Multifunctional graphene metamaterials based on polarization-insensitive plasmon-induced transparency.

In this paper, a 4L-shaped graphene patterned polarization-insensitive plasmon-induced transparency (PIT) metamaterial structure is proposed. The photoelectric switch based on this structure supports a variety of light sources, such as linearly polarized light with different polarization directions, left rotation circularly polarized light (LCP) and right rotation circularly polarized light (RCP). And the switch has excellent performance in the case of different light sources, the amplitude modulation is as high as 99.01%, and the insertion loss is as low as 0.04 dB. In addition, the PIT metamaterial has a high refractive index sensitivity of up to 49156 nm/RIU. The group index of the PIT metamaterial is as high as 980, which can achieve excellent slow light effect. This study provides a scheme and guidance for the design of optoelectronic devices.

Sulfonated porous organic polymer supported Ziegler-Natta catalysts for the synthesis of ultra-high molecular weight polyethylene.

Porous organic polymers (POPs) are attracting attention for their easy functionalization and potential as catalyst supports in olefin polymerization. In this study, sulfonated POP (s-POP) supported Ziegler-Natta catalysts were used for ethylene polymerization, producing ultra-high molecular weight polyethylene, with M ν reaching up to 6.83 × 106 g mol-1. The maximum M ν of polyethylene was achieved by Cat-3 with DIBP as the internal donor, albeit with a partial loss of catalytic activity. Polymerization conditions also play a pivotal role in determining the molecular weight of polyethylene. Hydrogen, being the most efficient chain transfer agent, can decrease the molecular weight to 9.68 × 104 g mol-1 at higher hydrogen concentrations ([H2] : [C2H4] = 0.83), and the s-POP-supported ethylene polymerization catalysts were observed to exhibit high sensitivity to hydrogen response. The effects of polymerization temperature, [Al] : [Ti] molar ratio, and ethylene pressure on ethylene polymerization were thoroughly investigated.

Feasibility Study on the Design and Synthesis of Functional Porous Organic Polymers with Tunable Pore Structure as Metallocene Catalyst Supports.

Porous organic polymers (POPs) are highly versatile materials that find applications in adsorption, separation, and catalysis. Herein, a feasibility study on the design and synthesis of POP supports with a tunable pore structure and high ethylene-polymerization activity was conducted by the selection of functional comonomers and template agents, and control of cross-linking degree of their frameworks. Functionalized POPs with a tunable pore structure were designed and synthesized by a dispersion polymerization strategy. The functional comonomers incorporated in the poly(divinylbenzene) (PDVB)-based matrix played a significant role in the porous structure and particle morphology of the prepared polymers, and a specific surface area (SSA) of 10⁻450 m²/g, pore volume (PV) of 0.05⁻0.5 cm³/g, bulk density with a range of 0.02⁻0.40 g/cm³ were obtained by the varied functional comonomers. Besides the important factors of thermodynamic compatibility of the selected solvent system, other factors that could be used to tune the pore structure and morphology of the POP particles have been also investigated. The Fe3O4 nanoaggregates as a template agent could help improve the porous structure and bulk density of the prepared POPs, and the highly cross-linking networks can dramatically increase the porous fabric of the prepared POPs. As for the immobilized metallocene catalysts, the pore structure of the prepared POPs had a significant influence on the loading amount of the Zr and Al of the active sites, and the typically highly porous structure of the POPs would contribute the immobilization of the active species. High ethylene-polymerization activity of 8033 kg PE/mol Zr h bar was achieved on the POPs-supported catalysts, especially when high Al/Zr ratios on the catalysts were obtained. The performance of the immobilized metallocene catalysts was highly related to the pore structure and functional group on the POP frameworks.

Crystal form control and particle size control of RG3487, a nicotinic α7 receptor partial agonist.

This paper describes solid form control and particle size control of RG3487, a nicotinic receptor partial agonist. Four crystal forms were identified by polymorph screen under ∼100 varying conditions. Form A and Form B are anhydrates, while Forms C and D are solvates. Forms A, which is enantiotropically related to Form B, is the more thermodynamically stable form under ambient conditions and the desired form selected for clinical development. The crystal form control of Form A was achieved by crystallization solvent selection which consistently produced the desired form. Several process parameters impacting particle size of Form A in the final crystallization step were identified and investigated through both online and offline particle size measurement. The investigation results were utilized to control crystallization processes which successfully produced Form A with different particle size in 500g scale.

1-Magnesiotetrahydroisoquinolyloxazolines as Chiral Nucleophiles in Stereoselective Additions to Aldehydes: Auxiliary Optimization, Asymmetric Synthesis of (+)-Corlumine, (+)-Bicuculline, (+)-Egenine, and (+)-Corytensine, and Preliminary (13)C NMR Studies of 1-Lithio- and 1-Magnesiotetrahydroisoquinolyloxazolines.

Transmetalation of 1-lithiotetrahydroisoquinolyloxazolines with magnesium halides affords Grignard reagents that add to aldehydes with up to 80% selectivity for one of the four possible diastereomeric products. An oxazoline chiral auxiliary derived from camphor provides an optimal blend of diastereoselectivity and isomer separability. Synthetic applications of the optimal auxiliary, patterned after a literature approach in the racemic series, comprise an improved (formal) synthesis of bicuculline, egenine, and corytensine, as well as an efficient synthesis of corlumine. Preliminary NMR studies show that both 1-lithio- and 1-magnesiotetrahydroisoquinolyloxazolines are dynamic mixtures in THF solution at low temperatures. The barrier to pyramidal inversion of the secondary Grignard reagent is in the 9.8-10.1 kcal/mol range, while an upper limit of about 8.2 kcal/mol can be assigned to the barrier to the organolithium inversion.