Long-Term Stable Thermal Emission Modulator Based on Single-Walled Carbon Nanotubes.

Dynamic control of a material's thermal emission could enable many emerging applications, such as thermal camouflage and infrared (IR) display. Low-dimensional carbon nanomaterials have shown great potential in these applications because of their tuneability in charge density via static gating or ionic intercalation. Herein, a thermal emission modulator based on single-walled carbon nanotubes (SWCNTs) is realized by ionic gating. The Fermi energy of the SWCNTs is shifted via the adsorption of ions on the surface, and the highest emissivity is observed at the neutral state while both P-type and N-type SWCNTs have a reduced emissivity. An emissivity modulation range is achieved approximately from 0.45 to 0.95 within the electrochemical window of the used ionic liquid. Thermal camouflage and IR display applications are then demonstrated by utilizing the tuneable thermal emissivity of the fabricated SWNCT films. More importantly, a single-layer structure allows effective dynamic control purely by static gating, without involving any ion interaction process that may cause structural damage, as observed in graphene and multi-walled nanotubes. Therefore, the SWCNT-based IR modulators exhibit long-term stability, with nearly identical modulation range and response time after 6000 dynamic tuning cycles, indicating great potential for practical applications.

Nanomaterial-Based Label-Free Electrochemical Aptasensors for the Detection of Thrombin.

Thrombin plays a central role in hemostasis and its imbalances in coagulation can lead to various pathologies. It is of clinical significance to develop a fast and accurate method for the quantitative detection of thrombin. Electrochemical aptasensors have the capability of combining the specific selectivity from aptamers with the extraordinary sensitivity from electrochemical techniques and thus have attracted considerable attention for the trace-level detection of thrombin. Nanomaterials and nanostructures can further enhance the performance of thrombin aptasensors to achieve high sensitivity, selectivity, and antifouling functions. In highlighting these material merits and their impacts on sensor performance, this paper reviews the most recent advances in label-free electrochemical aptasensors for thrombin detection, with an emphasis on nanomaterials and nanostructures utilized in sensor design and fabrication. The performance, advantages, and limitations of those aptasensors are summarized and compared according to their material structures and compositions.

Coupling Long-Range Facet Junction and Interfacial Heterojunction via Edge-Selective Deposition for High-Performance Z-Scheme Photocatalyst.

The construction of photocatalytic systems that have strong redox capability, effective charge separation, and large reactive surfaces is of great scientific and practical interest. Herein, an edge-connected 2D/2D Z-scheme system that combines the facet junction and the interfacial heterojunction to achieve effective long-range charge separation and large reactive surface exposure is designed and fabricated. The heterostructure is realized by the selective growth of 2D-layered MoS2 nanoflakes on the edge-sites of thin TiO2 nanosheets via an Au-promoted photodeposition method. Attributed to the synergetic coupling of the facet junction and the interfacial heterojunction that assures the effective charge separation, and the tremendous but physically separated reactive sites offered by layered MoS2 and highly-exposed (001) facets of TiO2 , respectively, the artificial Z-scheme exhibits excellent photocatalytic performance in photodegradation tests. Moreover, the junctional plasmonic Au nanoclusters not only act as electron traps to promote the edge-selective synthesis but also generate "hot electrons" to further boost photocatalytic performance. The Z-scheme charge-flow direction in the heterostructure and the roles of electrons and holes are comprehensively studied using in situ irradiated X-ray photoelectron spectroscopy and photodegradation tests. This work offers a new insight into designing high-performance Z-scheme photocatalytic systems.

Rational and wide-range tuning of CNT aerogel conductors with multifunctionalities.

Different from conventional conductors, elastic 3D nanoarchitectured conductors have shown promise in developing various flexible devices. However, rational design and control of their microstructures to achieve desired physicochemical properties is challenging and lacks comprehensive and profound investigation. In this study, we report an interesting quantitative correlation between density and physical properties when highly porous CNT aerogels are densified, enabling a wide-range tuning of CNT 3D networked structures with different functions. Upon densification by compressing the original thickness of a CNT aerogel by 100 fold, a linear double-logarithmic structure-property relationship in terms of both thickness and density is witnessed, with the resultant density increased by a factor of 100 from 3 to 286 mg cm-3, Young's modulus by 20 times (5.0-105 kPa), electrical conductivity by 400 times (0.4-163 s cm-1), and thermal conductivity by 140 times (0.048-6.7 W m-1 K-1). It can be thus inferred that the CNT aerogel can be regulated with desired mechanical, electrical and thermal properties in a quantitative manner over a wide range, making it promising as a multifunctional aerogel conductor. As a proof, two pieces of CNT aerogel conductors tailored with high conductivity and low thermal conductivity are employed to fabricate a flexible TE device using a simple all-carbon design, which yields a typical power density of 27.5 µW cm-2 and stable outputs under various deformations, demonstrating a potential strategy for design and fabrication of low-cost, flexible and portable power-generation devices.

Nature-Inspired, Graphene-Wrapped 3D MoS2 Ultrathin Microflower Architecture as a High-Performance Anode Material for Sodium-Ion Batteries.

In response to the increasing concern for energy management, molybdenum disulfide (MoS2) has been extensively researched as an attractive anode material for sodium-ion batteries (SIBs). The proficient cycling durability and good rate performance of SIBs are the two key parameters that determine their potential for practical use. In this study, nature-inspired three-dimensional (3D) MoS2 ultrathin marigold flower-like microstructures were prepared by a controlled hydrothermal method. These microscale flowers are constructed by arbitrarily arranged but closely interconnected two-dimensional ultrathin MoS2 nanosheets. The as-prepared MoS2 microflowers (MFs) have then been chemically wrapped by layered graphene sheets to form the bonded 3D hybrid MoS2-G networks. TEM, SEM, XRD, XPS, and Raman characterizations were used to study the morphology, crystallization, chemical compositions, and wrapping contact between MoS2 and graphene. The ultrathin nature of MoS2 in 3D MFs and graphene wrapping provide strong electrical conductive channels and conductive networks in an electrode. Benefitting from the 2 nm ultrathin crystalline MoS2 sheets, chemically bonded graphene, defect-induced sodium storage active sites, and 3D interstitial spaces, the prepared electrode exhibited an outstanding specific capacity (606 mA h g-1 at 200 mA g-1), remarkable rate performance (345 mA h g-1 at 1600 mA g-1), and long cycle life (over 100 cycles with tremendous Coulombic efficiencies beyond 100%). The proposed synthesis strategy and 3D design developed in the present study reveal a unique way to fabricate promising anode materials for SIBs.

Single-Step Selective Laser Writing of Flexible Photodetectors for Wearable Optoelectronics.

The increasing demand for wearable optoelectronics in biomedicine, prosthetics, and soft robotics calls for innovative and transformative technologies that permit facile fabrication of compact and flexible photodetectors with high performance. Herein, by developing a single-step selective laser writing strategy that can finely tailor material properties through incident photon density control and lead to the formation of hierarchical hybrid nanocomposites, e.g., reduced graphene oxide (rGO)-zinc oxide (ZnO), a highly flexible and all rGO-ZnO hybrid-based photodetector is successfully constructed. The device features 3D ultraporous hybrid films with high photoresponsivity as the active detection layer, and hybrid nanoflakes with superior electrical conductivity as interdigitated electrodes. Benefitting from enhanced photocarrier generation because of the ultraporous film morphology, efficient separation of electron-hole pairs at rGO-ZnO heterojunctions, and fast electron transport by highly conductive rGO nanosheets, the photodetector exhibits high, linear, and reproducible responsivities to a wide range of ultraviolet (UV) intensities. Furthermore, the excellent mechanical flexibility and robustness enable the photodetector to be conformally attached to skin, thus intimately monitoring the exposure dosage of human body to UV light for skin disease prevention. This study advances the fabrication of flexible optoelectronic devices with reduced complexity, facilitating the integration of wearable optoelectronics and epidermal systems.

Flexible electrochromic materials based on CNT/PDA hybrids.

Materials that change color in response to external stimuli can cater to diverse applications from sensing to art. If made flexible, stretchable and weavable, they may even be directly integrated with advanced technologies such as smart textiles. A new class of engineered composite based on polydiacetylene (PDA) functionalized carbon nanotubes (CNT) shows tremendous potential in this regard. While the inherent multi stimuli chromatic response of the polymer (blue to red) is retained, the underlying conducting CNTs invoke electrochromism in PDA. Further, the fiber form factor of dry-spun CNT yarns facilitate direct weaving of large scale electrochromic fabrics, where current flow and thus color change can be accurately controlled. This review summarizes the fundamental aspects of CNT yarns and PDAs, focusing especially on their interaction chemistry which results in the scientifically and commercially appealing electrochromic transition in these hybrids.

Enhanced Flexibility and Microwave Absorption Properties of HfC/SiC Nanofiber Mats.

Hafnium carbide (HfC) phase, with a high melting point, excellent strength, and high electrical conductivity, could be a suitable addition to enhance the microwave absorption properties of one-dimensional silicon carbide (SiC) nanomaterials without sacrificing its high-temperature thermal stability. In the present work, HfC/SiC hybrid nanofiber mats with different HfC loading contents are fabricated by electrospinning and high-temperature pyrolysis. HfC hybrids with sizes of 5-10 nm are embedded in the SiC nanofibers. As the HfC content increases from 0 to 6.3 wt %, the average diameter of the fibers drops from 2.62 µm to 260 nm. Meanwhile, the electrical conductivity rises from 7.9 × 10-8 to 4.2 × 10-5 S/cm. Moreover, the flexibility of the nanofiber mats is also greatly improved, according to a 200-times 180° bending test. Furthermore, compared with pure SiC fiber mats, the HfC/SiC nanofiber mats possess much larger dielectric loss because of higher electrical conductivity. At the optimal HfC content of 2.5 wt %, the HfC/SiC nanofibers/silicon resin composite (10 wt %) exhibits a minimal reflection loss (RL) of -33.9 dB at 12.8 GHz and a 3 mm thickness with a broad effective absorption bandwidth (RL < -10 dB) of 7.4 GHz. The above results prove that introducing HfC into SiC nanofiber mats is an effective way to enhance their flexibility, dielectric properties, and microwave absorption performance.

Flexible Fe3Si/SiC ultrathin hybrid fiber mats with designable microwave absorption performance.

Flexible Fe3Si/SiC ultrathin fiber mats have been fabricated by electrospinning and high temperature treatment (1400 °C) using polycarbosilane (PCS) and ferric acetylacetonate (Fe(acac)3) as precursors. The crystallization degree, flexibility, electrical conductivity, dielectric loss and microwave absorption properties of the hybrid fibers have been dramatically enhanced by the introduction of Fe. Fe3Si nanoparticles with a diameter around 500 nm are embedded in SiC fibers. As the Fe3Si content increases from 0 to 6.5 wt%, the related saturation magnetization (M s) values increase from 0 to 8.4 emu g-1, and the electrical conductivity rises from 7.9 × 10-8 to 3.1 × 10-3 S cm-1. Moreover, the flexibility of Fe3Si/SiC hybrid fiber mats is greatly improved and remains intact after 500 times 180°-bending testing. Compared with pure SiC fibers, the Fe3Si/SiC hybrid fibers process higher dielectric and magnetic loss, which would be further advanced as more Fe3Si phase is introduced. At the optimal Fe3Si content of 3.8 wt%, the Fe3Si/SiC fibers/silicon resin composite (5 wt%) exhibits minimal reflection loss (RL) of -22.5 dB at 16.5 GHz and 2.5 mm thickness with a wide effective absorption bandwidth (EAB, RL < -10 dB) of 8.5 GHz. The microwave absorption performance can be further promoted by multi component stacking fiber mat composites which contain both low and high Fe3Si content layers. Furthermore, the position of the microwave absorption bands can also be simply manipulated by designing the stacking components and structure.

All-Graphene-Based Highly Flexible Noncontact Electronic Skin.

Noncontact electronic skin (e-skin), which possesses superior long-range and high-spatial-resolution sensory properties, is becoming indispensable in fulfilling the emulation of human sensation via prosthetics. Here, we present an advanced design and fabrication of all-graphene-based highly flexible noncontact e-skins by virtue of femtosecond laser direct writing (FsLDW). The photoreduced graphene oxide patterns function as the conductive electrodes, whereas the pristine graphene oxide thin film serves as the sensing layer. The as-fabricated e-skins exhibit high sensitivity, fast response-recovery behavior, good long-term stability, and excellent mechanical robustness. In-depth analysis reveals that the sensing mechanism is attributed to proton and ionic conductivity in the low and high humidity conditions, respectively. By taking the merits of the FsLDW, a 4 × 4 sensing matrix is facilely integrated in a single-step, eco-friendly, and green process. The light-weight and in-plane matrix shows high-spatial-resolution sensing capabilities over a long detection range in a noncontact mode. This study will open up an avenue to innovations in the noncontact e-skins and hold a promise for applications in wearable human-machine interfaces, robotics, and bioelectronics.

SiC Nanofiber Mat: A Broad-Band Microwave Absorber, and the Alignment Effect.

Fiber alignment is a key factor that determines the physical properties of nanofiber mats. In this work, SiC nanofiber mats with or without fiber alignment are fabricated via electrospinning and the microwave electromagnetic properties of their silicone resin composites (5 wt %) are investigated in 2-18 GHz. By comparing with the composite containing SiC whisker, it is found that the nanofiber mats show superior dielectric loss and a minimal reflection loss (RL) of around -49 dB at 8.6 GHz and 4.3 mm thickness, associated with a broad effective absorption (<-10 dB) bandwidth (EAB) of about 7.2 GHz at 2.8 mm thickness. Moreover, the performance can be further enhanced (RL = -53 dB at 17.6 GHz and 2.3 mm thickness) by aligning the nanofiber in the plane of mat, accompanied by the shift of absorption peak to higher-frequency direction and broader EAB up to 8.6 GHz at 3 mm. In addition, the stacking ways of aligned SiC nanofiber mats (either parallel or perpendicular) are proved to have a negligible effect on their microwave properties. Compared with parallel stacking of the aligned mats, cross-stacking (perpendicular) only leads to a slight drop of the attenuation ability. It confirms that alignment of nanofiber in the mats offers a more effective approach to improve the microwave absorption properties than changing the ways of stacking. Furthermore, it is worth mentioning that the low loading fraction (5 wt %) is a great advantage to reduce the weight as well as the cost for large-scale production. All of these facts indicate that the aligned SiC nanofiber mats can serve as a great lightweight and broad-band microwave absorber.

Electrospinning of Fe/SiC Hybrid Fibers for Highly Efficient Microwave Absorption.

Fe/SiC hybrid fibers have been fabricated by electrospinning and subsequent high-temperature (1300 °C) pyrolysis in Ar atmosphere using polycarbosilane (PCS) and Fe3O4 precursors. It is found that the introduction of Fe has had a dramatic impact on the morphology, crystallization temperature, and microwave electromagnetic properties of the hybrid fibers. In addition, the Fe particles have acted as catalyst sites to facilitate the growth of SiCO nanowires on the surface of the hybrid fibers. As a result, the permittivity and permeability have been enhanced effectively, and the high reflection loss (RL) has been achieved at a low frequency band with a thin absorber thickness. At an optimal PCS/Fe ratio of 3:0.5, the hybrid fiber/silicone resin composite (35 wt %) with a 2.25 mm absorber thickness exhibits a minimal RL of about -46.3 dB at 6.4 GHz. The wide frequency band (4-9.6 GHz) and thin absorber thickness (1.5-3.5 mm) for effective absorption (<-20 dB) prove that the Fe/SiC hybrid fiber is a promising candidate to work as a highly efficient and lightweight absorber in the C band (4-8 GHz).

Direct Preparation of Carbon Nanotube Intramolecular Junctions on Structured Substrates.

Leveraging the unique properties of single-walled carbon nanotube (SWNT) intramolecular junctions (IMJs) in innovative nanodevices and next-generation nanoelectronics requires controllable, repeatable, and large-scale preparation, together with rapid identification and comprehensive characterization of such structures. Here we demonstrate SWNT IMJs through directly growing ultralong SWNTs on trenched substrates. It is found that the trench configurations introduce axial strain in partially suspended nanotubes, and promote bending deformation in the vicinity of the trench edges. As a result, the lattice and electronic structure of the nanotubes can be locally modified, to form IMJs in the deformation regions. The trench patterns also enable pre-defining the formation locations of SWNT IMJs, facilitating the rapid identification. Elaborate Raman characterization has verified the formation of SWNT IMJs and identified their types. Rectifying behavior has been observed by electrical measurements on the as-prepared semiconducting-semiconducting (S-S) junction.

Oxygen Evolution Assisted Fabrication of Highly Loaded Carbon Nanotube/MnO2 Hybrid Films for High-Performance Flexible Pseudosupercapacitors.

To date, it has been a great challenge to design high-performance flexible energy storage devices for sufficient loading of redox species in the electrode assemblies, with well-maintained mechanical robustness and enhanced electron/ionic transport during charge/discharge cycles. An electrochemical activation strategy is demonstrated for the facile regeneration of carbon nanotube (CNT) film prepared via floating catalyst chemical vapor deposition strategy into a flexible, robust, and highly conductive hydrogel-like film, which is promising as electrode matrix for efficient loading of redox species and the fabrication of high-performance flexible pseudosupercapacitors. The strong and conductive CNT films can be effectively expanded and activated by electrochemical anodic oxygen evolution reaction, presenting greatly enhanced internal space and surface wettability with well-maintained strength, flexibility, and conductivity. The as-formed hydrogel-like film is quite favorable for electrochemical deposition of manganese dioxide (MnO2 ) with loading mass up to 93 wt% and electrode capacitance kept around 300 F g(-1) (areal capacitance of 1.2 F cm(-2) ). This hybrid film was further used to assemble a flexible symmetric pseudosupercapacitor without using any other current collectors and conductive additives. The assembled flexible supercapacitors exhibited good rate performance, with the areal capacitance of more than 300 mF cm(-2) , much superior to other reported MnO2 based flexible thin-film supercapacitors.

Quantum dot decorated aligned carbon nanotube bundles for a performance enhanced photoswitch.

Photoactive materials that are triggered by the irradiation of light to generate an electrical response provide an ecofriendly platform to afford efficient power sources and switches. A chemical assembly of well-known elements with aligned carbon nanotube bundles is reported here, which was employed to form an efficient photo-induced charge transfer device. The primary elements of this device are ultra-long multi-walled carbon nanotube (MWCNT) bundles, polyaniline (PANI) thin film coating, and CdSe quantum dots (QDs). Highly ordered and horizontally aligned MWCNT bundles were coated with PANI to enhance charge transfer properties of active QDs in this platform. The obtained device (CdSe-MWCNT@PANI) constructed on a silicon base exhibits highly efficient power conversion capabilities owing to the aligned MWCNT bundle assisted enhanced charge transport pathways generated within the device. The device also shows a short circuit current density (Jsc) of 9.81 mA cm(-2) and an open circuit voltage (Voc) of 0.46 V. The power conversion efficiency (PCE) of the device is 5.41%, and the current response is quite stable, highly responsive, and reproducible.

[Safety and efficacy of gemcitabine combined with S-1 in the treatment of advanced pancreatic cancer].

OBJECTIVE: To evaluate the safety and efficacy of gemcitabine combined with S-1 in the treatment of advanced pancreatic cancer. METHODS: A retrospective analysis of the clinical data of 49 patients with advanced pancreatic cancer, who did not receive radiotherapy and chemotherapy, were divided into two groups: the study group (25 cases), and control group (24 cases). Patients in the study group received gemcitabine 1 000 mg/m² via intravenous drip at the first and 8th days, and received S-1 80 mg/m², morning and evening (twice a day) for the first 14 days, and 21 days as a treatment cycle of chemotherapy.The control group was given GEMOX regimen: Gemcitabine 1 000 mg/m² via intravenous drip at the first and 8 days, and oxaliplatin 130 mg/m² via intravenous drip at the first day, and 21 d for a treatment cycle of chemotherapy. The efficacy and adverse reactions in patients of the study and control groups were observed and compared. RESULTS: The efficiency of the study group was 32.0% and disease control rate was 72.0%. The efficiency of the control group was 25.0% and disease control rate was 58.3%. The differences between the two groups were statistically not significant (P > 0.05 for all). The clinical benefit rate in the study group and control group were 80.0% and 50.0%, respectively, showing a significant difference (P < 0.05). The median survival time was 9.7 months in patients of the study group and 9.0 months in the control group, with a significant difference (P < 0.05). The drug toxicity was well tolerated in both groups, and no chemotherapy-related death occurred. The major adverse reactions were myelosuppression and digestive tract reactions, and the adverse reactions in the study group were lower than those in the control group. CONCLUSIONS: Gemcitabine combined with S-1 is effective and safe in the treatment of advanced pancreatic cancer, with less side effects, and can be tolerated by the patients.

Interaction and charge transfer between isolated thylakoids and multi-walled carbon nanotubes.

Charge separation in photosynthetic light reactions has gained much interest in an attempt to fabricate biological photovoltaic devices through integration of photosynthetic material and conducting electrodes. Direct interaction between thylakoids, as representatives of photosynthetic materials, and multi-walled carbon nanotubes (MWCNTs) is expected to increase charge transfer. Thylakoids are isolated from spinach leaf chloroplasts and pristine MWCNTs are dispersed in Triton X-100 (TX-100) as a surfactant to retain their electronic properties through non-covalent interactions. The Raman and UV-Vis spectra suggest close interactions between the thylakoids and the MWCNTs. Stable thylakoids including the embedded protein subunits and light harvesting antennas can be detected from the non-shifted 680 nm absorbance peak. The 50% fluorescence quenching in the MWCNTs-thylakoids preparation as compared to thylakoids alone using single wavelength excitation suggests charge transfer between the thylakoids and the MWCNTs.

Three-dimensional plasmonic photoanodes based on Au-embedded TiO(2) structures for enhanced visible-light water splitting.

Plasmon-assisted visible light photocatalysis presents a possible solution for direct solar-to-fuel production. Here we investigate the plasmon-enhanced photocatalytic water splitting using different TiO2/Au electrode structures. Experimental data demonstrates that the Au embedded in TiO2 (Au-in-TiO2) electrode greatly outperforms the Au sitting on TiO2 (Au-on-TiO2) electrode. Numerical simulation shows that the local electric field is very intense in the semiconductor near Au nanoparticles, which causes the enhancement of electron-hole pair generation. A 3D Au-embedded TiO2 structure is thus proposed to further improve the light absorption and photocatalytic performance.

Effect of channel length on the electrical response of carbon nanotube field-effect transistors to deoxyribonucleic acid hybridization.

A single-walled carbon nanotube (SWCNT) in a field-effect transistor (FET) configuration provides an ideal electronic path for label-free detection of nucleic acid hybridization. The simultaneous influence of more than one response mechanism in hybridization detection causes a variation in electrical parameters such as conductance, transconductance, threshold voltage and hysteresis gap. The channel length (L) dependence of each of these parameters necessitates the need to include them when interpreting the effect of L on the response to hybridization. Using the definitions of intrinsic effective mobility (µe) and device field-effect mobility (µf), two new parameters were defined to interpret the effect of L on the FET response to hybridization. Our results indicate that FETs with ≈300 µm long SWCNT exhibited the most appreciable response to hybridization, which complied with the variation trend in response to the newly defined parameters.

Sequence-dependent electrical response of ssDNA-decorated carbon nanotube, field-effect transistors to dopamine.

Single-walled carbon nanotube (SWCNT)-based field-effect transistors (FETs) have been explored for use as biological/chemical sensors. Dopamine (DA) is a biomolecule with great clinical significance for disease diagnosis, however, SWCNT FETs lack responsivity and selectivity for its detection due to the presence of interfering compounds such as uric acid (UA). Surface modification of CNTs using single-stranded deoxyribonucleic acid (ssDNA) renders the surface responsive to DA and screens the interferent. Due to the presence of different bases in ssDNA, it is necessary to investigate the effect of sequence on the FET-based molecular recognition of DA. SWCNT FETs were decorated with homo- and repeated-base ssDNA sequences, and the electrical response induced by DA in the presence and absence of UA was gauged in terms of the variation in transistor electrical parameters including conductance, transconductance, threshold voltage and hysteresis gap. Our results showed that the response of ssDNA-decorated devices to DA, irrespective of the presence or absence of UA, was DNA sequence dependent and exhibited the trend: G > A > C and GA > GT > AC > CT, for homo- and repeated-base sequences, respectively. The different response of various SWCNT-ssDNA systems to DA underlines the sequence selectivity, whereas the detection of DA in the presence of UA highlights the molecular selectivity of the ssDNA-decorated devices.