bluuebunny/crossref_metadata_2025_split huggingface dataset:
Single-Walled Carbon Nanotubes Charge Management By Controlled Functionalization
Authors: Setaro Antonio , Fiebor Alphonse , Adeli Mohsen , Reich Stephanie 
Published: July 2022

Managing the density of charges in carbon nanotubes opens new ways to tune their optical response, their transport properties, and their physico-chemical features. Charge transfer from molecules adsorbed onto the sidewall or filled within the hollow cavity of the nanotubes has already been demonstrated, yet a fine-tunable control of the surface coverage/filling fraction (and thus the amount of transferred charge) remains challenging to achieve. Alternatively, we developed an optically nonperturbing covalent functionalization technique based on the inclusion of a triazine derivative into the carbon network [1]. The nitrogen atom sustaining the attached group becomes an integrated part of the pi-conjugated network and contributes with its lone electron pair to uplifting the position of the Fermi level of the tube. Since the density of attached groups can be varied by adapting the synthetic conditions, this technique offers the advantage of controlling the amount of charge injected into the tubes. Additional groups attached onto the other end of the triazine moiety, moreover, are able to inject charge into the tubes as well. This, for example, allowed us to modulate the photoluminescence of the tubes, switching their emission on and off through the attachment of the switchable spiropyran/merocyanine system [2]. Here we focus on a class of charge-transfer agents that either donate or withdraw electrons depending on the arrangements of their building units [3] and how their decoration affects the properties of the tubes.

Figure: Different number of methoxy groups can be attached onto aniline at different positions, resulting in compounds that can either donate or withdraw electrons from the tubes they are attached onto [3].
[1] Setaro et al. Nature Communications 8,
14281 (2017).
[2] Godin et al. Science Advances 5,
eaax1166 (2019).
[3] Fiebor et al. J. Phys. Chem. C. 125, 19925 (2021).

Figure 1
Exploring the Role of Photosensitizer in Guanine Functionalization of Single-Wall Carbon Nanotubes
Authors: Soltani Nima , Bachilo Sergei M. , Weisman R. Bruce 
Published: July 2022

Single-walled carbon nanotubes (SWCNTs) have attracted a great deal of attention during the past two decades because of their unique optoelectronic properties and their potential applications in biomedical theranostics as well as nanoelectronics. It was recently discovered that it is possible to spatially modulate the exciton band gap of carbon nanotubes through a process known as guanine functionalization. In this reaction, the guanine nucleotides of an ssDNA strand wrapping a nanotube become covalently bonded to sidewall carbon atoms upon exposure to singlet oxygen.1 In the original work, the authors used xanthene derivatives such as rose bengal and erythrosine B as photosensitizers in order to generate singlet oxygen. It was assumed that this process was an independent step that did not involve the nanotube. However, we have found that rose bengal has a strong tendency to form a charge transfer complex with SWCNTs, and these complexes appear to be essential in the functionalization reaction.
We have studied the complexation through a spectroscopic study of SWCNT fluorescence quenching and the appearance of a charge transfer absorption feature near 600 nm. Both are interpreted as results of nanotube p-doping when the dye adsorbs to the sidewall. We also observe that the charge transfer complex formation accelerates when the rose bengal is optically excited, apparently proceeding through the dye’s triplet state. A correlation between extent of guanine functionalization and the concentration of charge transfer complexes is found as ionic strength is changed. We infer that the functionalization reaction is enabled by adsorbed photosensitizers. Interestingly, the extent of SWCNT fluorescence quenching by rose bengal is found to vary significantly with (n,m) structure. This quenching effect therefore provides a simple approach to monitor structure-specific interactions between SWCNTs and coatings, including ssDNA and conventional ionic surfactants.
(1) Zheng, Y.; Bachilo, S. M.; Weisman, R. B. Controlled Patterning of Carbon Nanotube Energy Levels by Covalent DNA Functionalization. ACS Nano
13, 5222 (2019). https://doi.org/10.1021/acsnano.9b03488.
(Invited, Digital Presentation) Ortho-Substituent Structure Design in Aryldiazonium Salts for Defect Photoluminescence Modulation of Locally Functionalized Single-Walled Carbon Nanotubes
Authors: Shiraki Tomohiro , Yu Boda , Naka Sadahito , Kato Koichiro , Fujigaya Tsuyohiko 
Published: July 2022

Photoluminescence (PL) of single-walled carbon nanotubes (SWCNTs) appears in the near infrared (NIR) region, which is applicable to advanced optical applications such as bioimaging and telecommunication devices. Local chemical functionalization of SWCNTs has been gathering great attention because of the enhancement of their NIR PL properties. Therein, defects such as sp3 carbon are locally doped to the crystalline sp2 carbon network of the tube walls by the chemical functionalization process.[1-4] As a result, the locally functionalized SWCNTs (lf-SWCNTs) emit new PL with red-shifted wavelengths and increased quantum yields from the doped sites (E
11* PL) compared to original E
11 PL of pristine SWCNTs. It is due to the doping effects to change electronic structures for narrower bandgap formation, by which mobile excitons in the tubes are trapped at the doped sites to be localized states for efficient PL conversion.
The chemical functionalization approach allows us to use various chemical reactants for the doped site formation in lf-SWCNTs. The molecular effects including structural differences and molecular binding functions have resulted in versatile NIR PL wavelength modulation of lf-SWCNTs.[1-4] We have reported that E
11* PL generation phenomena were significantly varied depending on isomeric structures of substituted aryldiazonium salts (AD) used for lf-SWCNT synthesis.[5] Especially, ortho-substituted ADs (oADs) produced two PL around 1100 and 1250 nm-regions, respectively for the resulting lf-SWCNTs with (6,5) chirality. Here, we apply various substituent design for oADs and examine the substituent structure effects in terms of modulation of the PL emission properties of lf-SWCNTs. For example, oAD having a phenyl substituent resulted in enhancement of the ~1250 nm PL contribution. Other substituent effects are observed depending on substituent structures of oADs, from which interactions between the substituents and the tubes are considered to induce the observed PL spectral changes. The result indicates that local chemical functionalization using oAD has a high potential to largely modulate NIR PL wavelengths of lf-SWCNTs beyond 1000 nm regions.
[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, Chem. Lett., 50, 397 (2021). [5] T. Shiraki et al. Chem. Commun., 53, 12544 (2017).
(Invited) Optically Detected Magnetic Resonance of Triplet Excitons in Sorted (6,5) and (7,5) SWCNTs
Authors: Cambre Sofie , Sudakov Ivan , Goovaerts Etienne , Blackburn Jeff , Duque Juan , Wenseleers Wim 
Published: July 2022

Single-wall carbon nanotubes (SWCNTs) possess unique electronic and optical properties, strongly depending on their exact chiral structure. Their quasi one-dimensional character results in the formation of strongly bound electron-hole pairs (excitons) that can even be observed at room temperature (i.e. binding energies of the order of several hundred meV).[1] The exciton fine structure of SWCNTs is quite complex, with multiple singlet and triplet excitonic states, of which only one is optically allowed, thereby resulting in extremely low fluorescence (PL) quantum yields. While the singlet excitons have already been investigated thoroughly, little is known about the longer-living triplet excitons.
In this work, we report the characterization of triplet excitons in chirality-purified samples of (7,5) and (6,5) SWCNTs by means of optically detected magnetic resonance spectroscopy (ODMR), a technique that measures the influence on the emission of CNTs when making transitions between the spin levels of the triplet excitons. In both chiralities the nanotubes are shown to sustain two types of triplet exciton states, as shown by the symmetry and magnitude of their zero-field splitting parameters in the spin Hamiltonian, which are determined by careful fitting of magnetic-field orientation-dependent ODMR spectra of in-plane aligned SWCNTs. While the triplet excitons only weakly depend on the nanotube environment, an increase in zero-field splitting is found for (6,5) with respect to (7,5) nanotubes, in good agreement with the tighter confinement expected in the narrower-diameter nanotubes.
[1] M.S. Dresselhaus et al, Ann. Rev. Phys. Chem. 2007, 58, 719
[2] D. Stich et al, Nature Photon.
2014
, 8,139; J. Palotás et al, ACS Nano 2020, 14, 11254
(Invited) Hybrid Interfaces between Semiconducting Swcnts and Other Low-Dimensional Semiconductors
Authors: Blackburn Jeff , Hao Ji , Kim Young-Hoon , Lu Haipeng , Luther Joey , Phillips Alan , Gish Melissa , Myers Alexis 
Published: July 2022

Low-dimensional semiconductors provide a rich tapestry of tunable optical and electrical properties for a wide variety of applications. Semiconducting single-walled carbon nanotubes (s-SWCNTs) have shown tremendous potential in applications ranging from digital logic, biological imaging, quantum information processing, photovoltaics, and thermoelectric energy harvesting. Energy harvesting applications rely critically upon the creation of tailored interfaces that enable the movement of energetic species (excitons, electrons, holes) in specified directions. While organic energy harvesting devices often employ interfaces between distinct organic species such as polymers, fullerenes, and carbon nanotubes, hybrid interfaces between organic and inorganic semiconductors have unique properties that are relatively unexplored.
In this talk, I will discuss our recent efforts at constructing novel hybrid interfaces between s-SWCNTs and other low-dimensional semiconductors, including monolayer transition metal dichalcogenides and metal-halide perovskites. I will discuss time-resolved spectroscopy results exploring photoinduced separation of (in some case spin-polarized) charges across such interfaces, demonstrating utility for photovoltaics and novel photodetectors. Complementary device studies demonstrate exceptional efficiencies for conversion of photons into stable photocurrent, and I will highlight several novel applications in which these interfaces can be employed.
(Invited, Digital Presentation) Global Alignment of Carbon Nanotubes Via High Precision Microfluidic Dead-End Filtration
Authors: Rust Christian , Li Han , Gordeev Georgy , Spari Manuel , Guttmann Markus , Jin Qihao , Reich Stephanie , Flavel Benjamin S 
Published: July 2022

Single wall carbon nanotubes (SWCNTs) dispersed by negatively charged sodium deoxycholate (DOC) or positively charged cetrimonium bromide (CTAB) are shown to assemble into aligned films (3.8 cm²) on polycarbonate membranes by slow flow dead-end filtration. Global alignment (S2D max » 0.85) is obtained on both pristine polyvinylpyrrolidone (PVP) coated membranes and those with an intentional 150 nm – 600 nm groove pattern from hot-embossing. In all cases, a custom microfluidic setup capable of precise control and measurement of the volume rate, trans-membrane pressure and the filtration resistance is used to follow SWCNT film formation. Conditions associated with the formation of SWCNT crystallites or their global alignment are identified and these are discussed in terms of membrane fouling and the interaction potential between the surface of the membrane and nanotubes. SWCNT alignment is characterised by cross polarized microscopy, AFM, SEM and Raman spectroscopy.
https://doi.org/10.1002/adfm.202107411
(Digital Presentation) Thermoelectric and Electronic Transport Studies of Ultrahigh-Conductivity Aligned Carbon Nanotube Assemblies
Authors: Komatsu Natsumi , Marquez Peraca Nicolas , Ichinose Yota , Li Xinwei , Dewey Oliver S. , Taylor Lauren W. , Trafford Mitchell , Mojibpour Ali , Yomogida Yohei , Wehmeyer Geoff , Yanagi Kazuhiro , Pasquali Matteo , Foster Matthew , Kono Junichiro 
Published: July 2022

Macroscopic assemblies of aligned carbon nanotubes (CNTs) have been doubling in conductivity every three years and have now surpassed 10 MS/m [1]. They are promising for replacing copper- or aluminum-based electrical cables in applications where flexibility or weight savings are critical considerations. Understanding of transport processes in these ordered CNT assemblies is critical towards further conductivity improvement; yet, fiber-level transport is still poorly understood. Here, we studied thermoelectric and electrical properties of aligned CNT fibers and bundles produced by solution spinning. We first measured thermoelectric properties while tuning the Fermi energy and demonstrated a giant thermoelectric power factor [2]. We then performed temperature- and magnetic field-dependent conductivity measurements. In contrast to the majority of transport studies of CNT networks [3,4], our aligned CNT fibers exhibited a metallic behavior in a wide temperature range (30-300 K), i.e., conductivity monotonically increasing with decreasing temperature, which we attribute to the excellent sample morphology. At temperatures below 30 K, we observed a gradual decrease of conductivity with decreasing temperature, together with negative magnetoresistance, consistent with the weak localization theory for disordered metals. We determined the dimensionality and coherence lengths of carriers via analysis of the weak localization behavior. In addition to macroscopic CNT fibers with diameters of ~10 μm, we also conducted conductivity measurements on individual crystalline CNT bundles (with diameters ~ 50 nm and lengths ~ 30 μm) that constitute the fibers.
References
[1] L. W. Taylor, O. S. Dewey, R. J. Headrick, N. Komatsu, N. M. Peraca, G. Wehmeyer, J. Kono, and M. Pasquali, Carbon N. Y. 171, 689 (2021).
[2] N. Komatsu, Y. Ichinose, O. S. Dewey, L. W. Taylor, M. A. Trafford, Y. Yomogida, G. Wehmeyer, M. Pasquali, K. Yanagi, and J. Kono, Nat. Commun. 12, 4931 (2021).
[3] W. Zhou, J. Vavro, C. Guthy, K. I. Winey, J. E. Fischer, L. M. Ericson, S. Ramesh, R. Saini, V. A. Davis, C. Kittrell, M. Pasquali, R. H. Hauge, and R. E. Smalley, J. Appl. Phys. 95, 649 (2004).
[4] N. F. Zorn and J. Zaumseil, Appl. Phys. Rev. 8, 41318 (2021).
Effects of the Ultrasound-Guided Stellate Ganglion Block on Hemodynamics, Stress Response, and Gastrointestinal Function in Postoperative Patients with Colorectal Cancer
Authors: Xie An , Zhang Xianjie , Ju Feng , Li Wen , Zhou Yukai , Wu Dan 
Published: July 2022

Objective. The aim of the study was to study the effects of the ultrasound-guided stellate ganglion block on hemodynamics, stressful response, and postoperative gastrointestinal functions in patients with colorectal cancer. Methods. A total of 100 patients with colorectal cancer hospitalized from January 2021 to December 2021 were selected. After anesthesia induction, the right stellate ganglion block was performed under ultrasound guidance in the research group and the general anesthesia was performed in the control group. The heart rate (HR), mean arterial pressure (MAP), epinephrine, cortisol, self-rating anxiety scale (SAS), Ramsay sedation score (RSS), postoperative bowel sound recovery time, anal exhaust time, and the incidence of gastrointestinal adverse reactions 24 hours after operation were studied pre-and post-24-hour anesthesia induction. Results. Following 24-hour operation, the HR and MAP values were largely reduced

p
<
0.05

. Following 24-hour operation, epinephrine and cortisol became obviously higher

p
<
0.05

. After 24-hour operation, the levels of epinephrine and cortisol in the research group were greatly lower. The score of the SAS in the study cohort was less than that of the controls

p
<
0.05

. The RSS of the research group was obviously increased

p
<
0.05

. The recovery time of intestinal sound and the anal exhaust time of the study cohort became remarkably shorter

p
<
0.05

. The incidence of gastrointestinal adverse reactions 24 hours after operation of the study cohort was much less common

p
<
0.05

. Conclusion. The ultrasound-guided stellate ganglion block can reduce the fluctuation of blood circulation during radical resection of colorectal cancer, reduce postoperative gastrointestinal dysfunction and stress reaction, relieve patients’ anxiety, and contribute to the recovery of gastrointestinal function.
Mapping the Immune Landscape in Metastatic Melanoma Reveals Localized Cell–Cell Interactions That Predict Immunotherapy Response
Authors: Antoranz Asier , Van Herck Yannick , Bolognesi Maddalena M. , Lynch Seodhna M. , Rahman Arman , Gallagher William M. , Boecxstaens Veerle , Marine Jean-Christophe , Cattoretti Giorgio , van den Oord Joost J. , De Smet Frederik , Bechter Oliver , Bosisio Francesca M. 
Published: July 2022

Abstract

While immune checkpoint–based immunotherapy (ICI) shows promising clinical results in patients with cancer, only a subset of patients responds favorably. Response to ICI is dictated by complex networks of cellular interactions between malignant and nonmalignant cells. Although insights into the mechanisms that modulate the pivotal antitumoral activity of cytotoxic T cells (Tcy) have recently been gained, much of what has been learned is based on single-cell analyses of dissociated tumor samples, resulting in a lack of critical information about the spatial distribution of relevant cell types. Here, we used multiplexed IHC to spatially characterize the immune landscape of metastatic melanoma from responders and nonresponders to ICI. Such high-dimensional pathology maps showed that Tcy gradually evolve toward an exhausted phenotype as they approach and infiltrate the tumor. Moreover, a key cellular interaction network functionally linked Tcy and PD-L1+ macrophages. Mapping the respective spatial distributions of these two cell populations predicted response to anti-PD-1 immunotherapy with high confidence. These results suggest that baseline measurements of the spatial context should be integrated in the design of predictive biomarkers to identify patients likely to benefit from ICI.

Significance:
This study shows that spatial characterization can address the challenge of finding efficient biomarkers, revealing that localization of macrophages and T cells in melanoma predicts patient response to ICI.
See related commentary by Smalley and Smalley, p. 3198
“Efficiency Is Paramount in This Regard”: The Managerial Role of the ICC Presidency from Kirsch to Fernández
Authors: Clements Richard 
Published: July 2022

Abstract
Since the International Criminal Court commenced its work, much has been made of the institution-building role of successive ICC Prosecutors as central to the Court’s legal framework and as ambassadors for the “fight against impunity”. Much less has been said about the role of the ICC Presidency, as the Court’s smallest organ, and its successive Presidents. Yet the Presidency operates at the apex of the Court as an international organisation, manages relations with states, coordinates internal governance issues, and acts as the “public face” of the Court globally, not to mention its judicial functions. The ICC Presidency and its first three Presidents have been particularly influential in shaping the ICC into an institution prioritising the values of efficiency and effectiveness, with deeply political and distributive implications. This article traces those influences, from the Presidency of Philipp Kirsch, until the end of the third Presidency under the leadership of Silvia Fernández de Gurmendi in March 2018.
Parliamentary Inquiries: an Underestimated Anticorruption Tool
Authors: Hoppe Tilman , Ticona Juan 
Published: July 2022

Abstract
In countries with high levels of corruption, ruling elites rarely have an interest in meaningful anticorruption reforms. Thus, within state structures, the opposition is often key in controlling the government. At the same time, no state body has wider jurisdiction than parliament. Therefore, empowering the opposition to inquire into corruption (and other) scandals is a key factor in an integrity system. The German system of strong opposition rights in collecting evidence through parliamentary inquiry committees has been a unique selling point by global comparison until 2014, when it was emulated by Austria. An analysis of the 63 inquiry committees of the Bundestag since 1949 shows that a significant share concerned corruption cases. Had it not been for parliamentary inquiries, most of these cases would have remained without any follow-up by a state institution. In stark contrast to this finding, international anticorruption guidance more or less entirely ignores inquiry committees.
Observed Covariations in Boundary Layer and Cumulus Cloud-Layer Processes
Authors: Daub Brandon J. , Lareau Neil P. 
Published: July 2022

Abstract
In this study, we examine variations in boundary layer processes spanning the shallow-to-deep cumulus transition. This is accomplished by differentiating boundary layer properties on the basis of convective outcomes, ranging from shallow to deep, as observed at the Atmospheric Radiation Measurement (ARM) Southern Great Plains (SGP) site in Oklahoma. Doppler lidar, radar, and radiosonde data are combined to determine statistical differences in boundary layer and cloud-layer properties using a large sample (236) of days with a range of convective outcomes: shallow, congestus, and deep convection. In these analyses, the radar characterizes diurnal cloud depth, the lidar quantifies updraft and downdraft properties in the subcloud layer, and daily radiosonde data provide the convective inhibition (CIN). Combined, these data are used to test the hypothesis that deep convection occurs when the strength of the boundary layer turbulence (i.e., TKE) exceeds the strength of the energy barrier (i.e., CIN) at the top of the CBL. Results show that days with deep convective clouds have significantly lower vertical velocity variance and weaker updrafts within the subcloud layer. However, CIN values are also found to be significantly lower on deep convective days, allowing for these weaker updrafts to penetrate the energy barrier and reach the level of free convection. In contrast, shallow convective outcomes occur when the updrafts are strong in an absolute sense but are weak when compared with the strength of the energy barrier. These findings support the use of the CIN/TKE framework in parameterizing convection in coarse resolution models.
A Physical Model of Tropical Cyclone Central Pressure Filling at Landfall
Authors: Sparks Nathan , Toumi Ralf 
Published: July 2022

Abstract
We derive a simple physically based analytic model that describes the pressure filling of a tropical cyclone (TC) over land. Starting from the axisymmetric mass continuity equation in cylindrical coordinates, we derive that the half-life of the decay of the pressure deficit between the environment and TC center is proportional to the initial radius of maximum surface wind speed. The initial pressure deficit and column-mean radial inflow speed into the core are the other key variables. The assumptions made in deriving the model are validated against idealized numerical simulations of TC decay over land. Decay half-lives predicted from a range of initial TC states are tested against the idealized simulations and are in good agreement. Dry idealized TC decay simulations show that without latent convective heating, the boundary layer decouples from the vortex above leading to a fast decay of surface winds while a midlevel vortex persists.