Synthesis and characterization of paclitaxel-imprinted nanoparticles for recognition and controlled release of an anticancer drug

Imprinted nanoparticles as drug delivery carriers have been considered because owing to their cross-linked network, they act as the drug reservoir for controlled release. In this study, selective MIPs nanoparticles of paclitaxel (PTX) were successfully developed for application in the biological molecular recognition and in the design of new anticancer drug delivery systems. The MIPs nanoparticles prepared by miniemulsion polymerization technique using methacrylic acid (MAA) and methyl methacrylate as non-covalent functional monomer, ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate (TRIM) as cross-linker agent, azobisisobutyronitrile as initiator, and hexadecane as hydrophobic agent. In order to prepare of MIP nanoparticles, the synthesis conditions and effective parameters, such as: cross-linker agent, different molar ratios of template–functional monomer–cross-linker agent, were investigated. In addition, the effect of different molar ratios of template and monomers on polymers binding and morphology were characterized. Structure and thermal properties of MIPs were confirmed by FT-IR spectroscopy and thermogravimetric analysis. Imprinted nanoparticles showed significant drug loading and encapsulation efficiency, 17.8 and 100 %, respectively. The particle size of MIP nanoparticles varies between 187 and 726 nm, according the SEM images and laser light scattering data. The imprinted nanoparticles showed satisfactory affinity (84 %) to PTX with a binding of 12 times higher than non-imprinted nanoparticles in biological samples when MAA and TRIM were used as functional and cross-linker monomer, respectively. Results from release experiments of MIPs showed a very slow and controlled release of PTX which would be helpful for sustained drug delivery.     

Thermal sensor allocation for 3DICs using three dimensional thermal sensors

Stacking active layers leads to increased power density and overall higher temperatures in a three dimensional integrated circuit (3DIC). Thermal sensors are therefore crucial for run-time thermal management of 3DICs. A thermal sensor allocation method customized for 3DICs that utilizes ring oscillator based 3D sensors is introduced in this paper. A new 3D thermal map modeling method that facilitates efficient and very fast analyses is embodied in this thermal sensor distribution algorithm. Our results indicate that for a 4-layer stacked 3DIC, consisting of two layers of quad-core processors and one layer of L2 cache and one layer of main memory, less than 3.58% in maximum sensor reading error can be accomplished with a 53× speedup in the thermal evaluation time and thermal sensor distribution algorithm implementation.     

Alumina coated with oxazolone derivative for extraction of trace amounts of cadmium and copper from water and plant samples

A solid phase extraction procedure is proposed for simultaneous separation and preconcentration trace amounts of Cu(II) and Cd(II) using alumina coated with N'-{4-[4-{1-[4-(dimethylamino)phenyl]methylidene}-5-(4-H)oxazolone]phenyle}acetamide and determination by flame atomic absorption spectrometry. Using 0.1g of the sorbent, the metal ions were sorbed at pH 7 and recovered with 5.0 mL of 0.5 mol L(-1) HNO(3). It was found that extraction can be performed from the sample volumes of 2000 and 800 mL for Cu and Cd, respectively (preconcentration factors of 400 for Cu and 160 for Cd). Obtained sorption capacities for 1g sorbent were 8 mg Cu and 14 mg Cd. The linearity was maintained in the concentration range of 0.1 ng mL(-1) to 7.0 μg mL(-1) for Cu and 0.13 ng mL(-1) to 2.0 μg mL(-1) for Cd in the original solution. Eight replicate determinations of a mixture containing 1.0 μg mL(-1) each of the elements in the final solution gave relative standard deviation ±1.6 and ±1.3% for Cu and Cd, respectively. The detection limit was calculated as 0.06 and 0.05 ng mL(-1) for Cu and Cd, respectively. The proposed method was successfully applied to the determination trace amounts of Cu and Cd in the water and plant samples.     

Neodymium(III)-PVC membrane sensor based on a new four dentate ionophore

A new selective Nd(III) sensor has been made by using N,N′-bis(quinoline-2-carboxamido)-4,5-dimethylbenzene (H₂L₄) as a suitable ionophore. The sensor exhibits Nernstian response to Nd(III) ions in the concentration range of 5.0 × 10^− 6 to 1.0 × 10^− 2 M. It displays a Nernstian slope of 19.5 ± 0.4 mV/decade in the pH range of 2.9-9.2. The proposed sensor also exhibits a fast response time of < l0 s. The detection limit of the proposed sensor is 4.8 × 10^− 6 M, and it can be used over a period of 10 weeks without significant changes in its response. Furthermore, the electrode showed high selectivity toward Nd(III) ion respect to all other lanthanide ions tested. The practical utility of the sensor was demonstrated by using it as an indicator electrode in the potentiometric determination of Nd(III) ions in certified reference material and spiked water samples.     

Dipyridamole recognition and controlled release by uniformly sized molecularly imprinted nanospheres

We used novel synthetic conditions of precipitation polymerization to obtain uniformly sized molecularly imprinted nanospheres of dipyridamole for application in the design of new drug delivery systems. In addition, the morphology, drug release, and binding properties of molecularly imprinted polymers (MIPs) were studied, and the effects of morphology on other properties were investigated. The MIPs prepared by acetonitrile/chloroform (19:1, v/v) were uniformly sized nanospheres with an average mean diameter of approximately 88 nm at a wetted state, 50 nm at a dry state, and a polydispersity index of 0.062. The imprinted nanospheres showed excellent binding properties and had 62.7% of template binding compared with 17.1% of its blank polymer. The imprinted nanospheres with 67.5 (mg template/of polymer) of binding capacity had better imprinting efficiency than the 50.5% of binding capacity shown by irregularly shaped MIP particles that were prepared by chloroform. The molecular binding abilities of imprinted nanospheres in human serum were evaluated by HPLC analysis (binding about 77% of dipyridamole). Results from release experiments of MIPs showed a very slow, controlled, and satisfactory release of dipyridamole. The loaded drug was released up to 99% in 17 days for nanospheres and 22 days for irregularly shaped particles.     

Conformational changes of Mal d 2, a thaumatin-like apple allergen,induced by food processing

Mal d 2, a thaumatin-like protein from apple was previously described to react to almost 75% of the apple allergic patient sera. Based on the molecular structure of this protein, the present study focused on the conformational stability of Mal d 2 in relation to in vitro IgE-binding under different physico-chemical conditions and proteolysis. The structural integrity of Mal d 2 was monitored using SDS–PAGE, Western blotting using polyclonal antibodies and human sera, fluorescence spectrometry and circular dichroism. Results confirmed the stability of Mal d 2. However, Mal d 2 was reactive to human serum IgEs mainly after reduction of disulphide bridges fixing the α-helical domain II. Contrary to previous assumptions, the current findings suggest that the allergenic epitopes of Mal d 2 are hidden inside the protein structure and none of the rigorous conditions applied in industrial juice processing or digestive proteolysis enhance or reduce the binding to IgE molecules.     

Use of hollow fibre-based liquid–liquid–liquid microextraction and high-performance liquid chromatography–diode array detection for the determination of phenolic acids in fruit juices

This paper describes a simple method based on three-phase hollow-fibre liquid-phase microextraction (HF-LPME) for the determination of phenolic acids in fruit juices. Analytes including gallic acid, p-hydroxy benzoic acid, caffeic acid, syringic acid, p-coumaric acid, ferulic acid, and cinnamic acid were separated and determined using high-performance liquid chromatography–photodiode array detection (HPLC–DAD). Parameters affecting the enrichment factors (EFs) were investigated. These compounds were extracted from 5 mL aqueous samples (pH 2) to a thin layer of organic solvent (hexyl acetate) phase impregnated into the pores of the polypropylene hollow fibre wall, and then back extracted to a basic acceptor solution (0.02 M NaOH). EFs ranged from 15 (gallic acid) to 408 (cinnamic acid). The RSD of the method for the analysis of spiked water and fruit juice samples varied from 3.1% to 11.3%. The LODs ranged from 0.01 (cinnamic acid) to 2.0 (caffeic acid) μg/L.     

Swelling properties of CMC‐g‐poly (AAm‐co‐AMPS) superabsorbent hydrogel

A series of biopolymer‐based superabsorbent hydrogels based on carboxymethyl cellulose has been prepared by free‐radical graft copolymerization of acrylamide and 2‐acrylamido‐2‐methylpropan sulfonic acid (AMPS) in aqueous solution using methylenebisacrylamide as a crosslinking agent and ammonium persulfate as an initiator. The effect of variables on the swelling capacity such as: acrylamide/AMPS weight ratio, reaction temperature, and concentration of the initiator and crosslinker were systematically optimized. The results indicated that with increasing the amount of AMPS, the swelling capacity is increased. FT‐IR spectroscopy and scanning electron microscope analysis were used to confirm the hydrogel structure. Swelling measurements of the synthesized hydrogels in different salt solutions indicated considerable swelling capacity. The absorbency under load of the superabsorbent hydrogels was determined by using an absorbency under load tester at various applied pressures. A preliminary swelling and deswelling behaviors of the hydrogels were also studied. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Determination of picomolar silver concentrations by differential pulse anodic stripping voltammetry at a carbon paste electrode modified with phenylthiourea-functionalized high ordered nanoporous silica gel

This study introduces the design of an anodic stripping voltammetric (ASV) method for the silver ion determination at a carbon paste electrode (CPE), chemically modified with phenylthiourea-nanoporous silica gel (Tu-SBA-15-CPE). The electroanalytical pro includes two steps: preconcentration of metal ions at an electrode surface, followed by quantification of the accumulated species by differential pulse anodic stripping voltammetric methods. Factors affecting the performance of the anodic stripping were investigated, including the modifier quantity in the paste, the electrolyte concentrations, the solution pH and the accumulation potential or time. The most sensitive and reliable electrode contained 10% Tu-SBA-15 and 90% carbon paste. The accumulation potential and time were set at, −200 mV and 300 s, respectively, and the scan rate at 50 mV s⁻¹ in the scan range of −200 to 700 mV. The resulting electrode demonstrated a linear response over range of silver ion concentration of 8.0-80 pmol/L with detection limit (S/N = 3) of 5 pmol/L. The prepared electrodes were used for the silver determination in sea and tap water samples and very good recovery results were obtained. The accuracy was assessed through recovery experiments and independent analysis by graphite furnace atomic absorption spectrometry.     

Oxidative Aromatization of 1,3,5-trisubstituted 2-pyrazolines Using Oxalic Acid/Sodium Nitrite System

Oxidative aromatization of 1,3,5-trisubstituted 2-pyrazolines by in-situ generation of NO⁺ from oxalic acid/sodium nitrite system has been described. The main advantages of this procedure are the use of an inexpensive and readily available catalyst, facile work-up, and improved yields in aqueous ethanol.