Pyrazoline-Based Fluorescent Probe: Synthesis, Characterization, Theoretical Simulation, and Detection of Picric Acid.

2-Pyrazoline containing benzothiazole ring 2-[1-(1,3-benzothiazol-2-yl)-5-(4-methoxyphenyl)-4,5-dihydro-1H-pyrazol-3-yl]phenol (BP) have been synthesized for the effective identification of picric acid over other competing nitro compounds using fluorescence technique. The pyrazoline BP showed quenching efficiency as high as 82% comparative to other nitro aromatics. The limit of detection and limit of quantification were found to be 1.1 µM and 3.3 µM. The possible mechanism with the quenched PA detection efficiency was based on fluorescence energy transfer and photoinduced electron transfer. Moreover, the observed results were supported by the optimized structures of the compounds using the DFT/B3LYP/6-311G/LanL2DZ method. Eventually, the pyrazoline derivative BP was further utilized for natural water samples, showing recoveries in the 87.62-101.09% and RSD was less than 3%.

Schiff base-functionalized metal-organic frameworks as an efficient adsorbent for the decontamination of heavy metal ions in water.

Adsorptive removal of heavy metal ions from water is an energy- and cost-effective water decontamination technology. Schiff base functionalities can be incorporated into the pore cages of metal-organic frameworks (MOFs) via direct synthesis, post-synthetic modification, and composite formation. Such incorporation can efficiently enhance the interactions between the MOF adsorbent and target heavy metal ions to promote the selective adsorption of the latter. Accordingly, Schiff base-functionalized MOFs have great potential to selectively remove a particular metal ion from the aqueous solutions in the presence of coexisting (interfering) metal ions through the binding sites within their pore cages. Schiff base-functionalized MOFs can bind divalent metal ions (e.g., Pb(II), Co(II), Cu(II), Cd (II), and Hg (II)) more strongly than trivalent metal ions (e.g., Cr(III)). The adsorption capacity range of Schiff base-functionalized MOFs for divalent ions is thus much more broad (22.4-713 mg g-1) than that of trivalent metal ions (118-127 mg g-1). To evaluate the adsorption performance between different adsorbents, the two parameters (i.e., adsorption capacity and partition coefficient (PC)) are derived and used for comparison. Further, the possible interactions between the Schiff base sites and the target heavy metal ions are discussed to help understand the associated removal mechanisms. This review delivers actionable knowledge for developing Schiff-base functionalized MOFs toward the adsorptive removal of heavy metal ions in water in line with their performance evaluation and associated removal mechanisms. Finally, this review highlights the challenges and forthcoming research and development needs of Schiff base-functionalized MOFs for diverse fields of operations.

Schiff Base-functionalized Metal-organic Frameworks for Selective Sensing of Chromate and Dichromate in Water.

In this research, Zn- or Cd-based metal-organic frameworks (coded ZnMOF-1 and CdMOF-1) containing benzene-1,4-dicarboxylic acid (H2bdc) and pyridyl-based Schiff base (4-pyridylcarboxaldehydeisonicotinoylhydrazone (L)) dual ligands were successfully assembled via a conventional solvothermal method. The photoluminescence quenching response of ZnMOF-1 and CdMOF-1 and their sensing sensitivity and selectivity towards various inorganic anions were evaluated in aqueous media. Crystallographic and thermogravimetric studies confirm the formation of both MOFs with good crystallinity and thermal stability. Photoluminescence studies also verify the selectivity of ZnMOF-1 and CdMOF-1 for efficient sensing of inorganic oxyanions (like chromate/dichromate: CrO42- and Cr2O72-). Further, it was noted that only chromate/dichromate (CrO42-/Cr2O72-) anions showed a significant turn-off quenching effect while other anions (like F-, Br-, I-, Cl-, ClO4-, SCN-, SO42-, NO3-, and NO2-) have a low/negligible effect on the photoluminescence intensity of both MOFs. The limit of detection (LOD) of chromate/dichromate by ZnMOF-1 and CdMOF-1 was 9.79/10.94 µM and 2.68/1.48 µM, respectively. A probable mechanism for turn-off quenching response towards chromate and dichromate anions could be attributed to the spectral overlap of both excitation and emission spectra of ZnMOF-1/CdMOF-1 with the absorption spectra of chromate/dichromate anions. As a result, the energy transfer from ZnMOF-1 or CdMOF-1 to the target chromate and dichromate anions decreased fluorescence intensity (i.e., fluorescence quenching effect).

A Luminescent Cu(II)-MOF with Lewis Basic Schiff Base Sites for the Highly Selective and Sensitive Detection of Fe3+ Ions and Nitrobenzene.

A Schiff base functionalized Cu(II)-based metal-organic framework (MOF) denoted as Cu-L, was developed via a solvothermal method using low-cost starting material, i.e., Schiff base linker, 4,4'-(hydrazine-1,2-diylidenedimethylylidene)dibenzoic acid (L). Good crystallinity and thermal stability of synthesized Cu-L was confirmed by the crystallographic and thermogravimetric studies. An excellent photoluminescent properties of Cu-L ensure their suitability for the ultrafast detection of Fe3+ ions and nitrobenzene via a turn-off quenching response. The remarkable sensitivity of Cu-L towards Fe3+ ions and nitrobenzene was certified by the low limit of detection (LOD) of 47 ppb and 0.004 ppm, respectively. With incorporated free azine groups, this MOF could selectively capture Fe3+ ions and nitrobenzene in aqueous solution. The plausible mechanistic pathway for the quenching in the fluorescence intensity of the Cu-L in the presence of Fe3+ ions and nitrobenzene have been explained in detail through the density functional theory calculations, photo-induced electron transfer (PET), fluorescence resonance energy transfer (FRET), and competitive energy adsorption. This present study open a new avenue to synthesize novel crystalline MOF-based sensing materials from cheap Schiff base linkers for fast sensing of toxic pollutants.

Amine/hydrazone functionalized Cd(II)/Zn(II) metal-organic framework for ultrafast sensitive detection of hazardous 2,4,6-trinitrophenol in water.

Amine/hydrazone functionalized dual ligand Cd(II)/Zn(II) based metal-organic frameworks (MOFs) denoted as CdMOF- and ZnMOF-NH2, respectively were synthesized via a simple conventional high-yield reflux method using low-cost and readily available starting materials, i.e., a Schiff base linker, 4-pyridylcarboxaldehydeisonicotinoylhydrazone (L1) and 2-aminoterephthalic acid (H2ata) linker. Crystallographic and thermogravimetric studies confirmed the formation of MOFs with good crystallinity and thermal stability. Photoluminescence studies point out that both MOFs can be used efficiently for fast sensing of 2,4,6-trinitrophenol (TNP) in water with noticeable turn-off quenching response. Their limits of detection (LODs) for TNP were 7 ppb and 10 ppb, respectively with enhanced selectivity toward TNP (over other nitro explosives) as verified by competitive nitro explosive tests. Density functional theory calculations and spectral overlap were used to assess the sensing mechanism. These MOF-based fluorescent sensing systems for TNP are demonstrated to have easy recoverability and high sensitivity.

Fluorescence "Turn-off" Sensing of Iron (III) Ions Utilizing Pyrazoline Based Sensor: Experimental and Computational Study.

A simple pyrazoline-based ''turn off'' fluorescent sensor 5-(4-methoxyphenyl)-3-(5-methylfuran-2-yl)-1-phenyl-4,5-dihydro-1H-pyrazole (PFM) was synthesized and well characterized by different techniques such as FT-IR, 1H-NMR, 13C-NMR, and mass spectrometry. The synthesized sensor PFM was utilized for the detection of Fe3+ ions. Fluorescence emission selectively quenched by Fe3+ ions compared to other metal ions (Mn2+, Al3+, Fe2+, Hg2+, Cu2+, Co2+, Ni2+, Cd2+, Pb2+, and Zn2+) via paramagnetic fluorescence quenching and showed good anti-interference ability over the existence of other tested metals. Under optimum conditions, the fluorescence intensity of sensor quenched by Fe3+ in the range of 0 to 3 µM with detection limit of 0.12 µM. Binding of Fe3+ ions to PFM solution were studied by fluorescent titration, revealed formation of 1:1 PFM-Fe metal complex and binding constant of complex was found to be of 1.3 × 105 M-1. Further, the fluorescent sensor has been potentially used for the detection of Fe3+ in environmental samples (river water, tap water, and sewage waste water) with satisfactory recovery values of 99-101%.

Experimental and Theoretical Studies of the Pyrazoline Derivative 5-(4-methylphenyl)-3-(5-methylfuran-2-yl)-1-phenyl-4,5-dihydro-1H-Pyrazole and its Application for Selective Detection of Cd2+ ion as Fluorescent Sensor.

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.

Bis-dihydroisoxazolines: Synthesis, Structural Elucidation, Antimicrobial Evaluation, and DNA Photocleavage Assay.

AIM AND OBJECTIVE: Isoxazole is an active core found in many drugs. The aim of this work was to synthesize bis-isoxazoline compounds and to analyze the effect of linker chain length on biological activities. MATERIAL AND METHODS: A simple, convenient, and efficient method for the conversion of bischalcones to new bis(4,5-dihydroisoxazole) derivatives was developed by using hydroxylamine hydrochloride under basic medium. Synthesized moieties were also evaluated for their antimicrobial potencies and DNA photocleavage assay. RESULTS AND DISCUSSION: The synthesized compounds were more active than their chalcone precursors and the long-chain linkers (4e&4f) were more potent in antimicrobial, as well as in DNA photocleavage activity. CONCLUSION: It was found that many of the tested bischalcones and bis-isoxazolines exhibited moderate to significant antimicrobial activity against various strains. Furthermore, the present study also provides significant information and interesting outcomes regarding cyclization, increasing the length of linker chains, and their effects on the DNA photocleavage and antimicrobial activities.

New 1,3,4-bisthiadiazolines: synthesis, characterization and antimicrobial evaluations.

The bisthiadiazolines 4a-4g have been synthesized in good yields from the cyclization reactions of bisthiosemicarbazones 3a-3g with acetic anhydride. The condensation reaction of dibenzaldehydes 2a-2g with thiosemicarbazide in alcoholic medium provided 3a-3g and former were obtained from the O-alkylation of 3-hydroxybenzaldehyde with suitable 1,ω-dibromoalkanes under alkaline conditions in the presence of dry EtOH/DMF. The intermediates 3a-3g and bishetrocyclics 4a-4g were also screened for their in vitro antimicrobial activities against seven bacterial strains (Klubsellia pneumoniae, Pseudomonas aeruginosa, Escherichia coli, Straphylococcus aureus, Bacillius subtilis, Pseudomonas fluorescens and Streptoccus pyrogens) and five fungi strains (Aspergillius janus, Pencillium glabrum, Fusarium oxysporum, Aspergillus sclerotiorum, Aspergillus niger). The compounds 3f, 3g, 4f &4g were found to be significantly active against the tested microorganisms.

Photoinduced synthesis of new diisochromenochromen-4-ones and their antimicrobial activities.

The diisochromenochromen-4-one 3a-3b, 4a-4c, 5a-6a & 7 have been prepared from the photocyclization reaction of bischromen-4-one 2a-2e. The later compounds are obtained from the O-alkylation of the suitable 3-hydroxy-2-aryl-4H-chromen-4-one 1a-1e with 4,4'-bischloromethyl-diphenyl in dry acetone, anhydrous K2CO3, and PTC (Bu4N⁺I⁻) under refluxing conditions. The structures of compounds 2a-2e, 3a-3b, 4a-4c, 5a-6a & 7 have been characterized from the rigorous analysis of their IR, ¹H-NMR, ¹³C-NMR, ESI-Mass, and elemental analysis. The antibacterial and antifungal activities of the synthesized products were also evaluated against the Klebsiella pneumoniae, Pseudomonas aeruginosa, Escherichia coli, Staphylococcus aureus, Bacillus subtilis, and Aspergillus janus and Penicillium glabrum, respectively. Some of the tested compounds showed significant activity against the above-said microorganisms.

Synthesis, characterization and antimicrobial studies of new bispyrazolines linked via 3-aryl ring with aliphatic chains.

The bispyrazolines 4a(a'-f') and 4b(a'-f') built around the aliphatic chains of varying lengths have been prepared by refluxing bischalcones 3a(a'-f') and 3b(a'-f') with phenyl hydrazine in alcoholic medium. The reactions of chalcones 2a and 2b with suitable 1,ω-dibromoalkanes in the presence of anhydrous K(2)CO(3)/dry acetone and Bu(4)N(+)I(-) (PTC) provided 3a(a'-f') and 3b(a'-f'), respectively. The antibacterial and antifungal activities of the synthesized compounds were evaluated against five bacterial and four fungal strains. The compounds 3ba', 3bc', 3bd', 3be', 3af', 4aa' and 4ba' showed better MIC (µg/mL) against the tested microorganisms.

Synthesis, spectral studies and in vitro antibacterial activity of steroidal thiosemicarbazone and their palladium (Pd (II)) complexes.

We investigated the antibacterial activity of some new steroidal thiosemicarbazone and their Pd(II) metal complexes. Metal complexes were prepared from the reaction of steroidal thiosemicarbazone with [Pd(DMSO)(2)Cl(2)]. Coordination via the thionic sulphur and the azomethine nitrogen atom of the thiosemicarbazone to the metal ion, the thiosemicarbazone derivatives were obtained by the thiosemicarbazide with steroidal ketones. All the compounds have been confirmed by spectral data. The antibacterial activity of these compounds was first tested in vitro by the disk diffusion assay against two gram-positive and two gram-negative bacteria, and then the minimum inhibitory concentration (MIC) was determined. The results showed that steroidal complexes are better inhibit growth as compared to steroidal thiosemicarbazones of both types of the bacteria (gram-positive and gram-negative); compound Ia is better antibacterial agent as compared to amoxicillin.