Identification of metabolites of rupestonic acid in rat urine by liquid chromatography combined with electrospray ionization quadrupole time‐of‐flight tandem mass spectrometry

Rupestonic acid, a potential anti‐influenza agent, is an important and characteristic compound in Artemisia rupestris L., a well‐known traditional Uighur medicine for the treatment of colds. In the present study, high‐performance liquid chromatography combined with electrospray ionization quadrupole time‐of‐flight tandem mass spectrometry was used to detect and identify the metabolites in rat urine after oral administration of rupestonic acid. A total of 10 metabolites were identified or partially characterized. The structure elucidations of the metabolites were performed by comparing the changes in accurate molecular masses and fragment ions with those of the parent compound. The results showed that the main metabolites of rupestonic acid in rat urine were formed by oxidation, hydrogenation and glucuronidation. A metabolism pathway was proposed for the first time based on the characterized structures. This metabolism study can provide essential information for drug discovery, design and clinical application of rupestonic acid. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis of self‐healing polyurethane urea‐based supramolecular materials

Supramolecular polyurethane ureas are expected to have superior mechanical properties primarily due to the reversible, noncovalent interactions such as hydrogen bonding interactions. We synthesized polyurethane prepolymers from small molecular weight of poly(tetramethylene ether)glycol and isophorone diisocyanates, which were end capped with propylamine to synthesize polyurethane ureas with high contents of urea and urethane groups for hydrogen‐bonding formations to facilitate self‐healing. The effects of polyurethane urea molecular weight (3000 ≤ M_n ≤ 9000), crosslinking, and cutting direction were studied in terms of thermal, mechanical, and morphological properties with an emphasis on the self‐healing efficiency. It was found that the thermal self‐healability was more pronounced as the molecular weight of polyurethane urea decreased, showing a maximum of more than 96% with 3000 M_n when the sample was cut along the stretch direction. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 468–474     

Studies on metabolites and metabolic pathways of bulleyaconitine A in rat liver microsomes using LC‐MSn combined with specific inhibitors

Bulleyaconitine A (BLA) from Aconitum bulleyanum plants is usually used as anti‐inflammatory drug in some Asian countries. It has a variety of bioactivities, and at the same time some toxicities. Since the bioactivities and toxicities of BLA are closely related to its metabolism, the metabolites and the metabolic pathways of BLA in rat liver microsomes were investigated by HPLC–MSⁿ. In this research, the 12 metabolites of BLA were identified according to the results of HPLC‐MSⁿ data and the relevant literature. The results showed that there are multiple metabolites of BLA in rat liver microsomes, including demethylation, deacetylation, dehydrogenation deacetylation and hydroxylation. The major metabolic pathways of BLA in rat liver microsomes were clarified by HPLC‐MS combined with specific inhibitors of CYP450 isoforms. As a result, CYP3A and 2C were found to be the principal CYP isoforms contributing to the metabolism of BLA. Moreover, CYP2D6 and 2E1 are also more important CYP isoforms for the metabolism of BLA. While CYP1A2 only affected the formation rate of M11, its effect on the metabolism of BLA is very small. Copyright © 2014 John Wiley & Sons, Ltd.     

Finding any given 2‐factor in sparse pseudorandom graphs efficiently

Given an $n$‐vertex pseudorandom graph $G$ and an $n$‐vertex graph $H$ with maximum degree at most two, we wish to find a copy of $H$ in $G$, that is, an embedding $\phi :V\left(H\right)\to V\left(G\right)$ so that $\phi \left(u\right)\phi \left(v\right)\in E\left(G\right)$ for all $uv\in E\left(H\right)$. Particular instances of this problem include finding a triangle‐factor and finding a Hamilton cycle in $G$. Here, we provide a deterministic polynomial time algorithm that finds a given $H$ in any suitably pseudorandom graph $G$. The pseudorandom graphs we consider are $\left(p,\lambda \right)$‐bijumbled graphs of minimum degree which is a constant proportion of the average degree, that is, $\mathrm{\Omega }\left(pn\right)$. A $\left(p,\lambda \right)$‐bijumbled graph is characterised through the discrepancy property: $|e\left(A,B\right)?p|A||B||<\lambda \sqrt{|A||B|}$ for any two sets of vertices $A$ and $B$. Our condition $\lambda =O(p^{2}n/\log n)$ on bijumbledness is within a log factor from being tight and provides a positive answer to a recent question of Nenadov. We combine novel variants of the absorption‐reservoir method, a powerful tool from extremal graph theory and random graphs. Our approach builds on our previous work, incorporating the work of Nenadov, together with additional ideas and simplifications.     

On the capacity of the state‐dependent interference relay channel

This paper considers the state‐dependent interference relay channel (SIRC) in which one of the two users may operate as a secondary user and the relay has a noncausal access to the signals from both users. For discrete memoryless SIRC, we first establish the achievable rate region by carefully merging Han‐Kobayashi rate splitting encoding technique, superposition encoding, and Gelfand‐Pinsker encoding technique. Then, based on the achievable rate region that we derive, the capacity of the SIRC is established in many different scenarios including (a) the weak interference regime, (b) the strong interference regime, and (c) the very strong interference regime. This means that our capacity results contain all available known results in the literature. Next, the achievable rate region and the associated capacity results are also evaluated in the case of additive Gaussian noise. Additionally, many numerical examples are investigated to show the value of our theoretical derivations.     

Evolution of Local Structural Ordering and Chemical Distribution upon Delithiation of a Rock Salt–Structured Li1.3Ta0.3Mn0.4O2 Cathode

Lithium‐rich disordered rock‐salt oxides have attracted great interest owing to their promising performance as Li‐ion battery cathodes. While experimental and theoretical efforts are critical in advancing this class of materials, a fundamental understanding of key property changes upon Li extraction is largely missing. In the present study, single‐crystal synthesis of a new disordered rock‐salt cathode material, Li_1.3Ta_0.3Mn_0.4O₂ (LTMO), and its use as a model compound to investigate Li concentration–driven evolution of local cationic ordering, charge compensation, and chemical distribution are reported. Through the combined use of 2D and 3D X‐ray nanotomography, it is shown that Li removal accompanied by oxygen oxidation is correlated with the development of morphological defects such as particle cracking. Chemical heterogeneity, quantified by subparticle level distribution of Mn valence state, is minimal during Mn redox, which drastically increases upon the formation of cracks during oxygen redox. Density functional theory and bond valence sum mismatch calculations reveal the presence of local short‐range ordering in the pristine oxide, which gradually disappears along with the extraction of Li. The study suggests that with cycling the transformation into true cation–disordered state can be expected, which likely impacts the voltage profile and obtainable energy density of the oxide cathodes.     

Near‐Infrared (NIR) Organic Light‐Emitting Diodes (OLEDs): Challenges and Opportunities

The rapid development of the science and technology of organic semiconductors has already led to mass application of organic light‐emitting diodes (OLEDs) in television monitors of outstanding quality as well as in a large variety of smaller displays found in smartphones, tablets, and other gadgets, while introduction of the technology to the illumination sector is imminent. Notably, the requirements of all such applications for emission in the visible range of the electromagnetic spectrum are well tuned to the optical and electronic properties of typical organic semiconductors, thereby representing relatively “low‐hanging fruits,” in terms of material development and exploitation. However, the question arises as to whether developing materials suited for efficient near‐infrared (NIR, 700–1000 nm) emission is possible, and, crucially, desirable to enable new classes of applications spanning from through‐space, short‐range communications to biomedical sensors, night vision, and more generally security applications to name but a few. Here, the major fundamental hurdles to be overcome to achieve efficient NIR emission from organic π‐conjugated systems are discussed, recent progress is reviewed, and an outlook for further development of both materials and applications is provided.     

A Shell-by-Shell Approach for Synthesis of Mesoporous Multi-Shelled Hollow MOFs for Catalytic Applications

Over the past two decades, advanced materials with hollow interiors have received significant attention in materials research owing to their great application potential across a vast number of technological fields. Though with great difficulty, multi-shelled hollow metal–organic frameworks (MSHMs) have also been successfully synthesized in recent years. Herein, a rational shell-by-shell soft-templating protocol has been devised to fabricate highly uniform multi-shelled hollow cobalt-imidazole-based MOF (ZIF-67). For the first time, it has become possible to endow mesoporosity to this new type of functional material (i.e., mesoporous MOFs). When used as carrier materials in catalytic reactions, in principle, these mesoporous MSHMs with high surface area not only improve the dispersity of metal nanoparticles (NPs), but also efficiently facilitate the mass diffusion of the reactions, resulting in enhanced catalyst activity. Moreover, the obtained MSHMs/M nanocomposites serve as base-metal bifunctional catalysts for one-pot oxidation-Knoevenagel condensation cascade reaction, in which the MSHMs itself serves as a pristine active catalyst in addition to its role of catalyst support. The results demonstrate that excellent multifunctional catalysts can be achieved via preparing intrinsically microporous bulk MOFs into extrinsically mesoporous MSHMs which possess many structural merits that conventional bulk MOFs do not have.     

Microwave‐assisted polycondensation of 4‐octylaniline with dibromoarylene

The Pd‐catalyzed polycondensation of 4‐octylaniline with various dibromoarylenes was carried out under microwave heating. Microwave heating led to a decrease in the reaction time and an increase in the molecular weight of the polymers as compared to conventional heating. Microwave heating also allowed the catalyst loading to be reduced to 1 mol %, yielding polymerization results that were comparable to those under conventional heating and 5 mol % catalyst. Investigations regarding field‐effect transistors and organic photovoltaic cells using the obtained poly(arylamine) with azobenzene units revealed that increasing the molecular weight of the polymer led to improved device performance, including hole mobility and power conversion efficiency. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 536–542