Self-Propelling Macroscale Sheets Powered by Enzyme Pumps

Nanoscale enzymes anchored to surfaces act as chemical pumps by converting chemical energy released from enzymatic reactions into spontaneous fluid flow that propels entrained nano- and microparticles. Enzymatic pumps are biocompatible, highly selective, and display unique substrate specificity. Utilizing these pumps to trigger self-propelled motion on the macroscale has, however, constituted a significant challenge and thus prevented their adaptation in macroscopic fluidic devices and soft robotics. Using experiments and simulations, we herein show that enzymatic pumps can drive centimeter-scale polymer sheets along directed linear paths and rotational trajectories. In these studies, the sheets are confined to the air/water interface. With the addition of appropriate substrate, the asymmetric enzymatic coating on the sheets induces chemically driven, buoyancy flows that controllably propel the sheet's motion on the air/water interface. The directionality and speed of the motion can be tailored by changing the pattern of the enzymatic coating, type of enzyme, and nature and concentration of the substrate. This work highlights the utility of biocompatible enzymes for generating motion in macroscale fluidic devices and robotics and indicates their potential utility for in vivo applications.     

Autonomous Non-Equilibrium Self-Assembly and Molecular Movements Powered by Electrical Energy**

The ability to exploit energy autonomously is one of the hallmarks of life. Mastering such processes in artificial nanosystems can open technological opportunities. In the last decades, light- and chemically driven autonomous systems have been developed in relation to conformational motion and self-assembly, mostly in relation to molecular motors. In contrast, despite electrical energy being an attractive energy source to power nanosystems, its autonomous harnessing has received little attention. Herein we consider an operation mode that allows the autonomous exploitation of electrical energy by a self-assembling system. Threading and dethreading motions of a pseudorotaxane take place autonomously in solution, powered by the current flowing between the electrodes of a scanning electrochemical microscope. The underlying autonomous energy ratchet mechanism drives the self-assembly steps away from equilibrium with a higher energy efficiency compared to other autonomous systems. The strategy is general and might be extended to other redox-driven systems.     

External-energy-independent polymer capsule motors and their cooperative behaviors

The design and development of mobile nano-, micro-, and millimeter-scale autonomous systems have been perused over several decades. Here, we introduce a millimeter-sized polymer capsule motor with specific features and functionalities. It runs without any external energy sources or the consumption of external fuels such as H(2)O(2) or glucose. The occurrence of motion is due to the asymmetric release of organic solvent from the capsule and the asymmetric change in the surface tension of the surrounding liquid. The capsule moves from a place of lower surface tension to a place of higher surface tension (Marangoni effect) in an attempt by the system to attain the desirable lowest-free-energy state. The operation of the motor is versatile in terms of the environment, as it moves on a wide variety of liquid/air interfaces, including water, sea water, organic solvent/water mixtures, and acids. A high-motion velocity was observed, with a travelling distance of over 20 meters. The manipulation of its motion was achieved upon functionalization with nickel powder and application of an external magnetic field. Long-range interaction behaviors and surface-cleaning effects due to the chemotaxis effect were also demonstrated when the capsule was functionalized with sodium dodecyl sulfate (SDS). We believe that a plethora of applications can be envisioned with this motor, such as cargo delivery, manipulation of matter, sensing and detection, biorecognition, and environmental remediation.     

Shaping and exploring the micro- and nanoworld using bipolar electrochemistry

Bipolar electrochemistry is a technique with a rather young history in the field of analytical chemistry. Being based on the polarization of a conducting object which is exposed to an external electric field, it allowed recently the development of new methods for controlled surface modification at the micro- and nanoscale and very original analytical applications. Using bipolar electrodes, analyte separation and detection becomes possible based on miniaturized systems. Moreover, the modified objects that can be created with bipolar electrochemistry could find applications as key components for detection systems. In this contribution, the principles of bipolar electrochemistry will be reviewed, as well as recent developments that focus on the modification of objects at the nano- and microscale and their potential application in miniaturized analytical systems.     

An overview on water splitting photocatalysts

Photocatalytic splitting of water into H₂ is one of the most promising ways for converting solar energy into chemical energy. In the present paper, the basic physical and chemical principles of photocatalysts for hydrogen generating from aqueous solutions are outlined. Strategies for designing visible-light-induced photocatalysts have been reviewed. Besides, ultraviolet-light-induced photocatalysts, dye sensitization, photoelectrochemical water splitting and Z-scheme systems to effectively increase the light harvest are also discussed. Finally, the existing problems, possible solutions and prospects are presented.     

1H magic angle rotation NMR in polymer studies

The principles of the method of NMR line narrowing by measurement with spinning of the sample about the magic axis (MAR-NMR) are introduced, with particular emphasis on the effects of internal motion upon the possibilities and limitations of the method. The applications of the method in ¹H-NMR studies of polymer structure and dynamics are then reviewed. Due to both theoretical and experimental limitations, narrowing of dipolar broadened NMR lines by MAR can be observed in ¹H NMR spectra only in those cases where internal motion is anisotropic, or in heterogeneous systems where line width is limited by differences of magnetic susceptibility. In polymers, both solid and liquid, the method makes possible differentiation between isotropic and anisotropic internal motion. In systems with anisotropic internal motion, MAR-NMR makes possible a characterization of motional codes which normally are obscured by residual dipolar interactions, as well as of geometrical restrictions upon these motions.     

Microscale Ionic Diodes: An Overview

Ionic rectifier membranes or devices generate uni-directional ion transport to convert an alternating current (AC) ion current input into stored energy or direct current (DC) in the form of ion/salt gradients. Electrochemical experiments 80 years ago were conducted on biological membrane rectifier systems, but today a plethora of artificial ionic rectifier types has been developed and electroanalytical tools are employed to explore mechanisms and performance. This overview focuses on microscale ionic rectifiers with a comparison to nano- and macroscale ionic rectifiers. The potential is surveyed for applications in electrochemical analysis, desalination, energy harvesting, electrochemical synthesis, and in selective ion extraction.     

Signal Propagation in Multi‐Layer DNAzyme Cascades Using Structured Chimeric Substrates

Signal propagation through enzyme cascades is a critical component of information processing in cellular systems. Although such systems have potential as biomolecular computing tools, rational design of synthetic protein networks remains infeasible. DNA strands with catalytic activity (DNAzymes) are an attractive alternative, enabling rational cascade design through predictable base‐pair hybridization principles. Multi‐layered DNAzyme signaling and logic cascades are now reported. Signaling between DNAzymes was achieved using a structured chimeric substrate (SCS) that releases a downstream activator after cleavage by an upstream DNAzyme. The SCS can be activated by various upstream DNAzymes, can be coupled to DNA strand‐displacement devices, and is highly resistant to interference from background DNA. This work enables the rational design of synthetic DNAzyme regulatory networks, with potential applications in biomolecular computing, biodetection, and autonomous theranostics.     

Fabrication of Self-Propelled Micro- and Nanomotors Based on Janus Structures

Delicate molecular and biological motors are tiny machines capable of achieving numerous vital tasks in biological processes. To gain a deeper understanding of their mechanism of motion, researchers from multiple backgrounds have designed and fabricated artificial micro- and nanomotors. These nano-/microscale motors can self-propel in solution by exploiting different sources of energy; thus showing tremendous potential in widespread applications. As one of the most common motor systems, Janus motors possess unique asymmetric structures and integrate different functional materials onto two sides. This review mainly focuses on the fabrication of different types of micro- and nanomotors based on Janus structures. Furthermore, some challenges still exist in the implementation of Janus motors in the biomedical field. With such common goals in mind, it is expected that the elaborate and multifunctional design of Janus motors will overcome their challenges in the near future.     

A guide to design the trajectory of active particles: From fundamentals to applications

Active particles convert external energy into motility, displaying a variety of dynamical features. Recent progress in the field has marked a shift in focus from understanding the origin and sources of active motion to controlling the dynamics and trajectory of individual microswimmers. This review explores the advancements made in a two-fold perspective—the role of particle design and that of external factors. Our main goal is to highlight the guiding principles, which determine active particle trajectory. These include, on the one hand, the role of the morphology of active particles and their assemblies in driving translation, rotation, and corresponding coupling between the two. On the other hand, the effect of environmental parameters such as the presence of physicochemical heterogeneities including interfaces, suspended obstacles, and boundaries on the modality and trajectory of active colloids. We discuss the potential of using active particles in biomedical and environmental applications through recent examples.     

Aligned carbon nanostructures based 3D electrodes for energy storage

Electrochemical energy storage systems with high specific energy and power as well as long cyclic stability attract increasing attention in new energy technologies. The principles for rational design of electrodes are discussed to reduce the activation, concentration, and resistance overpotentials and improve the active material efficiency in order to simultaneously achieve high specific energy and power. Three dimensional(3D)nanocomposites are currently considered as promising electrode materials due to their large surface area,reduced electronic and ionic diffusion distances, and synergistic effects. This paper reviews the most recent progress on the synthesis and application of 3D thin film nanoelectrode arrays based on aligned carbon nanotubes(ACNTs) directly grown on metal foils for energy storages and special attentions are paid on our own representative works. These novel 3D nanoelectrode arrays on metal foil exhibit improved electrochemical performances in terms of specific energy, specific power and cyclic stability due to their unique structures.In this active materials coated ACNTs over conductive substrate structures, each component is tailored to address a different demand. The electrochemical active material is used to store energy, while the ACNTs are employed to provide a large surface area to support the active material and nanocable arrays to facilitate the electron transport. The thin film of active materials can not only reduce ion transport resistance by shortening the diffusion length but also make the film elastic enough to tolerate significant volume changes during charge and discharge cycles. The conductive substrate is used as the current collector and the direct contact of the ACNT arrays with the substrate reduces significantly the contact resistance. The principles obtained from ACNT based electrodes are extended to aligned graphene based electrodes. Similar improvements have been achieved which confirms the reliability of the principles obtained. In addition, we also discuss and view the ongoing trends in development of aligned carbon nanostructures based electrodes for energy storage.     

Ultrasensitive assays for proteins

Proteins are essential components of organisms and are involved in a wide range of biological functions. There are increasing demands for ultra-sensitive protein detection, because many important protein biomarkers are present at ultra-low levels, especially during the early stages of disease. Measuring proteins at low levels is also crucial for investigations of the protein synthesis and functions in biological systems. In this review, we summarize the recent developments of novel technology enabling ultrasensitive protein detection. We focus on two groups of techniques that involve either polymerase amplification of affinity DNA probes or signal amplification by the use of nano-/micro-materials. The polymerase-based amplification of affinity DNA probes indirectly improves the sensitivity of protein detection by increasing the number of detection molecules. The use of nano-/micro-materials conjugated to affinity probes enhances the measurement signals by using the unique electrical, optical, and catalytic properties of these novel materials. This review describes the basic principles, performances, applications, merits, and limitations of these techniques.     

Catalytic Motors—Quo Vadimus?

Self-propelled, active colloidal systems are of great current interest from both fundamental as well as practical standpoints, with potential applications in nanomachinery, nanoscale assembly, robotics, fluidics, and chemical/biochemical sensing. This perspective focuses on chemically powered catalytic nano- and micromotors. We review the major advances to date in motor design, propulsion mechanisms and directional control, and inter-motor communication leading to collective behavior. We conclude by discussing the next steps in going forward: the fundamental questions that remain to be addressed and new design principles required for useful applications.     

Self-assembled cyclodextrin nanoparticles and drug delivery

Drug/cyclodextrin complexes self-assemble in aqueous solutions to form nanosized aggregates or nanoparticles. These complex aggregates are responsible for many of the physicochemical and biological properties of cyclodextrin complexes. Due to the aggregate formation aqueous drug/cyclodextrin solutions can behave more like dispersed nanoscale systems, such as nano-suspensions and liposomes, rather than true solutions. The aggregation can result in enhanced cyclodextrin solubilization of poorly soluble lipophilic drugs; they can serve as building blocks for ternary or higher order complexes; they can be developed into nano- and microparticulated drug carriers for targeted drug delivery to, for example, hair follicles; they can be developed into sustained drug delivery systems; and they can possible be used as mucus-penetrating drug delivery vectors. All of this can be obtained without chemical modifications of the cyclodextrin monomers.     

Catalytic molecular motors: fuelling autonomous movement by a surface bound synthetic manganese catalase

A molecular approach to the powering of multi-component nano-devices capable of autonomous translational and rotational motion through the conversion of chemical to kinetic energy is reported.     

On the long way from the Coulombic Hamiltonian to the intermolecular energy surfaces: Concluding remarks at the tromsø conference,June 20–22, 1989

After a brief review of the main results given at the conference, the general properties of the Coulombic Hamiltonian for a system of electrons moving in a framework of moving atomic nuclei—considered as point charges—are discussed. Since this Hamiltonian is invariant under translations and rotations, the total momentum and the total angular momentum are constants of motion, which means that it is possible to separate the motion of the center of mass and the rotation of the system as a whole. Even if these separations are simple in principle, they lead to a mixing of the electronic and nuclear coordinates that complicates the transformed Hamiltonian. The general features of this Hamiltonian are discussed both in pure quantum mechanics and general quantum theory dealing with wave functions Ψ respective density matrices ρ or system operators T. The principles of the latter are derived from five simple axioms, and it is shown that pure quantum mechanics is a special case of the general theory and that the analogy between these two approaches is essential for the “economy of thinking.” It is indicated that the general theory of the shape and topology of the energy surface 〈H〉 = TrHΓ and its critical points, as a function of the system operator Γ involving both electronic and nuclear coordinates, is a very difficult mathematical problem and that calculation of this surface even for simple molecular systems represents a formidable computational problem, which has to be solved in order to be able to understand the nature of chemical reactions from first principles.     

A scanning force microscopy study on the motion of single brush-like macromolecules on a silicon substrate induced by coadsorption of small molecules

Scanning force microscopy was applied to visualise the motion of single poly(butanoate-ethylmethacrylate)-graft-poly(n-butyl acrylate) molecules on silicon and SrTiO(3) substrates. Macromolecular mobility was induced by cyclic exposure of the wafers with the adsorbed brush-like macromolecules to water and alcohol vapours. Exposure to saturated alcohol vapour induced collapse of the adsorbed individual polymer chains while exposure to saturated water vapour promoted their extension. The characteristic times of both conformational changes were long enough that it was possible to visualise step-by-step the morphology transformation in situ by means of an environment-controlled scanning force microscope. Several successive collapse-decollapse cycles were recorded, and small diffusive shifts of the macromolecular position on the substrate were detected after each cycle. Manipulating and visualising single polymer molecules in situ and real time on a silicon substrate opens up new possibilities for the controlled structure formation in ultrathin polymer films. As shown on the sample of a faceted SrTiO(3) wafer, upon extension the brush-like molecules can crawl or extend along nanoscopic surface structures. Silicon can be structured both topographically and chemically at dimensions comparable to those of single polymer molecules with a variety of fabrication techniques ranging from well established conventional silicon micro- nano- machining to new tools constantly developed as dip-pen and nanoimprint lithography.     

Polymer-induced fractal patterns of [60]fullerene containing poly(methacrylic acid) in salt solutions

Well-defined water-soluble pH-responsive [60]fullerene (C60) containing poly(methacrylic acid) (PMAA-b-C60) was synthesized using the atom transfer radical polymerization technique. By varying pH and salt concentration, different types of fractal patterns at nano- to microscopic dimensions were observed for negatively charged PMAA-b-C60, while such structure was not observed for positively charged poly(2-dimethylaminoethyl methacrylate)-b-C60. We demonstrated that negatively charged fullerene containing polymeric systems can serve as excellent nanotemplates for the controlled growth of inorganic crystals at the nano- to micrometer length scale, and the possible mechanism was proposed.     

用原子力显微镜操纵碳纳米管的研究

使用原子力显微镜,在接触模式下实现了对单壁碳纳米管束的各种可控操纵,包括弯折、切割和劈裂等.发现操纵结果与针尖作用力以及碳纳米管束在基底表面的受力状况有关.当碳纳米管在一定程度上被固定在表面上时,能够可控地完成各种操纵；当针尖作用力足够大时,碳管束能够被针尖劈裂.这种操纵技术将有助于碳纳米管特性的测试和纳米电子器件的构筑.