Breaking the activity-selectivity trade-off of CO2 hydrogenation to light olefins.

Catalytic hydrogenation of CO2 to value-added fuels and chemicals is of great importance to carbon neutrality but suffers from an activity-selectivity trade-off, leading to limited catalytic performance. Herein, the ZnFeAlO4 + SAPO-34 composite catalyst was designed, which can simultaneously achieve a CO2 conversion of 42%, a CO selectivity of 50%, and a C2-C4= selectivity of 83%, resulting in a C2-C4= yield of almost 18%. This superior catalytic performance was found to be from the presence of unconventional electron-deficient tetrahedral Fe sites and electron-enriched octahedral Zn sites in the ZnFeAlO4 spinel, which were active for the CO2 deoxygenation to CO via the reverse water gas shift reaction, and CO hydrogenation to CH3OH, respectively, leading to a route for CO2 hydrogenation to C2-C4=, where the kinetics of CO2 activation can be improved, the mass transfer of CO hydrogenation can be minimized, and the C2-C4= selectivity can be enhanced via modifying the acid density of SAPO-34. Moreover, the spinel structure of ZnFeAlO4 possessed a strong ability to stabilize the active Fe and Zn sites even at elevated temperatures, resulting in long-term stability of over 450 h for this process, exhibiting great potential for large-scale applications.

Identification of 5-HT2 Serotonin Receptor Modulators through the Synthesis of a Diverse, Tropane- and Quinuclidine-alkaloid-Inspired Compound Library.

The recombination of natural product (NP) fragments in unprecedented ways has emerged as an important strategy for bioactive compound discovery. In this context, we propose that privileged primary fragments predicted to be enriched in activity against a specific target class can be coupled to diverse secondary fragments to engineer selectivity among closely related targets. Here, we report the synthesis of an alkaloid-inspired compound library enriched in spirocyclic ring fusions, comprising 58 compounds from 12 tropane- or quinuclidine-containing scaffolds, all of which can be considered pseudo-NPs. The library displays excellent predicted drug-like properties including high Fsp3 content and Lipinski's rule-of-five compliance. Targeted screening against selected members of the serotonin and dopamine G protein-coupled receptor family led to the identification of several hits that displayed significant agonist or antagonist activity against 5-HT2A and/or 5-HT2C, and subsequent optimization of one of these delivered a lead dual 5-HT2B/C antagonist with a highly promising selectivity profile.

A Novel Method for Constructing EEG Large-Scale Cortical Dynamical Functional Network Connectivity (dFNC): WTCS.

As a kind of biological network, the brain network conduces to understanding the mystery of high-efficiency information processing in the brain, which will provide instructions to develop efficient brain-like neural networks. Large-scale dynamical functional network connectivity (dFNC) provides a more context-sensitive, dynamical, and straightforward sight at a higher network level. Nevertheless, dFNC analysis needs good enough resolution in both temporal and spatial domains, and the construction of dFNC needs to capture the time-varying correlations between two multivariate time series with unmatched spatial dimensions. Effective methods still lack. With well-developed source imaging techniques, electroencephalogram (EEG) has the potential to possess both high temporal and spatial resolutions. Therefore, we proposed to construct the EEG large-scale cortical dFNC based on brain atlas to probe the subtle dynamic activities in the brain and developed a novel method, that is, wavelet coherence-S estimator (WTCS), to assess the dynamic couplings among functional subnetworks with different spatial dimensions. The simulation study demonstrated its robustness and availability of applying to dFNC. The application in real EEG data revealed the appealing "Primary peak" and "P3-like peak" in dFNC network properties and meaningful evolutions in dFNC network topology for P300. Our study brings new insights for probing brain activities at a more dynamical and higher hierarchical level and pushing forward the development of brain-inspired artificial neural networks. The proposed WTCS not only benefits the dFNC studies but also gives a new solution to capture the time-varying couplings between the multivariate time series that is often encountered in signal processing disciplines.

Towards the development of the emerging process of CO2 heterogenous hydrogenation into high-value unsaturated heavy hydrocarbons.

The emerging process of CO2 hydrogenation through heterogenous catalysis into important bulk chemicals provides an alternative strategy for sustainable and low-cost production of valuable chemicals, and brings an important chance for mitigating CO2 emissions. Direct synthesis of the family of unsaturated heavy hydrocarbons such as α-olefins and aromatics via CO2 hydrogenation is more attractive and challenging than the production of short-chain products to modern society, suffering from the difficult control between C-O activation and C-C coupling towards long-chain hydrocarbons. In the past several years, rapid progress has been achieved in the development of efficient catalysts for the process and understanding of their catalytic mechanisms. In this review, we provide a comprehensive, authoritative and critical overview of the substantial progress in the synthesis of α-olefins and aromatics from CO2 hydrogenation via direct and indirect routes. The rational fabrication and design of catalysts, proximity effects of multi-active sites, stability and deactivation of catalysts, reaction mechanisms and reactor design are systematically discussed. Finally, current challenges and potential applications in the development of advanced catalysts, as well as opportunities of next-generation CO2 hydrogenation techniques for carbon neutrality in future are proposed.

Can Vitamin B12 Assist the Internalization of Antisense LNA Oligonucleotides into Bacteria?

The emergence of bacterial resistance to traditional small-molecule antibiotics is fueling the search for innovative strategies to treat infections. Inhibiting the expression of essential bacterial genes using antisense oligonucleotides (ASOs), particularly composed of nucleic acid mimics (NAMs), has emerged as a promising strategy. However, their efficiency depends on their association with vectors that can translocate the bacterial envelope. Vitamin B12 is among the largest molecules known to be taken up by bacteria and has very recently started to gain interest as a trojan-horse vector. Gapmers and steric blockers were evaluated as ASOs against Escherichia coli (E. coli). Both ASOs were successfully conjugated to B12 by copper-free azide-alkyne click-chemistry. The biological effect of the two conjugates was evaluated together with their intracellular localization in E. coli. Although not only B12 but also both B12-ASO conjugates interacted strongly with E. coli, they were mostly colocalized with the outer membrane. Only 6-9% were detected in the cytosol, which showed to be insufficient for bacterial growth inhibition. These results suggest that the internalization of B12-ASO conjugates is strongly affected by the low uptake rate of the B12 in E. coli and that further studies are needed before considering this strategy against biofilms in vivo.

Controlling the stereochemistry in 2-oxo-aldehyde-derived Ugi adducts through the cinchona alkaloid-promoted electrophilic fluorination.

In this report, we introduce a new strategy for controlling the stereochemistry in Ugi adducts. Instead of controlling stereochemistry directly during the Ugi reaction we have attempted to stereodefine the chiral center at the peptidyl position through the post-Ugi functionalization. In order to achieve this, we chose to study 2-oxo-aldehyde-derived Ugi adducts many of which partially or fully exist in the enol form that lacks the aforementioned chiral center. This in turn led to their increased nucleophilicity as compared to the standard Ugi adducts. As such, the stereocenter at the peptidyl position could be installed and stereodefined through the reaction with a suitable electrophile. Towards this end, we were able to deploy an asymmetric cinchona alkaloid-promoted electrophilic fluorination producing enantioenriched post-Ugi adducts fluorinated at the peptidyl position.

Gold-catalyzed post-Ugi alkyne hydroarylation for the synthesis of 2-quinolones.

A series of propargylamides containing an electron-rich benzene ring was prepared through the Ugi reaction of 3,5-dimethoxyaniline with various propiolic acids, aldehydes and isocyanides. Subjecting these adducts to a gold-catalyzed intramolecular alkyne hydroarylation process allowed to efficiently construct the 2-quinolone core bearing a branched substituent on the nitrogen atom.

Palladium-catalyzed carbene/alkyne metathesis with enynones as carbene precursors: synthesis of fused polyheterocycles.

An unprecedented palladium-catalyzed novel carbene/alkyne metathesis cascade reaction of alkyne-tethered enynones is described. This reaction affords fused polyheterocycles in moderate to good yields. The transformation begins with Pd-catalyzed 5-exo-dig cyclization of the enynone to form the donor/donor metal carbene, which then undergoes metathesis with the alkyne followed by electrophilic aromatic substitution.

Erratum: Directly converting CO2 into a gasoline fuel.

This corrects the article DOI: 10.1038/ncomms15174.

Directly converting CO2 into a gasoline fuel.

The direct production of liquid fuels from CO2 hydrogenation has attracted enormous interest for its significant roles in mitigating CO2 emissions and reducing dependence on petrochemicals. Here we report a highly efficient, stable and multifunctional Na-Fe3O4/HZSM-5 catalyst, which can directly convert CO2 to gasoline-range (C5-C11) hydrocarbons with selectivity up to 78% of all hydrocarbons while only 4% methane at a CO2 conversion of 22% under industrial relevant conditions. It is achieved by a multifunctional catalyst providing three types of active sites (Fe3O4, Fe5C2 and acid sites), which cooperatively catalyse a tandem reaction. More significantly, the appropriate proximity of three types of active sites plays a crucial role in the successive and synergetic catalytic conversion of CO2 to gasoline. The multifunctional catalyst, exhibiting a remarkable stability for 1,000 h on stream, definitely has the potential to be a promising industrial catalyst for CO2 utilization to liquid fuels.

1,3-Dipolar Cycloaddition of Alkyne-Tethered N-Tosylhydrazones: Synthesis of Fused Polycyclic Pyrazoles.

A general and transition-metal-free access to the fused polycyclic pyrazoles via an intramolecular 1,3-dipolar cycloaddition reaction of alkyne-tethered tosylhydrazones has been reported. The pure solid products could be obtained without column chromatography in high to excellent yields, and the obtained products are useful bioactive molecules or could be used as the key intermediate for synthesis of these compounds in one or two steps. Additionally, a [3+2]-cycloaddition followed by a direct H-shift aromatization reaction mechanism was proposed, which is different from the previously reported aryl or alkyl sequential [1,5]-sigmatropic rearrangement pathway.

Cu-Catalyzed direct cyanation of terminal alkynes with AMBN or AIBN as the cyanation reagent.

A Cu-catalyzed direct cyanation of terminal alkynes was reported with broad substrate generality in moderate to high yield, and AMBN (azobisisoamylonitrile)/AIBN (azobisisobutyronitrile) were used as less toxic and effective cyanating sources in open air. Interestingly, addition products were selectively achieved as the major product under the same conditions in argon.