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https://www.readbyqxmd.com/read/28212484/on-surface-site-selective-cyclization-of-corrole-radicals
#1
Stefano Tebi, Mateusz Paszkiewicz, Hazem Aldahhak, Francesco Allegretti, Sabrina Gonglach, Michael Haas, Mario Waser, Peter S Deimel, Pablo Casado Aguilar, Yi-Qi Zhang, Anthoula C Papageorgiou, David Andrew Duncan, Johannes V Barth, Wolf Gero Schmidt, Reinhold Koch, Uwe Gerstmann, Eva Rauls, Florian Klappenberger, Wolfgang Schöfberger, Stefan Müllegger
Radical cyclization is among the most powerful and versatile reactions for constructing mono- and polycyclic systems, but has, to date, remained unexplored in the context of on-surface synthesis. We report the controlled on-surface synthesis of stable corrole radicals on Ag(111) via site-specific dehydrogenation of a pyrrole N H bond in the 5,10,15-tris(pentafluoro-phenyl)-corrole triggered by annealing at 330 K under ultra-high vacuum conditions. We reveal a thermally-induced regioselective cyclization reaction mediated by a radical cascade and resolve the reaction mechanism of the pertaining cyclodefluorination reaction at the single-molecule level...
February 17, 2017: ACS Nano
https://www.readbyqxmd.com/read/28212306/metabolic-effects-of-berries-with-structurally-diverse-anthocyanins
#2
John Overall, Sierra A Bonney, Mickey Wilson, Arnold Beermann, Mary H Grace, Debora Esposito, Mary Ann Lila, Slavko Komarnytsky
Overconsumption of energy dense foods and sedentary lifestyle are considered as major causes of obesity-associated insulin resistance and abnormal glucose metabolism. Results from both cohort studies and randomized trials suggested that anthocyanins from berries may lower metabolic risks, however these reports are equivocal. The present study was designed to examine effects of six berries with structurally diverse anthocyanin profiles (normalized to 400 µg/g total anthocyanin content) on development of metabolic risk factors in the C57BL/6 mouse model of polygenic obesity...
February 15, 2017: International Journal of Molecular Sciences
https://www.readbyqxmd.com/read/28212297/inorganic-reactive-sulfur-nitrogen-species-intricate-release-mechanisms-or-cacophony-in-yellow-blue-and-red
#3
Marian Grman, Muhammad Jawad Nasim, Roman Leontiev, Anton Misak, Veronika Jakusova, Karol Ondrias, Claus Jacob
Since the heydays of Reactive Sulfur Species (RSS) research during the first decade of the Millennium, numerous sulfur species involved in cellular regulation and signalling have been discovered. Yet despite the general predominance of organic species in organisms, recent years have also seen the emergence of inorganic reactive sulfur species, ranging from inorganic polysulfides (HSx(-)/Sx(2-)) to thionitrous acid (HSNO) and nitrosopersulfide (SSNO(-)). These inorganic species engage in a complex interplay of reactions in vitro and possibly also in vivo...
February 15, 2017: Antioxidants (Basel, Switzerland)
https://www.readbyqxmd.com/read/28211691/lipophilized-grape-seed-proanthocyanidin-derivatives-as-novel-antioxidants
#4
Mingshun Chen, Shujuan Yu
Grape seed proanthocyanidin (GSP) is a natural food antioxidant. Natural proanthocyanidins (PC) in grape seed are usually polyhydroxy derivatives which exhibit hydrophilic character. GSP was modified structurally to improve its lipophilicity, expand its application in lipophilic media, and enhance its cellular absorption in vivo. Esterification of the water-soluble GSP was prepared by immobilized lipase Lipozyme TL IM with lauric acid, and their enhanced lipophilicity was confirmed by the 1-octanol/water partition coefficient...
February 17, 2017: Journal of Agricultural and Food Chemistry
https://www.readbyqxmd.com/read/28209950/-clinico-pathological-factors-and-prognosis-scale-for-portal-cholangiocarcinoma
#5
Yu O Zharikov, Yu A Kovalenko, A A Olifir, D V Kalinin, A V Czhao
INTRODUCTION: The objective of this study was to derive a prognostic scale to predict overall survival (OS) after a curative resection of perihilar cholangiocarcinoma (PHC). MATERIAL AND METHODS: The data of 55 patients with portal cholangiocarcinoma were analysed. Patients were treated at the A.V. Vishnevsky Institute of Surgery from 2011 to 2015. Surgical treatment after biliary decompression was performed in 37 (67.3%) patients. In the long-term period we observed 36 (97...
2017: Khirurgiia
https://www.readbyqxmd.com/read/28209309/cluster-headache-and-macroprolactinoma-case-report-of-a-rare-but-potential-important-causality
#6
Lukas Andereggen, Marie-Luise Mono, Frauke Kellner-Weldon, Emanuel Christ
While headache is not an uncommon symptom in patients suffering from pituitary adenomas, cluster headache (CH) has rarely been reported in such cases. Headache associated with hyperprolactinemia has been reported to be responsive to dopamine agonists (DA agonists) in many patients. We report on a patient with refractory CH secondary to a macroprolactinoma who showed immediate and permanent clinical and radiologic recovery following medical treatment with DA agonists. Measurement of prolactin levels in addition to cranial magnetic resonance imaging might be considered in patients with refractory CH, until the significance of this potential causality becomes clearer...
February 10, 2017: Journal of Clinical Neuroscience: Official Journal of the Neurosurgical Society of Australasia
https://www.readbyqxmd.com/read/28208765/synthesis-of-mono-and-di-glucosides-of-zearalenone-and-%C3%AE-%C3%AE-zearalenol-by-recombinant-barley-glucosyltransferase-hvugt14077
#7
Herbert Michlmayr, Elisabeth Varga, Francesca Lupi, Alexandra Malachová, Christian Hametner, Franz Berthiller, Gerhard Adam
Zearalenone (ZEN) is an estrogenic mycotoxin occurring in Fusarium-infected cereals. Glucosylation is an important plant defense mechanism and generally reduces the acute toxicity of mycotoxins to humans and animals. Toxicological information about ZEN-glucosides is limited due to the unavailability of larger amounts required for animal studies. HvUGT14077, a recently-validated ZEN-conjugating barley UDP-glucosyltransferase was expressed in Escherichia coli, affinity purified, and characterized. HvUGT14077 possesses high affinity (Km = 3 µM) and catalytic efficiency (kcat/Km = 190 s(-1)·mM(-1)) with ZEN...
February 9, 2017: Toxins
https://www.readbyqxmd.com/read/28208751/oxidative-stress-related-genetic-variants-may-modify-associations-of-phthalate-exposures-with-asthma
#8
I-Jen Wang, Wilfried J J Karmaus
Background: Phthalate exposure may increase the risk of asthma. Little is known about whether oxidative-stress related genes may alter this association. First, this motivated us to investigate whether genetic polymorphisms of the oxidative-stress related genes glutathione S-transferase Mu 1 (GSTM1), glutathione S-transferase pi 1 (GSTP1), superoxide dismutase 2 (SOD2), catalase (CAT), myeloperoxidase (MPO), and EPHX1 in children are associated with phthalate urine concentrations. Second, we addressed the question whether these genes may affect the influence of phthalates on asthma...
February 8, 2017: International Journal of Environmental Research and Public Health
https://www.readbyqxmd.com/read/28208630/cocoa-and-grape-seed-byproducts-as-a-source-of-antioxidant-and-anti-inflammatory-proanthocyanidins
#9
María De La Luz Cádiz-Gurrea, Isabel Borrás-Linares, Jesús Lozano-Sánchez, Jorge Joven, Salvador Fernández-Arroyo, Antonio Segura-Carretero
Phenolic compounds, which are secondary plant metabolites, are considered an integral part of the human diet. Physiological properties of dietary polyphenols have come to the attention in recent years. Especially, proanthocyanidins (ranging from dimers to decamers) have demonstrated potential interactions with biological systems, such as antiviral, antibacterial, molluscicidal, enzyme-inhibiting, antioxidant, and radical-scavenging properties. Agroindustry produces a considerable amount of phenolic-rich sources, and the ability of polyphenolic structures to interacts with other molecules in living organisms confers their beneficial properties...
February 10, 2017: International Journal of Molecular Sciences
https://www.readbyqxmd.com/read/28207952/di-nickel-salphen-complexes-as-binders-of-human-telomeric-dimeric-g-quadruplexes
#10
Ramon Vilar, Chun-Qiong Zhou, Ting-Cong Liao, Zi-Qi Li, Jorge Gonzalez-Garcia, Matthew Reynolds, Min Zou
Three new polyether-tethered di-nickel-salphen complexes (2a-c) have been synthesized and fully characterized by NMR spectroscopy, mass spectrometry and elemental analyses. The binding affinity and selectivity of these complexes and of the parent mono-nickel complex (1) towards dimeric quadruplex DNA have been determined by UV-Vis titrations, fluorescence spectroscopy, CD spectroscopy and electrophoresis. These studies have shown that the di-nickel-salphen complex with the longest polyether linker (2c) has higher binding affinity and selectivity towards dimeric quadruplexes (over monomeric quadruplexes) than the di-nickel-salphen complexes with the shorter polyether linkers (2a and 2b)...
February 16, 2017: Chemistry: a European Journal
https://www.readbyqxmd.com/read/28207920/paper-based-microfluidic-system-for-tear-electrolyte-analysis
#11
Ali K Yetisen, Nan Jiang, Ali Tamayol, Guillermo U Ruiz-Esparza, Yu Shrike Zhang, Sofía Medina-Pando, Aditi Gupta, James S Wolffsohn, Haider Butt, Ali Khademhosseini, Seok-Hyun Yun
The analysis of tear constituents at point-of-care settings has a potential for early diagnosis of ocular disorders such as dry eye disease, low-cost screening, and surveillance of at-risk subjects. However, current minimally-invasive rapid tear analysis systems for point-of-care settings have been limited to assessment of osmolarity or inflammatory markers and cannot differentiate between dry eye subclassifications. Here, we demonstrate a portable microfluidic system that allows quantitative analysis of electrolytes in the tear fluid that is suited for point-of-care settings...
February 16, 2017: Lab on a Chip
https://www.readbyqxmd.com/read/28207776/the-improved-efficacy-of-sifuvirtide-compared-with-enfuvirtide-might-be-related-to-its-selectivity-for-the-rigid-biomembrane-as-determined-through-surface-plasmon-resonance
#12
Ping Cao, Guifang Dou, Yuanguo Cheng, Jinjing Che
Most mechanistic studies on human immunodeficiency virus (HIV) peptide fusion inhibitors have focused on the interactions between fusion inhibitors and viral envelope proteins. However, the interactions of fusion inhibitors with viral membranes are also essential for the efficacy of these drugs. Here, we utilized surface plasmon resonance (SPR) technology to study the interactions between the HIV fusion inhibitor peptides sifuvirtide and enfuvirtide and biomembrane models. Sifuvirtide presented selectivity toward biomembrane models composed of saturated dipalmitoylphosphatidylcholine (DPPC) (32-fold higher compared with unsaturated 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine [POPC]) and sphingomyelin (SM) (31-fold higher compared with POPC), which are rigid compositions enriched in the HIV viral membrane...
2017: PloS One
https://www.readbyqxmd.com/read/28207763/an-inhibitory-mono-ubiquitylation-of-the-drosophila-initiator-caspase-dronc-functions-in-both-apoptotic-and-non-apoptotic-pathways
#13
Hatem Elif Kamber Kaya, Mark Ditzel, Pascal Meier, Andreas Bergmann
Apoptosis is an evolutionary conserved cell death mechanism, which requires activation of initiator and effector caspases. The Drosophila initiator caspase Dronc, the ortholog of mammalian Caspase-2 and Caspase-9, has an N-terminal CARD domain that recruits Dronc into the apoptosome for activation. In addition to its role in apoptosis, Dronc also has non-apoptotic functions such as compensatory proliferation. One mechanism to control the activation of Dronc is ubiquitylation. However, the mechanistic details of ubiquitylation of Dronc are less clear...
February 2017: PLoS Genetics
https://www.readbyqxmd.com/read/28207023/chelated-bis-nhc-complexes-of-saturated-imidazolin-2-ylidene-nhc-ligands-structural-authentication-and-facile-ligand-fragmentation
#14
Michael G Gardiner, David S McGuinness, Catriona R Vanston
The CH2-linked bis(NHC) complexes [{((S)MesIm)2CH2}PdBr2] and [{((S)MesIm)2CH2}Pd(NCMe)2][PF6]2 are reported. These represent the first structurally characterized chelated, saturated bis(NHC) complexes. The complexes are subject to facile ligand fragmentation during their synthesis. Longer (CH2)n-linkers in the imidazolin-2-ylidene-based series of ligands afforded the pendant imidazolinium mono(NHC) complexes [{((S)MesImH)((S)MesIm)(CH2)n}PdBr3] by reaction of the diimidazolinium salts (n = 2, 3) with palladium acetate...
February 16, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/28206706/efficient-synthesis-of-1-4-bis-heteroatom-substituted-tetraselanylbenzenes-via-1-4-dilithiation-of-hexaselanylbenzene-and-investigation-on-their-electronic-properties
#15
Masaichi Saito, Shunsuke Furukawa, Masahiro Fujita
We successfully synthesized mono- and bis-substituted polyselanylbenzenes 3 and 5 via mono- and dilithiation of hexakis(phenylselanyl)benzene (1), respectively. Introduction of various heteroatom functionalities into hexaselanylbenzene changed the electronic properties dependent on the σ-symmetric circular orbitals that were formed by the interactions between neighboring heteroatoms. In the cyclic voltammetry and theoretical studies on bis-heteroatom-substituted benzenes 5, the extent of the interactions in the circular orbitals with σ-symmetry affected the stability of the cationic species of 5...
February 16, 2017: Chemistry, An Asian Journal
https://www.readbyqxmd.com/read/28205651/metal-support-interaction-on-cobalt-based-ft-catalysts-a-dft-study-of-model-inverse-catalysts
#16
Tracey van Heerden, Eric van Steen
It is challenging to isolate the effect of metal-support interactions on catalyst reaction performance. In order to overcome this problem, inverse catalysts can be prepared in the laboratory and characterized and tested at relevant conditions. Inverse catalysts are catalysts where the precursor to the catalytically active phase is bonded to a support-like ligand. We can then view the metal-support interaction as a ligand interaction with the support acting as a supra-molecular ligand. Importantly, laboratory studies have shown that these ligands are still present after reduction of the catalyst...
February 16, 2017: Faraday Discussions
https://www.readbyqxmd.com/read/28204913/accumulation-of-alpha-fluoro-beta-alanine-and-fluoro-mono-acetate-in-a-patient-with-5-fluorouracil-associated-hyperammonemia
#17
Yoshitaka Nishikawa, Taro Funakoshi, Takahiro Horimatsu, Shin'ichi Miyamoto, Takeshi Matsubara, Motoko Yanagita, Shunsaku Nakagawa, Atsushi Yonezawa, Kazuo Matsubara, Manabu Muto
PURPOSE: High-dose 5-fluorouracil (5-FU) containing chemotherapy occasionally causes hyperammonemia and can be lethal. However, the mechanism of 5FU-associated hyperammonemia has not been known. The aim of this study was to reveal the pharmacokinetics of 5-FU-associated hyperammonemia in a recurrent colorectal cancer patient with end-stage renal disease (ESRD). METHODS: We experienced a case of hyperammonemia during mFOLFOX6 plus bevacizumab therapy for recurrent colorectal cancer...
February 15, 2017: Cancer Chemotherapy and Pharmacology
https://www.readbyqxmd.com/read/28199367/evaluation-of-different-mathematical-models-and-different-b-value-ranges-of-diffusion-weighted-imaging-in-peripheral-zone-prostate-cancer-detection-using-b-value-up-to-4500-s-mm2
#18
Zhaoyan Feng, Xiangde Min, Daniel J A Margolis, Caohui Duan, Yuping Chen, Vivek Kumar Sah, Nabin Chaudhary, Basen Li, Zan Ke, Peipei Zhang, Liang Wang
OBJECTIVES: To evaluate the diagnostic performance of different mathematical models and different b-value ranges of diffusion-weighted imaging (DWI) in peripheral zone prostate cancer (PZ PCa) detection. METHODS: Fifty-six patients with histologically proven PZ PCa who underwent DWI-magnetic resonance imaging (MRI) using 21 b-values (0-4500 s/mm2) were included. The mean signal intensities of the regions of interest (ROIs) placed in benign PZs and cancerous tissues on DWI images were fitted using mono-exponential, bi-exponential, stretched-exponential, and kurtosis models...
2017: PloS One
https://www.readbyqxmd.com/read/28198551/prevalence-and-clinical-profile-of-human-bocavirus-in-children-with-acute-gastroenteritis-in-chengdu-west-china-2012-2013
#19
Tao Zhou, Yuhang Chen, Jiayi Chen, Pengwei Hu, Tianli Zheng, Xin Xu, Xiaofang Pei
Viral acute gastroenteritis (AGE) is a major cause of mortality in childhood and leads to hospitalization in developing countries. Human bocavirus (HBoV) is a newly described virus associated with gastroenteritis. However, little is known about the clinical and epidemiological profile of human bocavirus (HBoV) in pediatric population in Chengdu, China. Between January 2012 and December 2013, 346 fecal samples from children admitted to hospital with acute gastroenteritis were tested for the presence of HBoV as well as other gastroenteritis viruses...
February 15, 2017: Journal of Medical Virology
https://www.readbyqxmd.com/read/28198182/synthesis-of-enantiopure-dabo-derivatives-c1-symmetric-chiral-1-2-diamines-with-a-rigid-bicyclic-backbone
#20
Pierre Milbeo, Laure Moulat, Claude Didierjean, Emmanuel Aubert, Jean Martinez, Monique Calmès
The synthesis of enantiopure 1,2-diaminobicyclo[2.2.2]octane (DABO) 1 and its two selectively N-Boc mono-protected derivatives 15 and 16 is described. Starting from bicyclic β-amino acid 3 or 5, strategies involving Curtius and Hofmann rearrangements were explored, demonstrating the unprecedented influence of the bicyclic backbone unsaturation for the preparation of the corresponding diamines that could be only obtained in good yield using the Hofmann rearrangement of unsaturated compound 3. The divergent outcome observed during the Hofmann rearrangement of 3 and 5 was investigated by DFT calculations...
February 15, 2017: Journal of Organic Chemistry
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