Heterocomponent ternary supramolecular complexes of porphyrins: A review

Porphyrins are prominent host molecules which are widely used due to their structural characteristics and directional interaction sites. This review summarizes non-covalently bound ternary complexes of porphyrins, constructed from at least three non-identical species. Progress in supramolecular chemistry allows the creation of complex molecular machinery tools, such as rotors, motors and switches from relatively simple structures in a single self-assembly step. In the current review, we highlight the collection of sophisticated molecular ensembles including sandwich-type complexes, cages, capsules, tweezers, rotaxanes, and supramolecular architectures mediating oxygen-binding and oxidation reactions. These diverse structures have high potential to be applied in sensing, production of new smart materials as well as in medical science.

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Nano-sandwich composite by kinetic trapping assembly from protein and nucleic acid

Nucleic Acids Research ◽

10.1093/nar/gkab797 ◽

2021 ◽

Vol 49 (17) ◽

pp. 10098-10105

Author(s):

Shi Chen ◽

Li Xing ◽

Douglas Zhang ◽

Alba Monferrer ◽

Thomas Hermann

Keyword(s):

Self Assembly ◽

Layered Composite ◽

Fluorescence Labeling ◽

Sandwich Composite ◽

Interaction Sites ◽

Supramolecular Architectures ◽

Dna And Rna ◽

Synthetic Protein ◽

Synthesis Strategy ◽

3D Architecture

Abstract Design and preparation of layered composite materials alternating between nucleic acids and proteins has been elusive due to limitations in occurrence and geometry of interaction sites in natural biomolecules. We report the design and kinetically controlled stepwise synthesis of a nano-sandwich composite by programmed noncovalent association of protein, DNA and RNA modules. A homo-tetramer protein core was introduced to control the self-assembly and precise positioning of two RNA–DNA hybrid nanotriangles in a co-parallel sandwich arrangement. Kinetically favored self-assembly of the circularly closed nanostructures at the protein was driven by the intrinsic fast folding ability of RNA corner modules which were added to precursor complex of DNA bound to the protein. The 3D architecture of this first synthetic protein–RNA–DNA complex was confirmed by fluorescence labeling and cryo-electron microscopy studies. The synthesis strategy for the nano-sandwich composite provides a general blueprint for controlled noncovalent assembly of complex supramolecular architectures from protein, DNA and RNA components, which expand the design repertoire for bottom-up preparation of layered biomaterials.

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DNA-Guided Assembly for Fibril Proteins

Mathematics ◽

10.3390/math9040404 ◽

2021 ◽

Vol 9 (4) ◽

pp. 404

Author(s):

Alexandru Amărioarei ◽

Frankie Spencer ◽

Gefry Barad ◽

Ana-Maria Gheorghe ◽

Corina Iţcuş ◽

...

Keyword(s):

Computational Model ◽

Structural Properties ◽

Self Assembly ◽

Structural Characteristics ◽

Computational Modelling ◽

Shape Reconstruction ◽

Raw Material ◽

Dna Assembly ◽

Mesh Structure ◽

Elementary Fibril

Current advances in computational modelling and simulation have led to the inclusion of computer scientists as partners in the process of engineering of new nanomaterials and nanodevices. This trend is now, more than ever, visible in the field of deoxyribonucleic acid (DNA)-based nanotechnology, as DNA’s intrinsic principle of self-assembly has been proven to be highly algorithmic and programmable. As a raw material, DNA is a rather unremarkable fabric. However, as a way to achieve patterns, dynamic behavior, or nano-shape reconstruction, DNA has been proven to be one of the most functional nanomaterials. It would thus be of great potential to pair up DNA’s highly functional assembly characteristics with the mechanic properties of other well-known bio-nanomaterials, such as graphene, cellulos, or fibroin. In the current study, we perform projections regarding the structural properties of a fibril mesh (or filter) for which assembly would be guided by the controlled aggregation of DNA scaffold subunits. The formation of such a 2D fibril mesh structure is ensured by the mechanistic assembly properties borrowed from the DNA assembly apparatus. For generating inexpensive pre-experimental assessments regarding the efficiency of various assembly strategies, we introduced in this study a computational model for the simulation of fibril mesh assembly dynamical systems. Our approach was based on providing solutions towards two main circumstances. First, we created a functional computational model that is restrictive enough to be able to numerically simulate the controlled aggregation of up to 1000s of elementary fibril elements yet rich enough to provide actionable insides on the structural characteristics for the generated assembly. Second, we used the provided numerical model in order to generate projections regarding effective ways of manipulating one of the the key structural properties of such generated filters, namely the average size of the openings (gaps) within these meshes, also known as the filter’s aperture. This work is a continuation of Amarioarei et al., 2018, where a preliminary version of this research was discussed.

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Luminescent Supramolecular Nano- or Microstructures Formed in Aqueous Media by Amphiphile-Noble Metal Complexes

Journal of Nanomaterials ◽

10.1155/2020/5395048 ◽

2020 ◽

Vol 2020 ◽

pp. 1-24 ◽

Cited By ~ 1

Author(s):

Carmen Cretu ◽

Loredana Maiuolo ◽

Domenico Lombardo ◽

Elisabeta I. Szerb ◽

Pietro Calandra

Keyword(s):

Noble Metal ◽

Smart Materials ◽

Self Assembly ◽

Noble Metals ◽

Photophysical Properties ◽

Aqueous Media ◽

Molecular Architecture ◽

Stimuli Responsive ◽

Panoramic View ◽

Amphiphilic Molecules

The involvement of metal ions within the self-assembly spontaneously occurring in surfactant-based systems gives additional and interesting features. The electronic states of the metal, together with the bonds that can be established with the organic amphiphilic counterpart, are the factors triggering new photophysical properties. Moreover, the availability of stimuli-responsive supramolecular amphiphile assemblies, able to disassemble in a back-process, provides reversible switching particularly useful in novel approaches and applications giving rise to truly smart materials. In particular, small amphiphiles with an inner distribution, within their molecular architecture, of various polar and apolar functional groups, can give a wide variety of interactions and therefore enriched self-assemblies. If it is joined with the opportune presence and localization of noble metals, whose chemical and photophysical properties are undiscussed, then very interesting materials can be obtained. In this minireview, the basic concepts on self-assembly of small amphiphilic molecules with noble metals are shown with particular reference to the photophysical properties aiming at furnishing to the reader a panoramic view of these exciting problematics. In this respect, the following will be shown: (i) the principles of self-assembly of amphiphiles that involve noble metals, (ii) examples of amphiphiles and amphiphile-noble metal systems as representatives of systems with enhanced photophysical properties, and (iii) final comments and perspectives with some examples of modern applications.

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Reversible Self-Assembly of Entrapped Fluorescent Gelators in Polymerized Styrene Gel Matrix: Erasable Thermal Imaging via Recreation of Supramolecular Architectures

Journal of the American Chemical Society ◽

10.1021/ja9072035 ◽

2009 ◽

Vol 131 (42) ◽

pp. 15122-15123 ◽

Cited By ~ 125

Author(s):

Sampath Srinivasan ◽

Palathingal A. Babu ◽

Sankarapillai Mahesh ◽

Ayyappanpillai Ajayaghosh

Keyword(s):

Self Assembly ◽

Thermal Imaging ◽

Supramolecular Architectures

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Structure–function relationships of the plant cuticle and cuticular waxes — a smart material?

Functional Plant Biology ◽

10.1071/fp06139 ◽

2006 ◽

Vol 33 (10) ◽

pp. 893 ◽

Cited By ~ 188

Author(s):

Hendrik Bargel ◽

Kerstin Koch ◽

Zdenek Cerman ◽

Christoph Neinhuis

Keyword(s):

Structure Function ◽

Smart Materials ◽

Self Assembly ◽

Water Repellency ◽

Cuticular Waxes ◽

Form Complex ◽

Symmetry Classes ◽

Research Activities ◽

Terrestrial Habitats ◽

Surface Waxes

The cuticle is the main interface between plants and their environment. It covers the epidermis of all aerial primary parts of plant organs as a continuous extracellular matrix. This hydrophobic natural composite consists mainly of the biopolymer, cutin, and cuticular lipids collectively called waxes, with a high degree of variability in composition and structure. The cuticle and cuticular waxes exhibit a multitude of functions that enable plant life in many different terrestrial habitats and play important roles in interfacial interactions. This review highlights structure–function relationships that are the subjects of current research activities. The surface waxes often form complex crystalline microstructures that originate from self-assembly processes. The concepts and results of the analysis of model structures and the influence of template effects are critically discussed. Recent investigations of surface waxes by electron and X-ray diffraction revealed that these could be assigned to three crystal symmetry classes, while the background layer is not amorphous, but has an orthorhombic order. In addition, advantages of the characterisation of formation of model wax types on a molecular scale are presented. Epicuticular wax crystals may cause extreme water repellency and, in addition, a striking self-cleaning property. The principles of wetting and up-to-date concepts of the transfer of plant surface properties to biomimetic technical applications are reviewed. Finally, biomechanical studies have demonstrated that the cuticle is a mechanically important structure, whose properties are dynamically modified by the plant in response to internal and external stimuli. Thus, the cuticle combines many aspects attributed to smart materials.

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The macroscopic shape of assemblies formed from microparticles based on host–guest interaction dependent on the guest content

Scientific Reports ◽

10.1038/s41598-021-85816-z ◽

2021 ◽

Vol 11 (1) ◽

Author(s):

Takahiro Itami ◽

Akihito Hashidzume ◽

Yuri Kamon ◽

Hiroyasu Yamaguchi ◽

Akira Harada

Keyword(s):

Molecular Recognition ◽

Smart Materials ◽

Self Assembly ◽

Early Stage ◽

Contact Point ◽

Sodium Acrylate ◽

Contact Points ◽

Assembly Behavior ◽

Small Clusters ◽

Macroscopic Shape

AbstractBiological macroscopic assemblies have inspired researchers to utilize molecular recognition to develop smart materials in these decades. Recently, macroscopic self-assemblies based on molecular recognition have been realized using millimeter-scale hydrogel pieces possessing molecular recognition moieties. During the study on macroscopic self-assembly based on molecular recognition, we noticed that the shape of assemblies might be dependent on the host–guest pair. In this study, we were thus motivated to study the macroscopic shape of assemblies formed through host–guest interaction. We modified crosslinked poly(sodium acrylate) microparticles, i.e., superabsorbent polymer (SAP) microparticles, with β-cyclodextrin (βCD) and adamantyl (Ad) residues (βCD(x)-SAP and Ad(y)-SAP microparticles, respectively, where x and y denote the mol% contents of βCD and Ad residues). Then, we studied the self-assembly behavior of βCD(x)-SAP and Ad(y)-SAP microparticles through the complexation of βCD with Ad residues. There was a threshold of the βCD content in βCD(x)-SAP microparticles for assembly formation between x = 22.3 and 26.7. On the other hand, the shape of assemblies was dependent on the Ad content, y; More elongated assemblies were formed at a higher y. This may be because, at a higher y, small clusters formed in an early stage can stick together even upon collisions at a single contact point to form elongated aggregates, whereas, at a smaller y, small clusters stick together only upon collisions at multiple contact points to give rather circular assemblies. On the basis of these observations, the shape of assembly formed from microparticles can be controlled by varying y.

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