Tuning of the alpha-terthiophene radical cation coupling reaction using mixed micelles with varying charge density.

The photophysics and photochemistry of alpha-terthiophene (alphaT), compartmentalized in mixed nonionic/anionic micelles, have been investigated with focus on the influence of the micellar surface charge density on the formation of the radical coupling product alpha-hexathiophene (alphaH). By varying the ratio of nonionic-to-anionic surfactants, and assuming ideal mixing, the charge density of the mixed micelles was varied. From Poisson-Boltzmann calculations, performed using the cell model, the electrostatic potential and the counterion activity were estimated as a function of the distance from the micellar surface. Upon excitation, the triplet state of alphaT is formed, from which the alphaT radical cation can be formed by absorption of a second photon. The radical cation can form alphaH if it encounters another alphaT radical cation. Under the experimental conditions used, this implies that the alphaH formation only occurs if the compartmentalized radical cation is able to migrate from its host micelle to another micelle, either via the surrounding bulk or by fusion of two micelles followed by mixing of their contents before micellar fission. The formation yield of the radical cation depends on the charge density of the mixed micelle; a lower charge density, that is, an increased amount of nonionic surfactant, lowers the yield. The yield of the coupling product alphaH, however, does not follow the same trend. A maximum yield of alphaH is found at intermediate nonionic surfactant molar ratios. This behavior is understood in terms of the Poisson-Boltzmann simulation results and by comparing charge-density changes as a function of molar fraction with the changes in counterion activity. The alphaH yield is a result of the balance between an increased possibility of radical cation bulk migration and a lowered electrostatic stabilization of the radical.     

Viscosity solutions of Isaacs' equations and differential games with Lipschitz controls

It is demonstrated that the upper and lower values of a two-person, zero-sum differential game solve the respective upper and lower Isaacs' equations in the viscosity sense (introduced by Crandall and Lions (Trans. Amer. Math. Soc. 277 (1983), 1–42). Since such solutions are unique, this yields a fairly simple proof that the game has value should the minimax condition hold. As a further application of viscosity techniques, a new and simpler proof that the upper and lower values can be approximated by the values of certain games with Lipschitz controls is given.     

Effect of pressure and temperature on electrolyte conductance in 2-propanol

Equivalent conductances for tetrabutylammonium chloride, bromide, iodide, and perchlorate and lithium chloride were determined in 2-propanol at 10, 25, and 40°C over the pressure range 1 to 3,000 kg-cm^?2. The data are analyzed with the 1975 Fuoss-Onsager equation. The limiting equivalent conductances and association constants show the same level of precision as generally obtained in high precision conductance measurements at 1 atmosphere. The unusual association pattern observed for electrolytes in alcohols persisted up to the highest pressures used in this study.     

Meso-oxidation of some metalloporphyrins

Treatment of porphyrins with thallium(III) trifluoroacetate in the presence of trifluoroacetic acid results in uncontrolled oxidation at the macrocyclic meso-positions, presumably via radical processes. For example, a mixture of the thallium(III) α γ-dioxoporphodimethene (4a; R = Et), the αβγ-trioxo compound (3), and octaethylxanthoporphyrinogen (6) is obtained when octaethylporphyrin (1; R = Et) is oxidised in the presence of air. More controlled oxidation is achieved when the meso-trifluoroacetoxyporphyrin complexes (8a, b) or metallo-oxophlorins (7a, b) are treated with mild bases in air, the major products being metallo-αγ-dioxoporphodimethenes (4b, c).β-Hydroxy-α-oxophlorins (16) are isolated and characterised for the first time; aspects of the chemistry of this novel oxygenated porphyrin system are reported.     

Tests for liquid chromatographs

Summary The paper describes tests for liquid chromatographs to assess the autosampler and pump flow rate precision; suitability of the instrument for normal phase chromatography; UV detector performance; and external band broadening characteristics. Tests for mixing and proportioning characteristics of solvent pumps and performance of diode array detectors are also considered. These tests are designed to evaluate the performance of both newly released liquid chromatography equipment and equipment already in operation. Data from evaluations carried out by instrument manufacturer’s and suppliers is reported and discussed. This data offers specifications to a common format for initial selection of instruments prior to purchase.     

Modified nucleosides in human serum.

Methylated purines and pyrimidines derived from the degradation of transfer ribonucleic acid have been shown to be excreted in abnormal amounts in the urine of patients with cancer. Recent technology developed by Gehrke and Kuo has allowed the separation and quantification of modified nucleosides in serum using reversed-phase high-performance liquid chromatography with diode-array measurement. Serum levels of ten modified nucleosides were measured in 37 normal healthy adults to establish normal values and to correlate activity with age and sex. In addition, serum levels of patients with several malignancies were measured to determine activity in these diseases. Levels of modified nucleosides in normal individuals were consistently reproducible and showed no significant variation among males versus females or with age. Patients with malignant diseases showed consistent elevations and these were highest in patients with more advanced disease. The evidence of no significant differences in the mean levels of modified nucleosides in serum with age or sex in normal adults and elevations in patients with malignancies demonstrate the potential value of modified nucleosides as cancer biomarkers.     

Probing the conformational features of a phage display polypeptide sequence directed against single-walled carbon nanohorn surfaces

Single-walled carbon nanohorns (SWNHs) are interesting carbon nanostructures that have applications to science and technology. Using M13 phage display technology, polypeptides directed again SWNHs surfaces have been created for a number of nanotechnology and pharmaceutical purposes, yet the molecular mechanism of polypeptide sequence interaction and binding to SWNHs surfaces is not known. Recently, we identified a linear 12-AA M13 phage pIII sequence, NH-12-5-2 (DYFSSPYYEQLF), that binds with high affinity to SWNHs surfaces. To probe the structure of this pIII tail polypeptide further, we investigated the conformation of a model peptide representing the 12 AA NH-12-5-2 sequence. At neutral pH, the NH-12-5-2 model polypeptide is conformationally labile and exhibits two-state conformational exchange involving the D1-S5 N-terminal segment. Simultaneous with this conformational exchange process is the observation that the P6 residue exhibits imido ring conformational variation. In the presence of the structure-stabilizing solvent, TFE, or at pH 2.5, both the exchange process and Pro ring motion phenomena disappear, indicating that the structure of this peptide sequence can be stabilized by extrinsic factors. Interestingly, we observe NMR parameters (ROEs, (3)J coupling constants) for NH-12-5-2 in 90% v/v TFE that are consistent with the presence of a partial helical structure, similar to what was observed at low pH in our earlier CD experiments. We conclude that the NH-12-5-2 model polypeptide sequence possesses an inherent conformational instability that involves the D1-S5 sequence segment and the P6 residue but that this instability can be offset by extrinsic factors (e.g., charge neutralization, imido ring interconversion, and hydrophobic-hydrophobic interactions). These nonbonding interactions may play a role in the recognition and binding of this phage sequence region to SWNHs surfaces.     

On the numerical evaluation of singular integrals

Product-integration rules of the form _–1 ¹ k(x)f(x)dx _i ⁼¹ⁿ w _ni f(x _ni ) are studied, with the points {w _ni } chosen to be the zeros of certain orthogonal polynomials, and the weights {w _ni } chosen to make the rule exact iff is any polynomial of degree less thann. If, in particular, the points are the Chebyshev points, and ifk L _p [–1, 1] for somep>1, then it is shown that the rule converges to the exact result for all continuous functionsf. With this choice of points, the practical application of the rule is shown to be straightforward in many cases, and to yield satisfactory rates of convergence. The casek(x)=|–x|, >–1, is studied in detail. Results of a similar, but weaker, kind are also obtained for other choices of the points {x _ni }.     

A study of the thermal and light induced spin transition in [FeL2](BF4)2 and [FeL2](ClO4)2 L=2,6-di(3-methylpyrazol-1-yl)pyrazine

The spin crossover compounds [FeL2](BF4)2, L=2,6-di(3-methylpyrazol-1-yl)pyrazine and [FeL2](ClO4)2 have very unusual two stage spin transitions which are initially steep and then become more gradual. A detailed variable temperature single crystal X-ray diffraction study has shown that the course of the spin transition is controlled by an order-disorder transition in the counter anions. The high and low spin states both crystallise in the tetragonal space group I4, the structures of the high and low spin states are presented at 290 and 30 K, respectively. The title compounds are shown to undergo LIESST (Light Induced Excited Spin State Trapping) under irradiation with either red or green laser light with wavelengths of 632.8 and 532.06 nm, respectively, at 30 K. The cell parameters for the tetragonal photo-induced metastable high spin state at this temperature are a= 9.169(6), c= 17.77(1) A for [FeL2](ClO4)2 with an increase in unit cell volume of 21 A3, and a= 9.11(1), c= 17.75(2) A and an increase in volume of 42.8 A3 for [FeL2](BF4)2.     

Recycling isoelectric focusing and isotachophoresis

A new apparatus for large scale preparative isoelectric focusing in free solution is described. Its main characteristic is rapid fluid recirculation with but short residues times in the electric field. For the first time the recycling principle was also applied to preparative isotachophoresis, by incorporating into the system a computer controlled leader counterflow. The rapid recirculation permits application of unusually high electrical power for rapid resolution, as it suppresses fluid flow instabilities arising from electrohydrodynamic effects.