Atom Transfer Radical Polymerization (ATRP) of Ethyl Acrylate: Its Mechanistic Studies

Atom transfer radical polymerization (ATRP) of ethyl acrylate was carried out in bulk using ethyl 2-bromoisobutyrate as initiator, CuBr as well as CuCl as catalyst in combination with different ligands e.g., 2,2′ bipyridine (bpy)andN,N, N′,N″,N″-pentamethyldiethylenetriamine (PMDETA). In most of the cases very high conversion (72–98%) was achieved. The polymerization was well controlled with a linear increase of molecular weight (M_n^SEC) with conversion and relatively narrow molecular weight distributions (polydispersity index 1.2–1.3). Use of PMDETA as the ligand resulted in faster polymerization rate (98% conversion in 1 h) than those using bipyridine (72% conversion in 5 h). The MALDI-TOF-MS analysis of poly (ethyl acrylate) (PEA) prepared by using bpy as ligand showed the presence of halogen as the end group. On the contrary, when PMDETA was used as the ligand, the mass analysis showed no trace of this end group.     

Natural Small Molecules in Gastrointestinal Tract and Associated Cancers: Molecular Insights and Targeted Therapies

Gastric cancer is one of the most common cancers of the gastrointestinal tract. Although surgery is the primary treatment, serious maladies that dissipate to other parts of the body may require chemotherapy. As there is no effective procedure to treat stomach cancer, natural small molecules are a current focus of research interest for the development of better therapeutics. Chemotherapy is usually used as a last resort for people with advanced stomach cancer. Anti-colon cancer chemotherapy has become increasingly effective due to drug resistance and sensitivity across a wide spectrum of drugs. Naturally-occurring substances have been widely acknowledged as an important project for discovering innovative medications, and many therapeutic pharmaceuticals are made from natural small molecules. Although the beneficial effects of natural products are as yet unknown, emerging data suggest that several natural small molecules could suppress the progression of stomach cancer. Therefore, the underlying mechanism of natural small molecules for pathways that are directly involved in the pathogenesis of cancerous diseases is reviewed in this article. Chemotherapy and molecularly-targeted drugs can provide hope to colon cancer patients. New discoveries could help in the fight against cancer, and future stomach cancer therapies will probably include molecularly formulated drugs.     

Convenient synthesis of α,β-unsaturated phosphonates via a Mizoroki-Heck reaction of arylboronic acids with diethyl vinylphosphonate

Palladium acetate catalyzed Mizoroki-Heck reactions of arylboronic acids with diethyl vinylphosphonates afford α,β-unsaturated phosphonates in good yields.     

A Trust Region SQP Algorithm for Equality Constrained Parameter Estimation with Simple Parameter Bounds

We describe a new algorithm for a class of parameter estimation problems, which are either unconstrained or have only equality constraints and bounds on parameters. Due to the presence of unobservable variables, parameter estimation problems may have non-unique solutions for these variables. These can also lead to singular or ill-conditioned Hessians and this may be responsible for slow or non-convergence of nonlinear programming (NLP) algorithms used to solve these problems. For this reason, we need an algorithm that leads to strong descent and converges to a stationary point. Our algorithm is based on Successive Quadratic Programming (SQP) and constrains the SQP steps in a trust region for global convergence. We consider the second-order information in three ways: quasi-Newton updates, Gauss-Newton approximation, and exact second derivatives, and we compare their performance. Finally, we provide results of tests of our algorithm on various problems from the CUTE and COPS sets.     

Construction of an inexpensive surface plasmon resonance instrument for use in teaching and research

The construction of an inexpensive SPR instrument that can be used for both teaching and research is described. Using a 2′ × 2′ optical table to construct this instrument allows both scientists and students full access to the operation of the spectrometer. Furthermore, the use of open platform instrumentation has the advantage of maintaining the focus on the relationship between emerging technology and analytical chemistry as well as allowing the user to modify the instrument to enhance the measurement process for a particular application. This is a change from the learning paradigm used in most research and teaching laboratories where commercial instrumentation is treated as a black box due to its complexity. Three studies, which were performed using this instrument, are presented to demonstrate the suitability of this instrument for both teaching and research. These studies include measuring the refractive index of alcohols, investigating the partitioning of ruthenium (II) trisbipyridine chloride into Nafion, and understanding the mechanism controlling metal ion adsorption by polyacrylamide hydrogels.     

Iodine-catalyzed efficient conjugate addition of pyrroles to α,β-unsaturated ketones

Iodine was used as a catalyst for the conjugate addition of pyrroles to α,β-unsaturated ketones at room temperature. Mono- and dialkylated products were obtained by using equimolar amounts of the reactants. However, the use of excess enones afforded only dialkylated products.     

Fabrication and Characterization of Cysteine-Functionalized Zinc Oxide Nanoparticles for Enzyme Immobilization

A green approach is reported for the synthesis of cysteine-functionalized zinc oxide nanoparticles using potato extract as a nontoxic and economical reducing agent. The cysteine-functionalized nanoparticles were used as a support for enzyme immobilization. The structural morphology, crystallinity, and surface functionalization were characterized by scanning electron microscopy, X-ray diffraction, and infrared spectroscopy, respectively. Spherical nanoparticles from 150 to 200?nm were used to evaluate the immobilization efficiency for urease through covalent attachment on the glutaraldehyde-activated amino group of cysteine. In comparison to the unmodified nanoparticles, 62.9% enzyme loading with 72.45% of enzyme specific activity was recovered which was 56% higher than on bare zinc oxide nanoparticles. The point of addition of cysteine during the nanoparticle synthesis had a direct effect on the immobilization efficiency. The immobilized enzyme-specific activity was reduced to 34.32% when cysteine was added following the nanoparticle synthesis. With a facile synthesis procedure and significant immobilization efficiency, cysteine-functionalized zinc oxide nanoparticles were shown to be suitable for various clinical and industrial applications.     

A method to carry out shape optimization with a large number of design variables

A new method for shape optimization with relatively large number of design variables is proposed. It is well known that gradient‐based methods converge to a local optimum. As a result, utilization of a richer design space does not necessarily lead to a better design. This is demonstrated via the design of an airfoil for maximum lift for Re = 1000 and α = 4° flow. The airfoil is represented by fourth‐order non‐uniform rational B‐splines, and the control points are used as design variables. Starting with a NACA0012 airfoil, it is found that the optimal airfoil obtained with 13 control points has far superior aerodynamic performance than the ones obtained with 39 and 61 control points. For effective utilization of a richer design space, it is proposed that the number of design variables be increased gradually. The method is demonstrated by designing high lift airfoils for Re = 1000 and 1 × 10⁴. The objective function is the maximization of the time‐averaged lift coefficient for α = 4°. The optimization cycle with 27 control points is initiated with the optimal airfoil obtained with 13 control points. The process is continued with gradual increase in the number of design variables. Beyond a certain number of control points, the optimization leads to a spontaneous appearance of corrugations on the upper surface of the airfoil. The corrugations are responsible for the generation of small vortices that add to the suction on the upper surface of the airfoil and lead to enhanced lift. A stabilized finite element method is used to solve the unsteady flow and adjoint equations. Copyright © 2012 John Wiley & Sons, Ltd.     

Tailor‐made poly(ethyl acrylate) by atom transfer radical polymerization

Atom transfer radical polymerization (ATRP) of ethyl acrylate (EA) was carried out using different initiators, CuBr or CuCl as catalyst in combination with different ligands e.g., 2,2′‐bipyridine (bpy) and N,N,N′,N″N″‐pentamethyl diethylenetriamine (PMDETA). Use of PMDETA as ligand resulted in faster polymerization rate (95% conversion in 15 min) than those using bipyridine (～58% conversion in 10.5 h). This is due to the lower reduction potential of copper‐amine than that of copper‐bpy complex, resulting in higher rates of activation of dormant halides. Use of ethylene carbonate as solvent lead to faster polymerization rate and better control in polymerization when compared with p‐xylene as solvent. The reaction temperature had a positive effect on polymerization rate and the optimum reaction temperature was found to be 90 °C. An apparent enthalpy of activation of ～85 kJ/mol was determined for the ATRP of ethyl acrylate, corresponding to an enthalpy of equilibrium of ～64 kJ/mol. By judicious choice of the reaction parameters it was possible to tailor the end group of the final polymer. MALDI‐TOF‐MS analysis and the chain extension experiment of poly(ethyl acrylate) (PEA) prepared using bpy as ligand showed the presence of ? Br as the end group. On the contrary, when PMDETA was used as the ligand, the mass spectra analysis showed hydrogen terminated polymer as the major species towards the end of polymerization. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1661–1669, 2007