Hopf–Hopf bifurcation analysis based on resonance and non-resonance in a simplified railway wheelset model

Nonlinear Dynamics - This paper mainly investigates the dynamics of the non-resonant and near-resonant Hopf–Hopf bifurcations caused by the interaction of the lateral and yaw motion in a...     

Generation of Oxazolidine‐2,4‐diones Bearing Sulfur‐Substituted Quaternary Carbon Atoms by Oxothiolation/Cyclization of Ynamides

A novel method for metal‐free oxothiolation of ynamides to construct oxazolidine‐2,4‐diones bearing sulfur‐substituted quaternary carbon atoms has been developed. It represents a rare C?O bond cleavage of ynamides, as well as a facile and tandem approach for the formation of C?O, C?S, and C?Cl bonds. This redox‐neutral protocol can be applied to the synthesis of multisubstituted oxazolidine‐2,4‐diones with good chemoselectivity and good yields of isolated products under mild conditions.     

Bifurcation of a modified railway wheelset model with nonlinear equivalent conicity and wheel–rail force

This paper presents the bifurcation behaviors of a modified railway wheelset model to explore its instability mechanisms of hunting motion. Equivalent conicity data measured from China high-speed railway vehicle are used to modify the wheelset model. Firstly, the relationships between longitudinal stiffness, lateral stiffness, equivalent conicity and critical speed are taken into account by calculating the real parts of the eigenvalues of the Jacobian matrix and Hurwitz criterion for the corresponding linear model. Secondly, measured equivalent conicity data are fitted by a nonlinear function of the lateral displacement rather than are considered as a constant as usual. Nonlinear wheel–rail force function is used to describe the wheel–rail contact force. Based on these modifications, a modified railway wheelset model with nonlinear equivalent conicity and wheel–rail force is set up, and then, some instability mechanisms of China high-speed train vehicle are investigated based on Hopf bifurcation, fold (limit point) bifurcation of cycles, cusp bifurcation of cycles, Neimark–Sacker bifurcation of cycles and 1:1 resonance. In particular, fold bifurcation of cycles can produce a vast effect on the hunting motion of the modified wheelset model. One of the main reasons leading to hunting motion is due to the fold bifurcation structure of cycles, in which stable limit cycles and unstable limit cycles may coincide, and multiple nested limit cycles appear on a side of fold bifurcation curve of cycles. Unstable hunting motion mainly depends on the coexistence of equilibria and limit cycles and their positions; if the most outward limit cycle is stable, then the motion of high-speed vehicle should be safe in a reasonable range. Otherwise, if the initial values are chosen near the most outward unstable limit cycle or the system is perturbed by noises, the high-speed vehicle will take place unstable hunting motion and even lead to serious train derailment events. Therefore, in order to control hunting motions, it may be the easiest way in theory to guarantee the coexistence of the inner stable equilibrium and the most outward stable limit cycle in a wheelset system.

     

Radical polymerization in the presence of peroxide and reducing agent monomer for branched polymers

In this article, we report the radical polymerization in the presence of peroxide and commercially available or designed reducing agent monomer (RAM) for the preparation of branched poly(methyl methacrylate)s (PMMAs). The reaction behavior of the RAM was studied by NMR. Triple‐detection SEC (TD‐SEC) analysis was used to confirm the branching structure of the prepared PMMAs and to investigate the influence of peroxide concentration and RAM concentration on molecular weight and branched structure. The obtained branched PMMAs exhibited high molecular weights and relatively narrow polydispersities at high conversion of MMA. Interestingly, a significant increase in molecular weight and degree of branching of the obtained polymers are observed in higher BPO concentration, these results are quite different from that reported in the literature. The unique radical polymerization mechanism in the RAM/BPO redox‐initiated radical polymerization system resulted in branched PMMAs with high molecular weights at relatively high RAM and BPO concentrations. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 833–840     

Hydration-Facilitated Fine-Tuning of the AIE Amphiphile Color and Application as Erasable Materials with Hot/Cold Dual Writing Modes

Hydration water greatly impacts the color of inorganic crystals, but it is still unknown whether hydration water can be utilized to systematically manipulate the emission color of organic luminescent groups. Now, metal ions with different hydration ability allow fine-tuning the emission color of a fluorescent group displaying aggregation induced emission (AIE). Because the hydration water can be removed easily by gentle heating or mechanical grinding and re-gained by solvent fuming, rewritable materials can be fabricated both in the hot-writing and cold-writing modes. This hydration-facilitated strategy will open up a new vista in fine-tuning the emission color of AIE molecules based on one synthesis and in the design of smart luminescent devices.     

Tetrabutylammonium Halides as Selectively Bifunctional Catalysts Enabling the Syntheses of Recyclable High Molecular Weight Salicylic Acid-Based Copolyesters

To synthesize high molecular weight poly(phenolic ester) via a living ring-opening polymerization (ROP) of cyclic phenolic ester monomers remains a critical challenge due to serious transesterification and back-biting reactions. Both phenolic ester bonds in monomer and polymer chains are highly active, and it is difficult so far to distinguish them. In this work, an unprecedented selectively bifunctional catalytic system of tetra-n-butylammonium chloride (TBACl) was discovered to mediate the syntheses of high molecular weight salicylic acid-based copolyesters via a living ROP of salicylate cyclic esters (for poly(salicylic methyl glycolide) (PSMG), M_n=361.8 kg/mol, Ð<1.30). Compared to previous catalysis systems, the side reactions were suppressed remarkably in this catalysis system because phenolic ester bond in monomer can be selectively cleaved over that in polymer chains during ROP progress. Mechanistic studies reveal that the halide anion and alkyl-quaternaryammonium cation work synergistically, where the alkyl-quaternaryammonium cation moiety interacts with the carbonyl group of substrates via non-classical hydrogen bonding. Moreover, these salicylic acid-based copolyesters can be recycled to dimeric monomer under solution condition, and can be recycled to original monomeric monomers without catalyst under sublimation condition.     

Photosynthesis of Benzonitriles on BiOBr Nanosheets Promoted by Vacancy Associates

Photocatalytic organic functionalization reactions represent a green, cost-effective, and sustainable synthesis route for value-added chemicals. However, heterogeneous photocatalysis is inefficient in directly activating ammonia molecules for the production of high-value-added nitrogenous organic products when compared with oxygen activation in the formation of related oxygenated compounds. In this study, we report the heterogeneous photosynthesis of benzonitriles by the ammoxidation of benzyl alcohols (99 % conversion, 93 % selectivity) promoted using BiOBr nanosheets with surface vacancy associates. In contrast, the main reaction of catalysts with other types of vacancy sites is the oxidation of benzyl alcohol to benzaldehyde or benzoic acid. Experimental measurements and theoretical calculations have demonstrated a specificity of vacancy type with respect to product selectivity, which arises from the adsorption and activation of NH₃ and O₂ that is required to promote subsequent C−N coupling and oxidation to nitrile. This study provides a better understanding of the role of vacancies as catalytic sites in heterogeneous photocatalysis.     

Chemical assay-guided natural product isolation via solid-supported chemodosimetric fluorescent probe

As a new model of chemical assay-guided natural product isolation, an effective chemodosimetric assay system was devised. Our chemical assay system features a fluorogenic chemodosimeter immobilized on a solid support, which offers advantages in identifying the desired compounds in complex natural product mixtures. To isolate only compounds with the target functional groups, the click chemistry concept was adopted. The model system presented here was developed for natural products with a terminal alkyne. Using our newly designed alkyne sensing beads with the aforementioned features, we have readily identified, quantified, and isolated compounds with a terminal alkyne group from plant extracts.