Dispersion of Single-Walled Carbon Nanotubes by Aromatic Cyclic Schiff Bases via Non-Covalent Interactions.

One of the challenging issues that hinders the application of single-walled carbon nanotubes (SWCNTs) is the poor solubility and the inevitable formation of bundles. Efforts still need to be made towards solving the problem. Herein, we report a non-covalent strategy to disperse aggregated SWCNTs by aromatic cyclic Schiff bases assisted by ultrasonic techniques. The aromatic cyclic Schiff base (OMM) was synthesized via Schiff base reactions, and the molecular structure was determined by ATR-FT-IR, solid-state 13C-NMR, and HRMS. Although the yielded product showed poor solubility in aqueous solution and organic solvents, it could interact with and disperse the aggregated SWCNTs in dimethyl formamide (DMF) under the condition of ultrasound. UV-vis-NIR, FL, Raman spectra, AFM, and TEM, along with computer simulations, provide evidence for the interactions between OMM molecules and SWCNTs and the dispersion thereof. The semiconductive (7,5), (8,6), (12,1), and (9,7)-SWCNTs expressed a preference for dissolution. The capability of dispersion is contributed by π-π, C-H·π, and lone pair (lp)·π interactions between OMM and SWCNTs based on the simulated results. The present non-covalent strategy could provide inspiration for preparing organic cyclic compounds as dispersants for SWCNTs and then facilitate their further utilization.

Tunable molecular packing modes via H- or J-aggregates in the supramolecular helical nanostructures from an achiral C3 symmetric molecule.

The self-assembly of a C3-symmetric molecule benzene-1,3,5-tricarboxylate substituted with methyl cinnamate (BTECM) has been investigated by a reprecipitation method in H2O and cetyltrimethylammonium bromide (CTAB) aqueous solution, respectively. The nanostructures and characteristics of the assemblies were monitored by UV-Vis spectroscopy, fluorescence (FL) spectroscopy, circular dichroism (CD) spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was found that helical nanostructures were successfully assembled from the achiral C3 molecule BTECM. More importantly, the helices aggregated via different packing modes in H2O and CTAB aqueous solution. In H2O, the nanostructures underwent a process of particles, fibers and helices via H-type aggregate upon aging. In the case of CTAB aqueous solution (1.2 mM), the helices were translated from particles and the molecules were inclined to aggregate via the J-type mode. In addition, the aggregation process could be accelerated by raising the temperature proved by UV-Vis spectra. A molecular aggregation mechanism was proposed based on the experimental results.

Supramolecular Self-Assembly of Perylene Bisimide Derivatives Assisted by Various Groups.

Anthra[2,1,9-def:6,5,10-d'e'f']diisoquinoline-1,3,8,10(2H,9H)-tetraone, namely, perylene bisimides (PBIs), belong to n-type organic semiconductors and possess potential applications in optoelectronic devices. The properties/performance of fabricated nanostructures/devices could be greatly influenced by both molecular structures of PBI building blocks and corresponding arrangement in assembled nanostructures. Many efforts have been made to modify the PBI core and then investigate the nanostructures and properties. However, it is still a great challenge to comprehensively understand the influence of molecular structures on the intermolecular interactions, the self-assembled structures, and the resulting performance. In the present contribution, we mainly summarize recent research aspects on supramolecular assembly behaviors of PBI derivatives assisted by various functional groups. First, a short introduction is given about basic molecular structure, properties, and self-assembly of PBI derivatives. Then, we mainly discuss the modulation of self-assembly of PBIs via introducing various functional groups (flexible or nonflexible chains, and biomolecules especially amino-acid-based groups). After that, the assembly of PBI derivatives from out-of-equilibrium states is described. Finally, a perspective is provided on the design of novel PBI derivatives and the fabrication of unique nanostructures with superior properties.

Discrete π-Stacks from Self-Assembled Perylenediimide Analogues.

The formation of well-defined finite-sized aggregates represents an attractive goal in supramolecular chemistry. In particular, construction of discrete π-stacked dye assemblies remains a challenge. Reported here is the design and synthesis of a novel type of discrete π-stacked aggregate from two comparable perylenediimide (PDI) dyads (PEP and PBP). The criss-cross PEP-PBP dimers in solution and (PBP-PEP)-(PEP-PBP) tetramers in the solid state are well elucidated using single-crystal X-ray diffraction, dynamic light scattering, and diffusion-ordered NMR spectroscopy. Extensive π-π stacking between the PDI units of PEP and PBP as well as repulsive interactions of swallow-tailed alkyl substituents are responsible for the selective formation of discrete dimer and tetramer stacks. Our results reveal a new approach to preparing discrete π stacks that are appealing for making assemblies with well-defined optoelectronic properties.

Design and Fabrication of Full Wheatstone-Bridge-Based Angular GMR Sensors.

Since the discovery of the giant magnetoresistive (GMR) effect, GMR sensors have gained much attention in last decades due to their high sensitivity, small size, and low cost. The full Wheatstone-bridge-based GMR sensor is most useful in terms of the application point of view. However, its manufacturing process is usually complex. In this paper, we present an efficient and concise approach to fabricate a full Wheatstone-bridge-based angular GMR sensor by depositing one GMR film stack, utilizing simple patterned processes, and a concise post-annealing procedure based on a special layout. The angular GMR sensor is of good linear performance and achieves a sensitivity of 0.112 mV/V/Oe at the annealing temperature of 260 °C in the magnetic field range from -50 to +50 Oe. This work provides a design and method for GMR-sensor manufacturing that is easy for implementation and suitable for mass production.

Nano-mechanical characterization of disassembling amyloid fibrils using the Peak Force QNM method.

The comprehensive understanding of disassembly mechanism of amyloid fibrils requires nano-scale characterization of the mechanical properties of amyloid fibrils during the disassembly process. In this work, gemini surfactant C12 C6 C12 Br2 micelles were used as a probe to disassemble Aß(1-40) fibrils. The microstructure evolution and nano-mechanical properties of Aß(1-40) fibrils during the disassembly process were systematically investigated by the Peak Force Quantitative Nano-mechanical (PF-QNM) technique. The results show an obvious decrease in Young's modulus of mature fibrils with high ß-sheet contents (2.4 ± 1.0 GPa) in comparison to the resulting peptide/surfactant complexes (1.1 ± 0.8 GPa) with loose surface structures. Interestingly, the Young's modulus of spherical peptide/surfactant complexes on the core was more than 3 GPa. This strategy can be used as a standard protocol to investigate the interaction mechanism between amyloid fibrils and small molecules, which may open up new possibilities to explore the mechanism of relevant human diseases.

Co-assembly of donor and acceptor towards organogels tuned by charge transfer interaction strength.

Co-assembly of n-type semiconductors NDI and PDI with p-type pyrene derivatives resulted in the formation of stable organogels, which was induced by the strong charge transfer (CT) interactions between acceptors and donors in chloroform. The dimension size of the aromatic core from the acceptors was found to have a significant impact on the organogels. The width of the fibers from CT gels with NDI is about twice that from gels with PDI. It was found that the acceptor NDI preferred an alternate stacking with donors, intercalated with each other via CT interactions. In contrast, the acceptor PDI preferred to stack among themselves within the assemblies and this arose from the stronger π-π interactions because they had larger aromatic cores than the acceptor NDI. The dimension size of the aromatic core has been proved to have a significant impact on the organogels. The substituent impact of the donors was also studied.

Role of halogenhalogen interactions in the 2D crystallization of n-semiconductors at the liquid-solid interface.

The impact of halogenhalogen interactions on the 2D crystallization of n-semiconductors was investigated. The 2D nanostructures and chirality could be altered by the introduction of bromine atoms for both single component and binary surface assembly supported by STM and simulation results.

Role of intrinsic hydrogen bonds in the assembly of perylene imide derivatives in solution and at the liquid-solid interface.

The impact of hydrogen bond formation on the supramolecular assembly of two perylene imide derivatives (PMAMI and PDINH) was systematically investigated in solution and at the liquid-solid interface. PDINH has intrinsic hydrogen bond sites, but this is not the case for PMAMI. The solution assembly was explored by morphological methods (SEM, AFM, TEM and cryo-TEM) and spectral characterization (UV-vis, FL, XRD, and FTIR spectra). The surface assembly at the liquid-solid interface was detected by scanning tunneling microscopy (STM). It was found that in a mixed solution (THF/MeOH, 10 v%/90 v%), PMAMI formed nanofibers together with large sheet structures and PDINH assembled into uniform nanosheets, suggesting different molecular packing routes. The assembled structures could be adjusted by varying the solvent polarity for both molecules. At the liquid-solid interface, clearly distinguished surface nanostructures from PMAMI and PDINH were easily observed. Based on all spectral and morphological characterizations, it was suggested that in solution the assembly of PMAMI was mainly derived by π-π stacking interactions; on the other hand, the synergetic interaction of hydrogen bonds and π-π stacking was the reason for the hierarchical assembly of PDINH. Hydrogen bonds could be formed both for PMAMI and PDINH and stabilized nanostructures at the liquid-solid interface. This investigation could be useful in designing perylene imide-based building blocks for fabricating supramolecular assemblies with predetermined nanostructures and properties.

Synthesis of one-dimensional Schiff base polymers that contain an oligothiophene building block on the graphite surface.

Surface-mediated Schiff base coupling reactions between oligothiophenes equipped with an aldehyde group and aromatic diamines were investigated on highly oriented pyrolytic graphite (HOPG) by means of scanning tunneling microscopy (STM) under ambient conditions. To investigate the evolution process from monomers to resultant polymers and the mechanism of reactions, we controlled the ratio of precursors and the reactive temperature, and we obtained high-resolution STM images of different stages of the surface reaction. The results suggest that preferential adsorption of one kind of monomer has a great influence on the on-surface Schiff base reaction.

Tetrapeptide-coumarin conjugate 3D networks based on hydrogen-bonded charge transfer complexes: gel formation and dye release.

Oligopeptide-based derivatives are important synthons for bio-based functional materials. In this article, a Gly-(L-Val)-Gly-(L-Val)-coumarin (GVGV-Cou) conjugate was synthesized, which forms 3D networks in ethanol. The gel nanostructures were characterized by UV-vis spectroscopy, FT-IR spectroscopy, X-ray diffraction (XRD), SEM and TEM. It is suggested that the formation of charge transfer (CT) complexes between the coumarin moieties is the main driving force for the gel formation. The capability of the gel to encapsulate and release dyes was explored. Both Congo Red (CR) and Methylene Blue (MB) can be trapped in the CT gel matrix and released over time. The present gel might be used as a functional soft material for guest encapsulation and release.

Single-Shot Laser-Induced Switching of an Exchange Biased Antiferromagnet.

Ultrafast manipulation of magnetic order has challenged the understanding of the fundamental and dynamic properties of magnetic materials. So far single-shot magnetic switching has been limited to ferrimagnetic alloys, multilayers, and designed ferromagnetic (FM) heterostructures. In FM/antiferromagnetic (AFM) bilayers, exchange bias (He) arises from the interfacial exchange coupling between the two layers and reflects the microscopic orientation of the antiferromagnet. Here the possibility of single-shot switching of the antiferromagnet (change of the sign and amplitude of He) with a single femtosecond laser pulse in IrMn/CoGd bilayers is demonstrated. The manipulation is demonstrated in a wide range of fluences for different layer thicknesses and compositions. Atomistic simulations predict ultrafast switching and recovery of the AFM magnetization on a timescale of 2 ps. The results provide the fastest and the most energy-efficient method to set the exchange bias and pave the way to potential applications for ultrafast spintronic devices.

Surface-induced diastereomeric complex formation of a nucleoside at the liquid/solid interface: stereoselective recognition and preferential adsorption.

With the aim of achieving surface-mediated enantioselective adsorption, the self-assembly of chiral oligo(p-phenylenevinylene) (OPV3T) with nucleosides is investigated at the liquid/solid interface by means of scanning tunneling microscopy and molecular modeling. OPV3T enantiomers form mirror related hexameric rosette patterns. The DNA nucleoside, thymidine, does not self-assemble into stable adlayers but coadsorbs with OPV3T on the surface, leading to a pattern transformation of OPV3T from rosettes to dimers, and a change in chiral expression as well. Diastereoselective recognition between OPV3T and thymidine enantiomers can be used to resolve thymidine enantiomers at an achiral surface with an OPV3T enantiomer as the resolving agent. The impact of molar ratio and concentration on the self-assembly and chiral resolution is systematically investigated. Because there is no interaction between OPV3T and thymidine in solution, the liquid/solid interface acts as the platform for the chiral resolution of thymidine enantiomers.

An enzyme-responsive electrochemical DNA biosensor achieving various dynamic range by using only-one immobilization probe.

Developing a simple and easy-to-operate biosensor with tunable dynamic range would provide enormous opportunities to promote the diagnostic applications. Herein, an enzyme-responsive electrochemical DNA biosensor is developed by using only-one immobilization probe. The immobilization probe was designed with a two-loop hairpin-like structure that contained the mutually independent target recognition and enzyme (EcoRI restriction endonuclease) responsive domains. The target recognition was based on a toehold-mediated strand displacement reaction strategy. The toehold region was initially caged in the loop of the immobilization probe and showed a relatively low binding affinity with target, which was improved via EcoRI cleavage of immobilization probe to liberate the toehold region. The EcoRI cleavage operation for immobilization probe demonstrated the well regulation ability in detection performance. It showed a largely extended dynamic range, a significantly lowered detection limit and better discrimination ability toward the mismatched sequences whether in two buffers (with high or low salt concentrations) or in the serum system. The advantages also includes simplicity in probe design, and facile biosensor fabrication and operation. It thus opens a new avenue for the development of the modulated DNA biosensor and hold a great potential for the diagnostic applications and drug monitoring.

Interfacial engineering of ferromagnetism in wafer-scale van der Waals Fe4GeTe2 far above room temperature.

Despite recent advances in exfoliated vdW ferromagnets, the widespread application of 2D magnetism requires a Curie temperature (Tc) above room temperature as well as a stable and controllable magnetic anisotropy. Here we demonstrate a large-scale iron-based vdW material Fe4GeTe2 with the Tc reaching ~530 K. We confirmed the high-temperature ferromagnetism by multiple characterizations. Theoretical calculations suggested that the interface-induced right shift of the localized states for unpaired Fe d electrons is the reason for the enhanced Tc, which was confirmed by ultraviolet photoelectron spectroscopy. Moreover, by precisely tailoring Fe concentration we achieved arbitrary control of magnetic anisotropy between out-of-plane and in-plane without inducing any phase disorders. Our finding sheds light on the high potential of Fe4GeTe2 in spintronics, which may open opportunities for room-temperature application of all-vdW spintronic devices.

Induction of chirality in an achiral monolayer at the liquid/solid interface by a supramolecular chiral auxiliary.

An achiral oligo(p-phenylene vinylene) derivative with a ureido-triazine hydrogen bonding unit self-assembles into rows of hydrogen bonded dimers at the liquid/solid interface. Scanning tunneling microscopy reveals the formation of chiral domains, but overall, the surface remains racemic. Addition of a chiral auxiliary which is able to interact with the dimers through hydrogen bonding, showed that global organizational chirality could be achieved since a majority of the domains show the same handedness. After removing the chiral auxiliary with a volatile solvent, the global organizational chirality could be trapped, revealing a memory effect. With this straightforward supramolecular approach, we were able to create a chiral surface with preferred handedness composed of achiral molecules at the air/solid interface.

Antiferromagnetic spintronics: An overview and outlook.

Over the past few decades, the diversified development of antiferromagnetic spintronics has made antiferromagnets (AFMs) interesting and very useful. After tough challenges, the applications of AFMs in electronic devices have transitioned from focusing on the interface coupling features to achieving the manipulation and detection of AFMs. As AFMs are internally magnetic, taking full use of AFMs for information storage has been the main target of research. In this paper, we provide a comprehensive description of AFM spintronics applications from the interface coupling, read-out operations, and writing manipulations perspective. We examine the early use of AFMs in magnetic recordings and conventional magnetoresistive random-access memory (MRAM), and review the latest mechanisms of the manipulation and detection of AFMs. Finally, based on exchange bias (EB) manipulation, a high-performance EB-MRAM is introduced as the next generation of AFM-based memories, which provides an effective method for read-out and writing of AFMs and opens a new era for AFM spintronics.

Nucleoside-assisted self-assembly of oligo(p-phenylenevinylene)s at liquid/solid interface: chirality and nanostructures.

The formation of DNA nucleoside-assisted π-conjugated nanostructures was studied by means of scanning tunneling microscopy (STM) and force field simulations. Upon adsorption of the achiral oligo(p-phenylenevinylene) (OPV) derivative at the liquid/solid interface, racemic conglomerates with mirror related rosettes are formed. Addition of the DNA nucleosides D- and L-thymidine, which act as "chiral handles", has a major effect on the supramolecular structure and the expression of chirality of the achiral OPV molecules. The influence of these "chiral handles" on the expression of chirality is probed at two levels: monolayer symmetry and monolayer orientation with respect to the substrate. This was further explored by tuning the molar ratio of the building blocks. Molecular modeling simulations give an atomistic insight into the monolayer construction, as well as the energetics governing the assembly. Thymidine is able to direct the chirality and the pattern of OPV molecules on the surface, creating chiral lamellae of π-conjugated dimers.

A mitochondria-targeted fluorescent probe for real-time imaging SO2/H2O2.

Studies have shown that changes in the redox state of cells might be closely related to pathological and physiological processes. Sulfur dioxide and hydrogen peroxide, as a significant redox couple in living cells, are endogenously produced by cells. Here, we report a long-wavelength fluorescent probe to reversibly monitor sulfur dioxide and hydrogen peroxide. This probe (NBD) displayed high selectivity and sensitivity, which could be accumulated in mitochondria for real-time imaging of SO2/H2O2. These results indicated that NBD would be an ideal tool for monitoring the redox cycle state in living cells.

Switchable circularly polarized luminescence from a photoacid co-assembled organic nanotube.

Materials with circularly polarized luminescence (CPL) are currently attracting great interest in view of their potential applications. Here, we reported self-assembled organic nanotubes with switchable CPL performance. A photoacid, 8-hydroxy-1,3,6-pyrenetrisulfonate (HPTS), was co-assembled with an amino-terminated dialkyl glutamide (LG or DG) in mixed solvents of DMF and water. The complex of LG (DG)/HPTS self-assembled into nanotube structures in the tested range of mixed solvents and showed CPL emission. Different mixing ratios of DMF to water in the solvent triggered CPL switching between different wavelengths. It was revealed that the switching of CPL resulted from the different emissions of the protonated (ROH) and deprotonated (RO-) forms of HPTS, which could be regulated by the solvent polarity. Interestingly, the addition of an acid or base could also switch the fluorescence of LG (DG)/HPTS co-assemblies and the corresponding CPL, leading to an acidity-regulated CPL switch. Thus, through a simple co-assembly strategy, switchable CPL was realized in the self-assembled organic nanotubes via both solvent polarity and acidity.