Impact of Design of Experiments in the optimisation of catalytic reactions in academia

Design of Experiments (DoE) is extensively and routinely used in industry; however, in the last decades, it has been gaining increasing interest in organic synthesis in academia. The use of Chemometrics is an attractive strategy to find the real optimum in chemical reactions, especially when affected by several variables. DoE has been applied in a growing number of synthetic transformations over the years, where it can undoubtedly help in the process optimisation, saving costs and time. This review concisely discusses the chemometric basis of Design of Experiments and highlights several examples in which DoE has been applied in organic synthesis. Table of contents 1 Introduction 2 Chemometric basis of DoE 3 DoE applied in catalysis: examples 4 Conclusions

Toward benchmarking theoretical computations of elementary rate constants on catalytic surfaces: formate decomposition on Au and Cu

With the emergence of methods for computing rate constants for elementary reaction steps of catalytic reactions, benchmarking their accuracy becomes important. The unimolecular dehydrogenation of adsorbed formate on metal surfaces...

Why Intermolecular Nitric Oxide (NO) Transfer? Exploring the Factors and Mechanistic Aspects of NO Transfer Reaction

Small molecule activation & their transfer reactions in biological or catalytic reactions are greatly influenced by the metal-centers and the ligand frameworks. Here, we report the metal-directed nitric oxide (NO)...

Investigating cyanogen rich Manihot esculenta efficacy for Ru phytomining and application in catalytic reactions

Effective catalytic transfer hydrogenation of furfural into furfural alcohol was accomplished using a bio-based Ru catalyst, Ru@CassCat. The catalyst was successfully produced from cassava biomass grown in Ru-rich laboratory soils.

Catalytic nanoparticles and magnetic nanocatalysts in organic reactions: A mini review

Nanocatalysts, as a part of nanotechnology, have been seen very useful for various fileds of applications capturing a large contribution of the world market. Indeed, several unsolved issues of catalysts have been reconsidered by employing the new nanocatalysts including single core metal atoms and ions with surrounding holes. Moreover, it was expected that the future of catalytic reactions, especially those organic ones, will deal with the nanocatalyst applications. To this aim, the features of catalytic nanoparticles and magnetic nanocatalysts regarding evaluation of their advantages and applications in organic reactions were investigated in this work. Developments of catalytic nanoparticles and magnetic nanocatalysts were discussed in this work regarding the novel applications of such materials at the nanoscale for approaching advantageous features. Increased availability, activity, and stability are very important for applications of the catalysts in various organic reactions. Therefore, it is a must to discuss features of such nanocatalytic systems to provide more information about their advantages and even disadvantages of their applications.

A guide to direct mechanocatalysis

Direct mechanocatalysis (DM) describes catalytic reactions in mechanochemical reactors such as ball mills with the distinctive feature that the milling equipment itself is the catalyst.

Subsurface Oxygen Defects Electronically Interacting with Active Sites on In2O3 for Enhanced Photothermocatalytic CO2 Reduction

Oxygen defects play an important role in many catalytic reactions. Increasing surface oxygen defects can be done through reduction treatment. However, excessive reduction blocks electron channels and deactivates the catalyst surface due to electron-trapped effects by subsurface oxygen defects. How to effectively extract electrons from subsurface oxygen defects which cannot directly interact with reactants is challenging and remains elusive. Herein, we report a metallic In-embedded In2O3 nanoflake catalyst over which the turnover frequency of CO2 reduction into CO increases by a factor of 866 (7615 h-1) and 376 (2990 h-1) at same light intensity and reaction temperature, respectively, compared to In2O3. Under electron-delocalization effect of O-In-(O)Vo-In-In structural units at the interface, the electrons in the subsurface oxygen defects are extracted and gather at surface active sites. This improves the electronic coupling with CO2 and stabilizes COOH intermediate. The study opens up new insights for exquisite electronic manipulation of oxygen defects.

Characterization of Two BAHD Acetyltransferases Highly Expressed in the Flowers of Jasminum sambac (L.) Aiton

Volatile benzenoid compounds are found in diverse aromatic bouquets emitted by most moth-pollinated flowers. The night-blooming Jasminum sambac is widely cultivated worldwide in the tropics and subtropics for ornamental and industrial purposes owing to its fragrant flowers. Benzylacetate is a characteristic constituent in jasmine scent which makes up to approximately 20–30% of the total emission in the headspace or extract, but the biosynthesis enzymes and the encoding genes have not yet been described. Here, we identify two cytosolic BAHD acyltransferases specifically expressed in the petals with a positive correlation closely to the emission pattern of the volatile benzenoids. Both JsBEAT1 and JsBEAT2 could use benzylalcohol and acetate-CoA as substrates to make benzylacetate in vitro. The recombinant GST-JsBEAT1 has an estimated apparent Km of 447.3 μM for benzylalcohol and 546.0 μM for acetate-CoA, whereas in the instance of the His-JsBEAT2, the Km values are marginally lower, being 278.7 and 317.3 μM, respectively. However, the catalytic reactions by the GST-JsBEAT1 are more efficient than that by the His-JsBEAT2, based on the steady-state kcat parameters. Furthermore, ectopic expression of JsBEAT1 and JsBEAT2 in the transgenic P. hybrida plants, driven by a flower-specific promotor, significantly enhances the biosynthesis of benzylbenzoate and benzylacetate, as well as the total VOCs.