Department of Chemical Sciences
School of Natural Sciences


July 10, 2018 at 2.30 pm in AG-69

Title :

Bioinorganic Chemistry Approach to Nanozymes for Cellular Redox Regulation

Abstract :

Organic/metal organic compounds that mimic the functional role of enzymes have been extensively investigated. Recently, few nanomaterials such as gold nanoparticles, ferromagnetic nanoparticles and graphene-based materials have been innovatively shown to exhibit unprecedented biochemical catalysis by mimicking certain enzymes (nanozymes). Owing to their simplicity of preparation and storage and stability, nanozymes have been investigated for their application in many fields such as biosensing, immunoassays, cancer diagnostic, therapeutic and pollutant removal, etc. Despite current interest on nanozymes, tackling with some of the difficulties associated with them such as selectivity, cooperativity with other enzymes, limited surface area due to functionalization, biocompatibility and activity in cells, etc. is a challenging task.


In this seminar, I will discuss about the novel antioxidant and phosophotriesterase nanozymes. We have recently reported the graphene-hemin hybrid material for its remarkable peroxynitrite reductase and isomerase antioxidant activities. Noncovalent interactions of hemin and reduced graphene oxide (RGO) resulted in synergistic activity to effectively scavenge peroxynitrite, which is a potent reactive nitrogen species (RNS) found in vivo.


In another related study, we found that vanadium pentoxide (V2O5), an oxidant, reveals an unexpected antioxidant role in its nano-form and exerts tremendous cytoprotective effects. The vanadia nanozyme exhibit excellent glutathione peroxidase (GPx)-like catalytic antioxidant activity and prevents oxidative damage to cells from reactive oxygen species (ROS) without affecting the expression level of other antioxidant enzymes. This work demonstrates the first experimental evidence that the biological property of a metal ion in its nano-form can be completely different from that of a bulk material. In a similar line, I will also briefly highlight about MnFe2O4 nanooctahedrons as oxidase and vacancy-engineered nanoceria as phosphotriesterase nanozymes for antibody-free detection of major biomarkers of oxidative stress and detoxification of sarin gas-related nerve agents, respectively.



1.       A. A. Vernekar, G. Mugesh, Chem. Eur. J. 2012, 18, 15122-15132.

2.       A. A. Vernekar, G. Mugesh, Chem. Eur. J. 2013, 19, 16699-16706.

3.       A. A. Vernekar, D. Sinha, S. Srivastava, U. P. Prasath, P. D’Silva, G. Mugesh, Nature Commun. 2014, 5, 5301.

4.       A. A. Vernekar, T. Das, S. Ghosh, G. Mugesh, Chem. Asian J. 2016, 11, 72-76.

5.    A. A. Vernekar, T. Das, G. Mugesh, Angew. Chem. Int. Ed.2016, 55, 1412-1416.

July 9, 2018 at 4.00 pm in AG-69

Title :

When Nano Break H2O

Abstract :

While H2O (water) is life to all living organisms on earth, it is also one of the key technological components of hydrogen economy. In an electrolysis cell, water can be decomposed into hydrogen and oxygen due to an electric current passing through it. Although hydrogen evolution reaction (HER) is the major reaction of interest, oxygen evolution reaction (OER) is the most energy intensive step. To overcome the activation barrier of splitting water, a catalyst is needed. The more active and stable the catalyst, more effective is the splitting. One of our major research interests is to develop nanoheterostructured electrocatalysts for OER and HER,1,2 thereby leading to overall water splitting.3 The best performances are obtained not only by designing a suitable catalyst but also by optimizing the substrate on which the catalyst nanoparticles are supported, among which flexible substrates are fascinating.4 When the electrolyzer is integrated to solar cells, water photolysis with high solar-to-hydrogen efficiency also becomes possible.


References :


1.Datta, A.; Kapri, S.; Bhattacharyya, S. J. Mater. Chem. A 2016, 4, 14614-14624.

2.Debnath, B.; Kumar, A.; Salunke, H. G.; Bhattacharyya, S. J. Phys. Chem. C 2017, 121, 25594-25602.

3.Kumar, A.; Bhattacharyya, S. ACS Appl. Mater. Interfaces 2017, 9, 41906-41915.


4.Sahasrabudhe, A.; Dixit, H.; Majee, R.; Bhattacharyya, S. Nat. Commun. 2018, 9, 2014.


June 25, 2018 at 4.45 pm in AG-69

Title :

Investigations on photocatalytic H2 generation using modified TiO2 and g-C3N4 semiconductors

Abstract :

Generation of hydrogen from renewable sources like water and solar energy is considered to be an attractive and viable solution for replacing fossil fuels. Photocatalytic water splitting has attracted much attention as it involves conversion of solar energy into useful chemical energy. The major challenge involved in the process is the development of stable and visible light active photocatalyst with required solar to fuel energy conversion efficiency (SFE). In the present work, studies were undertaken to improvise the optical and photocatalytic properties of several photocatalysts; conventionally known UV active TiO2 and novel organic semiconductor, graphitic carbon nitride (g-C3N4). Various strategies such as cationic doping by Cu in TiO2, composite formation with NiO and CuO inducing pn heterojunctions, carbon and TiO2 heterojunction to improve electronic conductivity, surface modification of g-C3N4 by dispersing carbon nanodots (CND) and noble metal (Pt, Pd, Cu, Ag and Au) were adopted to limit the e-/h+ recombination reaction and to enhance the photoresponse under visible light illumination. All samples were thoroughly characterized by relevant techniques and their potential for H2 generation was evaluated under sunlight and UV-visible light in presence of sacrificial reagent. Density functional theory calculations were performed and life time of e-/h+ from PL decay curves was measured to support the activity trend. Parameters such as illumination area, catalyst concentration, form of catalyst (powder/films) and different sacrificial reagents were optimized for maximum H2 yield. Performance of the screened photocatalysts was also tested in up-scaled photoreactors (volume = 0.5, 1 and 2 L). H2 yield @ 16 ml/h/g with apparent quantum efficiency (AQE) of 7.5 % and SFE of 3.9 % over Cu0.02Ti0.98O2-δ (without cocatalyst) was observed under sunlight suggesting that 0.96 m2 illumination area will yield H2 @ 1 L/h photocatalytically. Among modified g-C3N4 photocatalysts, maximum H2 yield of 398 μmol/h over 80 mg of Pt/CND/ g-C3N4 (0.48 wt %) under sunlight with AQE of 4.0 % and SFE of 2.0 % was achieved as compared to almost negligible yield over pristine carbon nitride. The present study is targeted to provide valuable inputs for actual large scale solar photocatalytic H2 production.

June 25, 2018 at 4.00 pm in AG-69

Title :

Development of metal oxide based photocatalysts for the CO2 reduction to fuel

Abstract :


Continuous depletion of fossil fuel resources and growing environmental concerns due to the huge CO2 emissions, have focused the need to develop renewable and clean energy resources. CO2 is a major greenhouse gas and cause of global warming. CO2 capture, storage and utilization particularly, catalytic conversions of CO2 to fuels and chemicals have attracted much attention in recent years.  Activation of CO2 requires high amount of energy due to its stability. Harvesting the photon energy and its storage in the form of fuels hold promise to address the current and future demand of energy supply. The photocatalytic conversion of CO2 over heterogeneous photocatalysts is a potential approach to mitigate CO2.


Designing of material with suitable band gap and product selectivity remained key challenges. Problems associated are: (i) massive recombination of generated charge carriers and (ii) low yield and less selectivity for product formation and (iii) development of stable visible light active catalyst. Metal oxides with suitable properties can convert solar energy to chemical energy using artificial photosynthesis and it will be a good technique to develop sustainable environment.


The talk will cover my work on designing and synthesis of metal oxide catalysts for the photocatalytic reduction of CO2 to fuel. 


June 22, 2018 at 2.30 pm in AG-69

Title :

Switching On and Off of Interfacial Water Ordering at Air/Water Interface

Abstract :

Carbon quantum dots (CQDs) are recently famed and well developed class of fluorescent probe and have shown tremendous potential in numerous fields such as biosensing, bioimaging, drug delivery, and optoelectronics. After its accidental discovery, it has created huge excitement due to their unique features like chemical inertness, high water solubility, excellent biocompatibility, resistance to photo bleaching. Mostly it has been extensively studied to exploit its fluorescence properties through displacement assay for various applications by using conventional fluorescence spectroscopy. Fluorescence spectroscopy does not provide any information directly related to the structural changes of the system or its impact on the surrounding aqueous medium during displacement assay process. In my talk, I will provide a thorough discussion about our recent work on interfacial activities of carbon quantum dots and its impact on perturbing the pristine hydrogen bonding network of interfacial water structure at air/water interface. We have used surface specific and chemically sensitive sum frequency generation (SFG) vibrational spectroscopy to probe the air/water interface with the presence of QCDs and various metal ions. SFG is a nonlinear optical spectroscopic tool based on second order nonlinear optical process. It is quite fascinating to observe the role of various intermolecular interactions in terms of hydrogen bonding, electrostatic interaction during the process of interaction of the QCDs with various metal ions at the air/aqueous interface. I will also extend my discussion about the physics of surface protein unfolding and its kinetics through diffusion and intermolecular interactions at a neutral air/water interface.

June 18, 2018 at 4.00 pm in AG-69

Title :

Designing Optical Probes for Sensing Signaling Lipids

June 11, 2018 at 4.00 pm in AG-69

Title :

Carbon-Fixation by Plasmonic Catalysts

Abstract :

Mimicking plant photosynthesis requires a synthetic photocatalyst that absorbs sunlight and uses that energy efficiently to convert CO2 into energy-dense hydrocarbons. My talk will make the case that noble metal nanostructures, which exhibit collective free electron resonances called plasmons, may be well-suited to this task. Not only do plasmonic nanoparticles of Au, Ag, and Cu offer a means to absorb visible light efficiently, their strong-light-matter interaction can be paired with their ability to activate small molecules, such as CO2. We have had preliminary success with plasmonic catalysts, which under visible-light-excitation, can drive kinetically challenging multi-electron multi-proton processes such as methane generation. Moreover, the product selectivity is controllable by the nature of the exciting light, which suggests that a novel phenomenon is at work. In order to understand the light-driven pathway for CO2 reduction, we have probed with single-site spatial resolution the dynamics of a plasmonic photocatalyst under operando conditions. From captured intermediates and density functional theory simulations, we are beginning to understand the mechanism which plasmonic excitation activates physisorbed CO2. It is clear that a close interplay between photoexcited states and surfaces is involved in this scheme of artificial photosynthesis. 

June 5, 2018 at 2.30 pm in AG-80

Title :

Applications of coherent Raman scattering microscopy in bioimaging

Abstract :

Much progress in biology and allied sciences is driven by optical microscopy methods. Techniques involving extraneous labels (e.g. fluorescent molecules) with affinity to one or more sample components are widely used, with some implementations even breaching the diffraction limit. Other than the fact that the introduction of these labels changes sample chemistry, availability of suitable labels, issues of photobleaching, and phototoxicity can limit the applicability of these methods.

Spectroscopy techniques, which rely on energy-level transitions of various molecular species in the sample are chemically specific, sensitive, and label-free. Coherent Raman scattering (CRS), namely coherent anti-Stokes Raman scattering (CARS) and stimulated Raman scattering (SRS) have been applied in bioimaging, with short acquisition times and promising results.

In this talk, I will discuss my research at Cardiff University (PhD) and KU Leuven, where I used CARS and SRS microscopy to image biological samples. Using volumetric hyperspectral CARS microscopy [1-3], I studied mitosis in human osteosarcoma (U-2OS) cells, revealing the sub-cellular distribution of various biomolecules. As an outlook to pharmacodynamical studies, I imaged the effects of two anti-cancer drugs in single cells. In addition to these, I will also show some results from an exploratory application of CARS to 3D tissue cultures- organoids. Not only a proof of principle, this work has revealed interesting information previously unresolved with CRS. 

As a classic example of how fluorescent molecules are not always the best choice for bioimaging, I will present results of SRS imaging of lipids in desert locust (Schistocerca gregaria) oocytes which do not stain efficiently using conventional methods.

When applied to statistically significant sample sizes, the methods demonstrated in this research could establish CARS and SRS as novel and extremely useful tools in biomedical/biochemical research. 



1.Pope I, Langbein W, Watson P, Borri P, Optics Express 21, 7096 (2013)

2.Masia F, Glen A, Stephens P, Borri P, Langbein W, Anal. Chem. 85, 10820 (2013)

3.Karuna A, Masia F, Borri P, Langbein W, Journ. Raman Spec. 47, 1167 (2016)


May 29, 2018 at 2.30 pm in AG-69

Title :

Hot Spot Engineering in Gold-DFNS  Plasmonic Nanostructures: Synthesis and Applications as Nano-Heaters

May 28, 2018 at 4.00 pm in AG-69

Title :

Disordered Proteins: Spontaneous Fluctuations, Membrane Interactions and Toxicity

May 24, 2018 at 2.30 pm in NMR Seminar Room

Title :

Revisiting the BIM-Trimethylamine and BIM-Ammonia H-Bonded Complexes

May 21, 2018, at 4.00 pm in AG-69

Title :

Comparative study of Native and Hybrid-enzymes: Preparation, Characterization and Reactivity

May 7, 2018 at 4.00 pm in AG-69

Title :

Beyond the Conventional Hybrid Perovskites

May 2, 2018 at 2.30 pm in AG-69

Title :

Viscoelastic response of Liquid at Nanoconfinement

Abstract :


Flow properties of confined liquids play crucial roles in a wide range of areas from biology to nanofluidics. Liquids, when confined between two surfaces that are tens of nanometers apart, exhibit unique structural, dynamic, and mechanical properties, which are significantly different from those observed in bulk. In the past, viscosity measurement of confined liquids by different techniques has resulted in contradictory findings. We have developed an experimental scheme, which has two key advantages over  previous techniques used to measure shear-viscosity for liquid films with thickness of few nanometers; (i) the spring measuring the viscous drag has very high stiffness (55000 N/m), and yet force sensitivity of few nN, thus reducing the thermal noise in our measurement. (ii) the force sensing spring stays out of the liquid, and hence has a high resonance frequency and quality factor, allowing us to perform off-resonance measurements with high shear frequency (5-20 kHz) and shear rates (104- 106 s-1). Using this novel shear rheometer, we investigated the role of confinement and substrate wettability on flow properties of polar (water) and non-polar (organic) liquids on several surfaces. We observed reduction in dissipation coefficient under confinement; which is modeled with Carreau-Yasuda model of shear thinning including finite slippage. We found that for purely wetting substrate the nonlinear rheological response solely originates due to nano-confinement, whereas both wettability and confinement play crucial role in case of non-wetting substrates. Finite Element Method (FEM) simulations were performed to understand the behavior of two prongs of our force sensor (tuning fork) at off resonance frequency in air and in liquid medium. Our study helps to separate out the effects of substrate wettability and confinement on shear resistance experienced by liquids at nano-confinement. The rheological response of nano-confined liquids is intriguing and we propose that it is result of criticality with respect to degree of confinement.     



May1, 2018 at 2.30 pm in AG-80

Title :

Dendritic Fibrous Nanosilica Coated Titanium Dioxide for Morphology Controlled Photocatalysis