Graphene nanoscrolls (GNS), due to their remarkably interesting properties, have attracted significant interest with applications in various engineering sectors. However, uncontrolled morphologies, poor yield and low quality GNS produced through traditional routes are major challenges associated. We demonstrate sustainable approach of utilizing bio-derived cellulose nanocrystals (CNCs) as template for fabrication of GNS with tunable morphological dimensions ranging from micron-to-nanoscale(controlled length < 1 μm or >1 μm), alongwith encapsulation of catalytically active metallic-species in scroll interlayers. The surface-modified magnetic CNCs acts as structural-directing agents which provides enough momentum to initiate self-scrolling phenomenon of graphene through van der Waals forces and π-π interactions, mechanism of which is demonstrated through experimental and molecular simulation studies. The proposed approach of GNS fabrication provides flexibility to tune physico-chemical properties of GNS by simply varying interlayer spacing, scrolling density and fraction of encapsulated metallic nanoparticles. The hybrid GNS with confined palladium or platinum nanoparticles (at lower loading ~1 wt.%) shows enhanced hydrogen storage capacity (~0.2 wt.% at~20 bar and ~273 K) and excellent supercapacitance behavior (~223–357 F/g) for prolonged cycles (retention ~93.5–96.4% at ~10000 cycles). The current strategy of utilizing bio-based templates can be further extended to incorporate complex architectures or nanomaterials in GNS core or inter-layers, which will potentially broaden its applications in fabrication of high-performance devices. The tubular nanochannels and high porosity present in GNS provides pathway for intercalation of ionic species in its inter-galleries resulting in higher electrical conductivities compared to graphene with practical applications in electrochemical charge storage devices3 and electronics4. In literature, molecular simulation-based studies on the formation of GNS and theoretical predictions of its properties, have been extensively studied6. However, self-assembly of GNS through real-time experiments is technically difficult to achieve. Despite the unique properties of GNS, it has been shown to undergo unwrapping leading to formation of defects7, due to which studies on potential applications of GNS in hydrogen (H2) storage devices8, CO2 capture9 and catalysis have been only possible through simulation studies. Some of the investigations for fabrication of GNS are based on self-assembly of graphene through controlled sonication approaches, Langmuir-Blodgett10, cyclic freezing-thawing12, chemical vapor deposition13 and ordered exfoliation or intercalation of graphitic inter-layers14. The aforementioned techniques are usually energy intensive processes utilizing harsh reaction conditions or chemicals with lower yields/poor quality of GNS and have issues related to environmental sustainability, which needs to be addressed through strategic modifications of GNS fabrication routes.Graphene nanoscrolls (GNS) are one of the most emerging carbon-based nanomaterials which have been the focus of several recent studies due to their interesting physico-chemical properties and one-dimensional topological structures produced through rolling of two-dimensional graphene sheets. GNS are morphologically similar to multiwalled carbon nanotubes(CNTs); however, their open end structures, variable scrolling density and tunable inter-layer spacing provides a unique opportunity to inherit favorable properties of both CNTs and graphene15 and produce it with higher monodispersity index, yield and quality through scalable approaches. From the application point of view, GNS with higher aspect ratio are preferred in case of energy storage devices (such as capacitors or batteries), due to their superior electrical transport behaviour over longer length scales and ability to form electric double layer capacitors3. Moreover, GNS with low aspect ratio and higher degree of porosity are preferred for potential applications in catalysis and hydrogen (H2) storage devices8 due to their ability to entrap H2 molecules in nanochannels. Introduction of catalytically active nanomaterials in core of GNS is expected to improve the electrochemical storage through formation of pseudocapacaitance16 and enhanced H2 uptake through spillover mechanism17. However, production of GNS with distinct morphological dimensions have been seldom reported through simulation studies18 but experimental techniques to synthesize size tunable GNS  with various metallic moieties encapsulated in its core as well as inter-galleries, is a challenging tasks and needs to be investigated.The major challenges in GNS processing is to effectively control the morphological dimensions2 storage and electrochemical performance as supercapacitors has been studied. Therefore, this study utilizes CNCs as a powerful tool to induce self-assembly of graphene to manipulate the structural and chemical properties of GNS through selective confinement of metallic nanoparticles, which may provide it exceptional features for potential high performance applications.In this paper, a facile and sustainable approach for fabrication of GNS with tunable dimensions and catalytically active metallic intercalates has been developed, through utilization of CNCs derived from bamboo stems as templates. CNCs are crystalline domains of cellulose with rod-like morphology which contains abundant hydroxyl groups, high surface area, tunable aspect ratio, higher modulus, surface reactivity, and interesting optical properties due to its non-toxic behavior, improved bio-compatibility and biodegradability, which finds growing interest in both fundamental as well as applied research. Surface modified magneto-responsive CNCs shows presence of both external stimuli forces (magnetic or electrostatic interactions) and acts as structural directing agents which is expected to have synergistic effect, leading to improved scrolling efficiency of graphene sheets with reduced defects. The variation in inherent characteristics of CNCs  in terms of structural, morphological behaviour and functionality , provides us a unique opportunity to tune physico-chemical properties of GNS. The rolling of graphene sheets into GNS in presence of magneto-responsive CNCs is a complex phenomenon, mechanism of which has been understood through combined experimental as well as molecular simulation studies. Furthermore, as a proof of concept, two different catalytically active platinum (Pt) and palladium (Pd) nanoparticles are confined in the core of GNS and their effect on H2  have high fractions (~35 wt%) of maghemite nanoparticles decorated on its surface, which integrates magnetic moment of ~43 emu/g alongwith the distinct rod-like morphology (length ~745 ± 63 nm and diameter ~56 ± 8 nm), makes it an ideal candidate for GNS fabrication , with length ~750 ± 230 nm and diameter ~174 ± 50 nm. Interestingly, it was observed that dimensions of fabricated Fe2O3-NS especially its length is found to be almost similar to that of Fe2O3-CNCs  with intercalated Fe2O3 nanoparticles in its core as well as inter-layers  which leads to the formation of size-specific GRO sheets with dimensional area of 0.56 ± 0.3 µmion Fig. . It is nion Fig.  fabricatphs Fig.  of indiv Fe Fig. . Therefo2O3-CNC-HR is formed using the CNCs derived from filter paper19 . Utilization of Fe2O3-CNC-HR (with length ~2.8 ± 0.8 μm and diameter ~82 ± 18 nm)  which have successfully inherited the structural properties of Fe2O3-CNC-HR 13, on utilization of low aspect ratio carbon nanotubes as structural directing agent which failed to initiate the nanoscroll formation process, due to its lowered van der Waals interaction energy. Figure 2O3-NS can be remotely controlled by simply tuning the density of maghemite nanoparticles as well as magnetic moment/dimensions of Fe2O3-CNCs (template), which provides a facile approach of fabricating GNS with tunable properties depending upon the targeted applications.To further investigate the effect of CNC dimensions on GNS formation, high aspect ratio precursor Fenm) Fig.  as templphs Fig. , respecture Fig.  which hales Fig. . The comles Fig.  which is-HR Fig.  shows pr2O3-NS formed with different aspect ratio which shows presence of peak at 2θ = 26.5° corresponding to graphene representing (002) planes11. The XRD spectra for Fe2O3-NS-HR, shows the presence of distinctive peaks at 2θ = 30.4°, 35.6°, 43.2°, 54.5°, 57.3° and 63.1° corresponding to (220), (311), (400), (422),(511) and (440) planes of Fe2O3 nanoparticles20 respectively, which confirms their presence in core of GNS. However, in case of Fe2O3-NS-LR, presence of small intensity peaks at 2θ = 43.2° and 62.5° represents (400) and (440) planes of Fe2O3 nanoparticles, respectively. The low intensity XRD peaks of Fe2O3 in case of Fe2O3-NS-LR, is probably due to presence of low fractions of Fe2O3 nanoparticles alongwith presence of graphene layers covering its surface. Therefore, XRD diffractograms of both high and low aspect ratio GNS confirms presence of Fe2O3 nanoparticles in scrolled graphene sheets. The SAED pattern of Fe2O3-NS interestingly shows the presence of sharp hexagonal spots which are concentric in nature with the presence of equatorial line showing that the diffraction pattern of GNS consists of intense spots along a line perpendicular to the needle axis. The presence of the multiple and concentric diffraction patterns (marked with dotted white lines) suggests that graphene sheets have undergone scrolling phenomenon to form a multilayered rolled structure, which arises due to the diffractions from the individual set of rolled graphene sheets21 present in the Fe2O3-NS. The presence of the equatorial line along the spots {0004} and {0002}22, suggest that the presence of the parallel graphene layers with stacking periodicity (and perpendicular orientation with respect to electron beam) which confirms the formation of Archimedean spiral in the inner core of the Fe2O3-NS. Figure 2O3-NS which shows the presence of the well-defined diffraction spots with an ordered continuity along the equatorial line. Information on the degree of packing of the multi-layered GRO sheets in the Fe2O3-NS can be obtained by considering the equatorial line of the SAED pattern. On the marked equatorial line, four spots can be distinguisly visualized from which the profile of the intensities was calculated to determine the structure and lattice parameter of the Fe2O3-NS. From the electron diffraction pattern, presence of the concentric hexagons represents the packing of the multi-layered graphene sheets which have occurred during the scrolling of the GRO sheets. Further, in line with the previously reported literature it was observed that the equatorial line rotates along the centre of polygon with the presence of high intensity spots present at its curves , suggesting, the circular morphology of the Fe2O3-NS (present at its cross-section). Evaluation of the SAED pattern and the intensity profiles  at ~1646 cm−1 (in CNCs) to 1652 cm−1  confirms the presence of epoxidized ring in modified Fe2O3-CNCs24. The FTIR spectrograph of the GRO sheets (after sonication in presence of the hydrogen peroxide) shows the presence of peaks at 3550 cm−1,1200 cm−1, 1070 cm−1 and 1720 cm−1 corresponding to O-H stretching, C-O epoxy stretching, C-O alkoxy stretching and C=O carbonyl stretching vibrations25. In Fe2O3-CNC-NS, the new peaks at ~3504 cm−1 corresponds to -OH stretching and 1595 cm−1 denotes skeletal vibrations from graphitic rings of GRO sheets25 alongwith the decrease in intensity of peaks at 1062 cm−1, 1114 cm−1 and 1158 cm−1  confirms scrolling of graphene onto Fe2O3-CNCs by ring opening in epoxidized Fe2O3-CNC through formation of C-O-C bonding. On calcination of Fe2O3-CNC-NS, it was observed that the intensity of the various oxygen functionalities suppressed which is possibly due to the reduction of the partially oxidized GRO sheets to graphene25. The Raman spectra of GRO sheets shows a G-band at ~1582 cm−1 and D-band at ~1354 cm−1 with an ID/IG ratio of ~0.97  sheets brings it in close proximity which is a necessary step to initiate the nanoscrolls formation process that occurs through п-п interactions and magnetic manipulation26. Due to such phenomenon, the epoxidized Fe2O3-CNCs adheres to inner core of GNS through sp3-hybridization, which leads to formation of open-ended GNS with more defects that could be evaluated through values of ID/IG ratio11. However, it was observed that presence of such scrolling phenomenon was completely absent in presence of the unmodified CNCs as shown in Fig. 2O3-CNCs are responsible to initiate the scrolling of the graphene sheets resulting in the formation of Fe2O3-NS. Further, the effect of Fe2O3-CNCs on morphology of GNS also lead to significant alteration in Raman spectra with increased ID/IG ratio ~1.03 for Fe2O3-NS-LR in comparison to Fe2O3-NS-HR ~1.01. As evident from morphological studies  , similar magnetic properties and loading fractions of Fe2O3 nanoparticles (~35 wt%) was prepared followed by its geometry optimization to obtain energy minimized morphology. The Fe2O3-CNC was placed at the centre of a graphene sheet (with length ~116.2 Å and width ~58.1 Å) along the axis of Fe2O3-CNC  interaction forces between graphene sheets and Fe2O3-CNC. The formation and growth mechanism of Fe2O3-NS can be classified into two steps: firstly the nucleation of Fe2O3-CNCs onto graphene sheets followed by the second step in which self-scrolling of graphene on its surface to form GNS takes place over a period of time to form tight scrolls  adhered to the surface of GRO. In next 300 ps, the graphene sheet starts to roll on the surface of Fe2O3-CNC from one end (left side first) and tries to adjust to obtain the best possible stable configuration  as structural directing agents. It is noteworthy to mention that the energy of the intermediate state of bending of the graphene sheets to form GNS will significantly depend upon the morphological, physico-chemical properties and functionalization of the structural directing agents as well as graphene sheets. Eventually, after simulation run of ~400 ps, a complete nanoscroll is formed with the encapsulated Fe2O3-CNC in its core with dimensions of length similar to the template. Interestingly, the simulated Fe2O3-NS have slightly larger diameter compared to the template which was also observed in the experimental studies (FESEM/TEM of both Fe2O3-NS-HR and Fe2O3-NS-LR) suggesting that the central hollow core of Fe2O3-NS will be slightly larger than template diameter. In experimental conditions, the CNCs are removed through a controlled calcination process which further helps in scrolling of graphene sheets into perfect nanoscrolls mimicking the morphological dimensions of template with confinement of catalytically active metallic nanoparticles in its core.In order to understand the mechanism and driving forces responsible for formation of GNS onto Fess) Fig. . As addrCNC Fig. . On geomphs Fig.  which shCNC Fig. . Due to 2O3-CNC and Pt-Fe2O3-CNC with high magnetic moment (~26.4 and 19.4 emu/g respectively)  Fig.  and distely Fig. . The disphs Fig.  shows unphs Fig.  shows th2O3-CNCs as structural directing agents for GNS formation, this study was further extended to encapsulate other forms of catalytically active Pt nanoparticles at lower loading fractions and evaluate the changes in its physico-chemical properties. Morphological analysis shows Pt-Fe2O3-NS are of length ~810 ± 90 nm and diameter ~95 ± 20 nm respectively, which is comparable with length of Fe2O3-NS with slight decrease in the diameter  distributed on its surface with thin layer of graphene sheets rolled on it  was also observed by Xu et al.27 on intercalation of different solvents followed by its swelling and drying. Pd-Fe2O3-NS, shows peaks at 2θ = 40.0°, 46.5° and 67.8° representing (111),(200) and (220) crystal planes of Pd nanoparticles28, peaks at 2θ = 35.5° corresponds to (311) crystal of Fe2O3 nanoparticles and low intensity peaks at 2θ = 38.6° and 53.4° designates (311) and (422) crystal planes of Fe3O4 nanoparticles. Similarly, Pt-Fe2O3-NS shows peaks at 2θ = 39.9°, 46.3° and 67.9° representing (111), (200) and (220) crystal planes of Pt nanoparticles29, peaks at 2θ = 35.6° corresponds to (311) crystal of Fe2O3 nanoparticles and a small peak at 2θ = 38.6° designates (311) crystal planes of Fe3O4 nanoparticles. The absence of any peak corresponding to CNCs crystallites suggests its complete removal, however, diffractograms shows presence of small intensity peaks of Fe3O4 nanoparticles which have plausibly formed during calcination process. Investigations of crystallites sizes of Pd/Pt nanoparticles (using Scherrer’s equation) encapsulated within GNS are ~8.6 nm and 10.7 nm respectively which comparatively matches with dimensions measured from TEM micrographs. This suggests that Pd/Pt nanoparticles adsorbed on CNCs can be effectively transferred to inner core of GNS without any significant agglomeration or accumulations of nanoparticles. From comparison of Raman spectra it was observed that ID/IG ratio for GRO ~0.97, which increased to ~1.01 and 1.03 for Pd and Pt-Fe2O3-NS respectively  transport and storage. The H2 uptake for Pt-Fe2O3-NS and Pd-Fe2O3-NS are found to be ~0.17 and ~0.14 wt.% respectively (measured at 273 K and 20 bar) which is improved by ~112% in comparison to GRO  and lower fractions of encapsulated Pt/Pd nanoparticles (~1 wt%), significant improvement in H2 capacity is observed. This is probably due to the presence of encapsulated Pt/Pd nanoparticles which could dissociate H2 into H atoms through spill over mechanism30 followed by its entrapment in the GNS nanochannels through physio or chemisorption with unsaturated graphene layers .The fabricated GNS have nanoscale hollow cylindrical channels doped with transition metal precursors such as Pd and Pt nanoparticles which is expected to provide a favourable route for hydrogen , I is average current (A), ΔVv is scan rate and m is mass of electroactive material32. The specific capacitance of Pd-Fe2O3-NS, Pt-Fe2O3-NS and Fe2O3-NS are calculated as 357, 223 and 152 F/g (at scan rate of 100 mV/s) respectively , representing ideal capacitive behaviour of the material. The higher Csp values for Pd-Fe2O3-NS in comparison to Pt-Fe2O3-NS is probably due to lowered defects and increased scrolling density which provides efficient pathways for diffusion of ions34, as evident from the Raman and XRD studies discussed in earlier section. The galvanostatic charge-discharge curves of Pt-Fe2O3-NS and Pd-Fe2O3-NS measured at a constant current density of 1 mA/cm2 are depicted in Fig. 2O3-NS, suggests that due to presence of lower defects, higher surface area and improved scrolling density resulted in the efficient transfer of ions into its nanochannels with the formation of strong EDL layers, which also resulted in significant improvement in performance of supercapacitors.The scrolled topology of GNS favours the formation of electric double layer capacitors (EDLCs) alongwith the encapsulated metallic nanoparticles causes reversible faradaic redox reactions on its surface (electrode/electrolyte) introducing pseudocapacaitance behaviour, both of which is expected to act synergistically for enhancement of supercapacitance behaviour. Figure ely Fig. , which i2O3-NS and Pt-Fe2O3-NS respectively measured at 1 A/g)  Fig.  which sh2O3-CNCs as templates is a thermodynamically favourable process which undergoes self-assembly in the presence of van der Waals forces and π-π interactions that are found to depend on several parameters such as density of maghemite nanoparticles, magnetic moment, morphology and dimension of CNCs. The metal nanoparticle encapsulated GNS with unique structural properties and physico-chemical characteristics shows potential applications in fabrication of enhanced hydrogen storage devices and supercapacitors possessing long-term cyclic stability (of ~10000 cycles). The utilization of biobased CNC precursors for fabrication of GNS with tunable morphology, controlled dimensions alongwith the encapsulation of metallic nanoparticles, opens up plethora of multifunctional applications of GNS in diverse platforms with promising commercial opportunities.CNCs derived from the renewable resources, acts as a unique template for fabrication of GNS with tunable morphologies ranging from micron to nanoscale dimensions (in length), which are otherwise difficult to control by traditional routes of GNS processing. Through strategic surface modification of CNCs, catalytically active metallic nanoparticles can be incorporated in GNS core (with desired loadings), tunable inter-layer spacings and scrolling density depending upon the targeted applications. From molecular simulation studies, it was observed that formation of GNS using Fe4) (>99% purity), hydrogen peroxide (30%), ferric (III) chloride (>96%), 4-nitrophenol (4-NP), sodium hydroxide (NaOH) (>97%), sodium hypochlorite (4%), and sulphuric acid (>99%), ) used in the study were obtained from SISCO Research laboratories . Bamboo pulp, was selected as the initial cellulosic precursor for the fabrication of CNCs, which was received from Hindustan Paper Corporation Limited . The platinum (PtCl2) (99.9%) and palladium chloride (PdCl2) (99%) salts used in this study were purchased from Sigma Aldrich, India.Expandable graphite  purchased from Asbury Carbons (USA) was used for fabrication of graphene. The chemical reagents such as sodium borohydride (NaBH35. FeCl3 (2.0 g), was selected as initial iron precursor and dispersed into CNC suspension (1.0 g in 50 ml of ~1 wt% NaOH solution) through sonication at an amplitude of ~30% for 5 min. The dispersed iron salt-CNC suspensions was stirred for ~3 hours at 80 °C purged under inert nitrogen gas flow for ~3 hours to remove the trace amount of oxygen, as per the protocol reported in our earlier studies36. The precipitation of iron nanoparticles was carried out by dropwise addition of the reducing agent, sodium borohydride (~50 mg/ml) under vigorous stirring (~500 rpm) at a temperature of ~90 °C. After ~6 hours, the iron salt-CNC suspension turned black suggesting the completion of reaction and was separated using permanent magnets followed by washing it with ethanol (for three times) and drying (at 50 °C in vacuum oven) to obtain the powdered form of Fe2O3-CNCs. Fe2O3-CNCs with higher aspect ratio were fabricated using CNCs derived from filter paper as initial cellulosic precursor19 following similar protocol for precipitation of iron nanoparticles as mentioned above. The detailed data for its characterization is available in the Supporting Information (Part I).CNCs were fabricated from the bamboo pulp through soda pulping cum bleaching pretreatments (to extract the purified cellulose) followed by stringent sulphuric acid (64 wt%) hydrolysis, as per our earlier reported studies37. The obtained graphene (~500 mg) was dispersed into methanol followed by its sonication (at amplitude of ~30%) for duration of ~30 mins in presence of the hydrogen peroxide (~2wt.%) as per the literature38 to introduce epoxy and hydroxyl functionalities.Graphene was fabricated through thermal exfoliation of expandable graphite with the optimized conditions mentioned in our earlier study2O3-CNCs was carried out through reaction of Fe2O3-CNCs (~50 mg dispersed in ~20 ml of water through sonication at an amplitude of ~30% for 5 min) with excess epichlorohydrin (~5 ml), at a temperature of ~85 °C for ~4 hours39. The epichlorohydrin modified Fe2O3-CNCs, was washed with water and ethanol (for ~3 times) to remove the unreacted components, followed by drying (at 50 °C in vacuum oven).Epoxidation of Fe2O3-CNCs as templates was carried out through reaction of epoxidized Fe2O3-CNCs with partially oxidized GRO (at a ratio of 1:1 dispersed in 50 ml methanol) at a temperature of 90 °C under reflux conditions which leads to covalent coupling between the two systems. The reaction was continued for ~6 hours followed by washing with ethanol (~3 times) and then subjected to controlled calcination. The calcination process was carried out in muffle furnace (samples placed in a silica crucible) with controlled temperature program of: 200 °C for 2 hours, 400 °C for 2 hours and 600 °C for 15 mins. Similar protocol was followed for fabrication of Fe2O3-NS with higher aspect ratio. The fabricated GNS are designated as Fe2O3-NS-HR and Fe2O3-NS-LR with high and low aspect ratio respectively, with the encapsulated iron oxide nanoparticles in core of GNS.Fabrication of GNS using Fe2O3-CNCs were fabricated through precipitation of the platinum and palladium chloride salts using sodium borohydride as reducing agent under inert conditions. A homogenous dispersion of Fe2O3-CNCs (of low aspect ratio) was formed by dissolving PtCl2 and PdCl2 (~50 mg) salts (in slightly acidic water), through sonication (for ~5 min) followed by stirring at ~500 rpm for 3 hours at 80 °C which led to formation of light yellowish/ brownish coloration. The impregnated salts on the surface of Fe2O3-CNCs were precipitated through dropwise addition of NaBH4 solution under vigorous stirring (~500 rpm) at a temperature of ~90 °C for 4 hours which subsequently led to formation of grey-black coloration.Platinum and palladium nanoparticles modified Fe-Fe2O3-CNCs and Pd-Fe2O3-CNCs (~20 mg/ml in water) was epoxidized following the similar protocol as mentioned above through reaction with epichlorohydrin for ~6 hours at ~85 °C. The scrolling of graphene sheets was carried out through reaction of epoxidized Pt-Fe2O3-CNCs or Pd-Fe2O3-CNCs (~50 mg dispersed in methanol) with GRO (~50 mg) at a temperature of 90 °C under reflux conditions for ~6 hours. After the reaction is complete, samples were centrifuged to obtain the precipitate followed by its washing (with ethanol) and drying. The obtained dried samples were placed on a silica crucible and calcined in a muffle furnace to remove the CNCs from its inner core following the similar temperature program as mentioned above. The fabricated samples are designated as Pd-Fe2O3-NS and Pt-Fe2O3-NS, with the encapsulated Pt and Pd nanoparticles in GNS.Pt2O3-CNC as substrate was carried out using the Discover module of the Materials Studio 7.0 software package. In this work, we have used universal force field (UFF) to describe the interatomic interactions between the graphene sheet and Fe2O3-CNCs. The MD simulation was performed in the NVT ensemble at 298 K for a total simulation time of ~500 ps with a time step of 1 fs. The data were recorded every 1 ps to determine the changes in the trajectory of atoms. The Nosé-Hoover thermostat was used to maintain the temperature constant. Further, the van der Waals interactions between the graphene sheets and Fe2O3-CNC were calculated with a cut-off distance of 9.5 Å. The electrostatic interactions were calculated using the Ewald summation method with the same cut-off distance of 9.5 Å. It should be noted that geometry optimization was carried out on all the prepared structures namely the graphene sheet, Fe2O3-CNC, and Fe2O3-CNC/graphene system before starting the MD simulation.Molecular dynamics (MD) simulation of the scrolling of graphene sheets onto Feα radiation (λ = 0.1541 nm) as X-ray source  measured at scan rate of 0.05° per 0.5 s in the 2θ range ~5–70°. The chemical functionalities in graphene nanoscrolls were analyzed by Raman spectroscopy using Horiba Jobin Vyon  equipped with a 1 W, 1064 nm Nd:YAG diode-pumped laser at an excitation wavelength of 514 nm, exposure time of ~5secs and 1024 scans. The surface area was calculated through Brunauer–Emmett–Teller (BET) method based on nitrogen adsorption-desorption at 77 K using a Beckman Coulter surface area analyzer . Prior to nitrogen physisorption, the nanoscrolls were degassed at 393 K for 2 hours to remove the adsorbed moisture. Morphological dimensions and structure of the fabricated nanoscrolls were characterized using TEM micrographs, high resolution TEM (HRTEM) and selected area electron diffraction (SAED) patterns. The uniformly dispersed graphene nanoscrolls suspensions (in methanol) were drop cast onto carbon-coated grids  and vacuum dried overnight at 60 °C. Images were captured using JEOL JEM 2100 TEM at an accelerating voltage of 200 kV, and the average dimensions were determined (using Image J software). The graphene nanoscrolls samples were coated with gold sputtering unit and the morphology was characterized using Field Emission SEM (FESEM)  at an accelerating voltage of 2–20 kV. The compositional analysis and mapping of the Pd and Pt nanoparticles in GNS were determined through energy dispersive X-ray analysis (EDX)  at an accelerating voltage of 20 kV using Aztec software.The powder X-ray diffraction (XRD) of fabricated nanoscrolls was recorded with D8 Advance diffractometer  utilizing Cu-K-Fe2O3-NS and Pt-Fe2O3-NS are measured over a varied pressure range using temperature programmed volumetric sorption apparatus . Prior to analysis the samples were initially outgassed at 150 °C for 30 min in presence of inert gas flow. Subsequently, the hydrogen was allowed to adsorb on the samples at a constant temperature of ~273 K with increasing pressure from 0 to 20 bar. Similarly, desorption of absorbed hydrogen was allowed to occur with the declining pressure maintained at a constant temperature.Hydrogen uptake by Pd2) and drying at 90 °C for overnight. The electrochemical measurements, cyclic voltammetry (CV) (at scan rate: 10–100 mV/s and voltage: 0.2 to 0.6 V), galvanostatic charge-discharge (GCD) and electrical impedance spectroscopy (EIS) (frequency range: 0.01 Hz-10 kHz) were measured using electrochemical workstation Metrohem Autolab PGSTAT 204 operated with a three electrode system, (reference electrode: Ag/AgCl/3 M KCl and counter electrode: platinum) in presence of 0.5 M KOH as electrolyte solution.The working electrode was fabricated by dispersing GNS (~6 mg) into iso-propyl alcohol with addition of binder 5% Nafion solution, followed by coating on Toray carbon paper (1 cmSupplementary Information


Idiopathic pulmonary fibrosis (IPF), a fatal lung disease of unknown origin, is characterized by chronic and progressive fibrosing interstitial pneumonia which progressively impairs lung function. Oxidative stress is one of the main pathogenic pathways in IPF. The aim of this systematic review was to describe the type of markers of oxidative stress identified in different biological specimens and the effects of antioxidant therapies in patients with IPF.We conducted a systematic search of publications listed in electronic databases  from inception to October 2017. Two investigators independently reviewed all identified articles to determine eligibility.n = 554) was excluded because they were duplicates, abstracts, irrelevant, or did not meet the selection criteria, we identified 30 studies. In each study, we critically appraised the type, site , and method used for measuring the identified oxidative stress biomarkers. Furthermore, the current knowledge on antioxidant therapies in IPF was summarized.After a substantial proportion of the initially identified articles (A number of markers of oxidative stress, with individual advantages and limitations, have been described in patients with IPF. Nevertheless, trials of antioxidant treatments have been unable to demonstrate consistent benefits, barring recent pharmacogenomics data suggesting different results in specific genotype subgroups of patients with IPF. Idiopathic pulmonary fibrosis (IPF) is a fatal lung disease of unknown cause that is characterized by chronic and progressive fibrosing interstitial pneumonia with worsening dyspnea and lung function , 2. ThouRisk factors for IPF include cigarette smoking, environmental factors, microbial agents, and gastroesophageal reflux , 2, 6; rAlthough IPF has long been considered a chronic inflammatory disorder, this concept has been revisited following the negative results of interventional studies with anti-inflammatory therapies . IPF is There is growing evidence that oxidative stress plays a significant role in IPF , 15. Oxi2O2 , (vi) detoxification enzyme systems , and (vii) other redox regulatory thiol proteins  . The authors concluded that, since hydroperoxides in IPF were significantly correlated with lower FVC and acute exacerbation, oxidative stress may be involved not only in IPF development, but also in its progression.Matsuzawa et al.  measuredUgurlu et al.  measuredVeith et al.  measuredDespite some discrepancy in the results and variability of the methods employed, studies on blood markers reported an increased OS in patients with IPF, which correlates with clinical and functional parameters. Furthermore, OS biomarkers were significantly altered in more severe and rapidly progressive forms and, in some circumstances, predicted the efficacy of inhaled therapy with NAC. This suggests their potential use in the assessment and monitoring of these patients.The non-invasive measurement of biomarkers in breath or sputum, albeit potentially attractive, is currently limited by issues regarding reproducibility and sensitivity.Kanoh et al.  measuredBeeh et al.  measuredThese studies suggest that the measurement of exhaled ethane or GSH in sputum might be useful in the clinical evaluation and monitoring of patients with IPF. Nevertheless, the evaluation of OS in breath or sputum in these patients warrant further investigations because of the relatively small sample size of published studies and the different OS biomarkers measured with different techniques.2O2 and 8-isoprostane in 16 patients with IPF and 15 healthy subjects. The mean concentration of H2O2 was significantly higher in patients than in healthy subjects [0.36 μmol/L (95% CI 0.24–0.47) vs. 0.16 μmol/L (95% CI 0.10–0.23)]. The authors observed non-detectable concentrations of H2O2 in four controls. The mean concentration of 8-isoprostane was also significantly higher in IPF patients compared to controls [74 pg/mL (95% CI 38–110) vs. 33 pg mL (95% CI 28–39)]. There was no significant correlation between H2O2 and 8-isoprostane concentrations in IPF patients. A negative correlation between H2O2 and DLCO was observed, however there were no other significant correlations between both markers and pulmonary function tests or pO2. Moreover, H2O2 and 8-isoprostane were not correlated with BALF cell count. In summary, this study evidenced that EBC H2O2 and 8-isoprostane concentrations are significantly higher in patients with IPF when compared to healthy subjects, and that the concentrations of H2O2 seem to be associated with disease progression.Several mediators have been detected in EBC. However, various factors, highlighted in the recent recommendations by the ERS, may affect their measurement . An impoBartoli et al.  did not 2O2 as exhaled nitric oxide (FeNO) and carbon monoxide (eCO). EBC 3-nitrotyrosine was higher in IPF patients compared to controls [2.5 ng/mL (range 0.7–8.9) vs 0.3 ng/mL (0.1–1.1). 3-NT concentrations significantly correlated with other biomarkers, such as total NOx, 8-isoprostane, total proteins, and H2O2. Moreover, there was a significant inverse relationship between EBC 3-NT concentrations and FEV1 (%), FVC (%), VC (%), and total lung capacity . No significant between-group differences in total NOx were observed. Furthermore, NOx did not correlate with parameters of lung function. The authors found that IPF patients had significantly higher EBC total protein concentrations than control subjects. Total proteins significantly correlated with 8-isoprostane, H2O2 and 3-NT, but not with lung function. Mean EBC 8-isoprostane concentrations were also higher in IPF patients when compared to normal subjects [0.2 ng/mL (range 0.1–0.4) vs 0.08 ng/mL (0.04–0.2). Correlation analysis showed significant associations between 8-isoprostane and total proteins, H2O2, NOx and 3-NT, but not with lung function. There were no between-group differences in EBC H2O2 concentrations. H2O2 concentrations were significantly associated with NOx, 3-NT, 8-isoprostane and total protein, but not with lung function.Chow et al.  collecte2α (8-isoPGF2α) in IPF patients and control subjects. Isoprostanes are prostaglandin (PG)-like substances that are generated through peroxidation of unsaturated fatty acids by free radicals [2α is an isomer of PGF1 that is generated by peroxidation of arachidonic acid. 8-isoPGF2α concentrations were significantly higher in IPF patients than control subjects , and suggested that oxidative stress may promote the progression of IPF via ROCK (Rho-associated coiled-coil containing protein kinase) activation. The ROCK pathway is involved in myofibroblast contractility via relaxin (an insulin family peptide) in lungs with IPF and in mice with bleomycin-induced lung fibrosis [Finally, Shimizu et al.  measuredradicals . The isofibrosis . ROCK acfibrosis , 40; botfibrosis , 42.2O2) and chloride anion (Cl−) or the equivalent from a non-chlorine halide during the neutrophil’s respiratory burst. Furthermore, it oxidizes tyrosine to tyrosyl radical using hydrogen peroxide. The cytotoxic action of hypochlorous acid and tyrosyl radical impairs antimicrobial capacity of neutrophils [2O2 caused increased cellular injury, which was suppressed by methionine, a myeloperoxidase system scavenger. The ability of IPF ELF to augment H2O2-mediated injury to lung parenchymal cells in vitro, additionally, correlated with the ELF concentration of MPO. Moreover, the VC deterioration rate was greater in patients with increased ELF MPO than in those without. These findings suggest that IPF ELF potentially increases epithelial cell cytotoxicity by highly reactive hypohalous anion formation. This toxic radical can oxidize various biomolecules, inducing alterations in critical cellular components and cell death, contributing, at least in part, to the severe epithelial cell injury typical of IPF.One of the first evidence of oxidative stress in IPF was described by Cantin et al.  in 1987,trophils , 45. TheThe same authors reported subsequently  that the2−) by alveolar macrophages was observed in all subjects.The findings of Cantin et al. in ELF GSH were confirmed by two further studies. Borok et al.  in 1991 Concentrations of tGSH in ELF were also measured by Meyer et al. , before These studies, other than their contribution on the understanding of some of the pathophysiological mechanisms leading to oxidative imbalance in IPF through GSH oxidation, showed that the measurement of GSH in ELF may be useful for the monitoring of OS reduction to specific treatments. Nevertheless, the clinical utility of these responses should be further investigated, because the ELF GSH concentrations were shown not to correlate with respiratory function tests in IPF patients.BALF is a diagnostic procedure assessing cellular and non-cellular components of the epithelial lining fluid of the alveolar and bronchial airspaces for diagnostic, therapeutic, and research purposes. Though BALF is an invasive approach, it is usually well-tolerated and safe in IPF patients . The quaBALF from patients with IPF were analysed by Lenz et al.  to evaluThe same authors  confirmeSimilarly, Rottoli et al.  found thAgain, by means of proteomic differential analysis, Carleo et al.  investigp > 0.5). After therapy with a total of 15 doses of 600 mg NAC, BALF GSH levels significantly increased to 1.54 ± 0.24 μmol/L, within the normal range. The authors emphasised that GSH levels remained high at 10 ± 0.5 h after the last treatment dose.Meyer et al.  measuredRahaman et al.  measuredMarkart et al.  measuredMalli et al. , other tThe quantification of biomarkers in BALF may be challenging, due to the lack of a satisfactory marker for the dilution of the saline lavage. This is one of the factors that may contribute to the variability in the measurements described, particularly in studies with small sample size. Nevertheless, some studies showing encouraging detection capacity, and previous adequate standardization, might provide alternative options in OS evaluation and monitoring in IPF.Kinnula et al.  reportedVuorinen et al.  studied Mazur et al.  analysedKorfei et al.  performeFinally, a metabolomics approach was used by Kang et al.  to charaThe contribution of studies on IPF tissues was essential for the understanding of several pathogenic mechanisms involving numerous OS protein networks and molecular interplays. The main advantage of lung biopsies is that they directly sample the parenchyma, maintaining the spatial relationships of structural components thus allowing to clearly identify tissue districts in which oxidative stress is present. However, its invasiveness limits patient’s acceptance and justifies its use primarily in situations where the diagnosis remains uncertain with less invasive approaches .Considering that oxidative stress is widely recognized as a central feature of IPF, antioxidant therapy has been proposed for many years. In particular, N-acetylcysteine has been widely used in IPF as antioxidant and antifibrotic agent since it is relatively inexpensive, well-tolerated, and easy to administer orally. However, scientific data were often conflictual or inconclusive, mainly due to the lack of placebo arm and the low statistical power.n = 1062) investigating the antioxidants NAC and lecithinized SOD, alone or in combination with other drugs such as pirfenidone, azathioprine, prednisone, to treat IPF. There was no evidence that antioxidant monotherapy had any beneficial effects on changes in predicted DLCO. Combined antioxidant therapy was more effective than monotherapy on VC and DLCO, however this did not translate into differences in death rates or adverse events.Two recent papers reported meta-analyses of trials investigating the efficacy of antioxidant therapy in IPF. Sun et al.  includedThese meta-analyses included the most relevant clinical trials, such as the IFIGENIA and PANORAMA studies , 68, whiAlthough the 2015 updated treatment guidelines for IPF recommended against NAC  NAC monoIt is currently accepted that IPF pathogenesis depends on repetitive chronic cell injury, which triggers fibrosis and oxidative imbalance within the lung. Causes of oxidative stress include, but are not limited to, cell injury itself, transition metal exposure, inflammation, or drugs that participate in reduction–oxidation reactions. The importance of oxidative modifications to the extracellular matrix, and how they alter cellular responses in human IPF, remains to be elucidated. Since 1987, when the first evidence of an imbalanced oxidant/antioxidant system was described in IPF ELF, several researchers have investigated oxidative stress biomarkers in this pathology. This review summarizes their work on oxidative stress indicators in IPF using different biological sample sources . Although interventional trials failed to demonstrate significant effects of antioxidant treatments (particularly NAC) recent evidence suggest the potential role of pharmacogenomics in predicting efficacy.


SIN3 is a global transcriptional coregulator that governs expression of a large repertoire of gene targets. It is an important player in gene regulation, which can repress or activate diverse gene targets in a context-dependent manner. SIN3 is required for several vital biological processes such as cell proliferation, energy metabolism, organ development, and cellular senescence. The functional flexibility of SIN3 arises from its ability to interact with a large variety of partners through protein interaction domains that are conserved across species, ranging from yeast to mammals. Several isoforms of SIN3 are present in these different species that can perform common and specialized functions through interactions with distinct enzymes and DNA-binding partners. Although SIN3 has been well studied due to its wide-ranging functions and highly conserved interaction domains, precise roles of individual SIN3 isoforms have received less attention. In this review, we discuss the differences in structure and function of distinct SIN3 isoforms and provide possible avenues to understand the complete picture of regulation by SIN3. The basic requirement for survival of any cell, whether prokaryotic or eukaryotic, is the accurate expression of appropriate genes. In prokaryotes, failure to express important metabolic enzyme or stress response genes can affect the organism’s ability to respond to environmental stimuli and ultimately result in cell death. In multicellular organisms, regulation of gene expression is critical not only for response to external stimuli but also to ensure timely expression of cell type-specific genes for the development of different tissues and organs. The presence of chromatin, a complex of the DNA molecule wrapped around a core of histone proteins, is key for gene regulation in eukaryotes.Saccharomyces cerevisiae  and consequently an increase in the level of neuronal markers, leading to the differentiation of P19 cells into neurogenic cells. Sin3b silencing in these cells, however, caused a very small effect on the expression of neuronal markers, and the differentiation into neuronal cells was less efficient relative to Sin3a knockdown. These data suggest that SIN3A plays a predominant role in REST-mediated suppression of neuronal differentiation in pluripotent cells. Furthermore, SIN3A is a player in the process of somatic cell reprogramming [Sin3a significantly reduced the efficiency of Oct4, Sox2, Klf4, Myc (OSKM)-mediated MEF reprogramming. This study also showed that co-expression of SIN3A with NANOG in partially reprogrammed neural stem cells increased the efficiency of reprogramming more than threefold as compared to NANOG alone. This reprogramming synergy with NANOG was not exhibited by SIN3B, indicating that this function is specific to SIN3A. These examples provide evidence of SIN3 isoform-specific function in regulating developmental cell fate decisions.Mammalian SIN3 proteins also impact pluripotency. While both isoforms function in pluripotent P19 cells, SIN3A exhibits a higher degree of repression of neuronal gene activity as compared to SIN3B . Knockdogramming . KnockdoSIN3A caused a significant increase in the number of invasive colonies in multiple human breast cancer cell lines, MDA-MB-231, MDA-MB-435, and MDA-MB-436. In contrast, SIN3B knockdown substantially decreased breast cancer cell invasion and resulted in reduced metastatic potential. Cells with dual knockdown of SIN3A and SIN3B behaved similar to those with loss of only SIN3B. In that same study, the authors performed correlation analysis, investigating SIN3A and SIN3B expression levels in a number of breast cancer subtypes. When all breast cancer subtypes were considered, longer relapse-free survival of patients correlated with high expression of either SIN3A or SIN3B. Analysis of triple-negative breast cancer samples, however, indicated that longer relapse-free survival is correlated with either high SIN3A or low SIN3B expression. These data suggest that there may be functional differences between the SIN3 isoforms in different molecular subtypes of cancer. This study is especially interesting in light of the current interest in SIN3 as a potential therapeutic target [Provided the data that SIN3 proteins play critical roles in the regulation of important biological processes, misregulation of SIN3 is implicated in several diseases. The role of SIN3 in cancer has been an area of particular focus. While well studied, the function of SIN3 in cancer cells is still ambiguous, since different investigations attribute either tumor suppressive or oncogenic functions to SIN3 proteins , 65. IntSIN3 was discovered as a transcriptional regulator three decades ago. In subsequent years, a plethora of studies have implicated SIN3 proteins in the regulation of several critical biological processes and revealed a large repertoire of binding partners. Despite this extensive research, we are far from understanding the complete picture of SIN3 regulation. Several pieces of the puzzle are still missing. As discussed above, the SIN3 protein consists of multiple protein interaction domains and hence is considered the scaffold that holds together the SIN3 histone-modifying complex. To the best of our knowledge, however, no study has been conducted to analyze complex integrity upon loss of SIN3. Systematic biochemical analysis of SIN3 complex structure and stability will provide further insight into the scaffolding function of SIN3. Additionally, SIN3 complexes are canonically considered as corepressor complexes that suppress gene expression through the activity of HDACs. This model has been challenged with the acquisition of gene expression and chromatin binding data indicating that SIN3 is likely required for direct activation of a subset of targets. The gene activation function of SIN3 histone-modifying complexes is not at all understood. Genome-wide analysis of histone modification patterns established by the distinct SIN3 complexes at target genes may help us better understand the role of SIN3 in both activation and repression of gene expression.Saccharomyces cerevisiae, a single gene that produces multiple isoforms in Drosophila and two separate genes that give rise to different isoforms in mammalian cells. Despite the diversity in the number and structure of genes, the SIN3 proteins in different species contain evolutionarily conserved functional domains and form similar histone-modifying complexes. It will be a worthy effort to investigate the evolution of SIN3 proteins and determine whether the presence of multiple isoforms in higher organisms contributes to the functional flexibility of SIN3. The SIN3 complexes are pleiotropic in nature, and this in part contributes to their wide-range of regulation of biologically important processes. Significant efforts must be directed toward identifying the diverse common and unique interaction partners of SIN3 isoforms in different cell types. This will aid in understanding the intricate network of transcriptional regulators and in turn the critical cellular processes that may be impacted upon deregulation of SIN3. There is also a gap in the existing knowledge regarding processes that regulate SIN3 protein expression. Understanding the mechanisms that regulate the global transcriptional regulator SIN3 is crucial, especially since altered levels of SIN3 have been detected in several types of cancer. Furthermore, the SIN3 isoforms may regulate distinct biological pathways in different cell types. It is imperative to carefully dissect the functional differences between SIN3 isoforms and identify gene targets that are differentially regulated. This will prove to be particularly important in designing therapeutics that are targeted for specific cancer subtypes.In this review, we have focused on isoforms of SIN3. There is a single SIN3 protein in the budding yeast, In summary, we provide here a few exciting avenues to further our understanding of epigenetic regulation of gene expression by SIN3 complexes. Although a great deal is known about the interactions of SIN3 proteins and the biological processes regulated by them, the current need is to delve deeper into the intricacies of this network. Ascertaining the overlapping and specialized functions of individual SIN3 isoforms will not only unravel novel strategies of gene regulation but will also expand the current repertoire of therapeutic targets.


The Fe3O4 particles with size in the range of 20–200 nm are uniformly aligned along the axial direction of the CNTs. The composite exhibits exceptionally high wave absorption capacity even at a very low thickness. Minimum reflection loss of −44.7 dB and absorbing bandwidth of 4.7 GHz at −10 dB are achieved in composites with one-layer graphene in six-layer CNT film-Fe3O4 prepared from 0.04 M FeCl3. Microstructural and theoretical studies of the wave-absorbing mechanism reveal a unique Debye dipolar relaxation with an Eddy current effect in the absorbing bandwidth.Graphene has sparked extensive research interest for its excellent physical properties and its unique potential for application in absorption of electromagnetic waves. However, the processing of stable large-scale graphene and magnetic particles on a micrometer-thick conductive support is a formidable challenge for achieving high reflection loss and impedance matching between the absorber and free space. Herein, a novel and simple approach for the processing of a CNT film-Fe EM waves consist of a time-varying electric and magnetic field, and EM wave absorption is achieved by the attenuation of EM wave energy through dielectric loss and magnetic loss as well as electromagnetic impedance match, which can minimize the reflection of the incident EM wave4. Therefore, dielectric loss and magnetic loss are the main factors determining absorption capability. The dielectric tangent loss (tan δε = ε″/ε′) is proportional to the dielectric loss, and it describes the dissipation of energy supplied by an external electric field as motion and heat5. Magnetic tangent loss (tan δμ = μ″/μ′) is known as magnetic loss factor or power factor; it is a measure of the energy loss inside a magnetic material due to the phase delay between the applied and induced magnetic fields.The rapid development of modern electronic equipment and wireless devices has resulted in severe electromagnetic (EM) radiation pollution, which has implications in human health and the normal functioning of electronics. Thus, the design and exploration of effective EM wave absorption materials is of basic scientific importance6Good impedance matching between the specimen and free space is necessary for enhancing EM wave absorption capability. The impedance matching coefficient |ZinZ0-1| can be expressed as0 is the characteristic impedance of free space (377 Ω)7. εr = ε′ − jε″ and μr = μ′ − jμ″ are, respectively, the complex permittivity and permeability of the absorber, c is the velocity of the EM wave in free space, f is the frequency of the EM wave, and d denotes the absorber thickness.And the reflection loss (RL) value is calculated according to the transmission line theory by Equation :2\docume8, the carrier mobility and current carrying capacity of CNTs is up to 105 cm2 V−1 s−1 and 109 A cm−1, respectively9. Most of the research effort to date has focused on CNTs decorated with magnetic metal or metal oxide particles for enhancing magnetic attenuation. However, the anticipated improvement in EM wave absorption performance has often been hindered by the poor dispersion of CNTs and their impedance mismatch with free space10. CNT films, on the other hand, not only retain the high permittivity of individual CNTs in an isotropic network structure but also greatly facilitate the dispersion of CNTs in the matrix11. Furthermore, the dispersion of Fe3O4 nanoparticles on the surface of CNTs can effectively improve permeability and impedance matching12. Thus, the CNT film-Fe3O4 absorber provides a highly desirable combination to enhance dielectric and magnetic loss and impedance matching as well as facilitate ease in composites processing.Carbon nanotubes (CNTs) offer the unique potential to be excellent EM wave absorbents. Besides their superior mechanical and thermal properties15. Graphene can support current densities greater than 108 A cm−2 16, its carrier mobility can exceed 15,000 cm2 V−1 s−1 even under ambient conditions17, and its real and imaginary parts of the theoretical permittivity exceed 104 at frequency less than 400 GHz18. Theoretical studies of large-scale graphene layers have shown strong EM wave absorption for normal incident wave. The maximum absorption reaches 50 percent at six layers of graphene and one-third of the incident EM energy is dissipated at a graphene-polymer interface20. Although large-scale multilayer graphene/methyl methacrylate for EM wave absorption has been suggested theoretically and realized in numerical simulations20, large-scale graphene absorption has never been demonstrated experimentally. This is due to the fact that large-scale graphene suffers from statistical fluctuations in strength and toughness as well as impedance mismatch with free space due to the high permittivity and negligible permeability21. Consequently, almost all published work so far on graphene-related EM-absorbing materials has focused on graphene powder; little research has been devoted to the EM wave-absorbing performance of large-scale graphene. Moreover, in order to enhance impedance matching and absorption of both electric and magnetic fields in graphene, the improved decoration and blend of magnetic metal or metal oxide particles have become effective approaches for researchers. Some reports demonstrated that the combination of Fe3O4 25, TiO226 and NiFe2O427 magnetic nanoparticles with reduced graphene oxide powders improved the EM wave-absorbing property. However, the magnetic nanoparticles supported on graphene particles are generally aggregated, resulting in uneven distribution25. Therefore, the design and processing of high-performance EM-absorbing materials based on CNT and graphene remain a formidable challenge.The other focus of this research is on graphene, which is well known for its excellent electronic, chemical and physical properties3O4 composites by the solvothermal method. The Fe3O4 nanoparticles on the surface of CNTs not only improved permeability but also enhanced impedance matching of the CNT film-Fe3O4-graphene composite. Then, the CNT film-Fe3O4 was used as a support substrate to prepare a large-scale graphene (LSG)-CNT film-Fe3O4 composite, which not only retained the dielectric performance of CNT and graphene but also avoided their aggregation.Here, a novel and simple approach was adopted to fabricate CNT film-Fe−3) with randomly oriented CNTs coated by Fe3O4 nanoparticles were used as absorbing layers, the single chemical vapor deposition graphene were laid on the surface of CNT-Fe3O4 film as blocking layer  was impedance matching layer. A schematic illustration of the fabrication process for constructing CNT film-Fe3O4-graphene-epoxy composites can be found as Supplementary Fig. To enhance the ability of EM wave absorption, highly conductive films , and the seven peaks at 18.17°, 30.07°, 35.48°, 43.01°, 53.42°, 57.04° and 62.55° are associated with the (111), (220), (311), (400), (422), (511) and (440) crystal planes of Fe3O4, respectively. No additional peaks belonging to other phases are observed, indicating the good crystallinity and high purity of the Fe3O4 nanoparticles. The energy dispersive spectroscopy (EDS) as shown in Fig. 3O4–0.05 M composite is mainly composed of C, O, and Fe elements.Figure ern Fig. , which i3O4 nanoparticles are calculated for the strongest peak (311) by the Debye–Scherrer formula. The nanocrystal sizes from the data of Fig. 3O4 composites prepared from 0.01, 0.02, 0.03, 0.04, 0.05 and 0.10 M FeCl3, respectively; this implies that the nanocrystal size increases significantly with increasing concentration of FeCl3. The saturation magnetization and relaxation values are directly related to the size of the nanocrystal size, and with the increase of Fe3O4 nanocrystal size, both the saturation magnetization and relaxation rate increase29.The average sizes of nanocrystals in the Fe3O4 composites at room temperature are shown in Fig. 3O4 composites  and remnant magnetization (Mr) of the CNT film-Fe3O4-0.01 M and 0.02 M remain nearly the same as those of the CNT film. At FeCl3 concentrations higher than 0.02 M, the Ms and Mr values increase rapidly, as shown in Fig. c) with FeCl3 concentration is shown in Fig. r and anisotropy energy, which are related to the values of Ms and Hc, affect the EM wave absorption capacities30.The magnetic properties of the CNT film-Fetes Fig. . The sat3O4-0.05 M composites with various numbers of layers were fabricated. The values of tan δε and tan δμ, impedance matching coefficient |Zin/Z0| and reflection loss of composites consisting of one to seven CNT film-Fe3O4-0.05 M layers were deduced from the measured data of relative complex permittivity εr, permeability μr and thickness d. The effect of the number of layers on the composite EM wave-absorbing properties was studied. The results of Fig. ε appear when the frequency is higher than 6 GHz. The locations of peaks shift toward lower frequencies with an increase in the number of layers of CNT film-Fe3O4 composite. The peak intensity varies with the number of layers and reaches a maximum value of 1.72 at four layers. Figure μ of the CNT film-Fe3O4 composites with frequency and number of layers. Strong peaks of tan δμ can be seen in the frequency range of 10–17 GHz, and the peak location also shifts toward lower frequencies with increasing number of layers. The peak intensity of tan δμ decreases from a maximum value of 0.58 at one layer to a minimum value of 0.08 at four layers. It should be noted that the values of tan δμ become negative in some frequency ranges, indicating that the magnetic energy radiated out from the composites due to the high carrier mobility of CNTs7. Overall, the above results demonstrate the dependence of the dielectric and magnetic responses on the number of layers of CNT film-Fe3O4 composite. In addition, the values of tan δε are larger than those of tan δε for almost the entire frequency range, suggesting that dielectric loss plays a major role in the intrinsic EM wave absorption.Based on the above magnetic property data and morphology observations, CNT film-Fein/Z0| and RL calculated from the relative permittivity and permeability data are given in Fig. in/Z0| is close to unity, most of the EM waves can effectively enter the composite and then dissipate as heat. Figure in/Z0| of the CNT film-Fe3O4 composites increases and reaches a maximum value of 1.73 at six layers and then decreases to 0.80 at seven layers. Only the values of |Zin/Z0| of the CNT film-Fe3O4 composites with five and six layers are close to unity in the frequency range of 10–17 GHz. Figure 3O4 composite with five layers, the minimum value of reflection loss is −19.3 dB, and the frequency bandwidth at −10 dB is 3.6 GHz. For the CNT film-Fe3O4 composite with six layers, the minimum value of reflection loss is −26.6 dB, and the frequency bandwidth at −10 dB is 2.9 GHz. However, although the CNT film-Fe3O4 composites with one, two, three, four and seven layers have higher dielectric loss, the frequency bandwidth at −10 dB and the magnitude of minimum reflection loss are far less than those of five- and six-layer composites.Results of |Z3O4 composites with different layers, CNT film-Fe3O4 composites of six layers with different FeCl3 concentrations were prepared. As shown in Fig. ε of the CNT film-Fe3O4 composites of 0.02–0.05 M are all less than that of the CNT film-Fe3O4–0.01 M composite, and the values of tan δμ are all higher than that of the CNT film-Fe3O4-0.01 M composite. It is interesting that tan δε of the CNT film-Fe3O4-0.10 M increases almost monotonically with frequency. The tan δμ value of the CNT film-Fe3O4-0.10 M is negative and shows a decreasing trend at frequencies higher than 8.5 GHz , and each semicircle is correlated with one Debye relaxation process6. The eddy current loss contribution to the imaginary part of permeability is related to the permeability of vacuum (μ0), thickness (d) and electrical conductivity (σ) of the composite as μ″ = 2πμ0(μ′)2σd2f/3. If the magnetic loss results from the eddy current effect, μ″(μ′)−2f−1 should be constant when the frequency varies. It is shown in Fig. −2f−1 drastically fluctuate in the frequency range of 2.0–8.0 GHz. However, when f >8.0 GHz, the values of μ″(μ′)−2f−1 remain essentially constant. Thus, it can be concluded that the magnetic loss at 2.0–8.0 GHz is caused by natural resonance, and the other peaks at 8.0–18.0 GHz are ascribed to the eddy current effect.In the microwave frequency band, magnetic loss mainly comes from the eddy current effect, along with natural and exchange resonance2O4 and CNT-La(NO3)3 absorbers 3 absorbers at 0.9, 1 and 1.4 mm, respectively, and the GO-Fe3O4 absorber also at 1.5 mm. However, the maximum reflection loss of this work is 1.2–2.5 times the values of the above five absorbers CNT-Ni, -Ag -CoFe2O4 and -La(NO3)3, GO-Fe3O4 . Ethanol, ferrocene, and thiophene were used as carbon source, catalyst precursor, and promotor, respectively. CNTs were synthesized and entangled in the hot zone forming a stocking-like aerogel. The CNT aerogel was then blown out continuously from the reactor and collected layer-by-layer by a wheel rotating perpendicularly to the gas flow, which formed macroscopic CNT film  with randomly oriented CNTs33. This CNT film was further densified by spraying ethanol onto it to enhance its mechanical and physical properties.CNT film was fabricated by floating catalyst chemical vapor deposition (FCCVD) method2 flow. Subsequently, a 20 sccm CH4 flow was introduced for graphene growth at 30 mTorr for 0.5 h. Then, the furnace was quickly cooled to room temperature under He flow, and the single-layer graphene on Cu foil was obtained34. The size of the graphen was 25 mm × 20 mm.The single-layer graphene films were synthesized on a Cu substrate using the CVD method. A Cu foil was annealed at 1000 °C for 1.5 h in a quartz tube with a 2 sccm H3O4 composites were prepared in a solvothermal system by the reduction reaction between FeCl3 and ethylene glycol in the presence of CNT film. FeCl3·6H2O was dissolved into 50 mL ethylene glycol followed by the addition of 3.0 NaAc (protective agent) and 10 mL ethylene diamine (EDA) to form a homogeneous solution with magnetic stirring. The mixture was then transferred to a 100 mL Teflon-lined stainless steel autoclave, and 30 cm2 CNT film was completely immersed in the solution for solvothermal reaction at 200 °C for 10 h , curing agent (DETDA) and ethyl acetate in the ratio of 10:1:100, followed by degassing in a vacuum oven for 30 min. Next, a CNT film-Fe3O4-graphene-epoxy composite was prepared by laminating the as fabricated films by spin coating Resin 862 and DETDA in the ratio of 10:1, followed by curing at 100 °C for 1 h. The thickness of one layer of CNT film-Fe3O4-epoxy composite was about 0.25 mm.The individual CNT-FeX-ray diffraction (XRD) patterns of the composites were measured on a Bruker D8 advance diffractometer using a Cu Kα source (λ = 0.154056 nm). Scanning electron microscopy (SEM) and transmission electron microscope (TEM) images were performed on the Auriga 60 and TEM Talos F200C, respectively. A magnetic study was performed by a vibrating sample magnetometer . The electromagnetic parameters of the samples were measured using a vector network analyzer (Agilent 8722ES) in the range of 1-18 GHz after a full two-port calibration .Superb electromagnetic wave-absorbing composites based on large-scale graphene and carbon nanotube films


The aim of this study is contribute to clinical practice of bilinguals around the globe, as well as to add to our understanding of bilingual aphasia processing, by analysing confrontation naming data from four Afrikaans/English bilingual individuals with acquired aphasia due to a left hemisphere stroke.This is a case series analysis of four Afrikaans/English bilingual aphasic individuals following a left cerebrovascular accident. Error analysis of confrontation naming data in both languages was performed. Research questions were directed toward the between language differences in lexical retrieval abilities, types of errors produced and degree of cognate overlap.Three of the four participants showed significantly higher naming accuracy in first acquired language (L1) relative to the second acquired language (L2) and the largest proportion of error type for those three participants in both L1 and L2 was omission. One of the four participants  showed no between language accuracy difference. Regarding cognate overlap, there was a trend for higher accuracy for higher cognate words (compared to low).This study showed that naming performance in these four individuals was reflective of their relative language proficiency and use patterns prior to their stroke. These findings are consistent with the hierarchical model, in normal bilingual speakers and with persons with bilingual aphasia. Aphasia is a chronic, pervasive and often debilitating impairment of language that is most often a consequence of stroke in the left cerebral hemisphere. Speech-language pathologists strive to provide effective clinical rehabilitative services to remediate language impairments in persons with aphasia (PWA); with increasing prevalence of bilingualism in the world, special consideration to bilingual aphasia is imperative. Bilingual aphasia is a complex topic largely because of the heterogeneity within and across bilingual speakers due to varying manners of acquisition, patterns of use and relative abilities across languages , a lexical layer   and typological characteristics of each language . Further, characteristics inherent to bilingual speakers that can influence production are related to patterns and relative use across languages  is a structural element of language that has also been shown to impact word processing in bilinguals  of persons with relatively balanced abilities across languages  who work in Pretoria hospitals, clinics and rehabilitation centres. Data were collected by two speech pathology students (third and fourth authors).Inclusion criteria included the presence of a left hemisphere stroke, the presence of aphasia determined by a clinical SLP, bilingual speaker of English/Afrikaans with one language indicated by the participant as the predominant language and adequate hearing thresholds to conduct all tasks. The participants had to be capable of using full sentences or phrases in L1 during communication to ensure adequate verbal ability to perform the task. Exclusion criteria included severe aphasia, severely compromised receptive language ability, psychiatric illness, degenerative neurological disease, chronic medical illness, severe impairment in vision or hearing and knowledge or use of a third language.The four participants were on average 73 years of age (SD 11.7) and ranged between four years and two months post stroke onset. There were two men and two women, all were right-handed and were bilingual in Afrikaans and English see .Participant 1 (P1), male, age 72 was three months post stroke onset, had a university education and worked premorbidly as a university lecturer. He stated that he was fully bilingual since an early age, with acquisition of Afrikaans first (L1) and English later (L2) at the age of three. He was exposed to English through family and school and predominately spoke English in his occupational setting.Participant 2 (P2), female, age 84 was two months post stroke onset, completed Grade 12 and worked as a homemaker. She stated that she learned English first in the home (L1) and was exposed to Afrikaans from the age of four years (L2). She indicated that she was exposed to both English and Afrikaans in both the community and school and reported to have mastered both languages equally. For approximately 20 years pre-onset she was mainly exposed to English (L1) and used only English at home.Participant 3 (P3), male, age 57 was three months post stroke onset, had a four-year university degree and worked as an engineer. He stated that his first language was Afrikaans (L1) and that his second language, English (L2), was acquired at approximately eight years, predominately through formal classes in school and by watching the television. He regarded himself as quite proficient in both languages, using English and Afrikaans interchangeably at work.Participant 4 (P4), female, age 76 was three years and five months post stroke onset, had a Grade 12 education and worked as a homemaker. She stated that her first and most used language was Afrikaans (L1) and that she was exposed to English (L2) at age eight from formal lessons at school. She stated that she had a good English vocabulary prior to her stroke; however, she did not use English as much as Afrikaans in her daily life.http://www.wordcount.org . This cognate scale indexes four different features: initial sound, number of syllables, percentage of overlapping consonants and percentage of overlapping vowels. A specific rating scale is employed to further describe each of the four features. Initial sound is scored between 0 and 3 points . Number of syllables was scored between 0 and 2 points . Consonants were scored between 0 and 3 points . Finally, vowels were scored between 0 and 2 points . All scores for each word were tallied. For the purposes of this study, we deemed that a word was judged to have high overlap if it was between 8 and 10, medium overlap between 5 and 7, low overlap between 1 and 4 and no overlap if 0. See Participants were seated in a quiet room and stimulus cards were randomised and presented one at a time without any cues. The participants were requested to first name all objects in the set of 40 pictures in L1. After completion of the set of pictures in L1 they were again presented with the pictures, which were again randomised, and asked to name the pictures in L2. L1 was consistently probed first to control the possible influence of uncertainty or higher demands in L2. Instructions were provided in both languages (English for the English naming and Afrikaans for the Afrikaans naming). Participant responses were not constrained with a time limit. Participant responses were audio recorded and later scored for overall accuracy, total number of phonemes correctly produced and error type by three members from the motor speech laboratory at the University of Pretoria .The first research question addressed confrontation picture naming whole word accuracy. The second question addressed total number of phonemes correct and types of errors made. The final question looked at naming accuracy as a function of high, medium and low overlapping cognate status. Methods and procedures for each of these outcome measures are described below.Digital recordings of participant responses were scored, by consensus, by three trained SLPs (first and last two authors), two of whom are proficient Afrikaans/English bilingual speakers. The English speaking only SLP scored just the English responses. Only the participants’ first responses were coded. Correct response included the correct lexical item only. Fillers such as ‘um’ and ‘I don't know’ were not counted. Incorrect responses were coded for error type using five categories:phonologic (P) – substitutions, additions, transpositions, omissions.semantic (S) – related within language (SR-w: ‘child’ for ‘girl’), unrelated within language (SU–w: ‘grape’ for ‘house’), related across language , unrelated across language .mixed (M) – real words with a phonologic relationship to the target.omission (O) – includes circumlocutions and non-responses.neologism (N) – nonwords that were not phonologically related to the target.Direct translations were coded (T), as well as translations with phonologic errors (Tp).To answer research question 1, paired-samples unequal variance t tests comparing confrontation naming accuracy between L1 and L2 were performed. For the error analysis questions, paired-samples t tests compared L1 and L2 for raw number of each error type and error type proportions . For the cognate question, percentage accuracy was documented for high, medium and low overlap cognate words and paired-samples t tests were used to compare L1 and L2 differences.Consensus reliability on 25% of the corpus resulted in 98% point-to-point reliability on accuracy scores and 83% reliability on error type coding.p = 0.209). Results for P2 were 58% (L1) and 28% (L2), showing a significant between language difference (p = 0.038). Results for P3 were 38% (L1) and 20% (L2) accurate, showing statistical significance (p = 0.047). Finally, results for P4 were 23% (L1) and 2.5% (L2) accurate, which was significantly different (p = 0.047) (see The first research question asked if there was a significant difference in confrontation naming abilities between L1 and L2 as measured by accuracy. Results for P1 showed 75% (L1) and 83% (L2) accuracy, resulting in no difference (047) see .The second research question asked if there was a significant difference for each participant between L1 and L2 in the number and types of errors produced as measured by raw number and proportion of errors. Results for each participant, for L1 and L2, are described and are shown in P1 (L1) had 10 raw errors (out of 40 words). Nine errors were semantic and one mixed. The L1 semantic errors were further subdivided into eight within language-related errors and one within language-unrelated error. Proportion of errors were 0.90 semantic and 0.10 mixed. In L2, he had seven total errors (out of 40 words). Four errors were semantic, two phonologic and one omission. The L2 semantic errors were further subdivided into three within language-related errors and one within language-unrelated error. Proportion of errors was 0.29 phonologic, 0.57 semantic and 0.14 omission.P2 (L1) had 17 raw errors (out of 40 words). Seven errors were semantic, 1 phonologic, 7 omission, 1 translation and 1 neologism. The L1 semantic errors were further subdivided into 5 within language-related, 1 within language-unrelated and 1 across language-related error categories. Proportion of errors was 0.41 semantic, 0.06 mixed, 0.06 translation and 0.06 neologism. In L2, she had 29 errors (out of 40 words). Ten errors were semantic, 18 omission and 1 translation. The L2 semantic errors were further subdivided into 7 within language related, 2 within language unrelated and 1 across language related categories. Proportion of errors was 0.34 semantic, 0.62 omission and 0.03 translation.P3 (L1) had 25 raw errors (out of 40 words). Eight errors were semantic, two phonologic, 10 omission, two translation and three neologism. The L1 semantic errors were further subdivided into two across language-unrelated, three within language-unrelated, one across language-related and two within language-related categories. Proportion of errors were 0.08 phonologic, 0.32 semantic, 0.40 omission, 0.08 translation and 0.12 neologism. In L2, he had 32 errors (out of 40 words). Ten errors were semantic, one phonologic, one mixed, 14 omission, three translation and three neologism. The L2 semantic errors were further subdivided into two across language-unrelated, four within language-related, one across language-related and one within language-related categories. Proportion of errors was 0.31 semantic, 0.03 phonologic, 0.03 mixed, 0.43 omission, 0.09 translation and 0.09 neologism.P4 (L1) had 31 raw errors (out of 40 words). Two errors were semantic, six phonologic, two mixed, 16 omission and five neologism. The L1 semantic errors were further subdivided into one within language-unrelated and one within language-related categories. Proportion of errors was 0.19 phonologic, 0.06 semantic, 0.07 mixed, 0.48 omission and 0.16 neologism. In L2, she had 39 errors (out of 40 words). Four errors were semantic, two phonologic, 14 omission, 17 translation and two neologism. The L2 semantic errors were further subdivided into one within language-unrelated and three across language-related categories. Proportion of errors was 0.14 semantic, 0.07 phonologic, 0.48 omission, 0.59 translation and 0.07 neologism.The third research question asked if any differences were observed in spoken word accuracy between L1 and L2 for high, medium and low overlapping cognates. As a reminder, out of 40 words there were 17 with high overlap, 9 with medium overlap and 14 low-overlapping cognate words. Data are displayed in p = 0.22). P2 was higher in L1 (65%) than L2 (35%) (p = 0.09). P3 was slightly higher in L1 (47%) than L2 (33%) (p = 0.30). P4 was more accurate in L1 (47%) than in L2 (29%) (p = 0.30).In regard to naming accuracy for the high overlap words, P1 showed similar performance between L1 (71%) and L2 (88%) (p = 1.0). P2 was higher in L1 (67%) than L2 (33%) (p = 0.18). P3 performed slightly higher in L1 (33%) than L2 (0%) (p = 0.08). P4 was slightly more accurate in L1 (33%) than in L2 (0%) (p = 0.08).Naming accuracy for the medium overlap words for P1 showed equivocal performance between L1 (89%) and L2 (89%) (p = 1.0). P2 was higher in L1 (43%) than L2 (14%) (p = 0.10). P3 performed higher in L1 (29%) than L2 (21%) (p = 0.68). P4 was slightly more accurate in L1 (29%) than in L2 (21%) (p = 0.68).Naming accuracy for the low overlap words for P1 showed similar performance for L1 (71%) and L2 (71%)  individuals with aphasia with the goal of elucidating psycholinguistic mechanisms involved in bilingual word production. Overall, this study showed that whilst all participants had a diagnosis of aphasia, their naming impairments were reflective of their reported relative use patterns prior to their stroke. These findings are consistent with the hierarchical model  appeared to be relatively balanced in use and proficiency in both languages and he is the only participant who did not show significant differences in accuracy across languages. On the other hand, although P2, P3 and P4 acquired both languages relatively young (≤10 years old) and demonstrated the most severe naming impairments of the group, they showed significant differences in accuracy between L1 and L2. The lower performance of these three participants, then, could be interpreted from the perspective of premorbid use patterns  as opposed to severity of aphasia. Although the amount of detail we have regarding the participants’ premorbid language use is limited, our findings are consistent with Pitre’s  L2 lexical representations see . Converset al., The second research question explored if there were any differences in the types of errors produced in L1 versus L2. The results revealed that the proportion of semantic, phonological and mixed, omission, cross-linguistic and neologistic errors was essentially the same, regardless if the words were being spoken in L1 or in L2 (excepting P1’s semantic errors and P4’s cross-linguistic errors). From the perspective of bilingual word processing, the linguistic system is shared between languages and, as such, a linguistic impairment would evidence similarly in both languages. So, if there is a decrease in activation of the semantic system, the spread of activation is target language nonspecific, resulting in similar errors in both languages Costa, . Thus, tOmission errors were evidenced by P2, P3 and P4, who exhibited a more severe form of anomia. The higher proportion of omission errors (relative to other error types as well as relative to milder P1) could be attributed to the combined effect of lower proficiency or usage and an overall decrease of lexical or semantic activation. Finally, P4 showed more cross-linguistic errors in L2 versus L1 . A cross-linguistic error is not a true omission (lack of activation in both languages); rather, it may evidence that she was relying on L1 when she was unable to produce a word in L2.With respect to the phonological errors, P1, the only participant to show more phonological errors in L2, had the highest accuracy overall and was closer to the target in general across all attempts. Further, his phonological errors occurred in the low overlap items, suggesting that these words might be most sensitive in L2, even for relatively balanced bilinguals. P4 showed more phonologic errors in L1 (six), compared to L2 (two) which may indicate that since a phonologic error is a ‘smart’ error, it would occur in L1 and not L2 (which is the less accurate or proficient language).et al., The third research question explored L1 and L2 differences as a function of cognate status. This issue was important, as degree of phonological and orthographic overlap between languages has been shown to impact word processing in bilinguals  compared to L1 (71%). Although not statistically significant, this trend is consistent with Roberts and Deslauriers , who shoet al. , thereby facilitating production. The converse is true as well. A trend of lower accuracy observed with the low overlap words spoken with the least proficient language supports this notion as well.Finally, phonological overlap may indeed be a good way to characterise words for bilinguals in addition to more conventional, psycholinguistic terms, such as frequency  on patterns of recovery should be addressed in future research studies. Finally, it is important to note that parallels to other African languages are limited as the results will be person-specific and may depend on the classification of the languages that are compared. Both languages in the current study were Germanic languages. The clinical implications for this study are that the clinician needs to gather necessary information during the assessment period on level of proficiency and use. Also, if possible, the clinician should evaluate the word retrieval impairment across languages to provide additional information regarding severity.Characterising phonological word equivalents across languages in word evaluations (i.e. translations) in evaluations of lexical retrieval in aphasia may provide additional insight into the interactions between premorbid proficiency and use, level of impairment and degree of phonological overlap across languages.