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The rational design of high-performance catalysts is hindered by the lack of knowledge of the structures of active sites and the reaction pathways under reaction conditions, which can be ideally addressed by an in situ/operando characterization. Besides the experimental insights, a theoretical investigation that simulates reaction conditions—so-called operando modeling—is necessary for a plausible understanding of a working catalyst system at the atomic scale. However, there is still a huge gap between the current widely used computational model and the concept of operando modeling, which should be achieved through multiscale computational modeling. This Perspective describes various modeling approaches and machine learning techniques that step toward operando modeling, followed by selected experimental examples that present an operando understanding in the thermo- and electrocatalytic processes. At last, the remaining challenges in this area are outlined.

Cerium oxide-based nanozymes have recently drawn much attention in the field of biomedical and antioxidant applications, because of their unique regenerative or autocatalytic properties. Herein, we studied the biomimetic superoxide dismutase (SOD) nanozymes CeO2-Gd that combines the fluorescence properties of rare earth Gd with the antioxidant properties of CeO2 nanoparticles, which was prepared via facile route. The structure and composition of the CeO2-Gd were measured and verified by X-ray powder diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), and X-ray electron spectroscopy (XPS). Confocal microscopy was used to image cells. Antioxidant performance and cell viability of these nanozymes were measured in vitro using BGC-803 cell. CeO2-Gd nanozymes with a higher Ce3+/Ce4+ ratio show higher superoxide dismutase (SOD) mimetic activity. Their antioxidant activity and fluorescence properties of CeO2-Gd in BGC-803 cancer cells are enhanced by oxygen vacancies generated by doping rare-earth elements Gd. This work may guide the future design of CeO2-Gd-based biomimetic nanozymes for anticancer and antioxidant applications.

Selective deconstructive functionalization of alkenes, other than the well-established olefin metathesis and ozonolysis, to produce densely functionalized molecular scaffolds is highly attractive but challenging. Here we report an efficient photo-mediated deconstructive germinal dihalogenation of carbon-carbon double bonds. A wide range of geminal diiodoalkanes and bromo(iodo)alkanes (>40 examples) are directly prepared from various trisubstituted alkenes, including both cyclic and acyclic olefins. This C=C cleavage is highly chemoselective and produces geminal dihalide ketones in good yields. Mechanistic investigations suggest a formation of alkyl hypoiodites from benzyl alcohols and N-iodoimides, which undergo light-induced homolytic cleavage to generate active oxygen radical species., Efficient synthetic pathways to geminal dihalides are quite limited, despite their versatility as chemical building blocks. Here, the authors report a photo-mediated deconstructive fragmentation of cyclic and acyclic trisubstituted alkenes to access a variety of geminal dihalides.

Deuterium labelled compounds are of significant importance in chemical mechanism investigations, mass spectrometric studies, diagnoses of drug metabolisms, and pharmaceutical discovery. Herein, we report an efficient hydrogen deuterium exchange reaction using deuterium oxide (D2O) as the deuterium source, enabled by merging a tetra-n-butylammonium decatungstate (TBADT) hydrogen atom transfer photocatalyst and a thiol catalyst under light irradiation at 390 nm. This deuteration protocol is effective with formyl C–H bonds and a wide range of hydridic C(sp3)–H bonds (e.g. α-oxy, α-thioxy, α-amino, benzylic, and unactivated tertiary C(sp3)–H bonds). It has been successfully applied to the high incorporation of deuterium in 38 feedstock chemicals, 15 pharmaceutical compounds, and 6 drug precursors. Sequential deuteration between formyl C–H bonds of aldehydes and other activated hydridic C(sp3)–H bonds can be achieved in a selective manner., A selective hydrogen deuterium exchange reaction with formyl C–H bonds and a wide range of hydridic C(sp3)–H bonds has been achieved by merging tetra-n-butylammonium decatungstate photocatalyst and a thiol catalyst under 390 nm light irradiation.

Summary Polarity-reversal catalysts enable otherwise sluggish or completely ineffective reactions which are characterized by unfavorable polar effects between radicals and substrates. We herein disclose that when irradiated by visible light, bromine can behave as a polarity-reversal catalyst. Hydroacylation of vinyl arenes, a three-component cascade transformation and deuteration of aldehydes were each achieved in a metal-free manner without initiators by using inexpensive N-bromosuccinimide as the precatalyst. Light is essential to generate and maintain the active bromine radical during the reaction process. Another key to success is that HBr can behave as an effective hydrogen donor to turn over the catalytic cycles., Graphical abstract, Highlights • Using bromine as a polarity-reversal catalyst to generate acyl radicals • Additive- and metal-free, atom- and step-economic, and operationally simple process • Using constant light-irradiation to induce and maintain bromine radicals • Access carbonyl compounds and deuterated aldehydes with wide substrate scope, Chemistry; Organic chemistry; Green chemistry

Polarity-reversal catalysts enable otherwise sluggish or completely ineffective reactions which are characterized by unfavorable polar effects between radicals and substrates. We herein disclose for the first time that when irradiated by visible light, bromine can behave as a polarity-reversal catalyst. Hydroacylation of vinyl arenes, a three-component cascade transformation and deuteration of aldehydes were each achieved in a metal-free manner without initiators by using N-bromosuccinimide as the precatalyst. Light is essential to generate and maintain the active bromine radical during the reaction process. Another key to success is that HBr can behave as an effective hydrogen-donor to turn over the catalytic cycles.

A visible-light-mediated radical Smiles rearrangement has been achieved using neutral eosin Y as a direct hydrogen atom transfer (HAT) photocatalyst. Novel N-heterocycles as single diastereomers fe...

CeO2 nanoparticles (Ce NPs) have received considerable interest due to their unique autocatalytic property. In this paper, the autocatalytic properties of Ce NPs of three different sizes were measured in vitro using a human gastric cancer cell line (BGC-803) at different concentrations ranging from 20 ng μL−1 to 200 ng μL−1. The evaluation model of the autocatalytic properties of the Ce NPs was built by partial least squares regression (PLSR) based on the Matlab software. Multiple variable factors were quantitatively analyzed in terms of regression and correlation. The model indicated that the concentration was the primary factor, followed by the size of the Ce NPs. The autocatalytic properties of the Ce NPs was also promoted by the specific surface area, the valence states of Ce, and the surface charge in the cell culture medium. This study attempted to establish a quantitative framework and supply a new strategy for evaluating the autocatalytic property of cerium oxide nanoparticles for their use in biological and medical fields.

Enantioenriched 1,4-dicarbonyl compounds are versatile synthons in natural product and pharmaceutical drug synthesis. We herein report a mild pathway for the efficient enantioselective synthesis of these compounds directly from aldehydes through synergistic cooperation between a neutral eosin Y hydrogen atom transfer photocatalyst and a chiral rhodium Lewis acid catalyst. This method is distinguished by its operational simplicity, abundant feedstocks, atom economy, and ability to generate products in high yields (up to 99 %) and high enantioselectivity (up to 99 % ee).

A mild in situ method was developed to construct an iron doped rutile TiO2 photocatalyst like cauliflower for degradation synthetic textile dye-methyl orange. The synthesized photocatalysts presented distinguished photocatalytic activity. At the optimal Fe concentration (0.5%), the decomposition rate of methyl orange (MO) was about 90% under 40 min of ultraviolet (UV) light irradiation. Whereas, to our knowledge, only 70% of the decomposition rate of MO was achieved by commercial photocatalyst P25 under the similar reaction condition. Additionally, the rutile preparation temperature did not exceed 100 &deg, C, which was much lower than the traditional preparation calcination temperature (e.g., 600 &deg, C). The specific surface area of Fe doped catalysts was bigger than that of the control sample and the catalyst characterization indicated that the doped iron was incorporated into the rutile TiO2 lattice and resulted in the lattice disorder. The lattice disorder would have generated surface defects in the crystal structure, which was in favor of the photocatalytic reaction. The UV-Vis diffuse refection characterization and Density Functional Theory (DFT) calculation suggested that doping a small amount of Fe into the lattice of rutile would lead to a narrower band gap and the formation of a doping energy level between conduction and valence bands of TiO2. This further increased the degradation efficiency of synthetic textile dyes in wastewaters. Our study has provided a relatively easy operation for synthesis Fe doped rutile TiO2, which is a benefit to decrease the cost in wastewater treatment process.