Ring‐closing C−H activation allowed for the convenient preparation of six singly and six doubly nitrogen‐substituted indolocarbazole derivatives in which ten of the materials have not been described in the literature before. The detailed photophysical and electrochemical characterization of the developed materials revealed a significant impact of the incorporation of pyridine‐like nitrogen into the fully planar indolocarbazole backbone. Furthermore, the nitrogen position decisively impacted intermolecular hydrogen bonding and thus the solid‐state alignment. Ultimately, the versatility of the azaindolocarbazoles scaffold makes this class of materials an attractive new building block for the design of functional organic materials.The preparation and characterization of 12 azaindolo[3,2,1‐ The development of π‐conjugated small molecules with tailored molecular properties has been one of the major driving forces for the rapid development of the field of organic electronics over the last decades.jk]carbazole (ICz) as new building block for optoelectronic materials.Recently, we introduced indolo3,2,1‐‐jkcarbazjk]carbazole as a building block for optoelectronic materials, we set out to further expand the concept of planarization to intrinsically modulate the acceptor strength by incorporation of electron‐withdrawing pyridine‐like nitrogen atoms into the ICz moiety  direction ; these rods surround the solvent filled voids.1,10NICz, in contrast, consist of two crystallographically independent molecules. These molecules are connected by H2⋅⋅⋅N10′ and H9′⋅⋅⋅N1 contacts, with each molecule of the pair acting as donor and acceptor  forming chains extending in the [010] direction. The two crystallographically independent molecules are nearly coplanar (angle between LS planes: 3.65°). Analogous to 2NICz and 2,5NICz, the chains are connected to layers by π–π interactions . Notably, the arrangement of the 1,10NICz chains closely resembles the structure formed by 2,5NICz (second polymorph). Chains in neighboring layers propagate in the same direction and the angle between the chains is 56.41° . In contrast to 1,10NICz these molecules are not related by pseudo‐symmetry. Molecules of the first kind are connected by C−H⋅⋅⋅N hydrogen bonds, in which each molecule connects to two others, acting as hydrogen‐bond donor and acceptor, respectively. Because the donor  and acceptor (N6) atoms are in close vicinity, a strong twisting of the two connecting molecules is required  and their LS planes are spaced by only 3.26 Å, indicating a strong interaction of the π systems .Finally, the entire 6,10NICz, only one of the N atoms is involved in hydrogen bonding. Similar to 6NICz, the connected molecules (related by a 21 screw rotation) are distinctly non‐coplanar (angle between LS planes: 53.0°). In the resulting chains , pairs of molecules are again connected by intrachain π–π interactions (distance between LS planes: 3.41 Å) and form rods along [100]. Thus, even though the chains are related topologically to one of the 6NICz chains (considering hydrogen bonding and π–π interactions), the actual geometry of the chains is influenced distinctly by packing effects. The chains are packed in a checkerboard pattern connected only by van der Waals interactions ; the rods are packed by van der Waals interactions .1NICz and 7NICz. Notably, the sole pyridine‐like nitrogen of these two compounds is located next to the annulation position and thus is not effectively available for hydrogen bonding due to steric reasons. Although the interactions between isolated molecules of the developed compounds are similar, the position of the nitrogen has a decisive impact on the exact packing of the crystals. Thus, depending on the nitrogen position one‐ or two‐dimensional supramolecular arrangements are formed. Compounds lacking hydrogen bonds are organized in rods by π–π stacking; the rods are packed by van der Waals interactions . When hydrogen bonding is possible, chains are formed and connect to neighboring chains by π–π stacking to ultimately form layers . Notably, the propagation direction of chains in adjacent layers depends on the nitrogen position. If the geometrical requirements of the hydrogen bonds prevent linear propagation of the chains in the direction of the molecular axis (C2−N8), twisted chains form and π–π stacking occurs between molecules of the same chain . In such a way, the chains are arranged to one‐dimensional rods.In summary, the investigated NICzs exhibited a rich crystallization behavior, in which π–π stacking and non‐classical C−H⋅⋅⋅N hydrogen bonds proved to be structure‐determining factors. Although all compounds featured π–π stacking of the planar aromatic scaffolds, intermolecular hydrogen bonds were not formed in crystals of jk]carbazoles as well as three symmetric doubly substituted derivatives and their unsymmetrical regioisomers. Notably, the presented C−H activation approach not only allows for the preparation of the azaindolocarbazole congeners described in this work, but the developed oxidation–reduction strategy also enables one to control the regioselectivity of the ring‐closing C−H activation step. Therefore, many other doubly substituted regioisomers are now accessible employing this method and additional nitrogen incorporation can be achieved. We investigated the photophysical and electrochemical properties as well as the solid‐state interactions of the developed materials and revealed the impact of nitrogen incorporation in different positions of the indolocarbazole scaffold. Ultimately, we have provided synthetic chemists with a toolbox full of NICz building blocks. The established structure–property relationships and the possibility to tune their molecular properties and control the supramolecular arrangement of individual molecules predestines the class of azaindolocarbazoles as a novel molecular platform and could guide material scientists in the design of functional organic materials with tailored properties.We have described the convenient synthesis of all six possible mono‐substituted azaindolo[3,2,1‐2O. Screening reactions were performed in glass vials under argon atmosphere in a controlled heating block using argon‐saturated substrate solutions including 1‐methylnaphthalene as internal standard as well as a catalyst solution. All screening experiments were performed three times independently. The depicted results represent the mean of these experiments. Yields of the screening reactions were determined by GC using a Thermo Scientific TRACE 1310 gas chromatograph with dual configuration consisting of two AS 1310 autosamplers, Thermo Scientific TR‐5MS columns and FID detectors. Absorption and photoluminescence measurements were conducted using a PerkinElmer Lambda 750 spectrometer and a PerkinElmer LS 55 fluorescence spectrometer, respectively. CH2Cl2 solutions (5 μm) were employed for solution measurements whereas phosphorescence spectra were recorded at 77 K using solid solutions of the materials in toluene/EtOH  with a delay of 1 ms. Cyclic voltammetry was measured using a three‐electrode configuration consisting of a Pt working electrode and counter electrode, and an Ag/AgCl reference electrode and a PGSTAT128N potentiostat provided by Metrohm Autolab B.V. The measurements were carried out in a 0.5 mm solution in HPLC‐grade acetonitrile employing nBu4NBF4 (0.1 m) as supporting electrolyte. Prior to the measurements, the solutions were purged with nitrogen for approximately 15 minutes. The HOMO and LUMO energy levels were calculated from the onset of the oxidation and reduction peaks, respectively. The onset potential was determined by the intersection of two tangents drawn at the background and the rising of the oxidation and reduction peaks. Synthetic details are described in the Supporting Information.All reagents and solvents were obtained commercially and used without further purification. Anhydrous solvents were prepared by filtration through drying columns. The water content of purchased DMA was determined by Karl Fischer titration using a Mitsubishi CA‐21 Moisture Meter and corrected to 3000 ppm for C−H activation screening reactions. Given that further experiments indicated no significant impact of the water content on the reaction outcome, large scale experiments were conducted using unmodified DMA with roughly 100 ppm HGeneral procedure for C−H activation: A glass vial was charged with the corresponding halogenated precursor (1 equiv.), K2CO3 (2 equiv.), and (NHC)PdCl (5 mol %) and flushed with argon. After addition of 10 mL mmol−1 degassed DMA, the reaction was stirred under argon atmosphere at 130 °C until full conversion was reached (4–8 h). After cooling, the reaction mixture was poured into water and repeatedly extracted with CH2Cl2. The organic phases were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by column chromatography.Computational details: DFT calculations were performed using the Gaussian 09 packageSingle‐crystal diffraction: X‐ray diffraction data of 1NICz⋅xCH3CN, 2NICz, 5NICz, 6NICz, 7NICz, 1,10NICz, 2,5NICz, and 6,10NICz were collected at T=100–270 K in a dry stream of nitrogen on a Bruker Kappa APEX II diffractometer system using graphite‐monochromatized MoKα radiation (λ=0.71073 Å) and fine sliced ϕ‐ and ω‐scans. Data was reduced to intensity values with SAINT and an absorption correction was applied with the multi‐scan approach implemented in SADABS or TWINABS.F2 with JANA2006.1NICz using the SQUEEZE routine of the PLATON2NICz, 5NICz, and 1,10NICz crystallize as twins by pseudo‐merohedry. Compound 7NICz forms twins with non‐overlapping reflections and was refined against HKLF5 data with information on reflection overlap. The absolute structure of non‐centrosymmetric crystals  was not determined owing to a lack of resonant scatterers. Molecular graphics were generated with the program MERCURY.CCDC 1864321 , 1864322 (1NICz⋅xCH3CN), 1864323 , 1864324 (2NICz), 1864325 (5NICz), 1864326 , 1864327 (6NICz) and 1864328 (7NICz) contain the supplementary crystallographic data. These data can be obtained free of charge by The Cambridge Crystallographic Data Centre.tion λ=0.073 Å andThe authors declare no conflict of interest.As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re‐organized for online delivery, but are not copy‐edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.SupplementaryClick here for additional data file.


CLL) cannot be fully accounted for by the 17p deletion (and/or TP53 mutation), a complex karyotype (CK), immunoglobulin heavy‐chain variable region genes (IGHV) status and gene mutations. Hence, we sought to assess the associations between recurrent genomic abnormalities in CLL and the disease's development and outcome. To this end, we analyzed 64 samples from patients with CLL and gain of the short arm of chromosome 2 (2p+), which is frequent in late‐stage and relapsed/refractory CLL. We found that fludarabine/cyclophosphamide/rituximab (a common first‐line treatment in CLL) is not effective in removing the 2p+ clone ‐ even in samples lacking a CK, the 17p deletion or unmutated IGHV. Our results suggest strongly that patients with CLL should be screened for 2p+ (using karyotyping and fluorescence in situ hybridization) before a treatment option is chosen. Longer follow‐up is now required to evaluate bendamustine‐rituximab, ibrutinib, and idelalisib‐rituximab treatments.The different types of drug resistance encountered in chronic lymphocytic leukemia ( The prevalence of CLL increases with age, and its clinical profile ranges from CLLs that may not require treatment to others that progress aggressively.Chronic lymphocytic leukemia  is characterized by the progressive accumulation of mature CD5TP53 mutation) is associated with the worst prognosis.TP53 mutations are found in up to 40% or 50% of patients with relapsing or refractory CLL, other genetic abnormalities may also be associated with drug resistances.Genetic alterations  have prognostic value in CLL, due to their significant impact on the drug response and overall survival (OS).IGHV) status. Moreover, we have shown that the gene coding for exportin 1  has a central role in drug resistance in 2p+ CLL.REL and MYCN) might also be associated with CLL drug resistance.We and others have previously reported that the gain of the short arm of chromosome 2 (2p+) is recurrent and frequent in late‐stage CLL (corresponding to about 15% of patients).With a view to gaining a better understanding of prognostic and drug resistance factors in CLL, we have evaluated the role of 2p+ in disease progression and its response to treatment.22.1IGHV status. Longitudinal cytogenetic analyses (ie at least two samples over time) were available for 26 of the 64 patients included in the study. In line with the ethical tenets of the Declaration of Helsinki, all the patients provided their informed consent to participation in the study. The study protocol was approved by the local investigational review board  on 21 May 2014.We retrospectively collected data on 47 patients with 2p+ CLL, all of whom were diagnosed and/or treated at Pitié‐Salpêtrière Hospital  between 1990 and 2018. We also included 17 patients with 2p+ CLL who had been included and prospectively assessed by other centers as part of the ICLL1 BOMP trial .2.2To obtain R‐banded chromosomes, cells from peripheral blood samples were stimulated with CpG‐oligonucleotides and interleukin‐2 (IL‐2) in culture for 72 hours, using standard techniques.XPO1 (RP11‐240F4+RP11‐477N2), REL (RP11‐373L24) and BIRC3 (RP11‐177O8) genes were selected using the University of California Santa Cruz Genome Bioinformatic database (NCBI37/hg19 build) and obtained from Genoscope . Results were recorded using a fluorescent microscope (Olympus) with appropriate filters, and Isis imaging software . All FISH preparations were scored by two independent assessors, with at least two independent counts of 100 nuclei/probe/assessor.Fluorescence in situ hybridization (FISH) was performed on metaphase and interphase nuclei, using the following panel of probes: MYCN , TP53/ATM , LSI D13S319/12cen , and “home‐grown” bacterial artificial chromosome probes for the 2.3Single nucleotide polymorphism (SNP) array analyses were performed as described previously.2.4TP53 mutations were analyzed using: (a) Sanger sequencing of exons 4‐10 (n = 2); (b) next‐generation sequencing on a MiSeq® system  using the CLL MASTR PLUS kit  (n = 6); or (c) as previously described in the report on BOMP trial (n = 11).For patients with more than one sample, 2.5IGHV mutation status, XPO1/REL/MYCN gain (homogeneous gain vs heterogeneous gain). Quantitative variables were reported as the median (range) or the median [95% confidence interval (CI)], and categorical variables were reported as the number (percentage).The time to first treatment (TTFT) was defined as the time interval between diagnosis and first‐line treatment. The OS time was defined as the time interval between diagnosis and death or (in the absence of death) last follow‐up. OS was analyzed using the Kaplan‐Meier method. The log‐rank test was used for intergroup comparisons of TTFT or OS curve. The variables analyzed were CK, HCK, del(13q), del(11q), 33.1IGHV status was unmutated in 50 of the 56 tested patients (89%).A total of 64 patients with 2p+ CLL were included in the study. Most of the patients were male , and the median (range) age at diagnosis was 60 (42‐78) Table . Of the The median (range) number of lines of treatment was two (0‐8). Twenty‐eight of the 64 patients (44%) died during the study period, with a median follow‐up from diagnosis of 79 months (0‐317). At last follow‐up, 61 of the 62 patients with available data (98%) had been treated Table .All 64 patients had a 2p+ , and 53 of them had been successfully karyotyped. Seven of these 53 patients 13%) had a normal karyotype (K), and 28 (53%) had a CK, including 14 (26%) HCKs. The results were similar when we considered only the 35 patients who had not been treated before karyotyping  Ks Table ; it was Using FISH and/or an SNP array, del13q) was identified in 39 of the 64 patients (61%), del(11q) in 34 (53%), del(17p) in 16 (25%), and tri12 in two (3%). When considering only the patients who had not been treated before analysis, the results were quite similar , we performed a locus‐specific FISH analysis of the 48 patients with available material  was gained in a higher proportion of tumor cells than the 2p24 region (MYCN) in eight of the 48 patients (17%). In five of these eight patients, a gain of the MYCN gene was not detected at all. Only two (4%) patients had a higher percentage of cells having gained the 2p24 region (including MYCN gene) than cells having gained the region 2p15‐16 (including the XPO1 and REL genes).To investigate the three main genes located on the short arm of chromosome 2  for 50 patients.ATM deletion, and 20 of these 24 cases (83%) had a BIRC3 deletion. In four of the 24 cases (25%), we observed the deletion of ATM alone, while none of the patients had a BIRC3 deletion alone. The percentages of cells with a deletion were similar for both genes in all cases. The median (range) percentage of cells with a deletion was 71% (11%‐99%)  Figure B.3.2P = .04). There were no statistically significant differences in the impact on OS for all the analyzed parameters , in whom a MYCN gain was detected at relapse (XPO1 and REL had been gained before treatment). The median (range) number of lines of treatment was two (1‐8), and the patients were assessed in detail as a function of the drugs included in each treatment regimen.We next analyzed the change in the 2p+ clone and recurrent chromosomal abnormalities in patients treated with a panel of drugs Table . To excl3.43.4.1Sixteen of the 19 patients treated with FCR in the longitudinal subgroup relapsed, after a median (range) time interval between the end of treatment and relapse of 24 months (5.4‐78); the other three patients have not finished their course of treatment. Cytogenetic data before front line FCR and at relapse  were available for six patients (Table ATM and BIRC3 in one patient (CLL_37), and ATM only in the other (CLL_40). In patient CLL_40, del(17p) was detected after FCR treatment, along with a HCK , the percentage of 2p+ cells was stable at relapse. Furthermore, the clone del(13q) remained large and stable in one patient (CLL_40) but could no longer be detected in the other (CLL_37). The clone del(11q) also remained large and stable in both patients; the deletion encompassed ATM and BIRC3. In patient CLL_12, the frequency of 2p+ and del(11q) had doubled after FCR treatment. Interestingly, del(11q) was detected at diagnosis in patient CLL_1; the 2p+ appeared after treatment  and CK) but the del(11q) disappeared  at relapse. The del(13q) remained stable in one of these patients (CLL_32) but disappeared in a second (CLL_42)  were stable but a del(13q) clone appeared (Table 1q were s3.53.5.1One patient (CLL_53) underwent splenectomy, and received chlorambucil and then FCR. The percentage of cells with 2p+ and del13q) remained stable at the time of relapse  with an elevated del(11q) clone at relapse, the deletion involved ATM alone in CLL_59 only. The number of karyotype abnormalities increased in five of the seven patients with available data.A total of 17 of the 64 patients were included in the BOMP trial, including one patient with a detectable 2p+ clone at relapse. All of them relapsed, with a median (range) time from inclusion to relapse of 13 months (5.4‐38.2). Cytogenetic data before BOMP treatment and at relapse  were available for 11 patients . It is noteworthy that even though three patients were in clinical remission , the abnormalities were still present in karyotyping and FISH analysis.Five patients with available cytogenetic data received ibrutinib, after 1‐6 other lines of treatment Table A. The pe3.6.2Two patients with available cytogenetic data were treated with idelalisib‐R after two other lines of treatment Table . In patiATM alone or both ATM and BIRC3 , the different treatment groups did not differ in terms of whether del(11q) encompassed C3 Table . The siz4IGHV status (in 89%) and—to a lesser extent—del(17p) (in 19%).IGHV and HCK.Here, we presented a detailed cytogenetic analysis of what is (to the best of our knowledge) the largest yet cohort of patients with 2p+ CLL (n = 64). A longitudinal analysis was possible in 26 cases (ie patients with more than one sample collected over the course of the disease). Our first key observation was that the male‐to‐female ratio 3.9:1) is higher than the one reported for CLL in general (1.5‐2:1).tent—del1p  was present in more than a half of our cohort of 2p+ CLL cases, we investigated the two genes. We found that del(11q) involves both genes in the majority of cases, and that BIRC3 is never deleted alone  is associated with a variety of tumors, including neuroblastoma.REL encodes a member of the NF‐Κb family of transcription factors involved in cell growth and differentiation, and is overexpressed in Hodgkin's lymphoma.XPO1 (coding for exportin 1) in the drug resistance associated with 2p+.MYCN is not gained. We therefore recommend investigating these two regions using FISH. As MYCN is never gained alone, at least one probe encompassing REL or XPO1 should be used.As 2p gain often involves the whole short arm of chromosome 2, we decided to study two previously described minimal regions of gain: 2p24 and 2p15‐16.IGHV status).IGHV‐U, del(17p), del(11q), and CK).To evaluate clonal changes in patients with 2p+ CLL, we assessed the consequences of different drug treatments on 2p gain and other abnormalities. Nineteen patients were treated with FCR; this remains a major first‐line option for many patients with CLL, and is considered to be effective in cases with favorable features  relapsed at 26 months but more follow‐up is required for the other two patients. Hence, we are not yet able to draw conclusions about BR and 2p+ CLL.Eleven patients received BOMP therapy. This regimen included the fully humanized anti‐CD‐20 antibody ofatumumab, which is considered to be feasible and effective in patients with relapsed/refractory CLL ‐ including those with high‐risk clinical and laboratory features.A number of new treatment options have recently emerged for patients with CLL, including inhibitors of Bruton's tyrosine kinase (ibrutinib) and phosphatidyl‐inositol 3‐kinase .IGHV status. The gain can appear during natural disease progression or after treatment. The commonly used first‐line treatment FCR is not effective with regard to the 2p+ clone, even when a CK or del(17p) is absent. Treatment with BOMP appears to have an effect on the 2p+ clone in some patients. We need more follow‐up data for ibrutinib, idelalisib‐R, and bendamustine‐R. Overall, our results strongly suggest that it is essential to systematically screen for 2p gain (using karyotyping and FISH) to better characterize CLL.In conclusion, the results of our large study indicate that 2p gain is frequent in relapsed/refractory CLL. The 2p gain is also associated with male gender, a HCK, del(11q), del(17p), and unmutated  Click here for additional data file. Click here for additional data file. Click here for additional data file. Click here for additional data file. Click here for additional data file. Click here for additional data file.


Conversely, graphene has a 2D layered structure, possessing an exceptionally large specific surface area and high carrier mobility. Likewise, other emerging graphene‐analogous 2D nanomaterials, such as graphitic carbon nitride (g‐C3N4), transition‐metal dichalcogenides (TMDs), hexagonal boron nitride (h‐BN), and black phosphorus (BP), show unique electronic, physical, and chemical properties, which, however, exist only in the form of a monolayer and are typically anisotropic, limiting their applications. Upon hybridization with fullerenes, noncovalently or covalently, the physical/chemical properties of 2D nanomaterials can be tailored and, in most cases, improved, significantly extending their functionalities and applications. Here, an exhaustive review of all types of hybrids of fullerenes and 2D nanomaterials, such as graphene, g‐C3N4, TMDs, h‐BN, and BP, including their preparations, structures, properties, and applications, is presented. Finally, the prospects of fullerene‐2D nanomaterial hybrids, especially the opportunity of creating unknown functional materials by means of hybridization, are envisioned.Fullerene has a definite 0D closed‐cage molecular structure composed of merely sp In particular, g‐C3N4, with a moderate band gap and indirect‐semiconductor nature, has become a promising metal‐free catalyst for water splitting and the degradation of pollutants due to the advantages of low cost and high specific surface area (2500 m2 g−1 for the monolayer) and has been applied in organic solar cells.3N4 exhibits a poor electrical conductivity and low photocatalytic activity owing to the rapid recombination of photogenerated electron–hole pairs. Thus, improvements in the photocatalytic activity of g‐C3N4 to extend this material to further applications are highly desired. To this end, the hybridization of g‐C3N4 with other functional materials, including fullerenes, has been developed in recent years and appears feasible since the polymeric nature of g‐C3N4 renders the chemical structure flexible.During the last decade, several other types of emerging graphene‐analogous 2D nanomaterials have been discovered.2, consisting of hexagonal rings with Mo and S atoms alternately located at the hexagon corners, is the most representative TMD with a direct band gap in monolayer form and high in‐plane carrier mobility, thus being suitable for versatile applications in electro and photocatalysis, photovoltaics, and photoelectric devices.2 in photocatalytic H2 production, since only its edges have a high catalytic activity, whereas its basal plane is inactive, a low photocatalytic activity has been achieved, even for single‐layer MoS2. Consequently, MoS2 is generally applied as a cocatalyst loaded on conventional metal‐based semiconductor photocatalysts, such as TiO2, CdS, and ZnO, to reduce the energy barrier of water splitting and to increase the stability of the photocatalysts. To enhance the photocatalytic H2 production activity of MoS2 itself, the construction of nanocomposites composed of MoS2 and other functional materials, such as graphenes and fullerenes, provides a practical solution.3N4 and the TMD MoS2, no Review has reported their hybridization with fullerenes, which is crucial for understanding such intriguing 0D–2D hybrid systems.The inorganic transition‐metal dichalcogenides (TMDs) represent another type of emerging 2D semiconducting nanomaterial and have been attracting widespread attention due to their intriguing electronic, optical, and mechanical properties.3N4, TMDs, h‐BN, and BP, all types of hybrids of fullerenes and 2D nanomaterials reported to date are exhaustively reviewed, with emphasis on the exclusive impact of fullerenes with unique electronic and chemical properties on the electronic and band structures of 2D nanomaterials. Upon attachment of fullerene molecules, noncovalently or covalently, the physical/chemical properties of 2D nanomaterials can be tailored, and in most cases, improved, and the mechanisms responsible for such improvements are discussed in detail. Furthermore, fullerene incorporation may induce new properties in 2D nanomaterials as a result of strong intermolecular interactions, thus extending the functionalities and applications of 2D nanomaterials. At the end, we envision the prospects of fullerene‐2D nanomaterial hybrids, especially the opportunity of creating unknown functional materials by means of hybridization.In this Review, we focus on the hybrids of 0D fullerenes and 2D nanomaterials, including their preparations, structures, properties, and applications. Based on known 2D nanomaterials, such as graphene, g‐C22.1TableNoncovalent hybridizations of fullerenes and graphenes have been fulfilled by depositing fullerene onto a graphene layer to form a graphene/fullerene bilayer film and by physically blending pristine fullerenes or fullerene derivatives and graphenes see Table1.2.1.160 onto a graphene film to form a bilayer hybrid; in this way, the interfacial electronic interactions and charge transfer between C60 and graphene can be investigated. In 2015, Heinz et al. fabricated a C60/graphene hybrid by depositing C60 onto single‐layer graphene and studied the ground and excited‐state charge transfers at the C60/graphene interface by using Raman spectroscopy and THz time‐domain spectroscopy. The authors concluded that at equilibrium the C60 layer functioned as an electron acceptor affording hole doping of the graphene with an injection of ≈0.04 holes per interfacial C60 molecule at the surface of the bilayer hybrid, as well as a downshift of the graphene Fermi level by 160 meV , which provided a unique surface with humps and valleys facilitating the assembly of Cop Figure2.23 Th60 films onto graphene sample surfaces using a spray coating method and investigated the electrical interaction and charge transfer kinetics at the graphene/adsorbate interface by using flicker noise, as an insightful probe, in combination with Raman spectroscopy and DC‐transport measurements.60 deposition, which was attributed to the carrier trapping/detrapping processes in the hybrid system, finally leading to an enhanced charge noise. Meanwhile, the charge exchange process was significantly suppressed with decreasing temperatures, indicating that the flicker noise acted as a powerful probe to elucidate the nature of the charge transfer in the graphene–fullerene hybrid device. Furthermore, the authors fabricated graphene field‐effect transistors to quantitatively evaluate the charge transfer between C60 molecules and graphene and found that a large number of carriers with a high Fermi energy for n‐doped graphene may overcome the energy barrier to occupy the LUMO of C60 molecules compared to that of p‐doped graphene.60 was estimated to be 0.6–1.3 × 1012 cm−2, ≈0.01 electrons captured by a single C60 molecule.In 2013, Qiu and co‐workers constructed a fullerene/graphene hybrid device by depositing self‐assembled C60 onto FLG films prepared by a chemical vapor deposition (CVD) technique. The electrical conductance of the C60/FLG system decreased when the system was under illumination and was attributed to a kind of negative photoconductivity.60/FLG system varied, FLG exhibited p‐type doped characteristics under low light intensities and presented n‐type doped behavior for high light intensities.Likewise, in 2014, Mendoza et al. constructed a fullerene/few‐layer graphene (FLG) bilayer system by thermally evaporating C60–graphene vertical heterostructure with a well‐ordered film morphology on the graphene, as confirmed by transmission electron microscopy (TEM).60 crystal and graphene lattice directions. The preferential growth of C60 crystals is prone to graphene's zigzag and armchair directions. Moreover, the C60–graphene vertical junction‐based transistors showed n‐type transport behavior. The energy barrier modulation at the C60–graphene Schottky junction can achieve a high on/off ratio above 3 × 103, which is difficult to obtain for conventional graphene transistors. Thus, graphene is demonstrated to offer an excellent substrate for the epitaxial assembly of organic semiconductors toward electronics applications.Later, in 2015, Bao et al. fabricated a C60 molecules at the graphene/Cu interface by annealing led to amorphous and crystalline structures.60 molecules imprinted a local strain/deformation on the graphene layer with various magnitudes controlled by the intermolecular distance.In the same year, Reinke and co‐workers reported that the intercalation of C60 molecules were encapsulated by two layers of graphene  results in the Fermi‐level energy of the system to align inside the broadened LUMO. When the gate voltage is changed, the charge transfer to the molecule increases through the Dirac  point of graphene to the electron‐doped side , resulting in a Fermi level deeper inside the LUMO.Bilayer films comprised of graphene and fullerene derivatives have also been studied. In 2011, Lofwander and co‐workers constructed a single‐molecule device consisting of graphene and a fullerene derivative, where the graphene was patterned to form a nanogap and can be used as electrodes for gate‐tunable molecular electronics, and a dumbbell fulleropyrrolidine consisting of a central wire of 1,4‐phenylenediamine attached to C60 end‐capped molecular wire comprised of two styrene units covalently connected via a paracyclophane moiety in the center, Weber and co‐workers fabricated graphene–fullerene–graphene junctions with ultraflat, transparent, and robust graphene nanogaps. The single‐molecule contacts were confirmed according to the measured I–V curves, which were similar to those obtained with the mechanically controlled break junction technique. Additionally, nonlinear I–V curves were obtained in a very low yield when molecules were applied at low concentration, thus ruling out the possibility of larger numbers in the junction.Similar single‐molecule junctions employing a fullerene derivative were later constructed by several other groups. In 2015, using a C60 bisadduct used as the junction and observed the redox‐dependent Franck–Condon blockade and avalanche transport phenomena. The C60 bisadduct was synthesized through a 1,3‐dipolar cycloaddition reaction between C60, 1‐pyrene carboxaldehyde, and N‐methylglycine.60 with pyrene anchor groups was verified to effectively modify the electron delocalization and energy levels, leading to HOMO‐dominated transport.f) to the microheater and measuring the thermovoltage (Vth) drop across the device at a frequency (2f) for different back gate voltages (Vg),kBT0 at the operating temperature, and (3) the tunnel couplings to the left and right electrodes need to be equal to achieve a maximum power factor.In 2016, Mol and co‐workers studied a similar graphene–fullerene–graphene single‐molecule transistor with a pyrene‐functionalized C2.1.260 into graphene nanosheets prepared by the exfoliation of a bulk graphite crystal and followed by a reassembling process.60 physical blend increased from 540 to 784 mAh g−1 after the incorporation of C60.60 hybrid, in 2015, Lee and co‐workers carried out DFT studies and found that charge transfer from the graphene to the C60 took place in the graphene–C60 hybrid system, leaving the graphene positively charged (+0.095 e) and the C60 negatively charged (−0.095 e). As a result, Li ions preferentially adsorbed on the C60 side, particularly in the midway region between graphene and C60 or between two C60 molecules.60 hybrid system (−2.285 eV) was higher than that on bare graphene (−1.375 eV), indicating that the Li adsorption on the graphene–C60 hybrid system is more stable.Noncovalent hybrids of fullerenes with graphene have also been facilely prepared by physically blending both components. In 2008, Honma and co‐workers reported a graphene–fullerene physical blend by incorporating C60, pristine single walled carbon nanotubes (SWCNTs), and GO sheets.60/SWCNTs/GO exhibited a surface roughness of only a few nanometers. After the thermal reduction of GO, the as‐prepared C60/SWCNTs/rGO composite was utilized as the active layer of a photovoltaic device  of 1.23 mA cm−2, an open‐circuit voltage (Voc) of 0.59 V, a fill factor (FF) of 0.29, and a power conversion efficiency (PCE) of 0.21%. Such a decent PCE was attributed to the presence of numerous clean p–n junctions distributed throughout the all‐carbon hybrid, facilitating the spontaneous dissociation and subsequent separation of the photogenerated excitons along the bicontinuous heterojunctions.60 with C70 in both the active layer and blocking layer, a nearly fourfold increase in Jsc from 1.23 to 4.95 mA cm−2 was achieved, leading to a dramatic increase in PCE from 0.21% to 0.85%.In addition to pristine graphene (pG) sheets, exfoliating graphite flakes to few‐layer graphene via chemical functionalization is currently commonly used as the most cost‐effective method of obtaining graphene due to its easiness, reliability, and scalability.ce Figure4, affo60 with rGO by the liquid–liquid interfacial precipitation method, resulting in rGO‐wrapped C60 wires.π–π interactions between rGO and C60. FET devices fabricated with rGO/C60 wires exhibited a p‐type semiconducting behavior both in vacuum and in air, indicating that the rGO, as a shell layer, can transport holes effectively. However, the pure C60 wires and rGO sheets showed n‐type and ambipolar behaviors, respectively, in vacuum. Furthermore, the photovoltaic devices based on rGO/C60 wires as the active layer exhibited a significant enhancement in short‐circuit current (JSC) from 0.07 to 0.19 mA cm−2 compared to the devices based on a pure rGO active layer. This result can be interpreted as the photoinduced electron transfer from rGO to C60 under light irradiation.Several efforts have since been made to prepare hybrid materials based on GO or reduced graphene oxide (rGO). In 2011, Shin and co‐workers reported the preparation of hybrids of C60/C70 with GO by a simple grinding method, and the material exhibited a solubility of 5.0 mg mL−1 in water when the weight ratio of the fullerenes to GO was 1:3 , a PTA–GO–fullerene nanofilm was further fabricated by a one‐step electrodeposition. Compared to either PTA or PTA–GO‐modified electrodes, the PTA–GO–fullerene composites showed improved catalytic activity for the oxidation of a variety of small biomolecules, including dopamine (DA), with enlarged peak currents and an apparent negative shift of peak potentials  were found to be sensitive to the direct oxidation of CJ and provided a short analysis time, convenience, and good accuracy.60–GO/GE was because the partially reduced C60 in the electropolymeric process exhibited a favorable conductivity as an effective electron‐transfer medium compared to that of the pure GO film.In 2013, Hu and co‐workers prepared a noncovalent hybrid of C:3 Figure5A.84 T60 composite by electrochemical reduction of a GO–C60 composite, which was then used as an immobilization matrix for GOx.i–t response of an rGO–C60/GOx‐modified electrode to different concentrations of glucose and in constantly stirred oxygen‐saturated phosphate buffer saline (PBS) with a working potential of −0.42 V showed that the amperometric reduction current decreased with the increase in glucose concentration up to 14.6 × 10−3m.i–t response current for the biosensor exhibited a linear pattern against the concentration of glucose in a range of 0.1–12.5 × 10−3m. Hence, the rGO–C60/GOx‐modified electrode showed good analytical ability when used as a sensor for glucose over a wide response range with a low limit of detection, fast response time (3 s), and high sensitivity.60‐wrapped GO by using a simple sonication method, and the material was used to modify a glassy carbon electrode.60 hybrid showed a good sensitivity with a lower oxidation overpotential toward DA than did those of the pristine GO and C60. The as‐prepared sensor for DA detection exhibited a linear response in a range of 0.02–73.5 × 10−6m and a detection limit of 0.008 × 10−6m (based on 3σ) with a sensitivity of 4.23 µA µm−1cm−2. The GO–C60 hybrid‐based sensor also showed a wide linear response and high selectivity along with good practicality toward the detection of DA in rat brain and commercial DA injection samples.Electrochemical sensing applications of noncovalent hybrids of fullerene–graphene have also been reported by other groups. Given that the direct electron transfer properties of enzymes are helpful for studying key biological reactions and for the construction of biosensors and biofuel cells,60/graphene hybrid by using a simple solution reaction of GO and C60 in a lithium hydroxide (LiOH) saturated solution.60 particles on the GO surface served as spacers in the C60/graphene hybrid to support the graphene sheets. The noncovalent C60/graphene hybrid was employed as electrodes in a supercapacitor affording a capacitance of 135.36 F g−1 at a current density of 1 A g−1, which was higher than that based on pure graphene electrodes (101.88 F g−1). Furthermore, a remarkable retention rate of 92.35% after 1000 charge/discharge cycles was obtained, indicating the potential of the C60/graphene hybrid as a supercapacitor electrode.In addition to the applications of fullerene–graphene hybrids in solar cells and electrochemical sensors, fullerene–graphene hybrids have also been applied in supercapacitors. In 2014, Qin and co‐workers constructed a C60 molecules by self‐assembly and the Langmuir–Schaefer deposition technique.60–GO hybrid deposited on hydrophobic substrates was characterized by X‐ray diffraction, Raman and X‐ray photoelectron spectroscopies, atomic force and scanning electron microscopies, and conductivity measurements, confirming that C60 indeed existed in the hybrid multilayer system and that intercalation of fullerene into the interlayer space of the organo‐GO nanosheets did not affect the structure of GO itself. More importantly, a considerable improvement of an order‐of‐magnitude increase in the electrical conductivity for the C60–GO hybrid was achieved because of the presence of C60 intercalated between the graphene layers.Apart from physical blending, a new approach for constructing fullerene–graphene noncovalent hybrids was developed by Gournis and co‐workers in 2015. The approach was based on a bottom‐up layer‐by‐layer process, which proceeded via the formation of a hybridized organo‐GO Langmuir film, followed by the intercalation of C2.1.360–graphene hybrid in which alkylated C60 molecules self‐organized into nanoscale flake‐like films on a CVD‐grown graphene layer.60–graphene hybrid devices exhibited a clear and highly reproducible change in conductance upon visible‐light illumination due to the hole generation in the alkylated C60 molecules and the transfer of the holes to the graphene, as deduced from the upshift in the Dirac point and the broadening of the resistance. Moreover, a hole‐doping effect was observed in the C60–graphene hybrid devices, with carrier mobility decreasing from 286 to 208 cm2 V−1 s−1 upon illumination with visible light.Different from the pristine fullerenes, fullerene derivatives bear versatile functional groups grafted via chemical functionalization, facilitating their assembly on different substrates, including graphene films. In 2012, Kim, Lee and co‐workers constructed a C60 derivative based on ‐phenyl‐C61‐butyric acid methyl ester (PCBM) to rGO via the noncovalent approach in which pyrene was used as an anchoring bridge to link the rGO and PCBM components  owing to the intramolecular π–π stacking interactions between the graphene sheet and pyrene–PCBM. Importantly, according to the proposed geometric configuration of rGO–pyrene–PCBM, the C60 moiety was far from the graphene sheet and was bridged to the graphene sheet via the pyrene anchor. The rGO–pyrene–PCBM hybrid was then applied as an electron‐extraction material in P3HT:PCBM bulk heterojunction polymer solar cell (BHJ‐PSC) devices . The configurations of the fullerene–graphene hybrids were studied by molecular mechanics/molecular dynamics (MD) calculations, predicting that fullerene derivatives favorably interacted with graphene through both the pyrene base and the C60 moiety  matrix for improved thermal and mechanical properties. By using GO as the starting material, they prepared the C60@graphene hybrid (C60: ≈47.9 wt% and graphene: ≈35.1 wt%) via a three‐step reaction, with highly active amino groups introduced to react with C60 and contribute to the subsequent in situ reactive compatibilization reaction to improve the dispersion of the hybrid. The incorporation of 2.0 wt% C60@graphene (relative to PP) remarkably increased the initial degradation temperature by ≈59 °C and simultaneously enhanced the tensile strength and Young's modulus by 67% and 76%. The improvement in the thermal stability of PP was speculated to be due to the free‐radical‐trapping effect of C60 and the thermal barrier effect of the graphene layers, while the mechanical enhancement was mainly attributed to the reinforcing effect of the graphene nanosheets and the effective load transfer from the polymer matrix to the graphene sheets.Guo and co‐workers developed a new strategy to synthesize a C2.1.460, endohedral fullerenes (EMFs) with metal ions or metallic clusters entrapped in the carbon cage have been attracting considerable attention during the last two decades due to the charge transfer from the internal species to the outer carbon cage.3N@hI‐C80 is so far the most abundant and has an excellent stability superseding other conventional EMFs.3N)6+@(C2n)6−, resulting from the six‐electron transfer from the endohedral species to the carbon cage, renders an enhanced chemical reactivity and adsorption energy on surfaces compared with that of hollow fullerenes.3N@C80 absorbed on pristine graphene nanoflakes (GNFs). The Sc3N@C80–graphene noncovalent hybrid model was constructed, for which the simulated graphene nanoflake, composed of 96 C and 24 H atoms (C96H24) with symmetric hexagonal units, served as a support for the deposition of fullerenes in the center.60, which adsorbed on GNFs with an energy of 0.76 eV, Sc3N@C80 adsorption on the GNF resulted in a higher binding energy of 1.00 eV for nearly degenerate isomers that have a pentagon and a hexagon facing the single‐layer graphene (SLG). Such a large binding energy was explained in terms of a higher dispersion interaction between Sc3N@C80 and the GNF, and the fact that charge separation in Sc3N@C80 favored binding with the GNF.Different from hollow fullerenes, such as C2.2TableAlthough the noncovalent approach has been extensively used to construct fullerene–graphene hybrids, being facile and effective in achieving improved properties relative to the single components of fullerene and graphene, the determination of their chemical structures is difficult, making the manipulation of their structures and properties unrealistic. Additionally, the noncovalent nature renders relatively weak intermolecular interactions between fullerenes and graphenes. Thus, the covalent hybridization of fullerene and graphene is highly desired to construct hybrids in a controllable manner.2.2.160–graphene, termed as periodic graphene nanobuds (PGNBs) in which C60 molecules covalently attach to a graphene monolayer and form a periodic lattice structure  hybrid, termed as NanoBuds, prepared in continuous aerosol  reactors by using particles grown in situ via ferrocene vapor decomposition or by using premade iron‐catalyst particles produced by a hot‐wire generator. The authors proposed that fullerenes were formed on the iron‐catalyst particles together with SWNTs during CO disproportionation.re Figure8.17 Si54 structure was proposed by removing a six‐membered ring from C60. Four different kinds of connection positions for the C54 structure on graphene were investigated. In two cases, where six carbon atoms of graphene formed covalent bonds with the fullerene, the graphene–fullerene nanobuds were ferromagnetic at their ground states with magnetic moments of nearly 6 μB; whereas, for the other two cases, nonmagnetic states were found since the connections of two atoms in different sublattices of graphene could not generate unpaired spins.Likewise, in 2011, Li et al. designed four kinds of all‐carbon graphene–fullerene nanobuds and studied their magnetic properties by spin‐polarized DFT.60 hybrid.60 onto the carbons at the edges of the defect did not have priority over attaching to a pristine graphene sheet because the distortion of the ideal π system in graphene perturbed the π–π stacking interactions with the fullerene and forced the fullerene to avoid the defective surface of graphene.Deymier et al. adopted the self‐consistent charge density functional tight‐binding (DFTB) and DFT methods to evaluate energy barriers for the formation of a single‐layer graphene−C180, C320, C540, and C720) as sandwich cores. According to their calculation results, dangling bonds on the reciprocal locations of both graphene and fullerenes promoted the formation of covalent bonds between the fullerene and graphene layers. Moreover, the thermodynamic stability of the fullerene–graphene hybrid was evaluated with potential energy profiles, and the total configuration energies for all systems were minimized and remained stable over a long period of time, suggesting good thermodynamic stability.In 2015, Kirca designed a novel fullerene–graphene hybrid composed of fullerene covalently sandwiched between parallel graphene sheets by using MD simulations.60 onto graphene nanosheets  was attributed to the improved electron transport because the introduction of the C60–graphene covalent hybrid could provide a direct conduction path for electron transport via percolation through the highly conducting 2D graphene sheets.The experimental synthesis of a fullerene–graphene covalent hybrid was not reported until 2011, when Dai et al. developed a simple lithiation method to covalently attach monosubstituted Cts Figure9A. In 60–graphene hybrid by ball milling in which C60 was directly bonded to the edges of graphene nanoplatelets via two C—C single bonds, as confirmed by high‐resolution transmission electron microscopy (HR‐TEM) , showing improved ORR electrocatalytic activity over the pristine graphite in terms of a higher limiting current (−3.4 mA cm−2) than those of the pristine graphite (−1.8 mA cm−2) and C60 (−2.2 mA cm−2). This was interpreted as the charge transfer from graphene to C60 enabling the graphene basal plane to be positively charged and thus to be more electrocatalytically active toward the ORR than the pristine graphite  Figure10A.104e Figure , I–IV.1060. After heating the pG/C60 mixture composed of a saturated solution of C60 in 1‐chloronaphthalene mixed with pG nanosheets at 300 °C for 2 h, C60 was impregnated into pG nanosheets with the evaporation of the solvent, affording the formation of the pG–C60 covalent hybrid , thermal gravimetric analysis (TGA), and HR‐TEM  onto the GO‐CCH scaffold ‐ethynylaniline via an aryl diazonium salt reaction, followed by cleavage of the trimethylsilyl groups using tetra‐ld Figure14.34 RFigure9 s−1 for C60•−, suggesting the efficient charge separation and formation of long‐lived charge separated species.Later, by using hydrolyzed PCBM as a fullerene precursor via a very mild process without the use of metal catalysts, Kumar et al. synthesized a novel fullerene–GO covalent hybrid (PCBGO) by grafting PCBM onto GO via flexible linkages Figure15.112 60 reacted with 2,5‐bis(trimethylsilyl)‐1,4‐phenylene bis(triflate) via a [2 + 2] cycloaddition yielding a C60‐aryne precursor  phthalocyanine (ZnPc), acting as electron donor, and fulleropyrrolidine, acting as electron acceptor, were covalently linked onto single‐layer graphene oxide (SLGO) simultaneously , as evidenced by the appearance of the cation (ZnPc•+) and anion (C60•−) radicals in the visible to near‐infrared (NIR) regions. In contrast, for the control samples, GO and binary hybrids ZnPc–GO and GO–C60, no cation and anion radicals were observed. Thus, the formation of the ternary hybrid is crucial for such a photoinduced electron transfer phenomenon.In addition to above‐mentioned binary fullerene–graphene hybrids, the inclusion of another functional material to form ternary hybrids with fullerene and graphene as building blocks has also been reported. In 2013, Souza and co‐workers reported a novel ternary covalent fullerene–graphene hybrid ZnPc–SLGO–Cly Figure17.19 T60 hybrid lubricating film by a multistep self‐assembly method on silicon surfaces.60, the GO films assembled on the silicon wafers were amine‐functionalized by (N‐[3‐(trimethoxysilyl)‐propyl]‐ethylenediamine) molecules, which contained primary and secondary amino groups capable of undergoing N—H addition reactions across the C=C bonds in C60. The successful grafting of C60 chemically to the amine‐functional GO by nucleophilic addition reactions was verified by FTIR, X‐ray powder diffraction (XRD), TGA, Raman spectroscopy and XPS. Colloidal probe measurements show that APTES‐a‐graphene–C60 exhibited a low nanofriction coefficient due to the existence of a more ordered C60 outer layer, which facilitated microsphere sliding because of the small contact area between the microspheres and films, in addition to the presence of the few‐layer graphene with excellent nanolubrication properties. Furthermore, the conclusion pointed out that the strong bonds, with stable and not easily damaged characteristics, between the carbon atoms of C60 facilitated the long‐lasting and effective lubrication.In 2014, Wang and co‐workers fabricated a graphene–C60 or graphene, rendering them stable in solution with the free movement of C60 coated on the graphene restricted.60 covalent hybrid incorporating folic acid (FA) and polyethylene glycol (PEG) onto GO via an imide linkage  effect of 44.4% compared with that for the Au nanoparticles of 30%. Furthermore, when the FA–GO–PEG/C60 is taken by tumor cells, it caused heating and significant intracellular reactive oxygen species (ROS) production under light irradiation, leading to a marked decrease in cell survival and to the elevation of oxidative stress  efficacy against cancer cells. FA–GO–PEG/C60 showed a combined PDT and PTT treatment with remarkably improved and synergistic effects compared to that of PTT or PDT alone, having potential for a synergistic phototherapy of cancer.Graphenes have been reported to act as an excellent drug carrier and photothermal agent, which can efficiently convert NIR light into heat and thus induce hyperthermia to cells and surrounding tissues.ge Figure18A. Th33N4 is the most stable allotrope of carbon nitrides under ambient conditions with the 2D, π‐conjugated plane of polymeric tri‐s‐triazine connected via tertiary amines  and the existence of contact resistance between the nanosheets.3N4 needs to be improved so as to extend its photocatalytic applications.g‐Ces Figure19.115 60, which is beneficial for a rapid photoinduced charge transfer with donor molecules and a relatively slow charge recombination, hybridizing g‐C3N4 with C60 has been implemented, and the effectiveness of such a strategy in improving the photocatalytic activity of g‐C3N4 has been examined. In 2014, Chai et al. prepared a g‐C3N4/C60 composite by simply blending g‐C3N4 powder into a C60 solution in toluene.3N4/C60 composites were characterized by XRD, scanning electron microscope (SEM), TEM, and FTIR. The photocatalytic activity of the g‐C3N4/C60 composite in the degradation of rhodamine B was further evaluated, indicating that the g‐C3N4/C60 composite with the optimal amount of C60 of 1 wt% had the highest photocatalytic performance. The improved photocatalytic performance of the g‐C3N4/C60 composite was attributed to the synergetic effect of g‐C3N4 and C60, which facilitated the separation of photogenerated electrons and holes.Considering the excellent electron‐accepting ability of C60/g‐C3N4 composite was prepared by Zhu et al. via the thermal treatment of dicyandiamide, a precursor for synthesis of g‐C3N4, at 550 °C in atmosphere in the presence of C60.60 into a matrix of g‐C3N4, the valance band of g‐C3N4 shifted to a lower energy position, affording a strong photooxidation capability under visible light. Under the optimal loading amount of C60 of 0.03%, the photocatalytic activity of the C60/g‐C3N4 composite for the degradation of phenol and methylene blue under visible light was found to be ≈2.9 and 3.2 times higher than that of pristine g‐C3N4. The enhanced photocatalytic activity of the C60/g‐C3N4 composite was attributed to the promoted generation of holes, and •OH originated from the strong interaction of the conjugated π‐bond between C60 and g‐C3N4, leading to a rapid photogenerated electron transfer rate and high charge separation efficiency of C60 in the C60/g‐C3N4 composite  remained at the interface between them. Interestingly, for different stacking patterns, g‐C3N4 and C60 were always linked by vdW forces and formed type‐II heterojunctions in most cases. The valence band maximum and conduction band minimum of these heterostructures were dominated by the unsaturated nitrogen (N2) atoms and C60 molecules, respectively, which strongly interacted with each other and resulted in a strong charge transfer between g‐C3N4 and C60 and a clear bending of the g‐C3N4 sheets. The unsaturated N2 atoms included at the interfaces have a significant influence on promoting the photocatalytic performance, while the existence of saturated nitrogen (N1 and N3) atoms lying at the interfaces would weaken the interfacial interactions between C60 molecules and the g‐C3N4 monolayers.A fundamental understanding of the corresponding mechanism behind the greatly enhanced photocatalytic activity of g‐C3N4 before and after C60 adsorption by using a larger model with 25 different adsorption configurations.60 preferred to stay upon the “junction nitrogen” with the carbon atom of fullerene being nearest to the monolayer. The adsorption of fullerene resulted in a change in the geometrical morphology of g‐C3N4 from flat to wrinkled via an irreversible process. The wrinkled structure was more stable by ≈5.6 eV compared with that of the flat one. The shortest distance between g‐C3N4 and C60 for all configurations was ≈3 Å, indicating the existence of vdW interactions. Furthermore, the analysis of the electronic properties indicated that the adsorption of C60 onto g‐C3N4 did not result in efficient carrier separation at interface. In fact, C60 in these systems mainly induced the geometrical distortion of g‐C3N4 monolayers, thus leading to the improved photocatalytic performance.Dai et al. reported a systematic theoretical study on the changes in the structure, stability, electronic properties, and light absorption of g‐C60/g‐C3N4 and C70/g‐C3N4 hybrids via a hydrothermal process.3N4. The photocatalytic disinfection activity of these hybrids on the inactivation of Escherichia coli (E. coli) O157:H7 showed that the bacterial cell could be damaged by the active oxygen radicals (•O2− and •OH) produced from the fullerene/g‐C3N4 hybrids under visible‐light irradiation.70/g‐C3N4 composite exhibited a higher photocatalytic inactivation activity for completely inactivating all E. coli O157:H7 cells within 4 h under visible‐light irradiation. The high catalytic performance was attributed to the effective transfer of the photoinduced electrons from the fullerene/g‐C3N4 hybrids under visible‐light irradiation.In 2017, Cai et al. synthesized C3N4 hybrids are based on noncovalent hybridization, for which C60 was blended physically into the pristine g‐C3N4 or its precursor in a low blending ratio (<2.0 wt%), and a large number of unreacted C60 are retained in the composites. On the other hand, the photocatalytic activity of the C60/g‐C3N4 composite was examined only via the degradation of dyes. These limitations were not broken until the recent success of our group in synthesizing the first fullerene–g‐C3N4 covalent hybrid via a facile solid‐state mechanochemical route by ball‐milling g‐C3N4 and C60 in the presence of LiOH as a catalyst . Under the optimized conditions, the g‐C3N4/C60‐12 wt% hybrid exhibited the highest H2 production rate of 266 µmol h−1 g−1, which was ≈4.0 times higher than that for the pristine g‐C3N4 photocatalyst )  to g‐C3N4 due to the lowering of the conduction band of g‐C3N4 and the inhibited recombination of photoinduced electron–hole pairs owing to the fast photoinduced electron transfer process from g‐C3N4 to C60  is the most representative TMD, consisting of hexagonal rings with Mo and S atoms alternately located at the hexagon corners. Monolayer MoS2 has the direct band gap of ≈1.8 eV and a high in‐plane carrier mobility, enabling broad applications in electro and photocatalysts, photovoltaics and photoelectric devices.As another type of emerging inorganic 2D semiconducting nanomaterials, TMDs have been attracting widespread attention due to their intriguing electronic, optical, and mechanical properties. Molybdenum disulfide  method  and RESET (−5.5 V) voltages and a high ON/OFF resistance ratio (≈4 × 103)  with exposed catalytically active edge sites, yielding a 3D architecture with a high surface‐to‐volume ratio beneficial to electrocatalytic applications.2 nanosheets were interfaced with nC60 clusters by a facile solution‐deposition method via immersing the MoS2/CFP samples into a C60 solution in chlorobenzene, and the nC60/MoS2 hybrid showed greatly improved hydrogen evolution reaction activity with an overpotential value of 172 mV at 10 mA cm−2, a Tafel slope of 60 mV dec−1, and a turnover frequency value of 2.33 H2/s per active site at −0.2 V versus RHE at a C60 deposition concentration of 0.5 mg mL−1. The improved activity of the nC60/MoS2 hybrid catalyst was explained by the interfacial doping of MoS2 induced by charge transfer from the nC60 clusters to MoS2, resulting in the relative positioning of their valence and conduction band edges.In 2016, Fang, Banerjee and co‐workers reported a stepwise sulfidation approach for the direct integration of vertically aligned high edge‐density MoS2–C60 hybrid onto a semiconducting SnO2 electrode via a two‐step methodology.2 and C60 yielded MoS2–C60 hybrid aggregates via self‐assembly, followed by electrophoretic deposition onto the SnO2 electrode in the second step. The time‐resolved microwave conductivity measurements for the MoS2–C60 hybrid revealed substantially increased transient conductivities under photoexcitation in comparison with the single components of MoS2 and C60, indicating that the nanosized heterojunction structure of MoS2 and C60 promoted charge separation. Furthermore, the C60 molecules on the surface of MoS2 effectively hindered the undesirable charge combination between an electron in the electrode and a hole in the MoS2 nanosheets. Moreover, the authors fabricated a WS2–C60 hybrid for comparison and found that, despite a more suppressed charge recombination in WS2–C60 than in MoS2–C60, the incident photon‐to‐current efficiency value of the device with WS2–C60 was smaller than that with MoS2–C60 owing to its inhomogeneous film structure.In 2018, Imahori et al. fabricated a MoS60 on WSe2, which served as a weakly interacting organic/2D vdW heterostructure system.60 molecules formed a monolayer that extended uniformly over WSe2 with large grain sizes (≈5 µm). The interplay and balance between the adsorbate–adsorbate and adsorbate–substrate interactions resulted in the formation of rotational arrays of self‐assembled 2 × 2 molecules. According to vdW‐corrected ab initio DFT simulations, the C60 molecules tended to be electronically coupled with a long‐range orientational ordering, as reflected in the high crystallinity of C60 on WSe2. Meanwhile, the electronic structure of the hybrid system showed a spatial delocalization of the molecular orbitals throughout the 2 × 2 superlattice.To thoroughly understand the basic physical and chemical phenomena that rule highly crystalline architectures comprised of crystals of organic molecules and 2D materials, Wang and co‐workers fulfilled the growth of high‐quality self‐assembled monolayers of C2–fullerene hybrid can promote the photocatalytic H2 production activity of MoS2 remains intriguing. In 2016, Huang et al. carried out first‐principles calculations based on density functional theory to investigate the effects of vdW interactions on changes in the electronic structure, charge transfer and photoactivity of three typical monolayer MoS2/fullerene  hybrids. For the MoS2/fullerene vdW heterostructures, strong noncovalent interactions between the MoS2 and fullerene were concluded. The band gap of the MoS2/fullerene vdW heterostructure was smaller than that of monolayer MoS2, and thus, the visible‐light absorption and photoinduced electron transfer can be enhanced. Furthermore, the amount of charge transfer at interface induced by vdW interactions was found to be dependent on the size of the fullerene.Whether the formation of a MoS2–C60 hybrid featuring a vdW heterostructure, as well as its application in photocatalytic H2 production. The MoS2–C60 hybrid was prepared via a facile and ecofriendly solid‐state mechanochemical route by ball‐milling a mixture of bulk MoS2 and C60. In the process of ball‐milling, the bulk MoS2 was exfoliated to few‐layer MoS2 nanosheets, and the basal plane was reduced into significantly smaller nanosheets; while the C60 molecules bonded to the edge of the cut MoS2 nanosheets in the form of vdW heterostructures  was revealed  in the raw mixture, the MoS2–C60 hybrid containing 2.8 wt% C60 exhibited a visible light photocatalytic H2 production rate of 6.89 mmol h−1 g−1 in the presence of the photosensitizer EY. This value was 9.5 times higher than that of the obtained MoS2 nanosheets. This result was because the C60 bonding resulted in the fast photoinduced electron transfer from MoS2 to C60, and this action was beneficial for the separation of electron–hole pairs by inhibiting their recombination.Experimentally, our group recently reported the first MoSes Figure24.67 U60/MoS2 and C60/WS2 hybrids were also studied theoretically by Cheng and co‐workers.60/MoS2, C60/WS2, C59B/MoS2, C59B/WS2, C59N/MoS2, and C59N/WS2, C60 preferred to sit at the S‐top site with a hexagon parallel to the monolayer. All of the interfacial interactions were found to be weak, such that the main electronic features of the components were preserved. Although both the C60/MoS2 and C60/WS2 systems behaved as type‐II heterojunctions, the built‐in potential in the C60/MoS2 hybrid was too small to achieve an efficient electron–hole separation, whereas the latter system had a large built‐in potential and was thus predicted to yield an excellent photovoltaic performance.The photovoltaic applications of C55.12‐hybridized wide band‐gap semiconductor with a structure analogous to graphene and belonging to a hexagonal system with sublattices occupied by equal numbers of boron and nitrogen atoms alternatingly arranged in a honeycomb configuration. Similar to graphene, the different h‐BN planes are dominated by weak van der Waals interactions, while the in‐plane nitrogen and boron atoms are combined by sp2 orbitals to form strong σ‐bonds, which are highly polarized because of the high asymmetry of the sublattices, resulting in the large band gap (5–6 eV) of h‐BN.2D h‐BN is a sp60 has a narrower band gap, hybridizing h‐BN with C60 has been regarded as an effective strategy for modulating the electronic properties of h‐BN. In 2005, Greber and co‐workers grew a C60 monolayer film on one monolayer of h‐BN on Ni(111), providing an atomically flat metal‐insulator interface. They observed that, between 150 and 250 K, the work function of C60 decreased, while the binding energy of the HOMO increased by ≈100 meV along with a strong charge in the LUMO of C60 by 0.4 ± 0.1 electrons. Such a charge redistribution was induced by the onset of a molecular rocking motion, and the magnitude of the charge transfer was an indication of strong electron–phonon interactions.Given that C5.22 V−1 s−1, makes BP an emerging member of 2D nanomaterials and renders its potential for application in transistors, biomedicine, and energy conversion and storage.3‐orbital hybridization, as well as the armchair and zigzag‐configurations along the x and y‐axial directions, respectively.BP with a century‐long history did not draw significant attention until the recent recognition of its anisotropic 2D layered structure.60 composite via a mechanochemical ball‐milling route in a comparative study with a BP–graphite composite synthesized under the same conditions. Prior to blending with BP, C60 or graphite was ball‐milled. Then, the mixture of BP and C60 (graphite) was sealed in an argon‐filled glove box, and high‐energy mechanical milling was performed under a 1.2 MPa Ar atmosphere with a rotation rate of 700 rpm for 12 h. According to their detailed characterizations of the BP–graphite composite, phosphorus–carbon bonds formed after ball‐milling and remained stable during lithium insertion/extraction. As a result, an excellent electrical connection between BP and the carbon material was established, contributing to a high initial discharge capacity of 2786 mAh g−1 at 0.2 C and an excellent cycle life of 100 cycles with 80% capacity retention. For comparison, within the BP–C60 composite, the content of the as‐formed phosphorus–carbon bonds was significantly lower than that for the BP–graphite composite, resulting in an inferior capability. Hence, the authors concluded that the carbon structures played essential roles in the formation of stable phosphorus–carbon bonds.Despite extensive reports on hybrids of BP with other 2D nanomaterials, especially graphenes, studies on hybrids of BP and fullerene have rarely been reported. In 2014, Cui and co‐workers made an attempt to synthesize a BP–C660 as the first fullerene in 1985 marks a milestone in nanoscience due to its unique spherical molecular structure merely composed of sp2‐hybridized carbon atoms. As the only soluble species among all known nanocarbons derived from the 0D structure, fullerenes have been popularly used as important building blocks useful for constructing versatile noncovalent/covalent nanohybrids with a variety of functional materials, including 2D nanomaterials, as elaborately reviewed in this paper.The discovery of C3N4, TMDs, h‐BN, and BP, which all exhibit similar electronic properties. Meanwhile, their intrinsic differences in lattice composition and interlayer distance bring about a clear diversity in specific functionalities and applications, greatly accelerating the field of 2D nanomaterials. Despite the tremendous progress in investigating the 2D nanomaterials themselves during the past decade, enhancing the existing properties for better performance and even exploring unknown functionalities toward extended applications are definitely necessary. To this end, hybridizing 2D nanomaterials with 0D fullerenes has been well established as a successful and powerful protocol based on the detailed analyses of versatile fullerene‐2D nanomaterial hybrid systems in this Review.In 2004, the paradigm‐shifting disclosure of graphene as the first and most representative 2D layered nanomaterial opened up a new era of nanoscience because of the material's exceptionally large specific surface area and high carrier mobility, which are achievable only in the 2D layered structure. The exceptional structure and property of graphene soon stimulated the recognition of other graphene‐analogous 2D nanomaterials, such as g‐CThere are yet considerable challenges in the emerging field of fullerene‐2D nanomaterial hybrids. First, most fullerene‐2D nanomaterial hybrids that have been reported so far were synthesized in the noncovalent style via the simple blending of two components, whereas only limited reports involved the successful construction of fullerene‐2D nanomaterial covalent hybrids, which are more promising in terms of strong intermolecular interactions between fullerene and 2D nanomaterial moieties. Clearly, the natural divergence in dimensions between 0D fullerene and 2D nanomaterials makes their covalent connection difficult. Therefore, prior to hybridization, chemically functionalizing the components of fullerene and/or the 2D nanomaterial appears critical. While the chemical derivatization of fullerenes has been well developed, chemical derivatizations of 2D nanomaterials are still in their infancy, and the development of novel derivatization approaches, especially for such less studied 2D nanomaterials as h‐BN and BP, is highly desired.Another pending problem is how to determine precisely the chemical structures of fullerene‐2D nanomaterial hybrids at the molecular level. In particular, for fullerene‐2D nanomaterial covalent hybrids, the additional pattern of covalent bonding between fullerene and the 2D nanomaterial, i.e., single‐bond addition or cycloaddition onto the fullerene cage, is essential for the disruption of the π‐conjugated system of the fullerene cage. Furthermore, since the properties of 2D nanomaterials are typically anisotropic, the addition site (surface vs edge) where fullerene bonds onto a 2D nanomaterial strongly affects the difficulty of the hybridization and the modulation extent of the 2D nanomaterial within the fullerene‐2D nanomaterial hybrid. For the latter point, the direct visualization of the fullerene addition sites within the hybrid is undoubtedly needed, and thus, further improvement of the resolution of HR‐TEM/scanning tunneling microscope (STM) for clearer morphological characterizations of the geometric structure of the hybrids is of high importance.As mentioned above, hybridizing 2D nanomaterials with fullerenes may not only fulfill the modulation of the physical/chemical properties of 2D nanomaterials but also induce new properties in the 2D nanomaterials, thus significantly extending the functionalities and applications of 2D nanomaterials. An intriguing question is whether the hybridization strategy can be used to further create unknown functional materials. For instance, on the basis of binary fullerene‐2D nanomaterial hybrids, by involving one or two other functional materials, which are either another 2D nanomaterial or even a 1D nanomaterial (such as a carbon nanotube or boron‐nitride nanotube), ternary or even quaternary hybrids are expected to form. However, due to a lack of experimental reports, whether the properties of such hybrids can surpass their binary counterparts is unknown. With the foreseeable development of chemical derivatizations of 2D nanomaterials, the syntheses of such unknown complex hybrids will likely come true in the near future, making the emerging fullerene‐2D nanomaterial hybrids even more exciting and promising for vast applications.The authors declare no conflict of interest.


This raises the question whether ApoE genotype also modifies the clinical phenotype in patients with FTD with tau pathology.Apolipoprotein E (ApoE) is the most important genetic risk factor for Alzheimer's disease (AD), with ApoE4 thought to enhance and accelerate amyloid-β (Aβ) pathology. ApoE4 has recently been described to increase neurodegeneration in a mouse model of frontotemporal dementia (FTD), We analyzed 704 patients with FTD, including a genetically and neuropathologically confirmed subset, and 452 healthy elderly controls. We compared ApoE4 genotype frequency and age at onset in tau+ or TDP43+ FTD patients with or without Aβ copathology.The ApoE4 genotype lowered age at onset in patients with FTD and tau pathology, particularly once accounting for confounding effects of Aβ pathology.MAPT mutations or FTLD-tau pathology, independent of Aβ.We conclude that ApoE4 accelerates neurodegeneration in FTD patients with  Several studies report an association between ApoE and FTD with a protective effect for ApoE2 and an increased risk conferred by ApoE4 MAPT gene mutation or by neuropathological examination. We found that the ApoE4 genotype lowered age at clinical onset in patients with dementia and tau pathology, and was a particularly strong effect once the confounding effects of amyloid β pathology were taken into account.Apolipoprotein E (ApoE) is the strongest known common genetic risk factor for Alzheimer's disease (AD) P = .003), carrying either one or two ApoE4 alleles. Based on Shi et al.MAPT gene mutation MAPT gene mutations or FTLD-tau neuropathology was significantly lower in the presence of an ApoE4 allele : for the tau+ ApoE4+ patients with FTD and available neuropathology data, 15 of 21 (71.4%) had Aβ copathology compared with 11/42 (26.2%) ApoE4− tau+ cases ; for the TDP+ ApoE4+ FTD cases, 8/13 (61.5%) had Aβ copathology compared with 10/47 (21.3%) of ApoE4− TDP+ cases . The prevalence of Aβ copathology was similar when tau+ cases were compared with TDP+ cases  and was associated with ApoE4 carrier status, both in cases with tau pathology  and without tau pathology . Patients who were positive for Aβ pathology were significantly older at onset than patients who were found to have no Aβ pathology at postmortem . In patients with FTLD-tau, ApoE genotype and Aβ copathology had independent associations with age at clinical onset . The effects of ApoE4+ carrier status and Aβ on AAO were independent of each other both in patients with and without tau .We went on to test whether the modifying effect of ApoE in FTD-tau might relate to the presence of Aβ copathology without meeting criteria for a formal pathological diagnosis of AD in 139 cases with available neuropathological data. Postmortem cases were neuropathologically staged according to Thal phases and Braak and Braak stages MAPT mutations or FTLD-tau pathology independent of Aβ—notably AAO in FTD-tau cases was on average about 3.9 years earlier in those who carried an ApoE4 allele. Previously, Shi et al. proposed that ApoE4 genotype acts through a toxic gain of function mechanism to exacerbate or modify tau pathology, neuroinflammation, autophagy, and reactive astrocyte activation; they provided extensive evidence in a mouse model of FTD and in neuropathological cases of tauopathies, as well as clinical support in an AD cohort 1..  little information on the effects of ApoE on primary tauopathies and FTD was available. Shi et al. established a primary effect of ApoE4 on tau pathology and neurodegeneration, independent of amyloid β (Aβ) pathology.Systematic review: We reviewed the literature searching for “ApoE” and “frontotemporal dementia” or “FTD”, establishing that other than Shi et al2.Interpretation: Our data in patients with FTD confirm that ApoE4 exacerbates the disease in patients with or expected to have tau pathology, lowering the age at clinical onset significantly. This effect is more pronounced if confounding effects of Aβ copathology are taken in to account.3.in vitro studies to elucidate the cellular mechanisms for this effect will be important.Future directions: Future studies should analyze the effects of ApoE genotype on FTD, accounting for differential effects on tau and Aβ copathology, to replicate the effects found here. Further Our analyses, carried out in a well-characterized cohort of patients with FTD, provide evidence that ApoE4 genotype accelerates neurodegeneration in patients with


The molecular weight distributions (Mw/Mn) of PNaSS–b–PAA and PNaSS–b–PNIPAM were 1.18 and 1.39, respectively, suggesting that these polymers have controlled structures. When aqueous solutions of PNaSS–b–PAA and PNaSS–b–PNIPAM were mixed under acidic conditions, water-soluble PNaSS–b–PAA/PNaSS–b–PNIPAM complexes were formed as a result of hydrogen bonding interactions between the pendant carboxylic acids in the PAA block and the pendant amide groups in the PNIPAM block. The complex was characterized by 1H NMR, dynamic light scattering, static light scattering, and transmission electron microscope measurements. The light scattering intensity of the complex depended on the mixing ratio of PNaSS–b–PAA and PNaSS–b–PNIPAM. When the molar ratio of the N-isopropylacrylamide (NIPAM) and acrylic acid (AA) units was near unity, the light scattering intensity reached a maximum, indicating stoichiometric complex formation. The complex dissociated at a pH higher than 4.0 because the hydrogen bonding interactions disappeared due to deprotonation of the pendant carboxylic acids in the PAA block.Poly(sodium styrenesulfonate)– Non-covalent interactions, such as hydrophobic , electroN-isopropylacrylamide-random-acrylic acid) (P(NIPAM–r–AA)) copolymers and examined their glass transition behavior. They found that the incorporation of acrylic acid units into the PNIPAM polymer enhances the glass transition temperature (Tg) due to intermolecular hydrogen bonding between the pendant isopropyl amide groups and the carboxylic acid groups using 1H NMR and Fourier-transform infrared analyses. As an example of such complex formation, Bian et al. 0 is the initial PNaSS58 macro–CTA concentration, xm is the conversion of the monomer, Mm is the molecular weight of the monomer, and MCTA is the molecular weight of PNaSS58 macro–CTA. The Mn(NMR) values for PNaSS58–b–PAA125 and PNaSS58–b–PNIPAM115 were calculated from the 1H NMR data. As shown in Mn(NMR) values for PNaSS58–b–PAA125 and PNaSS58–b–PNIPAM115 were in reasonable agreement with the Mn(theo) values. However, the Mn(theo) and Mn(GPC) values for both diblock copolymers were found to be slightly different. This may be because the volume-to-mass ratio for PNaSS is different from those for SS58–b–PAA125 and PNaSS58–b–PNIPAM115 [When the polymerization is assumed an ideally living process, then the theoretical number-average molecular weight  and 3.91 ppm (c) are attributed to the methyl and methine protons, respectively, in the pendant isopropyl group of the PNIPAM block are observed. Moreover, the resonance bands owing to the pendant phenyl protons in the PNaSS block are also detected at 6.1–7.9 ppm (a and b). The resonance bands in the 1.28–2.38 ppm region (d and e) are attributed to the sum of the main chain of the diblock copolymers. At pH 3, the intensities of the resonance peaks f and c derived from the PNIPAM block remarkably decreased, whereas those of a and b remained intact, as shown in d and e) became broad. From the significant reduction of the motional freedom for the PNIPAM block at pH 3, one can predict that the complexes are formed from PNaSS58–b–PAA125 and PNaSS58–b–PNIPAM115 owing to the hydrogen bonding interactions between the pendant carboxylic acids in the PAA block and the amide groups in the PNIPAM block. At pH 10, however, the complexes dissociated owing to the disappearance of the hydrogen bonding interactions as a result of deprotonation of the carboxylic acids in the PAA block.We attempted to monitor complex formation between PNaSS58–b–PAA125 and PNaSS58–b–PNIPAM115 in 0.1 M NaCl at pH 3 as a function of fNIPAM. The total polymer concentration was kept constant at 4.4 g/L. An increase in the scattering intensity suggests an increase in the size of the complex. The maximum scattering intensity was observed at fNIPAM = 0.5. This result indicates that a stoichiometric interaction in the mixture of PNaSS58–b–PAA125 and PNaSS58–b–PNIPAM115 led to form a complex with largest aggregation number. The complex with fNIPAM = 0.5 was studied unless otherwise stated.Rh) distributions for each diblock copolymer and the PNaSS58–b–PAA125/PNaSS58–b–PNIPAM115 complex at pH 3 and 10. The values of Rh were determined by DLS in 0.1 M NaCl and are indicated in the figure. The Rh values for PNaSS58–b–PAA125 and PNaSS58–b–PNIPAM115 were 3.5 and 3.7 nm, respectively, which are reasonable for a unimer state. The Rh values of the complex at pH 3 and 10 were 15.0 and 3.7 nm, respectively. When PNaSS58–b–PAA125 and PNaSS58–b–PNIPAM115 were mixed at pH 3, a water-soluble complex was formed due to hydrogen bonding interactions. On the other hand, at pH 10 the complex dissociated because the hydrogen bonding interactions disappeared as a result of deprotonation of the pendant carboxylic acids.q2) for the mixture of PNaSS58–b–PAA125 and PNaSS58–b–PNIPAM115 in 0.1 M NaCl at pH 3 in Rh values can be estimated at a fixed θ of 90° as the angular dependence is negligible.The relaxation rates (Γ) measured at different scattering angles (θ) are plotted as a function of the square of the magnitude of the scattering vector  in the concentration range from 0.9 to 4.4 g/L. The results suggest that the formation of the complex between PNaSS58–b–PAA125 and PNaSS58–b–PNIPAM115 starts to occur above a critical concentration of 0.9 g/L. The apparent critical aggregate concentration (CAC) value for the complex, estimated from the plots, is 0.9 g/L.Mw and Rg, determined by SLS measurements, are listed in 58–b–PAA125/PNaSS58–b–PNIPAM115 complex, which is formed from a mixture of PNaSS58–b–PAA125 and PNaSS58–b–PNIPAM115 in 0.1 M NaCl at pH 3. The aggregation number (Nagg) was defined as the number of polymer chains forming one complex, which can be estimated from the Mw values of the complex and unimer. The result of this calculation gives an Nagg of 46 for the complex. The chain numbers of PNaSS58–b–PAA125 and PNaSS58–b–PNIPAM115 for single complex are 22 and 24, respectively, as calculated from fNIPAM = 0.5 and the DP values of PAA and PNIPAM.The apparent values of Rg/Rh value indicates the shape of the molecular assemblies. The theoretical Rg/Rh value of a homogeneous hard sphere is 0.778 but this value increases substantially for less dense structures and polydisperse mixtures; for example, Rg/Rh = 1.5–1.7 for flexible linear chains in good solvents, whereas Rg/Rh ≥ 2 for a rigid rod [Rg/Rh ratio for the complex . %T) values monitored at 600 nm for 0.1 M NaCl aqueous solutions of PNaSS58–b–PNIPAM115 and a mixture of PNaSS58–b–PAA125 and PNaSS58–b–PNIPAM115 at pH 3 and 10, as a function of solution temperature. The diblock copolymer, PNaSS58–b–PNIPAM115, exhibited a significant %T change at 35–37 °C, which indicates the LCST. The mixture at pH 10 also exhibited a slight %T change at 35–37 °C. On the other hand, the mixture at pH 3 did not show any %T change in the temperature range from 20 to 80 °C. Ordinarily, the mechanism of LCST for PNIPAM can be explained as follows [58–b–PAA125/PNaSS58–b–PNIPAM115 complex at pH 3, the pendant amide groups in the PNIPAM block interact with the pendant carboxylic acid in the PAA block irrespective of the temperature. Hence, the pendant amide groups in the PNIPAM block are prevented from forming hydrogen bonds with water molecules. Therefore, the LCST of the complex at pH 3 cannot be observed. However, at pH 10, the mixture dissociated and hydrogen bonding interactions between the pendant amide groups in PNaSS58–b–PNIPAM115 and water molecules were formed at low temperature. Hence, the LCST can be observed for the mixture of PNaSS58–b–PAA125 and PNaSS58–b–PNIPAM115 at pH 10, although the decrease in %T at the LCST was small comparing to the PNaSS58–b–PNIPAM115 case. This is simply because the concentration of the NIPAM units in the former solution is lower than that in the latter solution.The NIPAM block in the PNaSS follows ,27. Belo58–b–PAA125 and PNaSS58–b–PNIPAM115 were prepared via RAFT-controlled radical polymerization using a PNaSS58 macro–CTA. Both polymerizations proceeded by a controlled mechanism. A mixture of PNaSS58–b–PAA125 and PNaSS58–b–PNIPAM115 formed a water-soluble complex under acidic conditions. The formation of the complex was confirmed by various measurement techniques. The 1H NMR data indicated restricted motion of the PNIPAM block at pH 3 in the complex owing to hydrogen bonding interactions between the pendant carboxylic acids in the PAA block and the pendant amide groups in the PNIPAM block. The DLS and SLS data suggested that the PNaSS58–b–PAA125/PNaSS58–b–PNIPAM115 complex was spherical in shape. When urea was added to the complex aqueous solution, the complex dissociated. This observation indicates that the driving force for the formation of the complex is hydrogen bonding interactions. The %T data indicated that the LCST of the complex was not observed at pH 3, owing to the complex formation. However, the complex dissociated to a unimer above pH 4.0.The diblock copolymers PNaSS


Several polymorphs of AlH3  have been successfully synthesized by wet chemical reaction of LiAlH4 and AlCl3 in ether solution followed by desolvation. However, the synthesis process of α'-AlH3 from wet chemicals still remains unclear. In the present work, α'-AlH3 was synthesized first by the formation of the etherate AlH3 through a reaction of LiAlH4 and AlCl3 in ether solution. Then, the etherate AlH3 was heated at 60°C under an ether gas atmosphere and in the presence of excess LiAlH4 to remove the ether ligand. Finally, α'-AlH3 was obtained by ether washing to remove the excess LiAlH4. It is suggested that the desolvation of the etherate AlH3 under an ether gas atmosphere is essential for the formation of α'-AlH3 from the etherate AlH3. The as-synthesized α'-AlH3 takes the form of rod-like particles and can release 7.7 wt% hydrogen in the temperature range 120–200°C.Aluminum hydride (AlH It theoretically has a high hydrogen capacity of 10 wt% and can release hydrogen at temperatures below 200°C ]. The precipitate LiCl was then removed by filtration, and the AlH3·nEt2O precipitated slowly during storage. The obtained solid, AlH3·nEt2O, was heated under certain conditions to remove the ether ligand [reaction (2)], which was called the desolvation process. Depending on the desolvation conditions used, AlH3 would crystalize in different structures.The synthesis of AlH3 have been successfully synthesized by the wet chemical method  was mixed with 1 M ether solution of AlCl3  at a molar ratio of 4:1. It should be noted that LiAlH4 was used in excess. Brower et al.  and LiCl precipitate based on reaction (3). The mixed solution was stirred for 2 min to ensure that the reaction was completed. Immediately after that, the LiCl precipitate was removed by filtration and the liquid ether was removed by slowly evacuation at room temperature. The dry and white residue obtained, which was a mixture of 4AlH3·nEt2O + LiAlH4, was ground to powder with a mortar and pestle for heating treatment. Powder samples were then heated at certain temperatures for various durations under certain atmospheres to remove the ether ligand [reaction (4)]. The conditions used for heat treatment significantly impact the desolvation products of the 4AlH3·nEt2O + LiAlH4 mixture, as will be shown in the next section. Finally, the desolvated 4AlH3·nEt2O + LiAlH4 mixture was ether-washed to remove the excess LiAlH4, and AlH3 was obtained.The synthesis process of α'-AlHr et al. . Howeverr et al.  found th3. The hydrogen desorption property of the as-synthesized α'-AlH3 was studied by using a home-made Sieverts-type hydrogen sorption measurement apparatus based on the volumetric method. Experimentally, the samples were sealed in a reactor and were heated under an initial vacuum gradually from room temperature to the set temperature with a heating rate of 2°C/min.Powder X-ray diffraction  was used to study the phase structures of the samples. The samples for XRD studies were sealed with an amorphous membrane to protect them from oxidation during the sample transformations and measurements. Scanning electronic microscopy  was used to study the morphology of the as-synthesized α'-AlH3 by the wet chemical reaction in the ether solution, the conditions  used in the desolvation stage [reaction (4)] significantly affect the desolvation product of AlH3·nEt2O , with which AlH3·nEt2O can easily transform to AlH3 without decomposition  is preferred in order to produce pure α'-AlH3.When the desolvation of the AlH3 was studied by SEM techniques, as shown in 3 takes the form of rod-like particles with lengths of about 1 μm and widths of about 100 nm. This unique particle morphology may benefit the hydrogen desorption process of α'-AlH3 because it possesses more surface area than other morphologies such as spheres of similar dimensions.The morphology of the as-synthesized α'-AlH3 with a heating rate of 2°C/min is shown in 3 and γ-AlH3 (Graetz and Reilly, The hydrogen desorption curve of the as-synthesized α'-AlH3 was successfully synthesized by the wet chemical reaction of LiAlH4 and AlCl3 in ether solution followed by desolvation. The conditions used in the desolvation stage are the essential factors in producing α'-AlH3. Desolvation under a gaseous ether atmosphere is the key to the transformation of AlH3·nEt2O into non-solvated α'-AlH3. The as-synthesized α'-AlH3 particles are rod-like and can release 7.7 wt% hydrogen in the temperature range 120–200°C. The purity of the α'-AlH3 needs to be improved in future work.Non-solvated α'-AlHAll datasets generated for this study are included in the article/supplementary material.All authors listed have made a substantial, direct and intellectual contribution to the work, and approved it for publication.LX and SL were employed by the company Global Energy Interconnection Research Institute Co., Ltd. The remaining 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.