The ultrafast dynamics of photoexcited charge carriers in condensed matter systems play an important role in optoelectronics and solar energy conversion. Yet it is challenging to understand such multidimensional dynamics at the atomic scale. Combining the real‐time time‐dependent density functional theory with fewest‐switches surface hopping scheme, we develop time‐dependent ab initio nonadiabatic molecular dynamics (NAMD) code Hefei‐NAMD to simulate the excited carrier dynamics in condensed matter systems. Using this method, we have investigated the interfacial charge transfer dynamics, the electron–hole recombination dynamics, and the excited spin‐polarized hole dynamics in different condensed matter systems. The time‐dependent dynamics of excited carriers are studied in energy, real and momentum spaces. In addition, the coupling of the excited carriers with phonons, defects and molecular adsorptions are investigated. The state‐of‐art NAMD studies provide unique insights to understand the ultrafast dynamics of the excited carriers in different condensed matter systems at the atomic scale. This article is categorized under: Structure and Mechanism > Computational Materials Science Molecular and Statistical Mechanics > Molecular Dynamics and Monte‐Carlo Methods Electronic Structure Theory > Ab Initio Electronic Structure Methods Software > Simulation Methods

New antifungal drugs are urgently needed to address the emergence and transcontinental spread of fungal infectious diseases, such as pandrug-resistant Candida auris. Leveraging the microbiomes of marine animals and cutting-edge metabolomics and genomic tools, we identified encouraging lead antifungal molecules with in vivo efficacy. The most promising lead, turbinmicin, displays potent in vitro and mouse-model efficacy toward multiple-drug–resistant fungal pathogens, exhibits a wide safety index, and functions through a fungal-specific mode of action, targeting Sec14 of the vesicular trafficking pathway. The efficacy, safety, and mode of action distinct from other antifungal drugs make turbinmicin a highly promising antifungal drug lead to help address devastating global fungal pathogens such as C. auris.

The interrogation of complex biological pathways demands diverse small molecule tool compounds, which can often lead to important therapeutics for the treatment of human diseases. Since natural products are the most valuable source for the discovery of therapeutics, the derivatization of natural products has been extensively investigated to generate molecules for biological screenings. However, most previous approaches only modified a limited number of functional groups, which resulted in a limited number of skeleta. Here we show a general strategy for the preparation of a library of complex small molecules by combining state-of-the-art chemistry – the site-selective oxidation of C-H bonds - with reactions that expand rigid, small rings in polycyclic steroids to medium-sized rings. This library occupies a unique chemical space compared to selected diverse reference compounds. The diversification strategy developed herein for steroids can also be expanded to other types of natural products.

Contrary to the generally held view, it is found that the rapid epimerization of (-)-menthyl (RP)-phenylphosphinate under basic conditions is not due to the so far believed inherent stereolability of its corresponding anion but due to a reaction of the hydrogen phosphinate ester with a metal alkoxide. This finding successfully leads to a discovery that, by adding an H-phosphinate to organolithiums or Grignard reagents at a low temperature, the nucleophilic substitution of the alkoxy group of the H-phosphinate with organolithiums or Grignard reagents proceeds stereospecifically with inversion of configurations at phosphorus to give a wide range of P-stereogenic secondary phosphine oxides and tertiary phosphine oxides, by quenching the reaction mixture with water and alkyl halides, respectively. This finding establishes a general protocol for the preparation of optically active secondary phosphine oxides and tertiary phosphine oxides from the easily accessible optically pure H-phosphinates. Mechanistic studies show that the substitution reactions of H-phosphinates with organolithiums and Grignard reagents proceed via two competing reaction paths, that is, a two-step reaction path involving first a deprotonation of H-phosphinates followed by a substitution of the corresponding anion with inversion of configuration at phosphorus and a direct substitution of RM with H-phosphinates generating the SPO directly.

The dynamic kinetic resolution of 6-hydroxypyranones with enals or alkynals through an asymmetric redox esterification is catalyzedb yachiral N-heterocyclic carbene. The resulting esters are obtained in good to high yields and with high levels of enantio-and diastereocontrol. The reaction products are further derivatized to obtain functionalizedsugar derivatives and natural products.

The dynamics of photoexcited polarons in transition-metal oxides (TMOs), including their formation, migration, and quenching, plays an important role in photocatalysis and photovoltaics. Taking rutile TiO 2 as a prototypical system, we use ab initio nonadiabatic molecular dynamics simulation to investigate the dynamics of small polarons induced by photoexcitation at different temperatures. The photoexcited electron is trapped by the distortion of the surrounding lattice and forms a small polaron within tens of femtoseconds. Polaron migration among Ti atoms is strongly correlated with quenching through an electron−hole (e−h) recombination process. At low temperature, the polaron is localized on a single Ti atom and polaron quenching occurs within several nanoseconds. At increased temperature, as under solar cell operating conditions, thermal phonon excitation stimulates the hopping and delocalization of polarons, which induces fast polaron quenching through the e−h recombination within 200 ps. Our study proves that e−h recombination centers can be formed by photoexcited polarons, which provides new insights to understand the efficiency bottleneck of photocatalysis and photovoltaics in TMOs.

We carried out a comprehensive study on the generality, scope, limitations, and mechanism of the palladium-catalyzed hydrophosphorylation of alkynes with P(O)-H compounds (i.e., H-phosphonates, H-phosphinates, secondary phosphine oxides, and hypophosphinic acid). For H-phosphonates, Pd/dppp was the best catalyst. Both aromatic and aliphatic alkynes, with a variety of functional groups, were applicable to produce the Markovnikov adducts in high yields with high regioselectivity. Aromatic alkynes showed higher reactivity than aliphatic alkynes. Terminal alkynes reacted faster than internal alkynes. Sterically crowded H-phosphonates disfavored the addition. For H-phosphinates and secondary phosphine oxides, Pd/dppe/PhP(O)OH was the catalyst of choice, which led to highly regioselective formation of the Markovnikov adducts. By using Pd(PPh) as the catalyst, hypophosphinic acid added to terminal alkynes to give the corresponding Markovnikov adducts. Phosphinic acids, phosphonic acid, and its monoester were not applicable to this palladium-catalyzed hydrophosphorylation. Mechanistic studies showed that, with a terminal alkyne, (RO)P(O)H reacted, like a Brønsted acid, to selectively generate the α-alkenylpalladium intermediate via hydropalladation. On the other hand, Ph(RO)P(O)H and PhP(O)H gave a mixture of α- and β-alkenylpalladium complexes. In the presence of PhP(O)OH, hydropalladation with this acid took place first to selectively generate the α-alkenylpalladium intermediate. A subsequent ligand exchange with a P(O)H compound gave the phosphorylpalladium intermediate which produced the Markovnikov adduct via reductive elimination. Related intermediates in the catalytic cycle were isolated and characterized.

The oxidative addition of pure (R(P))-menthyl phenylphosphinate 1 to a platinum (0) complex proceeds readily with retention of configuration at the chiral phosphorus center which was unambiguously confirmed by an X-ray analysis. In the presence of a catalytic amount of palladium, the hydrophosphinylation of a variety of alkynes with 1 also takes place stereospecifically, with retention of configuration, affording high yields of the corresponding vinylphosphinates bearing a single chirality at phosphorus.