Polar Isotactic and Syndiotactic Polypropylenes by Organozirconium-Catalyzed Masking-Reagent-Free Propylene and Amino-Olefin Copolymerization.

Polar functionalized isotactic and syndiotactic polypropylenes (PPs) are synthesized by direct, masking-reagent-free propylene and amino-olefin (AO, CH2 =CH(CH2 )x Nn Pr2 , x=2, 3, 6) copolymerizations using the activated precatalysts rac-[Me2 Si(indenyl)2 ]ZrMe2 and [Me2 C(Cp)(fluorenyl)]ZrMe2 , respectively. Polymerization activities at 25 °C are as high as 4208 and 535 kg/(mol h atm) with AO incorporation up to 4.0 mol % and 1.6 mol %, respectively. Remarkably, introducing the amino-olefin comonomers significantly enhances stereoselection for both isotactic (mmmm: 59.5 %→91.0 %) and syndiotactic (rrrr: 66.3 %→81.3 %) products.

Anionic polymerization of p-(2,2'-diphenylethyl)styrene and applications to graft copolymers.

Well-controlled anionic polymerization of an initiator-functionalized monomer, p-(2,2'-diphenylethyl)styrene (DPES), was achieved for the first time. The polymerization was performed in a mixed solvent of cyclohexane and tetrahydrofuran (THF) at 40 °C with n-BuLi as initiator. When the volume ratio of cyclohexane to THF was 20, the anionic polymerization of DPES showed living polymerization characteristics, and well-defined block copolymer PDPES-b-PS was successfully synthesized. Furthermore, radical polymerization of methyl methacrylate in the presence of PDPES effectively afforded a graft copolymer composed of a polystyrene backbone and poly(methyl methacrylate) branches. The designation of analogous monomers and polymers was of great significance to synthesize a variety of sophisticated copolymer and functionalize polymer materials.

Synthesis of hypergrafted poly[4-(N,N-diphenylamino)methylstyrene] through tandem anionic-radical polymerization of radical-inimer.

In this paper, we present a tandem anionic-radical approach for synthesizing hypergrafted polymers. We prepared 4-(N,N-diphenylamino)methylstyrene (DPAMS) as a new radical-based inimer. Linear PDPAMS was prepared through anionic polymerization. Hypergrafted PDPAMS was synthesized through the self-condensing vinyl polymerization of DPAMS with linear PDPAMS. The linear backbone of PDPAMS, which incorporated latent radical initiating sites, served as a 'hyperlinker' to link hyperbranched side chains. The molecular weights of hypergrafted polymers increased as the length of the linear backbone chain increased. The hypergrafted structure of the resulting polymer was confirmed using a conventional gel permeation chromatograph apparatus equipped with a multiangle light scattering detector, nuclear magnetic resonance, differential scanning calorimetry, and thermogravimetric analysis. This strategy can be applied to synthesize other complex architectures based on hyperbranched polymers by changing the structure of a polymer backbone through anionic polymerization.

Constructing multi-layer heterogeneous interfaces in liquid metal graphite hybrid powder: Towards microwave absorption enhancement.

Carbon based materials are widely used in the preparation of microwave absorption materials due to their low density, high attenuation loss and large specific surface area. However, their high conductivity usually leads to high reflection loss. In this study, multi-layer heterogeneous interfaces were constructed in liquid metal graphite hybrid powder to reduce reflection loss and enhance microwave absorption performance. Gallium oxide (Ga2O3) layer was formed in Ga coated graphite powder to improve impedance matching and attenuation constant via an annealing treatment. Specifically, the hybrid particles with 50 wt% Ga and being annealed at 120 °C for 2 h have a minimum reflection loss (RLmin) value of -42.68 dB and a maximum effective absorption bandwidth (EAB) of 4.11 GHz at a thickness of 3.3 mm. The hybrid particles not only have multi-layer structures with different electrical conductivity, but also form heterojunctions between different interfaces, which can further enhance dipole and interfacial polarization.

DNAJ heat shock protein family member C1 can regulate proliferation and migration in hepatocellular carcinoma.

Background: DNAJ heat shock protein family (Hsp40) member C1(DNAJC1) is a member of the DNAJ family. Some members of the DNAJ gene family had oncogenic properties in many cancers. However, the role of DNAJC1 in hepatocellular carcinoma (HCC) was unclear. Methods: In this study, expression and prognostic value of DNAJC1 in HCC were analyzed by bioinformatics. Quantitative real-time PCR and Western blotting were used to verify DNAJC1 expression in liver cancer cell lines. Furthermore, immunohistochemical (IHC) was used to detect DNAJC1 expression in liver cancer tissues. Subsequently, the effect of DNAJC1 on the proliferation, migration, invasion and apoptosis of HCC cells was detected by knocking down DNAJC1. Finally, gene set enrichment analysis (GSEA) was used to investigate the potential mechanism of DNAJC1 and was verified by Western blotting. Results: DNAJC1 was highly expressed in HCC and was significantly associated with the prognosis of patients with HCC. Importantly, the proliferation, migration and invasion of Huh7 and MHCC97H cells were inhibited by the knockdown of DNAJC1 and the knockdown of DNAJC1 promoted Huh7 and MHCC97H cell apoptosis. Furthermore, compared to the negative control group, DNAJC1 knockdown in Huh7 and MHCC97H cells promoted the expression of p21, p53, p-p53(Ser20), Bax and E-cadherin proteins, while inhibiting the expression of PARP, MMP9, Vimentin, Snai1, Bcl-2 and N-cadherin proteins. Conclusions: DNAJC1 had a predictive value for the prognosis of HCC. Knockdown of DNAJC1 may inhibit HCC cell proliferation, migration and invasion and promote the HCC cell apoptosis through p53 and EMT signaling pathways.

Heterointerface construction for permalloy microparticles through the surface modification of bilayer metallic organic frameworks: Toward microwave absorption enhancement.

Reasonable heterointerface modification can effectively regulate and enhance the microwave absorption of electromagnetic materials. The surface of magnetic permalloy (PM) microparticles is modified herein by coating double-layer metal organic frameworks (MOF), which are composed of a 2-methylimidazole cobalt salt (ZIF-67) layer and a 2-methylimidazole zinc salt (ZIF-8) layer. A stable heterointerface structure with cobalt/carbon (Co/C) and zinc/carbon (Zn/C) layers is formed on the surface of PM microparticles after pyrolysis. These particles include two types of composite particles of PM solely encapsulated by ZIF-67 or ZIF-8, PM@ZIF67 and PM@ZIF8, respectively, and two types of composite PM particles with a double-layered MOF outer shell structure obtained by exchanging the coating sequence (PM@ZIF8@ZIF67 and PM@ZIF67@ZIF8). Furthermore, the thermal decomposition temperature has a significant impact on the surface morphology and magnetic properties of the composite particles. After pyrolyzing at 500 °C, the PM@ZIF67@ZIF8 samples exhibit the highest microwave absorption performance among these samples. Specifically, the minimum reflection loss and effective absorption bandwidth of PM@ZIF67@ZIF8 after pyrolyzing at 500 °C can reach -47.3 dB at a matching thickness of 3.8 mm and 5.3 GHz at a matching thickness of 2.5 mm, respectively. A heterointerface with an electrical field orientation is created in the PM@ZIF67@ZIF8 particles, which effectively enhances the interface polarization and dipole polarization. Furthermore, the formation of a three-dimensional carbon network after pyrolysis is also useful for optimizing impedance matching and enhancing magneto-electric synergism.

Graphene quantum dots as the electrolyte for solid state supercapacitors.

We propose that graphene quantum dots (GQDs) with a sufficient number of acidic oxygen-bearing functional groups such as -COOH and -OH can serve as solution- and solid- type electrolytes for supercapacitors. Moreover, we found that the ionic conductivity and ion-donating ability of the GQDs could be markedly improved by simply neutralizing their acidic functional groups by using KOH. These neutralized GQDs as the solution- or solid-type electrolytes greatly enhanced the capacitive performance and rate capability of the supercapacitors. The reason for the enhancement can be ascribed to the fully ionization of the weak acidic oxygen-bearing functional groups after neutralization.