新型含吡啶基团二羧酸配体的合成及单晶培养

以1，4-二溴-2，5-二甲基苯和4-吡啶硼酸为原料，经两步合成了一种新颖的含吡啶基团的二羧酸配体。通过核磁共振氢谱及傅里叶变换红外光谱对配体结构进行表征，通过热重分析对配体的热稳定性进行了测试；通过溶剂热法对配体的单晶进行培养，并考察反应温度、时间、pH和溶剂等条件对单晶培养的影响。结果表明：在反应温度为80 ℃，反应时间为12 h、溶剂为蒸馏水、溶液pH=5的条件下可获得高质量单晶。该配体为单斜晶系，属于C2/c空间群，结构中含有4个氧原子和2个氮原子，可为金属离子的配位提供足够的位点，有望应用于配合物的设计或催化、吸附和医药载体等行业。     

Random copolymerization of macromonomers as a versatile strategy to synthesize mixed-graft block copolymers

The random copolymerization of norbornene-functionalized macromonomers was explored as a method of synthesizing mixed-graft block copolymers (mGBCPs). The copolymerization kinetics of a model system of polystyrene (PS) and poly(lactic acid) (PLA) macromonomers was first analyzed, revealing a gradient composition of side chains along the mGBCP backbone. The phase separation behavior of mGBCPs with PS and PLA side chains of various backbone lengths and side chain molar ratios was investigated, and increasing the backbone length was found to stabilize the phase-separated nanostructures. The graft architecture was also demonstrated to improve the processability of the mGBCP, compared to a linear counterpart. Investigations of mGBCPs comprised of polydimethylsiloxane and poly(ethylene oxide) side chains exemplified the diverse self-assembled morphologies, including a Frank-Kasper A15 phase, that can be obtained with mGBCPs synthesized by random copolymerization of macromonomers. Lastly, a ternary mGBCP was synthesized by the copolymerization of three macromonomers.     

Fracture behavior and mechanical,thermal, and rheological properties of biodegradable films extruded by flat die and calender

The development of biodegradable materials for tailored applications, particularly in the field of polymeric films and sheets, is a challenging technological goal as well as a contribution to help protect the environment. Poly(lactic) acid (PLA) is a promising substitute for several oil-based polymers; however, to overcome its thermal and mechanical drawbacks, researchers have developed solutions such as blending PLA with polybutylene adipate terephthalate (PBAT), which is capable of increasing the ductility of the final material. In this study, PLA/PBAT binary blends, with minimum possible content of nonrenewable materials, were examined from processing, thermal, morphological, and rheological perspective. An optimized PLA/PBAT ratio was chosen as the polymeric basis to obtain a biodegradable formulation by adding a biobased plasticizer and appropriate fillers to produce a micrometer film with tailored flexibility and tear resistance. The processing technology involved flat-die extrusion, followed by calendering. The tearing resistance of the produced film was investigated, and the results were compared with literature data. A study on the essential work of fracture was implemented to explore the mode III out-of-plane fracture resistance starting from a trouser tear test.     

Pentapnictogen heterocyclic monoanions: Structure,stability, and aromaticity

Inorganic planar ring-shape molecules with 4n + 2 π electrons are always the focus of experimental synthesis and theoretical research due to their potential aromaticity and stability. In this work, the whole series of five-membered heterocycle monoanions X _nY_5-n⁻ (X, Y = group 15 elements; n = 1-4) were thoroughly investigated by means of density functional theory calculations. They all have large formation energies and HOMO-LUMO gap energies, suggesting the potential thermodynamic and kinetic stability. Their aromaticities are comparable to that of typical aromatic hydrocarbons. Their thermal stabilities were firmly established by the ab initio molecular dynamics simulations. As most of them are predicted for the first time, their various spectra were simulated for experimental characterization. Furthermore, we demonstrate that these five-membered cyclic anions can be employed as η⁵-ligand to construct novel all-inorganic metallocenes, which may serve as the building blocks of low-dimensional nanomaterials.     

Synthesis and Self-Assembly of Mixed-Graft Block Copolymers

Mixed-graft block copolymers (mGBCPs) consist of two or more types of polymeric side chains grafted on a linear backbone in a random, alternating, or pseudo-alternating sequence. They can phase-separate with the backbone serving as the interface of the blocks, and the side chains dominate their self-assembly behavior. mGBCPs are an accessible polymer architecture for exploring the idea of encoding polymer properties through the macromolecular architecture, as there are two distinct structural components that can be tuned: the backbone and the side chains. In this Concept article, the current literature on the synthesis of mGBCPs is reviewed, and the advantages and disadvantages of each synthetic method are noted. The self-assembly of mGBCPs is also discussed where possible. Finally, directions for future research on mGBCP synthesis and self-assembly are suggested.     

The Landscape of the Spiked Tensor Model

We consider the problem of estimating a large rank-one tensor u ^⊗k ∈ (ℝⁿ)^⊗k , k ≥ 3 , in Gaussian noise. Earlier work characterized a critical signal-to-noise ratio λ  _Bayes = O(1) above which an ideal estimator achieves strictly positive correlation with the unknown vector of interest. Remarkably, no polynomial-time algorithm is known that achieved this goal unless λ ≥ Cn^{(k − 2)/4} , and even powerful semidefinite programming relaxations appear to fail for 1 ≪ λ ≪ n^{(k − 2)/4} . In order to elucidate this behavior, we consider the maximum likelihood estimator, which requires maximizing a degree-k homogeneous polynomial over the unit sphere in n dimensions. We compute the expected number of critical points and local maxima of this objective function and show that it is exponential in the dimensions n , and give exact formulas for the exponential growth rate. We show that (for λ larger than a constant) critical points are either very close to the unknown vector u or are confined in a band of width Θ(λ^{−1/(k − 1)}) around the maximum circle that is orthogonal to u . For local maxima, this band shrinks to be of size Θ(λ^{−1/(k − 2)}) . These “uninformative” local maxima are likely to cause the failure of optimization algorithms. © 2019 Wiley Periodicals, Inc.