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1.
ACS Appl Mater Interfaces ; 16(24): 31171-31180, 2024 Jun 19.
Artículo en Inglés | MEDLINE | ID: mdl-38845350

RESUMEN

SnS-based carbon composites have garnered considerable concentration as prospective anode materials (AMs) for lithium-ion batteries (LIBs). Nevertheless, most SnS-based carbon composites underwent a two-phase or multistep preparation process and exhibited unsatisfactory LIB performance. In this investigation, we introduce a straightforward and efficient one-step arc-discharge technique for the production of dual-layer carbon-coated tin sulfide nanoparticles (SnS@C). The as-prepared composite is used as an AM for LIBs and delivers a high capacity of 1000.4 mAh g-1 at 1.0 A g-1 after 520 cycles. The SnS@C still maintains a capacity of 476 mAh g-1 after 390 cycles despite a higher current of 5.0 A g-1. The high specific capacity and long life are mainly attributed to a unique dual-carbon layers coating structure. The dual-carbon layers not only could effectively improve electrical conductivity and reduce charge-transfer resistance but also limit the alteration in bulk and self-aggregation of SnS nanoparticles. The SnS@C produced by the arc-discharge technique emerges as a promising applicant for AM in LIBs, and the arc-discharge technique provides an alternative way for synthesizing other transition metal sulfides supported on carbonaceous materials.

2.
J Am Chem Soc ; 146(25): 17003-17008, 2024 Jun 26.
Artículo en Inglés | MEDLINE | ID: mdl-38865191

RESUMEN

We report here a new type of metal fluoride cluster that can be stabilized inside fullerene via in situ fluorine encapsulation followed by exohedral trifluoromethylation, giving rise to rare-earth metal fluoride clusterfullerenes (FCFs) M2F@C80(CF3) (M = Gd and Y). The molecular structure of Gd2F@C80(CF3) was unambiguously determined by single-crystal X-ray analysis to show a µ2-fluoride-bridged Gd-F-Gd cluster with short Gd-F bonds of 2.132(7) and 2.179(7) Å. The 19F NMR spectrum of the diamagnetic Y2F@C80(CF3) confirms the existence of the endohedral F atom, which exhibits a triplet with a large 19F-89Y coupling constant of 74 Hz and a high temperature sensitivity of the 19F chemical shift of 0.057 ppm/K. Theoretical studies reveal the ionic Y-F bonding nature arising from the highest electronegativity of the F element and an electronic configuration of [Y2F]5+@[C80]5- with an open-shell carbon cage, which thus necessitates the stabilization of FCFs by exohedral trifluoromethylation.

4.
Chemistry ; 27(52): 13242-13248, 2021 Sep 15.
Artículo en Inglés | MEDLINE | ID: mdl-34268813

RESUMEN

To design molecular spin qubits with enhanced quantum coherence, a control of the coupling between the local vibrations and the spin states is crucial, which could be realized in principle by engineering molecular structures via coordination chemistry. To this end, understanding the underlying structural factors that govern the spin relaxation is a central topic. Here, we report the investigation of the spin dynamics in a series of chemically designed europium(II)-based endohedral metallofullerenes (EMFs). By introducing a unique structural difference, i. e. metal-cage binding site, while keeping other molecular parameters constant between different complexes, these manifest the key role of the three low-energy metal-displacing vibrations in mediating the spin-lattice relaxation times (T1 ). The temperature dependence of T1 can thus be normalized by the frequencies of these low energy vibrations to show an unprecedentedly universal behavior for EMFs in frozen CS2 solution. Our theoretical analysis indicates that this structural difference determines not only the vibrational rigidity but also spin-vibration coupling in these EMF-based qubit candidates.

5.
Nanoscale ; 12(20): 11130-11135, 2020 May 28.
Artículo en Inglés | MEDLINE | ID: mdl-32400841

RESUMEN

Enhancing the exchange interaction between magnetic ions is a long-term target in molecular magnetism. Endohedral metallofullerenes (EMFs) provide a possibility for achieving such a goal by imprisoning multiple magnetic centers inside the confined inner space of a fullerene cage. Here, we report a new member of dimetallic azafullerene Dy2@C79N via crystallographic determination for the first time. Magnetic studies indicate that the strong ferromagnetic coupling between lanthanide ions and unpaired electrons enables Dy2@C79N to be a favorable SMM with large energy barrier of U = 669 K and observable hysteresis loops below 24 K.

6.
Inorg Chem ; 58(21): 14325-14330, 2019 Nov 04.
Artículo en Inglés | MEDLINE | ID: mdl-31622085

RESUMEN

The photoluminescence of lanthanide ions inside fullerenes is usually very weak due to the quenching effect of the fullerene cage. In the case of Er@C82, the near-infrared emission from the Er3+ ion is completely quenched by the C82 fullerene cage. It remains challenging to turn on the photoluminescence of Er@C82 and other monometallofullerenes. In this work, we adopt a covalent modification strategy to alter the electronic structure of the fullerene cage for sensitizing the near-infrared emission of Er3+ ions in metallofullerenes Er@C2n (2n = 72, 76, and 82). After covalent modification with trifluoromethyl, phenyl, or dichlorophenyl groups, the erbium metallofullerenes exhibit photoluminescence at 1.5 µm, which is the characteristic emission of the Er3+ ion. Particularly, the otherwise nonfluorescent metallofullerene Er@C82 is transformed into fluorescent derivatives by using this strategy. The photoluminescence from the Er3+ ion is ascribed to energy transfer from the fullerene cage to the Er3+ ion. According to theoretical calculations, the sensitization of the Er3+ ion by the fullerene cage is associated with the large HOMO-LUMO gap and the closed-shell electronic structure of the metallofullerene derivatives. This work provides useful guidance for the design and synthesis of new fluorescent metallofullerenes.

9.
J Am Chem Soc ; 140(3): 1123-1130, 2018 01 24.
Artículo en Inglés | MEDLINE | ID: mdl-29272584

RESUMEN

An anisotropic high-spin qubit with long coherence time could scale the quantum system up. It has been proposed that Grover's algorithm can be implemented in such systems. Dimetallic aza[80]fullerenes M2@C79N (M = Y or Gd) possess an unpaired electron located between two metal ions, offering an opportunity to manipulate spin(s) protected in the cage for quantum information processing. Herein, we report the crystallographic determination of Gd2@C79N for the first time. This molecular magnet with a collective high-spin ground state (S = 15/2) generated by strong magnetic coupling (JGd-Rad = 350 ± 20 cm-1) has been unambiguously validated by magnetic susceptibility experiments. Gd2@C79N has quantum coherence and diverse Rabi cycles, allowing arbitrary superposition state manipulation between each adjacent level. The phase memory time reaches 5 µs at 5 K by dynamic decoupling. This molecule fulfills the requirements of Grover's searching algorithm proposed by Leuenberger and Loss.

10.
RSC Adv ; 8(59): 33688-33694, 2018 Sep 28.
Artículo en Inglés | MEDLINE | ID: mdl-35548807

RESUMEN

Palladium nanoparticles with a diameter of 2-4 nm supported on nitrogen and boron dual-doped single-wall carbon nanohorns (Pd-NBCNHs) are synthesized via a one-step method and their electrocatalytic activities are investigated for the oxygen reduction reaction (ORR) in alkaline media. The electrochemical results demonstrate that the oxygen reduction peak potential of Pd-NBCNHs is similar to that of commercial 20% Pt-C. Furthermore, Pd-NBCNHs show a more positive half-wave potential than 20% Pt-C and display better long-term stability and resistance to methanol than 20% Pt-C, which is attributed to the synergetic effect of the Pd nanoparticles and NBCNHs. As NBCNHs have abundant pyrrolic nitrogen, charged sites and defective structures, they not only act as a carrier, but also provide the active sites for oxygen adsorption during the oxygen reduction reaction process. The outstanding electrochemical performance makes Pd-NBCNHs promising to be applied in fuel cells.

11.
J Org Chem ; 82(17): 9253-9257, 2017 09 01.
Artículo en Inglés | MEDLINE | ID: mdl-28748692

RESUMEN

The C70 δ-adducts with closed [5,6]-ring fusion are an important type of compound in classifying bond delocalization in the equatorial belt of C70. However, the formation of such compounds is severely restricted due to the low reactivity of the carbon atoms in the flat equatorial region. Such a restriction is lifted when reduced anionic C70 species are used, where the inert equatorial carbon atoms are activated.

12.
Int J Nanomedicine ; 12: 4177-4194, 2017.
Artículo en Inglés | MEDLINE | ID: mdl-28615944

RESUMEN

Single-wall carbon nanohorns (SWCNHs), which have multitudes of horn interstices, an extensive surface area, and a spherical aggregate structure, offer many advantages over other carbon nanomaterials being used as a drug nanovector. The previous studies on the interaction between SWCNHs and cells have mostly emphasized on cellular uptake and intracellular trafficking, but seldom on epithelial cells. Polar epithelium as a typical biological barrier constitutes the prime obstacle for the transport of therapeutic agents to target site. This work tried to explore the permeability of SWCNHs through polar epithelium and their abilities to modulate transcellular transport, and evaluate the potential of SWCNHs in drug delivery. Madin-Darby canine kidney (MDCK) cell monolayer was used as a polar epithelial cell model, and as-grown SWCNHs, together with oxidized and fluorescein isothiocyanate-conjugated bovine serum albumin-labeled forms, were constructed and comprehensively investigated in vitro and in vivo. Various methods such as transmission electron microscopy and confocal imaging were used to visualize their intracellular uptake and localization, as well as to investigate the potential transcytotic process. The related mechanism was explored by specific inhibitors. Additionally, fast multispectral optoacoustic tomography imaging was used for monitoring the distribution and transport process of SWCNHs in vivo after oral administration in nude mice, as an evidence for their interaction with the intestinal epithelium. The results showed that SWCNHs had a strong bioadhesion property, and parts of them could be uptaken and transcytosed across the MDCK monolayer. Multiple mechanisms were involved in the uptake and transcytosis of SWCNHs with varying degrees. After oral administration, oxidized SWCNHs were distributed in the gastrointestinal tract and retained in the intestine for up to 36 h probably due to their surface adhesion and endocytosis into the intestinal epithelium. Overall, this comprehensive investigation demonstrated that SWCNHs can serve as a promising nanovector that can cross the barrier of polar epithelial cells and deliver drugs effectively.


Asunto(s)
Carbono/química , Epitelio/efectos de los fármacos , Intestinos/citología , Nanoestructuras/química , Administración Oral , Animales , Perros , Sistemas de Liberación de Medicamentos/métodos , Endocitosis , Fluoresceína-5-Isotiocianato/análogos & derivados , Fluoresceína-5-Isotiocianato/química , Células de Riñón Canino Madin Darby , Ratones Desnudos , Microscopía Electrónica de Transmisión , Nanoestructuras/administración & dosificación , Técnicas Fotoacústicas , Albúmina Sérica Bovina/química
13.
Chem Commun (Camb) ; 52(31): 5391-3, 2016 Apr 07.
Artículo en Inglés | MEDLINE | ID: mdl-27006980

RESUMEN

Boron-, phosphorus-, nitrogen-doped and co-doped single-wall carbon nanohorns were produced using an arc-vaporization method. These as-prepared doped materials consist of uniform isolated nanohorns and exhibit greatly enhanced catalytic capabilities in the reduction reaction of nitrobenzene and a volcano-shape trend between their activities with a B dopant content is found. Moreover, the B-C3 and P-C3 species in doped nanohorns might act as the acidic and basic sites to promote this reaction.

14.
Soft Matter ; 11(23): 4621-9, 2015 Jun 21.
Artículo en Inglés | MEDLINE | ID: mdl-25959650

RESUMEN

Recent research has indicated that polydopamine and synthetic eumelanins are optoelectronic biomaterials in which one-dimensional aggregates composed of ordered-stacking oligomers have been proposed as unique organic semiconductors. However, improving the ordered-stacking of oligomers in polydopamine nanostructures is a big challenge. Herein, we first demonstrate how folic acid molecules influence the morphology and nanostructure of polydopamine via tuning the π-π interactions of oligomers. MALDI-TOF mass spectrometry reveals that porphyrin-like tetramers are characteristic of folic acid-polydopamine (FA-PDA) nanofibers. X-ray diffraction combined with simulation studies indicate that these oligomers favour aggregation into graphite-like ordered nanostructures via strong π-π interactions. High-resolution TEM characterization of carbonized FA-PDA hybrids show that in FA-PDA nanofibers the size of the graphite-like domains is over 100 nm. The addition of folic acid in polydopamine enhances the ordered stacking of oligomers in its nanostructure. Our study steps forward to discover the mystery of the structure-property relationship of FA-PDA hybrids. It paves a way to optimize the properties of PDA through the design and selection of oligomer structures.


Asunto(s)
Ácido Fólico/química , Indoles/química , Nanofibras/química , Polímeros/química , Nanofibras/ultraestructura
15.
Inorg Chem ; 54(9): 4243-8, 2015 May 04.
Artículo en Inglés | MEDLINE | ID: mdl-25782103

RESUMEN

Although a non-IPR fullerene cage is common for endohedral cluster fullerenes, it is very rare for conventional endofullerenes M@C2n, probably because of the minimum geometry fit effect of the endohedral single metal ion. In this work, we report on a new non-IPR endofullerene Sm@C2v(19138)-C76, including its structural and electrochemical features. A combined study of single-crystal X-ray diffraction and DFT calculations not only elucidates the non-IPR cage structure of C2v(19138)-C76 but also suggests that the endohedral Sm(2+) ion prefers to reside along the C2 cage axis and close to the fused pentagon unit in the cage framework, indicative of a significant metal-cage interaction, which alone can stabilize the non-IPR cage. Furthermore, electrochemical studies reveal the fully reversible redox behaviors and small electrochemical gap of Sm@C2v(19138)-C76, which are comparable to those of IPR species Sm@D3h-C74.


Asunto(s)
Fulerenos/química , Níquel/química , Cationes Bivalentes , Cristalografía por Rayos X , Técnicas Electroquímicas , Isomerismo , Estructura Molecular , Oxidación-Reducción , Teoría Cuántica
16.
Inorg Chem ; 54(5): 2103-8, 2015 Mar 02.
Artículo en Inglés | MEDLINE | ID: mdl-25679437

RESUMEN

Two Sm@C82 isomers have been well characterized for the first time by means of (13)C NMR spectroscopy, and their structures were unambiguously determined as Sm@C2v(9)-C82 and Sm@C3v(7)-C82, respectively. A combined study of single crystal X-ray diffraction and theoretical calculations suggest that in Sm@C2v(9)-C82 the preferred Sm(2+) ion position shall be located in a region slightly off the C2 axis of C2v(9)-C82. Moreover, the electrochemical surveys on these Sm@C82 isomers reveal that their redox activities are mainly determined by the properties of their carbon cages.

17.
ACS Appl Mater Interfaces ; 6(20): 18008-17, 2014 Oct 22.
Artículo en Inglés | MEDLINE | ID: mdl-25248075

RESUMEN

The biomedical applications of carbon nanomaterials, especially integrating noninvasive photothermal therapy (PTT) and photodynamic therapy (PDT), into a single system have enormous potential in cancer therapy. Herein, we present a novel and facile one-step method for the preparation of water-soluble single-walled carbon nanohorns (SWNHs) and metal phthalocyanines (MPc) hybrid for PTT and PDT. The hydrophilic MPc, tetrasulfonic acid tetrasodium salt copper phthalocyanine (TSCuPc), is coated on the surface of SWNHs via noncovalent π-π interaction using the sonication method. In this PTT/PDT nanosystem, SWNHs acts as a photosensitizer carrier and PTT agent, while TSCuPc acts as a hydrophilic and PDT agent. The EPR results demonstrated that the generated reactive oxygen species (ROS) not only from the photoinduced electron transfer process from TSCuPc to SWNHs but also from SWNHs without exciting TSCuPc to its excited state. The test of photothermal conversion proved that not only do SWNHs contribute to the photothermal therapy (PTT) effect, TSCuPc probably also contributes to that when it coats on the surface of SWNHs upon exposure to a 650-nm laser. More importantly, the results of in vitro cell viability revealed a significantly enhanced anticancer efficacy of combined noninvasive PTT/PDT, indicating that the SWNHs-TSCuPc nanohybrid is a hopeful candidate material for developing an efficient and biocompatible nanoplatform for biomedical application.


Asunto(s)
Hipertermia Inducida , Indoles/química , Nanopartículas/uso terapéutico , Nanotecnología/métodos , Fotoquimioterapia , Fototerapia , Agua/química , Carbono/química , Muerte Celular/efectos de los fármacos , Espectroscopía de Resonancia por Spin del Electrón , Células HeLa , Humanos , Isoindoles , Microscopía Confocal , Nanopartículas/toxicidad , Nanopartículas/ultraestructura , Fotoblanqueo , Espectroscopía de Fotoelectrones , Solubilidad , Espectrometría Raman , Termogravimetría , Factores de Tiempo
18.
Langmuir ; 30(19): 5497-505, 2014 May 20.
Artículo en Inglés | MEDLINE | ID: mdl-24773501

RESUMEN

Polydopamine is not only a multifunctional biopolymer with promising optoelectronic properties but it is also a versatile coating platform for different surfaces. The structure and formation of polydopamine is an active area of research. Some studies have supposed that polydopamine is composed of covalently bonded dihydroxyindole, indoledione, and dopamine units, but others proposed that noncovalent self-assembly contributes to polydopamine formation as well. However, it is difficult to directly find the details of supramolecular structure of polydopamine via self-assembly. In this study, we first report the graphite-like nanostructure observed in the carbonized polydopamine nanoparticles in nitrogen (or argon) environment at 800 °C. Raman characterization, which presents the typical D band and G band, confirmed the existence of graphite-like nanostructures. Our observation provides clear evidence for a layered-stacking supramolecular structure of polydopamine. Particularly, the size of graphite-like domains is similar to that of disk-shaped aggregates hypothesized in previous study about the polymerization of 5,6-dihydroxyindole [ Biomacromolecules 2012 , 13 , 2379 ]. Analysis of the hierarchical structure of polydopamine helps us understand its formation.


Asunto(s)
Indoles/química , Nanopartículas/química , Nanoestructuras/química , Polímeros/química
19.
Nanoscale ; 5(21): 10409-13, 2013 Nov 07.
Artículo en Inglés | MEDLINE | ID: mdl-24056947

RESUMEN

A metallofullerene Sm@D3h-C74 that contains a divalent rare-earth metal has been studied structurally and electrochemically. The crystallographic analysis revealed that the endohedral Sm atom is more or less motional rather than being localized at a site where the pyracylene motif is nearby. This suggests a weaker metal-pyracylene interaction in Sm@D3h-C74 relative to that in M(II)@C74 (M = Group II metal), thus confirming the importance of the metal variety. The electrochemical studies showed a major difference between the redox properties of Sm@D3h-C74 and other Sm-fullerenes and indicated a small band gap for the title compound.

20.
J Am Chem Soc ; 135(11): 4187-90, 2013 Mar 20.
Artículo en Inglés | MEDLINE | ID: mdl-23465292

RESUMEN

We report the synthesis, isolation, and characterizations of the novel trimetallofullerene Sm3@I(h)-C80. Importantly, the experimental X-ray structure of Sm3@I(h)-C80 verified for the first time that three metal atoms can be stabilized in a fullerene cage without a nonmetal mediator. Furthermore, computational studies demonstrated the electronic features of Sm3@I(h)-C80, which are similar to that of theoretically studied Y3@I(h)-C80. Electrochemical studies of Sm3@I(h)-C80 showed a major difference from those of the well-studied isoelectronic species Sc3N@I(h)-C80 and La2@I(h)-C80.

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