The first example of a bifunctional organocatalyst assembled through dynamic covalent chemistry (DCC) is described. The catalyst is based on reversible imine chemistry and can catalyze the Morita–Baylis–Hillman (MBH) reaction of enones with aldehydes or N‐tosyl imines. Furthermore, these dynamic catalysts were shown to be optimizable through a systemic screening approach, in which large mixtures of catalyst structures were generated, and the optimal catalyst could be directly identified by using dynamic deconvolution. This strategy allowed one‐pot synthesis and in situ evaluation of several potential catalysts without the need to separate, characterize, and purify each individual structure. The systems were furthermore shown to catalyze and re‐equilibrate their own formation through a previously unknown thiourea‐catalyzed transimination process. 相似文献
Purification and liquid chromatography-tandem mass spectrometry (LC-MS/MS) characterization of glycopeptides, originating from protease digests of glycoproteins, enables site-specific analysis of protein N- and O-glycosylations. We have described a protocol to enrich, hydrolyze by chondroitinase ABC, and characterize chondroitin sulfate-containing glycopeptides (CS-glycopeptides) using positive mode LC-MS/MS. The CS-glycopeptides, originating from the Bikunin proteoglycan of human urine samples, had ΔHexAGalNAcGlcAGalGalXyl-O-Ser hexasaccharide structure and were further substituted with 0-3 sulfate and 0-1 phosphate groups. However, it was not possible to exactly pinpoint sulfate attachment residues, for protonated precursors, due to extensive fragmentation of sulfate groups using high-energy collision induced dissociation (HCD). To circumvent the well-recognized sulfate instability, we now introduced Na+ ions to form sodiated precursors, which protected sulfate groups from decomposition and facilitated the assignment of sulfate modifications. Sulfate groups were pinpointed to both Gal residues and to the GalNAc of the hexasaccharide structure. The intensities of protonated and sodiated saccharide oxonium ions were very prominent in the HCD-MS2 spectra, which provided complementary structural analysis of sulfate substituents of CS-glycopeptides. We have demonstrated a considerable heterogeneity of the bikunin CS linkage region. The realization of these structural variants should be beneficial in studies aimed at investigating the importance of the CS linkage region with regards to the biosynthesis of CS and potential interactions to CS binding proteins. Also, the combined use of protonated and sodiated precursors for positive mode HCD fragmentation analysis will likely become useful for additional classes of sulfated glycopeptides.
This paper presents the Constructive Cooperative Coevolutionary (\(\mathrm {C}^3\)) algorithm, applied to continuous large-scale global optimisation problems. The novelty of \(\mathrm {C}^3\) is that it utilises a multi-start architecture and incorporates the Cooperative Coevolutionary algorithm. The considered optimisation problem is decomposed into subproblems. An embedded optimisation algorithm optimises the subproblems separately while exchanging information to co-adapt the solutions for the subproblems. Further, \(\mathrm {C}^3\) includes a novel constructive heuristic that generates different feasible solutions for the entire problem and thereby expedites the search. In this work, two different versions of \(\mathrm {C}^3\) are evaluated on high-dimensional benchmark problems, including the CEC’2013 test suite for large-scale global optimisation. \(\mathrm {C}^3\) is compared with several state-of-the-art algorithms, which shows that \(\mathrm {C}^3\) is among the most competitive algorithms. \(\mathrm {C}^3\) outperforms the other algorithms for most partially separable functions and overlapping functions. This shows that \(\mathrm {C}^3\) is an effective algorithm for large-scale global optimisation. This paper demonstrates the enhanced performance by using constructive heuristics for generating initial feasible solutions for Cooperative Coevolutionary algorithms in a multi-start framework. 相似文献
Microporous polymers (MPs) are studied for their intriguing chemistry and physics as well as their potential application in catalytic transformations, gas-separation processes, water purification and so on. Here, we critically review MPs with respect to the sustainability aspects of their synthesis as well as their applications that have sustainable character. Some MPs have been synthesized from monomers derived from biomass resources, but there is certainly a large potential for further developments. There are also opportunities to improve the sustainability of MP synthesis in terms of the use of solvents, catalysts, and related aspects. The applications of MPs in processes related to sustainability depend upon multiple properties. A rich and flexible chemistry is important to applications as catalysts for, among other useful reactions, the photoreduction of CO2 and selective oxidation. The (ultra)micropore volume of MPs are crucial in gas-separation applications such as CO2 capture, and the chemisorption of CO2 on MP-tethered alkylamines could offer a means to remove that gas from dilute mixtures. When it comes to the storage of H2 and CH4 in MPs for onboard use in fuel cell or biogas cars, volumetric capacity is paramount, meaning that the density of the MPs must be considered. Finally, for use in separation and purifications from liquid mixtures (aqueous or hydrocarbon-based), crosslinked MPs are more limited than the solution-processable MPs that can be more easily processed into films and membranes. 相似文献
We study the Dirichlet problem for non-homogeneous equations involving the fractional p-Laplacian. We apply Perron’s method and prove Wiener’s resolutivity theorem. 相似文献
Supported lipid bilayers (SLBs) are one of the most common model systems for cell membrane studies. We have previously found that when applying a bulk flow of liquid above an SLB the lipid bilayer and its constituents move in the direction of the bulk flow in a rolling type of motion, with the lower monolayer being essentially stationary. In this study, a theoretical platform is developed to model the dynamic behavior of a shear-driven SLB. In most regions of the moving SLB, the dynamics of the lipid bilayer is well explained by a balance between the hydrodynamic shear force arising from the bulk flow above the lipid bilayer and the friction between the upper and lower monolayers of the SLB. These two forces result in a drift velocity profile for the lipids in the upper monolayer of the SLB that is highest at the center of the channel and decreases to almost zero at the corners of the channel. However, near the front of an advancing SLB a very different flow behavior is observed, showing an almost constant drift velocity of the lipids over the entire bilayer front. In this region, the motion of the SLB is significantly influenced by gradients in the surface pressure as well as internal friction due to molecules that have accumulated at the front of the SLB. It is shown that even a modest surface fraction of accumulated molecules (~1%) can drastically affect the behavior of the SLB near the bilayer front, forcing the advancing lipids in the SLB away from the center of the channel out toward the sides. 相似文献
A voltammetric electronic tongue is described that was used for multicomponent analysis of drinking water. Measurements were performed on drinking water from a tap and injections of the compounds NaCl, NaN3, NaHSO3, ascorbic acid, NaOCl and yeast suspensions could be identified by use of principal component analysis (PCA). A model based on partial least square (PLS) was developed for the simultaneously prediction of identification and concentration of the compounds NaCl, NaHSO3 and NaOCl. By utilizing this type of non-selective sensor technique for water quality surveillance, it will be feasible to detect a plurality of events without the need of a specific sensor for each type of event. 相似文献
CHARMM force field parameter values for a class of oligothiophene derivatives have been derived with reference to density functional theory/B3LYP potential energy surfaces. The force field parametrization of these luminescent conjugated polyelectrolytes includes the electronic ground state as well as the strongly light absorbing first excited state. In conjunction with quantum chemical response theory calculations of transition state properties, a molecular dynamical model of the Stokes shift is obtained. The theoretical model is benchmarked against experimental data recorded at room temperature which refer to sodium salts of p-HTAA and p-FTAA with distilled water as a solvent. For p-HTAA the theoretically predicted Stokes shift of 112 nm is in good agreement with the experimental result of 124 nm, given the approximations about exciton localization that were introduced to obtain a force field for the excited state. 相似文献
Simmons and Cardy recently predicted a formula for the probability that the chordal SLE8/3 path passes to the left of two points in the upper half-plane. In this paper we give a rigorous proof of their formula. Starting from this result, we derive explicit expressions for several natural connectivity functions for SLE8/3 bubbles conditioned to be of macroscopic size. By passing to a limit with such a bubble we construct a certain chordal restriction measure and in this way obtain a proof of a formula for the probability that two given points are between two commuting SLE8/3 paths. The one-point version of this result has been predicted by Gamsa and Cardy. Finally, we derive an integral formula for the second moment of the area of an SLE8/3 bubble conditioned to have radius 1. We evaluate the area integral numerically and relate its value to a hypothesis that the area follows the Airy distribution. 相似文献