Magnetic-Field-Induced Orientational Phase Structure Transition

Magnetic field effect on the phase transition at high temperature (from 50 °C) inside the magnetic field has been found in C₁₄G₂ (<i>N</i>-tetradecyllactobionamide)/C₁₂EO₄ (tetraethylene glycol monododecyl ether)/D₂O system. The phase was transited quickly from lamellar phase to isotropic phases [bottom, micellar phase (L₁ phase) and top, sponge phase (L₃ phase)] induced by a magnetic field, which was demonstrated by ²H NMR and FF-TEM measurements. The isotropic phases induced by magnetic field were not stable, and the upper L₃ phase can recover to lamellar phase after being restored in a 55 °C thermostat outside the magnetic field for about one month. During the mechanism study, the C₁₂EO₄ molecule was proved to be the dominant component for the phase transition induced by the magnetic field, while the C₁₄G₂ molecule was the auxiliary and just affected the transition speed. The breaking and rebuilding of hydrogen bonds could play an important role in the phase transition and recovering. Moreover, the surfactant concentration had an effect on the speed of phase transiting and phase recovering. These observations could provide an understanding of the phase transition and also the applications for the controlled drug delivery system of bilayer membranes driving, induced by the magnetic field

Colloidal Wormlike Micelles with Highly Ferromagnetic Properties

For the first time, a new fabrication method for manipulating the ferromagnetic property of molecular magnets by forming wormlike micelles in magnetic-ionic-liquid (mag-IL) complexes is reported. The ferromagnetism of the mag-IL complexes was enhanced 4-fold because of the formation of wormlike micelles, presenting new evidence for the essence of magnetism generation at a molecular level. Characteristics such as morphology and magnetic properties of the wormlike micelle gel were investigated in detail by cryogenic transmission electron microscopy (Cryo-TEM), rheological measurements, circular dichroism (CD), FT-IR spectra, and the superconducting quantum interference device method (SQUID). An explanation of ferromagnetism elevation from the view of the molecular (ionic) distribution is also given. For the changes of magnetic properties (ferromagnetism elevation) in the wormlike micelle systems, the ability of CTAFe in magnetizing AzoNa₄ (or AzoH₄) can be ascribed to an interplay of the magnetic [FeCl₃Br]⁻ ions both in the Stern layer and in the cores of the wormlike micelles. Formation of colloidal aggregates, i.e., wormlike micelles, provides a new strategy to tune the magnetic properties of novel molecular magnets

Controlling the Capture and Release of DNA with a Dual-Responsive Cationic Surfactant

A dual-responsive cationic surfactant, 4-ethoxy-4′-(trimethyl- aminoethoxy) azobenzene trichloromonobromoferrate (azoTAFe), which contains both a light-responsive moiety azobenzene and a paramagnetic counterion, [FeCl₃Br]⁻, was designed and synthesized. Not only does this cationic surfactant abundantly utilize inexhaustible and clean sources, i.e., light and magnetic field, but it also serves as a powerful dual-switch molecule for effectively controlling the capture and release of DNA. Our results could provide potential applications in gene therapy for creating smart and versatile machines to control the transport and delivery of DNA more intelligently and robustly. It was proved that the light switch can independently realize a reversible DNA compaction. The introduction of a magnetic switch can significantly enhance the compaction efficiency, help compact DNA with a lower dosage and achieve a magnetic field-based targeted transport of DNA. In addition, the light switch can make up the irreversibility of magnetic switch. This kind of self-complementation makes the cationic azoTAFe be useful as a potential tool that can be applied to the field of gene therapy and nanomedicine

First Fluorinated Zwitterionic Micelle with Unusually Slow Exchange in an Ionic Liquid

The micellization of a fluorinated zwitterionic surfactant in ethylammonium nitrate (EAN) was investigated. The freeze-fracture transmission electron microscope (FF-TEM) observations confirm the formation of spherical micelles with the average diameter 25.45 ± 3.74 nm. The micellization is an entropy-driven process at low temperature but an enthalpy-driven process at high temperature. Two sets of ¹⁹F NMR signals above the critical micelle concentration (cmc) indicate that the unusually slow exchange between micelles and monomers exists in ionic liquid; meanwhile, surfactant molecules are more inclined to stay in micelle states instead of monomer states at higher concentration. Through the analysis of the half line width (Δν_1/2), we can obtain the kinetic information of fluorinated zwitterionic micellization in an ionic liquid

Magnetic Fullerene-DNA/Hyaluronic Acid Nanovehicles with Magnetism/Reduction Dual-Responsive Triggered Release

We created the dual-responsive nanovehicle that can effectively combine and abundantly utilize magnetic and glutathione (GSH)-reductive triggers to control the drug delivery and achieve more intelligent and powerful targeting. In the nanovehicles, paramagnetic fullerene (C₆₀@CTAF) was prepared via one-step modification of fullerene with magnetic surfactant CTAF by hydrophobic interaction for the first time. The perfect conjugation of C₆₀ and CTAF increased the solubility or dispersity of fullerenes and qualified CTAF with more powerful assembly capability with DNA. DNA molecule in the nanovehicles acted as an electrostatic scaffold to load anticancer drug Dox as well as the important building block for assembly with C₆₀@CTAF into C₆₀@CTAF/DNA. The further combination of deshielding and targeting functions in reduction-responsive disulfide modified HA-SS-COOH coating on C₆₀@CTAF/DNA complexes could reduce the agglomeration and regulate the morphology of C₆₀@CTAF/DNA complexes from irregular microstructures to more uniform ones. More importantly, the introduction of HA-SS-COOH provided a response to a simulating reductive extra-tumoral environment by efficient cleavage of disulfide linkages by GSH and site-specific drug delivery to HepG2 cells. Amazingly, the final nanovehicles presented an increased magnetic susceptibility compared with paramagnetic CTAF, and they “walked” under an applied magnetic field. Because of their facile fabrication, rapid responsiveness to extra tumoral environment, and external automatic controllability by external magnet, the drug delivery nanovehicles constructed by magnetic fullerene-DNA/hyaluronic acid might be of great interest for making new functional nucleic-acid-based drug carriers

Spontaneous Transformation of Lamellar Structures from Simple to More Complex States

Spontaneous transformation of lamellar structures, such as multilamellar vesicles from micelles or unilamellar vesicles, is an important challenge in the field of amphiphile molecules, which may serve as models to understand biologically relevant bilayer membranes. Herein, we report a progressive self-assembly progress of <i>N</i>-tetradecyllactobionamide (C₁₄G₂) and tetraethylene glycol monododecyl ether (C₁₂EO₄) mixtures in aqueous solution. Increasing temperature or surfactant compositions causes spontaneous transformation from simple to high-level aggregates, i.e., from unilamellar vesicles, to coexisting multilamellar vesicles, terraced planar bilayers, and finally terraced planar bilayers. Deuterium nuclear magnetic resonance (²H NMR), freeze-fracture transmission electron microscopy (FF-TEM), and small-angle X-ray scattering (SAXS) measurements clearly demonstrate the spontaneously progressive self-assembly process. The interlamellar spacing (<i>d</i>) of the bilayers decreases from unilamellar vesicles to the terraced planar bilayers with an increase of the temperature or surfactant compositions. Lamellar samples consisting of terraced planar bilayers at higher temperature still show viscoelastic properties, being Bingham fluids, and both the viscoelasticity and yield stress increase with the composition and decrease with the temperature. The spontaneous transformation of the progressive self-assembly progress of C₁₄G₂ and C₁₂EO₄ aqueous mixtures is due to a balance of three driving forces, hydrophobic interactions, hydrogen bonding, and steric effects

Nanocapsules of Magnetic Au Self-Assembly for DNA Migration and Secondary Self-Assembly

To endow valuable responsiveness to self-assemblies of Au nanoparticles (Au NPs), the magnetic Au nanoparticles (Au NPs)/C₁₆H₃₃(CH₃)₃N⁺[CeCl₃Br]⁻ (CTACe) mixtures were first prepared by using an emulsion self-assembly of a magnetic surfactant, C₁₆H₃₃(CH₃)₃N⁺[CeCl₃Br]⁻. A versatile morphology of self-assemblies of Au NPs could be controlled by the counterions in surfactants including [CeCl₃Br]⁻, [FeCl₃Br]⁻, and Br^– as well as solvent. In particular, the magnetic counterion, [CeCl₃Br]⁻, can induce self-growth of Au NPs in an emulsion self-assembly process due to the oxidability of [CeCl₃Br]⁻. It enhances the rigidity of Au NPs/CTACe scaffolds template compared with Au NPs/hexadecyltrimethylammonium bromide. [CeCl₃Br]⁻ engaged Au NPs/CTACe with fascinating capability of conglutination and targeted migration of DNA (150 μmol/L) under a magnet field. The conglutination capability of the DNA molecules can increase to 39.8% by adopting the magnetic strategy when using Au NPs/CTACe as a magnetic booster. Au NPs/CTACe mixtures can ideally self-assemble to be scaffolds, providing abundant conjugation sites of surface charges. Magnetic Au NPs/CTACe can serve as a template scaffold to secondary self-assemble with DNA (40 mmol/L) outside, producing smooth-faced and hollow DNA nanocapsules. We believe that the creative Au NPs/CTACe/DNA nanocapsules will extend the biological application field of Au NPs assemblies

Surfactant-Modified Ultrafine Gold Nanoparticles with Magnetic Responsiveness for Reversible Convergence and Release of Biomacromolecules

It is difficult to synthesize magnetic gold nanoparticles (AuNPs) with ultrafine sizes (<2 nm) based on a conventional method via coating AuNPs using magnetic particles, compounds, or ions. Here, magnetic cationic surfactants C₁₆H₃₃N⁺(CH₃)₃[CeCl₃Br]⁻ (CTACe) and C₁₆H₃₃N⁺(CH₃)₃[GdCl₃Br]⁻ (CTAGd) are prepared by a one-step coordination reaction, i.e., C₁₆H₃₃N⁺(CH₃)₃Br^– (CTABr) + CeCl₃ or GdCl₃ → CTACe or CTAGd. A simple strategy for fabricate ultrafine (<2 nm) magnetic gold nanoparticles (AuNPs) via surface modification with weak oxidizing paramagnetic cationic surfactants, CTACe or CTAGd, is developed. The resulting AuNPs can highly concentrate the charges of cationic surfactants on their surfaces, thereby presenting strong electrostatic interaction with negatively charged biomacromolecules, DNA, and proteins. As a consequence, they can converge DNA and proteins over 90% at a lower dosage than magnetic surfactants or existing magnetic AuNPs. The surface modification with these cationic surfactants endows AuNPs with strong magnetism, which allows them to magnetize and migrate the attached biomacromolecules with a much higher efficiency. The native conformation of DNA and proteins can be protected during the migration. Besides, the captured DNA and proteins could be released after adding sufficient inorganic salts such as at <i>c</i>_NaBr = 50 mmol·L^–1. Our results could offer new guidance for a diverse range of systems including gene delivery, DNA transfection, and protein delivery and separation

A Systematic Investigation and Insight into the Formation Mechanism of Bilayers of Fatty Acid/Soap Mixtures in Aqueous Solutions

Vesicles are the most common form of bilayer structures in fatty acid/soap mixtures in aqueous solutions; however, a peculiar bilayer structure called a “planar sheet” was found for the first time in the mixtures. In the past few decades, considerable research has focused on the formation theory of bilayers in fatty acid/soap mixtures. The hydrogen bond theory has been widely accepted by scientists to explain the formation of bilayers. However, except for the hydrogen bond, no other driving forces were proposed systematically. In this work, three kinds of weak interactions were investigated in detail, which could perfectly demonstrate the formation mechanism of bilayer structures in the fatty acid/soap mixtures in aqueous solutions. (i) The influence of hydrophobic interaction was detected by changing the chain length of fatty acid (C_<i>n</i>H_2<i>n</i>+1COOH), in which <i>n</i> = 10 to 18, the phase behavior was investigated, and the phase region was presented. With the help of cryogenic transmission electron microscopy (cryo-TEM) observations, deuterium nuclear magnetic resonance (²H NMR), and X-ray diffraction (XRD) measurements, the vesicles and planar sheets were determined. The chain length of C_<i>n</i>H_2<i>n</i>+1COOH has an important effect on the physical state of the hydrophobic chain, resulting in an obvious difference in the viscoelasticity of the solution samples. (ii) The existence of hydrogen bonds between fatty acids and their soaps in aqueous solutions was demonstrated by Fourier transform infrared (FT-IR) spectroscopy and molecule dynamical simulation. From the pH measurements, the pH ranges of the bilayer formation were at the p<i>K</i>_a values of fatty acids, respectively. (iii) Counterions can be embedded in the stern layer of the bilayers and screen the electrostatic repulsion between the COO^– anionic headgroups. FT-IR characterization demonstrated a bidentate bridging coordination mode between counterions and carboxylates. The conductivity measurements provided the degree of counterion binding (β = 0.854), indicating the importance of the counterions

Near-Infrared-Light-Responsive Magnetic DNA Microgels for Photon- and Magneto-Manipulated Cancer Therapy

Functional DNA molecules have been introduced into polymer-based nanocarrier systems to incorporate chemotherapy drugs for cancer therapy. Here is the first report of dual-responsive microgels composed of a core of Au nanorods and a shell of magnetic ionic liquid and DNA moieties in the cross-linking network simultaneously, as effective drug delivery vectors. TEM images indicated a magnetic polymer shell has an analogous “doughnut” shape which loosely surround the AuNRs core. When irradiated with a near-infrared-light (near-IR) laser, Au nanorods are the motors which convert the light to heat, leading to the release of the encapsulated payloads with high controllability. DNA acts not only as a cross-linker agent, but also as a gatekeeper to regulate the release of drugs. The internalization study and MTT assay confirm that these core–shell DNA microgels are excellent candidates which can enhance the cytotoxicity of cancer cells controlled by near-IR laser and shield the high toxicity of chemotherapeutic agents to improve the killing efficacy of chemotherapeutic agents efficiently in due course