Nanoarchitectonics: bottom-up creation of functional materials and systems

• Katsuhiko Ariga

Beilstein J. Nanotechnol. 2020, 11, 450–452, doi:10.3762/bjnano.11.36

• synthesis; nanoarchitectonics; nanotechnology; self-assembly; supramolecular; Given the significant and time-critical problems of energy shortage, environmental protection, and biomedical issues, the creation of new functional materials and systems for efficient energy production and storage [1][2

• other research fields such as atom/molecular manipulation, organic synthesis, supramolecular chemistry, and bio-related technology. This task is assigned to an emerging concept, nanoarchitectonics (Figure 1) [7][8][9]. The nanoarchitectonics concept was initially proposed by Masakazu Aono [10][11] who

Nanoparticles based on the zwitterionic pillar[5]arene and Ag⁺: synthesis, self-assembly and cytotoxicity in the human lung cancer cell line A549

• Dmitriy N. Shurpik,
• Denis A. Sevastyanov,
• Pavel V. Zelenikhin,
• Pavel L. Padnya,
• Vladimir G. Evtugyn,
• Yuriy N. Osin and
• Ivan I. Stoikov

Beilstein J. Nanotechnol. 2020, 11, 421–431, doi:10.3762/bjnano.11.33

• toxicity of Ag+ ions, multicore complexes prepared on the basis of macrocyclic ligands [9][10][11][12][13] and silver ions are of greatest interest. The ability of macrocyclic systems to form supramolecular associates, due to noncovalent interactions with Ag+, can reduce toxicity and preserve the

• the stability of supramolecular assemblies to pH changes [22][23]. Another remarkable property of sulfobetaine fragments is the ability to interact with silver ions [24][25][26] and participate in the stabilization of quantum dots [27]. It is worth noting that the use of polymer systems containing

• presence of a preorganized macrocyclic structure makes the process of controlled supramolecular self-assembly possible with certain coordination sites. In this paper, we report the first example of using nontoxic, water-soluble pillar[5]arene derivatives containing sulfobetaine fragments to produce

Rational design of block copolymer self-assemblies in photodynamic therapy

• Maxime Demazeau,
• Laure Gibot,
• Anne-Françoise Mingotaud,
• Patricia Vicendo,
• Clément Roux and
• Barbara Lonetti

Beilstein J. Nanotechnol. 2020, 11, 180–212, doi:10.3762/bjnano.11.15

• reducing power of glutathione (GSH) was exploited in a supramolecular micellar system formed through the host–guest interaction between a PEGylated cyclodextrin and adamantane moieties conjugated to a porphyrin photosensitizer through a disulfide bond. Once the disulfide link was cleaved by glutathione

• the affinity by adapting the amino acid sequence [145], as shown in Figure 10. Porphyrins have also been used in the polymer backbone to increase subsequent PS encapsulation [94]. Another approach to modulate the PS/vector affinity is the use of supramolecular complexes, particularly based on

Molecular architectonics of DNA for functional nanoarchitectures

• Debasis Ghosh,
• Lakshmi P. Datta and
• Thimmaiah Govindaraju

Beilstein J. Nanotechnol. 2020, 11, 124–140, doi:10.3762/bjnano.11.11

• short oligonucleotides are inexpensive to synthesize in-house or commercially available, and their coassembly with SFMs assures to generate novel nanoarchitectures with functional properties and applications. Although the field of classical DNA nanotechnology exploited the supramolecular bottom-up self

Internalization mechanisms of cell-penetrating peptides

• Ivana Ruseska and
• Andreas Zimmer

Beilstein J. Nanotechnol. 2020, 11, 101–123, doi:10.3762/bjnano.11.10

• molecules into cells and is one of the most studied CPPs thus far [25]. The first step in the internalization process is the formation of electrostatic interaction between the peptide and the cellular membrane, which affects the lipid supramolecular organization. This process may lead to changes in the

Review of advanced sensor devices employing nanoarchitectonics concepts

• Katsuhiko Ariga,
• Tatsuyuki Makita,
• Masato Ito,
• Taizo Mori,
• Shun Watanabe and
• Jun Takeya

Beilstein J. Nanotechnol. 2019, 10, 2014–2030, doi:10.3762/bjnano.10.198

• , which is a novel conceptual methodology to engineer functional materials and systems from nanoscale units through the fusion of nanotechnology with other research fields, including organic chemistry, supramolecular chemistry, materials science and biology. In this review article, we discuss recent

• selectivity, high efficiency, environmental friendliness, and with low cost and low emission. Various fundamental areas of science and technology, such as organic synthesis [28][29][30], supramolecular organization [31][32][33][34][35], physical fabrication [36][37][38] and biotechnology [39][40][41], are

• integrated connection, and high sensitivity [42][43]. In addition to these nanotechnological advancements in device fabrication, sensing materials for molecular recognition have been continuously explored on the basis of supramolecular chemistry with the aid of synthetic organic chemistry and materials

High-tolerance crystalline hydrogels formed from self-assembling cyclic dipeptide

• Yongcai You,
• Ruirui Xing,
• Qianli Zou,
• Feng Shi and
• Xuehai Yan

Beilstein J. Nanotechnol. 2019, 10, 1894–1901, doi:10.3762/bjnano.10.184

• Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China University of Chinese Academy of Sciences, Beijing 100049, China 10.3762/bjnano.10.184 Abstract Peptide-based supramolecular hydrogels, as a new type of biological nanoarchitectonic structure, hold great promise

• hydrogelator for the formation of supramolecular hydrogels. The unique hydrogen bonding in C-WY endows a high propensity for self-assembly and the resulting hydrogels are revealed to be crystalline. The crystalline hydrogels possess excellent mechanical capacity and superior tolerance to various harsh

• hydrogels with adjustable mechanical and physicochemical properties [29][30][31][32][33]. Peptide-based supramolecular hydrogels have been widely used in biological and nanotechnology fields [34]. However, linear peptide-based hydrogels usually have several deficiencies, such as poor molecular rigidity

Charge-transfer interactions between fullerenes and a mesoporous tetrathiafulvalene-based metal–organic framework

• Manuel Souto,
• Joaquín Calbo,
• Samuel Mañas-Valero,
• Aron Walsh and
• Guillermo Mínguez Espallargas

Beilstein J. Nanotechnol. 2019, 10, 1883–1893, doi:10.3762/bjnano.10.183

• electronics as conductors, switches, sensors or rectifiers [37][38]. Several studies have also been devoted to the development of TTF-based macrocyclic systems for their use as molecular machines or for supramolecular host–guest recognition [39][40][41]. In this context, donor–acceptor interactions between

• C60 and discrete π-extended TTF molecules have been extensively studied in solution during the last years [42][43][44][45][46][47]. In contrast, much less is known about their supramolecular interactions in solid-state polymeric structures such as metal–organic frameworks. MOFs using TTF as ligands

• boundary conditions (PBC). b) Supramolecular assemblies of C60@TTFTB extracted from the PBC-optimized C60@MUV-2 system in arrangements A and B. Intermolecular short contacts (in Å) and NCI surfaces (reduced density gradient isovalue = 0.3 a. u. (atomic units)) are displayed. Interaction energies (Eint) of

Biocatalytic oligomerization-induced self-assembly of crystalline cellulose oligomers into nanoribbon networks assisted by organic solvents

• Yuuki Hata,
• Yuka Fukaya,
• Toshiki Sawada,
• Masahito Nishiura and
• Takeshi Serizawa

Beilstein J. Nanotechnol. 2019, 10, 1778–1788, doi:10.3762/bjnano.10.173

• ; nanoribbon networks; oligomerization-induced self-assembly; organic solvent; Introduction Nanoarchitectonics is an emerging concept based on nanotechnology and other scientific fields, such as supramolecular chemistry, for constructing functional materials and systems in a bottom-up manner with the

The impact of crystal size and temperature on the adsorption-induced flexibility of the Zr-based metal–organic framework DUT-98

• Simon Krause,
• Volodymyr Bon,
• Hongchu Du,
• Rafal E. Dunin-Borkowski,
• Ulrich Stoeck,
• Irena Senkovska and
• Stefan Kaskel

Beilstein J. Nanotechnol. 2019, 10, 1737–1744, doi:10.3762/bjnano.10.169

• supramolecular building blocks (SBBs), which consist of Zr6 clusters interconnected by 3,6-carbazole dicarboxylate ligands [20]. An additional benzoate functionality of the ligand connects the SBB into a 3D framework with a structure (Figure 1) similar to MIL-53 [21][22]. Upon removal of the solvent molecules

Layered double hydroxide/sepiolite hybrid nanoarchitectures for the controlled release of herbicides

• Ediana Paula Rebitski,
• Margarita Darder and
• Pilar Aranda

Beilstein J. Nanotechnol. 2019, 10, 1679–1690, doi:10.3762/bjnano.10.163

• , iii) field-induced material control, iv) new manipulations of atoms and molecules, and v) theoretical modeling and design [1][2]. Based on these premises a large number of nanoarchitectonic materials have been prepared including mesoporous solids, self-organized block-copolymers, supramolecular

Chiral nanostructures self-assembled from nitrocinnamic amide amphiphiles: substituent and solvent effects

• Hejin Jiang,
• Huahua Fan,
• Yuqian Jiang,
• Li Zhang and
• Minghua Liu

Beilstein J. Nanotechnol. 2019, 10, 1608–1617, doi:10.3762/bjnano.10.156

• nm and 293 nm, respectively. This result suggests a H-like aggregation of NCLG molecules through π–π stacking. CD spectroscopy is considered to be a useful technique to monitor the supramolecular assembly. Consequently, distinct CD signals were obtained for the assemblies of the three NCLG molecules

• not show photo-responsive properties under UV-light irradiation, in the CD spectra or in the morphology of the nanostructures. Supporting Information File 1, Figure S2 shows that the morphology of all the nanostructures remained intact, and the supramolecular chirality of the self-assembled molecules

Materials nanoarchitectonics at two-dimensional liquid interfaces

• Katsuhiko Ariga,
• Michio Matsumoto,
• Taizo Mori and
• Lok Kumar Shrestha

Beilstein J. Nanotechnol. 2019, 10, 1559–1587, doi:10.3762/bjnano.10.153

• –Blodgett method, liquid–liquid interfacial precipitation, instructed assembly, and layer-by-layer assembly to give low-dimensional materials including nanowires, nanowhiskers, nanosheets, cubic objects, molecular patterns, supramolecular polymers, metal-organic frameworks and covalent organic frameworks

• . The nanoarchitecture materials can be used for various applications such as molecular recognition, sensors, photodetectors, supercapacitors, supramolecular differentiation, enzyme reactors, cell differentiation control, and hemodialysis. Keywords: film; interface; low-dimensional material

• bottom-up approaches are self-assembly and self-organization based on supramolecular chemistry [69]. These supramolecular mechanisms can be widely observed in various species including small molecules, nanomaterials, and biomolecules [70][71][72][73][74][75]. Despite this generality, there are still many

Synthesis of novel C-doped g-C₃N₄ nanosheets coupled with CdIn₂S₄ for enhanced photocatalytic hydrogen evolution

• Jingshuai Chen,
• Chang-Jie Mao,
• Helin Niu and
• Ji-Ming Song

Beilstein J. Nanotechnol. 2019, 10, 912–921, doi:10.3762/bjnano.10.92

• effective strategy, the combination of C-doping with nanocomposite semiconductors, is presented in this work. C-doped g-C3N4 (CCN) was prepared by supramolecular self-assembly and subsequently a number of CdIn2S4/CCN composite photocatalysts were designed and fabricated though in situ decoration of CdIn2S4

• -light irradiation. Results and Discussion Preparation and characterization of photocatalysts The preparation procedure of CdIn2S4/CCN photocatalysts is demonstrated in Figure 1. Firstly, carbon-bridged g-C3N4 (CCN) was prepared by a simple supramolecular self-assembly process using melamine and chitosan

• use of the additive Pt co-catalyst. As shown in Figure 8, the pristine g-C3N4 presents a negligible H2 generation rate, but after introduction of the self-doped C by a simple supramolecular self-assembly method, the CCN nanosheets display a higher H2 generation rate due to the presence of the large

Ultrathin hydrophobic films based on the metal organic framework UiO-66-COOH(Zr)

• Miguel A. Andrés,
• Clemence Sicard,
• Christian Serre,
• Olivier Roubeau and
• Ignacio Gascón

Beilstein J. Nanotechnol. 2019, 10, 654–665, doi:10.3762/bjnano.10.65

• supramolecular porous frameworks (NMOF-1) by coordination directed self-assembly of hydrophobic alkyl chains (OPE-C18) with Zn(II) and coated glass substrates using its ethanolic dispersions (thickness of the coating not specified). However, WCA values in most of the previous studies [34][36][48][49][50][51][52

Topochemical engineering of composite hybrid fibers using layered double hydroxides and abietic acid

• Liji Sobhana,
• Lokesh Kesavan,
• Jan Gustafsson and
• Pedro Fardim

Beilstein J. Nanotechnol. 2019, 10, 589–605, doi:10.3762/bjnano.10.60

• hydrophobic [10][11][12] with high tensile strength [13]. Topochemical engineering is a method of designing the fractionation (disassembly) and fabrication (assembly) of highly engineered functional materials using a combination of molecular and supramolecular techniques. Topochemical engineering is inspired

Polymorphic self-assembly of pyrazine-based tectons at the solution–solid interface

• Achintya Jana,
• Puneet Mishra and
• Neeladri Das

Beilstein J. Nanotechnol. 2019, 10, 494–499, doi:10.3762/bjnano.10.50

• supramolecular structures is crucial for realizing surface-supported functional molecular devices. Here, we report on the synthesis and surface self-assembly of a new pyrazine-derived molecule with pyridine pendants. Ambient scanning tunneling microscopy investigation at the solution–solid interface reveals

• the observed polymorphs. Such weak hydrogen bonding interactions are highly desirable for the formation of modular supramolecular architectures since they can provide sufficiently robust molecular structures and also facilitate error correction. Keywords: highly oriented pyrolytic graphite (HOPG

• –HOPG interface using scanning tunneling microscopy (STM) technique under ambient conditions. The molecules belong to a new class of pyrazine/triazine-based molecules, containing two or more pyridine pendant units, and can act as a precursor to several two- and three-dimensional supramolecular

pH-mediated control over the mesostructure of ordered mesoporous materials templated by polyion complex micelles

• Emilie Molina,
• Mélody Mathonnat,
• Jason Richard,
• Patrick Lacroix-Desmazes,
• Martin In,
• Philippe Dieudonné,
• Thomas Cacciaguerra,
• Corine Gérardin and
• Nathalie Marcotte

Beilstein J. Nanotechnol. 2019, 10, 144–156, doi:10.3762/bjnano.10.14

• , silica-based ordered mesoporous materials (OMMs) have attracted considerable attention in various fields such as adsorption, separation and catalysis. The formation of these mesostructures relies on a supramolecular assembly process between silicic species and surfactants or amphiphilic block copolymers

Size limits of magnetic-domain engineering in continuous in-plane exchange-bias prototype films

• Alexander Gaul,
• Daniel Emmrich,
• Timo Ueltzhöffer,
• Henning Huckfeldt,
• Hatice Doğanay,
• Johanna Hackl,
• Muhammad Imtiaz Khan,
• Daniel M. Gottlob,
• Gregor Hartmann,
• André Beyer,
• Dennis Holzinger,
• Slavomír Nemšák,
• Claus M. Schneider,
• Armin Gölzhäuser,
• Günter Reiss and
• Arno Ehresmann

Beilstein J. Nanotechnol. 2018, 9, 2968–2979, doi:10.3762/bjnano.9.276

• Interdisciplinary Nanostructure Science and Technology (CINSaT), University of Kassel, 34132 Kassel, Germany Faculty of Physics, Physics of supramolecular Systems and Surfaces, University of Bielefeld, 33501 Bielefeld, Germany PT-DESY, Deutsches Elektronen-Synchrotron DESY, 22607 Hamburg, Germany Peter Grünberg

The nanoscaled metal-organic framework ICR-2 as a carrier of porphyrins for photodynamic therapy

• Jan Hynek,
• Sebastian Jurík,
• Martina Koncošová,
• Jaroslav Zelenka,
• Ivana Křížová,
• Tomáš Ruml,
• Kaplan Kirakci,
• Ivo Jakubec,
• František Kovanda,
• Kamil Lang and
• Jan Demel

Beilstein J. Nanotechnol. 2018, 9, 2960–2967, doi:10.3762/bjnano.9.275

• order to avoid porphyrin aggregation various supramolecular structures have been designed [11][12][13]. In this context, porphyrin-based MOFs offer unique systems in which a regular arrangement prevents porphyrins from aggregation whereas the porosity enables fast diffusion of the ground state O2(3Σg

Block copolymers for designing nanostructured porous coatings

• Roberto Nisticò

Beilstein J. Nanotechnol. 2018, 9, 2332–2344, doi:10.3762/bjnano.9.218

• mild conditions can easily cleave the linkage between the blocks without affecting the block’s self-organization. Based on almost the same principle, nanoporous thin films with well-ordered cylindrical pores were obtained by preparing metallo-supramolecular block copolymers (where the two different

• polymeric blocks are linked via metal–ligand complexes) [63]. In this particular case, the approach consists of firstly, the self-assembly of the metallo-supramolecular block copolymer, forming a well-ordered thin film, and secondly, the opening of the metallo-complex via redox reaction, extracting the PEO

• in separation processes. Block copolymers and templating: theory and application Amphiphilic BCs (such as PS-b-PEO) are a subcategory of copolymers which can self-organize to form supramolecular aggregates with specific shapes, such as: spherical, rod (or short cylindrical), hexagonally packed rod

Nanoconjugates of a calixresorcinarene derivative with methoxy poly(ethylene glycol) fragments for drug encapsulation

• Alina M. Ermakova,
• Julia E. Morozova,
• Yana V. Shalaeva,
• Victor V. Syakaev,
• Aidar T. Gubaidullin,
• Alexandra D. Voloshina,
• Vladimir V. Zobov,
• Irek R. Nizameev,
• Olga B. Bazanova,
• Igor S. Antipin and
• Alexander I. Konovalov

Beilstein J. Nanotechnol. 2018, 9, 2057–2070, doi:10.3762/bjnano.9.195

• use as a supramolecular drug-delivery system. Keywords: calixresorcinarene; drug encapsulation; hemotoxicity; methoxy poly(ethylene glycol); temperature-controlled release; Introduction One of the acute problems of modern medicinal therapy is the development of novel drug-delivery systems with low

• outstanding class of synthetic macrocycles. With regard to supramolecular containers for drug encapsulation they offer a convenient platform that allows for the functionalization of upper and lower rim by different groups, offers an aromatic cavity capable to π–π, CH–π and cation–π interactions and can form

• of co-associates [6][7][8][9], demonstrating their ability to form supramolecular nanocontainers. The toxicity of such supramolecular nanocontainers remains a relevant challenge. One of the approaches for the introduction of hydrophilic groups into the macrocycle and to decrease its toxicity is the

SO₂ gas adsorption on carbon nanomaterials: a comparative study

• Deepu J. Babu,
• Divya Puthusseri,
• Frank G. Kühl,
• Sherif Okeil,
• Michael Bruns,
• Manfred Hampe and
• Jörg J. Schneider

Beilstein J. Nanotechnol. 2018, 9, 1782–1792, doi:10.3762/bjnano.9.169

• supramolecular contacts surrounding the pore [2]. The beneficial role of hydroxy groups on SO2 adsorption was also observed in the case of flue gas adsorption on MOFs [8]. All these studies point to the fact that the presence of oxygen functionalities can certainly influence the SO2 adsorption characteristics of

Closed polymer containers based on phenylboronic esters of resorcinarenes

• Tatiana Yu. Sergeeva,
• Rezeda K. Mukhitova,
• Irek R. Nizameev,
• Marsil K. Kadirov,
• Polina D. Klypina,
• Albina Y. Ziganshina and
• Alexander I. Konovalov

Beilstein J. Nanotechnol. 2018, 9, 1594–1601, doi:10.3762/bjnano.9.151

• the fluorescence spectrum remains practically unchanged. Apparently, Py is not released into the water, it remains in the aggregated state in supramolecular associates formed after the dissociation of p(SRA-B). In the case of Fl@p(SRA-B), both shape and intensity of the fluorescence spectrum are

Formation and development of nanometer-sized cybotactic clusters in bent-core nematic liquid crystalline compounds

• Yuri P. Panarin,
• Sithara P. Sreenilayam,
• Jagdish K. Vij,
• Anne Lehmann and
• Carsten Tschierske

Beilstein J. Nanotechnol. 2018, 9, 1288–1296, doi:10.3762/bjnano.9.121

• function of temperature and the bias field. Keywords: bent-core liquid crystals; biaxiality; clusters; dielectric spectroscopy; Introduction Biaxial liquid crystals (LCs) exhibit supramolecular structures with long-range orientational ordering of the long and the short molecular axes but without a long