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1.
Threading of a polymer through a macrocyclic ring may occur directly, that is, by finding the end of the polymer chain, or by a process in which the polymer chain first folds and then threads through the macrocyclic ring in a hairpin‐like conformation. We present kinetic and thermodynamic studies on the threading of a macrocyclic porphyrin receptor ( H21 ) onto molecular threads that are blocked on one side and are open on the other side. The open side is modified by groups that vary in ease of folding and in bulkiness. Additionally, the threads contain a viologen binding site for the macrocyclic receptor, which is located close to the blocking group. The rates of threading of H21 were measured under various conditions, by recording as a function of time the quenching of the fluorescence of the porphyrin, which occurs when receptor H21 reaches the viologen binding site. The kinetic data suggest that threading is impossible if the receptor encounters an open side that is sterically encumbered in a similar way as a folded polymer chain. This indicates that threading of polymers through macrocyclic compounds through a folded chain mechanism is unlikely.  相似文献   
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In ESR dating of Early Pleistocene fossil tooth enamel samples, the fitting function used for the evaluation of the DE value is undoubtedly among the major sources of uncertainty. Dose recovery tests performed on fossil tooth enamel showing DE values >1,000 Gy demonstrate: (i) that high precision ESR measurements (<0.5%) and high DE reproducibility (<5%) may be achieved; (ii) the appropriateness of the Double Saturating Exponential (DSE) fitting function for ESR dose reconstruction. In contrast, the SSE function, which has been almost exclusively used so far, does simply not correctly describe the behavior of the radiation induced ESR signal of tooth enamel with the dose.Several fitting functions and data weighting options were tested and the combination of a DSE with data weighted by the inverse of the squared intensities is the procedure providing the most accurate DE results. However, the SSE may nevertheless sometimes produce consistent results if Dmax does not exceed 6*DE. Further work is required in that direction in order to determine more precisely in which conditions the SSE could be used as a fair approximation of the DSE function for these samples.  相似文献   
4.
Biaryl compounds with axial chirality are very common in synthetic chemistry, especially in catalysis. Axially chiral biaryls are important due to their biological activities and extensive applications in asymmetric catalysis. Thus the development of efficient enantioselective methods for their synthesis has attracted considerable attention. This Minireview discusses the progress made in catalytic kinetic resolution of biaryl compounds and chronicles significant advances made recently in catalytic kinetic resolution of biaryl scaffolds.  相似文献   
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Helicenes and heterohelicenes are attractive compounds with great potential in materials sciences to be used in optoelectronics as ligand backbones in enantioselective catalysis and as chiral sensors. The properties of these materials are related to the stereodynamics of these helical chiral compounds. However, little is known about features controlling stereodynamics in helicenes; in particular, for heterohelicenes the position of the heteroatom could be relevant in this respect. Herein the complete stereodynamic characterization of monoaza[5]helicenes is shown by enantioselective dynamic HPLC and DFT calculations. At variance with previous theoretical calculations, 1‐aza[5]helicene shows a surprisingly high enantiomerization barrier, which is triggered by specific solvent interactions.  相似文献   
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Cyanide‐catalyzed benzoin condensation of terephthaldehyde produces a cyclic tetramer, which we propose to name cyclotetrabenzoin. Cyclotetrabenzoin is a square‐shaped macrocycle ornamented with four α‐hydroxyketone functionalities pointing away from the central cavity, the dimensions of which are 6.9×6.9 Å. In the solid state, these functional groups extensively hydrogen bond, resulting in a microporous three‐dimensional organic framework with one‐dimensional nanotube channels. This material exhibits permanent—albeit low‐porosity, with a Langmuir surface area of 52 m2 g?1. Cyclotetrabenzoin’s easy and inexpensive synthesis and purification may inspire the creation of other shape‐persistent macrocycles and porous molecular crystals by benzoin condensation.  相似文献   
7.
The effect of plasma screening on the dynamic dipole polarizability (DPP) of two‐electron ions Be2+, B3+, and C4+ has been investigated using highly correlated exponential wave functions within the framework of pseudostate summation technique and Debye screening concept. Plasma‐screening effect on the oscillator strengths (OS) of the ultraviolet and visible series has also been investigated for the systems Li+, Be2+, B3+, C4+. The DPP are reported as functions of screening parameters. The OS for S‐P transitions are also reported for various screening parameters. The OS and dynamic polarizability show interesting behavior with increasing screening strength and nuclear charge. © 2015 Wiley Periodicals, Inc.  相似文献   
8.
A collaborative study on the robustness and portability of a capillary electrophoresis‐mass spectrometry method for peptide mapping was performed by an international team, consisting of 13 independent laboratories from academia and industry. All participants used the same batch of samples, reagents and coated capillaries to run their assays, whereas they utilized the capillary electrophoresis‐mass spectrometry equipment available in their laboratories. The equipment used varied in model, type and instrument manufacturer. Furthermore, different types of sheath‐flow capillary electrophoresis–mass spectrometry interfaces were used. Migration time, peak height and peak area of ten representative target peptides of trypsin‐digested bovine serum albumin were determined by every laboratory on two consecutive days. The data were critically evaluated to identify outliers and final values for means, repeatability (precision within a laboratory) and reproducibility (precision between laboratories) were established. For relative migration time the repeatability was between 0.05 and 0.18% RSD and the reproducibility between 0.14 and 1.3% RSD. For relative peak area repeatability and reproducibility values obtained were 3–12 and 9–29% RSD, respectively. These results demonstrate that capillary electrophoresis‐mass spectrometry is robust enough to allow a method transfer across multiple laboratories and should promote a more widespread use of peptide mapping and other capillary electrophoresis‐mass spectrometry applications in biopharmaceutical analysis and related fields.  相似文献   
9.
In this paper, a solution for the equilibrium configuration of an elastic beam subject to three-point bending is given in terms of Jacobi elliptical functions. General equations are derived, and the domain of the solution is established. Several examples that illustrate a use of the solution are discussed. The obtained numerical results are compared with the results of other authors. An approximation formula by which the beam load is given as a polynomial function of beam deflection is also derived. The range of applicability of the approximation is illustrated by numerical examples.  相似文献   
10.
We consider the Korteweg–de Vries equation with a source. The source depends on the solution as polynomials with constant coefficients. Using the Painlevé test we show that the generalized Korteweg–de Vries equation is not integrable by the inverse scattering transform. However there are some exact solutions of the generalized Korteweg–de Vries equation for two forms of the source. We present these exact solutions.  相似文献   
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