Core-shell zirconia-coated magnetic nanoparticles offering a strong option to prepare a novel and magnetized heteropolyacid based heterogeneous nanocatalyst for three- and four-component reactions

A new type of magnetically-separable nanocatalyst was prepared through the immobilization of phosphomolybdic acid (H₃PMo₁₂O₄₀) in 10–30 wt.% on the surface of core-shell zirconia-coated magnetite nanoparticle (nano-Fe₃O₄@ZrO₂). The developed heterogeneous nano-sized acid catalyst named nano-Fe₃O₄@ZrO₂ supported PMA (or n-Fe₃O₄@ZrO₂/PMA) was characterized using several techniques such as FT-IR, XRD, FE-SEM, VSM, EDX, TEM and TGA. The characterization data derived from FT-IR spectroscopy exhibited that H₃PMo₁₂O₄₀ species on the support retained their Keggin structures. Additionally, the potentiometric titration with n-butylamine was employed to measure the acidity content of the as-obtained catalyst. Surprisingly, this novel active solid acid catalyst displayed to have a higher number of surface active sites compared to its homogeneous analogues. Besides, the catalytic activity of the catalyst was evaluated in multicomponent reactions (MRCs) for the rapid and efficient one-pot synthesis of 2, 4, 5-trisubstituted and 1, 2, 4, 5-tetrasubstituted imidazoles in high yields and selectivity. The sample of 20 wt.% displayed higher acidity content which led to its enhanced activity in the catalytic transformation. Moreover, the catalyst could be easily reused without deactivation after five runs, which made it a promising catalyst for practical and large-scale applications. This outstanding reusability was ascribed to the strong attachment of PMA molecules on the n-Fe₃O₄@ZrO₂ support material.     

光催化材料反应系数测量新方法

本文提出光催化材料反应系数测量新方法-Mass transfer based(MTB)方法,该方法不同于传统方法中忽略传质影响,而是通过CFD计算考虑传质影响,这种改进无需传统方法所需反应控制过程也可准确测量光催化材料反应系数。利用该方法测量了光催化材料降解甲醛的反应系数,实验验证了其可行性。     

Prediction of Compound Synthesis Accessibility Based on Reaction Knowledge Graph

With the increasing application of deep-learning-based generative models for de novo molecule design, the quantitative estimation of molecular synthetic accessibility (SA) has become a crucial factor for prioritizing the structures generated from generative models. It is also useful for helping in the prioritization of hit/lead compounds and guiding retrosynthesis analysis. In this study, based on the USPTO and Pistachio reaction datasets, a chemical reaction network was constructed for the identification of the shortest reaction paths (SRP) needed to synthesize compounds, and different SRP cut-offs were then used as the threshold to distinguish a organic compound as either an easy-to-synthesize (ES) or hard-to-synthesize (HS) class. Two synthesis accessibility models (DNN-ECFP model and graph-based CMPNN model) were built using deep learning/machine learning algorithms. Compared to other existing synthesis accessibility scoring schemes, such as SYBA, SCScore, and SAScore, our results show that CMPNN (ROC AUC: 0.791) performs better than SYBA (ROC AUC: 0.76), albeit marginally, and outperforms SAScore and SCScore. Our prediction models based on historical reaction knowledge could be a potential tool for estimating molecule SA.     

A Molecular-Wide and Electron Density-Based Approach in Exploring Chemical Reactivity and Explicit Dimethyl Sulfoxide (DMSO) Solvent Molecule Effects in the Proline Catalyzed Aldol Reaction

Modelling of the proline (1) catalyzed aldol reaction (with acetone 2) in the presence of an explicit molecule of dimethyl sulfoxide (DMSO) (3) has showed that 3 is a major player in the aldol reaction as it plays a double role. Through strong interactions with 1 and acetone 2, it leads to a significant increase of energy barriers at transition states (TS) for the lowest energy conformer 1a of proline. Just the opposite holds for the higher energy conformer 1b. Both the ‘inhibitor’ and ‘catalyst’ mode of activity of DMSO eliminates 1a as a catalyst at the very beginning of the process and promotes the chemical reactivity, hence catalytic ability of 1b. Modelling using a Molecular-Wide and Electron Density-based concept of Chemical Bonding (MOWED-CB) and the Reaction Energy Profile–Fragment Attributed Molecular System Energy Change (REP-FAMSEC) protocol has shown that, due to strong intermolecular interactions, the HN-C-COOH (of 1), CO (of 2), and SO (of 3) fragments drive a chemical change throughout the catalytic reaction. We strongly advocate exploring the pre-organization of molecules from initially formed complexes, through local minima to the best structures suited for a catalytic process. In this regard, a unique combination of MOWED-CB with REP-FAMSEC provides an invaluable insight on the potential success of a catalytic process, or reaction mechanism in general. The protocol reported herein is suitable for explaining classical reaction energy profiles computed for many synthetic processes.     

Efficient deep blue organic light emitting diodes based on [2,7,7,13,13-pentamethyl-9-(10-phenylanthracen-9-yl)-7,13-dihydrobenzo[5,6]-s-indaceno[1,2-g]quinoline] derivatives

Abstract

In this study, as the ongoing effort to develop efficient blue OLEDs, two deep blue emitters based on indenoquinoline-substituted anthracene derivatives have been synthesized and characterized. Multilayer organic light emitting diodes were fabricated with the following sequence: indium-tin-oxide (ITO)/4,4’,4’’-tris[2-naphthyl(phenyl)amino (2-TNATA)/4,4’-bis(N-(1-naphthyl)-N-phenylamino) biphenyl (NPB)/Blue emitting materials/Bathophenanthroline (Bphen)/lithium quinolate (Liq)/Al. All the devices showed efficient blue emissions. Particularly, a device using ‘2,7,7,13,13-pentamethyl-9-(10-phenylanthracen-9-yl)?7,13-dihydrobenzo[5,6]-s-indaceno[1,2-g] quinoline’ as an emitter showed a maximum external quantum efficiency (EQE) of 4.92% with the Commission Internationale De L’Énclairage (CIE) coordinates of (0.15, 0.10) at 8.0?V.     

One-step ultrasonic synthesis of Co/Ni-catecholates for improved performance in oxygen reduction reaction

The inherent periodically arranged M−N_X, M−S_X and M−O_X units (M are usually Fe, Co, Ni, etc.) in metal–organic frameworks (MOFs) can be promising active centers in electrocatalysis. In previous studies, MOFs were usually constructed by energy-consuming hydro- or solvo-thermal reactions. Ultrasonic synthesis is a rapid and environment-friendly technique when envisaging MOFs’ industrial applications. In addition, different synthetic pathways for MOFs may lead to difference in their microstructure, resulting in different electrocatalytic performance. Nevertheless, only a handful of MOFs were successfully prepared by ultrasonic synthesis and few were applied in electrochemical catalysis. Herein, we constructed Ni/Co-catecholates (Ni/Co-CATs) synthesized by one-step ultrasonic method (250 W, 40 KHz, 25 W/L, Ultrasonic clearing machine) and compared their performance in oxygen reduction reaction (ORR) with that of Ni/Co-CATs synthesized by hydrothermal method. Ni-CAT and Co-CAT prepared by ultrasonic showed the half-wave potential of −0.196 V and −0.116 V (vs. Ag/AgCl), respectively. The potentials were more positive than those prepared by hydro-thermal method. And they showed excellent electrochemical stability in neutral solution. The latter was only 32 mV lower than that of commercial Pt/C. The improved performance in ORR was attributed to higher specific surface area and mesopore volume as well as more structural defects generated in the ultrasonic synthesis process, which could facilitate their exposure of electrocatalytic active sites and their mass transport. This work gives some perspective into cost-effective synthetic strategies of efficient MOFs-based electrocatalysts.