Immobilization of copper ions onto α‐amidotriazole‐functionalized magnetic nanoparticles and their application in the synthesis of triazole derivatives in water

A new heterogeneous copper catalyst was synthesized by immobilization of copper ions onto magnetic nanoparticles with a new ligand based on triazole. The catalyst was characterized using scanning and transmission electron microscopies, atomic absorption and Fourier transform infrared spectroscopies, and thermogravimetric, elemental and energy‐dispersive X‐ray analyses. The results confirmed that a good level of organic groups was immobilized on the magnetic nanoparticles. Huisgen cycloaddition reaction was chosen as a model reaction for the investigation of catalyst activity under green conditions. Phenylacetylene and benzyl bromide derivatives were used for the synthesis of triazoles. The reaction proceeded with good to excellent yields for various alkynes and alkyl halides. To investigate catalyst activity for inactive alkynes, aliphatic alkynes were used in the model reaction. The corresponding triazoles were obtained in good to excellent yields and a high regioselectivity for products was obtained. The catalyst was easily separated using an external magnetic field and subsequently reused in ten reaction cycles without any loss of catalytic activity. Copyright © 2016 John Wiley & Sons, Ltd.     

Changes in the natural abundance of 13CO2/12CO2 in breath due to lipopolysacchride‐induced acute phase response

The natural abundance of carbon‐13 in blood proteins increases during the cachectic state and may be a biomarker for disease status. We hypothesized a corresponding drop in the relative abundance of ¹³C in breath CO₂. Using the lipopolysacchride (LPS)‐induced endotoxemia model of the acute cachectic state, we demonstrated that the acute phase response causes shifts in the stable isotopes of carbon in exhaled CO₂ (¹³CO₂/¹²CO₂ delta value) shortly after administration of LPS while glucocorticoid treatment does not. Mice were injected with LPS and stable isotopes of blood amino acids and carbon in exhaled CO₂ were monitored. An increase in the relative isotopic mass of serum alanine, proline and threonine was observed at 3 h after LPS injection. Breath delta values began dropping immediately after administration of LPS, and were 4–5 delta values lower than those of the control animals by 2.5 h after injection. A corresponding drop in delta value was not observed with dexamethasone treatment. Thus protein synthesis during the acute phase response probably caused the fractionation of stable isotopes observed in the plasma amino acids and in exhaled breath ¹³CO₂ delta values. The exhaled breath ¹³CO₂ delta value may be a valuable real‐time biomarker of cachexia associated with an acute phase response due to endotoxemia. Copyright © 2009 John Wiley & Sons, Ltd.     

A CONVENIENT METHOD FOR THE SYNTHESIS OF PHOSPHOROTHIOATES AND THEIR ANTICHOLINESTERASE ACTIVITIES

A simple, efficient, and general method has been developed for the synthesis of phosphorothioates through a one-pot reaction of alkyl halides with the mixture of diethyl phosphite in the presence of NH ₄ OAc/S/CaO under solvent–free conditions. The anticholinesterase activities of eight different phosphorothioates were investigated on acetylcholinesterase from electric eel.     

Aromatization of 1,4-Dihydropyridines Under Mild and Heterogeneous Conditions

A combination of Mg(HSO₄)₂ and NaNO₂ in the presence of wet SiO₂ was used as an effective oxidizing agent for the oxidation of dihydropyridines to their corresponding pyridine derivatives at room temperature with moderate to excellent yields.     

Quantitative evaluation of optimal imaging parameters for single-cell detection in MRI using simulation

Super-paramagnetic iron oxide (SPIO) nanoparticles are actively investigated to enhance disease detection through molecular imaging using magnetic resonance imaging (MRI). Detection of the cells labeled by SPIO depends on the MRI protocols and pulse sequence parameters that can be optimized. To evaluate the sensitivity and specificity of the image acquisition methods and to obtain optimal imaging parameters for single-cell detection, we further developed an MRI simulator. The simulator models an object (tissue) at a microscopic level to evaluate effects of spatial distribution and concentration of nanoparticles on the resulting image. In this study, the simulator was used to evaluate and compare imaging of the labeled cells by the gradient-echo (GE), true-FISP [fast imaging employing steady-state acquisition (FIESTA)] and echo-planar imaging (EPI) pulse sequences. Effects of the imaging and object parameters, such as field strength, imaging protocol and pulse sequence parameters, imaging resolution, cell iron load, position of SPIO within the voxel and cell division within the voxel, were investigated in the work. The results suggest that true-FISP has the highest sensitivity for single-cell detection by MRI.     

OH−/Silica-Mediated One-Pot Synthesis of Dithiocarbamates Under Solvent-Free Conditions

Abstract

An efficient, versatile, and environmentally benign method for the synthesis of dithiocarbamates under solvent-free conditions is reported. The Michael addition of electron-deficient alkenes with alkyl or aryl amines and CS₂ in the presence of OH^?/silica in a one-pot three-component reaction protocol gave the corresponding dithiocarbamates in good to excellent yields. This method is suitable for a wide range of amines and a variety of Michael acceptors in solvent-free conditions. The results of the present work show the desired products in excellent yields.     

Microextraction of Rosmarinic Acid Using CMK-3 Nanoporous Carbon in a Packed Syringe

CMK-3 nanoporous carbon was prepared and used as an efficient sorbent for microextraction in packed syringe of rosmarinic acid in Rosmarinus officinalis L. (rosemary). In the proposed method, only 2 mg of the nanoporous material, inserted between a syringe’s barrel and needle, was sufficient for the extraction with minimum consumption of organic solvents. Sample preparation was performed on the packed bed using a laboratory-made programmable apparatus. The apparatus was designed and used for automation of the conditioning, sampling, washing and elution steps of the method, and increasing the reproducibility of the experiments. For optimization of the experimental parameters, a central composite design method was used. Under the optimized conditions (i.e., number of adsorption cycles 14 times, number of elution cycles ten times and volume of elution 100 μL), an extraction recovery of 90 (±4.5) % was obtained for rosmarinic acid. The same packing bed could be used for at least 80 extractions without significant changes in its properties. The efficiency of the nanoporous sorbent was found to be superior to that of activated carbon, by a factor of about 17. The proposed method was successfully applied to the extraction of three rosemary samples before analysis by HPLC.

     

Dynamics of coral reef models in the presence of parrotfish

The decline of coral reefs characterized by macroalgae increase has been a global threat. We consider a slightly modified version of an ordinary differential equation (ODE) model proposed in Blackwood, Hastings, and Mumby [Theor. Ecol. 5 (2012), pp. 105–114] that explicitly considers the role of parrotfish grazing on coral reef dynamics. We perform complete stability, bifurcation, and persistence analysis for this model. If the fishing effort (f) is in between two critical values and , then the system has a unique interior equilibrium, which is stable if and unstable if . If is less (more) than these critical values, then the system has up to two (zero) interior equilibria. Also, we develop a more realistic delay differential equation (DDE) model to incorporate the time delay and treating it as the bifurcation parameter, and we prove that Hopf bifurcation about the interior equilibria could occur at critical time delays, which illustrate the potential importance of the inherent time delay in a coral reef ecosystem. Recommendations for Resource Managers

• One serious threat to coral reefs is overfishing of grazing species, including high level of algal abundance. Fishing alters the entire dynamics of a reef (Hughes, Baird, & Bellwood, 2003), for which the coral cover was predicted to decline rapidly (Mumby, 2006). One major issue is to reverse and develop appropriate management to increase or maintain coral resilience.
• We have provided a detailed local and global analysis of model (Blackwood, Hastings, & Mumby, 2012) and obtained an ecologically meaningful attracting region, for which there is a chance of stable coexistence of coral–algal–fish state.
• The healthy reefs switch to unhealthy state, and the macroalgae–parrotfish state becomes stable as the fishing effort increases through some critical values. Also, for some critical time delays, a switch between healthy and unhealthy reef states occurs through a Hopf bifurcation, which can only appear in the delay differential equation (DDE) model. Eventually, for large enough time delay, oscillations appear and an unhealthy state occurs.