Macroscopic Assembly of Chiral Hydrogen-bonded Metal-free Supramolecular Glasses for Enhanced Color-tunable Ultralong Room Temperature Phosphorescence.

Glassy materials, with desirable mechanical rigidity, shaping ability, high transparency, are attracting great interest in diverse fields. However, optically bulk molecule-based glasses are still rare, mainly due to limited monomeric species and harsh preparation conditions. Herein, we report a facile bottom-up solution fabrication process to obtain metal-free supramolecular glasses (SMGs) at the macroscopic scale using L-Histidine and hexamethylenetetramine as building blocks. The chiral SMGs possess color-tunable ultralong room temperature phosphorescence (decay lifetime up to 141.2 ms) and circular polarized luminescence (g factor up to 8.7×10-3 ). The strong hydrogen bonds effectively drive the formation of SMGs, and provide a rigid microenvironment to boost triplet exciton generation. By virtue of excitation- and temperature-dependent ultralong phosphorescence of the SMGs, applications including multicolored displays, visual UV detection, and persistently luminescent thermometer are demonstrated.

Macroscopic self-assembly based on complementary interactions between nucleobase pairs.

We have created a selective macroscopic self-assembly process by using polymer gels modified with complementary DNA oligonucleotides or nucleobases. The hydrogels modified with complementary DNA oligonucleotides adhered to each other by simple contact. The organogels modified with complementary nucleobases selectively formed macroscopic assemblies by agitation in nonpolar organic solvents. The adhesion strength of each gel was estimated semi-quantitatively by stress-strain measurements. We achieved direct adhesion between macroscopic materials both in water and in organic media, based on complementary hydrogen bonds.

pH-Switchable macroscopic assembly through host-guest inclusion.

A novel pH-switchable macroscopic assembly is reported using alginate-based hydrogels functionalized with host (α-cyclodextrin, αCD) and guest (diethylenetriamine, DETA) moieties. Since the interaction of αCD and DETA is pH sensitive, the host hydrogel and guest hydrogel could adhere together when the pH is 11.5 and separate when the pH is 7.0. Furthermore, this pH-controlled adhesion and dissociation shows a good reversibility. The host and guest polymers have good biocompatibility; therefore, this pH-sensitive macroscopic assembly shows great potential in biotechnological and biomedical applications.

Ultrafast Macroscopic Assembly of High-Strength Graphene Oxide Membranes by Implanting an Interlaminar Superhydrophilic Aisle.

A macroscopic-assembled graphene oxide (GO) membrane with sustainable high strength presents a bright future for its applications in ionic and molecular filtration for water purification or fast force response for sensors. Traditionally, the bottom-up macroscopic assembly of GO sheets is optimized by widening the interlaminar space for expediting water passage, frequently leading to a compromise in strength, assembly time, and ensemble thickness. Herein, we rationalize this strategy by implanting a superhydrophilic bridge of cobalt-based metal-organic framework nanosheets (NMOF-Co) as an additional water "aisle" into the interlaminar space of GO sheets (GO/NMOF-Co), resulting in a high-strength macroscopic membrane ensemble with tunable thickness from the nanometer scale to the centimeter scale. The GO/NMOF-Co membrane assembly time is only 18 s, 30800 times faster than that of pure GO (154 h). More importantly, the obtained membrane attains a strength of 124.4 MPa, which is more than 3 times higher than that of the GO membrane prepared through filtration. The effect of hydrophilicity on membrane assembly is also investigated by introducing different intercalants, suggesting that, except for the interlamellar spacing, the interlayered hydrophilicity plays a more decisive role in the macroscopic assembly of GO membranes. Our results give a fundamental implication for fast macroscopic assembly of high-strength 2D materials.

Filamentous fungal in situ biosynthesis of heterogeneous Au/Cd0.5Zn0.5S nano-photocatalyst: A macroscopic assembly strategy for preparing composite mycelial pellets with visible light degradation ability.

Visible light degradation is a green and economic technology for sewage treatment receiving widespread attention. Here, the filamentous fungus Phomopsis sp. XP-8 was developed as a bioreactor to successively biosynthesize Cd0.5Zn0.5S quantum dots and gold nanoparticles (AuNPs) in situ and formed heterogeneous Au/Cd0.5Zn0.5S nano-photocatalyst inside cells. This strategy synchronously mediates the microscopic and macroscopic assembly of zero-dimensional materials by microorganisms. The heterogeneous catalyst functionalized composite mycelium pellets (CMP) not only have excellent visible light degradation activity but some unique characteristics. The outstanding organic dye biosorption capacity of CMP increases the contact rate between organic dyes and nano-catalysts, improving catalytic activity. High mechanical strength makes CMP easy to separate and recycle, which overcomes the difficulty of nano-catalyst recovery after use and avoids creating secondary pollution to the environment. This study not only broadens the means of heterogeneous nano-catalyst synthesis but also provides a new perspective on the macroscopic assembly of nanomaterials.

2D Graphene-Based Macroscopic Assemblies for Micro-Supercapacitors.

Rapid development of portable and wearable electronic devices has triggered increased research interest in small-scale power sources, especially in micro-supercapacitors (MSCs) because of their high power densities, long service life, and ability to be charged and discharged quickly. Graphene, an ideal two-dimensional energy-storage electrode material with good conductivity, high quantum capacitance, and large specific surface area, can be used as a building block for MSCs with multi-dimensional architectures. Considerable efforts have been devoted to constructing structures with different dimensions for advanced graphene-based MSCs (GMSCS). In this Review, we summarize the recent progress of graphene-based macroscopic assemblies in MSCs, including 1D fiber GMSCs, 2D planar GMSCs; and 3D in-plane or stacked GMSCs, and discuss the relationship between the structures and applications of the devices. In addition, future prospects and challenges in the MSCs are also discussed.

Controlled Assembly of Luminescent Lanthanide-Organic Frameworks via Post-Treatment of 3D-Printed Objects.

Complex multiscale assemblies of metal-organic frameworks are essential in the construction of large-scale optical platforms but often restricted by their bulk nature and conventional techniques. The integration of nanomaterials and 3D printing technologies allows the fabrication of multiscale functional architectures. Our study reports a unique method of controlled 3D assembly purely relying on the post-printing treatment of printed constructs. By immersing a 3D-printed patterned construct consisting of organic ligand in a solution of lanthanide ions, in situ growth of lanthanide metal-organic frameworks (LnMOFs) can rapidly occur, resulting in macroscopic assemblies and tunable fluorescence properties. This phenomenon, caused by coordination and chelation of lanthanide ions, also renders a sub-millimeter resolution and high shape fidelity. As a proof of concept, a type of 3D assembled LnMOFs-based optical sensing platform has demonstrated the feasibility in response to small molecules such as acetone. It is anticipated that the facile printing and design approach developed in this work can be applied to fabricate bespoke multiscale architectures of functional materials with controlled assembly, bringing a realistic and economic prospect.

Toward Efficient Preconcentrating Photocatalysis: 3D g-C3N4 Monolith with Isotype Heterojunctions Assembled from Hybrid 1D and 2D Nanoblocks.

The macroscopic integration of the microscopic catalyst is one of the most promising strategies for photocatalytic technology in facing practical applications. However, in addition to the unsatisfactory photoactivated exciton separation, a new problem restricting the catalytic efficiency is the unmatched kinetics between the reactant diffusion and the photochemical reaction. Here, we report an isotype heterojunctional three-dimensional g-C3N4 monolith which is assembled from the hybrid building blocks of the nanowires and nanosheets. Benefiting from its hierarchically porous network and abundant heterojunctions, this catalytic system exhibits inherently promoted efficiency in light absorption and exciton separation, thus leading to a desirably improved photocatalytic performance. Furthermore, thanks to the structural and functional advantages of the constructed g-C3N4 monolith, a novel strategy of preconcentrating photocatalysis featuring the successive filtration, adsorption, and photocatalysis has been further developed, which could technically coordinate the kinetic differences and result in over-ten-time enhancement on the efficiency compared with the traditional photocatalytic system. Beyond providing new insights into the structural design and innovative application of the monolithic photocatalyst, this work may further open up novel technological revolutions in sewage treatment, air purification, microbial control, etc.

Self-Assembly of Hydrosoluble Carbon Nanotubes into Macroscopic Belts.

A simple approach for the synthesis of a truly neutral aqueous solution of shortened carbon nanotubes (CNTs) is presented. Upon evaporation of the solvent, the shortened CNTs self-assemble into belt-like macroscopic structures of approximately 3 cm in length. After the annealing process, the macroscopic assembly exhibits a good electrical conductivity of approximately 140 S cm-1 . The possible self-assembly process is also discussed.