Pillararene Host–Guest Complexation Induced Chirality Amplification: A New Way to Detect Cryptochiral Compounds

The contradiction between the rising demands of optical chirality sensing and the failure in chiral detection of cryptochiral compounds encourages researchers to find new methods for chirality amplification. Inspired by planar chirality and the host–guest recognition of pillararenes, we establish a new concept for amplifying CD signals of cryptochiral molecules by pillararene host–guest complexation induced chirality amplification. The planar chirality of pillararenes is induced and stabilized in the presence of the chiral guest, which makes the cryptochiral molecule detectable by CD spectroscopy. Several chiral guests are selected in these experiments and the mechanism of chiral amplification is studied with a non‐rotatable pillararene derivative and density functional theory calculations. We believe this work affords deeper understanding of chirality and provides a new perspective for chiral sensing.     

The adaptive sinogram restoration algorithm based on anisotropic diffusion by energy minimization for low-dose X-ray CT

Apparent streak artifacts will present in reconstructed images due to excessive quantum noise in low-dose X-ray imaging process. Estimating a noise-free sinogram to satisfy the filtered back-projection (FBP) reconstruction is an effective way to solve this problem. In this paper, we propose a novel sinogram noise reduction method by energy minimization. An adaptive smoothness parameter based on a modified anisotropic diffusion coefficient is applied for an optimal estimation. The smoothness parameter can make the method effectively adjust the degree of smoothness according to the noise level and the region feature in the sinogram. Visual effect together with quantitative analysis of the experimental result shows the developed approach has the excellent performance in protection of the edge and removal of streak artifacts in the reconstructed image.     

Unusual catalytic effect of the two-dimensional molecular space with regular triphenylphosphine groups

A novel organic-inorganic hybrid 2D molecular space with regular triphenylphosphine groups (triphenylphosphineamidephenylsilica, PPh(3)APhS) was successfully synthesized through grafting triphenylphosphine groups in the 2D structure of layered aminophenylsilica dodecyl sulfate (APhTMS-DS), which was developed in our previous research, with regular ammonium groups. The 2D structures were kept after the grafting reaction of triphenylphosphine groups in PPh(3)APhS. The catalytic potentials of 2D molecular space with regular triphenylphosphine groups were investigated. An unusual catalytic effect was found in a carbon-phosphorus ylide reaction. The PPh(3)-catalyzed reaction of modified allylic compounds, including bromides and chlorides with tropone yielded a [3 + 6] annulation product. However, an unusual [8 + 3] cycloadduct was obtained in the reaction of modified allylic compounds, including bromides and chlorides with tropone catalyzed by PPh(3)APhS. Otherwise, the stable catalytic intermediate was successfully separated, and the reaction activity of the catalytic intermediate was confirmed in the reaction of modified allylic compounds with tropone catalyzed by PPh(3)APhS. This research is the first successful example of directly influencing catalytic reaction processes and product structures by utilizing the chemical and geometrical limits of 2D molecular spaces with regular catalyst molecules and affords a novel method for controlling catalytic reaction processes and catalyst design.     

Dual Lewis Acid-Base Sites Regulate Silver-Copper Bimetallic Oxide Nanowires for Highly Selective Photoreduction of Carbon Dioxide to Methane

Highly selective photoreduction of CO₂ to valuable hydrocarbons is of great importance to achieving a carbon-neutral society. Precisely manipulating the formation of the Metal₁⋅⋅⋅C=O⋅⋅⋅Metal₂ (M₁⋅⋅⋅C=O⋅⋅⋅M₂) intermediate on the photocatalyst interface is the most critical step for regulating selectivity, while still a significant challenge. Herein, inspired by the polar electronic structure feature of CO₂ molecule, we propose a strategy whereby the Lewis acid-base dual sites confined in a bimetallic catalyst surface are conducive to forming a M₁⋅⋅⋅C=O⋅⋅⋅M₂ intermediate precisely, which can promote selectivity to hydrocarbon formation. Employing the Ag₂Cu₂O₃ nanowires with abundant Cu⋅⋅⋅Ag Lewis acid-base dual sites on the preferred exposed {110} surface as a model catalyst, 100 % selectivity toward photoreduction of CO₂ into CH₄ has been achieved. Subsequent surface-quenching experiments and density functional theory (DFT) calculations verify that the Cu⋅⋅⋅Ag Lewis acid-base dual sites do play a vital role in regulating the M₁⋅⋅⋅C=O⋅⋅⋅M₂ intermediate formation that is considered to be prone to convert CO₂ into hydrocarbons. This study reports a highly selective CO₂ photocatalyst, which was designed on the basis of a newly proposed theory for precise regulation of reaction intermediates. Our findings will stimulate further research on dual-site catalyst design for CO₂ reduction to hydrocarbons.