Effects of Polydispersity on the Phase Behavior of Additive Hard Spheres in Solution

The ability to separate enzymes, nucleic acids, cells, and viruses is an important asset in life sciences. This can be realised by using their spontaneous asymmetric partitioning over two macromolecular aqueous phases in equilibrium with one another. Such phases can already form while mixing two different types of macromolecules in water. We investigate the effect of polydispersity of the macromolecules on the two-phase formation. We study theoretically the phase behavior of a model polydisperse system: an asymmetric binary mixture of hard spheres, of which the smaller component is monodisperse and the larger component is polydisperse. The interactions are modelled in terms of the second virial coefficient and are assumed to be additive hard sphere interactions. The polydisperse component is subdivided into sub-components and has an average size ten times the size of the monodisperse component. We calculate the theoretical liquid–liquid phase separation boundary (the binodal), the critical point, and the spinodal. We vary the distribution of the polydisperse component in terms of skewness, modality, polydispersity, and number of sub-components. We compare the phase behavior of the polydisperse mixtures with their concomittant monodisperse mixtures. We find that the largest species in the larger (polydisperse) component causes the largest shift in the position of the phase boundary, critical point, and spinodal compared to the binary monodisperse binary mixtures. The polydisperse component also shows fractionation. The smaller species of the polydisperse component favor the phase enriched in the smaller component. This phase also has a higher-volume fraction compared to the monodisperse mixture.     

含羟基基团取代的氮氧自由基构筑的三个双核稀土化合物的结构及磁性表征

以三氟乙酰丙酮(tfac)为共配体的稀土配合物分别与5-溴-2-羟基苯取代的自由基配体和5-硝基-2-羟基苯取代的自由基配体进行反应,合成3个稀土-自由基配合物[Ln2(tfac)4(NIT-5Br-2PhO)2](Ln=Gd (1),Dy (2))和[Dy2(tfac)4(NIT-5NO2-2PhO)2](3)(NIT-5Br-2PhOH=2-(2′-hydroxy-5′-bromophenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide,NIT-5NO2-2PhOH=2-(2′-hydroxy-5′-nitrophenyl)-4,4,5,5-tetra-methylimidazoline-1-oxyl-3-oxide)。单晶结构分析表明这3个化合物中的稀土离子均通过自由基配体上的羟基氧基团连接为双核的结构。配合物1的直流磁化率表征揭示了Gd(Ⅲ)离子间的反铁磁耦合对其磁行为起主要作用。     

Cooperative Chemotaxis of Magnesium Microswimmers for Corrosion Spotting

Numerous artificial micro- and nanomotors, as well as various swimmers have been inspired by living organisms that are able to move in a coordinated manner. Their cooperation has also gained a lot of attention because the resulting clusters are able to adapt to changes in their environment and to perform complex tasks. However, mimicking such a collective behavior remains a challenge. In the present work, magnesium microparticles are used as chemotactic swimmers with pronounced collective features, allowing the gradual formation of macroscopic agglomerates. The formed clusters act like a single swimmer able to follow pH gradients. This dynamic behavior can be used to spot localized corrosion events in a straightforward way. The autonomous docking of the swimmers to the corrosion site leads to the formation of a local protection layer, thus increasing corrosion resistance and triggering partial self-healing.     

Noncovalent Axial I⋅⋅⋅Pt⋅⋅⋅I Interactions in Platinum(II) Complexes Strengthen in the Excited State

Coordination compounds of platinum(II) participate in various noncovalent axial interactions involving metal center. Weakly bound axial ligands can be electrophilic or nucleophilic; however, interactions with nucleophiles are compromised by electron density clashing. Consequently, simultaneous axial interaction of platinum(II) with two nucleophilic ligands is almost unprecedented. Herein, we report structural and computational study of a platinum(II) complex possessing such intramolecular noncovalent I⋅⋅⋅Pt⋅⋅⋅I interactions. Structural analysis indicates that the two iodine atoms approach the platinum(II) center in a “side-on” fashion and act as nucleophilic ligands. According to computational studies, the interactions are dispersive, weak and anti-cooperative in the ground electronic state, but strengthen substantially and become partially covalent and cooperative in the lowest excited state. Strengthening of I⋅⋅⋅Pt⋅⋅⋅I contacts in the excited state is also predicted for the sole previously reported complex with analogous axial interactions.     

Photovoltammetric behavior and photoelectrochemical determination of p-phenylenediamine on CdS quantum dots and graphene hybrid film

A photoelectroactive film composed of CdS quantum dots and graphene sheets (GS) was coated on F-doped SnO₂ (FTO) conducting glass for studying the electrochemical response of p-phenylenediamine (PPD) under photoirradiation. The result indicated that the cyclic voltammogram of PPD on CdS–GS hybrid film became sigmoidal in shape after exposed under visible light, due to the photoelectrocatalytic reaction. Such a photovoltammetric response was used to rapidly optimize the photoelectrocatalytic activity of hybrid films composed of different ratios of CdS to GS toward PPD. The influences of scan rate and pH on the photovoltammetric behavior of PPD on CdS–GS film revealed that although the controlled step for electrochemical process was not changed under photoirradiation, more electrons than protons might participate the photoelectrocatalytic process. Furthermore, the photoelectroactive CdS–GS hybrid film was explored for PPD determination based on the photocurrent response of film toward PPD. Under optimal conditions, the photocurrent signal on CdS–GS film was linearly proportional to the concentration of PPD ranging from 1.0 × 10⁻⁷ to 3.0 × 10⁻⁶ mol L⁻¹, with a detection limit (3S/N) of 4.3 × 10⁻⁸ mol L⁻¹. Our work based on CdS–GS hybrid film not only demonstrated a new facile photovoltammetric way to study the photoinduced electron transfer process of PPD, but also developed a sensitive photoelectrochemical strategy for PPD determination.     

Electrocatalytic activity of porous nanostructured Fe/Pt-Fe electrode for methanol electrooxidation in alkaline media

An electrochemical approach to fabricate a nanostructured Fe/Pt-Fe catalyst through electrodepo-sition followed by galvanic replacement is presented. An Fe/Pt-Fe nanostructured electrode was prepared by deposition of Fe-Zn onto a Fe electrode surface, followed by replacement of the Zn by Pt at open-circuit potential in a Pt-containing alkaline solution. Scanning electron microscopy and energy-dispersive X-ray techniques reveal that the Fe/Pt-Fe electrode is porous and contains Pt. The electrocatalytic activity of the Fe/Pt-Fe electrode for oxidation of methanol was examined by cyclic voltammetry and chronoamperometry. The electrooxidation current on the Fe/Pt-Fe catalyst is much higher than that on flat Pt and smooth Fe catalysts. The onset potential and peak potential on the Fe/Pt-Fe catalyst are more negative than those on flat Pt and smooth Fe electrodes for methanol electrooxidation. All results show that this nanostructured Fe/Pt-Fe electrode is very attractive for integrated fuel cell applications in alkaline media.     

Fabrication of microporous membranes from melt extruded polypropylene precursor films via stretching: Effect of annealing

In this work, the effects of annealing conditions on the microstructure of polypropylene(PP) precursor films and further on the porous structure and permeability of stretched membranes were investigated. Combinations of WAXD, FTIR, DSC and DMA results clearly showed the crystalline orientation and crystallinity of the precursor film increased with annealing temperature, while the molecular chain entanglements in the amorphous phase decreased. Changes in the deformation behavior suggested more lamellar separation occurred for the films annealed at higher temperatures. Surface morphologies of the membranes examined by SEM revealed more pore number and uniform porous structure as the annealing temperature increased. In accordance with the SEM results, the permeability of the membranes increased with annealing temperature. On the other hand, it was found that 10 min was almost enough for the annealing process to obtain the microporous membranes with an optimal permeability.     

邻位取代基对芳基杂环磷酸盐成核有效性的影响

以2,4-二叔丁基苯酚为原料分别合成2,2'-亚甲基双(4,6-二叔丁基苯基)磷酸钠(NA-1)和2,2'-亚甲基双(4-叔丁基苯基)磷酸钠(NA-2),并将其应用于等规聚丙烯(i PP),研究该类芳基杂环磷酸盐成核剂邻位取代基对其成核有效性的影响.通过红外吸收光谱(FTIR)、核磁共振谱(NMR)、X-Ray多晶粉末衍射(XRD)、扫描电镜分析(SEM)和热分析对其化学结构、凝聚态结构、颗粒形貌和物性特征进行了表征,确定了NA-1和NA-2的分子结构和凝聚态颗粒的结构、形貌和物性特征.利用偏光显微观察(POM)、扫描电镜(SEM)断口分析、示差式扫描量热分析(DSC)和雾度测试分析对其与i PP的复合材料的晶粒结构、结晶行为及宏观光学性能进行测试表征.结果表明,添加量0.2%时,邻位叔丁基(NA-1)的存在可使复合材料球晶尺度更加细密,结晶温度比无邻位叔丁基(NA-2)增加5.1 K,等温结晶速率提高至0.56 w/g是NA-2的7倍,半结晶时间由NA-2的11.55 min下降至2.36 min,邻位叔丁基存在对材料透光率和雾度值的影响分别达到4.3%,7.4%.SEM断口分析表明二者在i PP基体中分散均匀,平均粒径相近分别为0.79μm和0.82μm,粒径分布曲线相近,二者分散分布的差异性不显著.     

界面扩张流变法研究C12mimBr对Gemini12-2-12在空气/水界面聚集行为的影响

采用界面扩张流变技术研究了季铵盐偶联表面活性剂C₁₂-(CH₂)₂-C₁₂·2Br (Gemini12-2-12)及其与离子液体表面活性剂溴化1-十二烷基-3-甲基咪唑(C₁₂mimBr)复配体系的动态界面张力、扩张流变性质和界面弛豫过程等, 探讨了C₁₂mimBr 对C₁₂mimBr/Gemini12-2-12 混合体系界面性质的影响及C₁₂mimBr 对Gemini12-2-12界面聚集行为影响的机制. 结果表明, 随着离子液体表面活性剂的不断引入, 体系界面吸附达到平衡所需的时间逐渐缩短, 扩张模量和相角明显降低, 界面吸附膜由粘弹性膜转变为近似纯弹性膜; 同时, 界面及其附近的弛豫过程也发生显著变化, 慢弛豫过程消失, 快弛豫过程占主导地位, 且离子液体浓度越高, 快弛豫的贡献越大. 这些界面性质的变化主要归因于离子液体表面活性剂C₁₂mimBr参与界面形成及两表面活性剂在界面竞争吸附的结果. 少量离子液体表面活性剂C₁₂mimBr 的加入可以填补疏松的Gemini12-2-12 界面上的空位, 形成混合界面吸附膜. 随着C₁₂mimBr 含量的增加, 嵌入界面的C₁₂mimBr 分子数不断增多, 导致界面上相互缠绕的Gemini12-2-12烷基链“解缠”, 在体相和界面分子扩散交换的过程中“解缠”的Gemini12-2-12分子从界面上解吸回到体相, 与此同时, C₁₂mimBr 分子相对较小的空间位阻及较强的疏水作用促使其优先扩散至界面进而取代Gemini12-2-12分子, 最终界面几乎完全被C₁₂mimBr分子所占据.     

Li3V2（PO4）3/C正极材料在不同电压区间的电化学行为及容量衰减原因

采用溶胶-凝胶法制备锂离子电池正极材料Li3V2(PO4)3/C.通过恒电流充放电测试、循环伏安(CV)、电化学阻抗谱(EIS)等方法,研究了Li3V2(PO4)3/C在不同电压区间的电化学行为(3.0-4.5 V和3.0-4.8 V).结果表明,3.0-4.8 V电压区间的循环性能和倍率性能均不及3.0-4.5 V电压区间的.3.0-4.5 V区间0.1C (1C=150 mA?g-1)倍率首次放电比容量为127.0 mAh?g-1,循环50次后容量保持率为99.5%,而3.0-4.8 V区间的分别为168.2 mAh?g-1和78.5%.经过高倍率测试后再回到0.1C倍率充放电,3.0-4.5 V和3.0-4.8 V的放电比容量分别为初始0.1C倍率的99.0%和80.7%.经过3.0-4.8 V电压区间测试后,少部分第三个锂离子能够在低于4.5 V的电压脱出,使3.0-4.5 V电压区间的放电比容量提升了7.4%. CV结果表明3.0-4.8 V区间的容量损失主要表现为第一个锂离子的不可逆损失.极片的X射线衍射(XRD)和X射线光电子能谱(XPS)分析测试结果表明经过3.0-4.8 V测试后, Li3V2(PO4)3的结构发生了轻微的改变.电感耦合等离子体(ICP)测试结果表明循环后的电解液中含有少量的V.结构变形和V溶解可能是Li3V2(PO4)3在3.0-4.8 V区间容量衰减的主要原因.