Heck and oxidative boron Heck reactions employing Pd(II) supported amphiphilized polyethyleneimine‐functionalized MCM‐41 (MCM‐41@aPEI‐Pd) as an efficient and recyclable nanocatalyst

A novel nanocatalyst was developed based on covalent surface functionalization of MCM‐41 with polyethyleneimine (PEI) using [3‐(2,3‐Epoxypropoxy)propyl] trimethoxysilane (EPO) as a cross‐linker. Amine functional groups on the surface of MCM‐41 were then conjugated with iodododecane to render an amphiphilic property to the catalyst. Palladium (II) was finally immobilized onto the MCM‐41@PEI‐dodecane and the resulted MCM‐41@aPEI‐Pd nanocatalyst was characterized by FT‐IR, TEM, ICP‐AES and XPS. Our designed nanocatalyst with a distinguished core‐shell structure and Pd²⁺ ions as catalytic centers was explored as an efficient and recyclable catalyst for Heck and oxidative boron Heck coupling reactions. In Heck coupling reaction, the catalytic activity of MCM‐41@aPEI‐Pd in the presence of triethylamine as base led to very high yields and selectivity. Meanwhile, the MCM‐41@aPEI‐Pd as the first semi‐heterogeneous palladium catalyst was examined in the C‐4 regioselective arylation of coumarin via the direct C‐H activation and the moderate to excellent yields were obtained toward different functional groups. Leaching test indicated the high stability of palladium on the surface of MCM‐41@aPEI‐Pd as it could be recycled for several runs without significant loss of its catalytic activity.     

CuBr‐catalysed one‐pot multicomponent synthesis of 3‐substituted 2‐thioxo‐2,3‐dihydroquinazolin‐4(1H)‐one derivatives

A novel methodology is presented for the synthesis of 3‐substituted 2‐thioxo‐2,3‐dihydroquinazolin‐4(1H)‐one derivatives based on an efficient tandem multicomponent reaction using copper bromide as catalyst. This methodology is based on the multicomponent one‐pot reaction of methyl 2‐bromobenzoate, phenylisothiocyanate derivatives and sodium azide in the presence of copper bromide and l ‐proline under basic conditions. To show the generality of the method, various phenylisothiocyanates bearing electron‐donating or electron‐withdrawing functionalities were used and the desired products were obtained in high isolated yields.     

Characterization and surface reactivity of ferrihydrite nanoparticles assembled in ferritin

Ferrihydrite nanoparticles with nominal sizes of 3 and 6 nm were assembled within ferritin, an iron storage protein. The crystallinity and structure of the nanoparticles (after removal of the protein shell) were evaluated by high-resolution transmission electron microscopy (HRTEM), atomic force microscopy (AFM), and scanning tunneling microscopy (STM). HRTEM showed that amorphous and crystalline nanoparticles were copresent, and the degree of crystallinity improved with increasing size of the particles. The dominant phase of the crystalline nanoparticles was ferrihydrite. Morphology and electronic structure of the nanoparticles were characterized by AFM and STM. Scanning tunneling spectroscopy (STS) measurements suggested that the band gap associated with the 6 nm particles was larger than the band gap associated with the 3 nm particles. Interaction of SO2(g) with the nanoparticles was investigated by attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, and results were interpreted with the aid of molecular orbital/density functional theory (MO/DFT) frequency calculations. Reaction of SO2(g) with the nanoparticles resulted primarily in SO(3)2- surface species. The concentration of SO3(2-) appeared to be dependent on the ferrihydrite particle size (or differences in structural properties).     

A systematic investigation of recovery in preparative reverse phase high performance liquid chromatography/mass spectrometry

In this paper we report a systematic recovery study based on reversed phase high performance liquid chromatography (RP-HPLC) separation and mass spectrometric (MS) based fractionation. Factors including a compound's physicochemical properties, column mass loading and presence of impurities were investigated through commercially available compounds. Results suggest that the delay time between MS peak detection and fraction collection, fraction detector's signal-to-noise ratio and compound's base peak width in the chromatogram have the biggest impacts on purification recovery. In an effort to assess sample recovery within our high throughput purification process, re-purification was performed on four compound libraries that were synthesized in-house. Reproducible recoveries (>80%) were achieved in all tests.     

The Neuroprotective Role of Polydatin: Neuropharmacological Mechanisms,Molecular Targets,Therapeutic Potentials,and Clinical Perspective

Neurodegenerative diseases (NDDs) are one of the leading causes of death and disability in humans. From a mechanistic perspective, the complexity of pathophysiological mechanisms contributes to NDDs. Therefore, there is an urgency to provide novel multi-target agents towards the simultaneous modulation of dysregulated pathways against NDDs. Besides, their lack of effectiveness and associated side effects have contributed to the lack of conventional therapies as suitable therapeutic agents. Prevailing reports have introduced plant secondary metabolites as promising multi-target agents in combating NDDs. Polydatin is a natural phenolic compound, employing potential mechanisms in fighting NDDs. It is considered an auspicious phytochemical in modulating neuroinflammatory/apoptotic/autophagy/oxidative stress signaling mediators such as nuclear factor-κB (NF-κB), NF-E2–related factor 2 (Nrf2)/antioxidant response elements (ARE), matrix metalloproteinase (MMPs), interleukins (ILs), phosphoinositide 3-kinases (PI3K)/protein kinase B (Akt), and the extracellular regulated kinase (ERK)/mitogen-activated protein kinase (MAPK). Accordingly, polydatin potentially counteracts Alzheimer’s disease, cognition/memory dysfunction, Parkinson’s disease, brain/spinal cord injuries, ischemic stroke, and miscellaneous neuronal dysfunctionalities. The present study provides all of the neuroprotective mechanisms of polydatin in various NDDs. Additionally, the novel delivery systems of polydatin are provided regarding increasing its safety, solubility, bioavailability, and efficacy, as well as developing a long-lasting therapeutic concentration of polydatin in the central nervous system, possessing fewer side effects.     

Improvements on bed‐shear stress formulation for pier scour computation

This paper introduces an improved formula for the bed‐shear stress by applying the vorticity effect and its application in a 3D flow and sediment model to estimate scouring around bridge piers. Up to now, the sediment transport formulae used for computing pier scour were developed based on the general scouring in unobstructed flow. The capability for numerical models to predict local scour around bridge piers was severely restricted by the sediment transport formulae. The new formula introduced in this paper can take into account vortices that affect the local scour process by adding some terms into the classic bed‐shear stress equation. The 3D numerical model system used in this study consists of three modules: (a) an unsteady hydrodynamic module; (b) a sediment transport module; and (c) a Fation module. The hydrodynamic module is based on the 3D RANS equations. The sediment transport module is comprised of semi empirical models of suspended load and non‐equilibrium bed load. The bed‐deformation module is based on the mass balance for sediment. The model was used to simulate pier scour in tree different test cases: (1) a circular pier; (2) a square pier; and (3) a rectangular pier, by applying the ordinary sediment equation and the newly introduced sediment equation. Results of both numerical simulations were compared against laboratory measured data and also in case 1 with result of Olsen and Melaaen (J. Hydraul. Eng. 1993; 119 (9):1048–1054). Comparisons show that the new sediment formula could predict the scour more accurately than the ordinary one. Copyright © 2010 John Wiley & Sons, Ltd.     

A Potentiometric Sensor for Cd2+ Based on Carbon Nanotube Paste Electrode Constructed from Room Temperature Ionic Liquid,Ionophore and Silica Nanoparticles

A novel and effective potentiometric sensor for the rapid determination of Cd²⁺ based on carbon paste electrode consisting of the room temperature ionic liquid 1‐butyl‐3‐methylimidazolium hexafluorophosphate, multiwalled carbon nanotubes, silica nanoparticles and ionophore was constructed. The prepared composite has a low potential drift, high selectivity and fast response time, which leads to a more stable potential signal. A linear dynamic range of 4.50×10^?9–1.00×10^?1 mol L^?1 with a detection limit of 2.00×10^?9 mol L^?1 was obtained. The modified electrode was successfully applied to the accurate determination of trace amounts of Cd²⁺ in environmental and biological samples.     

A theoretical practice on grazing‐exit energy dispersive X‐ray spectroscopy as a surface analysis strategy to investigate BiVO4 nano‐films

In the current work, a thin film of bismuth vanadate was defined over a silicon substrate, and a calculative Monte Carlo approach was followed to achieve the best grazing‐exit angle to acquire compositional data from top few nanometers of surface. This strategy is very beneficial in order to increase X‐ray signals originated from surface and diminish the background X‐ray signals started off from the substrate. In this regard, grazing‐exit energy dispersive X‐ray spectroscopy can be considered as an accessible and economical analytical tool to investigate thin films and nano‐layers. The major advantage of this method is that just by applying a re‐arrangement in a scanning electron microscope, it can be used to study compositional properties of thin layers. In this contribution, a theoretical approach using Monte Carlo models was used to simulate the behavior of electron beams impinging onto BiVO₄ nano‐layers with thickness of 50 nm and electron trajectories inside the film. Characteristic X‐rays and spatial energy distribution of the backscattered electrons were also calculated. Under grazing‐exit angle of around 0.5°, the best surface signal/background noise ratio was achieved. Copyright © 2014 John Wiley & Sons, Ltd.