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https://www.readbyqxmd.com/read/29149539/dynamic-cross-exchange-in-halophosphonium-species-first-direct-observation-of-stereochemical-inversion-in-the-course-of-an-sn2-process
#1
Kirill Nikitin, Elizabeth V Jennings, Sulaiman Al Sulaimi, Yannick Ortin, Declan G Gilheany
The complex fluxional interconversions between, otherwise very similar, phosphonium bromides and chlorides R3PX+X- (R = Alk, Ar, X = Cl or Br) was studied by NMR techniques. Their energy barriers are typically ca. 11 kcal/mol but rise rapidly as bulky groups are attached to phosphorus, revealing the importance of steric factors. In contrast, electronic effects, as measured by Hammett analysis, are modest (rho 1.46) but still clearly indicate negative charge flow towards phosphorus in the transition state. Most significantly, detailed analysis of the exchange pathways unequivocally, and for the first time in any such process, shows that nucleophilic attack of the nucleophilic anion on the tetrahedral centre results in inversion of configuration...
November 17, 2017: Angewandte Chemie
https://www.readbyqxmd.com/read/29149501/the-weakly-coordinating-tris-trichlorosilyl-silyl-anion
#2
Marian Olaru, Maxie F Hesse, Elena Rychagova, Sergey Ketkov, Stefan Mebs, Jens Beckmann
Closely following the procedure for the preparation of the base-stabilized dichlorosilylene complex NHCDipp∙SiCl2 by Roesky and Stalke et al. (Angew. Chem. Int. Ed. 2009, 48, 5683-5686), besides the reported by-product [NHCDipp-H+∙∙∙Cl-], few crystals of the salt [NHCDipp-H∙∙∙Cl∙∙∙H-NHCDipp]Si(SiCl3)3 were isolated and characterized by X-ray crystallography (NHCDipp = N,N-di(2,6-isopropylphenyl)-imidazo-2-ylidene). They feature the weakly-coordinating anion Si(SiCl3)3-, which was more rationally obtained in high yields upon deprotonation of conjugate Brønsted acid HSi(SiCl3)3 with NHCDipp or PMP (PMP = 1,2,2,6,6-pentamethylpiperidine)...
November 17, 2017: Angewandte Chemie
https://www.readbyqxmd.com/read/29149498/association-between-a-single-nucleotide-polymorphism-in-the-grem1-gene-and-nonsyndromic-orofacial-cleft-in-the-chinese-population
#3
Xiaotong Wang, Hongquan Song, Xiaohui Jiao, Yanru Hao, Wei Zhang, Yuwei Gao, Yong Li, Na Mi, Jiaqun Yan
BACKGROUND: Nonsyndromic orofacial cleft (NSOC) is a common craniofacial deformity among newborns. The GREM1 gene is correlated with orofacial development. The aim of our study was to investigate the association between a single-nucleotide polymorphism in the GREM1 gene and this malformation in the Chinese population. METHODS: The SNaPshot mini sequencing technique was used to genotype the locus rs1258763 of the GREM1 gene in 331 patients with NSOC and 271 individuals in a control group...
November 17, 2017: Journal of Oral Pathology & Medicine
https://www.readbyqxmd.com/read/29148983/densification-of-chlorine-doped-continuous-cnt-sheet-polyvinylidene-fluoride-sandwich-film-and-improvement-of-mechanical-and-dielectric-properties
#4
Jiyong Liang, Yizhuo Gu, Zhenchong Zhang, Shaokai Wang, Min Li, Zuoguang Zhang
The compacting structure of chlorine-doped continuous CNT sheet/polyvinylidene fluoride (Cl-CNT sheet/PVDF) was successfully optimized by means of hot-press treatment to improve mechanical and dielectric properties with high densification degree. Then, the densified Cl-CNT sheet/PVDF dielectric layer was inserted between two PVDF insulating layers to fabricate sandwich composite. It is found that the dielectric and mechanical properties are effectively enhanced, with the dielectric permittivity of 40.4 (@102 Hz), dielectric loss of 0...
November 17, 2017: Nanotechnology
https://www.readbyqxmd.com/read/29147470/retrospective-analysis-of-inferior-vena-cava-collapsibility-with-point-of-care-ultrasound-and-urine-sodium-and-fena-in-patients-with-early-stage-acute-kidney-injury
#5
Faizan Babar, Gurkeerat Singh, Mustafa Noor, Bruce Sabath
Early stage acute kidney injury (AKI) is an independent risk factor for an increase in mortality. Accurate assessment of volume status is a major challenge during the early stages of acute renal injury. Determining volume status based on the history and physical exam lacks accuracy. Urine sodium and free excretion of sodium (FENa) provide objective evidence of intravascular volume status when interpreted carefully and is helpful to delineate prerenal from intrinsic renal failure. In recent years point of care ultrasound has been used to assess volume status...
2017: Journal of Community Hospital Internal Medicine Perspectives
https://www.readbyqxmd.com/read/29146933/coupled-motion-of-contact-line-on-nanoscale-chemically-heterogeneous-surfaces-for-improved-bubble-dynamics-in-boiling
#6
Arvind Jaikumar, Satish G Kandlikar
We demonstrate that the contact line (CL) motion on energetically heterogeneous solid surfaces occurs in a coupled fashion as against the traditional staggered stick-slip motion. Introducing chemical inhomogeneities at nanoscale induces a local change in dynamic contact angles which manifests as a smooth and continuous motion of the CL. Nanoscale chemically inhomogeneous surfaces comprising of gold, palladium and nickel were generated on copper substrates to demonstrate the underlying CL dynamics. The spatial variations of chemical constituents were mapped using elemental display scanning electron microscope images...
November 16, 2017: Scientific Reports
https://www.readbyqxmd.com/read/29146879/2-cl-mgv-1-ameliorates-apoptosis-in-the-thalamus-and-hippocampus-and-cognitive-deficits-after-cortical-infarct-in-rats
#7
Yicong Chen, Leo Veenman, Sukhdev Singh, Fubing Ouyang, Jiahui Liang, Weixian Huang, Ilan Marek, Jinsheng Zeng, Moshe Gavish
BACKGROUND AND PURPOSE: Focal cortical infarction causes neuronal apoptosis in the ipsilateral nonischemic thalamus and hippocampus, which is potentially associated with poststroke cognitive deficits. TSPO (translocator protein) is critical in regulating mitochondrial apoptosis pathways. We examined the effects of the novel TSPO ligand 2-(2-chlorophenyl)quinazolin-4-yl dimethylcarbamate (2-Cl-MGV-1) on poststroke cognitive deficits, neuronal mitochondrial apoptosis, and secondary damage in the ipsilateral thalamus and hippocampus after cortical infarction...
November 16, 2017: Stroke; a Journal of Cerebral Circulation
https://www.readbyqxmd.com/read/29146575/lumacaftor-vx-809-restores-the-ability-of-cf-macrophages-to-phagocytose-and-kill-pseudomonas-aeruginosa
#8
Roxanna Barnaby, Katja Koeppen, Amanda Nymon, Thomas H Hampton, Brent Berwin, Alix Ashare, Bruce Stanton
Cystic Fibrosis (CF), the most common lethal genetic disease in Caucasians, is characterized by chronic bacterial lung infection and excessive inflammation, which leads to progressive loss of lung function, and premature death. Although ivacaftor (VX-770) and the combination of ivacaftor and lumacaftor (VX-809) improve lung function in CF patients with the Gly551Asp and del508Phe mutation, respectively, the effects of these drugs on the function of human CF macrophages are unknown. Thus, studies were conducted to examine the effects of lumacaftor alone and in combination with ivacaftor (i...
November 16, 2017: American Journal of Physiology. Lung Cellular and Molecular Physiology
https://www.readbyqxmd.com/read/29146047/maternal-immune-activation-delays-excitatory-to-inhibitory-gamma-aminobutyric-acid-switch-in-offspring
#9
Irene Corradini, Elisa Focchi, Marco Rasile, Raffaella Morini, Genni Desiato, Romana Tomasoni, Michela Lizier, Elsa Ghirardini, Riccardo Fesce, Diego Morone, Isabella Barajon, Flavia Antonucci, Davide Pozzi, Michela Matteoli
BACKGROUND: The association between maternal infection and neurodevelopmental defects in progeny is well established, although the biological mechanisms and the pathogenic trajectories involved have not been defined. METHODS: Pregnant dams were injected intraperitoneally at gestational day 9 with polyinosinic:polycytidylic acid. Neuronal development was assessed by means of electrophysiological, optical, and biochemical analyses. RESULTS: Prenatal exposure to polyinosinic:polycytidylic acid causes an imbalanced expression of the Na(+)-K(+)-2Cl(-) cotransporter 1 and the K(+)-Cl(-) cotransporter 2 (KCC2)...
November 14, 2017: Biological Psychiatry
https://www.readbyqxmd.com/read/29145855/generation-of-a-platform-strain-for-ionic-liquid-tolerance-using-adaptive-laboratory-evolution
#10
Elsayed T Mohamed, Shizeng Wang, Rebecca M Lennen, Markus J Herrgård, Blake A Simmons, Steven W Singer, Adam M Feist
BACKGROUND: There is a need to replace petroleum-derived with sustainable feedstocks for chemical production. Certain biomass feedstocks can meet this need as abundant, diverse, and renewable resources. Specific ionic liquids (ILs) can play a role in this process as promising candidates for chemical pretreatment and deconstruction of plant-based biomass feedstocks as they efficiently release carbohydrates which can be fermented. However, the most efficient pretreatment ILs are highly toxic to biological systems, such as microbial fermentations, and hinder subsequent bioprocessing of fermentative sugars obtained from IL-treated biomass...
November 16, 2017: Microbial Cell Factories
https://www.readbyqxmd.com/read/29145426/buserelin-alleviates-chloride-transport-defect-in-human-cystic-fibrosis-nasal-epithelial-cells
#11
Marie-Laure Calvez, Nathalie Benz, Florentin Huguet, Aude Saint-Pierre, Elise Rouillé, Christelle Coraux, Claude Férec, Mathieu Kerbiriou, Pascal Trouvé
Cystic fibrosis (CF) is the most common autosomal recessive disease in Caucasians caused by mutations in the gene encoding the Cystic Fibrosis Transmembrane conductance Regulator (CFTR) chloride (Cl-) channel regulated by protein kinases, phosphatases, divalent cations and by protein-protein interactions. Among protein-protein interactions, we previously showed that Annexin A5 (AnxA5) binds to CFTR and is involved in the channel localization within membranes and in its Cl- channel function. The deletion of phenylalanine at position 508 (F508del) is the most common mutation in CF which leads to an altered protein (F508del-CFTR) folding with a nascent protein retained within the ER and is quickly degraded...
2017: PloS One
https://www.readbyqxmd.com/read/29145308/comparison-of-the-pentax-airwayscope-and-mcgrath-mac-videolaryngoscope-for-endotracheal-intubation-in-patients-with-a-normal-airway
#12
Jiyoung Lee, Hyun Jeong Kwak, Ji Yeon Lee, Min Young Chang, Sook Young Lee, Jong Yeop Kim
Various videolaryngoscopes (VLs) have been developed to provide a better laryngeal view and facilitate difficult intubations. The goal of this study was to compare 2 VLs, the Pentax AWS and the McGrath VL, with respect to intubation time and ease of intubation.One hundred forty patients aged 19 to 65 years (American Society of Anesthesiologists classification I or II), who required tracheal intubation for elective surgery, were randomly assigned to 1 of the 2 groups: the Pentax AWS (n = 70) or the McGrath VL (n = 70)...
November 2017: Medicine (Baltimore)
https://www.readbyqxmd.com/read/29145081/elimination-of-chlorine-refractory-carbamazepine-by-breakpoint-chlorination-reactive-species-and-oxidation-byproducts
#13
Wen-Long Wang, Qian-Yuan Wu, Ye Du, Nan Huang, Hong-Ying Hu
Breakpoint chlorination can be commonly observed in the chlorination of water treatments when ammonia is present. In this study, it was found that breakpoint chlorination can remarkably eliminate a ubiquitous and chlorine-refractory micropollutant, carbamazepine (CBZ), with the removal of 72% at neutral condition. At neutral pH, low CBZ elimination was observed at a chlorine/ammonia molar ratio (Cl/N) of 1.0 and higher CBZ elimination was observed as Cl/N ratio increased from 1.0 to 1.6 (breakpoint), indicating that CBZ elimination was closely related to the generation and decomposition of chloramines...
November 7, 2017: Water Research
https://www.readbyqxmd.com/read/29144763/iron-catalyzed-indolizine-synthesis-from-pyridines-diazo-compounds-and-alkynes
#14
Tim Douglas, Anca Pordea, James Dowden
The iron(III)-catalyzed synthesis of indolizines from commercially available alkyne, pyridine, and diazo precursors is reported. This mild, expedient method is tolerant of various solvents and proceeds with as little as 0.25 mol % [Fe(TPP)Cl]. Significantly, this multicomponent reaction is compatible with electrophilic alkynes; control experiments demonstrate the importance of the catalyst in promoting pyridinium ylide formation over background reactivity.
November 16, 2017: Organic Letters
https://www.readbyqxmd.com/read/29144560/large-proton-affinity-enhancements-triggered-by-non-covalent-interactions
#15
Carlos Martín-Fernández, M Merced Montero-Campillo, Ibon Alkorta, Manuel Yáñez, Otilia Mó, José Elguero
The proton affinity of the hydroxyl group of a series of compounds YHxOH (x=0-3, Y = Li, Na, Be, Mg, B, Al, Si, P, S, Cl, H) always increases upon interaction with Lewis bases LB = NH3, H2CNH, HCN, according to electronic structure calculations carried out at the G4 level of theory. The LB:YHxOH complexes experiment proton affinity enhancements from 24.8 to 304.8 kJ·mol-1 on its OH group with respect to the free compounds. This enhancement is related to the ability of these YHxOH compounds, acting as Lewis acids, to form non-covalent interactions of different kinds...
November 16, 2017: Chemistry: a European Journal
https://www.readbyqxmd.com/read/29144280/selective-ion-permeation-through-strained-and-charged-graphene-membranes
#16
Kun Li, Yi Tao, Zhongwu Li, Jingjie Sha, Yunfei Chen
By means of molecular dynamics (MD) simulations and density functional theory (DFT) calculations, we demonstrate that stretched and charged graphene can act as ion sieve membranes. It is observed that loading 30% strain on graphene can induce pores in the dense electron cloud to allow ions to pass through the aromatic rings. Meanwhile, charged surface is helpful to peel the hydration layers from the ions and decrease the energy barrier for ion translocation through nanopores. Our results suggest that with membrane charge density of 6...
November 16, 2017: Nanotechnology
https://www.readbyqxmd.com/read/29143559/k-cl-co-transporter-2-kcc2-a-membrane-trafficking-perspective
#17
Bor Luen Tang
K(+)-Cl(-) co-transporter 2 (KCC2/SLC12A5) is a neuronal specific cation chloride co-transporter which is active under isotonic conditions, and thus a key regulator of intracellular Cl(-) levels. It also has an ion transporter-independent structural role in modulating the maturation and regulation of excitatory glutamatergic synapses. KCC2 levels are developmentally regulated, and a postnatal upregulation of KCC2 generates a low intracellular chloride concentration that allows the neurotransmitters γ-aminobutyric acid (GABA) and glycine to exert inhibitory neurotransmission through its Cl(-) permeating channel...
November 16, 2017: Molecular Membrane Biology
https://www.readbyqxmd.com/read/29143340/k2p-task-2-and-kcnq1-kcne3-k-channels-are-major-players-contributing-to-intestinal-anion-and-fluid-secretion
#18
Francisca Julio-Kalajzić, Sandra Villanueva, Johanna Burgos, Margarita Ojeda, L Pablo Cid, Thomas J Jentsch, Francisco V Sepúlveda
Anion and fluid secretion across the intestinal epithelium, a process altered in cystic fibrosis and secretory diarrhoea, is mediated by cAMP-activated CFTR Cl(-) channels and requires the simultaneous activity of basolateral K(+) channels to maintain cellular ionic homeostasis and membrane potential. This function is fulfilled by the cAMP-activated K(+) channel formed by the association of pore-forming KCNQ1 with its obligatory KCNE3 β-subunit. Studies using mice show sizable cAMP-activated intestinal anion secretion in the absence of either KCNQ1 or KCNE3 suggesting that an alternative K(+) conductance must compensate for the loss of KCNQ1/KCNE3 activity...
November 16, 2017: Journal of Physiology
https://www.readbyqxmd.com/read/29143019/half-sandwich-ruthenium-ii-complexes-containing-n-n-chelated-imino-pyridyl-ligands-that-are-selectively-toxic-to-cancer-cells
#19
Meng Tian, Juanjuan Li, Shumiao Zhang, Lihua Guo, Xiangdong He, Deliang Kong, Hairong Zhang, Zhe Liu
Chemotherapy is limited by its poor selectivity towards cancer cells over normal cells. Herein, we designed half-sandwich ruthenium imino-pyridyl complexes [(η(6)-bz)Ru(N^N)Cl]PF6 to achieve selective cytotoxicity to cancer cells. This kind of ruthenium complex has unique characteristics and is worthy of further exploration in the design of new anticancer drugs.
November 16, 2017: Chemical Communications: Chem Comm
https://www.readbyqxmd.com/read/29142819/liposomes-modified-with-cardiolipin-can-act-as-a-platform-to-regulate-the-potential-flux-of-nadp-dependent-isocitrate-dehydrogenase
#20
Keishi Suga, Akari Hamasaki, Junpei Chinzaka, Hiroshi Umakoshi
Cardiolipin (CL) is a phospholipid found in the outer mitochondrial membrane (OMM) and inner mitochondrial membrane (IMM) in animal cells. Isocitrate dehydrogenase (ICDH) is an important catalytic enzyme that is localized at the cytosol and mitochondria; the metabolic pathway catalyzed by ICDH differs between the OMM and IMM. To estimate the possible role of lipid membrane in the enzymatic activity of NADP(+)-dependent ICDH, CL-modified liposomes were prepared using CL/1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC)/cholesterol (Ch), and their characteristics were analyzed based on the fluorescent probe method...
December 2016: Metabolic Engineering Communications
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