We studied complex formation in an aqueous salt-free system (pH approximately 3 and at 25 degrees C) between nanogel particles having opposite charges. Anionic gel (AG) and cationic gel (CG) particles consist of lightly cross-linked N-isopropylacrylamide (NIPA) copolymers with 2-acrylamido-2-methylpropane sulfonic acid and with 1-vinylimidazole, respectively. The number of charges per particle was -4490 for AG and +20 300 for CG, as estimated from their molar masses (3.33 MD for AG and 11.7 MD for CG) by static light scattering (SLS) and their charge densities (1.35 mmol/g for AG and 1.74 mmol/g for CG) by potentiometric titration. The complexes were formed through the addition of AG to CG and vice versa using a turbidimetric titration technique. At the endpoint of the titration, the aggregate formed was a complex based upon stoichiometric charge neutralization: CG(n)()(+) + xAG(m)()(-) --> CG(n)()(+) (AG(m)()(-))(x)() where x = (n)()/(m)(). At different stages of the titration before the endpoint, the resulting complexes were examined in detail using dynamic light scattering, SLS, and electrophoretic light scattering (ELS). The main results are summarized as follows: (i) When AG with a hydrodynamic radius (R(h)) of 119 nm is added to CG (R(h) approximately 156 nm), the (R(h)) of the complex size decreases from 156 to 80 nm. (ii) In contrast to this (R(h)) change, the molar mass increases from 11.7 MD to 24 MD with increasing amounts of added AG. (iii) Upon addition of CG to AG, the complex formed has the same size ((R(h)) approximately 80 nm) and the same molar mass (55 +/- 2.5 MD) until 55 +/- 5% of AG has been consumed in the complexation. To understand these results, we used the following two models: the random model (RM), in which the added AG particles uniformly bind to all of the CG particles in the system via a strong electrostatic attraction, and the all-or-none model (AONM), in which part of the AG particles in the system preferably bind to the added CG particles to neutralize their electric charges but the other AG particles are uncomplexed and remain in the system. The complex formations upon addition of AG to CG and CG to AG were elucidated in terms of RM and AONM, respectively.
Patients without a muscle layer in the specimen had high risk for progression. The initial TUR must have a muscle layer in the specimen. Variations of progression rates in previous studies might be due to different proportions of patients who had a muscle layer in TUR specimens.
It is well known that the selectivity of an ion-selective electrode (ISE) depends on the stoichiometry of the complexes between its ionophore and the target and interfering ions. It is all the more surprising that the possibility for the simultaneous occurrence of multiple target ion complexes with different complex stoichiometries was mostly ignored in the past. Here we report on the simultaneous formation of 1:1 and 1:2 complexes of a fluorophilic crown ether in fluorous ISE membranes, and how this results in what look like super-Nernstian responses. These increased response slopes are not caused by mass transfer limitations and can be readily explained with a phase boundary model, a finding that is supported by experimentally determined complex formation constants and excellent fits of response curves. Not only Cs+ but also the smaller ions Li+, Na+, K+, and NH4+ form 1:1 and 1:2 complexes with the fluorophilic crown ether, with cumulative formation constants of up to 1015.0 and 1021.0 for of the 1:1 and 1:2 complexes, respectively. Super-Nernstian responses of the type observed with these electrodes are probably not particularly rare, but lacking in the past an adequate discussion in the literature remained ignored or misinterpreted. Preliminary calculations also predict sub-Nernstian responses and potential dips of a similar origin. The proper understanding of such phenomena will facilitate the development of new ISEs based on ionophores that form complexes of higher stoichiometries.
A series of organoboron molten salts prepared by hydroboration of allyl imidazolium type molten salts with various hydroborating reagents such as monobromoborane dimethyl sulfide complex, 9-borabicyclo[3.3.1]nonane (9-BBN) and mesitylborane, and subsequent anion exchange reaction exhibited selective cation transporting property with ionic conductivity of 7.79 x 10(-5) - 6.25 x 10(-6) S cm(-1) at 323 K.
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