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.     

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.     

Self-Assembled BODIPY Derivative with A-D-A Structure as Organic Nanoparticles for Photodynamic/Photothermal Cancer Therapy

Organic nanomaterials have attracted considerable attention in the area of photodynamic and photothermal therapy, owing to their outstanding biocompatibility, potential biodegradability, well-defined chemical structure, and easy functionalization. However, it is still a challenge to develop a single organic molecule that obtains both photothermal and photodynamic effects. In this contribution, we synthesized a new boron-dipyrromethene (BODIPY)-based derivative (DPBDP) with an acceptor–donor–acceptor (A-D-A) structure by coupling 3,6-di(2-thienyl)-2,5-dihydropyrrolo [3,4-c] pyrrole-1,4-dione (DPP) and BODIPY. To enhance the hydrophilicity of the BODIPY derivative, the polyethylene glycol (PEG) chains were introduced to the meso- position of BODIPY core. The amphiphilic DPBDP was then self-assembled into related nanoparticles (DPBDP NPs) with improved hydrophilicity and enhanced absorbance in the NIR region. DPBDP NPs could simultaneously generate the singlet oxygen (¹O₂) and heat under the irradiation of a single laser (690 nm). The ¹O₂ quantum yield and photothermal conversion efficiency (PCE) of DPBDP NPs were calculated to be 14.2% and 26.1%, respectively. The biocompatibility and phototherapeutic effect of DPBDP NPs were evaluated through cell counting kit-8 (CCK-8) assay. Under irradiation of 690 nm laser (1.0 W/cm²), the half maximal inhibitory concentration (IC₅₀) of DPBDP NPs was calculated to be 16.47 µg/mL. Thus, the as-prepared DPBDP NPs could be acted as excellent candidates for synergistic photodynamic/photothermal therapy.     

Graphene Functionalized with Arginine Decreases the Development of Glioblastoma Multiforme Tumor in a Gene-Dependent Manner

Our previous studies revealed that graphene had anticancer properties in experiments in vitro with glioblastoma multiforme (GBM) cells and in tumors cultured in vivo. We hypothesized that the addition of arginine or proline to graphene solutions might counteract graphene agglomeration and increase the activity of graphene. Experiments were performed in vitro with GBM U87 cells and in vivo with GBM tumors cultured on chicken embryo chorioallantoic membranes. The measurements included cell morphology, mortality, viability, tumor morphology, histology, and gene expression. The cells and tumors were treated with reduced graphene oxide (rGO) and rGO functionalized with arginine (rGO + Arg) or proline (rGO + Pro). The results confirmed the anticancer effect of graphene on GBM cells and tumor tissue. After functionalization with amino acids, nanoparticles were distributed more specifically, and the flakes of graphene were less agglomerated. The molecule of rGO + Arg did not increase the expression of TP53 in comparison to rGO, but did not increase the expression of MDM2 or the MDM2/TP53 ratio in the tumor, suggesting that arginine may block MDM2 expression. The expression of NQO1, known to be a strong protector of p53 protein in tumor tissue, was greatly increased. The results indicate that the complex of rGO + Arg has potential in GBM therapy.     

A Bimetallic Nanozyme with Cascade Effect for Synergistic Therapy of Cancer

Novel nanocomposites were constructed through encapsulation of Au nanoparticles and Ru nanoparticles into dendritic mesoporous silica (DMSN-Au-Ru NPs). These exhibit improved effects due to a cascade catalytic ability for the synergistic therapy of cancer. Au nanoparticles with glucose oxidase-like properties were found to catalyze the oxidation of glucose to produce H₂O₂, while Ru nanoparticles could decompose H₂O₂ and produce toxic ¹O₂ for improved photodynamic therapy (PDT). In addition, the nanocomposites were found to have good photothermal performance under irradiation by near-infrared (NIR) light. Both in vitro and in vivo experiments show that the nanocomposites have good therapeutic effects due to the cascade catalytic effect and synergistic effect. These findings provide an effective way to design a new generation of nanodrugs for highly efficient cancer treatment.     

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.     

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%。     

Benefits in the Macrophage Response Due to Graphene Oxide Reduction by Thermal Treatment

Graphene and its derivatives are very promising nanomaterials for biomedical applications and are proving to be very useful for the preparation of scaffolds for tissue repair. The response of immune cells to these graphene-based materials (GBM) appears to be critical in promoting regeneration, thus, the study of this response is essential before they are used to prepare any type of scaffold. Another relevant factor is the variability of the GBM surface chemistry, namely the type and quantity of oxygen functional groups, which may have an important effect on cell behavior. The response of RAW-264.7 macrophages to graphene oxide (GO) and two types of reduced GO, rGO15 and rGO30, obtained after vacuum-assisted thermal treatment of 15 and 30 min, respectively, was evaluated by analyzing the uptake of these nanostructures, the intracellular content of reactive oxygen species, and specific markers of the proinflammatory M1 phenotype, such as CD80 expression and secretion of inflammatory cytokines TNF-α and IL-6. Our results demonstrate that GO reduction resulted in a decrease of both oxidative stress and proinflammatory cytokine secretion, significantly improving its biocompatibility and potential for the preparation of 3D scaffolds able of triggering the appropriate immune response for tissue regeneration.     

Virtual Vibrational Analytics of Reduced Graphene Oxide

The digital twin concept lays the foundation of the virtual vibrational analytics suggested in the current paper. The latter presents extended virtual experiments aimed at determining the specific features of the optical spectra of the studied molecules that provide reliable express analysis of the body spatial structure and chemical content. Reduced graphene oxide was selected as the virtual experiment goal. A set of nanosize necklaced graphene molecules, based on the same graphene domain but differing by the necklace contents, were selected as the relevant DTs. As shown, the Raman spectra signatures contained information concerning the spatial structure of the graphene domains, while the molecule necklaces were responsible for the IR spectra. Suggested sets of general frequency kits facilitate the detailed chemical analysis. Express analysis of a shungite carbon, composed of rGO basic structural units, revealed the high ability of the approach.     

INSIDIA 2.0 High-Throughput Analysis of 3D Cancer Models: Multiparametric Quantification of Graphene Quantum Dots Photothermal Therapy for Glioblastoma and Pancreatic Cancer

Cancer spheroids are in vitro 3D models that became crucial in nanomaterials science thanks to the possibility of performing high throughput screening of nanoparticles and combined nanoparticle-drug therapies on in vitro models. However, most of the current spheroid analysis methods involve manual steps. This is a time-consuming process and is extremely liable to the variability of individual operators. For this reason, rapid, user-friendly, ready-to-use, high-throughput image analysis software is necessary. In this work, we report the INSIDIA 2.0 macro, which offers researchers high-throughput and high content quantitative analysis of in vitro 3D cancer cell spheroids and allows advanced parametrization of the expanding and invading cancer cellular mass. INSIDIA has been implemented to provide in-depth morphologic analysis and has been used for the analysis of the effect of graphene quantum dots photothermal therapy on glioblastoma (U87) and pancreatic cancer (PANC-1) spheroids. Thanks to INSIDIA 2.0 analysis, two types of effects have been observed: In U87 spheroids, death is accompanied by a decrease in area of the entire spheroid, with a decrease in entropy due to the generation of a high uniform density spheroid core. On the other hand, PANC-1 spheroids’ death caused by nanoparticle photothermal disruption is accompanied with an overall increase in area and entropy due to the progressive loss of integrity and increase in variability of spheroid texture. We have summarized these effects in a quantitative parameter of spheroid disruption demonstrating that INSIDIA 2.0 multiparametric analysis can be used to quantify cell death in a non-invasive, fast, and high-throughput fashion.     

Dopamine-Modified Zero-Valent Iron Nanoparticles for Dual-Modality Photothermal and Photodynamic Breast Cancer Therapy

Phototherapy has the advantages of minimal invasion, few side effects, and improved accuracy for cancer therapy. The application of a polydopamine (PDA)-modified nano zero-valent iron (nZVI@PDA) as a new synergistic agent in combination with photodynamic/photothermal (PD/PT) therapy to kill cancer cells is discussed here. The nZVI@PDA offered high light-to-heat conversion and ROS generation efficiency under near-infrared (NIR) irradiation (808 nm), thus leading to irreversible damage to nZVI@PDA-treated MCF-7 cells at low concentration, without inducing apoptosis in normal cells. Irradiation of nZVI@PDA using an NIR laser converted the energy of the photons to heat and ROS. Our results showed that modification of the PDA on the surface of nZVI can improve the biocompatibility of the nZVI@PDA. This work integrated the PD and PT effects into a single nanodevice to afford a highly efficient cancer treatment. Meanwhile, nZVI@PDA, which combines the advantages of PDA and nZVI, displayed excellent biocompatibility and tumoricidal ability, thus suggesting its huge potential for future clinical research in cancer therapy.     

Aggregation-Induced Emission Luminogens for Mitochondria-Targeted Cancer Therapy

The importance of mitochondria in tumorigenesis makes these organelles an ideal target for cancer therapy. In recent years, luminogens with the aggregation-induced emission (AIE) effect have been developed for mitochondrial targeting and cancer treatment. The induction of mitochondrial dysfunction can be an effective pathway of chemotherapy, photodynamic therapy, and combination therapy against cancer. This review focuses on recent progress in the field of AIE luminogens (AIEgens) for cancer theranostics based on mitochondrial targeting and dysfunction. AIEgens for cancer treatment, including chemotherapy, photodynamic therapy, and combination therapy, are summarized herein. Molecular design efforts toward mitochondrial targeting and mitochondria-damaging mechanisms are also discussed. Finally, we discuss the challenges and future directions of development for AIEgens in mitochondria-targeted cancer treatment.     

Graphene Quantum Dots Modified Upconversion Nanoparticles for Photodynamic Therapy

Photodynamic therapy (PDT), as a novel technique, has been extensively employed in cancer treatment by utilizing reactive oxygen species (ROS) to kill malignant cells. However, most photosensitizers (PSs) are short of ROS yield and affect the therapeutic effect of PDT. Thus, there is a substantial demand for the development of novel PSs for PDT to advance its clinical translation. In this study, we put forward a new strategy for PS synthesis via modifying graphene quantum dots (GQDs) on the surface of rare-earth elements doped upconversion nanoparticles (UCNPs) to produce UCNPs@GQDs with core-shell structure. This new type of PSs combined the merits of UCNPs and GQDs and produced ROS efficiently under near-infrared light excitation to trigger the PDT process. UCNPs@GQDs exhibited high biocompatibility and obvious concentration-dependent PDT efficiency, shedding light on nanomaterials-based PDT development.     

Recent Progress on Reduced Graphene Oxide-Based Counter Electrodes for Cost-Effective Dye-Sensitized Solar Cells

Dye-sensitized solar cells (DSSCs) are one type of highly efficient low-cost solar cells among third-generation photovoltaic devices. Replacing the expensive components of DSSCs with alternative inexpensive and earth-abundant materials would further reduce their price in the solar cell market. Recently, graphene-based low-cost counter electrodes (CEs) have been developed, which could serve as a potential alternative to the expensive platinum-based CEs. In this review article, we have summarized recent research on various reduced graphene oxide (rGO)-based composite CE materials, methods for their synthesis, their catalytic activity, and the effective utilization of such CEs in DSSCs. The photovoltaic performance of DSSCs made of rGO-based composite CEs were compared with the reference Pt-based cells, and the photovoltaic parameters are summarized in tables.     

Chemically Functionalized Reduced Graphene Oxide as Additives in Polyethylene Composites for Space Applications

The discovery of radiation-shielding materials remains a critical technology to enable long-term space travel and extraterrestrial colonization. Hydrocarbon polymers, such as high-density polyethylene (HDPE), are among the best radiation attenuators due to their rich H content and lightweight. Due to their simple chemical structure that lacks larger heteroatoms, HDPE is also resistant to numerous radiation-induced degradation pathways that often limit the applicability of more sophisticated polymers. One drawback of hydrocarbon polymers is their inferior mechanical properties, such as tensile strength and impact toughness, relative to metals and other high-performance polymer systems. In this report, we develop an alkylated reduced graphene oxide that is used as an additive to enhance the storage and tensile moduli of HDPE by 10–15% across the lunar temperature range. These additives outperform unmodified reduced graphene oxide by 30% due to better dispersion through the polymer matrix as observed by cross-sectional scanning electron microscopy. POLYM. ENG. SCI., 60:86–94, 2020. © 2019 Society of Plastics Engineers     

High-Performance and Biobased Polyamide/Functionalized Graphene Oxide Nanocomposites through In Situ Polymerization for Engineering Applications

In this study, biobased polyamide/functionalized graphene oxide (PA-FGO) nanocomposite is developed using sustainable resources. Renewable PA is synthesized via polycondensation of hexamethylenediamine (HMDA) and biobased tetradecanedioic acid. Furthermore, GO is functionalized with HMDA to improve its compatibility with biobased PA and in situ polymerization is employed to obtain homogeneous PA-FGO nanocomposites. Compatibility improvement provides simultaneous increases in the tensile strength, storage modulus, and conductivity of PA by adding only 2 wt% FGO (PA-FGO2). The tensile strength and storage modulus of PA-FGO2 nanocomposite are enhanced dramatically by ≈50% and 30%, respectively, and the electrical conductivity reached 3.80 × 10^–3 S m⁻¹. In addition, rheology testing confirms a shear-thinning trend for all samples as well as a significant enhancement in the storage modulus upon increasing the FGO content due to a rigid network formation and strong polymer-filler interactions. All these improvements strongly support the excellent compatibility and enhanced interfacial interactions between organic–inorganic phases resulting from GO surface functionalization. It is expected that the biobased PA-FGO nanocomposites with remarkable thermomechanical properties developed here can be used to design high-performance structures for demanded engineering applications.     

Fabrication of Cellulose Nanofiber/Reduced Graphene Oxide/Nitrile Rubber Flexible Films Using Pickering Emulsion Technology for Electromagnetic Interference Shielding and Piezoresistive Sensor

With the rapid development of flexible electronics, the demand for flexible electromagnetic interference (EMI) shielding materials is increasing. This study develops a new green and effective strategy, consisting of graphene oxide (GO) and cellulose nanofibrils (CNF) co-stabilized Pickering emulsion combined with hot-pressing technology, to prepare flexible and conductive nitrile rubber (NBR) composite films. The composite films consist of a 3D network conductive skeleton structure of reduced GO (RGO) and an isolated NBR structure. This specific design results in a maximum high conductivity of 99 S m⁻¹, which is higher by an order of magnitude compared with that of the composites obtained using the traditional solution blending method, and a stable EMI shielding effectiveness of 25.81 dB in the X band. The introduction of the flexible NBR results in the excellent flexibility and structural strength of the composite film, and exhibits a decrease of 2.51% in the EMI shielding efficacy after 5000 cycles. As a piezoresistive sensor for wearable devices, the CNF-RGO/NBR flexible film can hold precise current signals and respond to finger motion. The findings of this study can provide new insights for the design of conductive and flexible composites as wearable and portable medical equipment and electronic devices.     

石墨烯/聚丙烯复合材料的等温结晶动力学研究

采用差示扫描量热仪(DSC)研究了石墨烯(RGO)/聚丙烯(PP)复合材料的等温结晶行为。结果表明:对于纯PP和RGO/PP复合材料,结晶温度(Tc)的提高将导致结晶速率(G1/2)变慢、绝对结晶度(Xc)提高;PP和RGO/PP复合材料的等温结晶在相当大的范围内符合Avrami方程;同纯PP相比,RGO/PP复合材料的G1/2相对增加,而结晶活化能相对减小,这意味着RGO对PP起到了外加成核剂的作用,促进了PP的结晶。     

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.