Electrostatic Anchoring of Mn4 Single‐Molecule Magnets onto Chemically Modified Multiwalled Carbon Nanotubes

Two different routes that enable the electrostatic grafting of cationic single‐molecule magnets (SMMs) onto the surface of chemically modified anionic multi‐walled carbon nanotubes (MWNTs) are described. The chemical nature and physical properties of the resulting hybrids are discussed on the basis of a complete battery of experimental techniques. The data show that the chemical nature of the SMM unit remains intact, while its magnetic response is significantly affected by the grafting process, which is likely due to surface effects.     

Analysis of Metallo‐Supramolecular Systems Using Single‐Molecule Force Spectroscopy

Single‐molecule force spectroscopy has been used for the investigation of the rupture behavior of individual metallo‐supramolecular systems. For this purpose, a specifically designed unsymmetrical α,ω‐functionalized poly(ethylene oxide) has been employed for mono‐termination with a terpyridine ligand and subsequently for the attachment onto atomic force microscopy (AFM) tips and microscope slide substrates. Metallo‐supramolecular complexes were formed by the use of ruthenium(III )–ruthenium(II ) chemistry. Vertical stretching with the AFM cantilever ruptured the coordinative bonds. The rupture force of individual bisterpyridine ruthenium(II ) complexes was determined to be 95 pN at a force loading rate of 1 nN s^–1. Simultaneous rupturing of multiple parallel metallo‐supramolecular bonds was also observed. Monte Carlo simulations corroborated the experimental observations. The presented results lay the basis for the application of such metallo‐supramolecular systems in advanced functional nanomaterials.     

3D Single‐Molecule Imaging of Transmembrane Signaling by Targeting Nanodiamonds

Fluorescent nanodiamonds (FNDs) have recently emerged as promising probes for imaging applications. A significant limitation of the applications is the use of FNDs as endogenous protein tags for long‐term 3D single molecule imaging to gain critical understanding of the underlying mechanism such as transmembrane signaling. Here, FNDs conjugated with transforming growth factor (TGF) are developed as an imaging probe for endogenous TGF‐beta (TGF‐β) receptor labeling and 3D single molecule imaging. FNDs display higher localization accuracy in 3D than organic dye making it an ideal candidate for nanoscopy applications. The real‐time dynamics of TGF‐β receptors after binding conjugated FNDs and in cells treated with therapeutic small molecule kinase inhibitors (SMI) are further monitored. The Bayesian treatment of hidden Markov models confirms and quantifies three different diffusive states and the transition rates between the three states. The kinetic reaction favors a faster diffusion population after therapeutic SMI treatment. The results show that immobilized TGF‐β is critical for active signaling. SMI treatment can release TGF‐β from the signaling complex. The results demonstrate the reported method that provides a powerful technique to study the mechanism of transmembrane signaling and valuable insights for developing better therapeutic for TGF‐β‐associated cancers.     

An On‐Chip Break Junction System for Combined Single‐Molecule Conductance and Raman Spectroscopies

Systems that are capable of robustly reproducing single‐molecule junctions are an essential prerequisite for enabling the wide‐spread testing of molecular electronic properties, the eventual application of molecular electronic devices, and the development of single‐molecule based electrical and optical diagnostics. Here, a new approach is proposed for achieving a reliable single‐molecule break junction system by using a microelectromechanical system device on a chip. It is demonstrated that the platform can (i) provide subnanometer mechanical resolution over a wide temperature range (≈77–300 K), (ii) provide mechanical stability on par with scanning tunneling microscopy and mechanically controllable break junction systems, and (iii) operate in a variety of environmental conditions. Given these fundamental device performance properties, the electrical characteristics of two standard molecules (hexane‐dithiol and biphenyl‐dithiol) at the single‐molecule level, and their stability in the junction at both room and cryogenic temperatures (≈77 K) are studied. One of the possible distinctive applications of the system is demonstrated, i.e., observing real‐time Raman scattering in a single‐molecule junction. This approach may pave a way to achieving high‐throughput electrical characterization of single‐molecule devices and provide a reliable platform for the convenient characterization and practical application of single‐molecule electronic systems in the future.     

Single‐Molecule Tracking of Fibrinogen Dynamics on Nanostructured Poly(ethylene) Films

Using fibrinogen (Fg) protein as a probe molecule, mapping using accumulated probe trajectories (MAPT) is performed on nanostructured melt‐drawn high‐density poly(ethylene) (HDPE) films composed of well‐oriented crystalline patches separated by amorphous regions. The spatially grouped molecular trajectories allow for identification of regions with distinct surface properties (i.e., crystalline vs. amorphous) while simultaneously determining the characteristic dynamic protein behavior within those regions. In the presence of solution with a sufficiently high Fg concentration, discrete patches of a dense, ordered protein layer form (presumably on crystalline HDPE regions), leading to a dramatic rise in the surface residence time (by more than two orders of magnitude) of molecules incorporated into the film. Within this ordered Fg layer, individual molecules exhibit slow anisotropic lateral diffusion; the mobility is restricted by the nanostructure boundaries of the underlying HDPE. On HDPE films at low Fg surface coverage, or on films that have been rendered hydrophilic with Ar plasma, short surface residence times and fast, isotropic diffusion are observed. These results demonstrate the ability of spatially resolved single‐molecule tracking to provide mechanistic information about biomolecule‐surface interactions in a highly heterogeneous environment.     

Dihydroazulene Photoswitch Operating in Sequential Tunneling Regime: Synthesis and Single‐Molecule Junction Studies

Molecular switches play a central role for the development of molecular electronics. In this work it is demonstrated that the reproducibility and robustness of a single‐molecule dihydroazulene (DHA)/vinylheptafulvene (VHF) switch can be remarkably enhanced if the switching kernel is weakly coupled to electrodes so that the electron transport goes by sequential tunneling. To assure weak coupling, the DHA switching kernel is modified by incorporating p‐MeSC₆H₄ end‐groups. Molecules are prepared by Suzuki cross‐couplings on suitable halogenated derivatives of DHA. The synthesis presents an expansion of our previously reported bromination–elimination–cross‐coupling protocol for functionalization of the DHA core. For all new derivatives the kinetics of DHA/VHF transition has been thoroughly studied in solution. The kinetics reveals the effect of sulfur end‐groups on the thermal ring‐closure of VHF. One derivative, incorporating a p‐MeSC₆H₄ anchoring group in one end, has been placed in a silver nanogap. Conductance measurements justify that transport through both DHA (high resistivity) and VHF (low resistivity) forms goes by sequential tunneling. The switching is fairly reversible and reenterable; after more than 20 “ON‐OFF” switchings, both DHA and VHF forms are still recognizable, albeit noticeably different from the original states.     

Biomimetic Formation of Hydroxyapatite Nanorods by a Single‐Crystal‐to‐Single‐Crystal Transformation

Uniform nanorods of hydroxyapatite (HAP) with an unusual orthorhombic shape have been synthesized from homogeneous solutions of Ca²⁺ and HPO₄^2– in the presence of gelatin and urea. The lengths of the nanorods are in the range of hundreds of micrometers, and the widths are about 100 nm. The HAP phase is generated by the transformation from its precursor phase of octacalcium phosphate (OCP), which has been monitored by X‐ray diffraction, NMR spectroscopy, scanning electron microscopy, and transmission electron microscopy. The rise in pH due to the decomposition of urea drives the OCP transformation to HAP. In the presence of gelatin, nanorods of OCP phase formed first and then transformed into the HAP phase, preserving the single‐crystal morphology. On the other hand, blade‐like OCP crystals form from the solution in the absence of gelatin. On increasing the pH of the solution, the large, blade‐like OCP crystals tend to crash into irregular, hexagonal HAP crystallites. A single‐crystal‐to‐single‐crystal topochemical transformation may be attributed to the evolution of HAP nanorods from the precursor OCP phase. This gives a strong indication as to the OCP to HAP transformation mechanism in the mineralization of biological apatite in tooth enamel and bone.     

An Efficient Chemical Solution Deposition Method for Epitaxial Gallium Nitride Layers Using a Single‐Molecule Precursor

An efficient chemical solution deposition (CSD) approach to growing epitaxial GaN layers at relatively low temperatures using a single‐molecule precursor (SMP) is described. The precursor employed was bisazido diethylaminopropyl gallium, which exists as a dimer in the solid state and decomposes at relatively low temperatures. Using this precursor, epitaxial GaN layers were grown and characterized for their morphology, microstructure, and composition by X‐ray diffraction (XRD), X‐ray rocking curve (XRC) analysis, pole figure measurements, reciprocal space mappings, scanning electron microscopy (SEM), Rutherford backscattering (RBS), X‐ray photoelectron spectroscopy (XPS), and room temperature photoluminescence (PL) measurements.     

Spin Filtering through Single‐Wall Carbon Nanotubes Functionalized with Single‐Stranded DNA

High spin polarization materials or spin filters are key components in spintronics, a niche subfield of electronics where carrier spins play a functional role. Carrier transmission through these materials is “spin selective,” that is, these materials are able to discriminate between “up” and “down” spins. Common spin filters include transition metal ferromagnets and their alloys, with typical spin selectivity (or, polarization) of ≈50% or less. Here carrier transport is considered in an archetypical one‐dimensional molecular hybrid in which a single wall carbon nanotube (SWCNT) is wrapped around by single stranded deoxyribonucleic acid (ssDNA). By magnetoresistance measurements it is shown that this system can act as a spin filter with maximum spin polarization approaching ≈74% at low temperatures, significantly larger than transition metals under comparable conditions. Inversion asymmetric helicoidal potential of the charged ssDNA backbone induces a Rashba spin‐orbit interaction in the SWCNT channel and polarizes carrier spins. The results are consistent with recent theoretical work that predicted spin dependent conductance in ssDNA‐SWCNT hybrid. Ability to generate highly spin polarized carriers using molecular functionalization can lead to magnet‐less and contact‐less spintronic devices in the future. This can eliminate the conductivity mismatch problem and open new directions for research in organic spintronics.     

Single‐Material Graphene Thermocouples

On‐chip temperature sensing on a micro‐ to nanometer scale is becoming more desirable as the complexity of nanodevices keeps increasing and their downscaling continues. The continuation of this trend makes thermal probing and management more and more challenging. This highlights the need for scalable and reliable temperature sensors, which have the potential to be incorporated into current and future device structures. Here, it is shown that U‐shaped graphene stripes consisting of one wide and one narrow leg form a single material thermocouple that can function as a self‐powering temperature sensor. It is found that the graphene thermocouples increase in sensitivity with a decrease in leg width, due to a change in the Seebeck coefficient, which is in agreement with previous findings and report a maximum sensitivity of ΔS ≈ 39 μV K^?1.     

Self‐Aligned Single‐Crystal Graphene Grains

The precisely controllable growth of self‐aligned single‐crystal graphene grains on liquid Cu surface by ambient pressure chemical vapor deposition is reported. Large scale monolayer graphene arrays are modulated by varying growth conditions such as flow rate of carbon source, growth temperature, and growth time. Further, bilayer graphene grains are also controllably prepared under optimized growth conditions. The self‐alignment mechanism of graphene is also studied and a growth model is proposed to explain that process involving surface tension of liquid phase. In all, the growth mechanism of graphene arrays is firstly probed and the grown graphene arrays show reasonable mobility and high current density, posing great potential for graphene‐based electronics.     

Single‐Crystalline Vanadium Dioxide Actuators

Actuators that convert other forms of energy to mechanical energy have attracted extensive interest for their critical applications in microelectromechanical systems and miniature robotics. Recently, it is discovered that vanadium dioxide (VO₂)‐based microscale bimorph actuators demonstrate comprehensive superiority of actuation performances, taking the good of the giant theoretical power density (7 J cm^?3) and ultrafast response (～picosecond) of crystalline VO₂, while they still suffer from the intrinsic shortcomings of complex structures. Here, “single‐crystalline VO₂ actuators” (SCVAs) that have unique self‐bending behavior upon temperature change are reported. This is realized by facilely and precisely controlling the phase structures via lateral stoichiometry‐engineering in VO₂ nanobeams at the nanoscale level. These SCVAs exhibit remarkable actuation performances and admirable stability, which are equivalent or even superior to the reported VO₂‐based conventional bimorph actuators. It is noteworthy that the gradual, reversible, and predictable bending of SCVAs enables a precise actuation control of related mechanics, such as the quantitative wind detector and thermal micromechanical claw. This work demonstrates the possibility of this strategy to enable single crystalline actuators excellent performance by internally lateral and gradual strain‐engineering.     

Wafer‐Scale Single‐Crystalline Ferroelectric Perovskite Nanorod Arrays

1D ferroelectric nanostructures are promising for enhanced ferroelectric and piezoelectric performance on the nanoscale, however, their synthesis at the wafer scale using industrially compatible processes is challenging. In order to advance the nanostructure‐based electronics, it is imperative to develop a silicon‐compatible growth technique yielding high volumetric density and an ordered arrangement. Here, a major breakthrough is provided in addressing this need and ordered and close‐packed single crystalline ferroelectric nanorod arrays, of composition PbZr_0.52Ti_0.48O₃ (PZT), grown on commercial grade 3 in. silicon wafer are demonstrated. PZT nanorods exhibit enhanced piezoelectric and ferroelectric performance compared to thin films of similar dimensions. Sandwich structured architecture utilizing 1D PZT nanorod arrays and 2D reduced graphene oxide thin film electrodes is fabricated to provide electrical connection. Combined, these results offer a clear pathway toward integration of ferroelectric nanodevices with commercial silicon electronics.     

Single‐Crystal‐to‐Single‐Crystal Transformation of a Europium(III) Metal–Organic Framework Producing a Multi‐responsive Luminescent Sensor

A sensor with a red‐emission signal is successfully obtained by the solvothermal reaction of Eu³⁺ and heterofunctional ligand bpydbH₂ (4,4′‐(4,4′‐bipyridine‐2,6‐diyl) dibenzoic acid), followed by terminal‐ligand exchange in a single‐crystal‐to‐single‐crystal transformation. As a result of treatments both before and after the metal–organic framework formation, accessible Lewis‐base sites and coordinated water molecules are successfully anchored onto the host material, and they act as signal transmission media for the recognition of analytes at the molecular level. This is the first reported sensor based on a metal–organic framework (MOF) with multi‐responsive optical sensing properties. It is capable of sensing small organic molecules and inorganic ions, and unprecedentedly it can discriminate among the homologues and isomers of aliphatic alcohols as well as detect highly explosive 2,4,6‐trinitrophenol (TNP) in water or in the vapor phase. This work highlights the practical application of luminescent MOFs as sensors, and it paves the way toward other multi‐responsive sensors by demonstrating the incorporation of various functional groups into a single framework.     

Single‐Atom Catalysts for Electrocatalytic Applications

The recent advances in electrocatalysis for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER), hydrogen oxidation reaction (HOR), carbon dioxide reduction reaction (CO₂RR), and nitrogen reduction reaction (NRR) are thoroughly reviewed. This comprehensive review focuses on the single‐atom catalysts (SACs) including Sc, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Sn, W, Bi, Ru, Rh, Pd, Ag, Ir, Pt, and Au with single‐metal sites or dual‐metal sites. The recent development of single‐atom electrocatalysts with novel configurations and compositions is documented. The understanding of the process–structure–property relationships is highlighted. For the SACs, their electrocatalytic performance and stability in fuel cells, zinc–air batteries, electrolyzers, CO₂RR, and NRR are summarized. The challenges and perspectives in the emerging field of single‐atom electrocatalysis are discussed.     

Ternary Emission of Fluorescence and Dual Phosphorescence at Room Temperature: A Single‐Molecule White Light Emitter Based on Pure Organic Aza‐Aromatic Material

Herein, a simple aza‐aromatic compound dibenzo[a,c]phenazine (DPPZ), which exhibits single‐molecule white light with a ternary emission, consisting of simultaneous fluorescence (S₁→S₀) and dual room‐temperature phosphorescence (RTP, T₂→S₀ and T₁→S₀) is reported. The Commission Internationale de l' Éclairage coordinates of DPPZ powder are (0.28, 0.33). To everyone's knowledge, this is the first case to achieve single‐molecule white emission with ternary emission of fluorescence and dual RTP. This finding provides a prototype strategy to realize low‐cost, stable pure organic single‐molecule white light emission with three standard primary colors through further precise modulation of excited states.     

Solution‐Processed Small‐Molecule Bulk Heterojunction Ambipolar Transistors

Solution‐processed small‐molecule bulk heterojunction (BHJ) ambipolar organic thin‐film transistors are fabricated based on a combination of [2‐phenylbenzo[d,d']thieno[3,2‐b;4,5‐b']dithiophene (P‐BTDT) : 2‐(4‐n‐octylphenyl)benzo[d,d ']thieno[3,2‐b;4,5‐b']dithiophene (OP‐BTDT)] and C₆₀. Treating high electrical performance vacuum‐deposited P‐BTDT organic semiconductors with a newly developed solution‐processed organic semiconductor material, OP‐BTDT, in an optimized ratio yields a solution‐processed p‐channel organic semiconductor blend with carrier mobility as high as 0.65 cm² V^?1 s^?1. An optimized blending of P‐BTDT:OP‐BTDT with the n‐channel semiconductor, C₆₀, results in a BHJ ambipolar transistor with balanced carrier mobilities for holes and electrons of 0.03 and 0.02 cm² V^?1 s^?1, respectively. Furthermore, a complementary‐like inverter composed of two ambipolar thin‐film transistors is demonstrated, which achieves a gain of 115.     

Optimizing Single‐Walled‐Carbon‐Nanotube‐Based Saturable Absorbers for Ultrafast Lasers

The application of single‐walled carbon nanotubes (SWCNTs) as saturable absorbers (SA) in a Nd:glass femtosecond laser is verified as a promising alternative to traditional semiconductor saturable‐absorber mirrors (SESAMs). The shortest laser pulses achieved with a SWCNT‐SA fabricated by the slow‐evaporation method are reported herein. Nearly Fourier‐limited 288 fs pulses are obtained with negative‐dispersion soliton mode‐locking. The importance of the properties of the starting material, such as the degree of purity and the chirality, and the successive slow‐evaporation deposition method is proven by using a multitechnique approach based on X‐ray diffractometry, scanning electron microscopy, and μ‐Raman spectroscopy. The high degree of nanotube alignment on the glass substrate and also the slight metallic character due to electron transfer between the glass matrix and the nanotubes themselves are identified as the main features responsible for the good laser response.