Charge density effects in salt‐free polyelectrolyte solution rheology

Solution rheology of 2‐vinyl pyridine and N‐methyl‐2‐vinyl pyridinium chloride random copolymers in ethylene glycol was studied over wide ranges of concentration and effective charge. The fraction of quaternized monomers α and the fraction of monomers bearing an effective charge f of these copolymers were measured using counterion titration and dielectric spectroscopy, respectively. Ethylene glycol is a good solvent for neutral poly(2‐vinyl pyridine), with very few ionic impurities. The viscosity η and relaxation time τ of dilute and semidilute unentangled solutions exhibit the scaling with concentration and effective charge expected by the Dobrynin model. Reduced viscosity data are independent of concentration in dilute solution, giving an intrinsic viscosity that depends on effective charge, and the experimental data obey the Fuoss law in the semidilute unentangled regime. Scaling concentration with the overlap concentration (c/c*) reduces these data to common curves, and c* ～ f ^?12/7 as predicted by the Dobrynin model, where f is the fraction of monomers bearing an effective charge. While the overlap concentration depends strongly on effective charge until counterion condensation occurs, the entanglement concentration c_e is surprisingly insensitive to effective charge, indicating that entanglement effects are not understood using the Dobrynin model. The terminal modulus G = η/τ depends only on the number density of chains G = ckT/N for c* < c < c_e, and G ～ c^3/2 for c > c_e independent of the effective charge. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2001–2013, 2006     

Branched polymers in a wedge geometry in three dimensions

We investigate the statistical and dimensional properties of uniform star polymers attached by the branching vertex of degreef in a wedge geometry in three dimensions and described by the wedge angles and. We show that the growth constant is equal to ^f , where is the self-avoiding walk limit. Thef and (, ) dependences of the corresponding critical exponent _f (, ) are studied using Monte Carlo techniques. In the casef=1, our results are compared with existing predictions obtained from series expansion and renormalization group methods. We have also estimated the amplitudes for the mean square radius of gyration and the mean square end-to-end branch length. Our results for the ratio of the mean square radius of gyration of anf-star to that of a linear polymer of the same degree of polymerization attached in a similar wedge, and the analogous ratio for the mean square end-to-end branch length, are consistent with these ratios being lattice-independent quantities.     

A hydrogen-bonding receptor that binds cationic monosaccharides with high affinity in methanol

A dicarboxylate host (1) binds cationic monosaccharides such as D-glucosamine HCl (2), D-galactosamine-HCl (3), and D-mannosamine-HCl (4) with high affinity (K1 = 8.0 x 10(4)-2.0 x 10(5) M(-1)) in methanol. In circular dichroism (CD) spectroscopy a positive exciton-coupling band was observed near 290 nm; this indicates that the saccharides are recognized by multiple point interactions. Since the corresponding neutral monosaccharides are not significantly bound, one may conclude that complex formation is primarily due to the electrostatic interaction between NH3+ in the guest and one carboxylate in the host and secondarily due to hydrogen-bonding interactions of OH groups with the other carboxylate and/or nitrogen bases. Molar ratio plots and Job plots indicate that host 1 and cationic monosaccharide guests form CD-active, pseudo-cyclic 1:1 complexes at low guest concentration followed by the formation of CD-silent, acyclic 1:2 1-saccharide complexes at high guest concentration. The possible binding modes are discussed in detail on the basis of molecular mechanics calculations and chemical shift changes in 1H NMR spectra. The results of competition experiments with several cationic reference compounds bearing fewer OH groups than 2-4 are consistent with the proposed binding model. Thus, the present study is a rare example of saccharide recognition in a protic solvent, where in general, hydrogen-bonding interactions are rarely useful because of strong solvation energy. These are apparently the strongest saccharide complexes involving noncovalent interactions between host and guest. We believe that the findings are significant as a milestone toward development of new saccharide recognition systems ultimately useful in aqueous solution.     

Deuterium exchange of 4-pyrimidones and 4-pyrimidthiones

The hydrogen-deuterium exchange of H-2 in 4-pyrimidone, a number of 1- and 3-alkyl-4-pyrimidones and several of their thione analogs in deuterium oxide at moderate temperatures is reported. This reaction is apparently not susceptible to acid or base catalysis. Cations of the 4-pyrimidones were found not to exchange H-2 at all in acid media. Catalytic amounts of bases do not alter the exchange rates whereas more concentrated alkali decompose the pyrimidone. However, 1,4(3,4)-dihydro-1,3-dimethyl-4-oxopyrimidinium iodide (and its 6-methyl analog) exchange H-2 quite rapidly in neutral deuterium oxide, almost instantly when triethylamine is added as a catalyst, and very slowly in dilute solutions of deuterium chloride in deuterium oxide. Mechanisms are proposed to account for these phenomena.     

Fragmentations and reactions of the organophosphate insecticide Diazinon and its oxygen analog Diazoxon studied by electrospray ionization ion trap mass spectrometry

The fragmentations and reactions of Diazinon and related compounds have been studied by electrospray ionization ion trap mass spectrometry. Several novel fragmentation and rearrangements have been observed, including an intramolecular thiono-thiolo rearrangement. The stability, in the gas-phase, of the protomers of 2-isopropyl-4-methyl-6-pyrimidinol has been demonstrated. The complexity of the gas phase ion processes observed suggest that, at present, caution should be exercised in using this approach for the analysis of environmental and other samples until our understanding of these processes increases considerably.     

On the relationship between differentiability and absolute continuity of measures on ℝn

Summary We give an elementary proof of the fact that a finite Borel measure on ⁿ is absolutely continuous with a C ¹ density if and only if it has directional derivatives which are continuous almost everywhere. The Radon-Nikodym derivative of a differentiable measure is given in terms of the directional derivatives.     

High-p T αα andαp interactions

Properties of secondaries associated with a high-p _T charged trigger particle (3<p _T <5 GeV/c) were studied for αp and αα interactions at c.m. energies \(\sqrt s = 88\) GeV and 125 GeV, respectively. Thep _T distributions of secondaries in the away-jet and trigger-jet regions were compared with those for high-p _{T pp} interactions. No statistically significant differences were seen, except at lowp _T . Momentum and angular distributions of spectator and leading protons were studied as a function of charge and rapidity of the trigger hadron. The observed correlations between trigger charge and number of spectator protons provide evidence of valence quark contributions to the trigger jet.