Synthesis and electrorheological characteristics of titanate nanotube suspensions under oscillatory shear

In this study, titanate nanotubes (TNTs) were synthesized by hydrothermal treatment of TiO₂ powders (P25) in a NaOH solution. The as-synthesized TNTs exhibit high surface area and large aspect ratio. Rheological properties of TNTs suspensions were then investigated under oscillatory shear. The TNTs fluid shows the viscoelastic behavior and the dynamic moduli (G′, G″) increase significantly by about 4 orders of magnitude as the electric field strength is up to 2.0 kV/mm. Transient response under dynamic shear reveals different changes in the microstructure of TNTs fluid from steady shear. The complex modulus of TNTs fluids is sensitive to temperature while that of P25 fluid become insensitive at higher temperature. Dynamic viscoelastic behavior suggests that structure of P25 to TNTs transition merits the enhancement of ER activity of TNTs fluid.     

Dilute solutions and phase behavior of polydisperse A-b-(A-co-B) diblock copolymers

The effect of polydispersity on dilute solution properties and microphase separation of polydisperse high-molecular-weight (M_w > 10⁵ g mol⁻¹) polystyrene-block-poly(styrene-co-acrylonitrile) diblock copolymers, PS-block-P(S-co-AN), was studied in this work. For experiments, a series of diblock copolymers with variable weight fractions of acrylonitrile units (w_AN = 0.08-0.29) and length of block P(S-co-AN) was synthesized using nitroxide-mediated radical polymerization (NMP) technique, namely, by chain extension of nitroxide-terminated polystyrene (PS-TEMPO). According to light scattering and viscometry measurements in dilute tetrahydrofuran (THF) solutions the studied diblock copolymers assumed random coil conformation with the values of characteristic structure factor R_g/R_h = 1.50-1.76. It was found that polydisperse diblock copolymers being in strong segregation limit (SSL) self-assembled into microphase-separated ordered morphologies at ordinary temperature. The long periods of lamellar microdomains were larger compared to theoretical predictions for hypothetical monodisperse diblock copolymers. It was demonstrated by means of SAXS and TEM that a transition from a lamellar (LAM) to irregular face-centered-cubic (FCC) morphology occurred with increasing volume fraction of P(S-co-AN) block.     

Improved Adhesion, Growth and Maturation of Vascular Smooth Muscle Cells on Polyethylene Grafted with Bioactive Molecules and Carbon Particles

High-density polyethylene (PE) foils were modified by an Ar⁺ plasma discharge and subsequent grafting with biomolecules, namely glycine (Gly), polyethylene glycol (PEG), bovine serum albumin (BSA), colloidal carbon particles (C) or BSA and C (BSA + C). As revealed by atomic force microscopy (AFM), goniometry and Rutherford Backscattering Spectroscopy (RBS), the surface chemical structure and surface morphology of PE changed dramatically after plasma treatment. The contact angle decreased for the samples treated by plasma, mainly in relation to the formation of oxygen structures during plasma irradiation. A further decrease in the contact angle was obvious after glycine and PEG grafting. The increase in oxygen concentration after glycine and PEG grafting proved that the two molecules were chemically linked to the plasma-activated surface. Plasma treatment led to ablation of the PE surface layer, thus the surface morphology was changed and the surface roughness was increased. The materials were then seeded with vascular smooth muscle cells (VSMC) derived from rat aorta and incubated in a DMEM medium with fetal bovine serum. Generally, the cells adhered and grew better on modified rather than on unmodified PE samples. Immunofluorescence showed that focal adhesion plaques containing talin, vinculin and paxillin were most apparent in cells on PE grafted with PEG or BSA + C, and the fibres containing α-actin, β-actin or SM1 and SM2 myosins were thicker, more numerous and more brightly stained in the cells on all modified PE samples than on pristine PE. An enzyme-linked immunosorbent assay (ELISA) revealed increased concentrations of focal adhesion proteins talin and vinculin and also a cytoskeletal protein β-actin in cells on PE modified with BSA + C. A contractile protein α-actin was increased in cells on PE grafted with PEG or Gly. These results showed that PE activated with plasma and subsequently grafted with bioactive molecules and colloidal C particles, especially with PEG and BSA + C, promotes the adhesion, proliferation and phenotypic maturation of VSMC.     

Notes on the Asymmetric Hydrogenation of Methyl Acetoacetate in Neoteric Solvents

Asymmetric hydrogenation of methyl acetoacetate to methyl (R)-3-hydroxybutyrate by [(R)- RuCl(binap)(p-cymen)]Cl has been studied in methanol-ionic liquid and methanol- dense CO₂ solvent systems. The ionic pairs triethylhexylammonium and 1-methylimidazolium with bis(trifluoromethane sulfonyl) imide and hexafluorophosphates were used. The role of ionic pairs on the kinetic parameters and (enantio)selectivity has been demonstrated. Although the CO₂ expanded methanol system suffered from a reduction in both reaction rate and product selectivity, this changed in the presence of water. The high selectivity of the optimized methanol-CO₂-water-halide system was designed as a consequence of observed additive effects.     

An adsorptive transfer technique coupled with brdicka reaction to reveal the importance of metallothionein in chemotherapy with platinum based cytostatics

The drugs based on platinum metals represent one of the oldest, but also one of the most effective groups of chemotherapeutic agents. Thanks to many clinical studies it is known that resistance of tumor cells to drugs is a frequent cause of chemotherapy failure. With regard to platinum based drugs, multidrug resistance can also be connected with increased expression of low-molecular weight protein metallothionein (MT). This study aimed at investigating the interactions of MT with cisplatin or carboplatin, using the adsorptive transfer technique coupled with differential pulse voltammetry Brdicka reaction (AdTS DPV Brdicka reaction), and a comparison of in vitro results with results obtained in vivo. The results obtained from the in vitro study show a strong affinity between platinum based drugs and MT. Further, we analyzed extracts of neuroblastoma cell lines treated with cisplatin or carboplatin. It is clear that neuroblastoma UKF-NB-4 cisplatin-resistant and cisplatin-sensitive cell lines unlikely respond to the presence of the platinum-based cytostatics cisplatin and carboplatin. Finally, we determined the level of MT in samples from rabbits treated with carboplatin and patients with retinoblastoma treated with the same drug.     

Adaptation of polystyrene/multi‐wall carbon nanotube composite properties in respect of its thermal stability

Polystyrene (PS)/multi‐wall carbon nanotube (MWCNT) nanocomposites were prepared by melt mixing and by coagulation of PS/MWCNT sonicated dispersion. Before mixing and coagulation particles of MWCNT were covered with PS nanospheres by microemulsion polymerization to increase their dispersibility and compatibility with the matrix. Microemulsion polymerization was carried out under sonication in the presence of surfactants and a cross‐linking agent. The structure of modified MWCNT filler was revealed by SEM and TEM microscopy analyses. They show that PS is well grafted onto surface of MWCNT in form of ca 30 nm nanospheres or as ca 3–8 nm PS film layer. Significant changes in properties were recorded mainly for the coagulated sample. Although no shift of T_g was recorded for the melt mixed composite, the coagulated sample shows an increase by 9°C. Also the reinforcing effect of MWCNT was more pronounced for the same method of preparation (further supported by the filler modification). The creep response of this material shifts to longer times not only in the T_g area, but also as low as 70°C below it, which is perceived as an improvement of temperature stability (the same properties kept for a longer time). This was also proved by the increase of creep modulus, and consequently by the prolonged time needed to reach the same tensile creep compliance after aging. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Physical Simulation of the Random Failure of Implanted Braided NiTi Stents

A problem of random clinical failures of the braided esophageal NiTi stents has been addressed by performing physical simulation experiments on helical NiTi springs loaded in cyclic tension in air, water, and simulated biological fluid. Strains and stresses involved in spring deformation were analyzed through simulation by FEM implemented SMA model. It was found that the fatigue life of NiTi springs is significantly lower in fluids than in the air pointing toward the corrosion fatigue mechanism. There is, however, a fatigue limit roughly corresponding to the onset of martensitic transformation in the wire, which is not common for corrosion fatigue. It is proposed that surface TiO₂ oxide cracking plays major role in that. Once the oxide layer on the NiTi wire surface fractures, typically during the first mechanical cycle, cracks in the oxide layer periodically open and close during subsequent mechanical cycling. This leads to the localization of mechanical and corrosion attacks under the oxide cracked regions. Microcracks within the surface oxide layer crossing over into the NiTi matrix were indeed revealed by scanning electron microscopy of FIB sections of fatigued wires. A corrosion assisted mechanism for fatigue crack nucleation at the interface between the surface oxide and NiTi matrix is proposed based on the available evidence. The approach opens a space for a better assessment of the corrosion fatigue performance of superelastic NiTi and ultimately for estimation of the lifetime of implanted braided NiTi stents.     

Impedance spectroscopy on porous materials: A general model and application to graphite electrodes of lithium-ion batteries

Electrochemical impedance spectroscopy (EIS) was applied to porous negative graphite electrodes for lithium-ion batteries in the EC:DMC, 1 M LiPF₆ electrolyte. The effect of porosity on the electrode response time was studied and a theoretical model was developed, based on free path of the current lines between subsequent reaction sites. The effect of porosity on the electrode response is evidenced by the impedance spectra in which the high frequency capacitive semicircle is distorted. Fresh electrodes (before the formation of the solid electrolyte interphase, SEI) and cycled electrodes have different shapes of the impedance spectra indicating a change of processes at the surface. In particular, the shape of the spectrum for a fresh electrode can be related to an adsorption process. Impedance spectra of fresh electrodes were fitted using a simple model that considers porosity and the assumed electrochemical processes, giving good agreement between model and data. A correlation was found between adsorption sites and irreversible charge capacity in the first cycle.     

Direct evidence of oxygen evolution from Li1+ x (Ni1/3Mn1/3Co1/3)1? x O2 at high potentials

Li_1+x (Ni_1/3Mn_1/3Co_1/3)_1−x O₂ (NMC) oxides are among the most promising positive electrode materials for future lithium–ion batteries. A voltage “plateau” was observed on the first galvanostatic charging curve of NMC in the extended voltage region positive to 4.5 V vs. Li/Li⁺ for compounds with x > 0 (overlithiated compounds). Differences were observed in the cycling stability of the overlithiated and stoichiometric (x = 0) NMC oxides in this potential region. A differential plot of the charge vs. potential profile in the first cycle revealed that, for the overlithiated compounds, a large irreversible oxidative peak arises positive to 4.5 V vs. Li/Li⁺, while in the same potential region only a small peak due to the electrolyte oxidation is detected for the stoichiometric material. Differential Electrochemical Mass Spectrometry (DEMS) was used to investigate the high voltage region for both compounds and experimental evidence for oxygen evolution was provided for the overlithiated compounds at potentials positive to 4.5 V vs. Li/Li⁺. No oxygen evolution was detected for the stoichiometric compound.