Large-Area Alignment of Supramolecular Columns by Photothermal Laser Writing

Controlling the orientation of highly periodic supramolecular structures of small feature size (<5 nm) is the first step for potential applications in optoelectronics, membranes, and template synthesis. A new method, namely, laser photothermal writing, is introduced to direct the orientation of supramolecular columns over a large area. Supramolecular columns consisting of taper-shaped molecules with long aliphatic tail groups are aligned by a thermal gradient, which is induced by exposing a near-infrared laser beam to a graphene photothermal conversion layer. Intriguingly, the orientation of the supramolecular columns can be controlled in a facile manner by varying the laser scanning velocity and power. In contrast to previous methodologies for aligning supramolecular structures, this laser photothermal mechanism allows the directional and continuous alignment of supramolecular structures over an arbitrary large area with the easy control of laser irradiation. Besides, the laser process also enables area-selective orientation of the supramolecular structures for device-oriented nanopatterning.     

Super‐Resolution Nonlinear Photothermal Microscopy

Super‐resolution fluorescence microscopy enables imaging of fluorescent structures beyond the diffraction limit. However, this technique cannot be applied to weakly fluorescent cellular components or labels. As an alternative, photothermal microscopy based on nonradiative transformation of absorbed energy into heat has demonstrated imaging of nonfluorescent structures including single molecules and ~1‐nm gold nanoparticles. However, previously photothermal imaging has been performed with a diffraction‐limited resolution only. Herein, super‐resolution, far‐field photothermal microscopy based on nonlinear signal dependence on the laser energy is introduced. Among various nonlinear phenomena, including absorption saturation, multiphoton absorption, and signal temperature dependence, signal amplification by laser‐induced nanobubbles around overheated nano‐objects is explored. A Gaussian laser beam profile is used to demonstrate the image spatial sharpening for calibrated 260‐nm metal strips, resolving of a plasmonic nanoassembly, visualization of 10‐nm gold nanoparticles in graphene, and hemoglobin nanoclusters in live erythrocytes with resolution down to 50 nm. These nonlinear phenomena can be used for 3D imaging with improved lateral and axial resolution in most photothermal methods, including photoacoustic microscopy.     

Thermal-feedback-controlled coagulation of egg white by the CO2 laser

Temperature feedback control during laser-assisted tissue coagulation was investigated and demonstrated with the egg-white model. We observed the dynamics of photothermal denaturation during CO2 laser irradiation by simultaneously controlling surface temperature and monitoring He-Ne laser transmission of egg-white samples. Once a quasi-constant surface temperature was established, transmission of egg white tended to decrease linearly with time. Analysis of experimental data strongly suggested a first-order rate process. Since transmission was primarily affected by heat-induced increase in the scattering coefficient and depth of coagulation, we speculated that changes in transmission were reliable indicators of accumulating photothermal damage. Our experiments demonstrated that thermal feedback can effectively control or limit photothermal damage.     

Graphene‐Based Smart Platforms for Combined Cancer Therapy

The extensive research of graphene and its derivatives in biomedical applications during the past few years has witnessed its significance in the field of nanomedicine. Starting from simple drug delivery systems, the application of graphene and its derivatives has been extended to a versatile platform of multiple therapeutic modalities, including photothermal therapy, photodynamic therapy, magnetic hyperthermia therapy, and sonodynamic therapy. In addition to monotherapy, graphene‐based materials are widely applied in combined therapies for enhanced anticancer activity and reduced side effects. In particular, graphene‐based materials are often designed and fabricated as “smart” platforms for stimuli‐responsive nanocarriers, whose therapeutic effects can be activated by the tumor microenvironment, such as acidic pH and elevated glutathione (termed as “endogenous stimuli”), or light, magnetic, or ultrasonic stimuli (termed as “exogenous stimuli”). Herein, the recent advances of smart graphene platforms for combined therapy applications are presented, starting with the principle for the design of graphene‐based smart platforms in combined therapy applications. Next, recent advances of combined therapies contributed by graphene‐based materials, including chemotherapy‐based, photothermal‐therapy‐based, and ultrasound‐therapy‐based synergistic therapy, are outlined. In addition, current challenges and future prospects regarding this promising field are discussed.     

Mid-infrared photothermal heterodyne spectroscopy in a liquid crystal using a quantum cascade laser

We report a technique to measure the mid-infrared photothermal response induced by a tunable quantum cascade laser in the neat liquid crystal 4-octyl-4'-cyanobiphenyl (8CB), without any intercalated dye. Heterodyne detection using a Ti:sapphire laser of the response in the solid, smectic, nematic and isotropic liquid crystal phases allows direct detection of a weak mid-infrared normal mode absorption using an inexpensive photodetector. At high pump power in the nematic phase, we observe an interesting peak splitting in the photothermal response. Tunable lasers that can access still stronger modes will facilitate photothermal heterodyne mid-infrared vibrational spectroscopy.     

The Antibacterial Applications of Graphene and Its Derivatives

Graphene materials have unique structures and outstanding thermal, optical, mechanical and electronic properties. In the last decade, these materials have attracted substantial interest in the field of nanomaterials, with applications ranging from biosensors to biomedicine. Among these applications, great advances have been made in the field of antibacterial agents. Here, recent advancements in the use of graphene and its derivatives as antibacterial agents are reviewed. Graphene is used in three forms: the pristine form; mixed with other antibacterial agents, such as Ag and chitosan; or with a base material, such as poly (N‐vinylcarbazole) (PVK) and poly (lactic acid) (PLA). The main mechanisms proposed to explain the antibacterial behaviors of graphene and its derivatives are the membrane stress hypothesis, the oxidative stress hypothesis, the entrapment hypothesis, the electron transfer hypothesis and the photothermal hypothesis. This review describes contributions to improving these promising materials for antibacterial applications.     

Janus Graphene Liquid Crystalline Fiber with Tunable Properties Enabled by Ultrafast Flash Reduction

Flash photothermal treatment via Xenon lamp with a broad wavelength spectrum can effectively remove oxygen functionalities and restore sp² domains at graphitic carbon materials. The chemical composition and relevant structure formation of flash reduced graphene oxide liquid crystal (GOLC) fibers are investigated in accordance with flash irradiation conditions. Owing to the spatial controllability of reduction level via anisotropic flash irradiation, the mechanical properties and electrical conductivity of graphene fibers can be delicately counterbalanced to attain desired properties. High sensitivity humidity sensors can be fabricated from the flash reduced fibers demonstrating notably higher sensitivity over the thermally reduced counterparts. This ultrafast flash reduction holds great promise for multidimensional macroscopic GO based structures, enabling a wide range of potential applications, including textile electronics and wearable sensors.     

Laser Fabrication of Graphene-Based Flexible Electronics

Recent years have witnessed the rise of graphene and its applications in various electronic devices. Specifically, featuring excellent flexibility, transparency, conductivity, and mechanical robustness, graphene has emerged as a versatile material for flexible electronics. In the past decade, facilitated by various laser processing technologies, including the laser-treatment-induced photoreduction of graphene oxides, flexible patterning, hierarchical structuring, heteroatom doping, controllable thinning, etching, and shock of graphene, along with laser-induced graphene on polyimide, graphene has found broad applications in a wide range of electronic devices, such as power generators, supercapacitors, optoelectronic devices, sensors, and actuators. Here, the recent advancements in the laser fabrication of graphene-based flexible electronic devices are comprehensively summarized. The various laser fabrication technologies that have been employed for the preparation, processing, and modification of graphene and its derivatives are reviewed. A thorough overview of typical laser-enabled flexible electronic devices that are based on various graphene sources is presented. With the rapid progress that has been made in the research on graphene preparation methodologies and laser micronanofabrication technologies, graphene-based electronics may soon undergo fast development.     

Optomechanics with silicon nanowires by harnessing confined electromagnetic modes

The optomechanical coupling that emerges in an optical cavity in which one of the mirrors is a mechanical resonator has allowed sub-Kelvin cooling with the prospect of observing quantum phenomena and self-sustained oscillators with very high spectral purity. Both applications clearly benefit from the use of the smallest possible mechanical resonator. Unfortunately, the optomechanical coupling largely decays when the size of the mechanical system is below the light wavelength. Here, we propose to exploit the optical resonances associated to the light confinement in subwavelength structures to circumvent this limitation, efficiently extending optomechanics to nanoscale objects. We demonstrate this mechanism with suspended silicon nanowires. We are able to optically cool the mechanical vibration of the nanowires from room temperature to 30-40 K or to obtain regenerative mechanical oscillation with a frequency stability of about one part per million. The reported optomechanical phenomena can be exploited for developing cost-optimized mass sensors with sensitivities in the zeptogram range.     

Laser–Material Interactions for Flexible Applications

The use of lasers for industrial, scientific, and medical applications has received an enormous amount of attention due to the advantageous ability of precise parameter control for heat transfer. Laser‐beam‐induced photothermal heating and reactions can modify nanomaterials such as nanoparticles, nanowires, and two‐dimensional materials including graphene, in a controlled manner. There have been numerous efforts to incorporate lasers into advanced electronic processing, especially for inorganic‐based flexible electronics. In order to resolve temperature issues with plastic substrates, laser–material processing has been adopted for various applications in flexible electronics including energy devices, processors, displays, and other peripheral electronic components. Here, recent advances in laser–material interactions for inorganic‐based flexible applications with regard to both materials and processes are presented.     

Cooperative Strategies for Enhancing Performance of Photothermal Therapy (PTT) Agent: Optimizing Its Photothermal Conversion and Cell Internalization Ability

Photothermal conversion ability (PCA) and cell internalization ability (CIA) are two key factors for determining the performance of photothermal agents. The previous studies mostly focus on improving the PCA by exploring new photothermal nanomaterials. Herein, the authors take the hybrids of graphene and gold nanostar (GGN) as an example to investigate the gradually enhanced phototherapy effect by changing the PCA and CIA of photothermal therapy (PTT) agent simultaneously. Based on the GGN, the GGN and the reduced GGN protected by bovine serum albumin (BSA) or BSA‐FA (folic acid) are prepared, which are named as GGNB, rGGNB, and rGGNB‐FA, respectively. The rGGNB showed an enhanced PCA compared to GGNB, leading to strong cell ablation. On the other hand, the 1,2‐dioleoyl‐3‐trimethylammoniumpropan (DOTAP) can activate the endocytosis and promote the CIA of rGGNB, further help rGGNB to be more internalized into the cells. Finally, rGGNB‐FA with the target ability can make itself further internalized into the cells with the aid of DOTAP, which can significantly destroy the cancer cells even at the low laser density of 0.3 W cm^?2. Therefore, a new angle of view is brought out for researching the PTT agents of high performance.     

Graphene Nanomesh Promises Extremely Efficient In Vivo Photothermal Therapy

Reduced graphene oxide nanomesh (rGONM), as one of the recent structures of graphene with a surprisingly strong near‐infrared (NIR) absorption, is used for achieving ultraefficient photothermal therapy. First, by using TiO₂ nanoparticles, graphene oxide nanoplatelets (GONPs) are transformed into GONMs through photocatalytic degradation. Then rGONMs functionalized by polyethylene glycol (PEG), arginine–glycine–aspartic acid (RGD)‐based peptide, and cyanine 7 (Cy7) are utilized for in vivo tumor targeting and fluorescence imaging of human glioblastoma U87MG tumors having α_νβ₃ integrin receptors, in mouse models. The rGONM‐PEG suspension (1 μg mL^?1) exhibits about 4.2‐ and 22.4‐fold higher NIR absorption at 808 nm than rGONP‐PEG and graphene oxide (GO) with lateral dimensions of ≈60 nm and ≈2 μm. In vivo fluorescence imaging demonstrates high selective tumor uptake of rGONM‐PEG‐Cy7‐RGD in mice bearing U87MG cells. The excellent NIR absorbance and tumor targeting of rGONM‐PEG‐Cy7‐RGD results in an ultraefficient photothermal therapy (100% tumor elimination 48 h after intravenous injection of an ultralow concentration (10 μg mL^?1) of rGONM‐PEG‐Cy7‐RGD followed by irradiation with an ultralow laser power (0.1 W cm^?2) for 7 min), whereas the corresponding rGO‐ and rGONP‐based composites do not present remarkable treatments under the same conditions. All the mice treated by rGONM‐PEG‐Cy7‐RGD survived over 100 days, whereas the mice treated by other usual rGO‐based composites were dead before 38 days. The results introduce rGONM as one of the most promising nanomaterials in developing highly desired ultraefficient photothermal therapy.     

Graphene Quantum Dots‐Capped Magnetic Mesoporous Silica Nanoparticles as a Multifunctional Platform for Controlled Drug Delivery,Magnetic Hyperthermia,and Photothermal Therapy

A multifunctional platform is reported for synergistic therapy with controlled drug release, magnetic hyperthermia, and photothermal therapy, which is composed of graphene quantum dots (GQDs) as caps and local photothermal generators and magnetic mesoporous silica nanoparticles (MMSN) as drug carriers and magnetic thermoseeds. The structure, drug release behavior, magnetic hyperthermia capacity, photothermal effect, and synergistic therapeutic efficiency of the MMSN/GQDs nanoparticles are investigated. The results show that monodisperse MMSN/GQDs nanoparticles with the particle size of 100 nm can load doxorubicin (DOX) and trigger DOX release by low pH environment. Furthermore, the MMSN/GQDs nanoparticles can efficiently generate heat to the hyperthermia temperature under an alternating magnetic field or by near infrared irradiation. More importantly, breast cancer 4T1 cells as a model cellular system, the results indicate that compared with chemotherapy, magnetic hyperthermia or photothermal therapy alone, the combined chemo‐magnetic hyperthermia therapy or chemo‐photothermal therapy with the DOX‐loaded MMSN/GQDs nanosystem exhibits a significant synergistic effect, resulting in a higher efficacy to kill cancer cells. Therefore, the MMSN/GQDs multifunctional platform has great potential in cancer therapy for enhancing the therapeutic efficiency.     

Click coupled stitched graphene sheets and their polymer nanocomposites with enhanced photothermal and mechanical properties

The chemically stitched graphene oxide (GO) sheets were obtained using a click chemistry reaction between azide-functionalized GO and alkyne-functionalized GO. The click coupled GO (GO-click-GO) sheets showed the largely increased electrical conductivity and near infrared laser-induced photothermal properties compared to the GO sheets, which result from formation of triazole ring as a bridging linker between the GO sheets. The polyurethane (PU) nanocomposites incorporating the GO-click-GO sheets exhibited enhanced mechanical properties of breaking stress and modulus than the GO/PU nanocomposites. The modulus of GO-click-GO/PU nanocomposites was higher than that of the GO/PU nanocomposites at the same filler loading of 0.1 and 0.5 wt%. The GO-click-GO/PU nanocomposites also showed a significantly improved photothermal properties compared to the GO/PU nanocomposites at the same filler loading. The click coupled stitched GO sheets in this study can be used as the superior reinforcing fillers for mechanically and photothermally high performance polymer nanocomposites.     

Low Temperature Direct of Graphene onto Metal Nano‐Spindt Tip with Applications in Electron Emission

Graphene has been known for its superior electronic properties ever since its discovery in 2004. The high aspect ratio and ballistic transport properties exhibited by this one‐dimensional material are especially useful for electron emission applications. However, they are typically grown horizontally and excess efforts, such as the use of transfer techniques, is required to orientate them before effective electron emission from the graphene edges can occur. These transfer techniques have been shown to lead to additional defects to the as‐grown graphene structure, thereby degrading its properties. Here, we present an approach to directly fabricate graphene onto metal nano‐sized spindt tips (or nanocones) using the solid‐state transformation of carbon deposited from a pulsed laser system at low temperature. Besides providing a layer of chemical and mechanical protection for the metal nanocones, the graphene‐on‐metal nanocones gave enhanced emission properties compared to bare metal nanocones. This was due to the reduction of effective field emission tunneling barrier, which was a result of graphene‐metal charge transfer interactions. Controlling the metal nanocones density was also an important factor in determining the field emission performance, as electron screening from neighboring cones should be minimized.     

Defects in Graphene:Generation,Healing,and Their Effects on the Properties of Graphene:A Review

Graphene has attracted immense investigation since its discovery.Lattice imperfections are introduced into graphene unavoidably during graphene growth or processing.These structural defects are known to significantly affect electronic and chemical properties of graphene.A comprehensive understanding of graphene defect is thus of critical importance.Here we review the major progresses made in defectrelated engineering of graphene.Firstly,we give a brief introduction on the types of defects in graphene.Secondly,the generation and healing of the graphene defects are summarized.Then,the effects of defects on the chemical,electronic,magnetic,and mechanical properties of graphene are discussed.Finally,we address the associated challenges and prospects on the future study of defects in graphene and other nanocarbon materials.     

新型二维层状纳米材料的抗菌研究进展

近年来,抗生素耐药菌在全球范围内得到迅速而广泛地传播,新型抗菌药物的开发刻不容缓。随着生物纳米技术的发展,二维层状纳米材料有望成为处理耐药菌的替代选择。本文综述了石墨烯及其衍生物(GMs)、过渡金属硫化物(TMDs)、层状双氢氧化物(LDHs)及MXenes二维层状纳米材料的结构特征及其抗菌应用的最新报道,讨论了材料的抗菌机制,例如物理/机械损伤、脂质提取、氧化应激和光热/光动力效应等。最后,本文针对二维层状纳米材料的抗菌应用前景进行了展望:(1)材料特有的空间结构及优异的生物相容性决定了其可以作为抗菌药物的理想载体;(2)优异的光动力和光热杀菌效应使它具有治疗局部皮肤感染的强大潜力;(3)拥有光催化抗菌特性的2D材料可制成抗菌涂层,实现简易的原位消毒,有望应用于无菌医疗设备中。     

Optomechanics for a four-stage hybrid-self-electro-optic-device-based free-space optical backplane

We present the design, fabrication, and testing of optomechanics for a free-space optical backplane mounted in a standard 6U VME backplane chassis. The optomechanics implement an optical interconnect consisting of lenslet-to-lenslet, as well as conventional lens-to-lens, links. Mechanical, optical, electrical, thermal, material, and fabrication constraints are studied. Design trade-offs that affect system scalability and ease of assembly are put forward and analyzed. Novel mounting techniques such as a thermal-loaded interference-fitted lens-mounting technique are presented and discussed. Diagnostic tools are developed to quantify the performance of the optomechanics, and experimental results are given and analyzed.     

Laminated Object Manufacturing of 3D‐Printed Laser‐Induced Graphene Foams

Laser‐induced graphene (LIG), a graphene structure synthesized by a one‐step process through laser treatment of commercial polyimide (PI) film in an ambient atmosphere, has been shown to be a versatile material in applications ranging from energy storage to water treatment. However, the process as developed produces only a 2D product on the PI substrate. Here, a 3D LIG foam printing process is developed on the basis of laminated object manufacturing, a widely used additive‐manufacturing technique. A subtractive laser‐milling process to yield further refinements to the 3D structures is also developed and shown here. By combining both techniques, various 3D graphene objects are printed. The LIG foams show good electrical conductivity and mechanical strength, as well as viability in various energy storage and flexible electronic sensor applications.     

High, size-dependent quality factor in an array of graphene mechanical resonators

Graphene's unparalleled strength, stiffness, and low mass per unit area make it an ideal material for nanomechanical resonators, but its relatively low quality factor is an important drawback that has been difficult to overcome. Here, we use a simple procedure to fabricate circular mechanical resonators of various diameters from graphene grown by chemical vapor deposition. In addition to highly reproducible resonance frequencies and mode shapes, we observe a striking improvement of the membrane quality factor with increasing size. At room temperature, we observe quality factors as high as 2400 ± 300 for a resonator 22.5 μm in diameter, about an order of magnitude greater than previously observed quality factors for monolayer graphene. Measurements of quality factor as a function of modal frequency reveal little dependence of Q on frequency. These measurements shed light on the mechanisms behind dissipation in monolayer graphene resonators and demonstrate that the quality factor of graphene resonators relative to their thickness is among the highest of any mechanical resonator demonstrated to date.