Effects of Graphene Oxide and Reduced Graphene Oxide Nanostructures on CD4+ Th2 Lymphocytes

The activation of T helper (Th) lymphocytes is necessary for the adaptive immune response as they contribute to the stimulation of B cells (for the secretion of antibodies) and macrophages (for phagocytosis and destruction of pathogens) and are necessary for cytotoxic T-cell activation to kill infected target cells. For these issues, Th lymphocytes must be converted into Th effector cells after their stimulation through their surface receptors TCR/CD3 (by binding to peptide-major histocompatibility complex localized on antigen-presenting cells) and the CD4 co-receptor. After stimulation, Th cells proliferate and differentiate into subpopulations, like Th1, Th2 or Th17, with different functions during the adaptative immune response. Due to the central role of the activation of Th lymphocytes for an accurate adaptative immune response and considering recent preclinical advances in the use of nanomaterials to enhance T-cell therapy, we evaluated in vitro the effects of graphene oxide (GO) and two types of reduced GO (rGO15 and rGO30) nanostructures on the Th2 lymphocyte cell line SR.D10. This cell line offers the possibility of studying their activation threshold by employing soluble antibodies against TCR/CD3 and against CD4, as well as the simultaneous activation of these two receptors. In the present study, the effects of GO, rGO15 and rGO30 on the activation/proliferation rate of these Th2 lymphocytes have been analyzed by studying cell viability, cell cycle phases, intracellular content of reactive oxygen species (ROS) and cytokine secretion. High lymphocyte viability values were obtained after treatment with these nanostructures, as well as increased proliferation in the presence of rGOs. Moreover, rGO15 treatment decreased the intracellular ROS content of Th2 cells in all stimulated conditions. The analysis of these parameters showed that the presence of these GO and rGO nanostructures did not alter the response of Th2 lymphocytes.     

Preparation and Characterization of Novel Poly(Urethane-Imide) Nanocomposite Based on Graphene,Graphene Oxide and Reduced Graphene Oxide

In this work in-situ preparation of novel poly(urethane-imide)/graphene, graphene oxide and reduced graphene oxide nanocomposite is reported by the reaction of 4,4´-diphenylmethane diisocyanate, polypropylene glycol, 3,3’,4,4′-benzophenone tetra carboxylic dianhydride and nanomaterials in the loadings levels of 0.5, 1.5, 2.5, and 3.5 pbw in propylene carbonate as an alternative green solvent. The synthesized poly(urethane-imide) nanocomposite was characterized by Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (¹HNMR), thermogravimetric analysis (TGA), attenuated total reflection (ATR), X-ray diffraction (XRD) and differential scanning calorimetry (DSC), respectively. The resulting nanocomposite showed enhanced thermal stability when compared with pristine and unfilled poly(urethane-imide) sample.     

有序介孔碳-石墨烯复合材料的制备及其对银纳米粒子吸附性能的研究

以溶剂挥发诱导有机-有机自组装法制备了有序介孔碳-石墨烯（OMC-RGO）复合材料。结果表明：当焙烧温度为800℃时,所得的OMC-RGO复合材料与OMC相比,其电导率从0.76S/m增加到32.5S/m,提高到42.8倍;但BET比表面积和孔容分别从670m2/g和0.40cm3/g下降到361m2/g和0.23cm3/g,降低的比率分别为46.1%和42.5%。随后,我们以OMC-RGO为载体,通过物理吸附制备了有序介孔碳-石墨烯-银纳米粒子（OMC-RGO-Ag）复合材料。结果表明：OMC-RGO表面上Ag纳米粒子的粒径在20～40nm之间;且OMC与RGO复合后,RGO表面上的含氧官能团有利于吸附较多的Ag纳米粒子。     

Functionalized Reduced Graphene Oxide as a Versatile Tool for Cancer Therapy

Cancer is one of the deadliest diseases in human history with extremely poor prognosis. Although many traditional therapeutic modalities—such as surgery, chemotherapy, and radiation therapy—have proved to be successful in inhibiting the growth of tumor cells, their side effects may vastly limited the actual benefits and patient acceptance. In this context, a nanomedicine approach for cancer therapy using functionalized nanomaterial has been gaining ground recently. Considering the ability to carry various anticancer drugs and to act as a photothermal agent, the use of carbon-based nanomaterials for cancer therapy has advanced rapidly. Within those nanomaterials, reduced graphene oxide (rGO), a graphene family 2D carbon nanomaterial, emerged as a good candidate for cancer photothermal therapy due to its excellent photothermal conversion in the near infrared range, large specific surface area for drug loading, as well as functional groups for functionalization with molecules such as photosensitizers, siRNA, ligands, etc. By unique design, multifunctional nanosystems could be designed based on rGO, which are endowed with promising temperature/pH-dependent drug/gene delivery abilities for multimodal cancer therapy. This could be further augmented by additional advantages offered by functionalized rGO, such as high biocompatibility, targeted delivery, and enhanced photothermal effects. Herewith, we first provide an overview of the most effective reducing agents for rGO synthesis via chemical reduction. This was followed by in-depth review of application of functionalized rGO in different cancer treatment modalities such as chemotherapy, photothermal therapy and/or photodynamic therapy, gene therapy, chemotherapy/phototherapy, and photothermal/immunotherapy.     

介孔CoMn2O4/还原氧化石墨烯复合材料的制备及其超级电容性能

采用共沉淀法制备了CoMn₂O₄/还原氧化石墨烯(CoMn₂O₄/rGO)复合电极材料,并研究了石墨烯含量对CoMn₂O₄/rGO复合材料形貌、微观结构及电化学性能的影响。结果表明:CoMn₂O₄纳米颗粒沉积在石墨烯纳米片的表面,随着石墨烯含量的增加,CoMn₂O₄纳米颗粒在r GO表面的分布逐渐均匀,聚集现象消失。CoMn₂O₄/rGO具有高的比表面积及优良的电化学性能,其中CoMn₂O₄/rGO20 (rGO质量分数为20%)电容性能最好,在电流密度1 A/g时具有1 420 F/g的比电容。CoMn₂O₄/rGO30(rGO质量分数为30%)的倍率性能和循环稳定性能最好。2 000次充放电后,样品CoMn₂O₄/rGO30在5 A/g时的比电容保持率为94%,样品CoMn₂O₄的比电容保持率为78%。     

Wood Pulp Fiber Wrapped by Fish-Scale Graphene as Flexible and Free-Standing Supercapacitor Electrode

Poplar wood pulp was adopted as both frame and precursor for the synthesis of pulp fiber (PF)/reduced graphene oxide composite via a simple and low-cost method. In this method, the PF based on graphene (PFG) composite film electrode was prepared by a simple vacuum filtration process with various ratios (PF: reduced graphene oxide (RGO)?=?5:1, PF:RGO?=?5:2, PF:RGO?=?5:3, PF:RGO?=?5:4, PF:RGO?=?5:5). In terms of special structures, the PFG can be used as electrodes without metal-collector, adhesives, and additives. The optimal ratio (PF:RGO?=?5:4) film electrode displayed a high areal-specific capacitance of 683 mF/cm² at 1?mA/cm² with a mass of 5.3?mg/cm² (specific capacitance of 129?F/g) and good cycling stability (87.5% capacitance retention after 10,000 cycles at 5?mA/cm²) as well as excellent rate capability and high flexibility (suitable for any angle, even 180°). Moreover, the device could possess a maximum energy density of 47.71?μWh/cm² and a maximum power density of 1251?μW/cm². These results suggest that the composite PGF film is a promising electrode material.     

Electrical-Triggered Multicolor Reversible Color-Changing Ag Nanoparticles/Reduced Graphene Oxide/Polyurethane Conductive Fibers

Smart color-changing fibers attract much attention owing to their importance as a component of flexible electronics. A facile and scalable method of multicolor reversible electro–thermochromic Ag nanoparticles/reduced graphene oxide/polyurethane conductive fiber (ETC AgNPs/rGO/PU conductive fiber) is fabricated, which contains the polyurethane (PU) as the inner layer, reduced graphene oxide (rGO) with Ag nanoparticles (AgNPs) as the conductive layer, and thermochromic paste as the outermost layer. It possesses excellent electrothermal and color-changing properties and rapidly generates Joule heat at 0.5 V, which makes the fiber surface temperature reach 39.81 °C rapidly. The color switching rate is fast and changes from green to yellow within 2 s. During the process of 250 times on/off voltage, ETC AgNPs/rGO/PU conductive fibers still maintain excellent electrical and thermal properties and color change stability; even in the washing, strong acid, and strong alkali environment, they still have excellent durability. This human subjective adjustable electrical–thermal–color multi-level induced modulation makes it possible to be applied to smart wearable fields such as visual camouflage, personal thermal management, and active information transfer.     

Emerging Concepts in Defective Macrophage Phagocytosis in Cystic Fibrosis

Cystic fibrosis (CF) is caused by mutations of the cystic fibrosis transmembrane conductance regulator (CFTR) gene. Chronic inflammation and decline in lung function are major reasons for morbidity in CF. Mutant CFTR expressed in phagocytic cells such as macrophages contributes to persistent infection, inflammation, and lung disease in CF. Macrophages play a central role in innate immunity by eliminating pathogenic microbes by a process called phagocytosis. Phagocytosis is required for tissue homeostasis, balancing inflammation, and crosstalk with the adaptive immune system for antigen presentation. This review focused on (1) current understandings of the signaling underlying phagocytic mechanisms; (2) existing evidence for phagocytic dysregulation in CF; and (3) the emerging role of CFTR modulators in influencing CF phagocytic function. Alterations in CF macrophages from receptor initiation to phagosome formation are linked to disease progression in CF. A deeper understanding of macrophages in the context of CFTR and phagocytosis proteins at each step of phagosome formation might contribute to the new therapeutic development of dysregulated innate immunity in CF. Therefore, the review also indicates future areas of research in the context of CFTR and macrophages.     

低结晶度NiMn2O4/还原氧化石墨烯复合材料的制备及其超级电容性能

采用溶剂热法制备了NiMn₂O₄/还原氧化石墨烯(NiMn₂O₄/r GO)复合材料,并对表面形貌、微观结构和电化学性能进行了表征和测试。结果表明:低结晶度的NiMn₂O₄以丝绒状均匀地沉积在rGO纳米片上,几乎没有rGO裸露在外,NiMn₂O₄纳米颗粒间的聚集现象消失;同时NiMn₂O₄的覆盖也有效地阻止了石墨烯层之间的团聚。由于其独特的结构,NiMn₂O₄/r GO具有较大的比表面积和良好的导电性。在1 A·g^–1时的比电容是1 675 F·g^–1。在5 A·g^–1时,经过2 000个充放电循环后,NiMn₂O₄/r GO的比电容保持率为91%。     

氧化石墨烯对卤化银微晶乳剂的超增感效应

使用反馈式微机控制双注乳化仪,制得了溴碘化银微晶乳剂。在特定条件下,将一定量的氧化石墨烯分别在乳剂乳化后、化学增感过程和光谱增感过程中加入,获得3个系列经过掺杂增感后的乳剂。对其进行感光性能测试,结果表明:(1)氧化石墨烯在化学增感过程中具有有效的防灰雾效应,可作为防灰雾剂;(2)氧化石墨烯在化学增感过程中,在达到平衡后,具有一定的增感效应;(3)氧化石墨烯在光谱增感过程中,随着染料吸附时间增加,对乳剂的增感作用愈明显,具有增感效应和防灰雾功能。     

Green Catalytic Process for Click Synthesis Promoted by Copper Oxide Nanocomposite Supported on Graphene Oxide

The catalytic activity of graphene oxide supported copper oxide (CuO–GO) has been investigated in Click synthesis of 1,2,3‐triazole derivatives under green reaction conditions. In the context of green approach, water is used as solvent under ligand free and aerobic conditions at room temperature, with low catalyst loading (0.2 mol %) while ensuring the recovery and reusability of the catalyst. The catalyst affords excellent selectivity in formation of the desired products in good to excellent yields. Further, the work‐up procedure adopted here is clean and simple, while recycling the organic solvents that one used for work‐up procedure. It is proposed that the functional groups present on the GO surface are effective for preventing the aggregation of the catalytically active copper oxide species during the reaction. Moreover, the excellent performance of CuO–GO nanocomposite is ascribed to the excellent dispersity of the catalyst in water, hydrophilic nature of the GO for the accumulation of organic substrates in water and the “Breslow effect.”

     

氧化石墨烯在萘氧化中的作用研究

石墨烯在催化领域的应用越来越受到人们的重视。本文构建了萘—叔丁基过氧化氢（TBHP）—氧化石墨烯的催化氧化体系,研究氧化石墨烯在萘氧化过程中的作用。考察了氧化石墨烯种类、溶剂种类、氧化剂含量、石墨烯用量、反应温度、反应时间等因素对萘氧化反应的影响。实验结果表明氧化石墨烯的引入可以提高萘的转化率和1,4-萘醌收率; 当萘用量为100mg,氧化剂（TBHP）2.4mL,氧化石墨烯RGO（10wt%）20mg,反应溶剂为乙酸（1.2mL）,反应温度100℃,反应时间22h 时,得到了较优的反应结果。在此基础上,初步探讨了氧化石墨烯对萘氧化的作用机理。     

氧化石墨烯增强环氧树脂复合材料的制备与性能

利用二乙烯三胺在氧化石墨烯(GO)表面引入氨基基团得到改性GO,然后与环氧树脂(EP)复合,制备出GO增强EP复合材料。性能测试结果表明,该复合材料具有良好的疏水性及力学性能。复合材料的吸水率随着改性GO含量增加先降低后提高,当改性GO含量为0.2%时,吸水率最低,浸泡12 d后吸水率为0.125%,与纯EP相比降低了81.48%,当改性GO含量继续增加,由于复合材料界面局部空隙的增加,吸水率反而大幅上升。复合材料的拉伸强度、冲击强度随着改性GO含量增加先提高后降低,当改性GO含量为0.05%时,拉伸强度、冲击强度最高,分别为50.94 MPa,5.78 k J/m2,相比纯EP增加了104%和90%。综合考虑,当改性GO含量为0.05%时,复合材料的分散性能、疏水性及力学性能较优。     

氧化石墨烯负载金纳米颗粒及其催化活性研究

在不外加任何还原剂的情况下,利用氯金酸和氧化石墨烯之间的氧化还原反应将金纳米颗粒成功负载到氧化石墨烯上,合成了金纳米颗粒/氧化石墨烯复合材料。利用透射电镜(TEM)和X-射线衍射(XRD)对复合材料进行了结构表征与形态分析,并研究了金纳米颗粒/氧化石墨烯复合材料对Suzuki-Miyaura偶联反应的催化效果。结果表明,通过调节氯金酸与氧化石墨烯的质量比,可以得到不同形状的金纳米颗粒;金纳米颗粒/氧化石墨烯复合材料对Suzuki-Miyaura偶联反应具有很高的催化活性,并且很容易从反应体系中回收。     

Highly Improved Microwave Absorbing and Mechanical Properties in Cold Sintered ZnO by Incorporating Graphene Oxide

The abruptly increased dielectric loss in graphene oxide (GO) induced by high-temperature sintering has prevented GO from being used as an absorbent in ceramic-matrix microwave absorbing composites (MACs). Here, we show the first example that the pristine structure of GO can be largely preserved in ceramic composite by using cold sintering technology. Compared with the composites densified by ordinary spark plasma sintering, cold sintered samples possess lower complex permittivity and superior impedance matching. Therefore, the cold sintered ZnO composite with 0.50 wt% GO loading shows the minimum reflection loss of -47.5 dB at thickness of 3.2 mm, and the effective absorption bandwidth of 4.4 GHz at thickness of 1.7 mm. Moreover, both flexural strength and hardness of the cold sintered composite are improved considerably compared to the monolithic cold sintered ZnO. These findings imply that cold sintering enables the thermally unstable materials to be applied in highly effective MACs with robust mechanical performance.     

Synergetic Effects of Graphene Oxide and Clay on the Microstructure and Properties of HIPS/Graphene Oxide/Clay Nanocomposites

In this paper, double-network structure nanocomposite with improved mechanical and thermal properties were prepared using high-impact polystyrene as a matrix phase, clay and graphene oxide as effective reinforcing fillers through a facile solution intercalation method. The structure and morphology of nanocomposites were characterized by transmission electron microscopy, scanning electron microscopy, X-ray diffraction analysis, and the synergetic effects of clay and graphene oxide on the final properties were investigated using tensile, dynamic mechanical thermal analysis (DMTA) and thermogravimetric analysis (TGA) analysis. Mechanical analysis showed that the combination of graphene oxide and clay exerted a favorable synergistic effect on the tensile modulus and the yield strength of the ternary composite that are greatly improved as compared with neat high-impact polystyrene, high-impact polystyrene/graphene oxide, and high-impact polystyrene/clay binary composites due to the double-network structure formation between the nanofillers as confirmed by the direct morphological observations using transmission electron microscopy and scanning electron microscopy analysis. The viscoelastic behavior showed that storage modulus of ternary composite significantly improvement over than that of the pure matrix, high-impact polystyrene/graphene oxide and high-impact polystyrene/clay while network structure made. TGA and DMTA measurements also demonstrated that thermal stability of high-impact polystyrene matrix modified by graphene oxide and clay slightly enhanced during the creation of dual network structure of graphene oxide and clay. Our data suggest a potential application for the combination of graphene oxide and clay in graphene-based composite materials.     

Low Intensity Shockwave Treatment Modulates Macrophage Functions Beneficial to Healing Chronic Wounds

Extracorporeal Shock Wave Therapy (ESWT) is used clinically in various disorders including chronic wounds for its pro-angiogenic, proliferative, and anti-inflammatory effects. However, the underlying cellular and molecular mechanisms driving therapeutic effects are not well characterized. Macrophages play a key role in all aspects of healing and their dysfunction results in failure to resolve chronic wounds. We investigated the role of ESWT on macrophage activity in chronic wound punch biopsies from patients with non-healing venous ulcers prior to, and two weeks post-ESWT, and in macrophage cultures treated with clinical shockwave intensities (150–500 impulses, 5 Hz, 0.1 mJ/mm²). Using wound area measurements and histological/immunohistochemical analysis of wound biopsies, we show ESWT enhanced healing of chronic ulcers associated with improved wound angiogenesis (CD31 staining), significantly decreased CD68-positive macrophages per biopsy area and generally increased macrophage activation. Shockwave treatment of macrophages in culture significantly boosted uptake of apoptotic cells, healing-associated cytokine and growth factor gene expressions and modulated macrophage morphology suggestive of macrophage activation, all of which contribute to wound resolution. Macrophage ERK activity was enhanced, suggesting one mechanotransduction pathway driving events. Collectively, these in vitro and in vivo findings reveal shockwaves as important regulators of macrophage functions linked with wound healing. This immunomodulation represents an underappreciated role of clinically applied shockwaves, which could be exploited for other macrophage-mediated disorders.     

Encapsulation of Cyclotetramethylenetetranitramine (HMX) by Electrostatically Self‐Assembled Graphene Oxide for Desensitization

To improve the safety of cyclotetramethylenetetranitramine (HMX) particles, a novel strategy was developed for the fabrication of graphene oxide encapsulated HMX (HMX@GO) by electrostatic self‐assembly between graphene oxide and HMX particles. The prepared samples were characterized by optical microscopy, scanning electron microscopy, Raman spectroscopy, X‐ray photon spectroscopy, thermogravimetry, differential scanning calorimetry and water contact angle tests. The results revealed that GO sheets were coated densely and homogeneously on the HMX particles in a HMX@GO composite at a low GO content of about 0.23 wt %. Compared with that of raw HMX, the impact sensitivity of the HMX@GO composite decreased from 100 % to 30 %, and the 50 % probability of required ignition energy (E₅₀) in the electrostatic spark sensitivity test increased from 0.66 J for HMX to 1.12 J for the HMX@GO composite, suggesting that the electrostatically self‐assembled GO coating layer could obviously enhance the safety of HMX.     

电化学法制备聚苯胺/氧化石墨烯复合膜及电容性能研究

利用电化学聚合法在导电玻璃ITO上原位制备了聚苯胺(PANI)/氧化石墨烯(GO)复合物薄膜。扫描电子显微镜表明,PANI/GO复合物呈颗粒状分布在ITO的表面;通过UV-vis光谱证实了GO和PANI之间存在着强烈的相互作用;充放电测试表明,PANI/GO复合膜具有良好的电荷储存特性,最高比电容可达265F/g,且具有较高的循环稳定性。