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https://www.readbyqxmd.com/read/28820192/comparison-of-classical-reaction-paths-and-tunneling-paths-studied-with-the-semiclassical-instanton-theory
#1
Jan Meisner, Max N Markmeyer, Matthias U Bohner, Johannes Kästner
Atom tunneling in the hydrogen atom transfer reaction of the 2,4,6-tri-tert-butylphenyl radical to 3,5-di-tert-butylneophyl, which has a short but strongly curved reaction path, was investigated using instanton theory. We found the tunneling path to deviate qualitatively from the classical intrinsic reaction coordinate, the steepest-descent path in mass-weighted Cartesian coordinates. To perform that comparison, we implemented a new variant of the predictor-corrector algorithm for the calculation of the intrinsic reaction coordinate...
August 18, 2017: Physical Chemistry Chemical Physics: PCCP
https://www.readbyqxmd.com/read/28820076/a-novel-danshensu-tetramethylpyrazine-conjugate-dt-018-provides-cardioprotection-by-preserving-mitochondrial-function-through-the-mef2d-pgc-1%C3%AE-pathway
#2
Xiaojing Zhang, Jingxiong Luo, Yali Huang, Huixing Deng, Huihui Hu, Pei Yu, Yewei Sun, Luchen Shan, Yuqiang Wang
In this work, we explored the protective effect of DT-018, a danshensu and tetramethylpyrazine conjugate, on mitochondrial injury induced by tert-butylhydroperoxide (t-BHP) and its possible mechanisms of action. DT-018 effectively quenched intracellular and mitochondrial reactive oxygen species (ROS), preserved the mitochondrial function, restored the intracellular level of ATP and augmented mitochondrial membrane potential (ΔΨm) while suppressed mitochondrial swelling in isolated myocardial mitochondria...
August 17, 2017: Current Pharmaceutical Design
https://www.readbyqxmd.com/read/28819667/synthesis-and-optical-and-electrochemical-properties-of-a-phenanthrodithiophene-fused-bibenzo-c-thiophene-derivative
#3
Yousuke Ooyama, Toshiaki Enoki, Satoshi Aoyama, Joji Ohshita
We designed and developed a fused-bibenzo[c]thiophene, namely, 2,9-bis(tert-butyldimethylsilyl)phenanthro[9,8-bc:10,1-b'c']dithiophene (PHDT-Si), as a new π-building block in the emitters, photosensitizers and semiconductors for organic optoelectronic devices. Based on photophysical (photoabsorption, fluorescence and time-resolved fluorescence spectroscopy) and electrochemical measurements (cyclic voltammetry), and density functional theory (DFT) calculations, this work reveals that the fused-bibenzo[c]thiophene PHDT-Si, which is prepared by an efficient synthesis method, has a rigid, high planar and expanded π-conjugation structure, and possesses intense photoabsorption and fluorescence properties (λ = 598 nm (εmax = 41 000 M(-1) cm(-1)) and λ = 613 nm (Φf = 0...
August 18, 2017: Organic & Biomolecular Chemistry
https://www.readbyqxmd.com/read/28818973/mutations-in-the-promoter-of-the-telomerase-gene-tert-contribute-to-tumorigenesis-by-a-two-step-mechanism
#4
Kunitoshi Chiba, Franziska K Lorbeer, A Hunter Shain, David T McSwiggen, Eva Schruf, Areum Oh, Jekwan Ryu, Xavier Darzacq, Boris C Bastian, Dirk Hockemeyer
TERT promoter mutations (TPMs) are the most common non-coding mutations in cancer. The timing and consequences of TPMs have not been fully established. Here we show that TPMs acquired at the transition from benign nevus to malignant melanoma do not support telomere maintenance. In vitro experiments revealed that TPMs do not prevent telomere attrition, resulting in cells with critically short and unprotected telomeres. Immortalization by TPMs requires a gradual upregulation of telomerase, coinciding with telomere fusions...
August 17, 2017: Science
https://www.readbyqxmd.com/read/28815966/trifluoromethyl-oxetanes-synthesis-and-evaluation-as-a-tert-butyl-isostere
#5
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/28815354/nf-e2-related-factor-2-suppresses-intestinal-fibrosis-by-inhibiting-reactive-oxygen-species-dependent-tgf-%C3%AE-1-smads-pathway
#6
Yadi Guan, Yue Tan, Weiyu Liu, Jun Yang, Dongxu Wang, Di Pan, Yan Sun, Changqing Zheng
BACKGROUND AND AIMS: This study aimed to evaluate the antifibrotic effects of NF-E2-Related Factor 2 (Nrf2) on intestinal fibrosis. Intestinal fibrosis is a common complication of Crohn's disease; however, its mechanism of intestinal fibrosis is largely unclear. METHODS: BALB/c mice received 2,4,6-trinitrobenzene sulfonic acid weekly via intrarectal injections to induce chronic fibrotic colitis. They also diet containing received 1% (w/w) tert-butylhydroquinone (tBHQ), which is an agonist of Nrf2...
August 16, 2017: Digestive Diseases and Sciences
https://www.readbyqxmd.com/read/28814981/cpg-location-and-methylation-level-are-crucial-factors-for-the-early-detection-of-oral-squamous-cell-carcinoma-in-brushing-samples-using-bisulfite-sequencing-of-a-13-gene-panel
#7
Luca Morandi, Davide Gissi, Achille Tarsitano, Sofia Asioli, Andrea Gabusi, Claudio Marchetti, Lucio Montebugnoli, Maria Pia Foschini
BACKGROUND: Oral squamous cell carcinoma (OSCC) is usually diagnosed at an advanced stage and is commonly preceded by oral premalignant lesions. The mortality rates have remained unchanged (50% within 5 years after diagnosis), and it is related to tobacco smoking and alcohol intake. Novel molecular markers for early diagnosis are urgently needed. The purpose of this study was to evaluate the diagnostic value of methylation level in a set of 18 genes by bisulfite next-generation sequencing...
2017: Clinical Epigenetics
https://www.readbyqxmd.com/read/28813500/telomere-biology-and-telomerase-mutations-in-cirrhotic-patients-with-hepatocellular-carcinoma
#8
Flávia S Donaires, Natália F Scatena, Raquel M Alves-Paiva, Joshua D Podlevsky, Dhenugen Logeswaran, Barbara A Santana, Andreza C Teixeira, Julian J-L Chen, Rodrigo T Calado, Ana L C Martinelli
Telomeres are repetitive DNA sequences at linear chromosome termini, protecting chromosomes against end-to-end fusion and damage, providing chromosomal stability. Telomeres shorten with mitotic cellular division, but are maintained in cells with high proliferative capacity by telomerase. Loss-of-function mutations in telomere-maintenance genes are genetic risk factors for cirrhosis development in humans and murine models. Telomerase deficiency provokes accelerated telomere shortening and dysfunction, facilitating genomic instability and oncogenesis...
2017: PloS One
https://www.readbyqxmd.com/read/28813153/copper-catalyzed-tbhp-mediated-radical-cross-coupling-reaction-of-sulfonylhydrazides-with-thiols-leading-to-thiosulfonates
#9
Guo-Yu Zhang, Shuai-Shuai Lv, Adedamola Shoberu, Jian-Ping Zou
A tert-butyl hydroperoxide (TBHP)-mediated coupling of sulfonylhydrazides with thiols catalyzed by CuBr2 to afford thiosulfonates via a radical process is described.
August 16, 2017: Journal of Organic Chemistry
https://www.readbyqxmd.com/read/28813019/grafting-modification-of-the-reactive-core-shell-particles-to-enhance-the-toughening-ability-of-polylactide
#10
Zhaokun Li, Shixin Song, Xuanchen Zhao, Xue Lv, Shulin Sun
In order to overcome the brittleness of polylactide (PLA), reactive core-shell particles (RCS) with polybutadiene as core and methyl methacrylate-co-styrene-co-glycidyl methacrylate as shell were prepared to toughen PLA. Tert-dodecyl mercaptan (TDDM) was used as chain transfer agent to modify the grafting properties (such as grafting degree, shell thickness, internal and external grafting) of the core-shell particles. The introduction of TDDM decreased the grafting degree, shell thickness and the Tg of the core phase...
August 16, 2017: Materials
https://www.readbyqxmd.com/read/28812412/an-investigation-into-discharge-visual-perception-and-appearance-concerns-of-prosthetic-eye-wearers
#11
Nicola S Pine, Ian de Terte, Keith R Pine
We investigate prosthetic eye wearers' initial and current concerns about mucoid discharge, visual perception, and appearance, and the reasons for their concerns. A retrospective, cross-sectional study of private practice patients was designed. Participants were 217 experienced prosthetic eye wearers, aged at least 16 years. An anonymous questionnaire was e-mailed or mailed to participants. Descriptive and inferential statistics were used to investigate differences or correlations between variables. Content analysis was used to analyze participants' open responses...
August 16, 2017: Orbit
https://www.readbyqxmd.com/read/28809555/electronic-magnetic-and-redox-properties-and-o2-reactivity-of-iron-ii-and-nickel-ii-o-semiquinonate-complexes-of-a-tris-thioether-ligand-uncovering-the-intradiol-cleaving-reactivity-of-an-iron-ii-o-semiquinonate-complex
#12
Peng Wang, Michelle M Killian, Mohamed R Saber, Tian Qiu, Glenn P A Yap, Codrina V Popescu, Joel Rosenthal, Kim R Dunbar, Thomas C Brunold, Charles G Riordan
The iron(II) semiquinonate character within the iron(III) catecholate species has been proposed by numerous studies to account for the O2 reactivity of intradiol catechol dioxygenases, but a well-characterized iron(II) semiquinonate species that exhibits intradiol cleaving reactivity has not yet been reported. In this study, a detailed electronic structure description of the first iron(II) o-semiquinonate complex, [PhTt(tBu)]Fe(phenSQ) [PhTt(tBu) = phenyltris(tert-butylthiomethyl)borate; phenSQ = 9,10-phenanthrenesemiquinonate; Wang et al...
August 15, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28808414/diiron-dithiolate-hydrides-complemented-with-proton-responsive-phosphine-amine-ligands
#13
Michaela R Carlson, Ryan Gilbert-Wilson, Danielle R Gray, Joyee Mitra, Thomas B Rauchfuss, Casseday P Richers
The reaction of Fe2(pdt)(CO)6 with two equivalents of Ph2PC6H4NH2 (PNH2) affords the amido hydride HFe2(pdt)(CO)2(PNH2)(PNH) {[H1H](0), pdt(2-) = CH2(CH2S(-))2}. Isolated intermediates in this conversion include Fe2(pdt)(CO)5-(κ(1)-PNH2) and Fe2(pdt)(CO)4(κ(2)-PNH2). X-ray crystallographic analysis of [H1H](0) shows that the chelating amino/amido-phosphine ligands occupy trans-dibasal positions. The (31)P NMR spectrum indicates that [H1H](0) undergoes rapid proton exchange between the amido and amine centers...
July 7, 2017: European Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/28803646/effect-of-solvent-composition-on-the-van-t-hoff-enthalpic-curve-using-amylose-3-5-dichlorophenylcarbamate-based-sorbent
#14
Ang-Yeh Lin, Kai-Tse Cheng, Sin-Chang Chen, Hung-Wei Tsui
Van't Hoff plots have been widely used for investigating the thermodynamic properties of adsorption processes in various chromatography systems. By measuring the retention factor k over a certain temperature range, the plot of ln k versus 1/T often yields a straight line with a slope of -ΔHvH(0)/R. Although this method provides information on adsorption enthalpy changes, its theoretical basis does not account for the effect of the solvent. In this paper, the relationship between apparent enthalpy changes determined directly from van't Hoff plots and solvent modifier concentrations is systematically investigated using three simple solutes-tetrahydrofuran, acetone, and tert-butanol-in an n-hexane-methyl tert-butyl ether (MTBE) mobile phase with an amylose 3,5-dichlorophenylcarbamate-based sorbent...
August 4, 2017: Journal of Chromatography. A
https://www.readbyqxmd.com/read/28802642/prognostic-value-of-tert-alterations-and-mutational-and-copy-number-alteration-burden-in-urothelial-carcinoma
#15
Sumit Isharwal, François Audenet, Esther Drill, Eugene J Pietzak, Gopa Iyer, Irina Ostrovnaya, Eugene Cha, Timothy Donahue, Maria Arcila, Gowtham Jayakumaran, Michael F Berger, Jonathan E Rosenberg, Dean F Bajorin, Jonathan Coleman, Guido Dalbagni, Victor E Reuter, Bernard H Bochner, David B Solit, Hikmat A Al-Ahmadie
Missense mutations in the TERT gene promoter occur at high frequency in multiple cancers, including urothelial carcinoma (UC). However, the relationship between TERT promoter mutations and UC patient outcomes is unclear due to conflicting reports in the literature. In this study, we examined the association of TERT alterations, tumor mutational burden per megabase (Mb), and copy number alteration (CNA) burden with clinical parameters and their prognostic value in a cohort of 398 urothelial tumors. The majority of TERT mutations were located at two promoter region hotspots (chromosome 5, 1 295 228 C>T and 1 295 250 C>T)...
August 9, 2017: European Urology Focus
https://www.readbyqxmd.com/read/28802494/toward-a-molecular-genetic-classification-of-spitzoid-neoplasms
#16
REVIEW
Michael T Tetzlaff, Alexandre Reuben, Steven D Billings, Victor G Prieto, Jonathan L Curry
The histopathologic spectrum of Spitzoid neoplasms includes Spitz nevi, atypical Spitz tumors, and Spitzoid melanomas. Advances in molecular genetics have evolved to the point that Spitzoid lesions can now be reasonably classified according to their distinctive molecular-genetic alterations: Spitzoid lesions with (1) 11p amplification and/or HRAS mutations; (2) isolated loss of 6q23 by fluorescence in situ hybridization (FISH); (3) homozygous deletion of 9p21 by FISH; (4) BAP1 loss and BRAFV600 E mutation; (5) translocations involving any of a number of different oncogenic kinase drivers, including ROS1, ALK, NTRK1, NTRK3, MET, BRAF, and RET; and (6) TERT promoter mutations...
September 2017: Clinics in Laboratory Medicine
https://www.readbyqxmd.com/read/28800228/stoichiometric-and-catalytic-aryl-perfluoroalkyl-coupling-at-tri-tert-butylphosphine-palladium-ii-complexes
#17
Devin M Ferguson, James R Bour, Allan J Canty, Jeff W Kampf, Melanie S Sanford
This Communication describes studies of Ph-RF (RF = CF3 or CF2CF3) coupling at Pd complexes of general structure (P(t)Bu3)Pd(II)(Ph)(RF). The CF3 analogue participates in fast Ph-CF3 coupling (<5 min at 80 °C). However, the formation of side products limits the yield of this transformation as well as its translation to catalysis. DFT and experimental studies suggest that the side products derive from facile α-fluoride elimination at the 3-coordinate Pd(II) complex. Furthermore, they show that this undesired pathway can be circumvented by changing from a CF3 to a CF2CF3 ligand...
August 11, 2017: Journal of the American Chemical Society
https://www.readbyqxmd.com/read/28796516/cesium-induced-ionic-conduction-through-a-single-nanofluidic-pore-modified-with-calixcrown-moieties
#18
Mubarak Ali, Ishtiaq Ahmed, Patricio Ramirez, Saima Nasir, Javier Cervera, Salvador Mafe, Christof M Niemeyer, Wolfgang Ensinger
We demonstrate experimentally and theoretically a nanofluidic device for the selective recognition of cesium ion by exploiting host-guest interactions inside confined geometry. For this purpose, a host molecule, i.e., the amine-terminated p-tert-butylcalix[4]arene-crown (t-BuC[4]C-NH2), is successfully synthesized and functionalized on the surface of a single conical nanopore fabricated in polyethylene terephthalate (PET) membrane through carbodiimide coupling chemistry. On exposure to cesium cation, the t-BuC[4]C-Cs+ complex is formed through host-guest interaction, leading to the generation of positive fixed charges on the pore surface...
August 10, 2017: Langmuir: the ACS Journal of Surfaces and Colloids
https://www.readbyqxmd.com/read/28796438/transforming-olefins-into-%C3%AE-%C3%AE-unsaturated-nitriles-through-copper-catalysis
#19
Xuesong Wu, Jan Riedel, Vy M Dong
We have developed a strategy to transform olefins into homoallylic nitriles through a mechanism that combines copper catalysis with alkyl nitrile radicals. The radicals are easily generated from alkyl nitriles in the presence of the mild oxidant di-tert-butyl peroxide. This cross-dehydrogenative coupling between simple olefins and alkylnitriles bears advantages over the conventional use of halides and toxic cyanide reagents. With this method, we showcase the facile synthesis of a flavoring agent, a natural product, and a polymer precursor from simple olefins...
August 10, 2017: Angewandte Chemie
https://www.readbyqxmd.com/read/28796000/genomic-analysis-of-pigmented-epithelioid-melanocytomas-reveals-recurrent-alterations-in-prkar1a-and-prkca-genes
#20
Jarish N Cohen, Nancy M Joseph, Jeffrey P North, Courtney Onodera, Artur Zembowicz, Philip E LeBoit
Pigmented epithelioid melanocytoma (PEM) is a rare cutaneous melanocytic tumor first described as epithelioid blue nevus in patients with the Carney Complex (CC). PEM was among the first established examples of an intermediate class of melanocytic tumors, including atypical Spitz tumors, with frequent metastasis to lymph nodes but only rare extranodal spread. Sporadic and CC-associated PEM are essentially histologically indistinguishable. A subset of PEM shows loss of cytoplasmic expression of the protein kinase A regulatory subunit alpha (PRKAR1A), a tumor suppressor gene mutated in 70% of families with CC...
August 8, 2017: American Journal of Surgical Pathology
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