A Potentially Limitless Chiral Pool via Conglomerate Crystallisation: Unidentified Spontaneous Resolution in the CSD.

Conglomerate crystallisation is the behaviour responsible for spontaneous resolution and the discovery of molecular chirality by Pasteur. The phenomenon of conglomerate crystallisation of chiral organic molecules has been left largely undocumented and offers synthetic chemists a potential new chiral pool not reliant on biological systems to supply stereochemical information. While other crystallographic behaviours can be interrogated by automated searching, conglomerate crystallisations are not identified within the Cambridge Structural Database (CSD) and are therefore not accessible by conventional means. By conducting a manual search of the CSD, a list of over 1,700 chiral species capable of conglomerate crystallisation was curated by inspection of the synthetic routes described in each publication. The majority of these are produced by synthetic chemists who seldom note and rarely exploit the implications this phenomenon can have on the enantioenrichment of their crystalline materials. We propose that this list represents a limitless chiral pool which will continually grow in size as more conglomerate crystals are synthesised and recorded.

Synthesis of zeolitic imidazolate framework-8 and gold nanoparticles in a sustained out-of-equilibrium state

The design and synthesis of crystalline materials are challenging due to the proper control over the size and polydispersity of the samples, which determine their physical and chemical properties and thus applicability. Metal − organic frameworks (MOFs) are promising materials in many applications due to their unique structure. MOFs have been predominantly synthesized by bulk methods, where the concentration of the reagents gradually decreased, which affected the further nucleation and crystal growth. Here we show an out-of-equilibrium method for the generation of zeolitic imidazolate framework-8 (ZIF-8) crystals, where the non-equilibrium crystal growth is maintained by a continuous two-side feed of the reagents in a hydrogel matrix. The size and the polydispersity of the crystals are controlled by the fixed and antagonistic constant mass fluxes of the reagents and by the reaction time. We also present that our approach can be extended to synthesize gold nanoparticles in a redox process.

Holistic Approach to R&D Products’ Evaluation for Commercialization under Open Innovations

A holistic approach to R&D products’ evaluation for commercialization under open innovations is developed. The approach is tested on the example of the device of the interferometric determination of the refractive index of crystalline materials in the optical range. The proposed approach will allow setting a price that will satisfy all the parties of a transfer agreement with a higher level of accuracy and will meet market requirements. Unlike popular methods of evaluating the R&D product, a holistic approach will, on the one hand, be based on the actual costs and the break-even level of a R&D product and, on the other hand, will determine how much the consumer is receptive to a R&D product, and, then again, will show how the added value of the product will develop under the influence of market effects. It is noted that the application of a holistic approach to R&D products’ evaluation for commercialization should be supplemented by assessing the willingness of potential customers to purchase this R&D product at a specific price. It is proved that the proposed holistic approach to R&D products’ evaluation for commercialization is multifunctional. The approach can be applied to different types of economic activity, R&D products, and types of markets. The obtained prices based on the application of a holistic approach to R&D products’ evaluation for commercialization and the results of marketing research of the interferometry market testified to potential prospects of the commercialization of a R&D product of the interferometric determination of the refractive index of crystalline materials in the optical range and its long-term competitiveness. Based on the results, the key provisions of the concept of providing competitive benefits for the period of implementation of the analyzed R&D product are identified. Taking into account fundamental elements of the open innovation paradigm underpins the authors’ holistic approach.

Catalytic applications of recent and improved covalent organic frameworks

Covalent organic frameworks (COFs) are porous crystalline materials that have emerged as promising molecular materials in optoelectronic, catalysis, and gas storage applications. COFs exhibit unique features such as adaptability for various substrates, high chemical stability, tunability, ease of working, and recyclability that render them efficient catalysts. The current mini-review article discusses the synthesis and applications of COFs as catalysts. We hope that the present review will be highly beneficial for researchers working in the area of COFs and their applications in catalysis.

Recent advances in structures and applications of coordination polymers based on cyclohexanepolycarboxylate ligands

Coordination polymers (CPs) are emerging crystalline materials constructed by metal entities and organic ligands through coordination bonds, containing infinite coordination units in one, two, or three dimensions. Here an overview...

Effects of Voigt diffraction peak profiles on the pair distribution function

Powder diffraction and pair distribution function (PDF) analysis are well established techniques for investigation of atomic configurations in crystalline materials, and the two are related by a Fourier transformation. In diffraction experiments, structural information, such as crystallite size and microstrain, is contained within the peak profile function of the diffraction peaks. However, the effects of the PXRD (powder X-ray diffraction) peak profile function on the PDF are not fully understood. Here, all the effects from a Voigt diffraction peak profile are solved analytically, and verified experimentally through a high-quality X-ray total scattering measurement on Ni powder. The Lorentzian contribution to the microstrain broadening is found to result in Voigt-shaped PDF peaks. Furthermore, it is demonstrated that an improper description of the Voigt shape during model refinement leads to overestimation of the atomic displacement parameter.

Mechanochemistry in Portugal—A Step towards Sustainable Chemical Synthesis

In Portugal, publications with mechanochemical methods date back to 2009, with the report on mechanochemical strategies for the synthesis of metallopharmaceuticals. Since then, mechanochemical applications have grown in Portugal, spanning several fields, mainly crystal engineering and supramolecular chemistry, catalysis, and organic and inorganic chemistry. The area with the most increased development is the synthesis of multicomponent crystal forms, with several groups synthesizing solvates, salts, and cocrystals in which the main objective was to improve physical properties of the active pharmaceutical ingredients. Recently, non-crystalline materials, such as ionic liquids and amorphous solid dispersions, have also been studied using mechanochemical methods. An area that is in expansion is the use of mechanochemical synthesis of bioinspired metal-organic frameworks with an emphasis in antibiotic coordination frameworks. The use of mechanochemistry for catalysis and organic and inorganic synthesis has also grown due to the synthetic advantages, ease of synthesis, scalability, sustainability, and, in the majority of cases, the superior properties of the synthesized materials. It can be easily concluded that mechanochemistry is expanding in Portugal in diverse research areas.