Engineering Bifunctional Host Materials of Sulfur and Lithium-Metal Based on Nitrogen-Enriched Polyacrylonitrile for Li–S Batteries

Lithium–sulfur batteries (LSBs) still suffer from the shuttle effect on the cathode and the lithium dendrite on the anode. Herein, polyacrylonitrile (PAN) is developed into a bifunctional host material to simultaneously address the challenges faced on both the sulfur cathode and lithium anode in LSBs. For the sulfur cathode, PAN is bonded with sulfur to produce sulfurized PAN (SPAN) to avoid the shuttle effect. The SPAN is accommodated into a conductive 3D CNTs-wrapped carbon foam to prepare a self-supporting cathode, which improves the electronic and ionic conductivity, and buffers the volume expansion. Thereby, it delivers reversible capacity, superb rate capability, and outstanding cycling stability. For the Li-metal anode, PAN aerogel is carbonized to give macroporous N-doped cross-linked carbon nanofiber that behaves as a lithiophilic host to regulate Li plating and suppress the growth of Li dendrite. Combining the improvements for both the cathode and anode realizes a remarkable long-term cyclability (765 mAh g⁻¹ after 300 cycles) in a full cell. It provides new opportunity to propel the practical application of advanced LSBs.     

Stimuli-Responsive Purely Organic Room-Temperature Phosphorescence Materials

This Minireview summarizes the recent progress of stimuli-responsive purely organic phosphorescence materials. Organic phosphorescence is closely related to the intermolecular interactions, because such interactions are beneficial to promote spin orbital coupling (SOC) and boost intersystem cross (ISC) efficiency and finally are conducive to satisfactory phosphorescence. It is found that the intermolecular interactions, which are essential for organic phosphorescence, are easily disturbed by external stimuli such as mechanical force, photon, acid, chemical vapor, leading to the luminescence change. According to this principle, various purely organic phosphorescence materials sensitive to external stimuli have been developed. This Minireview categorizes reported stimuli-responsive purely organic phosphorescence materials on the basis of different stimuli, including mechanochromism, mechanoluminescence, photoactivity, acid-responsiveness and other stimuli. Some prospective strategies for constructing stimuli-responsive purely organic phosphorescence molecules are provided.     

Comparative Study of the Supercapacitive Performance of Three Ferrocene-Based Structures: Targeted Design of a Conductive Ferrocene-Functionalized Coordination Polymer as a Supercapacitor Electrode

As redox-active based supercapacitors are known as highly desirable next-generation supercapacitor electrodes, the targeted design of two ferrocene-functionalized (Fc(COOH)₂) clusters based on coinage metals, [(PPh₃)₂AgO₂CFcCO₂Ag(PPh₃)₂]₂ ⋅ 7 CH₃OH (SC₁: super capacitor) and [(PPh₃)₃CuO₂CFcCO₂Cu(PPh₃)₃] ⋅ 3 CH₃OH (SC₂), is reported. Both structures are fully characterized by various techniques. The structures are utilized as energy storage electrode materials, giving 130 F g⁻¹ and 210 F g⁻¹ specific capacitance at 1.5 A g⁻¹ in Na₂SO₄ electrolyte, respectively. The obtained results show that the presence of Cu^I instead of Ag^I improves the supercapacitive performance of the cluster. Further, to improve the conductivity, the PSC₂ ([(PPh₃)₂CuO₂CFcCO₂]_∞), a polymeric structure of SC₂, was synthesized and used as an energy storage electrode. PSC₂ displays high conductivity and gives 455 F g⁻¹ capacitance at 3 A g⁻¹. The PSC₂ as a supercapacitor electrode presents a high power density (2416 W kg⁻¹), high energy density (161 Wh kg⁻¹), and long cycle life over 4000 cycles (93 %). These results could lead to the amplification of high-performance supercapacitors in new areas to develop real applications and stimulate the use of the targeted design of coordination polymers without hybridization or compositions with additive materials.     

大斯托克斯位移远红光至近红外荧光探针用于检测肝损伤过程中过氧化亚硝酸盐的动态变化

肝损伤是影响公众健康的重大问题之一, 已经引起了人们越来越多的关注. 而过表达的过氧化亚硝酸盐(ONOO^?)在肝损伤等疾病的发病机制中起着重要作用, 被认为是一种与早期肝损伤密切相关的生物活性分子. 因此, 为了探究ONOO^?在肝损伤过程中的作用, 开发可以实现肝损伤过程中ONOO^?高选择性和实时检测的分析方法具有重要意义. 本文报道了一种具有大斯托克斯位移的远红光至近红外(FR-NIR)ONOO^?荧光探针. 由于该探针具有大的斯托克斯位移, 可以有效消除光谱重叠和自吸收的干扰, 从而显著提高成像的信噪比. 此外, 该探针对ONOO^?具有高的灵敏度(检出限为25.8 nmol/L)和良好的选择性, 被成功用于药物诱导肝损伤过程中ONOO^?信号的成像检测.     

基于故事情景链语法的偶动画短片分析与建模

偶动画是动画领域一个重要的分支，与传统手绘动画同步出现，甚至更早。偶动画作品以其独特的拍摄方法和艺术魅力，为众多艺术家和观众所喜爱。偶动画影片设计周期长、工作量大、生产过程复杂、经济风险高，用传统手工工艺制作完成一部5 min的定格动画影片，通常需要数年。本文以丹麦知名动画导演克里多夫·皮拉丹的《柏树山上的风》及德国格里高利·祖坎导演的《龙焰火枪》为例，提出以故事情节(storyline(i)),?i∈1,2,…,n?与情景链（scenario?chain）语法有限集的形式语言表达式分解偶动画电影的故事元素，通过叙事空间（narrative?space）中镜头画面的组接逻辑，形成不同叙事结构，以分析定格动画电影的故事寓意（implied?meaning），从故事计算的角度将其转化为标准化设计流程，为构建偶动画电影故事建模理论以及辅助智能计算提供思路，方法提高了偶动画电影的设计与制作效率，为多学科协同创作提供了新模式，使普通偶动画爱好者也能参与创作。     

Structure elucidation and NMR assignment of two new eudesmane derivatives from Merremia yunnanensis

Two new eudesmane derivatives, 1α,6β,9β-trihydroxy-eudesm-3-ene-1-O-β-d -glucopyranoside ( 1 ) and 1α,6β,9β-trihydroxy-eudesm-3-ene-1-(6-cinnamoyl)-O-β-d -glucopyranoside ( 2 ) were discovered from Merremia yunnanensis. The structures were elucidated by analysis of their spectroscopic data including HR-ESI-MS, 1D, and 2D NMR. It should be noted that this is the first report about structure elucidation and NMR assignment of compounds from M. yunnanensis.     

Miktoarm star‐shaped poly(lactic acid) copolymer: Synthesis and stereocomplex crystallization behavior

The miktoarm star‐shaped poly(lactic acid) (PLA) copolymer, (PLLA)₂‐core‐(PDLA)₂, was synthesized via stepwise ring‐opening polymerization of lactide with dibromoneopentyl glycol as the starting material. ¹H NMR and FTIR spectroscopy proved the feasibility of synthetic route and the successful preparation of star‐shaped PLA copolymers. The results of FTIR spectroscopy and XRD showed that the stereocomplex structure of the copolymer could be more perfect after solvent dissolution treatment. Effect of chain architectures on crystallization was investigated by studying the nonisothermal and isothermal crystallization of the miktoarm star‐shaped PLA copolymer and other stereocomplexes. Nonisothermal differential scanning calorimetry and polarizing optical microscopy tests indicated that (PLLA)₂‐core‐(PDLA)₂ exhibited the fastest formation of a stereocomplex in a dynamic test due to its special structure. In isothermal crystallization tests, the copolymer exhibited the fast crystal growth rate and the most perfect crystal morphology. The results reveal that the unique molecular structure has an important influence on the crystallization of the miktoarm star‐shaped PLA copolymer. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 814–826     

Temperature-Responsive Electrocatalysis Based on Poly(N-Isopropylacrylamide)-Modified Graphene Oxide (PNIPAm-GO)

Poly(N-isopropylacrylamide)-modified graphene oxide (PNIPAm-GO), which is a type of thermally responsive GO, was designed and synthesized through a covalent “grafting-from” strategy. The as-prepared modified nanosheets integrated the individual advantages of two components, such as the thermal sensitivity of the PNIPAm terminal as well as the conductivity and the open 2D structure of the GO substrate. PNIPAm-GO was able to perform the reversible regulation of hydrophilicity/hydrophobicity in aqueous solution upon variations in the temperature. Such a unique property might also lead to the utilization of PNIPAm-GO as an intelligent electrode material to achieve a switchable electrochemical response toward a [Fe(CN)₆]^3−/4− probe. The PNIPAm-GO modified glassy carbon electrode (PNIPAm-GO/GC electrode) was able to exhibit better electrochemical performance in an ON/OFF switching effect than the PNIPAm-modified glassy carbon electrode (PNIPAm/GC electrode) without GO owing to the intrinsic properties and large surface area of the introduced GO. Moreover, it was found that the PNIPAm-GO/GC electrode also displayed excellent thermally responsive electrocatalysis toward the detection of 1,4-dihydro-β-nicotinamide adenine dinucleotide (NADH) and dopamine (DA), which resulted in two different catalytic statuses on the same electrode. This kind of switchable catalytic performance of the PNIPAm-GO/GC electrode might greatly enhance the flexibility of its application, and thus it is expected to have wide potential for applications in the fields of biosensors and biocatalysis.     

Pharmacokinetics of monoester‐diterpenoid alkaloids in myocardial infarction and normal rats after oral administration of Sini decoction by microdialysis combined with liquid chromatography–tandem mass spectrometry

Monoester‐diterpenoid alkaloids are the main bioactive components of Sini decoction, which is a well‐known traditional Chinese medicine formula for the treatment of myocardial infarction (MI) and heart failure in China. In this work, an ultra‐high‐performance liquid chromatography–mass spectrometry combined with microdialysis method was successfully established and applied for investigating for the first time comparative plasma pharmacokinetics of three monoester‐diterpenoid alkaloids (benzoylmesaconitine, benzoylaconitine and benzoylhypacoitine) in normal and MI rats after oral administration of Sini decoction. The statistical results of pharmacokinetic parameters demonstrated that benzoylmesaconitine, benzoylaconitine and benzoylhypacoitine showed lower peak concentration, longer half‐life, smaller area under the concentration–time curve, slower clearance, time to peak concentration and mean residence time in MI rats than in normal rats (p < 0.05), which indicated that monoester‐diterpenoid alkaloids exhibited lower systemic exposure and slower elimination in the MI rats. The results provided the experimental basis for understanding the metabolic fate and therapeutic effects of Sini decoction.