Department of Chemistry

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IIT Jodhpur

Humidity sensors have gained immense importance as non-invasive, wearable healthcare devices for personal care as well as disease diagnostics. However, non-specificity, poor stability at extreme conditions, and low sensitivity of the humidity sensor inhibit its usage as a health monitoring device. In the present study, N−F containing organic molecule, SelectfluorTM (F-TEDA) based humidity sensors with ∼1–2 mm long needle-shaped crystals is fabricated on interdigitated electrodes resulting in excellent performance. The unidirectional growth of crystals led to the formation of a conduction pathway for water molecules across the crystal, which otherwise are non-conducting. The as-fabricated humidity sensor at an operational voltage of 0.8 V displays a sensitivity of six orders in magnitude, best reported so far. The sensor does not exhibit any response upon exposure to various volatile organic compounds and reactive gases, indicating remarkable specificity. The sensor is tolerant to high moisture of 95 % for prolonged hours followed by monitoring over several days and degrades to 50 % of its original sensitivity only after continuous exposure for several days. Electrochemical impedance spectroscopy (EIS) shows reversal from resistive to capacitive behavior with increasing humidity levels. The fabricated humidity sensor acts as a healthcare device for breath rate monitoring and touch-free examination of skin moisture. © 2019 Wiley-VCH Verlag GmbH &amp; Co. KGaA, Weinheim

World University root node

Electroanalysis

Ultrasensitive Organic Humidity Sensor with High Specificity for Healthcare Applications

We analyse different Bayesian games where payoffs of players depend on the types of players involved in a two-player game. The dependence is assumed to commensurate with the CHSH game setting. For this, we consider two different types of each player (Alice and Bob) in the game, thus resulting in four different games clubbed together as one Bayesian game. Considering different combinations of common interest, and conflicting interest coordination and anti-coordination games, we find that quantum strategies are always preferred over classical strategies if the shared resource is a pure non-maximally entangled state. However, when the shared resource is a class of mixed state, then quantum strategies are useful only for a given range of the state parameter. Surprisingly, when all conflicting interest games (Battle of the Sexes game and Chicken game) are merged into the Bayesian game picture, then the best strategy for Alice and Bob is to share a set of non-maximally entangled pure states. We demonstrate that this set not only gives higher payoff than any classical strategy, but also outperforms a maximally entangled pure Bell state, mixed Werner states, and Horodecki states. We further propose the representation of a special class of Bell inequality-tilted Bell inequality, as a common as well as conflicting interest Bayesian game. We thereafter, study the effect of sharing an arbitrary two-qubit pure state and a class of mixed state as quantum resource in those games; thus verifying that non-maximally entangled states with high randomness help attain maximum quantum benefit. Additionally, we propose a general framework of a two-player Bayesian game for d-dimensions Bell-CHSH inequality, with and without the tilt factor. © Rinton Press.

Quantum Information and Computation

Nonlocality, entanglement, and randomness in different conflicting interest bayesian games

Halogen substituted analogues of formaldehyde, HXCO (X = F, Cl, Br, and I), play a crucial role in the degradation of stratospheric ozone. Several spectroscopic and quantum chemistry investigations of the dissociation chemistry of formyl halides have been reported in the literature. Due to their importance in combustion and atmospheric chemistry, we investigated the gas phase dissociation of formyl halides using electronic structure theory, direct chemical dynamics simulations, and Rice-Ramsperger-Kassel-Marcus rate constant calculations. Chemical dynamics simulations were performed using density functional B3LYP/6-31G* theory with suitable effective core potentials for the halogen atoms. Simulations showed multiple pathways and mechanisms for the dissociation of formyl halides. The major reaction products were HX + CO which formedviadirect and indirect pathways. Trajectory lifetime distribution calculations indicated non-statistical dissociation dynamics. © the Owner Societies 2020.

Physical Chemistry Chemical Physics

Theoretical investigation of the dissociation chemistry of formyl halides in the gas phase

Understanding lateral organizations of self-assembled bilayers is crucial to gain a control on functionally relevant topologies. We study self-assembled bilayers composed of a surfactant, behenyl trimethyl ammonium chloride (BTMAC), a cosurfactant, stearyl alcohol (SA), at a ratio of 2:1 in the presence of water at 283 K employing subsequent all-atom (AA) and coarse-grained (CG) molecular dynamics simulations. Differences in initial configurations lead to the formation of bilayers at ripple or square phases or interdigitated gel phases of varying trans-leaflet asymmetry. The AA ripple and gel phases are reproduced well at the CG level using bonded potentials from Boltzmann inversion of AA canonical sampling and nonbonded potentials from MARTINI. Inhomogeneous populations of disordered chains with higher per chain configurational entropy and tilt result in rippling stabilized by periodic hydrophobic energy barrier and strong interdigitation. Order parameters of the asymmetric bilayers are sufficiently coupled to the per chain entropies at both levels of resolutions to serve as a reflector of the per chain configurational entropy inaccessible by experiments. Thus, trans-bilayer asymmetry may be a controlling parameter to induce rippling in a bilayer of industrial importance. This work will be useful for future investigation on domain-associated transport and signaling in biomembranes at a low temperature. Copyright © 2020 American Chemical Society.

Journal of Physical Chemistry B

Asymmetry and Rippling in Mixed Surfactant Bilayers from All-Atom and Coarse-Grained Simulations: Interdigitation and per Chain Entropy †

The structure and dynamics of interfacial water in biological systems regulate the biochemical reactions. But, it is still enigmatic how the behavior of the interfacial water molecule is controlled. Here, we have investigated the effect of membrane fluidity on the structure and dynamics of interfacial water molecules in biologically relevant phopholipid vesicles. This study delineates that modulation of membrane fluidity through interlipid separation and unsaturation not only mitigate membrane rigidity but also disrupt the strong hydrogen bond (H-bond) network around the lipid bilayer interface. As a result, a disorder in H-bonding between water molecules arises several layers beyond the first hydration shell of the polar headgroup, which essentially modifies the interfacial water structure and dynamics. Furthermore, we have also provided evidence of increasing transportation through these modulated membranes, which enhance the membrane mediated isomerization reaction rate. ©

Langmuir

Modulation of Membrane Fluidity to Control Interfacial Water Structure and Dynamics in Saturated and Unsaturated Phospholipid Vesicles

Transparent electronics continues to revolutionize the way we perceive futuristic devices to be. In this work, we propose a technologically advanced volatile organic compound (VOC) sensor in the form of a thin-film transparent display fabricated using fluorinated SnO2 films. A solution-processed method for surface fluorination of SnO2 films using Selectfluor as a fluorinating agent has been developed. The doped fluorine was optimized to be &lt;1%, resulting in a significant increase in conductivity and reduction in persistent photoconductivity accompanied by a faster decay of the photogenerated charge carriers. A combination of these modified properties, together with the intrinsic sensing ability of SnO2, was exploited in designing a transparent display sensor for ppm-level detection of VOCs at an operating temperature of merely 150 °C. Even a transparent metal mesh heater is integrated with the sensor for ease of operation, portability, and less power usage. A sensor reset method is developed while shortening the UV exposure time, enabling complete sensor recovery at low operating temperatures. The sensor is tested toward a variety of polar and nonpolar VOCs (amines, alcohols, carbonyls, alkanes, halo-Alkanes, and esters), and it exhibits an easily differentiable response with sensitivity in line with the electron-donating tendency of the functional group present. This work opens up the door for multiplexed sensor arrays with the ability to detect and analyze multiple VOCs with specificity. Copyright © 2020 American Chemical Society.

ACS Applied Materials and Interfaces

Innovative Approach to Photo-Chemiresistive Sensing Technology: Surface-Fluorinated SnO2for VOC Detection

Materials with short-wave infrared (SWIR) emission are promising contrast agents for in vivo animal imaging, providing high-contrast and high-resolution images of blood vessels in deep tissues. However, SWIR emitters have not been developed as molecular labels for microscopy applications in the life sciences, which require optimized probes that are bright, stable, and small. Here, we design and synthesize semiconductor quantum dots (QDs) with SWIR emission based on HgxCd1-xSe alloy cores red shifted to the SWIR by epitaxial deposition of thin HgxCd1-xS shells with a small band gap. By tuning alloy composition alone, the emission can be shifted across the visible-to-SWIR (VIR) spectra while maintaining a small and equal size, allowing direct comparisons of molecular labeling performance across a broad range of wavelength. After coating with click-functional multidentate polymers, the VIR-QD spectral series has high quantum yield in the SWIR (14-33%), compact size (13 nm hydrodynamic diameter), and long-term stability in aqueous media during continuous excitation. We show that these properties enable diverse applications of SWIR molecular probes for fluorescence microscopy using conjugates of antibodies, growth factors, and nucleic acids. A broadly useful outcome is a 10-55-fold enhancement of the signal-to-background ratio at both the single-molecule level and the ensemble level in the SWIR relative to visible wavelengths, primarily due to drastically reduced autofluorescence. We anticipate that VIR-QDs with SWIR emission will enable ultrasensitive molecular imaging of low-copy number analytes in biospecimens with high autofluorescence. Copyright © 2020 American Chemical Society.

Journal of the American Chemical Society

Short-Wave Infrared Quantum Dots with Compact Sizes as Molecular Probes for Fluorescence Microscopy

In this article, we proposed a new chaotic map and is compared with existing chaotic maps such as Logistic map and Tent map. The value of maximal Lyapunov exponent of the proposed chaotic map goes beyond 1 and shows more chaotic behaviour than existing one-dimensional chaotic maps. This shows that proposed chaotic maps are more effective for cryptographic applications. Further, we are using one-dimensional chaotic maps to generate random time series data and define a method to create a network. Lyapunov exponent and entropy of the data are considered to measure the randomness or chaotic behaviour of the time series data. We study the relationship between concurrence (for the two-qubit quantum states) and Lyapunov exponent with respect to initial condition and parameter of the logistic map which is showing how chaos can lead to concurrence based on such Lyapunov exponents. © 2020, Springer Nature Singapore Pte Ltd.

Springer Proceedings in Mathematics and Statistics

Chaotic Maps: Applications to Cryptography and Network Generation for the Graph Laplacian Quantum States

Supercapacitors or electrochemical capacitors are receiving greater interest because of their high-power density, long life, and low maintenance. We have synthesized CuS nanoparticles and graphene oxide (CuS-GO) nanocomposites for supercapacitor applications because of their low cost and excellent electrochemical properties. The phase purity of each material was determined using powder XRD studies. The bandgap was determined by UV-visible spectrophotometric studies. Scanning electron microscope and transmission electron microscope images revealed the nano-scale morphology of the synthesized particles. All the electrochemical measurements were conducted in a standard three-electrode configuration, using a platinum wire as the counter electrode and Hg/HgO as the reference electrode. CuS and its composites with graphene oxide on nickel foam were used as working electrodes. All the electrochemical measurements were performed in 3M KOH solution. The CuS-GO nanocomposite electrode showed a specific capacitance of 250 F/g, 225 F/g, 182 F/g, 166 F/g, 161 F/g, and 158 F/g at a current density of 0.5 A/g, 1 A/g, 5 A/g, 10 A/g, 15 A/g, and 20 A/g, respectively. CuS-GO electrodes showed a specific capacitance retention of 70% after 5000 charge-discharge cycles at a current density of 5 A/g. © 2020 Author(s).

Fulltext

AIP Advances

Synthesis and characterization of CuS, CuS/graphene oxide nanocomposite for supercapacitor applications

2,2,2-Trifluoroethanol (TFE) is one of the fluoroalcohols that have been known to induce and stabilize an open helical structure in many proteins and peptides. The current study has benchmarked low-field 19F NMR relaxation and 19F Overhauser dynamic nuclear polarization (ODNP) by providing a brief account of TFE solvent dynamics in a model melittin (MLT, an antimicrobial peptide) solution with a TFE-D2O cosolvent mixture at pH 7.4. Further, this approach has been employed to reveal the solvation of MLT by TFE in a nonbuffered solution with pH 2.8 for the first time. The structural transition of MLT has been elucidated via solvent dynamics by measuring the 19F TFE relaxation rates at 0.34 T for various TFE-D2O compositions in the absence (bulk TFE) and in the presence of MLT at both the pH values. A complementary initial record of circular dichroism experiments on these aqueous MLT solutions with TFE as the cosolvent at two different pH conditions demonstrated the structural transition from a random coil to a helical or from a folded helical to an open helical structure. The molecular correlation time derived from the corresponding relaxation rates shows that TFE resides on the MLT surface in both pH conditions. However, the trends in the variation of molecular correlation time ratio as a function of TFE concentration represent that the mechanism and the extent to which TFE affects the MLT structural integrity are different at different pH values. The extraction of the DNP coupling parameter from steady-state 19F ODNP experiments performed in the presence of 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl at 0.34 T revealed changes in the solvation dynamics of TFE concomitant with the MLT structural transition. In summary, 19F relaxation and ODNP measurements made at a low field have allowed direct monitoring of TFE dynamics during the MLT structural transition in terms of preferential solvation. The choice of experiments performed at a moderately low field (0.34 T) enabled us to exploit on the one hand almost 1200-fold mitigation of the strong contribution of 19F chemical shift anisotropy at 11.76 T, whereas on the other hand, the ODNP experiment offered a window for probing molecular dynamics on timescales of the order of 10-1000 ps. Copyright © 2020 American Chemical Society.

Assessment of the Role of 2,2,2-Trifluoroethanol Solvent Dynamics in Inducing Conformational Transitions in Melittin: An Approach with Solvent 19F Low-Field NMR Relaxation and Overhauser Dynamic Nuclear Polarization Studies