Kinetic studies on the irinotecan release based on structural properties of functionalized mesoporous-silica supports

Building a detailed kinetic model for the drug release from an ordered mesoporous support is a difficult task due to various physico-chemical processes involved, including complex adsorption-desorption and diffusion steps. A compartmented mechanistic model for the drug release from a silica mesoporous (functionalized) support is elaborated to correlate the experimental drug release data under various release conditions. The identified model parameters are interpreted in relationship to the delivery system characteristics (drug, support, and linker properties) to be used for designing a system with a controlled release. Extended model predictions are compared with those of various semi-empirical or overall diffusion models in terms of quality (adequacy, validity, reliability) and parameter significance to determine the information loss when simplified models are used for design purposes. Exemplification is made for the release of irinotecan from a MCM-41 support unfunctionalized vs. functionalized with 3-aminopropyl triethoxysilane or triethoxyvinylsilane in a synthetic intestinal fluid.     

New method for determining the optical rotatory dispersion of hydroxypropyl cellulose polymer solutions in water

The proposed method employs the recorded channeled spectrum of an optical active medium (crystal or liquid solution) placed between two crossed polarizers. The method of channeled spectrum, previously validated for quartz samples, is used to determine the optical rotatory dispersion of hydroxypropyl cellulose solutions (HPC) in water. Both the specific rotation and dispersion parameter depend on the wavelengths of the maxima and minima from the channeled spectrum and on the thickness of the optical active sample. The circular birefringence and its dispersion determined for HPC solutions in water of concentrations 30% and 45% were estimated with a precision of about 0.5%. The rotatory birefringence of HPC in water at 45% is (119.75–57.60)10^?6 and the specific rotation determined in the visible range for these solutions has values between 4782 and 1402 degrees/dm, in agreement with the literature. The specific rotation (angle) of HPC solutions is independent of the polymer concentration and represents a dispersive parameter which decreases with the light wavelength. POLYM. ENG. SCI., 55:1077–1081, 2015. © 2014 Society of Plastics Engineers     

Nanoscale mapping of contact stiffness and damping by contact resonance atomic force microscopy

In this work, a new procedure is demonstrated to retrieve the conservative and dissipative contributions to contact resonance atomic force microscopy (CR-AFM) measurements from the contact resonance frequency and resonance amplitude. By simultaneously tracking the CR-AFM frequency and amplitude during contact AFM scanning, the contact stiffness and damping were mapped with nanoscale resolution on copper (Cu) interconnects and low-k dielectric materials. A detailed surface mechanical characterization of the two materials and their interfaces was performed in terms of elastic moduli and contact damping coefficients by considering the system dynamics and included contact mechanics. Using Cu as a reference material, the CR-AFM measurements on the patterned structures showed a significant increase in the elastic modulus of the low-k dielectric material compared with that of a blanket pristine film. Such an increase in the elastic modulus suggests an enhancement in the densification of low-k dielectric films during patterning. In addition, the subsurface response of the materials was investigated in load-dependent CR-AFM point measurements and in this way a depth dimension was added to the common CR-AFM surface characterization. With the new proposed measurement procedure and analysis, the present investigation provides new insights into characterization of surface and subsurface mechanical responses of nanoscale structures and the integrity of their interfaces.     

Synthesis, structural and magnetic characterization of iron-zinc-borate glass ceramics containing nanocrystalline zinc ferrite

Two different glass ceramics with the composition of the (Fe₂O₃)_x·(B₂O₃)_(60−x)·(ZnO)₄₀, where x = 12.5 and 15 mol%, have been synthesized using the melt-quench method. The X-ray diffraction (XRD) patterns show the presence of nanometric zinc ferrite (ZnFe₂O₄) crystals, with spinel structure, in a glassy matrix after cooling from melting temperature. The estimated amount of crystallized zinc ferrite varies between 16 and 35%, as a function of the chemical composition. Glass transition (T_g), crystallization (T_p) and melting (T_m) temperatures were determined by differential thermal analysis (DTA) investigations. Fourier transform infrared (FTIR) data revealed that the BO₃ and BO₄ are the main structural units of these glass ceramics network. FTIR spectra of these samples show features at characteristic vibration frequencies of ZnFe₂O₄. Electron paramagnetic resonance (EPR) measurements show the presence of isolated Fe³⁺ ions predominantly situated in rhombic vicinities and as well as the Fe³⁺ species interacting by dipole–dipole interaction or to their superexchange coupled pairs in clustered formations. The magnetic properties of the studied glass ceramics were investigated by vibrating sample magnetometer (VSM). From the magnetization curves for glass ceramic containing 15 mol% Fe₂O₃ it was found that the nanoparticles exhibit ferromagnetic interactions combined with superparamagnetism with a blocking temperature, T_B. For studied samples the hysteresis is present. The coercive field is dependent on composition and magnetic field being around 0.05 μ_B/f.u for measurements performed in maximum 0.4 T.     

Microfluidic devices modulate tumor cell line susceptibility to NK cell recognition

This study aims to adoptively reduce the major histocompatibility complex class I (MHC-I) molecule surface expression of cancer cells by exposure to microfluid shear stress and a monoclonal antibody. A microfluidic system is developed and tumor cells are injected at different flow rates. The bottom surface of the microfluidic system is biofunctionalized with antibodies (W6/32) specific for the MHC-I molecules with a simple method based on microfluidic protocols. The antibodies promote binding between the bottom surface and the MHC-I molecules on the tumor cell membrane. The cells are injected at an optimized flow rate, then roll on the bottom surface and are subjected to shear stress. The stress is localized and enhanced on the part of the membrane where MHC-I proteins are expressed, since they stick to the antibodies of the system. The localized stress allows a stripping effect and consequent reduction of the MHC-I expression. It is shown that it is possible to specifically treat and recover eukaryotic cells without damaging the biological samples. MHC-I molecule expression on treated and control cell surfaces is measured on tumor and healthy cells. After the cell rolling treatment a clear reduction of MHC-I levels on the tumor cell membrane is observed, whereas no changes are observed on healthy cells (monocytes). The MHC-I reduction is investigated and the possibility that the developed system could induce a loss of these molecules from the tumor cell surface is addressed. The percentage of living tumor cells (viability) that remain after the treatment is measured. The changes induced by the microfluidic system are analyzed by fluorescence-activated cell sorting and confocal microscopy. Cytotoxicity tests show a relevant increased susceptibility of natural killer (NK) cells on microchip-treated tumor cells.     

Acrylic blends based on polyaniline. Factorial design

Processable conducting materials for large-scale utilization were prepared by mechanical mixing of polyaniline (PANI) paste and commercially acrylic resin. Doped PANI with organic phosphorus acid was synthesized. These blends can be used for the production of semiconductive paints with good corrosion resistance. By mixing doped PANI with commercially acrylic acid (SMP 63 AZUR SA) hard semiconducting and low elastic films are obtain. The effect of four variables was simultaneously studied: PANI (concentration), stirring speed (ST), mixing time (MT), dispersing agent (DA). Due to the number of variables, a factorial-design was chosen in order to reduce the number of experiments required in order to obtain coatings with high hardness and elasticity and semiconductive behavior. The results indicated that the influences of control factors decrease in order: PANI (concentration), mixing time (MT), dispersing agent (DA) and stirring speed (ST). From the studied variables, the resistance is significantly influenced by the two control factors PANI and MT.     

Novel nanomaterials based on 5,10,15,20-tetrakis(3,4-dimethoxyphenyl)-21H,23H-porphyrin entrapped in silica matrices

The present study is dealing with the obtaining of transparent hybrid silica materials encapsulating 5,10,15,20-tetrakis(3,4-dimethoxyphenyl)-21H,23H-porphyrin designated for advanced optoelectronic devices. The porphyrin was synthesized by three methods: an Adler-type reaction between pyrrole and 3,4-dimethoxybenzaldehyde in propionic acid medium; by Lindsey condensation of pyrrole with 3,4-dimethoxybenzaldehyde in the presence of BF₃·OEt₂ and by a multicomponent reaction by simultaneously using of pyrrole and two different aldehydes: 3,4-dimethoxybenzaldehyde and 3-hydroxybenzaldehyde. The 3,4-dimethoxyphenyl substituted porphyrin was characterized by HPLC, TLC, UV-vis, FT-IR, ¹H NMR and ¹³C NMR analysis. Excitation and emission spectra were also discussed in terms of pH conditions. The hybrid materials, consisting in the porphyrin encapsulated in silica matrices, have been prepared successfully via the two steps acid-base catalyzed hydrolysis and condensation of tetraethylorthosilicate using different approaches of the sol-gel process: in situ, by impregnation and by sonication. The synthetic conditions and the compositions were monitored and characterized by using spectroscopic methods such as FT-IR, fluorescence and UV-vis. Atomic force microscopy (AFM) has been applied to observe the columnar or pyramidal nanostructures which are formed by the immobilization of porphyrin on the silica matrices.     

Defeating Colluding Nodes in Desktop Grid Computing Platforms

Desktop Grid systems reached a preeminent place among the most powerful computing platforms in the planet. Unfortunately, they are extremely vulnerable to mischief, because computing projects exert no administrative or technical control on volunteers. These can very easily output bad results, due to software or hardware glitches (resulting from over-clocking for instance), to get unfair computational credit, or simply to ruin the project. To mitigate this problem, Desktop Grid servers replicate work units and apply majority voting, typically on 2 or 3 results. In this paper, we observe that simple majority voting is powerless against malicious volunteers that collude to attack the project. We argue that to identify this type of attack and to spot colluding nodes, each work unit needs at least 3 voters. In addition, we propose to post-process the voting pools in two steps. i) In the first step, we use a statistical approach to identify nodes that were not colluding, but submitted bad results; ii) then, we use a rather simple principle to go after malicious nodes which acted together: they might have won conflicting voting pools against nodes that were not identified in step i. We use simulation to show that our heuristic can be quite effective against colluding nodes, in scenarios where honest nodes form a majority.     

Comparative analysis of the processes of collagen concentration by ultrafiltration using different types of membranes

Tangential flow filtration of the collagen protein solutions with a molecular weight 12, 14, and 24 kDa is investigated using flat sheet membranes. The effects of tangential ultrafiltration (UF) on the permeate properties using two regenerated celluloses (RCs) and two polyethersulfone (PES) membranes with molecular weight cut-off (MWCO) of 5 and 10 kDa are reported. The permeate and concentrate obtained in the UF experiments are characterized from a physical–chemical point of view by determining the temperature, pH, electrical conductivity, nitrogen content, and protein concentration. In addition, the experimental data are modeled using Hermia's model. The UF experiments demonstrated that permeate flux declined with increasing molecular weight of collagen at constant concentration (1%). Regardless of the molecular weight of collagen, the rejections decrease in the following order: PES 5 kDa > RC5kDa > RC10kDa > PES10kDa. In case of membrane with higher MWCO, the clogging phenomenon is mainly due to the blockage of the internal pores of the membrane than the formation of a polarization layer. Morphologies and characteristics of the membranes are characterized using scanning electron microscopy.