ChemInform Abstract: Efficient Synthetic Strategy to Construct Three-Dimensional 4f-5d Networks Using Neutral Two-Dimensional Layers as Building Blocks.

Two-dimensional (2D), supramolecular self-assembly at surfaces is now well-mastered with several existing examples. However, one remaining challenge to enable future applications in nanoscience is to provide potential functionalities to the physisorbed adlayer. This work reviews a recently developed strategy that addresses this key issue by taking advantage of a new concept, Janus tecton materials. This is a versatile, molecular platform based on the design of three-dimensional (3D) building blocks consisting of two faces linked by a cyclophane-type pillar. One face is designed to steer 2D self-assembly onto C(sp2)-carbon-based flat surfaces, the other allowing for the desired functionality above the substrate with a well-controlled lateral order. In this way, it is possible to simultaneously obtain a regular, non-covalent paving as well as supramolecular functionalization of graphene, thus opening interesting perspectives for nanoscience applications.

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High Throughput Printing of Two-Dimensional Materials into Wafer-scale Three-dimensional Architectures

10.21203/rs.3.rs-899522/v1 ◽

2021 ◽

Author(s):

Xuan Wei ◽

Chia-Ching Lin ◽

Christine Wu ◽

Ang-Yu Lu ◽

Nadeem Qaiser ◽

...

Keyword(s):

High Throughput ◽

Transition Metal Dichalcogenides ◽

Three Dimensional ◽

High Capacity ◽

Building Blocks ◽

High Rate ◽

Wearable Electronics ◽

Two Dimensional ◽

Critical Feature ◽

Wafer Scale

Abstract Architected materials that actively respond to external stimuli hold tantalizing prospects for applications in energy storage, harvesting, wearable electronics and bioengineering. Transition metal dichalcogenides (TMDs) which represent the three-atom-thick, two-dimensional (2D) building blocks, are excellent candidates but have found limited success compared to metallic, inorganic, and organic counterparts due to the lack of up-scalable manufacturing. Here we report the high-throughput printing of 2D TMDs into wafer-scale 3D architectures with structural hierarchy across seven orders of magnitude between critical feature sizes. Anode made of 3D MoS2 architectures comprises the concentric vortex-like intricacy that unites technological merits from architecture, mechanical engineering, and electrochemistry not found in its bulk or exfoliated/epitaxy counterparts. The result is, contrary to expectation, the high-rate, high-capacity, and high-loading lithium (Li)-storage, surpassing those state-of-the-art anode designs while the technique offers an evaporation-like simplicity for industrial scalability.

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Synthesis and characterization of two novel bimetallic macrocyclic complexes generated from 1,2,4-triazole-containing semi-rigid ligands andM(NO3)2units (M= Ni and Zn)

Acta Crystallographica Section C Structural Chemistry ◽

10.1107/s205322961600348x ◽

2016 ◽

Vol 72 (4) ◽

pp. 285-290 ◽

Cited By ~ 3

Author(s):

Xiang-Wen Wu ◽

Shi Yin ◽

Wan-Fu Wu ◽

Jian-Ping Ma

Keyword(s):

Hydrogen Bonds ◽

Mixed Solvents ◽

Three Dimensional ◽

Building Blocks ◽

Macrocyclic Complexes ◽

Organic Ligands ◽

Dimensional Structure ◽

Two Dimensional ◽

Coordination Environment ◽

Dimensional Network

Bimetallic macrocyclic complexes have attracted the attention of chemists and various organic ligands have been used as molecular building blocks, but supramolecular complexes based on semi-rigid organic ligands containing 1,2,4-triazole have remained rare until recently. It is easier to obtain novel topologies by making use of asymmetric semi-rigid ligands in the self-assembly process than by making use of rigid ligands. A new semi-rigid ligand, 3-[(pyridin-4-ylmethyl)sulfanyl]-5-(quinolin-2-yl)-4H-1,2,4-triazol-4-amine (L), has been synthesized and used to generate two novel bimetallic macrocycle complexes, namely bis{μ-3-[(pyridin-4-ylmethyl)sulfanyl]-5-(quinolin-2-yl)-4H-1,2,4-triazol-4-amine}bis[(methanol-κO)(nitrato-κ2O,O′)nickel(II)] dinitrate, [Ni2(NO3)2(C17H14N6S)2(CH3OH)2](NO3)2, (I), and bis{μ-3-[(pyridin-4-ylmethyl)sulfanyl]-5-(quinolin-2-yl)-4H-1,2,4-triazol-4-amine}bis[(methanol-κO)(nitrato-κ2O,O′)zinc(II)] dinitrate, [Zn2(NO3)2(C17H14N6S)2(CH3OH)2](NO3)2, (II), by solution reactions with the inorganic saltsM(NO3)2(M= Ni and Zn, respectively) in mixed solvents. In (I), two NiIIcations with the same coordination environment are linked byLligands through Ni—N bonds to form a bimetallic ring. Compound (I) is extended into a two-dimensional network in the crystallographicacplaneviaN—H...O, O—H...N and O—H...O hydrogen bonds, and neighbouring two-dimensional planes are parallel and form a three-dimensional structureviaπ–π stacking. Compound (II) contains two bimetallic rings with the same coordination environment of the ZnIIcations. The ZnIIcations are bridged byLligands through Zn—N bonds to form the bimetallic rings. One type of bimetallic ring constructs a one-dimensional nanotubeviaO—H...O and N—H...O hydrogen bonds along the crystallographicadirection, and the other constructs zero-dimensional molecular cagesviaO—H...O and N—H...O hydrogen bonds. They are interlinked into a two-dimensional network in theacplane through extensive N—H...O hydrogen bonds, and a three-dimensional supramolecular architecture is formedviaπ–π interactions between the centroids of the benzene rings of the quinoline ring systems.

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Crystal structures of tetramethylammonium (2,2′-bipyridine)tetracyanidoferrate(III) trihydrate and poly[[(2,2′-bipyridine-κ2N,N′)di-μ2-cyanido-dicyanido(μ-ethylenediamine)(ethylenediamine-κ2N,N′)cadmium(II)iron(II)] monohydrate]

Acta Crystallographica Section E Crystallographic Communications ◽

10.1107/s2056989016006848 ◽

2016 ◽

Vol 72 (5) ◽

pp. 741-746

Author(s):

Songwuit Chanthee ◽

Wikorn Punyain ◽

Supawadee Namuangrak ◽

Kittipong Chainok

Keyword(s):

Hydrogen Bonds ◽

Crystal Structures ◽

Layer Structure ◽

Three Dimensional ◽

Building Blocks ◽

Chain Structure ◽

Water Molecules ◽

Two Dimensional ◽

Lattice Water ◽

Π Stacking

The crystal structures of the building block tetramethylammonium (2,2′-bipyridine-κ2N,N′)tetracyanidoferrate(III) trihydrate, [N(CH3)4][Fe(CN)4(C10H8N2)]·3H2O, (I), and a new two-dimensional cyanide-bridged bimetallic coordination polymer, poly[[(2,2′-bipyridine-κ2N,N′)di-μ2-cyanido-dicyanido(μ-ethylenediamine-κ2N:N′)(ethylenediamine-κ2N,N′)cadmium(II)iron(II)] monohydrate], [CdFe(CN)4(C10H8N2)(C2H8N2)2]·H2O, (II), are reported. In the crystal of (I), pairs of [Fe(2,2′-bipy)(CN)4]−units (2,2′-bipy is 2,2′-bipyridine) are linked together through π–π stacking between the pyridyl rings of the 2,2′-bipy ligands to form a graphite-like structure parallel to theabplane. The three independent water molecules are hydrogen-bonded alternately with each other, forming a ladder chain structure withR44(8) andR66(12) graph-set ring motifs, while the disordered [N(CH3)4]+cations lie above and below the water chains, and the packing is stabilized by weak C—H...O hydrogen bonds. The water chains are further linked with adjacent sheets into a three-dimensional networkviaO—H...O hydrogen bonds involving the lattice water molecules and the N atoms of terminal cyanide groups of the [Fe(2,2′-bipy)(CN)4]−building blocks, forming anR44(12) ring motif. Compound (II) features a two-dimensional {[Fe(2,2′-bipy)(CN)4Cd(en)2]}nlayer structure (en is ethylenediamine) extending parallel to (010) and constructed from {[Fe(2,2′-bipy)(CN)4Cd(en)]}nchains interlinked by bridging en ligands at the Cd atoms. Classical O—H...N and N—H...O hydrogen bonds involving the lattice water molecule and N atoms of terminal cyanide groups and the N—H groups of the en ligands are observed within the layers. The layers are further connectedviaπ–π stacking interactions between adjacent pyridine rings of the 2,2′-bipy ligands, completing a three-dimensional supramolecular structure.

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NONORIENTABLE MANIFOLDS IN THREE-DIMENSIONAL VECTOR FIELDS

International Journal of Bifurcation and Chaos ◽

10.1142/s0218127403006777 ◽

2003 ◽

Vol 13 (03) ◽

pp. 553-570 ◽

Cited By ~ 15

Author(s):

HINKE M. OSINGA

Keyword(s):

Vector Field ◽

Periodic Orbit ◽

Vector Fields ◽

Invariant Manifolds ◽

Three Dimensional ◽

Period Doubling ◽

Building Blocks ◽

Two Dimensional ◽

Dimensional Vector ◽

Three Dimensional Vector Field

It is well known that a nonorientable manifold in a three-dimensional vector field is topologically equivalent to a Möbius strip. The most frequently used example is the unstable manifold of a periodic orbit that just lost its stability in a period-doubling bifurcation. However, there are not many explicit studies in the literature in the context of dynamical systems, and so far only qualitative sketches could be given as illustrations. We give an overview of the possible bifurcations in three-dimensional vector fields that create nonorientable manifolds. We mainly focus on nonorientable manifolds of periodic orbits, because they are the key building blocks. This is illustrated with invariant manifolds of three-dimensional vector fields that arise from applications. These manifolds were computed with a new algorithm for computing two-dimensional manifolds.

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Quick self-assembly of bio-inspired multi-dimensional well-ordered structures induced by ultrasonic wave energy

PLoS ONE ◽

10.1371/journal.pone.0246453 ◽

2021 ◽

Vol 16 (2) ◽

pp. e0246453

Author(s):

Connor Murphy ◽

Yunqi Cao ◽

Nelson Sepúlveda ◽

Wei Li

Keyword(s):

Ultrasonic Wave ◽

Wave Energy ◽

Self Assembly ◽

Mechanical Vibration ◽

Water Environment ◽

Three Dimensional ◽

Building Blocks ◽

Two Dimensional ◽

Ordered Structures ◽

Bottom Up

Bottom-up self-assembly of components, inspired by hierarchically self-regulating aggregation of small subunits observed in nature, provides a strategy for constructing two- or three-dimensional intriguing biomimetic materials via the spontaneous combination of discrete building blocks. Herein, we report the methods of ultrasonic wave energy-assisted, fast, two- and three-dimensional mesoscale well-ordered self-assembly of microfabricated building blocks (100 μm in size). Mechanical vibration energy-driven self-assembly of microplatelets at the water-air interface of inverted water droplets is demonstrated, and the real-time formation process of the patterned structure is dynamically explored. 40 kHz ultrasonic wave is transferred into microplatelets suspended in a water environment to drive the self-assembly of predesigned well-ordered structures. Two-dimensional self-assembly of microplatelets inside the water phase with a large patterned area is achieved. Stable three-dimensional multi-layered self-assembled structures are quickly formed at the air-water interface. These demonstrations aim to open distinctive and effective ways for new two-dimensional surface coating technology with autonomous organization strategy, and three-dimensional complex hierarchical architectures built by the bottom-up method and commonly found in nature (such as nacre, bone or enamel, etc.).

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Bio-assembling and Bioprinting for Engineering Microvessels from the Bottom Up

International Journal of Bioprinting ◽

10.18063/ijb.v7i3.366 ◽

2021 ◽

Vol 7 (3) ◽

pp. 366

Author(s):

Xiaoming Liu ◽

Tao Yue ◽

Masaru Kojima ◽

Qiang Huang ◽

Tatsuo Arai

Keyword(s):

Tissue Engineering ◽

Three Dimensional ◽

Building Blocks ◽

Two Dimensional ◽

Microvascular Network ◽

Bottom Up ◽

One Dimensional ◽

Micro Scale ◽

Formidable Challenge ◽

Manufacturing Techniques

Blood vessels are essential in transporting nutrients, oxygen, metabolic wastes, and maintaining the homeostasis of the whole human body. Mass of engineered microvessels is required to deliver nutrients to the cells included in the constructed large three-dimensional (3D) functional tissues by diffusion. It is a formidable challenge to regenerate microvessels and build a microvascular network, mimicking the cellular viabilities and activities in the engineered organs with traditional or existing manufacturing techniques. Modular tissue engineering adopting the “bottom-up” approach builds one-dimensional (1D) or two-dimensional (2D) modular tissues in micro scale first and then uses these modules as building blocks to generate large tissues and organs with complex but indispensable microstructural features. Building the microvascular network utilizing this approach could be appropriate and adequate. In this review, we introduced existing methods using the “bottom-up” concept developed to fabricate microvessels including bio-assembling powered by different micromanipulation techniques andbioprinting utilizing varied solidification mechanisms. We compared and discussed the features of the artificial microvessels engineered by these two strategies from multiple aspects. Regarding the future development of engineering the microvessels from the bottom up, potential directions were also concluded.

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Metastability relationship between two- and three-dimensional crystal structures: a case study of the Cu-based compounds

Scientific Reports ◽

10.1038/s41598-021-94034-6 ◽

2021 ◽

Vol 11 (1) ◽

Author(s):

Shota Ono

Keyword(s):

Crystal Structures ◽

Three Dimensional ◽

Building Blocks ◽

Two Dimensional ◽

3D Structures ◽

Metallic Element ◽

Computational Materials ◽

Dynamics Simulations ◽

Dimensional Crystal

AbstractSome of the three-dimensional (3D) crystal structures are constructed by stacking two-dimensional (2D) layers. To study whether this geometric concept, i.e., using 2D layers as building blocks for 3D structures, can be applied to computational materials design, we theoretically investigate the dynamical stability of copper-based compounds CuX (a metallic element X) in the B$$_h$$ h and L1$$_1$$ 1 structures constructed from the buckled honeycomb (BHC) structure and in the B2 and L1$$_0$$ 0 structures constructed from the buckled square (BSQ) structure. We demonstrate that (i) if CuX in the BHC structure is dynamically stable, those in the B$$_h$$ h and L1$$_1$$ 1 structures are also stable. Using molecular dynamics simulations, we particularly show that CuAu in the B$$_h$$ h and L1$$_1$$ 1 structures withstand temperatures as high as 1000 K. Although the interrelationship of the metastability between the BSQ and the 3D structures (B2 and L1$$_0$$ 0 ) is not clear, we find that (ii) if CuX in the B2 (L1$$_0$$ 0 ) structure is dynamically stable, that in the L1$$_0$$ 0 (B2) is unstable. This is rationalized by the tetragonal Bain path calculations.

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