Isoprene is used as a precursor to produce terpenes and terpenoids.However, the direct catalytic conversion of isoprene to terpenoids is challenging.Recently, a research team led by Prof. CHEN Qing'an from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS) realized nickel-catalysed asymmertric heteroarylative cyclotelomerization of isoprene to access a series of unnatural chiral monoterpenoids bearing quaternary carbon stereocenter.This study was published in Nature Catalysis on August 18.Terpenoids exist in almost all living organisms and function physiologically. In nature, terpenoids are biosynthesized under enzymatic catalysis, and are often further oxidized and rearranged to generate other monoterpenoids. However, creating an additional monoterpene skeleton by an artificial catalytic system is still challenging."In this work, we have developed a more efficient and simple catalytic system to realize the diversity construction of terpenoids," said Prof. CHEN.The researchers created an unnatural monoterpene skeleton that performed the cascade isoprene dimerization/C–H functionalization, leading to the heteroarylative telomerization of isoprene. They used nickel catalysis to tackle the challenges in simultaneous control of the chemo-, regio- and enantioselectivity.By studying the preliminary mechanism, they found that that this reaction proceeded through an enantioselective dimerization of isoprene and sequent C-H alkylation of heterocycles pathway."Our study not only provided an efficient enantioselective transformation of bulk chemical isoprene, but also helped to create another unnatural monoterpene framework with different biological activities," said Prof. CHEN.The above work was supported by DICP, Dalian Outstanding Young Scientific Talent, and the National Natural Science Foundation of China. (Text by ZHANG Gong)

Fatty acids and their derivatives are promising raw materials for manufacturing advanced biofuels, detergents, lubricants, surfactants and so on. Current supply of fatty acids is mainly through extraction from plants, which requires large amounts of arable land.Methanol is an ideal and renewable feedstock for bio-manufacturing. Methanol biotransformation might provide a sustainable route for fatty acid production with independence of arable land and fresh water.Recently, a research group led by Prof. ZHOU Yongjin from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS) has engineered yeast Ogataea polymorpha for efficient productions of free fatty acids (FFA) from sole methanol by rewiring cellular metabolism and relieving the methanol toxicity.This study was published in Nature Metabolism on July 11.Yeast is widely used for baking and brewing, which is an ideal host for methanol-based bio-manufacturing. However, cellular methanol metabolism is highly regulated and methanol toxicity might limit the biosynthetic efficiency. In particular, there is limited information connecting methanol toxicity, methanol metabolism and product biosynthesis.The researchers observed growth deficiency of engineered FFA producing Ogataea polymorpha in methanol, and this deficiency was restored by adaptive laboratory evolution. Multi-omics analysis (genomics, transcriptomics and lipidomics) showed that FFA overproduction perturbed phospholipid hemostasis.A metabolic rewiring in this superior host achieved a high level of FFA accumulation (up to 15.9 g/L)."This work reveals the mechanisms of methanol toxicity during bio-productions, and achieves efficient methanol biotransformation to value-added products for industrial applications," Prof. ZHOU said. (Text by GAO Jiaoqi)

Perovskite solar cells (PSCs) are promising solar technologies. Although low-cost wet processing has shown advantages in small-area PSC fabrication, the preparation of uniform charge transport layers with thickness of several nanometers from solution for meter-sized large area products is still challenging.Recently, a research group led by Prof. LIU Shengzhong from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS) has developed a facile surface redox engineering (SRE) strategy for vacuum-deposited NiOx to match the slot-die-coated perovskite, and fabricated high-performance large-area perovskite submodules.This work was published in Joule on July 21.Schematic illustration of SRE for NiOx films and photovoltaic parameters of SRE-perovskite devices (Image by DU Minyong)Inverted PSCs are potentially more valuable than their normal counterparts because the former have easily-mitigated hysteresis behavior and long-term durability. NiOx has been demonstrated as the hole transport materials for inverted PSCs. But for most vacuum-processed NiOx films, the relatively hydrophobic surface attenuates the adhesion of perovskite ink, making it challenging to deposit large-area perovskite films.Moreover, the surface chemistry of NiOx is rather complex as a large number of high-oxidative-state Ni species and chemically reactive hydroxyls can decompose perovskites, leading to an interface energy barrier and noncapacitive hysteresis.The SRE strategy not only eliminates the local de-wetting problem of perovskite ink, thus achieving uniform polycrystalline perovskite films at the decimeter level, but also imparts enhanced performance in electronic properties, stability, mechanical adhesion at the buried interface via modulating the NiOx surface features.In this study, the researchers achieved high-performance PSCs with stability of thousands of hours under various stressed conditions and outstanding photovoltaic performance. The power conversion efficiencies of PSCs were 23.4% and 21.3% for rigid and flexible devices, respectively.Furthermore, due to the scalability of SRE strategy to large-area configurations, they assembled perovskite submodules of area 156 × 156 mm2 with a remarkable efficiency of 18.6% along with negligible hysteresis and good stability."The SRE provides a proof of concept for combining vacuum-fabricated charge transport layers with wet-processed perovskites and facilitates the stacking engineering of large-scale, uniform thin films for the development of efficient and stable perovskite modules," said Prof. LIU.The above work was supported by the Strategic Priority Research Program of the Chinese Academy of Sciences, the National Nature Science Foundation of China, the Innovation Fund Project of DICP, and etc. (Text by DU Minyong Du and DUAN Lianjie)

A research team led by Prof. HOU Guangjin and Prof. BAO Xinhe from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS) has revealed the oxygenate-based routes in syngas conversion over oxide–zeolite (OXZEO) bifunctional catalysts by solid-state Nuclear Magnetic Resonance (NMR).This study was published in Nature Catalysis on June 23.OXZEO catalysis was proposed in 2016 by Prof. BAO Xinhe and Prof. PAN Xiulian from DICP. It provides a platform for the efficient utilization of coal and other carbon resources. However, the reaction mechanism in OXZEO catalysis still remains unclear.Oxygenate-based routes regulate syngas conversion over OXZEO bifunctional catalysts (Image by JI Yi and GAO Pan)In this study, the researchers chose the syngas conversion over the ZnAlOx/H-ZSM-5 bifunctional catalyst as a model system to highlight the mechanistic difference in the OXZEO-based syngas direct conversion. ZnAlOx is a typical metal oxide for syngas to methanol process while H-ZSM-5 is a typical zeolite for methanol to hydrocarbons (MTH) reaction.They used the quasi-in situ solid-state NMR (ssNMR)-Gas Chromatography (GC) analysis strategy to reveal the dynamic evolution of abundant critical and/or transient intermediates, including multi-carbon carboxylates, alkoxyls, acid-bounded methyl-cyclopentenones, and methyl-cyclopentenyl carbocations, from the very early induction period to the steady-state conversion under high-pressure flow-reaction conditions.Oxygenate-based routes were proved to be contributed to the outlet olefins and aromatics, where the feed, i.e., CO and H2, was also a vigorous participant in these secondary reactions. In addition to the ZnAlOx/H-ZSM-5 catalyst, the researchers also discovered that the key intermediates exist in multiple OXZEO catalysts, proving the universality of oxygenate-based routes in OXZEO-based syngas conversion."Our findings provide new insights into the reaction mechanism of syngas conversion on bifunctional catalysts, and may also help to better understand the mechanism of CO2 and biomass conversion," said Prof. HOU.This work was supported by the National Key R&D Programs of China, the National Natural Science Foundation of China, the Liaoning Revitalization Talents Programs, the China National Postdoctoral Programs for Innovative Talents, and the China Postdoctoral Science Foundation. (Text by JI Yi and GAO Pan)

Olefins, hydrogen, and carbon monoxide can be converted to aldehydes by the hydroformylation of olefins. Upon further conversion, chemicals including alcohols, acids, and esters are obtained.However, commercial hydroformylation mainly employs homogeneous technology, which can cause problems including separation between catalyst and product, leaching of precious metals and ligands, the massive solvent issues, and the inefficient use of the heat from the exothermic reaction.Now, a research team led by Prof. DING Yunjie and Prof. YAN Li from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS) has realized highly-efficient industrial production of propanal/n-propanol via heterogeneous ethylene hydroformylation.Based on heterogeneous ethylene hydroformylation technology, the facility with propanal/n-propanol yield of 50 kt/year was put into operation in August 2020 in Ningbo, China. So far, it has been in stable operation for 22 months.The heterogeneous hydroformylation technology adopts porous organic polymers with large specific surface area and hierarchical porous structure as both carrier and ligand. It metalates rhodium ions to form single-Rh-sites catalyst with good performance and high stability using multiple Rh-P coordination bonds."The utilization rate of precious metals of this heterogeneous hydroformylation technology is nearly 100%, thereby making the leaching of precious metals and ligand negligible," said Prof. DING. "And there is no cost in the separation of catalyst and product in this process.""The reaction system is solvent-free, and the products have high purity. Moreover, a large amount of low-grade reaction heat can be efficiently used in the hydroformylation and hydrogenation reaction," said Prof. YAN. (Text by JIANG Miao)The industrial facility of 50 kt/year propanal/n-propanol by heterogeneous ethylene hydroformylation (Image by LI Cunyao)

In the past decade, advances in synthetic biology paved the way toward the sustainable synthesis of complex natural products.The baking yeast Saccharomyces cerevisiae has been widely used in food industry and has become one of the main platforms for building cell factories due to its robustness, convenient cellular engineering, and reliable safety.Recently, a research group led by Prof. ZHOU Yongjin from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS), in collaboration with Prof. ZHANG Lei from Naval Medical University, has developed efficient cofactor engineering strategies to derive phenolic acid biosynthesis in yeast.This study was published in Nature Chemical Biology on April 28.The cofactor metabolism is tightly regulated and complicatedly distributed in sub-organelles in eukaryotic cell such as yeast. Thus, it requires novel and feasible engineering strategies to cope with the complex cofactor regulation.The researchers developed tailored engineering strategies to enhance the supply, re-localization, and recycling of cofactors NADPH, FAD(H2), and SAM, which enabled high-level production of caffeic acid (5.5 g/L) and ferulic acid (3.8 g/L)."This work reveals the regulation of different cofactors in yeast, especially the distribution of cofactors between different organelles in cells, and provides theoretical guidance for cofactor engineering," said Prof. ZHOU. "It also provides sufficient precursors for the efficient synthesis of complex active natural products."The study was supported by the National Key Research and Development Program of China, the National Natural Science Foundation of China, the Liaoning Revitalization Talents Program, and the Innovation Grant from DICP. (CHEN Ruibing)