Ruthenium (II) Catalyzed C(sp2)−H Bond Alkenylation of 2-Arylbenzo[d]oxazole and 2-Arylbenzo[d]thiazole with Unactivated Olefins

Functionalization of the bio-relevant heterocycles 2-arylbenzo[d]oxazole and 2-arylbenzo[d]thiazole has been achieved through Ru(II)-catalyzed alkenylation with unactivated olefins leading to selective formation of the mono-alkenylated products. This approach has a broad substrate scope with respect to the coupling partners, affords high yields, and works for gram scale synthesis using a readily available Ru-based catalyst. Mechanistic studies reveal a C−H activation pathway for the dehydrogenative coupling leading to the alkenylation. However, the results of the ESI-MS-guided deuterium kinetic isotope effect studies indicate that the C−H activation stage may not be the rate-determining step of the reaction. The use of a radical scavenging agent such as TEMPO did not show any detrimental effect on the reaction outcome, eliminating the possibility of the involvement of a free-radical pathway.     

Dye sensitization of a large band gap semiconductor by an iron(III) complex

The Fe(III) complex, [Fe^III(HQS)₃] (HQS = 8-hydroxyquinoline-5-sulfonic acid), is found to effect sensitization of the large band gap semiconductor, TiO₂. The role of interfacial electron transfer in sensitization of TiO₂ nanoparticles by surface adsorbed [Fe^III(HQS)₃] was studied using femtosecond time scale transient absorption spectroscopy. Electron injection has been confirmed by direct detection of the electron in the conduction band. A TiO₂-based dye-sensitized solar cell (DSSC) was fabricated using [Fe^III(HQS)₃] as a sensitizer, and the resulting DSSC exhibited an open-circuit voltage value of 425 mV. The value of the short-circuit photocurrent was found to be 2.5 mA/cm². The solar to electric power conversion efficiency of the [Fe^III(HQS)₃] sensitized TiO₂-based DSSC device was 0.75 %. The results are discussed in the context of sensitization of TiO₂ by other Fe(II)-dye complexes.     

A review on sources,toxicity and remediation technologies for removing arsenic from drinking water

Arsenic is a natural element found in the environment in organic and inorganic forms. The inorganic form is much more toxic and is found in ground water, surface water and many foods. This form is responsible for many adverse health effects like cancer (skin, lung, liver, kidney and bladder mainly), and cardiovascular and neurological effects. The estimated number of people in Bangladesh in 1998 exposed to arsenic concentrations above 0.05 mg/l is 28–35 million, and the number of those exposed to more than 0.01 mg/l is 46–57 million. The estimated number of people in West Bengal, India (the border province to Bangladesh), in 1997 actually using arsenic-rich water is more than 1 million for concentrations above 0.05 mg/l and is 1.3 million for concentrations above 0.01 mg/l. The United States Environmental Protection Agency (USEPA) has estimated that 13 million of the US population are exposed to arsenic in drinking water at 0.01 mg/l. The situation has prevailed for more than 10 years and is more severe now. The USEPA lowered the maximum contaminant level (MCL) for drinking water arsenic from 50 to 10 μg/l in 2001 based on international data analysis and research. This recommendation is now on hold. The level of 10 ppb become standard in the European Union (EU) in 2001. Arsenic may be found in water flowing through arsenic-rich rocks. The source is diverse. These include the earth's crust, introduced into water through the dissociation of minerals and ores, industrial effluents to water, combustion of fossil fuels and seafoods. Arsenic-removal methods are coagulation (ferric sulfate, ferrous sulfate, ferric chloride, aluminum sulfate, copper sulfate, and calcium hydroxide as coagulants), adsorption (activated carbon, activated alumina, activated bauxite) ion exchange, bio-sorption, etc.     

para-Selective Arylation of Arenes: A Direct Route to Biaryls by Norbornene Relay Palladation

Biaryl compounds are extremely important structural motifs in natural products, biologically active components and pharmaceuticals. Selective synthesis of biaryls by distinguishing the subtle reactivity difference of distal arene C−H bonds are significantly challenging. Herein, we describe para-selective C−H arylation, which is acheived by a unique combination of a meta-directing group and norbornene as a transient mediator. Upon direct meta-C−H palladation, one-bond relay palladation occurs in presence of norbornene and subsequently para-C−H arylation is achieved for sulfonates, phosphonates and phenols bearing 2,6-disubstitution patterns. The protocol is amenable to electron-deficient aryl iodides. Multisubstituted arenes and phenols are obtained by postsynthetic modification of the products. The protocol allows the synthesis of hexa-substituted benzene by sequential selective distal C−H functionalization.     

Coherence transfer delay optimisation in PSYCOSY experiments

PSYCOSY is an f1 broadband homonuclear decoupled version of the COSY nuclear magnetic resonance pulse sequence. Here, we investigate by a combination of experimental measurements, spatially distributed spin dynamics simulations, and analytical predictions the coherence evolution delay necessary in PSYCOSY experiments to ensure intensity discrimination in favour of the correlations typically arising from short range (ⁿJ, n ≤ 3) ¹H–¹H couplings and show that, in general, a coherence evolution delay of around 35 ms is optimum.     

Thermal conductivity of deep eutectic solvents

Journal of Thermal Analysis and Calorimetry - We have reported the thermal conductivities of three deep eutectic solvents (DESs). We have used choline chloride, N,N-diethyl ethanol ammonium...     

Effect of Controlled Deposition of ZnS Shell on the Photostability of CdTe Quantum Dots as Studied by Conventional Fluorescence and FCS Techniques

The effect of one and two monolayers of ZnS shells on the photostability of CdTe quantum dots (QDs) in aqueous and nonaqueous media has been studied by monitoring the fluorescence behavior of the QDs under ensemble and single‐molecule conditions. ZnS capping of the CdTe QDs leads to significant enhancement of the fluorescence brightness of these QDs. Considerable enhancement of the photostability of the shell‐protected QDs, including the suppression of photoactivation, is also observed. Fluorescence correlation spectroscopy measurements reveal an increase in the number of particles undergoing reversible fluorescent on–off transitions in the volume under observation with increasing excitation power; this effect is found to be more pronounced in the case of core‐only QDs than for core–shell QDs.     

Oxidation of Ru(III)‐Bound Thiocyanate with Peroxomonosulfate: Kinetic and Mechanistic Studies

The reaction of [Ru^III(edta)(SCN)]^2? (edta^4? = ethylenediaminetetraacetate; SCN^? = thiocyanate ion) with the peroxomonosulfate ion (HSO₅^?) has been studied by using stopped‐flow and rapid scan spectrophotometry as a function of [Ru^III(edta)], [HSO₅^?], and temperature (15–30ºC) at constant pH 6.2 (phosphate buffer). Spectral analyses and kinetic data are suggestive of a pathway in which HSO₅^? effects the oxidation of the coordinated SCN^? by its direct attack at the S‐atom (of SCN^?) coordinated to the Ru^III(edta). The high negative value of entropy of activation (ΔS^≠ = ?90 ± 6 J mol^?1 deg^?1) is consistent with the values reported for the oxygen atom transfer process involving heterolytic cleavage of the O‐O bond in HSO₅^?. Formation of SO₄^2?, SO₃^2?, and OCN^? was identified as oxidation products in ESI‐MS experiments. A detailed mechanism in agreement with the spectral and kinetic data is presented.     

Polar effects in nitride coupling reactions

The nucleophilic molybdenum nitride (Et(2)NCS(2))(3)MoN (1) reacts with the electrophilic osmium nitride complex TpOsNCl(2) (2, Tp = hydrotris(1-pyrazolyl)borate) to produce molecular nitrogen. Reaction of 1 at the nitride is accompanied by a substantial amount of reaction at a sulfur atom of the dithiocarbamate ligand, forming the osmium thionitrosyl complex TpOs(NS)Cl(2) (4). Labeling experiments establish that the N(2) produced comes specifically (>96%) from mixed-metal (molybdenum-osmium) coupling. The major transition-metal-containing product of the reaction is the mu-nitrido complex TpOsCl(2)(mu-N)Mo(S(2)CNEt(2))(3) (3), where the bridging nitride derives primarily (82%) from the osmium nitride 2. The mu-nitrido complex 3 has been characterized crystallographically, and shows a nitride bridge that is very asymmetric (Mo-N = 1.721(3) A, Os-N = 1.906(3) A), with less multiple bonding toward osmium and more toward molybdenum. Heterometallic coupling is much faster than either homometallic coupling reaction, in particular the osmium-osmium coupling, despite the greater oxidizing power of osmium over molybdenum. The origin and implications of this kinetic effect on nitride coupling and dinitrogen cleavage are discussed.