Static charge is an ionic molecular fragment.

What is static charge? Despite the long history of research, the identity of static charge and mechanism by which static is generated by contact electrification are still unknown. Investigations are challenging due to the complexity of surfaces. This study involves the molecular-scale analysis of contact electrification using highly well-defined surfaces functionalized with a self-assembled monolayer of alkylsilanes. Analyses show the elementary molecular steps of contact electrification: the exact location of heterolytic cleavage of covalent bonds (i.e., Si-C bond), exact charged species generated (i.e., alkyl carbocation), and transfer of molecular fragments. The strong correlation between charge generation and molecular fragments due to their signature odd-even effects further shows that contact electrification is based on cleavage of covalent bonds and transfer of ionic molecular fragments. Static charge is thus an alkyl carbocation; in general, it is an ionic molecular fragment. This mechanism based on cleavage of covalent bonds is applicable to general types of insulating materials, such as covalently bonded polymers. The odd-even effect of charging caused by the difference of only one atom explains the highly sensitive nature of contact electrification.

Functional polymeric molecules for performing autonomous synthesis of particles with core-shell structures and customizable shapes.

Self-organization by the directed migration of components within a system is an important process in many applications, such as the unidirectional migration of motor proteins for transporting items to specific sites in a cell. This manuscript describes a class of functional polymeric molecules that have a set of instructions written by specific chemical moieties. These instructions allow the functional polymeric molecules to be used for autonomous synthesis of particles: particles with both functional core-shell structure and customizable shapes are fabricated for the first time. The functional polymeric molecules direct the large-scale migration of the liquid molecules to specific sites for forming the required customized structure of the particle, thus overcoming previous challenges of fabricating this class of particles. This first synthesis of this class of particles enables the development of novel applications: the concept of shape specificity for targeting sites. Both the basic structural properties (core-shell structure and customizable shape) are used in the specific applications of targeted drug delivery and imaging. The secure physical fit due to the complementary shapes enables the particles to remain locked in position for the targeting. Polymeric molecules are first shown to be highly capable of being encoded with instructions for autonomous synthesis of structured materials.

Recent Advances in Triboelectric Nanogenerators: From Technological Progress to Commercial Applications.

Serious climate changes and energy-related environmental problems are currently critical issues in the world. In order to reduce carbon emissions and save our environment, renewable energy harvesting technologies will serve as a key solution in the near future. Among them, triboelectric nanogenerators (TENGs), which is one of the most promising mechanical energy harvesters by means of contact electrification phenomenon, are explosively developing due to abundant wasting mechanical energy sources and a number of superior advantages in a wide availability and selection of materials, relatively simple device configurations, and low-cost processing. Significant experimental and theoretical efforts have been achieved toward understanding fundamental behaviors and a wide range of demonstrations since its report in 2012. As a result, considerable technological advancement has been exhibited and it advances the timeline of achievement in the proposed roadmap. Now, the technology has reached the stage of prototype development with verification of performance beyond the lab scale environment toward its commercialization. In this review, distinguished authors in the world worked together to summarize the state of the art in theory, materials, devices, systems, circuits, and applications in TENG fields. The great research achievements of researchers in this field around the world over the past decade are expected to play a major role in coming to fruition of unexpectedly accelerated technological advances over the next decade.

Self-assembly of graphene oxide flakes for smart and multifunctional coating with reversible formation of wrinkling patterns.

One of the main purposes of smart and multifunctional coatings is to have the versatility to be applied in a wide range of applications. However, the functions of smart materials are often highly limited. In particular, the stimuli-responsive lateral expansion of coatings based on 2D materials has not been reported before. This manuscript describes small two-dimensional graphene oxide (GO) flakes (e.g., thin sheets with a thickness of a few nanometers and much larger lateral dimensions) that act as elementary agents for the formation of smart and multifunctional coatings. The coating can be self-assembled from the GO flakes and disassembled flexibly when required. The coating is stimuli-responsive: upon localized contact with water, it expands and forms wrinkling patterns throughout its whole surface. Evaporating the water allows the wrinkles to disappear; hence, the process is reversible. This stimuli-responsiveness can be controlled to be reduced or completely switched off by temperature or pressure. These features are fundamentally due to the reversible intermolecular interactions among the flakes and favorable packing structure of the coating. The smart coating is shown to be useful for patterned fluidic systems of the desired shapes and the development of channels between fluidic reservoirs via the shortest path. Importantly, these results showed that a simple collection of uniquely 2D elementary agents with small nanoscale thickness can self-assemble into macroscopic materials that perform interactive and multifunctional operations.

Performing calculus: Asymmetric adaptive stimuli-responsive material for derivative control.

Materials (e.g., brick or wood) are generally perceived as unintelligent. Even the highly researched "smart" materials are only capable of extremely primitive analytical functions (e.g., simple logical operations). Here, a material is shown to have the ability to perform (i.e., without a computer), an advanced mathematical operation in calculus: the temporal derivative. It consists of a stimuli-responsive material coated asymmetrically with an adaptive impermeable layer. Its ability to analyze the derivative is shown by experiments, numerical modeling, and theory (i.e., scaling between derivative and response). This class of freestanding stimuli-responsive materials is demonstrated to serve effectively as a derivative controller for controlled delivery and self-regulation. Its fast response realizes the same designed functionality and efficiency as complex industrial derivative controllers widely used in manufacturing. These results illustrate the possibility to associate specifically designed materials directly with higher concepts of mathematics for the development of "intelligent" material-based systems.

Customizable drug tablets with constant release profiles via 3D printing technology.

Medicine should ideally be personalized as each individual has his/her own unique biological, physical, and medical dispositions. Medicine can be personalized by customizing drug tablets with the specific drug dosages, release durations, and combinations of multiple drugs. This study presents a method for fabricating drug tablets with customizable dosages, durations, and combinations of multiple drugs by using the 3D printing technology. The method focuses on fabricating customizable drug tablets with a very simple structure for delivering the constant release profile due to its importance in treatment (i.e., the drug may produce side effects if too much is released andmay not have therapeutic value is too little is released). The method is simple: it involves first printing a template using the 3D printer and fabricating the drug tablet via the template. The tablets are customized by varying the amount of excipient used, the height of the tablet, and the numberand amount of drugs used. Three different common drugs (i.e., paracetamol, phenylephrine HCl and diphenhydramine HCl) and FDA-approved excipients are studied. The simplicity of the structure of the tablet and method via templating allows the fabrication of these fully customizable drug tablets to be easily performed, low-cost, efficient, and safe for consumption. These features enable the customizable tablets to be made widely accessible to the public; hence, the concept of personalized medicine can be realized.

Charging Organic Liquids by Static Charge.

Aqueous liquids can be charged effectively by a number of methods for many important applications. Organic liquids, however, cannot be charged effectively by existing methods due to their low conductivities, especially the insulating nonpolar organic liquids; hence, there has not been any significant application developed based on charged organic liquids. This study describes an effective fundamental strategy for charging organic liquids, including nonpolar organic liquids: static charge is simply mixed into the liquid. Analyses suggested that the charged species are molecular ions that reside in the bulk of the liquid after charging. This method is simple and general, and the amount and polarity of charge can be flexibly tunable. The effectiveness of this method gives rise to opportunities for the development of novel applications. Charged organic droplets are manipulated for the first time by an electric field for controlling organic reactions. Particles with charge embedded in their bulk matrices are fabricated for the first time (i.e., via polymerizing the liquid monomers mixed with static charge). The charge in this novel class of bulk-charged particles is stable and permanent, especially when compared to the typical surface-charged particles. Simultaneous bulk-charged and bulk-magnetic particles are fabricated for the first time via simply mixing both the static charge and magnetic nanoparticles into the liquid monomers. These highly versatile particles are responsive to both electric and magnetic fields for practical applications.

The Relationship between Static Charge and Shape.

The amount of charge of a material has always been regarded as a property (or state) of materials and can be measured precisely and specifically. This study describes for the first time a fundamental physical-chemical phenomenon in which the amount of charge of a material is actually a variable-it depends on the shape of the material. Materials are shown to have continuously variable and reversible ranges of charge states by changing their shapes. The phenomenon was general for different shapes, transformations, materials, atmospheric conditions, and methods of charging. The change in charge was probably due to a dynamic exchange of charge from the material to the surrounding atmosphere as the shape changed via the reversible ionization and deposition of air molecules. Similar changes in charge were observed for self-actuating materials that changed their shapes autonomously. This fundamental relationship between geometry and electrostatics via chemistry is important for the broad range of applications related to the charge of flexible materials.

On-demand fully customizable drug tablets via 3D printing technology for personalized medicine.

Personalized medicine should ideally be prescribed to every individual because of the unique characteristics (e.g., biological, physical, and medical) of each individual. It is, however, challenging to provide personalized medicine for the mass population of specific individuals effectively and efficiently. This manuscript describes a method of fabricating fully customizable drug tablets for personalized medicine by the 3D printing technology. This method involves the versatile fabrication of the tablets via the specifically designed 3D printed molds of different shapes and sizes, and an intuitive 1-dimensional release of drug that relates the shape of the drug-containing matrix to the release profile. The customization includes all the aspects of varying dosage, duration, release profiles, and combination of multiple drugs. In particular, it has previously been technically difficult to devise a single platform that fabricates carriers that release drug with any desired type of release profiles. This method of fabricating fully customizable tablets is simple, inexpensive, and efficient. Detailed selection and investigation of the materials ensured that the tablet and the method of fabrication are safe (e.g., biocompatible, FDA-approved ingredients used) and other desirable features (e.g., sustained release and high dosage) are achieved. These desirable characteristics of the method thus allow fully customizable drug tablets to be fabricated efficiently on the spot after the diagnosis of individual patients; at the same time, the method can be made widely accessible to the mass population. Hence, the concept of personalized medicine can truly be realized.

Nonconductive Noncharging Composites: Tunable and Stretchable Materials for Adaptive Prevention of Charging by Contact Electrification.

Static charge generated by contact electrification can cause a wide range of undesirable consequences in our lives and in industry (e.g., adhesion of particles on surfaces, damage to electronics, and explosions). It has, however, been challenging to develop methods to prevent charging due to the vast types of materials that charge easily by contact electrification and the frequent changes in process and environmental conditions. The most common method is to use conductive materials for dissipating charge away; however, it is ineffective for many circumstances. Here, we propose a general and effective materials framework that involves a two-level consideration for preparing noncharging materials: (1) the variation of the proportion of a two-material composite and (2) the extent of stretching the composite material. This materials strategy is achieved by infusing particles within a stretchable bulk material. Importantly, the preparation of the noncharging surface for (1) is based on a novel fundamental mechanism that involves combining an appropriate amount of a material (e.g., the particles) that tends to charge positively with another material (e.g., the bulk material) that tends to charge negatively. This mechanism does not rely on conductivity; both the contacting materials naturally prevent the generation of static charge even when only nonconductive materials are involved. When the composite material is stretchable, the change in proportion of the surface coverage of the particles allows the charging response to be changed. Therefore, the variation in composition and stretching provide a wide two-dimensional parameter space for achieving noncharging response for the vast range of contacting materials that are used in industry and our lives. In addition, stretchability allows the composite material to flexibly adapt to changes in process and environmental conditions. This stretchable composite material was also demonstrated to be capable of preventing the adhesion of particles and separating particles of different materials.

Eco-Friendly, Direct Deposition of Metal Nanoparticles on Graphite for Electrochemical Energy Conversion and Storage.

Simple, green, and energy-efficient methods for preparing electroactive materials used to generate and store renewable energy are important for a sustainable future. In this study, we showed that noble and certain non-noble metal nanoparticles can be deposited on graphite without the aid of any reducing agent. This method of reducing metal ions to metal nanoparticles by graphite involves only one step (i.e., immersion into a solution) and one chemical (i.e., a metal salt). Hence, the method is exceedingly simple, green, and does not require any energy input. Large amounts of metal nanoparticles are generated both on the surface and deep into the bulk of graphite (∼100 µm). Despite the simplicity of this method, the metal deposited on graphite showed good electrocatalytic performance for ethanol oxidation and oxygen evolution reactions and also functioned as electrodes for supercapacitors. This method is thus ideal for preparing electrocatalytic materials and electrochemical energy storage devices due to its simplicity and environmental sustainability. The simplicity of the method is due to the inherent reducing potential of graphite (i.e., a material that is generally perceived as inert). Results from analyses showed that functionalization of the reactive edges in the regions of defects allowed the graphite to serve as a reducing agent. Increasing the amount of defects (e.g., via chemical or simple mechanical treatments) is shown to be the fundamental principle for increasing the reactivity of graphite.

The Pathway to Intelligence: Using Stimuli-Responsive Materials as Building Blocks for Constructing Smart and Functional Systems.

Systems that are intelligent have the ability to sense their surroundings, analyze, and respond accordingly. In nature, many biological systems are considered intelligent (e.g., humans, animals, and cells). For man-made systems, artificial intelligence is achieved by massively sophisticated electronic machines (e.g., computers and robots operated by advanced algorithms). On the other hand, freestanding materials (i.e., not tethered to a power supply) are usually passive and static. Hence, herein, the question is asked: can materials be fabricated so that they are intelligent? One promising approach is to use stimuli-responsive materials; these "smart" materials use the energy supplied by a stimulus available from the surrounding for performing a corresponding action. After decades of research, many interesting stimuli-responsive materials that can sense and perform smart functions have been developed. Classes of functions discussed include practical functions (e.g., targeting and motion), regulatory functions (e.g., self-regulation and amplification), and analytical processing functions (e.g., memory and computing). The pathway toward creating truly intelligent materials can involve incorporating a combination of these different types of functions into a single integrated system by using stimuli-responsive materials as the basic building blocks.

Lévy-like movement patterns of metastatic cancer cells revealed in microfabricated systems and implicated in vivo.

Metastatic cancer cells differ from their non-metastatic counterparts not only in terms of molecular composition and genetics, but also by the very strategy they employ for locomotion. Here, we analyzed large-scale statistics for cells migrating on linear microtracks to show that metastatic cancer cells follow a qualitatively different movement strategy than their non-invasive counterparts. The trajectories of metastatic cells display clusters of small steps that are interspersed with long "flights". Such movements are characterized by heavy-tailed, truncated power law distributions of persistence times and are consistent with the Lévy walks that are also often employed by animal predators searching for scarce prey or food sources. In contrast, non-metastatic cancerous cells perform simple diffusive movements. These findings are supported by preliminary experiments with cancer cells migrating away from primary tumors in vivo. The use of chemical inhibitors targeting actin-binding proteins allows for "reprogramming" the Lévy walks into either diffusive or ballistic movements.

Drug delivery systems for programmed and on-demand release.

With the advancement in medical science and understanding the importance of biodistribution and pharmacokinetics of therapeutic agents, modern drug delivery research strives to utilize novel materials and fabrication technologies for the preparation of robust drug delivery systems to combat acute and chronic diseases. Compared to traditional drug carriers, which could only control the release of the agents in a monotonic manner, the new drug carriers are able to provide a precise control over the release time and the quantity of drug introduced into the patient's body. To achieve this goal, scientists have introduced "programmed" and "on-demand" approaches. The former provides delivery systems with a sophisticated architecture to precisely tune the release rate for a definite time period, while the latter includes systems directly controlled by an operator/practitioner, perhaps with a remote device triggering/affecting the implanted or injected drug carrier. Ideally, such devices can determine flexible release pattern and intensify the efficacy of a therapy via controlling time, duration, dosage, and location of drug release in a predictable, repeatable, and reliable manner. This review sheds light on the past and current techniques available for fabricating and remotely controlling drug delivery systems and addresses the application of new technologies (e.g. 3D printing) in this field.

Controlling Surface Charge Generated by Contact Electrification: Strategies and Applications.

Contact electrification is the phenomenon in which charge is generated on the surfaces of materials after they come into contact. The surface charge generated has traditionally been known to cause a vast range of undesirable consequences in our lives and in industry; on the other hand, it can also give rise to many types of useful applications. In addition, there has been a lot of interest in recent years for fabricating devices and materials based on regulating a desired amount of surface charge. It is thus important to understand the general strategies for increasing, decreasing, or controlling the surface charge generated by contact electrification. Herein, the fundamental mechanisms for influencing the amount of charge generated, the methods used for implementing these mechanisms, and some of the recent interesting applications that require regulating the amount of surface charge generated by contact electrification, are briefly summarized.

Reversible and Continuously Tunable Control of Charge of Close Surfaces.

Surfaces of almost all types of materials are often charged easily by contact electrification or deposition of ions; hence, surface charge is ubiquitous and has a vast range of influences in our lives and in industry. Since the 19th century, scientists have been measuring the charge of multiple materials collectively. The common expectation is that the total charge of multiple materials is equal to the sum of the charges of the individual materials. This study describes a previously unreported phenomenon in which the total charge of two insulating surfaces decreases when the surfaces are brought close to each other. The charge varies continuously and reversibly depending on the distance of separation between the surfaces. Experimental results derived from analyzing the movement of charge suggest that the changes are due to a rapid exchange of charge between the surfaces and their surrounding air. This change can be used to control the surface charge of the materials flexibly and reversibly.

Metal Nanowire-Based Hybrid Electrodes Exhibiting High Charge/Discharge Rates and Long-Lived Electrocatalysis.

Nanostructured electrodes are at the forefront of advanced materials research, and have been studied extensively in the context of their potential applications in energy storage and conversion. Here, we report on the properties of core-shell (gold-polypyrrole) hybrid nanowires and their suitability as electrodes in electrochemical capacitors and as electrocatalysts. In general, the specific capacitance of electrochemical capacitors can be increased by faradaic reactions, but their charge transfer resistance impedes charge transport, decreasing the capacitance with increasing charge/discharge rate. The specific capacitance of the hybrid electrodes is enhanced due to the pseudocapacitance of the polypyrrole shells; moreover, the electrodes operate as an ideal capacitive element and maintain their specific capacitance even at fast charge/discharge rates of 4690 mA/cm3 and 10 V/s. These rates far exceed those of other types of pseudocapacitors, and are even superior to electric double layer-based supercapacitors. The mechanisms behind these fast charge/discharge rates are elucidated by electrochemical impedance spectroscopy, and are ascribed to the reduced internal resistance associated with the fast charge transport ability of the gold nanowire cores, low ionic resistance of the polypyrrole shells, and enhanced electron transport across the nanowire's junctions. Furthermore, the hybrid electrodes show great catalytic activity for ethanol electro-oxidation, comparable to bare gold nanowires, and the surface activity of gold cores is not affected by the polypyrrole coating. The electrodes exhibit improved stability for electrocatalysis during potential cycling. This study demonstrates that the gold-polypyrrole hybrid electrodes can store and deliver charge at fast rates, and that the polypyrrole shells of the nanowires extend the catalytic lifetime of the gold cores.

Universal Nature-Inspired Coatings for Preparing Noncharging Surfaces.

Static charge generated by contact electrification on surfaces can lead to many undesirable consequences such as a reduction in the efficiency of manufacturing processes, damage to equipment, and explosions. However, it is extremely challenging to avoid contact electrification because it is ubiquitous: almost all types of materials charge on contact. Here, we coated materials with naturally occurring polydopamine (PDA) and tannic acid (TA) for preparing noncharging surfaces. Importantly, these coatings are very versatile and can be coated on a wide range of materials, including metals, inorganic materials, semiconductors, and polymers. Once coated, the amount of charge generated was found to reduce dramatically at different humidities. The reduction in charge may be due to the radical-scavenging property of PDA and TA. This simple general approach is ideal for coating the vast variety of materials that need to resist charging by contact electrification.

Performing Logical Operations with Stimuli-Responsive Building Blocks.

Chemical logic gates can be fabricated by synthesizing molecules that have the ability to detect external stimuli (e.g., temperature or pH) and provide logical outputs. It is, however, challenging to fabricate a system that consists of many logic gates using this method: complex molecules can be difficult to synthesize and these logic gates typically cannot be integrated together. Here, we fabricated different types of logic gates by assembling a combination of different types of stimuli-responsive hydrogels that change their size under the influence of one type of stimulus. Importantly, the preparation of these stimuli-responsive hydrogels is widely reported and technically simple. Through designing the geometry of the systems, we fabricated the YES, NOT, OR, AND, NOR, and NAND gates. Although the hydrogels respond to different types of stimuli, their outputs are the same: a change in size of the hydrogel. Hence, we show that the logic gates can be integrated easily (e.g., by connecting an AND gate to an OR gate). In addition, we fabricated a standalone system with the size of a normal drug tablet (i.e., a "smart tablet") that can analyze (or diagnose) different stimuli and control the release of a chemical (or drug) via the logic gates.

Solid-to-Liquid Charge Transfer for Generating Droplets with Tunable Charge.

Charged liquid droplets are typically generated by a high-voltage power supply. Herein, a previously unreported method is used for charging liquid droplets: by transferring charge from an insulating solid surface charged by contact electrification to the droplets. Charging the solid surface by contact electrification involves bringing it into contact with another solid surface for generating static charge. Subsequently, water droplets that flow across the surface are found to be charged-thus, the charge is readily transferred from solid to liquid. The charge of the droplets can be tuned continuously from positive to negative by varying the way the solid surface is charged. The amount of charge generated is sufficient for manipulating, coalescing, and sorting the water droplets by solid surfaces charged by contact electrification. This method of generating charged droplets is general, simple, inexpensive, and does not need any additional equipment or power supply.