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Matteo Bonomo, Danilo Dini, Andrea Giacomo Marrani
The adsorption of I(-) and I3(-) anions, i.e. the two species constituting the most common redox couple of dye-sensitized solar cells (DSCs), onto the surface of screen-printed nanoporous NiO was studied by means of X-ray photoelectron spectroscopy (XPS). Mesoporous NiO films were deposited on transparent metallic fluorine-doped tin oxide (FTO) and polarized as working electrodes in a three-electrode cell with differently concentrated I(-)/I3(-) electrolytes to simulate the different conditions experienced by the NiO cathodes during the lifecycle of a p-type DSC (p-DSC) at those atomic sites not passivated by the dye...
October 21, 2016: Langmuir: the ACS Journal of Surfaces and Colloids
Harshkumar H Patel, Matthew S Sigman
In this report, we describe the generation of remote allylic quater-nary stereocenters β, γ, and δ relative to a carbonyl in high enanti-oselectivity. We utilize the redox-relay Heck reaction between alkenyl triflates and acyclic trisubstituted alkenols of varying chain lengths. A wide array of terminal (E)-alkenyl triflates are suitable for this process. The utility of this functionalization is validated further by conversion of the products, via simple organic processes to access remotely functionalized chiral tertiary acid, amine and alcohol products...
October 21, 2016: Journal of the American Chemical Society
Yuying Sang, Yaru Wang, Hong Ni, Anne-Claire Cazalé, Yi-Min She, Nemo Peeters, Alberto P Macho
The subversion of plant cellular functions is essential for bacterial pathogens to proliferate in host plants and cause disease. Most bacterial plant pathogens employ a type-III secretion system to inject type-III effector (T3E) proteins inside plant cells, where they contribute to the pathogen-induced alteration of plant physiology. In this work, we found that the Ralstonia solanacearum T3E RipAY suppresses plant immune responses triggered by bacterial elicitors and by the phytohormone salicylic acid. Further biochemical analysis indicated that RipAY associates in planta with thioredoxins from Nicotiana benthamiana and Arabidopsis...
October 21, 2016: Molecular Plant Pathology
Jasmine S Berg, Dolma Michellod, Petra Pjevac, Clara Martinez-Perez, Caroline R T Buckner, Philipp F Hach, Carsten J Schubert, Jana Milucka, Marcel M M Kuypers
Iron redox reactions play an important role in carbon remineralization, supporting large microbial communities in iron-rich terrestrial and aquatic sediments. Stratified water columns with comparably low iron concentrations are globally widespread, but microbial iron cycling in these systems has largely been ignored. We found evidence for unexpectedly high iron turnover rates in the low (1-2 µmol·l(-1) ) iron waters of Lake Cadagno. Light-dependent, biological iron oxidation rates (1.4-13.8 µmol·l(-1) ·d(-1) ) were even higher than in ferruginous lakes with well-studied microbial iron cycles...
October 21, 2016: Environmental Microbiology
Kai Sheng, Jiahuan Lu
Quinones that exist in ambient particulate matter (PM) are hypothesized to be associated with adverse health effects through the generation of reactive oxygen species (ROS). However, the impacts of the quinones on the inflammatory processes have yet to be clearly understood. In this study, we examined the oxidative potentials and biological effects of typical airborne quinones in the human lung epithelial A549 cells. Significant change of redox status, loss of mitochondrial membrane potentials (△Ψ) and increase of superoxide dismutase (SOD) activity were induced by exposure to quinones...
October 21, 2016: Journal of Environmental Science and Health. Part A, Toxic/hazardous Substances & Environmental Engineering
Xiao-Bin Fang, Ying-Qi Xu, Hon-Fai Chan, Chun-Ming Wang, Qing Zheng, Fei Xiao, Mei-Wan Chen
Hepatocellular carcinoma (HCC) is an aggressive malignancy and the second leading cause of cancer death worldwide. Most current therapeutic agents lack the tumor-targeting efficiency and result in a nonselective biodistribution in the body. In our previous study, we identified a peptide Ala-Pro-Asp-Thr-Lys-Thr-Gln (APDTKTQ) that can selectively bind to the receptor of advanced glycation end-products (RAGE), an immunoglobulin superfamily cell surface molecule overexpressed during HCC malignant progression. Here, we report the design of a mixed micelles system modified with this peptide to target HCC cells...
October 21, 2016: Molecular Pharmaceutics
Allegra T Aron, Morten O Loehr, Jana Bogena, Christopher J Chang
Iron is essential for sustaining life, as its ability to cycle between multiple oxidation states is critical for catalyzing chemical transformations in biological systems. However, without proper regulation, this same redox capacity can trigger oxidative stress events that contribute to aging along with diseases ranging from cancer to cardiovascular and neurodegenerative disorders. Despite its importance, methods for monitoring biological iron bound weakly to cellular ligands-the labile iron pool-to generate a response that preserves spatial and temporal information remain limited, owing to the potent fluorescence quenching ability of iron...
October 21, 2016: Journal of the American Chemical Society
Xiaodong Tang, Jidan Yang, Zhongzhi Zhu, Meifang Zheng, Wanqing Wu, Huanfeng Jiang
A new strategy for thiazoles via copper-catalyzed [3+1+1]-type condensation reaction from oximes, anhydrides and potassiumthiocyanate (KSCN) is developed herein. The transformation has good functional group tolerance and various thiazoles were formed smoothly in good to excellent yields under mild reaction conditions. This process involves copper-catalyzed N-O/C-S bond cleavages, activation of vinyl sp2 C-H bond and C-S/C-N bond formations which is under redox-neutral conditions well as operational simplicity...
October 21, 2016: Journal of Organic Chemistry
Joshua R Biller, Deborah G Mitchell, Mark Tseytlin, Hanan Elajaili, George A Rinard, Richard W Quine, Sandra S Eaton, Gareth R Eaton
We demonstrate a superior method of 2D spectral-spatial imaging of stable radical reporter molecules at 250 MHz using rapid-scan electron-paramagnetic-resonance (RS-EPR), which can provide quantitative information under in vivo conditions on oxygen concentration, pH, redox status and concentration of signaling molecules (i.e., OH(•), NO(•)). The RS-EPR technique has a higher sensitivity, improved spatial resolution (1 mm), and shorter acquisition time in comparison to the standard continuous wave (CW) technique...
September 26, 2016: Journal of Visualized Experiments: JoVE
Jong Ho Park, Jung Jin Park, O Ok Park, Jung Hoon Yang
Capacity decay in vanadium redox flow batteries during charge-discharge cycling has become an important issue because it lowers the practical energy density of the battery. The battery capacity tends to drop rapidly within the first tens of cycles and then drops more gradually over subsequent cycles during long-term operation. This paper analyzes and discusses the reasons for this early capacity decay. The imbalanced crossover rate of vanadium species was found to remain high until the total difference in vanadium concentration between the positive and negative electrolytes reached almost 1 mol dm(-3) ...
October 21, 2016: ChemSusChem
Akihiro Orita, Michael G Verde, Masanori Sakai, Ying Shirley Meng
The versatility in design of redox flow batteries makes them apt to efficiently store energy in large-scale applications at low cost. The discovery of inexpensive organic electroactive materials for use in aqueous flow battery electrolytes is highly attractive, but is thus far limited. Here we report on a flow battery using an aqueous electrolyte based on the sodium salt of flavin mononucleotide. Flavins are highly versatile electroactive molecules, which catalyse a multitude of redox reactions in biological systems...
October 21, 2016: Nature Communications
Christophe Kahlfuss, Sandrine Denis-Quanquin, Nathalie Calin, Elise Dumont, Marco Garavelli, Guy Royal, Saioa Cobo, Eric Saint-Aman, Christophe Bucher
Viologen-centered electron transfer is used to trigger a complete dissociation of a porphyrin-based coordination polymer. In the oxidized state, self-assembly is induced by iterative association of individual porphyrin-based tectons. Dissociation of the self-assembled species is actuated upon changing the redox state of the bipyridium units involved in the tectons from their dicationic state to their radical cation state, the driving force of the disassembling process being the formation of an intramolecularly locked conformation partly stabilized by π-dimerization of both viologen cation radicals...
October 21, 2016: Journal of the American Chemical Society
Fatima El-Assaad, Steven A Krilis, Bill Giannakopoulos
The antiphospholipid syndrome (APS) is an autoimmune disease characterised by a procoagulant state that predisposes to recurrent thrombosis and miscarriages. Two major discoveries have advanced our understanding of the underlying complex pathogenesis of the APS. The first was the discovery that beta-2 glycoprotein-1 (β2GPI) is the major auto antigen in APS. The second was the discovery in more recent years that β2GPI contains allosteric disulphide bonds susceptible to posttranslational modification that may be involved in the development of autoantibodies in APS...
2016: Thrombosis Journal
Meng Li, Xin Li, Jianzeng Xin, Zheng Li, Guixia Li, Yan Zhang, Manting Du, Qingwu W Shen, Dequan Zhang
The influence of protein phosphorylation on meat color stability was investigated in this study. Phosphatase and protein kinase inhibitors were added to minced ovine Longissimus thoracis et lumborum (LTL) muscle to manipulate the global phosphorylation of sarcoplasmic proteins. The data obtained show that the rate and extent of pH decline, along with lactate accumulation in postmortem muscle, were related to protein phosphorylation. Analysis of meat color and the relative content of myoglobin redox forms revealed that meat color stability was inversely related to the phosphorylation of sarcoplasmic proteins...
March 15, 2017: Food Chemistry
Xianxiu Wan, Jian-Jun Wen, Sue-Jie Koo, Lisa Yi Liang, Nisha Jain Garg
Chronic chagasic cardiomyopathy (CCM) is presented by increased oxidative/inflammatory stress and decreased mitochondrial bioenergetics. SIRT1 senses the redox changes and integrates mitochondrial metabolism and inflammation; and SIRT1 deficiency may be a major determinant in CCM. To test this, C57BL/6 mice were infected with Trypanosoma cruzi (Tc), treated with SIRT1 agonists (resveratrol or SRT1720), and monitored during chronic phase (~150 days post-infection). Resveratrol treatment was partially beneficial in controlling the pathologic processes in Chagas disease...
October 2016: PLoS Pathogens
Li Zhou, Ji Wen, Zhao Huang, Edouard C Nice, Canhua Huang, Haiyuan Zhang, Qifu Li
Liver cancer is a major global health problem being the sixth most common cancer and the third cause of cancer-related death, with HCC representing more than 90% of primary liver cancers. Mounting evidence suggests that, compared with their normal counterparts, many types of cancer cell have increased levels of ROS. Therefore, cancer cells need to combat high levels of ROS, especially at early stages of tumour development. Recent studies have revealed that ROS-mediated regulation of redox-sensitive proteins (redox sensors) is involved in the pathogenesis and/or progression of many human diseases, including cancer...
October 20, 2016: Proteomics. Clinical Applications
Narcis Avarvari, Thomas Biet, Kévin Martin, Jihane Hankache, Nora Hellou, Andreas Hauser, Thomas Bürgi, Nicolas Vanthuyne, Tal Aharon, Marco Caricato, Jeanne Crassous
Introduction of heterocycles in the helical skeleton of helicenes allows modulation of their redox, chiroptical and photophysical properties. Herein, we describe the straightforward preparation and structural characterization by single crystal X-ray diffraction of thiadiazole-[7]helicene, which has been resolved into (M) and (P) enantiomers by chiral HPLC, together with its S-shaped double [4]helicene isomer, as well as the smaller congeners thiadiazole-[5]helicene and benzothiadiazole-anthracene. A copper(II) complex with two thiadiazole-[5]helicene ligands has been structurally characterized and it shows the presence of both (M) and (P) isomers coordinated to the metal centre...
October 20, 2016: Chemistry: a European Journal
Yang Li, Hebin Wang, Kai Wang, Qinglian Hu, Qi Yao, Youqing Shen, Guocan Yu, Guping Tang
A new type of tumor-targeted nanovehicle peptide-conjugated PSPG (PSPGP) is successfully synthesized for co-delivery of paclitaxel (PTX) and TR3 small interfering RNA (siRNA). In vitro and in vivo investigations demonstrate that the redox-responsive PSPGP exhibit enhanced endosomal escape and intracellular degradation, which facilitate PTX and TR3 siRNA release, effectively improving the antitumor efficacy.
October 20, 2016: Small
Caiyan Zhao, Leihou Shao, Jianqing Lu, Chenying Zhao, Yujie Wei, Junxing Liu, Mingjun Li, Yan Wu
Stimuli-responsive nanocarriers with the ability to respond to tumorous heterogeneity have been extensively developed for drug delivery. However, the premature release during blood circulation and insufficient intracellular drug release are still a significant issue. Herein, three disulfide bonds are introduced into the amphiphilic poly(ethylene glycol)-polycaprolactone copolymer blocks to form triple-sensitive cleavable polymeric nanocarrier (tri-PESC NPs) to improve its sensitivity to narrow glutathione (GSH) concentration...
October 20, 2016: Macromolecular Bioscience
Kenji Kakiage, Hiroyuki Osada, Yohei Aoyama, Toru Yano, Keiji Oya, Shinji Iwamoto, Jun-Ichi Fujisawa, Minoru Hanaya
A dye-sensitized solar cell (DSSC) fabricated by using a novel silyl-anchor coumarin dye with alkyl-chain substitutes, a Br3(-)/Br(-) redox electrolyte solution containing water, and a Mg(2+)-doped anatase-TiO2 electrode with twofold surface modification by MgO and Al2O3 exhibited an open-circuit photovoltage over 1.4 V, demonstrating the possibility of DSSCs as practical photovoltaic devices.
October 20, 2016: Scientific Reports
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