Simple synthesis of zwitterionic diblock copolymers for the application on metal nanoparticles preparation

AB diblock copolymers of poly(2-(dimethylamino)ethyl metharylate-block-potassiurn acrylate) were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. The structure of the block polymer was determined by the nuclear magnetic resonance (NMR) spectroscopy and the gel permeation chromatography. Moreover, it has also been shown that the diblock copolymers exhibit aggregate as function of the pH according to the result of ¹H-NMR spectroscopy, FT-IR absorption spectra, UV-vis transmittance spectroscopy, transmission electron microscopy and ultrasonic particle size analyzer. The result was attributed that such AB diblock copolymers were tailored to undergo pH-induced self-assembly. Furthermore, the aggregate can be as template of metal nanoparticles preparation, and the sizes of the aggregate, in turn, strongly control nanoparticle sizes.     

Perturbation solution to heat conduction in melting or solidification with heat generation

The Stefan problem involving a source term is considered in this technical note. As an example, planar solidification with time-dependent heat generation in a semi-infinite plane is solved by use of a perturbation technique. The perturbation solution is validated by reducing the problem to the case without heat generation whose exact solution is available. An application to the case with constant heat generation is presented, for which a closed-form solution is obtained. The effects of heat generation and Stefan number on the evolution of solidification are examined using the perturbation solution.     

纳米孔缺陷导致单层黑磷电荷局域极大抑制非辐射电子-空穴复合的时域模拟

通常认为缺陷加速黑磷的非辐射电子-空穴复合,阻碍器件性能的持续提高。实验打破了这一认识。采用含时密度泛函理论结合非绝热分子动力学,我们发现P-P伸缩振动驱动非辐射电子-空穴复合,使纳米孔修饰的单层黑磷的激发态寿命比完美体系延长了约5.5倍。这主要归因于三个因素。一,纳米孔结构不但没有在禁带中引入深能级缺陷,而且由于价带顶下移使带隙增加了0.22 eV。二,除了带隙增加,纳米孔减小了电子和空穴波函数重叠,并抑制了原子核热运动,从而使非绝热耦合降低至完美体系的约1/2。三,退相干时间比完美体系延长了1.5倍。前两个因素战胜了第三个因素,使纳米孔结构激发态寿命延长至2.74 ns,而其在完美体系中约为480 ps。我们的研究表明可以制造合理数量和形貌的缺陷,如纳米孔,降低黑磷非辐射电子-空穴复合,提高光电器件效率。这一研究对于理解和调控黑磷和其它二维材料的激发态性质有重要意义。     

Regulating Oxygen Configuration in Hierarchically Porous Carbon Nanosheets for High-Rate and Durable Na+ Storage

Surface oxygen functionalities (particularly C−O configuration) in carbon materials have negative influence on their electrical conductivity and Na⁺ storage performance. Herein, we propose a concept from surface chemistry to regulate the oxygen configuration in hierarchically porous carbon nanosheets (HPCNS). It is demonstrated that the C−O/C=O ratio in HPCNS reduces from 1.49 to 0.43 and its graphitization degree increases by increasing the carbonization temperature under a reduction atmosphere. Remarkably, such high graphitization degree and low C−O content of the HPCNS-800 are favorable for promoting its electron/ion transfer kinetics, thus endowing it with high-rate (323.6 mAh g⁻¹ at 0.05 A g⁻¹ and 138.5 mAh g⁻¹ at 20.0 A g⁻¹) and durable (96 % capacity retention over 5700 cycles at 10.0 A g⁻¹) Na⁺ storage performance. This work permits the optimization of heteroatom configurations in carbon for superior Na⁺ storage.     

细菌感染成像的研究进展

由致病菌或条件致病菌侵入机体繁殖而产生的毒素和其它代谢产物所引起的感染性疾病是目前全球范围内的主要死亡原因之一. 感染性疾病的早期诊断是对其进行有效治疗与控制的重要途径. 分子影像技术的快速发展给体内细菌感染的评估带来了前所未有的变化和机遇. 本文综合评述了计算机断层扫描、 正电子发射断层扫描、 超声成像、 磁共振成像、 荧光成像及光声成像等成像方式在细菌感染体内成像中的研究进展、 不足和发展方向等, 以期为活体细菌感染检测方法的发展提供参考.     

Positive Charges in the Brace Region Facilitate the Membrane Disruption of MLKL-NTR in Necroptosis

Necroptosis is a type of programmed cell death executed through the plasma membrane disruption by mixed lineage kinase domain-like protein (MLKL). Previous studies have revealed that an N-terminal four-helix bundle domain (NBD) of MLKL is the executioner domain for the membrane permeabilization, which is auto-inhibited by the first brace helix (H6). After necroptosis initiation, this inhibitory brace helix detaches and the NBD can integrate into the membrane, and hence leads to necroptotic cell death. However, how the NBD is released and induces membrane rupture is poorly understood. Here, we reconstituted MLKL_2–154 into membrane mimetic bicelles and observed the structure disruption and membrane release of the first brace helix that is regulated by negatively charged phospholipids in a dose-dependent manner. Using molecular dynamics simulation we found that the brace region in an isolated, auto-inhibited MLKL_2–154 becomes intrinsically disordered in solution after 7 ns dynamic motion. Further investigations demonstrated that a cluster of arginines in the C-terminus of MLKL_2–154 is important for the molecular conformational switch. Functional mutagenesis showed that mutating these arginines to glutamates hindered the membrane disruption of full-length MLKL and thus inhibited the necroptotic cell death. These findings suggest that the brace helix also plays an active role in MLKL regulation, rather than an auto-inhibitory domain.     

Eutectic Molecular Liquids Based on Hydrogen Bonding and π–π Interaction for Exfoliating Two‐dimensional Materials and Recycling Polymers

Eutectic molecular liquids (EMLs) based on hydrogen‐bonding interaction and π–π stacking were prepared. We found that the thermodynamic properties like initial decomposition temperature and glass transition temperature of EMLs are mainly dominated by the hydrogen bond donor, which is beneficial for designing and preparing new EMLs. These new liquid systems could be applied in the field of environmental and material science.     

A coordination polymer of CdCl2 with the novel zwitterionic dicarboxylate ligand 2,2′‐(2‐methylbenzimidazolium‐1,3‐diyl)diacetate (pda)

The title compound, poly[chlorido[μ₄‐2,2′‐(2‐methylbenzimidazolium‐1,3‐diyl)diacetato]cadmium(II)], [Cd(C₁₂H₁₁N₂O₄)Cl]_n, is an undulating two‐dimensional polymer consisting of a paddlewheel Cd₂(CO₂)₄ cluster which lies on an inversion centre. These paddlewheel clusters act as four‐connected square building units interlinked via bridging zwitterionic dicarboxylate ligands into a corrugated layer which is consolidated by π–π interactions between benzene rings of benzimidazole groups. Neighbouring layers are further assembled via interlayer π–π interactions into a three‐dimensional supramolecular structure. The key feature of this study is the synthesis of a paddlewheel‐based polymer constructed with a novel multifunctional zwitterionic dicarboxylate ligand.     

键合香豆素席夫碱基的杯[4]芳烃的合成及其对金属离子的荧光识别作用

通过5,17-二氨基杯[4]芳烃衍生物与7-羟基-8-甲酰基-4-甲基香豆素缩合,得到了一种以亚胺基团为离子载体、香豆素为荧光基团的新型杯芳烃荧光识别试剂。 采用IR、1H NMR、13C NMR和MS测试技术表征了合成化合物的结构。 通过紫外光谱和荧光光谱,研究了其对过渡金属和重金属离子的识别性能。 结果表明,该化合物对Fe3+和Cr3+离子具有选择识别能力,与Fe3+和Cr3+配合的化学计量比为1∶1,配合生成常数分别为4.1×105和1.07×105 L/mol。