N. Venkatramaiah

Fluoranthene based fluorescent chemosensors for detection of explosive nitroaromatics

A novel fluoranthene based fluorescent chemosensor for the detection of picric acid (PA) at the parts per billion (ppb) level was evaluated. Static fluorescence quenching was the dominant process by intercalative π-π interaction between fluoranthene (S(1)) and nitroaromatics.

Synthesis and structural, spectroscopic and nonlinear optical measurements of graphene oxide and its composites with metal and metal free porphyrins†

In this paper we present the structure and spectroscopic, photophysical and nonlinear optical studies of covalently functionalized novel graphene oxide–[Cu, Zn, Sn, H2 (metal free), VO] porphyrin composites. The composites were characterized by Field Enhanced Scanning Electron Microscopy (FE-SEM), micro-Raman, optical absorption, Fourier transform infrared (FT-IR), steady state and time resolved fluorescence spectroscopic techniques. The composites exhibit strong fluorescence quenching, suggesting strong electronic interactions between the porphyrin and graphene oxide molecules. Nonlinear optical absorption (NLA) studies of graphene oxide–porphyrin composites were investigated using the Z-scan technique at 532 and 800 nm with nanosecond (ns) and femtosecond (fs) laser pulses. Composites show strong two-photon absorption (TPA) as well as excited state absorption (ESA) leading to reverse saturable absorption (RSA) behaviour in the ns regime and saturable absorption (SA) behaviour was observed in fs regime. The metal free porphyrin–graphene oxide (GO) composite shows significant nonlinear absorption behaviour as well as highest fluorescence quenching behaviour compared to other GO–porphyrin composites. We further observed the enhanced figure of merit (FOM) values for composites in comparison with individual molecules.

Nonlinear optical properties of covalently linked graphene-metal porphyrin composite materials

The nonlinear optical (NLO) and optical limiting (OL) properties of covalently linked graphene-porphyrin composite materials were investigated using Z-scan technique in nanosecond regime. We observed enhanced NLO and OL properties of graphene-porphyrin composites in comparison to the individual graphene and porphyrins. The improved OL property of composites is attributed to energy transfer between porphyrin and graphene, which improved excited state absorption and nonlinear scattering. Nonlinear optical susceptibilities χ(3) of graphene and graphene-porphyrin composites were, in the order of 10−12 esu, measured using degenerate four wave mixing technique in nanosecond regime. High values of excited state absorption and two-photon absorption were observed for the composites.

Femtogram Detection of Explosive Nitroaromatics: Fluoranthene‐Based Fluorescent Chemosensors

Herein we report a novel fluoranthene-based fluorescent fluorophore 7,10-bis(4-bromophenyl)-8,9-bis[4-(hexyloxy)phenyl]fluoranthene (S(3)) and its remarkable properties in applications of explosive detection. The sensitivity towards the detection of nitroaromatics (NACs) was evaluated through fluorescence quenching in solution, vapor, and contact mode approaches. The contact mode approach using thin-layer silica chromatographic plates exhibited a femtogram (1.15 fg cm(-2)) detection limit for trinitrotoluene (TNT) and picric acid (PA), whereas the solution-phase quenching showed PA detection at the 2-20 ppb level. Fluorescence lifetime measurements revealed that the quenching is static in nature and the quenching process is fully reversible. Binding energies between model binding sites of the S(3) and analyte compounds reveal that analyte molecules enter into the cavity created by substituted phenyl rings of fluoranthene and are stabilized by strong intermolecular interactions with alkyl chains. It is anticipated that the sensor S(3) could be a promising material for the construction of portable optical devices for the detection of onsite explosive nitroaromatics.

Photophysical, electrochemical and solid state properties of diketopyrrolopyrrole based molecular materials: importance of the donor group

Diketopyrrolopyrrole (DPP) based molecular semiconductors have emerged as promising materials for high performance active layers in organic solar cells. It is imperative to comprehend the origin of such a property by investigating the fundamental structure property correlation. In this report we have investigated the role of the donor group in DPP based donor-acceptor- donor (D-A-D) structure to govern the solid state, photophysical and electrochemical properties. We have prepared three derivatives of DPP with varying strengths of the donor groups, such as phenyl (PDPP-Hex), thiophene (TDPP-Hex) and selenophene (SeDPP-Hex). The influence of the donor units on the solid state packing was studied by single crystal X-ray diffraction. The photophysical, electrochemical and density functional theory ( DFT) results were combined to elucidate the structural and electronic properties of three DPP derivatives. We found that these DPP derivatives crystallized in the monoclinic space group P21/c and show herringbone packing in the crystal lattice. The derivatives exhibit weak p-p stacking interactions as two neighboring molecules slip away from each other with varied torsional angles at the donor units. The high torsional angle of 32 degrees ( PDPP-Hex) between the phenyl and lactam ring results in weak intramolecular interactions between the donor and acceptor, while TDPP-Hex and SeDPP-Hex show lower torsional angles of 9 degrees and 12 degrees with a strong overlap between the donor and acceptor units. The photophysical properties reveal that PDPP-Hex exhibits a high Stokes shift of 0.32 eV and SeDPP- Hex shows a high molar absorption co-efficient of 33 600 L mol -1 1 cm -1 1 with a low band gap of similar to 2.2 eV. The electrochemical studies of SeDPP- Hex indicate the pronounced effect of selenium in stabilizing the LUMO energy levels and this further emphasizes the importance of chalcogens in developing new n-type organic semiconductors for optoelectronic devices.

Synthesis and photophysical characterization of dimethylamine-derived Zn(II)phthalocyanines: exploring their potential as selective chemosensors for trinitrophenol

We report a novel synthetic approach, with good yields, for the synthesis of selective dimethylamine-substituted phthalonitriles (1–3) in the presence of triethyl phosphite and dimethylformamide at 160 °C. The peripherally modified dimethylamine substituted Zn(II)phthalocyanines (ZnPc1–3) with varied numbers and positions of dimethylamine groups were prepared for a systematic investigation of the effect of the substituents on their electronic and spectroscopic properties. Compounds show strong aggregation behaviour in methanol and this behaviour decreases with the increase of the alkyl chain length of the alcohol solvents (i.e., from methanol to octanol). The fluorescence quantum yields of ZnPc1–3 showed an excellent correlation with the extent of the molecular aggregation. The versatility of the ZnPc1–5 compounds possessing both electron donating and electron withdrawing substituents at their periphery is investigated towards the detection of nitroaromatic compounds (NACs) in solution and in the vapour phase. It was found that ZnPc1–5 exhibit high selectivity towards trinitrophenol (TNP). A good linearity of fluorescence detection using ZnPc3 as the fluorescent probe was observed in the concentration range of 50 × 10−6 to 450 × 10−6 M in chloroform, with a detection limit (LOD) of 11 ± 2 ppm. Stern–Volmer (SV) and DFT studies reveal that the fluorescence quenching behaviour occurs through photo-induced electron transfer from the excited state of ZnPcs to TNP with static quenching behaviour occurring in a predominant fashion. The formation of a porous morphology of ZnPc3 thin films promotes high selectivity and accessibility to TNP vapours (7.7 × 10−3 ppb).

Phosphonate Appended Porphyrins as Versatile Chemosensors for Selective Detection of Trinitrotoluene

Fluorescent molecular probes based on phosphonate-functionalized porphyrin derivatives have been designed for selective detection of nitroaromatics. It is shown that molecular recognition is based on cooperative hydrogen bonding and π-π stacking interactions with electron-deficient molecules (nitroaromatic compounds, NACs), displaying superior detection toward trinitrotoluene (TNT). The P═O functional groups decrease the lowest unoccupied molecular orbital (LUMO) energy level of the porphyrins and, consequently, facilitate the electron inoculation to TNT through a photoinduced electron transfer (PET) process. The hydroxyl groups of the phosphonates and pyrrole -NH protons are further engaged in donor-acceptor interactions with TNT by strong intermolecular hydrogen bonding interactions (as evidenced by single crystal X-ray, NMR, and density functional theory (DFT)) showing turn off fluorescence behavior. The nonplanarity of the porphyrins induced by protonation at the central core of the porphyrin H4TPPA(2+) undergoes additional interactions, furnishing an anomalous increase in the selectivity of TNT at nanomolar levels in solution (limit of detection, LOD ∼ 5 nM). Porphyrin-doped hybrid PMMA [poly(methyl methacrylate)] polymer films demonstrate the reversibility of the fluorescence behavior and exhibit high photostability. The formation of discrete molecular aggregates on the surface of hybrid films and efficient diffusion of TNT vapors (10 ppb) displayed high selectivity in the solid state. The hybrid films are further used to demonstrate the detection of NACs in the aqueous medium, ultimately providing a platform for a practical strategy and implementation for the detection of toxic NACs.

Tetraphenylethene-Based Conjugated Fluoranthene: A Potential Fluorescent Probe for Detection of Nitroaromatic Compounds

This study reports the synthesis and photophysical properties of a star-shaped, novel, fluoranthene-tetraphenylethene (TFPE) conjugated luminogen, which exhibits aggregation-induced blue-shifted emission (AIBSE). The bulky fluoranthene units at the periphery prevent intramolecular rotation (IMR) of phenyl rings and induces a blueshift with enhanced emission. The AIBSE phenomenon was investigated by solvatochromic and temperature-dependent emission studies. Nanoaggregates of TFPE, formed by varying the water/THF ratio, were investigated by SEM and TEM and correlated with optical properties. The TFPE conjugate was found to be a promising fluorescent probe towards the detection of nitroaromatic compounds (NACs), especially for 2,4,6-trinitrophenol (PA) with high sensitivity and a high Stern-Volmer quenching constant. The study reveals that nanoaggregates of TFPE formed at 30 and 70% water in THF showed unprecedented sensitivity with detection limits of 0.8 and 0.5 ppb, respectively. The nanoaggregates formed at water fractions of 30 and 70% exhibit high Stern-Volmer constants (Ksv=79,998 and 51,120 M(-1), respectively) towards PA. Fluorescence quenching is ascribed to photoinduced electron transfer between TFPE and NACs with a static quenching mechanism. Test strips coated with TFPE luminogen demonstrate fast and ultra-low-level detection of PA for real-time field analysis.

Dual functionality of phosphonic-acid-appended phthalocyanines: inhibitors of urokinase plasminogen activator and anticancer photodynamic agents

Phthalocyanines (Pcs) bearing phosphonic acid groups at the periphery exhibit a potential photodynamic effect to induce phototoxicity on human bladder cancer epithelial cells (UM-UC-3). In vitro photophysical and biological studies show high intrinsic ability to inhibit the activity of urokinase plasminogen activator (uPA) and matrix metalloproteinase-9 (MMP-9).

Third order optical nonlinear studies and its use to estimate thickness of sandwiched films of tetra-phenyl porphyrin derivatives

Third-order nonlinear optical properties of tetra-phenyl porphyrin (H2TPP) derivatives viz., H2TPP(OH)4 and Zn(II)TPP doped in boric acid glass thin films were measured using single beam Z-scan and forward degenerate four-wave mixing (DFWM) techniques. Excited state lifetimes and absorption cross-sections were estimated from these experiments. Thickness of the porphyrin doped sandwich glass films were determined using DFWM technique for the first time. The values of nonlinear refractive index (n2) obtained for these systems are are found to be sensitive to the nature of substituents in porphyrin molecule. These results are interpreted in terms of delocalized π electrons contributing to the third-order optical nonlinearity.