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101.
Jessica E. Sharpe Nuno Bimbo Valeska P. Ting Andrew D. Burrows Dongmei Jiang Timothy J. Mays 《Adsorption》2013,19(2-4):643-652
Experimental excess isotherms for the adsorption of gases in porous solids may be represented by mathematical models that incorporate the total amount of gas within a pore, a quantity which cannot easily be found experimentally but which is important for calculations for many applications, including adsorptive storage. A model that is currently used for hydrogen adsorption in porous solids has been improved to include a more realistic density profile of the gas within the pore, and allows calculation of the total amount of adsorbent. A comparison has been made between different Type I isotherm equations embedded in the model, by examining the quality of the fits to hydrogen isotherms for six different nanoporous materials. A new Type I isotherm equation which has not previously been reported in the literature, the Unilan-b equation, has been derived and has also been included in this comparison study. These results indicate that while some Type I isotherm equations fit certain types of materials better than others, the T?th equation produces the best overall quality of fit and also provides realistic parameter values when used to analyse hydrogen sorption data for a model carbon adsorbent. 相似文献
102.
Seixas de Melo J Rondão R Burrows HD Melo MJ Navaratnam S Edge R Voss G 《The journal of physical chemistry. A》2006,110(51):13653-13661
Spectral and photophysical properties of the indigo derivative Cibalackrot in keto and reduced (leuco) forms were studied by absorption spectra, fluorescence and pulse radiolysis and compared with the structurally similar indigo. With the keto form of this dye, fluorescence (phiF = 0.76) and intersystem crossing (phiT = 0.11) are dominant, whereas with indigo, efficient internal conversion (phiIC = 0.99) is observed, probably involving proton transfer through intramolecular hydrogen bonds. With Cibalackrot, this pathway is blocked, supporting the above model for indigo. With the reduced form of Cibalackrot, more than 98% of the absorbed quanta are dissipated through S1 approximately --> S0 internal conversion, which contrasts with leuco-indigo, where fluorescence (phiF = 0.35), internal conversion (phiIC = 0.53) and intersystem crossing (phiT = 0.125) are found to be competitive. In addition, a synthetic precursor of Cibalackrot (preCiba) was also investigated. This has a rigid molecular structure (with a moiety identical to Cibalackrot and the other to indigo), but intra- or intermolecular proton transfer is allowed between adjacent carbonyl and N-H groups. With this precursor in its keto structure the photophysical parameters are generally very close to those of the keto form of indigo, and different from those of Cibalackrot. A more detailed investigation of the time-decay profiles of preCiba in dioxane (and with added water and D2O) has shown that these follow biexponential laws with a shorter component of 14-25 ps, which appears associated with a risetime at longer wavelength emissions (and to a positive preexponential at shorter emission wavelengths) and a longer lived (decay) component of 104-130 ps. In the steady-state spectra of preCiba, the variation with temperature reveals a blue shift of the emission maxima, which is interpreted as the presence (simultaneous emission) of two species (keto and enol) in the excited state. Indigo and deuterated indigo are also found to present a similar behavior. The overall data are interpreted as to be due to an excited-state process involving the proton transfer between keto and enol forms. Rate constants with values of 7 x 10(10) s-1 for preCiba and 1.6 x 10(11) s-1 for deuterated indigo were obtained. This inverse isotope effect is justified on the basis of the proposed model for proton-transfer excited-state deactivation. 相似文献
103.
C. J. Burrows 《Zeitschrift fur Physik C Particles and Fields》1980,5(3):243-246
We demonstrate that the constitutent interchange diagram for nucleon nucleon elastic scattering contains a pinch singularity. This means that it predicts that \(\frac{{d\sigma }}{{dt}} \sim s^{ - 9} f\left( \theta \right)\) for high energy elastic scattering, at least to any finite order in QCD. We also show how the dimensional counting rule may perhaps be recovered by summing a suitable infinite series of graphs. 相似文献
104.
Orphal J Perrin A Flaud J Smirnov M Himmelmann S Voigt S Burrows JP 《Journal of Molecular Spectroscopy》2000,204(1):72-79
New high-resolution Fourier transform absorption spectra of an (15)N(16)O(2) isotopic sample of nitrogen dioxide were recorded at the University of Bremen in the 6.3-μm region. Starting from the results of a previous study [Y. Hamada, J. Mol. Struct. 242, 367-377 (1991)], a new and more extended analysis of the nu(3) band located at 1582.1039 cm(-1) has been performed. The spin-rotation energy levels were satisfactorily reproduced using a theoretical model which takes into account both the Coriolis interactions between the spin-rotation energy levels of the (001) vibrational state with those of the (020) and (100) states and the spin-rotation resonances within each of the NO(2) vibrational states. Precise vibrational energies and rotational, spin-rotation, and coupling constants were obtained in this way for the first triad of (15)N(16)O(2) interacting states {(020), (100), (001)}. Finally, a comprehensive list of line positions and line intensities of the {nu(1), 2nu(2), nu(3)} interacting bands of (15)N(16)O(2) was generated, using for the line intensities the transition moment operators which were obtained previously for the main isotopic species. Copyright 2000 Academic Press. 相似文献
105.
106.
Joanne F. Kinneary Therese M. Roy Jeffrey S. Albert Heungsik Yoon Thomas R. Wagler Lucy Shen Cynthia J. Burrows 《Journal of inclusion phenomena and macrocyclic chemistry》1989,7(2):155-168
New nickel catalysts have been developed for the oxidation of alkenes to epoxides, alcohols, aldehydes and ketones. Mechanistic studies indicate that the oxidation reactions are very sensitive to the nature of the catalyst; only certain ligands including salen and the macrocycles cyclam and dioxocyclam render Ni(II) effective as a catalyst. A Ni(III) or Ni(IV)-oxo species has been postulated as the catalytically active oxidant which leads to oxygen atom transfer to alkenes in a stepwise process. Both iodosylbenzene and hypochlorite have been used as terminal oxidants; both systems give high yields of epoxidation of alkenes and varying amounts of C=C bond cleavage products. In order to reach an ultimate goal of hydrocarbon oxidation within a molecular recognition system, new molecular receptors for organic substrates have been investigated. The receptors are constructed from two subunits of cholic acid and display amphophilic character — a hydrophobic exterior and a hydrophilic interior. Conformational properties in the presence of polar guests in CDCl3 are described. 相似文献
107.
Synthesis,characterization and assessment of the cytotoxic activity of Cu(II), Fe(III) and Mn(III) complexes of camphoric acid‐derived salen ligands 下载免费PDF全文
Dina Murtinho Zênis N. da Rocha Ana Salomé Pires Roberto P. Jiménez Ana Margarida Abrantes Mafalda Laranjo Ana Catarina Mamede João Eduardo Casalta‐Lopes Maria Filomena Botelho Alberto A. C. C. Pais Sandra C. C. Nunes Hugh D. Burrows Telma Costa M. Elisa Silva Serra 《应用有机金属化学》2015,29(7):425-432
Novel Cu(II), Fe(III) and Mn(III) salen‐type metal complexes from (1R,3S)‐N,N′‐bis[salicylidene]‐1,3‐diamino‐1,2,2‐trimethylcyclopentane were synthesized and screened for their in vitro cytotoxic activity against three human cancer cell lines: melanoma, colorectal and breast. In vitro experiments carried out with the three metal complexes show that the copper complex exhibits the highest cytotoxic activity towards all cell lines studied, presenting IC50 values of 3.32–6.71 μM. A significant improvement in the anti‐proliferative effect, by 20‐fold, is observed with this complex when compared with conventional chemotherapy. The relationship between structure, redox characteristics and biological activity in human cancer cell lines was evaluated for the most efficient Cu(II) complex and associated with theoretical calculations. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
108.
P. N. Burrows 《Zeitschrift fur Physik C Particles and Fields》1988,41(3):375-384
Results on event and single particle characteristics are presented for the three most successful perturbative QCD+fragmentation models in the c.m. energy range 12.0≦W≦200 GeV. The models were optimised to describe the properties of the large sample of hadronic events obtained by TASSO atW=35 GeV. The energy evolution of the observables across the range spanned by the PETRA and PEP data, 12.0≦〈W〉≦41.5 GeV, is reasonably well described by all the models. However, for some quantities the predictions of the different models diverge at higher energies; distributions of observables are shown at c.m. energies of 93 and 200 GeV, where data are expected from thee + e ? colliders currently under construction. The ability to describe simultaneously, with the same parameter values, hadronic event features both at PETRA/PEP and LEP/SLC energies will provide a severe test of the models. The effects of top quark production on the event properties are illustrated for a top mass of 60 GeV/c2. Predictions are given for the rates of multijet events up toW=200 GeV, where ≧4-jet events dominate the cross section and will form a background to events containing heavy states which decay into hadron jets. 相似文献
109.
The reaction between N(alpha)-acetyllysine methyl ester (Lys) and 2'-deoxyguanosine (dGuo) was used to study structural aspects of DNA-protein cross-link (DPC) formation. The precise structure of DPCs depended on the nature of the oxidant and cross-linking reactions in which a series of different oxidation conditions generated a distribution of adducts, principally spirodiiminodihydantoins with lysine appended at the purine position of C5 (5-Lys-Sp), C8 (8-Lys-Sp), or both C5 and C8 (5,8-diLys-Sp). Singlet oxygen oxidation of dGuo produced 5-Lys-Sp exclusively when Rose Bengal or methylene blue was used to photochemically generate (1)O2 in the presence of Lys, whereas riboflavin or benzophenone-mediated photochemistry generated lysine radicals and led to C8 adduct formation, yielding 8-Lys-Sp and 5,8-diLys-Sp. Notably, the yield of dGuo modifications from riboflavin photooxidation increased dramatically in the presence of lysine. Oxidation of deoxyguanosine/lysine mixtures with Na2IrCl6 or sulfate radicals produced both 5-Lys-Sp and 8-Lys-Sp. The same adducts were formed in single and double-stranded oligodeoxynucleotides, and these could be analyzed after nuclease digestion. Adduct formation in duplex DNA was somewhat dependent on the accessibility of lysine to C5 vs C8 of the purine. No adduct formation was detected between lysine and the other nucleobases T, C, or A. Overall, the precise location of adduct formation at C5 vs C8 of guanine appears to be diagnostic of the oxidation pathway. 相似文献
110.
Inside Cover: An Iodine‐Vapor‐Induced Cyclization in a Crystalline Molecular Flask (Angew. Chem. Int. Ed. 20/2016) 下载免费PDF全文