Co/Co‐N nanoparticles incorporated nitrogen‐doped nanoporous carbon (Co/Co‐N@NPC) nanostructures were fabricated via pyrolysis of metal organic framework, ZIF‐67, under argon atmosphere. The ZIF‐67 derived Co/Co‐N@NPC modified carbon paste electrode exhibited excellent performance during electroanalysis of dopamine, displaying two linear ranges; 10 nM to 50 μM, and 50 μM–500 μM with sensitivity of 12.4±0.3 μA/μM/cm2 and11.69±0.06 μA/μM/cm2, respectively. The modified electrodes were observed to be highly selective towards dopamine even in presence of other interfering biomolecules such as ascorbic acid, glucose and uric acid. To the best of our knowledge, the sensing ability of Co/Co‐N@NPC with a lower limit of detection as 6 nM is the best compared to the previously reported cobalt mediated sensors for dopamine. Practical feasibility of the sensor was demonstrated in real sample analysis of dopamine measurement in human urine samples and dopamine hydrochloride injection samples.
Homo‐ and heteroleptic palladium(II) complexes of thiazoline derived ligand were synthesized and their catalytic application was reported. The reactions of [1‐(C3H4NS)‐2‐OH‐C6H4] (2) with PdCl2 and [(1‐(CH3)2NCH2C6H4)PdCl]2 in 2:1 molar ratios afforded the homoleptic palladium complex, [Pd{κ12, κ12‐N,O‐(1‐(C3H4NS)‐2‐O‐C6H4)2}] (3) and the heteroleptic palladium complex [{κ12‐N,O‐(1‐(C3H4NS)‐2‐O‐C6H4)}Pd{(κ22‐N,C‐(1‐(CH3)2NCH2C6H4)}] (4) respectively. Equimolar reactions of 2 with PdCl2 and 8‐quinolinol or 2‐methyl‐8‐quinolinol under reflux condition produced the heteroleptic palladium complexes [{κ12‐N,O‐(1‐(C3H4NS)‐2‐O‐C6H4)}Pd{(κ22‐N,O‐(8‐O‐C9H6‐1‐N)}] (5) or [{κ12‐N,O‐(1‐(C3H4NS)‐2‐O‐C6H4)}Pd{(κ22‐N,O‐(8‐O‐2‐CH3‐C9H5‐1‐N)}] (6) in good yields. The molecular structures of ligand 2 and palladium complexes 3–6 were confirmed through multinuclear NMR spectroscopic techniques and further the crystal structure for palladium complexes 3 and 4 were established. Under the optimized reaction condition, the heteroleptic palladium complex 4 display an excellent catalytic activity with a maximum turn over frequency of 49.5 h−1 for the conversion of bi‐aryls from aryl halides and unactivated phenylhydrazine. The energies, activation barriers and transition state structures of reaction involved in the catalytic cycle were assessed by utilizing quantum chemical method to confirm Csp2‐Csp2 bond formation reaction catalyzed by heteroleptic palladium complex 4.
Thiazoline functionalized periodic mesoporous organosilica (TPMO) supported palladium nanoparticles (Pd-TPMO) were fabricated through a co-condensation approach and successive incorporation of palladium nanoparticles using a doublesolvent technique. The TPMO and Pd-TPMO were characterized through 29 Si MAS NMR, FTIR, SAXS, XPS, FESEM, TEM and N 2 adsorption-desorption, which revealed the morphological and physicochemical properties of the materials. The catalytic performance of Pd-TPMO was evaluated for hydrogenation of industrially important compounds and C sp 2 À C sp 2 bond-formation reactions. The Pd-TPMO mediated catalytic reactions were found to be effective in producing the corresponding products with excellent yields and selectivity. The size and stability of palladium nanoparticles within the confined organosilica framework promotes excellent activity and recyclability of the catalyst without a significant loss in the yields for hydrogenation and C sp 2 À C sp 2 bond-formation reactions.[a] Dr.
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