Department of Chemistry
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Item Screening the Band Shape of Molecules by Optimal Tuning of Range-Separated Hybrid Functional with TD-DFT: A Molecular Designing Approach(ACS, 2022-08) Roy, Ram KinkarIn the present article we have demonstrated the effectiveness of optimally tuned range-separated hybrid (RSH) functional to determine the electronic transitions from two fluorophore moieties (blue and yellow/orange) within a single white light emitter (WLE). First, the optimally tuned range separation parameter (ω) is calculated for two white emitting fluorophores (W1 and W2) already reported in the literature. The success of the optimally tuned RSH functional ω*B97XD, used in the TDDFT study, encouraged the authors to design eight new single organic white light emitters with frustrated energy transfer between the two individual fluorophore moieties (blue and yellow/orange). The simulated spectra (the band shapes, to be more specific) generated by TDDFT study and outcomes through natural transition orbital (NTO) and natural bond orbital (NBO) studies clearly demonstrate that all the designed eight organic molecules are potential white light emitters and can be synthesized in future.Item Enantioselective Discrimination of Histidine by Means of an Achiral Cubane-Bridged Bis-Porphyrin(ACS, 2021-11) Grover, NitikaA Langmuir film of cubane-bridged bisporphyrin (H2por-cubane-H2por) at the air/water interface was developed and characterized. The floating film was successfully employed for the chiral discrimination between l- and d-histidine. The enantioselective behavior persisted after the deposition of the film on a solid support using the Langmuir–Schaefer method. Distinct absorption and reflection spectra were observed in the presence of l- or d-histidine, revealing that conformational switching was governed by the interaction between H2por-cubane-H2por and the histidine enantiomer. The mechanism of chiral selection was investigated using an ad hoc modified nulling ellipsometer, indicating the anti-conformation was dominant in the presence of l-histidine, whereas the presence of d-histidine promoted the formation of tweezer conformation.Item Long-Range Single-Molecule Förster Resonance Energy Transfer between Alexa Dyes in Zero-Mode Waveguides(ACS, 2020-03) Patra, SatyajitZero-mode waveguide (ZMW) nano-apertures milled in metal films were proposed to improve the Förster resonance energy transfer (FRET) efficiency and enable single-molecule FRET detection beyond the 10 nm barrier, overcoming the restrictions of diffraction-limited detection in a homogeneous medium. However, the earlier ZMW demonstrations were limited to the Atto 550–Atto 647N fluorophore pair, asking the question whether the FRET enhancement observation was an artifact related to this specific set of fluorescent dyes. Here, we use Alexa Fluor 546 and Alexa Fluor 647 to investigate single-molecule FRET at large donor–acceptor separations exceeding 10 nm inside ZMWs. These Alexa fluorescent dyes feature a markedly different chemical structure, surface charge, and hydrophobicity as compared to their Atto counterparts. Our single molecule data on Alexa 546–Alexa 647 demonstrate enhanced FRET efficiencies at large separations exceeding 10 nm, extending the spatial range available for FRET and confirming the earlier conclusions. By showing that the FRET enhancement inside a ZMW does not depend on the set of fluorescent dyes, this report is an important step to establish the relevance of ZMWs to extend the sensitivity and detection range of FRET, while preserving its ability to work on regular fluorescent dye pairs.Item Deep Ultraviolet Plasmonic Enhancement of Single Protein Autofluorescence in Zero-Mode Waveguides(ACS, 2019-09) Patra, SatyajitSingle molecule detection provides detailed information about molecular structures and functions but it generally requires the presence of a fluorescent marker which can interfere with the activity of the target molecule or complicate the sample production. Detecting a single protein with its natural UV autofluorescence is an attractive approach to avoid all the issues related to fluorescence labeling. However, the UV autofluorescence signal from a single protein is generally extremely weak. Here, we use aluminum plasmonics to enhance the tryptophan autofluorescence emission of single proteins in the UV range. Zero-mode waveguide nanoapertures enable the observation of the UV fluorescence of single label-free β-galactosidase proteins with increased brightness, microsecond transit times, and operation at micromolar concentrations. We demonstrate quantitative measurements of the local concentration, diffusion coefficient, and hydrodynamic radius of the label-free protein over a broad range of zero-mode waveguide diameters. Although the plasmonic fluorescence enhancement has generated a tremendous interest in the visible and near-infrared parts of the spectrum, this work pushes further the limits of plasmonic-enhanced single molecule detection into the UV range and constitutes a major step forward in our ability to interrogate single proteins in their native state at physiological concentrations.Item Microheterogeneity of Some Imidazolium Ionic Liquids As Revealed by Fluorescence Correlation Spectroscopy and Lifetime Studies(ACS, 2012-10) Patra, SatyajitThe microscopic structure and dynamics of the room temperature ionic liquids (RTILs) that are responsible for some of the peculiar properties of this class of solvents continue to intrigue the researchers and stimulate new investigations. Herein, we use the fluorescence correlation spectroscopy (FCS) technique to study the diffusion of some probe molecules in RTILs, the results of which, when combined with those obtained from fluorescence lifetime studies, provide insights into the microscopic structural details of this class of novel solvents. Experiments performed with three charged and neutral probe molecules in five carefully selected 1-alkyl-3-methylimidazolium ionic liquids reveal that unlike in conventional solvents these probes exhibit a bimodal diffusion behavior in RTILs thus indicating the presence of two distinct environments. It is found that the contribution of the slow component of the diffusion increases with increasing alkyl chain length of the cation. Not only are these results supported by the biexponential decay behavior of the fluorescence intensity of the systems, but the individual values of the lifetime components and their weight allow determination of the nature of the two major environments. In essence, the results point to the potential of the two combined techniques in unraveling some of the complex features of the ionic liquids.Item Dopamine Molecules on Aucore−Agshell Bimetallic Nanocolloids: Fourier Transform Infrared, Raman, and Surface-Enhanced Raman Spectroscopy Study Aided by Density Functional Theory(ACS, 2009) Pande, SurojitAdsorption of dopamine (DA) on a Aucore−Agshell bimetallic nanocolloidal surface has been investigated using surface-enhanced Raman spectroscopy (SERS). The normal Raman spectra (NRS) of DA molecules in bulk and in aqueous solution have been investigated in depth. The vibrational signatures, as observed from the Raman and FTIR spectra of the molecule, have been assigned from the potential energy distributions. The pH-dependent NRS of the DA molecule in aqueous solution has been recorded to elucidate the protonation effect and preferential existence of different forms of the molecule. The pH-dependent SERS spectra of the molecule adsorbed on the bimetallic Aucore−Agshell nanocolloidal surface are also reported. The enhancement of bands in the pH-dependent SERS spectra suggests that the molecules are adsorbed onto the bimetallic Aucore−Agshell surface with the molecular plane tilted with respect to the silver surface of Aucore−Agshell bimetallic nanoparticles. The model study authenticates the spectral disposition and orientation of the molecule. Thus, experiment and theory keep abreast of the variety of DA structures envisaged from SERS studies on a new substrate.Item Understanding the Enhancement Mechanisms in the Surface-Enhanced Raman Spectra of the 1,10-Phenanthroline Molecule Adsorbed on a Au@Ag Bimetallic Nanocolloid(ACS, 2011-05-11) Pande, SurojitAdsorption of 1,10-phenanthroline (PHEN) on the Aucore–Agshell (Au@Ag) bimetallic nanocolloid surface has been investigated. Bimetallic nanocolloids have been synthesized using β-cyclodextrin (β-CD) in alkaline solution. Nanocolloids of different Aucore:Agshell ratio were synthesized keeping the same Aucore size. Again, for the preparation, the total metal concentrations were always kept constant. The structure and composition of the bimetallic particles were characterized by UV–vis and high-resolution transmission electron microscopy. Detailed normal Raman (NRS) and surface-enhanced Raman spectra (SERS) of PHEN in aqueous solution have been studied. The relative contributions of the electromagnetic (EM) and charge-transfer (CT) mechanism to the overall enhancement of the SERS bands of the PHEN molecule have been estimated. PHEN molecules are adsorbed on the Agshell surface through both the nitrogen atoms with the molecular plane almost perpendicular to the surface, which has been confirmed from Ag–N stretching vibration. The three-dimensional finite difference time domain (3D-FDTD) method has been applied to simulate the local electric field on the spherical Au@Ag nanocolloid for various core/shell ratios. Comparative spectral information revealed the highest SERS effect from the 1:4 Aucore–Agshell bimetallic nanocolloid of 29 nm size. This observation has also been supported by theory. Thus, experiment and theory keep abreast the attachment of PHEN molecules on a new substrate from SERS studies.Item Encapsulation of Cobalt Phthalocyanine in Zeolite-Y: Evidence for Nonplanar Geometry(ACS, 2003-02) Ray, SaumiCobalt (II) phthalocyanine (CoPc) molecules have been encapsulated within the supercage of zeolite-Y. The square-planar complex, being larger than the almost spherical cage, is forced to adopt a distorted geometry on encapsulation. A comparative spectroscopic and magnetic investigation of CoPc encapsulated in zeolite-Y and in the unencapsulated state is reported. These results supported by molecular modeling have been used to understand the nature and extent of the loss of planarity of CoPc on encapsulation. The encapsulated molecule is shown to be the trans-diprotonated species in which the center of inversion is lost due to distortions required to accommodate the square complex within the zeolite. Encapsulation also leads to an enhancement of the magnetic moment of the CoPc. This is shown to be a consequence of the nonplanar geometry of the encapsulated molecule resulting in an excited high-spin state being thermally accessible.Item Experimental and Quantum Chemical Calculations of Imidazolium Appended Naphthalene Hybrid in Different Biomimicking Aqueous Interfaces(ACS, 2016) Sakhuja, Rajeev; Pant, Debi D.The effect of solvent polarity and micellar headgroup on a newly designed imidazolium based ionic liquid (IL) conjugated with naphthalene, 1,2-dimethyl-3-((6-(octyloxy)naphthalen-2-yl)methyl)-1H-imidazol-3-ium chloride (IN-O8-Cl), was studied using steady state and time-resolved fluorescence techniques. We observed that the dipole moment in the excited state is remarkably higher than the ground state. The effect of micellar surface charge on the photophysics of IN-O8-Cl in aqueous phase at room temperature was investigated. Formation of premicellar aggregates in sodium dodecylsulfate (SDS) was perceived; further the microenvironment of IN-O8-Cl was examined using steady-state fluorescence spectroscopy. Micropolarity of the micellar environment of SDS was found to be lower than that of cetyltrimethylammonium bromide (CTAB) and triton X-100 (TX100) following the order SDS < TX-100 < CTAB. The binding constant (Kb) and edge excitation red shift (EERS) from the emission maximum suggest that the probe binds strongly to the micelles. Multiexponential behavior was observed in time-resolved fluorescence lifetime studies in all micellar environments. We have observed an increase in rotational correlation time as we move from pure aqueous phase to solution containing surfactants of different head charge. Varieties of spectral parameters were used to justify the region in which the probe is present. The experimentally obtained dipole moment data were justified and explained by the DFT calculations of the electronic properties of IN-O8-Cl molecules in gas phase and in selected solvents.Item Exploration of Electrostatic Field Force in Surface-Enhanced Raman Scattering: An Experimental Investigation Aided by Density Functional Calculations(ACS, 2008-10-27) Basu, MrinmoyeeSurface chemical properties of metal nanoparticles must be tunable to create chemical specificity and are a key prerequisite for successful sensing and imaging platforms. To relate surface enhanced Raman scattering (SERS) to electrostatic field force, a simple colloidal chemistry approach has been deliberately exploited for syntheses of gold nanoparticles with negative and positive surface charges to study their interactions with charged analytes. We took up the challenge with sulfur-containing analytes because “Au−S” interaction is well-known. Thiocyanate ion, −SCN−, a well-known SERS analyte, has been proved to be chemically ligated/anchored on positively charged gold nanoparticles surface owing to favorable electrostatic attraction. The Au−S vibrational band at ∼240 cm−1 and blue-shifting of the −C≡N stretching frequency by ∼46 cm−1 in conjunction with its intensity enhancement by an order of ∼103 in the SERS spectrum clearly illustrate a chemisorption phenomenon. In contrast, physisorption of the −SCN− ion becomes evident on negatively charged colloid. Again, methylene blue has been shown to remain engrossed on the negatively charged gold surfaces. However, the electrostatic field force could not be accounted for from fluorescence quenching while methylaminopyrene was introduced because of the distance-dependence effect. The feasibility of such coordinative/chemical attachment also has been examined theoretically by density functional theory (DFT). Moreover, employment of this DFT calculation has been performed on five different metal−molecule interaction models to fruitfully interpret the experimental SERS findings and also the orientation of the SERS analyte. The observed Raman signals have been assigned from the potential energy distributions in terms of internal coordinates of adsorbate from the output of DFT calculations. The results thus provide a benchmark illustration of the value of DFT for aiding interpretation of adsorbate vibrational spectra attainable by using SERS.