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31.
Ole J. Nielsen Matthew S. Johnson Timothy J. Wallington Lene K. Christensen Jesper Platz 《国际化学动力学杂志》2002,34(5):283-291
Pulse radiolysis techniques were used to measure the gas phase UV absorption spectra of the title peroxy radicals over the range 215–340 nm. By scaling to σ(CH3O2)240 nm = (4.24 ± 0.27) × 10?18, the following absorption cross sections were determined: σ(HO2)240 nm = 1.29 ± 0.16, σ(C2H5O2)240 nm = 4.71 ± 0.45, σ(CH3C(O)CH2O2)240 nm = 2.03 ± 0.22, σ(CH3C(O)CH2O2)230 nm = 2.94 ± 0.29, and σ(CH3C(O)CH2O2)310 nm = 1.31 ± 0.15 (base e, units of 10?18 cm2 molecule?1). To support the UV measurements, FTIR‐smog chamber techniques were employed to investigate the reaction of F and Cl atoms with acetone. The F atom reaction proceeds via two channels: the major channel (92% ± 3%) gives CH3C(O)CH2 radicals and HF, while the minor channel (8% ± 1%) gives CH3 radicals and CH3C(O)F. The majority (>97%) of the Cl atom reaction proceeds via H atom abstraction to give CH3C(O)CH2 radicals. The results are discussed with respect to the literature data concerning the UV absorption spectra of CH3C(O)CH2O2 and other peroxy radicals. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 283–291, 2002 相似文献
32.
Wiklander J Karlsson BC Aastrup T Nicholls IA 《Analytical and bioanalytical chemistry》2011,400(5):1397-1404
A series of streptavidin-mimicking molecularly imprinted polymers has been developed and evaluated for their biotin binding characteristics. A combination of molecular dynamics and NMR spectroscopy was used to examine potential polymer systems, in particular with the functional monomers methacrylic acid and 2-acrylamidopyridine. The synthesis of copolymers of ethylene dimethacrylate and one or both of these functional monomers was performed. A combination of radioligand binding studies and surface area analyses demonstrated the presence of selectivity in polymers prepared using methacrylic acid as the functional monomer. This was predicted by the molecular dynamics studies showing the power of this methodology as a prognostic tool for predicting the behavior of molecularly imprinted polymers.
The biotin binding characteristics of a series of molecularly imprinted polymers have been evaluated and correlated to predictions made by molecular dynamics simulations and 1H-NMR titrations 相似文献
33.
We consider the Q-state Potts model in the random-cluster formulation, defined on finite two-dimensional lattices of size L×N with toroidal boundary conditions. Due to the non-locality of the clusters, the partition function Z(L,N) cannot be written simply as a trace of the transfer matrix TL. Using a combinatorial method, we establish the decomposition Z(L,N)=∑l,Dkb(l,Dk)Kl,Dk, where the characters Kl,Dk=i∑N(λi) are simple traces. In this decomposition, the amplitudes b(l,Dk) of the eigenvalues λi of TL are labelled by the number l=0,1,…,L of clusters which are non-contractible with respect to the transfer (N ) direction, and a representation Dk of the cyclic group Cl. We obtain rigorously a general expression for b(l,Dk) in terms of the characters of Cl, and, using number theoretic results, show that it coincides with an expression previously obtained in the continuum limit by Read and Saleur. 相似文献
34.
Jan Bornholdt Dr. Jakob Felding Dr. Rasmus P. Clausen Dr. Jesper L. Kristensen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(41):12474-12480
The pyrimidine‐2‐sulfonyl (pymisyl) group is introduced as a new protecting group that can be used to activate aziridines towards ring opening. It is readily introduced and removed under mild conditions. Regioselective ring opening of pymisyl‐protected 2‐methyl‐aziridine with organocuprates gives the corresponding sulfonamides in high yields, and the pymisyl group can subsequently be removed upon treatment with a thiolate. The versatility of this new nitrogen protecting group is illustrated with a new synthesis of Selegiline, a monoamine oxidase‐B inhibitor marketed for the treatment of Parkinson’s disease. 相似文献
35.
Andersson M Hedin J Johansson P Nordström J Nydén M 《The journal of physical chemistry. A》2010,114(50):13146-13153
Synthetic imidazole ligands are typically substituted at the N(1) ((1)-Im) position while natural imidazole ligands are substituted at the C(4) ((4)-Im) position. To outline the difference in coordination properties, the methyl-substituted imidazoles Me(4)-Im and Me(1)-Im were complexed with CuCl(2) and ZnCl(2) and investigated by NMR relaxometry, electron paramagnetic resonance, far-Fourier transform IR vibrational spectroscopy, and ab initio calculations. Me(4)-Im, Me(1)-Im, and Im in excess form the usual tetragonal D(4h) [CuL(4)X(2)] complexes with CuCl(2) whereas the methylated imidazoles form pseudotetrahedral C(2v) complexes instead of the usual octahedral O(h) [ZnIm(6)](2+) complex. All imidazoles display a high degree of covalence in the M-L σ- and π-bonds and the π-interaction strength affects the relative energies of complexation. Opportunities to tailor complexes by the chemical properties of the substituents are envisaged due to the role of the inductive and hyperconjugative effects, rather than position. 相似文献
36.
We argue that the four-state Potts antiferromagnet has a finite-temperature phase transition on any Eulerian plane triangulation in which one sublattice consists of vertices of degree 4. We furthermore predict the universality class of this transition. We then present transfer-matrix and Monte?Carlo data confirming these predictions for the cases of the Union Jack and bisected hexagonal lattices. 相似文献
37.
38.
Troels Martin Range Richard Martin Lusby Jesper Larsen 《European Journal of Operational Research》2014
This paper addresses the Patient Admission Scheduling (PAS) problem. The PAS problem entails assigning elective patients to beds, while satisfying a number of hard constraints and as many soft constraints as is possible, and arises at all planning levels for hospital management. There exist a few, different variants of this problem. In this paper we consider one such variant and propose an optimization-based heuristic building on branch-and-bound, column generation, and dynamic constraint aggregation to solve it. We achieve tighter lower bounds than previously reported in the literature and, in addition, we are able to produce new best known solutions for five out of twelve instances from a publicly available repository. 相似文献
39.
Jüstel T Bendix J Metzler-Nolte N Weyhermüller T Nuber B Wieghardt K 《Inorganic chemistry》1998,37(1):35-43
Reaction of LRu(III)Cl(3) (L = 1,4,7-trimethyl-1,4,7-triazacyclononane) with 1,2-phenylenediamine (opdaH(2)) in H(2)O in the presence of air affords [LRu(II)(bqdi)(OH(2))](PF(6)) (1), where (bqdi) represents the neutral ligand o-benzoquinone diimine. From an alkaline methanol/water mixture of 1 was obtained the dinuclear species [{LRu(II)(bqdi)}(2)(&mgr;-H(3)O(2))](PF(6))(3) (1a). The coordinated water molecule in 1 is labile and can be readily substituted under appropriate reaction conditions by acetonitrile, yielding [LRu(II)(bqdi)(CH(3)CN)](PF(6))(2) (2), and by iodide and azide anions, affording [LRu(II)(bqdi)I](PF(6)).0.5H(2)O (3) and [LRu(bqdi)(N(3))](PF(6)).H(2)O (4), respectively. Heating of solid 4 in vacuum at 160 degrees C generates N(2) and the dinuclear, nitrido-bridged complex [{LRu(o-C(6)H(4)(NH)(2))}(2)(&mgr;-N)](PF(6))(2) (5). Complex 5 is a mixed-valent, paramagnetic species containing one unpaired electron per dinuclear unit whereas complexes 1-4 are diamagnetic. The crystal structures of 1, 1a.3CH(3)CN, 3, 4.H(2)O, and 5.3CH(3)CN.0.5(toluene) have been determined by X-ray crystallography: 1 crystallizes in the monoclinic space group P2(1)/m, Z = 2, with a = 8.412(2) ?, b = 15.562(3) ?, c = 10.025 ?, and beta = 109.89(2) degrees; 1a.3CH(3)CN, in the monoclinic space group C2/c, Z = 4, with a = 19.858(3) ?, b = 15.483(2) ?, c = 18.192(3) ?, and beta = 95.95(2) degrees; 3, in the orthorhombic space group Pnma, Z = 4, with a = 18.399(4) ?, b = 9.287(2) ?, and c = 12.052(2) ?, 4.H(2)O, in the monoclinic space group P2(1)/c, Z = 4, with a = 8.586(1) ?, b = 15.617(3) ?, c = 16.388(5) ?, and beta = 90.84(2) degrees; and 5.3CH(3)CN.0.5(toluene), in the monoclinic space group P2(1)/c, Z = 4, with a = 15.003(3) ?, b = 16.253(3) ?, c = 21.196(4) ?, and beta = 96.78(3) degrees. The structural data indicate that in complexes 1-4 the neutral o-benzoquinone diimine ligand prevails. In contrast, in 5 this ligand has predominantly o-phenylenediamide character, which would render 5 formally a mixed-valent Ru(IV)Ru(V) species. On the other hand, the Ru-N bond lengths of the Ru-N-Ru moiety at 1.805(5) and 1.767(5) ? are significantly longer than those in other crystallographically characterized Ru(IV)=N=Ru(IV) units (1.72-1.74 ?). It appears that the C(6)H(4)(NH)(2) ligand in 5 is noninnocent and that formal oxidation state assignments to the ligands or metal centers are not possible. 相似文献
40.
We observe twofold shell filling in the spectra of closed one-dimensional quantum dots formed in single-wall carbon nanotubes. Its signatures include a bimodal distribution of addition energies, correlations in the excitation spectra for different electron number, and alternation of the spins of the added electrons. This provides a contrast with quantum dots in higher dimensions, where such spin pairing is absent. We also see indications of an additional fourfold periodicity indicative of K-K' subband shells. Our results suggest that the absence of shell filling in most isolated nanotube dots results from disorder or nonuniformity. 相似文献