Institute of Chemistry, Academia Sinica-Research

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Directions

The research thrusts of the Institute are currently grouped along three major directions: materials chemistry, chemical synthesis and catalysis, and chemical biology. The current topics of materials sector include organic electroluminescent materials and devices, organic field-effect transistor materials and devices, photovoltaic materials and devices. The chemical catalysis and synthesis sector is focusing on the development of new synthetic methodology, drug discovery, carbohydrate chemistry, and the development of new catalytic systems for the generation of renewal energies and green fuels. The chemical biology program has made important advances in the delineation of bio-macromolecular structures and the development of new analytical platforms for disease detection and diagnosis.

Materials Chemistry: Organic Electronic and Optoelectronic Materialsy

Applications of organic optoelectronic materials and molecular engineering of nanomaterials are two major research directions under the materials division. Noticeable results include developments of blue fluorescent molecular materials for high performance organic light-emitting diodes, rational design of field-effective organic memory devices based on pentacene and gold nanoparticles, the very first stable organic thin film transistor based on single crystal of hexacene, rare single-walled metal–organic nanotube (MONT) with a large exterior wall diameter, the applications of metal-organic framework as optoelectronic materials, and a number of high performance materials for efficient solar energy harvesting devices such as dye-sensitized solar cells, perovskite solar cells, or organic photovoltaics. Researchers in this sector also develop stimuli-responsive materials, core-shell nanomaterials, and biomaterials. A recent report shows that a cell membrane–mimicking conducting polymer is capable to integrate biochemical and electrical stimulation to promote neural cellular behavior with great enhancement of neurite outgrowth on this conducting polymer.

Chemical Catalysis and Synthesis: Green Catalysis and Synthetic Methodology

In response to the increasingly demands of sustainable fuel and green synthetic technology, researchers in the organic synthesis and chemical catalysis divisions have strived to advance the development of cutting-edge technology for chemical transformations. The synthetic chemistry division of this sector focuses on the advances of synthetic methodology and drug discovery. The research topics under catalysis division is reconciling to catalysis relating to renewable energy. Major research directions in this sector include: (1) synthetic methodology: silyl ethers for hydroxy- directed nucleophilic acyl alkylation, microwave-assisted carbohydrate synthesis, smart fluorescent probes for bioorthogonal sugar labeling; (2) coordination chemistry: approaching unconventional catalysis via amino-NHC and carbodicarbene, unconventional porphyrin complexes for small molecule activations, engineering cytochrome P450 BM3 and alkane hydroxylase (AlkB) for alkane oxidations; (3) renewable energy catalysis: catalytic hydrogen evolution and mechanistic studies, encapsulated tricopper cluster for methane to methanol conversion, and novel catalysts for valorization of lignocellulosic biomass feedstocks.

Chemical Biology: New Material and Method towards Sustainable Health

Chemical biology division focus on the development of new material and methodology to explore the structure and function of macromolecules associated with cellular function or human diseases. The research activities are directed to unravel the underlying pathological mechanism and to derive new diagnostic and therapeutic strategies. Research topics in this division cover (1) development of smart biomaterials based on novel molecular principles; (2) chemical probe and advanced techniques in bio-imaging and structural biology; (3) drug discovery in cancer, infectious and neurodegenerative diseases; (4) development of structural biology techniques for infectious diseases, and (5) development of advanced proteomics strategies for biomarker discovery. The major achievements from the chemical biology group include the establishment of multiplexed quantitative strategy for membrane proteomics and post-translational modification for delineating disease mechanism and mining therapeutic targets discovery of amyloid fibrils induced from the TDP-43 in the Amyotrophic Lateral Sclerosis (ALS), and development of a photocontrollable probe to induce TDP-43 aggregates in live cells, mapping of the RNA exit channel on transcribing RNA polymerase II by FRET analysis, development of nano velcro chip to capture circulating tumor cells for liquid biopsy, construction of a near-infrared- activatable enzyme platform using an up-conversion nanoparticle to remotely trigger intracellular signal transduction.

高活性雙原子碳分子作為一個廣用的配位基應用於過渡金屬配位以及催化反應當中

Reactive Dicarbon as a Flexible Ligand for Transition-Metal Coordination and Catalysis

The Journal of American Chemical Society 2022, 144, 28, 12996-13005
Ming-Chun Wu, Yu-Fu Liang, Titel Jurca, Glenn P. A. Yap, Tsz-Fai Leung,* Tiow-Gan Ong*

Dicarbon is a reactive carbon allotrope that naturally exists only in the high-temperature medium of stellar space. We report the successful preparation of a series of bottleable phosphine-stabilized dicarbon (PDC) molecules. We explore the use of these molecules as a new complementary class of carbenelike ligands featuring strong σ-donor (>NHCs and CAAcs) but weak π-acceptor properties. Steric map analysis of PDC based on Cavallo’s SambVca program reveals comparable steric volume bulk of 32.5%, similar to the conventional IMes carbene. However, our PDCs exhibit dynamic steric flexibility modulated by the nature of the metal complexes and catalytic reaction environment. We demonstrate the catalytic utility of the PDC framework by its successful implementation for Suzuki−Miyaura cross-coupling and the reductive coupling reaction of an aldehyde and alkyne. Detailed investigations of the reductive coupling reaction reveal an important secondary interaction between PDC and metal complexes, which plays a critical role in the catalytic system.

雙原子碳 (C₂) 是一種具有高活性的分子，在自然界中僅存在於外太空或者星際之間。在本論文中，我們選用了具有特定立體障礙的膦化物配位基，成功合成了於常溫下可穩定存在的單配位基雙原子碳分子 (phosphine-stabilized dicarbon, PDC)，並且發現 PDC 可作為一種新的類碳烯配位基，其具有很強的σ-予體能力（強於 NHCs 和 CAAcs）與稍弱的π-受體特性。在立體空間分析中，藉由 Cavallo 的 SambVca 軟體計算出 PDC 對於金屬中心的平均遮掩體積與傳統 IMes 碳烯相似，然而 PDCs 會受到金屬錯合物本身的特性或催化反應環境的調節，在立體空間上展現其可變動性。此外，通過 Suzuki-Miyaura 交叉耦合反應與醛基和炔基的還原偶聯實驗，充分證明了 PDC 於催化反應中所具有的效用，其中於還原偶聯反應的細部探討中，我們發現 PDC 與金屬錯合物的二次交互作用對於催化系統至關重要。