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The electrooxidation of 5-hydroxymethylfurfural (HMF) has emerged as a promising way to generate high-value-added products. However, evoking high-valence state NiOOH species as active sites to realize high current density remains a challenge. Herein, we report an efficient electrocatalyst for HMF electrooxidation based on phosphate anion intercalated layered double hydroxides (NiCo-Pi-LDHs). Onset potential at 1.16 V vs. RHE and current density of 200 mA/cm2 at 1.41 V vs. RHE were realized. The intercalated phosphates act as proton transfer intermediates, facilitating the dehydrogenation of hydroxides to form oxyhydroxides while the protonated phosphate generated. The obtained oxyhydroxide oxidized HMF to 2,5-furandicarboxylic (FDCA) while cycling backward to hydroxide, accompanied by the cycle of protonated phosphate to phosphate. This novel strategy with dual-cycle of phosphate and nickel species can effectively evoke NiOOH species, thereby speeding up the reaction rate and having a great potential for biomass upgrading. [Display omitted] • Phosphate intercalated NiCo-Pi-LDHs efficiently catalyzed HMF electrooxidation. • The protonation cycle of intercalated phosphate promoted nickel species cycle. • The dual-cycle mechanism effectively induced high-valence state NiOOH species. • The NiCo-Pi-LDHs realized 200 mA/cm2 current density at 1.41 V RHE in HMF oxidation. [ABSTRACT FROM AUTHOR]

Early reports indicate that metformin, a clinical drug administered to treat type 2 diabetes mellitus (T2DM), was found to be associated with a better prognosis of cancer. The objective of this study was retrospectively analyzed the effect of metformin on the outcomes of Chinese breast cancer patients with T2DM. A total of 3757 primary invasive breast cancer patients who underwent surgery from January 2010 to December 2013 were enrolled. According to the medication treatment, all the patients were divided as non-diabetes group, metformin group and insulin group. The follow-up data for disease-free survival (DFS) and overall survival (OS) were obtained from 3553 patients (median follow up of 85 months) and estimated with the Kaplan–Meier method followed by a log-rank test. Multivariate Cox proportional hazards regression model was applied. The results showed that there was a significant survival difference among non-diabetes group, metformin group and insulin group, 5-year DFS was 85.8%, 96.1%, 73.0%, and 5-year OS was 87.3%, 97.1%, 73.3% respectively (P < 0.05). Prognostic analysis showed metformin was significantly associated with better DFS and OS. Our results suggested that metformin may have a good effect on the survival of invasive breast cancer patients with T2DM. [ABSTRACT FROM AUTHOR]

• C@PtGa interface structure is constructed by H 2 /CO 2 atmosphere treatment using LDH as precursor. • PtGa alloys were covered by thin carbon layer with the characteristics of defective and permeable. • Preferred conversion compared to oxide layer catalyst is owing to high accessibility of metallic sites. • High selectivity is due to optimized adsorption mode of CAL on C@PtGa interface sites. • Amorphous carbon layer is stable after 5 times cycles under selective cinnamaldehyde hydrogenation reaction. In this work, an alloy catalyst with C@PtGa interface structure was synthesized under H 2 /CO 2 atmosphere by using PtCl 6 2−/MgAlGa-LDHs as precursor. Cs-corrected STEM, EELS and CO chemisorption clearly confirmed the PtGa alloy particles were well covered by amorphous carbon thin layer with the characteristics of porous and permeable. In selective cinnamaldehyde hydrogenation, the C@PtGa catalyst showed a higher selectivity than both bare PtGa catalyst and Ga 2 O 3 @PtGa catalyst. The enhanced selectivity was attributed to the geometric decoration of carbon layer as well as the formation of electron-rich Pt sites at C@PtGa interface, which optimized the adsorption mode of cinnamaldehyde. More importantly, the permeable characteristic of carbon layer which maintained the accessibility of reactants to the Pt sites, contributed to the higher conversion compared to Ga 2 O 3 @PtGa catalysts with traditional oxide interface layer. Additionally, C@PtGa catalyst exhibited a good reusability with conversion of 88.3% and selectivity of 91.9% after 5 cycles. This work provides an alternative way to realize the boost of activity and selectivity in selective hydrogenation of C=O bonds by intelligently fabricating non-oxides@metal interface. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Pd/MgAl-LDH catalyst with sandwich interface is fabricated by a two-step method. • This new approach leads to more Pd-LDH interface sites with boosted oxygen vacancy. • The catalyst with sandwich interface exhibits both high activity and selectivity. • Preferred activity is attributed to the improved hydrogen spillover ability. • High selectivity is owing to special adsorption mode of C O on the interface sites. Abstract In this work, a Pd/MgAl-LDH catalyst was synthesized by the ion-exchange and liquid-reduction process (IE), with impregnation method (IM) as contrast, to study the difference in the interfacial structure induced by the preparation methods and the catalytic behavior for selective hydrogenation of 2-ethylanthraquinone. STEM-EDS measurement reveals that the IE-Pd/MgAl-LDH catalyst possesses an obvious sandwich structure of which Pd nanoparticles uniformly located in the LDH interlayer space, and therefore exhibits more Pd-LDH interface sites due to the high intimacy. More importantly, it was confirmed that the Pd-LDH interface structure was characterized by rich oxygen vacancies (Vo) due to the loss of surface hydroxyl groups on the LDH layer during the ion-exchange process. As expected, the IE-Pd/MgAl-LDH catalyst exhibited a 127% higher H 2 O 2 yield than that of IM-Pd/MgAl-LDH catalyst. High activity was attributed to the facilitated hydrogen activation resulting from significantly enhanced hydrogen spillover over the Pd-LDH interface structure. Preferred selectivity was owing to the special adsorption mode of C O bond interacted with the Pd-Vo interfacial sites, which leads to the selective activation of C O bond. This work develops a feasible approach to fabricate the metal-hydroxide interface structure and provides a fundamental understanding on interfacial effect toward selective hydrogenation of C O bonds. [ABSTRACT FROM AUTHOR]

Selective hydrogenation of anthraquinone is critical in producing H2O2, the strong oxidant widely used in most industrial areas. More efforts were made on the selective hydrogenation of C=O in the anthraquinone process because the sides-product will negatively affect continuous H2O2 production and significantly reduce the project economics. A crucial step toward high H2O2 yield is the rational design of heterogeneous catalysts. In this review, the metal-based catalyst design for the selective anthraquinone hydrogenation is cataloged into two significant strategies: active metal regulation and support property regulation. Research accomplished in the past decade on the catalyst design for selective anthraquinone hydrogenation is systematically reviewed. The focus is on the catalytic performance-enhancing mechanism and the factors that influence the mechanism. In addition, the limitations and barriers encountered for supported catalysts in the current study, as well as potential research trends, are discussed. [ABSTRACT FROM AUTHOR]

[Display omitted] • A method has been designed for the low-temperature, low-pressure in-situ etching coupled with electro-deposition for the preparation of HER catalysts. • The synergistic effect of Fe and Pd optimizes the Pd-H binding energy. • The synergistic effect of Ni(OH) 2 , Fe(OH) 3 and Pd facilitates the dynamical process in HER. The development of highly efficient and innovative electrocatalysts is crucial for the commercialization of the hydrogen evolution reaction (HER) at high current densities. An electrocatalyst consisting of Pd nanoparticles electrodeposited on nickel foam (NF) treated with ferric chloride etching, yielding a Pd content of 0.53 wt%, was synthesized. This PdFe/NF-24 h catalyst demonstrated outstanding HER performance across a wide pH range, requiring overpotentials of only 302 mV, 96.4 mV and 637.9 mV to achieve a current density of 1000 mA/cm2 in 1 M KOH, 0.5 M H 2 SO 4 and 1 M Phosphate Buffer Saline (PBS) electrolytes, respectively. The ferric chloride etching increased the active surface area, while iron doping optimized the hydrogen adsorption free energy on Pd. Furthermore, the presence of metal hydroxides facilitated the dissociation of water into adsorbed hydrogen, which then bound to active sites on the Pd surface to produce hydrogen, thereby enhancing the efficiency of hydrogen production. The catalyst operated at 1000 mA/cm2 in 1 M KOH solution for 222 h without degradation; it maintained stability for 124 h in 30 % KOH solution; in 0.5 M H 2 SO 4 solution, it retained 99.6 % performance for 77 h and it remained stable for 230 h in 1 M PBS solution. [ABSTRACT FROM AUTHOR]

• A high-sensitivity, quasi-temperature-insensitive magnetic field sensor is experimentally demonstrated. • Temperature affect induced by thermal expansion is eliminated by the symmetry of optical structure. • Experimental results show that the maximum sensitivity could be 4.36 nm/mT. This paper proposed and experimentally demonstrated a high resolution and quasi-temperature-insensitive magnetic field sensor based on hybrid interferometer. The sensor is created by cascading a Mach Zehnder interferometer (MZI) and a Sagnac loop interferometer (SI). Due to the symmetry of the MZI's two arms, the length change induced by thermal expansion is approximate identical, meaning the temperature perturbation would be eliminated. Moreover, the free spectrum ranges of MZI and SI are extremely close, thus the sensitivity is amplified by the vernier effect. Experiment results indicate that the magnetic field sensitivity of the MZI is 118.8 pm/mT, while the sensitivity of the sensor is 4.36 nm/mT, which is about 36.9 times higher than it in the MZI. [ABSTRACT FROM AUTHOR]

[Display omitted] • Pt-Y/Beta as efficient catalyst for ethanol-to-n-butanol with bifunctional activity. • Y tetrahedrally coordinated in zeolite framework and Pt on surface as nanoparticles. • Synergistic catalysis is achieved by coupling different catalytic roles and close proximity. • Pt is responsible for dehydro- and hydro-genation whereas Y for condensation. • Reaction mechanism over Pt-Y/Beta follows the Guerbet pathway. Conversion of ethanol to high-value alcohols is an attractive approach for developing renewable biofuels, the key is to develop stable and high-efficient catalysts. In this work, based on the preparation strategy of heteroatomic Beta zeolites, a bifunctional Pt-Y/Beta catalyst was prepared by solid-state ion exchange and impregnation. Through characterization techniques such as TEM, NMR and XAS, it was confirmed that the Y species were incorporated into the framework of Beta zeolite by interacting with the silanol groups located at the defect sites, while the Pt species were confirmed to be present on the surface of the zeolite in the form of dispersed nanoparticles. The unique structure form and the favorable spatial proximity of the two metallic active sites lead to a synergistic catalysis, which enable a one-step conversion of ethanol to n-butanol with exceptionally high selectivity of 68 %. In situ DRIFT characterization, ethanol-TPD and relay experiment results show that in the ethanol to n-butanol reaction, the Pt species in Pt-Y/Beta catalyst serves as the active center for the dehydrogenation of ethanol and the hydrogenation of crotonaldehyde and crotyl alcohol, while the Y species is responsible for catalyzing the condensation reaction of acetaldehyde. [ABSTRACT FROM AUTHOR]

Cinnamaldehyde (CAL) is a typical sustainable biomass molecule which is classified as α, β‐unsaturated aldehydes. Selective hydrogenation of CAL to produce high‐value and fine chemical cinnamylalcohol (COL) is an attractive catalytic transformation process. However, the hydrogenation of C=O bond in CAL is more unfavorable than C=C bond in thermodynamics and kinetics, leading to great challenge on achieving high yield of unsaturated alcohol. In this work, a Pt/CoAl‐LDHs catalyst was prepared for hydrogenation of CAL to COL, showing outstanding intrinsic activity (TOF as high as 4.93 s−1) and finally achieving 93.6 % selectivity at 95.4 % conversion. In contrast, the yields of COL over Pt/Co(OH)2 and Pt/Al(OH)3 were only 73 % and 34 % respectively. Characterizations including Raman, O‐XAFS, XPS revealed that the Co2+−O2−−Al3+ structure in CoAl‐LDHs contributed to strengthened metal‐support interactions, and resulted in electron‐rich and geometric decoration Ptδ− sites. The electron‐rich Ptδ− provided preferable H2 activation capability, and also exposed abundant unsaturated sites which optimized the adsorption mode of cinnamaldehyde favorable for C=O hydrogenation. However, in Pt/Co(OH)2 and Pt/Al(OH)3 catalysts, the Pt0 without electron‐rich and unsaturated property cannot improve the H2 activation capability as well as electronic repellency to C=C bond. In addition, a possible catalytic mechanism was proposed to illustrate the role of Ptδ−−Co2+−O2−−Al3+ interfacial structure on enhancing activity and selectivity. [ABSTRACT FROM AUTHOR]

Abstract: Abuse of opiates, including morphine, induced remarkable synaptic adaptation in several brain regions including ventral tegmental area (VTA), which underlay the induction and maintenance of opioid dependence and addiction. Scaffolding protein postsynaptic density protein 95 (PSD-95) is critically involved in the glutamatergic synaptic maturation and plasticity in the central neurons. The present study revealed a significantly increased mRNA and protein expression of PSD-95 in the VTA of the rats conditioned with morphine. The further chromatin immunoprecipitation study found an increased histone H3 acetylation in the promoter region of Dlg4. An upregulation of expression of phosphorylated cAMP response element-binding protein (pCREB) and the occupancy of pCREB in the Dlg4 promoter region were shown in the VTA of the morphine-conditioned rats. Inhibition of pCREB activity significantly decreased the histone H3 acetylation in Dlg4 promoter region, PSD-95 upregulation, enhancement of glutamatergic strength and the preference to morphine-paired chamber in the rats with morphine conditioning. These results suggested that CREB-mediated epigenetic upregulation of PSD-95 critically contributed to the enhanced glutamatergic transmission and rewarding behavior induced by morphine conditioning. [Copyright &y& Elsevier]

Focusing on the simultaneous enhancement of activity and selectivity in α, β‐unsaturated aldehyde hydrogenation, we designed and prepared an ultrathin CoAl‐LDH supported Pt catalyst. A series of technologies revealed the ultrathin CoAl‐LDH support possesses the characteristic of dual defects, oxygen vacancy (VO) and cobalt vacancy (VCo). Then, two kinds of vacancy related interface sites were identified, namely Pt−VO−Coδ+ and Pt−VCo−OHδ−. Compared with the bulk catalyst, the ultrathin catalyst exhibits both enhanced intrinsic activity and C=O bond selectivity under the synergistic effect of the dual interface sites. Specifically, the Pt−VO−Coδ+ interface site changes the adsorption mode of cinnamaldehyde and promotes the activation of C=O bonds, thus leading to the improved cinnamyl alcohol selectivity. The H atoms of the Pt−VCo−OHδ− interface site participate in the hydrogenation process, which facilitates the mobility of active hydrogen and therefore promotes the intrinsic activity. More importantly, the ultrathin catalyst shows good reusability. [ABSTRACT FROM AUTHOR]

ADAMTS18 dysregulation plays an important role in many disease processes including cancer. We previously found ADAMTS18 as frequently methylated tumor suppressor gene ( TSG) for multiple carcinomas, however, its biological functions and underlying molecular mechanisms in breast carcinogenesis remain unknown. Here, we found that ADAMTS18 was silenced or downregulated in breast cancer cell lines. ADAMTS18 was reduced in primary breast tumor tissues as compared with their adjacent noncancer tissues. ADAMTS18 promoter methylation was detected in 70.8% of tumor tissues by methylation-specific PCR, but none of the normal tissues. Demethylation treatment restored ADAMTS18 expression in silenced breast cell lines. Ectopic expression of ADAMTS18 in breast tumor cells resulted in inhibition of cell migration and invasion. Nude mouse model further confirmed that ADAMTS18 suppressed breast cancer metastasis in vivo. Further mechanistic studies showed that ADAMTS18 suppressed epithelial-mesenchymal transition ( EMT), further inhibited migration and invasion of breast cancer cells. ADAMT18 deregulated AKT and NF- κB signaling, through inhibiting phosphorylation levels of AKT and p65. Thus, ADAMTS18 as an antimetastatic tumor suppressor antagonizes AKT and NF- κB signaling in breast tumorigenesis. Its methylation could be a potential tumor biomarker for breast cancer. [ABSTRACT FROM AUTHOR]

The KRAB–zinc-finger protein ZNF545 was recently identified as a potential suppressor gene in several tumors. However, the regulatory mechanisms of ZNF545 in tumorigenesis remain unclear. In this study, we investigated the expression and roles of ZNF545 in multiple myeloma (MM). ZNF545 was frequently downregulated in MM tissues compared with non-tumor bone marrow tissues. ZNF545 expression was silenced by promoter methylation in MM cell lines, and could be restored by demethylation treatment. ZNF545 methylation was detected in 28.3% of MM tissues, compared with 4.3% of normal bone marrow tissues. ZNF545 transcriptionally activated the p53 signaling pathway but had no effect on Akt in MM, whereas ectopic expression of ZNF545 in silenced cells suppressed their proliferation and induced apoptosis. We therefore identified ZNF545 as a novel tumor suppressor inhibiting tumor growth through activation of the p53 pathway in MM. Moreover, tumor-specific methylation of ZNF545 may represent an epigenetic biomarker for MM diagnosis, and a potential target for specific therapy. [ABSTRACT FROM AUTHOR]

Anthracyclines have a profound effect on breast cancer. However, at higher dosages, there are many toxic side effects associated with their use; these include bone marrow suppression, alopecia, gastrointestinal reactions and cardiotoxicity. Pegylated liposomal doxorubicin (PEG-LG) has been demonstrated to achieve equivalent efficacy to conventional doxorubicin, with significantly lower cardiotoxicity. We conducted an open-label, multicenter, single-armed clinical trial useing an NAC regimen based on four cycles of PEG-LD 40 mg/m2 plus cyclophosphamide (CPM) 600 mg/m2 on day 1 of a 21 day schedule, followed by four cycles of docetaxel (DTX) 85 mg/m2 on day 1 of a 21 day schedule. The primary endpoint analysed was the pathological complete response rate (pCR) in the breast, while treatment toxicities and safety were also assessed. The results showed that the breast pCR rate was 18.75% (95% CI 11.5–26.0%). Among the different molecular cancer types, the triple negative breast cancer patients had the highest pCR, at 43.75%. No significant decrease in left ventricular ejection fraction was observed. Our data tends to draw the conclusion that this regimen is a viable option for the neoadjuvant treatment of patients with LABC, especially in the triple-negative subtype and patients with heart abnormalities. We believe the efficacy and the safety of this regimen is likely to be the same based on published data from other studies but that this cannot be certain without a randomized trial. [ABSTRACT FROM AUTHOR]