Breaking of Lateral Symmetry in Two-Dimensional Crystallization-Driven Self-Assembly on a Surface.

Symmetry breaking is prevalent in nature and provides distinctive access to hierarchical structures for artificial materials. However, it is rarely explored in two-dimensional (2D) entities, especially for lateral asymmetry. Herein, we describe a unique symmetry breaking process in surface-initiated 2D living crystallization-driven self-assembly. The 2D epitaxial growth occurs only at one lateral side of the immobilized cylindrical micelle seeds, accessing unilateral platelets with the yield increasing with the seed length, the growth temperature, and poly(2-vinylpyridine) corona length (maximum = 92%). Generally, the tilted immobilization of seeds blocks one lateral side and triggers the lateral symmetry breaking, where the intensity and spatial arrangement of seed-surface interactions dictate the regulation. Segmented unilateral platelets with segmented corona regions are further fabricated with the addition of different blended unimers. Remarkably, discrete slope-like and dense blade-like platelet arrays grow off the surface when seeds are compactly aligned either with spherical micelles or themselves. This strategy provides nanoscale insights into the symmetry breaking in long-range self-assembly and would be promising for the design of innovative colloids and smart surfaces.

π-Extended Diaza[7]helicenes with Dual Negatively Curved Heptagons: Extensive Synthesis and Spontaneous Resolution into Strippable Homochiral Lamellae with Helical Symmetry.

We report a unique category of π-extended diaza[7]helicenes with double negative curvatures. This is achieved by two-fold regioselective heptagonal cyclization of the oligoarylene-carbazole precursors through either intramolecular C-H arylation or Scholl reaction. The fusion of two heptagonal rings in the helical skeleton dramatically increases the intramolecular strain and forces the two terminal carbazole moieties to stack in a compressed fashion. The presence of the deformable negatively curved heptagonal rings endows the resulting diaza[7]helicenes with dynamic chiral skeletons, aggregation-induced emission feature and relatively low racemization barrier of ca. 25.6 kcal mol-1 . Further π-extension on the carbazole moieties subsequently leads to a more sophisticated C2 -symmetric homochiral triple helicene. Notably, these π-extended diaza[7]helicenes show structure-dependent stacking upon crystallization, switching from heterochiral packing to intra-layer homochiral stacking. Interestingly, the C2 -symmetric triple helicene molecules spontaneously resolve into a homochiral lamellar structure with 31 helix symmetry. Upon ultrasonication in a nonsolvent, the crystals can be readily exfoliated into large-area ultrathin nanosheets with height of ca. 4.4 nm corresponding to two layers of stacked triple helicene molecules and relatively thicker nanosheets constituted by even-numbered molecular lamellae. Moreover, regular hexagonal thin platelets with size larger than 30 µm can be readily fabricated by flash aggregation.

Surface-Initiated Living Self-Assembly of Polythiophene-Based Conjugated Block Copolymer into Erect Micellar Brushes.

Nanostructured conjugated polymers are of widespread interest due to their broad applications in organic optoelectronic devices, biomedical sensors and other fields. However, the alignment of conjugated nanostructures perpendicular to a surface remains a critical challenge. Herein, we report a facile method to directly self-assemble a poly(3-(2-ethylhexyl)thiophene), P3EHT-based block copolymer into densely aligned micellar brushes through surface-initiated living crystallization-driven self-assembly. The presence of an ethyl pendant on the side group intrinsically moderates the crystallization rate of the polythiophene main chains, and hence favors the controlled living growth of long conjugated fibers and the subsequent fabrication of conjugated micellar brushes. The corona of the micellar brush can be further decorated with platinum nanoparticles, which enables the formation of erect nanoarrays with heights up to 2700 nm in the dried state. This also renders the micellar brush catalytically active toward hydrogen evolution reaction, which shows a low overpotential of 27 mV at 10 mA cm-2 . Notably, the P3EHT-based micellar brush can simultaneously grow with polyferrocenyldimethylsilane, PFS-based micellar brush on the same surface without any significant interference between the two systems. Thus, these two micellar brushes can be patterned through site-selective immobilization of two types of seeds followed by independent living self-assembly.

Polymer Coating with Balanced Coordination Strength and Ion Conductivity for Dendrite-Free Zinc Anode.

Decorating Zn anodes with functionalized polymers is considered as an effective strategy to inhibit dendrite growth. However, this normally brings extra interfacial resistance rendering slow reaction kinetics of Zn2+ . Herein, a poly(2-vinylpyridine) (P2VP) coating with modulated coordination strength and ion conductivity for dendrite-free Zn anode is reported. The P2VP coating favors a high electrolyte wettability and rapid Zn2+ migration speed (Zn2+ transfer number, tZn 2+ = 0.58). Electrostatic potential calculation shows that P2VP mildly coordinates with Zn2+ (adsorption energy = -0.94 eV), which promotes a preferential deposition of Zn along the (002) crystal plane. Notably, the use of partially (26%) quaternized P2VP (q-P2VP) further reduces the interfacial resistance to 126 Ω, leading to a high ion migration speed (tZn 2+ = 0.78) and a considerably low nucleation overpotential (18 mV). As a result of the synergistic effect of mild coordination and partial electrolysis, the overpotential of the q-P2VP-decorated Zn anode retains at a considerably low level (≈46 mV) over 1000 h at a high current density of 10 mA cm-2 . The assembled (NH4 )2 V6 O16 ·1.5H2 O || glass fiber || q-P2VP-Zn full cell reveals a lower average capacity decay rate of only 0.018% per cycle within 500 cycles at 1 A g-1 .

Initial analytical theory of plasma disruption and experimental evidence.

It is a great physical challenge to achieve controlled nuclear fusion in magnetic confinement tokamak and solve energy shortage problem for decades. In tokamak plasma, large-scale plasma instability called disruption will halt power production of reactor and damage key components. Prediction and prevention of plasma disruption is extremely urgent and important. However, there is no analytical theory can elucidate plasma disruption physical mechanism yet. Here we show an analytical theory of tokamak plasma disruption based on nonextensive geodesic acoustic mode theory, which can give the physical mechanism of disruption. The proposed theory has not only been confirmed by experimental data of disruption on T-10 device, but also can explain many related phenomena around plasma disruption, filling the gap in physical mechanism of tokamak plasma disruption.

Helicity-modulated remote C-H functionalization.

Remote C-H functionalization is highly important for the conversion and utilization of arenes, but the conventional routes are comprehensively developed with the assistance of transition metal catalysts or templates. We report a facile metal/template-free electrochemical strategy for remote C-H functionalization in a helical system, where aromatic or aliphatic hydrogen act as a directing group to promote the alkoxylation at the opposite site of the helical skeleton by generating a unique helical "back-biting" environment. Such helicity-modulated C-H functionalization is prevalent for carbo[n]helicenes (n = 6 to 9, primitive or substituted) and hetero[6]helicenes and also occurs when the aryl hydrogen on the first position is replaced by a methyl group or a phenyl group. Thus, the relatively inert helicene skeleton can be precisely furnished with a rich array of alkoxy pendants with tunable functional moieties. Notably, the selective decoration of a methoxy group on N-methylated aza[6]helicene close or distant to the nitrogen atom leads to distinct luminescence variation upon changing the solvents.

DNA-induced circularly polarized luminescence of helicene racemates.

Enantiopure helicenes have been extensively investigated due to their outstanding chiroptical properties, while helicene racemates are considered as chiroptically silent. Here, we describe a facile method to produce circularly polarized luminescence (CPL) from helicene racemates via supramolecular association with DNA in aqueous solution. Racemic cationic helicene derivatives are immobilized in the grooves of commercially available double-stranded right-handed DNA, and the discrimination of left- and right-handed helicenes by chiral DNA is monitored by single molecule force spectroscopy. This subsequently leads to the generation of prominent CPL with dissymmetric factor |glum | of close to 0.01, which is approximate to enantiopure helicenes. The strategy developed in this work avoids the tedious and expensive chiral resolution process and provides a distinctive insight into the fabrication of CPL-emitting systems.

Ultra-wideband-responsive photon conversion through co-sensitization in lanthanide nanocrystals.

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 Nd3+ and Ho3+ 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 (Er3+, Ho3+, Pr3+, and Tm3+). Transient spectra confirm the directional energy transfer from sensitizers to activators through the bridge of Yb3+. 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.

Molecular Engineering of Colloidal Atoms.

Creation of architectures with exquisite hierarchies actuates the germination of revolutionized functions and applications across a wide range of fields. Hierarchical self-assembly of colloidal particles holds the promise for materialized realization of structural programing and customizing. This review outlines the general approaches to organize atom-like micro- and nanoparticles into prescribed colloidal analogs of molecules by exploiting diverse interparticle driving motifs involving confining templates, interactive surface ligands, and flexible shape/surface anisotropy. Furthermore, the self-regulated/adaptive co-assembly of simple unvarnished building blocks is discussed to inspire new designs of colloidal assembly strategies.

[1,4]Diazocine-Embedded Electron-Rich Nanographenes with Cooperatively Dynamic Skeletons.

Curved nanographenes (NGs) are emerging as promising candidates for organic optoelectronics, supramolecular materials, and biological applications. Here we report a distinctive type of curved NGs bearing a [1,4]diazocine core that is fused with four pentagonal rings. This is formed by Scholl-type cyclization of two adjacent carbazole moieties through an unusual diradical cation mechanism followed by C-H arylation. Owing to the strain in the unique 5-5-8-5-5-membered ring skeleton, the resulting NG adopts an interesting concave-convex cooperatively dynamic structure. By peripheral π-extension, a helicene moiety with fixed helical chirality can be further mounted to modulate the vibration of the concave-convex structure, through which the distant bay region of the curved NG inherits the chirality of the helicene moiety in a reversed fashion. The [1,4]diazocine-embedded NGs show typical electron-rich characteristics and form charge transfer complexes with tunable emissions with a series of electron acceptors. The relatively protruding armchair edge also allows the fusion of three NGs into a C2 symmetric triple diaza[7]helicene which reveals a subtle balance of fixed and dynamic chirality.

Soft nanobrush-directed multifunctional MOF nanoarrays.

Controlled growth of well-oriented metal-organic framework nanoarrays on requisite surfaces is of prominent significance for a broad range of applications such as catalysis, sensing, optics and electronics. Herein, we develop a highly flexible soft nanobrush-directed synthesis approach for precise in situ fabrication of MOF nanoarrays on diverse substrates. The soft nanobrushes are constructed via surface-initiated living crystallization-driven self-assembly and their active poly(2-vinylpyridine) corona captures abundant metal cations through coordination interactions. This allows the rapid heterogeneous growth of MOF nanoparticles and the subsequent formation of MIL-100 (Fe), HKUST-1 and CUT-8 (Cu) nanoarrays with tailored heights of 220~1100 nm on silicon wafer, Ni foam and ceramic tube. Auxiliary functional components including metal oxygen clusters and precious metal nanoparticles can be readily incorporated to finely fabricate hybrid structures with synergistic features. Remarkably, the MIL-100 (Fe) nanoarrays doped with Keggin H3PMo10V2O40 dramatically boost formaldehyde selectivity up to 92.8% in catalytic oxidation of methanol. Moreover, the HKUST-1 nanoarrays decorated with Pt nanoparticles show exceptional sensitivity to H2S with a ppb-level detection limit.

Diverse Supports for Immobilization of Catalysts in Continuous Flow Reactors.

The rapid development of continuous flow processes is driving innovations in various chemical syntheses and industrial productions. Immobilizing catalysts in flow reactors allows transformations with high-efficiency and excludes the subsequent separation procedures. This concept outlines the approaches to incorporate catalysts within flow reactors, with particular focus on the application of additional supports including inorganic materials like silica, zeolite and reduced graphene oxide, polymeric materials like polymer packings, monoliths, cross-linked gels and polymer brushes, and other materials for specific conditions like transparent glass fibers and glass beads. Furthermore, advanced methods to develop ordered micro-/nanoarrays from internal walls of flow channels for immobilization of catalysts as well as application of innovative vortex fluidic devices are discussed to inspire new designs of supports for novel fluidic reactors with broad applications.

"Self-Adaptive" Coassembly of Colloidal "Saturn-like" Host-Guest Complexes Enabled by Toroidal Micellar Rubber Bands.

The creation of inclusion complexes with "Saturn-like" geometries has attracted increasing attention for supramolecular systems, but expansion of the concept to nanoscale colloidal systems remains a challenge. Here, we report a strategy to assemble toroidal polyisoprene-b-poly(2-vinylpyridine) (PI-b-P2VP) block copolymer micelles with a PI core and a P2VP corona and inorganic (e.g., silica) nanoparticles of variable shape and dimensions into "Saturn-like" constructs with high fidelity and yield. The precise nesting of the nanoparticles between the toroidal building units is realized by virtue of hydrogen bonding and self-adaptive expansion of the flexible toroidal units enabled by a flexible, low Tg PI core. Once the toroidal units are cross-linked, the self-adaptive feature is lost and coassembly yields instead out-of-cavity bound nanoparticles. "Saturn-like" assemblies can also be formed along silica nanosphere-decorated cylindrical micelles or, alternatively, at the hydroxyl-functionalized termini of cylindrical micelles to yield colloidal [3]rotaxanes.

Initial measurement of ion nonextensive parameter with geodesic acoustic mode theory.

The consideration of nonextensivity effects is crucial to the accurate diagnosis of plasma parameters; common plasma nonextensive parameters include electron nonextensive parameter and ion nonextensive parameter, and the former can be measured, while the ion nonextensive parameter cannot be measured yet. Here we show the measurement of ion nonextensive parameter of plasma based on the theory of nonextensive geodesic acoustic modes. We assume that the plasma to be measured can be described by nonextensive statistical mechanics, and on this basis, the nonextensive geodesic acoustic mode theory is established. Utilizing this theory, we have measured the ion nonextensive parameter [Formula: see text] which cannot be diagnosed even by a nonextensive single electric probe. Our research points out that the proposed measurement method of ion nonextensive parameter may play a role in plasma diagnosis and will help us to grasp the nonextensivity of plasma more precisely. We hope the proposed method of ion nonextensive parameter diagnosis based on the nonextensive geodesic acoustic mode theory can be the starting point of more complex ion nonextensive parameter diagnosis methods. In addition, the measurement of ion nonextensive parameter is closely related to the study of various plasma waves, instabilities, turbulence and abnormal transport, and a defined and quantitative test of nonextensive geodesic acoustic mode theory will bound up deeply with such developments.

Transformation of Crowded Oligoarylene into Perylene-Cored Chiral Nanographene by Sequential Oxidative Cyclization and 1,2-Phenyl Migration.

Synthetic innovation for constructing sophisticated nanographenes is of fundamental significance for a variety of advanced applications. Herein, we report a distinctive method to prepare π-extended chiral nanographenes with 29 benzenoid rings and two helical breaches from a highly crowded perylene-cored oligoarylene precursor. Under Scholl's conditions, the reaction predominantly involves the regioselective and sequential cyclization in the peri- and bay regions of the perylene core, and the complanation of the 1-phenyl[5]helicene intermediate module via 1,2-phenyl migration. The resulting chiral nanographenes are configurationally stable at 180 °C due to the high diastereomerization barriers of ca. 45 kcal mol-1 . These molecules also possess globally delocalized π-systems with low HOMO/LUMO gaps, leading to nearly panchromatic absorption, intensive electronic circular dichroism signals and deep-red circularly polarized luminescence.

Tailored Fabrication of Carbon Dot Composites with Full-Color Ultralong Room-Temperature Phosphorescence for Multidimensional Encryption.

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 B2 O3 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.

Nonplanar Helicene Benzo[4]Helicenium for the Precise Treatment of Renal cell Carcinoma.

Immune and targeted therapy are becoming the first-line treatment for renal cell carcinoma (RCC). However, therapeutic outcomes are limited due to the low efficiency and side effect. Here, it is found that helicenes are able to exhibit an anticancer capability through changing the molecular structure from planar to nonplanar. Furthermore, the cytotoxicity in vitro and cancer inhibition ability of nonplanar helicenes increase with its aromatic rings' number. It is further demonstrated that benzo[4]helicenium shows the specific killing efficiency against the RCC cancer as compared to normal kidney cells. This is majorly originated from a more selective damage of benzo[4]helicenium for mitochondria and DNA in RCC cancer cells, not the normal kidney. The selective killing ability of benzo[4]helicenium makes it have potential to be used as a targeted drug for the precise treatment of RCC.

Self-regulated co-assembly of soft and hard nanoparticles.

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.

Capillary-Bound Dense Micelle Brush Supports for Continuous Flow Catalysis.

Flow reactors are appealing alternatives to conventional batch reactors for heterogeneous catalysis. However, it remains a key challenge to firmly immobilize the catalysts in a facile and flexible manner and to simultaneously maintain a high catalytic efficiency and throughput. Herein, we introduce a dense cylindrical micelle brush support in glass capillary flow reactors through a living crystallization-driven self-assembly process initiated by pre-immobilized short micelle seeds. The active hairy corona of these micellar brushes allows the flexible decoration of a diverse array of nanocatalysts, either through a direct capture process or an in situ growth method. The resulting flow reactors reveal excellent catalytic efficiency for a broad range of frequently utilized transformations, including organic reductions, Suzuki couplings, photolytic degradations, and multistep cascade reactions, and the system was both recyclable and durable. Significantly, this approach is readily applicable to long capillaries, which enables the construction of flow reactors with remarkably higher throughput.