bluuebunny/crossref_metadata_2025_split huggingface dataset:
A Generic Covalent Functionalization Concept for Near-Infrared Fluorescent Carbon Nanotube Biosensors
Authors: Metternich Justus , Sistemich Linda , Herbertz Svenja , Kruss Sebastian 
Published: September 2023

Biosensors are powerful tools with wide applications in basic research and biomedical diagnostics. In the last decades, the use of nanomaterials decorated with biological recognition units have attracted significant attention and reformed the field. However, this development requires substantial input from the chemical sciences.
In this context, semiconducting single-walled carbon nanotubes (SWCNTs) are versatile near infrared (NIR, 870 – 2400 nm) emitting fluorophores. They have been non-covalently modified to create sensors that change their fluorescence when interacting with biomolecules. However, non-covalent chemistry has several disadvantages and prevents a consistent way to signal transduction and rational design. Here, we introduce a widely applicable covalent approach to create molecular sensors without destroying the fluorescence in the NIR. For this purpose, a new class of quantum defects in the SWCNT lattice is used to bind biomolecules and to guarantee colloidal stability. To showcase the potential of this approach we demonstrate sensing for different classes of biomolecular analytes (nucleic acids, proteins as well as macromolecular complexes). We analyze sensitivity and selectivity of this recognition approach and present a straightforward way for the generation of novel sensors. In summary, we introduce a novel quantum defect-based covalent functionalization approach of fluorescent SWCNTs with great potential for biosensing.
Prediction of Mycotoxin Response of DNA-Wrapped Nanotube Sensor with Machine Learning
Authors: Rabbani Yahya , Behjati Sara , Lambert Benjamin , Sajjadi Sayyed Hashem , Shariaty-Niassar Mojtaba , Boghossian Ardemis Anoush 
Published: September 2023

DNA-wrapped single-walled carbon nanotubes (SWCNTs) have demonstrated great versatility in their use as optical sensors. SWCNTs emit a near-infrared fluorescence that is responsive to even the slightest changes in the nanotube environment, enabling sensors that can respond to single-molecule fluctuations within the vicinity of their surfaces. The fluorescence response and surface interactions of these sensors are determined by the DNA wrapping sequence. However, the lack of information on the relationship between the DNA sequence and its effect on the SWCNT fluorescence remains a bottleneck for designing sequences that are specific to analytes of interest. We have recently demonstrated the use of directed evolution to control the fluorescence response of SWCNTs through DNA design. Iterative cycles of DNA mutation, screening, and selection allowed us to evolve sequences that yield DNA-wrapped SWCNT sensors with a desired fluorescence response to mycotoxins.
In this work, we apply the screening results of the DNA libraries used in this approach to train machine learning (ML) algorithms. Artificial neural network (ANN) and support vector machine (SVM) methods were used to predict the response of ssDNA-SWCNT sensors to a specific mycotoxin. The reliability of these models was further assessed through cross-validation. The ANN and SVM models with cross-validation were able to accurately classify the various DNA sequences as yielding either a high or low fluorescence response with an accuracy of 73 and 81%, respectively. The models were further used to predict the performance of alternative DNA sequences outside the initial training dataset, using the Hierarchy and k-means
++
clustering methods to evaluate the similarity and dissimilarity of each DNA sequence. Compared to the SVM model, the ANN model showed an improved ability to predict high responses for dissimilar DNA sequences. We further applied a combinatorial approach based on SVM and ANN models to design new DNA sequences for improving sensor performance. The success of this approach was validated experimentally, demonstrating the rational design of improved sensors with 95% prediction accuracy.
The application of ML algorithms to directed evolution libraries of DNA thus allows one to accurately map the performances of these sensors within a particular sequence space. The computational success of this mapping provides a framework for replacing current empirical approaches with the rational design of DNA sequences for SWCNT sensing.

Keywords: Nano Biosensor, DNA-SWCNT, Mycotoxin, Machine learning, Directed evolution method
Raman Characterization of Guanine Functionalized SWCNTs
Authors: Soltani Nima , Bachilo Sergei M. , Weisman R. Bruce 
Published: September 2023

Single-walled carbon nanotubes (SWCNTs) have unique photophysical properties that render them an important class of materials for future nanoelectronics and bio-nano sensor applications. A method was recently discovered for making spatially patterned modifications to SWCNT band gaps and thereby modulating their electronic and optical properties in a controlled manner. The reaction used for this is called guanine functionalization.1 It is achieved by generating singlet oxygen in a dispersion of SWCNTs coated with single-stranded DNA, resulting in covalent bond formation between the guanine nucleobases in the DNA coatings and the nanotube sidewalls. Each of the many covalently bonded guanine sites acts as a weak exciton trap, causing red-shifted SWCNT emission and absorption spectra. Fluorescence spectroscopy shows that the extent of guanine functionalization can depend strongly on SWCNT structure, but spectral broadening can hamper the precise deconvolution of emission features of different (n,m) species. To track such covalent functionalization through Raman scattering, the D to G band ratios are commonly used as a measure of sp3 defect density and therefore of the functionalization extent. However, this conventional Raman method cannot show which (n,m) species in unsorted samples have been functionalized, because they all contribute to the D and G band signals.
We will describe a novel Raman analysis based on the relative intensities of bands that have shifts located between the RBM and D regions. These Raman features are found to be diameter-specific, allowing estimation of (n,m)-resolved functionalization extents in unsorted SWCNT samples. In addition, we will present an assignment and interpretation of the relevant Raman features.

Zheng, Y.; Bachilo, S. M.; Weisman, R. B., Controlled patterning of carbon nanotube energy levels by covalent DNA functionalization. ACS Nano
2019,
13, 8222-8228.
(Invited) Chiral Bilayer Nanographenes: A New Family of Carbon Nanostructures
Authors: Martin Nazario , Izquierdo-García Patricia , Fernández Jesús Manuel 
Published: September 2023

Chirality is an important and fascinating concept which has not been properly addressed in nanocarbons science.1 We have previously reported the first inherently chiral bilayer nanographene with a helicene linker, both as the racemate and the M isomer.2,3 By extending precedented [6]helicene starting material, we obtained an unprecedented chiral nanographene comprised of two hexa-peri-hexabenzocoronene (HBC) layers fused to a [10]helicene . Furthermore, we have increased the family of bilayers by using the respective [5] and [7]helicenes, affording bilayers with [9] and [11]helicenes, respectively. These nanographenes are appealing systems for the study of further chemical reactions including redox reactions.4 In this presentation, the recent findings on this singular family of chiral nanographenes showing remarkable CPL values, as well as their less known outstanding photophysical properties will be discussed.

Acknowledgements

The author acknowledge support from the European Research Council (ERC) Synergy Grant “TOMATTO” (Project 951224).

References

1. J. M. Fernández-García, P. J. Evans, S. Filippone, M. A. Herránz, N. Martín, “Chiral Molecular Carbon Nanostructures”, Acc.
Chem. Res.
2019, 52, 1565-1574.
2. P. J. Evans, J. Ouyang, L. Favereau, J. Crassous, I. Fernández, J. Perles Hernáez, N. Martín "Synthesis of a Helical Bilayer Nanographene" Angew. Chem. Int. Ed.
2018, 57, 6774 –6779.
3. J. M. Fernández-García, P. Izquierdo-García, M. Buendía, S. Filippone, N. Martín. “Synthetic chiral molecular nanographenes: the key figure of the racemization barrier”, Chem. Commun. 2022, 58, 2634–2645.
4. Z. Zhou, J. M. Fernández-García, Y. Zhu, P. J. Evans, R. Rodríguez, J. Crassous, Z. Wei, I. Fernández, M. A. Petrukhina, N. Martín. "Site-Specific Reduction-Induced Hydrogenation of a Helical Bilayer Nanographene with K and Rb Metals: Electron Multiaddition and Selective Rb+ Complexation", Angew. Chem. Int. Ed.
2022, 61, e20211574.
(Invited) Donor-Acceptor Interaction in Two-Dimensional Materials
Authors: Imahori Hiroshi 
Published: September 2023

Two-dimensional materials have drawn significant attention because of their unique electronic properties. In particular, donor-acceptor interaction at the interface are one of the state-of-the-art topics for energy and optoelectronics applications. In this talk I will give an overview of our studies on their photophysical and photoelectrochemical properties.
[1] J. Baek, T. Umeyama, W. Choi, Y. Tsutsui, H. Yamada, S. Seki, H. Imahori, Chem. Eur. J., 24, 1561-1572 (2018).
[2] T. Umeyama, T. Ohara, Y. Tsutsui, S. Nakano, S. Seki, H. Imahori, Chem. Eur. J., 26, 6726-6735 (2020).
[3] T. Umeyama, H. Xu, T. Ohara, Y. Tsutsui, S. Seki, and H. Imahori, J. Phys.
Chem. C, 125, 13954-13962 (2021).
(Invited) Hybrid Nanodevices for Technology and Fun
Authors: García Pérez Cristina , García Pérez Julia , Marzoa Victor , Caballero Gabriel , Martínez Sandra , Sánchez Toural Juan Luis , Calero de Ory Marina , Rodriguez David , Magaz Maite , Jiménez-Urbanos Fernado , Acebrón María , Rodríguez Osorio Manuel , Cánovas Enrique , Menghini Mariela , Gómez Alicia , Bernardo-Gavito Ramón , Granados Daniel 
Published: September 2023

Two-dimensional materials like graphene or transition metal dichalcogenides have remarkable properties, making them very attractive from a technological point of view and incredibly fun to work with. The intrinsic properties of 2D materials change drastically when going from the bulk into the true 2D limit, where they exhibit exotic quantum properties. While many groups have focused on studying and exploiting these materials, very little work has been devoted to engineering their intrinsic properties. The “all-surface” nature makes device fabrication complex, and so far, only the most conventional nanofabrication or tailoring routes have been explored. In this talk, I will present novel routes currently under exploration in our group to tailor and exploit the properties of TMDS and MOF devices based on mechanical deformation or physical nanopatterning.
Also, the integration of 2D materials into superconducting circuits can lead to novel technological applications of interest for photon and radiation detectors or quantum computing.
In this talk, I will present some results concerning the development of retroreflectors based on MoS2 oscillating membranes and how they can be turned into electroluminescent diodes. I will also present the tailoring of conductive channels on MoS2 FET devices. Preliminary results on lateral PN homo-junctions, memristive field-effect transistors and photonic crystal cavities will also be presented. I will present preliminary results on the integration of MOF into Hall bar structures for metrology applications. To finish, I will also present results on the integration of Graphene and MoS2 onto Superconducting nanowire single photon detectors.

Figure 1
(Invited) Discovery of Longer Fullertubes: From Synthesis to Isolation
Authors: Bourret Emmanuel , Dorn Harry , Stevenson Steven 
Published: September 2023

Our recent laboratory findings are resulting in a growing list of newly discovered molecules within fullertube families. We are now isolating these individual fullertubes of increasing length in pure and pristine form. We now observe solubility of these fullertubes in organic solvents; hence it is unnecessary to use polymer wrapping or external derivatization that destroys the pristine fullertubular belt with pendant soluble groups. Initial purification and seminal characterization experiments for fullertubes in JACS, Angewandte Chemie, and Nanoscale (2020-2022) are generating excitement for application development. Likewise, investigations into the fundamental science of new fullertubes are also gathering momentum as scientists curiously and eagerly await their first characterization.
For historical context, the timeline of laboratory purified and unfunctionalized (pristine) fullertubes is [5,5] C90-D5h(1) in 2010, [5,5] C100-D5d(1) in 2020, and [5,5] C120-D5d(1) in 2022. A recurring question asked to me at conferences is “To what lengths can fullertubes be extended?” For this reason, I will discuss our most recent findings and explorations into longer fullertubes with higher aspect ratios.

Figure 1
(Invited) Precise Evaluation of Functional Group Distribution and Reaction Yield for Chemically Treated Carbon Nanohorns by Highly Sensitive SEM-EDS
Authors: Nakajima Hideaki , Okazaki Toshiya 
Published: September 2023

Single-walled carbon nanohorns (CNHs) have great potential in diverse applications such as catalyst support, energy conversion, and drug carriers. Although chemical functionalization of CNHs is critical for these applications, they inherently form robust spherical “dahlia-like” aggregates, which may inhibit chemical reactivity. Herein, highly sensitive energy-dispersive X-ray spectrometry (EDS) analysis in scanning electron microscopy (SEM) is employed to elucidate the functional group distribution and the reaction yield of CNH dahlia aggregates. First, the technique clearly visualizes the elemental distribution associated with the functional groups on dahlia structures with a sufficient spatial resolution of <10 nm.1 The result exposes that the outer surface of an individual aggregate is functionalized while the inner core remains almost unreacted. Second, the SEM-EDS precisely assesses the reaction yield for functionalized CNHs.2 The sensitive elemental analysis enables the evaluation of functionalization efficiency for sequentially grown polyamidoamine dendrimers on CNH surface, which consistently explains the change of chemical structure according to the reaction process. The details about the functionalization mechanism on CNH surface will be discussed in the conference.
[1] H. Nakajima, T. Morimoto, K. Kobashi, M. Zhang, I. K. Sideri, N. Tagmatarchis, and T. Okazaki, Outer-Surface Covalent Functionalization of Carbon Nanohorn Spherical Aggregates Assessed by Highly Spatial-Resolved Energy-Dispersive X-ray Spectrometry in Scanning Electron Microscopy, J. Phys. Chem. C
2020, 124, 25142-25147.
[2] H. Nakajima, K. Kobashi, C. Stangel, T. Morimoto, M. Zhang, N. Tagmatarchis, and T. Okazaki, Step-by-step Characterization of a Series of Polyamidoamine Dendrimers on Carbon Nanohorn Surface, submitted.
(Invited) Synthetic Exploration of Functional Nanographenes for Photonic Applications
Authors: Narita Akimitsu 
Published: September 2023

Nanographenes, or large polycyclic aromatic hydrocarbons (PAHs), have been attracting renewed attentions for their unique optical, electronic, and magnetic properties [1]. Nanographenes can also be considered as atomically precise graphene quantum dots (GQDs), which are promising as an environmentally friendly alternative of semiconductor quantum dots, especially for photonic applications ranging from light-emitting devices to bioimaging. To this end, we have been exploring the synthesis and functionalization of dibenzo[hi,st]ovalene (DBOV) as a nanographene with zigzag and armchair edges, which demonstrated high stability, strong red emission, and optical gain properties [1,2]. For example, the functionalization of DBOV with two fluoranthene imide (FAI) groups induced red-shift of the absorption and emission bands, increase of the Stokes shift, and enhancement of the stimulated emission (SE) signals with significantly reduced excited state absorption, allowing the efficient lasing at 720 nm [3]. More recently, we have synthesized dibenzo[a,m]dinaphtho[3,2,1-ef:1',2',3'-hi]coronene (DBDNC) with armchair, zigzag, and fjord edges, which also showed high stability and red emission [4]. Notably, DBDNC has a nonplanar structure around the fjord edges, as revealed by the single-crystal X-ray analysis, and displayed a SE signal at 710 nm with a longer lifetime than that of DBOV, presumably due to the suppression of intermolecular interactions. These results provide a further insight into the relationship between the PAH structures and their photophysical properties, paving the way toward their photonic applications.
[1] Paternò, G. M.; Goudappagouda, Chen, Q.; Lanzani, G.; Scotognella, F; Narita A., Adv. Optical Mater. 2021, 9, 2100508.
[2] Paternò, G. M.; Chen, Q.; Wang, X.-Y.; Liu, J.; Motti, S. G.; Petrozza, A.; Feng, X.; Lanzani, G.; Müllen, K.; Narita, A.; Scotognella, F., Angew. Chem. Int. Ed.
2017,
56, 6753–6757.
[3] Paternò, G. M.; Chen, Q.; Muñoz-Mármol, R.; Guizzardi, M.; Bonal, V.; Kabe, R.; Barker, A. J.; Boj, P. G.; Chatterjee, S.; Ie, Y.; Villalvilla, J. M.; Quintana, J. A.; Scotognella, F.; Müllen, K.; Díaz-García, M. A.; Narita, A.; Lanzani, G., Mater.
Horiz. 2022,9, 393–402.
[4] Xu, X.; Serra, G.; Villa, A.; Muñoz-Mármol, R.; Vasylevskyi, S.; Gadea, M.; Lucotti, A.; Lin, Z.; Boj, P. G.; Kabe, R.; Tommasini, M.; Díaz-García, M. Á.; Scotognella, F.; Paternò, G. M.; Narita, A., Chem. Sci.
2022, 13, 13040–13045
(Invited) Effect of the Electron-Donating and Electron-Withdrawing Substituent on the Diels-Alder Cycloaddition Reaction of Hemifullerenes with 1,3-Butadiene
Authors: Mojica Martha , Méndez Francisco , Alonso Julio A. , Richaud Arlette , López María J. 
Published: September 2023

In the search for an efficient method to synthesize C60, the dimerization strategy of two C30H12 fragments has been considered (1,2). Scott et. al. (3) have demonstrated that the Diels-Alder cycloaddition reaction in the bay regions of a polycyclic aromatic hydrocarbon (PAH) can occur at low temperatures (below 150ᵒC), they have also shown that the use of nitroethylene as masked-acetylene in a DA reaction over the bay regions of perylene and 7,14-dimesitylbisanthene leads to a rapid conversion of the bay regions of the PAH to new unsubstituted benzene rings (4) .This findings allow us to think that the use of a set of substituents on the C30H12 fragment would be a good strategy to favor the DA reaction of substituted C30H12 fragment with butadiene and reduce the activation energies of the reaction. Our previous calculations showed that the DA reaction of 1,3-butadiene with the rim of the C30H12 fragment might be possible, having an activation energy close to that calculated for the DA reaction with 1,3-butadiene and ethylene (5). In this work a theoretical study of the electronic, thermodynamic and kinetic parameters of the Diels-Alder reaction of butadiene with the rims of the substituted C30H12 fragments (triindenetriphenylene 1 and pentacyclopentacorannulene 2) as well as the aromatization of the obtained adducts was carried out (6).
(1) a) Scott, L.T. Angew. Chem. Int. Ed. 2004, 43, 4994.; b) Tsefrikas, V.M.; Scott, L.T. Chem. Rev. 2006, 106, 4868; c) Abdourazak, A.H.; Marcinow, Z.; Sygula, A.; Sygula, R.; Rabideau, P.W. J. Am. Chem. Soc. 1995, 117, 6410.
(2) Richaud, A.; López, M.J.; Mojica, M.; Alonso, J. A, Méndez, F. RSC Adv., 2020, 10, 3689.
(3) Fort, E.H.; Donovan, P.M.; L. T. Scott, L.T. J. Am. Chem. Soc., 2009, 131, 16006.
(4) E. H. Fort, L. T. Scott, Angew. Chem. Int. Ed. 2010, 49, 6626.
(5) Mojica, M.; Méndez, F.; Alonso, J.A. Molecules 2013, 18, 2243.
(6) Mojica, M.; Méndez, F.; Alonso, J.A. Molecules 2016, 21, 200.

Figure 1
(Invited) Giant Molecular Nanoribbons
Authors: Mateo-Alonso Aurelio 
Published: September 2023

In the last years, chemists have devoted significant efforts to the synthesis of increasingly larger molecular structures that push boundaries of the molecular world into the nanoscale. Among these structures, molecular nanoribbons have received considerable both as synthetic challenges and as a unique platform to develop new materials because the nanoribbon structure dominates the optical, electronic, electrical, and magnetic properties.
In these terms, we have introduced several approaches to prepare molecular graphene nanoribbons and nanographenes that reach dimensions (12.9 nm in length and 322 sp2 atoms in the aromatic core) that exceed both the largest lengths reported for molecular nanoribbons and the largest aromatic cores reported for nanographenes.[1-6] The most recent advances in the synthesis of such giant molecular nanoribbons will be discussed.

References
[1] D. Cortizo-Lacalle, J. P. Mora-Fuentes, K. Strutyński, A. Saeki, M. Melle-Franco and A. Mateo-Alonso Angew. Chem. Int. Ed. 57 (2018) 703.
[2] J.P. Mora-Fuentes, A. Riaño, D. Cortizo-Lacalle, A. Saeki, M. Melle-Franco, A. Mateo-Alonso Angew. Chem. Int. Ed. 58 (2019) 552.
[3] R. K. Dubey, M. Melle-Franco, and A. Mateo-Alonso J. Am. Chem. Soc. 143 (2021) 6593.
[4] R. K. Dubey, M. Melle-Franco, and A. Mateo-Alonso J. Am. Chem. Soc. 144 (2022) 2765.
[5] F. Hernández-Culebras, M. Melle-Franco, and A. Mateo-AlonsoAngew. Chem. Int. Ed. 61 (2022), e202205018.
[6] M. Martínez-Abadía, R. K. Dubey, M. Fernández, M. Martín-Arroyo, R. Aguirresarobe, A. Saeki, and A. Mateo-Alonso Chem. Sci. 13 (2022), 10773-10778.

Figure 1
(Invited) Photoinduced Electron Transfer in Dyads Involving Complexes of C60 and Nanohoops. Effect of π-Extension and Aromaticity of the Nanohoop
Authors: Solà Miquel , George Gibu , Stasyuk Olga A. , Stasyuk Anton , Voityuk Alexander A. 
Published: September 2023

Conversion of the sunlight into chemical energy is considered to be one of the most important and fundamental chemical reactions in nature. A broad variety of artificial photosynthetic systems based on dyads, triads and up to pentads involving electron donor and acceptor moieties have been designed and synthesized in order to investigate artificial photoinduced energy and electron transfer processes. One type of dyads with potential applications in solar cells is the one combining C60 complexed with nanohoops.[1] In this work, we discuss a series of computational studies that involves the photoinduced charge separation in complexes of C60 and Li+@C60 with a series of different nanohoops, such as the [10]cycloparaphenylene ([10]CPP) ring,[2] π-extended CPPs such as the hexa-peri-benzocoronene (HBC) or the tribenzo[fj,ij,rst]pentaphene (TBP),[3] and [n]cyclodibenzopentalenes ([n]CDBPs) as antiaromatic curved nanorings.[4] The analysis of complexes of C60 with nanohoops having different degrees of π-conjugation and aromaticity allow us to discuss the effect in the charge transfer separation and recombination on the level of π-extension and aromaticity present in the nanohoops.

References

[1] (a) M. Hermann, D. Wassy, B. Esser, Angew. Chem. Int. Ed. 60 (2021) 15743–15766; (b) J. S. Wössner, D. Wassy, A. Weber, M. Bovenkerk, M. Hermann, M. Schmidt, B. Esser, J. Am. Chem. Soc. 143 (2021) 12244–12252.
[2] A. J. Stasyuk, O. A. Stasyuk, M. Solà and A. A. Voityuk, Chem. Commun. 55 (2019) 11195-11198.
[3] Manuscript in preparation.
[4] G. George, O. A. Stasyuk, A. A. Voityuk, A. J. Stasyuk and M. Solà. Nanoscale, in revision.

Figure 1