scholarly journals 1,2,4-Triphospholyl anions – versatile building blocks for the formation of 1D, 2D and 3D assemblies

2015 ◽  
Vol 44 (22) ◽  
pp. 10245-10252 ◽  
Author(s):  
Claudia Heindl ◽  
Eugenia V. Peresypkina ◽  
Alexander V. Virovets ◽  
Vladislav Yu. Komarov ◽  
Manfred Scheer
Keyword(s):  
Supramolecular Chemistry ◽  
Self Assembly ◽  
Three Dimensional ◽  
Building Blocks ◽  
2D And 3D

The potential of K[P3C2R2] (R =tBu, Mes) as building blocks in metallo-supramolecular chemistry was investigated and self-assembly processes with Cu(i) halides resulted in the formation of a large variety of unprecedented one-, two- and even three-dimensional aggregates.

scholarly journals Supramolecular organic frameworks (SOFs): homogeneous regular 2D and 3D pores in water

2017 ◽  
Vol 4 (3) ◽  
pp. 426-436 ◽  
Author(s):  
Jia Tian ◽  
Hui Wang ◽  
Dan-Wei Zhang ◽  
Yi Liu ◽  
Zhan-Ting Li
Keyword(s):  
Solid State ◽  
Self Assembly ◽  
Organic Dyes ◽  
Three Dimensional ◽  
Building Blocks ◽  
Future Research ◽  
New Family ◽  
Molecular Building Blocks ◽  
Anionic Species ◽  
2D And 3D

Abstract Studies on periodic porosity and related properties and functions have been limited to insoluble solid-state materials. Self-assembly provides a straightforward and efficient strategy for the construction of soluble periodic porous supramolecular organic frameworks (SOFs) in water from rationally designed molecular building blocks. From rigid tri- and tetra-armed building blocks and cucurbitu[8]ril (CB[8]), a number of two-dimensional (2D) honeycomb, square and rhombic SOFs can be generated, which is driven by CB[8]-encapsulation-enhanced dimerization of two aromatic units on the periphery of the multi-armed molecules. By utilizing the same three-component host−guest motif as the driving force, three-dimensional (3D) diamondoid and cubic SOFs can be obtained from tetrahedral and [Ru(bipy)3]2+-derived octahedral monomers and CB[8]. All of the 2D and 3D periodic frameworks are soluble in water, and are able to maintain the periodicity as well as the pore sizes in the solid state. 3D SOFs are highly efficient homogeneous polycationic frameworks for reversible adsorption of anionic species including organic dyes, peptides, nucleic acids, drugs, dendrimers and Wells-Dawson-typed polyoxametallates (WD-POMs). WD-POM molecules adsorbed in the [Ru(bipy)3]2+-based SOF can catalyse the reduction of proton to H2 upon visible-light sensitization of [Ru(bipy)3]2+, which allows multiple electron transfer from [Ru(bipy)3]2+ to WD-POM. This review summarizes the design, formation and characterization of this new family of self-assembled frameworks, highlights their applications as homogeneous porous materials and finally outlines some future research directions.

Self-Assembly of Proteins into Three-Dimensional Structures Using Bio-Conjugation

2014 ◽  
Vol 1663 ◽  
Author(s):  
Garima Thakur ◽  
Kovur Prashanthi ◽  
Thomas Thundat
Keyword(s):  
Self Assembly ◽  
Three Dimensional ◽  
Gold Surface ◽  
Building Blocks ◽  
Growth Conditions ◽  
Base Layer ◽  
Chemical Structures ◽  
Molecular Building Blocks ◽  
Ring Structures ◽  
Self Assembled

ABSTRACTSelf–assembly of molecular building blocks provides an interesting route to produce well-defined chemical structures. Tailoring the functionalities on the building blocks and controlling the time of self-assembly could control the properties as well as the structure of the resultant patterns. Spontaneous self-assembly of biomolecules can generate bio-interfaces for myriad of potential applications. Here we report self-assembled patterning of human serum albumin (HSA) protein in to ring structures on a polyethylene glycol (PEG) modified gold surface. The structure of the self-assembled protein molecules and kinetics of structure formation entirely revolved around controlling the nucleation of the base layer. The formation of different sizes of ring patterns is attributed to growth conditions of the PEG islands for bio-conjugation. These assemblies might be beneficial in forming structurally ordered architectures of active proteins such as HSA or other globular proteins.

Case history of porphyrin J-aggregates: a personal point of view

2009 ◽  
Vol 13 (04n05) ◽  
pp. 461-470 ◽  
Author(s):  
Joaquim Crusats ◽  
Zoubir El-Hachemi ◽  
Carlos Escudero ◽  
Josep M. Ribó
Keyword(s):  
Supramolecular Chemistry ◽  
Self Assembly ◽  
Building Blocks ◽  
Point Of View ◽  
Water Soluble ◽  
The Self ◽  
Molecular Building Blocks ◽  
History Of ◽  
J Aggregates ◽  
The University

The formation and structure of the title aggregates are paradigms of the self-assembly of amphiphilic molecular building blocks in supramolecular chemistry. This review summarizes the research in the University of Barcelona on the homoassociation of the water soluble meso 4-sulfonatophenyl-and phenyl substituted porphyrins.

Salts of maleic and fumaric acids with organic polyamines: comparison of isomeric acids as building blocks in supramolecular chemistry

2003 ◽  
Vol 59 (1) ◽  
pp. 100-117 ◽  
Author(s):  
Katharine F. Bowes ◽  
George Ferguson ◽  
Alan J. Lough ◽  
Christopher Glidewell
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Supramolecular Chemistry ◽  
Fumaric Acid ◽  
Maleic Acid ◽  
Rotation Axis ◽  
Three Dimensional ◽  
Building Blocks ◽  
Ionic Components ◽  
Acid Compound

Maleic acid and fumaric acid both readily form adducts with organic diamines: maleic acid usually forms 2:1 adducts with bases, while fumaric acid usually forms 1:1 adducts, and the supramolecular stuctures within the two series are not simply related. The 1:2 adducts formed by 1,2-bis(4-pyridyl)ethane and by 4,4′-bipyridyl, respectively, with maleic acid, compounds (1) and (2), are salts [{(diamine)H2}2+]·[(C4H3O4)−]2 in which the cations lie across a centre of inversion and a twofold rotation axis, respectively. The ions are linked by N—H...O hydrogen bonds into three-ion aggregates, which are further linked by C—H...O hydrogen bonds into two- and three-dimensional arrays, respectively. In the fumarate salts formed by 2,2′-dipyridylamine (1:1) and 1,4-diazabicyclo[2.2.2]octane (1:2), compounds (3) and (4), the ionic components are linked into molecular ladders. The 1:1 adduct of 4,4′-bipyridyl and fumaric acid, compound (5), contains two neutral components, both of which lie across centres of inversion; these components are linked into chains by a single O—H...N hydrogen bond and thence into sheets by C—H...O hydrogen bonds. The corresponding adduct formed by 1,4-diazabicyclo[2.2.2]octane, compound (6), is a salt that again contains chains linked into sheets by C—H...O hydrogen bonds. In the 1:1 adducts, compounds (7), (8) and (10), that are formed between 1,2-bis(4-pyridyl)ethane, 4,4′-trimethylenedipyridine and hexamethylenetetramine, respectively, with fumaric acid, and in the 1:2 adduct, compound (9), of 2,2′-dipyridylamine and maleic acid, the chains that are generated by the hard hydrogen bonds are linked by C—H...O hydrogen bonds to form, in each case, a single three-dimensional framework. In the 1:1 adduct, compound (11), of 2,2′-bipyridyl and fumaric acid the hydrogen bonds generate two interwoven three-dimensional frameworks.

Zeolitic Host–Guest Interactions and Building Blocks for the Self-Assembly of Complex Materials

MRS Bulletin ◽  
2005 ◽  
Vol 30 (10) ◽  
pp. 713-720 ◽  
Author(s):  
Thomas Bein
Keyword(s):  
Self Assembly ◽  
Electrostatic Interactions ◽  
Spatial Organization ◽  
Organic Dyes ◽  
Three Dimensional ◽  
Internal Surface ◽  
Building Blocks ◽  
Three Dimensional Objects ◽  
Surface Areas ◽  
Catalyst Systems

AbstractOrdered nanoscale pore systems such as those represented by zeolites offer many opportunities for the design of complex functional systems via self-assembly.With their large internal surface areas and tunable, well-defined crystalline pore structures that allow molecular sieving and ion exchange, zeolites can be adapted for numerous applications. The nanoscale reactors present in zeolite pore systems have been explored as structural templates for the spatial organization of numerous guests. Examples from various fields are discussed, such as the stabilization of organic dyes for the construction of energy transfer and storage systems, the construction of host–guest hybrid catalyst systems, and the encapsulation of conducting or semiconducting nanoscale wires and clusters. More complex, hierarchical forms of nanostructured matter become accessible when zeolite crystals are used as building blocks for the selfassembly of thin films or three-dimensional objects. A combination of weaker and stronger interactions ranging from dispersive forces, hydrogen bonding, and electrostatic interactions to covalent bonding can be used to build functional hierarchical constructs. Several examples and novel applications of such systems will be discussed, including oriented channel systems, chemical sensors, and hierarchical pore systems for catalytic reactions.

scholarly journals A versatile strategy towards non-covalent functionalization of graphene by surface-confined supramolecular self-assembly of Janus tectons

2015 ◽  
Vol 6 ◽  
pp. 632-639 ◽  
Author(s):  
Ping Du ◽  
David Bléger ◽  
Fabrice Charra ◽  
Vincent Bouchiat ◽  
David Kreher ◽  
...  
Keyword(s):  
Self Assembly ◽  
Three Dimensional ◽  
Building Blocks ◽  
The Other ◽  
Two Dimensional ◽  
Covalent Functionalization ◽  
Flat Surfaces ◽  
Carbon Based

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.

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 A stimuli-responsive, pentapeptide, nanofiber hydrogel for tissue engineering

2019 ◽  
Author(s):  
James D. Tang ◽  
Cameron Mura ◽  
Kyle J. Lampe
Keyword(s):  
Tissue Engineering ◽  
Self Assembly ◽  
Amyloid Fibrils ◽  
Culture Media ◽  
Solvent Accessibility ◽  
Three Dimensional ◽  
Building Blocks ◽  
Weight Percent ◽  
Oligodendrocyte Progenitor Cells ◽  
Self Healing

ABSTRACTShort peptides are uniquely versatile building blocks for self-assembly. Supramolecular peptide assemblies can be used to construct functional hydrogel biomaterials—an attractive approach for neural tissue engineering. Here, we report a new class of short, five-residue peptides that form hydrogels with nanofiber structures. Using rheology and spectroscopy, we describe how sequence variations, pH, and peptide concentration alter the mechanical properties of our pentapeptide hydrogels. We find that this class of seven unmodified peptides forms robust hydrogels from 0.2–20 kPa at low weight percent (less than 3 wt. %) in cell culture media, and undergoes shear-thinning and rapid self-healing. The peptides self-assemble into long fibrils with sequence-dependent fibrillar morphologies. These fibrils exhibit a unique twisted ribbon shape, as visualized by TEM and Cryo-EM imaging, with diameters in the low tens of nanometers and periodicities similar to amyloid fibrils. Experimental gelation behavior corroborates our molecular dynamics simulations, which demonstrate peptide assembly behavior, an increase in β-sheet content, and patterns of variation in solvent accessibility. Our Rapidly Assembling Pentapeptides for Injectable Delivery (RAPID) hydrogels are syringe-injectable and support cytocompatible encapsulation of oligodendrocyte progenitor cells (OPCs), as well as their proliferation and three-dimensional process extension. Furthermore, RAPID gels protect OPCs from mechanical membrane disruption and acute loss of viability when ejected from a syringe needle, highlighting the protective capability of the hydrogel as potential cell carriers for trans-plantation therapies. The tunable mechanical and structural properties of these supramolecular assemblies are shown to be permissive to cell expansion and remodeling, making this hydrogel system suitable as an injectable material for cell delivery and tissue engineering applications.

Chiral versus racemic building blocks in supramolecular chemistry: malate salts of organic diamines

2002 ◽  
Vol 58 (3) ◽  
pp. 530-544 ◽  
Author(s):  
Dorcas M. M. Farrell ◽  
George Ferguson ◽  
Alan J. Lough ◽  
Christopher Glidewell
Keyword(s):  
Hydrogen Bonds ◽  
Supramolecular Chemistry ◽  
Malic Acid ◽  
Three Dimensional ◽  
Building Blocks ◽  
Partial Transfer ◽  
Molecular Components ◽  
N Vector ◽  
Hydrogen Bonded

(S)-Malic acid forms a salt with N,N′-dimethylpiperazine, [MeN(CH2CH2)2NMe]H2 2+·2C4H5O5 − (1) (triclinic, P1, Z′ = 1), in which the cations link pairs of hydrogen-bonded anion chains to form a molecular ladder. With 4,4′-bipyridyl, (S)-malic acid forms a 1:1 adduct which crystallizes from methanol to yield two polymorphs, (2) (triclinic, P1, Z′ = 1) and (3) (monoclinic, C2, Z′ = 1), while racemic malic acid with 4,4′-bipyridyl also forms a 1:1 adduct, (4) (monoclinic, P21/c, Z′ = 1). In each of (2), (3) and (4) the components are linked by O—H...N and N—H...O into chains of alternating bipyridyl and malate units, which are linked into sheets by O—H...O hydrogen bonds. In each of the 1:1 adducts (5) and (6), formed by, respectively, (S)-malic acid and racemic malic acid with 1,2-bis(4′-pyridyl)ethene, the diamine is disordered over two sets of sites, related by a 180° rotation about the N...N vector. In (5), (C12H10N2)H+·C4H5O5 − (triclinic, P1, Z′ = 1), the components are again linked by a combination of N—H...O and O—H...O hydrogen bonds into sheets, while in (6) (triclinic, P{\overline 1}, Z′ = 0.5) there is only partial transfer of the H atom from O to N and the malate component is disordered across a centre of inversion. With 1,4-diazabicyclo[2.2.2]octane, racemic malic acid forms a 1:2 salt, [(C6H12N2)H2]2+·2C4H5O5 − (7) (monoclinic, P21/c, Z′ = 2), while (S)-malic acid forms a 1:1 adduct, (8) (monoclinic, P21, Z′ = 3). There are thus six independent molecular components in each. In (7) the ions are linked by an extensive series of N—H...O and O—H...O hydrogen bonds into a three-dimensional framework, but in (8) there is extensive disorder involving all six components, and no refinement proved to be feasible.

Functional self-assembling polypeptide bionanomaterials

2012 ◽  
Vol 40 (4) ◽  
pp. 629-634 ◽  
Author(s):  
Tibor Doles ◽  
Sabina Božič ◽  
Helena Gradišar ◽  
Roman Jerala
Keyword(s):  
Self Assembly ◽  
Biological Systems ◽  
Three Dimensional ◽  
Coiled Coil ◽  
Chemical Properties ◽  
Building Blocks ◽  
External Signal ◽  
Form Complex ◽  
Cell Factories ◽  
Self Assembling

Bionanotechnology seeks to modify and design new biopolymers and their applications and uses biological systems as cell factories for the production of nanomaterials. Molecular self-assembly as the main organizing principle of biological systems is also the driving force for the assembly of artificial bionanomaterials. Protein domains and peptides are particularly attractive as building blocks because of their ability to form complex three-dimensional assemblies from a combination of at least two oligomerization domains that have the oligomerization state of at least two and three respectively. In the present paper, we review the application of polypeptide-based material for the formation of material with nanometre-scale pores that can be used for the separation. Use of antiparallel coiled-coil dimerization domains introduces the possibility of modulation of pore size and chemical properties. Assembly or disassembly of bionanomaterials can be regulated by an external signal as demonstrated by the coumermycin-induced dimerization of the gyrase B domain which triggers the formation of polypeptide assembly.

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