array detection was established to identify the origin of Achyranthes bidentata Blume and evaluate its quality, based on chromatographic fingerprint combined with the similarity analysis, hierarchical cluster analysis and the quantitative analysis of multi-components by single marker (QAMS). In the chromatographic fingerprint, 16 peaks were selected as the common model to evaluate the similarities among 18 batches (S1-S18) of A. bidentata Blume samples collected from different origins in China. The similarities values for 18 batches of samples were more than 0.75, which compared with control fingerprint. Furthermore, 18 batches of A. bidentata Blume samples were categorized into two groups for quantitative analysis, the quantification of three bioactive constituents (β-ecdysterone, cyasterone and 5-hydroxymethyl furfural) between QAMS and external standard method proved the consistency of the two methods, the three constituents showed good regression (R > 0.9995) within linear ranges, and their recoveries were within the range of 97.6-101.5%. This study demonstrated that the quality of A. bidentata Blume can be successfully evaluated by means of a combination of HPLC chromatographic fingerprint and QAMS approach.

Rheumatoid arthritis (RA) is a systemic, Th1 cytokine-predominant autoimmune disease result in a chronic and inflammatory disorder. Geniposide (GE), an iridoid glycoside compound that is purified from Gardenia jasminoides Ellis, has antiinflammatory and other immunoregulatory effects, but its exact mechanism of actions on RA is unknown. The aim of this study was to elucidate antiinflammation effects of GE on adjuvant arthritis (AA) rats and its possible immune tolerance mechanisms. Male Sprague-Dawley rats were administered with GE (30, 60, and 120 mg/kg) orally from day 17 to 24 after immunization. Lymphocyte proliferation was assessed by MTT. Levels of interleukin-2 (IL-2), IL-4, and transforming growth factor-β1 were tested by ELISA. The expression of β2-AR, GRK2, and β-arrestin-1 and β-arrestin-2 was detected by western blot. Geniposide was found to relieve the secondary hind paw swelling and arthritis scores, along with attenuating histopathologic changes and decreasing IL-2 and increasing IL-4, transforming growth factor-β1 in mesenteric lymph node (MLN) lymphocytes of AA rats. In addition, GE in vivo increased the expression of β2-AR and decreased the expression of GRK2, β-arrestin-1 and β-arrestin-2, and level of cyclic adenosine monophosphate of MLN lymphocytes in AA rats. From these results, we can infer that GE on immune tolerance effects, β2-AR desensitization, and β2-AR-AC-cyclic adenosine monophosphate transmembrane signal transduction of MLN lymphocytes plays crucial roles in antiinflammatory and immunoregulatory pathogeneses of RA. Copyright © 2017 John Wiley & Sons, Ltd.

Atomistic simulation was carried out to study the structural and elastic properties of MgCO $_{\boldsymbol {3}}$ magnesite within the pressure range of the Earth’s mantle based on a novel force field. The lattice parameters and elastic constants as a function of pressure up to 150 GPa are calculated. The results are in good agreement with the available experimental data and previous theoretical results, showing no phase transition over the pressure range of interest. We also found that magnesite exhibits a strong anisotropy throughout the lower mantle and that the nature of the anisotropy changes significantly with depth.

To understand the mechanisms of surface erosion induced by slow highly-charged ion (SHCI) bombardment, the surface nanostructure formation in Si (111) surface by single Xe44+ ion was studied by using molecular-dynamics (MD) simulations, based on analyzing the multiple electron emission of the substrate. The time evolutions of the temperature, energy, pressure and density of the substrate have been systematically studied. The results show the bombardment of the incident SHCI resulting in an explosive event in the surface. A shock wave propagating at ~104 m/s is formed in the system during the initial 175 fs. After this initial shock, many particles are ejected from the surface since the extreme non-equilibrium of the system. And at t=370 fs, a crater-like nanostructure with diameter of ~40 Å and depth of ~18 Å is formed at the incident site.

Objective Rheumatoid arthritis (RA) is a common inflammatory autoimmune disease characterized by the formation of joint synovitis and pannus. Sphingosine 1-phosphate (S1P) is an important mediator related to angiogenesis, inflammation and autoimmunity. As Geniposide (GE) has potent immuno-modulation function, we investigated the effects on the dynamic balance of angiogenesis-related factors and Sphingosine kinase 1 (SphK1)-S1P-S1P receptor 1 (S1PR1) signal transduction in adjuvant-induced arthritis (AA) rats. Method The model evaluation was performed from paw swelling degree, arthritis index and movement score. The immunohistochemistry and enzyme-linked immunosorbent assay were used to study the microvascular density (MVD) and pro/anti-angiogenic factors levels. The cell viability was examined by cell counting kit-8 assay. SphK1, S1PR1 mRNA and protein levels in fibroblast-like synoviocytes (FLSs) were detected by quantitative real-time polymerase chain reaction and Western blotting. Results The results showed that GE can apparently suppressed the inflammatory pathological status. The arthritis index, paw swelling and MVD of AA rats were decreased with dose dependence (⁎P Conclusion It indicated that GE reduces the activity of SphK1 by restoring the dynamic balance between pro/anti-angiogenic factors, thereby interfering with SphK1-S1P-S1PR1 signal transduction, reducing the formation of synovial microvessels and exerting anti-angiogenesis effect of RA.

Geniposide (GE) is an active component isolated from the fruit of Gardenia jasminoides Ellis that has anti-inflammatory and other pharmacological effects; however, the underlying mechanism of GE action has not been elucidated in rheumatoid arthritis (RA). Previous studies have shown that GE plays a therapeutic role in RA via regulation of the integrin beta 1 (Itgβ1)-mediated Ras-Erk1/2 signalling pathway. However, the specific mechanism of GE action on Itgβ1 has not been clarified. Recent evidence indicates that microRNAs (miRNAs) are involved in the development of RA. In this study, we developed a miRNA-124a-based synoviocyte repair strategy. We demonstrated that miRNA-124a can directly inhibit the expression of the Itgβ1 gene and decrease TNF-α-stimulated cell proliferation in vitro. MH7A cells were obtained from the patient with RA and treated with GE in the presence of TNF-α (10 ng/mL). Additionally, we demonstrated that the expression of miRNA-124a can be regulated by GE. GE upregulated the expression of miRNA-124a and decreased the expression of Itgβ1 at the mRNA and protein levels. The results of the present study are the first to suggest that GE inhibits TNF-α-stimulated cell proliferation and blocks the activation of the Ras-Erk1/2 pathway via the upregulation of miRNA-124a expression. Our study elucidates the role of miRNA-124a as a protected miRNA in RA and may provide a novel strategy for the diagnosis and treatment of RA in the future.

Geniposide (GE) is the extraction and purification of iridoid glycosides from the Gardenia jasminoides Ellis, which is a promising anti-inflammatory drug, but its mechanism of actions on rheumatoid arthritis (RA) has not been clarified. This study investigated the molecular mechanism behind GE reduced the high permeability of fibroblast-like synoviocytes (FLSs) derived from SD rats with adjuvant arthritis (AA), with the aims of observing the action of GE in AA rats and exploring new therapeutic strategies for RA treatment. The CCK-8 method was used to detect FLSs proliferation. The pro-inflammatory cytokines levels and anti-inflammatory cytokines levels in FLSs were determined by ELISA kits. FLSs permeability assay was performed on Transwell. Immunofluorescence was used to assay the arrangement and morphology of F-actin. The expression of the key molecules related to FLSs permeability (RhoA, p-p38MAPK, NF-κB p-p65 and F-actin) was detected by western blotting. After treatment with lipopolysaccharide (LPS), the proliferation and the permeability of the cells increased significantly (all P < 0.05). The expression of RhoA, p-p38MAPK, NF-κB p-p65 and F-actin in FLSs was higher compared with the control group, and F-actin was redistributed, with the formation of additional stress fibers. But, these conditions were moderated after treatment with GE. We demonstrated that the treatment of different concentrations of GE (25, 50, and 100 μg/mL) had a significant inhibitory effect on the proliferation and permeability of FLSs in vitro. Furthermore, the levels of interleukin (IL)-1β and IL-17 secreted by FLSs were decreased in different doses of GE groups, and the levels of anti-inflammatory cytokines (IL-4, TGF-β1) were increased. Under treatment with GE, low expression of RhoA downregulated expression of p-p38MAPK, NF-κB p-p65, and F-actin while compared with control group, and restored the hyperpermeability of FLSs due to LPS treatment. Taken together, GE might play its anti-inflammatory and immunoregulatory effects via regulating the relative equilibrium of pro-inflammatory cytokines and anti-inflammatory cytokines. GE attenuated the hyperpermeability of FLSs. The down-regulation of the conduction of RhoA/p38MAPK/NF-κB/F-actin signal may play a critical role in the mechanisms of GE on RA. GE could be an effective therapeutic agent for the treatment of RA.

Geniposide (GE), an iridoid glycoside compound derived from Gardenia jasminoides Ellis fruit, is known to have anti-inflammatory and immunoregulatory activities. The aim of this study was to investigate the protective mechanism of GE in the regulation of the mitogen-activated protein kinase (MAPK) signalling pathway and the cross-talk among the MAPK signalling pathway in fibroblast-like synoviocytes (FLS) of adjuvant arthritis (AA) rats. AA was induced by injecting with Freund’s complete adjuvant. Male SD rats and FLS were subjected to treatment with GE (30, 60 and 120 mg/kg) in vivo from day 14 to 21 after immunization and GE (25, 50 and 100 μg/mL) in vitro, respectively. The proliferation of FLS was assessed by MTT. IL-4, IL-17, IFN-γ, and TGF-β1 were determined by ELISA. Key proteins in the MAPK signalling pathway were detected by Western blot. GE significantly reduced the proliferation of FLS, along with decreased IFN-γ and IL-17 and increased IL-4 and TGF-β1. In addition, GE decreased the expression of p-JNK, p-ERK1/2 and p-p38 in FLS of AA rats. Furthermore, disrupting one MAPK pathway inhibited the activation of other MAPK pathways, suggesting cross-talk among MAPK signalling. In vivo study, it was also observed that GE attenuated histopathologic changes in the synovial tissue of AA rats. Collectively, the mechanisms by which GE exerts anti-inflammatory and immunoregulatory effects may be related to the synergistic effect of JNK, ERK1/2 and p38. Targeting MAPK signalling may be a new therapeutic strategy in inflammatory/autoimmune diseases.

The hillocks on highly oriented pyrolytic graphite (HOPG) surface induced by highly charged Ar q + , Xe q + ions are studied by using molecular-dynamics (MD) simulations. And a hybrid potential created by combining the ReaxFF potential with the repulsive ZBL potential is used to describe the interatomic interactions. The effects of incident highly charged ion (HCI)’s kinetic energy and the energy gain due to the interaction of HCI with its own image on the formation of the hillocks are considered in the present simulations. Our results show that both potential and kinetic energy of HCI may affect the hillock size. However, the potential energy of HCI increases dramatically with charge state, which is more important than kinetic energy in the formation of the hillock in extremely high charge states. And it is found that both the height and width of the hillock agree well with experimental data. In addition, the bond breaking and bond formation during the formation of the hillock are also investigated, and the results show that there are many σ bonds breaking and interlayer bonds formation in one layer or between two layers during this process. Furthermore, most of the interlayer bonds in HOPG surface induced by HCI impact are sp 2 bond, although some interlayer sp 3 bonds are also observed in the present work.

Rationale Microdialysis has been used to detect the concentrations of drugs in tissues. Geniposide (GE), an iridoid glycoside compound, is the main bioactive component of Gardenia jasminoides Ellis fruit. We previously demonstrated that GE could control the activity of cytokines and reduce levels of inflammation in adjuvant arthritis (AA) rats, but the topic of concentration changes over time in the joint synovia of AA is scarcely studied. Methods In this study, microdialysis technique combined with ultra-high-performance liquid chromatography-electrospray ionization coupled with tandem mass spectrometry (UHPLC-ESI-MS/MS) was set up and confirmed to assay GE in the dialysate of the joint cavity in AA rats. Mass detection was conducted in multiple reaction monitoring (MRM) mode with negative electro-spray ionization, and Paeoniflorin (Pae) was used as an internal standard (IS). Results A lower limit of quantitation (LLOQ) of 5 ng/mL was found in this method and with good linearity in the range of 5-4000 ng/mL. All the validation data including accuracy, precision, intra and inter-day repeatability and stability meet the requirements. The relative recoveries of GE were determined at approximately 40.01%. Conclusions The measurements based on microdialysis combined with UHPLC-ESI-MS/MS provide a method for sampling and rapid sensitive analysis of GE in dialysate of joint cavity in AA rats. This method should be considered for future pharmacokinetics studies.

Context: Development of a reliable and selective anti-inflammatory agent of cyclooxygenase-2 (COX-2), induced or up-regulated by inflammatory/injury stimulus such as IL-1β, TNF-α and LPS in the various types of organs, tissues and cells, with low side effects is a long-standing medicinal chemistry problem with significant social implications.Objective: To target druggable enzymome COX-2 by exploiting NSAIDs and genipin (GEP) in anti-inflammatory infection.Materials and methods: The compound aspirin GEP ester (AGE) was designed by computer-assisted screening, synthesized in the esterification of the acylate derivative and the methylate derivative with Et3N, and evaluated with 20, 40 and 60 mg/kg from days 18 to 24 after immunization in collagen-induced arthritis (CIA) rats by the sequential enzymatic experiments, western-blot analysis and pathological observation methods.Results: AGE exhibited higher binding affinity with COX-1 and displayed the lowest estimated free energy with COX-2 than other li...

Microdialysis, a sampling method for pharmacokinetics–pharmacodynamics (PK–PD) modeling in preclinical and clinical studies, is a convenient in vivo sampling technique. Geniposide (GE), an iridoid glycoside compound, is the major active ingredient of Gardenia jasminoides Ellis fruit which has an anti-inflammatory effect. In this study, an articular cavity microdialysis sampling system for adjuvant arthritic (AA) rats was established to study the effect of GE on the release of prostaglandin E2 (PGE2) in AA rats induced by Freund’s complete adjuvant (FCA). An UHPLC-MS/MS method was developed to determine the concentrations of GE and PGE2 in the dialysate. Through the determination of drug concentrations and PGE2 efficacy levels in the dialysate, the developed methods were successfully applied to set up concentration–time and effect–time profiles followed by PK–PD modeling of GE’s effect on decreasing PGE2 release after oral administration of GE. The effect was well described by the developed PK–PD modeling, indicating that GE may play an anti-inflammatory role via decreasing AA-induced elevated PGE2 levels. In the selection of suitable endogenous small molecules as effect markers, the establishment of AA rat joint-cavity microdialysis is an attractive technique for rational PK–PD studies.

A very sharp Brass {0 1 1}〈2 1 1〉 recrystallization texture with astonishingly high intensity has been successfully fabricated through rolling at room temperature by 98% and subsequent two-step annealing 423 K for 1200 s + 973 K for 5400 s in nitrogen in pure silver sheet that can be used as a substrate for coated Y-123 superconducting tapes without any buffer layers.

Texture transition in silver introduced by the addition of 10 at% Pd alloying element was analyzed in this study. Experimental results show that the dependence of rolling texture on rolling reduction in thickness rather than on rolling temperature has been mostly detected, and the recrystallization texture transition process in pure silver is so strongly influenced by the addition of alloying element palladium that the final stable state of recrystallization texture has been changed from Brass {011} orientation to Copper {112} orientation. The single cube {001} recrystallization texture in warm rolled silver, Brass {011} recrystallization texture in room-temperature rolled silver, and Copper {112} recrystallization texture in room-temperature rolled or warm rolled Ag-10 at% Pd alloy have been successfully developed for the fabrication of metallic substrates suitable for high-temperature superconducting tapes.

In order to demonstrate the effect of deformation temperature on texture formation in silver alloy sheet for superconducting types, the deformation and annealing textures of Ag-10 at% Pd alloy rolled at the temperatures from -1960C to 1600C and subsequently annealed were examined. A single Copper type texture with high intensity in ODFs has been realized in this study. Based on the experimental results, a metallurgical processing to get a sharp single orientation type texture in Ag-Pd alloy has been presented for manufacturing highly oriented superconducting substrate tapes.

In order to obtain a sharply cube textured silver sheet as the substrate for high temperature superconductor (HTS) film with high Jc (critical current density), warm rolling combined with two step annealing treatment has been performed to clarify the perspective of texture formation in pure silver. Two kinds of starting material, which are silver ingots of commercial purity obtained by casting in air and vacuum, were used to examine the effect of oxygen on texture development. The main feature of warm rolling texture obtained in this study was a strong Brass {011} component with minor S {123} component, and in some cases, cube {001} component or Copper {112} component appeared also depending on the warm rolling procedures. Upon crystallization, {001}, {124} and {13,6,15} orientations were formed as the dominant components in silver sheets and the relative amount of their orientation components depended on the concrete annealing conditions applied and on the oxygen content. A very sharp single-crystal like cube texture has been successfully realized in the specimen, which was cast in vacuum, warm rolled by 95 percent and subsequently annealed as 1500C×10 min-5000C×30 min in nitrogen. Finally, we discussed the technological basis on sharp cube texture formation in f.c.c. pure metals with low stacking fault energy.

Texture formation in pure silver was investigated in order to obtain sharply Brass {011} (211) type textured silver sheet that can be used as a substrate for Y-123 superconducting coated tapes without any buffer layers. The feature of recrystallization texture after the two-step annealing appeared as two peaks close to Goss {011}(100) orientation and Brass [011] (211) orientation respectively with other weak components along α-fiber in specimens rolled at room temperature, and only one peak close to Brass {011}(211) orientation with weak components limited to cube orientation, rotated cube orientation and orientation close to Copper {112}(111) orientation in those warm rolled at 150°C. By using the improved metallurgical processing, a very sharp Brass {011}(211) type texture has been successfully realized in specimen, which was cast in vacuum, warm rolled by 92% at 150°C and subsequently annealed as 200°C-20 min + 800°C-180 min in nitrogen. There are some critical conditions on the formation of sharp Brass {011}(211) type recrystallization texture: a low oxygen content in the starting material, elevated rolling temperature, and the selection of lower primary recrystallization temperature of two-step annealing process.

In order to demonstrate the effect of deformation temperature on texture formation in silver alloy sheet for superconducting tapes, the rolling and annealing textures of Ag-10 mol% Pd alloy rolled at the temperatures from-196 to 160°C and subsequently annealed were examined in detail. The roll ing texture for all deformed specimens rolled at temperatures from -196 to 160°C consisted of a certain component near the Brass {110} (112) orientation with some weak components. During annealing procedure, the characteristic components of deformation texture disappeared quickly in specimens rolled at room temperature or -196°C but slowly in those warm-rolled at 120°C or 160°C. The Copper component was found to be formed by higher temperature annealing in specimens warm-rolled at 160°C and those rolled at room temperature. Above all, a single {112} (111) Copper type texture with high intensity in ODFs has been realized in three different specimens, which were rolled by 92% at room temperature or warm-rolled by 92% or 95% at 160°C and subsequently annealed as 200°C-10 min + 500°C-30 min + 800°C-180 min + 950°C-180 min respectively. From the experimental results obtained here, a metallurgical processing to get a sharp single orientation type texture in Ag-10mol% Pd alloy was presented for the development of new technology on oriented superconducting substrate tapes.

In order to obtain a sharply textured silver sheet with a single orientation as a substrate, which is favorable for high temperature superconductor (HTS) film having high Jc (critical current density), the sheet metallurgical processing of pre-heated rolling combined with two step annealing treatment has been performed. We used two kinds of starting material, which are silver ingots of commercial purity obtained by casting in air and vacuum, to examine the effect of oxygen on texture development. The main feature of warm rolling texture obtained in this study was a strong Brass {011}‹211› component with minor S {123}‹412› component, and in some cases, cube {001}‹100› component or Copper {112}‹111› component appears also depending on the warm rolling procedures. Upon crystallization, it has been found that cube {001}‹100›, {124}‹4, 12, 7› and {13, 6, 15}‹365› orientations were formed as the dominant components in silver sheets and the relative amount of their orientation components depended on the concrete annealing conditions applied after the warm rolling and on the oxygen content. A very sharp single-crystal like cube texture has been successfully obtained in the specimen, which was cast “in vacuum”, warm rolled at 95 percent and subsequently annealed 10 minutes at 150°C and 30 minutes at 500°C in nitrogen. Finally, we discussed the technological basis on sharp cube texture formation in fcc pure metals with low stacking fault energy.