Selective hydrogenolysis of organohalides
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C(sp3)–heteroatom bond formation by iron-catalyzed soft couplings
Carbon–heteroatom bonds are of great importance due to their prevalence in pharmaceuticals, agrochemicals, materials, and natural products. Despite the effective use of metal-catalyzed cross-coupling reactions between sp2-hybridized organohalides and soft heteroatomic nucleophiles for carbon–heteroatom bond formation, the use of sp3-hybridized organohalides remain limited and the coupling with thiols remains elusive. Here, we report the coupling of sp3-hybridized benzyl or tertiary halides with soft thiol nucleophiles catalyzed by iron and extend the utility to alcohol and amine nucleophiles. The reaction is broad in substrate scope for both coupling partners and applicable in the construction of congested tri- and tetrasubstituted carbon centers as well as β-quaternary heteroatomic products. The synthetic utility is further emphasized by gram-scale synthesis and rapid herbicide library synthesis. Overall, we provide an efficient method to prepare pharmaceutically and materially relevant carbon–heteroatom bonds by expanding iron-catalyzed cross-coupling reactions to the coupling of sp3-hybridized organohalides with soft nucleophiles.
Solution-processable polymer membranes with hydrophilic subnanometre pores for sustainable lithium extraction
Membrane-based separation processes hold great promise for sustainable extraction of lithium from brines for the rapidly expanding electric vehicle industry and renewable energy storage. However, it remains challenging to develop high-selectivity membranes that can be upscaled for industrial processes. Here we report solution-processable polymer membranes with subnanometre pores with excellent ion separation selectivity in electrodialysis processes for lithium extraction. Polymers of intrinsic microporosity incorporated with hydrophilic functional groups enable fast transport of monovalent alkali cations (Li+, Na+ and K+) while rejecting relatively larger divalent ions such as Mg2+. The polymer of intrinsic microporosity membranes surpasses the performance of most existing membrane materials. Furthermore, the membranes were scaled up and integrated into an electrodialysis stack, demonstrating excellent selectivity in simulated salt-lake brines. This work will inspire the development of selective membranes for a wide range of sustainable separation processes critical for resource recovery and a global circular economy.
Convergent evolution of complex adaptive traits modulates angiogenesis in high-altitude Andean and Himalayan human populations
Convergent adaptations represent paradigmatic examples of the capacity of natural selection to influence organisms’ biology. However, the possibility to investigate the genetic determinants underpinning convergent complex adaptive traits has been offered only recently by methods for inferring polygenic adaptations from genomic data. Relying on this approach, we demonstrate how high-altitude Andean human groups experienced pervasive selective events at angiogenic pathways, which resemble those previously attested for Himalayan populations despite partial convergence at the single-gene level was observed. This provides additional evidence for the drivers of convergent evolution of enhanced blood perfusion in populations exposed to hypobaric hypoxia for thousands of years.
Detecting adaptive changes in gene copy number distribution accompanying the human out-of-Africa expansion
Genes with multiple copies are likely to be maintained by stabilizing selection, which puts a bound to unlimited expansion of copy number. We designed a model in which copy number variation is generated by unequal recombination, which fits well with several genes surveyed in three human populations. Based on this theoretical model and computer simulations, we were interested in determining whether the gene copy number distribution in the derived European and Asian populations can be explained by a purely demographic scenario or whether shifts in the distribution are signatures of adaptation. Although the copy number distribution in most of the analyzed gene clusters can be explained by a bottleneck, such as in the out-of-Africa expansion of Homo sapiens 60–10 kyrs ago, we identified several candidate genes, such as AMY1A and PGA3, whose copy numbers are likely to differ among African, Asian, and European populations.
Surface-hydroxylated single-atom catalyst with an isolated Co-O-Zn configuration achieves high selectivity in regulating active species
Single-atom catalysts (SACs) are emerging as potent tools for the selective regulation of active species, offering substantial promise for green and sustainable Fenton catalysis. However, current SACs face limitations due to the specificity of their supports, which only allow selective regulation within certain oxidant systems. This constraint makes targeted regulation across different systems challenging. In response, this study designs a SAC, termed CoSAs-ZnO, featuring surface hydroxylation and an isolated asymmetric Co-O-Zn configuration. This SAC can realize a nearly 100% selective generation of sulfate radicals (SO4•−) and singlet oxygen (1O2) in peroxymonosulfate (PMS) and peracetic acid (PAA) systems, respectively. Moreover, the PMS-activated system can efficiently treat electron-deficient-dominated and refractory benzoic acid wastewater, achieving 100.0% removal in multiple consecutive pilot-scale experiments. The PAA-activated system facilitates the rapid conversion of benzyl alcohol to benzaldehyde, with a high selectivity of 89.0%. Detailed DFT calculations reveal that the surface hydroxyl groups on ZnO play a critical role in modulating the adsorption configurations of the oxidants, thus enabling the selective generation of specific active species in each system. This study provides insights into the design of SACs for multifunctional applications and paves the way for their deployment in wastewater treatment and high-value chemical conversion.
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