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Sebastián Miranda-Rojas, Paulina Sierra-Rosales, Alvaro Muñoz-Castro, Ramiro Arratia-Pérez, José Heráclito Zagal, Fernando Mendizábal
The need of deeper insights regarding the inner working of catalysts represents a current challenge in the search of new ways to tune their activities towards new chemical transformations. Within this field, metallophthalocyanines-based (MPc) electrocatalysis has gained tremendous attention due to their versatility, low cost, great stability and excellent turn-over properties. In this concern, here we present a quantum chemical study of the formation of supramolecular complexes based on the adsorption of MPcs on gold substrates, and the effect of the substrate on their electrocatalytic properties...
October 17, 2016: Physical Chemistry Chemical Physics: PCCP
C Barraud, K Bouzehouane, C Deranlot, D J Kim, R Rakshit, S Shi, J Arabski, M Bowen, E Beaurepaire, S Boukari, F Petroff, P Seneor, R Mattana
Molecular spintronics is an effervescent field of research, which aims at combining spin physics and molecular nano-objects. In this article, we show that phthalocyanine molecules integrated in magnetic tunnel junctions (MTJs) can lead to magnetoresistance effects of different origins. We have investigated cobalt and manganese phthalocyanine molecule based magnetic tunnel junctions. CoPc MTJs exhibit both tunneling magnetoresistance (TMR) and tunneling anisotropic magnetoresistance (TAMR) effects of similar magnitude...
October 4, 2016: Dalton Transactions: An International Journal of Inorganic Chemistry
William Maixner, Roger B Fillingim, David A Williams, Shad B Smith, Gary D Slade
UNLABELLED: There is increasing recognition that many if not most common chronic pain conditions are heterogeneous with a high degree of overlap or coprevalence of other common pain conditions along with influences from biopsychosocial factors. At present, very little attention is given to the high degree of overlap of many common pain conditions when recruiting for clinical trials. As such, many if not most patients enrolled into clinical studies are not representative of most chronic pain patients...
September 2016: Journal of Pain: Official Journal of the American Pain Society
Zhen Song, Jinlong Dong, Wen Yuan, Caifeng Zhang, Yuehong Ren, Binsheng Yang
In this work, the mutant A85M of CopC was obtained. The stability of mutant A85M of CopC and the binding properties of metal ions were clarified through various spectroscopic techniques. The binding capacity of A85M to metal ions was measured by fluorescence spectroscopy and UV differential absorbance. The results suggested that Cu(2+) can bind with A85M in 1:1 form, and the constant of A85M was nearly the same as that of CopC. Ag(+) can occupy the Cu(+) binding site located at C-terminal, and the binding constant was (2...
August 2016: Journal of Photochemistry and Photobiology. B, Biology
Emilia Annese, Carlos E ViolBarbosa, Giorgio Rossi, Jun Fujii
We investigated the growth and electronic properties of Co-phthalocyanine (CoPc) molecule deposited on iron film with different structures (pseudomorph-fcc and bcc) and on iron nanowires by scanning tunnelling microscopy and X-ray absorption spectroscopy (XAS). CoPc molecules self-assemble in a two-dimensional (2D) arrangement with the molecular plane parallel to the iron surfaces, and the local order is lost after the first layer. The molecule-ferromagnet interaction causes the broadening of Co and N unoccupied molecular states as well as different electronic distribution of N states as a function of the atomic structure of iron surface...
May 31, 2016: Langmuir: the ACS Journal of Surfaces and Colloids
Jung Hwa Lee, Yoshito Kishi
One-pot ketone synthesis has been developed with in situ activation of alkyl halides to alkylzinc halides in the presence of thioesters and Pd-catalyst. The new method provides us with a reliable option for a coupling at a late stage in a convergent synthesis of complex molecules, with use of a near 1:1 molar ratio of coupling partners. First, two facile, orthogonal methods have been developed for preparation of alkylzinc halides: (1) direct insertion of zinc dust to 1°- and 2°-alkyl halides in the presence of LiI in DMI and (2) early transition-metal assisted activation of alkyl halides via a single electron transfer (SET) process...
June 8, 2016: Journal of the American Chemical Society
Laise Nayra Dos Santos Pereira, Iranaldo Santos da Silva, Thaylan Pinheiro Araújo, Auro Atsushi Tanaka, Lúcio Angnes
Batch injection analysis (BIA) with amperometric detection, using a pyrolytic graphite electrode modified with cobalt phthalocyanine (PG/CoPc), was employed for determination of α-lipoic acid (ALA) in pharmaceutical product and in synthetic urine samples. The proposed BIA method is based on the application of a potential of +0.9V vs. Ag/AgCl, KCl sat, enabling quantification of ALA over a concentration range from 1.3×10(-6) to 1.0×10(-4)molL(-1), with a detection limit of 1.5×10(-8)molL(-1). A sampling rate of 180 injections per hour was attained and measurements of the reproducibility of successive injections (100µmolL(-1) ALA on the same electrode) showed a RSD of 2...
July 1, 2016: Talanta
Kan Takahashi, Mamoru Satoh, Yuji Takahashi, Takuya Osaki, Takahito Nasu, Makiko Tamada, Hitoshi Okabayashi, Motoyuki Nakamura, Yoshihiro Morino
CAVD (calcific aortic valve disease) is the defining feature of AS (aortic stenosis). The present study aimed to determine whether expression of ossification-related miRNAs is related to differentiation intro COPCs (circulating osteogenic progenitor cells) in patients with CAVD. The present study included 46 patients with AS and 46 controls. Twenty-nine patients underwent surgical AVR (aortic valve replacement) and 17 underwent TAVI (transcatheter aortic valve implantation). The number of COPCs was higher in the AS group than in the controls (P<0...
July 1, 2016: Clinical Science (1979-)
Xinxin Li, Yonggen Zhang, Peiqiang Yu
The primary objective of this study was to develop a model to predict Cornell Net Carbohydrate Protein System (CNCPS) protein degradation and digestion based on protein molecular structure changes induced by bio-energy processing in different types of co-products (CoPR, CoPC, CoPS = co-products from bioprocessing of rapeseed, canola seed, and soybean, respectively). The results showed that the inherent structure changes induced by the processing had a close relationship with CNCPS predicted protein degradable, undegradable, and digestible contents...
May 25, 2016: Journal of Agricultural and Food Chemistry
Marco Caputo, Mirko Panighel, Simone Lisi, Lama Khalil, Giovanni Di Santo, Evangelos Papalazarou, Andrzej Hruban, Marcin Konczykowski, Lia Krusin-Elbaum, Ziya S Aliev, Mahammad B Babanly, Mikhail M Otrokov, Antonio Politano, Evgueni V Chulkov, Andrés Arnau, Vera Marinova, Pranab K Das, Jun Fujii, Ivana Vobornik, Luca Perfetti, Aitor Mugarza, Andrea Goldoni, Marino Marsi
Topological insulators are a promising class of materials for applications in the field of spintronics. New perspectives in this field can arise from interfacing metal-organic molecules with the topological insulator spin-momentum locked surface states, which can be perturbed enhancing or suppressing spintronics-relevant properties such as spin coherence. Here we show results from an angle-resolved photemission spectroscopy (ARPES) and scanning tunnelling microscopy (STM) study of the prototypical cobalt phthalocyanine (CoPc)/Bi2Se3 interface...
June 8, 2016: Nano Letters
Thomas J Lawton, Grace E Kenney, Joseph D Hurley, Amy C Rosenzweig
The CopC proteins are periplasmic copper binding proteins believed to play a role in bacterial copper homeostasis. Previous studies have focused on CopCs that are part of seven-protein Cop or Pco systems involved in copper resistance. These canonical CopCs contain distinct Cu(I) and Cu(II) binding sites. Mounting evidence suggests that CopCs are more widely distributed, often present only with the CopD inner membrane protein, frequently as a fusion protein, and that the CopC and CopD proteins together function in the uptake of copper to the cytoplasm...
April 19, 2016: Biochemistry
Julian G West, David Huang, Erik J Sorensen
The dehydrogenation of unactivated alkanes is an important transformation both in industrial and biological systems. Recent efforts towards this reaction have revolved around high temperature, organometallic C-H activation by noble metal catalysts that produce alkenes and hydrogen gas as the sole products. Conversely, natural desaturase systems proceed through stepwise hydrogen atom transfer at physiological temperature; however, these transformations require a terminal oxidant. Here we show combining tetra-n-butylammonium decatungstate (TBADT) and cobaloxime pyridine chloride (COPC) can catalytically dehydrogenate unactivated alkanes and alcohols under near-UV irradiation at room temperature with hydrogen as the sole by-product...
2015: Nature Communications
Grażyna Antczak, Wojciech Kamiński, Agata Sabik, Christopher Zaum, Karina Morgenstern
We used time-lapsed scanning tunneling microscopy between 43 and 50 K and density functional theory (DFT) to explore the basic surface diffusion steps of cobalt phthalocyanine (CoPc) molecules on the Ag(100) surface. We show that the CoPc molecules translate and rotate on the surface in the same temperature range. Both processes are associated with similar activation energies; however, the translation is more frequently observed. Our DFT calculations provide the activation energies for the translation of the CoPc molecule between the nearest hollow sites and the rotation at both the hollow and the bridge sites...
December 2, 2015: Journal of the American Chemical Society
Wei-Dong Dou, Shu-Ping Huang, Chun-Sing Lee
Interfacial electronic structures of copper-phthalocyanine (CuPc), cobalt-phthalocyanine (CoPc), and graphene were investigated experimentally by using photoelectron spectroscopy. While the CuPc/graphene interface shows flat band structure and negligible interfacial dipole indicating quite weak molecule-substrate interaction, the CuPc/CoPc/graphene interface shows a large interfacial dipole and obvious energy level bending. Controlled experiments ruled out possible influences from the change in film structure of CuPc and pure π-π interaction between CoPc and CuPc...
October 7, 2015: Journal of Chemical Physics
Zhenfu Huang, Yuyuan Yao, Jiateng Lu, Chenhui Chen, Wangyang Lu, Sanqing Huang, Wenxing Chen
The design of catalytic oxidation processes with high efficiency has attracted considerable attention for a long while in environmental catalysis. In this work, a novel oxidation system, CFs-CoPc/PMS, was developed by coupling cellulosic fibers-bonded cobalt phthalocyanine (CFs-CoPc) with peroxymonosulfate (PMS). CFs-CoPc/PMS system could effectively decolorize azo dyes such as Acid Red 1 (AR1) with almost 100% decolorization efficiency in 35 min, suggesting that the CFs-CoPc/PMS system was a highly efficient oxidation process...
January 15, 2016: Journal of Hazardous Materials
Zhen Song, Jie Ming, Binsheng Yang
In this work, results of studies on the interactions of CopC and its mutants with the cationic surfactant Cetyltrimethyl Ammonium Bromide (CTAB) monitored by fluorescence spectroscopy, far- UV circular dichroism (CD) and fluorescence lifetime have been presented and discussed. The interaction of CTAB with CopC leads to stabilize a second intermediate, which is considered that the structure of C-terminal was unfolded completely and the structure of the N-terminal was partially unfolded. Notably, GdnHCl leads to refolding of the second intermediate and form the first intermediate, which has also been found on unfolding of CopC by sodium dodecyl sulfate (SDS)...
2015: Protein and Peptide Letters
Jian Zhou, Qian Wang, Qiang Sun, Yoshiyuki Kawazoe, Puru Jena
Motivated by the recent success in synthesizing two-dimensional Fe-phthalocyanine (poly-FePc) porous sheets, we studied strain-induced spin crossover in poly-TMPc (TM = Mn, Fe, Co, and Ni) systems by using first-principle calculations based on density functional theory. A small amount of biaxial tensile strain is found to not only significantly enhance the magnetic moment of the central TM atoms by 2 μB when the strain reaches a critical value, but also the systems undergo low-spin (LS) to high-spin (HS) transition...
November 1, 2012: Journal of Physical Chemistry Letters
Ashwini Kumar, Soumen Samanta, Ajay Singh, Mainak Roy, Surendra Singh, Saibal Basu, Mohmad M Chehimi, Kallol Roy, Niranjan Ramgir, M Navaneethan, Y Hayakawa, Anil K Debnath, Dinesh K Aswal, Shiv K Gupta
The room temperature chemiresistive response of n-type ZnO nanowire (ZnO NWs) films modified with different thicknesses of p-type cobalt phthalocyanine (CoPc) has been studied. With increasing thickness of CoPc (>15 nm), heterojunction films exhibit a transition from n- to p-type conduction due to uniform coating of CoPc on ZnO. The heterojunction films prepared with a 25 nm thick CoPc layer exhibit the highest response (268% at 10 ppm of H2S) and the fastest response (26 s) among all samples. The X-ray photoelectron spectroscopy and work function measurements reveal that electron transfer takes place from ZnO to CoPc, resulting in formation of a p-n junction with a barrier height of 0...
August 19, 2015: ACS Applied Materials & Interfaces
Jingcheng Li, Bin Li, Yu Wang, Aidi Zhao, Bing Wang
We investigate the modification of electronic properties of single cobalt phthalocyanine (CoPc) molecule by an extra Co atom co-adsorbed on Au (111) surface using scanning tunneling microscopy (STM), joint with density functional theory (DFT) calculations. By manipulating CoPc molecules using the STM tip to contact individually adsorbed Co atom, two types of relatively stable complexes can be formed, denoted as CoPc-Co(I) and CoPc-Co(II). In CoPc-Co(I), the Co atom is at an intramolecular site close to aza-N atom of CoPc, which induces significant modifications of the electronic states of CoPc, such as energy shifts and splitting of nonlocal molecular orbitals...
July 21, 2015: Journal of Chemical Physics
Simon J Altenburg, Marie Lattelais, Bin Wang, Marie-Laure Bocquet, Richard Berndt
Iron phthalocyanine (FePc) is adsorbed to graphene on Ir(111) at cryogenic temperature. In addition to mobile FePc with four lobes, imaging and spectroscopy with a scanning tunneling microscope reveal immobile molecules that exhibit fewer lobes. A reversible transformation between four- and three-lobed molecules has been induced by current injection. The data are consistent with chemical bonding of lobes to graphene on Ir, pinning down the graphene area toward Ir. Similar observations are made from NiPc, CoPc, CuPc, and H2Pc...
July 29, 2015: Journal of the American Chemical Society
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