Highly Selective Turn-on Fluorescence Sensor for Cd2+ Ions by Tripodal Organic Ligand.

Organic fluorescence sensor for selectively detecting and quantifying toxic heavy metal ions has received significant interest due to their environmental hazards. Herein, we have designed and synthesized a simple tripodal Schiff base ligand (1) based on hydroxy-naphthaldehyde and tris(2-aminoethyl)amine (TREN) and demonstrated highly selective turn-on fluorescence sensing of Cd2+ ions. The free ligand did not show any fluorescence in DMF. In contrast, Cd2+ (10- 4 M) addition exhibited a strong enhancement of fluorescence at 450 nm. Interestingly, other metal ions including Zn2+, which exhibit similar chemistry, did not show any turn-on fluorescence. The concentration-dependent studies of 1 with Cd2+ showed the detection limit of 6.78 × 10- 8 M. NMR spectra of 1 with Cd2+ and computational studies were performed to understand the mechanism of sense.

NaHSO4/SiO2 catalyzed generation of o-quinone/ o-thioquinone methides: synthesis of arylxanthenes/ arylthioxanthenes via oxa-6π-electrocyclization.

ortho-Quinone methides, very reactive transient intermediates, are utilized successfully in synthesizing complex organic molecules of natural and biological significance. Among several synthetic protocols, the acid catalyzed generation of ortho-quinone methides from suitably substituted phenols is a promising method for further exploitation in organic synthesis. Such an interesting reactive species is conveniently employed in the synthesis of conformationally restricted triarylmethane derivatives such as 12/9-arylxanthenes/arylthioxanthenes starting from symmetrical/unsymmetrical 2-(hydroxydiarylmethyl)phenol/thiophenol, respectively, using SiO2-NaHSO4. Conformationally restricted 12/9-arylxanthenes/arylthioxanthenes were obtained in 52 to 96% yields using this protocol, which is believed to involve the formation of o-quinone methides followed by electrocyclic ring closure and isomerization at elevated temperature. Photophysical studies of selected examples in acidic media showed turn-on fluorescence by hydride ion transfer mediated π-conjugated xanthylium salt formation and suggested the application potential in bio-imaging and fluorescent sensors.

Green synthesis of silver nanoparticles using Nardostachys jatamansi and evaluation of its anti-biofilm effect against classical colonizers.

In this communication, we present the green synthesis of silver nanoparticles (AgNPs) using medicinally important Nardostachys jatamansi rhizome extract in the presence of sunlight. UV-vis spectroscopy, Fourier Transform Infrared spectroscopy (FTIR), Transmission electron microscope (TEM) and Energy dispersive X-ray analysis (EDX) were employed to characterize the synthesized AgNPs. UV-visible spectroscopic studies confirmed the presence of biosynthesized AgNPs. Transmission Electron Microscopic studies revealed the structure of spherical AgNPs in the diameter range of 10-15 nm. Energy dispersive X-ray analysis and elemental mapping clearly confirmed the presence of silver in AgNPs samples. Interestingly, biomolecules functionalised AgNPs exhibited a remarkable antioxidant, anti-inflammatory, and anti-biofilm activities and hence biosynthesized AgNPs from N. jatamansi can be used as a promising biomaterial for biomedical applications.

Synthesis of Strongly Fluorescent Imidazole Derivatives: Structure Property Studies, Halochromism and Fluorescent Photoswitching.

New series of methoxy and hydroxyl group substituted triphenylamine (TPA)-imidazole fluorescent molecules (5-(diphenylamino)-2-(1H-phenanthro[9,10-d]imidazol-2-yl)phenol (1), 5-(diphenylamino)-2-(1-phenyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenol (2), 5-(diphenylamino)-2-(4,5-diphenyl-1H-imidazol-2-yl)phenol (3), 5-(diphenylamino)-2-(1,4,5-triphenyl-1H-imidazol-2-yl)phenol (4), N-(3-methoxy-4-(1H-phenanthro[9,10-d]imidazol-2-yl)phenyl)-N-phenylbenzenamine (5), N-(3-methoxy-4-(1-phenyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenyl)-N-phenylbenzene amine (6), and N-(3-methoxy-4-(4,5-diphenyl-1H-imidazol-2-yl)phenyl)-N-phenylbenzenamine (7)) have been synthesized that exhibited strong solution fluorescence and molecular structure and conformation controlled fluorescence photoswitching, solid state fluorescence and halochromism. Hydroxyl substituted molecules (1-4) showed moderate to strong fluorescence in solution depend on solvent polarity and very weak solid state fluorescence. Methoxy substituted molecules (5-7) displayed strong fluorescence both in solution and solid state. Solid state structural studies revealed strong intramolecular H-bonding in the crystal lattice. Interestingly, highly twisted structure (6) showed rare light induced reversible fluorescence switching in CHCl3. The observation of isobestic point in time dependent fluorescence photoswitching studies indicated structural isomer conversion. Further, acid sensitive imidazole nitrogen has been made use to demonstrate solid state fluorescence switching via halochromism. Thus the present studies attempted to develop new fluorescent molecules and establish structure-property relationship for designing fluorescence switching materials. Graphical Abstract Molecular structure controlled solid state fluorescence, halochromism and a rare fluorescence photoswitching in chloroform have been observed with triphenylamine-imidazole derivatives.

Unusual fluorescent photoswitching of imidazole derivatives: the role of molecular conformation and twist angle controlled organic solid state fluorescence.

Molecular photoswitching, light induced reversible color/fluorescence modulation, has mostly been realized in organic molecules via E/Z isomerization of azobenzenes and stilbenes and ring opening/closing reactions of spiropyrans and diarylethenes. We report here new fluorescent molecular photoswitches based on triphenylamine (TPA)-imidazole derivatives, N-phenyl-N-(4-(1,4,5-triphenyl-1H-imidazol-2-yl)phenyl)benzenamine (NTPB) and N-phenyl-N-(4-(1-phenyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenyl)benzenamine (NPPB), that exhibited light induced reversible fluorescence switching via conformational change from a twisted molecular structure to more planar. NTPB and NPPB in CHCl3 showed red shift of absorption and fluorescence upon UV light irradiation whereas white light exposure reversed both absorption as well as fluorescence. The role of the TPA-imidazole twisted molecular structure in photoswitching was established based on structure property, computational and photophysical studies. The isobestic point observed in time dependent fluorescence change under UV light irradiation clearly demonstrated the presence of two different conformational isomers. Interestingly, polymorphism and torsion angle (τ) dependent fluorescence of NTPB and NPPB in the solid state also supported the role of the twisted molecular structure of TPA-imidazole in fluorescence switching/tuning. Interestingly, NTPB showed fluorescence photoswitching in the solid state also whereas rigid phenanthrene based NPPB did not show fluorescence photoswitching. Thus the present studies provide structural insight for designing a new type of fluorescent organic molecular photoswitches based on conformational modulation that could be of potential interest in optoelectronic devices.

Bay Functionalized Perylenediimide with Pyridine Positional Isomers: NIR Absorption and Selective Colorimetric/Fluorescent Sensing of Fe3+ and Al3+ Ions.

Bay functionalized perylene diimide substituted with pyridine isomers, (2-pyridine (2HMP-PDI), 3-pyridine (3-HMP-PDI) and 4-pyridine (4-HMP-PDI)) have been synthesized and explored for selective coloro/fluorimetric sensing of heavy transition metal ions. HMP-PDIs showed strong NIR absorption (760-765 nm) in DMF. The absorption and fluorescence of HMP-PDIs have been tuned by make use of pyridine isomers. Reddish-orange color was observed for 2-HMP-PDI (λmax = 437, 551, 765 nm) whereas 4-HMP-PDI exhibited light green (λmax = 432, 522, 765 nm). 3-HMP-PDI showed orange-yellow (λmax = 431, 524, 762 nm). The fluorescence spectra of 2-, 3- and 4-HMP-PDI showed λmax at 585, 538, 546 nm, respectively. Interestingly, HMP-PDI dyes showed selective color change (intense pink color) and fluorescence quenching for Fe3+ and Al3+ metal ions in DMF. Absorbance spectra revealed complete disappearance of NIR absorption and intensification/appearance of new peak at lower wavelength. The concentration dependent studies suggest that 4-HMP-PDI can detect up to 36.52 ppb of Fe3+ and 43.12 ppb of Al3+ colorimetrically. The interference studies in presence of other metal ions confirmed the good selectivity for Fe3+ and Al3+. The mechanistic studies indicate that Lewis acidic character of Fe3+ and Al3+ ions were responsible for selective color change and fluorescence quenching.

Effect of surfactant in mitigating cadmium oxide nanoparticle toxicity: Implications for mitigating cadmium toxicity in environment.

Cadmium (Cd), classified as human carcinogen, is an extremely toxic heavy metal pollutant, and there is an increasing environmental concern for cadmium exposure through anthropogenic sources including cigarette smoke. Though Cd based nanoparticles such as cadmium oxide (CdO) are being widely used in a variety of clinical and industrial applications, the toxicity of CdO nanoparticles has not been well characterized. Herein we report the toxicity of CdO nanoparticles employing zebrafish as a model. Two different CdO nanoparticles were prepared, calcination of Cd(OH)2 without any organic molecule (CdO-1) and calcination of Cd-citrate coordination polymer (CdO-2), to evaluate and compare the toxicity of these two different CdO nanoparticles. Results show that zebrafish exposed to CdO-2 nanoparticles expressed reduced toxicity as judged by lower oxidative stress levels, rescue of liver carboxylesterases and reduction in metallothionein activity compared to CdO-1 nanoparticles. Histopathological observations also support our contention that CdO-1 nanoparticles showed higher toxicity relative to CdO-2 nanoparticles. The organic unit of Cd-citrate coordination polymer might have converted into carbon during calcination that might have covered the surface of CdO nanoparticles. This carbon surface coverage can control the release of Cd2+ ions in CdO-2 compared to non-covered CdO-1 nanoparticles and hence mitigate the toxicity in the case of CdO-2. This was supported by atomic absorption spectrophotometer analyses of Cd2+ ions release from CdO-1 and CdO-2 nanoparticles. Thus the present study clearly demonstrates the toxicity of CdO nanoparticles in an aquatic animal and also indicates that the toxicity could be substantially reduced by carbon coverage. This could have important implications in terms of anthropogenic release and environmental pollution caused by Cd and human exposure to Cd2+ from sources such as cigarette smoke.

Perylene Diimide Based Fluorescent Dyes for Selective Sensing of Nitroaromatic Compounds: Selective Sensing in Aqueous Medium Across Wide pH Range.

Water soluble perylenediimide based fluorophore salt, N,N'-bis(ethelenetrimethyl ammoniumiodide)-perylene-3,4,9,10-tetracarboxylicbisimide (PDI-1), has been used for selective fluorescence sensing of picric acid (PA) and 4-nitroaniline (4-NA) in organic as well as aqueous medium across wide pH range (1.0 to 10.0). PDI-1 showed strong fluorescence in dimethylformamide (DMF) (Φf = 0.26 (DMF) and moderate fluorescence in water. Addition of picric acid (PA) and 4-nitroaniline (4-NA) into PDI-1 in DMF/aqueous solution selectively quenches the fluorescence. The concentration dependent studies showed decrease of fluorescence linearly with increase of PA and 4-NA concentration. The interference studies demonstrate high selectivity for PA and 4-NA. Interestingly, PDI-1 showed selective fluorescence sensing of PA and 4-NA across wide pH range (1.0 to 10.0). Selective fluorescence sensing of PA and 4-NA has also been observed with trifluoroacetate (PDI-2), sulfate (PDI-3) salt of PDI-1 as well as octyl chain substituted PDI (PDI-4) without amine functionality. These studies suggest that PA and 4-NA might be having preferential interaction with PDI aromatic core and quenches the fluorescence. Thus PDI based dyes have been used for selective fluorescent sensing of explosive NACs for the first time to the best our knowledge.

A Facile Method for the Synthesis Fluorescent Zinc Chalcogenide (ZnO, ZnS and ZnSe) Nanoparticles in PS and PMMA Polymer Matrix.

A simple method for the synthesis of fluorescent zinc chalcogenide (ZnO, ZnS and ZnSe) nanoparticles directly in the transparent PMMA and PS polymer matrices were reported. Highly dispersed small spherical ZnO nanoparticles (3-5 nm) was obtained by hydrothermal reaction of PMMA/PS-Zn(acac)2H2O in toluene. ZnS and ZnSe nanoparticles were prepared by heterogeneous stirring of PMMA/PS-Zn(acac)2H2O in toluene with aqueous solution of thiourea or NaHSe. Interestingly, ZnO and ZnS-PMMA thin film showed strong fluorescence quenching upon exposure to ammonia.

Off-on Fluorescent Sensor from On-off Sensor: Exploiting Silver Nanoparticles Influence on the Organic Fluorophore Fluorescence.

Turn-off fluorescence of organic fluorophore, 2-{[4-(2H-Naphtho[1,2-d][1,2,3]triazol-2-yl)-phenyl]carboxylic acid (NTPC), with metal ions (Fe(3+), Cu(2+), Pb(2+)) was converted into turn-on fluorescent sensor for biologically important Zn(2+), Cu(2+) and Fe(3+) metal ions in aqueous solution at ppb level by exploiting strong fluorescence quenching phenomena of metal nanoparticles when organic fluorophores assembled in the vicinity of metallic surface. Amino acid attached phenolic ligands (L) were used as reducing as well as functional capping agents in the synthesis of silver nanoparticles (AgNPs). The hydrogen bonding functionality of L facilitated the assembling of NTPC in the vicinity of metallic surfaces that leads to complete quenching of NTPC fluorescence. The strong and selective coordination of L with metal ions (Zn(2+), Cu(2+) and Fe(3+)) separates the NTPC from the AgNPs surface that turn-on the NTPC fluorescence. HR-TEM and absorption studies confirm the metal coordination with L and separation of NTPC from the AgNPs surface. Mn(2+) showed selective red shifting of NTPC fluorescence after 12 h with all sample. Effects of different amino acid attached phenolic ligands were explored in the metal ion sensitivity and selectivity. This approach demonstrates the multifunctional utility of metal NPs in the development of turn-on fluorescence sensor for paramagnetic heavy metal ions in aqueous solution. ᅟ

Propeller shaped triarylamine acid: An ultra-sensitive fluorescence probe for distinguishing propanol isomers and water sensing in organic solvents.

The photophysical properties of conformationally flexible (TPA-C) and partially rigidified (Cz-C) triarylamine acids were explored in solid as well as solution state and correlated with the structure. TPA-C and Cz-C exhibited moderate solid-state fluorescence (Φf = 6.2 % (TPA-C) and 5.6 % (Cz-C)) and self-reversible mechanofluorochromism. TPA-C produced fluorescent polymorphs (TPA-C-1 and TPA-C-2) with tunable fluorescence. TPA-C-1 showed unusual carboxylic acid intermolecular interactions whereas TPA-C-2 and Cz-C showed usual carboxylic acid dimer. TPA-C exhibited strong solvent polarity dependent tunable fluorescence (Φf = 0.01 to 0.11 compared to quinine sulphate standard) but Cz-C was non-emissive in the solution state. The dual emissive TPA-C showed highly sensitive fluorescence changes in organic solvents (CH3CN, THF, DMF, EtOH) when trace amount of water was added. In CH3CN, TPA-C showed weak fluorescence at 474 nm and addition of water (1 %) exhibited significant blue shift (λmax = 416 nm). The fluorescence intensity was gradually decreased with blue shifting in DMF, THF and EtOH with water addition. Importantly, TPA-C showed drastically different fluorescence in n-propanol (n-PA) and iso-propanol (IPA). TPA-C in n-PA showed fluorescence at 408 nm that was clearly red shifted to 438 nm with 0.1 % addition of IPA. The limit of detection (LOD) of water in CH3CN, DMF, THF and EtOH by TPA-C revealed 0.02, 0.7, 0.08 and 0.77 %, respectively. The LOD of IPA sensing in n-PA is 0.05 % and indicated the very efficient sensing and distinguishing propanol isomers. Thus, simple triphenylamine acid showed excellent water sensing and propanol isomers discrimination that could be attributed to the twisted intramolecular charge transfer (TICT) formation.

Deep blue emitting dual state fluorescent triphenylamine-dicyclohexylurea derivative: Multi-stimuli responsive fluorescence switching and methanol/water sensing.

A new deep blue emissive organic fluorophore (N-cyclohexyl-N-(cyclohexylcarbamoyl)-4-(diphenylamino)benzamide (NCDPB)) was designed and synthesized, which showed strong fluorescence both in solution and solid-state. Solid-state structural analysis of NCDPB revealed non-planar twisted molecular conformation with extended hydrogen bonding between the amide functionalities. The propeller shaped triphenylamine (TPA) and non-planar cyclohexyl unit prevented close π…π stacking and produced strong deep blue emission in the solid state (λmax = 400 nm, quantum yield (Φf) = 12.6 %). NCDPB also exhibited strong solvent polarity dependent tunable emission in solution (λmax = 402-462 nm, Φf = 1.15 (compared to quinine sulphate)). NCDPB showed reversible fluorescence switching between two fluorescence states upon mechanical crushing and heating/solvent exposure. Mechanical crushing caused red shifting of fluorescence from 400 to 447 nm and heating/solvent exposure reversed the fluorescence. Further, NCDPB also displayed off-on reversible/self-reversible fluorescence switching upon exposure to trifluoracetic acid (TFA) and NH3. The repeated fluorescence switching cycles indicated high reversibility without any significant change of fluorescence intensity. The drastically different fluorescence of NCDPB in CH3OH and EtOH was utilized to distinguish them and monitor CH3OH contamination in ethanol and benzene. It showed limit of detection (LOD) of methanol up to 0.25 % and 7 % in benzene and ethanol, respectively. The water sensitive fluorescence modulation of NCDPB in organic solvents was used to sensing water contamination in common organic solvents. Thus, integration of twisted TPA with H-bonding urea produced dual state emitting organic fluorophore with multi-responsive fluorescence switching and solvent sensing.

Green synthesized silver nanoparticles for selective colorimetric sensing of Hg2+ in aqueous solution at wide pH range.

In the present study, the syntheses of crystalline silver and gold nanoparticles (NPs) has been demonstrated in a green and environmentally friendly approach using citrus fruit extracts (lemon, Citrus limon (Cl-1) and sweet orange, Citrus limetta (Cl-2)). In addition, potentially hazardous metal ion sensing properties of these NPs in aqueous solution has been explored. Cl-1 and Cl-2 that predominantly contained citric and ascorbic acid, exhibited different reducing abilities towards silver and gold ions into NPs. Cl-1 reduces silver ions into AgNPs only in the presence of sunlight whereas AuNPs from gold ions were formed without exposure to sunlight. In contrast, Cl-2 converts both silver and gold ions into the corresponding NPs in the absence of sunlight. The colorimetric sensor studies of these green synthesized AgNPs (Cl-1-AgNPs) showed selective sensing of the potentially hazardous Hg(2+) ion in water at micromolar concentrations. More importantly, green synthesized Cl-1-AgNPs sensor systems detected Hg(2+) ions in water in a wide pH range (3.2 to 8.5).

Enhancing the oxygen evolution reaction of cobalt hydroxide by fabricating nanocomposites with fluorine-doped graphene oxide.

Fluorine and nitrogen codoped cobalt hydroxide-graphene oxide nanocomposites (N,F-Co(OH)2/GO) were synthesized by a simple hydrothermal method and demonstrated highly enhanced oxygen evolution activity in an alkaline medium. N,F-Co(OH)2/GO synthesized under optimized reaction conditions required an overpotential of 228 mV to produce the benchmark current density of 10 mA cm-2 (scan rate 1 mV s-1). In contrast, N,F-Co(OH)2 without GO and Co(OH)2/GO without fluorine required higher overpotentials (370 (N,F-Co(OH)2) and 325 mV (Co(OH)2/GO)) for producing the current density of 10 mA cm-2. The low Tafel slope (52.6 mV dec-1) and charge transfer resistance, and high electrochemical double layer capacitance of N,F-Co(OH)2/GO compared to N,F-Co(OH)2 indicate faster kinetics at the electrode-catalyst interface. The N,F-Co(OH)2/GO catalyst showed good stability over 30 h. High-resolution transmission electron microscope (HR-TEM) images showed good dispersion of polycrystalline Co(OH)2 nanoparticles in the GO matrix. X-ray photoelectron spectroscopic (XPS) analysis revealed the coexistence of Co2+/Co3+ and the doping of nitrogen and fluorine in N,F-Co(OH)2/GO. XPS further revealed the presence of F in its ionic state and being covalently attached to GO. The integration of highly electronegative F with GO stabilizes the Co2+ active centre along with improving the charge transfer and adsorption process that contributes to improved OER. Thus, the present work reports a facile method for preparing F-doped GO-Co(OH)2 electrocatalysts with enhanced OER activity under alkaline conditions.

A water coordinated Ni complex and a 2D Ni-MOF: topology dependent highly enhanced electrocatalytic OER activity.

Metal-organic frameworks (MOFs) with their tunable topology, functionality and coordination environment have been considered as potential materials for various applications including electrocatalysis. Herein, we have synthesised a water coordinated nickel based 2D metal-organic framework (Ni-MOF) and a coordination complex (Ni-C) and investigated their electrocatalytic OER activity. The Ni-MOF showed a 2D sheet structure with one water coordination whereas a four water molecule coordinated charged complex was formed in the Ni-C. Thermogravimetric analysis (TGA) confirmed their water coordination and good thermal stability. Interestingly, electrocatalytic OER studies showed strongly enhanced activity for the Ni-MOF and that it required a low overpotential (194 mV) to produce a geometric current density of 10 mA cm-2. The Ni-C required 225 mV to produce 10 mA cm-2. The post-catalytic analysis suggested that the Ni-MOF and Ni-C are converted to nickel hydroxides/oxyhydroxides during electrocatalysis and acted as the catalytic centre. The low Tafel slope and charge transfer resistance further supported the higher activity of Ni-MOF based nickel hydroxides/oxyhydroxides. Chronoamperometric studies revealed the excellent stability of the Ni-MOF based catalyst over 72 h. The present study revealed the potential of developing highly active electrocatalysts based on Ni-MOFs by optimizing the topology and coordination environment.

Highly enhanced electrocatalytic OER activity of water-coordinated copper complexes: effect of lattice water and bridging ligand.

The use of metal-organic compounds as electrocatalysts for water splitting reactions has gained increased attention; however, a fundamental understanding of the structural requirement for effective catalytic activity is still limited. Herein, we synthesized water-coordinated mono and bimetallic copper complexes (CuPz-H2O·H2O, CuPz-H2O, CuBipy-H2O·H2O, and CuMorph-H2O) with varied intermetallic spacing (pyrazine/4,4'-bipyridine) and explored the structure-dependent oxygen evolution reaction (OER) activity in alkaline medium. Single crystal structural studies revealed water-coordinated monometallic complexes (CuMorph-H2O) and bimetallic complexes (CuPz-H2O·H2O, CuPz-H2O, CuBipy-H2O·H2O). Further, CuPz-H2O·H2O and CuBipy-H2O·H2O contained lattice water along with coordinated water. Interestingly, the bimetallic copper complex with lattice water and shorter interspacing between the metal centres (CuPz-H2O·H2O) showed strong OER activity and required an overpotential of 228 mV to produce a benchmark current density of 10 mA cm-2. Bimetallic copper complex (CuPz-H2O) without lattice water but the same intermetallic spacing and bimetallic complex with increased interspacing but with lattice water (CuBipy-H2O·H2O) exhibited relatively lower OER activity. CuPz-H2O and CuBipy-H2O·H2O required an overpotential of 236 and 256 mA cm-2, respectively. Monometallic CuMorph-H2O showed the lowest OER activity (overpotential 271 mV) compared to bimetallic complexes. The low Tafel slope and charge transfer resistance of CuPz-H2O·H2O facilitated faster charge transfer kinetics at the electrode surface and supported the enhanced OER activity. The chronoamperometric studies indicated good stability of the catalyst. Overall, the present structure-electrocatalytic activity studies of copper complexes might provide structural insight for designing new efficient electrocatalysts based on metal coordination compounds.

F and rare V4+ doped cobalt hydroxide hybrid nanostructures: excellent OER activity with ultralow overpotential.

Highly efficient and stable Earth abundant transition metal electrocatalysts are in great demand for the oxygen evolution reaction (OER), a bottleneck process involved in the water splitting reaction and metal-air batteries. Herein, we have demonstrated a single step direct fabrication of cobalt hydroxide (Co(OH)2) nanowires doped with vanadium(V) in a less stable +4 oxidation state and fluoride (F) ions (V-Co(OH)2) on a carbon cloth electrode that showed highly enhanced OER activity under alkaline conditions. V-Co(OH)2 nanowires synthesized under the optimized conditions produced excellent OER activity with an ultralow overpotential of 136 mV at 10 mA cm-2 (scan rate 1 mV s-1), a small Tafel slope (51.6 mV dec-1) and good stability over 72 h. To the best of our knowledge, this is the lowest overpotential reported for cobalt-based electrocatalysts to achieve a geometric current density of 10 mA cm-2. The controlled synthesis and HR-TEM studies revealed the formation of hybrid nanostructures (nanowires along with spherical assembly of nanoparticles) and codoping of V and F ions played an important role in enhancing the OER activity. The detailed chemical composition and oxidation state analysis by X-ray photoelectron spectroscopy (XPS) confirmed the doping of V4+ and ionic F in V-Co(OH)2 with mixed valence states of Co2+/Co3+ and a higher Co2+ ratio. The outstanding OER activity of V-Co(OH)2 is attributed to the formation of a spherical assembly of nanoparticles with nanowires, which provided a high number of catalytically active sites with enhanced charge transport, and doping of higher valence V4+ and strongly electronegative F in V-Co(OH)2 with a higher ratio of Co2+/Co3+ promoted OOH* intermediate generation and significantly boosted the OER activity. Overall, the present work highlights the possibility of achieving highly active Earth abundant OER electrocatalysts by controlling the mixed oxidation state of Co with a judicious choice of dopants along with maintaining optimal nanostructure morphologies.

Methoxy substituent facilitated wide solvatofluorochromism, white light emission, polymorphism and stimuli-responsive fluorescence switching in donor-π-acceptor.

Introducing methoxy substituent into triphenylamine-acetophenone based donor-π-acceptor fluorophore, 3-(4-(diphenylamino)phenyl)-1-phenylprop-2-en-1-one (1), produced strong solvatofluorochromism including white light emission, fluorescent polymorphs and mechano-responsive fluorescence switching. The unsubstituted and methoxy substituted compounds displayed strong solvent polarity mediated tunable emission in the solution. Interestingly, 3-(4-(diphenylamino)phenyl)-1-(4-methoxyphenyl)prop-2-en-1-one (2) and 3-(4-(diphenylamino)-2-methoxyphenyl)-1-(4-methoxyphenyl)prop-2-en-1-one (3) showed single molecule white light emission in DMSO and ethanol, respectively. 1-3 exhibited strong green/yellow fluorescence in the solid-state (Quantum yield (Φf) = 10 to 23%). 2 produced fluorescent polymorphs (green (2-G) and yellow (2-Y). Single crystal structural analysis revealed that donor and acceptor phenyl units adopted coplanar conformation in 2-G and 3 whereas twisted molecular conformation in 1 and 2-Y. Further, 2-G exhibited π…π interactions facilitated isolated dimers whereas 2-Y showed well separated molecules in the crystal lattice. Aggregation induced emission (AIE) studies showed morphological transformation induced fluorescence tuning for 2. The intramolecular charge transfer (ICT) from TPA to acetophenone was confirmed by computational studies. Mechanofluorochromic (MFC) studies of 1 showed only slight reduction of intensity without modulating fluorescence wavelength significantly but 2 and 3 exhibited visible emissive colour change from yellow to green and vice versa by crushing and heating. Both 2 and 3 also exhibited self-reversible fluorescence switching that was confirmed by PXRD pattern. Thus, methoxy group introduction resulted in obtaining white light emitting fluorescence molecules in the solution state and self-reversible fluorescence switching materials.

Carbazole fluorophore with an imidazole/thiazole unit: contrasting stimuli-induced fluorescence switching, water-sensing and deep-blue emission.

Carbazole-based, π-conjugated donor-acceptor fluorophores were synthesized by integrating imidazole/thiazole units. Then, we investigated the impact of subtle structural changes on fluorescence properties. Carbazole integrated with imidazole (Cz-I) and carbazole integrated with thiazole (Cz-T) showed strong fluorescence in solution (quantum yield (Φ f) = 0.18 (Cz-I) and 0.14 (Cz-T) compared with the standard quinine sulfate) and solid-state (Φ f = 8.0% (Cz-I) and 14.6% (Cz-T)). Cz-I showed relatively more blue-shifted emission in solution compared with the solid-state (λ max = 417 nm (CH3CN) and 460 nm (solid)). Cz-T exhibited deep-blue emission in the solid-state compared with solution (λ max = 455 nm (CH3CN) and 418 nm (solid)). Interestingly, Cz-T exhibited a drastic change in fluorescence in organic solvents (CH3CN, THF, CH3OH, DMSO) with a low percentage (1%) of water. Cz-I showed reversible fluorescence switching between two fluorescence states upon exposure to trifluoracetic acid (TFA)/ammonia (NH3). In contrast, Cz-T displayed reversible/self-reversible off-on fluorescence switching upon exposure to TFA or NH3. Mechanofluorochromic studies of Cz-I showed a slight reduction in fluorescence intensity upon crushing and reversal to the initial state upon heating. Cz-T exhibited off-on reversible/self-reversible fluorescence switching upon crushing/heating. Computational studies indicated that thiazole integration improved the electron-withdrawing characteristics compared with imidazole and contributed to contrasting fluorescence responses. Thus, a simple change of nitrogen with sulfur produced contrasting self-assembly in the solid-state that led to different functional properties and stimuli-induced fluorescence switching.

Highly enhanced dye adsorption of MoO3 nanoplates fabricated by hydrothermal-calcination approach in presence of chitosan and thiourea.

Water pollution by organic dyes poses great challenge to the environment and living organism. Hence effective removal of organic dyes by cost effective methods have received significant attention in recent years. Herein, we report the complete removal of organic dyes (rhodamine B), methylene blue) and eosin yellow) from water via effective adsorption by MoO3 catalyst. Hydrothermally synthesised MoO2 (1) and amorphous MoSx (2) using ammonium molybdate without and with thiourea exhibited low dye adsorption. In contrast, crystalline micro/nanoplates of MoO3 (3 and 4) obtained from calcination of 1 and 2 showed highly enhanced dye adsorption. Particularly 4 showed higher dye adsorption compared to 3. UV-Visible absorption studies confirmed complete removal of organic dyes upon stirring with MoO3 catalyst. Dye removal studies further revealed that cationic dyes are adsorbed faster than anionic dye that could be attributed to the surface charge of MoO3. Interestingly, the adsorbed dyes were not released from MoO3 for more than 50 days. The exhausted MoO3 catalyst can be recovered by annealing at 400 °C. MoO3 catalyst has also been used as packing materials in dropper column and demonstrated effective removal of dyes by passing through dyes separately as well as mixture.