Design Principles for Aqueous Interactive Materials: Lessons from Small Molecules and Stimuli-Responsive Systems

Interactive materials are at the forefront of current materials research with few examples in the literature. Researchers are inspired by nature to develop materials that can modulate and adapt their behavior in accordance with their surroundings. Stimuli-responsive systems have been developed over the past decades which, although often described as “smart,” lack the ability to act autonomously. Nevertheless, these systems attract attention on account of the resultant materials' ability to change their properties in a predicable manner. These materials find application in a plethora of areas including drug delivery, artificial muscles, etc. Stimuli-responsive materials are serving as the precursors for next-generation interactive materials. Interest in these systems has resulted in a library of well-developed chemical motifs; however, there is a fundamental gap between stimuli-responsive and interactive materials. In this perspective, current state-of-the-art stimuli-responsive materials are outlined with a specific emphasis on aqueous macroscopic interactive materials. Compartmentalization, critical for achieving interactivity, relies on hydrophobic, hydrophilic, supramolecular, and ionic interactions, which are commonly present in aqueous systems and enable complex self-assembly processes. Relevant examples of aqueous interactive materials that do exist are given, and design principles to realize the next generation of materials with embedded autonomous function are suggested.     

Vision Statement: Interactive Materials—Drivers of Future Robotic Systems

A robot senses its environment, processes the sensory information, acts in response to these inputs, and possibly communicates with the outside world. Robots generally achieve these tasks with electronics-based hardware or by receiving inputs from some external hardware. In contrast, simple microorganisms can autonomously perceive, act, and communicate via purely physicochemical processes in soft material systems. A key property of biological systems is that they are built from energy-consuming “active” units. Exciting developments in material science show that even very simple artificial active building blocks can show surprisingly rich emergent behaviors. Active nonequilibrium systems are therefore predicted to play an essential role in realizing interactive materials. A major challenge is to find robust ways to couple and integrate the energy-consuming building blocks to the mechanical structure of the material. However, success in this endeavor will lead to a new generation of sophisticated micro and soft-robotic systems that can operate autonomously.     

Vision Statement: Materials in Motion

At the dawn of a new era of interactive and responsive materials and dynamic molecular systems there is ample opportunity to raise the level of complexity enabling mechanical motion, autonomous behavior, or interactive self-regulatory functions. Some of the major challenges and opportunities are discussed with a brief perspective toward future developments on responsive materials.     

Integrative Approaches to Hybrid Multifunctional Materials: From Multidisciplinary Research to Applied Technologies

Achieving nanostructured or hierarchical hybrid architectures involves cross‐cutting synthetic strategies where all facettes of chemistry (organic, polymers, solid‐state, physical, materials chemistries, biochemistry, etc…?), soft matter and ingenious processing are synergistically coupled. These cross‐cutting approaches are in the vein of bio‐inspired synthesis strategies where the integration of different areas of expertise allows the development of complex systems of various shapes with perfect mastery at different size scales, composition, porosity, functionality, and morphology. These strategies coined “Integrative Chemistry” open a land of opportunities to create advanced hybrid materials with organic‐inorganic or bio‐inorganic character. These hybrid materials represent not only a new field of basic research where creative chemists can express themselves, but also, via their remarkable new properties and multifunctional nature, hybrids are allowing the emergence of innovative industrial applications in extremely diverse fields.     

Viewpoint: Homeostasis as Inspiration—Toward Interactive Materials

Homeostatic systems combine an ability to maintain integrity over time with an incredible capacity for interactive behavior. Fundamental to such systems are building blocks of “mini-homeostasis”: feedback loops in which one component responds to a stimulus and another opposes the response, pushing the module to restore its original configuration. Particularly when they cross time and length scales, perturbation of these loops by external changes can generate diverse and complex phenomena. Here, it is proposed that by recognizing and implementing mini-homeostatic modules—often composed of very different physical and chemical processes—into synthetic materials, numerous interactive behaviors can be obtained, opening avenues for designing multifunctional materials. How a variety of controlled, nontrivial material responses can be evoked from even simple versions of such synthetic feedback modules is illustrated. Moreover, random events causing seemingly random responses give insights into how one can further explore, understand and control the full interaction space. Ultimately, material fabrication and exploration of interactivity become inseparable in the rational design of such materials. Homeostasis provides a lens through which one can learn how to combine and perturb coupled processes across time and length scales to conjure up exciting behaviors for new materials that are both robust and interactive.     

Beyond solvents and electrolytes: Ionic liquids-based advanced functional materials

Instead of being seen as alternative solvents and electrolytes for organic reactions, catalysis, separation, electrochemistry, and so on, ionic liquids (ILs) consisting of discrete cations and anions have recently emerged as versatile building blocks for advanced functional materials. A number of functional ILs and IL-containing composite materials have been realized by either chemical modification (covalent functionalization or ion-exchange metathesis) or physical integration of ILs and traditional materials. The unique structure and behavior of ILs as a platform not only provides additional opportunities to adjust the physicochemical properties of these ionic materials for task-specific applications, but also offers other attractive features such as intrinsic ionic conductivity and high thermal, chemical, and electrochemical stability. These soft materials combine the favorable features of ILs and the original chemistries of the functional groups or materials; some even possess unexpected functions resulting from synergetic interaction between these two components. Materialization of ILs is truly a novel, promising research direction for both IL chemistry and materials science. In this article, we review recent advances in IL-based functional materials, focusing on smart and sensitive materials, optical materials, energetic materials, and IL/carbon hybrid materials.     

软物质力学:行为特性、理论模型和测试方法

软物质已成为物理学、化学、材料、力学和生命科学重要的前沿研究课题,在技术和生产上有广阔的应用前景,是国际上普遍重视的多学科交叉研究领域,更是通向研究生命体系的桥梁。软物质力学是力学的一个新兴方向,其研究对推动多学科的交集协同发展有着极其重要的作用。然而,软物质组成复杂,常是多相集合体,且往往涉及与硬物质的界面相互作用,其运动和变化规律与一般流体和固体迥异。软物质中结构单元之间的作用力弱,在一般流体和固体中作用较小的力,如表、界面作用力、范德华力等,可能在软物质中起到主导作用,传统的流体/固体理论已无法全面刻画软物质所呈现的许多独特现象。软物质的本构关系比较复杂,涉及到流变、大变形、熵等新概念。目前,除了软物质物理、化学、生物等相关研究以外,研究者们开始从力学的角度对软物质的行为特性及其理论分析模型与测试方法进行深入探索,在生物力学、界面和接触力学、胶体力学、实验力学等领域取得了丰硕的成果。近几年来,学者们对生物组织、细胞和生物大分子、水凝胶、形状记忆聚合物、活性软材料、柔性电子器件、颗粒、液晶等多种软物质体系进行了力学分析、模拟及实验,探索了软物质微结构形成的物理机制和动力学引起的新生长规律。也有学者将软物质的不稳定性和自组装行为用于开发低成本、高性能的新材料和新设备。还有许多学者考虑学科交叉,从新的角度研究软物质材料,将连续介质力学中的本构关系、计算技术和建模方法引入到软物质模拟计算中,实现对软物质的自组装行为及表面不稳定性的理论分析,并将综合的力学测试方法和技术带入到软物质力学实验中,实现对软物质复杂力学响应的小尺度性能测试。本文论述了软物质材料的力学行为及特性:包括复杂力学响应、自组织行为和表面不稳定性及其相关研究进展;重点讨论了软物质在生物力学、界面和接触力学、胶体力学和实验力学等力学领域的研究发展;对软物质力学的发展前景做了展望,提出了值得进一步研究的方向,以期推动国内软物质力学学科的发展。     

Biomechano‐Interactive Materials and Interfaces

The reciprocal mechanical interaction of engineered materials with biointerfaces have long been observed and exploited in biomedical applications. It contributes to the rise of biomechano‐responsive materials and biomechano‐stimulatory materials, constituting the biomechano‐interactive interfaces. Here, endogenous and exogenous biomechanical stimuli available for mechanoresponsive interfaces are briefed and their mechanistic responses, including deformation and volume change, mechanomanipulation of physical and chemical bonds, dissociation of assemblies, and coupling with thermoresponsiveness are summarized. The mechanostimulatory materials, however, are capable of delivering mechanical cues, including stiffness, viscoelasticity, geometrical constraints, and mechanical loads, to modulate physiological and pathological behaviors of living tissues through the adaptive cellular mechanotransduction. The biomechano‐interactive materials and interfaces are widely implemented in such fields as mechanotriggered therapeutics and diagnosis, adaptive biophysical sensors, biointegrated soft actuators, and mechanorobust tissue engineering, which have offered unprecedented opportunities for precision and personalized medicine. Pending challenges are also addressed to shed a light on future advances with respect to translational implementations.     

Soft Matter Technology at KIT: Chemical Perspective from Nanoarchitectures to Microstructures

Bioinspiration has emerged as an important design principle in the rapidly growing field of materials science and especially its subarea, soft matter science. For example, biological cells form hierarchically organized tissues that not only are optimized and designed for durability, but also have to adapt to their external environment, undergo self‐repair, and perform many highly complex functions. Being able to create artificial soft materials that mimic those highly complex functions will enable future materials applications. Herein, soft matter technologies that are used to realize bioinspired material structures are described, and potential pathways to integrate these into a comprehensive soft matter research environment are addressed. Solutions become available because soft matter technologies are benefitting from the synergies between organic synthesis, polymer chemistry, and materials science.     

Stimuli–Responsive Mechanoadaptive Elastomeric Composite Materials: Challenges,Opportunities, and New Approaches

Stimuli–responsive mechanoadaptive materials, capable of reversibly changing their mechanical properties when exposed to an external stimulus, are the next generation of smart materials with immense transformative potential for various technological applications. Although the concept of adaptive mechanical properties has been proven for some materials, it remains very challenging for soft elastomeric materials. The aim of this review is to provide new ideas and strategies for the development of mechanoadaptive elastomeric composites using commercial rubber as the matrix polymer. The fundamental question addressed here is as follows: How do the phase-responsive functional fillers alter the mechanical properties? For a given physical network environment, what is the mechanism that gives rise to the stimuli–responsive properties of the resulting composites? Herein, the preparation, structure, and properties of recently developed mechanoadaptive elastomeric materials are summarized. Furthermore, based on their structure–property relationships, plausible applications of these smart materials in various technology-specific applications such as soft robotics, actuators, sensors, smart tires, automotive design, aerospace, etc. are demonstrated with representative examples. Finally, the article critically discusses the existing challenges in the field of mechanoadaptive elastomers in order to provide valuable insights in this area.     

Design of untethered soft material micromachine for life-like locomotion

Living organisms composed of composite materials with complex structures support autonomous and intelligent behaviors, such as motility, perception and response to changes of the environment. By studying the biological structures and their environmental interactions, researchers are now using these natural systems as models for building soft material machines. In this review, we discuss materials and machine engineering principles to achieve life-like locomotion and functionalities in untethered soft micromachines. Through the various mechanochemical or physical mechanisms, we show how molecular motion can be collectively amplified into versatile macroscopic deformation by materials engineering across multiple length scales. In controlled ways, mobile micromachines are made to crawl, roll or jump and adaptive to various terrains, typically inspired by the terrestrial animals while propulsion of swimming micromachines are guided by aquatic organisms. Besides, out-of-equilibrium behaviors of living systems, such as cell cycling, have stimulated the design of autonomous movement. Furthermore, we review the recent efforts on robotic locomotion intelligence to achieve adaptive, functional locomotion and navigation in complex environment. We finally provide a critical perspective for the field of soft micromachines, and highlight the key challenges of different material systems that need to be overcome to realize practical use.     

Application of Fracture Mechanics Concepts to Hierarchical Biomechanics of Bone and Bone-like Materials

Fracture mechanics concepts are applied to gain some understanding of the hierarchical nanocomposite structures of hard biological tissues such as bone, tooth and shells. At the most elementary level of structural hierarchy, bone and bone-like materials exhibit a generic structure on the nanometer length scale consisting of hard mineral platelets arranged in a parallel staggered pattern in a soft protein matrix. The discussions in this paper are organized around the following questions: (1) The length scale question: why is nanoscale important to biological materials? (2) The stiffness question: how does nature create a stiff composite containing a high volume fraction of a soft material? (3) The toughness question: how does nature build a tough composite containing a high volume fraction of a brittle material? (4) The strength question: how does nature balance the widely different strengths of protein and mineral? (5) The optimization question: Can the generic nanostructure of bone and bone-like materials be understood from a structural optimization point of view? If so, what is being optimized? What is the objective function? (6) The buckling question: how does nature prevent the slender mineral platelets in bone from buckling under compression? (7) The hierarchy question: why does nature always design hierarchical structures? What is the role of structural hierarchy? A complete analysis of these questions taking into account the full biological complexities is far beyond the scope of this paper. The intention here is only to illustrate some of the basic mechanical design principles of bone-like materials using simple analytical and numerical models. With this objective in mind, the length scale question is addressed based on the principle of flaw tolerance which, in analogy with related concepts in fracture mechanics, indicates that the nanometer size makes the normally brittle mineral crystals insensitive to cracks-like flaws. Below a critical size on the nanometer length scale, the mineral crystals fail no longer by propagation of pre-existing cracks, but by uniform rupture near their limiting strength. The robust design of bone-like materials against brittle fracture provides an interesting analogy between Darwinian competition for survivability and engineering design for notch insensitivity. The follow-up analysis with respect to the questions on stiffness, strength, toughness, stability and optimization of the biological nanostructure provides further insights into the basic design principles of bone and bone-like materials. The staggered nanostructure is shown to be an optimized structure with the hard mineral crystals providing structural rigidity and the soft protein matrix dissipating fracture energy. Finally, the question on structural hierarchy is discussed via a model hierarchical material consisting of multiple levels of self-similar composite structures mimicking the nanostructure of bone. We show that the resulting “fractal bone”, a model hierarchical material with different properties at different length scales, can be designed to tolerate crack-like flaws of multiple length scales.     

尖晶石结构磁介电材料的研究进展

随着通信技术的发展,对无限通信设备的集成度有了更高的要求,天线小型化成为目前重要的研究方向。等磁介电材料是一种既具有磁导率又具有介电常数,且磁导率和介电常数几乎相等的材料,使用等磁介电材料作为天线的基板,能有效的减小天线的尺寸,提高带宽,增加辐射效率。铁氧体是由Fe2O3和一种或多种金属氧化物复合而成,具有较高的磁导率和介电常数,由于其同时具有磁特性和介电特性,是一种潜在的等磁介电材料。综述了近几年尖晶石结构磁介电材料的国内外研究进展,着重讨论了掺杂改性对烧结温度、磁导率、介电常数、直流电阻等电磁特性的影响。最后指出目前研究中存在的问题,并展望了该材料在未来发展的方向。     

The Modeling of Magnetorheological Elastomers: A State-of-the-Art Review

The magnetorheological elastomers (MREs) are novel multifunctional materials wherein their viscoelastic properties can be varied instantly under an application of applied magnetic field. Due to their field-dependent stiffness and damping properties, MREs are widely used in the development and design of MRE-based adaptive vibration isolators and absorbers and also biomedical engineering. Moreover, MREs due to their inherent magnetostriction effect have enormous potential for the development of soft actuators. The dynamic behavior of MREs is affected by various material parameters (e.g., matrix and particle types, particle concentration, additives) as well as mechanical and magnetic loading parameters (e.g., frequency, amplitude, temperature, magnetic flux density). Understanding and predicting the effect of materials and loading parameters on the response behavior of MREs are of paramount importance for the design of MRE-based adaptive structures and systems. This review paper mainly aims to provide a comprehensive study of material constitutive models to predict the nonlinear magnetomechanical behavior of MREs. Particular emphasis is paid to physics-based models including continuum- and microstructure-based models. Moreover, phenomenological models describing the dynamic magnetoviscoelastic behavior of MREs as well as the effect of temperature on the magnetomechanical behavior of such materials are properly addressed.     

Materials for Immunotherapy

Breakthroughs in materials engineering have accelerated the progress of immunotherapy in preclinical studies. The interplay of chemistry and materials has resulted in improved loading, targeting, and release of immunomodulatory agents. An overview of the materials that are used to enable or improve the success of immunotherapies in preclinical studies is presented, from immunosuppressive to proinflammatory strategies, with particular emphasis on technologies poised for clinical translation. The materials are organized based on their characteristic length scale, whereby the enabling feature of each technology is organized by the structure of that material. For example, the mechanisms by which i) nanoscale materials can improve targeting and infiltration of immunomodulatory payloads into tissues and cells, ii) microscale materials can facilitate cell-mediated transport and serve as artificial antigen-presenting cells, and iii) macroscale materials can form the basis of artificial microenvironments to promote cell infiltration and reprogramming are discussed. As a step toward establishing a set of design rules for future immunotherapies, materials that intrinsically activate or suppress the immune system are reviewed. Finally, a brief outlook on the trajectory of these systems and how they may be improved to address unsolved challenges in cancer, infectious diseases, and autoimmunity is presented.     

自适应伪装材料在军用服饰产品的设计应用研究

目的 总结和展望可见光波段自适应伪装材料和红外波段自适应伪装材料的发展趋势及应用现状,为进一步研究和应用提供参考.方法 基于军用服饰对抗的不同波段,总结归纳了光致变色材料、电致变色材料、热致变色材料、相变材料、电致变发射率材料、电致变温材料和光子晶体材料的发展现状.结果 自适应伪装材料在军用服饰上的应用形式多,且相关产品在不断更新换代.结论 光学自适应伪装材料可适应不同场景不同要求下的变色需求,电致变发射率材料等红外自适应伪装材料可以用于军用红外伪装中,进一步完善可实现自适应红外隐身,人工光子晶体材料作为自适应伪装材料也可用于军用产品,目前已从多角度进行研发、实验,具有很大的应用前景及发展潜力.     

Living Materials Herald a New Era in Soft Robotics

Living beings have an unsurpassed range of ways to manipulate objects and interact with them. They can make autonomous decisions and can heal themselves. So far, a conventional robot cannot mimic this complexity even remotely. Classical robots are often used to help with lifting and gripping and thus to alleviate the effects of menial tasks. Sensors can render robots responsive, and artificial intelligence aims at enabling autonomous responses. Inanimate soft robots are a step in this direction, but it will only be in combination with living systems that full complexity will be achievable. The field of biohybrid soft robotics provides entirely new concepts to address current challenges, for example the ability to self‐heal, enable a soft touch, or to show situational versatility. Therefore, “living materials” are at the heart of this review. Similarly to biological taxonomy, there is a recent effort for taxonomy of biohybrid soft robotics. Here, an expansion is proposed to take into account not only function and origin of biohybrid soft robotic components, but also the materials. This materials taxonomy key demonstrates visually that materials science will drive the development of the field of soft biohybrid robotics.     

氢敏材料及氢气传感器的研究进展

对氢气进行快速、准确、原位测量,具有重要的学术意义和广阔的应用前景.氢气传感器发高品质氢敏材料的研制,氢敏材料的敏感响应性、重现性等决定着氢气传感器的工作性能.综述了近年来研究较多的半导体型、热电型、光学型、电化学型4类氢气传感器及相应氢敏材料的研究进展,并展望了氢敏材料及氢气传感器的发展方向.     

Layered Organic–Inorganic Materials: A Way towards Controllable Magnetism

The search for new materials for tailor‐made applications and new devices involves not only solid‐state chemists, physicists or materials engineers, but also the area molecular and organo‐metallic chemistry, and even biochemistry. This is especially clear in the field of organic–inorganic multifunctional materials, whose design necessitates to investigate new concepts and principles developed in these different disciplines. Here, the authors review the structure‐magnetic property relationships in layered structures, made of organic and inorganic subunits.     

Progress and Opportunities in Soft Photonics and Biologically Inspired Optics

Optical components made fully or partially from reconfigurable, stimuli‐responsive, soft solids or fluids—collectively referred to as soft photonics—are poised to form the platform for tunable optical devices with unprecedented functionality and performance characteristics. Currently, however, soft solid and fluid material systems still represent an underutilized class of materials in the optical engineers' toolbox. This is in part due to challenges in fabrication, integration, and structural control on the nano‐ and microscale associated with the application of soft components in optics. These challenges might be addressed with the help of a resourceful ally: nature. Organisms from many different phyla have evolved an impressive arsenal of light manipulation strategies that rely on the ability to generate and dynamically reconfigure hierarchically structured, complex optical material designs, often involving soft or fluid components. A comprehensive understanding of design concepts, structure formation principles, material integration, and control mechanisms employed in biological photonic systems will allow this study to challenge current paradigms in optical technology. This review provides an overview of recent developments in the fields of soft photonics and biologically inspired optics, emphasizes the ties between the two fields, and outlines future opportunities that result from advancements in soft and bioinspired photonics.