Aniruddha Kundu

Highly Fluorescent Graphene Oxide-Poly(vinyl alcohol) Hybrid: An Effective Material for Specific Au3+ Ion Sensors

We have developed a new highly fluorescent graphene oxide (GO)/poly(vinyl alcohol) (PVA) hybrid (GO-PVA) in an acidic medium (pH 4). Fourier transform infrared (FTIR) spectra indicate the formation of hydrogen bonds between the hydroxy group of PVA and the hydroxy groups of GO. The hybrid is highly fluorescent, because of passivation by hydrogen bonding, as evident from Raman spectra. The quantum yields of GO-PVA hybrids are higher than that of GO. The fluorescent microscopic images of the hybrids exhibit a fibrillar morphology, and all of them emit highly intense green light. Field-emission scanning electron microscopy (FESEM) micrographs also show a fibrillar morphology, which is produced due to the supramolecular organization of GO-PVA complex. The highly fluorescent GO-PVA1 hybrid has been used as a fascinating tool for selective sensing of Au(3+) ions in aqueous media with a detectable limit of ~275 ppb. The sensitivity of the Au(3+) ion (300 μM) in the presence of 600 μM concentrations of each ion (Cu(2+), Ag(+), Mg(2+), Ca(2+), Zn(2+), K(+), Pb(2+), Co(2+), Ni(2+), Pd(2+), Fe(2+), Fe(3+), and Cr(3+)), taken together, is unique, exhibiting a quenching efficiency of 76%. The quenching efficiency in the presence of a biologically analogous mixture (d-glucose, d-lysine, BSA, Na(+), K(+), Ca(2+), Mg(2+), Zn(2+)) (600 μM each) is 73%, which suggests that the GO-PVA1 hybrid is an efficient sensor of Au(3+) ions. The average lifetime of GO at pH 4 increases in the GO-PVA1 hybrid, indicating the formation of a more stable excited state but the increase in lifetime value after addition of Au(3+) salt solution to the hybrid solution indicates dynamic quenching. The selectivity of sensing of Au(3+) is attributed to its reduction potential being higher than that of other metal ions and XPS data of GO-PVA1 hybrid with 300 μM Au(3+) substantiate the reduction of Au(3+) to Au(0), because of the transfer of excitons from the hybrid facilitating the selective photoluminescence (PL) quenching.

Enhanced fluorescent intensity of graphene oxide–methyl cellulose hybrid in acidic medium: Sensing of nitro-aromatics

Graphene oxide (GO) in acidic media (pH = 4) emits blue light but in neutral and alkaline media (pH = 7 and 9.2) the emission is negligible. On addition of 0.85, 1.7 and 3.4% (w/v) methyl cellulose (MC) to GO solution (0.005% w/v) the emission intensity increases dramatically at every pH but with an increase in pH the PL (photoluminescence) intensity decreases for every composition of the hybrid solution. The average lifetime of GO at pH = 4 increases on addition of MC. Fluorescent microscopic images of GO–MC hybrids for different MC content indicate that the morphology of the hybrids at pH 4 is ribbon type but at pH 7 and 9.2 no characteristic morphology is produced. The decrease of glass transition temperature by 9 °C of the GMC0.85 system (produced from drying GO-MC hybrid solution containing 0.85% MC solution) from that of pure MC suggests the presence of supramolecular interaction in the system. There is a drastic decrease in PL intensity on addition of nitroaromatics to the GMC0.85 system and it is very large (91%) for the addition of picric acid. Thus, the hybrid system acts as a good sensor for the detection of nitro aromatics by instantaneous photoluminescence quenching with a detectable limit of 2 ppm.

Fluorescent Graphene Oxide via Polymer Grafting: An Efficient Nanocarrier for Both Hydrophilic and Hydrophobic Drugs

Functionalized graphene-based drug delivery vehicles have conquered a significant position because functionalization improves its biocompatibility and stability in cell medium, leaving sufficient graphitic basal plane for drug loading through π-π stacking. In this study, poly(N-isopropylacrylamide) (PNIPAM) is covalently grafted from the surface of graphene oxide (GO) via a facile, eco-friendly and an easy procedure of free radical polymerization (FRP) using ammonium persulfate initiator. Various spectroscopic and microscopic studies confirm the successful grafting of PNIPAM from GO surface. PNIPAM-grafted GO (GPNM) exhibits enhanced thermal stability, improved dispersibility both in aqueous and cell medium, and better biocompatibility and cell viability compared to GO. Interestingly, GPNM displays an exciting fluorescence property in aqueous medium, which is a hike of intensity at 36 °C due to the lower critical solution temperature (LCST) of PNIPAM chains (32 °C). Moreover both hydrophilic (doxorubicin (DOX)) and hydrophobic (indomethacin (IMC)) drugs loaded on the surface of GPNM hybrid exhibits its efficacy as an efficient carrier for both types of drugs. Cellular uptakes of free DOX and DOX-loaded GPNM (GPNM-DOX) are evidenced both from optical and fluorescence imaging of live cells, and the efficiency of drug is significantly improved in the loaded system. The release of DOX from GPNM-DOX was achieved at pH 4, relevant to the environment of cancer cells. The pH-triggered release of hydrophobic drug was also studied using UV-vis spectroscopy via alginate encapsulation, showing a great enhancement at pH = 7.4. The IMC is also found to be released by human serum albumin using dialysis technique. The GPNM nanomaterial shows the property of simultaneous loading of DOX and IMC as well as pH-triggered simultaneous release of both of the drugs.

Fluorescence Resonance Energy Transfer from Sulfonated Graphene to Riboflavin: A Simple Way to Detect Vitamin B2

We have prepared sulfonated graphene (SG) by diazonium coupling technique and it has been characterized by UV-vis absorption spectroscopy, Raman spectroscopy, electron microscopy, energy-dispersive spectroscopy (EDS), EDS elemental mapping, X-ray photoelectron spectroscopy (XPS), and FTIR spectroscopy. The photoluminescence (PL) property of SG at different pH (pH 4, 7, and 9.2) has been investigated and SG shows highest PL-intensity and quantum yield at pH 4 compared to those at higher pH and that of GO at pH 4. Due to the strong overlap between the emission spectrum of SG and absorption spectrum of riboflavin (RF, vitamin B2) at pH 4, it has been tactfully used as donor for the fluorescence resonance energy transfer (FRET) process. However, graphene oxide (GO) does not exhibit any FRET with RF at an identical condition due to its much lower quantum yield. We have demonstrated a selective detection of vitamin B2 in presence of nucleic acid (DNA, RNA), protein (BSA), amino acid (Lysine) and other water-soluble vitamins (Becosules, Zevit capsules) based on the spontaneous FRET from PL-active SG (donor) to RF (acceptor). The calibration curve indicates excellent affirmation to detect vitamin B2 using FRET and it is superior to the ordinary fluorescence method of detecting RF in presence of different biomolecules.

Facile and green approach to prepare fluorescent carbon dots: Emergent nanomaterial for cell imaging and detection of vitamin B2

Carbon dots (CDs) are a new representative in carbonaceous family and have initiated remarkable research interests over the past one decade in a large variety of fields. Herein, we have utilized a facile, one-step carbonization method to prepare fluorescent carbon dots using poly(vinyl alcohol) (PVA) both as a carbon source and as a surface passivating agent. The as prepared CDs emit bright blue fluorescence under ultraviolet illumination. The structure and optical properties of the CDs are thoroughly investigated by several methods such as high-resolution transmission electron microscopy; dynamic light scattering; UV-vis, fluorescence and Fourier transform infrared spectroscopy. The CDs exhibit excellent water solubility and demonstrate average hydrodynamic diameter of 11.3 nm, holding great promise for biological applications. The biocompatibility evaluation and in vitro imaging study reveals that the synthesized CDs can be used as effective fluorescent probes in bio-imaging without noticeable cytotoxicity. In addition, a unique sensor for the detection of vitamin B2 in aqueous solution is proposed on the basis of spontaneous fluorescence resonance energy transfer from CD to vitamin B2. These findings therefore suggest that the CDs can find potential applications in cellular imaging along with sensing of vitamin B2.

Nondestructive characterization of Li+ ion-doped multifunctional poly(vinylidene fluoride)-g-poly(dimethyl amino ethyl methacrylate) by impedance spectroscopy.

Poly(vinylidene fluoride) (PVDF)-graft-poly(dimethyl amino ethyl methacrylate) (PDMAEMA) (PD copolymer) is produced via atom transfer radical polymerization from PVDF solution in N-methyl-2-pyrrolidone. PD copolymer is doped with 1% and 5% (w/w) Li(+) ion to produce PDLi1 and PDLi5 samples, respectively. In PD copolymer, the crystalline structure of PVDF changes from α polymorph to a mixture of α and β polymorph, and it transforms completely to piezoelectric β polymorph on doping with 1% (w/w) Li(+) ion. The impedance behavior of PVDF changes on grafting, and that of the PD graft copolymer also changes with increasing Li(+) ion dopant concentration. In the Nyquist plots, PVDF exhibits a straight line character, and a curvature has appeared in the PD graft copolymer; on doping the latter with Li(+) ion (1% w/w), the curvature increases and a semicircle is completed on 5% Li(+) doping. Fitting the data from the Z-view program, the Ohmic resistance of PDLi1 is found to be 78 MΩ having capacitance with constant phase element (CPE) = 1.38 nF while for the PDLi5 sample the resistance decreases to16.1 MΩ with a small increase in CPE to 1.46 nF. The modulus plane plots for PDLi1 and PDLi5 samples also exhibit only one peak supporting the presence of only one equivalent resistance-capacitance circuit with constant phase element in both PDLi1 and PDLi5 samples. Both the impedance and modulus vs frequency plots of PDLi1 and PDLi5 samples exhibit a single Debye peak suggesting isotropic nature of the samples. For PVDF and PDMAEMA, ac-conductivity increases linearly with angular frequency, but in the case of PDLi1 and PDLi5 samples, it remains at first invariant in the frequency range 1-10(2) Hz, and above 10(2) Hz, an increase in conductivity with frequency occurs obeying the double power law. In the temperature variation of conductivity, PVDF exhibits its typical insulating nature, and in the PD graft copolymer, the conductivity decreases with increase of temperature (metallic-like behavior) due to gradual breaking of supramolecular interaction. The temperature variation of ac-conductivity of the Li(+)-doped PD graft copolymer suggests that both the ionic and supramolecular contributions of conductivity operate; the former increases and the latter decreases with rise in temperature showing a maximum. The temperature-dependent FTIR spectra of PDLi1 and PDLi5 samples support the gradual breaking of supramolecular interactions with increase of temperature.

Nanojacketing and Dejacketing of ds-DNA: A Nondestructive Characterization of a Nanojacketed Sample by Impedance Spectroscopy

A facile approach of nanojacketing DNA in intact conformation is evolved by the in situ polymerization of o-methoxyaniline (OMA) at 30 °C using HAuCl4 as an oxidant and DNA as a soft template. It concomitantly produces poly(o-methoxyaniline) (POMA) and a Au nanojacket encapsulating the double stranded DNA (ds-DNA). The POMA chains remain adhered to the Au nanojacket, facilitating the dissolution of nanojacketed DNA (DNA-Au-POMA) in organic solvent without affecting its conformation. Digestion of the nanojacketed system with saturated iodine solution dejackets the ds-DNA with retention of its conformation, leaving the POMA nanotube. The nanojacketing and dejacketing phenomena are established by transmission electron microscopy (TEM), UV-vis spectroscopy, and CD spectroscopy, and the nanostructure is further characterized by FTIR, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The impedance study of the DNA-Au-POMA sample suggests the Cole-Cole plots at both the impedance and modulus planes and the values of capacitance and electron-transfer resistance of the material (R(et)) are calculated to be 13.74 pF and 388 kΩ, respectively. The presence of a single Debye peak in both the impedance and modulus vs frequency plots suggests an isotropic nature of the system, and the frequency dependent ac-conductivity suggests the presence of short-range translational and reorientational (localized) hopping of charge carriers at lower and higher frequency region.