Thermal instabilities of organic carbonates with discharged cathode materials in lithium-ion batteries

Thermal instability of lithiated cathode materials with organic carbonate were investigated using DSC. Lithium transition metal oxides of LiFePO₄, LiMn₂O₄, and LiCoO₂ were mixed with diethyl carbonate, dimethyl carbonate, ethylene carbonate, ethyl methyl carbonate, and propylene carbonate then dynamically screened to about 500 °C. Curves were acquired and analyzed to determine exothermic onset temperatures and reaction enthalpies. These data for assessing the thermal hazards of lithium-ion batteries under discharged conditions were compared to those data published in the literature.     

Neo‐Fused Hexaphyrin: A Molecular Puzzle Containing an N‐Linked Pentaphyrin

The first neo‐confused hexaphyrin(1.1.1.1.1.0) was synthesized by oxidative ring closure of a hexapyrrane bearing two terminal “confused” pyrroles. The new compound displays a folded conformation with a short interpyrrolic C???N distance of 3.102 Å, and thus it readily underwent ring fusion to afford a neo‐fused hexaphyrin with an unprecedented 5,5,5,7‐tetracyclic ring structure. Furthermore, coordination of Cu^II triggered a ring opening/contracting reaction to afford a Cu^II complex of an N‐linked pentaphyrin derivative. The roles of reactive N? C bonds in the porphyrinoid macrocycles were demonstrated.     

Hydrogen bond induced chiral symmetry breaking in the crystallization of nickel(II) complexes

A pair of enantiomers formulated as {Δ-cis-[Ni(en)₂OAc][ClO₄]} _n (Δ-1) and {Λ-cis-[Ni(en)₂OAc][ClO₄]} _n (Λ-1) (en = diaminoethane, OAc^? = acetate anion) were obtained when nickel acetate was reacted with diaminoethane and sodium perchlorate in the absence of any chiral source, whereas the reactions of nickel acetate with 1,3-propanediamine and sodium perchlorate only gave a centrosymmetric complex [Ni(1,3-pn)₂OAc][ClO₄] (2) (1,3-pn = 1,3-propanediamine). Single-crystal X-ray diffraction analyses of all three complexes indicated that the central Ni(II) atoms all have a distorted octahedral coordination geometry, being coordinated by four nitrogen atoms of the diamine ligands, plus two oxygen atoms of OAc^?. In complexes Δ-1 and Λ-1, the monomers of {Δ-cis-[Ni(en)₂OAc]}⁺ and {Λ-cis-[Ni(en)₂OAc]}⁺ are connected through intermolecular hydrogen bonds to generate one-dimensional right- and left-handed homochiral helical chains, respectively, while the monomers of [Ni(1,3-pn)₂OAc]⁺ are linked by similar intermolecular hydrogen bonds to form one-dimensional zigzag chains instead of helical chains. The chiral natures of complexes Δ-1 and Λ-1 have been confirmed by circular dichroism spectroscopy.     

Thermal and Nonthermal Effects in Plasmon-Mediated Electrochemistry at Nanostructured Ag Electrodes

Hot carriers (HCs) and thermal effects, stemming from plasmon decays, are crucial for most plasmonic applications. However, quantifying these two effects remains extremely challenging due to the experimental difficulty in accurately measuring the temperature at reaction sites. Herein, we provide a novel strategy to disentangle HCs from photothermal effects based on the different traits of heat dissipation (long range) and HCs transport (short range), and quantitatively uncover the dominant and potential-dependent role of photothermal effect by investigating the rapid- and slow-response currents in plasmon-mediated electrochemistry at nanostructured Ag electrode. Furthermore, the plasmoelectric surface potential is found to contribute to the rapid-response currents, which is absent in the previous studies.     

Host Differential Sensitization toward Color/Lifetime-Tuned Lanthanide Coordination Polymers for Optical Multiplexing

Optical multiplexing based on luminescent materials with tunable color/lifetime has potential applications in information storage and security. However, the available tunable luminescent materials reported so far still suffer from several drawbacks of low efficiency or poor stability, thus restraining their further applications. Herein, we demonstrate a strategy to develop efficient and stable lanthanide coordination polymers (LCPs) with tunable luminescence as a new option for optical multiplexing. Their multicolor emission from green to red and naked-eye-sensitive green emission with tunable lifetime (from ca. 300 to ca. 600 μs) can be controlled by host differential sensitization and energy transfer between lanthanide ions. The quantum efficiencies of developed samples range from around 20 % to 46 % and the luminescence intensity/lifetime appear quite stable in polar solvents up to ten weeks. Furthermore, with the aid of inkjet printing and concepts of luminescence lifetime imaging and time-gated imaging, we illustrate their promising applications of information storage and security in spatial and temporal domains.     

Noninvasive prenatal paternity testing by maternal plasma DNA sequencing in twin pregnancies

SNPs, combined with massively parallel sequencing technology, have proven applicability in noninvasive prenatal paternity testing (NIPPT) for singleton pregnancies in our previous research, using circulating cell-free DNA in maternal plasma. However, the feasibility of NIPPT in twin pregnancies has remained uncertain. As a pilot study, we developed a practical method to noninvasively determine the paternity of twin pregnancies by maternal plasma DNA sequencing based on a massively parallel sequencing platform. Blood samples were collected from 15 pregnant women (twin pregnancies at 9–18 weeks of gestation). Parental DNA and maternal plasma cell-free DNA were analyzed with custom-designed probes covering 5226 polymorphic SNP loci. A mathematical model for data interpretation was established, including the zygosity determination and paternity index calculations. Each plasma sample was independently tested against the alleged father and 90 unrelated males. As a result, the zygosity in each twin case was correctly determined, prior to paternity analysis. Further, the correct biological father was successfully identified, and the paternity of all 90 unrelated males was excluded in each case. Our study demonstrates that NIPPT can be performed for twin pregnancies. This finding may contribute to development in NIPPT and diagnosis of certain genetic diseases.     

Stretchable Perovskite Solar Cells with Recoverable Performance

Perovskite solar cells (PSCs) are a promising photovoltaic technology for stretchable applications because of their flexible, light‐weight, and low‐cost characteristics. However, the fragility of crystals and poor crystallinity of perovskite on stretchable substrates results in performance loss. In fact, grain boundary defects are the “Achilles’ heel” of optoelectronic and mechanical stability. We incorporate a self‐healing polyurethane (s‐PU) with dynamic oxime–carbamate bonds as a scaffold into the perovskite films, which simultaneously enhances crystallinity and passivates the grain boundary of the perovskite films. The stretchable PSCs with s‐PU deliver a stabilized efficiency of 19.15 % with negligible hysteresis, which is comparable to the performance on rigid substrates. The PSCs can maintain over 90 % of their initial efficiency after 3000 hours in air because of their self‐encapsulating structure. Importantly, the self‐healing function of the s‐PU scaffold was verified in situ. The s‐PU can release mechanical stress and repair cracks at the grain boundary on multiple levels. The devices recover 88 % of their original efficiency after 1000 cycles at 20 % stretch. We believe that this ingenious growth strategy for crystalline semiconductors will facilitate development of flexible and stretchable electronics.     

Microfluidic chip electrophoresis for biochemical analysis

Microfluidic chip electrophoresis has been widely employed for separation of various biochemical species owing to its advantages of low sample consumption, low cost, fast analysis, high throughput, and integration capability. In this article, we reviewed the development of four different modes of microfluidics‐based electrophoresis technologies including capillary electrophoresis, gel electrophoresis, dielectrophoresis, and field (electric) flow fractionation. Coupling detection schemes on microfluidic electrophoresis platform were also reviewed such as optical, electrochemical, and mass spectrometry method. We further discussed the innovative applications of microfluidic electrophoresis for biomacromolecules (nucleic acids and proteins), biochemical small molecules (amino acids, metabolites, ions, etc.), and bioparticles (cells and pathogens) analysis. The future direction of microfluidic chip electrophoresis was predicted.     

SiO2交联剂交联MMA聚合制备PMMA/SiO2纳米复合材料

用SiO2交联剂(SiO2HPA)交联甲基丙烯酸甲酯(MMA)自由基聚合制备PMMA SiO2纳米复合材料。采用两步法将可聚合乙烯基单体以化学键的形式键接到SiO2表面合成SiO2交联剂,首先利用过量的甲苯2,4二异氰酸酯(TDI)对SiO2纳米粒子表面进行化学修饰合成出表面带有高反应活性NCO基团的功能化SiO2粒子(SiO2TDI),SiO2TDI与丙烯酸羟丙酯(HPA)反应合成SiO2交联剂。系统研究了MMA单体与SiO2交联剂投料比及聚合时间对聚合反应的影响。此外,利用红外光谱(FT IR)、DSC、TGA、可见光光谱仪等实验手段对纳米复合材料进行了表征分析。结果表明,纳米SiO2粒子在复合材料中起着物理交联点和化学交联点作用,复合材料玻璃化转变温度(Tg)明显地高于其纯PMMA的玻璃化转变温度,随着纳米SiO2粒子含量的增加,复合材料玻璃化温度升高,而透明度明显降低。     

对正负一级能量之比测量光栅参量方法的改进

提出利用同一波长的入射光在双面入射时两个能量之比的比值对光栅的参量进行测量,进一步提高准确度。首先从理论上比较正弦面形光栅在单一面入射及双面入射时各种衍射效率对光栅表面粗糙度的敏感程度;然后模拟测量出该正弦面型光栅在双面入射情况下的光栅参量;最后成功反演出体积相位全息光栅的三个参量,其测量结果为0.080μm,1.452μm,20.5μm准确度比单一入射面情况(0.080μm,1.451μm,20.1μm)时要高。同时该法继承了原来方法的无损伤、操作简便、可重复、易推广、成本低等优点。