Sujit S. Panja

A Rhodamine-Based Dual Chemosensor for Cu(II) and Fe(III)

An “off-on” rhodamine-based fluorescence probe for the selective signaling of Cu(II) and Fe(III) has been designed and synthesized. The optical properties of this compound have been investigated in acetonitrile-water (1:1) binary solution. Very interestingly, this compound showed sensitivity and selectivity towards Cu(II) during absorption process and towards Fe(III) during emission process. So this is a nice example of an excellent dual chemosensor for two biologically/physiologically very important transition metal ions using only the two very different techniques (absorption and emission); both cases displayed only intensity enhancement.

Absorption-Dominated Electromagnetic Wave Suppressor Derived from Ferrite-Doped Cross-Linked Graphene Framework and Conducting Carbon

To minimize electromagnetic (EM) pollution, two key parameters, namely, intrinsic wave impedance matching and intense absorption of incoming EM radiation, must satisfy the utmost requirements. To target these requirements, soft conducting composites consisting of binary blends of polycarbonate (PC) and poly(vinylidene fluoride) (PVDF) were designed with doped multiwalled carbon nanotubes (MWCNTs) and a three-dimensional cross-linked graphene oxide (GO) framework doped with ferrite nanoparticles. The doping of α-MnO2 onto the MWCNTs ensured intrinsic wave impedance matching in addition to providing conducting pathways, and the ferrite-doped cross-linked GO facilitated the enhanced attenuation of the incoming EM radiation. This unique combination of magnetodielectric coupling led to a very high electromagnetic shielding efficiency (SE) of -37 dB at 18 GHz, dominated by absorption-driven shielding. The promising results from the composites further motivated us to rationally stack individual composites into a multilayer architecture following an absorption-multiple reflection-absorption pathway. This resulted in an impressive SE of -57 dB for a thin shield of 0.9-mm thickness. Such a high SE indicates >99.999% attenuation of the incoming EM radiation, which, together with the improvement in structural properties, validates the potential of these materials in terms of applications in cost-effective and tunable solutions.

Conformations of indan and 2-indanol: A combined study by UV laser spectroscopy and quantum chemistry calculation

Three conformational isomers of 2-indanol are identified by use of resonance enhanced two-photon ionization (R2PI) and single vibronic level dispersed fluorescence spectroscopy in a supersonic jet expansion. By combining the experimental results with the predictions of the ab initio quantum chemistry calculations at the MP2/6-311++G(d,p) level of theory, the major species is identified as a conformational isomer in which the hydroxyl hydrogen is involved in an intramolecular hydrogen bonding with the π-electrons of the aromatic ring. The theoretical estimate of the hydrogen bond energy is ∼6.5 kJ/mol. A comparative investigation with indan reveals that this weak hydrogen bonding in the former significantly affects the puckering potential of the five-member side ring. The dispersed fluorescence data indicate for a much higher ring-puckering barrier in the ground state than what has been suggested recently by measuring rotational spectra of the unsubstituted indan.

Fluorescence spectroscopy of jet-cooled chiral (±)-indan-1-ol and its cluster with (±)-methyl- and ethyl-lactate

The laser-induced fluorescence excitation, dispersed fluorescence, and IR-UV double resonance spectra of chiral (+/-)-indan-1-ol have been measured in a supersonic expansion. Three low energy conformers of the molecule have been identified, and the ground state vibrational modes of each conformer are tentatively assigned with the aid of quantum chemistry calculations. The frequencies of the nu(OH) and nu(CH) stretch modes of the two most abundant conformers have been measured by fluorescence dip IR spectroscopy and have been used for their assignment. The dispersed fluorescence spectra clearly indicate the coupling of low-frequency modes, as was seen in other substituted indanes such as 1-aminoindan and 1-amino-2-indanol. (R)- and (S)-indan-1-ol distinctly form different types of clusters with (R)- and (S)- methyl- and ethyl-lactate. Both hetero- and homochiral clusters are characterized by complex spectra which exhibit a progression built on low-frequency intermolecular modes.

Conformational stability of allylbenzene: A combined study by dispersed fluorescence spectroscopy and quantum chemistry calculation

Two conformational isomers of allylbenzene are identified in a supersonic free jet expansion by use of laser-induced fluorescence excitation and dispersed fluorescence spectroscopy. With the aid of the predictions of ab initio quantum chemistry calculations at the MP2 level for a series of extended basis sets [6-311+G(d,p), 6-311++G(d,p), and cc-pVTZ], the major species of the electronic spectrum is shown to be an eclipsed conformer in which the allyl group is oriented perpendicular to the plane of the benzene ring and a terminal hydrogen atom of the ethylene moiety is poised nearly above the aromatic π electrons. The minor species is identified as an internal rotational isomer that is obtained by rotating the ethylene group about the Cα–Cβ bond by 120° from the eclipsed configuration. This predicted order of conformational preference is reversed for calculations at relatively low levels of theory: MP2/6-31G(d,p), HF/6-311++G(d,p), HF/6-31G(d,p), and B3LYP/6-31G(d,p). The relative intensities of the vibro...

Specific and nonspecific interactions in a molecule with flexible side chain: 2-phenylethanol and its 1:1 complex with argon studied by high-resolution UV spectroscopy

Using high-resolution resonance-enhanced two-photon ionization spectroscopy in combination with genetic-algorithm-based computer-aided rotational fit analysis and ab initio quantum chemistry calculations we determined the conformational structure and transition moment orientation in 2-phenylethanol and its 1:1 clusters with argon. The results clearly demonstrate that the gauche structure of 2-phenylethanol, which is stabilized by the intramolecular pi-hydrogen bond between the folded side chain and the benzene ring, is the most abundant in the cold molecular beam. In this conformer the transition moment is rotated by 18 degrees from the short axis of the aromatic ring. Two distinct 1:1 complexes of 2-phenylethanol with argon in a cis- and trans-configuration with respect to the side chain have been found. Employing the Kraitchman [Am. J. Phys. 21, 17 (1953)] analysis we have found that the structure of the 2-phenylethanol moiety and the orientation of the transition moment do not change after the complexation with argon within the experimental accuracy. From the measured band intensities we conclude that in addition to the dispersion interaction of the argon atom with the aromatic ring a hydrogen-bond-type interaction with the terminal -OH group of the side chain stabilizes the cis-structure of the 1:1 complex of 2-phenylethanol with argon.

A novel fluorophore–spacer–receptor to conjugate MWNTs and ferrite nanoparticles to design an ultra-thin shield to screen electromagnetic radiation

A novel fluorophore–spacer–receptor has been designed with hydrazono methyl phenol as the receptor, anthracene as the fluorophore and imine (CN) groups as the spacer. This newly designed fluorophoric system has a receptor that can bind with ferrites and a fluorophore core that can conjugate non-covalently with multiwalled carbon nanotubes (MWNTs) via π–π conjugation. The hybrid nanoparticles were thoroughly characterized using Raman, UV-vis and fluorescence spectroscopy. This unique hybrid is further explored as a novel material to screen electromagnetic (EM) radiation. By precisely localizing these hybrids in a given phase of an immiscible co-continuous blend, unique microstructures can be constructed. Herein, blends of polyvinylidene fluoride (PVDF) and polycarbonate (PC) were chosen as a model system. The hybrid nanoparticles were selectively localized in the PVDF phase owing to its higher polarity and were systematically characterized by electron microscopic and solution–dissolution techniques. The hybrid nanoparticles that were designed to shield from the incident EM radiation resulted in >99.99% attenuation, dominated mostly by absorption. This non-covalent approach of conjugating MWNTs with ferrites, aided by the fluorophoric system, was noted to be a more effective way to improve the properties (both bulk electrical conductivity and structural) than direct physical mixing/covalent conjugation approaches. In order to further enhance the shielding effectiveness (SE), a layer-by-layer architecture was constructed essentially with outer layers containing PC/PVDF blends with a MWNT–ferrite hybrid and the inner layers consisting of PC/PVDF blends with only MWNTs. An ultra-thin shield of 0.90 mm showed >99.9999% attenuation suggesting new pathways for designing lightweight, flexible EMI shielding materials.

Conformationally induced vibronic transitions in S0←S1 spectra of n-propylbenzene

Dispersed fluorescence spectra (S0←S1) of two conformational isomers of n-propylbenzene have been measured in a supersonic free jet expansion. The results show that the vibronic features in emission from the S1 zero-point levels in two conformers are significantly different, and most notably, the transitions due to ring-chain torsional mode are active only in the spectra of the gauche conformer. Relative stability of the conformers in the ground state has been reinvestigated by the ab initio quantum chemistry method at the MP2/6-311++G(d,p) and MP2/ccpVTZ levels of theory. In contrast to earlier reports, the present theoretical studies predict that the gauche conformer is ∼2.5 kJ/mol more stable [MP2/6-311++G(d,p)] than the trans. The effects of propyl substitution on phenyl ring vibrational modes have been analyzed by comparing the calculated (ab initio, DFT/B3LYP/6-31G**) displacements of ring atoms for different normal modes with those of the vibrational modes of unsubstituted benzene. The implications...

Graphene oxide co-doped with dielectric and magnetic phases as an electromagnetic wave suppressor

The fabrication of thin multilayer polymer nanocomposite films and their judicious arrangement in a sandwich structure to attenuate incoming electromagnetic (EM) radiation, mostly by absorption, is discussed herein. Two key properties (reasonably high conductivity, with high dielectric loss and magnetic permeability) were targeted here by using multiwall nanotubes (MWCNTs) and BaTiO3/Fe3O4 (BT/Fe) co-doped graphene oxide (GO) sheets to design soft functional nanocomposites using bi-component blends of PC (polycarbonate) and PVDF (polyvinylidene fluoride). High dielectric loss and magnetic permeability were achieved by uniformly distributing BT and Fe nanoparticles on the huge specific surface area provided by the GO sheets. The MWCNTs were non-covalently modified to exfoliate the nanotubes and to get a well-connected structure of the blend components. The MWCNTs were thoroughly characterized by TEM, UV-vis, fluorescence emission, Raman and TGA. This surface modification of the MWCNTs also helps with their specific localization in the continuous bi-component blends. BT and Fe were co-doped onto the GO sheets by a well-designed step-by-step synthesis protocol, and the product can facilitate the absorption of incoming EM radiation. This hybrid structure was thoroughly characterized by various microscopic and spectroscopic techniques. By following a sequential mixing protocol, the BT/Fe co-doped GO sheets can be specifically localized in the PC components of the blends while the MWCNTs localize in the PVDF phase through a process driven by thermodynamics. This provides excellent heterogeneous boundaries with multiple scattering within the engineered nanostructures, in addition to retaining the conducting network and the associated dielectric loss properties. The resultant local field variation of such boundaries and the presence of highly lossy materials readily enhance the EM attenuation coefficient. The bulk compositions exhibited a high shielding effectiveness (SE) of −35 dB at 18 GHz (>85% absorption), and when rationally stacked into a multilayer architecture with absorption–multiple reflection–absorption pathways, the SE was further enhanced to −46 dB for a thin shield of 0.9 mm thickness. Such a high SE indicates >99.99% attenuation of the incoming EM radiation. This new-generation EM suppressor, distinguished by its multifunctionality and tunable dielectric and magnetic properties, hence offers an amendable, cost-effective replacement to existing solutions.

Tailored distribution of nanoparticles in bi-phasic polymeric blends as emerging materials for suppressing electromagnetic radiation: challenges and prospects

Regardless of its location, our electronic equipment does not always escape the threats of electromagnetic interference (EMI). Unrestrained radio and microwave radiation from communication devices, broadcasting stations, power lines and other electric equipment constantly bombards us and our precise circuitry equipment. Although its effects on human beings have not yet been directly demonstrated, our electronic gadgets are not that fortunate. A plethora of research work has already been published in the search for a perfect shielding material. Studies in the last decade reveal that dielectric ceramics, magnetic oxides/ferrites/particles, semiconductors, metal particles/foams, intrinsically conducting polymers, conducting carbon black/fibers/nanotubes and other carbon derivatives such as graphene etc. have been widely researched. The particles are either embedded in a wax medium or in a thermoplastic matrix to design an effective shield. To this end, polymer-based nanocomposites have been much discussed owing to their technology-matching properties, light weight, ease of fabrication and adaption, lack of corrosion, and design flexibility. However, the high dosage of nanofillers needed to meet the requirements of an effective shield mars their utility in many respects. Although bi-phasic polymer blends have been researched from different perspectives, utilizing them as a template for microwave shielding is currently drawing enormous interest compared with single-polymer-based nanocomposites. This review highlights the stepwise advancement of bi-phasic polymer blends towards EMI shielding applications. We in this manner endeavor to provide a necessary overview and point out the direction in which future research will keep on thriving as this new class of material emerges as an effective EMI shield.