Computational Material Design of Two Dimensional Materials and Their Energy Applications
Two-dimensional materials have attracted attention from both fundamental aspects and application. In this work, we will present some of our recent effort to using first-principles based computational tools to design two-dimensional materials for energy applications. We have explored new possible ionic two dimensional materials and discover some that have not been synthesized yet1. Furthermore, their potential applications to adsorption of Li (for battery and hydrogen storage)2 and hydrogen evolution reactions3 are also examined.
1.Chung-Huai Chang, Xiaofeng Fan, Shi-Hsin Lin, J-L Kuo, Phys. Rev. B, 88, 195420 (2013)
2.S-H Lin, and J-L Kuo, Phys. Chem. Chem. Phys., 16, 20763 (2014)
3.Yun-Wen Chen, Yaojun Du, and J-L Kuo, J. Phys. Chem. C, 118, 20383 (2014)
4.D. B. Putungan, S-H Lin, and J-L Kuo, Phys. Chem. Chem. Phys., 17, 11367 (2015)
Vibrational Anharmonicity and IR Spectra of Hydrogen Bonded Clusters
Structure of hydrate proton is typically classified into Eigen (H3O+) and Zundel (H5O2+) forms. While this is a textbook knowledge, it remains very challenging to keep track of their vibrational signatures owing to the strong vibrational coupling. We have developed several computational scheme to reveal the vibrational couplings (from strong to weak) with the hope to link vibrational spectra and the structure of these clusters. Gas-phase ionic spectra collected over the last two decades have provided plenty of experimental vibrational spectra that allow us to examine the vibrational motion of proton in H-bonded cations. In this talk, we will present our recent systematic theoretical studies both different types of Zundel1,2 and H3O+ under different solvation environments3,4. Our theoretical studies engage ab initio treatment on a selected set of quantum degrees of freedom and treat their vibrational anharmonicity/coupling explicitly. If time permits, we will also access the performance of a few approximate treatments on vibrational coupling/anharmonicity to treat larger hydrogen-bonded molecular clusters5.
1.J.A. Tan and J.-L. Kuo. J. Phys. Chem. A., 119, 11320 (2015)
2.J.A. Tan and J.-L. Kuo. Phys. Chem. Chem. Phys., 18, 14531 (2016)
3.J-W Li, M. Morita, T. Takahashi, and J-L Kuo, J. Phys. Chem. A, 119, 10887 (2015)
4.J. Tan, J-W Li, C-c Chiu, H. Huynh, H-Y Liao, and J-L Kuo, Phys. Chem. Chem. Phys., 18, 30721 (2016)
5.K-L Ho, L-Y Lee, M. Katada, A. Fujii, and J-L Kuo, Phys. Chem. Chem. Phys., 18, 30498 (2016)
Energy Relevant Processes Catalyzed by Corrole Metal Complexes
We have recently introduced corrole metal complexes (metallocorroles) as catalysts for various energy-relevant reactions. This includes those that are of prime importance for the electrochemical splitting of water into its elements, as well as the hydrogen and oxygen evolution reactions. Tuning of the redox potentials, M(I)/M(II) for proton reduction, M(II)/M(III) for oxygen reduction, and M(III)/M(IV)/M(V) for water oxidation (M= Fe, Co, or Mn), is achieved via variations of substituents on the corrole ligand. Practical catalysis is achieved via immobilization onto carbon electrodes, while mechanism-of-action insight is obtained by performing homogenous catalysis and characterization of reaction intermediates. The thus achieved conclusions are used for hypothesis-driven changes in the catalyst’s structures as to achieve the desired properties required for optimal catalytic efficacy and selectivity. This will be demonstrated by the introduction of newly developed catalysts with trifluoromethyl substituents.
•"Metallocorroles as photocatalysts for driving endergonic reactions, exemplified by bromide to bromine conversion", Angew. Chem. 2015, 54, 12370 –12373.
•"Metallocorroles as Non-Precious Metal Catalysts for Oxygen Reduction", Angew. Chem. 2015, 54, 14080 –14084.
•“Metallocorroles as Non-Precious Metal Electrocatalysts for Highly Efficient Oxygen Reduction in Alkaline Media" ChemCatChem 2016, 8, 2832-2837.
•“Metallocorroles as Electrocatalysts for the Oxygen Reduction Reaction (ORR)", Israel J. Chem. 2016, 56, 756– 762 (invited review).
•“Dioxygen bound Cobalt Corroles”, Chem. Commun. 2017, 53, 877-880.
•“Selective CF3 Substitution for Affecting the Physical and Chemical Properties of Gold Corroles” Angew. Chem. 2017, 56, 9837-9841.
•“Corroles as Triplet Photosensitizers”, Coord. Chem. Rev. 2017, 0000.
•“One-pot synthesis of contracted and expanded porphyrins with meso-CF3 groups, from affordable precursors” Angew. Chem. 2017, 56, 0000.
Exploring the Diverse Conformations and Biological Functions of IDPs
Intrinsically disordered proteins and regions (IDPs/IDRs) constitute about one third of protein sequence space in humans and enable complex conformational and functional behaviors that underlie diverse biological processes. IDPs can function in the context of discrete multi-component assemblies but recently have been shown to undergo phase separation for form mesoscale cellular structures such as membraneless organelles and transcriptionally silent regions of chromatin. Due to their heterogeneous and transient conformations, IDPs/IDRs are challenging to characterize at atomic resolution, making it difficult to establish detailed “disorder-function relationships”. We will discuss our multidisciplinary strategies toward understanding the roles of protein disorder in regulation of apoptosis and cell division, nucleolar structure and function, and interactions with small molecules. A key goal is to illustrate the diversity and uniqueness of disorder-function relationships
Femtosecond Stimulated Raman Spectroscopy as a New Tool to Identify Twisted Intramolecular Charge Transfer States
Studies on Transition Metal Complexes of Flexible Polydentate Schiff Base Ligands
The primary objective of this research work was to explore the structure-activity relationship between several kinds of biological, chemical as well as material properties and various complex structures tuned by flexible Schiff base ligands. In this regards several Ni(II) and Cu(II) Schiff base complexes have been synthesized by exploiting the flexibility of the piperazinyl moiety. The specific effectiveness towards DNA/Protein binding and catecholase like properties was observed due to flexibility and nuclearity in case of nickel and copper complexes respectively. Furthermore an interesting counter anion directed flexibility was observed in metal complexes after little modification in Schiff base ligands. Apart from protease, nuclease and catecholase like activities, these complexes have shown effective cytotoxicity towards HeLa cells.
Pseudo-halide promoted and nuclearity driven enhanced corrosion inhibition activity of Zn(II) and Cd(II) Schiff base complexes was also observed to investigate the material applications of Schiff base complexes.
Thus, it could be the stepping stone for further tuning of ligand using flexibility and to develop high nuclearity coordination compounds for more effectiveness in terms of biological and material applications.
Synthesis and Comparative Evaluation of Carbon Dots from Glucose Based Saccharides
Functional Supramolecular and Polymeric Materials of Extended π-Systems
Hierarchical organization of supramolecular assemblies of π-conjugated molecules plays an important role to device the synthetic systems for efficient lightharvesting1,2. Though supramolecular assemblies of various π-systems are elegantly designed to fine-tune their optical properties, there are several limitations2. Hence, the development of new class of materials is not only important to overcome the existing limitations but also to provide opportunities to uncover their novel properties. In this talk I will discuss about the design, synthesis, optical properties and other novel attributes of two kinds of materials we have developed, namely, organicinorganic soft-hybrids and dynamic conjugated microporous polymers3–6.
1. Schenning et al. Chem. Rev. 2005, 105, 1491.
2. Ajayaghosh et al. Chem. Soc. Rev. 2008, 37, 109.
3. K. V. Rao et al. Angew. Chem. Int. Ed. 2011, 50, 1179.
4. K. V. Rao et al. Adv. Mater. 2013, 25, 1713.
5. K. V. Rao et al. Chem. Eur. J. 2012, 18, 4505.
6. K. V. Rao et al. Phys. Chem. Chem. Phys. 2016, 18, 156.
Functional Supramolecular Polymers of Extended π-Systems
Supramolecular polymers derived from novel π-conjugated molecules are promising candidates for modern electronic and photonic devices owing to their high internal order and strong exciton coupling1. Moreover, they are easy to process, dynamic, reversible and recyclable which are not observed in many of the covalent polymers. However, most of the supramolecular polymers are reported to have low mobility of charge carriers and often depolymerize into monomers at high temperatures2. In my talk, I will discuss about some of our strategies to improve the charge carrier mobility and thermal stability of supramolecular polymers of various extended π-systems3–5.
1. Aida et al. Science 2012, 335, 813.
2. Meijer et al. Chem. Rev. 2009, 109, 5687.
3. K. V. Rao et al. Angew. Chem. Int. Ed. 2010, 49, 4218.
4. A. Sagade et al. Adv. Mater. 2013, 25, 559.
5. K. V. Rao et al. Nature Chem. 2017, in press (DOI: 10.1038/NCHEM.2812).
Mechanistic Insights into the Protein-metal and Protein-protein Interactions of β-rich Globular Proteins
Chemical Detoxification of Neurotoxic Methylmercury by Smart Molecules
Methylmercury (MeHg+) is considered to be the most toxic form of mercury due to its ability to accumulate in fat tissues leading to its bio-magnification within the food chain. The toxicological implications associated with the ingestion of MeHg+ may also differ according to its chemical form.1 All seafood, mainly fish, contains mercury, primarily in the form of methylmercury. Consumption of mercury contaminated fish on a regular basis therefore could cause adverse neurodevelopmental, cardiovascular, and immunological health effects. High levels of mercury in fish stocks have been found in mining (Singrauli region in MP and Sonbhadra district in UP), and coastal areas, particularly Ulhas River Estuary and Thane Creek areas, Mumbai (mercury levels in fish from these contaminated areas: 0.89-1.78 mg total Hg/kg dry weight (dw); crabs had 1.42-4.94 mg total Hg/kg dw mercury compared to the permissible limit of 0.5 mg/kg).2
In nature, however, several microorganisms have been reported as being MeHg+ tolerant due to their ability to convert highly toxic MeHg+ to either less toxic volatile elemental mercury, Hg0 or biologically inert insoluble HgS (metacinnabar). For instance, bacterial organomercurial lyase (MerB) catalyzes the protolytic cleavage of the otherwise inert Hg-C bond of MeHg+ and produces methane (CH4) gas and ionic mercury Hg2+, while a second enzyme mercuric ion reductase (MerA) reduces the product Hg2+ to volatile Hg0. On the other hand, several sulfate reducing bacteria (SRB) convert highly toxic MeHg+ to less toxic insoluble HgS(s) by producing H2S during metabolism.3 In addition, insoluble mercury selenide (HgSe) particles have also been found in a wide range of tissues of marine mammals (whales and dolphins) and also detected in various organs (kidney, liver, muscle, and brain) of humans exposed to MeHg+. HgSe is considered to be much less toxic than mobile, soluble MeHg+ species including MeHgCys and MeHgSG. In this talk I will mainly focus on how small organic molecules can be used intelligently to detoxify highly neurotoxic methylmercury by two distinct pathways, similar to those observed in nature.4-8
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- Roy, G. et al. Angew. Chem., 2015, 127, 9455; Angew. Chem. Int. Ed., 2015, 54, 9323. This work is highlighted in Cover Page; Angew. Chem., 2015, 127, 9551; Angew. Chem. Int. Ed., 2015, 54, 9419.
- Roy, G. et al. Chem. Eur. J, 2017, 23 (24), 5696. This article is highlighted in "Frontispiece" and considered as "Hot Paper"
- International Patent filed (PCT): WO2017168451.
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Insights into the mechanical properties of polymers by probing their functional group, and segmental motions using solid-state NMR
Predicting mechanical properties like ductility of polymers is, in general, a very difficult problem. However, it is well known that ductility of a single component amorphous glassy polymer is related to the inter- and intra-molecular cooperative segmental motions that occur in the glassy state. These, in turn, are related to the motions of functional groups in the repeat unit of the polymer. In the case of semi-crystalline polymers, the morphology, in addition is also very crucial to the mechanical property of the polymer.
In this talk the results from a study of functional group, and segmental motions in amorphous and semi crystalline polymers using solid-state nuclear magnetic resonance (SSNMR) will be presented. The separated local field NMR has been used to probe the functional group motion. The Center Band only Detection of Exchange (CODEX) experiments have been used to probe the slow segmental motions. We have carried out studies on polycarbonates and polysulfones which are purely amorphous. Results from the studies carried out on polyoxymethyline, a semi-crystalline polymer will be presented. In this study we have shown that the mechanical property is closely linked to the morphology of this polymer.
Control of Actin Assembly by Polyphosphoinositides
Polyphosphoinositides (PPIs) such as phosphatidylinositol (4,5) bisphosphate (PIP2), are phospholipids that control many cellular events and bind to dozens of intracellular proteins, including many regulators of the actin-based cytoskeleton. How phosphoinositides affect their ligands is much less understood than are the mutations that produce abnormal PPI production, but defining how these lipids exert their biological control at the membrane-cytoskeletal interface could lead to new approaches to limiting or reversing the abnormal function of these lipids in disease. The large number of proteins characterized as ligands for PPIs, usually PI(4,5)P2, suggests that specificity within the cell might be attained by changing the physical state of the lipid within the membrane, in addition to its local or global concentration. Recent experiments show that cholesterol-induced redistribution of PIP2 in the lipid bilayer strongly alters its ability to inhibit the actin severing protein gelsolin at constant total PIP2 concentrations and that nucleation of actin polymerization in brain extracts occurs preferentially from liquid disordered membrane domains and from 80 nm PIP2 clusters that form in the presence of µM Ca2+. These results suggest that PPI lateral distribution within cell membranes is structured by cholesterol and divalent or multivalent counterions and affects PPI interactions with the myriad of proteins they appear to regulate in vivo. Therefore reagents that bind PIP2 and alter its distribution the cell can have important effects on cell function and potentially practical applications.
Structural Aspects of Ferritin Protein Cage for Designing Inorganic Biomaterials
Ferritin is a self-assembled 24-mer spherical cage shaped iron storage protein which has an internal cavity of diameter 8 nm. The internal cage is connected with several symmetric pores and interestingly, small metal complexes and organic molecules can easily pass through these pores. The cage is very stable up to 80ºC but disassembles beyond the pH range of 2-11 which can reassemble again at neutral pH. This interesting feature is useful for incorporating larger molecules into the cage. Although the disassembly-reassembly mechanism of ferritin cage has been studied using various spectroscopic and analytical methods, it remains challenging to have a direct structural insight into this mechanism. We used high-speed AFM to observe the phenomena at single molecule level in real-time scale. Due to unique structural features, the ferritin cage is widely utilized for preparing uniform metal nanoparticles which have important catalytic and biomedical applications. For example, magnetic iron oxide nanoparticles grown inside ferritin cage can promote catalytic reactions in the cell and can target and visualize cancer cells. Despite many promising applications, it remains challenging to explore the basic structural features of protein-nanoparticle interactions. In this context, we promoted the chemical reduction of gold ions within a crystalline ferritin cage and analyzed the X-ray crystal structures at various steps. This gives a direct visualization on the formation of gold nanocluster in protein environment and is considered to be an intermediate stage of nanoparticle growth. In another aspect, multiple metal complexes were incorporated simultaneously into the ferritin cage to construct protein-based microcompartment similar to bacterial microcompartment where several enzymes work together for metabolic functions. We studied the X-ray crystal structures and performed the catalytic cascade reactions in confined ferritin environment as a proof of concept.
This presentation includes various structural aspects of metal immobilized ferritin protein cage with X-ray crystal structure analysis and their applications in catalysis as well as understanding the growth of metal nanoparticles in protein environment.
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Development of Heterojunction Based Photocatalysts for Hydrogen Evolution Reaction and Dye Degradation Applications
Due to the increasing industrialization and population growth, energy crises and environmental pollution have become major challenging problems to the human society in the 21st century. Photocatalysis gain immense interest in the field of green energy as a photoconversion technology of converting solar fuel to chemical fuel. The rapid recombination of photogenerated charge carriers, poor light absorption and lack of satisfactory visible light active materials are the major hurdles for single component system to achieve descent photocatalytic activity under solar light.
This presentation will address our investigations of how the heterojunction based photocatalysts (metal/semiconductor-semiconductor) has constructive effect on the photocatalytic activity and overcomes drawbacks of single component photocatalysts. The main part of the work is to enhance the separation and transfer efficiency of photogenarated charge carriers and improve visible light absorption. In order to do this we have synthesized different heterojunction based photocatalysts Pd-SrIn2O4-TiO2, Pd-CdS@CdO-TiO2, In2S3-gC3N4 and ZnCo2O4 marigold flowers and investigated their photocatalytic activity for hydrogen evolution reaction and dye degradation applications. We found that heterojunction based photocatalysts exhibit the enhanced photocatalytic activity as compared to its individual parts. This enhancement may be due to the combined effect of increased visible light absorption, separation and transfer efficiency of photogenerated charge carriers, effective surface area and co-catalytic effect of Pd NPs through the formation of Schottky junction. The structural, morphological and optical properties were studied using XRD, RAMAN, XPS, SEM, TEM and UV-Vis spectroscopy. Time resolved PL spectroscopy, photocurrent and electrochemical measurements were used to study the photoinduced charge-transfer in the composite samples. The band potentials were calculated from Mott-Schottky plot and UV-Vis spectroscopy. Based on the band potentials, probable charge transfer schemes in binary and ternary heterojunction photocatalysts were also proposed. The photocatalytic activity of these heterojunction photocatalysts were also investigated for dye degradation application. To investigate the degradation reaction mechanism in depth, the active species formed during the reaction process and pH dependence were studied.