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We report DNA thermotropic liquid crystal (TLC) formation by positively charged catanionic surfactant bilayer vesicles. The properties of DNA TLCs were found to be manipulated by both the chemical structures of cationic and anionic surfactants and the DNA amount. Positively charged catanionic bilayer vesicles bond to negative DNA sites resulting in the transition from vesicles to long range ordered lamellar crystals of DNA-catanionic surfactants, as confirmed by cryo- and freeze-fracture (FF) TEM observations and small-angle X-ray scattering (SAXS) measurements.

Hypothesis: Electrostatic self-assembly is used as a facile and convenient method to fabricate soft materials with synergetic novel properties. The structural transition of building blocks could easily lead to the formation of assembly structures with various morphologies. Hence, the self-assembly behavior of DNA/surfactant vesicles could be driven by DNA base pair (bp) variation and the stimulated responsiveness of vesicles., Experiments: We report the bilayer transition of catanionic redox-switchable surfactant vesicles controlled by adding DNA with different chain lengths. Cryogenic transmission electron microscopy (cryo-TEM) was used to characterize the aggregation behavior of DNA and vesicles., Findings: Cryo-TEM images revealed that short-chain inflexible DNA with 50 bp can act as anionic glue in the construction of catanionic bilayer vesicles to form tubular vesicles. Medium-long DNA of 250 bp adsorbs onto bilayer vesicles via electrostatic interactions to produce slightly thickened bilayer vesicles. Long-chain DNA with 2000 bp can be used as a building block to fabricate super-wall thickened (SWT) redox-responsive DNA bilayer vesicles with an average wall-thickness of 14.0 nm. The greater number of charges and more flexible of long-chain DNA may account for the construction of these SWT bilayer vesicles with high stability. In addition, the SWT DNA vesicles can even undergo structural rearrangement to generate over-sized bilayer vesicles by redox stimulation., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Self-assembly exploits noncovalent interactions to offer a facile and effective method for the construction of soft materials with multifunctionalities and diversity. In this work, fluorescence carbon quantum dots coordinated by Ce 3+ ions (CQDCe) have been synthesized and exploited as building blocks to generate a series of hierarchical structures through the ionic self-assembly of CQDCe and biomolecules, namely DNA, myoglobin (Mb), and hyaluronic acid (HA). In particular, vesicles can be constructed by the simple mixing of oppositely charged CQDCe and DNA in water. The formation of unusual vesicles can be explained by the self-assembly of CQDCe with a rearranged structure and the rigid DNA biomolecular scaffolds. This facile noncovalent self-assembly method has inspired the innovative use of virgin DNA as a building block to construct vesicles rather than resorting to a sophisticated synthesis. The self-assembly of CQDCe-biopolymers was accompanied by aggregation-induced photoluminescence (PL) quenching. The biosensing platform was designed to detect polypeptides and deoxyribonuclease I through competitive binding of CQDCe and enzymatic hydrolysis of the DNA backbone, respectively. We believe that the integrative self-assembly of CQDCe and DNA will enrich the theoretical study of vesicle formation by DNA molecules and extend the application of fluorescence carbon quantum dots in the biological field., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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 (C 60 @CTAF) was prepared via one-step modification of fullerene with magnetic surfactant CTAF by hydrophobic interaction for the first time. The perfect conjugation of C 60 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 C 60 @CTAF into C 60 @CTAF/DNA. The further combination of deshielding and targeting functions in reduction-responsive disulfide modified HA-SS-COOH coating on C 60 @CTAF/DNA complexes could reduce the agglomeration and regulate the morphology of C 60 @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.

The thermo-reversible capture and release of DNA were studied by the protonation and deprotonation of alkyldimethylamine oxide (CnDMAO, n = 10, 12 and 14) in Tris-HCl buffer solution. DNA/C14DMAO in Tris-HCl buffer solution with pH = 7.2 is transparent at 25 °C, indicating that DNA molecules exist mainly in individuals and the binding of C14DMAO is weak. With the increase of temperature, the pH of the buffer solution continuously decreases, which leads to protonation of C14DMAO (C14DMAO + H(+)→ C14DMAOH(+)) and an obvious increase of the turbidity of the samples. This indicates a stronger binding of the protonated C14DMAOH(+) to DNA. Further investigations demonstrated the formation of DNA/C14DMAOH(+) complexes, in which the stretched DNA molecules are effectively compacted as evidenced from UV-vis absorptions, circular dichroism (CD) measurements, atomic force microscopy (AFM) observations, dynamic light scattering (DLS) measurements and agarose gel electrophoresis (AGE). Interestingly, when the temperature is turned back to 25 °C, the compacted DNA molecules can fully recover to the stretched conformation. This cycle can be repeated several times without obvious loss of efficiency. The effect of the chain length of CnDMAO has also been investigated. When C14DMAO was replaced by C12DMAO, similar phenomena can be observed with a slightly higher critical surfactant concentration for DNA compaction and a slightly lower pH of Tris-HCl buffer solution with pH = 6.8. For the DNA/C10DMAO system, however, no DNA compaction was observed even in Tris-HCl buffer solution with a much lower pH and a much higher C10DMAO concentration. The negative charges of DNA molecules can easily be neutralized by positive charges of cationic CnDMAOH(+) (n = 12 and 14) micelles. DNA was compacted and then insoluble DNA/CnDMAOH(+) complexes were formed. Because of the much higher critical micelle concentration (cmc) of the shorter chain length C10DMAOH(+), cationic C10DMAOH(+) micelles cannot form under the studied condition to compact DNA. The strategy may provide an efficient and alternative approach for stimuli-responsive gene therapy and drug release.

Nonionic surfactant, tetraethylene glycol monododecyl ether (C12EO4), cannot compact DNA because of its low efficiency in neutralizing the negative charges of the phosphate groups of DNA. It is also well-known that nonionic surfactants as a decompaction agent can help DNA be released from cationic surfactant aggregates. Herein, with the "bridge" Fe(3+) of C12EO4, we found that C12EO4 can efficiently compact DNA molecules into globular states with a narrow size distribution, indicating that the cooperative Fe(3+) can transform C12EO4 molecules from decompaction agents to compaction ones. The mechanism of the interaction of DNA and C12EO4 by "bridge" Fe(3+) is that the Fe(3+)-C12EO4 complexes act as multivalent ions by cooperative and hydrophobic interaction. The improved colloidal-stability and endosome escape effect induced by C12EO4 would provide the potential applications of nonionic surfactant in the physiological characteristics of DNA complexes. Cell viability assay demonstrates that Fe(3+)-C12EO4 complexes possess low cytotoxicity, ensuring good biocompatibility. Another advantage of this system is that the DNA complexes can be de-compacted by glutathione in cell without any other agents. This suggests the metal ion-nonionic surfactant complexes as compaction agent can act as the potential delivery tool of DNA in future nonviral gene delivery systems., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Here we construct for the first time ordered surfactant-DNA hybrid nanospheres of double-strand (ds) DNA and cationic surfactants with magnetic counterion, [FeCl3Br](-). The specificity of the magnetic cationic surfactants that can compact DNA at high concentrations makes it possible for building ordered nanospheres through aggregation, fusion, and coagulation. Cationic surfactants with conventional Br(-) cannot produce spheres under the same condition because they lose the DNA compaction ability. When a light-responsive magnetic cationic surfactant is used to produce nanospheres, a dual-controllable drug-delivery platform can be built simply by the applications of external magnetic force and alternative UV and visible light. These nanospheres obtain high drug absorption efficiency, slow release property, and good biocompatibility. There is potential for effective magnetic-field-based targeted drug delivery, followed by photocontrollable drug release. We deduce that our results might be of great interest for making new functional nucleic-acid-based nanomachines and be envisioned to find applications in nanotechnology and biochemistry.

A systematic work concerning the DNA compaction and decompaction controlled by cationic surfactants, cetyltrimethylammonium with [FeCl3Br](-) (CTAFe), Br(-) (CTABr) and Cl(-) (CTACl) as counterions, respectively, was performed. We discovered that cationic surfactants with complex counterions, [FeCl3Br](-), cannot promote the decompaction of DNA like those with Br(-) and Cl(-) as counterions. The rod-like CTAFe micelles were found to remain free in supernatants and cannot directly promote any redissolution or decompaction of DNA. These interesting findings could provide a better understanding of the interaction behavior of DNA and cationic surfactants. We conclude that the fundamental reason of the DNA decompaction lies upon the electrostatic competition between the counterions and DNA for associating with the cationic aggregates. At a high concentration, the binding of counterions to cationic CTA(+) aggregates is promoted, which weakens and screens the electrostatic attraction between DNA and cationic aggregates. This could cause the decompaction of DNA as the cases of CTABr/DNA and CTACl/DNA mixtures. Our data revealed the fundamental reason of the compaction and decompaction behavior of DNA induced by cationic surfactants independently, a reasonable three-step model of the conformational changes of DNA controlled by different amounts of cationic surfactants was presented. The current work could provide a clear guidance in gene delivery, gene therapy and biomedicine fields., (Copyright © 2015 Elsevier B.V. All rights reserved.)

A protocol was developed for preparing magnetic gold nanoparticles via one-step modification with a paramagnetic cationic surfactant. These magnetic gold nanoparticles can bind to and manipulate a low strength magnetic field-based delivery of DNA and proteins powerfully and non-invasively.

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.

Cationic and anionic (catanionic) vesicles were constructed from the mixtures of sodium laurate (SL) and alkyltrimethylammonium bromide (CnTAB, n = 12, 14, and 16) and were used to control the loading capacity of DNA. The binding saturation point (BSP) of DNA to catanionic vesicles increases with the chain length of cationic surfactants, which is at 1.0, 1.3 and 1.5 for CnTAB with n = 12, 14, and 16, respectively. Our measurements showed that the loading capacity and affinity of DNA can be controlled by catanionic vesicles. It increases with the chain length of cationic surfactants. Because of a large reduction in surface charge density, catanionic vesicles are prone to undergo re-aggregation or fusion with the addition of DNA. DNA molecules can still maintain original coil state during the interaction with catanionic CnTAL vesicles. (1)H NMR data reveals that the obvious dissociation of anionic ions, L(-), from catanionic C14TAL vesicles is due to the interaction with DNA; however, this phenomenon cannot be observed in C12TAB-SL vesicles. Agarose gel electrophoresis (AGE) results demonstrate that the electrostatic interaction between the two oppositely charged cationic and anionic surfactants is stronger than that between DNA and cationic surfactant, CnTAB (n = 12, 14, and 16). Not only is the dissociation of L(-) simply determined by the charge competition, but it also depends largely on the variations in the surface charge density as well as the cationic and anionic surfactant competing ability in geometry configuration of catanionic vesicles. The complicated interaction between DNA and catanionic vesicles induces the deformation of cationic vesicles. Our results should provide clear guidance for choosing more proper vectors for DNA delivery and gene therapy in cell experiments.

Here we develop a synthetic protocol for assembling DNA with participating metal ions into multiple shapes. DNA molecules first form coordination complexes with metal ions and these coordination complexes become nucleation sites for primary crystals of metal inorganic salt, and then elementary units of space-filling architectures based on specific geometry form, and finally elementary units assemble into variously larger multiple architectures according to different spatial configurations. We anticipate that our strategy for self-assembling various custom architectures is applicable to most biomolecules possessing donor atoms that can form coordination complexes with metal ions. These multiple architectures provide a general platform for the engineering and assembly of advanced materials possessing features on the micrometer scale and having novel activity.

The interaction of DNA with salt-free tetradecyltrimethylammonium hydroxide and lauric acid lamellar vesicles with positive charges was investigated to probe potential applications of vesicles in DNA transfection. The aggregation morphology of the vesicles changes greatly with the addition of DNA due to the dissociation of anionic surfactants, as indicated by (1)H nuclear magnetic resonance, and the expelled surfactant molecules self-assemble into micelles at high concentrations of DNA. Salt-free cationic and anionic (catanionic) vesicles have a much higher binding saturation point with DNA at R = 2.3 (the ratio of DNA to the excess positive charge in vesicles) than formerly reported salt-containing systems, implying high transfection efficiency. DNA retains its native stretched state during the interaction process. This very interesting result shows that catanionic vesicles could help transport undisturbed and extended DNA molecules into the target cells, which is of great importance in gene delivery, nanomedicine field, and controlling the formation of certain morphological aggregates.

Self-assembly exploits noncovalent interactions to offer a facile and effective method for the construction of soft materials with multifunctionalities and diversity. In this work, fluorescence carbon quantum dots coordinated by Ce3+ ions (CQDCe) have been synthesized and exploited as building blocks to generate a series of hierarchical structures through the ionic self-assembly of CQDCe and biomolecules, namely DNA, myoglobin (Mb), and hyaluronic acid (HA). In particular, vesicles can be constructed by the simple mixing of oppositely charged CQDCe and DNA in water. The formation of unusual vesicles can be explained by the self-assembly of CQDCe with a rearranged structure and the rigid DNA biomolecular scaffolds. This facile noncovalent self-assembly method has inspired the innovative use of virgin DNA as a building block to construct vesicles rather than resorting to a sophisticated synthesis. The self-assembly of CQDCe-biopolymers was accompanied by aggregation-induced photoluminescence (PL) quenching. The biosensing platform was designed to detect polypeptides and deoxyribonuclease I through competitive binding of CQDCe and enzymatic hydrolysis of the DNA backbone, respectively. We believe that the integrative self-assembly of CQDCe and DNA will enrich the theoretical study of vesicle formation by DNA molecules and extend the application of fluorescence carbon quantum dots in the biological field. [ABSTRACT FROM AUTHOR]

Abstract Microgels are colloidal particles with crosslinked polymer networks and dimensions ranging from tens of nanometers to micrometers. Specifically, smart microgels are fascinating capable of responding to biological signals in vivo or remote triggers and making the possible for applications in biomaterials and biomedicines. Therefore, how to fundamentally design microgels is an urgent problem to be solved. In this review, we put forward our important fundamental opinions on how to devise the intelligent microgels for cancer therapy, biosensing and biological lubrication. We focus on the design ideas instead of specific implementation process by employing reverse synthesis analysis to programme the microgels at the original stage. Moreover, special insights will be, for the first time, as far as we know, dedicated to the particles completely composed of DNA or proteins into microgel systems. These are discussed in detail in this review. We expect to give readers a broad overview of the design criteria and practical methodologies of microgels according to the application fields, as well as to propel the further developments of highly interesting concepts and materials. Graphical abstract Unlabelled Image Highlights • We expect to give readers a broad overview of the design criteria and practical methodologies of microgels. • We focus on design ideas instead of specific implementation process. • A reverse synthesis analysis was employed to programme the microgels at the original stage. • For the first time, it decicated to the particles composed completely of DNA or proteins into microgel systems. • The mechanism of the most basic and the most commonly used methods for synthesizing microgels are briefly reviewed. [ABSTRACT FROM AUTHOR]

Graphical abstract Abstract Self-assembly exploits a facile non-covalent way to couple structurally different building blocks for creating soft materials with synergetic novel properties and functions. Taking advantage of magneto-properties from magnetic surfactants as well as versatile functional ligand formed by carbon quantum dots with cysteine (cys-CQDs), the magnetic network materials were firstly constructed by using magnetic surfactants and cys-CQDs as self-assembly building blocks. Counterions of Br−, [GdCl 3 Br]−, [HoCl 3 Br]− in surfactants could control the morphology of magnetic network structures, and the concentration of magnetic surfactants manoeuvres a versatile scenario of self-assembly behavior. Self-assembly of cys-CQDs and CTAHo brought out a 10-fold increase in magnetic moment of CTAHo. The fluorescent property of carbon quantum dots firstly served as an effective indicator element to dissect the collective effect in self-assembly process. For the sake of capturing the target sequence-specific DNA molecules, in situ growth of Ag nanoparticles (AgNPs) upon the magnetic network structures was realized by synergetically electrostatic and coordinated interaction of carboxyl groups and Ag ions. The magnetic Ag self-assemblies anchored thiol-containing DNA, serving as a magnetic separation booster for the target sequence-specific DNA molecules under an applied magnetic field, which will bring light on designing magneto-functional self-assembly materials according to practical application requirements. [ABSTRACT FROM AUTHOR]

Controlled compaction and decompaction of DNA by zwitterionic surfactants, alkyldimethylamine oxides (C n DMAO, n = 10, 12, and 14), were investigated by various analytical tools. It was found that DNA could effectively be compacted by cationic micelles of C n DMAOH + which were produced by the protonation of C n DMAO in acidic media leading to the formation of water-insoluble C n DMAOH + /DNA complexes. The DNA molecules were compacted at pH 4–5 when the concentration of C 10 DMAOH + , C 12 DMAOH + , and C 14 DMAOH + reached 8.0, 1.6, and 0.9 mmol L −1 , respectively. Interestingly, the precipitates of C n DMAOH + /DNA complexes can re-dissolve which indicated that the DNA molecules were released from the complexes by regulating the pH of the solution to ∼4 and increasing the surfactant concentration to 40, 9.0, and 1.8 mmol L −1 for C 10 DMAOH + , C 12 DMAOH + , and C 14 DMAOH + , respectively. This phenomenon was attributed to the hydrogen bonding formed between cationic C n DMAOH + and zwitterionic C n DMAO species. These hydrogen-bonded species screen the electrostatic forces between the positively charged C n DMAOH + micelles and the negatively charged backbones of DNA. Our results demonstrated that the release of DNA from the C n DMAOH + /DNA precipitates depended on the concentration of cationic C n DMAOH + and the pH of the solution. Compared with the conventional release of DNA by the addition of β-cyclodextrin, the present strategy allowed for a specific controlled release, which favored the penetration of DNA into cells and could protect the DNA molecules from nucleases degradation. [ABSTRACT FROM AUTHOR]

Thermotropic liquid crystals (TLCs) have created unpredictable applications ranging from sensor to electronic devices. DNA can interact with positively charged cationic and anionic (catanionic) vesicles by electrostatic interaction to form DNA-based TLCs. In the present work, the polarizing optical microscopy (POM) images clearly demonstrate the formation of DNA-involved liquid crystals, we explore the general role of DNA-involved TLC formation and the regulating factors of properties of DNA-based TLCs. We verify the effect of the chain lengths of surfactants and DNA on the formation and properties of TLCs. We found that DNA-involved TLCs constructed by the different surfactants with same chain length present the excellent properties. The position of functional group of ferrocenyl surfactants greatly affects the formation of TLCs. The bulky group closing to the headgroup of surfactant and the strong electrostatic interaction between positively charged catanionic vesicles and DNA affect the formation of TLCs. Furthermore, we found that the shorter DNA strand length, the more consistent fit better with the vesicles to enhance the thermal stability of DNA-based TLCs. The influence factors of the formation of DNA-based TLCs were explored and the importance of interactions to the architecture of DNA-based TLCs also was underscored. Our results may direct the design and synthesis of functional DNA-based TLCs and lay the foundation of applications in the field of electrochemistry and flexible electronic devices. [Display omitted] • Formation of DNA-involved thermotropic liquid crystals (TLCs) and the regulating factors of TLCs properties were explored. • The effect of the chain lengths of surfactants and DNA on the formation and properties of TLCs was verified. • The results may direct the design and synthesis of DNA-based TLCs [ABSTRACT FROM AUTHOR]