bluuebunny/crossref_metadata_2025 huggingface dataset:
Deciphering Drug Targets and Actions with Single-Cell and Spatial Resolution
Authors: Pang Zhengyuan , Cravatt Benjamin F. , Ye Li
Published: September 2023

Recent advances in chemical, molecular, and genetic approaches have provided us with an unprecedented capacity to identify drug-target interactions across the whole proteome and genome. Meanwhile, rapid developments of single-cell and spatial omics technologies are revolutionizing our understanding of the molecular architecture of biological systems. However, a significant gap remains in how we align our understanding of drug actions, traditionally based on molecular affinities, with the in vivo cellular and spatial tissue heterogeneity revealed by these newer techniques. Here, we review state-of-the-art methods for profiling drug-target interactions and emerging multiomics tools to delineate the tissue heterogeneity at single-cell resolution. Highlighting the recent technical advances enabling high-resolution, multiplexable in situ small-molecule drug imaging (clearing-assisted tissue click chemistry, or CATCH), we foresee the integration of single-cell and spatial omics platforms, data, and concepts into the future framework of defining and understanding in vivo drug-target interactions and mechanisms of actions.
Physics-Integrated Machine Learning for Efficient Design and Optimization of a Nanoscale Carbon Nanotube Field-Effect Transistor
Authors: Fan Guangxi , Low Kain Lu
Published: September 2023

We propose an efficient framework for optimizing the design of Carbon Nanotube Field-Effect Transistor (CNTFET) through the integration of device physics, machine learning (ML), and multi-objective optimization (MOO). Firstly, we leverage the calibrated TCAD model based on experimental data to dissect the physical mechanisms of CNTFET, gaining insights into its operational principles and unique physical properties. This model also serves as a foundation, enabling multi-scale performance evaluations essential for dataset construction. In the ML phase, a chain structure of Support Vector Regression (SVR Chain) guided by a comprehensive statistical analysis of the design metrics is utilized to predict the design metrics. The surrogate model based on the SVR Chain achieves an average mean absolute percentage error (MAPE) of 1.59% across all design metrics without overfitting, even with limited data. The established ML model exhibits its competence in rapidly producing a global response surface for multi-scale CNTFET. Remarkably, an anomalous equivalent oxide thickness (EOT) and ON-state current (I

on
) relationship is observed in CNTFET behavior due to extreme gate length scaling in long channel devices. This intriguing observation is further elucidated through a physics-based explanation. We further compare shallow and deep learning-based TCAD digital twins for model selection guidance. Using the Non-Dominated Sorted Genetic Algorithm-II (NSGA-II) in MOO, we harmonize metrics at both device and circuit levels, significantly reducing the design space. The closed-loop framework expedites the early-stage development of advanced transistors, overcoming the challenges posed by limited data.
(Invited) Signatures of Charge Carrier (De)Localization in Semiconducting Single-Walled Carbon Nanotubes
Authors: Blackburn Jeff , Hermosilla Palacios Martha Alejandra , Reid Obadiah , Ferguson Andrew
Published: September 2023

Semiconducting single-walled carbon nanotubes (s-SWCNTs) are attractive materials for a variety of opto-electronic devices and applications due their strong and energetically tunable optical absorption, and high charge carrier mobilities that result from the delocalized nature of the π-electron system. To realize the full potential of s-SWCNTs in these applications, it is critical to understand the generation, transport, interfacial transfer, and recombination of free charge carriers (electrons and holes). As with many pi-conjugated semiconductors, there remain uncertainties regarding the degree of (de)localization for charge carriers generated in s-SWCNTs either through photogenerated exciton dissociation or through charge injection by adsorbed redox dopants or gating. In this presentation, I will compare the various signatures of charge carrier localization and delocalization that appear in spectroscopic and transport studies of s-SWCNTs in a variety of different environments and over several decades of carrier density. These comparisons help to elucidate the important roles of intrinsic and extrinsic factors on carrier (de)localization and the information that spectroscopic signatures in the visible, near-IR, and mid-IR can provide on such (de)localization.
CNT Film Chemically Bonding to Metal Surfaces
Authors: Nawarathne Chaminda P , Hoque Md Abdul , Dangel Gabrielle R. , Alvarez Noe T
Published: September 2023

Carbon nanotubes can be considered as a chemically stable material with exceptional electrical and thermal conductive properties. Electrically conductive applications of carbon nanotubes (CNTs) have been limited by several factors, among them a lack of robust connections to metal surfaces is significant affecting for CNT widespread applications. In this work CNT side walls bonded to different metal surfaces including Cu, Al, Stainless steel, Au and ITO with electrically conductive aminophenyl linkers which can react with metal substrates via diazonium grafting reaction leaving basic functional groups on the metal surface to react with acidic functional groups of the oxidized CNTs. The chemical nature and robustness of the linker-metal bonding was investigated using X-ray photoelectron spectroscopy and Infrared spectroscopy following ultrasonication. Thin layer of CNTs were observed on the surface of the metal surfaces with scanning electron microscopy analysis after ultrasonication. CNT modified metal surfaces showed enhanced current densities compared to the bare metal surfaces in electrochemical analysis in Ru2+/Ru3+ aqueous solution. Finally, ability of the metal-linker-CNT bonding to enhanced the metal-CNT interface conductivity was demonstrated by measuring interface resistance of the CNT-linker-Au system compared to the direct CNT-metal contacts.
(Invited) DNA-Wrapped CNTs: From Precise Assembly to Energy-Efficient Electronic Switches
Authors: Zhao Mengyu , Chen Yahong , Liu Zhihan , Shen Jie , Zhu Zhi , Sun Wei
Published: September 2023

Since the invention of the first transistor, the interdisciplinary researches involving chemistry, materials science, and solid-state physics have contributed to the development of semiconductor electronics. At the crossroads towards future electronics, biological systems inspire the evolving of computing architectures and manufacturing framework. For instance, the high-resolution DNA self-assembly tools, developed in synthetic biology, have recently been used to construct ultra-scaled CNT transistors at a resolution superior to conventional lithography, which displayed fast on/off switching characteristics. Meanwhile, by wiring multiple individual CNT transistors, we demonstrated Boolean logic gates within the bio-templated electronics. Our works suggest the potentials of building complex energy-efficient circuits from the bio-templated assembly of CNTs.
(Invited) The Impact of Carbon Nanotube Length and Diameter on Their Global Alignment by Dead-End Filtration
Authors: Rust Christian , Shapturenka Pavel , Spari Manuel , Jin Qihao , Li Han , Bacher Andreas , Guttmann Markus , Zheng Ming , Adel Tehseen , Hight Walker Angela , Fagan Jeffrey , Flavel Benjamin S
Published: September 2023

Dead-end filtration on polyvinylpyrrolidone-coated polycarbonate track-etched membranes has proven to be an effective method to prepare macroscopically (3.8 cm²) aligned thin films from solution-based single-wall carbon nanotubes (SWCNTs). However, to make this technique broadly applicable, the role of SWCNT length and diameter on the alignment process must be understood. To date, most groups report the alignment of unsorted large diameter (» 1.4 nm) SWCNTs, but systematic studies on their small diameter (» 0.78 nm) counterparts are rare and in the case of sorted SWCNT species, non-existent. In this work, films are prepared from two series of length sorted fractions comprised of small and large diameter SWCNTs, respectively. The degree of alignment is characterized by cross polarized microscopy, scanning electron microscopy and Raman spectroscopy. For the longest fractions, the two-dimensional order parameter, , values of » 0.66 and » 0.76 are reported for the small and large diameter SWCNTs, respectively, and Raman maps over an area of 2500 μm2 are presented. A comparison of Derjaguin, Landau, Verwey and Overbeek (DLVO) theory calculations with the aligned domain size is then used to propose a law identifying the required length of a carbon nanotube with a given diameter and zeta potential for alignment.
Assembly and Characterization of Length-Sorted, Aligned Boron Nitride/Carbon Nanotube Thin Film Composites Via Slow Vacuum Filtration
Authors: Shapturenka Pavel , Fagan Jeffrey
Published: September 2023

Globally aligned single-wall carbon nanotubes (SWCNTs) are a promising, scalable platform for studying fundamental physical phenomena and an important vehicle for optoelectronic device applications. Recent work by Rust et al. [1] has identified nanotube length as an important mediating factor in the degree and scale of SWCNT alignment via slow vacuum filtration (SVF).

Building on this work and that of Walker et al. [2,3], we explore the co-assembly of length-sorted SWCNTs and boron nitride nanotubes (BNNTs) atop polycarbonate track-etched membranes. BNNTs have recently gained interest as a chirality-agnostic, wide-bandgap material for encapsulation, insulation, thermal/mechanical robustness, and visible-light transparency, while also having a similar high aspect ratio morphology, making them an exceptional and alignable host matrix for individualized CNT species. To prepare such hybrid assemblies, a polymer-assisted, depletion-based method was first used to length-sort different diameter SWCNT (alkane filled electric-arc, CoMoCAT, metallic-sorted Tuball), and BNNT nanotube populations. Thereafter, we investigated the impacts of tube lengths, relative BN/C fraction, mass loading, and presence of a global director force on the multi-scale assembly behavior. A combination of birefringence microscopy and polarized Raman spectroscopy probed and identified trends in global and local ordering under these conditions.

[1] Rust, C., Shapturenka, P., Spari, M., Jin, Q., Li, H., Bacher, A., Guttmann, M., Zheng, M., Adel, T., Hight Walker, A. R., Fagan, J. A., & Flavel, B. S. (2022). The Impact of Carbon Nanotube Length and Diameter on their Global Alignment by Dead-End Filtration. Small (forthcoming).

[2] Walker, J. S., Fagan, J. A., Biacchi, A. J., Kuehl, V. A., Searles, T. A., Hight Walker, A. R., & Rice, W. D. (2019). Global Alignment of Solution-Based Single-Wall Carbon Nanotube Films via Machine-Vision Controlled Filtration. Nano Letters, 19(10), 7256–7264.

[3] Walker, J. S., Macdermid, Z. J., Fagan, J. A., Kolmakov, A., Biacchi, A. J., Searles, T. A., Walker, A. R. H., & Rice, W. D. (2022). Dependence of Single‐Wall Carbon Nanotube Alignment on the Filter Membrane Interface in Slow Vacuum Filtration. Small, 18, 2105619.
Electroneutrality Breakdown and Perm-Selective End Groups in Carbon Nanotube Porins
Authors: Markiewitz Daniel M. , de Souza J. Pedro , Noy Aleksandr , Bazant Martin Z.
Published: September 2023

Sub-nanometer carbon nanotube porins (n-CNTP) have been shown to achieve high water permeation with significant permselectivity precluding anion transport. Therefore, n-CNTPs are useful model systems to probe and optimize the nanoscale transport phenomena relevant for selective ionic separations. Surprisingly, these n-CNTPs demonstrate a unique conductance scaling behavior with ionic concentration, which has led to various continuum models being constructed in pursuit of determining the underpinning physics governing nanoscale ionic transport. Here, we formulate a continuum model to capture the conductance and permselectivity of n-CTNPs considering the breakdown of electroneutrality within the pore. Electroneutrality breakdown occurs when the ionic charge within the pore is not balanced by the charge on the pore walls. While electroneutrality is commonly assumed in the analysis of nanopore transport, we predict a departure from electroneutrality due to the extreme one-dimensional confinement in n-CNTPs, strongly influencing the conductance and selectivity of the pore. Furthermore, our analysis demonstrates the importance of the entrance groups in modulating ion transport through n-CNTPs. Lastly, we provide a framework for future refinements to incorporate additional microscopic physics into the phenomenological model.
(Invited) Microenvironment Responsiveness of Defect Photoluminescence of Locally Functionalized Single-Walled Carbon Nanotubes and Its Sensing Applications
Authors: Shiraki Tomohiro , Niidome Yoshiaki , Fujigaya Tsuyohiko
Published: September 2023

Photoluminescence (PL) of single-walled carbon nanotubes (SWCNTs) in the near infrared (NIR) region is applicable to advanced optical applications such as bio-imaging and sensing. Local chemical functionalization (slight amount of chemical modification) of SWCNTs has been developed to introduce sp3 carbon defects in the sp2 carbon network of the tube walls for the luminescent defect formation.[1-3] The resultant locally functionalized SWCNTs (lf-SWCNTs) show defect PL (E
11* PL) with red-shifted wavelengths and increased quantum yields compared to original E
11 PL of pristine SWCNTs. For lf-SWCNTs, molecularly designed modifier molecules have enabled the defect PL wavelength modulation[4] and the sensing function creation.[5,6]

Recently, we have reported the unique microenvironment responsiveness of defect PL of lf-SWCNTs; namely, the greater wavelength shifts of E
11* PL than E
11 PL by dielectric effects[7] and the PL shifting behavior modulation based on the chemical structure difference of the functionalized sites and the exciton localization effects[8] were observed. The microenvironment responsiveness of the defect PL was applied to the biological sensing application development.[9] To investigate protein detection/recognition functions of lf-SWCNTs, we introduced an avidin-biotin interaction with a selective and strong binding fashion at the functionalized sites of lf-SWCNTs. The lf-SWCNTs tethering biotin groups (lf-SWCNTs-b) were synthesized through diazonium chemistry, followed by its subsequent-modification. When neutravidin was mixed with a lf-SWCNTs-b solution, E
11* PL peak was red-shifted, indicating the higher polarity environment formation by the neutravidin adsorption on lf-SWCNTs-b. When avidin or streptavidin was used, wavelength shifting behaviors of E
11* PL of lf-SWCNTs-b were clearly changed depending on the used avidin derivatives. The results indicate the different polarity environment formation deriving from structural differences of each avidin derivative. Moreover, the detection signal enhancement was observed in a film device using lf-SWCNTs-b. Therefore, lf-SWCNTs have a high potential for development of advanced protein detection/recognition systems using NIR PL.

[1] T. Shiraki et al. Acc. Chem. Res., 53, 1846 (2020). [2] S. Tretiak et al., Acc. Chem. Res., 53, 1791(2020) [3] Y. Wang et al. Nat. Rev. Chem., 3, 375 (2019). [4] T. Shiraki et al. ACS Nano, DOI: 10.1021/acsnano.2c09897 (2022). [5] T. Shiraki et al. Chem. Commun., 52, 12972 (2016). [6] S. Kruss et al, Angew. Chem. Int. Ed., 59, 17732 (2020). [7] T. Shiraki et al. Chem. Commun., 55, 3662 (2019). [8] T. Shiraki et al. J. Phys. Chem. C, 125, 12758 (2021). [9] T. Shiraki et al. Nanoscale, 14, 13090 (2022).

Figure 1
(Invited) Mechanically Interlocked Derivatives of SWNTs: What, Why, How, and What for?
Authors: Perez Emilio M
Published: September 2023

In the last few years, the mechanical bond has been added to the chemistry toolbox for SWNT modification.[1] In this presentation, I will first discuss the characteristics of the mechanical bond that make it appealing for SWNTs. I will then describe the potential advantages of making mechanically-interlocked derivatives of SWNTs (MINTs), as compared to covalent or classic supramolecular derivatives of SWNTs, and go on to explain our approach for the synthesis of MINTs.[2,3] Finally, I will illustrate with examples how the making of MINTs can contribute to modifying the surface properties of SWNTs,[4] modulating their electronic properties,[5] and linking them to functional molecular fragments.[6,7]

References

[1] A. López-Moreno, J. Villalva, E. M. Pérez, “Mechanically interlocked derivatives of carbon nanotubes: synthesis and potential applications” Chem. Soc. Rev. 2022, 51, 9433-9444.

[2] A. de Juan, Y. Pouillon, L. Ruiz-González, A. Torres-Pardo, S. Casado, N. Martín, A. Rubio, E. M. Pérez, Angew. Chem., Int. Ed. 2014, 53, 5394-5400.

[3] E. M. Pérez, Chem. Eur. J. 2017, 23, 12681-12689.

[4] A. López-Moreno, B. Nieto-Ortega, M. Moffa, A. de Juan, M. M. Bernal, J. P. Fernández-Blázquez, J. J. Vilatela, D. Pisignano, E. M. Pérez, ACS Nano 2016, 10, 8012-8018.

[5] M. Blanco, B. Nieto-Ortega, A. de Juan, M. Vera-Hidalgo, A. López-Moreno, S. Casado, L. R. González, H. Sawada, J. M. González-Calbet, and E. M. Pérez, Nat. Commun. 2018, 9, 2671.

[6] S. Moreno-Da Silva, J. I. Martínez, A. Develioglu, B. Nieto-Ortega, L. de Juan-Fernández, L. Ruiz-Gonzalez, A. Picón, S. Oberli, P. J. Alonso, D. Moonshiram, E. M. Pérez, E. Burzurí, J. Am. Chem. Soc. 2021, 143, 21286-21293.

[7] W. Zhang, M. Guillén-Soler, S. Moreno-Da Silva, A. López-Moreno, M. L. Ruiz-González, M. Giménez, E. M. Pérez Chem. Sci., 2022, 13, 9706-9712.

Figure 1
(Invited) Nanostructuration and Application of Supramolecular Materials through 1D, 2D and 3D-Hydrogen Bond-Directed Self-Assembly
Authors: Curiel David , Gómez Paula , Giménez Isaac , Carrera Manuel , Más-Montoya Miriam , Georgakopoulos Stamatis , Mora-Seró Iván , Méndez Javier
Published: September 2023

Self-assembly is a useful tool in Chemistry for the development of organized supramolecular systems stabilized by non-covalent interactions.[1] The rational design of organic molecules that suitably integrate different interacting sites into their structure becomes an attractive approach to control the molecular arrangement by exploiting the driving force of those non-covalent interactions.[2] With this objective in mind, we have synthesized a series of π-conjugated molecules that incorporate the 7-azaindole unit as building block to induce the supramolecular self-assembly in the solid state through reciprocal hydrogen bonding.[3]

The judicious alteration of the molecular geometry has demonstrated the adequacy of this self-assembly strategy to achieve the control on the directionality of N-H···N hydrogen bond interactions. Consequently, 1D, 2D and 3D-supramolecular systems have been obtained with interesting structural properties.[4] In this communication we present our recent advances in this approach towards supramolecular materials, particularly focusing on their application as organic semiconductors in devices such as Organic Field Effect Transistors and perovskite solar cells.[5] The performance of these novel molecules as hole transporting materials has revealed a remarkable robustness despite their non-covalent nature. Accordingly, these results offer a proof of concept about the potential utility of supramolecular self-assembly in the development of novel nanostructured materials.

References

[1] S. I. Stupp, L. C. Palmer, Chem. Mater.
2014, 26, 507-518.

[2] a) K. S. Mali, N. Pearce, S. De Feyter, N. R. Champness, Chem. Soc. Rev.
2017, 46, 2520-2542; b) R.-B. Lin, Y. He, P. Li, H. Wang, W. Zhou, B. Chen, Chem. Soc.
Rev.
2019, 48, 1362-1389.

[3] P. Gómez, J. Cerdá, M. Más-Montoya, S. Georgakopoulos, I. da Silva, A. García, E. Ortí, J. Aragó, D. Curiel, J. Mater. Chem. C
2021, 9, 10819-10829.

[4] L. M. Rodríguez, P. Gómez, M. Más-Montoya, J. Abad, A. Tárraga, J. I. Cerdá, J. Méndez, D. Curiel, Angew. Chem. Int. Ed.
2021, 60, 1782-1788.

[5] a) P. Gómez, J. Wang, M. Más-Montoya, D. Bautista, C. H. L. Weijtens, D. Curiel, R. A. J. Janssen, Solar RRL
2021, 5, 2100454; b) P. Gómez, S. Georgakopoulos, M. Más-Montoya, J. Cerdá, J. Pérez, E. Ortí, J. Aragó, D. Curiel, ACS Appl.
Mater. Interfaces
2021, 13, 8620-8630.

Acknowledgements

Ministry of Science, Innovation and Universities (Project RTI2018-101092-B-I00). Fundación Séneca - Agencia de Ciencia y Tecnología de la Región de Murcia (Project 20959/PI/18). Programa Estatal de Fomento de la Investigación Científica y Técnica de Excelencia (RED2018-102815-T).

Figure 1
(Invited) Smart Molecular/2D Heterostructures
Authors: Coronado Eugenio
Published: September 2023

Graphene and other 2D materials are almost exclusively based on inorganic lattices. Except for the chemical functionalization of the surface of the 2D material, molecules have been scarcely considered in this area. Here I propose to create hybrid heterostructures by interfacing stimuli-responsive molecular systems with graphene and semiconducting transition metal dichalcogenides (MoS2 and WSe2). The aim is that of tuning the properties of the “all surface” 2D material via an active control of the hybrid interface. This concept will provide an entire new class of smart molecular/2D heterostructures, which may be at the origin of a novel generation of hybrid materials and devices of direct application in highly topical fields like electronics, spintronics and energy storage. As smart-molecular systems I will choose magnetic spin-crossover materials able to switch between two spin states upon the application of an external stimulus (temperature, light or pressure) [2]. This spin transition is always accompanied by a significant change of volume in the material (by ca. 10%), so it can generate strain in its surroundings. I will show that in these heterostructures the electronic properties of graphene and the optical photoluminescence of monolayers of semiconducting metal dichalcogenides can be switched by light or by varying the temperature due to the strain concomitant to the spin transition [3, 4].

References

[1] J. Lopez-Cabrelles et al., J. Am. Chem. Soc. 143 18502-18510 (2021).

[2] E. Coronado, Nature Rev. Mater. 5 87-104 (2020).

[3] R. Torres-Cavanillas et al. Nature Chem. 13 1101-1109 (2021).

[4] C. Boix-Constant et al. Adv. Mater. 34 2110027 (2022).
(Invited) Modification of Properties of N- and B-Doped Graphene by Heteroatom Functionalization
Authors: Arellano Luis M , Barrejon Myriam , Gómez-Escalonilla Romojaro Maria , Langa Fernando
Published: September 2023

Since its discovery in 2004, the graphene has attracted great attention owing to its unique chemical bonding structure, which has excellent chemical, thermal, mechanical, electrical and optical properties. Due to the graphene being a zero band-gap material, it has a limited development in the field of nano electronics. Therefore, to broaden its application scope, it is very important to carry out a study on opening the band gap of graphene. One general strategy for achieving this goal is doping graphene with heteroatoms; in this approach, the properties of graphene are controlled by the nature of the dopant elements and by the percentage of doping being N-doped graphene is of n-type doping, while B-doped graphene is of p-type doping. Compared with that of the intrinsic graphene, the Fermi level of N doped graphene moves up 5 eV; on the contrary, the Fermi level of B doped graphene moves down 3 eV.

However, it would be convenient to develop additional tools to achieve further control of the electronic properties of graphene materials. In this context, one of the possibilities would be to functionalize those dopant elements on the graphene sheet in such a way that the electron density and electronegativity of the heteroatom are effectively controlled. This objective could, in principle, be achieved by applying concepts from organic chemistry. Organic synthesis offers proven chemical reactions that are applicable to different types of nitrogen and boron compounds.

In the work described here, we´ll present our results on the covalent functionalization of the nitrogen atom or boron atom of N-doped and B-doped graphene. In a simple strategy, electron-donating and -withdrawing groups present on aromatic rings can be used to modulate the electronic properties of the material.

References

[1] M. Barrejón, A. Primo, M. J. Gómez-Escalonilla, J. L. García-Fierro, H. García, F. Langa, Chem. Comm. 2015, 51, 16916-16919.

[2] M. Barrejón, L. M. Arellano, H. B. Gobeze, M. J. Gómez-Escalonilla, J. L. García-Fierro, F. D’Souza, F. Langa, Chem. Sci. 2018, 9, 8221–8227.

[3] H. B. Gobeze, L. M. Arellano, A. M. Gutiérrez-Vílchez, M. J. Gómez-Escalonilla, Á. Sastre-Santos, F. Fernández-Lázaro, F. Langa, F. D’Souza, Nanoscale Adv, 2019, 1, 4009-4015.

[4] L. M. Arellano, S. Yue, P. Atienzar, M.J. Gómez-Escalonilla, F.J. Ortega-Higueruelo, J.L.G. Fierro,H. García, F. Langa. Chem. Commun., 2019, 55, 9999.

[5] L. M. Arellano, H. B. Gobeze, Y. Jang, M. Barrejón, C. Parejo, J. C. Álvarez, M. J. Gómez-Escalonilla, A. Sastre-Santos, F. D’Souza, F. Langa, Chem. Eur. J, 2022 (https://doi.org/10.1002/chem.202200254)
(Invited) Conjugated Metallophthalocyanine as Hole-Transporting Materials for Improved Stability in Perovskite Solar Cells
Authors: Sastre-Santos Ángela
Published: September 2023

Perovskite solar cells (PSCs) are promising candidates to reach the market to complement the current offer of photovoltaic cells although for such a thing they still have to overcome some challenges such as long-term stability. The hole transporting layer (HTL) is a crucial component in n-i-p PSC, since it must favor an adequate movement of charges and protect the perovskite layer from environmental conditions. In this sense, the commonly used HTL, spiro-OMeTAD, does not provide PSCs with sufficient stability and is too expensive. Cheaper molecular materials such as metallophthalocyanines are proving to be a good alternative, as they provide greater stability.[1]

In this communication, we will present the synthesis of novel ZnPcs and CuPcsmonomers [2] and ZnPc dimers [3] (see as examples Figure 1) as efficient, stable, and low cost HTMs in PSCs. The MPcs are substituted with functional groups that possesses a very good solubility in a wide range of organic solvents, adequate HOMO LUMO levels and thus can be applied from solution processing in a wide range of perovskite solar cell devices.

References

1. M. Urbani, M. E. Ragoussi, M. K. Nazeeruddin, T. Torres, Coord. Chem. Rev.
2019, 381, 1-64.

2. P. Huang, A. Hernández, J. Follana-Berná, S. Kazim, J. Ortíz, Á. Sastre-Santos, S. Ahmad, ACS Appl. Energy Mater.
2021, 4, 9, 10124–1013

3. D. Molina, M. Pegu, M. João Álvaro-Martins, L. Ferrer, M. Castillo, S. Kazim, S. Ahmad, Á. Sastre-Santos, J. Mater. Chem. C, 2022, 10, 11975-11982.

Figure 1
(Invited) Hole-Transporting Materials for Perovskite Solar Cells: A Theoretical Insight
Authors: Ortí Enrique , Cerdá Jesús , Calbo Joaquín , Aragó Juan
Published: September 2023

Hole-transporting materials (HTMs) are a crucial component in obtaining high power conversion efficiencies (PCEs) in perovskite-based solar cells (PSCs). They play the important roles of extracting the photogenerated holes, formed within the perovskite film, and transporting them to the electrodes. Among the wide number of chemical structures proposed as HTMs for PSCs, small organic molecules have received special attention with spiro-OMeTAD (2,2´,7,7´-tetrakis(N,N-di-p-methoxyphenylamine)-9,9´-spirobifluorene) as a reference.1 In this communication, we first focus on how the donor ability and hole reorganization energy change with the chemical structure of the HTM. Sulfur-rich compounds, such as the anthracene-tetrathiophene ATT-OMe system displayed in Figure 1a, that have been used as HTMs in PSCs achieving remarkable PCEs, are theoretically described.2 Second, we investigate a series of HTMs based on fused polyheteroaromatic molecules incorporating 7-azaindole terminal moieties bearing hydrogen-bond donor and hydrogen-bond acceptor sites (Figure 1b). The 7-azaindole units induce the hydrogen-bond self-assembly of the conjugated molecules thus increasing the supramolecular ordering in the HTM layer. The effects of this ordering on the charrier transport in the HTM semiconducting layer are theoretically discussed.3 Third, we briefly present how the optical properties (energy bandgap) of Cs2AgBiBr6 lead-free double perovskites can be tuned by substituting the monovalent Ag1+ and trivalent Bi3+ cations by divalent Sn2+, Ge2+ and Zn2+ cations.4

Figure 1. Chemical structure of the sulfur-rich ATT-OMe (a) and the H-bond-promoting ADAI (b) HTM molecules. Both HTMs are based on an anthracene central core.

References

J. Urieta, I. García-Benito, A. Molina-Ontoria, N. Martín, Chem. Soc. Rev.
2016, 47, 8541.

I. Zimmermann, J. Urieta-Mora, P. Gratia, J. Aragó, G. Grancini, A. Molina-Ontoria, E. Ortí, N. Martín, M. K. Nazeeruddin, ACS Appl. Mater. Interfac.
2017, 7, 1601674.

P. Gómez, S. Georgakopoulos, M. Más-Montoya, J. Cerdá, J. Pérez, E. Ortí, J. Aragó, D. Curiel, J. Mater. Chem. C
2021, 13, 8620.

P. Sebastiá-Luna, J. Calbo, N. Albiach-Sebastián, M. Sessolo, F. Palazón, E. Ortí, H. J. Bolink, Chem. Mater.
2021, 33, 8028.

Figure 1
(Invited) Organic Charge Transporting-Layers and Additives in Perovskite Solar Cells
Authors: Delgado Juan L
Published: September 2023

In the present communication we will focus on the use of organic charge transporting materials that have synthesized in our lab and used to prepare Perovskite-based Solar Cells.1,2

In our research group we have dedicated a great effort on the preparation and study of novel organic compounds for their incorporation in perovskite solar devices, either as hole or electron-transporting layers. Thus, we have reported the use of fullerenes3,4 and NDIs5 as electron transporting layers in PSCs, to prepare efficient and stable devices. On the other hand we have prepared a great variety of hole transporting materials, including polymers,6 and Oligotryarylamine (OTA) functionalized with different cores such as HexaArylBenzene (HAB),7fullerene,8 or pillarene9 among others, to prepare highly efficient and stable in PSCs.

Acknowledgments

We would like to thank the research groups of Prof. Mora-Seró (Castellón, Spain), Prof. Martín (Madrid, Spain), Prof. Grätzel / Zakeeruddin (Lausanne, Switzerland), Prof. Chuvilin (San Sebastián, Spain), Prof. Nazeeruddin (Sion, Switzerland), Prof. Abate (HBZ, Berlin), Prof Seki (Kyoto, Japan), Prof. Nierengarten (Strasbourg, France).

References

1) Pascual, J.; Delgado, J. L.; Tena-Zaera, R. J. Phys. Chem. Lett. 2018, 9, 28933; 2) S. F. Volker, S. Collavini, J. L. Delgado, ChemSusChem 2015, 8, 3012. 3) Collavini, S.; Kosta, I.; Völker, S. F.; Cabanero, G.; Grande, H. J.; Tena-Zaera, R.; Delgado, J. L. ChemSusChem 2016, 9, 1263; 4) Pascual, J.; Kosta, I.; Ngo, T. T.; Chuvilin, A.; Cabanero, G.; Grande, H. J.; Barea, E. M.; Mora-Seró, I.; Delgado, J. L.; Tena-Zaera, R. ChemSusChem VIP 2016, 9, 2679; 5) S. Valero, A. Cabrera-Espinoza, S. Collavini, J. Pascual, N. Marinova, I. Kosta, J. L. Delgado, Eur. J. Org. Chem. 2020, 5329; 6) S. Valero, S. Collavini, S. F. Völker, M. Saliba, W. R. Tress, S. M. Zakeeruddin, M. Grätzel, and J. L. Delgado, Macromolecules, 2019, 52, 2243; 7) M. Shasti, S. F. Völker, S. Collavini, S. Valero, F. Ruipérez, A. Mortezaali, S. M. Zakeeruddin, M. Grätzel, A. Hagfeldt, J. L. Delgado, Org. Lett,. 2019 21, 3261; 8) S. F. Völker, M. Vallés-Pelarda, J. Pascual, S. Collavini, F. Ruiperez, E. Zuccatti, L. E. Hueso, R. Tena-Zaera, I. Mora-Seró and J. L. Delgado, Chem.–Eur. J., 2018, 24, 8524; 9) O.Bettucci, J. Pascual, S.-H. Turren-Cruz, A. Cabrera-Espinoza, W. Matsuda, S. F. Völker, H. Köbler, I. Nierengarten, G. Reginato, S. Collavini, S. Seki, J.-F. Nierengarten, A. Abate, J. L. Delgado, Chem. Eur. J. 2021, 27, 8110–8117

Figure 1
(Invited) Interplay Between π–Conjugation and Exchange Magnetism in One-Dimensional Porphyrinoid Polymers
Authors: Biswas Kalyan , Urbani Maxence , Sánchez-Grande Ana , Soler Diego , Lauwaet Koen , Miranda Rodolfo , Ecija David , Torres Tomas , Jelínek Pavel , Urgel Jose
Published: September 2023

The field of carbon magnetism has gained an increased attention in view of the recent progress made in the synthesis and characterization of open-shell polycyclic aromatic hydrocarbons following a bottom-up synthetic approach[1,2]. Under this scenario, the comprehensive fabrication of magnetic porphyrinoid-based polymers emerges as a highly appealing field of research. However, the vast majority of the porphyrinoid species and polymers studied to date exhibit a closed-shell ground state[3].

In this work, we introduce an exemplary approach toward the bottom-up fabrication of unprecedented magnetic porphyrinoid-based polymers homocoupled via surface-catalyzed [3 + 3] cycloaromatization of isopropyl substituents studied on Au(111) under ultra-high vacuum (UHV) conditions. The chemical structure of the polymer, formed by thermal-activated intra- and intermolecular oxidative ring closure reactions followed by controlled tip-induced hydrogen dissociation from the porphyrinoid units, have been clearly elucidated by scanning tunneling microscopy (STM) and non-contact atomic force microscopy (nc-AFM). Scanning tunneling spectroscopy (STS), complemented by computational investigations reveals the open-shell character, i.e. antiferromagnetic singlet ground state (S=0) of the formed polymers, which display singlet−triplet inelastic excitations observed between spins of adjacent porphyrinoid units only along a specific π-conjugation pathway, thus revealing the interplay between π-conjugation and magnetic exchange. We envision that our approach can be a highly relevant step towards the on-surface synthesis of covalently linked 1D magnetic organic polymers with prospects in nanoscale spintronic devices.

References:

[1] Auwärter, W.; Écija, D.; Klappenberger, F.; Barth, J. V. Porphyrins at Interfaces. Nat Chem. 2015, 7 (2), 105–120.

[2] Gottfried, J. M. Surface Chemistry of Porphyrins and Phthalocyanines. Surf. Sci. Rep. 2015, 70 (3), 259–379.

[3] Shimizu, D.; Osuka, A. Porphyrinoids as a Platform of Stable Radicals. Chem. Sci. 2018, 9 (6), 1408–1423.

Figure caption: On-surface reaction scheme toward the synthesis of one-dimensional porphyrinoid polymers starting from precursor 1 to magnetic porphyrinoid polymer 3 with intermediate non-magnetic porphyrinoid-based polymer 2

Figure 1
(Nanocarbons Division Robert C. Haddon Research Award) Nano Carbons in Mimicking the Early Events of Photosynthetic Reaction Center: ‘Simple’ and ‘Not-so-Simple’ Donor-Acceptor Conjugates
Authors: D'Souza Francis
Published: September 2023

Light-induced electron transfer is a key step in solar energy conversion, and a process with myriad relevance in the fields of artificial photosynthesis, photocatalysis, photoconductivity, and photovoltaics. In a donor-acceptor, D-A system, light absorption by a chromophore results in the formation of an excited state species, followed by a charge transfer between an electron donor (D) and an electron acceptor (A) leading to a charge-separated D
.+
-A
.-
species.The optimization of these processes and comprehending their mutual interplay to ultimately achieve charge-separated species is of paramount importance for the development of efficient systems in solar light conversion schemes.

The present talk summarizes our research over the years focused on utilizing nano carbons, viz., fullerenes, endohedral fullerenes, carbon nanotubes, and graphene in the construction of donor-acceptor systems capable of undergoing photoinduced energy and electron transfer events. Both, covalently linked with rigid, semi-rigid, flexible, or conjugated spacers, and self-assembled via metal-ligand axial coordination, ion-pairing, ion-dipole, or hydrogen bonding strategies were utilized in the construction of donor-acceptor conjugates. Multi-modular donor-acceptor constructs were designed, synthesized, and studied to probe sequential energy and electron transfer events, finally resulting in long-lived charge-separated states. In some instances, these molecular systems were also used as photocatalytic energy conversion schemes. The pros and cons of utilizing nanocarbon materials as photo-active functional materials will be highlighted.

D’Souza, F.; Sandanayaka, A. S. D.; Ito, O. ‘SWNT-Based Supramolecular Nanoarchitectures with Photosensitizing Donor and Acceptor Molecules’ Phys. Chem. Letts. 2010, 1. 2586-2593.

D’Souza, and O. Ito ‘Photosensitized electron transfer processes of nano carbons applicable to solar cells,’ Chem. Soc. Rev. 2012,
41, 86-96.

B. KC, F. D’Souza, ‘Design and photochemical study of supramolecular donor-acceptor systems assembled via metal-ligand axial coordination Coord. Chem. Rev. 2016, 322, 104-141.

Bottari, M. A. Herranz, L. Wibmer, M. Vollard, L. Rodriguez-Perez, D. M. Guldi, A. Hirsch, N. Martin, F. D’Souza, T. Torres, Chemical functionalization and characterization of graphene-based materials, Chem. Soc. Rev. 2017, 46, 4464-4500.

Barrejon, L. M. Arellano, F. D’Souza, F. Langa, ‘Bidirectional charge transfer in carbon-based hybrid nanomaterials’ Nanoscale, 2019, 11, 14978-14992.

Kazemi, Y. Jang, A. Liyanage, P. A. Karr, and F. D’Souza, ‘A Carbon Nanotube Binding Bis(pyrenylstyryl)BODIPY-C60 Nano Tweezer: Charge Stabilization through Sequential Electron Transfer’, Angew. Chem. Int. Ed.
2022, in press
(Invited, Digital Presentation) Wafer-Scale Epitaxial Growth of Transition Metal Dichalcogenide Monolayers on Sapphire for Large Area Device Applications
Authors: Redwing Joan M.
Published: September 2023

Wafer-scale epitaxial growth of semiconducting transition metal dichalcogenide (TMD) monolayers such as MoS2, WS2 and WSe2 is of significant interest for device applications to circumvent size limitations associated with the use of exfoliated flakes. Epitaxy is required to achieve single crystal films over large areas via coalescence of TMD domains. Our research has focused on epitaxial growth of 2D semiconducting TMDs on c-plane sapphire substrates using metalorganic chemical vapor deposition (MOCVD). Steps on the miscut sapphire surface serve as preferential sites for nucleation and can be used to induce a preferred crystallographic direction to the TMD domains which enables a reduction in twin boundaries in coalesced films. The step-directed growth is dependent on the surface termination of the sapphire which can be altered through pre-growth annealing in H2 and chalcogen-rich environments. Uniform growth of TMD monolayers with significantly reduced inversion domains is demonstrated on 2” diameter c-plane sapphire substrates enabling large area transfer of monolayers for characterization and device fabrication and testing. Applications for wafer-scale TMD monolayers in nanoelectronics, sensing and photonics will be discussed.
(Invited) Water-Based and Defect-Free 2D Material Inks for Printed Electronics
Authors: Casiraghi Cinzia
Published: September 2023

2D materials show great promise for use in flexible electronics because their atomic thickness allows for maximum electrostatic control, optical transparency, sensitivity and mechanical flexibility. In addition, different 2D crystals can be easily combined in one stack, offering unprecedented control on the performance and functionalities of the resulting heterostructure-based device. In addition, solution processing of 2D materials allows simple and low-cost techniques, such as ink-jet printing, to be used for fabrication of heterostructure-based devices of arbitrary complexity.

Our group has developed highly concentrated, defect-free, biocompatible, inkjet printable and water-based 2D crystal formulations, by exploiting a supramolecular approach based on non-covalent functionalization of 2D materials with pyrene derivatives [1]. Examples of printed heterostructures, such as arrays of photosensors, programmable logic memories, transistors and memristors will be discussed [2-3]. I will show that inkjet printing can be easily combined with semiconducting 2D materials produced by chemical vapor deposition, allowing simple and quick fabrication of complex circuits on paper, compatible with CMOS technology [4-5] and also offers a simple way to integrate 2D materials into Si-based technology [6].

References:

[1] Chen-Xia Hu, Yuyoung Shin, Oliver Read, Cinzia Casiraghi, Dispersant-assisted liquid-phase exfoliation of 2D materials beyond graphene, Nanoscale, 2021, 13, 460

[2] McManus, D., Vranic, S., Withers, F. et al. Water-based and biocompatible 2D crystal inks for all-inkjet-printed heterostructures. Nature Nanotech 12, 343–350 (2017)

[3] Shiheng Lu Shiheng Lu Department of Electrical and Computer Engineering, Duke University, Durham, North Carolina 27708, United States More by Shiheng Lu Orcidhttp://orcid.org/0000-0002-5323-7787 , Jorge A. Cardenas, Robyn Worsley, Nicholas X. Williams, Joseph B. Andrews, Cinzia Casiraghi, and Aaron D. Franklin, Flexible, Print-in-Place 1D–2D Thin-Film Transistors Using Aerosol Jet Printing, ACS Nano 2019, 13, 10, 11263–11272

[4] Silvia Conti, Lorenzo Pimpolari, Gabriele Calabrese, Robyn Worsley, Subimal Majee, Dmitry K Polyushkin, Matthias Paur, Simona Pace, Dong Hoon Keum, Filippo Fabbri, Giuseppe Iannaccone, Massimo Macucci, Camilla Coletti, Thomas Mueller, Cinzia Casiraghi, Gianluca Fiori, Low-voltage 2D materials-based printed field-effect transistors for integrated digital and analog electronics on paper. Nat Commun 11, 3566 (2020)

[5] Brunetti, I., Pimpolari, L., Conti, S. et al. Inkjet-printed low-dimensional materials-based complementary electronic circuits on paper. npj 2D Mater Appl 5, 85 (2021).

[6] Alessandro Grillo, Zixing Peng, Aniello Pelella, Antonio Di Bartolomeo, Cinzia Casiraghi, Etch and Print: Graphene-Based Diodes for Silicon Technology, in press
Real-Time Detection and Speciation of Mn Dissolution in a Li-Ion Battery Cathode
Authors: Zhao Dongni , Mertens Stijn F. L.
Published: September 2023

Rechargeable lithium-ion batteries (LIB) are widely used in portable electronic devices, electric vehicles, medical devices, etc. thanks to their improved performance in recent decades. The properties of the cathode still largely limit the overall performance, as the cathode usually has lower theoretical capacity and suffers from more serious degradation effects.1 Among these, dissolution of transition metals is an important but poorly understood side reaction. On the one hand, it dominates the cathode capacity fading by causing irreversible loss of active redox sites, phase transformation, cation mixing, grain fracture, etc. On the other hand, the dissolved transition metal ions can exacerbate the formation of the solid electrolyte interphase (SEI) on the anode through a dissolution-migration-deposition (DMD) process.2

Here, we focus on the dissolution of manganese from LiMn2O4 (LMO), a benchmark cathode material, through real-time analysis of the electrolyte by combining online inductively coupled plasma–optical emission spectroscopy (online ICP-OES) and rotating ring-disc electrode (RRDE) collection, Figure 1. Both methods offer real-time dissolution information as functions of time and potential/state of charge, while the former shows superior detection limits and the latter provides oxidation state information of the dissolving species.

According to online ICP-OES, we find that Mn dissolves readily from fully lithiated LMO when brought in contact with aqueous 0.2 M Li2SO4, but that a dissolution-passivation process stops further detectable dissolution until well past fully delithiated λ-MnO2. The dissolution becomes detectable again on the returning scan to the potential of pristine LMO, and grows exponentially in the overlithiated region.3 Our RRDE results indicate that Mn2+ is the dominating dissolved Mn species only in overlithiation region, whereas it only accounts for a minor proportion in the dissolved species from delithiation region. The data from both techniques suggest that the dissolution of Mn is related to the surface state of the electrode, rather than its degree of lithiation, as widely believed in the past.4

Our results provide a better understanding of the mechanism of transition metal dissolution in cathode materials, as well as an entry point for screening next-generation cathodes and metal ion batteries with superior degradation characteristics.5

References:

C. Zhan, T. Wu, J. Lu and K. Amine, Energy Environ. Sci., 2018, 11, 243–257.

Y. K. Lee, J. Park and W. Lu, J. Electrochem. Soc., 2017, 164, A2812–A2822.

S. Nikman, D. Zhao, V. Gonzalez-Perez, H. E. Hoster and S. F. L. Mertens, Electrochim. Acta, 2021, 386, 138373.

J. C. Hunter, J. Solid State Chem., 1981, 39, 142–147.

N. Tapia-Ruiz, S. F. L. Mertens et al., J. Phys.: Energy, 2021, 3, 031503.

Figure 1
Rechargeable Battery for Ultra Low Temperature Environments
Authors: Zhang Duhan , Chiang Yet-Ming
Published: September 2023

Rechargeable energy storage systems that can efficiently operate at ultra-low temperatures down to -50°C or lower are needed to support Arctic zone development and aerospace exploration. Existing batteries today such as Li-ion and Pb-acid batteries all lose functions at colder temperatures. We have discovered a battery chemistry for which the amount of energy stored actually increases as temperature decreases, and storage cost commensurately decreases. Furthermore, this novel battery is composed of low-cost, widely available materials, and has a simple design that is self-assembling. In our study, we develop the zinc battery system composed of a pair of immiscible liquid electrodes that density-based self-assembly into a layered configuration without a membrane separator. This allows the zinc negative electrode to use low-cost iron or steel packaging that simultaneously serves as the current collector, while a reversible chlorine electrode serves as the positive electrode. The use of liquid electrolytes allows inherent stress relaxation suggesting high cycle life. We investigate anode and cathode solution chemistry, chlorine electrode redox kinetics including catalyst development, and integration of components into prototype batteries. Our progress shows promising battery cycling performance below 0°C, and indicates the technoeconomic feasible through technoeconomic analysis.

This abstract submission is for session A1-Triple I.

Reference:

Li, Zheng, et al. "Air-breathing aqueous sulfur flow battery for ultralow-cost long-duration electrical storage." Joule1.2 (2017): 306-327.

Landolt, D.; Ibl, N. (1972). "Anodic chlorate formation on platinized titanium". Journal of Applied Electrochemistry. Chapman and Hall Ltd. 2(3): 201–210. DOI:10.1007/BF02354977. S2CID 95515683.

Hale, Arthur (1918). The Applications of Electrolysis in Chemical Industry. Longmans, Green, and Co. p. 13. Retrieved 2019-09-15.