bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Improved Charge and Exciton Transport in Polymer-Removed SWCNT Thin Films: Implications for Photovoltaic and Thermoelectric Energy Harvesting
Authors: Ferguson Andrew John , Blackburn Jeffrey L. , Hart Stephanie , Kang Hyun Suk , Ihly Rachelle , MacLeod Bradley A. , Stanton Noah H. 
Published: February 2020

The chemical and physical structure of semiconducting single-walled carbon nanotubes (SWCNTs) results in optical and electronic properties of promise for a wide variety of applications. Until quite recently the presence of metallic SWCNT impurities has hampered efforts to gain a deeper understanding of their true potential, with the additional complication that most commercially available materials contain tens of different chiral species. Significant effort has been devoted to elegant enrichment strategies aimed at extracting tailored semiconducting SWCNT species from the raw soot, from the use of subtly tunable surfactant interactions to the exploitation of specific DNA sequences. However, conjugated polymers, typically based on the fluorene moiety, appear to show the greatest promise with regards to their high selectivity and viability for scalable manufacturing approaches.
Unfortunately, the van de Waals forces between the pi-electron systems of the polymer and SWCNT that enable the selective extraction of semiconducting SWCNTs with high purity also make removal of the polymer difficult. Since these polymers typically have a wide bandgap they act as an insulating coating on the surface of the individual SWCNTs within functional networks, inhibiting the transport of energy in the form of excitons and/or charge carriers.
Here we demonstrate approaches aimed at replacing the strongly-bound polymers with variants that can be removed using simple solution-based chemical strategies, resulting in networks with vastly improved energy transport properties. We show that removal of the polymer results in a significant enhancement of the charge carrier mobility and electrical conductivity in the SWCNT networks, allowing optimization of the thermoelectric properties for both p-type and n-type transport. Finally, we extend the approach to samples strongly enriched in a single chiral SWCNT species, which allows us to employ transient spectroscopic techniques to probe enhanced exciton transport through the SWCNT network with high spectral fidelity. Our studies highlight a methodology by which high-performance SWCNT thin films can be prepared that could realize their potential for electronic and optoelectronic applications.
(Invited) Antiviral Activity of Self-Assembled Glycodendro[60]Fullerene Monoadducts
Authors: Martín Nazario 
Published: February 2020

A variety of different chemical and bio-inspired scaffolds have previously been used in the search for new glycoconjugates bearing the carbohydrates located in the appropriate spatial arrangement. Actually, there are a many examples where multivalency drastically enhances the interactions between biomolecules in comparison to the analogous monovalent binding.
In order to design multivalent peripheral ligands with glycomimetic properties that structurally can attach to the receptor sites of complex biological structures, a broad variety of ‘‘artificial glycoforms’’ have been created to study and understand the mechanisms involved in multivalent binding interactions. In this regard, we have recently shown that hexakis-adducts of [60]fullerene endowed with 12, 24 or 36 mannoses, act as strong inhibitors for DC-SIGN in an Ebola infection assay model.1 Furthermore, a drastic increase in the inhibition process at the subnanomolar scale has been observed when the size and mannoses´ number are increased in the firstly reported tridecafullerenes endowed with 120 mannose units decorating the periphery of the molecule.2

From the work carried out by our group on glycofullerenes with globular symmetry, it is possible to bring to light the significance of size and shape of the glycomimetic, being even more determinant that the number of carbohydrate moieties in the glycoparticle.
In the present work, the synthetic approach is simplified, using C60
mono-adducts instead of C60
hexakis-adducts, without compromising the spherical form of the final glycomimetic, provided by the supramolecular aggregate resulting from the self-assembly of mono-adducts.3 The efficiency to block DC-SIGN mediated viral infection by an artificial Ebola virus has been tested in a cellular experimental assay finding that, these systems are potent inhibitors of viral infection.
References

a) B. M. Illescas, J. Rojo, R. Delgado, N. Martín, "Multivalent Glycosylated Nanostructures To Inhibit Ebola Virus Infection" J. Am. Chem. Soc., 2017, 139, 6018−6025; b) J. Luczkowiak, A. Muñoz, M. Sánchez-Navarro, R. Ribeiro-Viana, A. Ginieis, B. M. Illescas, N. Martín, R. Delgado, J. Rojo, Biomacromolecules
2013, 14, 431-437; c) J.-F. Nierengarten, J. Iehl, V. Oerthel, M. Holler, B. M. Illescas, A. Muñoz, N. Martín, J. Rojo, M. Sánchez-Navarro, S. Cecioni, S. Vidal, K. Buffet, M. Durka, S. P. Vincent, Chem.
Commun.
2010, 46, 3860-3862; d) M. Sánchez-Navarro, A. Muñoz, B. M. Illescas, J. Rojo, N. Martín, Chem. Eur. J.
2011, 17, 766-769.

A. Muñoz, D. Sigwalt, B. M. Illescas, J. Luczkowiak, L. Rodríguez, I. Nierengarten, M. Holler, J.-S. Remy, K. Buffet, S. P. Vincent, J. Rojo, R. Delgado, J.-F. Nierengarten, N. Martín, Nat. Chem., 2016, 8, 50-57.

A. Muñoz, B. M. Illescas, J. Luczkowiak, F. Lasala, R. Ribeiro-Viana, J. Rojo, R. Delgado, N. Martín, J. Mater. Chem. B, 2017, 5, 6566-6571.
(Invited) Inner- and Outer-Wall Sorting of Double-Walled Carbon Nanotubes
Authors: Flavel Benjamin S 
Published: February 2020

Double walled carbon nanotubes (DWCNTs) consist of two coaxially aligned single walled carbon nanotubes (SWCNTs) and previous sorting methods only achieved outer-wall electronic type selectivity. Here a separation technique capable of sorting DWCNTs by semiconducting (S) or metallic (M) inner- and outer- wall electronic type is presented. Electronic coupling between the inner- and outer- wall is used to alter the surfactant coating around each of the DWCNT types and aqueous gel permeation is used to separate them. Aqueous methods are used to remove SWCNT species from the raw material and prepare enriched DWCNT fractions. The enriched DWCNT fractions are then transferred into either chlorobenzene or toluene using the copolymer PFO-BPy to yield the four inner@outer combinations of M@M, M@S, S@M and S@S. The high-purity of the resulting fractions is verified by absorption measurements, TEM, AFM, resonance Raman mapping and high-density field effect transistor devices.
[1] Han Li, Georgy Gordeev, Soeren Wasserroth, Venkata Sai Kiran Chakravadhanula, Shyam Kumar Chethala Neelakandhan, Frank Hennrich, Ado Jorio, Stephanie Reich, Ralph Krupke, Benjamin Flavel, Nature Nanotechnology (2017) DOI: 10.1038/nnano.2017.207
[2] Katherine Moore, Moritz Pfohl, Daniel Tune, Frank Hennrich, Simone Dehm, Venkata Sai Kiran Chakravadhanula, Christian Kuebel, Ralph Krupke, Benjamin Flavel, ACS Nano (2015) DOI: 10.1021/nn506869h
[3] Katherine Moore, Moritz Pfohl, Frank Hennrich, Venkata Sai Kiran Chakravadhanula, Christian Kuebel, Manfred Kappes, Joe Shapter, Ralph Krupke, Benjamin Flavel, ACS Nano (2014) DOI: 10.1021/nn500756a
Molecular Recognition at Local Doped Sites of Locally Functionalized Single-Walled Carbon Nanotubes for Selective Wavelength Shift of Near Infrared Photoluminescence
Authors: Shiraki Tomohiro , Onitsuka Hisashi , Shiga Tamehito , Nakashima Naotoshi 
Published: February 2020

Locally functionalized single-walled carbon nanotubes (lf-SWNTs) have local defects on the sp2 carbon networks of the tube wall through a limited amount of chemical modification, by which they emit red-shifted and quantum yield-enhanced photoluminescence (PL) in comparison to that of pristine SWNTs.[1-6] The newly generated PL (E
11*) of lf-SWNTs shows spectral shifts depending on the chemical structures of the modified molecules and dynamic wavelength shifts have been observed by protonation of amino groups[1] and saccharide recognition[6] at the doped sites. Such external stimuli responsiveness would be applicable to develop advanced sensing and imaging materials and optical devices using the near infrared (NIR) PL functions.
Based on findings in the saccharide recognition study[6], we extend molecular designs of our molecular recognition approach for development of stimuli-responsive wavelength-shift systems using lf-SWNTs. Crown ethers, which bind cations such as metal ions with selectivity based on ring sizes and donor atoms, are useful molecular motifs for metal sensing and supramolecular self-assemblies. We newly synthesized azacrown ether-modified lf-SWNTs (crown-SWNTs) and crown-SWNTs showed a new PL peak at 1138 nm (E
11*), which was red-shifted and intensified in comparison to E
11 PL at 989 nm. When a AgNO3 solution was added to the crown-SWNTs solution, the E
11* PL showed a larger peak shift to a longer wavelength region compared to the E
11 PL. According to the cation recognition mechanism of the azacrown ether, it is considered that the observed wavelength shift is induced by electronic character changes from electron donating to withdrawing of the modified groups due to the Ag+ inclusion in the ring. The molecular recognition approach, therefore, is promising to create new types of NIR PL nanomaterials whose PL properties can be modulated by the molecular actions.

References: [1] Schatz, G. C. and Wang, Y. et al., J. Am. Chem. Soc.
2016, 138, 6878-6885. [2] Htoon, H. and Doorn, S. K. et al., Nat. Photon.
2017, 11, 577-582. [3] Shiraki, T. and Nakashima, N. et al., Chem. Commun.
2017, in press, DOI:10.1039/C7CC06663E. [4] Shiraki, T. and Nakashima, N. et al., Nanoscale.
2017, in press, DOI:10.1039/C7NR05480G. [5] Shiraki, T. and Nakashima, N. et al., Sci. Rep.
2016, 6, 28393. [6] Shiraki, T. and Nakashima, N. et al., Chem. Commun.
2016, 52, 12972-12975.

Figure 1
New Methods Towards Designer DNA Sequences for Enantiomeric-Chiral Selective Sorting of Single-Wall Carbon Nanotubes
Authors: Meany Brendan , Zheng Ming 
Published: February 2020

To date methods in producing structurally defined single-wall carbon nanotubes are inadequate leaving purification or sorting a viable option for obtaining nanotubes of a certain chirality. While several procedures have been developed for structure specific isolation of nanotubes, there are differences in purity, scalability, and economic feasibility. The use of single-stranded DNA sequences has evolved and been refined to select for both nanotube helicity and handedness. These developments through brute force screening of hundreds of sequences show the unique recognition of DNA for nanotube structure. Going a step further DNA recognition combined with a second technique, aqueous two-phase separation, allows for high purity sorting of multiple chiralities.
We introduce a few new experimental and computational methods as the next step in discovering new DNA sequences for sorting single-wall carbon nanotubes. Utilizing these new methods followed by experimental verification, novel DNA sequences are discovered for dispersing and sorting single-wall carbon nanotubes.
(Invited) Substituted Aryl Structure Effects on Photoluminescence Properties of Locally Functionalized Single-Walled Carbon Nanotubes
Authors: Shiraki Tomohiro , Uchimura Shunsuke , Shiraishi Tomonari , Toshimitsu Fumiyuki , Nakashima Naotoshi 
Published: February 2020

Sp3 defect doping to semiconducting single-walled carbon nanotubes (SWNTs) provides fascinating near infrared photoluminescence (NIR PL) properties, in which, compared to PL (E
11) of pristine SWNTs, redshifted PL with enhanced quantum yields (E
11*) is observed by local functionalization through the doping.[1-6] In the locally functionalized SWNTs (lf-SWNTs), chemical structures of the modified molecules on the doped sites play an important role to determine and control the E
11* PL wavelengths. For example, we have succeeded in generation of remarkably redshifted PL on the basis of a proximal modification approach [5] and development of dynamic wavelength shift systems driven by molecular recognition at the doped sites [6].
Here, we report recent findings of the chemical structure factors that modulate the E
11* PL properties of aryl functionalized lf-SWNTs. When positional isomeric structures of the substituted aryl groups are introduced for the doped sites of lf-SWNTs (Figure), significantly different PL is observed from that of typical para-aryl modified lf-SWNTs.[3] Namely, the meta-aryl modified lf-SWNTs show deviation from the reported liner relationship between the Hammett substituent constants and ΔE = E
11*-E
11 of the para-aryl modified lf-SWNTs. For the ortho-aryl modified lf-SWNTs, two PL peaks generate by the functionalization and one of them appears in the largely redshifted region compared to typically observed E
11* PL. The present findings, therefore, are expected to provide new designs for the molecule-based PL modulation of lf-SWNTs. In this presentation, more details about the structural factors will be discussed.

References: [1] Schatz, G. C. and Wang, Y. et al., J. Am. Chem. Soc.
2016, 138, 6878-6885. [2] Htoon, H. and Doorn, S. K. et al., Nat. Photon.
2017, 11, 577-582. [3] Shiraki, T. and Nakashima, N. et al., Chem. Commun.
2017, in press, DOI:10.1039/C7CC06663E. [4] Shiraki, T. and Nakashima, N. et al., Nanoscale.
2017, in press, DOI:10.1039/C7NR05480G. [5] Shiraki, T. and Nakashima, N. et al., Sci. Rep.
2016, 6, 28393. [6] Shiraki, T. and Nakashima, N. et al., Chem. Commun.
2016, 52, 12972-12975.

Figure 1
Dielectrics & Electrostatics: Their Effect on Carbon Nanotube Network Field-Effect Transistors and Gas Sensors
Authors: Lapointe François , Malenfant Patrick R. L. , Lefebvre Jacques 
Published: February 2020

Due to their high surface area, monoatomic wall thickness, electronic structure (band gap, van Hove singularities) and properties (high mobility, ambipolar transport), single-walled carbon nanotubes (SWNTs) stand as a promising active material for chemical sensors. In a sensor context, they however suffer from lack of selectivity. For the same reasons that they are highly sensitive to analytes, they will be affected by their environment: interference from ambient gases (i.e. O2 / H2O redox couple) are to be expected [1,2], and vicinal charges and dipoles [3,4] will change the local electrostatics felt by the SWNTs. The dielectric environment being an integral part of the field-effect transistor (FET) stack, we sought to understand its effect on the transfer characteristics of devices with a carbon nanotube network as the active channel component.
References
[1] Aguirre, C. M. et al. The Role of the Oxygen/Water Redox Couple in Suppressing Electron Conduction in Field-Effect Transistors. Adv. Mater.
21, 3087–3091 (2009).
[2] Lefebvre, J. et al. Hysteresis free carbon nanotube thin film transistors comprising hydrophobic dielectrics. Appl. Phys. Lett.
107, 243301 (2015).
[3] Kobayashi, S. et al. Control of carrier density by self-assembled monolayers in organic field-effect transistors. Nat. Mater.
3, 317–322 (2004).
[4] Lee, S.-H. et al. Effect of Polymer Gate Dielectrics on Charge Transport in Carbon Nanotube Network Transistors: Low-k Insulator for Favorable Active Interface. ACS Appl. Mater. Interfaces
8, 32421–32431 (2016).
(Invited) Design and Synthesis of Hybrid Nanomaterials for Electrochemical Energy Storage Applications
Authors: Song Min-Kyu 
Published: February 2020

The aspiration to lessen the dependency on fossil fuels and the desire to secure a clean, sustainable energy system have become stronger, resulting in endeavors headed for developing next-generation batteries. Currently, Li-ion batteries are the most commercially successful and dominating battery system. It is well known, however, that the energy densities of current Li-ion batteries are unable to meet the ever-increasing demands of newly emerging technologies. Therefore, investigations of new materials/chemistries and novel architectures are required to go beyond incremental developments in the energy densities of existing batteries.
Silicon or Tin-based anodes and Chalcogen group-based (Sulfur and Oxygen) cathodes have gained much attention for next-generation batteries because they have the potential of providing much higher specific energy than those of current Li-ion batteries. However, there remain fundamental challenges for these systems to be considered as a practically viable option. In this presentation, a brief discussion of scientific challenges and some latest developments in hybrid nanostructured materials for advanced batteries will be provided. In particular, the direct utilization of CO2 in synthesis of Silicon or Tin-based composite materials will be discussed in the context of improving the energy/power density of current Li-ion batteries. Furthermore, if time allows, our group’s recent efforts based on metal-organic frameworks to extend cycle life of beyond Li-ion (Li/S and Li/O2) batteries will be introduced.
(Invited) Two-Dimensional Organic Network Structures for Energy Conversion and Storage
Authors: Mahmood Javeed , Baek Jong-Beom 
Published: February 2020

Since the discovery of graphene in 2004,1 conjugated two-dimensional (2D) organic network structures have attracted immense interest due to their unusual electronic, optoelectronic, magnetic and electrocatalytic properties. In addition, their tunable structures and properties promise to offer more opportunities than graphene in various applications. However, even after years of intensive exploration of 2D materials in science and technology, facile and scalable methods capable of producing stable 2D network polymers with uniformly decorated heteroatoms with/without holes remain limited. To overcome these issues, new layered 2D organic network structures have been designed and synthesized. They have uniformly distributed heteroatoms,2 holes with heteroatoms3 and transition metal nanoparticles on the holes.4 The structures were confirmed by scanning tunneling microscopy (STM). Based on the stoichiometry of the basal plane, they were, respectively, designated C3N, C2N and M@C2N (M = Co, Ni, Pd, Pt, Ru). Their electronic and electrical properties were evaluated by electrooptical and electrochemical measurements along with density-functional theory (DFT) calculations. The results suggest that these newly-developed 2D network polymers offer greater opportunities, from wet-chemistry to device applications.

References:

[1] Konstantin Novoselov, et al. Electric field effect in atomically thin carbon film. Science 2004, 306: 666.
[2] Javeed Mahmood, et al. Two-dimensional polyaniline (C3N) from carbonized organic single crystals. Proceedings of National Academy of Sciences, USA 2016, 113: 7414.
[3] Javeed Mahmood, et al. Nitrogenated holey two-dimensional structure. Nature Communications 2015, 6: 6486.
[4] Javeed Mahmood, et al. An efficient and pH-universal ruthenium-based catalyst for the hydrogen evolution reaction. Nature Nanotechnology 2017, 12: 441.
(Invited) Functionalization and Application of Carbon Nanostructures
Authors: Istif Akcan , Gajewska Agnieszka , Carini Marco , Armuzza Valentina , Gonzalez Dominguez Jose Miguel , Hadad Caroline , DaRos Tatiana 
Published: February 2020

Since from the discovery of the new allotropic forms of carbon, their potential applications in many different fields appeared to be very interesting. The increasing of components in the Carbon NanoStructure (CNS) family is still widening these potentialities. However, in the majority of the cases, a chemical functionalization of these derivatives is needed and results to be challenging.
We will survey the recent years’ achievements in this field on various CNSs.
Vertically Oriented MoS2 with Spatially Controlled Geometry on Nitrogenous Graphene Sheets for High-Performance Sodium-Ion Batteries
Authors: Jeong Jong Yeob , Park Jong Hyeok 
Published: February 2020

Lithium-ion battery (LIB) has been a tremendous success for decades. As the demand for rechargeable batteries surges, a need has arisen for low-cost secondary batteries. Among various studies, sodium-ion battery (SIB) is the most promising secondary batteries due to its similar working principles and the abundance of sodium in the natural world. Among many anode materials for SIB, MoS­­2 has attracted attention because it can intercalate sodium ions in its layered structure. However, in the repeated intercalation of Na+
, MoS2 suffers from collapse of its layered structure.
Herein, we present vertically grown MoS2 on nitrogenous reduced graphene oxides (N-RGO) with controlled sheet density and height of MoS2 sheets as SIB anode active material. The MoS2 materials are synthesized by gel-precursor based method. By adjusting the nucleation and growth processes, we controlled the height and density of MoS2 sheets to find optimal condition that show great performance and high stability. Control of the partial geometry can achieve these improved property because the high sheet density can prevent additional SEI layer and the shortened sheet length reduces the resistance of Na+ diffusion. It shows remarkably high reversible discharging capacity of 255mAh/g at 1C and 245mAh/g at 5C discharging with a capacity reduction of 5.35% after 1300 cycles. And closely packed MoS2 sheets shows specific capacity of 254, 243, 153, 86 mAh/g at 0.2, 2, 10, 50A/g current density, respectively. Furthermore, vertically grown MoS2 is paired with Na3V2(PO4)3 to fabricate SIB full cell, and the full cell shows a specific capacity of 262mAh/g (based on the mass of anode material) during 50 cycles.

Figure 1
(Invited) Chiral-at-Metal Fullerene Hybrids for Catalysis
Authors: Filippone Salvatore , Girón Rosa María , Vidal Sara , Martin Nazario 
Published: February 2020

Fullerenes have found their main application in organic photovoltaic devices thanks to their ability to give rise a high efficient photo-induced electron transfer process and to their behaviour as n-type charge carriers.[1]

On the other hand, in face of the great interest for carbon based materials in catalysis, the use of fullerenes in this field has been completely neglected as probably due to the difficult to endow fullerene cages with suitable active sites. In this regards, as a first step to address this issue, we have reported recently a wide range of asymmetric metal mediated or organocatalytic methodologies for a precise stereocontrol in the fullerenes functionalizations.[2]
Herein, we present the enantioselective catalytic synthesis of fullerene hybrids where C60 is endowed with metal atoms such us iridium, rhodium and ruthenium with high enantiomeric excesses. A complete control on the stereochemistry of all the asymmetric centers was achieved, even on the stereogenic metal center.[3]
The catalytic and photo-electrocatalytic properties of these new fullerene derivatives will be discussed together with their ability to transfer chirality in hydrogen transfer processes.[4]
[1] (a) B. C. Thompson, J. M. J. Fréchet, Angew. Chem. Int. Ed.
2008, 47, 58; (b) J. L. Delgado, P.-A. Bouit, S. Filippone, M. A. Herranz, N. Martin, Chem.Commun.
2010, 46, 4853.
[2] (a) Maroto, E. E.; Izquierdo, M.; Reboredo, S.; Marco-Martínez, J.; Filippone, S.; Martín, N. Acc.
Chem. Res.
2014, 47, 2660. (b) Filippone, S.; Maroto, E. E.; Martín-Domenech, A.; Suárez, M.; Martín, N. Nat. Chem.
2009, 1, 578. (c) Maroto, E. E.; Mateos, J.; Garcia-Borràs, M.; Osuna, S.; Filippone, S.; Herranz, M. Á.; Murata, Y.; Solà, M.; Martín, N. J. Am. Chem. Soc.
2015, 137, 1190. (d) Marco-Martínez, J.; Reboredo, S.; Izquierdo, M.; Marcos, V.; López, J. L.; Filippone, S.; Martín, N. J. Am. Chem. Soc.
2014, 136, 2897. (e) Marco-Martínez, J.; Marcos, V.; Reboredo, S.; Filippone, S.; Martín, N. Angew. Chem. Int. Ed.
2013, 52, 5115.
[3] J. Marco-Martínez, S. Vidal, I. Fernández, S. Filippone and N. Martín, Angew.
Chem. Int. Ed., 2017, 56, 2136.
[4] R. Maria Giron, J. Marco-Martinez, S. Bellani, A. Insuasty, H. Comas Rojas, G. Tullii, M. R. Antognazza, S. Filippone and N. Martin, J. Mater. Chem. A, 2016, 4, 14284.

Figure 1