Thermal behavior of metallodendrimers possessing bis(terpyridinyl)Ru(II) connectivity and different surface functionality

A series of metallodendrimers, assembled by means of bis(terpyridinyl)Ru^(II) connectivity on poly(propylene imine) dendrimer scaffolds, with homogeneous or heterogeneous surfaces, were prepared. Differential scanning calorimetry and thermogravimetric analysis were used to determine their thermal behavior, glass‐transition temperatures, and the decomposition kinetics and temperatures; no synergy effects for these properties were observed for the heterogeneously surfaced constructs in contrast to the corresponding homogeneously coated materials, which exhibited different values depending on their surface functionalities. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1487–1495, 2004     

A new luciferase reporter gene assay for the detection of androgenic and antiandrogenic effects based on a human prostate specific antigen promoter and PC3/AR human prostate cancer cells.

We developed a new mammalian cell-based luciferase reporter gene assay for androgenic and antiandrogenic activities of chemicals and environmental samples. Environmental samples usually have a complex matrix that may contain the constituents acting as androgen receptor (AR) agonists, AR antagonists or aryl hydrocarbon receptor (AhR) agonists. AhR agonists are known to elicit the antiandrogenic effect through cross-talk between AR and AhR signal transduction pathways. In this study, PC3/AR human prostate carcinoma cells were transiently transfected with a prostate-specific antigen (PSA) promoter-driven luciferase expression plasmid. The cells were treated with a test compound or an environmental sample for 24 h at 37 degrees C and then measured for luciferase activity. The luciferase activity was induced by dihydrotestosterone (DHT) in a concentration-dependent manner in a concentration range from 10 fM to 1 nM. R1881, a synthetic androgen receptor agonist, induced luciferase activity and its inductive effects was additive to that of DHT. The luciferase activity was not induced by cortisol, a glucocorticoid, progesterone, a progestin, and 17beta-estradiol, an estrogen in a concentration range of up to 1 microM. DHT-induced luciferase activity was reduced by bicalutamide and cyproterone acetate, AR antagonists, and also by benzo[a]pyrene, an aryl hydrocarbon receptor agonist, through AhR-mediated pathways. All of these findings indicate that the present assay system correctly responds to AR agonists, AR antagonists and AhR agonist and, therefore, it is a powerful tool for the sensitive and selective screening of chemicals and environmental samples for their androgenic and antiandrogenic activities. We developed the first assay system, in which the expression of luciferase was driven by the promoter of a prostate-specific antigen gene, a typical human androgen-regulated gene.     

Determination of nickel in alloys and plant leaves with salicylaldehyde 3-oxobutanoylhydrazone by spectrophotometry.

A simple and highly sensitive reagent of salicylaldehyde 3-oxobutanoylhydrazone (salicylaldehyde acetoacetic acid hydrazone, SAAH) was synthesized and studied for the spectrophotometric determination of nickel in detail. In the pH range 6, which greatly increased the selectivity, nickel reacted with SAAH to form a 1:1 yellow complex, having a sensitive absorption peak at 405 nm. Under the optimal conditions, Beer's law was obeyed over the range from 0.0117 to 0.1174 microg cm(-3). The apparent molar absorptivity was 3.025 x 10(5) dm3 mol(-1) cm(-1). The detection limit and the variation coefficient were found to be 1.752 ng cm(-3) and 1.0%, respectively. The method has been applied to the quantitative determination of nickel in different alloys and leaves.     

Dynamic surface tension measurements of surfactant solutions using the maximum bubble pressure method – limits of applicability

One of the essential differences in the design of bubble pressure tensiometers consists in the geometry of the measuring capillaries. To reach extremely short adsorption times of milliseconds and below, the so-called deadtime of the capillaries must be of the order of some 10 ms. In particular, for concentrated surfactant solutions, such as micellar solutions, short deadtimes are needed to minimize the initial surfactant load of the generated bubbles. A theoretical model is derived and confirmed by experiments performed for a wide range of experimental conditions, mainly in respect to variations in deadtime and bubble volume.     

Wide‐angle X‐ray diffraction and differential scanning calorimetry study of the crystallization of poly(ethylene naphthalate), poly(butylene naphthalate), and their copolymers

The crystallization behavior of a series of poly(ethylene‐co‐butylene naphthalate) (PEBN) random copolymers was studied. Wide‐angle X‐ray diffraction (WAXD) patterns showed that the crystallization of these copolymers could occur over the entire range of compositions. This resulted in the formation of poly(ethylene naphthalate) or poly(butylene naphthalate) crystals, depending on the composition of the copolymers. Sharp diffraction peaks were observed, except for 50/50 PEBN. Eutectic behavior was also observed. This showed isodimorphic cocrystallization of the PEBN copolymers. The variation of the enthalpy of fusion of the copolymers with the composition was estimated. The isothermal and nonisothermal crystallization kinetics were studied. The crystallization rates were found to decrease as the comonomer unit content increased. The tensile properties were also measured and were found to decrease as the butylene naphthalate content of the copolymers increased. For initially amorphous specimens, orientation was proved by WAXD patterns after drawing, but no crystalline reflections were observed. However, the fast crystallization of drawn specimens occurred when they were heated above the glass‐transition temperature. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 843–860, 2004     

Structure of a poly(2,5‐benzimidazole)/phosphoric acid complex

As‐cast films of poly(2,5‐benzimidazole) exhibit uniplanar orientation in which the planes of the aromatic rings lie parallel to the film surface. Upon doping with phosphoric acid, the original crystalline order is lost, but the doped film can be stretched to produce films with uniaxial orientation. After thermal annealing at 540 °C, nine Bragg reflections are resolved in the fiber diagram, and these are indexed by an orthorhombic unit cell with the dimensions a = 18.1 Å, b = 3.5 Å, and c = 11.4 Å, containing four monomer units of two chains. The absence of odd‐order 00l reflections points to a 2₁ chain conformation, which is probably planar so that the aromatic units can be stacked along the b axis. The water and phosphoric acid contents of the crystalline structure cannot be determined exactly because of the presence of extensive amorphous regions that probably have different solvation. The best agreement between the observed and calculated intensities is for an idealized structure containing two phosphoric acids and two water molecules per unit cell. However, the phosphoric acid is probably present mainly in the form of pyrophosphoric acid and its higher oligomers. In addition, the X‐ray data are consistent with a more disordered structure containing chains with random (up and down) polarity and a lack of c‐axis registry. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2576–2585, 2004     

Plasticized microporous poly(vinylidene fluoride) separators for lithium-ion batteries. III. Gel properties and irreversible modifications of poly(vinylidene fluoride) membranes under swelling in liquid electrolytes

Microporous poly(vinylidene fluoride) (PVdF) separators for lithium-ion batteries, used in liquid organic electrolytes, have been characterized with respect to the swelling phenomena on dense PVdF membranes (obtained through hot pressing). In the first and second parts of this study, we have described the swelling equilibria and swelling kinetics of dense PVdF. Here the thermal properties of PVdF gels and their irreversible modifications induced by swelling are characterized. Particular attention is paid to crystallinity modifications, polymer plasticization, and membrane degradation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2308–2317, 2004     

Statistical thermodynamics evaluation of polymer–polymer miscibility

The Simha and Somcynsky (S–S) statistical thermodynamics theory was used to compute the solubility parameters as a function of temperature and pressure [δ = δ(T, P)], for a series of polymer melts. The characteristic scaling parameters required for this task, P*, T*, and V*, were extracted from the pressure–temperature–volume (PVT) data. To determine the potential polymer–polymer miscibility, the dependence of δ versus T (at ambient pressure) was computed for 17 polymers. Close proximity of the δ versus T curves for four miscible polymer pairs: PPE/PS, PS/PVME, and PC/PMMA signaled the usefulness of this approach. It is noteworthy, that the tabulated solubility parameters (derived from the solution data under ambient conditions) propounded the immiscibility of the PVC/PVAc pair. The computed values of δ also suggested miscibility for polymer pairs of unknown miscibility, namely PPE/PVC, PPE/PVAc, and PET/PSF. In recognizing the limitations of the solubility parameter approach (the omission of several thermodynamic contributions), these preliminary results are auspicious because they indicate a new route for estimating the miscibility of any polymeric material at a given temperature and pressure. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2909–2915, 2004     

Non-protein amino acids in peptide design

An overview of the use of non-protein amino acids in the design of conformationally well-defined peptides, based on work from the author’s laboratory, is discussed. The crystal structures of several designed oligopeptides illustrate the useα-aminoisobutyric acid (Aib) in the construction of helices, D-amino acids in the design of helix termination segments and^DPro-Xxx segments for nucleating ofβ-hairpin structures.β- andγ-amino acid residues have been used to expand the range of designed polypeptide structures. Dedicated to Professor C N R Rao on his 70th birthday     

Karhunen–Loeve representations of turbulent channel flows using the method of snapshots

For three‐dimensional flows with one inhomogeneous spatial coordinate and two periodic directions, the Karhunen–Loeve procedure is typically formulated as a spatial eigenvalue problem. This is normally referred to as the direct method (DM). Here we derive an equivalent formulation in which the eigenvalue problem is formulated in the temporal coordinate. It is shown that this so‐called method of snapshots (MOS) has some numerical advantages when compared to the DM. In particular, the MOS can be formulated purely as a matrix composed of scalars, thus avoiding the need to construct a matrix of matrices as in the DM. In addition, the MOS avoids the need for so‐called weight functions, which emerge in the DM as a result of the non‐uniform grid typically employed in the inhomogeneous direction. The avoidance of such weight functions, which may exhibit singular behaviour, guarantees satisfaction of the boundary conditions. The MOS is applied to data sets recently obtained from the direct simulation of turbulence in a channel in which viscoelasticity is imparted to the fluid using a Giesekus model. The analysis reveals a steep drop in the dimensionality of the turbulence as viscoelasticity is increased. This is consistent with the results that have been obtained with other viscoelastic models, thus revealing an essential generic feature of polymer‐induced drag reduced turbulent flows. Published in 2006 by John Wiley & Sons, Ltd.