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Supported nickel catalysts are promising candidates for dry reforming of methane, but agglomeration of Ni0 and coke deposition hinder the industrial applications. Herein, we report a novel interface-directed synthetic approach to construct distinct metal ensembles by carefully tuning the compositions of the carriers. A Zr-Mn-Zn ternary oxide-supported Ni catalyst, together with the respective binary oxide-supported analogues, was synthesized by adopting a sequential co-precipitation and wetness impregnation method. Combined characterization techniques identify distinct catalyst models, including (i) conventional NiO nanoparticles with different sizes on Zr-Mn and Zr-Zn, and (ii) epitaxially growing NiO ensembles of a few nanometers thickness at the periphery of MnZnOx particles. These catalysts exhibit divergent responses in the catalytic testing, with the ternary oxide system significantly outperforming the binary analogues. The strong electronic interactions between Mn-Ni increase Ni dispersion and the activity while the stability is strengthened upon Zn addition. Both high activity, high selectivity, and remarkable stability are attained upon co-adding Mn and Zn. The interfaces between Ni and Zr-Mn-Zn rather than the physical contacts of individual oxide-supported analogues through mechanical mixing are keys for the outstanding performance.

The development of robust catalysts for selective hydrogenation of dimethyl oxalate (DMO) is key for the expansion of ethylene glycol (EG) production from C1 and renewable feedstocks. Copper-based catalysts promoted with Cr are industrially used, but it is desirable to develop more environmentally-benign alternatives. Silica-supported copper-zinc bimetallic catalysts featuring intimate metal contact are designed and used to establish the structure-performance relationships through combining in-depth characterizations with steady-state catalytic testing. Our study highlights: i) that the surface Cu0/Cu+ ratio is a reliable catalytic descriptor that determines the activity and selectivity, and ii) the importance of copper-zinc interface in stabilizing copper nanoparticles both under reduction and hydrogenation conditions. Controlled zinc doping allows fine tuning of these properties for the targeted reaction. Excellent performance has been achieved on the best-performing catalyst with >99.6% DMO conversion, >96.0% EG selectivity, and unprecedented stability of 800 h without catalyst deactivation, which represents a significant advance in the selective hydrogenations.

Decorating small copper nanoparticles with isolated and/or clustered oxophilic rhenium species enables the first low-copper catalytic technology for intensified and stable ethanol production under mild conditions in dimethyl oxalate hydrogenation. Addition of rhenium induces hydrogenolysis functionality and strong electronic interactions with copper, accounting for the remarkable performance.

This paper presents a comparative study on high voltage β-Ga 2 O 3 and 4H-SiC Schottky diodes based on device TCAD numerical simulations. Different Schottky diode structures are comparative investigated, and the results show that the Ga 2 O 3 Schottky diodes achieve much lower specific on-resistance (R on,sp ), much higher figure of merit (FOM) and better reverse recovery characteristics in comparison with that of the SiC Schottky diodes at almost the same level of breakdown voltage (BV). And the leakage current in reverse bias state of different structures is also evaluated, and the trench structure achieves much lower leakage current. The results of this paper can be used as a guideline for the design of high-voltage Ga 2 O 3 and SiC Schottky diodes.

Oxidative stress and inflammation play an important role in hypertensive animals and patients. Hydrogen plays a role of antioxidation and anti-inflammation. Calcium and magnesium play an important role in reducing hypertension and antioxidant. Filtered water contains abundant hydrogen and a large number of other essential elements of the human body. We investigated the protective effects of filtered water on hypertensive mice. To establish hypertension model, ICR mice were administered with N′-nitro-L-arginine methyl ester (L-NAME) hydrochloride 64 mg/kg per day for 1 month. The hypertensive mice were, respectively, administered with pure water, tap water, and filtered water for 2 months. Lipid peroxidation, antioxidant enzymatic activity, endothelin-1 (ET-1), angiotensin II (Ang II), and proinflammatory cytokines (TNF-α, IL-6, and IL-1β) were assessed. Expressions of phosphorylated NF-κB P65 in the kidney were analyzed by western blot. qRT-PCR analysis was adopted to determine the expression levels of the proinflammatory cytokines and NF-κB P65. The results demonstrated that filtered water can reduce the blood pressure. Filtered water treatment restored the activity of antioxidant enzymes, downregulated ET-1, and Ang II in the serum of mice. Filtered water treatment suppressed proinflammatory cytokines and decreased the mRNA expression of TNF-α, IL-6, IL-1β, and NF-κB P65. Consumption of filtered water inhibited the expression of NF-κB P65. This suggests that filtered water can reduce the blood pressure. The protection mechanisms include downregulating oxidative stress and inhibiting inflammation, which is partly due to the inhibition of the NF-κB signaling pathway.

The catalytic transformation of aryl esters to hydroxyacetophenonesviaFries rearrangement over solid acids is of interest to avoid the use of corrosive and toxic Lewis and Bronsted acids traditionally applied. Microporous zeolites are known to catalyze the reaction of simple substrates such as phenyl acetate, but their application to substituted derivatives has received limited attention. To refine structure-activity relationships, here we examine the impact of various parameters including the solvent polarity, water content, acidic properties, and framework type on the reaction scheme in the Fries rearrangement ofp-tolyl acetate over common solid acids. The results confirm the importance of providing a high concentration of accessible Bronsted acid sites, with beta zeolites exhibiting the best performance. Extension of the substrate scope by substituting methyl groups in multiple positions identifies a framework-dependent effect on the rearrangement chemistry and highlights the potential for the transformation of dimethylphenyl acetates. Kinetic studies show that the major competitive path of cleavage of the ester C-O bond usually occurs in parallel to the Fries rearrangement. The possibility of sequentially acylating the resulting phenol depends on the substrate and reaction conditions., Catalysis Science & Technology, 10 (13), ISSN:2044-4753, ISSN:2044-4761

The present study was designed to investigate the protective effect of moracin on primary culture of nucleus pulposus cells in intervertebral disc and explore the underlying mechanism. Moracin treatment significantly inhibited the LPS-induced inflammatory cytokine accumulation (IL-1β, IL-6 and TNF-α) in nucleus pulposus cells. And moracin also dramatically decreased MDA activity, and increased the levels of SOD and CAT induced by LPS challenge. Moreover, the expressions of Nrf-2 and HO-1 were decreased and the protein levels of p-NF-κBp65, p-IκBα, p-smad-3 and TGF-β were increased by LPS challenge, which were significantly reversed after moracin treatments. Moracin treatments also decreased the levels of matrix degradation enzymes (MMP-3, MMP-13) as indicated by RT-PCR analysis. However, Nrf-2 knockdown abolished these protective effects of moracin. Together, our results demonstrated the ability of moracin to antagonize LPS-mediated inflammation in primary culture of nucleus pulposus in intervertebral disc by partly regulating the Nrf2/HO-1 and NF-κB/TGF-β pathway in nucleus pulposus cells.

Ozone (O3) is widely used in drinking water disinfection and wastewater treatment. However, when applied to bromide-containing water, ozone induces the formation of bromate, which is carcinogenic. Our previous study found that graphene oxide (GO) can enhance the degradation efficiency of micropollutants during ozonation. However, in this study, GO was found to promote bromate formation during ozonation of bromide-containing waters, with bromate yields from the O3/GO process more than twice those obtained using ozone alone. The promoted bromate formation was attributed to increased hydroxyl radical production, as confirmed by the significant reduction (almost 75%) in bromate yield after adding t-butanol (TBA). Cerium oxide (less than 5 mg/L) supported on reduced GO (xCeO2/RGO) significantly inhibited bromate formation during ozonation compared with reduced GO alone, and the optimal Ce atomic percentage (x) was determined to be 0.36%, achieving an inhibition rate of approximately 73%. Fourier transform infrared (FT-IR) spectra indicated the transformation of GO into RGO after hydrothermal treatment, and transmission electron microscope (TEM) results showed that CeO2 nanoparticles were well dispersed on the RGO surface. The X-ray photoelectron spectroscopy (XPS) spectra results demonstrated that the Ce3+/Ce4+ ratio in xCeO2/ RGO was almost 3–4 times higher than that in pure CeO2, which might be attributed to the charge transfer effect from GO to CeO2. Furthermore, Ce3+ on the xCeO2/RGO surface could quench Br· and BrO· to further inhibit bromate formation. Meanwhile, 0.36CeO2/RGO could also enhance the degradation efficiency of N,N-diethyl-m-toluamide (DEET) in synthetic and reclaimed water during ozonation.

Osteoarthritis is one of the major causes of disability in elderly adults. Chondrocytes are responsible for the formation and remodeling of articular cartilage in joint tissue. The dysfunction of chondrocytes is a significant factor in the development of osteoarthritis. In the current study, we found that theobromine, a constituent of the cacao plant, possesses a preventive effect against interleukin (IL)-1β-induced chondrocyte dysfunction. Theobromine ameliorates IL-1β-induced production of cellular reactive oxygen species (ROS) and inflammatory mediators including cyclooxygenase-2 (COX-2) and prostaglandin E2 (PGE2). The presence of theobromine suppresses IL-1β-induced inducible nitro oxide synthase (iNOS) expression and cellular nitro oxide (NO) production. Theobromine also suppresses IL-1β-induced production of the pro-inflammatory cytokines tumor necrosis factor-α (TNF-α) and monocyte chemoattractant protein-1 (MCP-1), as well as matrix metalloproteinases (MMP)-3 and MMP-13. Additionally, theobromine mitigates IL-1β-induced type II collagen degradation. Mechanistically, we show that theobromine inhibits IL-1β-induced IκBα activation, nuclear factor-κB (NF-κB) protein p65 accumulation, and transfected NF-κB promoter activity, indicating that theobromine suppresses the NF-κB pathway in chondrocytes. Collectively, our study demonstrates that the natural molecule theobromine has a protective effect to counter cytokine-induced chondrocyte dysfunction, implying its beneficial effect in the prevention of osteoarthritis.

Chemical Science, 10 (2), ISSN:2041-6520, ISSN:2041-6539

Malaria causes nearly one million deaths each year and with its recent re-emergence, several fatal complications are seen such as cerebral malaria, hypotension or shock, renal failure, pulmonary oedema/adult respiratory distress syndrome, and hypoglycaemia. Symmetric peripheral gangrene (SPG) is a severe but extremely rare complication of malaria. It has a rapid and sudden onset leading to necrosis which cannot be reversed. A 26 year old male was admitted and treated for complicated malaria and developed SPG. He was given intravenous artesunate, doxycyline, clopidogrel and acetyl salicyclic acid for the gangrene; however, he went into multiple organ dysfunction syndrome and septic shock and thus could not be resuscitated. We report this case to highlight that physicians treating malaria should always look for these signs for timely correction and to improve the patient outcome.

// Amruta Ronghe 1 , Anwesha Chatterjee 1 , Nimee K. Bhat 1 , Subhash Padhye 2 , Hari K. Bhat 1 1 Division of Pharmacology and Toxicology, School of Pharmacy, University of Missouri-Kansas City, Kansas City, Missouri, USA 2 Interdisciplinary Science and Technology Research Academy, Abeda Inamdar Senior College, Department of Chemistry, University of Pune, Pune, India Correspondence to: Hari K. Bhat, email: bhath@umkc.edu Keywords: breast cancer, tamoxifen, resveratrol analogs, synergistic inhibition, combination therapy Received: December 20, 2015 Accepted: May 22, 2016 Published: June 16, 2016 ABSTRACT We have recently shown that 4-(E)-{(4-hydroxyphenylimino)-methylbenzene, 1,2-diol} (HPIMBD) and 4-(E)-{(p-tolylimino)-methylbenzene-1,2-diol} (TIMBD), novel analogs of resveratrol (Res), selectively inhibited the proliferation of breast cancer cells. In the current study, we tested HPIMBD and TIMBD individually in combination with tamoxifen (Tam) for inhibition of growth of breast cancer cells. Tamoxifen was first tested on non-neoplastic breast epithelial cell lines and its dose that does not inhibit their growth was determined. A combination of this low dose of Tam with either of the Res analogs HPIMBD or TIMBD, resulted in synergistic inhibition of proliferation of breast cancer cells. Both estrogen receptor (ER)-positive and negative breast cancer cell lines responded to the combination. The combination resulted in a substantial decrease in IC 50 values of Res analogs in all breast cancer cell lines tested. Mechanistic studies showed a synergistic increase in apoptosis and autophagy genes (beclin-1 and LC3BII/I) with the combination in ER-negative MDA-MB-231 cells. In ER-positive MCF-7 and T47D cells, the mechanism of synergy was found to be inhibition of expression of ERα and oncogene c-Myc. The combination treatment had a synergistic effect in inhibiting the colony forming and spheroid forming ability of cancer cells. Taken together, our findings indicate that a combination of Tam and Res analogs HPIMBD or TIMBD represents a novel approach to enhancing the use of Tam in therapy for breast cancers. Considering the urgent need for novel therapeutic strategies to treat ER-negative breast cancers and overcoming resistance in ER-positive cancers, this combinatorial approach is worthy of continued investigation.

In this communication, a general technology for improving the electrochemical performances of metal oxide based electrode materials has been demonstrated via in situ growth of the electrode materials on Ni nanowire array (NNA) current collector films, which can attain a loading level up to ∼25 mg cm−2. The NNA@MoO3 electrode delivered a high areal capacity ∼477 mF cm−2 and superior longevity (∼5% capacitance loss after 20 000 cycles). Moreover, crystalline VO2 was electro-deposited on NNA as the cathode, which was assembled with the NNA@MoO3 anode into an all-metal oxide-based asymmetric supercapacitor (AAS). The AAS can deliver an open circuit voltage of 1.6 V in an aqueous electrolyte and a high energy density (2.19 mW h cm−3) at the power density of 8.2 mW cm−3. This work provides an example of a flexible AAS device featuring a high areal capacity (307 mF cm−2) and excellent cyclability (116% retention after 20 000 cycles) simultaneously purely involved with metal oxide electrodes.

Gold catalysts have been reported to exhibit good performance in aerobic oxidation of alcohols, but the intrinsic origin of the catalytic reactivity is still illusive. The catalyst preparation method, the morphology of the gold particles, and even the support might be key factors that determine the activity. Here, we prepared a series of gold catalysts with different supports, i.e., the hydrotalcite (HT), ZnO, MgO, Al2O3, and SiO2, by using the atomically controlled Au25 nanoclusters (NCs) as the gold precursor. The characterization results of the X-ray diffraction (XRD), UV-vis and transmission electron microscopy (TEM) show that the gold particles were mostly uniformly distributed on the supports, with a mean particle size within 3 nm. In aerobic oxidation of benzyl alcohol, the MgAl-HT- and Al2O3-supported Au25 NCs display good performances, with turnover frequency (TOF) values of ~2927 and 2892 h&minus, 1, respectively, whereas the SiO2-, MgO-, and ZnO-supported analogues show much inferior activity. The high resolution TEM and X-ray photoelectron spectra (XPS) results suggest that the interactions between gold and the supports in different samples are differing, which influences the morphology and the nature of gold. Our results further point to the importance of acid-base property of the support and the metal-support synergy rather than the gold particle size alone in achieving high-performance in selective alcohol oxidation. Moreover, this work provided a good way to design gold catalysts with controllable sizes that is crucial for understanding the reaction process in aerobic oxidation of alcohol.

FR4 is presently the most commonly used substrate for designing microwave devices. This paper presents how the proposed modified PTFE (PolyTetraFluoroEthylene) is better than FR4 through a comparative study between the two substrates by observing the performance characteristics of the antenna. Improvement in bandwidth and gain without disturbing the radiation pattern is observed with the use of PTFE with hexagonal-Boron Nitride (h-BN) as a filler over the use of FR4 substrate. The antenna performance could be enhanced with the adoption of PTFE+h-BN as substrate.

ACS Catalysis, 8 (2), ISSN:2155-5435

BACKGROUND: Cisplatin chemotherapy and surgery are effective treatments for children with standard-risk hepatoblastoma but may cause considerable and irreversible hearing loss. This trial compared cisplatin with cisplatin plus delayed administration of sodium thiosulfate, aiming to reduce the incidence and severity of cisplatin-related ototoxic effects without jeopardizing overall and event-free survival. METHODS: We randomly assigned children older than 1 month and younger than 18 years of age who had standard-risk hepatoblastoma (≤3 involved liver sectors, no metastatic disease, and an alpha-fetoprotein level of >100 ng per milliliter) to receive cisplatin alone (at a dose of 80 mg per square meter of body-surface area, administered over a period of 6 hours) or cisplatin plus sodium thiosulfate (at a dose of 20 g per square meter, administered intravenously over a 15-minute period, 6 hours after the discontinuation of cisplatin) for four preoperative and two postoperative courses. The primary end point was the absolute hearing threshold, as measured by pure-tone audiometry, at a minimum age of 3.5 years. Hearing loss was assessed according to the Brock grade (on a scale from 0 to 4, with higher grades indicating greater hearing loss). The main secondary end points were overall survival and event-free survival at 3 years. RESULTS: A total of 109 children were randomly assigned to receive cisplatin plus sodium thiosulfate (57 children) or cisplatin alone (52) and could be evaluated. Sodium thiosulfate was associated with few high-grade toxic effects. The absolute hearing threshold was assessed in 101 children. Hearing loss of grade 1 or higher occurred in 18 of 55 children (33%) in the cisplatin-sodium thiosulfate group, as compared with 29 of 46 (63%) in the cisplatin-alone group, indicating a 48% lower incidence of hearing loss in the cisplatin-sodium thiosulfate group (relative risk, 0.52; 95% confidence interval [CI], 0.33 to 0.81; P=0.002). At a median of 52 months of follow-up, the 3-year rates of event-free survival were 82% (95% CI, 69 to 90) in the cisplatin-sodium thiosulfate group and 79% (95% CI, 65 to 88) in the cisplatin-alone group, and the 3-year rates of overall survival were 98% (95% CI, 88 to 100) and 92% (95% CI, 81 to 97), respectively. CONCLUSIONS: The addition of sodium thiosulfate, administered 6 hours after cisplatin chemotherapy, resulted in a lower incidence of cisplatin-induced hearing loss among children with standard-risk hepatoblastoma, without jeopardizing overall or event-free survival. (Funded by Cancer Research UK and others; SIOPEL 6 ClinicalTrials.gov number, NCT00652132 ; EudraCT number, 2007-002402-21 .).

In recent years, hepatitis B core protein virus-like particle (HBc VLP) is an impressive biomaterial, which has attracted considerable attention due to favorable properties such as structural stability, high uptake efficiency, and biocompatibility in biomedical applications. Heretofore, only a few attempts have been made to apply it in physical, chemical, and biological therapy for cancer. In this study, a tumor-targeting RGD-HBc VLP is first fabricated through genetic engineering. For image-guided cancer phototherapy, indocyanine green (ICG) is loaded into RGD-HBc VLP via a disassembly/reassembly pathway and electrostatic attraction with high efficiency. The self-assembled stable RGD-HBc VLP significantly improves body retention (fourfold longer), aqueous stability, and target specificity of ICG. Remarkably, these positive reformations promote more accurate and sensitive imaging of U87MG tumor, as well as prolonged tumor destruction in comparison with free ICG. Moreover, the photothermal and photodynamic effect on tumors are quantitatively differentiated by multiple linear regression analysis. Overall, less-potent medicinal ICG can be perfectly rescued by bioengineered HBc VLP to realize enhanced cancer optotheranostics.

The heterogenization of homogeneous catalysts is of critical importance for both fundamental research and practical applications. The key obstacle to industrial applications of heterogenized homogeneous catalysts is the long-term stability of the immobilized molecular complexes. We unambiguously demonstrate in this report that the vinyl-functionalized PPh3 polymers supported single Rh sites (Rh/POL-PPh3) catalyst provided not only excellent catalytic activity but also ultrahigh stability for fixed-bed olefins hydroformylation, which is one of the most important industrial homogeneous catalytic processes for the synthesis of aldehydes and alcohols. HAADF-STEM and EXAFS results indicated that the Rh atoms were present in single Rh sites which were strongly coordinated with the exposed phosphorous atoms of the POL-PPh3 support. The Rh/POL-PPh3 catalyst provided high activity and selectivity because it maintained the catalytic functionalities similar to the homogeneous HRh(CO)(PPh3)(3) complex, as demonstrated both by P-31 MAS NMR and in situ FT-IR experiments. Thus a reaction mechanism, similar to that over the homogeneous HRh(CO)(PPh3)(3) complex, was proposed for olefin hydroformylation over the novel Rh/POL-PPh3 catalyst. (C) 2015 Elsevier B.V. All rights reserved.

This article studied the difference between two 3V-PPh3 polymer (POL-PPh3) supported Rh catalysts synthesized via different synthetic strategies, one-pot and post-synthesis, respectively. The catalytic performance of the two catalysts was further evaluated for the hydroformylation of propylene on a fixed-bed reactor. The catalyst prepared through post-synthesis (Rh/POL-PPh3) showed better catalytic activity compared to the one-pot sample (Rh-POL-PPh3), and exhibited excellent long-term stability. N-2 sorption, SEM, EXAFS and FT-IR characterization results suggested that the possible reasons for the different catalytic performance of two catalysts can be ascribed to the fact that part of Rh species was probably embedded into the framework of POL-PPh3 in the Rh-POL-PPh3 catalyst. Moreover, it might restrict the accessibility of reagents to Rh species and block the flexible coordination between Rh species and POL-PPh3. The Rh/POL-PPh3 catalyst synthesized via post-synthesis and the Rh species were uniformly distributed on the surface of PO-LPPh3, which might have a positive effect on the improvement of the mass transfer and the flexible coordination of Rh species with POL-PPh3.

Angewandte Chemie. International Edition, 56 (33), ISSN:1433-7851, ISSN:1521-3773, ISSN:0570-0833

Chemical Reviews, 117 (5), ISSN:0009-2665, ISSN:1520-6890

The objective of the present study was to characterize the role of novel resveratrol (Res) analogs: 4-(E)-{(4-hydroxyphenylimino)-methylbenzene, 1, 2-diol} (HPIMBD) and 4-(E)-{(p-tolylimino)-methylbenzene-1,2-diol} (TIMBD) as potent antioxidants against breast cancer. Non-neoplastic breast epithelial cell lines MCF-10A and MCF-10F were treated with 17β-estradiol (E2), Res, HPIMBD, and TIMBD for up to 72 h. mRNA and protein levels of antioxidant genes, superoxide dismutase 3 (SOD3) and N-quinoneoxidoreductase-1 (NQO1) and transcription factors, nuclear factor erythroid 2-related factor (Nrf) 1, 2 and 3 were quantified after the above treatments. Generation of reactive oxygen species (ROS) was measured by CM-H2-DCFDA and oxidative-DNA damage was determined by measuring 8-hydroxy-2-deoxyguanosine (8-OHdG). HPIMBD and TIMBD scavenged cellular ROS production, attenuated oxidative DNA damage, increased mRNA and protein expression levels of SOD3 and NQO1 and activated Nrf signaling pathway. Our studies demonstrate that HPIMBD and TIMBD have the potential as novel antioxidants to prevent development of breast cancer.

Photoacoustic tomography (PAT) with Prussian blue (PB) was applied to non-invasively monitor brain injury and recovery with stem cell therapy. Hemorrhage was clearly imaged and PB-labeled stem cells were successfully visualized by PAT in vivo.

Breast cancer is the second leading cause of death among women in the United States. Estrogens have been implicated as major risk factors in the development of breast neoplasms. Recent epidemiologic studies have suggested a protective role of phytoestrogens in prevention of breast and other cancers. Resveratrol, a naturally occurring phytoestrogen found notably in red grapes, berries and peanuts, has been shown to possess potent anti-cancer properties. However, the poor efficacy of resveratrol has prevented its use in a clinical setting. In order to improve the efficacy of resveratrol, we have synthesized a small combinatorial library of azaresveratrol analogs and tested them for their ability to inhibit the growth of breast cancer cell lines. We have recently shown that one of the synthesized analogs, 4-(E)-{(4-hydroxyphenylimino)-methylbenzene, 1, 2-diol} (HPIMBD), has better anti-cancer properties than resveratrol. The objective of this study was to investigate the differential regulation of estrogen receptors (ERs) α and β as a potential mechanism of inhibition of breast cancer by HPIMBD. Estrogen receptors α and β have been shown to have opposing roles in cellular proliferation. Estrogen receptor α mediates the proliferative responses of estrogens while ERβ plays an anti-proliferative and pro-apoptotic role. We demonstrate that HPIMBD significantly induces the expression of ERβ and inhibits the expression of ERα. HPIMBD also inhibits the protein expression levels of oncogene c-Myc, and cell cycle protein cyclin D1, genes downstream to ERα and important regulators of cell cycle, and cellular proliferation. HPIMBD significantly induces protein expression levels of tumor suppressors p53 and p21 in MCF-7 cells. Additionally, HPIMBD inhibits c-Myc in an ERβ-dependent fashion in MCF-10A and ERβ1-transfected MDA-MB-231 cells, suggesting regulation of ERs as an important upstream mechanism of this novel compound. Molecular docking studies confirm higher affinity for binding of HPIMBD in the ERβ cavity. Thus, HPIMBD, a novel azaresveratrol analog may inhibit the proliferation of breast cancer cells by differentially modulating the expressions of ERs α and β.

Rh catalysts supported on knitting aryl network polymers (Rh/KAPs) were prepared for the hydroformylation of higher olefins. Rh catalysts supported on triphenylphosphine-benzene-base polymers (Rh/KAPs-1) showed higher activity for the higher olefins than Rh/SiO2 catalysts. Fourier transform infrared spectroscopy, thermogravimetry, N-2 adsorption-desorption, X-ray diffraction, transmission electron microscopy, C-13 NMR, and P-31 NMR showed that the Rh/ICAPs-1 catalysts have high thermal stability, high surface area, hierarchical porosity, highly dispersed Rh nanoparticles, and in situ formed homogeneous active species during the reaction. (C) 2014, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

The objective of the present study was to characterize the role of resveratrol (Res) and vitamin C (VC) in prevention of estrogen-induced breast cancer through regulation of CNC b-zip transcription factors. Human breast epithelial cell line MCF-10A was treated with 17β-estradiol (E2) and VC or Res with or without E2. mRNA and protein expression levels of CNC b-zip transcription factors: Nrf1, Nrf2, Nrf3 and Nrf2-regulated antioxidant enzymes SOD3 and NQO1 were quantified. Treatment with E2 suppressed while VC and Res prevented E2-mediated decrease in the expression levels of SOD3, NQO1, Nrf2 mRNA and protein in MCF-10A cells. Treatment with E2, Res or VC significantly increased mRNA and protein expression levels of Nrf1. 17β-estradiol treatment significantly increased but VC or Res decreased Nrf3 mRNA and protein expression levels. Our studies demonstrate that estrogen-induced breast cancer might be prevented through up-regulation of antioxidant enzymes via Nrf-dependent pathways.

Three kinds of bulk iron phosphates were prepared via different methods and employed as model catalysts in the oxy-bromination of methane (OBM). Na3Fe2(PO4)3 was obtained via a fluoride route for the first time that showed even superior catalytic performance than FePO4. Phase evolution from Na3Fe2(PO4)3 to Na2Fe3(PO4)3 after the OBM was confirmed both by X-ray diffraction and 57Fe Mossbauer spectroscopy. Temperature-programmed reduction of hydrogen and desorption of CH3Br revealed that the redox capacity of iron phosphates were responsible for the generation of bromine radicals on catalyst surfaces while CH3Br-involved reactions likely belonged to gas-phase reactions. Model iron phosphate catalysts were synthesized by three different methods. It was found that the Na3Fe2(PO4)3 catalyst prepared by a fluoride route showed superior OBM performance than the other two catalysts both with the phase of FePO4, especially for producing higher CH3Br selectivity.

Silica-supported tricobalt tetraoxide (Co3O4/SiO2) catalysts prepared by the impregnation approach with different cobalt loadings were evaluated in the Baeyer–Villiger oxidation of cyclohexanone under Mukaiyama conditions. Among those catalysts with different cobalt contents, 0.5 wt% Co3O4/SiO2 afforded the best cyclohexanone conversion. Also, it provided comparable activity to regular cubic Co3O4, which was synthesized by a sophisticated hydrothermal method, under similarly mild conditions. Results of various physico-chemical characterizations, including XRD, HRTEM, TEM, H2-TPR and O2-TPD, revealed that highly dispersed Co3O4 catalysts showed higher reducibility than those lower dispersed catalysts and possessed more surface oxygen species which seemed reasonable to enhance catalytic activity. The application of Co3O4/SiO2 catalyst in oxidation of cyclohexanone is promising due to its relatively low-cost, high efficiency and excellent stability.

Rhodium- and iron phosphate-based catalysts are by far the most promising catalysts for oxy-bromination of methane (OBM) reaction. However, most literature reported either Rh- or FePO4-based catalysts, and the results were rarely studied in a uniform environmental condition. In this report, comparative study was conducted on silica- and silicon carbide-supported rhodium and iron phosphate catalysts with the main focuses on stability performance and coke deposition. The catalytic results demonstrated that the stability of both Rh- and FePO4-based catalysts was greatly influenced by the supports used, and silicon carbide-supported catalysts showed much better anti-coking ability as compared with silica-supported ones. Temperature-programmed oxidation over the used catalysts further indicated that the coke formation mechanisms were completely different between silica-supported rhodium and iron phosphate catalysts. While cokes might be caused by condensation of CH2Br2 over supported iron phosphate, methane decomposition might be the reason for coke formation over silica-supported rhodium catalyst. These findings might pave the way for designing highly efficient and stable catalysts of the OBM reaction.

Novel porous polymers can serve as self-supporting solid carriers and provide abundant coordination or charged sites for single-site metals, and thus are emerging as advanced functional materials in heterogeneous catalysis for various transformations traditionally catalyzed by homogeneous systems. A brief overview of the development of this heterogenization given, including the recent advances regarding electrovalent bonds by employing charged supports represented by porous ionic polymers (PIPs), which is exemplified herein with a novel single-site Rh1 /PIP catalyst, featuring a new active site [Rh(CO)I3 ]2- dual-ionically bound onto a quaternary phosphonium cationic framework polymer, different from the single-ionically bound [Rh(CO)2 I2 ]- in previous studies. Such a unique metal configuration of Rh1 /PIP leads to excellent performance in vapor-phase methanol carbonylation, outperforming commercial homo- and heterogeneous catalysts.

Summary Background The objective of this study was to establish the efficacy and safety of a new treatment regimen consisting of dose-dense cisplatin-based chemotherapy and radical surgery in children with high-risk hepatoblastoma. Methods SIOPEL-4 was a prospective single-arm feasibility study. Patients aged 18 years or younger with newly diagnosed hepatoblastoma with either metastatic disease, tumour in all liver segments, abdominal extrahepatic disease, major vascular invasion, low α fetoprotein, or tumour rupture were eligible. Treatment consisted of preoperative chemotherapy (cycles A1–A3: cisplatin 80 mg/m 2 per day intravenous in 24 h on day 1; cisplatin 70 mg/m 2 per day intravenous in 24 h on days 8, 15, 29, 36, 43, 57, and 64; and doxorubicin 30 mg/m 2 per day intravenous in 24 h on days 8, 9, 36, 37, 57, and 58) followed by surgical removal of all remaining tumour lesions if feasible (including liver transplantation and metastasectomy, if needed). Patients whose tumour remained unresectable received additional preoperative chemotherapy (cycle B: doxorubicin 25 mg/m 2 per day in 24 h on days 1–3 and 22–24, and carboplatin area under the curve [AUC] 10·6 mg/mL per min per day intravenous in 1 h on days 1 and 22) before surgery was attempted. After surgery, postoperative chemotherapy was given (cycle C: doxorubicin 20 mg/m 2 per day in 24 h on days 1, 2, 22, 23, 43, and 44, and carboplatin AUC 6·6 mg/mL per min per day in 1 h on days 1, 22, and 43) to patients who did not receive cycle B. The primary endpoint was the proportion of patients with complete remission at the end of treatment. Analysis was by intention to treat. This trial is registered at ClinicalTrials.gov, NCT00077389. Findings We report the final analysis of the trial. 62 eligible patients (39 with lung metastases) were included and analysed. 60 (98%, 95% CI 91–100) of 61 evaluable patients (one child underwent primary hepatectomy) had a partial response to preoperative chemotherapy. Complete resection of all tumour lesions was achieved in 46 patients (74%). At the end of therapy, 49 (79%, 95% CI 67–88) of 62 patients were in complete remission. With a median follow-up of 52 months, 3-year event-free survival was 76% (95% CI 65–87) and 3-year overall survival was 83% (73–93). 60 (97%) patients had grade 3–4 haematological toxicity (anaemia, neutropenia, or thrombocytopenia) and 44 (71%) had at least one episode of febrile neutropenia. Other main grade 3 or 4 toxicities were documented infections (17 patients, 27%), anorexia (22, 35%), and mucositis (seven, 11%). One child died of fungal infection in neutropenia. Moderate-to-severe ototoxicity was documented in 31 (50%) patients. 18 serious adverse events (including two deaths) reflecting the observed side-effects were reported in the trial (the most common was ototoxicity in five patients). Interpretation The SIOPEL-4 treatment regimen is feasible and efficacious for complete remission at the end of treatment for patients with high-risk hepatoblastoma. Funding Cancer Research UK and Cancer Research Switzerland/Oncosuisse.

FePO4-SBA-15 (OP) was directly synthesized via a one-pot hydrothermal technique, using Fe(NO3)(3) and H3PO4 as the precursors. FePO4/SBA-15 (IMP) was also prepared as a reference, using an impregnation method and commercially available SBA-15 as the support. The yielding samples were employed to catalyze the harsh oxy-bromination of methane (OBM) reaction, showing similar initial catalytic performances. The fresh and spent samples after catalytic reaction were thoroughly characterized by N-2-physisoption, inductively coupled plasma, wide- and small-angle X-ray diffraction, transmission electron microscopy, diffuse reflectance UV-vis spectroscopy, temperature-programmed oxidation, and room temperature Fe-57 Mossbauer spectroscopy. It was found that the FePO4 was in good crystalline in the OP sample while it was in amorphous for the IMP catalyst. Despite this difference, both FePO4 phases in the fresh samples were transformed into Fe-2(PO4)(6) and Fe2P2O7 in the spent ones. Furthermore, the OP catalyst showed excellent stability in a period of 1000 h time-on-stream performance without apparent deposition of cokes. The losses of P and Fe after the catalytic evaluation were only 9.5% and 15.5%, respectively, while the ratio of P/Fe remained close to 1.0. N-2-adsorption and TEM observations confirmed that the mesoporous pores were extremely stable under the harsh reaction ambience, which might play a crucial role in the stability test. (C) 2012 Elsevier B.V. All rights reserved.

Supercapacitors with an outstanding electrochemical performance have emerged as a rapidly rising star on the horizon of energy storage devices and consumer electronics applications. With the rapid development of miniaturized and portable electronic technology, flexible ultrathin micro-supercapacitors have become more important than ever. The 2D network structure of graphene oxide (GO) with excellent mechanical and electrochemical performances has been reduced into reduced graphene oxide (rGO) by a pulse laser, which is a competitive candidate for the preparation of micro-planar supercapacitors. Micro-supercapacitors based on laser-reduced graphene with an ultrathin thickness of 20 µm exhibit a very high area capacitance up to 4.8 mF/cm2 at a current density of 0.3 mA/cm2 in LiCl-PVA gel electrolyte. Additionally, the energy storage device can possess a fantastic aesthetic property by virtue of the laser technology, which not only reveals the aesthetic art side of supercapacitors, but also provides a palette for the state-of-the-art micro-supercapacitors.

CrystEngComm, 18, ISSN:1466-8033

10514Background: SIOPEL 6 is a phase III randomized trial in SR-HB which is defined as tumor extension limited to PRETEXT I, II or III, no portal or hepatic vein involvement, no intra-abdominal ext...

Different FePO4/SiO2 catalysts have been synthesized and employed for the oxy-bromination of methane reaction. The long-term stability experiments and the influences of FePO4 loading and reaction temperature have been investigated. It was demonstrated that the FePO4/SiO2 catalysts were very stable during 200 h time-on-stream. High total selectivity for CH3Br plus CO with equimolar ratio could be achieved by manipulating the reaction variables. However, coke deposition was found on the used catalysts after a long running period. Characterization techniques such as N-2-adsorption, Fourier-transform infrared spectroscopy and temperature-programmed oxidation were employed to investigate the fresh and used samples. The characterization results implied that the accumulation of CH2Br2 during the reaction could be the direct cause of coke deposition. (C) 2010 Elsevier B. V. All rights reserved.

SiO2-supported Pt/WO3/TiO2 catalysts were prepared; they were found to be more active and selective than the Pt/WO3/TiO2 catalyst for glycerol hydrogenolysis to 1,3-propanediol in a slurry batch reactor. The influences of catalyst component, reaction medium, reaction temperature, H2 pressure and reaction time on glycerol hydrogenolysis over the Pt/WO3/TiO2/SiO2 catalyst were investigated. XRD, TEM, NH3-TPD and Py-IR characterization were employed to reveal the roles of WO3 and TiO2 in the performance of the Pt based-catalysts. XRD patterns and TEM images showed that the presence of TiO2 species in the catalyst favored the dispersion of platinum. The weak Bronsted acid sites formed by addition of WO3 to the catalyst were concluded to play a key role in selective formation of 1,3-propanediol, based on the results of NH3-TPD and Py-IR characterization.

Background Radiotherapy remains a widely accepted postoperative treatment modality for unresectable or recurrent low-grade glioma (LGG). However, there is increasing evidence to suggest that chemotherapy can delay and may obviate the need for radiotherapy in progressive/recurrent LGG. The majority of the published experience is in children with hypothalamic/optic chiasmatic lesions and little information is available regarding its use in LGG of the brainstem. Procedure We describe clinical characteristics and course of children with LGG of the brainstem who received carboplatin-based chemotherapy in two institutions over 10 years (1996–2006). This was a retrospective review of consecutively treated children with LGG of the brainstem (midbrain, pons, medulla, and upper cervical cord). Vincristine and carboplatin were first-line chemotherapy regimen used in all patients. Results In this series, there were 16 children (9 males) with median age at diagnosis of 4.2 years (range 0.5–8). Eight children were treated at diagnosis while the remaining eight received chemotherapy after either radiological progression or clinical deterioration. After a median follow-up of 57 months (range 20–136) from initiation of chemotherapy all children are alive and 11 remain progression free (1 complete response, 8 with partial response + minor response, and 2 stable diseases). Conclusions The efficacy of this chemotherapy regimen in this series supports its role in children with progressive unresectable LGG of brainstem. Pediatr Blood Cancer. 2010;55:471–477. © 2010 Wiley-Liss, Inc.

In this work, the Fe-doped mixed crystal TiO2 photocatalyst which can utilize visible light was prepared by sol-gel and heat-treated methods. During heat-treatment, the phase transformation of Fe-doped TiO2 powder occurs and the process is characterized by XRD and TG-DTA technologies. Otherwise, the sizes and shapes of Fe-doped and undoped TiO2 powders were also compared using TEM images. The azo fuchsine in aqueous solutions, as a model compound, was treated under visible light irradiation using Fe-doped mixed crystal TiO2 powders as photocatalyst. The results showed that, under visible light irradiation, the (0.25%) Fe-doped mixed crystal TiO2 powder heat-treated at 600°C for 3.0 h behaved very high photocatalytic activities for degradation of azo fuchsine. The remarkable improvement of the photocatalytic activity of TiO2 powder was elucidated through the cooperative effects of iron doping and phase transformation. The iron doping can restrain the recombination of photogenerated electron-hole pairs and the phase transformation can enhance the absorption of visible light. Furthermore, other influence factors such as azo fuchsine concentration, solution acidity, Fe3+ ion content and irradiation time were also studied. Thus, this method is applicable for the treatment of wastewater.

A tethered ligand-modified rh/sio2 catalyst was developed for hydroformylation with high stability. the catalyst was prepared by fastening both organic ligand and metal directly on the surface of support to avoid leaching, while at the same time the active species were formed in situ by coordination of the flexible ligand to the metal on the surface of sio2. the immobilization of ligand on sio2 and the interaction between ligand and metal were investigated by means of tg, solid-state nmr and ftir. hydroformylation of ethylene was selected as a probe reaction to evaluate the immobilization and coordination of ligand to the nano-metal particles. high activity and excellent stability were observed during a 1000-h run. (c) 2008 elsevier b.v. all rights reserved.

Oxidative bromination of methane, mediated by HBr/H(2)O (solution), provides an original route for the production of oxygenates and gasoline directly from natural gas. However, the reported catalysts for this reaction all involved noble metals. From the consideration of replacing noble metal catalysts with cheaper oxides, various silica-supported oxide catalysts were surveyed. It was found that the redox ability of different metals had a strong impact on the product distribution. On the catalysts with metals that lack facile redox ability, such as BaO/SiO(2), both CH(3)Br and CO were main products. Otherwise, deep oxidation proceeded. Moreover, methanol was firstly reported in this system. In order to obtain a molar ratio of (CH(3)OH + CH(3)Br): CO = 1, which can provide a perfect feedstock for the synthesis of acetic acid, the process variables were optimized on BaO/SiO(2). It was demonstrated that 44.0% methane conversion and 95% total selectivity of CH(3)Br, CH(3)OH and CO could be achieved at 620 degrees C. and the molar ratio of (CH(3)Br + CH(3)OH): CO was close to 1. Time-on-stream tests showed declined catalytic performance after 30 h. The results from N(2)-adsorption, XRF and XRD implied that aggregation of barium particles occurred, making the metathesis between BaO and BaBr(2) difficult. The functions of BaO were also proposed. Additionally, the activity data were compared with those of noble metal catalysts. (C) 2008 Elsevier B.V. All rights reserved.

The phase transformation from anatase to rutile of titanium dioxide (TiO2) was attempted by heat-treatment and a novel TiO2 catalyst with high photocatalytic activity under sunlight irradiation was obtained. The heat-treated anatase TiO2 powders at various transition stages were characterized by X-ray diffraction (XRD), fourier transform infrared (FTIR), and transmission electron microscopy (TEM). The tests of photocatalytic activities of the heat-treated anatase TiO2 powders were conducted by the photocatalytic degradation of rhodamine B in aqueous solution under sunlight irradiation. The results reveal that the anatase TiO2 powder heat-treated at 700°C for 60 min shows the highest photocatalytic activity, which can effectively degrade rhodamine B in aqueous solution under sunlight irradiation. The remarkable improvement of photocatalytic activity of the anatase TiO2 powders was mainly elucidated by the formation of special interphase between rutile and anatase phases, which can limit the recombination of photogenerated electrons and holes efficiently. Therefore, this method may be envisaged as a technology for treating dye wastewaters using solar energy. © 2008 American Institute of Chemical Engineers Environ Prog, 2008

In order to use the sunlight efficiently, a new titanium dioxide (TiO 2 ) photocatalyst with high catalytic activity under visible light irradiation was prepared with sol–gel technique. In this work, an upconversion luminescence agent, crystallized Er 3+ :Y 3 Al 5 O 12 , was synthesized and its characters were determined. It is found that this crystallized Er 3+ :Y 3 Al 5 O 12 can emit three upconversion fluorescent peaks below 387 nm under the excitation of 488 nm visible light. Hence, this upconversion luminescence agent could transform visible light into ultraviolet light, which could satisfy the genuine requirement of TiO 2 photocatalyst. Additionally, the upconverison mechanisms were also discussed. Meanwhile, the prepared TiO 2 photocatalysts coating upconversion luminescence agent were characterized by powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). The photocatalytic activity of prepared TiO 2 powder was tested through the degradation of congo red in aqueous solution as a model compound under visible and sunlight irradiation. To affirm the complete mineralization, the ion chromatography and total organic carbon (TOC) were used to observe the mineralized anions and organic residues. The experimental results proved that the prepared TiO 2 photocatalyst coating crystallized Er 3+ :Y 3 Al 5 O 12 behaved much higher photocatalytic activity under visible light and sunlight irradiation, and was able to decompose the congo red in aqueous solution efficiently. Therefore, this method may be envisaged as a novel technology for treating dyes wastewater using solar energy, especially for textile industries in developing countries.

The partial phase transformation of nanometer TiO2 powder from anatase phase to rutile phase was realized by heat-treatment and a new TiO2 photocatalyst which could be excited by visible light was obtained. The heat-treated TiO2 powder at different stage of transition crystal was characterized and monitored by XRD, TEM, FT-IR and UV–vis DRS methods. The test of photocatalytic activity of the heat-treated TiO2 powder was carried out by the photocatalytic degradation of rhodamine B and acid orange II dyes, respectively, in aqueous solution under visible light irradiation. The results indicate that the nanometer TiO2 photocatalyst heat-treated at 500°C for 60 min shows the highest photocatalytic activity, that is, it can effectively degrade the rhodamine B and acid orange II under visible light irradiation. The remarkable improvement of photocatalytic activity of heat-treated TiO2 powder at 500°C for 60 min was mainly illustrated by the formation of special interphase between rutile and anatase phases, which not only restrains the recombination of photogenerated electrons and holes, but also reduces the adsorbability of nanometer anatase TiO2 powder properly for various dyes. Additionally, the effects of dye-assisting chemicals such as Na2CO3 and NaCl on the photocatalytic degradation were also studied.

The transition crystal TiO2 catalyst with high sonocatalytic activity was obtained utilizing the microwave irradiation in hydrogen peroxide solution. At the same time a series of affecting factors (microwave irradiation time, heat-treated time and heat-treated temperature) to prepare the TiO2 catalyst on the sonocatalytic degradation of parathion were considered in this paper. The ultrasound of low power was used as an irradiation source to induce treated TiO2 particles to perform catalytic activity. The results show that the sonocatalytic activity of the transition crystal TiO2 powder is obviously higher than those of pure ordinary rutile and anatase TiO2 powders. At last, the parathion in aqueous solution was degraded completely and became some simple inorganic ions such as NO 3 - , PO 4 3 - , SO 4 2 - , etc. The degradation ratio of parathion in the presence of the transition crystal TiO2 catalyst attains nearly 80% within 60 min ultrasonic irradiation, while corresponding ones are only 65.23% and 53.88%, respectively, for pure ordinary rutile and anatase TiO2 powders.

Micron-sized and nano-sized rutile titanium dioxide (TiO2) powders were used as the catalysts for the sonocatalytic degradation of methyl parathion, an organophosphorus insecticide. The ultrasound of low power was used as an irradiation source to induce the catalytic activity of the rutile TiO2 particles. It was found that the degradation of methyl parathion sonocatalytically progressed more rapidly in the presence of TiO2 particles than only with ultrasonic irradiation in the absence of TiO2 catalyst. Moreover, the sonocatalytic activity of the micron-sized rutile TiO2 particles was obviously higher than that of nano-sized rutile TiO2 particles. The influences of reaction parameters, such as the species of TiO2 particles, methyl parathion concentration, TiO2 amount, pH value, ultrasonic intensity, ultrasonic frequency and temperature have been investigated and the optimal conditions for eliminating methyl parathion have been established. The processes of methyl parathion degradation have been monitored by high performance liquid chromatography (HPLC), ion chromatography and UV–vis spectra. The results showed that methyl parathion in aqueous solution was completely degraded to give simple inorganic ions, such as NO2−, NO3−, PO43−, SO42−, etc. The kinetics of the degradation of methyl parathion followed the first-order reaction. The degradation percentage of methyl parathion surpassed 95% within 80 min in the optimal experimental conditions.

Breast cancer is a public health concern worldwide. Prolonged exposure to estrogens has been implicated in the development of breast neoplasms. Epidemiologic and experimental evidence suggest a chemopreventive role of phytoestrogens in breast cancers. Resveratrol, a naturally occurring phytoestrogen, has been shown to have potent anti-cancer properties. However, poor efficacy and bioavailability have prevented the use of resveratrol in clinics. In order to address these problems, we have synthesized a combinatorial library of azaresveratrol analogs and tested them for their ability to inhibit the proliferation of breast cancer cells. We have recently shown that 4-(E)-{(p-tolylimino)-methylbenzene-1,2-diol} (TIMBD), has better anti-cancer properties than resveratrol and any other resveratrol analog we have synthesized so far. The objective of this study was to investigate the regulation of estrogen receptors (ERs) α and β by TIMBD in breast cancer cell lines. We demonstrate that TIMBD significantly induces the mRNA and protein expression levels of ERβ and inhibits that of ERα. TIMBD inhibits mRNA and protein expression levels of oncogene c-Myc, and cell cycle protein cyclin D1, which are important regulators of cellular proliferation. TIMBD significantly induces protein expression levels of tumor suppressor genes p53 and p21 in MCF-7 cells. TIMBD inhibits c-Myc in an ERβ-dependent fashion in MCF-10A and ERβ1-transfected MDA-MB-231 cells, suggesting regulation of ERs as an important upstream mechanism of this analog. ERβ plays a partial role in inhibition of proliferation by TIMBD while ERα overexpression does not significantly affect TIMBD's inhibition.

Previous studies have demonstrated that exposure to polycyclic aromatic hydrocarbons (PAHs) and its derivatives is associated with an increased risk of skin cancers, and the carcinogenic effect of PAHs is thought to involve both tumor initiation and promotion. Whereas PAH tumor initiation is well characterized, the mechanisms involved in the tumor promotion of PAHs remain elusive. In the present study, we investigated the effects of PAHs on vascular endothelial growth factor (VEGF) expression by comparison of its induction between the active metabolite and its parent compound (B[a]PDE versus B[a]P) or between active compound and its relatively inactive analog (5-MCDE versus CDE). We found that exposure of cells to (+/-)-anti-benzo-[a]pyrene-7,8-diol-9,10-epoxide (B[a]PDE) or (+/-)-anti-5-methylchrysene-1,2-diol-3,4-epoxide (5-MCDE) led to marked induction of VEGF in Cl41 cells, whereas benzo[a]pyrene (B[a]P) or chrysene-1,2-diol-3,4-epoxide (CDE) did not exhibit significant inductive effects. Exposure of cells to B[a]PDE and 5-MCDE did not induce HIF-1alpha activation, whereas AP-1 was significantly activated. Moreover, overexpression of TAM67 (a dominant-negative mutant c-Jun) dramatically blocked that VEGF induction. Electrophoretic mobility shift assay showed that AP-1 was only able to specifically recognize and bind to its AP-1 potential binding site within -1136 and -1115 of the VEGF promoter region. Site-directed mutation of this AP-1 binding site eliminated the VEGF transcriptional activity induced by B[a]PDE, suggesting that the AP-1 binding site between -1136 and -1115 in the VEGF promoter region is critical for VEGF induction by B[a]PDE. In addition, overexpression of Deltap85 (a dominant-negative mutant PI-3K) impaired B[a]PDE- and 5-MCDE-induced VEGF induction. Considering our previous findings that PI-3K is an upstream mediator for c-Jun/AP-1 activation, we conclude that the VEGF induction by B[a]PDE and 5-MCDE is through PI-3K/AP-1-dependent and HIF-1alpha-independent pathways. These findings may help us to understand the mechanisms involved in PAH carcinogenic effects.