Simple and Rapid Detection of Ibuprofen─A Typical Pharmaceuticals and Personal Care Products─by a Liquid Crystal Aptasensor.

This work established a liquid crystal (LC) aptasensor for simple and rapid detection of ibuprofen, a typical pharmaceuticals and personal care products (PPCPs) pollutant. A negatively charged DNA aptamer specific for ibuprofen and a positively charged amphiphilic surfactant, hexadecyltrimethylammonium bromide (CTAB), were incubated with the sample and then directly added onto the LC interface. In the presence of ibuprofen, the specific binding of ibuprofen with the DNA aptamer will release CTAB, which then adsorbed at the LC-aqueous interface and induced the orientational change of LCs to homeotropic orientation with a dark optical signal output. While in the absence of ibuprofen, the DNA aptamer binds with CTAB through hydrophobic and electrostatic interactions, LCs remained in the planar orientation with a bright optical signal output. This LC aptasensor also has good specificity for ibuprofen and can even detect ibuprofen drug in tap water. Moreover, the response time of the LC aptasensor is fast in minutes. Additionally, this LC aptasensor benefits in monitoring the water quality and inspires the exploration of a general platform for PPCPs detection.

Ultrafast, High-Contractile Electrothermal-Driven Liquid Crystal Elastomer Fibers towards Artificial Muscles.

Liquid crystal elastomer (LCE) fibers are capable of large and reversible deformations, making them an ideal artificial muscle. However, limited to stimulating source and structural design, current LCE fibers have not yet achieved both large contraction ratio and fast contraction rate to perform the intense motion. In this work, electrothermal-responsive liquid metal (LM) containing LCE (LM-LCE) fibers is reported. By introducing flexible liquid metal, LM-LCE fibers retain deformability with a large contraction ratio similar to that of pure LCE fibers and are endowed with electrical responsiveness. Applying precisely controlled electrical stimulation, the contraction ratio and rate of LM-LCE fibers can be programmed by adjusting voltage value and pulse time. Under electrical stimulation at 1.25 V cm-1 , 0.1 s, LM-LCE fibers can produce over 40% contraction ratio at an ultrafast contraction rate of up to 280% s-1 . Furthermore, LM-LCE fibers mimic human triceps muscle and can conduct precise ball shooting. LM-LCE fibers with excellent contraction ratio and rate extend their functionality as artificial muscles to perform intense movements and are expected to enrich the challenging applications of soft robots.

Simple, rapid and sensitive detection of Parkinson's disease related alpha-synuclein using a DNA aptamer assisted liquid crystal biosensor.

Alpha-synuclein (αS) has been proposed as a potential biomarker for the diagnosis of Parkinson's disease (PD). However, the detection of αS using a simple, rapid and sensitive approach is still challenging. Herein, we construct a new type of biosensor for the detection of αS, combining the stimuli-responsiveness of liquid crystals (LCs) and the specific interaction of a DNA aptamer with proteins. In principle, the positively charged surfactant hexadecyltrimethylammonium bromide (CTAB) binds with the negatively charged DNA aptamer via electrostatic interactions; in the presence of αS, the DNA aptamer specifically binds with αS and releases CTAB, which is an amphiphilic molecule and subsequently assembles at the LC-aqueous interface, resulting in a homeotropic alignment of LCs with a dark optical signal. In the absence of αS, CTAB binds with the DNA aptamer without affecting the alignment of LCs, which shows planar anchoring with a bright optical signal. The response time of LCs towards αS is rapid and can be down to minutes. The LC biosensor established here has a good specificity for αS and can recognize αS even from a mixture of proteins. The LC biosensor also exhibits high sensitivity with a limit of detection of αS as low as 10 pM, which is comparable to that of the enzyme-linked immunosorbent assay. This work provides a new strategy for the detection of αS in a simple, rapid and sensitive manner, possessing promising potentials towards early diagnosis and clinical applications.

Modified Voronoi Analysis of Spontaneous Formation of Interfacial Droplets on Immersed Oil-Solid Substrates.

The nucleation and growth of liquid droplets on solid substrates have received much attention because of the significant relevance of these multiphase processes to both nature and practical applications. There have been extensive studies on the condensation of water from the air phase on solid substrates. Here, we focus on water diffusion through the oil phase and subsequent settlement on solid substrates because such interfacial droplets are formed. Voronoi diagram analysis is proposed to statistically characterize the size distribution of the growing droplets. It is found that modification of the standard Voronoi diagram is required for systems of interfacial droplets which have a noncircular shape and/or whose centers change with time. The modified Voronoi analysis of the growing droplets provides an automatic quantification of the droplet distribution and reveals that (i) during the nucleation stage, the interfacial droplets do not nucleate at the same time because the nucleation of newly formed droplets competes with the growth of the existing ones; (ii) the growth of interfacial droplets comes from water diffusion from the bulk water layer, and/or from adjacent interfacial droplets, and/or from coalescence of interfacial droplets; and (iii) the sizes of interfacial droplets become more polydispersed on P-glass but more monodispersed on OTS-glass as time goes. This work opens a new perspective on the formation of interfacial droplets at the interface between oil and the solid substrate and demonstrates the capability of an automatic analysis method, which can be potentially applied to similar interfacial multiphase systems.

Spatially arranging interfacial droplets at the oil-solid interface.

The controlling and patterning of small droplets on a solid surface is of significant interest to understand interfacial phenomena and for practical applications. Among interfacial phenomena, the formation of interfacial droplets attracts scientists' attention, as the mechanism of this phenomenon where water molecules can spontaneously accumulate at the hydrophobic oil/solid interface is still not fully understood. Further investigation is needed to find out specifically where the driving force comes from and how to spatially arrange the interfacial droplets. Herein, self-assembled monolayers are formed on a gold substrate, and it turns out that the hydrophobic surface with a monolayer formed from HS(CH2)11CH3 could inhibit the formation of interfacial droplets; by contrast, the hydrophilic surfaces with monolayers formed from HS(CH2)11COOH, HS(CH2)11NH3·Cl and HS(CH2)11OH, all promote water accumulation. It suggests that the hydrogen bonding between the surface and water proves to be critical in inducing interfacial droplet formation but this has been neglected in past studies. Taking advantage of microcontact printing, the surface chemistry can be controlled at the micron scale and allows spatial arrangement of interfacial droplets at specific regions. This work moves a further step in understanding the mechanism of interfacial droplet formation, and can be potentially exploited for the collection of water and fabrication of microtemplates.

Investigation of the Assembly Behavior of an Amphiphilic Lipopeptide at the Liquid Crystal-Aqueous Interface.

In this article, we designed an amphiphilic lipopeptide molecule, 5(6)-carboxyfluorescein-KKKKKKSKTK-Cys(C12H25)-OMe (FAM-lipopeptide-C12), and studied its assembly behavior at the 4-cyano-4'-pentylbiphenyl (5CB)-aqueous interface. The ordering transitions of liquid crystals (LCs) revealed that FAM-lipopeptide-C12 can assemble at the LC-aqueous interface (both planar and curved interfaces). The assembly can be destroyed by adding trypsin, which catalyzes the hydrolysis of lipopeptides. Fluorescence measurements further confirmed the assembly and deassembly behavior of FAM-lipopeptide-C12 at the LC-aqueous interface. Overall, our work provides a general method for the construction of a biointerface by directly assembling amphiphilic lipopeptides at the LC-aqueous interface, which can potentially be used in selectively detecting the activity of specific enzymes and other biomolecular interactions.

Folding DNA into a Lipid-Conjugated Nanobarrel for Controlled Reconstitution of Membrane Proteins.

Building upon DNA origami technology, we introduce a method to reconstitute a single membrane protein into a self-assembled DNA nanobarrel that scaffolds a nanodisc-like lipid environment. Compared with the membrane-scaffolding-protein nanodisc technique, our approach gives rise to defined stoichiometry, controlled sizes, as well as enhanced stability and homogeneity in membrane protein reconstitution. We further demonstrate potential applications of the DNA nanobarrels in the structural analysis of membrane proteins.

Cuboid Vesicles Formed by Frame-Guided Assembly on DNA Origami Scaffolds.

We describe the use of a frame-guided assembly (FGA) strategy to construct cuboid and dumbbell-shaped hetero-vesicles on DNA origami nanostructure scaffolds. These are achieved by varying the design of the DNA origami scaffolds that direct the distribution of the leading hydrophobic groups (LHG). By careful selection of LHGs, different types of amphiphiles (both polymer and small-molecule surfactants) were guided to form hetero-vesicles, demonstrating the versatility of the FGA strategy and its potential to construct asymmetric and dynamic hetero-vesicle assemblies with complex DNA nano-scaffolds.

Using Small Molecules to Prepare Vesicles with Designable Shapes and Sizes via Frame-Guided Assembly Strategy.

Following the principle of frame-guided assembly (FGA), a small amphiphilic molecule, sodium dodecyl sulfate, is shown to form vesicles with cholesterol as the leading hydrophobic group. These findings not only demonstrate the generality of the FGA but also provide a clue to understand the formation mechanism of the cell membrane, and even the origin of life.

Preparation and self-folding of amphiphilic DNA origami.

Amphiphilic DNA origami is prepared by dressing multiple hydrophobic molecules on a rectangular single layer DNA origami, which is then folded or coupled in sandwich-like structures with two outer DNA origami layer and one inner hydrophobic molecules layer. The preference to form different kinds of structures could be tailored by rational design of DNA origami.

A writable polypeptide-DNA hydrogel with rationally designed multi-modification sites.

A polypeptide-DNA hydrogel is prepared by employing the "X"-shaped DNA assembling structure as crosslinker. The hydrogel can be modified with multifunctional components (here fluorescent molecules as a model) and possesses excellent self-healing and thixotropic properties, enabling the direct-writing of arbitrary 3D structures. This study provides a simple, universal strategy for the assembly of functionalized hydrogels.

DNA nanotechnology based on i-motif structures.

CONSPECTUS: Most biological processes happen at the nanometer scale, and understanding the energy transformations and material transportation mechanisms within living organisms has proved challenging. To better understand the secrets of life, researchers have investigated artificial molecular motors and devices over the past decade because such systems can mimic certain biological processes. DNA nanotechnology based on i-motif structures is one system that has played an important role in these investigations. In this Account, we summarize recent advances in functional DNA nanotechnology based on i-motif structures. The i-motif is a DNA quadruplex that occurs as four stretches of cytosine repeat sequences form C·CH(+) base pairs, and their stabilization requires slightly acidic conditions. This unique property has produced the first DNA molecular motor driven by pH changes. The motor is reliable, and studies show that it is capable of millisecond running speeds, comparable to the speed of natural protein motors. With careful design, the output of these types of motors was combined to drive micrometer-sized cantilevers bend. Using established DNA nanostructure assembly and functionalization methods, researchers can easily integrate the motor within other DNA assembled structures and functional units, producing DNA molecular devices with new functions such as suprahydrophobic/suprahydrophilic smart surfaces that switch, intelligent nanopores triggered by pH changes, molecular logic gates, and DNA nanosprings. Recently, researchers have produced motors driven by light and electricity, which have allowed DNA motors to be integrated within silicon-based nanodevices. Moreover, some devices based on i-motif structures have proven useful for investigating processes within living cells. The pH-responsiveness of the i-motif structure also provides a way to control the stepwise assembly of DNA nanostructures. In addition, because of the stability of the i-motif, this structure can serve as the stem of one-dimensional nanowires, and a four-strand stem can provide a new basis for three-dimensional DNA structures such as pillars. By sacrificing some accuracy in assembly, we used these properties to prepare the first fast-responding pure DNA supramolecular hydrogel. This hydrogel does not swell and cannot encapsulate small molecules. These unique properties could lead to new developments in smart materials based on DNA assembly and support important applications in fields such as tissue engineering. We expect that DNA nanotechnology will continue to develop rapidly. At a fundamental level, further studies should lead to greater understanding of the energy transformation and material transportation mechanisms at the nanometer scale. In terms of applications, we expect that many of these elegant molecular devices will soon be used in vivo. These further studies could demonstrate the power of DNA nanotechnology in biology, material science, chemistry, and physics.

A brief review of methods for terminal functionalization of DNA.

The functionalized DNA has been widely developed and played a more and more important role in life science and material science during last decades. Therefore, methods to effectively endue DNA new functions by modifying DNA have been developed quickly. In this review, we will give an introduction in the methods for covalent terminal functionalization of DNA, including solid-phase functionalization and solution coupling functionalization, mainly on the technical aspect. The application of these functionalized DNA will be also introduced.

Rapid formation of a supramolecular polypeptide-DNA hydrogel for in†situ three-dimensional multilayer bioprinting.

A rapidly formed supramolecular polypeptide-DNA hydrogel was prepared and used for in situ multilayer three-dimensional bioprinting for the first time. By alternative deposition of two complementary bio-inks, designed structures can be printed. Based on their healing properties and high mechanical strengths, the printed structures are geometrically uniform without boundaries and can keep their shapes up to the millimeter scale without collapse. 3D cell printing was demonstrated to fabricate live-cell-containing structures with normal cellular functions. Together with the unique properties of biocompatibility, permeability, and biodegradability, the hydrogel becomes an ideal biomaterial for 3D bioprinting to produce designable 3D constructs for applications in tissue engineering.

Tetrahedron DNA dendrimers and their encapsulation of gold nanoparticles.

DNA dendrimers have achieved increasing attention recently. Previously reported DNA dendrimers used Y-DNA as monomers. Tetrahedron DNA is a rigid tetrahedral cage made of DNA. Herein, we use tetrahedron DNA as monomers to prepare tetrahedron DNA dendrimers. The prepared tetrahedron DNA dendrimers have larger size compared with those made of Y-DNA. In addition, thanks to the central cavity of tetrahedron DNA monomers, some nanoscale structures (e.g., gold nanoparticles) can be encapsulated within tetrahedron DNA monomers. Tetrahedron DNA encapsulated with gold nanoparticles can be further assembled into dendrimers, guiding gold nanoparticles into clusters.

Thermally triggered frame-guided assembly.

We report a thermally triggered frame-guided assembly (FGA) strategy for the preparation of vesicles. We employ thermally responsive poly(propylene oxide) (PPO) to make the leading hydrophobic groups (LHGs) thermally responsive, so that they are hydrophilic below the low critical solution temperature (LCST) and the frame forms in a homogeneous environment. When the temperature is increased above the LCST, the LHGs become hydrophobic and the assembly process is triggered, which drives DNA-b-PPO to assemble around the LHGs, forming vesicles. This work verified that FGA is a general strategy and can be applied to polymeric systems. The thermally triggered assembly not only provides more controllability over the FGA process but also promotes an in-depth understanding of the FGA strategy and in a broad view, the formation mechanism and functions of cell membrane.

Frame-guided assembly of vesicles with programmed geometry and dimensions.

In molecular self-assembly molecules form organized structures or patterns. The control of the self-assembly process is an important and challenging topic. Inspired by the cytoskeletal-membrane protein lipid bilayer system that determines the shape of eukaryotic cells, we developed a frame-guided assembly process as a general strategy to prepare heterovesicles with programmed geometry and dimensions. This method offers greater control over self-assembly which may benefit the understanding of the formation mechanism as well as the functions of the cell membrane.

Ultrasound pretreatment enhances moisture migration and drying quality of mulberry via microstructure and cell-wall polysaccharides nanostructure modification.

The effects of ultrasound pretreatment (20 kHz, 30 W/L) on mulberries' texture, microstructure, characteristics of cell-wall polysaccharides, moisture migration, and drying quality were investigated over exposure times ranging from 15 to 45 min. Ultrasound induced softening of mulberry tissue, accompanied by an increase in water-soluble pectin and a decrease in chelate-soluble pectin and Na2CO3-soluble pectin concentrations. Noticeable depolymerization of the pectin nanostructure was observed in the pretreated mulberries, along with a decrease in molecular weight, attributed to side-chain structure cleavage. Ultrasound loosened the cell wall structure, increased free water content and freedom, thereby reducing water diffusion resistance. Ultrasound pretreatment reduced drying time by 11.2 % to 23.3 % at various processing times compared to controls. Due to significantly enhanced drying efficiency, the optimal pretreatment time (30 min) yielded dried mulberries with higher levels of total phenolics and total anthocyanins, along with an increased antioxidant capacity. The results of this study provide insights into the mechanisms by which ultrasound pretreatment can effectively enhance the mulberry drying process.

Regulation of an enzyme cascade reaction by a DNA machine.

A strategy for the regulation of enzyme cascade reaction efficiency by a DNA machine in vitro is presented. Two cascade enzymes (GOx and HRP) are attached to the DNA machine, and the enzyme cascade reaction shows much higher efficiency when the two enzymes are brought closer by the DNA machine than when they are distant.

3D printing programmable liquid crystal elastomer soft pneumatic actuators.

Soft pneumatic actuators (SPAs) rely on anisotropic mechanical properties to generate specific motions after inflation. To achieve mechanical anisotropy, additional stiff materials or heterogeneous structures are typically introduced in isotropic base materials. However, the inherent limitations of these strategies may lead to potential interfacial problems or inefficient material usage. Herein, we develop a new strategy for fabricating SPAs based on an aligned liquid crystal elastomer (LCE) by a modified 3D printing technology. A rotating substrate enables the one-step fabrication of tubular LCE-SPAs with designed alignments in three dimensions. The alignment can be precisely programmed through printing, resulting in intrinsic mechanical anisotropy of the LCE. With a specially designed alignment, LCE-SPAs can achieve basic motions-contraction, elongation, bending, and twisting-and accomplish diverse tasks, e.g., grabbing objects and mixing water. This study provides a new perspective for the design and fabrication of SPAs.