Assembling Photo- and Electroresponsive Molecules and Nano-Objects

MRS Bulletin ◽  
2007 ◽  
Vol 32 (7) ◽  
pp. 556-560 ◽  
Author(s):  
Michael Busby ◽  
Luisa De Cola ◽  
Gregg S. Kottas ◽  
Zoran Popović
Keyword(s):  
Self Assembly ◽  
Building Blocks ◽  
Supramolecular Systems ◽  
Natural Systems ◽  
Design And Synthesis ◽  
Zeolite L ◽  
Solid Substrates ◽  
Potential Applications ◽  
Collective Interactions ◽  
Spectroscopic Behavior

The self-assembly of small molecules into large, functional nanostructures has led to the construction of supramolecular systems, both in solution and on solid substrates, with defined dimensions that display unique properties through collective interactions, much like natural systems. In this article, we show how one assembles photo- and electroluminescent molecules through coordination chemistry for the purpose of producing novel materials that can be used for displays and lighting applications. In a stepwise process, we discuss the design and synthesis of the components, their spectroscopic behavior, and finally the properties arising from the assembly. We then move from molecules to more complex systems such as zeolite L nano-objects that can be used as nanocontainers and functionalized in different ways. We show how it is possible to organize rods of micron length in a geometrically controlled manner in solution and on surfaces. The assemblies are built by coordinative bonds and are luminescent materials that can be constructed from fluorescent building blocks, with potential applications as optoelectronic materials, in analogy to their molecular counterparts.

Self-assembly and properties of low-dimensional nanomaterials based on π-conjugated organic molecules

2008 ◽  
Vol 80 (3) ◽  
pp. 639-658 ◽  
Author(s):  
Jing Lv ◽  
Huibiao Liu ◽  
Yuliang Li
Keyword(s):  
Physical Properties ◽  
Self Assembly ◽  
Materials Science ◽  
Hydrophobic Interactions ◽  
Building Blocks ◽  
Supramolecular Systems ◽  
Nanoscale Structures ◽  
Design And Synthesis ◽  
Supramolecular Architectures ◽  
Low Dimensional

Building supramolecular architectures with well-defined shapes and functions is of great importance in materials science, nanochemistry, and biomimetic chemistry. In recent years, we have devoted much effort to the construction of well-defined supramolecular structures through noncovalent forces such as hydrogen bonding, π-stacking, metal-ligand bonds, and hydrophilic and hydrophobic interactions, with the aid of functional building blocks. The morphologies and their physical properties were studied, and new methods for the construction of one-dimensional nanoscale structures have been developed. In this review, we summarize our recent studies on the design and synthesis of the supramolecular systems, as well as the physical properties of nanoscale structures.

scholarly journals A Structurally Variable Hinged Tetrahedron Framework from DNA Origami

2011 ◽  
Vol 2011 ◽  
pp. 1-9 ◽  
Author(s):  
David M. Smith ◽  
Verena Schüller ◽  
Carsten Forthmann ◽  
Robert Schreiber ◽  
Philip Tinnefeld ◽  
...  
Keyword(s):  
Self Assembly ◽  
Gel Electrophoresis ◽  
Imaging Techniques ◽  
Building Blocks ◽  
Dna Origami ◽  
Microscopy Technique ◽  
Wire Frame ◽  
Wide Range ◽  
Potential Applications ◽  
Linker Molecules

Nanometer-sized polyhedral wire-frame objects hold a wide range of potential applications both as structural scaffolds as well as a basis for synthetic nanocontainers. The utilization of DNA as basic building blocks for such structures allows the exploitation of bottom-up self-assembly in order to achieve molecular programmability through the pairing of complementary bases. In this work, we report on a hollow but rigid tetrahedron framework of 75 nm strut length constructed with the DNA origami method. Flexible hinges at each of their four joints provide a means for structural variability of the object. Through the opening of gaps along the struts, four variants can be created as confirmed by both gel electrophoresis and direct imaging techniques. The intrinsic site addressability provided by this technique allows the unique targeted attachment of dye and/or linker molecules at any point on the structure's surface, which we prove through the superresolution fluorescence microscopy technique DNA PAINT.

scholarly journals Beyond icosahedral symmetry in packings of proteins in spherical shells

2017 ◽  
Vol 114 (34) ◽  
pp. 9014-9019 ◽  
Author(s):  
Majid Mosayebi ◽  
Deborah K. Shoemark ◽  
Jordan M. Fletcher ◽  
Richard B. Sessions ◽  
Noah Linden ◽  
...  
Keyword(s):  
Self Assembly ◽  
De Novo ◽  
Multiple Scales ◽  
Building Blocks ◽  
Icosahedral Symmetry ◽  
Protein Cages ◽  
Natural Systems ◽  
Wide Range ◽  
Stable Arrangement ◽  
Symmetric Structures

The formation of quasi-spherical cages from protein building blocks is a remarkable self-assembly process in many natural systems, where a small number of elementary building blocks are assembled to build a highly symmetric icosahedral cage. In turn, this has inspired synthetic biologists to design de novo protein cages. We use simple models, on multiple scales, to investigate the self-assembly of a spherical cage, focusing on the regularity of the packing of protein-like objects on the surface. Using building blocks, which are able to pack with icosahedral symmetry, we examine how stable these highly symmetric structures are to perturbations that may arise from the interplay between flexibility of the interacting blocks and entropic effects. We find that, in the presence of those perturbations, icosahedral packing is not the most stable arrangement for a wide range of parameters; rather disordered structures are found to be the most stable. Our results suggest that (i) many designed, or even natural, protein cages may not be regular in the presence of those perturbations and (ii) optimizing those flexibilities can be a possible design strategy to obtain regular synthetic cages with full control over their surface properties.

scholarly journals Towards Complex Matter: Supramolecular Chemistry and Self-organization

2009 ◽  
Vol 17 (2) ◽  
pp. 263-280 ◽  
Author(s):  
Jean-Marie Lehn
Keyword(s):  
Supramolecular Chemistry ◽  
Self Assembly ◽  
Building Blocks ◽  
Intermolecular Forces ◽  
Self Organization ◽  
Irreversible Processes ◽  
Continuous Change ◽  
Supramolecular Systems ◽  
Molecular Information ◽  
Complex Matter

Chemistry has developed from molecular chemistry, mastering the combination and recombination of atoms into increasingly complex molecules, to supramolecular chemistry, harnessing intermolecular forces for the generation of informed supramolecular systems and processes through the implementation of molecular information carried by electromagnetic interactions. Supramolecular chemistry is actively exploring systems undergoing self-organization, i.e. systems capable of spontaneously generating well-defined functional supramolecular architectures by self-assembly from their components, on the basis of the molecular information stored in the covalent framework of the components and read out at the supramolecular level through specific molecular recognition interactional algorithms, thus behaving as programmed chemical systems. Supramolecular entities as well as molecules containing reversible bonds are able to undergo a continuous change in constitution by reorganization and exchange of building blocks. This capability defines a Constitutional Dynamic Chemistry (CDC) on both the molecular and supramolecular levels. CDC introduces a paradigm shift with respect to constitutionally static chemistry. It takes advantage of dynamic constitutional diversity to allow variation and selection and thus adaptation. The merging of the features of supramolecular systems – information and programmability; dynamics and reversibility; constitution and structural diversity – points towards the emergence of adaptive chemistry. A further development will concern the inclusion of the arrow of time, i.e. of non-equilibrium, irreversible processes and the exploration of the frontiers of chemical evolution towards the establishment of evolutive chemistry, where the features acquired by adaptation are conserved and transmitted. In combination with the corresponding fields of physics and biology, chemistry thus plays a major role in the progressive elaboration of a science of informed, organized, evolutive matter, a science of complex matter.

scholarly journals Unveiling the Key Templates in the Self-Assembly of Gigantic Molybdenum Blue Wheels

2018 ◽  
Author(s):  
Weimin Xuan ◽  
Robert Pow ◽  
Qi Zheng, ◽  
Nancy Watfa ◽  
De-Liang Long ◽  
...  
Keyword(s):  
Self Assembly ◽  
Electrostatic Interactions ◽  
Structural Evolution ◽  
Functional Materials ◽  
Building Blocks ◽  
Underlying Mechanism ◽  
The Self ◽  
Supramolecular Systems ◽  
Structure Directing Agent ◽  
Molybdenum Blue

Template synthesis is a powerful and useful approach to build a variety of functional materials and complicated supramolecular systems. Systematic study on how templates structurally evolve from basic building blocks and then affect the templated self-assembly is critical to understand the underlying mechanism and gain more guidance for designed assembly but remains challenging. Here we describe the templated self-assembly of a series of gigantic Mo Blue (MB) clusters 1-4 using L-ornithine as structure-directing agent. L-ornithine is essential for the formation of such kind of template⊂host assemblies by providing directional forces of hydrogen bonding and electrostatic interactions. Based on the structural relationship between encapsulated templates of {Mo8} (1), {Mo17} (2) and {Mo36} (4), a plausible pathway of the structural evolution of templates is proposed, thus giving more insight on the templated self-assembly of Mo Blue clusters.

scholarly journals Patchy Nanoparticle Synthesis and Self-Assembly

2020 ◽  
Author(s):  
Ahyoung Kim ◽  
Lehan Yao ◽  
Falon Kalutantirige ◽  
Shan Zhou ◽  
Qian Chen
Keyword(s):  
Self Assembly ◽  
Nanoparticle Synthesis ◽  
Building Blocks ◽  
Design And Synthesis ◽  
Patchy Particles ◽  
Living Organisms ◽  
Directional Bonding ◽  
Patchy Nanoparticles ◽  
Assembly Pathways ◽  
Physical Principles

Biological building blocks (i.e., proteins) are encoded with the information of target structure into the chemical and morphological patches, guiding their assembly into the levels of functional structures that are crucial for living organisms. Learning from nature, researchers have been attracted to the artificial analogues, “patchy particles,” which have controlled geometries of patches that serve as directional bonding sites. However, unlike the abundant studies of micron-scale patchy particles, which demonstrated complex assembly structures and unique behaviors attributed to the patches, research on patchy nanoparticles (NPs) has remained challenging. In the present chapter, we discuss the recent understandings on patchy NP design and synthesis strategies, and physical principles of their assembly behaviors, which are the main factors to program patchy NP self-assembly into target structures that cannot be achieved by conventional non-patched NPs. We further summarize the self-assembly of patchy NPs under external fields, in simulation, and in kinetically controlled assembly pathways, to show the structural richness patchy NPs bring. The patchy NP assembly is novel by their structures as well as the multicomponent features, and thus exhibits unique optical, chemical, and mechanical properties, potentially aiding applications in catalysts, photonic crystals, and metamaterials as well as fundamental nanoscience.

scholarly journals α-Cyclodextrin-Based Polypseudorotaxane Hydrogels

Materials ◽  
2019 ◽  
Vol 13 (1) ◽  
pp. 133 ◽  
Author(s):  
Adrian Domiński ◽  
Tomasz Konieczny ◽  
Piotr Kurcok
Keyword(s):  
Self Assembly ◽  
Polymeric Nanoparticles ◽  
Functional Materials ◽  
Building Blocks ◽  
Polymer Chains ◽  
Physical Interaction ◽  
Wide Range ◽  
Potential Applications ◽  
Noncovalent Bonds ◽  
Significant Attention

Supramolecular hydrogels that are based on inclusion complexes between α-cyclodextrin and (co)polymers have gained significant attention over the last decade. They are formed via dynamic noncovalent bonds, such as host–guest interactions and hydrogen bonds, between various building blocks. In contrast to typical chemical crosslinking (covalent linkages), supramolecular crosslinking is a type of physical interaction that is characterized by great flexibility and it can be used with ease to create a variety of “smart” hydrogels. Supramolecular hydrogels based on the self-assembly of polypseudorotaxanes formed by a polymer chain “guest” and α-cyclodextrin “host” are promising materials for a wide range of applications. α-cyclodextrin-based polypseudorotaxane hydrogels are an attractive platform for engineering novel functional materials due to their excellent biocompatibility, thixotropic nature, and reversible and stimuli-responsiveness properties. The aim of this review is to provide an overview of the current progress in the chemistry and methods of designing and creating α-cyclodextrin-based supramolecular polypseudorotaxane hydrogels. In the described systems, the guests are (co)polymer chains with various architectures or polymeric nanoparticles. The potential applications of such supramolecular hydrogels are also described.

scholarly journals Development of Natural-Drugs-Based Low-Molecular-Weight Supramolecular Gels

Gels ◽  
2021 ◽  
Vol 7 (3) ◽  
pp. 105
Author(s):  
Xiaoyi Feng ◽  
Yuning Luo ◽  
Fangjie Li ◽  
Xueting Jian ◽  
Yang Liu
Keyword(s):  
Molecular Weight ◽  
Self Assembly ◽  
Water Solubility ◽  
Drug Loading ◽  
Building Blocks ◽  
Low Molecular Weight ◽  
Assembly Mechanism ◽  
Supramolecular Gels ◽  
Potential Applications ◽  
Natural Drugs

Natural small molecular drugs with excellent biocompatibility, diverse pharmacological activities, and wide sources play an increasingly important role in the development of new drug and disease treatment. In recent years, the utilization of paclitaxel, camptothecin, rhein, curcumin, and other natural small molecular drugs with unique rigid backbone structures and modifiable multiple sites as building blocks to form gels by self-assembly has attracted widespread attention. The obtained low-molecular-weight supramolecular gel not only retains the general characteristics of the gel but also overcomes the shortcomings of natural drugs, such as poor water solubility and low bioavailability. It has the advantages of high drug loading, low toxicity, and outstanding stimulus responsiveness, which is widely used in biomedical fields. Here, we provided a comprehensive review of natural-drugs-based low-molecular-weight supramolecular gels reported in recent years and summarized their assembly mechanism, gel structure, gel properties, and potential applications. It is expected to provide a reference for further research of natural-drugs-based supramolecular gels.

scholarly journals Viologen capped by nucleobase—building blocks for functional materials: synthesis and structure–properties relationship

2021 ◽  
Author(s):  
Marius Ciobanu ◽  
Carmen-Simona Jordan
Keyword(s):  
Self Assembly ◽  
Liquid Crystalline ◽  
Functional Materials ◽  
Building Blocks ◽  
Benzene Sulfonate ◽  
Materials Synthesis ◽  
Substantial Impact ◽  
Design And Synthesis ◽  
Thermochromic Properties ◽  
Structure Properties

AbstractThe current study presents a new class of functional derivatives (1–3) consisting of a dicationic viologen (4,4’-bipyridinium unit) (V2+) capped by nucleobases thymine (NB1), adenine (NB2), thymine/adenine (NB1, NB2), and ion-paired with amphiphilic anion 3,4,5-tris(dodecyloxy)benzene sulfonate (DOBS−). The target of our work focuses on the design and synthesis of molecular building blocks in which three different functionalities are combined: chromophore (V2+ unit), molecular recognition (NB unit), and thermotropic liquid crystal (DOBS unit). The resulted materials exhibit liquid crystalline properties at ambient temperature with significant particularities-induced by nucleobases in the mesogen structure. Structure–properties relationship study focuses on providing knowledge about (1) how the thermotropic, redox properties, thermochromism, or ionic conductive properties are influenced by the presence of purinic or pyrimidinic nucleobases, and (2) how effective is their ability to self-assembly by hydrogen bonding in nonpolar solvents. The presence of nucleobases has been proved to have a substantial impact on electron transfer rate during the reduction of viologen moieties by intermolecular aggregation. Ionic conductivity and thermochromic properties of derivatives 1–3 were investigated and compared to a non-containing nucleobase analog methyl viologen with 3,4,5-tris(dodecyloxy)benzene sulfonate anion (MV) as reference. Graphical abstract

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