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1.
Shaobo Cheng Vidushi Sharma Altug S. Poyraz Lijun Wu Xing Li Amy C. Marschilok Esther S. Takeuchi Kenneth J. Takeuchi Marivi Fernndez-Serra Yimei Zhu 《Chemical science》2020,11(19):4991
Tunneled metal oxides such as α-Mn8O16 (hollandite) have proven to be compelling candidates for charge-storage materials in high-density batteries. In particular, the tunnels can support one-dimensional chains of K+ ions (which act as structure-stabilizing dopants) and H2O molecules, as these chains are favored by strong H-bonds and electrostatic interactions. In this work, we examine the role of water molecules in enhancing the stability of K+-doped α-Mn8O16 (cryptomelane). The combined experimental and theoretical analyses show that for high enough concentrations of water and tunnel-ions, H2O displaces K+ ions from their natural binding sites. This displacement becomes energetically favorable due to the formation of K2+ dimers, thereby modifying the stoichiometric charge of the system. These findings have potentially significant technological implications for the consideration of cryptomelane as a Li+/Na+ battery electrode. Our work establishes the functional role of water in altering the energetics and structural properties of cryptomelane, an observation that has frequently been overlooked in previous studies.Water displaces potassium ions and initiates the formation of a homonuclear dimer ion (K2+) in the tunnels of hollandite. 相似文献
2.
Consider a portfolio containing heterogeneous risks. The premiums of the policyholders might not cover the amount of the payments which an insurance company pays the policyholders. When setting the premium, this risk has to be taken into consideration. On the other hand the premium that the insured pays has to be fair. This fairness is measured by a function of the difference between the risk and the premium paid—we call this function a distance function. For a given small probability of insolvency, we find the premium for each class, such that the distance function is minimized. Next we formulate and solve the dual problem, which is minimizing the insolvency probability under the constraint that the distance function does not exceed a given level. This paper generalizes a previous paper [Zaks, Y., Frostig, E., Levikson, B., 2006. Optimal pricing of a heterogeneous portfolio for a given risk level. Astin Bull. 36 (1), 161–185] where only a square distance function was considered. 相似文献
3.
4.
Björn Wängler Carmen Beck Esther Schirrmacher Frank Rösch Michael Eisenhut 《Tetrahedron letters》2006,47(33):5985-5988
The synthesis of tris-allyl-DOTA starting from cyclen and its application in the preparation of DOTA-peptide conjugates is reported. Clinically important conjugates such as DOTA-Tyr3-octreotide (DOTA-TOC), DOTA-Tyr3-octreotate (DOTA-TATE) as well as a DOTA-RGD peptide were synthesized in high yields with Fmoc solid phase peptide synthesis. The final, extremely reliable de-allylation was achieved on solid phase by different methods identifying morpholine/Pd(0) as the most suitable one obtaining all DOTA peptide conjugates in high yields. All DOTA-peptides were purified by reversed phase HPLC and structural identity was proved using MALDI-TOF mass spectrometry. 相似文献
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6.
A molecularly imprinted polymer (MIP) tailored for the HPLC determination of the fungicide thiabendazole (TBZ) has been synthesised in one single preparative step by precipitation polymerisation in an acetonitrile/toluene co-solvent, using TBZ as template molecule, methacrylic acid as functional monomer and divinylbenzene-80 as crosslinker. The imprinted polymer particulates obtained were characterised by scanning electron microscopy and nitrogen sorption porosimetry. These analyses showed clearly that spherical polymer particulates (polymer microspheres) with narrow size distributions (average particle diameter approximately 3.5 microm) and well-developed pore structures had been produced. The imprinted microspheres were packed into a stainless steel HPLC column (50 x 4.6 mm id) and evaluated as an imprinted stationary phase. The imprinting effect was demonstrated clearly, i.e., the column was observed to bind TBZ selectively, and the effect of different chromatographic parameters (e.g., temperature, flow-rate and elution solvents) on TBZ retention/elution studied. Under optimised conditions, the TBZ-imprinted column was used for the HPLC-fluorescence (HPLC-F) determination of TBZ directly from orange (both whole fruit and juice), lemon, grape and strawberry extracts at low concentration levels in less than 15 min, without any need for a clean-up step in the analytical protocol. 相似文献
7.
A detailed analysis of one- and two-dimensional 1H and 13C NMR data for the endo and the exo adducts, obtained by Diels-Alder reaction of thuriferic and epithuriferic acids with cyclopentadiene is described. The unequivocal spectral data assignment of the endo and exo structures was complemented with molecular modelling studies and confirmed through X-ray diffraction studies. 相似文献
8.
García ME Riera V Ruiz MA Sáez D Vaissermann J Jeffery JC 《Journal of the American Chemical Society》2002,124(48):14304-14305
Protonation of [Mo2Cp2(mu-H)(mu-PHR*)(CO)4] (Cp = eta5-C5H5, R* = 2,4,6-C6H2tBu3) with HBF4.OEt2 gives the hydridophosphinidene complex [Mo2Cp2(mu-H)(mu-PR*)(CO)4]BF4, which is easily deprotonated with H2O to give the known phosphinidene complex [Mo2Cp2(mu-PR*)(CO)4] in 95% yield. Reaction of the latter with I2 gives the unsaturated phosphinidene complex [Mo2Cp2I2(mu-PR*)(CO)2], which exhibits an intermetallic distance of 2.960(2) A. Irradiation of solutions of [Mo2Cp2(mu-PR*)(CO)4] with UV light gives a mixture of the triply bonded [Mo2Cp2(mu-PR*)(mu-CO)2] and the hydridophosphido derivative [Mo2Cp2(mu-H){mu-P(CH2CMe2)C6H2tBu2}(CO)4] as major species. The latter complex results from an intramolecular C-H bond cleavage from a tBu group and has been characterized by spectroscopy and an X-ray study. Irradiation in the presence of HCC(p-tol) results in the insertion of the alkyne into the Mo-P bond to give [Mo2Cp2{mu-eta1:eta2,kappa-C(p-tol)CHPR*}(CO)4] structurally characterized through an X-ray study. 相似文献
9.
Cabrerizo FM Petroselli G Lorente C Capparelli AL Thomas AH Braun AM Oliveros E 《Photochemistry and photobiology》2005,81(5):1234-1240
Pterins are heterocyclic compounds with important biological functions, and most of them may exist in two acid-base forms in the pH range between 3 and 13 in aqueous solution. In this work, the photophysical properties of acid and basic forms of six compounds of the pterin family (6-hydroxymethylpterin [HPT], 6-methylpterin [MPT], 6,7-dimethylpterin [DPT], rhamnopterin [RPT], N-methylfolic acid [MFA], and pteroic acid [PA]) have been studied. The effects of the chemical nature of the substituents at position 6 of the pterin moiety and the effects of the pH on the absorption and emission properties are analyzed. The fluorescence characteristics (spectra, quantum yields, lifetimes) of these compounds have been investigated using the single-photon-counting technique. Results obtained for pterin derivatives containing small substituents with 1 carbon atom (HPT, MPT, DPT) and short hydrocarbon chain (4 carbon atoms) (RPT) are different from those found for pterin derivatives containing a p-aminobenzoic acid (PABA) moiety in the substituent (MFA and PA). Fluorescence quantum yields (Phi(F)) of the first group of compounds are relatively high (>/=0.4), whereas MFA and PA exhibit very small Phi(F) values (=0.01). 相似文献
10.
Carmen Moscoso-Pérez Purificación López-Mahía Soledad Muniategui-Lorenzo Esther Fernández-Fernández Darío Prada-Rodríguez 《Analytica chimica acta》2004,526(2):185-192
A highly sensitive and simple method, based on hydride generation and atomic fluorescence detection, has been developed for the determination of As, Bi, Sb, Se(IV) and Te(IV) in aqua regia extracts from atmospheric particulate matter samples. Atmospheric particulates matter was collected on glass fiber filters using a medium volume sampler (PM1 particulate matter). Two-level factorial designs have been used to optimise the hydride generation atomic fluorescence spectrometry (HG-AFS) procedure. The effects of several parameters affecting the hydride generation efficiency (hydrochloric acid, sodium tetrahydroborate and potassium iodide concentrations and flow rates) have been evaluated using a Plackett-Burman experimental design. In addition, parameters affecting the hydride measurement (delay, analysis and memory times) have been also investigated. The significant parameters obtained (sodium tetrahydroborate concentration, sodium tetrahydroborate flow rate and analysis time for As; hydrochloric acid concentration and sodium tetrahydroborate flow rate for Se(IV); and sodium tetrahydroborate concentration and sodium tetrahydroborate flow rate for Te(IV)) have been optimized by using 2n + star central composite design. Hydrochloric acid concentration and sodium tetrahydroborate flow rate were the significant parameters obtained for Sb and Bi determination, respectively. Using a univariate approach these parameters were optimized. The accuracy of methods have been verified by using several certified reference materials: SRM 1648 (urban particulate matter) and SRM 1649a (urban dust). Detection limits in the range of 6 × 10−3 to 0.2 ng m−3 have been achieved. The developed methods were applied to several atmospheric particulate matter samples corresponding to A Coruña city (NW Spain). 相似文献