β-Elemene, a sesquiterpenoid from the traditional Chinese herb Rhizoma zedoariae, has been widely applied in cancer therapies. Currently, β-elemene is mainly extracted from traditional plant, which cannot meet market demand.
　　Microbial cell factories may provide a feasible route for sustainable production of β-elemene toward industrial applications.
　　Recently, a research group led by Prof. ZHOU Yongjin from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS) established a sesquiterpenoid platform by extensively rewiring the nonconventional yeast Ogataea polymorpha for β-elemene production.
　　This study was published in Metabolic Engineering on Feb. 22.
　　High-level production of sesquiterpenoid β-Elemene (Image by YE Min)
　　O. polymorpha featured with high-density fermentation and thermal tolerance is a nonconventional Crabtree-negative microorganism, which is beneficial for constructing superior cell factories.
　　In this study, the researchers achieved a global metabolic rewiring of Ogataea polymorpha by optimizing the mevalonate (MVA) pathway and enhancing the supply of acetyl-CoA and cofactor nicotinamide adenine dinucleotide phosphate hydrogen (NADPH). They obtained the highest titers of 4.7 g/L in fed-batch fermentations in shake-flask.
　　"This work proved the potential of Ogataea polymorpha as a chassis cell for production of sesquiterpenoids and other acetyl-CoA derived chemicals, which might contribute to the large-scale production of β-elemene in industries," said Prof. ZHOU.
　　This work was supported by the National Key Research and Development Project and the Innovation Grant of DICP.

Ammonia (NH3) is a promising energy vector for the storage and utilization of renewable energies. Artificially synthesizing NH3 from its elements (Haber-Bosch process) requires harsh reaction conditions (400-500 °C, 10-30 MPa) because N2 is inert and nonpolar with a strong N≡N bond. The synthesis of NH3 under mild conditions is still challenging.Recently, Assoc. Profs. CAO Hujun and GAO Wenbo and their collaborators from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS) have proposed a new process for ammonia synthesis using Li2NH as an N carrier via the method of electrodriven chemical looping.This study was published in ACS Energy Letters on Feb. 23.This electrodriven chemical looping ammonia synthesis (ECLAS) process is developed based on the conversion between LiH and Li2NH (Image by FENG Sheng and GAO Wenbo)The researchers carried out this electrodriven chemical looping ammonia synthesis (ECLAS) in a LiCl-NaCl-KCl eutectic electrolytic cell using a nickel foam as electrode.Electric energy input not only improved the hydrogenation rate of Li2NH, but also promoted the nitrogen fixation reaction of LiH. In addition, the average ammonia production rate of this ECLAS process was nearly eight times higher than that of the thermal-driven CLAS process.They found that the process contained two electrochemical reactions, one was the nitridation of LiH to form Li2NH, and the other was the hydrogenation of Li2NH to produce ammonia and regenerate LiH. This was different from the reported Li3N-mediated electrochemical ammonia synthesis process, which included three-step reactions: Li ion was reduced to Li, Li fixed dinitrogen to form Li3N, and Li3N was then protonated to produce ammonia and Li+."This ECLAS process has a low theoretical operating voltage than the Li3N-mediated electrochemical ammonia synthesis process, and it could work under as low voltages as 2.0V," said CAO."Our findings open new possibilities for developing electrodriven CLAS over imides," said CAO.The above work was supported by the National Key R&D Program of China, the National Natural Science Foundation of China, the Youth Innovation Promotion Association of CAS, and the Liaoning Revitalization Talents Program.

A research group led by Prof. SHI Quan from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS) has proposed a new concept of "Spatiotemporal Phase Change Materials" (STPCMs) long-term storage and controllable release of thermal energy based on phase change materials (PCMs).This study was published in Journal of Energy Chemistry on Feb.16.PCMs are promising in the field of thermal energy storage and temperature control. However, PCMs usually release their stored latent heat spontaneously as the temperature below the phase transition temperature, which renders thermal energy storage and release uncontrollable, and thus hinders their practical application.Schematic diagram of the Spatiotemporal PCMs (Image by DENG Chengxin)To overcome this issue, the researchers developed erythritol/sodium carboxymethylcellulose/tetrasodium ethylenediaminetetraacetate (ERY/CMC/EDTA-4Na) composite PCMs with novel spatiotemporal thermal energy storage properties. They were defined as spatiotemporal PCMs (STPCMs), and exhibited capacity of long-term storage and controllable release of thermal energy.They found that the composite PCMs were unable to lose latent heat due to spontaneous crystallization during cooling, but could controllably release thermal energy through cold crystallization during reheating. The cold-crystallization temperature and enthalpy of composite PCMs could be adjusted by proportional addition of EDTA-4Na to the composite.When the mass fractions of CMC and EDTA-4Na were both 10%, the composite PCMs exhibited optical cold-crystallization temperature of 51.7 °C and enthalpy of 178.1 J/g. The supercooled composite PCMs without latent heat release maintained at room temperature (10–25 °C) for up to more than two months, and subsequently the stored latent heat was controllably released by means of thermal triggering or heterogeneous nucleation."Our findings provide novel insights into the design and construction of new PCMs with spatiotemporal performance of thermal energy long-term storage and controllable release, and open a new door for the development of advanced solar thermal utilization techniques on the basis of STPCMs," said Prof. SHI.The above work was supported by the Joint Fund of Yulin University and Dalian National Laboratory for Clean Energy, and the National Nature Science Foundation of China.

　　Sodium-ion batteries (SIBs) are promising alternatives to lithium-ion batteries (LIBs) due to the abundant sodium resources, suitable redox potential, and similar charge store mechanism.
　　However, the larger diameter of Na ions compared to Li ions makes the sodiation/desodiation process more difficult with a larger volumetric variation of the electrode material, thus leading to poor capacity and cycling stability. Therefore, a rational design of electrode materials is critical for improving the electrochemical performance of SIBs.
　　A research group led by Prof. DENG Dehui from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS), in collaboration with Prof. ZHANG Jianan from Zhengzhou University, reported a synergetic effect of atomic-interface from well-constructed 2H-MoS2/Fe(SA)-N-C anode assembled with 2H-MoS2 layer on N-doped carbon confined Fe atom, which boosts the reversible sodium storage capacity.
　　This study was published in Angewandte Chemie International Edition on Feb.2.
　　Regulating the catalytic process by atomic-interface for enhanced sodium ion storage (Image by XIA Huicong and ZAN Lingxing)
　　The researchers found that driven by the work function difference at the heterointerface, the electron could transfer from Fe(SA)-N-C to 2H-MoS2 easily, enhancing the adsorption Na+ ion at the S sites of electron-rich MoS2.
　　Meanwhile, they also indicated that the spin-state of Fe site of Fe(SA)-N-C optimized the electronic structure and catalytic activity of the Fe site.
　　Compared with nitrogen-doped carbon (N-C) and pure carbon, the Fe sites of Fe(SA)-N-C could effectively promote the phase transition and structural evolution of 1T/2H-MoS2 during the sodiation/desodiation process, thus prolonging the lifetime of the materials. The 2H-MoS2/Fe(SA)-N-C anode showed a robust long-term cycling performance with a capacity of 350 mA h g-1 after 2000 cycles at 2.0 A g-1.
　　This work was supported by the National Natural Science Foundation of China, the Strategic Priority Research Program of CAS, and the Danish company Haldor Topsoe A/S.

　　Due to exactly atomic composition and crystal structure, atomically precise copper nanoclusters are used as model catalysts for catalytic reaction mechanisms study. However, the efficient synthesis of copper nanoclusters still remains challenging.
　　Recently, a joint group led by Prof. HUANG Jiahui and Prof. FAN Hongjun from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS) has developed a new strategy for synthesis of atomically precise copper nanoclusters by solvent-mediated precipitation.
　　This study was published in Chemical Science on Dec. 20, 2022.
　　The total crystal structure and absorption optical spectrum of Cu13H10(SR)3(PPh3)7 nanoclusters (Image by LIN XinZhang)
　　"We named the new strategy as 'solvent-mediated precipitation synthesis (SMPS)', it was realized to efficiently synthesize Cu13H10(SR)3(PPh3)7 nanoclusters where SR was a thiolate ligand," said Prof. HUANG.
　　The copper nanoclusters, Cu13 for short, were prepared via precipitation, and the excess raw materials and by-products were remained in the solution, solving the problems of separation and low yield of Cu nanoclusters.
　　Single crystal X-ray diffraction analysis showed that the core of the Cu13 nanocluster with a triple axis of symmetry consists of four vertices-sharing tetrahedrons. Electrospray ionization mass spectrometry and nuclear magnetic resonance spectroscopy confirmed the types and number of hydrogen atoms in Cu13 nanoclusters. Density functional theory calculations simulated the location of 10 hydrides in the crystal structure.
　　Moreover, steady-state ultraviolet-visible absorption and fluorescence spectra of Cu13 nanoclusters exhibited unique optical absorbance and photoluminescence.
　　"This study not only provides a novel SMPS strategy for the efficient synthesis of Cu13 nanoclusters, but also explains the relationship between the structure and optical properties of copper nanoclusters," said Prof. HUANG.
　　The work was supported by the National Natural Science Foundation.

Maintaining the protein high-order structures and interactions during the transition from aqueous solution to gas phase is essential to the structural analysis of native mass spectrometry (nMS).Recently, a research group led by Prof. WANG Fangjun from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS), in collaboration with Prof. SHUN Feng from Southwest Jiaotong University, systematically interrogated the effects of charge state and crown ether complexation on the gas-phase native-like protein structure by integrating nMS with 193 nm ultraviolet photodissociation (UVPD). They have revealed the molecular mechanism of crown ether microsolvation effect on the gas-phase native-like protein structure.This study was published in Journal of the American Chemical Society on Dec. 30, 2022.nMS and UVPD exploration of the molecular details of the CE microsolvation effect on the native-like protein structure in the gas phase (Image by LIU Zheyi and ZHOU Lingqiang)The nMS is a cutting-edge technique for studying the composition and structure of proteins and their complexes. Non-denaturing electrospray ionization use biocompatible solutions to transfer proteins from liquid to gas phase while maintaining higher order structure and interactions.However, positive charged residues in protein will form hydrogen bonds with protein backbone carbonyls to stabilize the positive charges of the side chains through intramolecular solvation.Although the change of protein collision cross-sectional area caused by intramolecular solvation has been detected by ion mobility-mass spectrometry, there is still a lack of effective analytical means to accurately characterize the specific site where it occurs and the region that causes structural changes.In this work, the researchers applied the self-built nMS-UVPD platform and home-developed MS data process software to monitor the conformational changes induced by intramolecular solvation. Based on the UVPD fragmentation pattern of myoglobin-heme complex, they determined the detailed microsolvation sites and the regions with conformational changes.Then, they systematically characterized the protein structure alternations between protein ions with different charge states. They found that the gas phase structure of proteins in the high charge state was easily affected by the intramolecular solvation effect and deviated from the solution state structure, and the gas phase structure of low charge protein ions was closer to solution state.Furthermore, they proved that the complexation of the crown ether 18C6 with protein mainly occurred in solution, and then played an important role in stabilizing the protein structure during the electrospray ionization process.UVPD-nMS analysis revealed that the crown ether was mainly bound to protein region with high charge density, and the gas phase structure of the protein was closer to the solution state by blocking the intramolecular solvation of the charged side chain."This work demonstrates the significant advantages of UVPD-nMS in simultaneously obtaining protein sequence and dynamic structure information, and provides theoretical and technical insights for the maintenance and efficient characterization of protein solution structures in nMS," said Prof. WANG.