This is why the PA66/graphene film produced a more subtle secondary network with the addition of graphene, used as a charge capture site to increase its surface charge. Additionally, all the layered structures of TENGs were composed of breathable electrospun films and plain conductive cloth, with water vapor transmittance (WVT) of 9.6 Kgm−2d−1, reflecting excellent wearing comfort. The study showed that TENGs, based on all electrospinning, have great potential in the field of wearable energy supply devices.Triboelectric nanogenerators (TENGs) are considered to be the most promising energy supply equipment for wearable devices, due to their excellent portability and good mechanical properties. Nevertheless, low power generation efficiency, high fabrication difficulty, and poor wearability hinder their application in the wearable field. In this work, PA66/graphene fiber films with 0, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt% graphene and PVDF films were prepared by electrospinning. Meanwhile, TENGs were prepared with PA66/graphene fiber films, PVDF films and plain weave conductive cloth, which were used as the positive friction layer, negative friction layer and the flexible substrate, respectively. The results demonstrated that TENGs prepared by PA66/graphene fiber films with 2 wt% grapheme showed the best performance, and that the maximum open circuit voltage and short circuit current of TENGs could reach 180 V and 7.8 μA, respectively, and that the power density was 2.67 W/m With the development of Internet of Things technology (IoT), portable, flexible wearable electronic devices with various functions have been widely considered. In the IoT society, various devices offer many possibilities through data transmission and processing ,2,3,4, s2 under hand patching. Incorporating functional materials into polymer nanofibers could improve electrical output performance. Currently, most research focuses on improving output performance, such as selection of friction materials [All electrospun nanofiber films are widely used in TENGs design. The electrospun fibrous films have remarkable properties, such as inherent rough structure, large specific surface area and hierarchical porous structure ,17, whicaterials ,23,24, saterials ,26,27 anaterials ,29,30. H2. Water vapor transmission rate could be up to 9.6 Kgm−2d−1. In addition, the TENGs prepared could be placed anywhere on the body, detecting various human movements, and the mechanical energy that is wasted in life could be obtained. This energy can instead be used to power wearable electronic devices in daily life.In this work, a method for all-electrospun fiber-based TENGs, consisting of two parts, including a PA66/graphene nanofiber-film-rubbed positive base layer and PVDF-rubbed negative electrode layer, was proposed. On the one hand, a PA66/graphene nanofiber film with multi-layer micro-nano structure could not only increase the effective friction area of contact, but also graphene dispersed in the PA66 fiber could be used as a charge capture site, which could increase the surface charge on the film surface, greatly improving its triboelectric properties . In addiPolyamide66 (PA66) was bought from Aladdin Pharmaceuticals . Graphene was sold by Shenzhen Turing Artificial Intelligence Black Technology Co., Ltd. . Polyvinylidene Difluoride  was produced by Arkema . Formic Acid and Polyethylene Oxide (PEO) were bought from Macklin . N, N-Dimethylformamide (DMF) and Acetone were produced by Sinopharm . Plain weave conductive fabric was produced by Saintyear Electronic .Firstly, 0.5 wt% PEO was added to 10 mL of Formic Acid and a magnetic stirrer was used to stir for 1 h to increase the viscosity of the solution, so that it could be well electrospun. Secondly, 15 wt% PA66 particles were put into Formic Acid/PEO solution, which were fully dissolved via a magnetic stirrer for 4 h to obtain 15 wt% PA66 solutions. Finally, different mass fractions of graphene  were put into the prepared PA66 solution, respectively, and stirred to fully mix. Further, ultrasonic dispersion was applied for 6 h to make the graphene evenly dispersed in the solution.The electrospinning process was performed with a supply voltage of 20 kV, a working distance between the spray nozzle and the substrate was 15 cm and the PA66/graphene solution was injected into a 10 mL syringe with a blunt needle (0.6 mm inner diameter). The injection rate of the syringe was 0.1 mL/h. PA66/graphene nanofiber films were collected on plain weave conductive cloth (Ni-Cu) fabric electrodes, which were prepared at 25 °C and relative humidity of 50 ± 5%. The thickness of PA66/graphene fiber film was 80 ± 10 μm, measured by Talysurf Profiler .Firstly, 3 mL Acetone was added into 7 mL DMF to obtain a DMF/Acetone solution in a 7-to-3 volume ratio. Secondly, 10 wt% PVDF powder was added into the mixed solution and magnetically stirred for 4 h under heating in a 60 °C water bath. Finally, the 10 wt% clear and transparent PVDF solution was obtained.The electrospinning process was performed with a supply voltage of 12 kV, while the working distance between the spray nozzle and the substrate was 10 cm. The advance rate of the syringe was 0.4 mL/h. The PVDF nanofiber membrane was collected on the conductive fabric electrode, which was also collected under the same conditions, mentioned in Based on the electrospinning process, the composite fabric of the two friction layers of TENGs was prepared. Firstly, the double-sided conductive tape was used as the electrode lead, which was tightly pasted on the back of the conductive fabric substrate where the different films were located. Then, the required size could be trimmed, such as 4 cm × 4 cm. Finally, these breathable films could be pasted on the corresponding positions of daily clothes, collecting the mechanical energy generated by wasted human movement.SC and VOC were measured by Keithley System Electrometer .The surface morphologies of PA66 films, PA66/graphene films and PVDF films were characterized by the Field Emission Scanning Electron Microscopy . X-ray Diffraction  was used to study the elements and material structure of the electrospun fiber films. The IThe main concept of the design in this work was to use common fabric materials as the basic building unit to construct a wearable TENGs platform, so as to achieve effective harvesting of low-frequency, ubiquitous and easily wasted human biomechanical energy, such as walking and running. The all-electrospinning-based power-generating textile had multiple secondary structures and it could be better integrated with personal clothing, powering wearable electronic devices. These power-generating fabrics with excellent mechanical properties exhibited excellent breathability and cutability. It was an ideal device to make energy harvesters and sensors of a flexible wearable electronic system integrated, which guaranteed the integration of TENGs and wearable electronic devices with clothing.A detailed preparation process for the PA66/graphene nanofiber film and PVDF film are schematically illustrated in The prepared TENGs were composed of three functional components, including a PA66/graphene fiber film and PVDF film with two tribological polarities for contact electrification, and a plain weave conductive cloth for charge conduction. Based on previous studies , construTo study the elements in the films, the XRD patterns of PA66/graphene thin-film layers with different mass fractions of graphene were observed, shown in To study the effect of graphene doping on the output performance, contact-separation-mode TENGs based on PA66/graphene and PVDF films were designed. The two films were glued to two 3D-printed slabs with bosses a,b. The C(x) was the capacitance between the two electrodes at different time-varying displacements x; ε0 was the vacuum dielectric constant; S was the surface area of the friction layer; d0 was the effective thickness of the dielectric layer; σ was the triboelectric surface charge density; SCQ(x) was the amount of short-circuit charge transfer at displacement x; and f was the frequency. Therefore, according to Equations (1) and (2), we could observe that the open-circuit voltage of TENGs was independent of frequency f and increased only with larger displacement between the two contact surfaces, and the short-circuit current was proportional to the frequency f, so the measured maximum short-circuit current increased with the frequency f, shown in SCI) and open-circuit voltage (OCV) of the TENGs and an external force exerted with a frequency of 4 Hz, a higher circuit signal and output power could be obtained.According to previous studies ,34,35, wOCV and SCI were both increased by about four-times. Therefore, the TENGs made of PA66/graphene fiber film with 2 wt% graphene content were the most suitable experimental sample. Further, the piezoelectric properties of PVDF films were tested by the method reported by Yin [With the increase in graphene, the dielectric constant of the electrospun film also had an effect on the output performance. The enhanced dielectric constant of the triboelectric layer could improve the ability to transfer charge density and the surface potential also had a large impact on the performance of TENGs. A higher dielectric constant could use the electrospun PA66/graphene film as a friction layer to store more charge. However, an excessively large dielectric constant would generate a larger dielectric loss, which leads to the leakage of charge. Due to the changes in frequency and external strain during human motion, it was necessary to explore their effects on the output performance of wearable devices. As shown in d by Yin , so the P = I2R, the power of TENGs could be calculated. At 113 MΩ resistance, the maximum power density could reach 2.67 W/m2. The generated output power was sufficient to drive some low-energy electronic devices, solving the problem of sustainable power supply for wearable systems in a stable and reliable manner effectively.To study the effects of load resistance on output of the voltage and current, the output performance of nanofiber-film-based TENGs was researched, shown in m1 was the test cup mass before the test; m2 was the test cup mass after the test; S was the test cup mouth area; and the obtained WVT rate was 9.6 Kgm−2d−1, which could confirm that the all-electrospun textile film had excellent air permeability. In other words, electrospun nanofibers had excellent wearing comfort, ensuring human thermal comfort and wide personal practical applications after their integration into wearable electronic devices.Due to the striking features of the porous structure, the fabricated power generation fabric had excellent water vapor permeability, which can be visually seen in To explore the durability and stability of TENGs, the fabric current outputted after bending the two friction layers for 1000 cycles was tested and compared. It could be clearly seen that there was no significant mechanical damage to the surface, shown in To accurately evaluate the practical application of TENGs, a series of tests was carried out and the combined light chain composed of 110 LEDs in series could be lit by using the TENGs a, which To demonstrate the charging capability of TENGs, a circuit composed of a commercial capacitor and bridge rectifier was designed to test its charging efficiency. The charge in the capacitors  to 1.2V with 4 s, 36 s, 180 s, respectively, is shown in To further demonstrate the application of TENGs based on all-electrospun nanofilms, they could be easily combined with textiles to harvest the mechanical energy generated from the human body, As shown in 2, respectively. In addition, TENGs maintained excellent performance after 1000 cycles under cyclic pressure, keeping its advantages in durability and stability. TENGs with good comfort and high flexibility could obtain biomechanical energy from various human motions. There are great prospects in the system integration of wearable electronic devices.In this work, an electrospun PA66/graphene nanofiber film with a secondary nano-network structure, as a tribo-cathode layer, was fabricated, and it was assembled with the electrospun PVDF film as the tribo-anode layer to form all-electrospun film-based TENGs. The rough surface of the two friction layers not only increased the effective contact area, but also improved the breathability. Furthermore, the porous fiber network in each functional layer guaranteed the air permeability of the TENGs. Compared with the pure PA66 fiber film, the introduced graphene increased the effective contact area of the PA66 nanofiber film and graphene could act as a charge trapping site, enhancing the electrical properties of the TENGs. The fabricated TENGs exhibited high Voc, Isc and peak power density of 180 V, 7.8 µA and 2.67 W/m


Generally, the pore shape and diameter of GAs are difficult to control or the preparation process is complicated, requiring a multi-step operation. Herein, a soft-template one-step hydrothermal synthesis process was proposed to produce GAs with controllable pore sizes. Cyclohexane and n-butanol were added to a graphene oxide suspension to form a uniform aqueous dispersion under emulsification by sodium lauryl sulfate. The reduction process may have occurred around the organic droplets during the hydrothermal reaction, and a large number of organic droplets became countless physical barriers inside the hydrogel. In the later freeze-drying and high-temperature calcination procedures, the droplets evaporated to form a rich pore structure. Compared to the conventional templating method, the organic template was volatilized during the drying process such that no additional process for removing the template was required. In addition, GAs prepared by the template method possessed lower density (2.66 mg cm−3) and better compression performance and, as an adsorbent material, absorbed organic matter and petroleum from wastewater more efficiently than GAs obtained by the traditional one-step hydrothermal method; Q for n-hexane reached 116, and Q for xylene reached 147; also, the GAs prepared by the soft template method can absorb all crude oil in water samples within 30 s.Graphene aerogels (GAs) were synthesized  via a one-step hydrothermal method.Graphene aerogels (GAs) were synthesized  Therefore, three-dimensional (3D) graphene aerogels (GAs) have attracted more attention. GA has an ultrahigh specific surface area,2,12 high electrical conductivity,13 very low density,8,13,14 abundant pore structure,15–18 and certain hydrophobic and lipophilic properties,19 and it not only effectively retains the properties of graphene but is also easy to assemble into parts for use in macroscopic materials.Graphene has excellent electrical and mechanical properties and can be widely applied in supercapacitors,20 chemical crosslinking,21 and polymerization.22 Graphene oxide (GO) contains many oxygen-containing functional groups and is often used as a precursor for the construction of graphene aerogels. GO can be uniformly dispersed in a solvent, such as water, using ultrasound. In a hydrothermal process23 using a solvent or a chemical reduction with a reducing agent,24 GO loses most of its oxygen-containing functional groups and is converted to reduced GO (rGO). Because of its low hydrophilicity, rGO cannot be stably dispersed in water and the resulting layers stack spontaneously to form a stable hydrogel under the action of π–π bonding interactions. However, due to the special 2D structure of GO, with a very high aspect ratio, rGO is more inclined to stack via self-assembly rather than chaotic aggregation. During the stacking process, rGO sheets undergo a hydrophobic action that captures large amounts of solvent to form a graphene hydrogel (GAH). The density, pore size, and wall thickness of the GAH are randomly synthesized and cannot be precisely controlled and, thus, a template method has been proposed. There are two mature ideas for the synthesis of GAHs and/or GAs by the template method; one is a chemical vapor deposition (CVD) process and the other is a solution assembly method. The CVD method mainly deposits graphene directly onto commercially available foamed nickel25 or a special functional template.26 The process maximizes the excellent properties of graphene and allows for custom shapes through using a stencil, but the CVD process is relatively expensive and can only produce small quantities in the laboratory, with, in most cases, the original stencil etched away. In contrast, self-assembled templates are relatively simple to use and GA can be produced in mass and, thus, are widely used.In recent years, researchers have developed a variety of methods to assemble 2D materials into 3D forms in more efficient and applicable ways, including chemical reduction,27–29 is considered to be the easiest method for constructing 3D graphene aerogels. In the process of synthesizing a GAH, when the system is about to reach the gel point, the precursor is immediately frozen in liquid nitrogen or in a refrigerator and ice crystals formed during the freezing process are used as templates. Before the gel point, the GO has been partially deoxidized into a hydrophobic material, such that the ice crystals divide the system into a porous structure. The GAH formed by the reheating reaction has a special pore structure, which can be controlled by the freezing temperature, freezing time, and freezing direction. At the same time, however, the pore size of the GA synthesized by the ISISA method is generally nonuniform, mainly due to the difference in temperature gradients at different locations. Porous solid monoliths have also been used by many researchers as templates for GA synthesis, such as some common polymeric porous materials,30,31 silica,32 and even everyday sponges. Different from the CVD method, these monoliths can accommodate large amounts of GO suspension. And GO is then reduced to rGO using an appropriate method and the template is etched by calcination or strong acid to form a 3D porous GA. The porous monolithic template can adjust the pore size and distribution very conveniently according to needs and the prepared GA has good mechanical strength, chemical properties, and thermal stability. However, the etching process is time consuming and environmentally unfriendly. Although no high temperature treatment is needed during the etching process, further high temperature reactions are required to obtain better electrical performance compared to the CVD method. Pickering emulsions are also a popular method for preparing GA materials. A Pickering emulsion utilizes solid particles33–35 as an emulsifier and has better stability than conventional emulsions. As an amphiphilic particle, GO can form a stable oil-in-water (O/W) emulsion. The monomer is polymerized as a foreign phase to form a skeleton and then the solvent is removed to obtain a polymer/graphene monolith. However, to obtain a pure GA, it is still necessary to etch away the already-formed polymer, thus limiting its application. Shi36 proposed a better and simpler method for controlling the pore structure. By dispersing a certain amount of n-hexane into the GO suspension, GO is reduced and assembles into a 3D structure in the hydrothermal reaction. Droplets of n-hexane do not disperse GO and, being incompatible with water, form a spherical physical barrier, such that the pore size of the formed GAH is affected by the oil droplet size, which can be controlled by adjusting the amounts of n-hexane and stirring, and thus the GA pore size can be predetermined. A further advantage is that the removal of n-hexane as a template does not require an additional step, with n-hexane being removed along with water during dialysis and freeze-drying. However, n-hexane droplets are easily separated from water without the aid of an emulsifier, resulting in an uneven pore diameter in the GA upper and lower positions, thus the method needs to be further improved.An ice template process, called ice-segregation-induced self-assembly (ISISA),n-hexane systems were improved by introducing cyclohexane and n-butanol into GO suspensions and forming more stable aqueous cyclohexane–butanol/GO emulsions with the help of emulsifiers and dispersers. The prepared GO emulsions were then used to synthesize graphene hydrogels by a one-step hydrothermal method and the obtained hydrogels, named GAH-Ts, were then freeze-dried to form graphene aerogels, named GA-Ts. To obtain better graphene performance, residual oxygen atoms were removed from GA-Ts by calcination to form aerogels (FGAs) with improved graphene structures. By adjusting the ratio of aqueous to organic phases (cyclohexane and butanol), the pore structures of these hydrogels and aerogels, as well as the final FGA structure, were adjusted.In this study, unstable water/2.2.12SO4), cyclohexane, n-butanol, HCl, KMnO4, ethylenediamine , hydrogen peroxide (H2O2), phosphoric acid (H3PO4), and sodium dodecyl sulfate (SDS) were all analytical grade and purchased from Aladdin Chemistry Co. Ltd . All chemicals were used as received.Flake graphite (325 mesh) was supplied by Unigram Carbon Graphene Materials Co., Ltd, . Concentrated sulfuric acid (H2.2−1) was mixed with cyclohexane (50 ml) and n-butanol (37.5 ml) in a 150 ml beaker and then SDS (0.9 g) as emulsifier and 250 μl of EDA as reducing agent were added to the mixture. The mixture was dispersed by subsequent treatment with a high-speed homogenizer at 13 500 rpm for 5 min to obtain an off-white uniform emulsion. After the emulsion was degassed under vacuum, 10 g of the emulsion was fed into a hydrothermal kettle with a Teflon lining. Graphene hydrogels (GAH-Ts) were then obtained by keeping the hydrothermal kettle in a 150 °C muffle furnace for 6 h. GAH-T was carefully purged with 20% ethanol solution and freeze-dried for 48 h to form absolutely dry aerogels (GA-Ts). The product was further calcined at 600 °C for 5 h under N2 protection in a high temperature tube furnace such that GA-Ts were completely reduced to form the porous aerogels (FAGs).GO was prepared by a modified Hummers' process and the detailed steps can be found in the ESI.via the conventional hydrothermal method, in which only GO suspension (6 mg ml−1) and EDA (reducing agent) were used in the hydrothermal reaction without a soft template (cyclohexane and butanol). These obtained hydrogels and aerogels were termed GAH and GA, respectively.For comparison, graphene hydrogels and aerogels were also prepared 2.3α radiation (λ = 0.15418 nm) at a scan rate (2θ) of 5° min−1. Raman spectra of the samples were recorded using a laser Raman spectrometer  with an excitation wavelength of 532 nm. Surface element composition analysis was performed by using Thermo ESCALAB Model 250XI X-ray photoelectron spectroscopy , in which the binding energy was calibrated to the C-1s peak (284.8 eV) with a reference.37 Thermal gravimetric analysis (TGA) was performed using a thermal analyser  under a nitrogen flow of 20 ml min−1, at a heating rate of 10 °C min−1, and in a range from 25 to 800 °C. The surface roughness and morphology of GO were measured by using atomic force microscopy  in tapping mode and with 256 × 256-pixel resolution. Samples for AFM imaging were prepared by spin-coating the GO dispersion in water (1 × 10−5 mg ml−1) onto a freshly cleaved mica surface (200 rpm and 60 s) and allowing it to dry in air.The morphology of the graphene hydrogels (or aerogels) was characterized by using scanning electron microscopy . The chemical functional groups were characterized by using Fourier transform-infrared spectroscopy . The crystal structure was characterized by using X-ray diffraction , operating with Cu-K2.4n-hexane and xylene were selected as representatives of hydrocarbons and aromatic hydrocarbons, respectively, and a water/crude oil mixture as a model for spilled-oil wastewater.The solvent/oil adsorption capacity was measured according to the ASTM F726-99: Standard Test Method for Sorbent Performance of Adsorbents. Here, w1) and then placed in a 150 ml beaker, to which 100 ml of organic solvent (n-hexane or xylene) was added. The adsorbent was removed after 60 s of immersion, gently wiped with filter paper, and then immediately weighed (w2).Graphene aerogel samples (GA or GA-T) were weighed (Q) was calculated using the weight of the aerogels before (w1) and after adsorption (w2) asFor evaluation of adsorbent performance in spilled oil adsorption, 5 g of crude oil was mixed with 95 g of distilled water in a beaker to obtain the simulated petroleum-contaminated wastewater. The subsequent test method was the same as that for the organic solvent above. The adsorption capacity  and the density was very low (<10 mg cm−3), such that it could stand on a flower easily  and GO sheets were dispersed in water, the organic droplets formed a dispersed phase and the GO sheets adhered to the droplet surfaces (Under the effect of agitation by a high-speed disperser and with the emulsifier (SDS), the GO suspension was converted to a relatively stable oil-in-water emulsion with cyclohexane and surfaces . An optisurfaces . The grasurfaces .GA prepared without a soft template exhibited disordered porous structures . The gra3.2The GO transformation to the final aerogels was analyzed by using XRD, Raman spectroscopy, XPS, and TGA . The ID/IG values (ratio of the intensities of peak D to peak G) of GA, GA-T, and FGA were ∼1.00/1.05/1.06, respectively. The results showed that the chemical compositions of GA, GA-T, and FGA were very similar. However, the 3D structures (rGO sheet packing structures) of GA and GA-T were very different, which was attributed to the effects of the soft-template  of GO was 1.60/1. After the hydrothermal reaction, GO was converted to GA-T and C/O rose slightly to 2.91/1, indicating that GO reduction was not complete at the lower temperature . After cThe TGA curves of GA and GA-T are very different . In the 2 carbon (C–C 284.8 eV), carbon–nitrogen (C–N 285.4 eV), epoxy/hydroxyl (C–O 256.1 eV), and carbonyl  scale" fill="currentColor" stroke="none"><path d="M0 440 l0 -40 320 0 320 0 0 40 0 40 -320 0 -320 0 0 -40z M0 280 l0 -40 320 0 320 0 0 40 0 40 -320 0 -320 0 0 -40z"/></g></svg>O 288.2 eV)  . It was C, C–N, C–O, and CO bonds, but the contents of these various chemical bonds were quite different  and graphitic nitrogen  of GA-T and FGA for n-hexane and xylene were greatly improved compared to that of GA  and a richer pore structure. In organic adsorption experiments, the newly prepared graphene aerogels absorbed 90 times their weight of n-hexane and 139 times their weight of xylene. In the treatment of wastewater containing spilled oil, these graphene aerogels absorbed oil quickly and efficiently. These results show that graphene aerogels prepared with this improved soft-template method possess great potential for applications in wastewater treatment and organic matter separation and recycling from water.Graphene aerogels were synthesized by a simple one-step hydrothermal method, in which droplets of cyclohexane and There are no conflicts to declare.RA-010-C9RA10988A-s001


Background and Objectives: It is still unclear whether sarcoidosis is likely to be associated with tumors. In addition, the use of an immune checkpoint inhibitor has been reported to initiate the onset of sarcoidosis. We retrospectively analyzed tumor development before and after the diagnosis of sarcoidosis and examined the impact of having a history of tumors on the activity or the severity of sarcoidosis. Materials and Methods: We recruited 312 consecutive cases of sarcoidosis and analyzed the tumor development before and after the onset of sarcoidosis. Results: Among them, 25 cases were diagnosed with malignant tumor after diagnosis of sarcoidosis. In the analysis of the tumor-development group after diagnosis of sarcoidosis, both serum angiotensin I-converting enzyme and mediastinal lymph node size were significantly reduced at the time of malignant tumor diagnosis compared to at the onset of sarcoidosis, indicating that the decreasing activity of sarcoidosis may be partly associated with tumor development. Furthermore, we examined 34 cases having tumor history before the onset of sarcoidosis and analyzed the effect of tumor history on the severity of sarcoidosis. Cases with a malignant tumor in the past were older and had less complicated organs of sarcoidosis than cases without malignant tumors in the past. Oral corticosteroid therapy was administrated more frequently in cases without malignant tumors in the past, indicating that the history of a malignant tumor may influence the severity of sarcoidosis. Conclusion: These results indicate that tumor development may be partly associated with the activity or severity of sarcoidosis. Sarcoidosis is an unexplained systemic granulomatous disease. Occupational exposure to silica dust increases the risk of sarcoidosis in younger men . The risThe advent of ICI treatment is advancing research into the development of Th17 balance-mediated sarcoidosis. Furthermore, epidemiologically, research on silica exposure and the development of sarcoidosis is also progressing . Not onlInvestigations regarding sarcoidosis along with a history of malignant tumors have been limited. In this study, we retrospectively analyzed tumor development before and after the diagnosis of sarcoidosis and examined the impact of having a history of tumors on the activity or the severity of sarcoidosis.Consecutive patients diagnosed with sarcoidosis at Gunma University Hospital were recruited retrospectively. We applied the opt-out method to obtain consent for this study by declaring an information disclosure statement. The information disclosure statement was approved by the Gunma University Institutional Review Board. Patients were diagnosed with sarcoidosis by multiple respiratory specialists in this study.A total of 312 consecutive patients were enrolled in this study from those that were diagnosed with sarcoidosis at our hospital between January 2007 to December 2017. We excluded two cases in which malignant tumors and sarcoidosis were diagnosed at the same time to exclude sarcoid reactions. The diagnostic criteria of sarcoidosis were based on the statement of American Thoracic Society (ATS)/European Respiratory Society (ERS)/World Association of Sarcoidosis and Other Granulomatous Disorders (WASOG) ,29. BronStatistical information was collected from the medical record, including patient’s age, sex, height, weight at the time of diagnosis, hematological data on the course of treatment, imaging, allergy history, and preference history, which may potentially affect the course of sarcoidosis. Patient’s body mass index (BMI) was calculated using their height and weight at the time of analysis. Alcohol history defined patients’ daily consumption habits. A history of smoking was defined as an individual who currently smokes or has smoked previously more than 100 cigarettes in total . MethotrMost patients underwent contrast-free computed tomography (CT). It was difficult to measure hilar lymph nodes because the borderline between hilar lymph nodes and blood vessels was unclear. Therefore, we evaluated the most measurable lymph nodes, # 4 and 7, as lesions there can be measured by contrast-free CT. The measurements of lymph nodes were performed according to resist criteria 1.1 .p-value of <0.05 was considered statistically significant. All analyzes were done using SPSS version 24 .Cases with tumor development/history of a tumor (tumor group) and without tumor development/history of a tumor (non-tumor group) were divided into groups. For each factor of the tumor group and the non-tumor group, the number of cases and the ratio were calculated on the nominal and average scale, and the standard deviation was calculated on the order scale. Missing data were replaced by dummy variables. The Fisher’s accuracy test was used to analyze the nominal scale, while the numerical scale used the Mann–Whitney’s test. A First, we analyzed the relationship between the activity of sarcoidosis and the development of malignant tumors. Of the 312 sarcoidosis patients, 25 cases were later diagnosed with malignancies. In our study, lung cancer was the most common in seven cases, followed by malignant lymphoma in four cases . One casA statistical comparison of the background of patients did not show any significant differences between the tumor development group and the non-tumor development group .We analyzed the relationship between the activity of sarcoidosis and the development of malignant tumors. Serological data in patients with sarcoidosis having tumor development showed that serum angiotensin I-converting enzyme (ACE) was significantly reduced at the onset of malignant tumors compared to at the time of diagnosis of sarcoidosis. The major and minor diameters of the mediastinal lymph nodes were measured. The major and minor diameters of lymph node # 7 and the minor diameters of lymph node # 4 were significantly reduced at the diagnosis of malignant tumors compared to the size of initial lymphadenopathy at the onset of sarcoidosis . Lymph nNext, we analyzed the effect of tumor history on the development of sarcoidosis. Thirty-four cases had a history of having a malignant tumor in the past . One case had a history of two types of cancer in the past. Tumor types are shown in p = 0.009). Diabetes mellitus, smoking history, and alcohol intake were not significantly different between both groups.A statistical comparison of the background of patients was made between the past-tumor group and the non-past-tumor group . The agep = 0.061, 782 ± 351 vs. 1093 ± 889, p = 0.072, respectively). Although we recently reported that serum neuron-specific enolase levels could be a diagnosing and monitoring marker of sarcoidosis, there was no significant difference in serum neuron-specific enolase levels [p = 0.038) -2 receptor tended to be lower in past tumor groups  .n = 3) vs. 28.1% (n = 78), p = 0.013). Furthermore, oral corticosteroid therapy was administrated more frequently in the non-tumor group than in those cases that had a malignant tumor in the past (5.9% (n = 2) vs. 23.0% (n = 64), p = 0.024). There was no significant difference in the follow-up period and mortality.Furthermore, we analyzed the severity of sarcoidosis with or without tumor history. A comparison of the affected organs and the severity of sarcoidosis between the past tumor and the non-past-tumor group are shown in P. acnes or mycobacteria. Various symptoms are observed in systemic organs such as the eyes, lungs, heart, nerves, and skin, with oral corticosteroids being administrated as needed [Sarcoidosis is an unexplained systemic granulomatous disease. Sarcoidosis is characterized by the activation of the Th1 immune response induced by antigen exposure such as s needed ,21. In ts needed . Consists needed . AlthougIn this study, both the number of patients with systemic oral corticosteroids (OCSs) and the number of affected organs were significantly lower in the past-tumor group. The serum ACE and soluble IL-2 receptor, which reflects the activity of sarcoidosis, showed a decreasing trend in the past-tumor group. To our knowledge, this is first report describing the influence of malignant tumor history on the severity of sarcoidosis. As the number of diseased organs and frequency of OCSs treatment may reflect on the activity of sarcoidosis, immune status after tumor development is possibly associated with the severity of sarcoidosis after its onset.+ cells [+ T cells [There have been several reports on the relationship between sarcoidosis and tumors. Bonifaze et al. reported that skin tumors, blood tumors, upper gastrointestinal tumors, kidney tumors, liver tumors, and colon tumors are more frequently found with sarcoidosis . Askling+ cells ,37,38 (F T cells ,40. In tTh17-dominant CD4-positive T cells are abundant in BALF and granulomatous lesions of sarcoidosis ,42. Th17Interestingly, a transition from Th1- to Th2-dominant balance is thought to be particularly relevant in the development of advanced pulmonary sarcoidosis . The shiThere are several limitations to this study. Firstly, this was a retrospective study at a single facility, and as such, the number and the background of the cases were limited. A multicenter prospective study with a greater number of sarcoidosis cases will be required to clarify the relationship between sarcoidosis and tumor immunity. Furthermore, this was a cohort study of patients with sarcoidosis but not with tumors. Future analysis on a cohort of patients with tumors is also required to elucidate the relationship between the severity of sarcoidosis and tumor history.Serum ACE levels and mediastinal lymph node size were significantly reduced at subsequent tumor occurrence. Past-tumor history in patients with sarcoidosis was associated with a lower rate of OCS administration and fewer organ complications. Tumor development may be partly associated with the pathology or severity of sarcoidosis with regard to anti-tumor immunity.


Caenorhabditis elegans reproductive tract is orchestrated by the anchor cell (AC). This occurs in part through a cell invasion event that connects the uterine and vulval tissues. Several key transcription factors regulate AC invasion, such as EGL-43, HLH-2, and NHR-67. Specifically, these transcription factors function together to maintain the post-mitotic state of the AC, a requirement for AC invasion. Recently, a mechanistic connection has been made between loss of EGL-43 and AC cell-cycle entry. The current model states that EGL-43 represses LIN-12 (Notch) expression to prevent AC proliferation, suggesting that Notch signaling has mitogenic effects in the invasive AC. To reexamine the relationship between EGL-43 and LIN-12, we first designed and implemented a heterologous co-expression system called AIDHB that combines the auxin-inducible degron (AID) system of plants with a live cell-cycle sensor based on human DNA helicase B (DHB). After validating AIDHB using AID-tagged GFP, we sought to test it by using AID-tagged alleles of egl-43 and lin-12. Auxin-induced degradation of either EGL-43 or LIN-12 resulted in the expected AC phenotypes. Lastly, we seized the opportunity to pair AIDHB with RNAi to co-deplete LIN-12 and EGL-43, respectively, which revealed that LIN-12 is not required for AC proliferation following loss of EGL-43.Development of the  Summary: Using a dual depletion approach, i.e., combining auxin-inducible degradation with RNAi, we show that LIN-12 is not required for proliferation of the C. elegans anchor cell following EGL-43 loss. Caenorhabditis elegans larval development, a specialized uterine cell, the anchor cell (AC), breaches BM to contact the underlying vulval epithelium. This developmental event initiates the attachment of the uterus to the vulva, which later forms the reproductive tract of the animal. Several laboratories, including ours, have taken advantage of the animal's simple anatomy, transparent body, and genetic amenability to characterize molecular and cellular features of C. elegans AC invasion. Collectively, this has yielded important insights into the regulation of BM invasion in vivo (Cell invasion through basement membrane (BM) is essential for animal development, tissue inflammation, and cancer metastasis. During  in vivo .C. elegans, though its paralog, GLP-1, has a well-established role in promoting germline proliferation throughout post-embryonic development  system enables rapid degradation of proteins . It requradation B. Here, radation , which uradation .rpl-28 promoter and a self-cleaving T2A peptide that separates both transgenes (We co-expressed TIR1(F79G) with a small fragment of human DNA helicase B (DHB) fused to two copies of mKate2 (DHB::2xmKate2) A. Co-expansgenes . DHB::2xansgenes   larval stage when anchor cell (AC) invasion normally occurs  leads to the formation of two ACs and/or post-specification defects such as AC proliferation and failure to breach BM.The null phenotype of ethality  and L1 lethality . RNAi diinvasion . Specifiegl-43 null mutants. To explore this, we examined AC phenotypes using AIDHB with a new internally AID-tagged allele of egl-43 that targets the long and short isoforms of endogenous EGL-43 (lag-2 (LAG-2::P2A::H2B::mTurquoise2) (lam-2 (LAM-2::mNeonGreen) (egl-43(RNAi)   and lam-onGreen)  to labelonGreen) B-D. Of t43(RNAi) .lin-12 null mutant, both cells become ACs. To further test AIDHB, we combined it with an endogenous allele of lin-12 tagged at the C-terminus with mNeonGreen::AID  with and without 5-Ph-IAA. At the time of AC invasion, 30/30 auxin-treated animals and 26/29 control animals displayed the proliferative AC phenotype (n=196 versus 118). The higher total is expected for animals with two post-specified ACs that then entered the cell cycle and proliferated. Lastly, we confirmed the presence of LIN-12::mNeonGreen::AID in proliferating ACs of auxin controls after egl-43(RNAi)  , which legl-43 or lin-12 for degradation beginning in the L1 larval stage before AC specification. These experiments produced the expected AC phenotypes observed with either LIN-12 or EGL-43 depletion. Whereas loss of LIN-12 results in the formation of two ACs due to a defect in AC specification (egl-43(RNAi) results in ectopic LIN-12 expression in proliferating ACs, we did not observe localization in the nucleus, suggesting that ectopic LIN-12 may not be representative of active Notch signaling  can force the AC to proliferate . The NIC12 locus . The eme elegans  should fegl-43, and (iii) postulate that in the absence of EGL-43, LIN-12 expression is not necessary for AC proliferation. It is our hope that investigators will use AIDHB to interrogate the function of diverse proteins that may be required for cell-cycle-driven cellular behaviors.In summary, we (i) created a heterologous co-expression system called AIDHB, which we later paired with RNAi, (ii) generated a new AID-tagged allele of bmd284[rpl-28p::TIR1(F79G)::T2A::DHB::2xmKate2]; LG II: wy1514[egl-43::TagRFP-T::AID::egl-43]; LG III: ljf33[lin-12::mNeonGreen::AID] ::T2A::DHB::2xmKate2), pWZ192 (NotI-ccdB-SphI-DHB::2xmKate2) was double digested with NotI and SphI to excise ccdB and a PCR product representing rpl-28p::TIR1(F79G)::T2A was amplified from plasmid pCMH2123 using primers DQM1136 and DQM1137. pWZ259 was constructed by Gibson assembly (NEB) using the backbone from pWZ192 and the PCR product from pCMH2123. After sequence confirmation, pWZ259 was used as a repair template for insertion into the genome at a safe harbor site on chromosome I corresponding to the MosSCI insertion site ttTi4348 . pAP082 egl-43 locus was PCR amplified and purified using a PCR purification kit (Qiagen). 3 μl of 10 μM tracRNA (IDT) was incubated with 0.5 μl of 100 μM of a crRNA (IDT) targeting exon 6 of the egl-43 locus at 95°C for 5 min, followed by 25°C for 5 min. Following incubation, the mixture was incubated with 0.5 μl of Cas9 protein (IDT) at 37°C for 10 min. Repair template and a co-injection marker (pRF4) were added to the mixture to a final concentration of 200 ng/μl and 50 ng/μl, respectively. Young adult worms were transformed using standard microinjection techniques and progeny were genotyped for successful insertions . The egl-43(RNAi) feeding construct was published previously (Synchronized L1 larvae were plated on NGM plates containing 0.1 mM 5-Ph-IAA (MCE) and fed either OP50 or eviously , and it Images were collected using a custom-built spinning disk confocal microscope (Nobska Imaging), which was configured for automation with Metamorph software (Molecular Devices). This confocal consists of a Hamamatsu ORCA EM-CCD camera mounted on an upright Zeiss Axio Imager.A2 with a Borealis-modified Yokogawa CSU-10 spinning disk scanning unit and a Zeiss Plan-Apochromat 100x/1.4 oil DIC objective. Animals were anesthetized for imaging by picking them into a drop of M9 on a 5% agarose pad containing 7 mM sodium azide and secured with a coverslip.Acquired images were processed using ImageJ/Fiji . AID::GFP-values, and statistical tests used are specified.To determine the number of animals (N) needed per condition, a power analysis was performed . In each10.1242/biolopen.059668_sup1Supplementary informationClick here for additional data file.


The accurate modeling of frequency-dispersive materials is a challenging task, especially when a scheme with a transient nature is utilized, as it is the case of the finite-difference time-domain method. In this work, a novel implementation for the modeling of graphene-oriented dispersive materials via the piecewise linear recursive convolution scheme, is introduced, while the time-varying conductivity feature is, additionally, launched. The proposed algorithm is employed to design a reduced graphene-oxide antenna operating at  Since the discovery of isolated and stable graphene films , grapheny KMnO4) . The prey nature . In ordey nature . The proy nature , such asy nature .In particular, the research for efficient graphene-oxide-based sensors has, lately, escalated, owing to their remarkable properties ,24,25. Aetection ,28, althetection ,30 are p minutes ,32. Fina minutes ,34,35.Essentially, the aforementioned applications rely on the appropriate modeling of the involved media. In general, the characterization of graphene-based materials is achieved through their surface conductivity. Specifically, graphene itself is considered as a truly two-dimensional layer and its conductivity is evaluated via the Kubo formula . The latNevertheless, the analysis of modern devices is not feasible through analytical solutions; therefore, the surface conductivity features must be incorporated into powerful numerical algorithms, such as the finite-difference time-domain (FDTD) method . The latBased on these aspects, the main contribution of this work is the development of a novel scheme for the modeling of graphene-oriented conductive materials with frequency-dispersive response in the popular FDTD method. The transient nature of the latter is exploited to enable the simulation of planar materials with time-varying features and properties, which offers many possibilities for the design of complex devices for advanced applications. Moreover, the frequency dispersion is handled using an efficient PLRC algorithm that is appropriately adjusted to the surface conductivity function of the involved materials. Then, the developed implementation is applied to the design of an rGO antenna. An observation of the rGO transient response for sensing applications is performed, and some concepts for the enhancement of the device’s response are proposed by means of the time-varying rGO traits.The rest of the paper is organized as: Initially, the featured FDTD scheme for the modeling of the rGO is introduced in Two challenging tasks are encountered for the effective transient modeling of frequency-dependent conductive layers, such as the graphene, the GO, and the rGO. Initially, we consider that any planar material is characterized through its surface conductivity Here, we included the Dirac delta function, Equation , using tIt is important to mention that the Now, the second challenge appears, namely the robust implementation of the frequency dispersion for the conductive layer. In particular, the second-order accurate PLRC method is modified appropriately to model the surface current dispersion. First of all, the transition of Equation  into theJp(t)=σpσrGOEquation : (15)χi=It is obvious that the exponential term leads to the convenient computation of the recursion constant: Finally, the time-domain nature of the FDTD method enables the powerful feature of transient conductivity alteration, a feature that is absent from the majority of the commercial packages. Particularly, the conductivity of various planar materials can be adjusted externally, such as the electrostatic bias of graphene or the gas and humidity dependence of rGO . As a coThe previously described scheme is verified in terms of its accuracy via its thorough comparison with analytical solutions as well as with well-established a numerical software. Firstly, a finite rGO layer is considered and the transmission coefficient is evaluated at microwave frequencies. The conductivity of the rGO at this regime is almost constant; thus, the relaxation time is selected to be Additionally, the more complex setup of io Suite , where tFinally, the featured modeling methodology is compared to some well-established techniques in In this section, the newly introduced modeling of planar conductive materials is applied on the design of a patch antenna that includes an rGO patch. The transient nature of the method is exploited to perform an analysis on the effect of the planar material’s conductivity changes on the performance of the antenna. Moreover, it is shown how the conductivity variations can result on an enhancement of the antenna radiation characteristics, and, thus, can be used for sensing purposes.The proposed patch antenna has the dimensions depicted in er (PML) ,42,45.Firstly, we investigate the effect of rGO conductivity changes on the antenna response, both for constant and time-modulated values of Subsequently, taking avantage of the transient nature of the FDTD method, Equation . Both thOn the other hand, the variation of the modulation frequency leads to different antenna responses. Explicitly, the deepest resonant pick is reached for a modulation frequency of It becomes apparent that the optimal rGO antenna with the time-modulated conductivity exhibits a definite improvement of around Moreover, the total efficiency (gain) is calculated as As already demonstrated in A new implementation of the PLRC scheme for the accurate modeling of graphene-based materials with time-varying properties has been introduced in this paper. Using this scheme, the rGO has been efficiently modeled and integrated within a patch antenna operating at


Tg) and storage modulus. These properties have been compared with previously reported values using pristine graphene (Gr) as a filler. The increase in thermal mechanical properties on addition of silanized graphene (SiGr) showed a large shift in the Tg and more increase in storage modulus by chemically binding SiGr sheets on the aramid chains. Aminophenyl-trialkoxysilane was found to give better results due to the presence of phenyl groups which were more rigid than propyl groups present in aminopropyl-trialkoxysilane. The effect of chemical bonding and the possible π–π secondary bond interactions between the matrix and graphene platelets on the properties of the resulting hybrids are discussed.The synthesis and characterization of aramid composites reinforced with graphene platelets are reported. Hydroxy-functionalised graphene platelets were modified with two sol–gel binders  and then chemically linked with aramid chains. The effect of the two sol–gel binders on the physiochemical and mechanical properties was evaluated. Chemical changes during the sol–gel reaction and subsequent amidation process in the nano-composite preparation were evaluated by the XPS and FTIR analyses. Thin films of these composites with different proportions of graphene were prepared. Morphology of the hybrids prepared was studied by the SEM technique. Properties of the composite films were studied by dynamical mechanical thermal (DMT) analysis to measure their glass transition temperature ( The synthesis and characterization of aramid composites reinforced with graphene platelets are reported. Polymer composites can provide high mechanical strength and thermal stability with diverse properties which are substantially different or even better as required for the advanced applications. This is possible, in particular, when the filler is present at the nanoscale5–7 and is distributed homogenously in the matrix. Due to the unique and tunable properties of network structures, the use of inorganic materials in combination with high performance polymers has attracted a lot of interest in the recent past for numerous applications in the aerospace and electronics industries.8–10 A good number of the publications have been focussed on nano-inorganic particles produced by in situ sol–gel processes11,12 in the matrix or as surface coating materials. The layered silicate structures13–15 using different types of clays also became very popular to enhance the toughness of the polymeric materials. Carbon-based nano-fillers in the recent times, however, are being preferred in comparison to clay or other inorganic metal oxides to improve the mechanical strength of polymers. Polymer composites using carbon black16,17 carbon nanotubes (CNTs)18–24 carbon fibre25,26 and graphene (Gr)27–29 have shown a large improvement in thermal, mechanical, conductive and flame-retardant properties.The last few decades have witnessed a rapid development in the field of polymer composites18–24,30,31 Chemical functionalization of CNTs can increase their interaction with the polymeric matrix facilitating their processability.21,32 The presence of a suitable solvent can greatly enhance their de-aggregation required for a uniform dispersion33 in the matrix. The present authors have shown that strong interfacial interactions of the matrix with the surface-modified CNTs reduced the stress-transfer problem in the composite material and resulted in higher modulus of 4.26 GPa and a glass transition temperature of 338.5 °C, whereas the CTE was reduced to 101.8 ppm on addition of only 2.5 wt% CNTs in aramid matrix24,35. Because of their high aspect ratio, the alignment of the CNTs in a matrix can create a large polymer–filler interface thus producing large reinforcement. But one of the major disadvantages with CNTs is their entanglement tendencies due to which the increased viscosity with higher loadings may lead to a significantly poorer dispersion.34 The alignment of CNTs, even at a laboratory scale35 seems difficult to achieve at present. Another disadvantage with CNTs is their higher cost of production which may discourage their uses for production of such composites on the industrial scale.31,36 Graphene on the other hand is cheaper in comparison to CNTs with exceptionally good mechanical, thermal and electrical properties. Owing to their high surface area, large aspect ratio and high tensile strength and thermal conductivity these can be very suitable to improve the properties of polymeric matrices.27,37,38 It is also much easier to process these platelets at higher loadings in the matrix, as the viscosity of the polymer–graphene mixture is significantly lower than the CNT composites. These platelets due to their micron-size wrinkled layered structure have been found to be a highly efficient load bearer filler in comparison to the CNTs for the polymer matrices.39 The improvement in the ultimate physicochemical characteristics of such composites, however, depends on the distribution of Gr layers in the polymer matrix as well as on the interfacial bonding between the Gr and the matrix.40 Modification of the Gr surface is usually carried out by oxidation followed by its chemical functionalization.41 The oxidized graphene (GrO) bearing various polar i.e., hydroxyl and carboxyl functional groups can alter the van der Waals interactions significantly. These methods make Gr more compatible with organic polymers.42 The covalent or the noncovalent functionalization facilitate dispersion and stabilize Gr in the matrix by preventing its agglomeration.43–45 For this reason, GrO is now being used extensively in industry as a nanofiller in the polymer composites.46,47Among the carbon materials, CNTs have proven to be very effective as conductive fillers and a wide variety of CNT–polymer composites using different techniques have been reported.et al.48 modified GrO surfaces using tetraethoxysilane and the silanized graphene (SiGr) was found to improve the protective properties of composite coatings. High performance benzoxazine–bismaleimide resin based SiGr composites were prepared by Jiang et al.49 who showed that SiGr has good dispersity in the matrix. Thermal decomposition temperature and char yield of the composites were reported to improve markedly. Organically modified silanes represented by M–Si–(OR)3 can be used through the sol–gel processing to link the oxidized graphene with polymer chain. The trialkoxy (OR) can be easily hydrolysed and condensed using sol–gel process and linked with hydroxy functionalized Gr. Depending on the nature of the functional group M, the silanized graphene then can be linked to a polymer chain. The silica network produced during the silanization process can greatly increase the interlayer distance and creates a disorder in the Gr lattice thus ensuring a uniform distribution in the matrix. The GrO was modified by Liu et al.50 using γ-glycidoxypropyltrimethoxysilane to prepare the polyurethane composites. The SiGr provided a good compatibility with the matrix thus increasing the thermal decomposition temperature of polyurethane matrix.The GrO surface can be further modified by the sol–gel process using different types of silanes. The silica network structure can help to increase the interlayer distance thus reducing the agglomeration tendencies of the Gr platelets. Jing Li 51 due to their high specific strength and thermal stability with a lower density are considered as very important commercial fibers. In the present work thermal mechanical properties of such easily processable aromatic polyamide chains were improved by reinforcement with SiGr using two different types of organically modified silanes i.e., aminophenyltrimethylsilane APhTMS and aminopropyltriethoxysilane APrTES. To improve the solubility (processability) of poly chains, generally known as Kevlar© in industry, they were modified by introducing an optimum number of meta-linkages in the chains. The sol–gel process was used to bond the aminosilanes on the surface of hydroxy functionalised graphene, which then acted as a link between the graphene platelets and the polymer matrix chain. Viscoelastic properties of these chemically bonded hybrids with different proportions of SiGr have been determined and compared with our earlier work with those hybrids, which were reinforced with the pristine Gr.43Aromatic polyamidespara- and meta-phenylenediamines (99%) and aminopropyltriethoxysilane (98%) (APrTES), HCl and the solvent dimethyl acetamide (DMAc) with water contents less than 0.004%, all of analytical reagents (AR) grades were procured from Sigma-Aldrich. Graphene oxide powder (99.4%), (plate diameter Ø: 1.5–5.5 μm and thickness: 0.43–1.23 nm) was obtained from Nano US Research Nano materials. 3-Aminophenyltrimethoxysilane (90%) (APhTMS) was obtained from Gelest.The monomers terephthaloyl chloride (99%), meta- and para-phenylenediamines taken respectively in the molar ratio 35 : 65 was placed in a 300 ml conical flask in a glove box under complete anhydrous conditions. The total moles of amines taken were 0.025 and, in this mixture, 110 g of DMAc as solvent was added. The mixture was stirred with magnetic stirrer for 30 min until dissolved completely. Under complete anhydrous condition terephthaloyl chloride (0.025 mol) was then added to react with phenylenediamines. Stirring of the reaction mixture continued for the 24 h to complete the polymerization reaction. The –COCl terminated aramid matrix chains were prepared by further addition of 2.8 millimole of terephthaloyl chloride in the reaction mixture. Further stirring continued for 3 h to complete the endcapping of the chains with –COCl groups.A mixture of i.e., APhTMS and APrTES were used in this work  and 2.8 millimole of each silane was separately added to the graphene solution and the mixture was stirred for 30 min for complete mixing. To this solution, water was added in the form of DMAc solution (taken in 5 : 95 ratio respectively by weight) to carry out the sol–gel reaction. The ratio of silane to water was kept respectively at 1 : 1.5. Few drops of HCl (0.05 M) were added to catalyze the sol–gel reaction. The mixture was continuously stirred at 70 °C for 4 h on a magnetic hotplate. The stirring further continued at room temperature for 24 h. The silanized graphene solution was used as stock solution to prepare (The oxidized graphene (0.30 g) was taken in 20 g DMAc in a 150 ml flask and stirred for 24 h then followed by 2 h sonification. The sol–gel process was then carried out to functionalize the surface of graphene with aminosilanes. Two different types of silanes  prepare  the silaDifferent amounts of two silanized graphene solutions were added separately to a known amount of ClOC-endcapped polymer solution with stirring continued for another 24 h to get the complete mixing . Thin hy−1 using the JASCO FTIR Spectrometer-6300 to monitor the silanization procedure. The composition of different elements i.e., carbon, oxygen, nitrogen and silicon present on the film surface were determined by XPS to identify the functional groups present during the preparation of the hybrid materials. Thermo ESCALAB 250 Xi with a monochromatic radiation source was used for this purpose. FESEM was using to study the morphology of the composite films. The films fractured using the microtome at very low temperature and coated with gold were examined at 15 kV using SEM User, Interface with Model: SUPRA 50 VP(JDISS). The visco-elastic properties of the hybrid films were measured on Dynamic Mechanical Analyzer Q-800 (TA instruments). The storage modulus of the hybrid films at different loadings of SiGr were measured as function of temperature. The glass transition temperature was measured from the peak of tan δ plot vs. temperature. The measurements were taken under tension mode in the temperature range 50–500 °C, at the heating rate of 5 min °C−1 using frequency 5 Hz under nitrogen gas at the floating pressure of 60 Pa. Thermogravimetry was performed on approximately 10 mg of the sample from ambient to 800 °C at a heating rate of 10 °C min−1 in a dynamic nitrogen atmosphere (50 ml min−1), using TGA-50 TA automatic analyzer.The absorption spectra were obtained for the pristine and oxidized Gr, SiGr, ArPhSiGr and ArPrSiGr hybrid films in the range of 400–4000 cm−1 for  scale" fill="currentColor" stroke="none"><path d="M0 440 l0 -40 320 0 320 0 0 40 0 40 -320 0 -320 0 0 -40z M0 280 l0 -40 320 0 320 0 0 40 0 40 -320 0 -320 0 0 -40z"/></g></svg>C) bonds in spectrum (A) shows the presence of the hexagonal structure of pristine Gr whereas the peaks significant in spectrum (B) for GrO correspond to the functionalities created by the oxidation of Gr. A broad absorption peak between the 2600 cm−1 and 3500 cm−1 is mainly related to the hydroxyl groups on the GrO that were used in the present work for the sol–gel reaction. Two small peaks at 2921 cm−1 and 2846 cm−1 can be attributed to the (C–H) asymmetric and symmetric stretching vibrations derived from long alkyl chain of Gr. The adsorption band at 1730 cm−1 and 1625.6 cm−1 correspond to the CO stretching (from carbonyl and carboxyl groups) and aromatic CC vibration that results from skeletal vibration from unoxidized graphitic domains respectively. Besides, two weak peaks present at 1167 cm−1 and at 1051 cm−1 are from the C–O stretching deformation mode of the carboxylic acid group and epoxide functional group respectively. The peak at 1368 cm−1 can be attributed to single bonded carboxyl group (C–O)–O. The high intensity of the peaks due to oxygen functional groups is useful to develop further links of GrO platelets surface with silica by the sol–gel processing and then through amine groups with the matrix chain .52 The new bands at 1116 cm−1 and 1034 cm−1 are, therefore, assigned to the Si–O–Si network. The study conducted by Musto et al.53 has shown that Si–O–Si absorption at higher wave numbers represent the cyclic whereas at the lower wave number the linear silica structure. The absorption at 914 cm−1 is due to Si–OH bonds. The presence of APhTMS in the spectrum (C) is also confirmed by presence of the Si–C bond appearing at 720 cm−1.54 The decrease of broad peak of carboxylic –OH and C–OH around 3000–3500 cm−1 means that the amount of silane used was sufficient to cover the majority of the surface of graphene.Spectrum (C) in −1, 1543 cm−1 and 1320 cm−1 are attributed to amide functional groups which are from aramid and from the amidation reaction between the amine group of APhTMS and –COCl groups of aramid whereas the peak at 3315 cm−1 is due to –NH stretching. The new composite bands at 1119 cm−1 and higher wavenumber and at 864 cm−1 are assigned to the and Si–O–Si and Si–OH respectively. A small peak at 3449 cm−1 seems due to OH groups from the Si–OH produced during sol–gel reaction. The FTIR results shown in the spectra (C) and (D) approves the silanization process. The results obtained for the silanization process and the hybrids using APrTES were of similar nature, and these are not presented here to avoid the repetition chemical binding between the graphene and amide chain has further been investigated by the XPS analysis.The spectrum (D) in the 2 carbon bonds, C–O bonds, CO bonds respectively. In the spectrum (A) as expected N 1s peak is absent.XPS analysis was employed to elucidate the surface composition of Gr, GrO, SiGr, aramid and the hybrid films to provide more information on the interactions between silane coupling agent and the bonding between SiGr and aramid matrix chains. In the XPS spectrum (A) obtained for GrO, the peaks at 284.68 eV, 286.79 eV and 288.43 eV are attributed to the spi.e., from 29.43% to 7.96%. The peak from unreacted –NH2 groups of APhTMS is still present at 401.8 eV which indicates the silanization reaction occurred through alkoxy groups of APhTMS and the NH2 groups are retained.The spectrum (B) shows the presence of both Si and N elements in the SiGr and the concomitant reduction of carbon atoms with respect to GrO that confirm the silane functionalization by APhTMS through the reaction of the alkoxy group of the silane with –OH groups of GrO. Additional peaks at 283.97 eV and 285.37 can be assigned to C bonded to Si owing to the reaction with silane coupling agent. The atomic wt% of carbonyl carbon structure in the SiGr in comparison to GrO decreased considerably C bond. The (C–N) bond formed in the aramid chain or (C–N)–Ar appears at 287.90 eV. The unreacted COCl on aramid chains are confirmed in the carbon spectrum at 289.08 eV. Oxygen peaks from OC–C appears at 531.2 whereas OC–N can be seen at 532.06 eV. The unreacted terminal acid chloride peak OC–Cl is seen at 533.38 eV and N–C and N–H peaks can be at seen at 399.51 eV and at 400.05 eV. In spectrum (D) for ArPhSiGr-8 hybrid film the disappearance of COCl at 289.08 eV and OC–Cl at 533.38 eV and that of –NH2 peak at 401.79 eV confirms the reaction taking place between the acid chloride terminated aramid resin and silanized Gr. The atomic wt% of OC–N in the composite increased as well due to the amide bond formation. The peak of the binding energy (BE) for a specific element depends on the structure and local chemical environment of that element. The OC–C peaks from GrO and silanized Gr are at 532.5 eV and that from neat aramid and its hybrids at 531.2 eV and 531.23 eV respectively. The BE values in the hybrid film are closer to aramid since the matrix contributed more than 92 wt% of the hybrid system.The XPS spectrum (C) for the aramid chains end-capped with –COCl groups shows peaks at 284.67 eV for C–C as well as 285.11 eV for the CScanning electron microscopy imaging was used to evaluate the surface morphology and graphene distribution in the matrix of the composite films produced from two different aminosilanes. Comparing the morphology of the films obtained using APhTMS  with thoE′) and tangent psi (tan δ) as a function of the temperature. The temperature dependence of tan δ can reveal different relaxation processes in the material denoted by α, β and γ transitions. δ curve for ArPhSiGr (δ curve for neat aramid and this peak corresponds to the α-relaxation temperature (Tg). With increase in the loading of silanized graphene the maxima of the curve shifts to higher temperature in both types of hybrids indicating that the reduced mobility of the polymer chains. The surface of graphene is covered with porous silica network and the polymer chains are not only linked with it chemically, but the chains were imbibed within this network as seen in the SEM images. The strong adhesion of the polymer chains with SiGr is also confirmed from the dampening of the tan d curves, which increases as the elastic nature of the material increases as SiGr is increased in the matrix. The Tg for the pure polymer increased from 330 °C to 379 °C for the ArPrSiGr system and to 389 °C for the ArPhSiGr system with 8% SiGr. The increment in Tg is attributed to the suppressed mobility of aramid back bone due to the increased interfacial interaction and the chemical bonding of the polymer chain and on the surface of Gr. This can be attributed to the presence of silica network produced by the sol–gel process has separated the sheets apart thus increasing its free surface to interact with polymer matrix. Chemical bonding between the amine groups of the silanized graphene and the acid chloride end-groups from aramid matrix has further improved their adhesion with the matrix resulting an increase in the Tg of the hybrid material.Thermal mechanical properties of aramid-silanized graphene hybrid films were studied by measuring the stress response during the exposure of the film to a sinusoidal strain within the temperature range of 25 to 500 °C. The results were obtained in terms of the storage modulus , present on both sides of the Gr sheets can have multiple π–π interactions with phenyl rings of aramid matrix we used. Even using pristine Gr, therefore, we found an increase in the Tg on loading with pristine Gr. A comparison in Fig. S2Tg is, therefore, observed when SiGr used as fillers (Liao  fillers .E′) for the two types of composites i.e., ArPrSiGr and ArPhSiGr with different amounts of SiGr is shown in E′ values above 480 °C is due to a softening of the polymer.The effect of temperature on the storage modulus  chain known as Kevlar© has a thermal decomposition temperature around 528 °C.56 To make this type of fiber processable we introduced nearly 20% meta-linkages and a thermal decomposition temperature of the matrix was slightly reduced (A) to 512 °C  and (C) in By a careful choice of choosing an organically modified silane, the silica network structure can be produced by the sol–gel process on graphene surface which help to increase the interlayer distance thus disaggregating the graphene platelets and ensuring their uniform distribution in the polymer matrix. With an appropriate choice of functional groups present on silane it can further be utilized to develop chemical bonding between the filler and the matrix. Greater adhesion between the silanized graphene using 3-aminophenyltrimethoxysilane and the aramid chain resulted in a much higher increase in the glass transition temperature and storage modulus, and it was possible to reinforce the polymer with higher contents of filler.There are no conflicts to declare.RA-012-D2RA04797G-s001


The presented work is devoted to the study of the formation of the thinnest diamond film (diamane). We investigate the initial stages of diamond nucleation in imperfect bilayer graphene exposed by the deposition of H atoms . We show that defects serve as nucleation centers, their hydrogenation is energy favorable and depends on the defect type. Hydrogenation of vacancies facilitates the binding of graphene layers, but the impact wanes already at the second coordination sphere. Defects influence of 5|7 is lower but promotes diamondization. The grain boundary role is similar but can lead to the final formation of a diamond film consisting of chemically connected grains with different surfaces. Interestingly, even hexagonal and cubic two-dimensional diamonds can coexist together in the same film, which suggests the possibility of obtaining a new two-dimensional polycrystal unexplored before. Diamond is probably the best-known crystalline compound of carbon. Diamond nanostructures of different dimensions have also attracted much attention along with the two-dimensional diamond or diamane , which i2, we can expect the appearance of a significant nucleation barrier which can be overcome only by high pressure and temperature, for instance, in the case of single-layer graphene hydrogenation is problematic [The most promising way to obtain a two-dimensional diamond seems to be the use of graphene as a precursor, by deposition of reference atoms  on its surface. In this case the thermodynamic stability of the material is reversed, the previously unstable diamond film becomes energy favorable, and graphene layers tend to bond to each other . Despiteblematic ,14.However, the real structure of graphene contains structural defects that can be used as nucleation centers which may allow the synthesis of diamane under less severe conditions. Here we investigate such an effect in detail. For this purpose, we study one of the most common structural defects in graphene and reveal their impact on diamond nucleation.−5 a.u. while maximum force components were found less than 10−4 Hartree/Bohr.An isolated bigraphene cluster was chosen as the model system. The edge atoms of bigraphene were passivated by hydrogen atoms. The flake diameter was about 30 Å which made it possible to neglect the influence of edge effects on the process of nucleation in the flake center. For geometry relaxation and calculation of the structure energy, the DFTB method was used . In this2 molecule calculated in the framework of DFTB differs from the reference DFT data. Thus, we used in our calculations the reference value of difference (0.23 eV/atom) between the H-H and C-H binding energy for H2 molecule and infinite graphane [The bonding energy of the Hgraphane , respectn chemisorbed H atoms the average formation energy εb (n) is gE is the energy of either monolayer or bilayer graphene substrate, εH is the energy of a single H atom, and nHEg@ is the total energy of the hydrogenated structure.The growth of the diamond phase in multilayer graphene has a nucleating character . This me2 molecule .b (n) intersection with The presence of several nearby vacancies can facilitate diamond formation. In contrast to the vacancy located only in one layer, we considered the agglomeration of cross layer vacancies in bilayer AB stacked graphene which can be obtained by its irradiation with low-energy ion beams of high density. In this structure, the defects affect each other. It leads to the formation of a reactive area between them which easily binds hydrogen atoms and forms interlayer bonds. We considered an agglomerate of vacancies separated from each other by about 5 Å, as seen in In the case of the Stone–Wales (SW) defect commonly observed in graphene , we founNote that the Stone–Wales defect is a constituent part of the grain boundary (GB) in polycrystalline graphene connecting the graphene domains with different orientations . Since sThus, hydrogenation appears to be a prospective way to obtain a specific two-dimensional diamond structure that combines different surfaces. The grain boundary energy of the studied junction is ~1.3 eV/Å, which is only slightly higher than other considered two-dimensional carbon interfaces, namely graphene (<0.4 eV/Å ) and graIn summary, we found that type and concentration of structural defects can sufficiently impact the initial stages of diamond nucleation. At the same time, it does not influence further diamond formation. Defects impact on C-H bonding strength is disappearing at the second coordination sphere already. We show that vacancies agglomeration (that can be produced by low energy ion irradiation) can sufficiently expand the reactive region which vanishes the nucleation barrier for the first stages of nucleation. Stone–Wales defects impact is lower but promotes the hydrogenation and bonding of the graphene layers. We show that 1D defect (dislocation) not only facilitates the diamondization but also may lead to the appearance of 2D diamond consisting of chemically connected grains of different crystallographic orientations. Therefore, polycrystalline graphene usually observed in the experiment can produce specific 2D diamond polycrystals containing different surfaces. Even hexagonal and cubic 2D diamonds can coexist together in the same film with grain boundary energy comparable with the same values for other two-dimensional carbon structures.Our study can be further expanded by more detailed investigation of the thermodynamic stability of formed diamond clusters and the explicit calculations of nucleation barrier dependence on a pressure. Other possible structural defects  as well as multilayer graphene (more than two layers) should be also considered in further work.We believe that the present study will help in further research on the diamondization of multilayer graphene and producing of new carbon nanomaterials with tunable properties for various applications.


C. elegans hermaphrodite germline, and how this redundancy may contribute to robustness. We focus on the various types of redundancy utilized to regulate this balance, as well as the approaches that have enabled these redundant mechanisms to be uncovered.The proper production of gametes over an extended portion of the life of an organism is essential for a high level of fitness. The balance between germline stem cell (GSC) proliferation  and differentiation (production of gametes) must be tightly regulated to ensure proper gamete production and overall fitness. Therefore, organisms have evolved robust regulatory systems to control this balance. Here we discuss the redundancy in the regulatory system that controls the proliferation vs. differentiation balance in the  C. elegans germline to ensure proper regulation of the balance between germline stem cell (GSC) proliferation and differentiation.Proper development of multicellular organisms requires the ability to adapt to both internal and external perturbations. The ability of an organism to adapt to such changes requires its biological processes to be robust, meaning they are able to continue to develop and function, even when perturbations are encountered . This roStem cells are necessary for proper development and tissue homeostasis; therefore, the processes regulating their behavior must be robust. Stem cells have the ability of maintaining themselves over much of the life of the animal, while also providing the cells that form the differentiated tissue . For steThe reproductive success of animals within a population is key to that population being maintained; therefore, the processes involved in ensuring proper gamete formation must be robust. This includes the balance between proliferation and differentiation of GSCs. If this balance is disrupted, or is unable to withstand various environmental insults, the reproductive success of the animal would be significantly reduced; too much self-renewal would result in germline tumors of proliferating cells and a reduction or elimination of differentiated gametes that are formed, while too much differentiation would result in the GSC population being depleted and a lack of sustained gamete formation.C. elegans germline has revealed a core genetic pathway that contains many redundant factors, and many additional inputs that appear to fine-tune the balance. This regulatory mechanism has been extensively reviewed elsewhere , which is a somatic cell that caps the distal end of the gonad arm and serves as the niche cell for the GSC stem cell population (sygl-1 (synthetic germline proliferation defective) and lst-1  genes (fem-3 mRNA binding factor) and other PUF (Pumilio and FBF) homologues (PROM−1 (skp1-cullin-F-box protein progression of meiosis-1) pathways, based on their founding members  genes  (Kershnet) genes , whose pmologues . This PUmologues . These p members .PROM−1 pathways to increase  of a loss of the redundant effectors, but also the mechanism by which each effector functions. With many of the examples of redundancy in regulating the proliferation vs differentiation balance in the C. elegans germline has proven to be a powerful system to uncover redundant factors and mechanisms due, in part, to the availability of sensitive genetic backgrounds and the ease with which subtle phenotypes can be observed. C. elegans are transparent, allowing observation of the germline in living animals [reviewed in  gain-of-function allele, perhaps the strongest identified glp-1 gain-of-function allele, and which also contain an additional wild-type copy of glp-1 on a free duplication, have completely tumorous germlines with no evidence of cells entering meiosis , all stem cells differentiate prematurely in early larval development, resulting in a total of approximately four to eight stem cells, which differentiate into 16–32 sperm  and glp-1(q175null) result in these extreme opposite phenotypes, there are many other alleles of glp-1, including weak gain-of-function alleles, and partial loss-of-function alleles, which result in milder phenotypes, especially at permissive temperatures (glp-1(oz264gf) or glp-1(ar202gf) at higher temperatures result in increased proliferation of the mitotic cells and a delay of entry into the differentiation pathway, resulting in a larger than wild-type progenitor zone , have stem cells entering the differentiation pathway more distally in the gonad arm, resulting in a smaller progenitor zone than wild-type  as potentially being involved in regulating the proliferation vs. differentiation balance whose involvement have been characterized by analyzing the Glp and tumorous phenotypes that result when combined with weak glp-1 loss and gain-of-function alleles [Reviewed in , function downstream of GLP-1/Notch signaling within the C. elegans germline   . The higof fem-3 . No singfbf RNAi , supportfbf-1 and fbf-2 identified an additional role for fbf in regulating the balance between proliferation and differentiation of GSCs  mutants as the progenitor zone did not become fully depleted until later in larval development, and depletion did not fully occur at higher temperatures , a catalytic subunit of the CCR4-NOT (carbon catabolite repressor factor 4—negative on TATA-less) deadenylation complex   . Localizality 1) . Therefoality 1) . Althougality 1) . These vality 1)  for discality 1) .fbf-1 and fbf-2 within the C. elegans germline suggested that these genes displayed molecular redundancy, with their highly conserved PUF domains allowing them to recognize and repress the same mRNA targets; however, more recent evidence of differing binding partners and localization, combined with their single mutant phenotypes, has uncovered that these two genes likely function using distinct mechanisms to repress target gene expression    works redundantly with fbfs to robustly promote GSC proliferation. PUF-11 was identified as a strong candidate as it displays similar RNA-binding specificity to FBF and interacts with LST-1 in a large scale yeast two-hybrid screen (Although the complete loss of the GSC pool in adult enotype) . In the /animal) . The inad screen . PUF-3, d screen .puf-11 and puf-3, have ∼90% nucleotide identity with each other, and 88% identity at the amino acid level  mutants , based on mRNA in situ data showing expression within the GSC pool  knockdown, resulted in a Glp phenotype during larval development  normally and result in over-proliferation of the mitotic cells, with most cells failing to enter meiosis . Its placement in this pathway is based on the finding that gld-2; nos-3 double mutants show synthetic tumors while gld-1; nos-3 double mutants have normal meiotic entry )  that functions in parallel to the GLD-1 and GLD-2 pathways to inhibit proliferation and/or promote meiotic entry. First, the synthetic tumorous germlines in ic cells . Second,p-1(gf)) . Finally mutants . Therefoic entry .PROM−1 was found to bind CYE-1, potentially targeting it for degradation  that functions redundantly with the GLD-1, GLD-2 and SCFPROM−1 pathways to promote meiotic entry and/or inhibit proliferation  E3 ubiquitin-ligase complex which includes the PROM-1 F-box protein. SCFradation . Loss ofpathways . Further mutants . Howeverferation .PROM−1 pathways display cellular process redundancy in their regulation of the proliferation vs differentiation decision in the C. elegans germline ) and prp-17 (Yeast PRP17 related splicing factor) were identified , cyn-4/mog-6 and prp-19  mutants , which encodes an ⍺-subunit of the 20S proteasome  was found to be one of these proliferation promoting proteins, and is targeted for degradation by the E3 ubiquitin ligase RFP-1 (ring finger protein) (glp-1(gf) background, suggesting that there could be multiple targets whose regulated degradation is necessary for the proliferation vs differentiation decision to be properly maintained  . Other fintained . As mentintained .glp-1 partial loss-of-function alleles, or enhance the tumorous phenotype of glp-1 gain-of-function alleles [reviewed in , which could impact over-proliferation and under-proliferation phenotypes. Additionally, the type and degree of redundancy may not be constant throughout development and ageing. For example, it is possible that some factors are redundant in early larval development as the progenitor zone is being established, but not in adulthood while it is being maintained.The genetic pathway regulating the proliferation vs. differentiation decision in the Presumably, even slight disruptions in the proliferation vs. differentiation balance would negatively impact long-term reproductive success. Therefore, there is likely significant evolutionary pressure ensuring that the system regulating the proliferation vs differentiation balance is robust, which could involve a significant level of redundancy. It is thought that redundancy can provide robustness to a system by decreasing the phenotypic consequence of mutations, or by broadening the flexibility of the system so that signals can still be properly controlled in fluctuating cellular environments, different genetic backgrounds, and environmental stresses such as changes in temperature and availability of food . TherefoC. elegans germline. In some cases, the initial discovery of redundant factors and their presence or lack of similarity suggested that they were an example of one class of redundancy. However, for some redundant factors, as understanding increased as to their modes of action and their potential targets, it actually became less clear as to which class of redundancy most accurately described their relationship. Furthermore, some redundant factors may exist in more than one class; for example, two redundant proteins with a high degree of amino acid sequence identity may function on a group of common targets, but may also have targets that are unique to each redundant factor. Conclusive classification of redundant factors requires complete understanding of the biochemical functions of the factors and a knowledge of all their targets. Obviously, we are not yet at that level of understanding with respect to the regulation of the proliferation vs differentiation decision in the C. elegans germline. However, perhaps our level of understanding of the biochemical functions and targets involved in this process is relatively high, which has revealed that the redundant relationships between factors are more complex than previously appreciated. Indeed, the relationships between redundant factors in other systems may also be found to be more complex than once thought as more is learned about the biochemical functions and targets of these redundant factors. However, what is clear is that many types of redundancy are utilized in regulating this proliferation vs. differentiation balance in the C. elegans germline, and that this redundancy likely contributes to its reproductive success and fitness.In this review we have discussed some of the different types of redundancy, highlighted with specific examples, that are utilized in regulating the proliferation vs differentiation decision in the