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High-amylose maize starch has great potential for widespread industrial use due to its ability to form strong gels and film and in the food processing field, thus serving as a resistant starch source. However, there is still a substantial shortage of high-amylose maize due to the limitation of natural germplasm resources, although the well-known amylose extender (ae) gene mutants have been found to produce high-amylose maize lines since 1948. In this context, high-amylose maize lines (13 inbreds and 18 hybrids) originating from a natural amylose mutant in our testing field were utilized to study the correlation between amylose content (AC) and phenotypic traits (kernel morphology and endosperm glossiness), grain filling characteristics, gene expression, and amylose inheritance. Our results showed that AC was negatively correlated with total starch content but was not correlated with grain phenotypes, such as kernel fullness, kernel morphology and endosperm glossiness. Maize lines with higher amylose had a greater grain filling rate than that of the control (B73) during the first 20 days after pollination (DAP). Both starch debranching enzyme (DBE) groups and starch branching enzyme IIb (SBEIIb) groups showed a greater abundance in the control (B73) than in the high-amylose maize lines. Male parents directly predicted AC of F1, which was moderately positively correlated with the F2 generation.

This paper is dedicated to experimentally investigate the liquid galinstan based minichannel cooling for high heat flux and large heat power thermal management. Firstly, a compact electromagnetic pump towards effectively driving liquid metals was developed, which can provide high pressure head up to 100 kPa. Then, the minichannel heat sink was designed and manufactured, with width of channel 1 mm, height of channel 5 mm. Furthermore, the galinstan based minichannel cooling system was established and experimentally tested under different heating loads and pumping powers. The results show that galinstan based minichannel cooling system can dissipate heat with heat flux 300 W/cm2 and heat power 1500 W. And the thermal performance and hydrodynamic characteristic of minichannel heat sink using galinstan as coolant were obtained. It indicates that compared to water based minichannel cooling, galinstan based minichannel cooling can obtain a rather larger heat transfer enhancement, and the pressure losses of galistan based minichannel heat sink is much lower than that of water based microchannel cooling. Moreover, it is also found that heat capacity thermal resistance becomes a rather important factor for the thermal performance of galinstan based minichannel, due to the high thermal conductivity and lower heat capacity of galinstan. Furthermore, the galinstan based minichannel cooling system can operate silently, steadily and smoothly by using electromagnetic pump, which has no moving parts. Overall, the galinstan based minichannel cooling is proven to be a powerful and practical way for the thermal management of high heat flux and large heat power devices.

The demand for rare earths in aluminum alloy industry has experienced substantial growth in recent years. The erbium and scandium are two effective rare earth additives, mainly due to its remarkable improvement to aluminum alloy performance. However, the production process of rare earth has caused significant environmental problems. Hence, the analysis of environmental impacts associated with erbium and scandium processing is gaining importance. In this study, a life cycle analysis on the environment impacts of erbium oxide (Er2O3) and scandium oxide (Sc2O3) was carried out based on life cycle assessment (LCA) method. The life cycle assessment results showed that the production of 1 kg of Er2O3 and Sc2O3 generated 21.7 kg CO2 eq. and 743 kg CO2 eq., respectively. The leaching and purification process accounting for 95% of the overall water usage of Er2O3 production. For Sc2O3, energy and chemical consumption played a key role in reducing environmental impacts. Furthermore, Er2O3 appeared to have less environmental impact than Sc2O3 on most environmental issues. A detailed review of contribution was conducted and recommendations for further research were given.

Bacillus thuringiensis BMB181 (Bt BMB181), with high melanin production, is an ideal candidate for industrial scale production of light-stable insecticides. However, its melanogenic pathways remain unclear. In the present study, we demonstrated that Bt BMB181 failed to produce melanin after treatment with mesotrione, an inhibitor of 4-hydroxyphenylpyruvate dioxygenase in the homogentisic acid pathway of melanin synthesis. Heterologous expression experiments suggested that homogentisate-1,2-dioxygenase (HmgA) in Bt BMB171 functions normally, yet HmgA in Bt BMB181 had lost its activity, at least partly. Using the CRISPR-Cas9 system, the hmgA gene in Bt BMB171 was knocked out and the mutant strain gained the ability to produce melanin. Furthermore, the complemented strain reverted to the wild-type phenotype. In addition, overexpression of its own hmgA gene in Bt BMB181 also resulted in failure to produce the pigment. BLAST results indicated that the amino acid alteration (G272E) in HmgA of Bt BMB181 was caused by a single point mutation (815G→ A). The enzyme activity of purified HmgA171 was more than 10-fold higher than that of HmgA181. Finally, we determined that the mutation in hmgA was responsible for melanin accumulation in Bt BMB181. Our results provided new insights into the synthesis and regulation of melanin production in B.thuringiensis and will promote its future industrial application.

Extracellular glutamine represents an important energy source for many cancer cells and its metabolism is intimately involved in maintaining redox homeostasis. The heightened metabolic activity within tumor tissues can result in glutamine deficiency, necessitating metabolic reprogramming responses. Here, dual mechanisms involving the stress‐responsive transcription factor DDIT3 (DNA damage induced transcript 3) that establishes an interrelationship between glycolysis and mitochondrial respiration are revealed. DDIT3 is induced during glutamine deprivation to promote glycolysis and adenosine triphosphate production via suppression of the negative glycolytic regulator TIGAR. In concert, a proportion of the DDIT3 pool translocates to the mitochondria and suppresses oxidative phosphorylation through LONP1‐mediated down‐regulation of COQ9 and COX4. This in turn dampens the sustained levels of reactive oxygen species that follow glutamine withdrawal. Together these mechanisms constitute an adaptive survival mechanism permitting tumor cells to survive metabolic stress induced by glutamine starvation., Glutamine shortages within the tumor microenvironment necessitate adaptive survival mechanisms in cancer cells. Activation of the transcription factor DNA damage induced transcript 3 under prolonged glutamine deficiency serves to balance cellular adenosine triphosphate energy production and enable cell survival by upregulating glycolysis via transcriptional effects while also dampening oxidative phosphorylation through direct interactions with mitochondrial respiratory chain components.

There are two main molecules in asymmetric unit of the title compound, C27H21N3O6·0.5C2H5OH. In both, the indole ring systems are approximately perpendicular to each other, at dihedral angles of 69.3 (5) and 82.8(4)°. In the crystal, molecules are linked by N—H...O and O—H...O hydrogen bonds into a three-dimensional supramolecular architecture. The solvent ethanol molecule acts as a donor, forming an O—H...O hydrogen bond, reinforcing the structure.

An efficient one-pot synthesis of 3-cyano-4-quinolinone derivatives has been developed via the intramolecular cyclization of cyanoacetylenaminones 1 with N,N-dimethylformamide dimethyl acetal (DMF-DMA) 2 under catalyst-free conditions in CH3CN. The reaction offers several advantages, including operational simpleness, easily available starting materials, target molecular diversity, and facile purification. Additionally, the 3-cyano substituted quinolinones may undergo further functionalization and assist in the discovery of novel drugs.

High capacity Li-rich materials are mighty contenders for building rechargeable batteries that coincide with the demand in energy density. Fully realizing the extraordinary capacity involves oxygen evolution and related cation migration, resulting in phase transitions and deteriorations that would hinder their practical application. In an attempt to enhance the anodic redox participation and stabilize the structure at the same time, we proposed a structural modulation strategy with modification on anion hybridization intensifying and cation doping. Spectator ions with large ionic radius were introduced into the lattice during calcination with stannous chloride and the d-p hybridization between transition metal 3d and oxygen 2p orbitals was subsequently intensified along with expelling weakly bonded chloride species in the reheating process. Both of the reversible capacity and stability upon cycling were remarkably improved through the cooperation of bond alteration and dopant. This strategy might provide new insight into the modulation of the structure to truly fulfill the potential of Li-rich materials.

Nickel-rich layered materials, such as LiNi0.80Co0.15Al0.05O2 (NCA), have been considered as one alternative cathode materials for lithium-ion batteries (LIBs) due to their high capacity and low cost. However, their poor cycle life and low thermal stability, caused by the electrode/electrolyte side reaction, prohibit their prosperity in practical application. Herein, AlPO4 has been homogeneously coated on the surface of NCA via wet chemical method towards the target of protecting NCA from the attack of electrolyte. Compared with the bare NCA, NCA@AlPO4 electrode delivers high capacity without sacrificing the discharge capacity and excellent cycling stability. After 150 cycles at 0.5 C between 3.0–4.3 V, the capacity retention of the coated material is 86.9%, much higher than that of bare NCA (66.8%). Furthermore, the thermal stability of cathode is much improved due to the protection of the uniform coating layer on the surface of NCA. These results suggest that AlPO4 coated NCA materials could act as one promising candidate for next-generation LIBs with high energy density in the near future.

High-capacity Li-rich cathode materials can significantly improve the energy density of lithium-ion batteries, which is the key limitation to miniaturization of electronic devices and further improvement of electrical-vehicle mileage. However, severe voltage decay hinders the further commercialization of these materials. Insights into the relationship between the inherent structural stability and external appearance of the voltage decay in high-energy Li-rich cathode materials are critical to solve this problem. Here, we demonstrate that structural evolution can be significantly inhibited by the intentional introduction of certain adventive cations (such as Ni2+) or by premeditated reservation of some of the original Li+ ions in the Li slab in the delithiated state. The voltage decay of Li-rich cathode materials over 100 cycles decreased from 500 to 90 or 40 mV upon introducing Ni2+ or retaining some Li+ ions in the Li slab, respectively. The cations in the Li slab can serve as stabilizers to reduce the repulsion between the two neighboring oxygen layers, leading to improved thermodynamic stability. Meanwhile, the cations also suppress transition metal ion migration into the Li slab, thereby inhibiting structural evolution and mitigating voltage decay. These findings provide insights into the origin of voltage decay in Li-rich cathode materials and set new guidelines for designing these materials for high-energy-density Li-ion batteries.

High energy density storage systems can be achieved by utilizing a lithium metal anode in solid-state Li secondary batteries. Herein, we report for the first time the use of a lithium-free cathode coupled with lithium metal for solid-state Li metal batteries. This lithium-free cathode composed of iron oxyfluoride (FeOF) nanorods can not only reduce the consumption of lithium resources, but also provide a good electrochemical performance. After being encapsulated by a highly conductive poly(3,4-ethylenedioxythiophene) (PEDOT) nanolayer, the coated FeOF nanorods exhibit a superior cycling stability (ca. 75% capacity retention after 200 cycles at 100 mA g−1) at 60 °C in a PEA solid electrolyte. This performance demonstrates the great potential of lithium-free cathodes for application in solid-state Li metal batteries.

International audience; Sufficient swelling pressure of compacted bentonite upon wetting is necessary to provide long-term stability to an engineered barrier system under conditions of thermal gradient and variable water chemistry in a high-level radioactive waste repository. To investigate the combined thermal and saline effects on the swelling pressure of Gaomiaozi (GMZ) bentonite, constant-volume swelling pressure tests were performed on densely compacted specimens inundated with deionized water, NaCl, and CaCl2 solutions at 20 °C and 60 °C. The results indicate that high temperature and saline solutions decrease the swelling pressure. Crystalline swelling dominates the constant-volume swelling of densely compacted bentonite. For a given cation type, a higher temperature or higher solution concentration resulted in a lower swelling pressure. The decreasing surface potential and increasing osmotic suction with solution concentration both weaken the clay swelling. The effects of temperature on the swelling pressure are explained by the role of the lattice contraction. The degeneration of the interlamellar adsorbed water at high temperature weakens the crystalline swelling. The effects of cation types are interpreted by their difference in chemical activity. Ca2+ ions possess higher exchange capacity and larger hydrated radius than those of the Na+ ions. When densely compacted Na-bentonite is wetted with CaCl2 solution, the possible change of the interlamellar cations from Na+ to Ca2+ ions would promote the crystalline swelling. The osmotic suction imposed by CaCl2 solution may offset the role of the cation exchange to a small extent. The effect of temperature on the swelling pressure exceeds that of the cation types. For a given solution concentration, the specimen wetted with NaCl solution developed lower swelling pressure than that with CaCl2 solution at 20 °C, whereas the opposite tendency appeared at 60 °C. In addition, specimens saturated with deionized water and NaCl solution at 20 °C obtained insignificant difference in pore size distribution, whereas identifiable differences in pore size distribution occured at 60 °C. The combined thermal and saline effects on the swelling pressure may be explained by the role of the lattice contraction at varied clay structure. When CaCl2 solution is used, the quasicrystals contain more montmorillonite layers than the case of the NaCl solution. The role of the lattice contraction at high temperature is expected to decrease the swelling pressure to a greater degree in the case of the CaCl2 solution. The remarkable increase in the osmotic suction at high temperature and high solution concentration could also enlarge the decrease in the swelling pressure. These conjectures, however, still require quantitative interpretations via microscopic tests such as X-ray powder diffraction tests on bulk samples.

A new coordination polymer [Ag3(1,2,4-btc)]n (1) (1,2,4-H3btc = 1,2,4-benzenetricarboxylate) has been synthesized by hydrothermal method and characterized by X-ray single crystal diffraction, elemental analysis, IR spectrum and TGA. Compound 1 exhibits a three-dimensional (3D) network consisting of the 2D layer connected by the ligand 1,2,4-btc3− which adopts a new coordination mode. Moreover, blue fluorescence at 480 nm emission was observed under 320 nm excitation.

Significance We report in this article that c-Myc-mediated repression of lncRNA IDH1-AS1 sustains activation of the Warburg effect by HIF1α under normoxic conditions. IDH1-AS1 would otherwise enhance IDH1 enzymatic activity through promoting its homodimerization, leading to increased production of α-KG, which, along with decreases in ROS levels similarly resulting from increased IDH1 activity, causes down-regulation of HIF1a and a reduction in glycolysis. Collectively, our results have identified a signaling axis c-Myc-(IDH1-AS1)-IDH1-αKG/ROS-HIF1α that is important for activation of the Warburg effect under normoxia. Moreover, the results reveal IDH1 as a member of c-Myc-responsive metabolic enzymes and demonstrate that c-Myc plays an important part in balancing mitochondrial respiration and glycolysis to ensure glycolysis be executed efficiently in cancer cells under normoxia., The oncoprotein c-Myc plays an important role in regulating glycolysis under normoxia; yet, in cancer cells, HIF1α, which is essential for driving glycolysis under hypoxia, is often up-regulated even in the presence of oxygen. The relationship between these two major regulators of the Warburg effect remains to be fully defined. Here we demonstrate that regulation of a long noncoding RNA (lncRNA), named IDH1-AS1, enables c-Myc to collaborate with HIF1α in activating the Warburg effect under normoxia. c-Myc transcriptionally repressed IDH1-AS1, which, upon expression, promoted homodimerization of IDH1 and thus enhanced its enzymatic activity. This resulted in increased α-KG and decreased ROS production and subsequent HIF1α down-regulation, leading to attenuation of glycolysis. Hence, c-Myc repression of IDH1-AS1 promotes activation of the Warburg effect by HIF1α. As such, IDH1-AS1 overexpression inhibited cell proliferation, whereas silencing of IDH1-AS1 promoted cell proliferation and cancer xenograft growth. Restoring IDH1-AS1 expression may therefore represent a potential metabolic approach for cancer treatment.

By hydrothermal method, two new coordination polymers [Co(ca)(phdat)]{sub n} (1), [Ni(ca)(phdat).0.125H{sub 2}O]{sub n} (2) (H{sub 2}ca=D-camphoric acid, phdat=2-phenyl-4,6-diamino-1,3,5-triazine) have been achieved and structurally characterized by IR, elemental analyses, X-ray single-crystal diffraction and TGA. The X-ray single-crystal diffraction reveals that compounds 1 and 2 are isostructural, both of which exhibit two-dimensional layered network built up from paddle-wheel Co{sub 2}(CO{sub 2}){sub 4}/Ni{sub 2}(CO{sub 2}){sub 4} SBUs by ca{sup 2−} ligand. In the existence of π…π stacking interactions between triazine rings and phenyl rings, the 3D networks are constructed with the hanging phdat filled between the neighboring layers. Furthermore, compounds 1–2 exhibit antiferromagnetic behavior and compound 2 displays a good activity for methanol oxidation. - Graphical abstract: Two new coordination compounds 1–2 have been synthesized and characterized by single-crystal X-ray diffractions, IR spectra, elemental analyses, thermogravimetric analyses, magnetic and electrochemical measurement. - Highlights: • This paper reports two new coordination polymers based on D-camphoric acid. • Both the compounds feather two-dimensional layered networks built up from paddle-wheel SBUs. • The magnetism and electrochemical property are investigated.

Transition-metal phosphides have recently been identified as low-cost and efficient electrocatalysts that are highly active for the hydrogen evolution reaction. Unfortunately, to achieve a controlled phosphidation of nonprecious metals toward a desired nanostructure of metal phosphides, the synthetic processes usually turned complicated, high-cost, and even dangerous due to the reaction chemistry related to different phosphorus sources. It becomes even more challenging when considering the integration of those active metal phosphides with the structural engineering of their conductive matrix toward a favorable architecture for optimized catalytic performance. Herein, we identified that the biomass itself could act as an effective synthetic platform for the construction of supported metal phosphides by recovering its inner phosphorus upon reacting with transition-metals ions, forming well-dispersed, highly active nanoparticles of metal phosphides incorporated in the nanoporous carbon matrix, which promised high catalytic activity in the hydrogen evolution reaction. Our synthetic protocol not only provides a simple and effective strategy for the construction of a large variety of highly active nanoparticles of metal phosphides but also envisions new perspectives on an integrated utilization of the essential ingredients, particularly phosphorus, together with the innate architecture of the existing biomass for the creation of functional nanomaterials toward sustainable energy development.

Objective: To explore the promoting apoptosis and antitumor activities of ferulic acid (FA) in human osteosarcoma and its potential mechanism. Methods: The SaOS-2 and MG63 osteosarcoma cell lines were opted to experiment and these cells were, respectively, cultured with various concentrations of FA (0 μM, 10 μM, 20 μM, 40 μM) for 72 hours at 37°C. The viabilities of the FA treated cells were monitored by MTT. Apoptosis cells were evaluated using annexin V/PI by flow cytometry. Apoptosis proteins caspase-3, procaspase-3, Bcl-2 and Bax were detected by western blot. Expressions of apoptotic genes Bcl-2 and Bax were quantified by qPCR. Results: The cell viabilities were critically declined in the concentration-dependent manner in FA groups (P < 0.01). The apoptosis cells were increased proportionately with the concentration of FA (P < 0.05). The procaspase-3 protein contents, and Bcl-2 mRNA and protein contents were significantly decreased while caspase-3 protein contents, and Bax mRNA and protein contents were concomitantly increased in the concentration-dependent manner in FA groups (P < 0.05). The response to FA by the SaOS-2 osteosarcoma cell was similar with the MG63 osteosarcoma cell (P > 0.05). Conclusion: Ferulic acid could significantly descend osteosarcoma cell viability through the promoting apoptosis pathway in which FA activates both caspase-3 and Bax and inactivates Bcl-2.

Two tetra-nuclear cyanide-bridged molecular square complexes [MII(dppm)2(CN)2(CoIICl2)]2 (M = Ru, 1; M = Os, 2) (dppm = bis(diphenylphosphino) methane) were synthesized and characterized by elemental analysis, IR, electronic absorption spectra and single-crystal X-ray diffraction analysis. Both the isostructure complexes 1 and 2 crystallize in monoclinic space group P21/c, and possess two cis-M(dppm)2(CN)2 (M = Ru, 1; M = Os, 2) and two CoCl2 units through cyanido bridges. What’s more, the environment around the Co(II) atoms in 1 and 2 define a slightly distorted tetrahedron, and are coordinated by two nitrogen atoms from the cyanide groups with cis-configuration and by two chlorine atoms. Temperature dependence of magnetic susceptibilities show both 1 and 2 are weak antiferromagnetic coupling between the paramagnetic Co(II) ions across a diamagnetic cyanidometal –NC–M(II)–CN– bridge. Furthermore, complex 1 exhibits spin-canted behavior. However, there is no such magnetic behavior in complex 2, which may result from the more diffuse nature of the 5d orbits with respect to 4d.

Liquid nitrogen was used as a coolant in the freeze-drying method to synthesize nano-Li 3 V 2 (PO 4 ) 3 /reduced graphene oxide (LVPG N ) for the first time. In this material, reduced graphene oxide (rGO) (6.6 wt% in content) formed a 3D-framework and Li 3 V 2 (PO 4 ) 3 nanoparticles (30–150 nm) were strongly adhered to the surface of the rGO and enwrapped into the rGO sheets uniformly. The LVP nanoparticles can decrease the lithium ion diffusion length and the rGO can effectively improve the electronic conductivity. The material shows great rate performance with a capacity of 105.7 mAh g −1 at 20C for 3.0–4.3 V, and a good cycling performance with a discharge capacity of 123.2 mAh g −1 (96.7% of the first discharge capacity 127.4 mAh g −1 ) after 100 cycles at 0.1C.

Two genuine supramolecular isomers [Co(1,4-NDC)(5,5′-dmbpy)]n (1α and 1β) and compound {[Co(1,4-NDC)(5,5′-dmbpy)(H2O)2]2}n (2) (1,4-NDCH2 = 1,4-naphthalenedicarboxylic acid, 5,5′-dmbpy = 5,5′-dimethyl-2,2′-dipyridyl) have been synthesized under conventional hydro(solvo)thermal reactions. The highly crystalline single-phases of 1β and 2 with a well-defined morphology could also be quickly prepared through microwave-assisted syntheses within 5 min. Compared with 2, which possesses a one-dimensional (1D) single-chain-like structure, 1α and 1β feature the structures of 1D ladder-like chain and two-dimensional (2D) layer, respectively, constructed from the ring-like [Co2(OOCR)2] dimeric units interlinked by the 1,4-NDC ligands. The drastic structural transformation from 1α to 2, as well as the interconversion between 1β and 2, was observed, which involved the reversible destruction and reconstruction of the Co2(OOCR)2 unit during the transformation and was associated with remarkable changes in magnetic propert...

Five transition-metal coordination polymers, namely, [Zn7Cl6(oba)4]n (1), [Cd7Cl6(oba)4]n (2), [Zn(oba)(H2O)]n (3), [Ag2(oba)]n (4) and [Co(oba)(H2O)2]n (5) (H2oba=4,4′-oxydibenzoic acid), have been achieved under hydrothermal conditions and structurally characterized by IR, elemental analyses, X-ray single-crystal diffraction and TGA. The X-ray single-crystal diffraction reveals that compounds 1 and 2 are isomorphism, featuring pillared-layer 3D motifs, in which the 2D inorganic layers (Zn6Cl7)n (or (Cd6Cl7)n) are connected by oba2− pillars. Compound 3 exhibits 1D stair-like chain and extends to a 3D network by two different interchain O–H–O hydrogen bonding interactions while compound 4 features wave chains and stretches to 2D layer by interchain Ag–O weak contacts. Compound 5 shows 2D network in which Co-chains are pillared by oba2− ligand and then forms a 3D network by four different O–H–O hydrogen bonding interactions. Furthermore, 1–4 exhibit luminescent properties at a solid state and 5 shows antiferromagnetic behavior.

Phytochemical investigation of whole plants of Euphorbia pilosa led to the isolation and identification of two new daphnane-diterpenoid glucosides, euphopilosides A and B (1 and 2, resp.), and a new ent-abietane, euphopilolide (3), together with eight known compounds. Compounds 1 and 2 are the first daphnane-type diterpenoid glycosides. Their structures were elucidated by a combination of 1D- and 2D-NMR, and MS analyses, and acid hydrolysis. Compounds 1-9 were evaluated for their in vitro cytotoxicities against five human tumor cell lines, HL-60, SMMC-7721, A-549, MCF-7, and SW-480. Compound 7 showed moderate inhibitory activity against all five cell lines.

A pcu network based on the dinuclear Ni(II) units, [Ni2(hfipbb)2(1,3-bix)2]n (1 )( H 2hfipbb = 4,4 0 (Hexafluoroisopropylidene)bis(benzoic Acid); 1,3-bix = 1,3-bis(imidazol-1-ylmethyl)benzene), has been hydrothermally synthesized and structurally characterized. Interestingly, the two Ni(II) cations are bridged by two carboxylate groups in the rarely-seen syn-anti mode. The magnetic data reveal the dominant ferromagnetic interactions between Ni(II) ions.

The direct electrochemical reduction of solid titanium dioxide (TiO2) is conducted in [BMIM]BF4-CaCl2 ionic liquid (IL) at 100 °C using sintered TiO2 as cathode and graphite rod as anode at an electrolysis potential of 3.2 V. Cyclic voltammetry is used to investigate the mechanism and feasibility of the direct electrochemical reduction of solid TiO2 in [BMIM]BF4-CaCl2 IL at 100 °C. The surface morphologies of the cathode are examined by scanning electron microscopy（SEM）. The crystal phase structure of the cathode is examined using a D8 Advance X-ray diffractometer(XRD). The results indicate that the direct electrochemical reduction of solid TiO2 in [BMIM]BF4-CaCl2 IL is feasible. A significant increase in conductivity is obtained by doping graphite into the cathode, thereby enhancing deoxidation. TiO2 reduction is conducted step by step, from outside to inside, and from high to low valence variation.

A 3D ten-connected self-penetrating network based on the pentacobalt(II) clusters, [Co5(1,4-ndc)4(OH)2(1,3-bix)2]n (1) (1,4-H2ndc = 1,4-naphthalenedicarboxylic acid; 1,3-bix = 1,3-bis(imidazol-1-ylmethyl)benzene), is synthesized and characterized. Topological analysis indicates that it has ile-364345362 network. The magnetic data reveals the dominant antiferromagnetic interactions between the Co(II) cations.

Cis- and trans-isomeric heterotrinuclear-metallic complexes and their two-electron-oxidation products, cis-/trans-[Cp(dppe)Fe(μ-CN)Ru(bpy)2(μ-CN)Fe(dppe)Cp][PF6]2 (cis-/trans-1[PF6]2) and cis-/trans-[Cp(dppe)Fe(μ-CN)Ru(bpy)2(μ-CN)Fe(dppe)Cp][PF6]4 (cis-/trans-1[PF6]4), have been synthesized and structurally characterized. To the best of our knowledge, the complexes are the first example of a cis-/trans-isomer with multistates. Although separated by the diamagnetic cyanido-metal bridge, the two distant paramagnetic metal centers in both the oxidized complexes exhibit quite strong magnetic couplings. As a unique example, cis-1[PF6]4 is antiferromagnetic, and trans-1[PF6]4 is ferromagnetic. Density functional theory (DFT) calculations suggest that the spin-delocalization mechanism should be responsible for the magnetic interactions between the two distant paramagnetic Fe(III) centers across the diamagnetic cyanido-metal in both cis- and trans-1(4+). Most importantly, the DFT calculations revealed that the type (antiferromagnetic or ferromagnetic) and strength (J) of the magnetic interactions in such compounds can be controlled by the variation (cis or trans) of the diamagnetic central metal configurations.

Two new transition metal coordination complexes, ([MnO(nda)](H{sub 2}dmt)(H{sub 2}O)){sub n} (1), [Ag{sub 5}(nda){sub 2.5}(dmt)]{sub n} (2), (H{sub 2}nda=naphthalene-1,4-dicarboxylic acid, dmt=2,4-diamine-6-methyl-1,3,5-triazine) have been hydrothermally synthesized by the reactions of H{sub 2}nda and dmt with the homologous MnCl{sub 2}·4H{sub 2}O and AgNO{sub 3}, respectively, and characterized by single-crystal X-ray diffraction, IR spectra, elemental analysis, thermogravimetric analysis (TGA). The compound 1 exhibits a 3D network comprising 1D metal chain (MnO(CO{sub 2}){sub 2}){sub n} connected by the ligand nda{sup 2−}, featuring a four-connected uninodal diamond -like topology. In compound 2, it is firstly observed that decanuclear silver units as secondary building units to construct 3D network by the ligands dmt and nda{sup 2−}, with a rare 2-nodal (3,8)-connected tfz-d topology ((4{sup 3}){sub 2}(4{sup 6}.6{sup 18}.8{sup 4})). The interactions within each Mn(II)—Mn(II) pair of compound 1 are antiferromagnetic (g=2.07, J=−1.42(1) cm{sup −1}, zj′=−0.73(2) cm{sup −1}). In addition, compound 2 exhibits photoluminescent property at about 472 nm (λ{sub ex}=394 nm). - Graphical abstract: Two new transition metal coordination complexes 1–2 have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, IR spectra, elemental analysis thermogravimetric analysis (TGA). Highlights: • The compound 1 exhibits a 3D network with four-connected uninodal diamond-like topology. • The first 3D networkmore » of 2 with a rare tfz-d topology consists of decanuclear silver clusters as secondary building units. • The magnetic measurement indicates the compound 1 shows antiferromagnetic interactions. • The photoluminescent property of 2 has been measured.« less

The properties of a Cu-Pb oxide ore are investigated by XRD and SEM. Results show that the ore is characterized by chalcocite, galena, azurite and cerusite. Copper and lead phases analysis show that the oxidation rates of copper and lead are up to 70% and 72%, respectively. In order to get a good flotation performance for the difficult-to-treat ore, an efficient flotation technology of bulk flotation of Cu-Pb sulfides，separation of Cu-Pb sulfides, copper and lead oxides flotation has been developed. By applying the combined depressants (sodium thiosulfate + peroxide), activator Disulhydroxybenzen Thiodiazole (developed by Kunming Metallurgy Research Institute) in copper oxide flotation and sodium sulfide in flotation of lead oxide, chalcocite and galena can be separated and the Cu-Pb oxides can be activated. Results in closed circuit test show that when the feed assays 0.59% Cu, 2.40% Pb and 39.87 g/t Ag, marketable copper sulfide and oxide concentrates, lead sulfide and oxide concentrates can be obtained. At the same time, silver got enriched in the concentrates too. This study is expected to give a technical support in utilizing this complex Cu-Pb oxide ores.

The properties of a lead-zinc ore are investigated by XRD and SEM analysis methods. Results show that the ore assays 1.27 per cent Pb and 1.62 per cent Zn, mainly occurring in the form of sulfide minerals. Through lead and zinc phase analysis, it is known that the distribution of galena reaches 63.78 per cent, and that of sphalerite is up to 77.16 per cent. And the oxidation rates of lead and zinc will become much more serious as the depth of exploitation increases, which is a great trouble that the mine faces with. So how to improve the recovery of mineral beneficiation is an important means to enhance the economical benefits in the mine. Many tests work have been done to develop a new bulk flotation process to enhance the Pb and Zn recovery. Flotation results of the closed circuit test indicate that the Pb and Zn recovery from the new bulk flotation process can be increase by 10 per cent and 2 per cent, respectively, which makes very considerable benefit for the mine.

Li-rich layered materials have been considered as the most promising cathode materials for future high-energy-density lithium-ion batteries. However, they suffer from severe voltage decay upon cycling, which hinders their further commercialization. Here, we report a Li-rich layered material 0.5Li2MnO3·0.5LiNi0.8Co0.1Mn0.1O2 with high nickel content, which exhibits much slower voltage decay during long-term cycling compared to conventional Li-rich materials. The voltage decay after 200 cycles is 201 mV. Combining in situ X-ray diffraction (XRD), ex situ XRD, ex situ X-ray photoelectron spectroscopy, and scanning transmission electron microscopy, we demonstrate that nickel ions act as stabilizing ions to inhibit the Jahn-Teller effect of active Mn(3+) ions, improving d-p hybridization and supporting the layered structure as a pillar. In addition, nickel ions can migrate between the transition-metal layer and the interlayer, thus avoiding the formation of spinel-like structures and consequently mitigating the voltage decay. Our results provide a simple and effective avenue for developing Li-rich layered materials with mitigated voltage decay and a long lifespan, thereby promoting their further application in lithium-ion batteries with high energy density.

The oxidation resistance of Ni-Si-Ti-C, Ni-Si-C-Nb in-situ reinforcement clad layers has been investigated by cyclic oxidation tests at the temperature 1100°C. The oxidation performance were characterized by Thermo-gravimetric (TG),scanning electron microscopy (SEM) and X-ray diffractometer (XRD),the TG date indicates good oxidation resistant was reached for the clad layers. The kinetic constant Kp and the micrograph of oxidized samples shown that NbC reinforce clad layers which oxide products including NiO, SiO2 and Nb2O5 has better oxidation resistant than TiC reinforce clad layers which oxide products including NiO, some SiO2 and TiO2.

Using laser cladding technique, TiC reinforced Ti matrix composite coatings were fabricated by preplacing TiC, (Ti+C), (Ti+TiC) powders respectively on the TA2 pure titanium surface.By means of XRD, SEM and Hv-Test, microstructures and microhardness were investigated. The results show that phases of the coatings are all composed of TiC and α-Ti. Delamination phenomenon appears when laser clad pure TiC coating, which has deleterious effect on properties. TiC phase is in-situ synthesized during laser clad (Ti+C) coating, but microstructure is coarse. Microstructure of (Ti+TiC) coating is the most uniform and dense of the three coatings. The microhardness sequence of the three coatings is (Ti+TiC)>TiC>(Ti+C), and the maximum value is Hv1246, Hv1213 and Hv1135 respectively. The main reason leads to the highest micro-hardness of (Ti+TiC) coating is the Ti powder is beneficial to laser cladding and large amount of TiC reinforcement formed which is compact and uniform.

A further phytochemical investigation on the whole plants of Ypsilandra thibetica yielded three new spirostane glycosides, named ypsilandrosides MO (13). Their structures were established as (3 beta,11a,25R)-3,11-dihydroxyspirost-5-en-12-one 3-{O-a-L-rhanmopyranosyl-(1?4)-O-L-rhanmopyranosyl-(1?4)-O-[a-L-rhanmopyranosyl-(1?2)]-beta-D-glucopyranoside} (1), (3 beta,7 beta,25R)-spirost-5-ene-3,7-diol 3-{O-a-L-rhanmopyranosyl-(1?4)-O-a-L-rhanmopyranosyl-(1?4)-O-[a-L-rhanmopyranosyl-(1?2)]-beta-D-glucopyranoside} (2), and (3 beta,7a,25R)-spirost-5-ene-3,7,17-triol 3-{O-a-L-rhanmopyranosyl-(1?4)-O-a-L-rhanmopyranosyl-(1?4)-O-[a-L-rhanmopyranosyl-(1?2)]-beta-D-glucopyranoside} (3) by means of a combination of MS, 1D- and 2D-NMR spectroscopic methods, and chemical degradation. Among them, compound 3 is the first pennogenin (=(3 beta,25R)-spirost-5-ene-3,17-diol) saponin whose aglycone contains an OH group at C(7). Compounds 13 were evaluated for the inhibition of the growth of five tumor cell lines, but all of them proved to be inactive.

An initial model of the HBV epsilon RNA was built by the Biopolymer module of Insight II. While its three-dimensional structure was obtained through structure optimization based on molecular dynamics simulation, the two active sites were found. A comparison with the experimental result indicated that the active sites may be the binding sites of the epsilon RNA in the RT–epsilon interaction. The result will be helpful to further discussion about the mechanism of RT–epsilon interaction and the study of HBV genome replication.

Two 3D cobalt-organic frameworks formulated as [Co3(2,4-pydc)2(micro3-OH)2]n.5nH2O (1) and [Co3(2,4-pydc)2(micro3-OH)2(H2O)]n.7nH2O (2) (2,4-pydc=pyridine-2,4-dicarboxylate) have been hydrothermally synthesized and characterized. Both compounds 1 and 2 exhibit the 3D porous frameworks with hydroxyl-bridged metal Delta-chains. However, in comparison with only two crystallographically independent CoII ions in a unit of 2, three crystallographically independent CoII ions are found in an asymmetric unit of 1, where their Delta-chains are constructed by two types of vertexes sharing quadrangles formed via edge-sharing triangles. Magnetic studies show that 1 exhibits spin-canted antiferomagnetism and a field-induced spin-flop transition while 2 behaves as a normal antiferromagnet. The magnetic properties are largely retained by the porous frameworks of dehydrated 1 and 2 compounds. Gas adsorption measurements indicate that both the dehydrated compounds absorb H2 into their pores.

A total of 1400 soil samples from the plow layer (0-20cm) at an approximate interval of 5km were collected in the autumn of 2002 over the entire black soil arable crops region to determine the spatial variability of seven variables, such as total organic matter content (OMC), total N, total P, total K, alkali-dissolvable N (AN), available P (AP) and available K (AK), with classical statistics and geostatistical analysis across the entire black soil area in Northeast China. In nonsampled areas ordinary kriging was utilized for interpolation of estimated nutrient determinations. Classical statistics revealed highly significant (P≤0.01) correlations with all seven of the soil properties, except for OMC with AP and total K with AK. In addition, using coefficients of variation, all soil properties, except for total K, were moderately variable. A geostatistical analysis indicated that structural factors, such as parent material, terrain, and water table, were the main causes of the spatial correlations. Strong spatial correlations were noted with OMC, total N, total P, AN, and AP, while they were moderate for total K and AK. The effective spatial autocorrelation of OMC, total N, total P, and AN ranged from 1037 to 1353km, whereas the ranges of total K, AP, and AK were only from 6 to 138km. The fit of the experimental semi-variograms to the theoretical models indicated that except for AN, kriging could successfully interpolate other six variables. Thus, the geostatistical method used on a large scale could accurately evaluate the spatial variability of most black soil nutrient properties in Northeast China.

An efficient and copper-free catalyst system for Sonogashira cross-coupling reaction is presented. In the presence of 3 mol-% of Pd(OAc)2 and 6 mol-% of 2-aminopyrimidine-4,6-diol, various aryl iodides and bromides can be coupled smoothly with terminal alkynes to afford the corresponding coupled alkynes in moderate to excellent yields under mild conditions. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

A combination of Pd(OAc) 2 and 2-aminopyrimidine-4,6-diol was found to be a stable and efficient catalytic system for the Suzuki-Miyaura cross-coupling of aryl halides with arylboronic acids. In the presence of Pd(OAc) 2 and 2-aminopyrimidine-4,6-diol, various ArX (X = I, Br, and Cl) were coupled with arylboronic acids efficiently to afford the corresponding cross-coupled products in moderate to excellent yields. Furthermore, high turnover numbers (up to 1000000 for the reaction of iodobenzene with phenylboronic acid) for the palladium-catalyzed Suzuki-Miyaura cross-coupling reaction were observed.

An efficient and copper-free palladium-catalyzed Sonogashira cross-coupling reaction protocol is presented. In the presence of 3 mol% of Pd(OAc) 2 and 6 mol% of DABCO, cross-coupling of various aryl halides (iodides and bromides) with terminal alkynes afforded the corresponding alkynes in moderate to excellent yields. Moreover, high TONs (turnover numbers, up to 720 000 for the reaction of 1-iodo-4-nitrobenzene with phenylacetylene) for the Sonogashira cross-coupling reaction were observed.

An efficient, amine- and phosphine-free palladium(II)-catalyzed homocoupling of terminal alkynes has been developed. In the presence of PdCl2, CuI, Me3NO, and NaOAc, homocoupling of various terminal alkynes underwent smoothly to afford the corresponding diynes in moderate to high yields without any phosphine ligands. In contrast, the presence of a phosphine ligand (PPh3) disfavored this palladium-catalyzed homocoupling procedure. Bases, solvents, and CuI have fundamental influence on the palladium-catalyzed homocoupling of terminal alkynes.

Purpose: To investigate the clinical benefits and underlying mechanisms of action of betulin in the treatment of cancer using a neuroblastoma (NB) cell model. Method: Cell viability assay (MTT assay) was applied to investigate the effects of betulin on proliferation and apoptosis of SK-N-SH cell. The expression or translocation of apoptosis-related biomarkers, which include protein kinase C (PKC) family members, were analyzed and quantified by Western blotting, caspase activity assay or enzyme-linked immunosorbent assay (ELISA). Results: Betulin treatment significantly inhibited the growth of SK-N-SH cells ( p < 0.001), with halfmaximal inhibition concentration (IC 50 ) of 8 μmol/mL. Furthermore, betulin treatment increased the activity of PKC-δ, which subsequently activated caspases 3, 8 and 9, thus initiating mitochondriamediated endogenous apoptotic pathways in SK-N-SH cells Conclusion: Data generated in this study suggest that betulin inhibits cell proliferation and promotes apoptosis via PKC-δ activation, which may provide new insights into NB treatment from the perspective of adjuvant chemotherapy and prevention of tumor recurrence. Keywords: Betulin, Neuroblastoma, Apoptosis, protein kinase C-δ, Adjuvant chemotherapy, Tumor recurrence, Caspase

isolation, structure and in vitro cytotoxicities of two new daphnane-diterpenoid glucosides, euphopilosides A (I) and B (II), and a new ent-abietane, euphopilolide (III) along with eight known compounds

Four new one-dimensional (1D) zigzag chain cyanide-bridged complexes [cis-MII(L)2(CN)2FeIII(salen)](PF6) (M = Fe, L = bpy, 3; M = Fe, L = phen, 4; M = Ru, L = bpy, 5; M = Os, L = bpy, 6) (bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline, salen = N,N′-ethylenebis(salicylideneaminato) dianion) have been synthesized and structurally as well as magnetically characterized, especially 3 and 4 are mixed-valence complexes. Fortunately, the crystals of complexes 3, 4 and 6 suitable for single-crystal X-ray diffraction analysis were obtained. In addition, the electronic absorption spectra indicate the existence of the MMCT (metal-to-metal charge transfer) bands in complexes 3–6. The temperature dependent magnetic susceptibilities reveal that the Fe(III)–Fe(III) exchange coupling separated by a diamagnetic cyanidometal –NC–M(II)–CN– bridge is weakly ferromagnetic for 3–5, but weakly anti-ferromagnetic for 6. Moreover, the specific heat measurements suggest complexes 3–5 exhibit a phase transition at 2.8 K, 2.7 K and 2.6 K, respectively.

By a stepwise growth process, an axial-fan-like and high-nuclearity [Gd6Cu12] cluster compound (1) was obtained, in which six [Cu2] blade fragments encapsulate a “hollow” [Gd6(μ3-OH)8] octahedral core. Without the support of a centered μ6-O ligand for the octahedral core, its mean Gd−μ3-O−Gd bridging angle (φ) is the largest one among the polynuclear [Gdn] (n ≥ 3) clusters. From the exchange and structural parameters of the reported complexes containing the GdO2Gd unit, an empirical formula was at the first time obtained. It can be concluded that φ > 110.9° is a prerequisite for a GdO2Gd complex exhibiting molecular ferromagnetism. The positive exchange constants for the Gd−Gd coupling from the empirical estimation and data fitting suggest the [Gd6] core in 1 is the first example of high-nuclearity Lnn cluster exhibiting the molecular ferromagnetism. The magnetic property for 1 is mainly predominated by the antiferromagnetic interaction of Cu−Cu coupling and the ferromagnetic interactions of Gd−Gd and of ...

From 1989 to 1993, trunk implants of acephate were tested for the control of seed and cone insect damage to conifer species in France and northeastern China. The treatments were promising for the control of the major pests that feed on cone and seed tissues, including cone flies, coneworms, and seedworms, in European and Siberian larch, Norway spruce, Scots and mountain pine. In contrast, acephate implants did not prevent seed chalcid damage nor that of gall midges in Douglas-fir, European larch, and Siberian larch. Treatment generally increased seed yield, but a significant increase in the number of filled seeds was seen only when chalcids and midges were absent. The 2-year effect of implants seemed limited. Acephate implantation did not seem to affect seed germination.

Supercapacitors (also known as ultracapacitors) are considered to be the most promising approach to meet the pressing requirements of energy storage. Supercapacitive electrode materials, which are closely related to the high-efficiency storage of energy, have provoked more interest. Herein, we present a high-capacity supercapacitor material based on the nitrogen-doped porous carbon nanofibers synthesized by carbonization of macroscopic-scale carbonaceous nanofibers (CNFs) coated with polypyrrole (CNFs@polypyrrole) at an appropriate temperature. The composite nanofibers exhibit a reversible specific capacitance of 202.0 F g(-1) at the current density of 1.0 A g(-1) in 6.0 mol L(-1) aqueous KOH electrolyte, meanwhile maintaining a high-class capacitance retention capability and a maximum power density of 89.57 kW kg(-1). This kind of nitrogen-doped carbon nanofiber represents an alternative promising candidate for an efficient electrode material for supercapacitors.

[reaction: see text] A novel and selective palladium-catalyzed annulation of 2-alkynylphenols method for the synthesis of 2-substituted 3-halobenzo[b]furans is presented. In the presence of PdX(2), CuX(2), and HEt(3)NX, 2-substituted 3-halobenzo[b]furans were selectively obtained as the major products. The mechanism of the reaction was also discussed.