SI2018 – Supplemental material for Theoretical investigations on charge transport properties of tetrabenzo[<i>a,d,j,m</i>]coronene derivatives using different density functional theory functionals (B3LYP, M06-2X, and wB97XD)

Supplemental material, SI2018 for Theoretical investigations on charge transport properties of tetrabenzo[a,d,j,m]coronene derivatives using different density functional theory functionals (B3LYP, M06-2X, and wB97XD) by Ziran Chen, Yuan Li, Zhanrong He, Youhui Xu and Wenhao Yu in Journal of Chemical Research</p

THEORETICAL INVESTIGATION OF THE EFFECT OF CONJUATION OF THIOPHENE RINGS ON THE CHARGE TRANSPORT OF THIENOCORONENE DERIVATIVES

Based on density functional theory, quantum chemical calculations of the charge-transport rates were performed for five disc-shaped coronene derivatives with varying numbers of fused thiophene rings, using different basis sets 6-31+G(d) and 6-311++G(d,p), hybrid functionals (B3LYP, M06-2X, CAM-B3LYP, WB97XD, M08-HX), and a dispersion-corrected hybrid functional (M06-2X+D3). Our results indicate that increasing the basis set and adding diffusion and polarisation functions had little effect on the molecular reorganisation energy, charge-transport matrix element t, and charge carrier mobility μ. The charge carrier mobility calculated using B3LYP were relatively large, whereas the results calculated using CAM-B3LYP and WB97XD were similar. Among the five coronene derivatives, molecule b with one thiophene ring could be candidates for a n-type organic semiconductor, and molecule c with two thiophene rings can be designed as a p-type semiconductor.</div

Defect-Engineered Bi₂₄O₃₁Cl₁₀ Nanosheets for Photocatalytic CO₂ Reduction to CO

The photocatalytic CO2 conversion efficiency of semiconductor materials still suffers from the faint CO2 surface adsorption capacity and sluggish reaction kinetics. Among the modification strategies, defect engineering is considered as a promising approach for ameliorating the catalytic performance of the bulk materials. Herein, an ionic liquid 1-dodecyl-3-methylimidazolium chloride-assisted alkali solvothermal method was employed for the synthesis of ultrathin Bi24O31Cl10 nanosheets with abundant surface oxygen vacancies (Bi24O31Cl10-OV). The existence of the surface oxygen vacancy provided sufficient catalytic sites and greatly strengthened the CO2 adsorption and activation capacity. Furthermore, a newly created energy level in the forbidden band of the Bi24O31Cl10-OV sample facilitated the photogenerated charge separation and transfer, boosting the reaction rate. Under the conditions of pure water and high-purity CO2, the total CO yield of the Bi24O31Cl10-OV sample was achieved up to 330 μmol/g after irradiation with a 300 W Xe lamp for 10 h, which was 3 and 7 times higher than the bulk counterpart and partial oxygen-repaired Bi24O31Cl10-OV sample, respectively. Furthermore, isotope labeling experiments also verified that the actual carbon source in the product CO was from CO2 molecules. These results reveal that surface oxygen vacancy engineering is an effective approach for developing high-performance bismuth-based solar fuel generation systems

Data_Sheet_1_Multi-modal data combination strategy based on chest HRCT images and PFT parameters for intelligent dyspnea identification in COPD.ZIP

IntroductionBecause of persistent airflow limitation in chronic obstructive pulmonary disease (COPD), patients with COPD often have complications of dyspnea. However, as a leading symptom of COPD, dyspnea in COPD deserves special consideration regarding treatment in this fragile population for pre-clinical health management in COPD. Methods: Based on the above, this paper proposes a multi-modal data combination strategy by combining the local and global features for dyspnea identification in COPD based on the multi-layer perceptron (MLP) classifier.MethodsFirst, lung region images are automatically segmented from chest HRCT images for extracting the original 1,316 lung radiomics (OLR, 1,316) and 13,824 3D CNN features (O3C, 13,824). Second, the local features, including five selected pulmonary function test (PFT) parameters (SLF, 5), 28 selected lung radiomics (SLR, 28), and 22 selected 3D CNN features (S3C, 22), are respectively selected from the original 11 PFT parameters (OLF, 11), 1,316 OLR, and 13,824 O3C by the least absolute shrinkage and selection operator (Lasso) algorithm. Meantime, the global features, including two fused PFT parameters (FLF, 2), six fused lung radiomics (FLR, 6), and 34 fused 3D CNN features (F3C, 34), are respectively fused by 11 OLF, 1,316 OLR, and 13,824 O3C using the principal component analysis (PCA) algorithm. Finally, we combine all the local and global features (SLF + FLF + SLR + FLR + S3C + F3C, 5+ 2 + 28 + 6 + 22 + 34) for dyspnea identification in COPD based on the MLP classifier.ResultsOur proposed method comprehensively improves classification performance. The MLP classifier with all the local and global features achieves the best classification performance at 87.7% of accuracy, 87.7% of precision, 87.7% of recall, 87.7% of F1-scorel, and 89.3% of AUC, respectively.DiscussionCompared with single-modal data, the proposed strategy effectively improves the classification performance for dyspnea identification in COPD, providing an objective and effective tool for COPD management.</p

Pathway toward Large Two-Dimensional Hexagonally Patterned Colloidal Nanosheets in Solution

We report the solution self-assembly of an ABC block terpolymer consisting of a polystyrene-<i>block</i>-poly­(ethylene oxide) (PS-<i>b</i>-PEO) diblock copolymer tail tethered to a fluorinated polyhedral oligomeric silsesquioxane (FPOSS) cage in 1,4-dioxane/water. With increasing water content, abundant unconventional morphologies, including circular cylinders, two-dimensional hexagonally patterned colloidal nanosheets, and laterally patterned vesicles, are sequentially observed. The formation of toroids is dominated by two competing free energies: the end-cap energy of cylinders and the bending energy to form the circular structures. Incorporating the superhydrophobic FPOSS cages enhances the end-cap energy and promotes toroid formation. Lateral aggregation and fusion of the cylinders results in primitive nanosheets that are stabilized by the thicker rims to partially release the rim-cap energy. Rearrangement of the parallel-aligned FPOSS cylindrical cores generates hexagonally patterned nanosheets. Further increasing the water content induces the formation of vesicles with nanopatterned walls

Synthesis of Shape Amphiphiles Based on POSS Tethered with Two Symmetric/Asymmetric Polymer Tails via Sequential “Grafting-from” and Thiol–Ene “Click” Chemistry

A series of shape amphiphiles based on functionalized polyhedral oligomeric silsesquioxane (POSS) head tethered with two polymeric tails of symmetric or asymmetric compositions was designed and synthesized using sequential “grafting-from” and “click” surface functionalization. The monofunctionalization of octavinylPOSS was performed using thiol–ene chemistry to afford a dihydroxyl-functionalized POSS that was further derived into precisely defined homo- and heterobifunctional macroinitiators. Polymer tails, such as polycaprolactone and polystyrene, could then be grown from these POSS-based macroinitiators with controlled molecular weight via ring-opening polymerization and atom transfer radical polymerization (ATRP). The vinyl groups on POSS were found to be compatible with ATRP conditions. These macromolecular precursors were further modified by thiol–ene chemistry to install surface functionalities onto the POSS cage. The polymer chain composition and POSS surface chemistry can thus be tuned separately in a modular and efficient way

Chain Overcrowding Induced Phase Separation and Hierarchical Structure Formation in Fluorinated Polyhedral Oligomeric Silsesquioxane (FPOSS)-Based Giant Surfactants

The self-assembly behaviors of fluorinated polyhedral oligomeric silsesquioxane (FPOSS)-based giant surfactants, consisting of an FPOSS cage and a polystyrene-<i>block</i>-poly­(ethylene oxide) (PS-<i>b</i>-PEO) diblock copolymer tail, are studied in the bulk. The tethering point of the FPOSS cage on the PS-<i>b</i>-PEO diblock copolymer chain can be controlled precisely either at the end of the PS block or the junction point between the PS and PEO blocks, resulting in topological isomer pairs with almost identical chemical compositions but different architectures. Phase separation between the FPOSS head and the block copolymer tail creates a spatially confined environment for the PS-<i>b</i>-PEO component, which are uniformly end- or junction-point-immobilized on the FPOSS layer, providing a unique model system to study phase behaviors and chain conformation of tethered diblock copolymer in the condensed state. The polymer tails are highly stretched because the cross-sectional area of FPOSS head is smaller than that of the unperturbed block copolymer tail, which facilitates further phase separation between the low molecular weight PS and PEO blocks and leads to the formation of hierarchical lamellar structures among three mutually immiscible components

Exactly Defined Half-Stemmed Polymer Lamellar Crystals with Precisely Controlled Defects’ Locations

We describe highly unconventional situations in which the polymer chain ends remain trapped in and are located in the middle of the lamellar crystal core as defects. Such structures are observed in giant molecular shape amphiphiles constructed by a polyhedral silsesquioxane (POSS) nanoparticle tethered with a poly­(ethylene oxide) (PEO) tail. The cross-sectional area of the POSS located on the PEO lamellar surfaces imposes that the crystalline, chain-folded PEO tails generate a surface area that is at least comparable to the POSS requirements. Metastable PEO crystal structures with 1.5, 2, and 2.5 stem numbers have been observed with different thermodynamic stabilities