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Jinbo Chen
Hyper-accumulator biomass, Pteris vittata L., was hydrothermally converted into bio-oils via hydrothermal liquefaction (HTL) in sub-supercritical water. The distributions and characterizations of various products as well as energy recovery under different temperatures (250-390 °C) were investigated. The highest bio-oil yield of 16.88% was obtained at 350 °C with the hydrothermal conversion of 61.79%, where the bio-oil was dominated by alcohols, esters, phenols, ketones and acidic compounds. The higher heating values of bio-oil were in the range of 19...
June 14, 2018: Bioresource Technology
Fiona Hollis, Ellen Siobhan Mitchell, Carles Canto, Dongmei Wang, Carmen Sandi
Medium-chain triglycerides (MCT) are emerging as unique dietary supplements potentially relevant to improve brain dysfunctions. MCT are converted into ketones and free medium chain fatty acids that, in the brain, are highly effective energy sources to mitochondria and potentially less harmful than glucose metabolism to neurons. Given the recently established link between mitochondrial dysfunction and high anxiety and depression, we set this study to investigate the effectiveness of an MCT-enriched diet to ameliorate anxiety- and depression-related behaviors in rats...
June 13, 2018: Neuropharmacology
Shan Chen, Jonatan C Campillo-Brocal, Per Berglund, Maria Svedendahl Humble
The amine transaminase from Vibrio fluvialis (Vf-ATA) is an attractive enzyme with applications within Biocatalysis for the preparation of chiral amines. Various catalytic properties of Vf-ATA have been investigated, but a biophysical characterization of its stability has been lacking. Today, the industrial application of Vf-ATA is limited by its low operational stability. In order to enhance the knowledge regarding the structural stability of ATAs, general characterizations of different ATAs are required. In this work, the stability of Vf-ATA was explored...
June 12, 2018: Journal of Biotechnology
Robert E Mulvey, Victoria A Pollard, Maria Angeles Fuentes, Alan R Kennedy, Ross McLellan
Bimetallic lithium aluminates and neutral aluminium counterparts are compared as catalysts in hydroboration reactions with aldehydes, ketones, imines and alkynes. Possessing Li-Al cooperativity, ate catalysts are found to be generally superior. Catalytic activity is also influenced by the ligand set, alkyl and/or amido. Devoid of an Al-H bond, iBu2Al(TMP) operates as a masked hydride reducing benzophenone through β-H elimination. This catalyst library therefore provides an entry point into the future design of Al catalysts targeting substrate specific transformations...
June 15, 2018: Angewandte Chemie
C Henrique Alves Esteves, Maria Koyioni, Kirsten E Christensen, Peter D Smith, Timothy J Donohoe
Pd-catalyzed α-arylation of methyl-OBO-ketone (OBO = 4-methyl-2,6,7-trioxabicyclo[2.2.2]octan-1-yl) gives rise to arylated OBO-protected pyruvates. By appropriate prefunctionalization of the aryl ring or by subsequent functionalization at the α-carbonyl position of the arylated OBO-ketones, useful diketo OBO-protected carboxylates can be generated. Cyclization, aromatization, and OBO deprotection of these intermediates, using two distinct routes, gives access to valuable α-acyl heteroaromatic compounds.
June 15, 2018: Organic Letters
Jiaoyan Li, Yingmiao Ma, Zheng Wang, Qingbin Liu, Gregory A Solan, Yanping Ma, Wen-Hua Sun
Reaction of 8-amino-5,6,7,8-tetrahydroquinoline with RuCl2(PPh3)3 at room temperature affords the ruthenium(ii) chelate (8-NH2-C9H10N)RuCl2(PPh3)2 (E), in which the two triphenylphosphine ligands are disposed mutually cis. By contrast, when the reaction is performed at reflux ligand oxidation/dehydrogenation occurs along with cis-trans reorganization of the triphenylphosphines to form the 8-imino-5,6,7-trihydroquinoline-ruthenium(ii) complex, (8-NH-C9H9N)RuCl2(PPh3)2 (F). Complex F can also be obtained in higher yield by heating a solution of E alone to reflux...
June 15, 2018: Dalton Transactions: An International Journal of Inorganic Chemistry
Matteo Paoletti, Ana Bacila, Anna Pichiecchio, Lisa Maria Farina, Elisa Rognone, Riccardo Cremascoli, Simona Fanucchi, Raffaele Manni, Stefano Bastianello
Common postictal MRI findings include transient cortical T2 hyperintensity, restricted diffusion, and gyral and/or adjacent leptomeningeal contrast enhancement. In certain uncommon pathological conditions, other signal abnormalities can be present, suggesting a different underlying pathogenic mechanism. We report the case of a 66-year-old man, recently diagnosed with diabetes mellitus type 2, presenting with new-onset visual and auditory hallucinations, "absence" seizures, and repeated peaks of hyperglycaemia without hyperketonaemia or increased serum osmolarity...
June 15, 2018: Epileptic Disorders: International Epilepsy Journal with Videotape
Jakub Brześkiewicz, Rafał Loska, Mieczyslaw Makosza
Readily available α,α-dichlorotoluenes enter a vicarious nucleophilic substitution (VNS) reaction with electron-deficient arenes to give α-chlorobenzylated nitrobenzenes, as well as six- and five-membered heterocycles. Oxidation of the initially formed α-chlorobenzylic carbanions instead of protonation results in formation of bis(aryl) ketones, providing a means of overall nucleophilic C-H-benzoylation of electron-deficient aromatic rings. Alternatively, benzoylated nitroarenes can be obtained via the reaction of isolated α-chlorodiarylmethanes with sodium azide...
June 15, 2018: Journal of Organic Chemistry
Ernesto Manzo, Abigail G O'Conner, Jordan M Barrows, Dakotah D Shreiner, Gabriel J Birchak, Daniela C Zarnescu
ALS patients exhibit dyslipidemia, hypermetabolism and weight loss; in addition, cellular energetics deficits have been detected prior to denervation. Although evidence that metabolism is altered in ALS is compelling, the mechanisms underlying metabolic dysregulation and the contribution of altered metabolic pathways to disease remain poorly understood. Here we use a Drosophila model of ALS based on TDP-43 that recapitulates hallmark features of the disease including locomotor dysfunction and reduced lifespan...
2018: Frontiers in Molecular Neuroscience
Francielle Pelegrin Garcia, Marlène Rippe, Mychelle V P Companhoni, Talitha Fernandes Stefanello, Benoit Louage, Simon Van Herck, Lucie Sancey, Jean-Luc Coll, Bruno G De Geest, Celso Vataru Nakamura, Rachel Auzély-Velty
The development of biopolymer-based nanogels has gained particular interest to achieve successful delivery of therapeutics for the treatment of various diseases, such as cancer, infection and diabetes. Herein, we report a new and simple methodology for the covalent stabilization of self-assembled gel nanoparticles based on hyaluronic acid (HA) modified with a thermoresponsive ketone-functional copolymer. This relies on the selective formation of hydrazone crosslinks with bishydrazides within the globular domains of the copolymer chains formed above the cloud point temperature...
June 14, 2018: Biomaterials Science
Vincent A Pistritto, Joshua M Paolillo, Kathryn A Bisset, Nicholas E Leadbeater
We present an alcohol oxidation strategy to access α-trifluoromethyl ketones (TFMKs) merging catalytic oxoammonium cation oxidation with visible-light photoredox catalysis. This work uses 4-acetamido-(2,2,6,6-tetramethyl-piperidin-1-yl)oxyl as an organic oxidant capable of generating TFMKs in good yields. The methodology serves as an improvement over previous reports of an analogous oxidation strategy requiring superstoichiometric quantities of oxidant. Both primary and secondary non-fluorinated alcohols can also be oxidised in good yields...
June 14, 2018: Organic & Biomolecular Chemistry
Gordon Sloan, Tania Kakoudaki, Nishant Ranjan
We report a case of a 63-year-old man who developed diabetic ketoacidosis (DKA) associated with canagliflozin, a sodium glucose co-transporter 2 (SGLT-2) inhibitor. He presented acutely unwell with a silent myocardial infarction, diverticulitis and DKA with a minimally raised blood glucose level. Standard therapy for DKA was initiated. Despite this, ketonaemia persisted for a total of 12 days after discontinuation of canagliflozin. Glucosuria lasting for several days despite discontinuation of the medications is a recognised phenomenon...
2018: Endocrinology, Diabetes & Metabolism Case Reports
Rohan Volpe, Romain J Lepage, Jonathan M White, Elizabeth H Krenske, Bernard L Flynn
Carbometalation of oxazolidinone ( Ox )-substituted ynamides is used to generate highly substituted Ox -divinyl (and aryl vinyl) ketones for use in Nazarov cyclizations. The Ox -group serves as a remarkably effective chiral activating group, enabling the torquoselective Nazarov cyclization of these sterically congested substrates to be performed under mild conditions. It also serves as a charge-stabilizing group in the intermediate oxyallyl cation, suppressing undesired [1,2]-sigmatropic shifts of neighboring substituents and facilitating the regio- and stereoselective incorporation of nucleophiles to yield cyclopentanoids containing up to three contiguous all-carbon quaternary (4°) stereocentres...
May 28, 2018: Chemical Science
Amanda C Warken, Leandro S Lopes, Nathieli B Bottari, Patrícia Glombowsky, Gabriela M Galli, Vera M Morsch, Maria Rosa C Schetinger, Aleksandro S DA Silva
The aim of this study was to evaluate whether the use of subcutaneous mineral supplementation would affect metabolic parameters, immunological response, milk quality and composition of dairy cows in the postpartum period. Twelve pregnant primiparous Holstein cows, were divided into two groups: six animals supplemented with the mineral complex (magnesium, phosphorus, potassium, selenium and copper), and six animals used as controls. Milk samples were collected every two other weeks postpartum up to sixty days of lactation to analyze composition and quality...
April 2018: Anais da Academia Brasileira de Ciências
Md Nasir Uddin, Emily M Tarsis, Chia-Hua Wu, Judy I Wu, Don M Coltart
A chiral auxiliary-based diastereoselective transformation that entirely avoids the stereochemically mismatched pairing, providing equally high levels of asymmetric induction in the formation of each diastereomer is described. In particular, we show that chiral nonracemic methyl ketones undergo α,α-bisalkylation using phenylalanine-derived N-amino cyclic carbamate (ACC) auxiliaries with essentially perfect diastereoselectivity, as well as excellent yield and regioselectivity. Significantly, with the use of a single enantiomer of the auxiliary, either diastereomeric product can be synthesized with an equally high level of asymmetric induction...
June 13, 2018: Organic Letters
Jingtuo Zhang, Soo Jung Yang, Federico Gonzalez, Jiaying Yang, Yumiao Zhang, Maomao He, Nilabh Shastri, Niren Murthy
ERAAP is an intracellular amino-peptidase that plays a central role in determining the repertoire of peptides displayed by cells by MHC class I molecules, and dysfunctions in ERAAP are linked to a variety of diseases. There is therefore great interest in developing probes that can image ERAAP in cells. In this report we present a fluorescent probe, termed Ep, that can image ERAAP activity in live cells. Ep is composed of a 10 amino acid ERAAP substrate that has a donor quencher pair conjugated to it, composed of BODIPY and dinitro-toluene...
June 13, 2018: Chemical Communications: Chem Comm
A Erler, D Riebe, T Beitz, H-G Löhmannsröben, D Grothusheitkamp, T Kunz, F-J Methner
Mold fungi on malting barley grains cause major economic loss in malting and brewery facilities. Possible proxies for their detection are volatile and semivolatile metabolites. Among those substances, characteristic marker compounds have to be identified for a confident detection of mold fungi in varying surroundings. The analytical determination is usually carried out through passive sampling with SPME, gas chromatographic separation and detection by EI-MS, which often does not allow a confident determination due to the absence of molecular ions...
June 13, 2018: Journal of Mass Spectrometry: JMS
Olga V Zatolochnaya, Sonia Rodríguez, Yongda Zhang, Kendricks S Lao, Sergei Tcyrulnikov, Guisheng Li, Xiao-Jun Wang, Bo Qu, Soumik Biswas, Hari P R Mangunuru, Daniel Rivalti, Joshua D Sieber, Jean-Nicolas Desrosiers, Joyce C Leung, Nelu Grinberg, Heewon Lee, Nizar Haddad, Nathan K Yee, Jinhua J Song, Marisa C Kozlowski, Chris H Senanayake
A new class of tunable heterophosphole dimeric ligands have been designed and synthesized. These ligands have enabled the first examples of Cu-catalyzed hydrogenation of 2-substituted-1-tetralones and related heteroaryl ketones via dynamic kinetic resolution, simultaneously creating two contiguous stereogenic centers with up to >99 : 1 dr and 98 : 2 er. The ligand-Cu complexes were isolated and characterized by single crystal X-ray, and DFT calculations revealed a novel heteroligated dimeric copper hydride transition state...
May 21, 2018: Chemical Science
Ethan A Wappes, Avassaya Vanitcha, David A Nagib
A radical relay strategy for mono- and di-halogenation (iodination, bromination, and chlorination) of sp3 C-H bonds has been developed. This first example of β C-H di-halogenation is achieved through sequential C-H abstraction by iterative, hydrogen atom transfer (HAT). A double C-H functionalization is enabled by in situ generated imidate radicals, which facilitate selective N˙ to C˙ radical translocation and tunable C-X termination. The versatile, geminal di-iodide products are further elaborated to β ketones and vinyl iodides...
May 21, 2018: Chemical Science
Prakash Basnet, Roshan K Dhungana, Surendra Thapa, Bijay Shrestha, Shekhar Kc, Jeremiah M Sears, Ramesh Giri
We disclose a [(PhO)3P]/NiBr2-catalyzed regioselective β,δ-diarylation of unactivated olefins in ketimines with aryl halides and arylzinc reagents. This diarylation proceeds at remote locations to the carbonyl group to afford, after simple H+ workup, diversely substituted β,δ-diarylketones that are otherwise difficult to access readily with existing methods. Deuterium-labelling and crossover experiments indicate that diarylation proceeds by ligand-enabled contraction of transient nickellacycles.
June 12, 2018: Journal of the American Chemical Society
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