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https://www.readbyqxmd.com/read/28494999/modeling-and-control-of-operator-functional-state-in-a-unified-framework-of-fuzzy-inference-petri-nets
#1
Jian-Hua Zhang, Jia-Jun Xia, Jonathan M Garibaldi, Petros P Groumpos, Ru-Bin Wang
BACKGROUND AND OBJECTIVE: In human-machine (HM) hybrid control systems, human operator and machine cooperate to achieve the control objectives. To enhance the overall HM system performance, the discrete manual control task-load by the operator must be dynamically allocated in accordance with continuous-time fluctuation of psychophysiological functional status of the operator, so-called operator functional state (OFS). The behavior of the HM system is hybrid in nature due to the co-existence of discrete task-load (control) variable and continuous operator performance (system output) variable...
June 2017: Computer Methods and Programs in Biomedicine
https://www.readbyqxmd.com/read/28451130/nanorings-with-copper-ii-and-zinc-ii-centers-forcing-copper-porphyrins-to-bind-axial-ligands-in-heterometallated-oligomers
#2
Jonathan Cremers, Sabine Richert, Dmitry V Kondratuk, Tim D W Claridge, Christiane R Timmel, Harry L Anderson
The affinity of copper(ii) porphyrins for pyridine ligands is extremely weak, but oligo-pyridine templates can be used to direct the synthesis of Cu-containing cyclic porphyrin oligomers when they also have Zn centers. We report the synthesis of two heterometallated nanorings: a six-porphyrin ring prepared from a Zn/Cu/Zn linear trimer and a ten-porphyrin ring prepared from a Zn/Zn/Cu/Zn/Zn pentamer. Both these macrocycles have copper porphyrins at two specific positions across the diameter of the ring and zinc at other sites...
December 1, 2016: Chemical Science
https://www.readbyqxmd.com/read/28387507/subtle-structural-changes-in-cu-ii-l-2mn-ii-complexes-to-induce-heterometallic-cooperative-catalytic-oxidase-activities-on-phenolic-substrates-h2l-salen-type-unsymmetrical-schiff-base
#3
Prithwish Mahapatra, Soumavo Ghosh, Sanjib Giri, Vinayak Rane, Ramakant Kadam, Michael G B Drew, Ashutosh Ghosh
A new Cu(II) complex of an asymmetrically dicondensed Schiff base (H2L = N-(2-hydroxyacetophenylidene)-N'-salicylidene-1,3-propanediamine) derived from 1,3-propanediamine, salicylaldehyde, and o-hydroxyacetophenone has been synthesized. Using this complex, [CuL] (1), as a metalloligand, two new trinuclear Cu-Mn complexes, [(CuL)2Mn(N3)(H2O)](ClO4)·H2O (2) and [(CuL)2Mn(NCS)2] (3), have been prepared. Single-crystal structural analyses reveal that complexes 2 and 3 both have the same bent trinuclear {(CuL)2Mn}(2+) structural unit in which two terminal bidentate square-planar (CuL) units are chelated to the central octahedral Mn(II) ion...
April 7, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28379004/cation-binding-to-xanthorhodopsin-electron-paramagnetic-resonance-and-magnetic-studies
#4
Elena Smolensky Koganov, Gregory Leitus, Rinat Rozin, Lev Weiner, Noga Friedman, Mordechai Sheves
Xanthorhodopsin (xR) is a member of the retinal protein family and acts as a proton pump in the cell membranes of the extremely halophilic eubacterium Salinibacter ruber. In addition to the retinal chromophore, xR contains a carotenoid, which acts as a light-harvesting antenna as it transfers 40% of the quanta it absorbs to the retinal. Our previous studies have shown that the CD and absorption spectra of xR are dramatically affected due to the protonation of two different residues. It is still unclear whether xR can bind cations...
May 4, 2017: Journal of Physical Chemistry. B
https://www.readbyqxmd.com/read/28315749/integrated-structural-biology-to-unravel-molecular-mechanisms-of-protein-rna-recognition
#5
REVIEW
Andreas Schlundt, Jan-Niklas Tants, Michael Sattler
Recent advances in RNA sequencing technologies have greatly expanded our knowledge of the RNA landscape in cells, often with spatiotemporal resolution. These techniques identified many new (often non-coding) RNA molecules. Large-scale studies have also discovered novel RNA binding proteins (RBPs), which exhibit single or multiple RNA binding domains (RBDs) for recognition of specific sequence or structured motifs in RNA. Starting from these large-scale approaches it is crucial to unravel the molecular principles of protein-RNA recognition in ribonucleoprotein complexes (RNPs) to understand the underlying mechanisms of gene regulation...
March 16, 2017: Methods: a Companion to Methods in Enzymology
https://www.readbyqxmd.com/read/28293947/water-solubilizing-hydrophobic-znaginse-zns-qds-with-tumor-targeted-crgd-sulfobetaine-pima-histamine-ligands-via-a-self-assembly-strategy-for-bioimaging
#6
Tao Deng, Yanan Peng, Rong Zhang, Jie Wang, Jie Zhang, Yueqing Gu, Dechun Huang, Dawei Deng
Exploring the organic-to-aqueous phase transfer of quantum dots (QDs) is significant for achieving their versatile applications in biomedical fields. In this thematic issue, surface modification, size control, and biocompatibility of QDs and QDs-based nanocomposites are core problems. Herein, the new highly fluorescent tumor-targeted QDs-clusters consisting of ZnAgInSe/ZnS (ZAISe/ZnS) QDs and sulfobetaine-PIMA-histamine (SPH) polymer with the ανβ3 integrin receptor cyclic RGD (c-RGD) were developed via ligand exchange and an accompanying self-assembly process...
March 23, 2017: ACS Applied Materials & Interfaces
https://www.readbyqxmd.com/read/28263437/hierarchical-growth-of-supramolecular-structures-driven-by-pimerization-of-tetrahedrally-arranged-bipyridinium-units
#7
Marianna Marchini, Massimo Baroncini, Giacomo Bergamini, Paola Ceroni, Mila D'Angelantonio, Paola Franchi, Marco Lucarini, Fabrizia Negri, Tomasz Szreder, Margherita Venturi
A shape-persistent molecule, featuring four bipyridinium units, has been synthesized that upon reduction undergoes intermolecular pimerization because of the rigid architecture of the molecule. The pimerization process has been investigated by a variety of techniques, such as absorption measurements, EPR spectroscopy, as well as gamma and pulse radiolysis, and compared with the behavior of a model compound. Computational studies have also been performed to support the experimental data. The most interesting feature of the tetramer is that pimerization occurs only above a threshold concentration of monoreduced species, on the contrary to the model compound...
March 6, 2017: Chemistry: a European Journal
https://www.readbyqxmd.com/read/27549247/a-dicobalt-complex-with-an-unsymmetrical-quinonoid-bridge-isolated-in-three-units-of-charge-a-combined-structural-spectro-electrochemical-magnetic-and-spectroscopic-study
#8
Margarethe van der Meer, Yvonne Rechkemmer, Uta Frank, Frauke D Breitgoff, Stephan Hohloch, Cheng-Yong Su, Petr Neugebauer, Raphael Marx, María Dörfel, Joris van Slageren, Biprajit Sarkar
Quinonoid ligands are excellent bridges for generating redox-rich dinuclear assemblies. A large majority of these bridges are symmetrically substituted, with examples of unsymmetrically substituted quinonoid bridges being extremely rare. We present here a dicobalt complex in its various redox states with an unsymmetrically substituted quinonoid bridging ligand. Two homovalent forms and one mixed-valent form have been isolated and characterized by single crystal X-ray diffraction. The complex displays a large comproportionation constant for the mixed-valent state which is three orders of magnitude higher than that observed for the analogous complex with a symmetrically substituted bridge...
September 19, 2016: Chemistry: a European Journal
https://www.readbyqxmd.com/read/27246459/crystal-structure-analysis-of-the-repair-of-iron-centers-protein-ytfe-and-its-interaction-with-no
#9
Feng-Chun Lo, Chang-Chih Hsieh, Manuel Maestre-Reyna, Chin-Yu Chen, Tzu-Ping Ko, Yih-Chern Horng, Yei-Chen Lai, Yun-Wei Chiang, Chih-Mao Chou, Cheng-Hung Chiang, Wei-Ning Huang, Yi-Hung Lin, D Scott Bohle, Wen-Feng Liaw
Molecular mechanisms underlying the repair of nitrosylated [Fe-S] clusters by the microbial protein YtfE remain poorly understood. The X-ray crystal structure of YtfE, in combination with EPR, magnetic circular dichroism (MCD), UV, and (17) O-labeling electron spin echo envelope modulation measurements, show that each iron of the oxo-bridged Fe(II) -Fe(III) diiron core is coordinatively unsaturated with each iron bound to two bridging carboxylates and two terminal histidines in addition to an oxo-bridge. Structural analysis reveals that there are two solvent-accessible tunnels, both of which converge to the diiron center and are critical for capturing substrates...
July 4, 2016: Chemistry: a European Journal
https://www.readbyqxmd.com/read/27207587/the-h-bond-network-surrounding-the-pyranopterins-modulates-redox-cooperativity-in-the-molybdenum-bispgd-cofactor-in-arsenite-oxidase
#10
Simon Duval, Joanne M Santini, David Lemaire, Florence Chaspoul, Michael J Russell, Stephane Grimaldi, Wolfgang Nitschke, Barbara Schoepp-Cothenet
While the molybdenum cofactor in the majority of bisPGD enzymes goes through two consecutive 1-electron redox transitions, previous protein-film voltammetric results indicated the possibility of cooperative (n=2) redox behavior in the bioenergetic enzyme arsenite oxidase (Aio). Combining equilibrium redox titrations, optical and EPR spectroscopies on concentrated samples obtained via heterologous expression, we unambiguously confirm this claim and quantify Aio's redox cooperativity. The stability constant, Ks, of the Mo(V) semi-reduced intermediate is found to be lower than 10(-3)...
September 2016: Biochimica et Biophysica Acta
https://www.readbyqxmd.com/read/27192943/exceptional-photosensitivity-of-a-polyoxometalate-based-charge-transfer-hybrid-material
#11
Jian-Zhen Liao, Chen Wu, Xiao-Yuan Wu, Shui-Quan Deng, Can-Zhong Lu
An unusual room-temperature light sensitivity was realized in a polyoxometalate-based hybrid material due to cooperative multicomponent molecular charge-transfer interactions taking place in this material, mainly among POMs, NDIs, and other molecules. The functional π-acidic NDI linkers and POM clusters in the discussed hybrid material were individually designed as photosensors and electron reservoirs. To propose a photo-induced charge-transfer mechanism, EPR, XPS, UV-Vis and computational studies were carried out, and indicated the presence of active charge-transfer interactions among several of the components...
May 31, 2016: Chemical Communications: Chem Comm
https://www.readbyqxmd.com/read/27138102/divergent-assembly-mechanisms-of-the-manganese-iron-cofactors-in-r2lox-and-r2c-proteins
#12
Yuri Kutin, Vivek Srinivas, Matthieu Fritz, Ramona Kositzki, Hannah S Shafaat, James Birrell, Eckhard Bill, Michael Haumann, Wolfgang Lubitz, Martin Högbom, Julia J Griese, Nicholas Cox
A manganese/iron cofactor which performs multi-electron oxidative chemistry is found in two classes of ferritin-like proteins, the small subunit (R2) of class Ic ribonucleotide reductase (R2c) and the R2-like ligand-binding oxidase (R2lox). It is unclear how a heterodimeric Mn/Fe metallocofactor is assembled in these two related proteins as opposed to a homodimeric Fe/Fe cofactor, especially considering the structural similarity and proximity of the two metal-binding sites in both protein scaffolds and the similar first coordination sphere ligand preferences of Mn(II) and Fe(II)...
April 16, 2016: Journal of Inorganic Biochemistry
https://www.readbyqxmd.com/read/27104767/cyanide-scavenging-by-a-cobalt-schiff-base-macrocycle-a-cost-effective-alternative-to-corrinoids
#13
Elisenda Lopez-Manzano, Andrea A Cronican, Kristin L Frawley, Jim Peterson, Linda L Pearce
The complex of cobalt(II) with the ligand 2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]heptadeca-1(17)2,11,13,15-pentaene (CoN4[11.3.1]) has been shown to bind two molecules of cyanide in a cooperative fashion with an association constant of 2.7 (±0.2) × 10(5). In vivo, irrespective of whether it is initially administered as the Co(II) or Co(III) cation, EPR spectroscopic measurements on blood samples show that at physiological levels of reductant (principally ascorbate) CoN4[11.3.1] becomes quantitatively reduced to the Co(II) form...
June 20, 2016: Chemical Research in Toxicology
https://www.readbyqxmd.com/read/26618248/transition-metal-free-self-hydrogen-transferring-allylic-isomerization
#14
Hong-Xing Zheng, Zu-Feng Xiao, Chuan-Zhi Yao, Qiang-Qiang Li, Xiao-Shan Ning, Yan-Biao Kang, Yong Tang
Phenanthroline and tert-butoxide have been established as powerful radical initiators in reactions such as the SRN1-type coupling reactions due to the cooperation of large heteroarenes and a special feature of tert-butoxide. The first phenanthroline-tert-butoxide-catalyzed transition-metal-free allylic isomerization is described. The resulting ketones are key intermediates for indenes. The control experiments rule out the base-promoted allylic anion pathway. The radical pathway is supported by experimental evidence that includes kinetic study, kinetic isotope effect, isotope-labeling experiments, trapping experiments, and EPR experiments...
December 18, 2015: Organic Letters
https://www.readbyqxmd.com/read/26577473/a-generalized-architecture-of-quantum-secure-direct-communication-for-n-disjointed-users-with-authentication
#15
Ahmed Farouk, Magdy Zakaria, Adel Megahed, Fatma A Omara
In this paper, we generalize a secured direct communication process between N users with partial and full cooperation of quantum server. So, N - 1 disjointed users u1, u2, …, uN-1 can transmit a secret message of classical bits to a remote user uN by utilizing the property of dense coding and Pauli unitary transformations. The authentication process between the quantum server and the users are validated by EPR entangled pair and CNOT gate. Afterwards, the remained EPR will generate shared GHZ states which are used for directly transmitting the secret message...
2015: Scientific Reports
https://www.readbyqxmd.com/read/26508306/synergistic-anti-tumor-therapy-by-a-comb-like-multifunctional-antibody-nanoarray-with-exceptionally-potent-activity
#16
Huafei Li, Yun Sun, Di Chen, He Zhao, Mengxin Zhao, Xiandi Zhu, Changhong Ke, Ge Zhang, Cheng Jiang, Li Zhang, Fulei Zhang, Huafeng Wei, Wei Li
Simultaneously blocking multiple mediators offers new hope for the treatment of complex diseases. However, the curative potential of current combination therapy by chronological administration of separate monoclonal antibodies (mAbs) or multi-specific mAbs is still moderate due to inconvenient manipulation, low cooperative effectors, poor pharmacokinetics and insufficient tumor accumulation. Here, we describe a facile strategy that arms distinct mAbs with cooperative effectors onto a long chain to form a multicomponent comb-like nano mAb...
2015: Scientific Reports
https://www.readbyqxmd.com/read/26416772/correction-assessing-dimerisation-degree-and-cooperativity-in-a-biomimetic-small-molecule-model-by-pulsed-epr
#17
K Ackermann, A Giannoulis, D B Cordes, A M Z Slawin, B E Bode
Correction for 'Assessing dimerisation degree and cooperativity in a biomimetic small-molecule model by pulsed EPR' by K. Ackermann et al., Chem. Commun., 2015, 51, 5257-5260.
October 28, 2015: Chemical Communications: Chem Comm
https://www.readbyqxmd.com/read/26280846/bimetallic-complexes-supported-by-a-redox-active-ligand-with-fused-pincer-type-coordination-sites
#18
Denan Wang, Sergey V Lindeman, Adam T Fiedler
The remarkable chemistry of mononuclear complexes featuring tridentate, meridionally chelating "pincer" ligands has stimulated the development of ligand frameworks containing multiple pincer sites. Here, the coordination chemistry of a novel pentadentate ligand (L(N3O2)) that provides two closely spaced NNO pincer-type compartments fused together at a central diarylamido unit is described. The trianionic L(N3O2) chelate supports homobimetallic structures in which each M(II) ion (M = Co, Cu, Zn) is bound in a meridional fashion by the bridging diarylamido N atom and O,N-donors of the salicyaldimine arms...
September 8, 2015: Inorganic Chemistry
https://www.readbyqxmd.com/read/26185962/chiral-bimetallic-catalysts-derived-from-chiral-metal-phosphates-enantioselective-three-component-asymmetric-aza-diels-alder-reactions-of-cyclic-ketones
#19
Yongming Deng, Chamini V Karunaratne, Erika Csatary, David L Tierney, Kraig Wheeler, Hong Wang
A new type of chiral bimetallic catalyst is disclosed. These chiral bimetallic catalysts are easily formed through mixing a metal Lewis acid and a metal binaphthyl phosphate (MLA/M[P]3) in solution. (1)H and (31)P NMR spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, and X-ray crystallographic analysis reveal a bimetallic structure of the Y(Yb)(III)/Y[P]3 complexes with bridging binaphthyl phosphate ligands...
August 21, 2015: Journal of Organic Chemistry
https://www.readbyqxmd.com/read/26030841/cobalt-catalyzed-2%C3%AF-2%C3%AF-cycloadditions-of-alkenes-scope-mechanism-and-elucidation-of-electronic-structure-of-catalytic-intermediates
#20
Valerie A Schmidt, Jordan M Hoyt, Grant W Margulieux, Paul J Chirik
Aryl-substituted bis(imino)pyridine cobalt dinitrogen compounds, ((R)PDI)CoN2, are effective precatalysts for the intramolecular [2π + 2π] cycloaddition of α,ω-dienes to yield the corresponding bicyclo[3.2.0]heptane derivatives. The reactions proceed under mild thermal conditions with unactivated alkenes, tolerating both amine and ether functional groups. The overall second order rate law for the reaction, first order with respect to both the cobalt precatalyst and the substrate, in combination with electron paramagnetic resonance (EPR) spectroscopic studies established the catalyst resting state as dependent on the identity of the precatalyst and diene substrate...
June 24, 2015: Journal of the American Chemical Society
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