Aqueous phase behavior of polyelectrolytes with amphiphilic counterions modulated by cyclodextrin: the role of polyion flexibility

Polyelectrolytes with amphiphilic counterions, PEACs, are water insoluble because the amphiphiles self-assemble into highly charged micelles that strongly associate with the equally highly charged polyions. However, in the presence of water soluble cyclodextrins (CDs) that form inclusion complexes with the amphiphiles and prevent micellization, PEACs become soluble as the dispersed amphiphiles behave essentially as simple monovalent counterions. In this paper, we illustrate, by example, how strongly the ternary phase behavior of PEAC:CD:water depends on the polyion flexibility; for a highly flexible polyion (polyacrylate) the amphiphilic aggregates dictate the phase behavior, whereas a much stiffer polyion (DNA) itself dictates liquid crystalline ordering.     

Phase behavior of a DNA-based surfactant mixed with water and n-alcohols

The self-assembly behavior of a cationic surfactant (dodecyltrimethylammonium, DTA) with DNA as counterion in mixtures of water and n-alcohols (decanol, octanol, hexanol, butanol, and ethanol) was investigated. The phase diagrams were established and the different regions of the phase diagram characterized with respect to microstructure by (2)H NMR, small-angle X-ray scattering (SAXS), and other techniques. The DNA-DTA surfactant is soluble in all of the studied alcohols, showing increased solubility from decanol down to ethanol. All of the phase diagrams are analogous with respect to the occurrence of liquid crystalline (LC) regions, but the area of the LC region increases as one goes from decanol to ethanol. In all phase diagrams, hexagonal phases (of the reversed type) for the alcohol-rich side and lamellar phases for the other side were detected. For balanced proportions of the components, there is a coexistence of the lamellar and the hexagonal phase, here detected with a double quadrupole splitting in the (2)H NMR spectra. The correctness of the phase diagrams is confirmed by the fact that along the tie-lines the splitting magnitude remains nearly constant. All of the alcohols except for ethanol act as cosurfactants penetrating the DNA-DTA film. Adding salt to the ternary mixtures causes an increase in the unit cell dimension of the lamellar and the hexagonal phases. The phase diagram becomes more complicated when butanol is used for the alcohol phase. Here, there is the occurrence of a new isotropic phase with some properties analogous to those of the disordered sponge (L3) phase obtained for simple surfactant systems.     

Void fraction measurement by X-ray absorption

An X-ray tube and scintillation detectors were mounted on test pipes containing static voids of air–water mixture. Due to fluctuations in the X-ray tube output, void fraction measurements were carried out by using two detectors, one as a reference and the other as a void monitor. The intensity of a narrow (30–100 kV) X-ray beam transmitted through test pipes of different I.D. was measured to obtain the void fraction. The uncertainty in measuring static void fraction, was found to decrease as the void fraction increases, and to increase as X-ray energy increases. It was found that for a certain test-section pipe diameter, there exist an optimum X-ray energy that gives a minimum uncertainty in void fraction measurement.     

Current relaxation in microporous silicon

Current relaxation in samples of microporous silicon is observed at rates that depend on the applied voltage and the composition of the gaseous atmosphere. A possible physical mechanism for this phenomenon is discussed. Zh. Tekh. Fiz. 69, 141–142 (November 1999)     

Cyclodextrin-surfactant coassembly depends on the cyclodextrin ability to crystallize

Full equilibrium phase diagrams are presented for two ternary systems composed of the cationic surfactant dodecyltrimethylammonium bromide (DTAB), water (D(2)O), and a cyclodextrin, either β-cyclodextrin (β-CD) or (2-hydroypropyl)-β-cyclodextrin (2HPβCD). (2)H NMR, SAXS, WAXS, and visual examination were used to determine the phase boundaries and characterize the nature of the phases formed. Additionally, diffusion (1)H NMR was used to investigate parts of the diagrams. The water solubility of 2HPβCD is 80% (w/w), whereas it is only 1.85% (w/w) for β-CD. Solubility increases for both species upon complexation with DTAB; while the increase is minute for 2HPβCD, it is dramatic for β-CD. Both systems displayed an isotropic liquid solution (L(1)) one-phase region, the extension of which differs extensively between the two systems. Additionally, the DTAB:2HPβCD:water system also comprised a normal hexagonal (H(1)) area, which was not found for the DTAB:β-CD:water system. In the DTAB:β-CD:water system, on the other hand, we found cocrystallization of DTAB and β-CD. From this work we conclude that DTAB and CD molecules form 1:1 inclusion complexes with high affinities. Moreover, we observed indications of an association of 2HPβCD to DTAB micelles in the isotropic solution phase, which was not the case for β-CD and DTAB micelles. This is, to our knowledge, the first complete phase diagrams of surfactant-CD mixtures; as a novel feature it includes the observation of cocrystallization at high concentrations.     

Proof-of-concept prototype development of the self-propelled capsule system for pipeline inspection

This paper studies the prototype development for the self-propelled capsule system which is driven by autogenous vibrations and impacts under external resistance forces. This project aims for proof-of-concept of its locomotion in pipeline environment in order to mitigate the technical complexities and difficulties brought by current pressure-driven pipeline inspection technologies. Non-smooth multibody dynamics is applied to describe the motion of the capsule system, and two non-smooth nonlinearities, friction and impact, are considered in modelling. The prototype of the self-propelled capsule system driven by a push-type solenoid with a periodically excited rod has been designed to verify the modelling approach. The prototype contains a microcontroller, a power supply, and a wireless control module, which has been tested in a clear uPVC pipe via remote control. Various control parameters, e.g. impact stiffness, frequency and amplitude of excitation, are studied experimentally, and finally, the fastest progression of the system is obtained.     

Influence of halide mixing on thermal and photochemical stability of hybrid perovskites: XPS studies

The effect of I^–/Cl^–and I^–/Br^–mixing on the thermal and photochemical degradation of organometallic perovskite MeNH₃PbI₃ (MAPbI₃) was studied by X-ray photoelectron spectroscopy, which revealed the opportunity to essentially increase the photo and thermal stabilities of the material depending on the level and position of halide-mixing. The largest positive effect was observed for the small concentration of chloride substituent (MAPbI_2.7Cl_0.3), while the full halide substitution (MAPbBr₃) had a negative effect on the stability of hybrid perovskite.     

Activated Carbon/Pectin Composite Enterosorbent for Human Protection from Intoxication with Xenobiotics Pb(II) and Sodium Diclofenac

The use of enterosorbents—materials which can be administered orally and eliminate toxic substances from the gastrointestinal tract (GIT) by sorption—offers an attractive complementary protection of humans against acute and chronic poisoning. In this study, we report the results of developing a microgranulated binary biomedical preparation for oral use. It was designed with a core-shell structure based on pectin with low degree of esterification as the core, and nanoporous activated carbon produced from rice husk, AC-RH, as the shell, designated as AC-RH@pectin. The adsorption properties of the synthesized materials were studied in aqueous solutions for the removal of lead (II) nitrate as a representative of toxic polyvalent metals and sodium diclofenac as an example of a medicinal drug. The composite enterosorbent demonstrated high adsorption capacity for both adsorbates studied. Adsorption kinetics of lead and diclofenac adsorption by AC-RH, pectin, and AC-RH@pectin, fitted well a pseudo-second-order model. According to the Langmuir adsorption isotherm model, the best fitted isotherm model, the maximum adsorption capacity, q_max, of AC-RH@pectin for diclofenac and for lead (II) was 130.9 mg/g and 227.8 mg/g, respectively. Although q_max of AC-RH for diclofenac, 537.6 mg/g, and q_max of pectin for lead (II), 245.7 mg/g, were higher, the maximum adsorption capacity of AC-RH for lead (II), 52.7 mg/g, was much lower than that of the composite AC-RH@pectin and the adsorption capacity of pectin for diclofenac was negligible. Therefore, the composite material AC-RH@pectin demonstrated substantial efficiency of removing both species which potentially defines it as a more universal enterosorbent suitable for treating poisoning caused by substances of different chemical nature.