Ultrasound-induced cell lysis and sonoporation enhanced by contrast agents.

The enhancement of ultrasound-induced cell destruction, lysis, and sonoporation in low cell concentration suspensions (2 x 10(5)/mL) by the presence of contrast agents (gas bubble to cell ratio = 230) was demonstrated using cervical cancer cells (HeLa S3) suspensions containing micron-size denatured albumin microspheres filled with air (Albunex) or octafluoropropane (Optison). The suspensions were insonificated by 2-MHz continuous or tone burst ultrasound in near field. The spatial peak-pressure amplitude was 0.2 MPa. The enhancement of cell destruction due to Optison was shown to be much higher than that due to Albunex for similar bubble concentration and ultrasound conditions. For tone burst exposures, significant lysis and sonoporation only occurred in the presence of a contrast agent. The majority of the bioeffects observed occurred in the first 5 min of exposure. The relationship between the enhancement of bioeffects and duty cycle of tone burst ultrasound appears to indicate that both stable gas spheres of contrast agents and cavitation nuclei created by the disruption of the gas spheres play a significant role in causing the bioeffects.     

Transient natural convection between concentric and vertically eccentric spheres with mixed boundary conditions

Transient analysis has been investigated numerically to determine heat transfer by natural convection between concentric and vertically eccentric spheres with constant heat flux on the inner wall and a specified isothermal temperature on the outer wall. The governing equations, in terms of vorticity, stream function and temperature are expressed in a spherical polar coordinate system. The alternating direction implicit method and the successive over-relaxation techniques are applied to solve the finite difference form of governing equations. A physical model is introduced which accounts for the effects of fluid buoyancy as well as eccentricity of the outer sphere. Transient solutions of the entire flow field are obtained for a range of modified Rayleigh number (10³<Ra?<5×10⁵), for a Prandtl number of 0.7 and a radius ratio of 2.0, with the outer sphere near the top and bottom of the inner sphere (ε=±0.625). Results of the parametric study conducted further reveal that the heat and flow fields are primarily dependent on the modified Rayleigh number and the eccentricity of the spherical annulus. The results of average Nusselt numbers are also compared with the results obtained for flow between two isothermal spheres.     

Syntheses,Structures and Anticancer Activity of NNO‐Tridentate Schiff Base Copper(II) Complexes

A series of heteroleptic copper(II) complexes [Cu( ^R QYMP )(Py]] ( 1a ‐ 4d ) supported on NNO‐tridentate Schiff base ( ^R QYMP ‐H) and bipyridine (Py=bpy, a ; phen, b ; dpq, c ; dppz, d ) co‐ligands have been synthesized and characterized. X‐ray crystal structural studies of complexes 1b , 2c , 3d and 4a displays that these complexes are mononuclear with a distorted square pyramidal geometry around the copper center. Cytotoxicity results indicate that all of these complexes have much higher activity against HeLa, SCC15, BCC and Ca9‐22 cancer cell lines as compared to cisplatin. Further, copper complex bearing suitable bulky group Schiff base ligands with dppz co‐ligand could be considered in designing efficient metalbased anticancer agents.     

A method to calculate the one‐electron reduction potentials for nitroaromatic compounds based on gas‐phase quantum mechanics

Nitroaromatic compounds (NACs) are widespread environmental contaminants, and the one‐electron reduction potential (E) is an important parameter used in modeling their environmental fate. We have identified a method that is both accurate and efficient to predict E values for NACs, using gas‐phase quantum mechanics (QM) calculations combined with empirical correlations. First, the adiabatic electron affinity (EA) at 0 K is calculated using the B98/MG3S method, and the predictions are scaled by a factor of 0.802 to account for systematic errors in the density functional calculations. Second, the E values are predicted from a linear correlation between E and EA. Using this method, E values were predicted with a mean absolute deviation from measured values of 0.021 V for the 14 NACs used to obtain the correlation and 0.029 V for six additional NACs. This represents a substantial improvement in accuracy over predictions by other QM methods, which are affected by large errors in solvation or aqueous‐phase calculations for some compounds. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010.     

Preparation of pH- and thermo-sensitive chitosan-PNIPAAm core–shell nanoparticles and evaluation as drug carriers

Environmentally sensitive polysaccharide nanoparticles (NPs) were prepared by in situ polymerization of N-isopropylacrylamide (NIPAAm) monomer in the presence of chitosan (CS) micelles. First, CS was found to develop a cationic micelle-like structure in the acetic acid solution when its concentration was increased to above the critical micelle concentration, as evidenced by fluorescence and TEM. When the NIPAAm was polymerized in the CS micelle solution by using potassium persulfate as initiator, the produced PNIPAAm with anionic chain end(s) became hydrophobic, as long as the reaction temperature was above its phase transition temperature; and therefore it would diffuse into the hydrophobic core of the CS micelles, producing CS-PNIPAAm core–shell NPs. Increasing the feeding amount of NIPAAm increased the monomer conversion and therefore the particle size; yet it decreased the surface zeta potential. Moreover, the CS-PNIPAAm NPs were sensitive to both pH value and temperature. For the study of drug release properties, doxycycline hyclate was used as a model drug and loaded into the NPs at pH 4.5 and 25 °C. The result illustrated that these NPs had a continuous drug release behavior up to 1 week, depending on the pH value and temperature. In addition, enzyme or hydrogen peroxide capable of degrading CS shell was added in the solution to facilitate the drug release.     

Low-level radioactive waste measurement comparisons of three gamma-ray counting systems

Three different gamma-ray counting systems constructed by 1–3 HPGe detectors were used in this study to compare their system performance. One measurement scheme involved positioning a single HPGe detector on a movable cart with a 90° collimation angle to the observed item. The other two waste assay systems were configured with two or three HPGe detectors towards the sample drums, while the three-HPGe-detector counting system was in a shielded counter cavity. The measurement consistency of 38 low-level waste drums, system operating costs and acquisition times to achieve the same MDA for these counting systems were compared and discussed in this study.     

Electrospun nylon-4,6 nanofibers: solution rheology and Brill transition

Polyelectrolyte solutions of nylon-4,6 in 99 vol.% formic acid were electrospun, and then the concentration effect on the solution spinnability was studied. The microstructure of the as-spun nanofibers was characterized by differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD). Based on the solution rheology, the concentration of the entangled regime and the concentrated regime (? _D ) were 1 and 10 wt.%, respectively. To prepare bead-free fibers, the minimum polymer concentration used was 10 wt.%, yielding a fiber diameter of 49?±?13 nm. The fiber diameter (d _f) was dependent on the solution viscosity ( $ {\eta_{\mathrm{o}}} $ ) or the polymer concentration (?_w) through the following simple scaling law relation: d _f?～? $ \eta_{\mathrm{o}}^{0.62 } $ and d _f?～? $ {{({\phi_{\mathrm{w}}}/{\phi_{\mathrm{D}}})}^{2.25 }} $ . DSC heating trace on the as-spun nanofibers exhibited double-melting behavior. However, after cooling, the second heating trace showed a single melting peak. WAXD intensity profiles showed that the as-spun nanofibers possessed lamellae with small lateral dimensions, and the lattice parameter difference between a-axis and b-axis was significantly reduced due to the rapid electrospinning process. Both structural features induce the occurrence of the Brill transition of nylon-4,6 in the nanofibers at a much lower temperature of 80 °C than that in the melt-processed film, as-revealed by the temperature-variable WAXD.     

Rheological properties of a telechelic associative polymer in the presence of alpha- and methylated beta-cyclodextrins

The viscosity of hydrophobic ethoxylated urethane (HEUR) solution decreased in the presence of alpha-CD or m-beta-CD; however their interactions were quite different. When the alpha-CD/hydrophobe molar ratio exceeded 5.0, the viscosity was close to that of a PEO solution of similar molecular weight. Oscillatory shear indicated that the mechanically active chains in HEUR solution decreased with the addition of alpha-CD. This agreed with the hypothesis that alpha-CD formed an inclusion complex with the hydrophobic moiety of the HEUR polymer, thereby destroying the transient hydrophobic associative network. The viscosity/temperature relationship of the alpha-CD/HEUR system (for HEUR with 70% of the PEO chains capped at both ends) did not obey the Arrhenius relationship for alpha-CD/hydrophobe molar ratio in the range 0.8-5.0. The low shear viscosity increased with increasing temperature at molar ratio of 1.0, and this was attributed to the competitive complexation of the alpha-CD/hydrophobe and the alpha-CD/PEO chain. Increasing temperature favored alpha-CD/PEO complexation. Comparison between the behavior of alpha-CD/HEUR and m-beta-CD/HEUR resulting from the different binding characteristics was discussed.     

Growth of Cu nanobelt and Ag belt-like materials by surfactant-assisted galvanic reductions

We demonstrate the syntheses of single crystalline Cu nanobelt and Ag belt-like materials via CTAC-assisted (CTAC, cetyltrimethylammonium chloride) galvanic reductions. The single crystalline face-centered cubic phase Cu nanobelt was prepared by reacting CuCl2(aq) with Al(s) in an aqueous solution of CTAC and HNO3. The Cu nanobelt exhibited a high-quality ribbon-like nanostructure with a thickness less than 15 nm, a width of 30-150 nm, and a length up to 10 microm. The belt-like Ag, with a thickness less than 10 nm, a width of 30-100 nm, a length up to 5 microm, and a novel single crystalline 4H structure, was prepared by reacting AgNO3(aq) and Cu(s) in an aqueous solution of CTAC.