Surface complexation of DNA with a cationic surfactant

We have studied the surface complexation of DNA with a cationic surfactant (DTAB) using a combination of methods: dynamic surface tension, ellipsometry and Brewster angle microscopy. Below the surfactant critical aggregation concentration (cac), complexation occurs only at the surface, and the results are consistent with neutralization of the surfactant charges by the free polymer ions. Above the cac, surfactant starts to bind cooperatively to DNA in the bulk, and adsorption of the preformed hydrophobic surfactant DNA aggregate is now possible, leading to thick surface layers. At still higher concentrations of surfactant (still below saturation of binding in the bulk), there is decrease in adsorption due to competition with bulk aggregates. Finally, as surfactant concentration is increased still further, bulk aggregates become less soluble and large amounts are adsorbed, forming a surface layer, which is solid-like and brittle.     

Interaction of DNA oligomers with cationic lipidic monolayers: complexation and splitting

Interactions of native DNA with octadecylamine (ODA) and hexadecymdimethylammonium bromide (HTAB) monolayers at the air/water interface were studied by pi-A isotherms, ellipsometry, and X-ray reflectivity. We show that the microscopic structure of ODA-DNA complexes is definitely consistent with a single-stranded form for DNA. On the contrary, with HTAB, DNA complexes in its native form. The crucial difference in the behavior of these two fairly similar lipids is due to the presence of the amine group in ODA. These results should be relevant to applications such as DNA chips and sensors.     

Interaction of monovalent and divalent counterions with some carboxylic polysaccharides

Eleven samples of carboxylic polysaccharides were studied. The activity coefficients γ have been measured for monovalent (Na⁺) and divalent (Ca²⁺) counterions. There is no specific influence of the structure of the chain on γ values. Agreement with theoretical values confirms the rigidity of the chain; for low charge density, the theoretical treatment seems to be incorrect. Selectivity is discussed in term of selectivity coefficient K and free energy of exchange ΔG; ΔG is linearly related to the charge density but K which characterizes the competition of the two counterions is sensitive to the nature of the chain. The carboxymethylamyloses present a larger selectivity whose origin is not discussed here. The last point treated is the intrinsic constant of dissociation of polyacids. The pK₀ values are practically independent of the nature of the polyelectrolyte and of the charge density; the values are close to the pK₀ of monomeric unit and are not affected by the position of ? COOH in the anhydroglucose ring.     

New polycationic polynorbornene latexes bearing an amphiphilic sugar corona of counterions: synthesis and complexation with DNA

A new family of polycationic polynorbornene with ω-gluconamidoalkanoates and ω-lactobionamidoalkanoates as amphiphilic counterions has been prepared. These polymers spontaneously form stable latexes in water with an amphiphilic sugar corona around the particles. With these counterions, the sugar moieties are separated from the surface of latex particles by the aminoalkanoic acid residue and consequently are remote from the surface of such latexes. Such location of sugar may promote their stronger interaction with cell receptors. These original amphiphilic compartmentalized surface polycationic latexes are able to bind and efficiently complex DNA in very small complexes. Furthermore, because of the effect of the sugar corona on the formation of the complexes, there is only a slight influence of the hydrophobicity of the counterions on DNA packing.     

Absence of charge inversion on rodlike polyelectrolytes with excess divalent counterions

Filamentous viruses such as fd and M13 are highly charged rodlike polyelectrolytes. In this study, we employ fd virus to test the recent prediction of charge inversion [Nguyen, Rouzina, and Shklovskii, J. Chem. Phys. 112, 2562 (2000)]. Light scattering measurements show bundle formation and resolubilization of fd viruses when MgCl(2) was added from 0 to 600 mM. The effective charge of fd was studied by measuring their electrophoretic mobility using a filament tracking method uniquely suited for the system. Monte Carlo simulations were performed under canonical ensemble to predict the charge distribution around the rodlike virus. Charge inversion, which has been suggested theoretically to accompany with bundle resolubilization, was not observed in either experiments or simulations. A modified analysis of force balance is called upon to account for these new findings.     

Osmotic coefficients of polystyrenesulphonates in dioxane-water mixtures—II. Divalent counterions and mixtures of mono- and divalent counterions

The osmotic pressures of solutions of magnesium and calcium polystyrenesulphonate in water and in 25 wt % mixture of dioxane in water have been measured for concentrations from 0?002 to 0?06 molal in monomer units. The osmotic coefficient derived from these measurements is almost independent of concentration. Its values for solutions in dioxane-water mixtures are much lower than for aqueous solutions. The osmotic coefficients of solutions containing mixtures of polystyrenesulphonic acid and its calcium salt in 25 wt % dioxane have also been determined. The osmotic coefficient of these solutions has a distinct maximum at a certain value of the equivalent fraction of the acid. The experimental results are compared with the predictions of the cylindrical cell model and infinite line charge model. Satisfactory agreement between theory and experiment is found.     

Surface potential switching by metal ion complexation/decomplexation using bipyridinethiolate monolayers on gold

Surface potential switching on gold(111) surfaces is induced by complexation/decomplexation reactions of a bipyridine (BP) derivative and palladium(II) chloride, as observed by Kelvin probe force microscopy (KFM). On the basis of the theoretical predictions, a 4-(5-phenylethynyl-2,2'-bipyridine-5'-yl-ethynyl)benzenethiol (PhBP) derivative was synthesized and used as an active monolayer to catch transition metal ions. By using the microcontact printing (CP) technique, micron-size patterned PhBP monolayers, which act as effective hosts to coordinate palladium(II) chloride, were prepared on gold(111) surfaces. The KFM signal decreases by complexation of the Pd(II) chloride in PhBP monolayers and is recovered by removal of Pd ions using an ethylenediamine solution, as confirmed by X-ray photoelectron spectroscopy. This process is reversible, indicating that the surface potential switching is realized by complexation/decomplexation of Pd(II). A CP PhBP monolayer, when it detects the target palladium ion, shows sensitivity for the picomolar level detection judged from surface potential changes in KFM measurements. The dipole moment estimated by the surface potentials is much smaller than the calculated value, indicating that mechanisms for the reduction of the surface dipole moment exist in real monolayers prepared by the CP method.     

Time-dependent complexation of glucose-reduced gold nanoparticles with octadecylamine Langmuir monolayers

We report on the reduction of aqueous chloroaurate ions by glucose to form gold nanoparticles of uniform size. We further demonstrate the complexation of these particles with octadecylamine (ODA) monolayers at the air-water interface. Pressure-area (pi-A) isotherms as a function of time of complexation revealed a significant expansion of the monolayer. Surface pressure variation with time for constant areas after spreading of the monolayer was carried out to observe the kinetics of complexation of the colloidal particles at the interface. The kinetics of complexation of the particles at the interface was also monitored by Brewster angle microscopy (BAM) measurements. Langmuir-Blodgett films of the particles complexed with ODA were formed at a subphase pH of 9 onto different substrates. Quartz crystal microgravimetry (QCM) was used to quantify the amount of particles deposited per immersion cycle of the quartz crystal. The LB films were further characterized by UV-vis and transmission electron microscopy (TEM) measurements. TEM measurements indicate a close packed and equidistant arrangement of colloidal particles in the LB film, probably due to hydrogen-bonding interactions.     

Interaction of DNA fragments with counterions in aqueous solution

Monte Carlo simulation of the hydration of metal ion—DMP⁻ and metal ion—9-methylguanine complexes was performed. A comparative analysis of the results for Na⁺ and K⁺ ions was carried out. The main stages of dissociation were revealed. The energy effects of dissociation were evaluated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2174–2177, November, 1998.     

Equilibrium constants of ion exchange reactions between fatty acid monolayers and dissolved counterions

Equations for equilibrium constants of ion exchange between fatty acid monolayers and subsolution counterions are derived. The approach of Matsubara et al. [4], where the monolayer is considered as a two-dimensional regular mixture is employed, but the different molar volumes of its components are taken into account. Using the equations obtained theK _ex values are calculated on the basis of published data on the monolayer composition in the systems Cd²⁺/HArch, Ba²⁺/HArch, Ca²⁺/HSt, Pb²⁺/ HSt and Cu²⁺/HSt. The stability constants of the corresponding soaps formed in the monolayer are also obtained.     

Characterization of complexation of PVP copolymer with DNA

Interactions of amphiphilic copolymer poly(N‐vinylpyrrolidone‐co‐N‐t‐Boc‐ tryptophanamido‐N′‐methacrylthiourea) [P(NVP‐co‐TrpAMT)] and poly(N‐vinylpyrrlidone) (PVP) with DNA were studied with the aim to understand the difference in their complexation efficiencies when considered as a potential non‐viral delivery vector. Fluorescence spectroscopy, ethidium bromide (EB) quenching, ζ potential measurement, and agarose gel electrophoresis were all carried out in Tris‐HCl (pH 7.4) solution to assess the degree of interaction between the (co)polymers P(NVP‐co‐TrpAMT) and DNA. All of these measurements show that the high affinity of the copolymer for DNA can be demonstrated. We also found that P(NVP‐co‐TrpAMT)‐I (PVP/PTrpAMT molar ratio was 100:2.88) exhibited a high DNA cleavage activity and induced the supercoiled form of the plasmid cleavage in the nicked and linear forms. Moreover, P(NVP‐co‐TrpAMT)‐I exhibited stronger affinity for DNA than PVP and P(NVP‐co‐TrpAMT)‐II (PVP/PTrpAMT molar ratio of 100:6.35). This phenomenon is believed to be related to the structure of TrpAMT and the hydrophobic nature of the copolymer. P(NVP‐co‐TrpAMT)‐II with higher hydrophobic segments creates a strong hydrophobic interaction and induces a steric barrier which hinders their complexation with DNA. The study reveals important information about the inner mechanisms involved in the interaction of the PVP copolymer with DNA, which aids in the design of novel efficient non‐ionic gene carriers. Copyright © 2008 John Wiley & Sons, Ltd.     

Rearrangement and complexation of 5-substituted-1,3,4-thiadiazolidine-2-thiones with divalent transition metals

The reactions of a variety of divalent transition metal ions with 3-methyl-5-(2-hydroxypheny)-, 3-methyl-5-(2-thienyl)-and 3-methyl-5-(2-furyl)-1,3,4-thiadiazolidine-2-thiones (htt, ttt and ftt, respectively) are accompanied by opening of the thiadiazolidine ring and rearrangement to the corresponding Schiff base (Hhts, Htts and Hfts, respectively) with the concomitant formation of complexes of the general formulae, [M(hts)] (M=Ni, Cu, Zn or Pd), [M(hts) (py)] (M=Ni, Cu), [Co(Hhts)hts)], and [ML₂] (M=Ni, Cu, Zn or Cd); L=tts or fts). The complexes have been characterised by physico-chemical and spectroscopic methods. The fungitoxicities of the corresponding Schiff base metal complexes have been investigated. TMC 2568     

Influence of surfactant counterions during electrophoretic particle deposition

This study demonstrates the influence of a cationic surfactant on colloidal particle electrodeposition (migration and adhesion). Three cetyltrimethylammonium salts (CTA+) with various counterions (bromide, chloride, and hydrogenosulphate) were studied. Particle transport toward the electrode was driven by the electrophoretic force. Once particles reached the electrode, a wide variety of behaviors were observed, depending on surfactant concentration and counterions: particles would stick permanently or slide along the electrode surface, remain or detach upon potential switching, act as nuclei for aggregate growth, or produce a homogeneous particle film. The experimental results also demonstrate the specific influence of surfactant counterions on the deposited film morphology.     

Langmuir monolayer properties of perfluorinated double long-chain salts with divalent counterions of separate electric charge at the air-water interface

The novel perfluorinated double long-chain salts with divalent counterions of separate electric charge, 1,1-(1,omega-alkanediyl)-bispyridinium perfluorotetradecane- carboxylate [CnBP(FC14)2 : n = 2, 6, 10, 14], were newly synthesized and their interfacial behavior was investigated by Langmuir monolayer methods. Surface properties [surface pressure (pi)-, surface potential (DeltaV)-, dipole moment (micro perpendicular)-area (A) isotherms] and morphological images of CnBP(FC14)2 monolayers on a subphase of water and on various NaCl concentrations were measured by employing the Wilhelmy method, the ionizing electrode method, fluorescence microscopy (FM), and Brewster angle microscopy (BAM). CnBP(FC14)2 formed a stable monolayer on water at 298.2 K, where these pi-A isotherms shifted to a larger molecular area with increasing charge separation and had no transition point from a disordered phase to an ordered one. On the contrary, the pi-A isotherms on NaCl solutions moved to the smaller areas, showed the transition and higher collapse pressures compared to the pi-A isotherms on water. These results suggested that a sodium chloride subphase induced the condensation of CnBP(FC14)2 molecules upon compression. In addition, it is quite noticeable that a dissociation of CnBP counterion from CnBP(FC14)2 occurs on NaCl solutions, depending on the extent of charge separation. This phenomenon was supported by the changes of the limiting area, transition pressure, collapse pressure, repeated compression-expansion cycle curve, and DeltaV behavior of perfluorotetradecanoic acid (FC14). Furthermore, temperature dependence of these monolayers was investigated, and an apparent molar quantity change on the phase transition was evaluated on 0.15 M NaCl. The morphological behavior of CnBP(FC14)2 and FC14 monolayers was also confirmed by FM and BAM images.     

Surface complexation by caesium fluoride. The case of sulphur tetrafluoride

The heterogeneous, room temperature complexation reaction between caesium fluoride and sulphur tetrafluoride is conveniently observed using ¹⁸F and ³⁵S radiotracer methods. The major surface species is weakly adsorbed SFe₄, SF₅^? being a minor species. Neither undergo observable ¹⁸F exchange with CsF at room temperature.