Pervaporation of benzene/cyclohexane mixtures using ion-exchange membrane containing copper ions

The sorption, diffusion, and pervaporation (PV) properties of benzene/cyclohexane (Bz/Cx) mixtures on cation-exchange membranes containing copper ions (Cu(II)) were investigated. The equilibrium sorption isotherms of pure vapors in the membranes and the partial solubility of binary solutions in the membranes were described using the UNIQUAC model. The τ_iM and τ_Mi values were 0.978 and 0.591 for Bz, and 0.922 and 0.475 for Cx. The transient regimes of vapor sorption were employed to calculate the concentration-dependent diffusion coefficients. Long’s model sufficiently explained the diffusivity of Bz and Cx in the membranes. The pre-exponential factors were 3×10⁻¹³ m²/s and the plasticization factors were 3.0 and 3.6 for Bz and Cx, respectively. Excellent agreement was found with the experimental results applying the solubility and diffusivity data to simulate the pervaporation performance (flux and selectivity) using the modified Maxwell–Stefan equation. The membrane containing Cu(II) demonstrates better facilitating capability for Bz transport than that with Na(I), mainly due to its preferential sorption property toward Bz. Replacing Na(I) with Cu(II) into a Neosepta membrane resulted in better separation efficiency and higher Bz flux throughout the entire Bz concentration range.     

PHYCOBILIPROTEINS: COMPARISON OF SOLUTION AND SINGLE CRYSTAL FLUORESCENCE FOR C-PHYCOCYANIN AND B-PHYCOERYTHRIN*

Abstract— Trimeric and hexameric solution forms of C-phycocyanin (CPC) from the cyanophyte Agme-nellum quadruplicatum have been isolated and their spectral properties compared to those obtained from single crystals. Although the absorbance peak of a suspension of small C-phycocyanin crystals is red-shifted only 7 nm relative to the solution forms, the single crystal fluorescence is red-shifted 60 nm relative to the solution forms. The crystal fluorescence spectrum exhibits a single peak at LD_max= 708 nm when excited at 514.5 or 530.9 nm and two peaks (LD_max= 661 and 708 nm) when excitation occurs at 568.2 nm. Fluorescence depolarization measurements indicate that extensive energy transfer could occur for both solution and crystal forms with the latter being dependent upon the relative orientation of the crystal with respect to the excitation dipole. Similar results were obtained with B-phycoerythrin (BPE) from the red alga Porphyridium cruentum where the single crystal fluorescence is red-shifted =50nm relative to the solution spectra with two peaks (LD_max= 583 and 617 nm) observed whose relative intensities are dependent on the excitation wavelength (LD_max– 514.5 and 530.9 nm). Single crystal fluorescent lifetimes exhibited considerable shortening relative to that observed for the solution forms. The implications of these results are discussed with respect to the possible relationships of the crystalline structures to the assembly forms present within phycobilisomes.     

Spontaneous macroscopic spin polarization in independent spinor Bose-Einstein condensates

We present experimental evidence for the spontaneous formation of a macroscopic spin polarization in overlapping regions of two independent Bose-Einstein condensates produced in different hyperfine states of 87Rb. The condensates are independent in the sense that we do not explicitly introduce a relative phase between them. A single "spin-tip" pulse maps the transverse spin polarization into longitudinal spin polarization, and the atomic density distributions are measured with a Stern-Gerlach imaging method. The resulting matter-wave interference patterns are anticorrelated.     

Determination of multiresidue pesticides in green tea by using a modified QuEChERS extraction and ion-trap gas chromatography/mass spectrometry

The pesticide residues in exported and imported tea products must not exceed the maximum residue limits (MRLs) regulated by the import countries. Tea is a complex matrix that obfuscates the determination of pesticide residues. Many available methods for multiresidue pesticide analysis of tea are time-consuming and require many cleanup steps. The objective of this study was to develop a simple multiresidue method by using a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction and ion-trap GC/MS/MS, which can identify, confirm, and quantify pesticides in complex matrixes. A tea product was homogenized with water, and the pesticides were extracted with acetonitrile containing 1% acetic acid. The extract was subjected to centrifugation, initial cleanup with dispersive SPE (dSPE), solvent exchange, and final cleanup with dSPE. Diethyl-d10-parathion and triphenyl phosphate were used as the internal standard and surrogate, respectively. The final extract was injected into an ITQ 700 gas chromatograph/mass spectrometer. Quantitation of individual pesticides was based on matrix-matched calibration curves with a correlation coefficient of > 0.9930 for the 22 pesticides selected for the study. The recoveries of the 22 pesticides ranged from 78 to 115%, except those for diazinon (130%) and malathion (122%), with an average RSD of 8.7%. The LOD values of all of the pesticides, except for terbufos, were below the MRLs set by the European Union and Japan.     

Stable Anticancer Gold(III)–Porphyrin Complexes: Effects of Porphyrin Structure

In the design of physiologically stable anticancer gold(III) complexes, we have employed strongly chelating porphyrinato ligands to stabilize a gold(III) ion [Chem. Commun. 2003 , 1718; Coord. Chem. Rev. 2009 , 253, 1682]. In this work, a family of gold(III) tetraarylporphyrins with porphyrinato ligands containing different peripheral substituents on the meso‐aryl rings were prepared, and these complexes were used to study the structure–bioactivity relationship. The cytotoxic IC₅₀ values of [Au(Por)]⁺ (Por=porphyrinato ligand), which range from 0.033 to >100 μM , correlate with their lipophilicity and cellular uptake. Some of them induce apoptosis and display preferential cytotoxicity toward cancer cells than to normal noncancerous cells. A new gold(III)–porphyrin with saccharide conjugation [Au(4‐glucosyl‐TPP)]Cl ( 2 a ; H₂(4‐glucosyl‐TPP)=meso‐tetrakis(4‐β‐D ‐glucosylphenyl)porphyrin) exhibits significant cytostatic activity to cancer cells (IC₅₀=1.2–9.0 μM ) without causing cell death and is much less toxic to lung fibroblast cells (IC₅₀>100 μM ). The gold(III)–porphyrin complexes induce S‐phase cell‐cycle arrest of cancer cells as indicated by flow cytometric analysis, suggesting that the anticancer activity may be, in part, due to termination of DNA replication. The gold(III)–porphyrin complexes can bind to DNA in vitro with binding constants in the range of 4.9×10⁵ to 4.1×10⁶ dm³ mol^?1 as determined by absorption titration. Complexes 2 a and [Au(TMPyP)]Cl₅ ( 4 a ; [H₂TMPyP]⁴⁺=meso‐tetrakis(N‐methylpyridinium‐4‐yl)porphyrin) interact with DNA in a manner similar to the DNA intercalator ethidium bromide as revealed by gel mobility shift assays and viscosity measurements. Both of them also inhibited the topoisomerase I induced relaxation of supercoiled DNA. Complex 4 a , a gold(III) derivative of the known G‐quadruplex‐interactive porphyrin [H₂TMPyP]⁴⁺, can similarly inhibit the amplification of a DNA substrate containing G‐quadruplex structures in a polymerase chain reaction stop assay. In contrast to these reported complexes, complex 2 a and the parental gold(III)–porphyrin 1 a do not display a significant inhibitory effect (<10 %) on telomerase. Based on the results of protein expression analysis and computational docking experiments, the anti‐apoptotic bcl‐2 protein is a potential target for those gold(III)–porphyrin complexes with apoptosis‐inducing properties. Complex 2 a also displays prominent anti‐angiogenic properties in vitro. Taken together, the enhanced stabilization of the gold(III) ion and the ease of structural modification render porphyrins an attractive ligand system in the development of physiologically stable gold(III) complexes with anticancer and anti‐angiogenic activities.     

Sorption of Organic Solvents in Poly(Dimethyl Siloxane) Membrane. I. Permeant States Quantification using Differential Scanning Calorimetry

The permeant states of various solvents in poly(dimethyl siloxane) (PDMS) film were evaluated using low temperature differential scanning calorirnetry (DSC) on both vapor and liquid penetrants. Water, cyclohexane, benzene, toluene, and m‐xylene may be present in the freezable and nonfreezable state. At low sorption levels, solvents sorbed in PDMS were in the nonfreezable state until a threshold value was reached. Beyond that, the increased solvent sorption values all occurred in a freezable state. The partition pattern between the freezable and nonfreezable states for a vapor penetrant showed an identical trend with that for the liquid penetrant. The maximum nonfreezable amount of solvent in PDMS depended on the solvent's chemical compatibility with the membrane but not on the sorption temperature. Compared with that at 10°C, the higher solvent solubility at 25°C was due to the increase in the freezable solvent content without any change in the maximum nonfreezable content. The permeant states for equilibrium and nonequilibrium samples did not differ from one another.     

Increasing Reduction Potentials of Type 1 Copper Center and Catalytic Efficiency of Small Laccase from Streptomyces coelicolor through Secondary Coordination Sphere Mutations

The key to type 1 copper (T1Cu) function lies in the fine tuning of the Cu^II/I reduction potential (E°′_T1Cu) to match those of its redox partners, enabling efficient electron transfer in a wide range of biological systems. While the secondary coordination sphere (SCS) effects have been used to tune E°′_T1Cu in azurin over a wide range, these principles are yet to be generalized to other T1Cu-containing proteins to tune catalytic properties. To this end, we have examined the effects of Y229F, V290N and S292F mutations around the T1Cu of small laccase (SLAC) from Streptomyces coelicolor to match the high E°′_T1Cu of fungal laccases. Using ultraviolet-visible absorption and electron paramagnetic resonance spectroscopies, together with X-ray crystallography and redox titrations, we have probed the influence of SCS mutations on the T1Cu and corresponding E°′_T1Cu. While minimal and small E°′_T1Cu increases are observed in Y229F- and S292F-SLAC, the V290N mutant exhibits a major E°′_T1Cu increase. Moreover, the influence of these mutations on E°′_T1Cu is additive, culminating in a triple mutant Y229F/V290N/S292F-SLAC with the highest E°′_T1Cu of 556 mV vs. SHE reported to date. Further activity assays indicate that all mutants retain oxygen reduction reaction activity, and display improved catalytic efficiencies (k_cat/K_M) relative to WT-SLAC.     

Drug permeation modeling through the thermo-sensitive membranes of poly(N-isopropylacrylamide) brushes grafted onto micro-porous films

Temperature-sensitive N-isopropylacrylamide (NIPAAm) polymer brushes of known molecular weight (20k–25k) were grafted onto micro-porous polycarbonate (PC) films (pore size 0.4 μm) using argon plasma treatment. The resulting composite membranes were tested for controlled drug release at various grafted chain density, which was controlled using 1–3% polymer concentrations. The composites were also characterized in terms of graft yield, membrane thickness, Fourier transform infrared (FTIR) spectra and scanning electron micrography (SEM). The drug permeabilities of 4-acetamidophenol and ranitidine HCl in the resulting membranes were determined at temperatures between 30 and 40 °C. The drug permeability changed remarkably at 34 °C, near the lower critical solution temperature (LCST). The drug passage was regulated by swelling (which occurs at a temperature lower than the LCST) or shrinkage (occurring at an elevated temperature) of the PNIPAAm polymer brushes. These membranes demonstrated on–off ratios of drug permeabilities up to 11 and 14 for the model drugs, respectively. These values are higher than most literature data with similar-size model molecules. The excellent on–off valve mechanism was discussed in terms of the suitable molecular weight and grafted chain density in relation to the pore size and porosity of the PC support. A mathematical model was proposed to predict the drug permeation flux based on the gel conformation data, graft density, characteristics of the micro-porous support, and drug concentrations and diffusivities in water and in the PNIPAAm gel. The model can successfully estimate the drug permeation flux through the composite with higher (0.42 mg cm⁻²) graft density with a coefficient of determination of 0.95. The discrepancy between the predicted and experimental data at the lower graft density (0.12 mg cm⁻²) was ascribed to pore channel narrowing resulting from the uneven polymer chain distribution.     

Cosmological solutions with charged black holes

We consider the problem of constructing cosmological solutions of the Einstein–Maxwell equations that contain multiple charged black holes. By considering the field equations as a set of constraint and evolution equations, we construct exact initial data for N charged black holes on a hypersphere. This corresponds to the maximum of expansion of a cosmological solution, and provides sufficient information for a unique evolution. We then consider the specific example of a universe that contains eight charged black holes, and show that the existence of non-zero electric charge reduces the scale of the cosmological region of the space. These solutions generalize the Majumdar–Papapetrou solutions away from the extremal limit of charged black holes, and provide what we believe to be some of the first relativistic calculations of the effects of electric charge on cosmological backreaction.     

Introduction of Primary Amino Groups on Poly(ethylene terephthalate) Surfaces by Ammonia and a Mix of Nitrogen and Hydrogen Plasma

With the aim of introducing primary amino groups on the surface of poly(ethylene terephthalate) (PET), two methods were compared—the use of ammonia or a combination of nitrogen and hydrogen low-pressure microwave plasma. Several plasma parameters were optimized on the reactor to increase the –NH₂ surface density, which was estimated by colorimetric titration and X-ray photoelectron spectroscopy (XPS). These techniques show that whatever the plasma treatment, almost 2 –NH₂/nm2 are incorporated on PET films. Emission spectroscopy highlighted a correlation between the density of primary amino groups and the ratio between an NH peak intensity and an Ar peak intensity (I_NH/I_Ar). Variation in surface hydrophilicity with aging in air after plasma treatment was monitored with contact angle measurements and showed a hydrophobic recovery. This was confirmed by XPS, which suggests also that surfaces treated by NH₃ plasma are more stable than surfaces treated by N₂/H₂.