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111.
Battle PD Blundell SJ Brooks ML Hervieu M Kapusta C Lancaster T Nair SP Oates CJ Pratt FL Rosseinsky MJ Ruiz-Bustos R Sikora M Steer CA 《Journal of the American Chemical Society》2004,126(39):12517-12527
The temperature dependence of the crystal structure and electronic properties of brownmillerite-like Ca(2.5)Sr(0.5)GaMn(2)O(8) has been studied by neutron powder diffraction and muSR spectroscopy. The results show that short-range 2D magnetic order begins to develop within the perovskite-like bilayers of MnO(6) octahedra approximately 50 K above the 3D Néel temperature of approximately 150 K. The bilayers show a structural response to the onset of magnetism throughout this temperature range whereas the GaO(4) layers that separate the bilayers only respond below the 3D ordering temperature. XANES spectroscopy shows that the sample contains Mn(3+) and Mn(4+) cations in a 1:1 ratio, and the behavior in the region of the Néel transition is interpreted as a local charge ordering. Electron diffraction and high-resolution electron microscopy have been used to show that the local microstructure is more complex than the average structure revealed by neutron diffraction, and that microdomains exist in which the GaO(4) tetrahedra show different orientations. It is argued that the bonding requirements of diamagnetic gallium control the electronic behavior within the perovskite-like bilayers. 相似文献
112.
Patricia M. Nassar Rose M.Z.Georgetto Naal Silvia H. de Pauli João B.S. Bonilha Laura T. Okano Frank H. Quina 《Journal of colloid and interface science》1997,190(2):461
In aqueous solution, the interaction between sodium dodecyl sulfate (SDS) and poly(ethylene glycol) (PEG) results in the formation of small aggregates or clusters of SDS attached to the PEG polymer chain. Selectivity coefficients for exchange of two monovalent (N-methyl-4-cyanopyridinium cation and Tl+) and two divalent (methylviologen cation and Cu2+) counterions at the surface of SDS–PEG clusters, determined employing photophysical techniques, are similar, but not identical, to those for exchange at the surface of SDS micelles in the absence of PEG. The principal factor affecting ion exchange selectivity in SDS–PEG clusters does not appear to be aggregate size or surface charge density but rather the presence of poly(oxyethylene) subunits at the aggregate surface. 相似文献
113.
Yiyi Weng Xingxing Ding Joo C. A. Oliveira Xiaobin Xu Nikolaos Kaplaneris Meijie Zhu Hantao Chen Zhuo Chen Lutz Ackermann 《Chemical science》2020,11(34):9290
There is a strong demand for novel native peptide motifs for post-synthetic modifications of peptides without pre-installation and subsequent removal of directing groups. Herein, we report an efficient method for peptide late-stage C(sp3)–H arylations assisted by the unmodified side chain of asparagine (Asn) without any exogenous directing group. Thereby, site-selective arylations of C(sp3)–H bonds at the N-terminus of di-, tri-, and tetrapeptides have been achieved. Likewise, we have constructed a key building block for accessing agouti-related protein (AGRP) active loop analogues in a concise manner.An efficient method for peptide late-stage C(sp3)-H arylations assisted by unmodified side chain of asparagine (Asn) without any exogenous directing group has been reported. 相似文献
114.
Silvia Gimnez-Santamarina Salvador Cardona-Serra Juan M. Clemente-Juan Alejandro Gaita-Ario Eugenio Coronado 《Chemical science》2020,11(39):10718
Molecular spin qubits are chemical nanoobjects with promising applications that are so far hampered by the rapid loss of quantum information, a process known as decoherence. A strategy to improve this situation involves employing so-called Clock Transitions (CTs), which arise at anticrossings between spin energy levels. At CTs, the spin states are protected from magnetic noise and present an enhanced quantum coherence. Unfortunately, these optimal points are intrinsically hard to control since their transition energy cannot be tuned by an external magnetic field; moreover, their resilience towards geometric distortions has not yet been analyzed. Here we employ a python-based computational tool for the systematic theoretical analysis and chemical optimization of CTs. We compare three relevant case studies with increasingly complex ground states. First, we start with vanadium(iv)-based spin qubits, where the avoided crossings are controlled by hyperfine interaction and find that these S = 1/2 systems are very promising, in particular in the case of vanadyl complexes in an L-band pulsed EPR setup. Second, we proceed with a study of the effect of symmetry distortions in a holmium polyoxotungstate of formula [Ho(W5O18)2]9− where CTs had already been experimentally demonstrated. Here we determine the relative importance of the different structural distortions that causes the anticrossings. Third, we study the most complicated case, a polyoxopalladate cube [HoPd12(AsPh)8O32]5− which presents an unusually rich ground spin multiplet. This system allows us to find uniquely favorable CTs that could nevertheless be accessible with standard pulsed EPR equipment (X-band or Q-band) after a suitable chemical distortion to break the perfect cubic symmetry. Since anticrossings and CTs constitute a rich source of physical phenomena in very different kinds of quantum systems, the generalization of this study is expected to have impact not only in molecular spin science but also in other related fields such as molecular photophysics and photochemistry.We employ a python computational tool to compare 3 relevant case studies with increasingly complex ground states: vanadyl complexes, Ho(iii) square antiprisms and Ho(iii) cubic structures. 相似文献
115.
Vilar RB da Silva R Schossler P Cataluña Veses R Piatnicki C Samios D Caramão EB 《Journal of chromatography. A》2003,985(1-2):367-373
This work reports preliminary studies on the characterisation of anhydrous ethanol (AEA) used as an automotive fuel mixed with gasoline in Porto Alegre (South Brazil). Pre-concentration of the impurities contained in 1000 ml of AEA was carried on through solid-phase extraction using XAD4 resin. The main compounds in the extract were identified by means of spectral data from the library of the equipment. The concentrate was then fractionated using a preparative liquid chromatographic column filled with activated silica gel and the elution procedure was carried out with, n-hexane, n-hexane-benzene (1:1, v/v) and dichloromethane. Prior to analysis by GC-MS, each fraction was reduced to 1 ml with a gentle stream of nitrogen. Saturated linear hydrocarbons and aromatic hydrocarbons eluted in the first fraction and oxygenated compounds such as aldehydes. ketones and alcohols, eluted in the second one. were the main compounds detected in the sample. 相似文献
116.
A.B. Lugo B.W.H. Artel A. Yoshiga L.F.C.P. Lima D.F. Parra J.R. Bueno S. Liberman M. Farrah W.R. Terariol H. Otaguro 《Radiation Physics and Chemistry》2007,76(11-12):1691-1695
High melt strength polypropylene (HMS-PP) has been recently developed and introduced in the market by the major international producers of polypropylene. Therefore, BRASKEM, the leading Brazilian PP producer, together with EMBRARAD, the leading Brazilian gamma irradiator, and the IPEN (Institute of Nuclear Energy and Research) worked to develop a national technology for the production of HMS-PP. One of the effective approaches to improve melt strength and extensibility is to add chain branches onto polypropylene backbone using gamma radiation. Branching and grafting result from the radical combinations during irradiation process. Crosslinking and main chain scission in the polymer structure are also obtained during this process. In this work, gamma irradiation technique was used to induce chemical changes in commercial polypropylene with two different monomers, Tri-allyl-isocyanurate (TAIC) and Tri-methylolpropane-trimethacrylate (TMPTMA), with concentration ranging from 1.5 to 5.0 mmol/100 g of polypropylene. These samples were irradiated with a 60Co source at dose of 20 kGy. It used two different methods of HMS-PP processing. The crosslinking of modified polymers was studied by measuring gel content melt flow rate and rheological properties like melt strength and drawability. It was observed that the reaction method and the monomer type have influenced the properties. However, the concentration variation of monomer has no effect. 相似文献
117.
Clovis Peppe Paola de Azevedo Mello Rafael Pavão das Chagas 《Journal of organometallic chemistry》2006,691(11):2335-2339
The organoindium compound derived from indium monobromide and dibromoacetonitrile reacts with carbonyl compounds to afford the corresponding 2-bromo-2-cyano-indium(III) alkoxide. The action of a second equivalent of indium monobromide onto the alkoxides derived from aldehydes promotes the Boord elimination of the β-related oxygen and bromine atoms leading to 2-alkenenitriles. 相似文献
118.
We show that the Ashtekar-Isham extension
of the configuration space of Yang-Mills theories
is (topologically and measure-theoretically) the projective limit of a family of finite dimensional spaces associated with arbitrary finite lattices.These results are then used to prove that
is contained in a zero measure subset of
with respect to the diffeomorphism invariant Ashtekar-Lewandowski measure on
. Much as in scalar field theory, this implies that states in the quantum theory associated with this measure can be realized as functions on the extended configuration space
. 相似文献
119.
120.
The diluted-field Ising model, a random nonnegative field ferromagnetic model, is shown to have a unique Gibbs measure with probability I when the field mean is positive. Our methods involve comparisons with ordinary uniform field Ising models. They yield as a corollary a way of obtaining spontaneous magnetization through the application of a vanishing random magnetic field. The correlation lengths of this model defined as (lim
n-(1/n) log 0;
n)-1, wheren is the site on the first coordinate axis at distancen from the origin and 0;
n
is the origin ton two-point truncated correlation function, is non-random. We derive an upper bound for it in terms of the correlation length of an ordinary nonrandom model with uniform field related to the field distribution of the diluted model. 相似文献