Abstract
Controlled self-assembly of colloidal particles into predetermined organization facilitates the bottom-up manufacture of artificial materials with designated hierarchies and synergistically ...integrated functionalities. However, it remains a major challenge to assemble individual nanoparticles with minimal building instructions in a programmable fashion due to the lack of directional interactions. Here, we develop a general paradigm for controlled co-assembly of soft block copolymer micelles and simple unvarnished hard nanoparticles through variable noncovalent interactions, including hydrogen bonding and coordination interactions. Upon association, the hairy micelle corona binds with the hard nanoparticles with a specific valence depending exactly on their relative size and feeding ratio. This permits the integration of block copolymer micelles with a diverse array of hard nanoparticles with tunable chemistry into multidimensional colloidal molecules and polymers. Secondary co-assembly of the resulting colloidal molecules further leads to the formation of more complex hierarchical colloidal superstructures. Notably, such colloidal assembly is processible on surface either through initiating the alternating co-assembly from a micelle immobilized on a substrate or directly grafting a colloidal oligomer onto the micellar anchor.
The use of crystallization as a tool to control the self-assembly of polymeric and molecular amphiphiles in solution is attracting growing attention for the creation of non-spherical nanoparticles ...and more complex, hierarchical assemblies. In particular, the seeded growth method termed living crystallization-driven self-assembly (CDSA) has been established as an ambient temperature and potentially scalable platform for the preparation of low dispersity samples of core-shell fiber-like or platelet micellar nanoparticles. Significantly, this method permits predictable control of size, and access to branched and segmented structures where functionality is spatially-defined. Living CDSA operates under kinetic control and shows many analogies with living chain-growth polymerizations of molecular organic monomers that afford well-defined covalent polymers of controlled length except that it covers a much longer length scale (
ca.
20 nm to 10 μm). The method has been applied to a rapidly expanding range of crystallizable polymeric amphiphiles, which includes block copolymers and charge-capped homopolymers, to form assemblies with crystalline cores and solvated coronas. Living CDSA seeded growth methods have also been transposed to a wide variety of π-stacking and hydrogen-bonding molecular species that form supramolecular polymers in processes termed "living supramolecular polymerizations". In this article we outline the main features of the living CDSA method and then survey the promising emerging applications for the resulting nanoparticles in fields such as nanomedicine, colloid stabilization, catalysis, optoelectronics, information storage, and surface functionalization.
The use of crystallization as a tool to control the self-assembly of polymeric and molecular amphiphiles in solution is attracting growing attention for the creation of non-spherical nanoparticles and more complex, hierarchical assemblies.
Ultralong room‐temperature phosphorescence (RTP) is highly useful for information encryption, organic electronics, bioelectronics, etc. However, the preparation of related metal‐free materials with ...multiple colors across the full spectrum remains a major challenge. Herein, a facile method is developed to fabricate boron‐doped carbon dot (B‐CD) composites with full‐color long lifetime RTP continuously tailorable in the range of 466–638 nm simply by pyrolysis of the citric acid and boric acid precursors with various mass ratios at different temperatures. This leads to the formation of luminescent B‐CD centers in a rigid polycrystalline B2O3 matrix, which effectively stabilizes the triplet excited states of B‐CDs. Thus, the composites become phosphorescent over a relatively long period (5–12 s) after the removal of the irradiation source. Meanwhile, the increased particle size and oxidation degree of B‐CDs obtained at larger citric acid feeding or higher pyrolysis temperature continuously shift the phosphorescence from blue to red. Due to the formation of multiple luminescence centers, the RTP can also be finely modulated by the excitation wavelength. The resulting B‐CD composites with highly tunable long lifetime RTP further allow a variety of distinctive applications in multidimensional encryption handily utilizing space, time, and color variations.
Simple pyrolysis of citric acid and boric acid leads to the formation of carbon dot composites with highly tailorable full‐color ultralong room temperature phosphorescence, which subsequently favors a variety of distinctive applications in multidimensional encryption.
Nanographenes are emerging as a distinctive class of functional materials for electronic and optical devices. It is of remarkable significance to enrich the precise synthetic chemistry for these ...molecules. Herein, we develop a facile strategy to recompose helicenes into chiral nanographenes through a unique oxidative cyclo-rearrangement reaction. Helicenes with 7~9 ortho-fused aromatic rings are firstly oxidized and cyclized, and subsequently rearranged into nanographenes with an unsymmetrical helicoid shape through sequential 1,2-migrations. Such skeletal reconstruction is virtually driven by the gradual release of the strain of the highly distorted helicene skeleton. Importantly, the chirality of the helicene precursor can be integrally inherited by the resulting nanographene. Thus, a series of chiral nanographenes are prepared from a variety of carbohelicenes and heterohelicenes. Moreover, such cyclo-rearrangement reaction can be sequentially or simultaneously associated with conventional oxidative cyclization reactions to ulteriorly enrich the geometry diversity of nanographenes, aiming at innovative properties.
Self-assembly of molecular and block copolymer amphiphiles represents a well-established route to micelles with a wide variety of shapes and gel-like phases. We demonstrate an analogous process, but ...on a longer length scale, in which amphiphilic P-H-P and H-P-H cylindrical triblock comicelles with hydrophobic (H) or polar (P) segments that are monodisperse in length are able to self-assemble side by side or end to end in nonsolvents for the central or terminal segments, respectively. This allows the formation of cylindrical supermicelles and one-dimensional (1D) or 3D superstructures that persist in both solution and the solid state. These assemblies possess multiple levels of structural hierarchy in combination with existence on a multimicrometer-length scale, features that are generally only found in natural materials.
Symmetry breaking in the self-assembly of achiral constituents is of vital importance for the origin of molecular homochirality and developing advanced chiral materials. Here, we report a unique mode ...of spontaneous symmetry breaking in the aggregates of aza4helicenes with an achiral vibrating helical conjugated structure. The achiral molecules initially form clustered aggregates with a slight chiral bias of the P and M isomers, and subsequently the chiral imbalance is amplified by the conversion of the P and M conformations to favor a more thermodynamic stable π–π stacking (from PM to PP or MM stacking). The dynamical P/M transformation not only promotes the evolution of optical activity following the initial spontaneous symmetry breaking but also favors the healing of chirality after the majority is eliminated by heating. Notably, the aggregates reveal prominent circularly polarized luminescence with the absolute dissymmetry factor approaching 0.01. This work provides additional insights into the pathway of chiral symmetry breaking and illustrates a unique route to develop optically active materials from achiral helical molecules.
Fabrication of chiral materials and revealing the mechanisms involved in their formation are crucial issues in scientific research. The combination of cooperative self-assembly routes and the chiral ...templating process favors the formation of inorganic chiral materials with highly ordered mesostructures. This tutorial review highlights the recent research on chiral mesoporous silica (CMS) of hierarchical helical constructions transcribed from organic templates. The rules and mechanisms involved in the synthesis of CMS and related materials, especially the novel expression of chirality and imprinting of helical micellar superstructure by the functional groups immobilized on the mesopore surface, provide us with a deeper insight into the chiral self-assembly process and new strategies for the design and application of chiral materials. This review is addressed to researchers and students interested in chiral chemistry, supramolecular chemistry and mesoporous materials (53 references).
Life is an extremely delicate self-assembly system, where a rich array of small molecules, macromolecules and other entities associate and organize in an intrinsically diverse and precise manner. ...During the past few decades, scientists have devoted enormous efforts to fabricate functional materials, including the interesting self-assembled molecular devices that recently crowned with the 2016 Nobel Chemistry Prize, by self-assembly of natural and synthetic molecules/mac- romolecules. Nevertheless, it still remains an incredibly big challenge to approach the elegance of life self-assembly, predominantly as a consequence of limited diversity and accuracy of chemistry, structure, and supramolecular asso- ciation of the building blocks.
Distinctive upconversion or downshifting of lanthanide nanocrystals holds promise for biomedical and photonic applications. However, either process requires high-energy lasers at discrete wavelengths ...for excitation. Here we demonstrate that co-sensitization can break this limitation with ultrawide excitation bands. We achieve co-sensitization by employing Nd
and Ho
as the co-sensitizers with complementary absorptions from the ultraviolet to infrared region. Symmetric penta-layer core-shell nanostructure enables tunable fluorescence in the visible and the second near-infrared window when incorporating different activators (Er
, Ho
, Pr
, and Tm
). Transient spectra confirm the directional energy transfer from sensitizers to activators through the bridge of Yb
. We validate the features of the nanocrystals for low-powered white light-emitting diode-mediated whole-body angiography of mice with a signal-to-noise ratio of 12.3 and excitation-regulated encryption. This co-sensitization strategy paves a new way in lanthanide nanocrystals for multidirectional photon conversion manipulation and excitation-bandwidth-regulated fluorescence applications.
The preparation of colloidally stable, self-assembled materials with tailorable solid or hollow two-dimensional (2D) structures represents a major challenge. We describe the formation of uniform, ...monodisperse rectangular platelet micelles of controlled size by means of seeded-growth methods that involve the addition of blends of crystalline-coil block copolymers and the corresponding crystalline homopolymer to cylindrical micelle seeds. Sequential addition of different blends yields solid platelet block comicelles with concentric rectangular patches with distinct coronal chemistries. These complex nano-objects can be subject to spatially selective processing that allows their disassembly to form perforated platelets, such as well-defined hollow rectangular rings. The solid and hollow 2D micelles provide a tunable platform for further functionalization and potential for a variety of applications.
PDF
