Dalian Institute of Chemical Physics

Synthetic transformation of terpenoids represents a long‐standing research topic in organic synthesis. Due to the presence of multiple oxidation states and isomers in naturally abundant terpenoids, their separation and efficient utilization pose challenges. Convergent transformations of various terpenes can circumvent these issues. We herein developed a convergent and divergent strategy for control of oxidation states, enabling the construction of sulfur‐containing terpenoid derivatives using various terpenes. This protocol features broad substrate scope, good functional compatibility, and high redox‐selectivity. Convergent synthesis strategy was implemented smoothly by using drug and plant extracts. The synthesis of sulfoxide and sulfone products was further achieved by modulating the oxidation conditions, respectively. Additionally, the products can undergo an array of elaborate transformations, which highlight the potential applications of this strategy.

Fluorescence imaging has emerged as a powerful technique for in situ monitoring of self‐assembly dynamics providing critical insights into structural evolution and functional potential. However, the inherent complexity of supramolecular systems presents significant challenges for real‐time visualization, particularly in capturing the growth kinetics of individual assemblies and the hierarchical formation of network structures at the single‐assembly level. Here, we visualized the dynamic growth and network formation of benzyl‐naphthalimide dye assemblies in situ by confocal laser scanning microscopy (CLSM). In situ time‐lapse imaging revealed distinct dynamic growth mechanisms among the three assemblies. Theoretical calculations demonstrated that different amino substituents significantly influenced assembly morphologies by modulating the planarity of the naphthalene ring. Furthermore, fluorescence lifetime imaging revealed pronounced intra‐assembly heterogeneity, highlighting diverse molecular packing arrangements within individual assemblies. The confocal in situ visualization technique provided single‐assembly growth dynamics, offering insights unattainable through conventional spectroscopic methods. Our work reveals that naphthalimide‐based molecules can self‐assemble into a variety of distinct architectures, underscoring their potential for designing advanced functional materials with tunable properties.

Oxide‐zeolite (OXZEO) catalyst design concept provides an alternative approach for the direct syngas‐to‐olefins (STO) with superior selectivity. Enhancing the activity of oxide components remains a critical and long‐pursued target in this field. However, rational design strategies for optimizing oxides and improving the catalyst performance in such complex reaction networks are still lacking. We employed energetic descriptors such as the adsorption energies of CO* and O* (GadCO* and GadO*) through reaction phase diagram (RPD) analysis to predict the catalyst performance. The prediction was initially validated by the catalytic activity trends measured by experiments. Machine learning (ML) was further utilized to accelerate the screening of new catalysts. Ultimately, Bi‐doped and Sb‐doped ZnCrOx were theoretically predicted as optimized oxide candidates for the OXZEO reaction, which was experimentally verified to be more active than the currently best ZnCrOx counterpart. This work demonstrated enhanced OXZEO catalysts for STO as well as a research paradigm integrating theory and experiment to optimize bifunctional catalysts for complex reaction networks.

Reversible hydrogen storage is a key challenge for the implementation of hydrogen energy, with dehydrogenation being particularly difficult because of its endothermic nature, slow kinetics, poor selectivity, etc. Solar energy‐driven hydrogen uptake/release represents an interdisciplinary approach that provides an effective solution to those problems. Herein, we report the solar‐driven reversible hydrogen uptake of 4.9 wt.% over sodium cyclohexanolate/phenoxide pair, achieving over 99.9% conversion and selectivity in both hydrogenation and dehydrogenation via photocatalysis without external heating. Notably, the initial dehydrogenation rate reaches 23.4 mmolH2gcat−1h−1${\mathrm{mmo}}{{{\mathrm{l}}}_{{{{\mathrm{H}}}_2}}}{{{\mathrm{g}}}_{{\mathrm{cat}}}}^{ - 1}{{{\mathrm{h}}}^{ - 1}}$ that is ca. 2 orders of magnitude higher than thermocatalysis. The superior photocatalytic performance stems from the synergy between high‐ and low‐frequency light, i.e., low‐frequency light mainly provides heat, high‐frequency light drives the desorption of product from the catalyst surface. This approach offers a path toward a sustainable solar‐driven hydrogen energy system.

Fluorophore–ligand conjugates play a pivotal role in cellular imaging, providing high target specificity. However, simultaneously achieving conjugates with high brightness and ligand‐targeting diversity presents significant challenges. Traditional strategies often require complex, multistep modifications for fluorophore enhancement and ligand conjugation. Here, we present an azetidinecarboxamide strategy that addresses these challenges by integrating brightness enhancement and ligand conjugation capabilities within a single molecular framework. The azetidinecarboxamide core suppresses twisted intramolecular charge transfer (TICT), thereby enhancing fluorescence quantum yield. Its carbonyl group provides a versatile site for conjugating a wide range of targeting ligands, enabling the rapid development of diverse and tunable fluorophore–ligand conjugates. This streamlined approach reduces synthetic complexity, accelerates probe development, and is compatible with a wide variety of fluorophores, such as coumarin, naphthalimide, NBD, rhodol, rhodamine, and silicon–rhodamine, facilitating the creation of high‐performance, multifunctional probes for advanced cellular imaging.

Oxide‐zeolite (OXZEO) catalyst design concept provides an alternative approach for the direct syngas‐to‐olefins (STO) with superior selectivity. Enhancing the activity of oxide components remains a critical and long‐pursued target in this field. However, rational design strategies for optimizing oxides and improving the catalyst performance in such complex reaction networks are still lacking. We employed energetic descriptors such as the adsorption energies of CO* and O* (GadCO* and GadO*) through reaction phase diagram (RPD) analysis to predict the catalyst performance. The prediction was initially validated by the catalytic activity trends measured by experiments. Machine learning (ML) was further utilized to accelerate the screening of new catalysts. Ultimately, Bi‐doped and Sb‐doped ZnCrOx were theoretically predicted as optimized oxide candidates for the OXZEO reaction, which was experimentally verified to be more active than the currently best ZnCrOx counterpart. This work demonstrated enhanced OXZEO catalysts for STO as well as a research paradigm integrating theory and experiment to optimize bifunctional catalysts for complex reaction networks.

Reversible hydrogen storage is a key challenge for the implementation of hydrogen energy, with dehydrogenation being particularly difficult because of its endothermic nature, slow kinetics, poor selectivity, etc. Solar energy‐driven hydrogen uptake/release represents an interdisciplinary approach that provides an effective solution to those problems. Herein, we report the solar‐driven reversible hydrogen uptake of 4.9 wt.% over sodium cyclohexanolate/phenoxide pair, achieving over 99.9% conversion and selectivity in both hydrogenation and dehydrogenation via photocatalysis without external heating. Notably, the initial dehydrogenation rate reaches 23.4 mmolH2gcat‐1h‐1 that is ca. 2 orders of magnitude higher than thermocatalysis. The superior photocatalytic performance stems from the synergy between high‐ and low‐frequency light, i.e., low‐frequency light mainly provides heat, high‐frequency light drives the desorption of product from the catalyst surface. This approach offers a path toward a sustainable solar‐driven hydrogen energy system.

A trigonometric discrete variable representation with two well-designed scaling functions (mapping functions) was introduced for solving the Schrödinger equation with the singular Coulomb potential, which have distinctly different distributions of the grid points. The method has surprisingly rapid convergence, even faster than the best available (pseudo-)spectral methods. Since the fast Fourier transformation technique could be directly adopted with this method, it is expected to be of a wide range of applications for solving the Schrödinger equation of the electronic motion in atoms, such as the attosecond physical processes. The findings of the work also revealed the marvelous convergence behaviors of the (pseudo-)spectral methods for the singular Coulomb potential.

Fluorophore‐ligand conjugates play a pivotal role in cellular imaging, providing high target specificity. However, simultaneously achieving conjugates with high brightness and ligand‐targeting diversity presents significant challenges. Traditional strategies often require complex, multi‐step modifications for fluorophore enhancement and ligand conjugation. Here, we present an azetidinecarboxamide strategy that addresses these challenges by integrating brightness enhancement and ligand conjugation capabilities within a single molecular framework. The azetidinecarboxamide core suppresses twisted intramolecular charge transfer (TICT), thereby enhancing fluorescence quantum yield. Its carbonyl group provides a versatile site for conjugating a wide range of targeting ligands, enabling the rapid development of diverse and tunable fluorophore‐ligand conjugates. This streamlined approach reduces synthetic complexity, accelerates probe development, and is compatible with a wide variety of fluorophores, such as coumarin, naphthalimide, NBD, rhodol, rhodamine, and silicon‐rhodamine, facilitating the creation of high‐performance, multifunctional probes for advanced cellular imaging.

Fluorescence super‐resolution microscopy has enabled nanoscale imaging of intracellular structures, but it remains challenging to simultaneously achieve structural imaging and quantitative functional characterization, such as pH measurement, within the same region. Here, we introduce two‐color single‐molecule blinking ratiometricity (2C‐SMBR), a novel method that integrates structural and functional imaging with single‐molecule precision. By loading lysosomes with two pH‐dependent spontaneously blinking fluorophores of distinct colors, 2C‐SMBR leverages single‐molecule localization of either fluorophore to achieve nanoscale structural imaging of lysosomes, whereas the ratiometric analysis of blinking dynamics between the two fluorophores provides quantitative pH measurement at the single‐lysosome level. This dual‐color ratiometric approach at the single‐molecule level enables precise quantification of lysosomal pH with exceptional spatiotemporal resolution. Using 2C‐SMBR, we reveal that lysosomal pH is highly heterogeneous at the single‐lysosome level, with distinct subpopulations exhibiting diverse pH values. Our measurements show a pH range of 4.0–6.0 within lysosomes, with perinuclear lysosomes averaging a pH of approximately 4.88, whereas peripheral lysosomes average around 5.64. Crucially, 2C‐SMBR enables real‐time correlation between lysosomal dynamics and pH changes, overcoming a key limitation of super‐resolution imaging. This approach not only advances nanoscale organelle characterization but also provides mechanistic insights into lysosomal physiology and function.

The formation of complexed molecules through intramolecular hydrogen bond to facilitate chemical reactions is an applicable strategy in organic synthesis. Among the lactones, γ‐butyrolactones is a class of biologically active and important structures. In this work, a series of γ‐butyrolactones were synthesised in a green and efficient manner by carbonylation of alkenes. This reaction is also applicable to the synthesis of lactones containing natural product modules. The formation of an intramolecular hydrogen bond between the pyridine group and the hydroxyl group is imperative for enhancing the nucleophilicity of the large steric alcohol, which are challenge to lactonize. The existence of intramolecular hydrogen bond was proven with the aid of FT‐IR and NMR characterisation.

We report experimental generation and numerical simulations of deep ultraviolet (DUV) dispersive waves in a tapered single-ring anti-resonant hollow-core fiber. Using multi-pass cell compression technology, we compress Yb-doped laser pulses to 35 fs. These pulses, with energies in the microjoule range, propagate through a tapered single-ring hollow core photonic crystal fibers (SR-PCF), where tunable DUV pulses in the 202 nm to 210 nm wavelength range are generated under 6–7 bar argon. Both experimental and simulation results demonstrate that the tapering process helps reduce the detrimental influence of resonant bands, enabling more efficient extension of the ultraviolet spectrum. The experimental setup is straightforward and compact, making it feasible for the development of table-top devices for DUV generation that could address specific requirements in medical and spectroscopy applications.

Using the MRPD based time-dependent wave packet approach, we calculate the first fully converged state-to-state differential cross sections for the H2(v=1)+OD→H+HOD reaction on a highly accurate neural network PES. Two distinctive peaks are found in the J=0 reaction probabilities and the backward scattering differential cross sections. Detailed analysis reveals that these peaks originate from the Feshbach resonance states trapped in the peculiar well on the HOD(vOH=3) vibrationally adiabatic potential caused by chemical bond softening, and produces mainly HOD(vOH=2) product.

Fluorescence super‐resolution microscopy has enabled nanoscale imaging of intracellular structures, but it remains challenging to simultaneously achieve structural imaging and quantitative functional characterization, such as pH measurement, within the same region. Here, we introduce Two‐Color Single‐Molecule Blinking Ratiometricity (2C‐SMBR), a novel method that integrates structural and functional imaging with single‐molecule precision. By loading lysosomes with two pH‐dependent spontaneously blinking fluorophores of distinct colors, 2C‐SMBR leverages single‐molecule localization of either fluorophore to achieve nanoscale structural imaging of lysosomes, while the ratiometric analysis of blinking dynamics between the two fluorophores provides quantitative pH measurement at the single‐lysosome level. This dual‐color ratiometric approach at the single‐molecule level enables precise quantification of lysosomal pH with exceptional spatiotemporal resolution. Using 2C‐SMBR, we reveal that lysosomal pH is highly heterogeneous at the single‐lysosome level, with distinct subpopulations exhibiting diverse pH values. Our measurements show a pH range of 4.0 to 6.0 within lysosomes, with perinuclear lysosomes averaging a pH of approximately 4.88, while peripheral lysosomes average around 5.64. Crucially, 2C‐SMBR enables real‐time correlation between lysosomal dynamics and pH changes, overcoming a key limitation of super‐resolution imaging. This approach not only advances nanoscale organelle characterization but also provides mechanistic insights into lysosomal physiology and function.

Alkyl halides are a class of important organic feedstock with wide availability in organic synthesis. Minisci C-H alkylation is a classical radical-type reaction to effectively introduce alkyl groups into heteroaromatics. The attempt to utilize alkyl halides as radical precursors in Minisci reaction is challenging, which has attracted widespread attention. Although halogen-atom transfer (XAT) provides an available strategy to convert alkyl halides into corresponding carbon radicals, the usage of equivalent XAT reagents and excess oxidants is usually inevitable in Minisci reactions. Herein, we present a traceless aminoalkyl radical-induced XAT process for Minisci reaction, especially without the participation of excess XAT reagents and oxidants. This protocol is compatible with a wide array of sensitive functional groups. Mechanistic experiments indicated the formation of comparable aminoalkyl radicals occurred through SET reduction of protonated heteroaromatics, a process differing from the conventional oxidation method used to generate α-aminoalkyl radicals. Notably, this photocatalytic mode for such aminoalkyl radical generation and XAT-induced Minisci reaction contributes to a redox neutral strategy for coupling of two electrophilic molecules.

Vertically inhomogeneous strain within perovskite crystalline layers remains a critical challenge for achieving high efficiency and enhanced stability in perovskite solar cells. Herein, we address this issue by integrating ascorbyl glucoside into hydrothermally synthesized TiO 2 nanocrystals from TiCl 4 to reduce the surface energy of the TiO 2 electron transport layer. The reduced surface energy establishes a liquid/solid/air interface, creating a dewetting effect to trigger stressed perovskite lattice at the bottom region. This design aligns with the liquid/air interface at the top, typically accompanied by formation of an inevitably strained top surface of the perovskite crystals. By precisely controlling the crystallization conditions of the liquid/solid/air interface, we successfully achieved a compressively strained perovskite film that is homogeneously strained throughout the out-of-plane direction. This uniformly strained perovskite film exhibits a significant efficiency, along with remarkable operational stability, maintaining over 95% of its initial efficiency (T95) for over 2,000 hours.

By providing highly functionalized building blocks in an efficient approach, catalytic hydration of alkenes plays a significant role in fundamental chemical transformations and pharmaceutical synthesis. However, hydration reactions have predominantly involved addition reactions of water and alkenes double bond. Herein, we developed a regio‐ and redox divergent hydrated ring expansion protocol of butafulvenes. With the aid of PdII or acid catalysis, various highly functionalized and unsaturated cyclopentanone derivatives could be obtained in high regioselectivities under oxidative or redox neutral conditions. Isotope labeling experiments suggest that the carbonylic oxygen atom of target product is derived from water. In addition, the unsaturated cyclopentanone intermediate could undergo divergent transformations and serve as a key molecule to create skeletal editing compounds of butafulvenes via one‐pot protocol, which highlights the potential applications of this strategy.

Methanol is an ideal feedstock for biomanufacturing that can be produced from CO2 in massive quantities. Methanol biotransformation to promote the production of the biodegradable plastic monomer lactate is a promising approach for mitigating white pollution in a carbon-neutral manner. However, it is still challenging to engineer microbes for lactate production from methanol because of the strong competition between product synthesis and cell growth. Here, we extensively modified the methylotrophic yeast Ogataea polymorpha to synthesize L-lactate from methanol alone and found that the cofactor ratio of NADPH/NADP+ was higher than that of NADH/NAD+ during methanol metabolism. By engineering the gene expression and cofactor preference levels of lactate dehydrogenase, enhancing cell viability, modifying cofactor homeostasis, and performing mitochondrial compartmentalization, 2.5 g/L L-lactate was produced from 10 g/L methanol in a shake flask. Fed-batch fermentation in a 1 L bioreactor resulted in the highest yield of 25.0 g/L L-lactate from methanol, which was chemically synthesized from CO2 with a yield of 0.22 g/g. A technoeconomic analysis and life cycle assessment were performed to evaluate the commercial potential of CO2-derived L-lactate, its environmental impacts, and its greenhouse gas mitigation performance. This study could lay the foundation for the carbon-neutral production of biodegradable plastic polylactic acid from CO2, thus establishing a circular economy.

Single‐atom catalysts (SACs) have emerged as a focal point of research in the field of heterogeneous catalysis. This paper reviews the progress in the studies of single atoms as promoters in various catalytic reactions, elucidating their distinctive role in comparison to the dominant active sites. We provide a discussion on the application of single‐atom promoters (SAP) within host‐guest systems in various catalysts, including metal oxide supported catalysts, molybdenum carbide‐based catalysts, bimetallic catalysts, and others. The behavior of SAP is diverse. They often promote the formation of oxygen vacancies for oxide support, leading to local site reconstruction that creates specific reaction route. Moreover, they can also precisely modify the electronic structure of hetero‐metal atomic or nanoparticle sites, then regulating the adsorption of reactants or intermediates and catalytic performance. Finally, the potential for the development of SAP is outlined, proposing novel approach for the design of SACs with enhanced activity and stability.