Nitrile Oxide‐Norbornene Cycloaddition as a Bioorthogonal Crosslinking Reaction for the Preparation of Hydrogels

This communication describes the first application of cycloaddition between an in situ generated nitrile oxide with norbornene leading to a polymer crosslinking reaction for the preparation of poly(ethylene glycol) hydrogels under physiological conditions. Hydrogels with high water content and robust physical strength are readily formed within 2–5 min by a simple two‐solution mixing method which allows 3D encapsulation of neuronal cells. This bioorthogonal crosslinking reaction provides a simple yet highly effective method for preparation of hydrogels to be used in bioengineering.

     

Well‐Defined High Molecular Weight Polystyrene with High Rates and High Livingness Synthesized via Two‐Stage RAFT Emulsion Polymerization

A highly living polymer with over 100 kg mol⁻¹ molecular weight is very difficult to achieve by controlled radical polymerization since the unavoidable side reactions of irreversible radical termination and radical chain transfer to monomer reaction become significant. It is reported that over 500 kg mol⁻¹ polystyrene with high livingness and low dispersity could be synthesized by a facile two‐stage reversible addition–fragmentation transfer emulsion polymerization. The monomer conversion reaches 90% within 10 h. High livingness of the product is ascribed to the extremely low initiator concentration and the chain transfer constant for monomer unexpectedly much lower than the well‐accepted values in the conventional radical polymerization. The two‐stage monomer feeding policy much decreases the dispersity of the product.

     

Removal of Anionic Dyes from Aqueous Solution with Layered Cationic Aluminum Oxyhydroxide

It is highly desired yet challenged to find an adsorbent with low cost and excellent performance in the removal of organic dyes from aqueous solution. Here we reported that a layered cationic aluminum oxyhydroxide material hydrothermally synthesized from the low-cost source materials of AlCl₃∙6H₂O, CaO and H₂O, known as JU-111, can meet such criterion in removing methyl orange(MO) and Congo red(CR). JU-111 shows fast adsorption kinetics[especially for CR(15 s)] and high adsorption capacity(MO:>1000 mg/g; CR:>2900 mg/g), surpassing most of the reported adsorbents. Comprehensive characterizations of the adsorption process of MO and CR revealed that both adsorptions were achieved via the anion exchange process. The characteristics of extremely low cost and excellent performance render JU-111 great potential in the practical applications in the removal of anionic dyes.     

Influence of Substitutional Defects in ZIF-8 Membranes on Reverse Osmosis Desalination: A Molecular Dynamics Study

In this study, molecular dynamics simulation is used to investigate the effects of water-based substitutional defects in zeolitic imidazolate frameworks (ZIF)-8 membranes on their reverse osmosis (RO) desalination performance. ZIF-8 unit cells containing up to three defect sites are used to construct the membranes. These substitutional defects can either be Zn defects or linker defects. The RO desalination performance of the membranes is assessed in terms of the water flux and ion rejection rate. The effects of defects on the interactions between the ZIF-8 membranes and NaCl are investigated and explained with respect to the radial distribution function (RDF) and ion density distribution. The results show that ion adsorption on the membranes occurs at either the nitrogen atoms or the defect sites. Complete NaCl rejection can be achieved by introducing defects to change the size of the pores. It has also been discovered that the presence of linker defects increases membrane hydrophilicity. Overall, molecular dynamics simulations have been used in this study to show that water-based substitutional defects in a ZIF-8 structure reduce the water flux and influence its hydrophilicity and ion adsorption performance, which is useful in predicting the type and number of defect sites per unit cell required for RO applications. Of the seven ZIF-8 structures tested, pristine ZIF-8 exhibits the best RO desalination performance.     

Computational studies on two novel energetic nitrogen‐rich compounds based on tetrazolone

Two novel energetic nitrogen‐rich compounds 1,4‐diaminotetrazol‐5‐one ( DATO ) and 1,4‐dinitrotetrazol‐5‐one ( DNTO ) were proposed first and studied by quantum chemistry method with B3LYP/6‐31G* level of theory. The optimized geometry, IR predicted spectrum and thermochemical parameters, frontier molecular orbitals and molecular electrostatic potential were calculated for inspecting the electronic structure, molecular stability and chemical reactivity. The important macroscopic properties including density, enthalpy of formation, detonation parameters and impact sensitivity have been predicted as well. As a result, two designed compounds DATO and DNTO possess positive enthalpy of formation (395.79 and 342.77 kJ/mol), impressive detonation parameters (D = 8.80 km/s, P = 33.69 GPa; D = 8.89 km/s, P = 34.98 GPa) superior to the remarkable explosive RDX, acceptable sensitivities and might be promising candidates of energetic materials. Copyright © 2015 John Wiley & Sons, Ltd.     

真空中铝单丝电爆炸的实验研究

开展了铝单丝在负极性电流脉冲作用下电爆炸特性的研究.利用皮秒激光探针,搭建了阴影、纹影和干涉的光学诊断平台,得到了不镀膜铝丝典型的能量沉积过程,在电压崩溃时刻其沉积能量为2.4 eV/atom.为了增加金属丝内的沉积能量,开展了相同电参数及金属丝尺寸下的镀膜铝丝电爆炸实验,其沉积能量可达到5 eV/atom,实现了在电压崩溃之前铝丝完全气化(完全气化所需能量为4 eV/atom).阴影图像展示了高密度丝核区域的膨胀过程,不镀膜铝丝平均膨胀速度为2.2 km/s,而镀膜铝丝因为沉积能量大,其膨胀速度约为不镀膜铝丝的2.3倍,高密度区域膨胀速度为5 km/s.由于阴影不能反映低密度等离子体的膨胀,开展了平行双丝实验,通过测量自发光辐射,估算了低密度等离子体的膨胀速度.利用条纹相机拍摄了不镀膜铝丝电爆炸过程中自发光区域的图像.纹影图像清晰地展示了不镀膜铝丝在电爆炸过程中形成的核冕结构,而镀膜铝丝电爆炸过程中核冕结构得到了一定程度的抑制.从干涉图像计算了相移,在轴对称假设下对相移进行阿贝尔逆变换,重构了三维的铝原子数密度分布.     

Real time microscopy, kinetics, and mechanism of giant fullerene evaporation

We report in situ high-resolution transmission electron microscopy observing the shrinkage of single-layer giant fullerenes (GF). At temperatures approximately 2000 degrees C, the GF volume reduces by greater than one 100-fold while the fullerene shell remains intact, evolving from a slightly polygonized to a nearly spherical shape with a smaller diameter. The number of carbon atoms in the GF decreases linearly with time until the small subbuckyball cage opens and rapidly disappears. Theoretical modeling indicates that carbon atoms are removed predominantly from the weakest binding energy sites, i.e., the pentagons, leading to the constant evaporation rate. The fullerene cage integrity is attributed to the collective behavior of interacting defects. These results constitute the first experimental evidence for the "shrink-wrapping" and "hot-giant" fullerene formation mechanisms.     

Analytical analysis of anisotropic thermophoresis of a charged spheroidal colloid in aqueous media for extremely thin EDL cases

Thermophoresis of charged spheroids has been widely applied in biology and medical science. In this work, we report an analysis of the anisotropic thermophoresis of diluted spheroidal colloids in aqueous media for extremely thin EDL cases. Under the boundary layer approximation, we formulate the thermophoretic velocity, the thermophoretic force, and the thermodiffusion coefficient of a randomly dispersed spheroid. The parametric studies show that under the aforementioned conditions, the thermophoresis is anisotropic and its thermodiffusion coefficient should be considered as a vector, D _T. The thermodiffusion coefficient values and directions of D _T are strongly related to the aspect ratio and the angle θ between the externally applied temperature gradient and the particle's axis of revolution: The increasing aspect ratio enlarges the thermodiffusion coefficient value D_T of prolate (oblate) spheroids to a constant value when θ < 60° (θ > 45°), and it reduces D_T of prolate (oblate) spheroids to a constant value when θ > 60° (θ < 45°). The thermodiffusion coefficient direction of both prolate and oblate spheroids deviates slightly from −∇T_∞ for a small aspect ratio, and such deviation becomes serious for a large aspect ratio.     

Platinum nanoparticle-doped multiwalled carbon-nanotube-modified glassy carbon electrode as a sensor for simultaneous determination of atenolol and propranolol in neutral solution

Ionics - In this paper, the simultaneous determination of β-blockers (atenolol (ATN) and propranolol (PRO)) was investigated using cyclic voltammetry (CV) and differential pulse voltammetry...     

纳米金刚石掺混纳米氧化锌的场发射特性

利用水热法制备了菊花状的氧化锌纳米棒,并进行表征,将纳米氧化锌掺入纳米金刚石中配制成电泳液,超声分散后电泳沉积到钛衬底上,再经热处理后进行场发射特性的测试.结果表明:未掺混的金刚石阴极样品的开启电场为7.3V/μm,在20V/μm的电场下,场发射电流密度为81μA/cm2;掺混后阴极样品的场发射开启电场降低到4.7~6.0V/μm,在20V/μm电场下,场发射电流密度提高到140~158μA/cm2.原因是纳米ZnO掺入后,增强了涂层的电子输运能力、增加了有效发射体数目,提高了场增强因子β,而金刚石保证了热处理后涂层与衬底的良好键合,形成了欧姆接触,降低了场发射电流的热效应.场发射电流的稳定性随掺混ZnO量的增加而下降,要兼顾场发射电流密度及其稳定性,适量掺入ZnO可有效提高纳米金刚石的场发射性能.