Effects of pressure and solvent on the diffusion of aromatic compounds through polymers

The diffusion of six azo and five anthraquinone derivatives through nylon 6, poly(ethylene terephthalate) and secondary cellulose acetate films were studied under high hydrostatic pressures of up to 3000 bar and at temperatures 80–130 °C, by analyzing the diffusion profiles yielded in a stacked multiple film, placed in the solution of the diffusant. It was found that the diffusion coefficient,D, of the diffusant decreased with increasing pressure, giving a linear relationship between InD and the pressure, the slope of which gave the activation volume for the diffusion,V . It was revealedV increased linearly with increasing intrinsic molecular volume of the diffusant,V _w , the slopes being different between the azo and the anthraquinone derivatives. The ratio ofV toV _w (V /V _w ) ranged from 0.13 to 0.93, depending in a sensitive manner on the degree of swelling of the polymer matrix which in turn was varied by the solvent. The overall results could be explained in accordance with the formulation,V _{f, local} +V =V _w , whereV _{f, local} represents the free volume contribution. It was proposed thatV _w is increased by solvation when the solvent is good for the diffusant.     

Biosensors based on gold nanoelectrode ensembles and screen printed electrodes

Gold nanowires were synthesized within polycarbonate membranes according to an electroless deposition method, obtaining nanoelectrode ensembles (NEEs) with special electrochemical features. NEEs were coupled with home-produced carbon graphite screen printed electrodes and the electrochemical properties of the original nanoelectrode ensemble on screen printed substrate (NEE/SPS) assembly has been tested for sensors application. Glucose oxidase has been used as model enzyme in order to verify the feasibility of disposable gold NEE/SPS biosensors. Finally, different immobilisation and electrochemical deposition techniques based on either self assembled monolayers of cysteamine (CYS) or amino-propyl-triethoxysilane (APTES) and conductive polyaniline (PANI) molecular wires were used. Spatial patterning of the enzyme on the polycarbonate surface and of PANI wires on gold nanoelectrodes was obtained. Possible direct electron transfer between the enzyme and the PANI modified gold nanoelectrodes has been evaluated.     

Phosphoproteome Profiling Using a Fluorescent Phosphosensor Dye in Two-Dimensional Polyacrylamide Gel Electrophoresis

We validated the novel PhosphoQUANTI SolidBlue Complex (PQSC) dye for the sensitive fluorescent detection of phosphorylated proteins in polyacrylamide- and two-dimensional gel electrophoresis (PAGE and 2DE, respectively). PQSC can detect as little as 15.6 ng of ß-casein, a pentaphosphorylated protein, and 61.3 ng of ovalbumin, a diphosphorylated protein. Fluorescence intensity correlates with the number of phosphorylated residues on the protein. To demonstrate the specificity of PQSC for phosphoproteins, enzymatically dephosphorylated lysates of Swiss 3T3 cells were separated in 2DE gels and stained by PQSC. The fluorescence signals in these gels were markedly reduced following dephosphorylation. When the phosphorylated proteins in Swiss 3T3 cell lysates were concentrated using a phosphoprotein enrichment column, the majority of phosphoproteins showed fluorescence signals in the pI 4–5 range. Finally, we performed phosphoproteome analysis to study differences in the protein phosphorylation profiles of proliferating and quiescent Swiss 3T3 cells. Over 135 discernible protein spots were detected, from which a selection of 15 spots were identified by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI TOF-MS). The PQSC staining procedure for phosphoprotein detection is simple, reversible, and fully compatible with MALDI TOF-MS.     

Frequency stabilization of a HeNe laser using a thin film heater coated on the laser tube

The cavity length of an internal-mirror HeNe laser was controlled using a thin film heater coated on the tube. The response speed was about ten times higher than that of the usual tube wound with a ribbon heater. The high response speed brought two merits in frequency stabilization of the laser; one was improvement of stability in the short time region and the other was the realization of a thermal modulation method, by which the cavity was stabilized at Lamb's dip.     

Analytical and numerical studies of the boundary slip in the immersed boundary‐thermal lattice Boltzmann method

We analytically and numerically investigate the boundary slip, including the velocity slip and the temperature jump, in immersed boundary‐thermal lattice Boltzmann methods (IB‐TLBMs) with the two‐relaxation‐time collision operator. We derive the theoretical equation for the relaxation parameters considering the effect of the advection velocity on the temperature jump of the IB‐TLBMs. The analytical and numerical solutions demonstrate that the proposed iterative correction methods without the computational cost of the sparse matrix solver reduce the boundary slip and boundary‐value deviation as effectively as the implicit correction method for any relaxation time. Because the commonly used multi‐direct forcing method does not consider the contributions of the body force to the momentum flux, it cannot completely eliminate the boundary slip because of the numerical instability for a long relaxation time. Both types of proposed iterative correction methods are more numerically stable than the implicit correction method. In simulations of flow past a circular cylinder and of natural convection, the present iterative correction methods yield adequate results without the errors of the velocity slip, the temperature jump, and the boundary‐value deviation for any relaxation time parameters and for any number of Lagrangian points per length. The combination of the present methods and the two‐relaxation‐time collision operator is suitable for simulating fluid flow with thermal convection in the multiblock method in which the relaxation time increases in inverse proportion to the grid size.     

Synthesis and in vitro antifungal activities of novel triazole antifungal agent CS-758.

Synthesis and in vitro antifungal activities of a novel triazole antifungal agent CS-758 (former name, R-120758) are described. The minimum inhibitory concentrations (MICs) of a series of dioxane-triazole compounds related to R-102557 were examined. Variation of the length of the chain between the dioxane ring and the phenyl ring revealed that the linkage with two double bonds is the most preferable. When a cyano group was introduced to the C4 position on the benzene ring, MICs improved further. A fluorine atom was introduced to obtain CS-758. The MICs of CS-758 surpassed those of fluconazole and itraconazole against Candida, Aspergillus and Cryptococcus species. The precursor (E,E)-aldehyde was synthesized stereoselectively from 3-fluoro-4-methylbenzonitrile using the Horner-Wadsworth-Emmons reaction.     

Nanofibrous Membranes Containing Carbon Nanotubes: Electrospun for Redox Enzyme Immobilization

Summary: Nanofibrous membranes that possess reactive groups are fabricated by the electrospinning process from PANCAA solutions that contain MWCNTs. Field emission scanning electron microscopy is used to evaluate the morphology and diameter of the nanofibers. Potentials for applying these nanofibrous membranes to immobilize redox enzymes by covalent bonding are explored. It is envisaged that the electrospun nanofibrous membranes could provide a large specific area and the MWCNTs could donate/accept electrons for the immobilized redox enzymes. Results indicate that, after blending with MWCNTs, the diameter of the PANCAA nanofiber increases slightly. The PANCAA/MWCNT nanofibrous membranes immobilize more enzymes than that without MWCNTs. Moreover, as the concentration of the MWCNTs increases, the activity of the immobilized catalase is enhanced by about 42%, which is mainly attributed to the promoted electron transfer through charge‐transfer complexes and the π system of MWCNTs.

The covalent immobilization of redox enzymes, such as catalase, on a PANCAA/MWCNTs nanofiber.     

Diffusion of linear aliphatic esters in polyethylene as a function of chain length of the esters,pressure and temperature

Diffusion of linear aliphatic mono- and diesters (C _N ) havingN main chain atoms (N=13–68) in bulk medium-density polyethylene (MDPE) has been studied under hydrostatic pressures up to 2500 bar at temperatures between 60°C and 125°C. Three triglycerides, phenyl stearate, and p-aminoazobenzene (pAAB, 80°C) as the diffusants and low-density (LDPE) and high-density (HDPE) polyethylenes as polyethylene substrate were used for comparison. Diffusion coefficientD was determined from concentration distribution of the diffusants through stacked PE sheets as substrate. Regarding the linear esters at 90°C, the relationshipD N holds at constant pressures. Under the atmospheric pressure, became –2.10 in accordance with de Gennes's proposal (1971)D N ^–2 as well as with the experimental results reported by Klein and Briscoe (1979) forN larger than 30.D's for the glycerides deviate from the relationshipD N ^–2 toward the smaller values by comparison at the sameN. The exponent is pressure-dependent. It decreases with increasing pressure according to =–2.10–0.000942P, whereP is measured by the unit of bar. Plots of lnD vsP for all the diffusants show linear relationships with negative slopes, from which activation volume for the diffusion V was calculated. At 90°C, V increases slowly with increasingN and increasingV _Ki, the intrinsic molecular volume of the diffusant, from 39.3 cm³/mol for ethyl caprate (C ₁₃,V _Ki=136 cm³/mol) to 76.8 cm³/mol for behenyl behenate (C₄₅,V _Ki=466 cm³/mol). Observed V s are explainable on the basis of the reptation mode of the chain molecule diffusion. V s for C₂₅ and C₄₅ are found to increase with increasing degree of crystallinity where MDPE, heat-treated MDPE, LDPE, and HDPE were used. The results obtained by varying temperature are as follows. V for C₄₅ was always found to be larger than C₂₅. Both decreased linearly with increasing temperature, giving two linear lines with different slopes whose extensions intersected at 132°C, the melting point of the MDPE, where the difference in V disappeared. The apparent activation energiesE _Ds for the diffusion of C₂₅ and C₄₅ increased linearly with increasing pressure, whose slopes are explainable according toE _D=E ₀+PV [1-(dln V /dlnT) _P ].     

Dosage potentiometrique des ions alkyl-trimethyl-ammonium a longue chaine et tetrabutyl-ammonium

A method of potentiometric titration of dodecyltrimethylammonium, tetradecyltrimethylammonium, hexadecyltrimethylammonium and tetrabutylammonium ions in aqueous solution is described. The ion-selective electrode which is used is a new liquid element electrode model. The principle of titration involves some results of the study of liquid phase electric cells.

Zusammenfassung

Eine Methode zur potentiometrischen Titration von Dodecyl-trimethyl-ammonium-, Tetradecyl-trimethylammonium-, Hexadecyl-trimethylammonium- und Tetrabutyl-ammonium-Ionen in wässrigen Lösungen wird beschrieben. Die ionen-selektive Elektrode, die hier angewandt wird, ist ein neues Modell einer Elektrode mit Flüssigkeitszelle. Das Prinzip der Titration schliesst einige Ergebnisse der Untersuchung von elektrischen Flüssigkeitszellen ein.