bluuebunny/crossref_metadata_2025_split huggingface dataset:
Psychiatrists’ experiences of involuntary care in South Africa: dilemmas for practice in challenging contexts
Authors: Freeman Alex Morung , Asmal Laila , Swartz Leslie 
Published: August 2024

Providing for people with psychosocial conditions in crisis is a complex and controversial endeavour that has gained significant attention over the past decade. This increased focus is driven by global calls to reduce coercion, including by the United Nations Committee on the Rights of Persons with Disabilities, who interpret Article 12 of the United Nations Convention on the Rights of Persons with Disabilities in General Comment 1 to advocate for the replacement of substituted decision-making with supported decision-making. Psychiatrists occupy a central role in determining how to care for and respond to individuals with psychosocial conditions in crisis in the midst of these debates. They must protect the rights of people with psychosocial conditions in crisis and provide appropriate support within challenging and dynamic contexts. This responsibility includes promoting the autonomy of people with psychosocial condition while ensuring their long-term health, safety and well-being.In this study, we conducted a phenomenological analysis with a sample of nine psychiatrists in South Africa to explore their experiences with involuntary care and the complex dilemmas they face in delivering healthcare to individuals with mental health conditions. Our findings indicate that psychiatrists encounter significant challenges in preserving patient autonomy, particularly within the resource-limited context of South Africa. Pervasive stigma and insufficient support infrastructure complicate efforts to prioritise autonomy. At the same time, professionals must address the critical need to ensure the long-term safety and well-being of their patients. The absence of involuntary care can exacerbate a person’s vulnerability to community stigma and inadequate community support, posing severe risks to their welfare. Balancing between protecting a person’s autonomy and addressing the limitations of support structures creates a complex predicament for mental health professionals, often resulting in feelings of isolation and moral distress among psychiatrists.
Deep Learning Based 3D Resolution Recovery for Breakthrough Imaging of Electrochemical Energy Devices
Authors: Kelly Stephen T , Trenikhina Yulia , Johnson Nathan , Harris William 
Published: August 2024

Many energy materials can only be understood within the context of the (often sealed) devices they make up. Batteries and fuel cells contain intricate mixtures of materials with features and arrangements that span across many orders of magnitude in size and operate under non-ambient conditions. In these devices, the microstructures of the constituent materials and how they are arranged with respect to each other is directly linked to the device performance and degradation behaviors. Complicating matters, opening the devices for inspection and analysis can irreversibly alter the very microstructures in question and can pose safety hazards to researchers if not done correctly. Furthermore, critical material and device properties such as tortuosity or ion transport pathways can only be accurately quantified in 3D. As such, observing microstructures and their evolution in 3D and in their native state is essential for developing a robust understanding of how to engineer new battery and fuel cell materials and architectures with improved performance.
X-ray microscopy (XRM) provides a unique method for observing these microstructures in 3D at high resolutions without needing to open them. However, microscopy techniques like XRM make tradeoffs between FOV and resolution, which can pose challenges for strongly multiscale systems like batteries and fuel cells. For example, if images are acquired at high enough resolution to observe critical features like electrode particle sizes in lithium-ion batteries or gas diffusion layer fiber weaves, catalyst distributions, and microporous layer cracks in polymer electrolyte fuel cells, the field of view of that image is restricted to a small local region of the sample. This means that broader defect distributions or larger scale inhomogeneities will be missed. Additionally, for quantitative analysis applications, this means that statistical relevance will be sacrificed because of the limited analysis volume at the appropriate resolution. And for computational modelling efforts, device level phenomena will not be captured well due to the restricted field of view.
Advances in modern AI-based resolution recovery methods combined with the non-destructive multiscale imaging capabilities of X-ray microscopy have allowed researchers to overcome this dependency between resolution and field of view to produce 3D images with both high resolution and large field of view. We present here examples of applying these methods to applications in lithium-ion battery and polymer electrolyte fuel cell research [1].
[1] Wang, Y.D., Meyer, Q., Tang, K. et al. Large-scale physically accurate modelling of real proton exchange membrane fuel cell with deep learning. Nat Commun 14, 745 (2023).
Multi-Stage Engineered Co-Free Li[Ni1-X-Y
Ti
x
Al
y
]O2 Cathode for High-Energy Li-Ion Batteries
Authors: Park Geon-Tae , Yoon Jung-In , Sun Yang-Kook 
Published: August 2024

Since the global blueprint for carbon net zero emissions has been drawn, a part of the internal combustion engine (ICE) market share of vehicles has been continually shifting toward electric powered public and personal transportation. However, the serious remaining challenges regarding the price and performance issues of lithium-ion batteries (LIBs), which are the primary power source for electric vehicles (EVs), have impeded the large-scale adoption of EVs. Solving the affordability issue of current layered cathodes requires reducing the reliance on Co, which is extremely expensive with supply uncertainty. The aim of developing Co-poor or Co-free cathodes has led to an interest in LiNiO2 (LNO).1 LNO is one of the most promising cost-effective Co-free cathodes for LIBs because the cathode can achieve a high specific capacity of over 250 mAh g-1 with a typical upper voltage of 4.3 V versus Li/Li+. However, its poor cycling durability and thermal instability make its practical use difficult.2 In this study, we propose a highly stable Co-free Ni-enriched layered cathode based on LNO through a new doping strategy that incorporates heteroelements at different doping stages, i.e., the introduction of Ti during Ni(OH)2 synthesis and doping excess amounts of Al during the lithiation step. In combination with cathode surface protection, i.e., electrolyte modification or cathode surface coating, the proposed cathode retains 72.0% of its initial capacity after 3,500 cycles, which is the state-of-the-art for Co-free layered cathodes.

Reference
s
:

[1] M. Bianchini, M. Roca-Ayats, P. Hartmann, T. Brezesinski, J. Janek, Angew. Chem. Int. Ed., 58 (2019) 10434-10458.
[2] H.-J. Noh, S. Youn, C.S. Yoon, Y.-K. Sun, J. Power Sources, 233 (2013) 121-130.
Prediction of Lithium Deposition By Electrochemical Noise Method in Li-Ion Batteries
Authors: Karaoglu Gozde , Ülgüt Burak 
Published: August 2024

Electrochemical noise measurement methods have established a significant presence in corrosion literatures and through these measurements, it becomes feasible to discern the corrosion mode and make a clear distinction between localized and uniform corrosion types, particularly when examined alongside post-mortem studies.
In recent years, the increase in the use of lithium-ion batteries demands that the tests to be performed on the batteries are faster, easier, cheaper and, if possible, non-destructive and non-perturbing. While some electrochemical noise studies on batteries have commenced, the existing literature on this subject is limited and questionable. Electrochemical noise measurement, in Lithium based batteries has the potential to serve as a non-invasive diagnostic tool for assessing battery health. One of our previous studies has demonstrated an increased voltage noise in non-rechargeable batteries with Li/MnO2 chemistry upon exposure to a short circuit, indicating detectable morphological changes in metallic lithium due to non-homogenous depletion of lithium anode through electrochemical noise measurement.
In Lithium-Ion batteries, lithium deposition refers to the undesired formation of metallic lithium, commonly in the form of dendrites, on the battery’s anode during charge and discharge cycles. This phenomenon is a consequence of uneven lithium-ion plating and stripping, leading to localized overplating. This growth of lithium dendrites poses significant risk, including internal short circuits, compromised battery integrity, and the potential for thermal runaway. These issues can result in reduced battery performance, safety concerns, and shortened cycle life. Effectively addressing lithium deposition is essential for enhancing the safety and reliability of lithium-ion batteries in various applications.
Similarly to our previous publication, the electrochemical noise method shows promise as a non-invasive approach to investigate the understand deposition of metallic lithium by monitoring the voltage noise during charge and discharge cycling of batteries. For this purpose, NMC/Graphite pouch and coin cells are employed. In this presentation, we will delve into the details of electrochemical noise in lithium-based batteries, discussing the method’s reliability in assessing lithium deposition in NMC/Graphite lithium-ion batteries and presenting preliminary results.

Figure 1
(Invited) Is the [5,5] C120-D5d Fullertube a Metal?
Authors: Dorn Harry , Stevenson Steven 
Published: August 2024

Single-walled nanotubes (SWNTs) with a roll-up vector (n = m) have long been predicted to exhibit metallic behavior at infinite nanotube lengths.1 Moreover, in contrast with normal metals, armchair nanotubes e.g., [5,5] should result in exceptional ballistic transport properties.2 However, the question remains at what finite length of a SWNT or fullertube does metallic character begin, if at all. From a computational viewpoint, Cioslowski has shown that the HOMO-LUMO bandgap decreases to ~1 eV in an oscillatory fashion in approaching [5,5] C200 fullertubes.3 Although the HOMO-LUMO gap has been extensively used to predict the kinetic stability of fullerenes and metallofullerenes with less than 100 carbon atoms, Fowler has argued that the HOMO-LUMO gap can not be used to predict the kinetic stability of large fullerenes.4 More recently, Lilijeroth and coworkers have measured the experimental and DFT HOMO-LUMO gap for graphene nanoribbons (GNR) and find that GNRs with lengths of 5 nm have bandgaps of ~0.1 eV.5 These workers also point out that DFT calculated HOMO-LUMO bandgaps are always overestimated relative to experimental values. In this presentation, I will present the evidence in support of metallic character for [5,5] C120-D5d.6,7

References:
1. Mintmire, J. W.; Dunlap, B. I.; White, C. T. Are Fullerene Tubules Metallic? Phys. Rev. Lett. 1992, 68, 631−634.
2. White, C. T.; Todorov, T. N. Carbon Nanotubes as Ballistic Conductors. Nature 1998, 393, 240−242.
3. Cioslowski, J.; Rao, N.; Moncrieff, D. Electronic Structures and Energetics of [5,5] and [9,0] Single-Walled Carbon Nanotubes. J. Am. Chem. Soc. 2002, 124 (28), 8485−8489.
4. Fowler, P., Nature (London), 1991, 350, 20.
5. Kimouche, A., Ervasti, M. M., Drost, R., Halonen, S., Harju, A,. Joensuu, M. P., Sainio, J., Liljeroth P., Ultra-narrow metallic armchair graphene nanoribbons. Nature Communications, 2015, 6 (1) 1-5.
6. Stevenson, S.; Liu, X.; Sublett, D. M., Jr; Koenig, R. M.; Seeler, T. L.; Tepper, K. R.; Franklin, H. M.; Wang, X.; Huang, R.; Feng, X.; et al. Semiconducting and Metallic [5,5] Fullertube Nanowires: Characterization of Pristine D5h(1)-C90 and D5d(1)-C100. J. Am. Chem. Soc. 2021, 143 (12), 4593−4599.
7. Liu, X.; Bourret, E.; Noble, C. A.; Cover, K.; Koenig, R. M.; Huang, R.; Franklin, H. M.; Feng, X.; Bodnar, R. J.; Zhang, F.; et al. Gigantic C120 Fullertubes: Prediction and Experimental Evidence for Isomerically Purified Metallic [5,5] C120-D5d(1) and Nonmetallic [10,0] C120-D5h(10766). J. Am. Chem. Soc. 2022, 144 (36), 16287−16291.
(Invited) Synthesis and Functionalization of Nanographenes with Red to Near-Infrared Emission for Photonic Applications
Authors: Narita Akimitsu 
Published: August 2024

Nanostructures of graphene demonstrate a wide range of optical, electronic, and magnetic properties depending on their size and chemical structures, which renders them promising as next-generation carbon-based nanomaterials, e.g., for nanoelectronics, spintronics, and photonics. However, it is challenging to accurately control the chemical structures while “cutting” graphene. To this end, large polycyclic aromatic hydrocarbons (PAHs) with nanoscale graphene structures are attracting a renewed attention as atomically precise nanographenes [1]. We have developed the synthesis of dibenzo[hi,st]ovalene (DBOV) as an unprecedented nanographene with high stability, strong red fluorescence, and stimulated emission, demonstrating the potential for organic lasers [2]. The functionalization of DBOV was achieved through regioselective bromination and Suzuki coupling, enabling the introduction of various substituents, for example fluoranthene imide (FAI) groups, inducing the red-shift of the emission to the near-infrared (NIR) region [3]. Different effects on the photophysical properties of the DBOV core have been observed by changing the peripheral functional groups. More recently, we have synthesized hexabenzoperihexacene (HBPH) with zigzag and fjord edges, which displayed high stability and NIR emission with maximum at ~800 nm [4]. Notably, HBPH could be made chiral by introducing bulky tert-butyl groups on the helical fjord edges, allowing the separation of the enantiomers and showing the circular dichroism responses up to 830 nm. These results provide a new insight into the structure-property relationship of such nanographenes and pave 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.; Muñoz-Mármol, R.; Vasylevskyi, S.; Villa, A.; Folpini, G.; Scotognella, F.; Paternò, G. M.; Narita, A., Angew. Chem. Int. Ed.
2023, 62, e202218350.
(Invited) Electrochemistry of the 1,1,N,N-Tetramethyl[N](2,11)Teropyrenophanes
Authors: Hahn Nolan , Unikela Kiran Sagar , Boeré René , Bodwell Graham 
Published: August 2024

Polycyclic aromatic hydrocarbons (PAH) have been of broad interest for many decades. This is due largely to their extended π systems, which imbue them with optical and electronic properties that can be exploited in a variety of organic electronic devices. A current trend in PAH chemistry is the construction of ever-larger and more elaborate aromatic systems. A major challenge associated with this work is to maintain solubility. For innately planar PAH, the standard tactic is to append multiple solubilizing groups to the periphery of the aromatic system. The drawbacks to this are that 1) the mass of solubilizing groups can outweigh that of the PAH, 2) the presence of the solubilizing groups severely limits or rules out doing chemistry on the periphery and 3) the tactic becomes less and less effective as the size of the PAH becomes very large. An alternative and very effective way to boost solubility is to bring about nonplanarity in a PAH. This can be achieved through the presence of nonbonded interactions (as in helicenes), the presence of non-6-membered rings (as in corannulene) and by bridging the aromatic system (i.e. incorporating it into a cyclophane).
Cyclophanes constitute a very large and diverse class of compounds. The simplest cyclophanes (the [n]cyclophanes) consist of just one aromatic system and one aliphatic bridge. These cyclophanes are especially interesting because the structure of the aromatic system can be changed by varying the length of the bridge. This enables the study of how the chemical and physical properties of a particular PAH are affected by incremental changes in structure without any complications arising from intramolecular π-π interactions or changes in the character or position of the substituents (the bridge). Understanding the relationships between structure and properties can underpin efforts to tailor properties of organic compounds for use as materials in devices. Very few [n]cyclophanes that have a large PAH are known, so there is plenty of room for exploration in this area.
The PAH of interest in this work is teropyrene. It is a member of the ropyrene series of aromatic compounds, which evolve into armchair-edged graphene nanoribbons (GNR) as they propagate. Teropyrene has 10 6-membered rings, 36 carbon atoms and vanishingly low solubility. Only a handful of teropyrene derivatives are known. We have developed a synthetic route to a series of 1,1,n,n-tetramethyl[n](2,11)teropyrenophanes (n = 7-10), which feature a teropyrene system with an end-to-end bend ranging from 145° (n = 10) to 178° (n = 7) and have very good solubility in a variety of organic solvents. Details of the redox behaviour of these teropyrenophanes will be presented.

Figure 1
(Invited) Distance Dependent Electron Transfer Kinetics in Water Soluble Axially Connected Silicon Phthalocyanine-Fullerene Conjugates
Authors: Sastre-Santos Angela 
Published: August 2024

The effect of donor-acceptor distance in controlling the rate of electron transfer in axially linked silicon phthalocyanine – C60 dyads has been investigated. Herein we will presented the synthesis and photophysical properties of two water soluble C60-SiPc-C60 dyads, 1 and 2, varying in their donor-acceptor distance.In previous investigation for C60-SiPc-C60 dyads where the SiPc and C60 are separated by a phenyl spacer, faster electron transfer was observed with k
cs equal to 2.7 x 109 s-1 in benzonitrile. However, in the case of C60-SiPc-C60, where SiPc and C60 are separated by a biphenyl spacer, a slower electron transfer rate constant, k
cs equal to 9.1 x108 s-1 was recorded. The addition of an extra phenyl spacer in 2 increased the donor-acceptor distance by ~ 4.3 Å, and consequently, slowed down the electron transfer rate constant by a factor of ~3.7. The charge separated state lasted over 3 ns, monitoring time window of our femtosecond transient spectrometer. Complimentary nanosecond transient absorption studies revealed formation of 3SiPc* as the end product and suggested that the final lifetime of charge separated state to be in the 3-20 ns range. Energy level diagram established to comprehend these mechanistic details indicated that the comparatively high-energy SiPc
.+
-C60

.-
charge separated states (1.57 eV) to populate the low-lying 3SiPc* (1.26 eV) prior returning to the ground state.[1]
Here we will present our recent results using water soluble SiPc-C60
1-2 systems where the SiPc is substituted with pyridine units.[3]
Acknowledgments
This work was supported by the Ministerio de Ciencia e Innovación of Spain and FEDER funds (Grants PID2020-117855RB-I00 to ASS) and National Science Foundation (Grant No. 1401188 and 2000988 to FD).
References

L. Martín-Gomis, S. Seetharaman, D. Herrero, P. A. Karr, F. Fernández-Lázaro, F. D’Souza, and Á. Sastre-Santos, Chem Phys. Chem.,
2020, 21, 2254-2262.

V. Sobrino, L. Martín-Gomis, S. Seetharaman, P. A. Karr, D’Souza, and Á. Sastre-Santos, under preparation.

Figure 1
(Invited) Highly Water-Soluble Fullerene Derivatives for Durable Polymer Electrolyte Membrane Fuel Cells
Authors: Matsuo Yutaka , Miwa Kazuhira , Balgis Ratna , Kawasumi Masaya 
Published: August 2024

Recently, the focus of proton-exchange membrane fuel cell (PEMFC) applications has shifted from fuel cell vehicles (FCVs) to heavy-duty vehicles (HDVs), necessitating enhanced fuel cell durability. The degradation of carbon-supported metal nanoparticle catalysts and electrolyte membranes are the primary factors responsible for fuel cell durability. Particularly in the context of HDVs, augmenting the chemical stability of electrolyte membranes, such as Nafion, stands as a crucial factor in improving fuel cell lifetime. The degradation mechanism of Nafion is believed to involve the cleavage of polymer chains by OH∙ radicals, formed by crossover hydrogen and crossover oxygen in the presence of trace transition metal ions. A common strategy to mitigate Nafion's chemical degradation involves adding radical quenchers like cerium ion (Ce+) to Nafion. However, Ce+ may migrate out of Nafion during fuel cell operation, leading to a decline in its highly efficient radical quenching ability over extended operational periods.
In this study, we demonstrate that a fullerene-derived radical quencher with multiple hydroxy groups significantly contributes to enhancing the durability of Nafion. Our approach involves synthesizing fullerene derivatives with various kind of hydroxy and functional groups for remarkable water solubility to realize their homogeneous dispersion within the Nafion membrane. The abundant functional groups also aid in improving proton conductivity. Moreover, the chelating effect of the spherically distributed functional groups immobilizes themselves, preventing any observed leakage from the Nafion membrane. These fullerene-derivative radical quenchers effectively enhance fuel cell durability and hold promise for future applications in HDVs.
This study was supported by the New Energy and Industrial Technology Development Organization (NEDO), Japan (JPNP20003).
(Invited) Fullerenes for Bio-Applications: The Way of Water
Authors: Porfyrakis Kyriakos 
Published: August 2024

Nano-materials are emerging as important components for a series of bio-applications. In this context, carbon nanostructures such as graphene, carbon nanotubes and fullerenes have unique chemical and physical properties that make them attractive for such applications. Carbon nanomaterials have been used in tissue engineering, biosensing and drug delivery. They have also shown anti-microbial activity. They can be loaded with drugs for controlled local delivery. More importantly, the surface of carbon nanomaterials can be functionalised to enhance their biocompatibility by increasing their water-solubility.
In this talk, I will present an update on our work in using fullerenes and their derivatives for developing bio-nanomaterials. I shall focus on the combination of carbon nanostructures and polymeric materials which can result in supramolecular hydrogels with interesting properties. Hydrogels are emerging as important materials in applications such as cellular scaffoldings in regenerative medicine/tissue engineering, tissue replacements, wound dressings, etc.
I will present the synthesis of supramolecular hydrogels made from fullerenes of different sizes (C60, C84 and C90–92) that have been hydroxylated and functionalised with hydrophilic oligoethylene glycol chains. To the best of our knowledge, there have been no attempts made at incorporating higher fullerenes and their derivatives into such extended supramolecular structures, before now.
I will also show possibilities for extending our approach to endohedral fullerenes such as N@C60. I will show how we can use advanced techniques including AFM to characterise the elasticity of the hydrogels formed. The ability to incorporate endohedral fullerenes in hydrogels may be important in extending the possibility for using these materials as sensors in vitro or even in vivo, exploiting the quantum properties of such molecular systems such as their extended electron and nuclear spin lifetimes.