Andreas Lendlein

Shape‐Memory Polymers

Material scientists predict a prominent role in the future for self-repairing and intelligent materials. Throughout the last few years, this concept has found growing interest as a result of the rise of a new class of polymers. These so-called shape-memory polymers by far surpass well-known metallic shape-memory alloys in their shape-memory properties. As a consequence of the relatively easy manufacture and programming of shape-memory polymers, these materials represent a cheap and efficient alternative to well-established shape-memory alloys. In shape-memory polymers, the consequences of an intended or accidental deformation caused by an external force can be ironed out by heating the material above a defined transition temperature. This effect can be achieved because of the given flexibility of the polymer chains. When the importance of polymeric materials in our daily life is taken into consideration, we find a very broad, additional spectrum of possible applications for intelligent polymers that covers an area from minimally invasive surgery, through high-performance textiles, up to self-repairing plastic components in every kind of transportation vehicles.

Light-induced shape-memory polymers

Materials are said to show a shape-memory effect if they can be deformed and fixed into a temporary shape, and recover their original, permanent shape only on exposure to an external stimulus. Shape-memory polymers have received increasing attention because of their scientific and technological significance. In principle, a thermally induced shape-memory effect can be activated by an increase in temperature (also obtained by heating on exposure to an electrical current or light illumination). Several papers have described light-induced changes in the shape of polymers and gels, such as contraction, bending or volume changes. Here we report that polymers containing cinnamic groups can be deformed and fixed into pre-determined shapes—such as (but not exclusively) elongated films and tubes, arches or spirals—by ultraviolet light illumination. These new shapes are stable for long time periods, even when heated to 50 °C, and they can recover their original shape at ambient temperatures when exposed to ultraviolet light of a different wavelength. The ability of polymers to form different pre-determined temporary shapes and subsequently recover their original shape at ambient temperatures by remote light activation could lead to a variety of potential medical and other applications.

Multifunctional shape-memory polymers.

The thermally-induced shape-memory effect (SME) is the capability of a material to change its shape in a predefined way in response to heat. In shape-memory polymers (SMP) this shape change is the entropy-driven recovery of a mechanical deformation, which was obtained before by application of external stress and was temporarily fixed by formation of physical crosslinks. The high technological significance of SMP becomes apparent in many established products (e.g., packaging materials, assembling devices, textiles, and membranes) and the broad SMP development activities in the field of biomedical as well as aerospace applications (e.g., medical devices or morphing structures for aerospace vehicles). Inspired by the complex and diverse requirements of these applications fundamental research is aiming at multifunctional SMP, in which SME is combined with additional functions and is proceeding rapidly. In this review different concepts for the creation of multifunctionality are derived from the various polymer network architectures of thermally-induced SMP. Multimaterial systems, such as nanocomposites, are described as well as one-component polymer systems, in which independent functions are integrated. Future challenges will be to transfer the concept of multifunctionality to other emerging shape-memory technologies like light-sensitive SMP, reversible shape changing effects or triple-shape polymers.

Bcl‐2 Engineered MSCs Inhibited Apoptosis and Improved Heart Function

Engraftment of mesenchymal stem cells (MSCs) derived from adult bone marrow has been proposed as a potential therapeutic approach for postinfarction left ventricular dysfunction. However, limited cell viability after transplantation into the myocardium has restricted its regenerative capacity. In this study, we genetically modified MSCs with an antiapoptotic Bcl‐2 gene and evaluated cell survival, engraftment, revascularization, and functional improvement in a rat left anterior descending ligation model via intracardiac injection. Rat MSCs were manipulated to overexpress the Bcl‐2 gene. In vitro, the antiapoptotic and paracrine effects were assessed under hypoxic conditions. In vivo, the Bcl‐2 gene‐modified MSCs (Bcl‐2‐MSCs) were injected after myocardial infarction. The surviving cells were tracked after transplantation. Capillary density was quantified after 3 weeks. The left ventricular function was evaluated by pressure‐volume loops. The Bcl‐2 gene protected MSCs against apoptosis. In vitro, Bcl‐2 overexpression reduced MSC apoptosis by 32% and enhanced vascular endothelial growth factor secretion by more than 60% under hypoxic conditions. Transplantation with Bcl‐2‐MSCs increased 2.2‐fold, 1.9‐fold, and 1.2‐fold of the cellular survival at 4 days, 3 weeks, and 6 weeks, respectively, compared with the vector‐MSC group. Capillary density in the infarct border zone was 15% higher in Bcl‐2‐MSC transplanted animals than in vector‐MSC treated animals. Furthermore, Bcl‐2‐MSC transplanted animals had 17% smaller infarct size than vector‐MSC treated animals and exhibited functional recovery remarkably. Our current findings support the premise that transplantation of antiapoptotic gene‐modified MSCs may have values for mediating substantial functional recovery after acute myocardial infarction.

Polymeric triple-shape materials

Shape-memory polymers represent a promising class of materials that can move from one shape to another in response to a stimulus such as heat. Thus far, these systems are dual-shape materials. Here, we report a triple-shape polymer able to change from a first shape (A) to a second shape (B) and from there to a third shape (C). Shapes B and C are recalled by subsequent temperature increases. Whereas shapes A and B are fixed by physical cross-links, shape C is defined by covalent cross-links established during network formation. The triple-shape effect is a general concept that requires the application of a two-step programming process to suitable polymers and can be realized for various polymer networks whose molecular structure allows formation of at least two separated domains providing pronounced physical cross-links. These domains can act as the switches, which are used in the two-step programming process for temporarily fixing shapes A and B. It is demonstrated that different combinations of shapes A and B for a polymer network in a given shape C can be obtained by adjusting specific parameters of the programming process. Dual-shape materials have already found various applications. However, as later discussed and illustrated by two examples, the ability to induce two shape changes that are not limited to be unidirectional rather than one could potentially offer unique opportunities, such as in medical devices or fasteners.

Shape-memory polymers as a technology platform for biomedical applications

Polymeric materials are clinically required for medical devices, as well as controlled drug delivery systems. Depending on the application, the polymer has to provide suitable functionalities, for example, mechanical functions or the capability to actively move, so that an implant can be inserted in a compact shape through key-hole incisions and unfold to its functional shape in the body. Shape-memory polymers, as described herein regarding their general principle, compositions and architectures, have developed to a technology platform that allows the tailored design of such multifunctionality. In this way, defined movements of implants triggered either directly or indirectly, tailored mechanical properties, capability for sterilization, biodegradability, biocompatibility and controlled drug release can be realized. This comprehensive review of the scientific and patent literature illustrates that this technology enables the development of novel medical devices that will be clinically evaluated in the near future.

Actively moving polymers

The ability of polymers to move actively in response to an external stimulus such as heat or light is of high scientific and technological significance. In any instance stimuli-responsive effects on the molecular level are converted into macroscopic movement, whereby generally two different moving behaviors have to be differentiated for polymer-based materials: the shape-memory effect and the shape-changing capability. Basic concepts for the molecular design of suitable polymer architectures for shape-memory polymers as well as tailored programming processes are presented. The thermally-induced shape-memory effect of polymers is described as well as the extension of this concept to other stimuli than heat. Indirect actuation of the thermally-induced effect by IR-irradiation, electric current, humidity or alternating magnetic fields are outlined as well as recent work on light-induced shape-memory polymers. For shape-changing polymers, two basic concepts are presented: shape changes occurring during phase orientation of liquid crystal elastomers (LCE) and the photomechanical effect based on photoisomerization of moieties, such as azo-groups incorporated in suitable polymer systems.

Design and preparation of polymeric scaffolds for tissue engineering

Polymeric scaffolds for tissue engineering can be prepared with a multitude of different techniques. Many diverse approaches have recently been under development. The adaptation of conventional preparation methods, such as electrospinning, induced phase separation of polymer solutions or porogen leaching, which were developed originally for other research areas, are described. In addition, the utilization of novel fabrication techniques, such as rapid prototyping or solid free-form procedures, with their many different methods to generate or to embody scaffold structures or the usage of self-assembly systems that mimic the properties of the extracellular matrix are also described. These methods are reviewed and evaluated with specific regard to their utility in the area of tissue engineering.

Shape-Memory Polymers and Shape-Changing Polymers

The ability of polymers to respond to external stimuli is of high scientific and technological significance. In the last few years, research activities have been intensified substantially, exploring whether stimuli-sensitive polymers can be designed that move actively. In this review actively-moving materials were classified according to the underlying mechanisms enabling the shape changes: shape-memory polymers and shape-changing polymers/shape-changing gels were identified. The application spectra of these materials as well as the current developments were elucidated and general molecular design principles presented. When applicable, a further distinction according to the applied stimulus was made.

Reversible Bidirectional Shape‐Memory Polymers

Free-standing copolymer network samples with two types of crystallizable domains are capable of a fully reversible bidirectional shape-memory effect. One set of crystallizable domains determines the shape-shifting geometry while the other provides the thermally controlled actuation capability.