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https://www.readbyqxmd.com/read/28829145/rearrangements-of-%C3%AE-diazo-%C3%AE-hydroxyketones-for-the-synthesis-of-bicyclo-m-n-1-alkanones
#1
Zhengning Li, Shuk Mei Lam, Ignatius Ip, Wing-Tak Wong, Pauline Chiu
Rhodium-catalyzed decomposition of fused bicyclic α-diazo-β-hydroxyketones results in good yields of bridged bicyclo[m.n.1]ketones via a rearrangement pathway.
August 22, 2017: Organic Letters
https://www.readbyqxmd.com/read/28829100/copper-catalyzed-transformation-of-ketones-to-amides-via-c-co-c-alkyl-bond-cleavage-directed-by-picolinamide
#2
Haojie Ma, Xiaoqiang Zhou, Zhenzhen Zhan, Daidong Wei, Chong Shi, Xingxing Liu, Guosheng Huang
Copper catalyzed chemoselective cleavage of the C(CO)-C(alkyl) bond leading to C-N bond formation with chelation assistance of N-containing directing groups is described. Inexpensive Cu(ii)-acetate serves as a convenient catalyst for this transformation. This method highlights the emerging strategy to transform unactivated alkyl ketones into amides in organic synthesis and provides a new strategy for C-C bond cleavage.
August 22, 2017: Organic & Biomolecular Chemistry
https://www.readbyqxmd.com/read/28829070/homoleptic-iron-ii-and-cobalt-ii-bis-phosphoranimide-complexes-for-the-selective-hydrofunctionalization-of-unsaturated-molecules
#3
Tao Bai, Trevor Janes, Datong Song
Low-coordinate homoleptic bulky M2(NP(t)Bu3)4 (M = Fe (A), Co (B)) complexes were synthesized and characterized as dimeric structures by crystallographic studies. The iron complex A can catalyze the hydroboration reaction of aldehydes and ketones. The cobalt complex B outperformed its iron counterpart in hydrogenations of several typical alkenes and alkynes under mild conditions. Poisoning experiments indicate that the Co(ii)/HBpin catalytic system could be homogeneous.
August 22, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/28826372/%C3%AE-hydroxybutyrate-a-signaling-metabolite
#4
John C Newman, Eric Verdin
Various mechanisms in the mammalian body provide resilience against food deprivation and dietary stress. The ketone body β-hydroxybutyrate (BHB) is synthesized in the liver from fatty acids and represents an essential carrier of energy from the liver to peripheral tissues when the supply of glucose is too low for the body's energetic needs, such as during periods of prolonged exercise, starvation, or absence of dietary carbohydrates. In addition to its activity as an energetic metabolite, BHB is increasingly understood to have cellular signaling functions...
August 21, 2017: Annual Review of Nutrition
https://www.readbyqxmd.com/read/28822013/biomonitoring-of-chemicals-in-biota-of-two-wetland-protected-areas-exposed-to-different-levels-of-environmental-impact-results-of-the-previeni-project
#5
Cristiana Guerranti, Guido Perra, Eva Alessi, Davide Baroni, Dante Caserta, Donatella Caserta, Augusto De Sanctis, Emiliano Leonida Fanello, Cinzia La Rocca, Michela Mariottini, Monia Renzi, Sabrina Tait, Carlo Zaghi, Alberto Mantovani, Silvano Ettore Focardi
The PREVIENI project (funded by the Ministry of Environment) investigated the exposure to endocrine disrupters in samples of human population and environmental biota in Italy. The environmental biomonitoring considered two Italian WWF Oasis, with the aim to compare the presence and effects of endocrine disruptors in organisms from two protected natural areas, respectively, upstream and downstream a chemical emission site. Chemical analysis of pollutants' tissue levels was made on tissues from earthworm, barbell, trout, and coot, selected as bioindicator organisms...
August 18, 2017: Environmental Monitoring and Assessment
https://www.readbyqxmd.com/read/28821850/comparative-metabonomics-of-wenxin-keli-and-verapamil-reveals-differential-roles-of-gluconeogenesis-and-fatty-acid-%C3%AE-oxidation-in-myocardial-injury-protection
#6
Miaomiao Jiang, Qiuying Wang, Jingrui Chen, Yanan Wang, Guanwei Fan, Yan Zhu
Metabonomics/metabolomics is a rapid technology for comprehensive profiling of small molecule metabolites in cells, tissues, or whole organisms, the application of which has led to understanding pathophysiologic mechanisms of cardiometabolic diseases, defining predictive biomarkers for those diseases, and also assessing the efficacious effects of incident drugs. In this study, proton nuclear magnetic resonance (NMR)-based metabonomics was employed to identify the metabolic changes in rat plasma caused by myocardial ischemia-reperfusion injury (MIRI), and to compare the metabolic regulatory differences between traditional Chinese medicine Wenxin Keli (WXKL) and Western medicine verapamil...
August 18, 2017: Scientific Reports
https://www.readbyqxmd.com/read/28820963/ketone-body-acetoacetate-buffers-methylglyoxal-via-a-non-enzymatic-conversion-during-diabetic-and-dietary-ketosis
#7
Trine Salomón, Christian Sibbersen, Jakob Hansen, Dieter Britz, Mads Vandsted Svart, Thomas Schmidt Voss, Niels Møller, Niels Gregersen, Karl Anker Jørgensen, Johan Palmfeldt, Thomas Bjørnskov Poulsen, Mogens Johannsen
The α-oxoaldehyde methylglyoxal is a ubiquitous and highly reactive metabolite known to be involved in aging- and diabetes-related diseases. If not detoxified by the endogenous glyoxalase system, it exerts its detrimental effects primarily by reacting with biopolymers such as DNA and proteins. We now demonstrate that during ketosis, another metabolic route is operative via direct non-enzymatic aldol reaction between methylglyoxal and the ketone body acetoacetate, leading to 3-hydroxyhexane-2,5-dione. This novel metabolite is present at a concentration of 10%-20% of the methylglyoxal level in the blood of insulin-starved patients...
August 17, 2017: Cell Chemical Biology
https://www.readbyqxmd.com/read/28820737/when-one-disease-is-not-enough-succinyl-coa-3-oxoacid-coenzyme-a-transferase-scot-deficiency-due-to-a-novel-mutation-in-oxct1-in-an-infant-with-known-phenylketonuria
#8
Jan-Niclas Schwade, Matthias Endmann, Thomas Hofmann, Stephan Rust, Jörn Oliver Sass, Frank Rutsch
A 9-month-old Turkish girl was admitted several times within 3 months to the hospital in reduced general condition and with extreme tachypnea. The patient had been diagnosed with phenylketonuria (PKU) in newborn screening and has been treated with a low phenylalanine diet and amino acid supplements. Each time an unexplained pronounced metabolic acidosis was noted, and the child was treated with sodium-bicarbonate and glucose-electrolyte infusions. The acidosis with only slightly abnormal glucose, normal lactate levels and pronounced ketonuria suggested a defect in ketone body utilization...
August 18, 2017: Journal of Pediatric Endocrinology & Metabolism: JPEM
https://www.readbyqxmd.com/read/28820583/processing-2-methyl-l-tryptophan-through-tandem-transamination-and-selective-oxygenation-initiates-indole-ring-expansion-in-the-biosynthesis-of-thiostrepton
#9
Zhi Lin, Jia Ji, Shuaixiang Zhou, Fang Zhang, Jiequn Wu, Yinlong Guo, Wen Liu
Thiostrepton (TSR), an archetypal member of the family of ribosomally synthesized and post-translationally modified thiopeptide antibiotics, possesses a biologically important quinaldic acid (QA) moiety within the side-ring system of its characteristic thiopeptide framework. QA is derived from an independent L-Trp residue; however, its associated transformation process remains poorly understood. We here report that during the formation of QA, the key expansion of an indole to a quinoline relies on the activities of the pyridoxal-5'-phosphate-dependent protein TsrA and the flavoprotein TsrE...
August 18, 2017: Journal of the American Chemical Society
https://www.readbyqxmd.com/read/28816397/a-flow-through-column-electrolytic-cell-for-supercritical-fluid-chromatography
#10
Kazuhiro Yamamoto, Tatsuya Ueki, Naoyuki Higuchi, Kouji Takahashi, Akira Kotani, Hideki Hakamata
A novel flow-through column electrolytic cell was proposed as a detector to obtain current signals for supercritical fluid chromatography. The electrochemical cell consisted of two electrodes and its holder, and a working and a counter electrode were fabricated from 192 carbon strings, which were composed of 400 carbon fibers of 10 μm in diameter filled into a heat-shrinkable tube. These electrodes were placed in the center of a holder made from polyether ether ketone blocks and they were separated by polytetrafluoroethylene membrane filters...
August 17, 2017: Journal of Separation Science
https://www.readbyqxmd.com/read/28816392/phosphine-catalyzed-enantioselective-formal-4-4-annulation-of-alpha-beta-unsaturated-imines-and-allene-ketones-construction-of-eight-membered-rings
#11
Yixin Lu, Huanzhen Ni, Xiaodong Tang, Wenrui Zheng, Weijun Yao, Nisar Ullah
The first highly enantioselective phosphine-catalyzed formal[4+4] annulation has been developed. In the presence of amino acid-derived phosphines, the unprecedented formal [4+4] annulations between benzofuran/indole derived α,β-unsaturated imines and allene ketones proceeded smoothly, affording azocines bearing a benzofuran or an indole moiety in excellent yields and with nearly perfect enantioselectivities (≥98% ee in most cases). This work marks the first efficient asymmetric construction of optically enriched eight-membered rings via phosphine catalysis...
August 17, 2017: Angewandte Chemie
https://www.readbyqxmd.com/read/28816320/formation-of-titanium-dioxide-core-shell-microcapsules-through-a-binary-phase-spray-technique
#12
Jonatan Bergek, Björn Elgh, Anders E C Palmqvist, Lars Nordstierna
Core-shell microcapsules consisting of a titanium dioxide shell and a hydrophobic solvent core have been prepared with diameters of a few micrometers and a narrow size distribution using a simple and fast airbrush technique. These microcapsules were prepared at room temperature in a single-step process in which an oil with a dissolved titanium alkoxide precursor was forced together with an aqueous solution, containing a surface-active polymer, through a narrow spray nozzle using a nitrogen gas propellant. Several different parameters of chemical, physical, and processing origin were investigated to find an optimal recipe...
August 17, 2017: Physical Chemistry Chemical Physics: PCCP
https://www.readbyqxmd.com/read/28815966/trifluoromethyl-oxetanes-synthesis-and-evaluation-as-a-tert-butyl-isostere
#13
Paramita Mukherjee, Martin Pettersson, Jason K Dutra, Longfei Xie, Christopher W Am Ende
The synthesis of a new trifluoromethyl oxetane was developed utilizing a Corey-Chaykovsky epoxidation/ring-expansion reaction of trifluoromethyl ketones. The reaction was shown to proceed under mild conditions and displays a broad substrate scope. The trifluoromethyl oxetane was also evaluated as a tert-butyl isostere in the context of the γ-secretase modulator (GSM) program. We demonstrate that the trifluoromethyl oxetane-containing GSM has reduced lipophilicity, improved lipophilic efficiency (LipE) and metabolic stability relative to the corresponding tert-butyl GSM analog, thus highlighting several benefits of trifluoromethyl oxetane as a more polar tert-butyl isostere...
August 16, 2017: ChemMedChem
https://www.readbyqxmd.com/read/28815838/wacker-type-oxidation-using-an-iron-catalyst-and-ambient-air-and-its-application-to-late-stage-oxidation-of-complex-molecules
#14
Wei Han, Binbin Liu, Fengli Jin, Tianjiao Wang, Xiaorong Yuan
We present a practical and general iron-catalyzed Wacker-type oxidation of olefins to ketones which uses ambient air as the sole oxidant. The mild oxidation conditions enable exceptional functional group tolerance, which has not been demonstrated for any other Wacker-type reaction to date. The inexpensive and nontoxic reagents [iron(II) chloride, PMHS (polymethylhydrosiloxane), and air] can, therefore, also be employed to oxidize complex natural-product derived and polyfunctionalized molecules.
August 16, 2017: Angewandte Chemie
https://www.readbyqxmd.com/read/28815357/carbon-fiber-reinforced-peek-fixation-system-in-the-treatment-of-spine-tumors-a-preliminary-report
#15
Stefano Boriani, Giuseppe Tedesco, Lu Ming, Riccardo Ghermandi, Maurizio Amichetti, Piero Fossati, Marco Krengli, Loredana Mavilla, Alessandro Gasbarrini
BACKGROUND: Protocols including combination of surgery and radiotherapy are more and more frequent in the treatment of bone tumors of the spine. In metastatic disease, combination of surgery and radiotherapy is since long time accepted, as based on clinical evidence. In primary tumors, combination of surgery and radiotherapy can be considered in all the cases in which a satisfactory oncological margin cannot be achieved: high-grade malignancies, recurrent tumors, huge tumors expanding in an extracompartimental area, and when tumor-free margin requires unacceptable functional sacrifices...
August 16, 2017: European Spine Journal
https://www.readbyqxmd.com/read/28815162/clinical-application-of-ceramics-in-anterior-cervical-discectomy-and-fusion-a-review-and-update
#16
REVIEW
Shayan Abdollah Zadegan, Aidin Abedi, Seyed Behnam Jazayeri, Hirbod Nasiri Bonaki, Alexander R Vaccaro, Vafa Rahimi-Movaghar
STUDY DESIGN: Narrative review. OBJECTIVES: Anterior cervical discectomy and fusion (ACDF) is a reliable procedure, commonly used for cervical degenerative disc disease. For interbody fusions, autograft was the gold standard for decades; however, limited availability and donor site morbidities have led to a constant search for new materials. Clinically, it has been shown that calcium phosphate ceramics, including hydroxyapatite (HA) and tricalcium phosphate (TCP), are effective as osteoconductive materials and bone grafts...
June 2017: Global Spine Journal
https://www.readbyqxmd.com/read/28814987/green-tea-polyphenols-ameliorate-the-early-renal-damage-induced-by-a-high-fat-diet-via-ketogenesis-sirt3-pathway
#17
Weijie Yi, Xiao Xie, Miying Du, Yongjun Bu, Nannan Wu, Hui Yang, Chong Tian, Fangyi Xu, Siyun Xiang, Piwei Zhang, Zhuo Chen, Xuezhi Zuo, Chenjiang Ying
SCOPE: Several reports in the literature have suggested the renoprotective effects of ketone bodies and green tea polyphenols (GTPs). Our previous study found that GTP consumption could elevate the renal expression of the ketogenic rate-limiting enzyme, which was decreased by a high-fat diet (HFD) in rats. Here, we investigated whether ketogenesis can mediate renoprotection by GTPs against an HFD. METHODS AND RESULTS: Wistar rats were fed a standard or HFD with or without GTPs for 18 weeks...
2017: Oxidative Medicine and Cellular Longevity
https://www.readbyqxmd.com/read/28813167/lipophagy-maintains-energy-homeostasis-in-the-kidney-proximal-tubule-during-prolonged-starvation
#18
Satoshi Minami, Takeshi Yamamoto, Yoshitsugu Takabatake, Atsushi Takahashi, Tomoko Namba, Jun Matsuda, Tomonori Kimura, Jun-Ya Kaimori, Isao Matsui, Takayuki Hamano, Hiroaki Takeda, Masatomo Takahashi, Yoshihiro Izumi, Takeshi Bamba, Taiji Matsusaka, Fumio Niimura, Yoshitaka Isaka
Macroautophagy/autophagy is a self-degradation process that combats starvation. Lipids are the main energy source in kidney proximal tubular cells (PTCs). During starvation, PTCs increase fatty acid (FA) uptake, form intracellular lipid droplets (LDs), and hydrolyze them for use. The involvement of autophagy in lipid metabolism in the kidney remains largely unknown. Here, we investigated the autophagy-mediated regulation of renal lipid metabolism during prolonged starvation using PTC-specific Atg5-deficient (atg5-TSKO) mice and an in vitro serum starvation model...
August 16, 2017: Autophagy
https://www.readbyqxmd.com/read/28812767/mild-synthesis-of-triarylsulfonium-salts-with-arynes
#19
Lei Zhang, Xiaojin Li, Yan Sun, Weizhao Zhao, Fan Luo, Xin Huang, Lihui Lin, Ying Yang, Bo Peng
Reactions between arynes and alkyl sulfides have been extensively studied over the past few decades. These reactions commonly end with a dealkylation process and thus deliver thioethers as final products. In contrast, the transformation described furnishes valuable triarylsulfonium salts, in lieu of thioethers, from arynes and diarylsulfides. The reaction features mild conditions and a broad substrate scope. A suite of functional groups such as ketones, esters, nitriles, aryl ethers and aryl halides is tolerated, which can be issues faced by traditional synthetic methods...
August 16, 2017: Organic & Biomolecular Chemistry
https://www.readbyqxmd.com/read/28812076/a-hydrophilic-inorganic-framework-based-on-a-sandwich-polyoxometalate-unusual-chemoselectivity-for-aldehydes-ketones-with-in-situ-generated-hydroxylamine
#20
Songzhu Xing, Qiuxia Han, Zhuolin Shi, Shugai Wang, PeiPei Yang, Qiang Wu, Mingxue Li
A hydrophilic inorganic porous catalyst was prepared via the hydrothermal method. The combination of [WZn3(H2O)2(ZnW9O34)2](12-) and Co(ii) provides a synergistical catalytic way to promote oximation of aldehyde/ketone with in situ generated hydroxylamine that initially produces an oxime, which further either dehydrates into a nitrile or undergoes a Beckmann rearrangement to form an amide.
August 16, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
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