Magnetite tethered mesoionic carbene‐palladium (II): An efficient and reusable nanomagnetic catalyst for Suzuki‐Miyaura and Mizoroki‐Heck cross‐coupling reactions in aqueous medium

In this paper, a highly active, air‐ and moisture‐stable and easily recoverable magnetic nanoparticles tethered mesoionic carbene palladium (II) complex (MNPs‐MIC‐Pd) as nanomagnetic catalyst was successfully synthesized by a simplistic multistep synthesis under aerobic conditions using commercially available inexpensive chemicals for the first time. The synthesized MNPs‐MIC‐Pd nanomagnetic catalyst was in‐depth characterized by numerous physicochemical techniques such as FT‐IR, ICP‐AES, FESEM, EDS, TEM, p‐XRD, XPS, TGA and BET surface area analysis. The prepared MNPs‐MIC‐Pd nanomagnetic catalyst was used to catalyze the Suzuki–Miyaura and Mizoroki–Heck cross‐coupling reactions and exhibited excellent catalytic activity for various substrates under mild reaction conditions. Moreover, MNPs‐MIC‐Pd nanomagnetic catalyst could be easily and rapidly recovered by applying an external magnet. The recovered MNPs‐MIC‐Pd nanomagnetic catalyst exhibited very good catalytic activity up to ten times in Suzuki–Miyaura and five times in Mizoroki–Heck cross‐coupling reactions without considerable loss of its catalytic activity. However, MNPs‐MIC‐Pd nanomagnetic catalyst shows notable advantages such as heterogeneous nature, efficient catalytic activity, mild reaction conditions, easy magnetic work up and recyclability.     

Palladium-catalyzed denitrogenative cross-coupling of aryl halides with arylhydrazines under mild reaction conditions

Transition Metal Chemistry - A greener approach for the synthesis of various functionalized biaryl frameworks in good to excellent yield through palladium-catalyzed denitrogenative cross-coupling...     

Design and synthesis of novel thiopheno-4-thiazolidinylindoles as potent antioxidant and antimicrobial agents

A novel and convenient synthesis of thiopheno-4-thiazolidinyl indole analogues is presented (IVa-IVi), with the aim of obtaining biologically active compounds. 3,5-disubstituted indol-2-carboxyhydrazides (Ia-If) were allowed to react with 3-acetyl-2,5-dichlorothiophene (II) to yield the corresponding 3,5-disubstituted indol-2-carbohydrazides (IIIa-IIIf). The pre-formed indolecarbohydrazides (IIIa-IIIf) were allowed to react with 2-mercaptoacetic acid or 2-mercaptopropanoic acid to produce thiopheno-4-thiazolidinylindoles (IVa-IVi). This reaction protocol affords a simple, eco-friendly, non-hazardous, easier preparation and high yields. The antioxidant (free radical scavenging, total antioxidant capacity and ferric-reducing antioxidant power) and antimicrobial activities of the synthesised compounds were evaluated. The structures and purity of the products were confirmed by their IR, ¹H NMR, ¹³C NMR and mass spectral and analytical data. Most of the compounds tested showed very significant scavenging, antioxidant and antimicrobial activities. Compounds containing electron donor group (CH₃) at the fifth position of indole exhibit an excellent ferric-reducing activity. The present study suggests that compounds IIIa-IIIb, IIIf, IVa-IVc, IVf-IVi, may serve as promising lead scaffolds for antioxidant and antimicrobial agents.     

Enantioselective formal total syntheses of Clavukerin A and isoclavukerin A via a ring-closing metathesis reaction

Enantioselective formal total syntheses of the marine trisnorsesquiterpenes clavukerin A and isoclavukerin A, starting from (R)-limonene employing an RCM reaction as the key step, are described.     

Chiral synthons from campholenaldehyde: enantiospecific synthesis of diquinane and linear triquinanes

Enantiospecific syntheses of diquinane and linear triquinanes were accomplished, starting from the readily available α-campholenaldehyde employing a Nazarov reaction as the key step.     

Direct numerical simulation of modulation of isotropic turbulence by poly‐dispersed particles

A direct numerical simulation technique based on two‐way coupling is presented to study a particle‐laden, decaying isotropic turbulent flow. Physical characteristics of turbulence modulation because of the mono‐dispersed (i.e., particles with single Stokes number) and poly‐dispersed particles (i.e., particles with more than one Stokes number) were investigated. A scale dependent effective viscosity that summarizes the aspects of the interaction between the velocity field and particles is defined in the study. Particles of Stokes number (St) 3.2,6.4 and 12.8 were used in performing the simulations. Poly‐dispersed particles were acquired by mixing particles of two different Stokes numbers at a time. As a whole, decay of turbulence because of the poly‐dispersed particles is observed to be larger than that of the decay of turbulence because of the mono‐dispersed particles. Simulations of poly‐dispersed particle indicate nonlinear characteristics in the modification of the temporal evolution of turbulence energy and dissipation. The scale dependent effective viscosity, which correlates with the energy spectrum plot, indicates that the decay of turbulence is mostly observed at the intermediate scales of turbulence. The effective viscosity for the simulations of the poly‐dispersed particles was calculated to be higher than that of the simulations of the mono‐dispersed particles. Copyright © 2011 John Wiley & Sons, Ltd.     

Differentiation of chronic obstructive pulmonary disease (COPD) including lung cancer from healthy control group by breath analysis using ion mobility spectrometry

Non-invasive methods with potential for diagnosis of lung diseases gain increasing interest. Within the present study the exhaled breath of 132 persons (97 Chronic obstructive pulmonary disease (COPD) patients [35 COPD without lung cancer, 62 COPD with lung cancer] and 35 healthy volunteers) was investigated using an Ion Mobility Spectrometer (IMS) coupled to a Multi-Capillary Column (MCC) without any pre-separation or pre-enrichment. One hundred four different peaks were considered within the IMS-Chromatograms of the 10 mL breath samples of both groups. A principal component analysis (PCA) of these 104 peaks identified a single analyte, that allowed a separation of the healthy persons and the COPD patients (with and without lung cancer). The sensitivity obtained was 60%, the specificity 91%, the positive predictive value 95%. The peak was characterized as cyclohexanone (CAS 108-94-1). Subsequent studies must validate the identity of the peak used for separation of the two groups with a greater population and external standards. Breath gas analysis using ion mobility spectrometry offers a chance of separating healthy persons and COPD patients using a single analyte at a defined concentration.     

Dynamic admission and service rate control of a queue

This paper investigates a queueing system in which the controller can perform admission and service rate control. In particular, we examine a single-server queueing system with Poisson arrivals and exponentially distributed services with adjustable rates. At each decision epoch the controller may adjust the service rate. Also, the controller can reject incoming customers as they arrive. The objective is to minimize long-run average costs which include: a holding cost, which is a non-decreasing function of the number of jobs in the system; a service rate cost c(x), representing the cost per unit time for servicing jobs at rate x; and a rejection cost κ for rejecting a single job. From basic principles, we derive a simple, efficient algorithm for computing the optimal policy. Our algorithm also provides an easily computable bound on the optimality gap at every step. Finally, we demonstrate that, in the class of stationary policies, deterministic stationary policies are optimal for this problem.     

An enantiospecific total synthesis of (−)-patchouli alcohol

An enantiospecific total synthesis of patchouli alcohol, starting from the readily available monoterpene (R)-carvone, has been accomplished. A tandem double Michael reaction–alkylation sequence and single electron mediated 6-endo trig cyclisation reaction have been employed as key steps.