Koushik Dhara

A new functionalized mesoporous matrix supported Pd(II)-Schiff base complex: an efficient catalyst for the Suzuki-Miyaura coupling reaction.

A new Pd(II) bounded 2D-hexagonally ordered functionalized MCM-41 type material (IV) has been synthesized. Functionalization was carried out by the anchoring of 3-aminopropyltriethoxysilane in the MCM-41 type mesoporous material, followed by grafting with 2,6-diacetylpyridine (DAP) to give a N3-type Schiff base chelating attachment for the Pd(II) species. Fourier transform infrared (FTIR), powder X-ray diffraction (PXRD) and high resolution transmission electron microscopy (HRTEM) studies have been used to characterize the material. Material IV behaves as a highly active catalyst towards Suzuki-Miyaura cross-coupling reaction for the synthesis of biaryl organics. In addition, IV acts as a true heterogeneous catalyst in coupling reaction. It was found that this catalyst is highly efficient and recyclable towards Suzuki-Miyaura reaction with high turn over frequencies. X-Ray photoelectron spectroscopic (XPS) analysis was employed to understand the oxidation state of the palladium atom in the catalyst (IV) and its loading in the material.

A New Half-Condensed Schiff Base Compound: Highly Selective and Sensitive pH-Responsive Fluorescent Sensor

A new probe, 3-[(3-benzyloxypyridin-2-ylimino)methyl]-2-hydroxy-5-methylbenzaldehyde (1-H) behaves as a highly selective fluorescent pH sensor in a Britton-Robinson buffer at 25 °C. The pH titrations show a 250-fold increase in fluorescence intensity within the pH range of 4.2 to 8.3 with a pK(a) value of 6.63 which is valuable for studying many of the biological organelles.

A highly selective fluorescent chemosensor for zinc ion and imaging application in living cells.

A new 2,6-bis(5,6-dihydrobenzo[4,5]imidazo[1,2-c]quinazolin-6-yl)-4-methylphenol (1) serves as a highly selective and sensitive fluorescent probe for Zn(2+) in a HEPES buffer (50 mM, DMSO:water = 1:9 (v/v), pH = 7.2) at 25 °C. The increase in fluorescence in the presence of Zn(2+) is accounted for by the formation of dinuclear Zn(2+) complex [Zn(2)(C(35)H(25)N(6)O)(OH)(NO(3))(2)(H(2)O)] (2), characterized by X-ray crystallography. The fluorescence quantum yield of the chemosensor 1 is only 0.019, and it increases more than 12-fold (0.237) in the presence of 2 equiv of the zinc ion. Interestingly, the introduction of other metal ions causes the fluorescence intensity to be either unchanged or weakened. By incubation of cultured living cells (A375 and HT-29) with the chemosensor 1, intracellular Zn(2+) concentrations could be monitored through selective fluorescence chemosensing.

Crystal engineering of zinc(II) metal–organic frameworks: role of steric bulk and angular disposition of coordinating sites of the ligands

Three novel 2D and 3D coordination polymers, [Zn(TPA)(H2MDP)]n (1), [Zn(IPA)(H2MDP)]n (2) and [Zn(HTMA)(H2MDP)]n (3) (H2MDP = methylenebis(3,5-dimethylpyrazole), H2TPA = terephthalic acid, H2IPA = isophthalic acid and H3TMA = trimesic acid), have been synthesized under hydrothermal conditions and structurally characterized by single crystal X-ray diffraction. For all three structures, the zinc atoms show a coordination number of four and adopt tetrahedral geometry, and subsequently form a diamondoid, a (2,4) and a (4,4) network. The employment of sterically hindered H2MDP ligand, on the other hand, successfully prohibits interpenetration among the 2D grids. The complex 1 features a metal–organic framework exhibiting a three-fold interpenetrated diamondoid network with linear dicarboxylate ligand (H2TPA) as an auxiliary ligand. The bent dicarboxylate ligands (H2IPA and H3TMA), on the other hand, lead to 2D non interpenetrative grid networks for 2 and 3. A comparative study of 2 and 3 underpins the importance of the hydrogen bond and π–π interaction in the synthesis of coordination polymers.

A water soluble FRET-based ratiometric chemosensor for Hg(II) and S2− applicable in living cell staining

A new highly sensitive and selective Hg(II) probe, 2-(rhodamine-b-hydrazido)-N-(quinolin-8-yl)acetamide (L1) was developed and characterized. L1 specifically binds to Hg(II) in the presence of a large excess of other competing ions with visually observable changes in both electronic and fluorescence spectral behaviour to make possible the naked eye detection of Hg(II) at a very low level (up to 4.5 × 10−7 M) through a fluorescence resonance energy transfer (FRET) process in HEPES buffer (1 mM, pH 7.4; 2% EtOH) at 25 °C. The theoretical and experimental kinetic study also support the binding of Hg(II) ion to induce the opening of the spirolactam ring in L1 for enabling the FRET process. Further studies reveal that the selective dissociation of the L–Hg complex in the presence of sulphide anions to restore the native structure of L1 is also useful in the detection of sulfide anions with a detection limit of a submicromolar range in the same medium of HEPES buffer (1 mM, pH 7.4; 2% EtOH) at 25 °C. L1 could be employed as a FRET based time dependent reversible chemosensor for imaging Hg(II) in living cells and whole bodies, and also could be used as an imaging probe for the detection of sulfide anions in HeLa cells.

Attenuated Leishmanial sphingolipid induces apoptosis in A375 human melanoma cell via both caspase-dependent and -independent pathways

A fraction of attenuated Leishmanial lipid (ALL) rich in sphingolipids, previously shown to have apoptosis inducing activity in mouse melanoma (B16F10) and human melanoma (A375) cells, was resolved to isolate the bioactive sphingolipid. The mechanism of apoptosis induction by this bioactive attenuated Leishmanial sphingolipid (ALSL) was studied in A375 cells. Apoptosis induced by ALSL in A375 cells was found to be dose and time-dependent. Exposure of cells to ALSL resulted in a rapid increase in reactive oxygen species generation. Pretreatment of cells with the antioxidant N-acetyl-cystein reduced ROS generation and attenuated apoptosis induced by ALSL. Again, ALSL sensitization resulted in the activation of caspase-3 and -9 but not caspase-8. However, inhibitors of these caspases could not protect the cells completely from ALSL-induced apoptosis. N-acetyl-cystein pretreatment was again found to attenuate the activation of caspase-3 and -9. ALSL treatment also resulted in the alteration of mitochondrial membrane potential, and release of pro-apoptotic factors such as cytochrome c and apoptosis inducing factor (AIF) from mitochondria. Furthermore, c-Jun N-terminal kinase was activated that resulted in apoptosis of A375 cells, whereas p38 MAPK was activated to counteract the stress generated in cells in response to ALSL treatment. Taken together, our results indicate that ALSL-induced apoptosis of A375 cells is mediated by both mitochondrial caspase-dependent and -independent pathways and it involves ROS and JNK activation in the mitogen-activated protein kinase cascade.

Nanowires of metal-organic complex by photocrystallization: a system to achieve addressable electrically bistable devices and memory elements.

A new method has been achieved to form a Cu:benzoquinone derivative (DDQ) charge-transfer complex by the photoexcitation of [Cu(DDQ)2(CH 3COO)2] ( 1) that has been synthesized by the reaction of DDQ and hydrated cupric acetate in acetonitrile. Photoexcitation of coordinated complex 1 leads to the formation of charge-transfer complex Cu2+(DDQ(.-)2 ( 2). The charge transfer complex 2, when spun on solid substrates, forms nanowires. Sandwich structures of 2 exhibit electrical bistability associated with memory phenomenon. Read-only and random-access memory phenomena are evidenced in nanowires of 2 providing a route to attend the issues pertaining to the addressibility of organic memory devices.

A naphthalimide-based fluorescence ‘‘turn-on’’ chemosensor for highly selective detection of carbon monoxide: imaging applications in living cells

A naphthalimide-based fluorescence chemosensor, COFP, was designed and synthesized for the detection of carbon monoxide (CO) in HEPES buffer (pH 7.4, 37 °C). The detection process is highly selective towards CO, over a variety of relevant reactive oxygen, nitrogen, and sulfur species. Also, the fluorescence response is not hampered in the presence of biologically relevant metal ions and/or species. The detection method was achieved through the transformation of the nitro group of COFP to an amino functionalized derivative in the presence of CO without using any heavy metals e.g. Pd, Rh, Ru etc. The chemosensor prompted a ‘turn-on’ fluorescence response to CO with a simultaneous increase of the fluorescence intensity by more than 33 times. The LOD (limit of detection) was calculated to be as low as 123 nM using the 3σ method. Moreover, the chemosensor is capable of monitoring the changes in intracellular CO in the C6 glioma cell line.

Highly Sensitive Ratiometric Chemosensor and Biomarker for Cyanide Ions in the Aqueous Medium

A newly designed cyanide-selective chemosensor based on chromone containing benzothiazole groups [3-(2,3-dihydro-benzothiazol-2-yl)-chromen-4-one (DBTC)] was synthesized and structurally characterized by physico-chemical, spectroscopic, and single-crystal X-ray diffraction analyses. The compound DBTC can detect cyanide anions based on nucleophilic addition as low as 5.76 nM in dimethyl sulfoxide–N-(2-hydroxyethyl)piperazine-N′-ethanesulfonic acid buffer (20 mM, pH 7.4) (v/v = 1:3). The binding mode between receptor DBTC and cyanide nucleophile has also been demonstrated by experimental studies using various spectroscopic tools and theoretical studies, and the experimental work has also been verified by characterizing one supporting compound of similar probable structure of the final product formed between DBTC and cyanide ion (DBTC–CN compound) by single-crystal X-ray analysis for detailed structural analyses. In theoretical study, density functional theory procedures have been used to calculate the molecular structure and the calculation of the Fukui function for evaluation of the electrophilic properties of each individual acceptor atom. Furthermore, the efficacy of the probe (DBTC) to detect the distribution of CN– ions in living cells has been checked by acquiring the fluorescence image using a confocal microscope. Notably, the paper strips with DBTC were prepared, and these could serve as efficient and suitable CN– test kits successfully.