IG and ID) were used to identify the graphene domain boundaries. The domain boundaries were also identified using Raman images of ID/IG and I2D/IG ratios and 2D spectral widths. Interestingly, the ID maps showed that the defects within individual domains significantly increased for the graphene with large domain size. The correlation analysis between the G and 2D peak energies showed that biaxial tensile strain was more developed in the graphene with large domain size than in the graphene with small domain size. Furthermore, spatial variations in the spectral widths of the 2D peaks over the graphene layer showed that strain fluctuations were more pronounced in the graphene with large domain size. It was observed that the mobility (sheet resistance) was decreased (increased) for the graphene with large domain size. The degradation of the electrical transport properties of the graphene with large domain size is mainly due to the defects, tensile strains, and local strain fluctuations within the individual domains.We report spatially resolved Raman scattering results of polycrystalline monolayer graphene films to study the effects of defects, strains, and strain fluctuations on the electrical performance of graphene. Two-dimensional Raman images of the integrated intensities of the G and D peaks ( In the CVD-grown large-area graphene, however, the formation of graphene domain boundaries, structural defects, and built-in strains cannot be avoided. Consequently, the electrical, mechanical, and thermal properties of polycrystalline graphene are inevitably altered by the presence of the domain boundaries, defects, and strains5. Defects at the domain boundaries can act as scattering sites of charge carriers, leading to inferior electrical transport properties. For example, the carrier mobility of polycrystalline graphene tends to decrease for a small domain size, suggesting that the charge transport is influenced by scattering at the domain boundaries7. In contrast, the presence of defects within the graphene domain can lead to a reduction in mobility even for a large domain size11. The tensile strain in the graphene layer induces a decrease in the carrier mobility and an increase in the sheet resistance of the graphene14. Furthermore, random strain fluctuations and wrinkles also limit the carrier mobility16. Therefore, the physical properties of polycrystalline graphene are influenced by not only the defects at the domain boundaries but also other defects, strains, and strain fluctuations within the individual domains.Large-scale growth of high-quality crystalline graphene is a prerequisite for improving the device performance in graphene-based nanoscale applications. Chemical vapor deposition (CVD) is one of the widely used methods to grow graphene over a large area17. The 2D peak originates from a double-resonance electron-phonon scattering process involved with the electronic dispersion of graphene17. Therefore, the 2D peak facilitates the determination of the graphene thickness because the electronic band structure of graphene varies as a function of the number of layers17. The symmetric 2D peak of single-layer graphene becomes dispersive with an increase of the number of layers owing to the interlayer coupling, leading to the broadening of spectral width18. The G peak has E2g symmetry involving the C–C bond stretching and originates from a first-order Raman scattering process17. Both the G and 2D peaks are sensitive to strain20. Further, a correlation study of the G and 2D peak energies can explore the residual strain, which would affect the electrical transport properties of graphene21. Therefore, two-dimensional Raman images of the energies, intensities, and/or widths of the D, 2D, and G peaks scanned over a large area of graphene can provide useful information on the spatial distributions of defects, strains, strain fluctuations, etc. In this study, Raman mapping measurements were carried out on single-layer graphene samples to investigate the influence of defects, strains, and strain fluctuations on the transport properties in the presence of domain boundaries. We observed previously that the sheet resistance (mobility) increased (decreased) for the graphene with a large domain size11. Raman images revealed direct evidence that the spatial distributions of defects and strains were different for graphene samples with different domain sizes. Consequently, we observed that the electrical transport properties of the graphene devices could be affected by not only the carrier scattering at the domain boundaries but also the defects, strains, and strain fluctuations within the individual domains.Raman scattering is a powerful tool to probe defects in graphene because the D peak is activated in the presence of disorder11. Thermal annealing leads to the oxidation of the Cu foil. Since the Cu foil underneath the domain boundaries is more vulnerable to the penetration of O2 molecules through defects in graphene, the domain boundaries are distinctly visible as the bright lines in the SEM images22. The electrochemical polishing (ECP) treatment combined with an annealing process suppresses the formation of graphene nucleation sites, resulting in an increase in the domain size23. Indeed, the average domain size of sample B (∼293 μm2) grown using the ECP-treatment followed by the atmospheric pressure H2 annealing process is significantly larger than that of the untreated sample A (∼66 μm2). Generally, the sheet resistance of polycrystalline graphene is expected to decrease as the graphene domain size increases24. In the current study, the sheet resistance was observed to increase for the larger domain size: ∼552 Ω sq−1 for sample A and ∼777 Ω sq−1 for sample B11. Moreover, the mobilities were measured to be approximately 1530 and 910 cm2/V·s for samples A and B, respectively11. The decrease of the mobility of sample B may be caused by the copper oxide on the surface which was not fully removed due to the suppressed sublimation of copper and oxygen in the atmospheric pressure of H2. The copper oxide may induce defects and strain by forming carbon-oxygen bonds and/or small pores on graphene11.Figure −1. The 2D peak energy for sample A is observed at 2700 cm−1, that is consistent with the 2D energy value for an excitation laser energy of 2.54 eV (488 nm)25. The 2D peak has a narrow, single Lorentzian line shape and is much more intense than the G peak: a typical signature of monolayer graphene17. The weak Raman mode at ∼2450 cm−1 corresponds to a multi-phonon response that originates from the combination of the D peak and the longitudinal acoustic phonon17. Interestingly, both the G and 2D peaks of sample B are shifted downward in energies compared to the corresponding peak energies of sample A. Moreover, the spectral width of the 2D peak of sample B is much broader than that of sample A. The changes in the G and 2D peak energies and spectral widths in monolayer graphene usually originate from strain and/or strain fluctuations. In order to clarify the differences observed between the samples in more detail, it is necessary to perform spatially resolved Raman measurements over a large area.Figure 26. Polycrystalline graphene consists of single-crystal domains with different crystallographic orientations. The individual domains are merged together with the formation of defects, wrinkles, and/or overlapped structures at the domain boundaries27. Moreover, defective or atomically smooth connections can be formed at the domain boundaries with flat interfaces27.Raman intensity changes in CVD-grown monolayer graphene are mainly related to defects, (folded) wrinkles, and overlaps of the graphene layers. Wrinkles are usually formed during the post-growth cooling of graphene on a Cu substrate owing to the difference in thermal expansion coefficients between graphene and Cu27. The integrated intensities of the G and 2D peaks may not vary regardless of the nature of the interface: either a perfect or a defective flat interface28. In contrast, for the multilayer graphene boundary and the folded wrinkle, the integrated intensity of the G peak (IG) usually increases owing to an increase in the number of graphene layers compared to the surrounding monolayer region30. The integrated intensity of the 2D peak (I2D) decreases at the wrinkle (not folded) owing to a structural curvature effect, whereas the integrated intensities of the G and D peaks do not change at the wrinkle26. At the overlapped bilayer domain boundary, I2D depends on the twisted stacking angle between the misoriented monolayer graphene domains31. Therefore, spatial mappings of the integrated intensity changes in the graphene Raman modes can provide direct spectral evidence on the defects and domain boundary characteristics in polycrystalline monolayer graphene.The D peak is activated for a defective interface but not for an atomically smooth, perfect interface at the domain boundaryIG and ID for samples A and B. Note that the samples were not mild dry annealed. Interestingly, the IG image shows individual domains separated by boundaries with a relatively large IG (marked by dashed curves). Furthermore, the ID image also exhibits the same boundary structures. The representative Raman spectra in Fig. IG and ID are usually developed at a folded wrinkle or a bilayer domain boundary26. Therefore, the domain features observed in both IG and ID images suggest that the enhancements in the G and D peak intensities are mainly attributed to the formation of the graphene domain boundaries. The shape and size of the domains in the Raman mapping images are very similar to those shown in the SEM images  is usually related to an increase of defect density, which occurs more at the domain boundaries. It has been reported that the ID/IG ratio does not show a discernable enhancement at the folded wrinkle10. Therefore, it is likely that the domain boundary consists of the overlapped graphene. Although sample B shows similar features as sample A in the ID, IG and ID/IG images, two noticeable differences are clearly observed. The average domain size increases significantly from ∼52 μm2 (sample A) to ∼254 μm2 (sample B) and the D peaks are developed not only at the domain boundaries but also within the domains. The macro-Raman spectra in Fig. −1) is higher than that of sample A (∼552 Ω sq−1). Therefore, one of the main causes of the increase in the sheet resistance of sample B is attributed to the significant increase of defect density within the domains  and spectral width (Γ2D) are mainly sensitive to strain and strain fluctuations, whereas ωG and ΓG are sensitive to not only strain but also doping21. Figure ω2D and Γ2D for sample A over the same area shown in Fig. 2D image of sample A clearly illustrates that the spectral widths are broadened at the domain boundaries, whereas the ω2D image does not resolve the domain boundary structure. In comparison, the domain structures are not resolved in both the ωG and ΓG images  in the sheet resistance (mobility) of graphene14. Therefore, the increase (decrease) in the sheet resistance (mobility) of sample B is partly attributed to the tensile strain in sample B as compared to sample A.In comparison to sample A, the 2D peak energies are significantly shifted downward over the entire area in sample B, indicating the presence of tensile strain. The spatially averaged values of the 2D peak energies for samples A and B are ω2D and ωG maps provide the variations in the 2D and G peak energies over the scanned areas. Histograms extracted from the distributions of ω2D and ωG over the scanned areas show that the energy variations are more dispersive in sample B than in sample A  than in sample A (−1). The increase in the spatially averaged value of Γ2D of sample B compared to that of sample A is a signature of a larger magnitude of random strain fluctuations15. Therefore, the statistical broadenings of both the 2D peak energy and width distributions as well as the larger average value of the 2D spectral width in sample B suggest that strain fluctuations are more pronounced in sample B than in sample A. These observations provide evidence that the random strain fluctuations are one of the dominant sources of disorder that limits the carrier mobility observed in the electrical transport measurements .Spatially resolved e A Fig. . This is ΓG Fig. . EspeciaωG and ω2D provides useful information on strain and can differentiate the effect of strain from that of doping on graphene35. For example, for monolayer graphene under biaxial tension, the strain-induced shift of the 2D peak energy is approximately twice that of the G peak energy36. Local strain fluctuations in monolayer graphene can cause spatial variations in the G and 2D peak energies over the graphene layer. Consequently, the correlation points  of the G and 2D peak energies scatter along a line with a slope of 21. Similarly, in our case, the correlation points  extracted from the Raman images in Fig. 21. The scattered points  in sample B are located in the lower part of the correlation plot, clearly indicating that sample B is relatively under tensile strain as compared to sample A.The correlation analysis of ID and IG but also ID/IG and I2D/IG ratios reveal domain boundary characteristics. Interestingly, the Γ2D image also reveals the domain boundary structures. As indicated by the increase of ID within the domains, the decrease in Two-dimensional Raman imaging measurements show that the spatial mappings of the spectral variations in the graphene Raman modes provide a unique opportunity to simultaneously probe domain boundary structures, defect distributions, strains, and strain fluctuations, all of which limit the transport properties of polycrystalline graphene. Raman images of not only 2) flow condition for 45 min. The graphene films were synthesized on the Cu foils using methane (CH4) and H2 gas mixture for 12 min. The sample A (B) was grown on a Cu foil annealed at low (atmospheric) pressure condition of H2 without (with) the ECP treatment. After the synthesis of the graphene films, the CVD chamber was rapidly cooled to room temperature.Single layer graphene films were synthesized on copper (Cu) foils using CVD method. Two different types of Cu foils were used: one was annealed at low pressure without ECP treatment and the other was annealed at atmospheric pressure after ECP treatment. ECP treatment was performed in a mixed solution of phosphoric acid and deionized water. Pre-treated Cu foils were cleansed with deionized water, acetone, and isopropanol in a regular sequence. The Cu foils were heat treated at 1050 °C under hydrogen  at room temperature. The power of the excitation laser was less than 0.5 mW, at which any laser-induced thermal effects on the samples were not observed. Scattered light from the graphene surface was collected through the same objective lens, dispersed through a spectrometer with a grating of 1200 grooves/mm, and detected using a thermoelectrically cooled charge-coupled device detector. The incident laser polarization was parallel to the scattered light polarization throughout the Raman mapping measurements. The spectral resolution was ∼1 cm−1. The spectrometer was calibrated using the known spectral lines of a mercury gas light source.Spatially resolved Raman scattering measurements were performed on the graphene films transferred onto SiO


Antibody blockade of the PD-1/PD-L1 pathway has elicited durable antitumor responses in the therapy of a broad spectrum of cancers. PD-L1 is constitutively expressed in certain tumors and host immune cells, and its expression can be induced or maintained by many factors. The expression of PD-L1 on tumor tissues has been reported to be positively correlated with the efficacy of anti-PD-1/PD-L1 therapy in patients. However, multiple clinical trials indicate that patients with PD-L1-negative tumors also respond to this blockade therapy, which suggests the potential contribution of PD-L1 from host immune cells. Recently, six articles independently evaluated and verified the contributions of PD-L1 from tumor versus non-tumor cells in various mouse tumor models. These studies confirmed that PD-L1 on either tumor cells or host immune cells contributes to tumor escape, and the relative contributions of PD-L1 on these cells seem to be context-dependent. While both tumor- and host-derived PD-L1 can play critical roles in immune suppression, differences in tumor immunogenicity appear to underlie their relative importance. Notably, these reports highlight the essential roles of PD-L1 from host myeloid cells in negatively regulating T cell activation and limiting T cell trafficking. Therefore, comprehensive evaluating the global PD-L1 expression, rather than monitoring PD-L1 expression on tumor cells alone, should be a more accurate way for predicting responses in PD-1/PD-L1 blockade therapy in cancer patients. Antibody blockade of the programmed death-1 receptor/programmed death-ligand 1(PD-1/PD-L1) signaling pathway has shown unprecedented durable therapeutic responses in patients with a variety of cancers. Accumulating studies in animal models and clinical trials have contributed to our current understanding of mechanisms underlying the efficacy of PD-1/PD-L1 pathway blockade in cancer immunotherapy. Since PD-L1 on tumor cells plays an important role in preventing T cell-mediated killing, beneficial outcome of PD-1/PD-L1 blockade therapy has been correlated with PD-L1 expression on tumor cells , suggestElucidation on the contributions of tumor cells and host immune cells-derived PD-L1 has important clinical implications as PD-L1 expression may predict the sensitivity of anti-PD-1/PD-L1 immunotherapy in cancer patients. Within 1 year from early of 2017, six independent research groups published papers in high impact journals and explained their points of view on the contributions of PD-L1 expressed from relevant cells –8. Mouse−/− mice to test whether PD-L1 expression on tumor cells was required for tumor immune escape. While growing T3ΔPDL1 tumors were observed in all of the Rag2−/− mice, the majority of inoculated T3ΔPDL1 clones were spontaneously rejected in syngeneic WT mice. Furthermore, T3ΔPDL1 cells with enforced expression of PD-L1 regained the capacity to form progressively growing tumors in WT mice. These facts revealed that PD-L1 expression on T3 sarcoma cells was functional in suppressing antitumor immunity in the model. In addition, Noguchi et al. [Noguchi et al.  generateLau et al.  used gen+ T cells for the antitumor effects of PD-L1 antibody therapy.Kleinovink et al.  have als−/− PD-L2−/− mice, PD-L1 expression on the tumor cells is the only source of ligands for PD-1.They found that MC38 tumor growth was similarly robust in PD-L1−/− PD-L2−/− and WT mice, which indicates that engagement of PD-1 by PD-L1 on tumor cells alone is sufficient to suppress antitumor immunity to MC38 tumors. Consistently, administration of PD-L1-blocking antibody to MC38 tumor-bearing PD-L1−/− mice resulted in tumor clearance in the majority of mice. Juneja et al. [−/− mice compared with WT mice. This suggests that PD-L1 expression on non-tumor cells in WT mice plays a nonnegligible role in inhibiting antitumor immunity to melanoma tumors.Juneja et al.  first tea et al.  also use−/− mixed bone marrow chimera mice model, they elegantly demonstrated that blocking PD-L1 on CD11b+ myeloid cells is indispensable for effective antitumor immunity in PD-L1 blockade therapy.Tang et al.  used MC3−/−, NSG, PD-L1−/− and PD-1−/− mice, for studying PD-L1 and PD-1 signaling blockade in MC38, ID8 (ovarian cancer), B16-F10 (melanoma), and LLC (lung cancer) tumor models. First, they verified that host immunity determines anti-PD-L1-induced tumor immunity. While WT mice bearing various tumors had effective response to PD-L1 blockade, anti-PD-L1 treatment had no antitumor effect in NSG and Rag1−/− mice. Their further experiments indicate that anti-PD-L1 treatment reduced tumor growth in mice bearing PD-L1-deficient MC38, ID8 and B16-F10 tumors, which implies that host- but not tumor-derived PD-L1, is indispensable for the therapeutic efficacy of anti-PD-L1 treatment. Mechanistically, the authors experimentally proved that anti-PD-L1 treatment activates T cells in tumor and draining lymph nodes. They demonstrated that tumor-associated APCs (antigen-presenting cells), as the major PD-L1+ immune cells, are the major immune targets of anti-PD-L1 therapy. Additionally, they observed a well correlation between expression of PD-L1 on dendritic cells (DCs)/macrophages and the efficacy of treatments with either anti–PD-1 alone or in combination with anti-CTLA-4 in ovarian cancer and melanoma patients. They concluded that the host immune system is indispensable for PD-1/PD-L1 blockade therapy, and the host DCs and macrophages-derived PD-L1, rather than cancer cell-intrinsic PD-L1, predominantly accounts for the blockade therapeutical efficacy.Lin et al.  used mic−/− and PD-L1+/+ tumors in WT host, Lin et al. demonstrated the critical role of host-derived PD-L1 by treating the host with anti-PD-L1 antibody, which resulted in significant tumor regression [+ T cell cytotoxicity and suppressing antitumor immunity in their model [From multiple angels and using various techniques and pre-clinical tumor models, these studies reveal that PD-L1 on tumor cells and host cells is involved in tumor immune evasion. All the studies employed gene silencing technologies to knock out of PD-L1 in tumors, and these tumors were inoculated to WT immune competent hosts to test the roles of PD-L1 in tumor immune escape Fig. a. While gression . Both Tair model , Tang etir model , 8. The ir model . This su−/−PD-L2−/− and WT mice [−/− mice compared with WT mice [Most of these studies implanted PD-L1-sufficient tumors to PD-L1 knock out hosts to test the contribution of PD-L1 in suppressing the antitumor T cell responses Fig. b. While  WT mice . This di WT mice . In addi WT mice , 8. Howe WT mice , 8.Besides, functional consequences of different levels of PD-L1 expression on tumors were assessed from Noguchi et al. by comparing physiological level and over-expressed level of PD-L1. They found that abnormally high expression of PD-L1, but not levels of PD-L1 expression that can be induced on tumor cells under physiologic conditions, is required to prevent immune elimination of highly immunogenic unedited MCA sarcoma cells that express strong neoantigens . Their w+ T cells dependent cell-extrinsic pathways [−/− tumors, including reduced MHC-I expression and increased PD-L2 expression [+ cytotoxic T lymphocytes (CTLs), and is dominant in suppression of antitumor immunity in their mouse model [+PD-L1+ myeloid cells and enhancing effective T cell trafficking in contributing to the efficacy of PD-L1 blockade therapy [Collectively, these findings demonstrate that both tumor- and host-derived PD-L1 can play a critical role in inhibiting antitumor immunity, and the relative contribution of tumor- or host-derived PD-L1 is context-dependent. All the studies confirmed the role of PD-L1, either from tumors or host cells, in suppressing T cell functions, as evidenced by changes in cytotoxicity of effector T cells and the secretion of effector cytokines like IFNγ. However, these articles have different focuses on revealing mechanisms of PD-L1 in suppressing anti-tumor immunity. Noguchi et al. conclude that tumor-associated macrophages (TAMs) are the major host cell type that contributes PD-L1 in the sarcoma tumor model both quantitatively and temporally. In their study, while in vivo up-regulation of PD-L1 on T3 tumor cells was in a transient and time-dependent manner, PD-L1 expression on TAMs was retained for long period of time, and can be induced by CD4se model . Tang et therapy . The wor therapy .+ PD-L1+ innate myelolymphoblastoid effector cells (IMLECs) [+ PD-L1+ myeloid cells in contributing to the efficacy of PD-1/PD-L1 blockade therapy in some tumors [Taking together, these independent studies largely complement and validate each other. Their work extends the mechanisms of action of PD-1/PD-L1 blockade therapy into the tumor microenvironment, and largely supports the concept that PD-L1 acts as a molecular shield on both tumor cells and host immune cells to prevent tumors from cytolysis by T cells. PD-L1 expressed on cancerous cells is not exclusively responsible for the therapeutic effect of PD-1/PD-L1 checkpoint blockade, whereas PD-L1 on both malignant cells and immune cells works concretely to functionally modulate the CTLs in the tumor microenvironment Fig. . Therefo(IMLECs) . It is we tumors , 8. Ther


When making financial decisions bank customers are confronted with two types of uncertainty: first, return on investments is uncertain and there is a risk of losing money. Second, customers cannot be certain about their financial advisor’s true intentions. This might decrease customers’ willingness to cooperate with advisors. However, the uncertainty management model and fairness heuristic theory predict that in uncertain situations customers are willing to cooperate with financial advisors when they perceive fairness. In the current study, we investigated how perceived fairness in the twofold uncertain situations increased people’s intended future cooperation with an advisor. We asked customers of financial consultancies about their experienced uncertainty regarding both the investment decision and the advisor’s intentions. Moreover, we asked them about their perceived fairness, as well as their intention to cooperate with the advisor in the future. A three-way moderation analysis showed that customers who faced high uncertainty regarding the investment decision and high uncertainty regarding the advisor’s true intentions indicated the lowest intended cooperation with the advisor but high fairness increased their cooperation. Interestingly, when people were only uncertain about the advisor’s intentions (but certain about the decision) they indicated less cooperation than when they were only uncertain about the decision (but certain about the advisor’s intentions). A mediated moderation analysis revealed that this relationship was explained by customers’ lower trust in their advisors. Ninety-four-year-old Mrs X, whose cognitive and physical abilities are impaired by old age, received a sizeable amount of money from her disbursed life insurance. To reduce her uncertainty on how to reinvest the money, she consulted a financial advisor. The advisor recommended that the “optimal” solution was to put her money in a long-term investment—obviously not considering Mrs X’s age . Thus, oUncertainty is experienced when people feel unable to predict future events or when they feel inconsistencies between important cognitions, experiences, or behaviors . UncertaOne way to cope with uncertainty about one’s decisions is to look for advice , clients also have to cope with uncertainty regarding the advisor (UnA).Accordingly, in situations where people are uncertain regarding their decisions, customers focus on cues allowing them to gain the needed confidence for their decisions. However, in financial consultancies, people do not only have to cope with uncertainty regarding the decision but also regarding the advisor’s true intentions either to support the client or to pursue self-interest. Therefore, in addition to having to cope with Uncertainty regarding the advisor refers to the difficulty to identify his/her true intentions. Usually, the financial advisor possesses information and knowledge that the client lacks. The lack of knowledge makes it difficult for the client to assess whether the advisor is acting in the best interest of the client. According to Principal–Agent Theory , agents Knowing the advisor’s intentions is crucial to the client’s continued reliance on the advisor . A studyTo find answers to this question, we build on two theoretical models from justice research – the Uncertainty Management Model (UMM) and the Fairness Heuristic Theory FHT,  which miThe Uncertainty Management Model  describeThe Fairness Heuristic Theory  explainsBank customers are in uncertain situations and do not know if they can trust their advisor. To investigate how people cope with such uncertainty we tested – based on the UMM and FHT – whether uncertainty increases people’s sensitivity to fairness cues and increase their willingness to cooperate with financial advisors regarding their investment decisions.1): the distribution of resources . Our participants were either approached in a shopping mall when the University of Salzburg was having a public event there or via the experimenter’s social networks. All participants were asked to fill out a questionnaire in which they had to think about their financial service providers and indicated their agreement to several items on a scale from 1  to 6 (= completely).Two-hundred and forty-two participants answered our questionnaire. Due to missing data on the scales cooperation intention, UnA, and trust, we had to exclude nine participants, leaving us with a final sample of 233 This measure focused on the uncertainty about investment decisions . Five items asked about the success of the participants’ investment .Participants were asked to think about the behavior of their financial advisor and describe his/her behavior with the help of the following items: the strategic behavior scale covered the three agency problems described above . For further analyses we combined the subscales to produce a general uncertainty scale about the advisor .5 was excluded. Procedural fairness was assessed with eight items . Distributive fairness was represented with three items . Informational fairness was measured with seven items  and interpersonal fairness with four items . In the following calculations we combined these subscales to a general fairness scale .Participants evaluated their advisor’s fairness behavior with items from the German version  of the O6; see complete questionnaire in the appendix).Trust in the financial advisor was measured with items from a questionnaire designed by Table 1.7This scale measured the intention of the participants to further use the consulting services of the current financial advisor . For the means, standard deviations, and intercorrelations of all measured variables, see According to the two theoretical models dealing with uncertainty—UMM  and FHT We conducted a multiple regression including three continuous predictors , and all of their interactions regarding the dependent variable intention to cooperate ; Model 3SE = 0.06, t(225) = -2.65, p = 0.009, [95% CI: -0.29 to -0.04]), UnA  = -8.37, p < 0.001, [95% CI: -0.72 to -0.45]), and perceived fairness  = 3.36, p = 0.001, [95% CI: 0.11 to 0.40]) indicating that all three variables  decreased people’s cooperation intentions.The analysis revealed significant main effects of UnD  = -2.19, p = 0.030, [95% CI: -0.11 to -0.01]. Simple slopes indicated that when UnA and UnD were low, high and low fairness did not make a difference regarding people’s intentions to cooperate (p = 0.773). However, when any kind of uncertainty was involved (high UnA or/and high UnD), high fairness led to more cooperation intentions than low fairness . Furthermore, when both uncertainties were high, people had the lowest intentions to cooperate in both the low and high fairness conditions .In addition and most importantly, the three-way interaction between UnA, UnD, and fairness was significant, β = -0.06, ps < 0.001). In contrast, high UnD (compared to low UnD) led to lower cooperation when UnA was high and fairness low (p = 0.023). See Table 2 for a summary.Moreover, the regression weights show that the weight for UnA was higher than for UnD. This suggests that UnA had a larger impact on client’s cooperation intentions than UnD. In all conditions, whether fairness and/or UnD were high or low, high UnA always led to lower cooperation intentions than low UnA  = -2.19, p = 0.030; distributive fairness × UnA × UnD, β = -0.05, SE = 0.03, t(225) = -1.78, p = 0.076; interpersonal fairness × UnA × UnD, β = -0.06, SE = 0.03, t(225) = -1.67, p = 0.096; see Tables 6). This suggests that especially procedural fairness is important to compensate for the uncertainties.Additionally, we performed separate moderation analyses for the four fairness dimensions and found significant three-way interactions for the procedural fairness dimension, and marginal significant three-way interactions for the distributive and interpersonal fairness dimensions, all pointing into the same direction  = 1.97, p = 0.050, [95% CI: 0.00 to 0.12]. Trust had a significant effect on cooperation intentions, β = 0.25, SE = 0.06, t(230) = 4.12, p < 0.001, [95% CI: 0.13 to 0.37]. The direct effect of UnA on cooperation intentions was significant as well, β = -0.67, SE = 0.06, t(225) = -11.09, p < 0.001, [95% CI: -0.79 to -0.55].We conducted a mediated moderation analysis using PROCESS SPSS macro  and perceive low fairness, trust in the advisor does no longer seem to be involved in the process between UnA and intention to cooperate.For the slopes, we found that trust mediated the conditional indirect effect of UnA on cooperation when UnD was high and fairness was low, β = -0.13, We opened this paper by referring to the dilemma faced by financial consulting customers. On the one hand, customers want and need advice to reduce uncertainty regarding their risky decisions. On the other hand, they have to deal with uncertainty regarding the advisor’s true intentions, i.e., whether they pursue their own interests instead of the clients’ best interests. This dilemma describes two different forms of uncertainty: uncertainty regarding investment decisions and uncertainty regarding the advisor’s intentions. The current study examined customers’ intended future cooperation with an advisor when they were facing these two forms of uncertainty. Furthermore, as research has shown that in uncertain situations people need cues to regain their confidence, we introduced fairness as an important predictor for cooperation in consultancies.We based our study on the UMM and the FHT predicting that people react more strongly to fair treatment when uncertainty salience is high. Therefore, we suggested that perceived fairness is important when any uncertainty is high and especially important when both uncertainties are high. In the present study we asked participants to think about their experiences with “saving and investing money,” assessed their uncertainty regarding the decision and regarding the advisor’s intention, and their perception of fairness in the consultancy. Our findings indicated that whenever people were uncertain in a consultancy, whether uncertain about the decision or/and advisor, their intentions to cooperate with the advisor increased with perceived fairness. Moreover, both uncertainties together led to the lowest intentions to cooperate.Interestingly, a higher regression weight for UnA than for UnD indicated that in our study, UnA had a larger impact on client’s cooperation intentions than UnD. Thus, high UnA seems to be most costly for financial advisors regarding the customers’ intention to cooperate in the future. High experienced UnA seems to be especially detrimental for the relationship between the financial advisor and his/her customer. What changes in the relationship between customers and their advisors when they are confronted with uncertainty regarding the advisor’s intention, i.e., when people face the risk of being exploited by their advisor? The mediation analysis suggests that trust can help to explain this process: because clients mistrust that their advisors act in the client’s best interest and instead pursue their own goals, they refrain from cooperating with the advisor. However, if people want to work together in interdependent relationships, they need to trust each other . If custIn the current article, we have introduced fairness as a crucial cue in uncertain consultancies. Fairness is a cue displayed in the social interaction itself and thus differs from variables such as the advisor’s expertise or confidence which stem from the classic Judge-Advisor Research  or authority-oriented based situations (FHT). The current results expanded this line of reasoning by taking into account both uncertainties together and found that both are important in explaining cooperation intentions but that uncertainty regarding the advisor was more influential. However, they did not reinforce each other. This might be different in other consultancy situations. For example in health-related contexts – when people ask themselves what the best decision is and whether they can trust their advisors but they are anxiously aroused because they worry about their health – cues that induce mistrust might lead to overreactions. A potential mediator in this situation might be perceived loss of control. In future research, it would be fruitful to investigate the influence of different kinds of uncertainties and their relationship in various advisor–client interactions and to shed light on relevant mediators.Resulting from the economic crisis, people seem to be highly aware of both types of uncertainty (UnA and UnD) and even more vigilant to advisor’s trustworthiness. Therefore, since then, bank customers may evaluate the financial consultancy through the eyes of uncertainty. Consequently, it is important for banks to develop strategies that help their customers overcome this uncertainty. Our findings suggest that fair treatment might be such a strategy. Fairness increased people’s intentions to cooperate even when uncertainty was high. Nevertheless, it is essential to not understand fairness as a substitute which can easily eliminate people’s uncertainty. Rather, our findings indicated the lowest willingness to cooperate with the advisor when UnA and UnD was high. Fairness slightly improved the willingness but did not set people’s willingness back to baseline (when there was no uncertainty present). Thus, the way how advisors treat their customers and explain their products is critical and should not be neglected in the day-to-day running of a financial business. Fair treatment during consultancy is one way to help customers to reduce uncertainty and regain trust in their financial advisors.An advantage and disadvantage at the same time is that we collected our data in the field. On the one hand, a limitation of our research is that we could not control for further variables , on the other hand and at the same time it may be an advantage because we were able to directly examine how people cope with the insecure situation after the economic crisis. Moreover, manipulating a general uncertainty (UMM) and personal uncertainty (FHT) independently of each other in the laboratory could have helped to understand the interplay between different types of uncertainty and the role of fairness in this interplay. It would be important for future research to investigate different types of uncertainty in combination with the risk of losing real money  in the controlled environment of the laboratory. For future research it would also be interesting to investigate the long-term process of uncertainty and the reconstruction of trust in the advisor. Uncertainty regarding the advisor’s intentions might lead to mistrust, and fair treatment might be a way to regain trust. We are aware that we only measured people’s intention to cooperate in the future with the advisor, which is not the same as real behavior. Nevertheless, we believe that future studies might benefit from our findings and we hope that researchers further investigate the positive effect of fairness on cooperation in uncertain financial conditions.Uncertainties are part of our daily lives and especially part of our social interactions. In particular in financial consultancies, where uncertainty regarding an investment decision and uncertainty regarding the advisor’s intentions are high, we need cues helping us to deal with those uncertainties. We identified fairness as one cue helping people to compensate for uncertainty. Furthermore, our results indicate that customers’ uncertainty about the advisor is most costly for the customers’ intention to cooperate in future. However, our further analysis could identify loss of trust as a mediator, which can explain why customers facing high uncertainty about the advisor are not willing anymore to cooperate with their financial advisor.We are grateful to Barbara Grall for helping in the data collection and to Thomas Scherndl for his statistical advice.Although this study used human subjects, the approval of an ethical committee does not seemed necessary. The study was only about non-intrusive issues.BM and EJ developed together the research question, hypothesis and the research design. BM and CM did mainly the data analysis; together we did the writing of the manuscript.The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.


Despite U.S. mothers’ wide adoption of pumps and bottles to provide human milk (HM) to their infants, mothers lack comprehensive, evidence-based guidelines for these practices. Thus, some women use online sources to seek information from each other. We aimed to characterize the information women sought online about pumping. We used data provided by ~25,000 women in an open cohort within a discussion forum about parenting. We examined 543 posts containing questions about providing pumped HM cross-sectionally and longitudinally in three time intervals: prenatal, 0 through 1.5 months postpartum, and 1.5 to 4.5 months postpartum. We used thematic analysis with Atlas.ti to analyze the content of posts. During pregnancy, women commonly asked questions about how and where to obtain pumps, both out-of-pocket and through insurance policies. Between 0–1.5 months postpartum, many mothers asked about how to handle pumped HM to ensure its safety as fed. Between 1.5–4.5 months postpartum, mothers sought strategies to overcome constraints to pumping both at home and at work and also asked about stopping pumping and providing their milk. Women’s questions related to ensuring the safety of pumped HM represent information women need from health professionals, while their questions related to obtaining pumps suggest that women may benefit from clearer guidelines from their insurance providers. The difficulties women face at home and at work identify avenues through which families and employers can support women to meet their goals for providing HM. In the United States, mothers whose infants are fed human milk (HM) have rapidly and widely adopted using pumps and bottles to provide HM in place of some or all feeding at the breast . Of the Because of mothers’ need or desire to work outside the home in their first postpartum year ,16,17,18The impetus for this work is that, in the absence of comprehensive, evidence-based guidelines for pumping and providing pumped HM, and without the benefit of generational knowledge and influence that may be available with feeding at the breast , women mWe aimed to characterize the information women sought over time about pumping on an online parenting discussion forum. The information women seek from each other may represent information that is not currently accessible to them from professional resources, and understanding their questions will provide knowledge of the information needed to better support women in their practices of pumping and providing HM.We conducted a qualitative, longitudinal and cross-sectional analysis of data provided by a cohort of women within an online discussion forum whose infants were born in April 2014. We used BabyCenter , one of To investigate how the number and nature of questions changed over time, we examined questions women asked about pumping for three age groups: when women were pregnant, from delivery through 1.5 months postpartum, and from 1.5 to 4.5 months postpartum. These infant age groups were chosen to reflect prior analyses of the IFPS II by others , who divPrevious qualitative work  has idenThe unit of analysis was publicly accessible posts on BabyCenter forums  that incWe identified posts to be examined for inclusion in analyses using relevant keywords such as “pump”, “pumping”, and “expressing”. We saved all posts about pumping from the web as PDF files. Posts were divided in the three infant age groups, according to the date of the post . Inasmuch as the majority of the women did not include their infants’ due dates or ages in their posts, we assumed a mean sample due date of 15 April 2014. We then used 1 April 2014 as a reference point for infants’ birth dates in this sample, as the median length of pregnancy in the U.S. is about two weeks short of full term . Thus, tThroughout the sorting process, some posts were excluded from analyses. We excluded posts that did not include questions (n = 21), such as those that were sharing information about pumping but not as a question. We also excluded posts in which the question was not about pumping or providing pumped HM (n = 21), and general, non-informative questions about pumping or providing pumped HM (n = 11). Non-informative posts included questions and polls that asked about others’ general opinions on pumping and providing pumped HM instead of a specific aspect of these practices. The inclusion of data into analyses is described in Included posts were examined with a thematic analysis using open- and closed-coding in Atlas.ti . Primary analysis was done by a single coder (RY), using the code book created by JPF for prior qualitative work , and modThe April 2014 Birth Club had 18,303 members at the beginning of the data collection period and steadily grew through 4.5 months postpartum. Women in the April 2014 Birth Club posted 543 eligible questions, which were grouped by theme and infant age group . Women aWomen’s questions related to strategies for and difficulties with pumping were similar, whether they were asking about pumping at home, away from home, or both. As a result, findings from this theme, and those related to integrating pumping into work, were grouped together. Examples of topics raised by women whose posts were analyzed are listed in Women commonly asked questions about choosing pumps in the prenatal period, with some describing a desire to obtain their pumps before they delivered their infants or concerns that their insurance policies would not provide pumps until after they delivered. Before they delivered their infants, women also asked about how long it would take to obtain a pump through their insurance policies, and, thus, when they should start the process so as to receive a pump by the time they planned to use it.Questions about obtaining pumps indicated that women commonly purchased pumps out-of-pocket or through their insurance policies. Women who asked about purchasing a pump out-of-pocket either did not have an insurance policy that covered a pump or were unsatisfied with the pumps covered by their insurance policies. Some of the women who planned to purchase a pump out-of-pocket asked about how and where to obtain an affordable pump.I really want to get a breast pump but there just so expensive i’ve looked online and my [husband] is just like no thats to much but ive really want to get one until i seen the prices! Any one know of a good cheaper place to get them? Cus 200+ is just to much!—prenatalSome women whose insurance policies covered the purchase of a pump asked about which brands and models were offered by their policies, and about the processes by which they could obtain a pump through their policy. For example, some asked whether a doctor’s prescription was needed and whether and how they should obtain a pump from a special vendor.[Insurance provider] told me insurance would cover a breast pump. Well fast forward & I’m just a couple of days away from delivery & need to get mine ASAP. Has anyone with the same plan been able to pick up the pump from a med supply store? Are they shipped only? And did you need to get a prescription first?—prenatalMost questions about storing and preparing pumped HM were posted after mothers delivered their infants. Questions they asked in the prenatal period related to selecting supplies, such as bags and bottles to store and feed HM. In some of these questions, women described considerations, such as the maintenance required to keep supplies clean. In contrast, questions they asked after delivery commonly related to storing and preparing pumped HM that was safe for their infants .Mothers sought information about how to safely store their pumped HM, such as where, how, and in what containers to store their milk until it was fed. For example, they asked about how long pumped HM could be kept at room temperature or stored in the refrigerator or freezer: “How long do you store in the fridge? 5 days is the max? Then do you freeze the milk in bags?” (0–1.5 months postpartum). Some mothers asked whether it was safe for their infants to be fed milk that was stored and/or prepared by combining HM from different pumping sessions: “I am pumping after I feed and only getting about an ounce or less and would like to get to at least 4 if im freezing it. Can i combine??” (0–1.5 months postpartum).Mothers also sought information about how to safely prepare their pumped HM to be fed. They asked if infants should be fed fresh milk instead of frozen milk to ensure the safety of the milk, while describing that they did not want to waste their stock of frozen milk by providing only fresh milk. Mothers also asked whether bottled HM that had been refused or unfinished by their infants was safe to be fed to their infants later: “Is it safe once he starts drinking out of one bottle and he doesn’t finish all of it to save the rest in the fridge and give it to him at the next feeding?” (0–1.5 months postpartum). Further, mothers asked about the effect of consuming alcohol, caffeine, or medications on the safety of their milk. Some asked if they should pump and discard after consumption, and if so, for how long to do it to ensure the safety of the pumped HM as fed.Some questions focused on whether or not and how mothers could recognize the safety or nutritional value of their pumped HM by its taste, smell, and appearance. For example, some mothers asked how to interpret changes to the smell or taste of their pumped HM after refrigeration and freezing.I usually store the milk in the fridge for a couple of days and then freeze it if its not consumed…I noticed/tasted milk freshly expressed – it has a sweet taste. Milk stored in fridge, then in the freezer, when unfrozen, it seems slight acidic. Is this normal? [sic]—postpartum (1.5–4.5 months)Other mothers asked how to interpret the appearance of their pumped HM: “[My breast milk] has the thinnest layer of creamy hind milk on top after it’s been in the fridge for a while and separated. What’s up with that? I think it should be fattier,” (1.5–4.5 months postpartum).Mothers posted most questions about strategies for and difficulties with pumping between 0–1.5 months postpartum, when they were first attempting to pump. However, mothers asked most questions about pumping at work outside the home between 1.5–4.5 months postpartum, when they were preparing to, or had already, returned to work.Many questions related to strategies for and difficulties with pumping came from mothers who were transitioning from primarily feeding at the breast to pumping regularly. Mothers commonly indicated that this transition was in response to or in preparation for returning to work. Some mothers asked for advice about overcoming physical difficulties, such as nipple pain or bleeding from using pumps or engorgement from not pumping enough. Some mothers had already unsuccessfully tried other strategies for these problems. It seems like everyday my breasts get fuller, and never empty…I’ve tried heating pads, but only helped for a few pumps. Today my breasts are so sore, my nipples are cracked even though I use lanolin before and after pumping. Any suggestions?—postpartum (0–1.5 months)Other mothers had questions about or difficulties with their pumps, and sought information about using pump features and fixing pump malfunctions.Some of the mothers’ questions related to the barriers to pumping that they either experienced or anticipated. These barriers included the presence of infants who needed care, workloads that were heavy or inflexible, a lack of designated place to pump, and travel: “How do you handle meetings (both in and out office) and pumping? I’m more worried about a few all day meetings I have off-site. Do you bring your pump with you?” (1.5–4.5 months postpartum).Mothers only posted questions about stopping pumping in the postpartum period, and most often between 1.5–4.5 months postpartum.In their questions about stopping pumping, mothers described a number of considerations, including their infants’ age, their own emotional and physical burdens related to pumping, and how important it was to them to provide HM.Some mothers described reasons for stopping pumping, such as feeling burdened from the additional tasks of pumping, and asked questions related to whether those reasons were appropriate or acceptable. Some mothers were generally interested in what others were doing or planned to do, or asked for advice on when they should plan to stop pumping.When will you stop pumping? …I guess I’m not sure what my end goal should be. A certain age? A certain amount frozen? What is your situation, how long will you pump for? Maybe hearing others situations will help me decide what I want to do.—postpartum (0–1.5 months)Some posts about stopping pumping were related to the mothers’ personal experiences with stopping or transitioning away from pumping. Some mothers asked general questions about this experience, while others asked questions about specific challenges they anticipated related to stopping pumping, such as guilt.I have been exclusively pumping since day 1 and [my baby] is now 16 weeks old. For various reasons I am ready to give up on pumping and put him on formula. However, how do I deal with the guilt of now doing something that feels right for me instead of what’s obviously best for him?! Pumping is tiresome, I find it very hard to do other things like make healthy lunches for myself for example, and I’m going nuts with constantly washing and storing the paraphernalia.—postpartum Even though some mothers were themselves ready to stop pumping, they described difficulties related to family members who wanted them to continue to pump.I am mentally and physically exhausted from the strenuous schedule of pumping and taking care of a newborn. I return to work in one week and don’t want to stress about pumping there. Not to mention physically I am fed up [with] having boobs that weigh a million pounds, sweat, and hurt when I don’t pump every 2 to 3 h, specifically if I try to sleep longer. [My husband] wants me to continue to pump [because] he feels like the benefits outweigh all the physical, mental and emotional stresses I’m going thru. What would You do?—postpartum Some mothers reported or anticipated physical discomfort  that would result from stopping pumping and asked for advice on how to manage it. Both mothers who experienced and anticipated this discomfort asked how long it typically took for HM supply to dry up. Mothers who anticipated this discomfort in the future asked whether weaning gradually or all at once would lead to less pain.The findings presented here provide the first detailed insights into the information women seek from each other online about pumping and providing pumped HM. In this work, we identified a range of questions asked by pregnant and lactating women about these practices, which are paraphrased in Our findings highlight the need for comprehensive, evidence-based best practice guidelines for safe storage and preparation of pumped HM. Previous research has shown that the additional handling involved in pumping, storing, and preparing pumped HM may increase the risks of infant infections ,25. In tThere is also an indication of a need for clearer guidelines from insurance providers on how to obtain pumps as well as earlier access to pumps. In this study, we observed that many women relied on their health insurance policies to obtain pumps. However, women asked a range of questions about how and where they could obtain pumps, which suggests that they need guidelines on this process that are more understandable and readily available. Furthermore, the frequency of these questions in the prenatal period suggests that some women may prefer and benefit from earlier access to pumps from their insurance providers. Previous research suggests that, for mothers of very low-birth-weight infants, pumping in the first hour postpartum is important to mothers’ long-term HM output ,27. The Many of the mothers on BabyCenter reported feeling emotionally burdened by pumping in the early postpartum period, which suggests that mothers may benefit from more support from their partners and families. Social support, such as education about breast pumps from friends and relatives, is positively associated with longer durations of feeding HM . MothersMothers on BabyCenter also reported obstacles specific to pumping at work, which indicate that they may benefit from more support from employers and coworkers in managing and reducing such obstacles. These obstacles, such as inflexible work arrangements and lack of a designated place to pump, may explain, in part, why working IFPS II mothers who only pumped at work stopped feeding HM earlier than mothers who also, or only, fed their infants at the breast at work ,19. ThusThe qualitative work described here is not without its limitations. First, the sample of posts came from an open group of women whose demographic characteristics are unidentified, so the findings may not be generalizable to the larger population. For example, the analyses may not have captured the knowledge sought by women of lower income, who may not have access to the Internet or smartphones. Second, some posts on BabyCenter were randomly and irretrievably removed from forums for unspecified reasons and, as such, it is likely that some posts related to pumping and providing pumped HM were not collected. However, we gathered data every other day until the end of data collection period to reduce the number of missed posts. Third, when dividing posts into three intervals, we assumed that all infants in the April 2014 Birth Club were born on April 1, 2014. Thus, some questions may have been grouped in the incorrect postpartum interval, introducing unknown bias into the tally of questions in each interval. However, we expect such misclassification to be minimal in the prenatal and 0–1.5 months intervals, as many mothers indicated whether they were still pregnant or had recently delivered. Moreover, we do not anticipate that this limitation materially impacted the content or reliability of these findings. Finally, we did not analyze the responses to the women’s questions. Thus, the knowledge exchanged among mothers through their responses is an area of interest for further research. This work also has several strengths. First, the study methods and analyses were informed by analyses of IFPS II data  and by fThe findings presented here illustrate a wide range of information that women sought on social media about pumping and providing pumped HM to their infants. This information may represent what women are not receiving from their health professionals or insurance providers. This information may also suggest modifiable constraints to women’s practices for pumping and providing their milk. The questions women asked about how to safely store and prepare their pumped HM indicate their need for comprehensive, evidence-based guidelines for these practices. Furthermore, these findings highlight that mothers and their infants may benefit from early receipt of pumps and access to clearer guidelines from insurance providers on how to obtain pumps. Finally, this study highlights the difficulties women face in attempting to pump their milk at home and at work and, thus, identifies potential avenues through which families and employers may help women meet their goals for pumping and providing HM.


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


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.