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Zhen Hu, Cheng Wang, Feng Zhao, Xirong Xu, Shuhong Wang, Long Yu, Dayu Zhang, Yudong Huang
The wonderful chemical structures and characteristics of low-dimensional carbon materials have exciting applications in life sciences. In the present study, we developed a facile strategy to conjugate C60 with graphene via host-guest chemistry for targeted phototherapy. A versatile carrier based on folic acid-functionalized graphene (GO-FA) and comprising γ-cyclodextrin (γ-CD) at its surface was assembled via π-π interaction, creating hybrid structures with drug storage and tumor targeting properties. This γ-CD-modified graphene (GO-FA/Py-γ-CD) is capable of hosting pristine C60 molecules for the fabrication of a GO-FA/Py-γ-CD/C60 nanohybrid...
June 20, 2017: Nanoscale
Rasim Mirzayev, Kimmo Mustonen, Mohammad R A Monazam, Andreas Mittelberger, Timothy J Pennycook, Clemens Mangler, Toma Susi, Jani Kotakoski, Jannik C Meyer
Two-dimensional (2D) materials have considerably expanded the field of materials science in the past decade. Even more recently, various 2D materials have been assembled into vertical van der Waals heterostacks, and it has been proposed to combine them with other low-dimensional structures to create new materials with hybridized properties. We demonstrate the first direct images of a suspended 0D/2D heterostructure that incorporates C60 molecules between two graphene layers in a buckyball sandwich structure...
June 2017: Science Advances
Norihito Fukui, Taeyeon Kim, Dongho Kim, Atsuhiro Osuka
Porphyrin tapes possessing meso-meso β-β β-β triple direct linkages have been targets of extensive studies because of their fully conjugated characteristic π-electronic networks. In this paper, we report porphyrin arch-tapes that bear additional carbonyl group(s) or methylene group(s) inserted between one of the β-β linkage(s) of the porphyrin tapes. The carbonyl-inserted porphyrin arch-tapes were efficiently synthesized by double fusion reactions of β-to-β carbonyl-bridged porphyrin oligomers with DDQ and Sc(OTf)3, and were converted to the methylene-bridged porphyrin arch-tapes via Luche reduction with NaBH4 and CeCl3 followed by ionic hydrogenation with HBF4·OEt2 and BH3·NEt3...
June 16, 2017: Journal of the American Chemical Society
Tao Li, Luoyi Fan, Hao Gong, Zeming Xia, Yanpeng Zhu, Nianqiang Jiang, Gaofeng Liu, Long Jiang, Yang Li, Jiaobing Wang
We report a kind of homoditopic molecular host, janusarene, which has two back-to-back compactly arranged nanocavities for guest complexation. The unique two-face structural feature of janusarene allows it to bind and align various guest compounds, concurrently, which include the spherical pristine fullerene C60 and the planar polycyclic aromatic hydrocarbons (PAHs) such as pyrene, perylene, and 9,10-dimethylanthracene. The host-guest interactions were characterized by single crystal X-ray diffraction. A pairwise encapsulation of the PAH guests by janusarene enables us to obtain PAH dimers which deliver emerging spectroscopic properties distinct from those of PAHs dissolved in solution, or in the bulk state...
June 16, 2017: Angewandte Chemie
T Terlier, G Zappalà, C Marie, D Leonard, J-P Barnes, A Licciardello
Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is a high performance tool for molecular depth profiling of polymer films, in particular when they are structured in microphases. However, a major issue is the degradation of polymer materials under ion irradiation in reactions such as cross-linking, chain breaking, or reorganization processes of polymers which have been demonstrated for materials such as polystyrene (PS) and poly(methyl methacrylate) (PMMA). This work aims at comparing ToF-SIMS molecular depth profiling of structured polymers (polystyrene (PS)-b-polymethyl methacrylate (PMMA) block copolymers (BCP)) using either ultralow energy cesium or the more recently introduced C60(++) (under NO dosing and with sample cooling) and argon cluster ion beams (using Ar1500(+) ions at 5 keV)...
June 15, 2017: Analytical Chemistry
Francis D'Souza, Shuai Shao, Habtom Gobeze, Paul Karr
BF2-chelaed dipyrromethene, BODIPY, was functionalized to carry two stryryl crown ether tails and a secondary electron donor at the meso-position. Using a 'two-point' self-assembly strategy, a bis-alkyl ammonium functionalized fullerene, C60 was allowed to self-assemble the crown ether voids of BODIPY to obtain multi-modular donor-acceptor conjugates. As a consequence of the two-point binding, the 1:1 stoichiometric complexes formed yielded complexes of higher stability in which fluorescence of BODIPY was found to be quenched suggesting occurrence of excited state processes...
June 13, 2017: Chemistry, An Asian Journal
Aaron Zhenghui Thong, Milo S P Shaffer, Andrew P Horsfield
Three rules for creating highly effective unimolecular rectifiers that utilize asymmetric anchoring groups have been proposed by Van Dyck and Ratner [Ratner et al., Nano Lett., 2015, 15, 1577-1584]. This study investigates their proposed rectification mechanism in a functionalised azafullerene system (4TPA-C60) and identifies a fourth rule. NEGF-DFT shows that 4TPA-C60 fulfills the three design rules and finds that a saturated bridge is not required to fulfil the third rule, contrary to previous belief. Instead a twisted-π bridge decouples the donor and acceptor states whilst still providing a high conductance pathway...
June 12, 2017: Nanoscale
Li-Yun Yang, Si-Yu Hua, Zhi-Qiang Zhou, Guan-Chao Wang, Feng-Lei Jiang, Yi Liu
Fullerenols, known as polyhydroxylated derivatives of fullerene, have attracted great attention due to their distinctive material properties and potential applications in biology and medicine. As a step toward the elucidation of basic behavior in biological systems, a variety of spectroscopic measurements as well as isothermal titration calorimetry (ITC) were applied to study the interaction between fullerenol (C60(OH)44) and serum proteins (bovine serum albumin (BSA) and γ-globulins). The results of fluorescence spectra indicated that the intrinsic fluorescence of proteins could be effectively quenched by the dynamic mechanism...
May 31, 2017: Colloids and Surfaces. B, Biointerfaces
M P Szymański, H Jędrzejewska, M Wierzbicki, A Szumna
Molecular encapsulation of C60 inside a hydrogen-bond-sealed semi-flexible peptidic capsule is hindered in solution, yet it proceeds effectively after mechanical milling of a solid sample. We show that the molecular mechanism involves the generation of non-covalently disordered forms that are active in guest uptake. We also show that the solvent-free mechanochemical covalent synthesis of capsules directly results in obtaining disordered, active forms.
June 21, 2017: Physical Chemistry Chemical Physics: PCCP
Francis D'Souza, Yi Hu, Michael Thomas, Waruna Jinadasa, Hong Wang
Simultaneous occurrence of energy and electron transfer events involving different acceptor sites in a newly assembled supramolecular triad comprised of covalently linked free-base porphyrin-zinc porphyrin dyad, H2P-ZnP axially coordinated to electron acceptor fullerene, has been successfully demonstrated. The dyad was connected through the -pyrrole positions of the porphyrin macrocycle for better electronic communication. Interestingly, the -pyrrole functionalization modulated the optical properties to such an extent that it was possible to selectively excite the ZnP entity in the supramolecular triad...
June 7, 2017: Chemistry: a European Journal
Marinos Tountas, Yasemin Topal, Ermioni Polydorou, Anastasia Soultati, Apostolis Verykios, Andreas Kaltzoglou, Theodoros A Papadopoulos, Florian Auras, Kostas Seintis, Mihalis Fakis, Leonidas C Palilis, Dimitris Tsikritzis, Stella Kennou, Matroni Koutsoureli, George Papaioannou, Mustafa Ersoz, Mahmut Kus, Polycarpos Falaras, Dimitris Davazoglou, Panagiotis Argitis, Maria Vasilopoulou
Effective interface engineering has been shown to play a vital role in facilitating efficient charge carrier transport thus boosting the performance of organic photovoltaic devices. Herein we employ water soluble lacunary polyoxometalates (POMs) as multifunctional interlayers between the titanium oxide (TiO2) electron extraction/transport layer and the organic photoactive film to simultaneously enhance the efficiency, lifetime and photostability of polymer solar cells. A significant reduction in work function (WF) of TiO2 upon POM deposition was observed, with the magnitude being controlled by the negative charge of the anion and the selection of the addenda atom (W or Mo)...
June 6, 2017: ACS Applied Materials & Interfaces
Yan Xiao Su, Chao Zhi Zhang, Ming Xia Song
Electron-donating molecules play an important role in the development of organic solar cells. (Z)-2-(2-Phenylhydrazinylidene)acenaphthen-1(2H)-one (PDAK), C18H12N2O, was synthesized by a Schiff base reaction. The crystal structure shows that the molecules are planar and are linked together forming `face-to-face' assemblies held together by intermolecular C-H...O, π-π and C-H...π interactions. PDAK exhibits a broadband UV-Vis absorption (200-648 nm) and a low HOMO-LUMO energy gap (1.91 eV; HOMO is the highest occupied molecular orbital and LUMO is the lowest unoccupied molecular orbital), while fluorescence quenching experiments provide evidence for electron transfer from the excited state of PDAK to C60...
June 1, 2017: Acta Crystallographica. Section C, Structural Chemistry
Bettina D Gliemann, Volker Strauss, Jakob F Hitzenberger, Pavlo O Dral, Frank Hampel, Jean-Paul Gisselbrecht, Thomas Drewello, Walter Thiel, Dirk M Guldi, Milan Kivala
We describe the synthesis and the electronic and photophysical characterization of novel N-heterotriangulene derivatives decorated with methoxycarbonyl- and methylsulfanyl-substituted dithiafulvenyl moieties. The association of these electron-rich compounds with fullerene C60 as electron acceptor was investigated by means of photophysical, voltammetric, and mass spectrometric methods and rationalized by DFT calculations. Importantly, light-induced interactions between the dithiafulvene-substituted N-heterotriangulene bearing methoxycarbonyl substituents with C60 leads to cooperative fluorescence...
June 2, 2017: Chemistry: a European Journal
Michael Renzler, Lorenz Kranabetter, Marcelo Goulart, Paul Scheier, Olof Echt
We report on the formation and ionization of cesium and C60Cs clusters in superfluid helium nanodroplets. Size distributions of positively and negatively charged (C60) m Cs n(±) ions have been measured for m ≤ 7, n ≤ 12. Reproducible intensity anomalies are observed in high-resolution mass spectra. For both charge states, (C60) m Cs3(±) and (C60) m Cs5(±) are particularly abundant, with little dependence on the value of m. Distributions of bare cesium cluster ions also indicate enhanced stability of Cs3(±) and Cs5(±), in agreement with theoretical predictions...
May 25, 2017: Journal of Physical Chemistry. C, Nanomaterials and Interfaces
Dexuan Xu, Yang Gao, Wanrun Jiang, Zhigang Wang
First-principles calculations show that a carbon adatom defect at the Def[5, 6] site on the surface of C60 can produce a more stable spin-polarized singlet electronic state instead of a magnetic triplet state. This is clearly different from the cases of graphene and nanotubes. The mechanism results from the electron population of the adatom, which produces antiferromagnetic coupling around the C60 cage and the adatom itself. Our calculations show the same phenomenon occurs in other IPR fullerenes, such as C70 and C80...
May 31, 2017: Nanoscale
Tihomir Kovač, Bojan Šarkanj, Tomislav Klapec, Ivana Borišev, Marija Kovač, Ante Nevistić, Ivica Strelec
Increased use of fullerols in various fields and expected increase of their environmental spread impose the necessity for testing fullerol nanoparticles (FNP) effects on microbiota. There is little information available on the interaction of mycotoxigenic fungi and FNP, despite FNP having a great potential of modifying mycotoxin production. Namely, FNP exhibit both ROS-quenching and ROS-producing properties, while oxidative stress stimulates mycotoxin synthesis in the fungi. In order to shed some light on the extent of interaction between FNP and mycotoxigenic fungi, the effects of fullerol C60(OH)24 nanoparticles (10, 100, 1000 ng/mL) on mycelial growth, aflatoxin production and oxidative stress modulation in an aflatoxigenic strain of Aspergillus flavus (NRRL 3251) during 168 h of incubation in a liquid culture medium were examined...
May 30, 2017: Environmental Science and Pollution Research International
Jie Guan, David Tománek
Superconducting behavior even under harsh ambient conditions is expected to occur in La@C60 if it could be isolated from the primary metallofullerene soot when functionalized by CF3 radicals. We use ab initio density functional theory calculations to compare the stability and electronic structure of C60 and the La@C60 endohedral metallofullerene to their counterparts functionalized by CF3. We found that CF3 radicals favor binding to C60 and La@C60 and have identified the most stable isomers. Structures with an even number m of radicals are energetically preferred for C60 and structures with odd m for La@C60 due to the extra charge on the fullerene...
June 14, 2017: Nano Letters
Eduardo Victor Peris, Carmen Mejuto, Luis Escobar, Gregorio Guisado-Barrios, Pablo Ballester, Dmitry Gusev
The deprotonation of a corannulene-based bisazolium salt allowed to prepare a corannulene-based NHC di-Au(I) complex. The prepared di-Au(I)-complex was tested in the recognition of fullerene-C60, demonstrating good binding affinity in toluene solution, and producing a host:guest complex with 3:1 stoichiometry, as evidenced by a combination of NMR and ITC titrations. The experimental results are fully supported by DFT calculations. The binding of C60 with the di-Au(I) complex in toluene solution is enthalpically and entropically favored...
May 26, 2017: Chemistry: a European Journal
Tao Wei, M Eugenia Pérez-Ojeda, Andreas Hirsch
An unprecedented hybrid dumbbell consisting of a metallofullerene and an empty fullerene was afforded via simple click reaction of suitable precursor derivatives of Sc3N@C80 and a C60 hexakisadduct.
May 30, 2017: Chemical Communications: Chem Comm
Liting Ju, Pingxiao Wu, Xiaolin Lai, Shanshan Yang, Beini Gong, Meiqing Chen, Nengwu Zhu
In this study, ZnAlTi layered double hydroxide (ZnAlTi-LDH) combined with fullerene (C60) was fabricated by the urea method, and calcined under vacuum atmosphere to obtain nanocomposites of C60-modified ZnAlTi layered double oxide (ZnAlTi-LDO). The morphology, structure and composition of the nanocomposites were analyzed by Scanning Electron Microscopy, High-resolution transmission electron microscopy, X-ray diffraction patterns, Fourier transform infrared and specific surface area. The UV-vis diffuse reflectance spectra indicated that the incorporation of C60 expanded the absorption of ZnAlTi-LDO to visible-light region...
May 23, 2017: Environmental Pollution
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