Nitroxide Radicals@US‐Tubes: New Spin Labels for Biomedical Applications

The encapsulation of nitroxide radicals within ultrashort (ca. 50 nm) single‐walled carbon nanotubes (US‐tubes) is achieved. Tempo‐ and Iodo‐Tempo@US‐tubes are characterized by thermogravimetric analysis (TGA), X‐ray photoelectron spectroscopy (XPS), and Raman spectroscopy. Electron paramagnetic resonance (EPR) spectra display characteristic signals due to the detection of the spin probes within the US‐tubes. Longitudinal proton relaxivities (r₁) of both nitroxide@US‐tubes samples are 7 to 13 times greater than the free nitroxide radicals in solution, giving relaxivities comparable to the clinical contrast agent (CA) Magnevist. In addition, transverse proton relaxivities (r₂) show unprecedented proton relaxation enhancement in comparison to any other reported nitroxide radical‐based system or the clinically approved T₂ CA, Resovist, under the same conditions. T₂‐weighted magnetic resonance imaging (MRI) phantom images show that the encapsulation of nitroxide radicals within the US‐tubes produces good contrast enhancement due to their high r₂ relaxivities. The nitroxide radicals@US‐tube agents are a new promising class of spin probes for MRI and electronic paramagnetic resonance imaging (EPRI) labeling, tracking, and diagnosis.     

Amorphous Carbon Nanotubes with Tunable Properties via Template Wetting

Amorphous carbon nanotubes have been prepared by casting thin films of polyacrylonitrile (PAN) and polystyrene‐block‐polyacrylonitrile (PS‐b‐PAN) within a porous anodic aluminum oxide (AAO) membrane followed by pyrolysis. Raman and wide‐ angle X‐ray diffraction (WAXD) measurements indicate that the carbon nanotubes are of low crystallinity. The thickness of the carbon nanotube walls is controlled by either changing the concentration of the precursor solution or by using multiple casting and pyrolysis steps. When diblock copolymers of PS‐b‐PAN are used, it is found that nanopores are created within the nanotube walls after pyrolysis. The carbon nanotubes can be used to create carbon coated nanorods of polystyrene‐block‐polybutadiene (PS‐b‐PBD).     

Single‐Crystalline LiMn2O4 Nanotubes Synthesized Via Template‐Engaged Reaction as Cathodes for High‐Power Lithium Ion Batteries

Single‐crystalline nanotubes of spinel LiMn₂O₄ with a diameter of about 600 nm, a wall thickness of about 200 nm and a length of 1–4 μm have been synthesized via a template‐engaged reaction using β‐MnO₂ nanotubes as a self‐sacrifice template. In this fabrication, a minimal structural reorganization can be responsible for the chemical transformation from [001]‐oriented β‐MnO₂ template to [110]‐oriented LiMn₂O₄. Galvanostatic charge/discharge measurements indicate that the nanotubes exhibit superior high‐rate capabilities and good cycling stability. About 70% of its initial capacity can be retained after 1500 cycles at 5 C rate. Importantly, the tubular nanostructures and the single‐crystalline nature of the most LiMn₂O₄ nanotubes are also well preserved after prolonged charge/discharge cycling at a relatively high current density, indicating good structural stability of the single‐crystalline nanotubes during lithium intercalation/deintercalation process. As is confirmed from Raman spectra analyses, no evident microstructural changes occur upon long‐term cycling. These results reveal that single‐crystalline nanotubes of LiMn₂O₄ will be one of the most promising cathode materials for high‐power lithium ion batteries.     

Analysis of groove NRD waveguide bend using the coupled-mode theory

In this paper, the propagation characteristics of the dominant mode in GNRD guide bend are analysed employing the coupled-mode theory. The curves of bending loss vs. The groove depth or width, radius of curvature and frequency are given, which caused by the mode conversion of the operatingLSM ₁₁ ^x mode to the parasiticLSE ₁₁ ^x mode. It is found that the groove depth has a great influence upon the bending loss than the other parameters. According to the theoretical results, appropriate sizes of groove and radius of curvature should be chosen in designing a GNRD bend structure.     

A General Strategy to Disperse and Functionalize Carbon Nanotubes Using Conjugated Block Copolymers

A general strategy to disperse and functionalize pristine carbon nanotubes in a single‐step process is developed using conjugated block copolymers. The conjugated block copolymer contains two blocks: a conjugated polymer block of poly(3‐hexylthiophene), and a functional non‐conjugated block with tunable composition. When the pristine carbon nanotubes are sonicated with the conjugated block copolymers, the poly(3‐hexylthiophene) blocks bind to the surface of de‐bundled carbon nanotubes through non‐covalent π–π interactions, stabilizing the carbon nanotube dispersion, while the functional blocks locate at the outer surface of carbon nanotubes, rendering the carbon nanotubes with desired functionality. In this paper, conjugated block copolymers of poly(3‐hexylthiophene)‐b‐poly(methyl methacrylate), poly(3‐hexylthiophene)‐b‐poly(acrylic acid), and poly(3‐hexylthiophene)‐b‐poly(poly(ethylene glycol) acrylate) are used to demonstrate this general strategy.     

High‐Efficiency Near‐Infrared Fluorescent Organic Light‐Emitting Diodes with Small Efficiency Roll‐Off: A Combined Design from Emitters to Devices

The simultaneous realization of high quantum yield and exciton utilizing efficiency (η_r) is still a formidable challenge in near‐infrared (NIR) fluorescent organic light‐emitting diodes (FOLEDs). Here, to achieve a high quantum yield, a novel NIR dye, 4,9‐bis(4‐(diphenylamino)phenyl)‐naphtho[2,3‐c ][1,2,5]selenadiazole, is designed and synthesized with a large highest occupied molecular orbital/lowest unoccupied molecular orbital overlap and an aggregation‐induced emission property, which demonstrates a high photoluminescence quantum yield of 27% at 743 nm in toluene and 29% at 723 nm in a blend film. For a high η_r, an orange‐emitting thermally activated delayed fluorescent material, 1,2‐bis(9,9‐dimethyl‐9,10‐dihydroacridine)‐4,5‐dicyanobenzene, is chosen as the sensitizing host to harvest triplet excitons in devices. The optimized devices achieve a good η_r of 45.7% and a high external quantum efficiency up to 2.65% at 730 nm, with a very small efficiency roll‐off of 2.41% at 200 mA cm^?2, which are among the most efficient values for NIR‐FOLEDs over 700 nm. The effective utilization of triplet excitons via the thermally activated delayed fluorescence‐sensitizing host will pave a way to realize high‐efficiency NIR‐FOLEDs with small efficiency roll‐off.     

Ultrasmall Water‐Soluble and Biocompatible Magnetic Iron Oxide Nanoparticles as Positive and Negative Dual Contrast Agents

Monodispersed water‐soluble and biocompatible ultrasmall magnetic iron oxide nanoparticles (UMIONs, D = 3.3 ± 0.5 nm) generated from a high‐temperature coprecipitation route are successfully used as efficient positive and negative dual contrast agents of magnetic resonance imaging (MRI). Their longitudinal relaxivity at 4.7 T (r₁ = 8.3 mM^?1 s^?1) is larger than that of clinically used T₁‐positive agent Gd‐DTPA (r₁ = 4.8 mM^?1 s^?1), and three times that of commercial contrast agent SHU‐555C (r₁ = 2.9 mM^?1 s^?1). The transversal relaxivity (r₂ = 35.1 mM^?1 s^?1) is six times that of Gd‐DTPA (r₂ = 5.3 mM^?1 s^?1), half of SHU‐555C (r₂ = 69 mM^?1 s^?1). The in vivo results show that the liver signal from T₁‐weighted MRI is positively enhanced 26%, and then negatively decreased 20% after injection of the iron oxide nanoparticles, which is stronger than those obtained from Gd‐DTPA (<10%) using the same dosage. The kidney signal is positively enhanced up to 35%, similar to that obtained from Gd‐DTPA. Under T₂‐weighted conditions, the liver signal is negatively enhanced ?70%, which is significantly higher than that from Gd‐DTPA (?6%). These results demonstrate the great potential of the UMIONs in dual contrast agents, especially as an alternative to Gd‐based positive contrast agents, which have risks of inducing side effects in patients.     

Self‐Assembling Nanotubes Consisting of Rigid Cyclic γ‐Peptides

Self‐assembling cyclic peptide nanotubes (SPNs) have been extensively studied due to their potential applications in biology and material sciences. Cyclic γ‐peptides, which have a larger conformational space, have received less attention than the cyclic α‐ and β‐peptides. The self‐assembly of cyclic homo‐γ‐tetrapeptide based on cis‐3‐aminocyclohexanecarboxylic acid (γ‐Ach) residues, which can be easily synthesized by a one‐pot process is investigated. Fourier transform infrared (FTIR) and NMR analysis along with density functional theory (DFT) calculations indicate that the cyclic homo‐γ‐tetrapeptide, with a non‐planar conformation, can self‐assemble into nanotubes through hydrogen‐bond‐mediated parallel stacking. Atomic force microscopy (AFM) and transmission electron microscopy (TEM) experiments reveal the formation of bundles of nanotubes in CH₂Cl₂/hexane, but individual nanotubes and bundles of only two nanotubes are obtained in water. The integration of TEG (triethylene glycol) monomethyl ether chains and cyclopeptide backbones may allow the control of width of single nanotubes.     

Application of Inhibitor‐Loaded Halloysite Nanotubes in Active Anti‐Corrosive Coatings

Halloysite particles are aluminum‐silicate hollow cylinders with a length of 0.5–1 µm, an outer diameter of ca. 50 nm and a lumen of 15 nm. These nanotubes are used for loading and sustained release of corrosion inhibitors. The inhibitor is kept inside the particles infinitely long under dry conditions. Here, halloysite nanotubes filled with anticorrosive agents are embedded into a SiO_x–ZrO_x hybrid film. An aluminum plate is dip‐coated and immersed into 0.1 M sodium chloride aqueous solution for corrosion tests. A defect in the sol–gel coating induces pitting corrosion on the metal accompanied by a strong anodic activity. The inhibitor is released within one hour from halloysite nanotubes at corrosion spots and suppresses the corrosion process. The anodic activity is successfully restrained and the protection remains for a long time period of immersion in NaCl water solution. The self‐healing effect of the sol–gel coating doped with inhibitor‐loaded halloysite nanotubes is demonstrated in situ via scanning vibrating electrode technique measurements.     

Controlled Topology of Block Copolymer Gate Insulators by Selective Etching of Cylindrical Microdomains in Pentacene Organic Thin Film Transistors

We investigate the effect of surface topology of a block copolymer/neutral surface/SiO₂ trilayered gate insulator on the properties of pentacene organic thin film transistor (OTFT) by the controlled etching of self assembled poly(styrene‐b‐methyl methacrylate) (PS‐b‐PMMA) block copolymer. The rms roughness of the uppermost block copolymer film directly in contact with pentacenes was systematically controlled from 0.27 nm to approximately 12.5 nm by the selective etching of cylindrical PMMA microdomains hexagonally packed and aligned perpendicular to SiO₂ layer with 20 and 38 nm of diameter and periodicity, respectively. Both mobility and On/Off ratio were significantly reduced by more than 3 orders of magnitudes with the film roughness in OTFTs having 60 nm thick pentacene active layer. The poor device performance observed with the etched thin film of block copolymer dielectric is attributed to a defective pentacene active layer and the mixed crystalline structure consisting of thin film and bulk phase arising from the massive nucleation of pentacene preferentially at the edge of each cylindrical etched hole.     

Polymer‐Stabilized Chromonic Liquid‐Crystalline Polarizer

Robust coatable polarizer is fabricated by the self‐assembly of lyotropic chromonic liquid crystals and subsequent photo‐polymerizing processes. Their molecular packing structures and optical behaviors are investigated by the combined techniques of microscopy, scattering and spectroscopy. To stabilize the oriented Sunset Yellow FCF (H‐SY) films and to minimize the possible defects generated during and after the coating, acrylic acid (AA) is added to the H‐SY/H₂O solution and photo‐polymerized. Utilizing cross‐polarized optical microscopy, phase behaviors of the H‐SY/H₂O/AA solution are monitored by varying the compositions and temperatures of the solution. Based on the experimental results of two‐dimensional wide angle X‐ray diffraction and selected area electron diffraction, the H‐SY crystalline unit cell is determined to be a monoclinic structure with the dimensions of a = 1.70 nm, b = 1.78 nm, c = 0.68 nm, α = β = 90.0° and γ = 84.5°. The molecular arrangements in the oriented H‐SY films were further confirmed by polarized Fourier‐transform infrared spectroscopy. The polymer‐stabilized H‐SY films show good mechanical and chemical stabilities with a high polarizability. Additionally, patterned polarizers are fabricated by applying a photo‐mask during the photo‐polymerization of AA, which may open new doors for practical applications in electro‐optic devices.     

Exploring How to Increase the Brightness of Surface‐Enhanced Raman Spectroscopy Nanolabels: The Effect of the Raman‐Active Molecules and of the Label Size

Due to the surface‐enhanced Raman scattering (SERS) effect, SERS labels based on noble‐metal nanoparticles loaded with Raman‐active molecules are good candidates for ultrasensitive multiplexed assays and in vitro/in vivo imaging. However, understanding how to maximize the brightness of such labels is of paramount importance for their widespread application. The effective differential Raman scattering cross‐section (dσ_R/dΩ) of SERS labels made of pegylated gold nanoparticles loaded with various Raman active molecules (Raman reporters) is studied. It is found that proper choice of the Raman reporter and of nanoparticle size can enhance the dσ_R/dΩ by several orders of magnitude. The experimental results are understood by considering the molecular cross‐section for resonant Raman scattering and the local electromagnetic enhancement factor (G_SERS) in the nearby of gold nanoparticles. These results are useful to guide the design of SERS labels with improved performances and to provide a reference for the comparison of the absolute value of the dσ_R/dΩ of SERS labels based on metal nanoparticles.     

A Facile Strategy for Preparation of Fluorescent SWNT Complexes with High Quantum Yields Based on Ion Exchange

The fluorescent imidazolium salt (1,3‐bis(9‐anthracenylmethyl)imidazolium chloride, [bamim]Cl) has been grafted onto the surfaces of single‐walled carbon nanotubes (SWNTs) using an ion exchange strategy based on metathesis of the K⁺ ion in CO₂K derivatized SWNTs with [bamim]⁺. The resulting SWNT‐[bamim] complex has been characterized with high‐resolution transmission electron microscopy (HR‐TEM), X‐ray photoelectron spectroscopy (XPS), elemental mapping, and elemental linear profiles analysis. A blue light emission can be observed at 392, 414 and 438 nm for SWNT‐[bamim] upon being excited at 254 nm. The quantum yield (QY) of the SWNT‐[bamim] complex (0.40) is much higher than that of SWNT/[bamim]Cl (0.02), used as a control, and prepared using a π‐π stacking method, indicating that ion exchange is a far more effective strategy for retaining a high QY. Additionally, UV‐Vis‐NIR and Raman spectroscopy show that the SWNT‐[bamim] complex can maintain the one‐dimensional electronic states of SWNTs. Other imidazolium salts have also been successfully grafted onto SWNTs via the same strategy, indicating that the ion exchange process can serve as a universal strategy for the functionalization of SWNTs.     

Dimensional Regulation of Titanosilicate by Kinetically Controlled Intergrowth Crystals

Dimensional regulation of titanosilicates from conventional 3D to revolutionary 2D without extra additives is limited by the Ostwald ripening process together with the mismatch of hydrolysis rate between Ti and Si species. Herein, the kinetically controlled and additive-free strategy is devised to continuously regulate the dimensionality of intergrowth titanosilicate from 3D bulk to 2D nanosheets. The kinetic relative growth rate of orthorhombic MFI to tetragonal MEL (r_MFI/r_MEL) dominated by temperature control can determine the morphology of intermediates. Crisscross intermediates assembled by MFI branches along a direction and MEL connectors along a/b directions restrain the Ostwald ripening of titanosilicate and further transform into 2D nanosheets (≈2 nm), which show enhanced olefin epoxidation performance due to boosted diffusion ability. This kinetically controlled strategy unlocks green and efficient regulation of titanosilicate dimension.     

Mechanical Strain‐Tunable Microwave Magnetism in Flexible CuFe2O4 Epitaxial Thin Film for Wearable Sensors

Purely mechanical strain‐tunable microwave magnetism device with lightweight, flexible, and wearable is crucial for passive sensing systems and spintronic devices (noncontact), such as flexible microwave detectors, flexible microwave signal processing devices, and wearable mechanics‐magnetic sensors. Here, a flexible microwave magnetic CuFe₂O₄ (CuFO) epitaxial thin film with tunable ferromagnetic resonance (FMR) spectra is demonstrated by purely mechanical strains, including tensile and compressive strains, on flexible fluorophlogopite (Mica) substrates. Tensile and compressive strains show remarkable tuning effects of up‐regulation and down‐regulation on in‐plane FMR resonance field (H_r), which can be used for flexible tunable resonators and filters. The out‐of‐plane FMR spectra can also be tuned by mechanical bending, including H_r and absorption peak. The change of out‐of‐plane FMR spectra has great potential for flexible mechanics‐magnetic deformation sensors. Furthermore, a superior microwave magnetic stability and mechanical antifatigue character are obtained in the CuFO/Mica thin films. These flexible epitaxial CuFO thin films with tunable microwave magnetism and excellent mechanical durability are promising for the applications in flexible spintronics, microwave detectors, and oscillators.     

Rectangular AgIn(WO4)2 Nanotubes: A Promising Photoelectric Material

Rectangular AgIn(WO₄)₂ nanotubes with a diameter range of 80 to 120 nm and length up to 2 µm have been synthesized by a hydrothermal method. These nanotubes exhibit interesting white light emissions when using 320 nm as the excitation wavelength. A photocatalytic reaction for water decomposition to evolve H₂ was performed under UV irradiation, and the rate of H₂ evolution is nearly seven times that of the sample prepared by a solid‐state reaction, which shows much higher photocatalytic activities compared with their bulk counterparts. The activity of AgIn(WO₄)₂ nanotubes for degrading rhodamine B in water irradiated by UV light was about twice that of using bulk materials. The formation mechanism of the rectangular nanotubes is proposed based on the anisotropic intrinsic crystalline structure of AgIn(WO₄)₂. The enhancement of the photoelectric properties is attributed to the nanometer‐scale size and tubular structure.     

Sub-Nanowires Boost Superior Capacitive Energy Storage Performance of Polymer Composites at High Temperatures

Polymer dielectrics with high breakdown strength (E_b) and high efficiency are urgently demanded in advanced electrical and electronic systems, yet their energy density (U_e) is limited due to low dielectric constant (ε_r) and high loss at elevated temperatures. Conventional inorganic fillers with diameters from nano to micrometers can only increase ε_r at the cost of compromised E_b and U_e due to their poor compatibility with polymer matrix. Herein, hydroxyapatite (HAP) sub-nanowires with a diameter of ≈0.9 nm are incorporated in polyetherimide (PEI) matrix to form HAP/PEI sub-nanocomposites. ε_r and E_b of the composites are concomitantly enhanced with only 0.5 wt.% of HAP sub-nanowires, leading to high U_e of 5.14 (@150 °C) and 3.1 J cm⁻³ (@200 °C) with efficiency of 90% and high-temperature stability up to 3 × 10⁵ charge-discharge cycles at 200 °C. Microstructural analysis and molecular dynamics simulations indicate that the sub-nanowires with comparable diameter as polymer chains induce enormous interfacial area, substantially increase mobility of polymer chains and form dense traps for charge carriers. This work extends the current research scope of polymer-inorganics composite dielectrics to the sub-nano-level incorporation and provides a novel strategy for fabricating high performance polymer dielectrics at elevated temperatures.     

ZnO纳米管的制备及光学特性研究

ZnO nanotubes have been fabricated through a carbon thermal reduction deposition process. Structure characterization results show that the ZnO nanotubes have a single crystalline wurtzite hexagonal structure pref- erentially oriented in the c-axis. The diameters of ZnO nanotubes are in the range of 90-280 nm and the wall thickness is about 50-100 nm. Room-temperature photoluminescence measurements of the ZnO nanotubes exhibit an intensive ultraviolet peak at 377 nm and a broad peak centered at about 517 nm. The UV emission is caused by the near band edge emission while the green emission may be attributed to both oxygen vacancy and the surface state. Raman and cathodoluminescence spectra are also discussed. Finally, a possible growth mechanism of the ZnO nanotubes is proposed.     

Hydrothermal Synthesis of Rare Earth (Tb,Y) Hydroxide and Oxide Nanotubes

In this paper, Tb(OH)₃ and Y(OH)₃ single‐crystalline nanotubes with outer diameters of 30–260 nm, inner diameters of 15–120 nm, and lengths of up to several micrometers were synthesized on a large scale by hydrothermal treatment of the corresponding oxides in the presence of alkali. In addition, Tb₄O₇ and Y₂O₃ nanotubes can be obtained by calcination of Tb(OH)₃ and Y(OH)₃ nanotubes at 450 °C. X‐ray diffraction (XRD), field‐emission scanning electron microscopy, transmission electron microscopy (TEM), electron diffraction (ED), energy‐dispersive X‐ray spectroscopy (EDS), thermogravimetry, and differential scanning calorimetry (DSC) have been employed to characterize these nanotube materials. The growth mechanism of rare earth hydroxide nanotubes can be explained well by the highly anisotropic crystal structure of rare earth hydroxides. These new types of rare earth compound nanotubes with open ends have uses in a variety of promising applications such as luminescent devices, magnets, catalysts, and other functional materials. Advantages of this method for easily realizing large‐scale production include that it is a simple and unique one‐pot synthetic process without the need for a catalysts or template, is low cost, has high yield, and the raw materials are readily available. The present study has enlarged the family of nanotubes available, and offers a possible new, general route to one‐dimensional single‐crystalline nanotubes of other materials.     

Photoconductivity of a Low‐Bandgap Conjugated Polymer

The photoconductive properties of a novel low‐bandgap conjugated polymer, poly[2,6‐(4,4‐bis‐(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b;3,4‐b′]dithiophene)‐alt‐4,7‐(2,1,3‐benzothiadiazole)], PCPDTBT, with an optical energy gap of E_g ～ 1.5 eV, have been studied. The results of photoluminescence and photoconductivity measurements indicate efficient electron transfer from PCPDTBT to PCBM ([6,6]‐phenyl‐C61 butyric acid methyl ester, a fullerene derivative), where PCPDTBT acts as the electron donor and PCBM as the electron acceptor. Electron‐transfer facilitates charge separation and results in prolonged carrier lifetime, as observed by fast (t > 100 ps) transient photoconductivity measurements. The photoresponsivities of PCPDTBT and PCPDTBT:PCBM are comparable to those of poly(3‐hexylthiophene), P3HT, and P3HT:PCBM, respectively. Moreover, the spectral sensitivity of PCPDTBT:PCBM extends significantly deeper into the infrared, to 900 nm, than that of P3HT. The potential of PCPDTBT as a material for high‐efficiency polymer solar cells is discussed.