A series of five new terbium(III) ion complexes with 4,4-difluoro-1-phenylbutane-1,3-dione (HDPBD) and anciliary ligands was synthesized. The composition and properties of complexes were analyzed by elemental analysis, IR, NMR, powder X-ray diffaraction, TG-DTG and photoluminescence spectroscopy. These complexes exhibited ligand sensitized green emission at 546 nm associated with 5D4?→?7F5 transitions of terbium ion in the emission spectra. The photoluminescence study manifested that the organic ligands act as antenna and facilitate the absorbed energy to emitting levels of Tb(III) ion efficiently. The enhanced luminescence intensity and decay time of ternary C2-C5 complexes observed due to synergistic effect of anciliary ligands. The CIE color coordinates of complexes came under the green region of chromaticity diagram. The mechanistic investigation of intramolecular energy transfer in the complexes was discussed in detail. These terbium(III) complexes can be thrivingly used as one of the green component in light emitting material and in display devices.
In this study the researcher reports a novel, one step synthesized rod-like nanoparticles of cerium (III)—tetraphenylporphyrin sandwich complex as a spectrofluorometric sensor to measure trace amount of Hg (II) and Cu (II) metal ions. Moreover, the synthesized fluorescent probe was able to detect higher amounts (>10?4 M) of Hg (II) in aqueous media by changing the color which can also be used as a selective mercury naked-eye sensor. The selectivity and sensitivity of the sensor based on its fluorescence quenching in the presence of Hg (II) and Cu (II) were studied according to the Stern-Volmer equation. The detection limit of the sensor was 16 nM for Hg (II) and about 2.34 μM for Cu (II) ions.
Hexadentate ligand L and its Ln3+ complexes EuLCl3 (1), TbLCl3 (2), SmLCl3 (3) are synthesised. All these complexes are well characterized for their photophysical properties such as luminescence lifetime decay(τ) and overall quantum yield(Φ). These complexes being water soluble, depicts their intense metal centred luminescence. Effect of pH on these complexes suggest that their emission intensities are stable in the pH range 4–9 and show their compatibility to function in the physiological pH.
Two new Cu(II) complexes with Picolinic acid and Tryptophan [Cu(II)(DPTR)(H2O)2](1:1) (1) and [Cu(II)(DPTR)(Phen)] (1:1:1) (2) were synthesized, characterized and studied their DNA binding, cleavage, docking and anti-cancer properties. The molecular modeling studies were carried out with energy minimized structures of metal complexes. CT-DNA binding studies revealed that the complexes bind through an intercalative mode and show good binding propensity. The docking study also confirms the intercalative mode of binding. The hydrolytic DNA cleavage activity of these complexes has been studied using gel electrophoresis. Complex 2 shows better efficiency than 1. Cell viability experiments indicated that the ligand, complexes show significant dose dependent cytotoxicity in selected cell lines.
Graphical Abstract Two new Cu(II) complexes with Picolinic acid and Tryptophan, [Cu(II)(DPTR)(H2O)2](1:1) (1) and [Cu(II)(DPTR)(Phen)] (1:1:1) (2) were synthesized, characterized and studied their DNA binding, cleavage, docking and anti-cancer properties.
A simple fluorescent chemosensor 5-(4-methylphenyl)-3-(5-methylfuran-2-yl)-1-phenyl-4, 5-dihydro-1H-pyrazole (PY) has been synthesized for the detection of Cd2+ ion.The fluorescent probe PY shows high selectivity for Cd2+in the presence of othermetal ions (Co2+, Cu2+, Hg2+, Mn2+, Zn2+, Fe3+, Pb2+, Ni2+, and Al3+). The fluorescence intensity of the PY has been strongly quenched with increasing concentration of Cd2+ (0–0.9 μM)via photoinduced electron transfer mechanism. The binding constant of Cd2+ to PY for the 1:1 complex isfound to be 5.3?×?105 M?1with a detection limit of 0.09 μM. The chemosensor was successfully applied for determination of Cd2+ in different water samples (tap, river, and bottled water) showing good recovery values in the range of 94.8–101.7% with RSD less than 3%. Density functional theory (DFT) calculations were also performed to investigate electronic and spectral characteristics which are quite agreeable with the experimental value. The results show that the synthesized fluorescent chemosensor shows good selectivity towards Cd2+ and can be readily applied for the detection of Cd2+ in real samples including water samples.
The development of a highly sensitive, selective, and efficient sensor for the determination and detection of Cr(III) ions remains a great challenge. Recently, some fluorescent chemosensors have been developed for the recognition of Cr(III) ions. But, the main drawbacks of the reported fluorescent chemosensors are the lack of selectivity and interference of anions and other trivalent cations. Herein, we designed and synthesized a novel thiazole-based fluorescent and colorimetric Schiff base chemosensor SB2 for the detection of Cr(III) ion by chemodosimetric approach. Using different analytical techniques including UV–vis, 13C-NMR, 1H-NMR, and FT-IR analysis the chemosensor SB2 was structurally characterized. The fully characterized chemosensor SB2 was used for the spectrofluorimetric and colorimetric detection of Cr(III) ions. Interestingly, chemosensor SB2 upon interaction with various metal cations including Ni2+, Na+, Cd2+, Ag+, Mn2+, K+, Zn2+, Cu2+, Hg2+, Co2+, Pb2+, Mg2+, Sn2+, Al3+ and Cr3+ displays highly selective and sensitive fluorescent (turn-on) and colorimetric (yellow to colorless) response toward Cr(III) ions. The fluorescence and UV–vis techniques confirmed the selective hydrolysis of azomethine group (-C?=?N-) of Schiff base chemosensor SB2 by Cr(III) ions. As a result, the fluorescence enhancement was observed that is corresponding to 2-hydroxy-1-nepthaldehyde (fluorophore). The chemosensor SB2 exhibits high interference performance towards Cr(III) ions over other metal cations in a wide pH range. Mover, the quite low detection limit was calculated to be 0.027 µg ml-1 (0.5 µM) (3σ/slop), lower than the maximum tolerable limits of Cr(III ions (10 µM) in drinking water permitted by the United States Environmental Protection Agency (EPA). These results show that chemosensor SB2 has great potential to detect selectively Cr(III) ions in the agricultural, environmental and biological analysis system.
In this paper, we report on the results of spectrofluorimetric study of new fluorescent sensor based on [Zn2L2] doped in ethyl cellulose. The sensor optical signal is based on the rapid fluorescence quenching in the presence of acetone vapor. The acetone vapor detection limit in a gas mixture by means of sensor based on [Zn2L2] doped in ethyl cellulose is 1.68 ppb. Being highly sensitive to the acetone acetone presence, instant in response and easy to use, the sensor can find an application for the noninvasive diagnostics of diabetes as well as for the monitoring of the content of acetone acetone in the air at industrial and laboratory facilities.
The present study aimed to develop a carbon dots-based fluorescence (FL) sensor that can detect more than one pollutant simultaneously in the same aqueous solution. The carbon dots-based FL sensor has been prepared by employing a facile hydrothermal method using citric acid and ethylenediamine as precursors. The as-synthesized CDs displayed excellent hydrophilicity, good photostability and blue fluorescence under UV light. They have been used as an efficient “turn-off” FL sensor for dual sensing of Fe3+ and Hg2+ ions in an aqueous medium with high sensitivity and selectivity through a static quenching mechanism. The lowest limit of detection (LOD) for Fe3+ and Hg2+ ions was found to be 0.406 µM and 0.934 µM, respectively over the concentration range of 0-50 µM. Therefore, the present work provides an effective strategy to monitor the concentration of Fe3+ and Hg2+ ions simultaneously in an aqueous medium using environment-friendly CDs.
Merocyanine dye based fluorescent organic compound has been synthesized for the detection of glutamine. The probe showed remarkable fluorescent intensity with glutamine through ICT (Intermolecular Charge Transfer Mechanism). Hence, it is tested for the detection of glutamine using colorimetric and fluorimetric techniques in physiological and neutral pH (7.2). Under optimized experimental conditions, the probe detects glutamine selectively among other interfering biomolecules. The probe has showed a LOD (lower limit of detection) of 9.6?×?10–8 mol/L at the linear range 0–180 µM towards glutamine. The practical application of the probe is successfully tested in human biofluids.
Multidentate 1,3,5-benzenetricarboxylic acid (organic linker), Zn (II) based Zn-BTC has been synthesized via electrochemical method. Quantitative and Qualitative analyses of synthesized metal–organic framework (MOF) have been done using Fourier Transform Infrared (FTIR) Spectroscopy, Energy Dispersive X- Ray Spectroscopy (EDS), and Photoluminescence (PL). Powder X-Ray Diffraction (PXRD) and Scanning Electron Microscopy (SEM) have been used for crystallographic and morphological & topographical analyses, respectively. Crystallographic studies confirm the formation of face-centered cubic (fcc) crystal structure with good crystallinity. Photo-catalytic activity of synthesized MOF has been tested using Methylene Blue (MB) dye as a test contaminant in aqueous media under sunlight irradiation. Recorded results reveal that the synthesized MOF efficiently degrade MB dye upto 96% under sunlight exposure after 270 min. Photoluminescence studies indicate that Zn-BTC could be used as an efficient material for sensing of nitroaromatic compounds (NACs): 4-Nitroaniline (4-NA), 2-Nitroaniline (2-NA), 3- Nitroaniline (3-NA), 2,4-Dinitrotoulene (2,4-DNT), 4-Nitrotoulene (4-NT) in N,N’-Dimethylformamide (DMF) by fluorescence quenching and shows maximum quenching efficiency towards 3-NA (72.80%). Notably, the variation in luminescence intensity of 3-NA@Zn-BTC shows a linear relationship over its different concentrations from 0–1000 ppb range with KSV?=?2.7?×?104 M?1 and R2?=?0.9924 with limit of detection 0.889 ppb (6.43 µM) (LOD). The possible ways of luminescence quenching are successfully explained by the combination of Photoinduced Electron Transfer (PET) and Resonance Energy Transfer (RET) mechanisms. Additionally, the Density Functional Theory (DFT) calculations have been employed to support the experimental results. Zn-BTC fully demonstrates the power of a multi component MOF, which provides a feasible pathway for the design of novel material towards fast responding luminescence sensing and photocatalytic degradation of pollutants.
Specific functionalized calix[4]arene based fluorescent chemosensor was synthesized for cations and anions binding efficiency examination. Receptor C4MA displayed strong affinity for Al3+and S2O72? with enhanced fluorescence intensity. The selective response of C4MA was investigated in the presence of different co-existing competing ions. The limit of detection (LOD) of Al3+and S2O72? was calculated as 2.8?×?10?6 M and 2.6?×?10?7 M respectively. Sensor C4MA forms (1:1) stoichiometric complex with both Al3+ and S2O72? and their binding constants were calculated as 12.1?×?104 and 8.3?×?103 respectively. Complexes were also characterized through FT-IR spectroscopy.
A bis(naphthalimide-piperazine) derivative (1) was synthesized as a pH-sensitive Off-On fluorescent probe. Operation mechanism of 1 is based on photo-induced electron transfer (PET) and its pH-dependent optical changes were investigated by using absorption and fluorescence spectroscopy. In the pH range of 11–4.5, this probe undergoes PET process from the piperazine to the naphthalimide moiety, leading to a fluorescence quenching. However, in the pH range of 4.5–1, the PET is inhibited to give a fluorescence enhancement. Moreover, the fluorescence ‘turn-on’ response of 1 is highly selective for protons (H+) over other metal cations, biomolecules and it shows a good reversibility between acidic and basic conditions.
A triplet diphenylcarbene, bis[3-bromo-5-(trifluoromethyl)[1,1'-biphenyl]-4-yl]methylidene (B3B), with exceptional stability was discovered by chemists from Japan's Mie University. To investigate its different quantum chemical features, a theoretical analysis was predicated on Density Functional Theory (DFT) and Time Dependent-DFT (TD-DFT) based technique. According to the findings, the singlet–triplet energy gap (ES-T), as well as HOMO–LUMO energy bandgap (EH-L), was found to be diminished when nucleophilicity (N) rose. We looked at the geometrical dimensions, molecular orbitals (MOs), electronic spectra, electrostatic potential, molecular surfaces, reactivity characteristics, and thermodynamics features of the title carbene (B3B). Its electronic spectra in different solvents were calculated using TD-DFT and Polarizable Continuum Model (PCM) framework. The estimated absorption maxima of B3B were seen between 327 and 340 nm, relying on the solvents, and were attributed to the S0?→?S1 transition. Estimated fluorescence spectral peaks were found around 389 and 407 nm with the S1 and S0 transitions being identified. Its fluorescence/absorption intensities revealed a blue shift change when the solvent polarity was increased. The least exciting state has been discovered to be the π?→?π* charge-transfer (CT) phase. According to the Natural Bonding Orbital (NBO) exploration, ICT offers a significant role in chemical system destabilization. Furthermore, several hybrid features were used to determine the NLO (nonlinear optical) features (polarizability, first-order hyperpolarizability, and dipole moment). The calculated values suggest that B3B is a promising candidate for further research into nonlinear optical properties.
Arsenic (As3+) is a hazardous and ubiquitous element; hence the quantitative detection of arsenic in various kinds of environmental sample is an important issue. Herein, we reported L-cysteine capped CdTe Quantum dot based optical sensor for the fluorometric detection of arsenic (III) in real water sample. The method is based on the fluorescence quenching of QDs with the addition of arsenic solution that caused the reduction in fluorescence intensity due to strong interaction between As3+ and L-cysteine to form As(Cys)3. The calibration curve was linear over 2.0 nM-0.5 μM arsenic with limit of detection (LOD) of 2.0 nM, correlation coefficient (r2) of 0.9698, and relative standard deviation (RSD %) of 5.2%. The Stern-Volmer constant for the quenching of CdTe QDs with As3+ at optimized condition was evaluated to be 1.17 × 108 L mol?1 s?1. The feasibility of the sensor has been analyzed by checking the inference of common metal ions available in the water such as K+, Na+, Mg2+, Ca2+, Ba2+, Cu2+, Ni2+, Zn2+, Al3+, Co2+, Cr2+, Fe3+ and its higher oxidation state As5+.
A new efficient chemosensor 1 was prepared, for the detection of Fe3+ in solutions as a colorimetric and fluorescent sensor. The visual and fluorescent behaviors of the receptor toward various metal ions were also explored. The receptor shows exclusive response toward Fe3+ ions and also distinguishes Fe3+ from other cations by color change and fluorescence enhancement in hydroalcoholic solution (MeOH/H2O = 9/1, v/v). Thus, the receptor can be used as a colorometric and fluorescent sensor for the determination of Fe3+ ion. The fluorescence microscopy experiments showed that the chemosensor is efficient for detection of Fe3+ in vitro, developing a good image of the biological organelles.
In this work, we introduce a highly selective and sensitive fluorescent sensor based on pyrene derivative for Fe(III) ion sensing in DMSO/water media. 2-(pyrene-2-yl)-1-(pyrene-2-ylmethyl)-1H-benzo[d]imidazole (PEBD) receptor was synthesized via simple condensation reaction and confirmed by spectroscopic techniques. The receptor exhibits fluorescence quenching in the presence of Fe(III) ions at 440 nm. ESI–MS and Job’s method were used to confirm the 1:1 molar binding ratio of the receptor PEBD to Fe(III) ions. Using the Benesi-Hildebrand equation the binding constant value was determined as 8.485?×?103 M?1. Furthermore, the limit of detection (LOD, 3σ/K) value was found to be 1.81 µM in DMSO/water (95/5, v/v) media. According to the Environmental Protection Agency (EPA) of the United States, it is lower than the acceptable value of Fe3+ in drinking water (0.3 mg/L). The presence of 14 other metal ions such Co2+, Cr3+, Cu2+, Fe2+, Hg2+, Pb2+, K+, Ni2+, Mg2+, Cd2+, Ca2+, Mn2+, Al3+, and Zn2+ did not interfere with the detection of Fe(III) ions. The fluorescence life-time of the receptor PEBD with and without Fe3+ ion was found to be 1.097?×?10?9 s and 0.9202?×?10?9 s respectively. Similarly, the quantum yield of the receptor PEBD with Fe3+ and without Fe3+ ion was calculated, and found as 0.05 and 0.25 respectively. Computational studies of the receptor PEBD were carried out with density functional theory (DFT) using B3LYP/ 6-311G (d, p), LANL2DZ level of theory.
Solvent free synthesis of 6,7-dihydroxy-3-(3-chlorophenyl) coumarin (CFHC) was designed and obtained by the interaction of 2-(2,4,5-trimethoxyphenyl)-1-(3-chlorophenyl)acrylonitrile with pyridinium hydrochloride in the presence of silica gel by using microwave irradiation. The characterization of CFHC was confirmed by FT-IR, 1H, 13C, 13C–APT and 2D HETCOR spectroscopy methods. The optical behavior of CFHC towards metal ions was investigated by UV-visible and fluorescence spectroscopy. CFHC showed “on–off” type fluorescence response towards Cu2+ with high selectivity in aqueous solution (CH3CN/H2O, 9/1, v/v). Once binding with Cu2+, CFHC-Cu2+ complex also displayed high selectivity for sulfide, resulting in “off–on” type sensing of sulfide anion.
Graphical abstract Visual fluorescence changes upon addition of various metal ions (5.0 eq.) to CFHC in CH3CN/H2O (90:10, v/v) under UV excitation (365 nm)
Based on the characteristics of a nitro-group, which can be partially or totally reduced to an amino-group in hypoxic cells,
two series of hypoxic sensors containing 7H-Benzimidazole [2,1-a]benz[de]isoquinolin-7-one cores with nitro groups in different
positions were designed, synthesized and evaluated. The target compounds exhibited significantly different fluorescence characteristics
(fluorescence enhancement or quenching). The strong fluorescences of some partially reduced compounds could be explained through
the examination of their infrared spectra, which showed a restriction of the nitro-group vibration. These compounds exhibited
significant hypoxic–oxic fluorescence differences not only in numerical values but also in their fluorescent imaging properties
as reported for the first time.
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A series of MZr4(PO4)6:Dy3+ (M = Ca, Sr, Ba) phosphors were prepared by the solid state diffusion method. Confirmation of the phase formation and morphological studies were performed by X-ray powder diffraction (XRD) measurements and scanning electron microscopy, respectively. Photoluminescence (PL) properties of these phosphors were thoroughly analyzed and the characteristic emissions of Dy3+ ions were found to arise from them at an excitation wavelength of 351 nm. The PL emission spectra of the three phosphors were analyzed and compared. The CIE chromaticity coordinates assured that the phosphors produced cool white-light emission and hence, they are potential candidates for UV excited white-LEDs (WLEDs).
New substituted thieno[3,2-c]pyridine derivatives 5 were synthesized by the reaction of 3-bromo-4-chlorothieno[3,2-c]pyridine 1 with cyclic amine 2, which further on Suzuki reaction with boronic acids 4 converted to corresponding 3-arylthieno[3,2-c]pyridine 5. Substituent R3 has predominant effect on fluorescence properties of thienopyridines. However, the electron donor amine at C4 has no effect on fluorescence properties of thienopyridines.
Graphical Abstract New thieno[3,2-c]pyridine derivatives were synthesized from 3-bromo-4-chlorothieno[3,2-c]pyridine and cyclic amines, which by on Suzuki reaction with boronic acids converted to corresponding 3-arylthieno[3,2-c]pyridine. Substituent R3 has predominant effect on fluorescence properties of thienopyridines. However, the electron donor amine at C4 has no effect on fluorescence properties of thienopyridines
