Coumarin Derivative and Gold Nanoparticle Conjugate as a Selective Fluorescent Sensor for Mercury Ion in Real Sample.

A biphenyl based coumarin fluorescent molecule, N,N'-bis(7-diethylamino-2-oxo-2 H-chromen-3-yl)methylene)biphenyl-2-2'-dicarbohydrazide (molecule 1) has been synthesized and characterised. Photophysical studies of 1 exhibit solvent polarity dependent absorption and emission maxima. Citrate capped gold nanoparticles (AuNPs) have been mixed with molecule 1 for the preparation of AuNPs/1 conjugate. The association constant of the AuNPs/1 conjugate has been calculated to 4.54 × 104 M- 1. The AuNPs/1 conjugate has been found to detect Hg2+ ion selectively by fluorescence enhancement. While addition of molecule 1 into the solution of AuNPs, fluorescence intensity of 1 quenched. On addition of several monovalent, divalent and trivalent metal ion into the solution of AuNPs/1 conjugate separately, there was no change in fluorescence intensity of 1 has been observed. However, upon addition of Hg2+ ion into the solution of AuNPs/1 conjugate, the fluorescence intensity enhancement occurred, indicating released of 1 from the surface of AuNPs and probably aggregation of AuNPs took place in presence of Hg2+ ion. The AuNPs/1 conjugate has been found to have a detection limit of 2.3 × 10- 9 M for Hg2+ ion in aqueous solvent. Meanwhile, the AuNPs/1 conjugate have also been successfully applied for the determination of Hg2+ in real water samples.

Crystallographic elucidation of an aluminium-bound amido Schiff base chemosensor: a selective turn-on fluorescent chemosensor for Al3+ ions.

We have synthesized a biphenyl-derived two arm-containing amido Schiff base, bis((2-hydroxynaphthalen-1-yl) methylene)-[1,1'-biphenyl]-2,2'-dicarbohydrazide (sensor 1), having hard donors to facilitate chelation with hard metal centers. The crystal structure of sensor 1 reveals that it crystallizes in the monoclinic system with the space group I2/a and shows several types of intra/inter-molecular H-bond interactions, which stabilized the crystal lattice. The sensing property of sensor 1 towards different metal ions has been demonstrated using different analytical techniques. In fact, sensor 1 shows high fluorescence selectivity and sensitivity towards Al3+ ions in aqueous DMF media. Importantly, we have reported the first structurally characterized six-coordinate dinuclear Al3+ complex ([Na(Al2L2)·2H2O·4DMF], complex 1 (where ligand, L = sensor 1). Complex 1 crystallizes in the space group P1̄. X-ray single crystal diffraction studies for complex 1 reveal that each Al3+ ion is hexa-coordinated by four oxygen and two nitrogen atoms from each arm of the two ligands. The sodium ion has penta-coordination in a highly distorted trigonal bipyramidal geometry, surrounded by two µ-bridging naphtholate oxygen atoms and three solvent DMF oxygen atoms. Upon addition of Na2EDTA to complex 1, no spectral change or naked-eye colour change was observed. Furthermore, "test kits" coated with sensor 1 showed successful selective detection of Al3+ ions under UV light.

A solvent sensitive coumarin derivative coupled with gold nanoparticles as selective fluorescent sensor for Pb2+ ions in real samples.

A coumarin based fluorescent molecule, 3-amino-2-cynano-3-(7-diethylamino-2-oxo-2H-chromen-3-yl)-acrylic acid ethyl ester (1) has been synthesized and characterised. Photophysical studies of 1 exhibit polarity dependent shift of its emission maxima which have been explained on the basis the existence of polar excited state of the molecule. Combination of compound 1 and citrate capped AuNPs (AuNPs/1 conjugate) has been used as a sensing tool for heavy metals. AuNPs/1 conjugate has been found to detect Pb2+ selectively by naked-eye color change as well as fluorescence enhancement. On addition of molecule 1 to gold nanoparticles solution, the color of the solution becomes reddish followed by quenching in fluorescence intensity. With gradual addition of Pb2+, the solution of AuNPs/1 conjugate becomes violet accompanied by a fluorescence enhancement. Excited state lifetime measurement revealed that compound 1 exhibits very fast decay pattern in aqueous medium whereas in AuNPs medium the lifetime of 1 increases. Upon addition of Pb2+ ions to that AuNPs/1 solution the lifetime of 1 decreases again. Based on the experimental observations the mechanism of sensing of lead has been proposed thoroughly. Initially compound 1 gets absorbed on the surface of the spherical gold nanoparticles. When Pb2+ is added, probably gold nanoparticles aggregates to form bigger particles by releasing compound 1 from its surface to show fluorescence enhancement.

Crystallographic Elucidation of Stimuli-Controlled Molecular Rotation for a Reversible Sol-Gel Transformation.

To get an idea about the most probable microporous supramolecular environment in the gel state, gelator molecule 1 has been crystallized from its gelling solvent (dimethylformamide). Crystal structure analysis of 1 shows a strong π···π stacking interaction between the electron-deficient pentafluorophenyl ring and electron-rich naphthyl ring. The gelling solvent situated in the "molecular pocket" stitches the gelators through weak H-bonding interactions to facilitate the formation of an organogel. Scanning electron microscopy analysis exhibits a ribbonlike fibrous morphology that resembles the supramolecular arrangement of 1 in its crystalline state, as evidenced by powder X-ray diffraction. In the presence of external stimuli (tetrabutylammonium fluoride), the organogel of 1 disassembles into sol. This sol-gel transformation phenomenon has been explained on the basis of X-ray single-crystal analysis. Single crystals obtained from the sol state show that naphthylic -OH of 1 gets deprotonated, resulting in C-C bond rotation that plays a major role in the sol-gel transformation. Gelator 1 exhibits weak green fluorescence in the gel state, whereas it shows highly intense yellow fluorescence in the sol state. Furthermore, a reversible sol-gel transformation associated with changes in the spectroscopic properties has been observed in the presence of acids and fluoride ions, respectively.

Binding mode dependent signaling for the detection of Cu2+: An experimental and theoretical approach with practical applications.

Two amido-schiff bases (3-Hydroxy-naphthalene-2-carboxylic acid pyren-1-ylmethylene-hydrazide and Naphthalene-2-carboxylic acid pyren-1-ylmethylene-hydrazide) have been synthesized having a common structural unit and only differs by a -OH group in the naphthalene ring. Both of them can detect Cu2+ ion selectively in semi-aqueous medium in distinctly different output modes (one detects Cu2+ by naked-eye color change where as the other detects Cu2+ by fluorescence enhancement). The difference in the binding of Cu 2+ with the compounds is the reason for this observation. The detection limit is found to be micromolar region for compound which contains -OH group whereas the compound without -OH group detects copper in nano-molar region. DFT calculations have been performed in order to demonstrate the structure of the compounds and their copper complexes. Practical utility has been explored by successful paper strip response of both the compounds. The biological applications have been evaluated in RAW 264.7.

A selective chemosensor for fluoride ion and its interaction with Calf Thymus DNA.

The amido-Schiff base 1 (N1, N3-bis (2-nitrobenzylidene)benzene-1,3-dicabohydrazide) containing a CONH group and CHN linkage has been synthesized by the condensation between isophthalic acid dihydrazide and o-nitrobenzaldehyde. This molecule can act as a fluoride ion sensor with high selectivity and sensitivity. Presence of nitro group in the phenyl ring may be responsible for the detection of fluoride ion visually with a dramatic color change from colorless to deep red in aqueous dimethyl sulphoxide solution. This Schiff base can be used as test kit for sensing of fluoride ion in the solid state. Compound 1 can detect fluoride also in commercially available toothpaste. As the compound has adequate solubility in DMSO-water mixture (7:93, v/v) and having some hydrogen bond donor and acceptor centers, we have investigated its nature of binding with Calf Thymus-DNA (CT-DNA) using theoretical molecular modelling and other experimental methods like UV-vis spectroscopy, circular dichroic and thermal melting studies. Thermodynamic parameters have been obtained using the well known Van't Hoff's equation. From both theoretical and experimental findings it has been observed that it can interact effectively with CT-DNA with binding energy -7.55kcal/mol to -7.50kcal/mol.

Dual mode selective chemosensor for copper and fluoride ions: a fluorometric, colorimetric and theoretical investigation.

A pyrene containing chemosensor viz. has been designed for the efficient and selective detection of Cu(2+) and F(-) ions in dual sensing mode which do not interfere with each other. The chemosensing behavior of towards Cu(2+) was demonstrated through fluorescence, time resolved fluorescence spectroscopy, and visual fluorescence colour changes, and towards F(-) through naked-eye colour changes, absorption and (1)H NMR titrations. The chemosensor shows excellent selectivity towards Cu(2+) through an excimer switch-off mechanism. Density Functional Theory (DFT) calculations were performed to show the structure and electronic properties of and its copper complex [-Cu(2+)]. The selectivity and sensitivity towards F(-) were explained in terms of H-bonding interactions between and F(-), then deprotonation of . The biological application of has been evaluated in HEK 293 cells and it exhibits good membrane permeability for the detection of Cu(2+). The sensor also shows appreciable sensitivity towards fluoride in toothpaste.

Amido-Schiff base derivatives as colorimetric fluoride sensor: Effect of nitro substitution on the sensitivity and color change.

A series of Schiff bases synthesized by the condensation of benzohydrazide and -NO2 substituted benzaldehyde have been used as selective fluoride ion sensor. Test paper coated with these synthetic Schiff bases (test kits) can detect fluoride ion selectively with a drastic color change and detection can be achieved by just using the naked-eye without the help of any optical instrument. Interestingly, the position of -NO2 group in the amido Schiff bases has an effect on the sensitivity as well as on the change of color of species.

"Test kit" for detection of biologically important anions: a salicylidene-hydrazine based Schiff base.

Test paper coated with Schiff base [(N,N(/)-bis(5-nitro-salicylidene)hydrazine] receptor 1 (host) can selectively detect fluoride and acetate ions (guest) by developing yellow color which can be detected by naked-eye both in aqueous-acetonitrile solution and in solid supported test kit. UV-vis spectral analysis shows that the absorption peaks at 288 and 345 nm of receptor 1 gradually decrease its initial intensity and new red shifted absorption bands at 397 nm and 455 nm gradually appear upon addition of increasing amount of F(-) and AcO(-) ions over several tested anions such as H(2)PO(4)(-), Cl(-), Br(-), I(-), NO(3)(-), NO(2)(-), HSO(4)(-), HSO(3)(-), and ClO(4)(-) in aqueous-acetonitrile solvent. The colorimetric test results and UV-vis spectral analysis are in well agreement with (1)H NMR titration results in d(6)-DMSO solvent. The receptor 1 forms 1:2 stable complexes with F(-) and AcO(-) ions. However, similar kind of observation obtained from UV-vis titrations in presence of AcOH corresponds to 1:1 complexation ratio indicating the formation of H-bonding interaction between the receptor and anions (F(-) and AcO(-) ions). So, the observed 1:2 complexation ratio can only be explained on the basis of deprotonation (∼1 eqv.) and H-bonding (∼1 eqv.) interactions [1]. The ratiometric analysis of host-guest complexes corroborates well with the proposed theoretical model optimization at Density Functional Theory (DFT) level.

Discotic ionic liquid crystals of triphenylene as dispersants for orienting single-walled carbon nanotubes.

Orient and conduct: Triphenylene-based discotic ionic liquid crystals (ILCs) with six imidazolium ion pendants can disperse pristine single-walled carbon nanotubes (SWNTs). When the ILC is columnarly assembled, doping with SWNTs results in macroscopic homeotropic columnar orientation. Combination of shear and annealing treatments gives rise to three different orientation states, which determine the anisotropy of electrical conduction.

Reusable amine-based structural motifs for green house gas (CO2) fixation.

A series of compounds with an amine based structural motif (ASM) have been synthesized for efficient atmospheric CO(2) fixation. The H-bonded ASM-bicarbonate complexes were formed with an in situ generated HCO(3)(-) ion. The complexes have been characterized by IR, (13)C NMR, and X-ray single-crystal structural analysis. ASM-bicarbonate salts have been converted to pure ASMs in quantitative yield under mild conditions for recycling processes.

Spectroscopic, colorimetric and theoretical investigation of salicylidene hydrazine based reduced Schiff base and its application towards biologically important anions.

A reduced Schiff base anionic receptor 1 [N,N'-bis-(2-hydroxy-5-nitro-benzyl)hydrazine] has been synthesized, characterized and reported as a selective chromogenic receptor for fluoride, acetate and phosphate anions over the other tested anions such as chloride, bromide, iodide and hydrogensulphite. Colorimetric naked-eye detection and UV-vis absorption spectroscopic techniques were used to distinguish the recognition behaviours towards various anions. The receptor-anion complexation mainly occurs via hydrogen bonding interactions which facile to generate the charge transfer band in the UV-vis spectra and cause large bathochromic shift as well as naked-eye colour change. Complexation stoichiometry, binding constant and free energy change due to complex formation were determined from Benesi-Hildebrand plot. The binding constant and the free energy change values are well interactive for spontaneous complexation. The experimental results have been correlated with the theoretical calculations using B3LYP hybrid functional and 6-311++G(d,p) basis set for both the receptor and complex by Density Functional Theory (DFT) method.

"Bicontinuous cubic" liquid crystalline materials from discotic molecules: a special effect of paraffinic side chains with ionic liquid pendants.

Triphenylene (TP) derivatives bearing appropriate paraffinic side chains with imidazolium ion-based ionic liquid (IL) pendants were unveiled to display a phase diagram with liquid crystalline (LC) mesophases of bicontinuous cubic (Cub(bi)) and hexagonal columnar (Col(h)) geometries. While their phase transition behaviors are highly dependent on the length of the side chains and the size of the ionic liquid pendants, TPs with hexadecyl side chains exclusively form a Cub(bi) LC assembly over an extremely wide temperature range of approximately 200 degrees C from room temperature when the anions of the IL pendants are relatively small. Wide-angle X-ray diffraction analysis suggested that the Cub(bi) LC mesophase contains pi-stacked columnar TP arrays with a plane-to-plane separation of approximately 3.5 A. Consistently, upon laser flash photolysis, it showed a transient microwave conductivity comparable to that of a Col(h) LC reference.

Unusual side-chain effects on charge-carrier lifetime in discotic liquid crystals.

When hexa-peri-hexabenzocoronene (HBC) carries paraffinic side chains with ester-ether termini (1a-1c), a hexagonal columnar liquid-crystalline (LC) mesophase forms, which is characterized by a very wide temperature range (ca. 0-300 degrees C). The LC materials from these HBC derivatives show characteristic electronic properties with an extremely long photocarrier lifetime. For example, by means of a flash-photolysis time-resolved microwave conductivity technique, the photocarrier lifetime, observed for liquid-crystalline 1a, is as long as 14 ms, which is four-orders of magnitude longer than that of fully paraffinic HBC 4 (0.0011 ms). The maximum transient photoconductivities of liquid-crystalline 1a-1c are comparable to one another and also to those of HBCs without ester-ether terminals. Liquid-crystalline 1a exhibits an obvious photocurrent generation in response to light illumination.

Structural characterization of an enantiopure hydroxo-bridged binuclear iron(III) complex with empty one-dimensional helical channels.

A H-bond capable chiral tetradentate ligand, Fe3+, and acetate ion assembles into a hydroxo-bridged binuclear complex with the formula [FeIII2(mu-OH)(mu-OAc)(S-L)2] x 4H2O (1) where H2S-L = S-2-(2-hydroxy-benzylamino)-3-(1H-imidazol-4-yl)-propionic acid. The crystal of 1 contains right-handed one-dimensional (1D) helical channels with 7.3-9.8 A diameter. A similar reaction with a ligand having opposite chirality forms the complex with left-handed helical channels (1a). Heating the crystals of 1 at 95 degrees C under reduced pressure selectively removes three waters from the channel forming an enantiopure porous crystal with empty channels (solvent accessible voids 18% v/v). Intermolecular hydrogen bonding between the imidazole N-H and phenolate oxygen in 1-2 forms a C6 symmetric helix with bridging hydroxo groups pointing inside the channels. All the H-bond capable atoms in the ligand along with one water molecule form an extended H-bonded network throughout the crystal. Exposing the empty channels of 2 to iodine vapor indicates partial filling of the channels with iodine. Crystal data for 1 x 4H2O include the following: hexagonal, P61, a = b = 13.164(3) A, c = 36.305 (11) A, alpha = beta = 90 degrees , gamma = 120 degrees , Z = 6, R1 = 0.0387, wR2 = 0.0842. Crystal data for 1a x 2H2O include the following: hexagonal, P6(5), a = b = 13.151(4) A, c = 36.558(2) A, alpha = beta = 90 degrees , gamma = 120 degrees , Z = 6, R1 = 0.0416, wR2 = 0.1190. Crystal data for 2 x H2O include the following: hexagonal, P61, a = b = 13.160(7) A, c = 36.559 (4) A, alpha = beta = 90 degrees , gamma = 120 degrees , Z = 6, R1 = 0.0574, wR2 = 0.1423.