Activity-Directed Synthesis: A Flexible Approach for Lead Generation

Activity-directed synthesis (ADS) is a structure-blind, functional-driven molecular discovery approach. In this Concept, four case studies highlight the general applicability of ADS and showcase its flexibility to support different medicinal chemistry strategies. ADS deliberately harnesses reactions with multiple possible outcomes, and allows many chemotypes to be evaluated in parallel. Resources are focused on bioactive molecules, which emerge in tandem with associated synthetic routes. Some of the future challenges for ADS are highlighted, including the realisation of an autonomous molecular discovery platform. The prospects for ADS to become a mainstream lead generation approach are discussed.     

Association of solid fuel use with risk of stunting in children living in China

Stunting adversely affects physical and mental outcomes of children. It has not been examined whether household air pollution from solid fuel combustion is a risk factor for stunting in children. In a total of 41,439 children aged 6-17 across China, height was measured using a unified protocol. Multivariable linear regression models and logistic regression models were used to assess the associations of solid fuel use for cooking/heating with stunting in children. Adjusted for covariates, cooking/heating with solid fuel was significantly associated with a lower z-score for height for age and sex (β = −0.21 [−0.32 to −0.09] and −0.17 [−0.31 to −0.03], respectively) and an increased risk of stunting with an estimated ORs of 1.34 [1.07~1.68] and 1.37 [1.02~1.83], respectively. The risk of stunting associated with solid fuel use was statistically significant in high-age children. And the effect was greater on girls than on boys, though the difference was not statistically significant. Our study suggested that Chinese children living in households using solid fuel had a significantly higher risk of stunting than those living in households using cleaner fuel.     

Fabrication and performances of high lithium-ion conducting solid electrolytes based on NASICON Li1.3Al0.3Ti1.7-xZrx(PO4)3 (0≤ x≤ 0.2)

Solid electrolytes are the key component in designing all-solid-state batteries. The Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) structure and its derivatives obtained by doping various elements at Ti and Al site acts as good solid electrolytes. However, there is still scope for enhancing the ionic conductivity using simple precursors and preparation methods. In this study, the Li superionic conductors Li_1.3Al_0.3Ti_1.7-xZr_x(PO₄)₃ (LATZP) with 0 ≤ x ≤ 0.2 have been successfully prepared by the solid-state reaction route. The structural, morphological, and ionic transport properties were analyzed using several experimental techniques including powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and impedance spectroscopy (IS). The presence of two relaxation processes corresponding to grain and grain boundary was studied using various formalisms. We have observed that grain effects dominate at lower temperatures (<100 °C) while the grain boundary at higher temperatures (> 200 °C) on ionic conductivity. The relaxation mechanisms of grain and grain boundaries were investigated by the Summerfield scaling of AC conductivity. The highest total ionic conductivity of 2.48 × 10^-4 S/cm at 150 °C and 5.50 × 10^-3 S/cm at 250 °C was obtained for x = 0.1 in Li_1.3Al_0.3Ti_1.6Zr_0.1(PO₄)₃ sintered at 950 °C/6 h in the air. The ionic conductivity value was found to be higher than the ionic conductivity reported for LATP prepared via solid-state reaction mechanism using the same precursors and conditions.     

Study of the effect of noble metal promotion in Ni-based catalyst for the Sabatier reaction

This paper reports the preparation and the evaluation of the performance of Ni-based powder catalysts with low nickel loading on the CO2 methanation reaction, that is an integral part of the power-to-gas (PtG) technology. CeO₂, CeZrO₄ and CeO₂/SiO₂ were selected as possible supports, and the results of this first screening pointed out that 10%Ni/CeO₂ catalyst could offer the best reaction performances because of ceria's peculiar characteristics. Moreover, the promotion of this promising formulation with the addition of a small amount of noble metals (Pt, Ru, Rh) was investigated, showing that platinum in particular can enhance the catalyst performances. A further study related to the noble metal loading pointed out that platinum and ruthenium have a different optimum loading condition: this result, together with the activity tests performed on monometallic formulations with only the noble metal, suggested that the two metals are able to catalyse two different reactions, thus promoting two different reaction mechanisms.     

Improved Input and State Estimation for Linear Stochastic Systems with Direct Feedthrough

This paper is concerned with the problem of joint input and state estimation for linear stochastic systems with direct feedthrough. Based on the fact that each unknown input between any two time steps is always bounded, a novel improved algorithm is proposed. Compared with existing results, this algorithm can effectively enhance estimation accuracy. Moreover, the stability of the algorithm is also discussed. Finally, an illustrative example is given to demonstrate the effectiveness of the proposed approach.     

Real‐time monitoring by proton relaxometry of radical polymerization reactions of acrylamide in aqueous solution

The potential of time‐domain nuclear magnetic resonance (TD‐NMR) for the real‐time monitoring of solution radical polymerizations is demonstrated. A model system composed of a redox‐pair initiator system, acrylamide as monomer and water as solvent was investigated. A second‐generation continuous wave free precession technique was employed to measure the longitudinal relaxation time constant (T₁) of the samples throughout the polymerization reactions. This parameter was shown to be sensitive to the reactant feed free‐radical enhancement of the water molecule relaxation time, making it a good probe to monitor monomer conversion in real time in an automated, non‐destructive fashion. It was found that the T₁ value was better than the transverse relaxation time constant (T₂) for describing the evolution of the polymerization reactions, due to its greater sensitivity to paramagnetic effects. The TD‐NMR signal variation observed was linked to the formation, propagation and termination steps of the radical polymerization kinetics scheme. These first results may contribute to the application of real‐time monitoring of radical polymerization reactions employing low‐cost and robust TD‐NMR spectrometers. © 2018 Society of Chemical Industry     

Ab initio calculations of the NO2 fission for CL-20 conformers

NO₂ fission is regarded to be the most important initial decomposition process of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20). In this study, four CL-20 conformers based on the ε-CL-20 were obtained after the optimization at m062x/cc-pvtz level, and the bond length, bond order and bond dissociation energy of the N-N bonds were examined to investigate the stability of these bonds. In addition, the rate constants and activation energy of the NO₂ fission were evaluated using the microcanonical variational transition state theory (μVT). The calculation results have shown that N-N bonds in the case of pseudo-equatorial and axial of nitro groups are the most stable and the least stable, respectively, by evaluating the bond length, bond order and minimum energy path (MEP). The NO₂ fission rate constants are affected by not only the stability of N-N bonds but also the repulsion forces from the other nitro groups, and the fission process for pseudo-equatorial positioning of nitro groups is easier to be accelerated due to the increase of the repulsion forces. The decomposition of CL-20 conformer may mainly originate from the fission of the pseudo-equatorial positioning of nitro groups, especially for CL-20 III conformer because of the significant low activation energy.     

Covalent triazine framework with efficient photocatalytic activity in aqueous and solid media

Covalent triazine frameworks (CTFs) have been recently employed for visible light-driven photocatalysis due to their unique optical and electronic properties. However, the usually highly hydrophobic nature of CTFs, which originates from their overall aromatic backbone, leads to limitations of CTFs for applications in aqueous media. In this study, we aim to extend the range of the application media of CTFs and design hybrid material of a CTF and mesoporous silica (SBA-15) for efficient photocatalysis in aqueous medium. A thiophene-containing CTF was directly synthesized in mesopores of SBA-15. Due to the high surface area and the added hydrophilic properties by silica, the hybrid material demonstrated excellent adsorption of organic molecules in water. This leads not only to high photocatalytic performance of the hybrid material for the degradation of organic dyes in water, but also for efficient photocatalysis in solvent-free and solid state. Furthermore, the reusability, stability and easy recovery of the hybrid material offers promising metal-free heterogeneous photocatalyst for broader applications in different reaction media.