A low-temperature method was developed to synthesize orange-red luminescence phosphor-doped carbon dots (CDs) without complicated purification procedures. These CDs showed excitation wavelength-independent narrow emission (photo-luminescence quantum yield, Φf â¼ 12 to 22%) with single exponential time-resolved decay in weakly polar/non-polar solvents, indicating the presence of one kind of chromophore. In contrast, the same CDs showed excitation wavelength-dependent broad emission (Φf â¼ 1 to 8%) with multi-exponential fluorescence decay in polar solvents. These CDs exhibited poor solubility in polar solvents, resulting in CD aggregates contributed by excitation wavelength-dependent weak luminescence. The CDs embedded in polymethyl methacrylate (PMMA) polymer film displayed bright orange-red fluorescence under UV 365 nm illumination, indicating their potential application in solid-state luminescence. Further, an analytical method was developed for the naked-eye detection of trifluoracetic acid (red emission) and triethylamine (green emission) under UV 365 nm illumination with reversible two switch-mode luminescence. Additionally, this efficient orange-red luminescence of CDs was utilized for possible bioimaging applications with negligible cytotoxicity in 3T3 mouse fibroblast cells.
Photoswitches are molecules that can absorb light of specific wavelengths and undergo a reversible transformation between their trans and cis isomeric forms. In phenylazo photoswitches, it is common for the less stable cis (Z) isomer to convert back to the more stable trans (E) isomer either through photochemical or thermal means. In this research, we designed new derivatives of phenylazothiazole (PAT) photoswitches, PAT-Fn, which feature fluorine substituents on their phenyl component. These derivatives can reversibly isomerize under visible light exposure with the enrichment of E and Z isomers at photostationary state (PSS). Surprisingly, we observed an unconventional phenomenon when these PAT-Fn (nâ§2) photoswitches were in their cis isomeric state in the absence of light. Instead of the anticipated transformation from cis to trans isomer, these compounds converted to an oligomeric compound. Our detailed experimental investigation and theoretical calculations, indicated the crucial role of fluorine substituents and the distinctive geometric arrangement of the cis isomer in driving the unexpected oligomerization process originating from the cis isomeric state.
A novel class of photoswitches based on a phenylazothiazole scaffold that undergoes reversible isomerization under visible-light irradiation is reported. The photoswitch, which comprises a thiazole heteroaryl segment directly connected to a phenyl azo chromophore, has very different spectral characteristics, such as a redshifted absorption maximum wavelength and well-separated absorption bands of the trans and cis isomers, than conventional azobenzene and other heteroaryl azo compounds. Substituents at the ortho and para positions of the phenyl ring of the photoswitch resulted in a further shift to longer wavelengths up to 525 nm at the absorption maximum with a small thermal stability compensation. These photoswitches showed excellent photostationary distributions of the trans and cis isomers, thermal half-lives of up to 7.2 h, and excellent reductant stability. The X-ray crystal structure analysis revealed that the trans isomers exhibited a planar geometry and the cis isomers exhibited a T-shaped orthogonal geometry. Detailed ab initio calculations further demonstrated the plausible electronic transitions and isomerization energy barriers, which were consistent with the experimental observations. The fundamental design principles elucidated in this study will aid in the development of a wide variety of visible-light photoswitches for photopharmacological applications.
Herein, excitation wavelength-independent, tunable emissive and amphiphilic CDs with high quantum yield were synthesized by a low-temperature oxidation method employing banana peel waste as a carbon source. These CDs showed longer wavelength emissions (green to yellow) independent of the excitation wavelength when dispersed in different polar to non-polar solvents. The quantum yields of the same CDs were 9-32% in different solvent polarities for different emissions. On the other hand, a large stokes-shifted emission (â¼9606 cm-1) was observed for CDs in the non-polar and weak polar solvents. The particle size of CDs increases from a hydrophobic to a hydrophilic environment with the change in emission colour from yellow to green. A polar and a non-polar host matrix were used to overcome the limitation of aggregation-caused quenching of CDs in the solid state to obtain bright emissions. These CDs were potentially used for naked-eye detection of trifluoroacetic acid (TFA) by changing the emission colour from yellow to orange under UV 365 nm. Sensing of TFA was also shown reversibly switch emission colour and average lifetime for multiple cycles. Additionally, the highly emissive CDs show negligible cytotoxicity in 3T3 fibroblast cells, indicating possible bioimaging applications in 3T3 cells.
Quantum Dots , Animals , Mice , Quantum Dots/chemistry , Carbon/chemistry , Solvents/chemistry , Particle Size
FDAPT (2-formyl-5-(4'-N,N-dimethylaminophenyl)thiophene) is an efficient environment-sensitive fluorescent probe, which senses the alteration of its microenvironment with six different fluorescent parameters, namely, emission intensity, wavelength, fluorescence anisotropy, and corresponding three time-dependent parameters fluorescence lifetime, time-resolved emission spectrum, and anisotropy decay. In the present work, the nature of saccharide-induced dehydration of a F127 polymeric micelle is investigated in detail with FDAPT emission. Using a multiparametric fluorescence approach, it is observed that the saccharide molecules not only decrease the critical micellization temperature of the F127 solution but also strongly alter the physical properties inside the micellar structures. The local polarity and fluidity significantly decrease in the saccharide-induced micelle as compared to the normal F127 micelle. The probe solvation dynamics study reveals that the water content in the core as well as corona domain diminishes significantly in the saccharide-induced micelle as compared to the normal micelle. More precisely, dehydration occurs more in the core region than in the corona region. Also, the saccharide-induced dehydration alters the relative size of the core and corona regions. The extent of dehydration varies with different saccharide molecules. It is also found that the dehydration efficiency order is trisaccharide (raffinose) > disaccharide (sucrose) > monosaccharide (glucose and fructose).
Phosphor materials with broad spectral range and an average emission lifetime (20â µs) have been achieved from carbon dots (CDs)-NaCl crystals. A one-pot synthesis pathway has been developed for CDs-NaCl crystals formation at room temperature. Precursor for CDs materials was screened at room temperature by oxidation methodology from different simple sugar molecules. CDs (size less than 10â nm) prepared from the fructose sugar exhibit most intense emission. Utilizing ripe banana peel (contains â¼27% of fructose) as a precursor for the carbon dot formation, white-light emission with a CIE index of (0.29, 0.34) has been achieved from the single source with CDs-NaCl crystals upon excitation at 430â nm. The crystals also function as Fabry-Perot (F-P) mode resonator for lasing, with a laser threshold value of 0.9â mW and a resonating Q-factor of 207. These results outline a new approach for realizing F-P lasing and white light emission from a non-toxic green source with a quick, facile and low-cost synthesis procedure.
FDAPT (2-formyl-5-(4'-N,N-dimethylaminophenyl)thiophene) efficiently senses the minimum alteration of lipid bilayer microenvironment with all six different fluorescence parameters namely emission wavelength, fluorescence intensity, steady-state anisotropy, and their corresponding time-dependent parameters (Sahu et al., J. Phys. Chem. B 2018, 122, 7308-7318). In the present work, the effect of poly(ethylene glycol) on the small unilamellar vesicle is demonstrated with the emission behavior of the FDAPT probe. A medium and a high molecular weight PEG were chosen to perturb the lipid vesicles. The alteration of the bilayer polarity, water content inside bilayer, lipid packing density in the perturbed vesicles reflect significant changes in different fluorescence parameters of FDAPT probe. The effect of PEG on the unilamellar vesicle was rationalized with the alteration of the emission behavior, fluorescence lifetime, steady-state anisotropy and anisotropy decay of the probe. The simple and convenient fluorescence measurements provide new insights into the effect of PEG on the packing density, water volume, micro polarity, and microviscosity of the small unilamellar vesicle. The physiological understanding was extended to rationalize the cryoprotecting behavior of PEG.
The proton transfer of 3,5-bis(2-hydroxyphenyl)-1H-1,2,4-triazole (bis-HPTA), a fluorophore proficient in self-aided twin proton transfer, has been explored in the presence of dimethylformamide (DMF). The proton transfer is completely altered in the presence of DMF (compared to that in other solvents). Bis-HPTA forms a hydrogen bonded complex with DMF molecules, which shift the conformer equilibrium. Theoretical calculations predicted that the DMF complexes of bis-HPTA-II and bis-HPTA-III are more stable than the complexes of other conformers. Upon excitation, bis-HPTA-II transfers a proton to a DMF molecule to form an anion and bis-HPTA-III transfers a proton to a ring nitrogen to form a keto form. Silver particles reverse the effect of DMF. They regenerate bis-HPTA-I by removing the intermolecular hydrogen bond and thereby they reestablish the proton transfer triggered proton transfer (PTTPT).
The double excited state intramolecular proton transfer (ESIPT) of 3,5-bis(2-hydroxyphenyl)-1H-1,2,4-triazole (bis-HPTA), a molecule possessing two intramolecular hydrogen bonded donor-acceptor pairs, has been investigated. The molecule undergoes not only a single ESIPT, but also a rare twin ESIPT. The most interesting fact is that initially, only one acid-base pair is ESIPT active and the other pair is ESIPT inactive. The first proton transfer triggers the proton transfer in the second acid-base pair by creating appropriate conditions. This new type of sequential proton transfer is labeled as 'proton transfer triggered proton transfer' (PTTPT). The PTTPT has been demonstrated by steady state and time resolved fluorescence techniques. It was further substantiated by theoretical data and using a chemically modified system 3-(2-hydroxyphenyl)-5-(2-methoxyphenyl)-1H-1,2,4-triazole.
Successful applications of solid lipid nanoparticles (SLNs) rely on their physicochemical properties which are mainly governed by their comprising materials (e.g., lipids, emulsifiers) and preparation methods. We have prepared biocompatible solid lipid nanoparticles with glycerol monostearate as lipid and varying combinations of bile salts sodium deoxycholate and sodium cholate (bile salts to lipid ratio 8% w/w) as emulsifiers. The detailed characterization of solid lipid nanoparticles was performed using a combination of light scattering, microscopic, calorimetric, and spectroscopic techniques. It was seen that different compositions of bile salts yield nanoparticles with different sizes. The use of only sodium deoxycholate (8% w/w) produces nanoparticles with average sizes â¼487 nm. The average particle size increases with increasing cholate fraction. A higher average particle size around â¼652 nm is obtained with 8% (w/w) sodium cholate. All the SLNs show good physical stability at room temperature and do not show polymorphic transformation during the storage. In order to study the microenvironments, solid lipid nanoparticles are loaded with an external fluorescent-probe fisetin (probe to lipid ratio 1% w/w). Photophysical properties of fisetin loaded SLNs indicate the micro-heterogenicity inside the nanoparticles.
Bile Acids and Salts/chemistry , Chemical Phenomena , Glycerol/chemistry , Lipids/chemistry , Nanoparticles/chemistry , Calorimetry, Differential Scanning , Flavonoids/pharmacology , Flavonols , Humidity , Nanoparticles/ultrastructure , Particle Size , Spectrometry, Fluorescence , Temperature , Thermogravimetry , X-Ray Diffraction
Push-pull type fluorophores are often exploited as a biological probe because of their high environment-sensitivity nature. Herein, we report the potentiality of a push-pull fluorophore, 2-formyl-5-(4'- N, N-dimethylaminophenyl)thiophene, as a membrane probe. This molecule exhibits strong absorbance in the violet region (â¼400 nm) and a high emission quantum yield (≤0.6). The emission is highly sensitive to the surrounding environment, and a high Stokes shift (>7000 cm-1) appears in strong polar solvents. The molecule is highly susceptible to the fluorescence quenching by protic solvents. The neutral probe efficiently senses aprotic environments such as lipid bilayer membranes through all six fluorescence parameters: emission maxima, intensity, and anisotropy as well as the corresponding time-dependent parameters. The small and flat shape, nonemissive nature in the aqueous medium along with the high susceptibility to all six fluorescence parameters of the molecule strongly suggests a promising fluorescence probe for biological medium.
Fluorescent Dyes/chemistry , Lipid Bilayers/chemistry , Liposomes/chemistry , Spectrometry, Fluorescence , Thiophenes/chemistry , Water/chemistry
The anion sensitivity and the deprotonation nature of the nitrogenous analogues of 2-(2'-hydroxyphenyl)benzimidazole (HPBI) are investigated in a polar aprotic medium. It is observed that the substitution of pyridyl nitrogen enhances the anion sensitivity. However, despite the enhanced sensitivity of the nitrogenous analogues the deprotonation of these molecules in the presence of strong anions is less favored as compared to HPBI. This anomalous trend observed for the nitrogenous analogs is discussed and explained using theoretical calculations and experimental findings. It is also found that the sensitivity towards anions and the formation of anions also depend on the position of the pyridyl nitrogen.
Despite the fact that 2-(2'-hydroxyphenyl)benzimidazole (HPBI) exists as the cis and trans enol in neutral form, it was reported to exist only in the trans form upon deprotonation in an aqueous medium. It was also shown that the dianion formed in the ground state can be re-protonated to form the trans-anion in the excited state. In the present study, the cis-anion and dianion could be obtained upon proper stabilization in suitable environments. Switching between the cis and trans-anion was demonstrated to be possible by changing the environment. Theoretical calculations were performed to substantiate the existence of the cis-anion and dianion. In contrast to a literature report, it was shown that the 'OH' group deprotonates before the 'NH' group to form a monoanion not only in protic solvents but also in aprotic solvents.
Logic gates with different radixes have been constructed using a biologically active molecule, 2-(4'-N,N-dimethylaminophenyl)imidazo[4,5-b]pyridine (DMAPIP-b). Taking advantage of the multiple binding sites of the fluorophore, a series of different molecular logic gates are developed using fluorescence intensities at different wavelengths. The high emission of the molecule is drastically quenched in the presence of Fe(3+). It is regained by the addition of an equivalent amount of F(-). The fluorescence On-Off nature has been used to construct molecular full subtractor and molecular keypad lock system with Boolean logic. A ternary system is generated by considering three defined fluorescence intensities at particular wavelengths. The smooth dependency of emission intensities with analyte concentration is utilized to construct an infinite-valued fuzzy logic system. The fuzzy logic system is further coupled with a neuro-adaptation method to predict more accurately the dependency of molecular intensity on external inputs.
Fluorescent Dyes/chemistry , Ferric Compounds/chemistry , Fluorides/chemistry , Pyridines/chemistry
The spectral characteristics of trans-2-[4'-(N,N-dimethylamino)styryl]imidazo[4,5-b]pyridine (t-DMASIP-b) have been investigated using absorption and fluorescence techniques, and compared with 2-(4'-N,N-dimethylamino)imidazo[4,5-b]pyridine (DMAPIP-b). The study reveals that introduction of a C[double bond, length as m-dash]C double bond strongly perturbs the photophysics of the system. Unlike DMAPIP-b, t-DMASIP-b emits a single emission in aprotic and protic solvents. The emission occurs from the locally excited state in nonpolar solvents and from a planar intramolecular charge transfer (PICT) state in polar solvents. Multiple linear regression analysis suggests that among the different solvent parameters, the dipolar interaction contributes more to the stabilization of the system in both the ground and excited states. Theoretical calculations suggest that, unlike in DMAPIP-b, proton coupled twisted intramolecular charge transfer (TICT) emission does not occur in t-DMASIP-b. The higher quantum yield obtained in the viscous solvent glycerol is attributed to the restriction of the twisting of the olefinic bond. The photoirradiation of t-DMASIP-b shows that isomerization takes place in all solvents, including viscous glycerol. The theoretically simulated potential energy surface shows that isomerization occurs via a phantom state, which is a nonradiative process. The rise in temperature favors the photoisomerization, thus, the fluorescence quantum yield decreases. The prototropic study indicates that, unlike in DMAPIP-b, the protonation takes place at different places to form the monocations.
Carbon/chemistry , Imidazoles/chemistry , Photochemical Processes , Pyridines/chemistry , Electron Transport , Ethylenes/chemistry , Hydrogen-Ion Concentration , Isomerism , Temperature
The semirigid ligands 1,4-bis(2-(2-hydroxyphenyl)benzimidazol-1-ylmethyl)benzene (H2-pBC) and 1,3-bis(2-(2-hydroxyphenyl)benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene (H2-mBC), containing two hydroxyphenylbenzimidazolyl units as bis-chelating (or bis(bidentate)) Nâ©OH donor, were synthesized and were used to assemble neutral, luminescent heteroleptic, unsaturated double-hetero-stranded, rhenium(I)-based helicate (1) and mesocate (2) with the flexible bis(monodentate) nitrogen donor (1,4-bis(benzimidazol-1-ylmethyl)benzene/1,3-bis(benzimidazol-1-ylmethyl)benzene), and Re2(CO)10. The photophysical properties of the complexes were studied. Both complexes 1 and 2 exhibit dual emissions in both solution and solid state. In solution, these complexes show both fluorescence and phosphorescence. Complex 1 undergoes a predominantly ligand-centered oxidation, resulting in the generation of phenoxyl radicals.
Coordination Complexes/chemistry , Luminescent Agents/chemistry , Rhenium/chemistry , Benzene/chemistry , Coordination Complexes/chemical synthesis , Electrochemistry , Ligands , Luminescent Agents/chemical synthesis , Models, Molecular , Molecular Conformation , Quantum Theory , Spectrum Analysis
The binding interactions of Cu(2+), an essential trace metal ion, and Cd(2+), a deleterious metal ion, with 2-(4'-N,N-dimethylaminophenyl)oxazolo[4,5-b]pyridine (DMAPOP) were studied in acetonitrile and sodium dodecyl sulphate (SDS). The studies show that the surfactant can formulate the metal ions to bind at a specific binding site. In acetonitrile, the Cu(2+) binds at the dimethylamino nitrogen and pyridine nitrogen to form two different types of complexes with DMAPOP. On the other hand, Cd(2+) coordinates through the dimethylamino nitrogen and oxazole nitrogen to form two different types of complexes with DMAPOP in acetonitrile. But SDS effectively controls the binding site and both metal ions bind at the same ring nitrogen in SDS. The binding affinities of both metal ions with DMAPOP vary with the concentration of SDS.
Fluorescent Dyes/metabolism , Metals/metabolism , Micelles , Oxazoles/metabolism , Pyridines/metabolism , Binding Sites/physiology , Fluorescent Dyes/chemistry , Hydrogen-Ion Concentration , Metals/chemistry , Oxazoles/chemistry , Pyridines/chemistry
The spectral characteristics of N,N-dimethyl-4-(4-methyl-4H-imidazo[4,5-b]pyridin-2-yl)benzenamine (PyN-Me), 1-methyl-2-(4'-(N,N-dimethylaminophenyl)imidazo[4,5-b]pyridine (ImNH-Me), and 2-phenylimidazo[4,5-b]pyridine (PIP) are investigated to understand the mechanism of protic solvent induced dual fluorescence of 2-(4'-N,N-dimethylaminophenyl)imidazo[4,5-b]pyridine (DMAPIP-b). No dual emission is observed from PyN-Me where pyridyl nitrogen blocked from hydrogen bonding with protic solvents confirms the importance of hydrogen bonding of protic solvents with the pyridyl nitrogen in dual emission of DMAPIP-b. Like DMAPIP-b, ImNH-Me also exhibits weak emission and has a shorter fluorescence lifetime in methanol. However, single emission is observed from ImNH-Me in all solvents including protic solvents. This suggests that the imidazole >NH hydrogen also plays a role in the dual emission process. The longer wavelength emission of DMAPIP-b in water increases with increase in pH of the solution owing to deprotonation of the imidazole >NH group. On the basis of these results, the mechanism for the dual emission of DMAPIP-b is proposed.
Aniline Compounds/chemistry , Imidazoles/chemistry , Protons , Pyridines/chemistry , Fluorescence , Models, Molecular
