Rack-mounted chemistry IV: the thermal rearrangement of 7-oxabenzonorbornadienes into benzo[b]oxepines on and off the polycyclic rack

The thermal rearrangement of [3]polynorbornane bis-imide rack-mounted 7-oxabenzonorbornadienes has been conducted using flash vacuum pyrolysis (FVP) at 520 °C and is compared with the FVP of similar 7-oxabenzonorbornadienes off the rack. The isomerisation is considered to involve (a) C–O bond cleavage to a vinylogous 1,5-dipole, (b) formation of a benzene epoxide by nucleophilic ring-closure and (c) valence-isomerisation of the benzene epoxide to the oxepine. Competing fragmentation to the isobenzofuran by ejection of acetylene and other rearrangements become prominent pathways off the rack, whereas isomerisation to the oxepine is highly favored on the rack.     

A novel intramolecular reversible reaction between the hydroxyl group and isobutenylene chain in a cyclophane-type macrocycle

A novel Hg²⁺ ion induced reversible ring contraction was achieved employing the intramolecular reaction of isobutylene with an aromatic hydroxyl group of cyclophane; reversibility of the reaction was facilitated by excess addition of NaBH₄ which also resulted in complexation. The ring contraction and expansion was monitored by UV-VIS absorption, and by fluorescence and ¹H NMR spectra. Switchable fluorescence behavior (on—off—on) was observed when the ring-size was tuned from a 19-membered ring to an 18-membered and vice versa. This fine tuning has the potential to be applied in the construction of new supramolecular devices.     

Recommendation in evolving online networks

Recommender system is an effective tool to find the most relevant information for onlineusers. By analyzing the historical selection records of users, recommender system predictsthe most likely future links in the user-item network and accordingly constructs apersonalized recommendation list for each user. So far, the recommendation process ismostly investigated in static user-item networks. In this paper, we propose a model whichallows us to examine the performance of the state-of-the-art recommendation algorithms inevolving networks. We find that the recommendation accuracy in general decreases with timeif the evolution of the online network fully depends on the recommendation. Interestingly,some randomness in users’ choice can significantly improve the long-term accuracy of therecommendation algorithm. When a hybrid recommendation algorithm is applied, we find thatthe optimal parameter gradually shifts towards the diversity-favoring recommendationalgorithm, indicating that recommendation diversity is essential to keep a high long-termrecommendation accuracy. Finally, we confirm our conclusions by studying therecommendation on networks with the real evolution data.     

A novel efficient medium for chromogenic catalysis of tetramethylbenzidine with horseradish peroxidase

The traditional surfactant sodium dodecyl sulfate (SDS) and ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate ([Emim][BF₄]) have been combined to create a novel efficient medium for chromogenic catalysis of 3,3',5,5'-tetramethylbenzidine with horseradish peroxidase in presence of H₂O₂. The results have shown the [Emim][BF₄] in the mediums can promote the rate of formation of the blue chromogen, the SDS is responsible for the stabilization of the blue chromogen due to the electrostatic attraction between positively charged blue chromogen and the negatively charged surfactant. The SDS/[Emim][BF₄] combination not only enhance catalytic activity of HRP remarkably but also stabilize the blue chromogen formed in the HRP oxidation of the substrate TMB compared to the conventional medium. Based on the superior combination of SDS and [Emim][BF₄], the colorimetric assay for detecting HRP activity and H₂O₂ concentration was established. This work demonstrates a novel efficient medium for chromogenic catalysis with potential applications in biosensors and clinical diagnosis.     

The invariant of the stiffness filter function with the weight filter function of the power function form

Based on the independent, continuous and mapping (ICM) method and homogenization method, a research model is constructed to propose and deduce a theorem and corollary from the invariant between the weight filter function and the corresponding stiffness filter function of the form of power function. The efficiency in searching for optimum solution will be raised via the choice of rational filter functions, so the above mentioned results are very important to the further study of structural topology optimization.     

Carbon-Based Materials as Lithium Hosts for Lithium Batteries

Lithium (Li) metal has attracted significant attention in areas that range from basic research to various commercial applications due to its high theoretical specific capacity (3860 mA h g⁻¹) and low electrochemical potential (−3.04 vs. standard hydrogen electrode). However, dendrites often form on the surfaces of Li metal anodes during cycling and thus lead to battery failure and, in some cases, raise safety concerns. To overcome this problem, a variety of approaches that vary the electrolyte, membrane, and/or anode have been proposed. Among these efforts, the use of three-dimensional frameworks as Li hosts, which can homogenize and minimize the current density at the anode surface, is an effective approach to suppress the formation of Li dendrites. Herein, we describe the development of using carbon-based materials as Li hosts. While these materials can be fabricated into a variety of porous structures, they have a number of intrinsic advantages including low costs, high specific surface areas, high electrical conductivities, and wide electrochemical stabilities. After briefly summarizing the formation mechanisms of Li dendrites, various methods for controlling structural and surface chemistry will be described for different types of carbon-based materials from the viewpoint of improving their performance as Li hosts. Finally, we provide perspective on the future development of Li host materials needed to meet the requirements for their use in flexible and wearable devices and other contemporary energy storage techniques.     

A continuum model for intermittent deformation of single crystal micropillars

Strain bursts are often observed during compression tests of single crystal micropillars. In this work, we formulate a new continuum model that accounts for the strain bursts within the framework of crystal plasticity. The strain bursts are separated from the loading stage (nearly elastic loading) by introducing a dimensionless constant in the continuum model, and are detected by load serrations. The boundary conditions in the context of micropillar compression are studied and they are shown to be changing and unpredictable as plastic deformation proceeds. To evaluate the validity of our model, finite element simulations of the uniaxial compression tests on nickel micropillars are performed. Our simulations produce clearly visible strain bursts during the plastic flow and the produced intermittent flows are comparable with the experimental observations. For the bulk crystal, a series of strain bursts is identified in the course of plastic flow, despite an apparently smooth stress–strain response. We also show that the intermittent flow is intensified in the micrometer-scale due to both increasing numbers of the successive strain bursts and increasing amplitude of the strain burst, when the specimen size decreases. Finally, we show that the occurrences of the strain bursts are always associated with negative values of the second-order work.     

A monocular pose measurement method of a translation-only one-dimensional object without scene information

A monocular method to measure the pose of a translation-only one-dimensional (1D) object containing at least two known characteristic points is presented. The position of any other point on the 1D object can be located after the pose measurement. Scene information is not needed to apply the method. If the distance between the characteristic points is unknown, there is a scale factor between the object's real positions and the measurement results. The method can also be used to measure the pose and shape parameters of a parallelogram, prism or cylinder object.