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101.
Svedberg F Alaverdyan Y Johansson P Käll M 《The journal of physical chemistry. B》2006,110(51):25671-25677
The effect of thiol and selenol functionalization on the vibrational spectra and photochemical stability of terthiophene based molecular wires was investigated using surface-enhanced Raman scattering (SERS). The molecules were found to exhibit markedly different properties at the silver surface of the SERS substrate, despite having almost identical Raman spectra in solution and in the solid state. In contrast to terthiophene (3T), the bisthiolterthiophene (T3) and biselenol-terthiophene (Se3) molecules were stable against photoinduced structural changes when adsorbed to the metal surface at low concentrations. This indicates that the strong bonds to the silver surface, via S or Se terminal atoms, leads to a rapid decay of photoexcited states. Comparison with ab initio calculations shows that both T3 and Se3 bind with only one of the functional groups to the Ag surface. 相似文献
102.
This paper deals with Mellin transforms of rational functions g/f in several variables. We prove that the polar set of such a Mellin transform consists of finitely many families of parallel hyperplanes, with all planes in each such family being integral translates of a specific facial hyperplane of the Newton polytope of the denominator f. The Mellin transform is naturally related to the so-called coamoeba $\mathcal{A}'_{f}:=\mathrm{Arg}(Z_{f})$ , where Z f is the zero locus of f and Arg denotes the mapping that takes each coordinate to its argument. In fact, each connected component of the complement of the coamoeba $\mathcal{A}'_{f}$ gives rise to a different Mellin transform. The dependence of the Mellin transform on the coefficients of f, and the relation to the theory of A-hypergeometric functions is also discussed in the paper. 相似文献
103.
Janne Weisell Jouko Vepsäläinen Mikael Peräkylä 《Journal of Physical Organic Chemistry》2013,26(4):360-366
Correct net charge and protonation pattern in the polyamine backbone is one of the major factors that define the interactions of this class of compounds. 1,12‐diamino‐3,6,9‐triazadodecane (SpmTrien) is a isosteric charge deficient analogue of naturally occurring spermine (Spm) with different biological features. The tautomeric populations of each SpmTrien charge state were estimated with computer simulations, molecular dynamics (MD) and quantum mechanical calculations, and cluster expansions separately. In the computer simulations, tautomeric populations of each charge state were obtained by constrained least‐squares fitting the theoretically calculated (GIAO B3LYP/6‐311 + G**) 15 N NMR chemical shieldings of SpmTrien tautomers to the experimentally measured chemical shifts. Theoretical chemical shieldings were calculated for water complexes of SpmTrien obtained from MD simulations in explicit water. Both methods gave highly similar realistic results. SpmTrien has many major populations of tautomers at biologically relevant charge states of three (+3) and four (+4) thus enabling a large variety of structures for specific ionic interactions. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
104.
Let ${u \in \mathcal{H}(\mathbb{D})}$ and φ be an analytic self-map of ${\mathbb{D}}$ . We estimate the essential norms of weighted composition operators uC φ acting on Zygmund type spaces in terms of u, φ, their derivatives and the n-th power φ n of φ. Moreover, we give similar characterizations for boundedness of uC φ between Zygmund type spaces. 相似文献
105.
We show that under tension a classical many-body system with only isotropic pair interactions in a crystalline state can, counterintuitively, have a negative Poisson's ratio, or auxetic behavior. We derive the conditions under which the triangular lattice in two dimensions and lattices with cubic symmetry in three dimensions exhibit a negative Poisson's ratio. In the former case, the simple Lennard-Jones potential can give rise to auxetic behavior. In the latter case, a negative Poisson's ratio can be exhibited even when the material is constrained to be elastically isotropic. 相似文献
106.
Rechtsman MC Jeong HC Chaikin PM Torquato S Steinhardt PJ 《Physical review letters》2008,101(7):073902
A photonic quasicrystal consists of two or more dielectric materials arranged in a quasiperiodic pattern with noncrystallographic symmetry that has a photonic band gap. We use a novel method to find the pattern with the widest TM-polarized gap for two-component materials. Patterns are obtained by computing a finite sum of density waves, assigning regions where the sum exceeds a threshold to a material with one dielectric constant, epsilon1, and all other regions to another, epsilon0. Compared to optimized crystals, optimized quasicrystals have larger gaps at low constrasts epsilon1/epsilon0 and have gaps that are much more isotropic for all contrasts. For high contrasts, optimized hexagonal crystals have the largest gaps. 相似文献
107.
The relative reactivity of conformationally armed thioglycosides is quantified. 相似文献
108.
Severinsen R Bourne GT Tran TT Ankersen M Begtrup M Smythe ML 《Journal of combinatorial chemistry》2008,10(4):557-566
A biphenyl privileged structure library containing three attachment points were synthesized using a catechol-based safety-catch linker strategy. The method requires the attachment of a bromo-acid to the linker, followed by a Pd-catalyzed Suzuki cross-coupling reaction. Further derivatization, activation of the linker with strong acid and aminolysis afforded the respective products in high purity and good overall yield. To show the versatility of the synthesis, a 199-member library was generated. The library samples both conformational and chemical diversity about a well-known privileged substructure. 相似文献
109.
A convenient experimental method for thermodynamical studies based on partial-filling affinity CE is presented. The advantages of this approach are the possibility to determine binding energies from relatively weak interactions as well as the small amounts of samples consumed. In order to explore the affinity and selectivity of the cellobiohydrolase Cel7A, a number of propranolol analogues were recently designed. The affinities of a selection of these ligands were determined in the temperature interval 15-40 degrees C, and DeltaG degrees , DeltaH degrees and DeltaS degrees were obtained by means of Van't Hoff plots. Through these experiments, the importance of the entropy contribution in the complexation between the ligands and Cel7A has been demonstrated. 相似文献
110.
Salomonsson ML Bondesson U Hedeland M 《Rapid communications in mass spectrometry : RCM》2008,22(17):2685-2697
For the first time chemical derivatization of isomeric drug glucuronides with 1,2-dimethylimidazole-4-sulfonyl chloride (DMISC) has been successfully applied as a tool for determining the site of conjugation. This provides a way to differentiate between glucuronide isomers containing aliphatic and phenolic hydroxyl groups. The analyses were performed with liquid chromatography/electrospray ion trap mass spectrometry (LC/ESI-MSn). DMISC has previously been shown to react selectively with phenols in estrogens, thus improving sensitivity in ESI-MS. The model compounds selected for this study were commercially available standards of formoterol, morphine, morphine-3-glucuronide (M3G), and morphine-6-glucuronide (M6G). Formoterol glucuronides were produced with an enzymatic method in house. Both formoterol and morphine possess one phenolic and one aliphatic hydroxyl group where glucuronidation could take place. The product ion mass spectra of the native morphine glucuronides were indistinguishable due to the initial neutral loss of monodehydrated glucuronic acid (176 u). However, a significant difference between the isomers was observed with DMISC derivatization, as only the form with a free phenol, M6G, gave a detectable reaction product. Formoterol formed two detectable glucuronide isomers in the enzymatic reaction. Their respective sites of conjugation could not be directly determined from the product ion spectra. Reaction with DMISC, however, gave a detectable product with only one of the isomers. Based on previous experience of the preferred DMISC reactions with phenols, and interpretation of the fragmentation pattern of the derivative, it was concluded that the reactive isomer had a free phenol, and was thus conjugated on the aliphatic chain. 相似文献