bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synthesis and Characterization of Supramolecules of Li
+
@C60 and Fluorinated Porphyrins
Authors: Miwa Kazuhira , Aoyagi Shinobu , Ueno Hiroshi , Okada Hiroshi , Kawachi Kazuhiko , Kasama Yasuhiko , Kwon Eunsang 
Published: May 2020

Metal endohedral [60]fullerenes (M@C60) have a unique structure encapsulating a metal atom (M) inside the π−conjugated spherical C60 cage. Lithium cation endohedral fullerene (Li
+
@C60) is a commercially available M@C60 and has a potential for application in nano material fields. The cationic Li+@C60 crystallizes with weakly coordinated anions such as SbCl6
− [1], PF6
− [2], Tetrakis[3,5-bis(trifluoromethyl)phenyl]borate anion (TFPB−) [3], and bis(trifluoromethanesulfonyl)imide anion (TFSI−) [3]. Due to the inside Li+ cation, the first reduction potential of Li+@C60 is shifted to positive direction by 0.7 eV than that of pristine C60. As a result, Li+@C60 has larger electron acceptability than C60 [1]. Li+@C60 also forms a guest–host type supramolecule with [10]cycloparaphenylene ([10]CPP) [4] and π−π stacking supramolecules with porphyrins or phthalocyanines [5][6]. A supramolecule of Li+@C60 and 5,10,15,20-tetrakis(4–sulfonatophenyl) zinc porphyrin anion (ZnTPPS4
–), [Li+@C60 – ZnTPPS4
–] with the binding constant of ca. 105 M–
1 shows a long−lived electron charge separation state by photoinduced electron transfer and can be used in photovoltaic cells [5]. The [Li+@C60 – ZnTPPS4
–] based photovoltaic cell shows maximum incident photon-to-photocurrent efficiency (IPCE) value of 78% under the certain condition [7]. The performance of the photovoltaic cells would be changed by the chemical modification of porphyrins.
Here, we synthesized two kinds of porphyrins to obtain new supramolecules of Li+@C60. The first one is neutral 5,10,15,20-Tetrakis(1,2,4,5-tetrafluorophenyl) porphyrin (H2TTFPP). H2TTFPP was synthesized by Lindsey method and characterized by 1H NMR, 19F NMR, UV-vis, CV, DPV, and XRD. The second one is anionic 5,10,15,20-Tetrakis(4-carboxymethylthio-2,3,5,6-tetrafluorophenyl) zinc porphyrin tetrabutylammonium (ZnTFPP4TC4
−4TBA+). ZnTFPP4TC4
−4TBA+ was synthesized according to the modified Lourenço method [8] and characterized by 1H NMR, 19F NMR, UV-vis, CV, and DPV.
H2TTFPP was confirmed to form supramolecular structure with Li+@C60 in the co-crystal by X-ray structure analysis. ZnTFPP4TC4
− was confirmed to form a supramolecule with Li+@C60 in solution by UV-vis titration experiment. The binding constant of [ZnTFPP4TC4
− − Li+@C60] is significantly larger than that of [H2TTFPP − Li+@C60] because of strong coulomb interactions between anionic ZnTFPP4TC4
− and cationic Li+@C60.

References

[1] S. Aoyagi et al., Nature Chem., 2, 678–683 (2010).
[2] S. Aoyagi et al.,
Angew. Chem. Int. Ed., 51, 3377–3381 (2012).
[3] S. Aoyagi et al.
, R Soc Open Sci., 5, 180337 (2018).
[4] H. Ueno et al., Angew. Chem. Int. Ed., 54, 3707–3711 (2015).
[5] K. Ohkubo et al., Chem. Commun., 48, 4314–4316 (2012).
[6] Y. Kawashima et al., J. Phys. Chem. B, 119, 7690−7697 (2015).
[7] K. Ohkubo et al., Chem. Commun., 49, 4474–4476, (2013).
[8] L. M.O. Lourenço et al.,
J. Porphyrins Phthalocyanines, 18, 967–974, (2014).
(Invited) Heteroatom Functionalization of N- and B-Doped Graphene
Authors: Langa Fernando , Barrejon Myriam , Arellano Luis M , Gomez-Escalonilla Maria J. 
Published: May 2020

One of the most important issues in the field of graphene for electronic and optoelectronic applications is how to modulate effectively the density of charge carriers, their mobility and their energy levels. 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. For example, by substituting carbon atoms with nitrogen or boron, it is possible to turn graphene into a semiconductor of n- or p-type, respectively. Both elements are by far the most common dopant elements and graphene doped with these heteroatoms have been widely used in electrocatalysis, as photocatalysts and as electronic materials.
Here, we will present our work in the N- and B- functionalization of N- and B-graphene [1-4] and the influence of the nature of substituent on the electronic properties of the material.
[1] M. Barrejón et al. Chem. Commun. 2015, 51, 16916
[2] M. Barrejón et al. Chem. Sci. 2018, 9, 8221
[3] L.M. Arellano et al. Chem. Commun. 2019, 55, 9999
[4] H. Gobeze et al. Nanoscale Adv. 2019, 1, 4009
(Invited) Supramolecular Assembly of Curved Carbon-Rich Molecules
Authors: Tan Yuanzhi 
Published: May 2020

Aromatic carbon-rich molecules (CRMs) show fascinating electronic properties, which are promising in organic electronics, photovoltaics, sensing [1]. The nature of sp2 hybrid carbon prefers the planar geometrical structure, however, introducing additional strain to carbon framework can distort the planar structure, resulting in curved CRMs. Generally, incorporating non-hexagonal rings into the skeleton of CRMs will create the curvature, for example, fullerenes and geodesic polyarenes. Alternatively, the stereo-hindrance of bulky peripheral functional groups can highly distort the carbon framework, forming another class of curved CRMs, such as persubstituted polyarenes. Their curved conjugate structure leads to the polarized π-faces, which are particularly attractive for supramolecular assembly. Comparing with the face-to-face planar π-π complexes, the supramolecular assembly of curved CRMs requires both geometrical and electronic matching, which promotes the heterogeneous assembly for multi-components. Sequential functionalization with adaptable substituents can modulate and reinforce the supramolecular assembly. In addition, the substituents can not only tune the electronic nature of CRMs, but also can introduce additional supramolecular interactions.

REFERENCES

1. Wu, J. S.; Pisula, W.; Mullen, K. Chem. Rev. 2007, 107, 718.
2. Liu, Y. M.; Xia, D.; Li, B. W.; Zhang, Q. Y.; Sakurai, T.; Tan, Y. Z.*; Seki, S.; Xie, S. Y.*; Zheng, L. S. Angew. Chem., Int. Ed. 2016, 55, 13047.
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Figure 1
(Invited) Trapping Metallic Oxide Cluster inside Fullerene Cage
Authors: Feng Lai 
Published: May 2020

The sub-nanometer sized void inside fullerene cage permits the accommodation of a single atom, atomic cluster or even small molecule, resulting in the formations of endohedral fullerenes. Particularly, clusterfullerenes can be formed by encapsulating multiple metallic ions in most cases along with non-metal ions (i.e., N3-, C2
2-, S2-, O2-) inside the fullerene cage. Such an association makes clusterfullerene more functional than empty fullerenes and conventional mono-metallofullerenes. Up to date, a variety of clusterfullerenes have been reported, including metal nitrides, carbides, oxides, sulfides, cyanides and so on. Among them, oxide clusterfullerenes (OCFs) can contain variable oxide clusters (i.e., M4O2, M4O3, M3O and M2O; M=Sc or other metal), yielding one of the most versatile families. Thus, OCFs may provide a more convenient platform for developing new functional molecules and for studying the previously less-explored topics such as formation mechanism of clusterfullerenes.
In this Account, we review recent progress in the field of OCFs, including their synthesis, isolation, structural and electrochemical studies as well as the preliminary exploration in their potential functions and applications. Thanks for the concrete crystallographic results of an OCF series, we can track the transition of endohedral cluster and fullerene cage. It is suggested that the configuration and internal dynamics of oxide cluster are highly dependent on not only the cage size but also cage structure. On the other hand, based on the experimental observations, two competitive transformation pathways are established for the majority of OCFs, verifying the bottom-up or top-down formation mechanism. It is also found that the redox behaviors of OCFs are more or less comparable to their isoelectronic species with common cage structure and similar cluster geometry, but varied greatly with the cluster variety (i.e., Sc2O vs Sc4O2-3). The mechanism behind such phenomena has been discussed. In addition, the potential of Dy-based OCFs as single molecular magnets (SMMs) is presented theoretically. Nevertheless, experimental advance remains to be achieved.

Figure 1
(Invited) Three-Dimensional Nanocrystals of Endohedral Fullerenes
Authors: Yang Shangfeng 
Published: May 2020

Fullerenes exhibit fascinating physical and chemical properties, rendering promising applications in such functional devices as organic solar cells, light emitting diodes, field effect transistors, and sensors. Constructing ordered micro- or nano-sized fullerene molecular assemblies is crucial for realizing such applications. We developed a universal approach to prepare shape-tunable three-dimensional (3D) crystals of several metal nitride clusterfullerenes (NCFs), including cubes and dices (i.e., hollow cubes with holes at the center of each faces), which can be readily switched by changing the volume ratio of good (mesitylene) and poor (isopropanol) solvents, or turning on/off ultrasonication upon mixing the good/poor (mesitylene/isopropanol) solvents. The 3D nanocrystals were applied in electrocatalysis, revealing the improved methanol oxidation reaction (MOR) activity compared to the cubic-shaped Sc3N@C80 crystals due to its larger surface area resulting from the dice (hole) structure. Moreover, due to the enhanced light absorption, the dice-shaped crystals exhibited anomalously enhanced photoluminescence (PL) relative to that of the cubes.
References:
1. S. F. Yang, T. Wei, F. Jin, Chem. Soc. Rev.
2017, 46, 5005-5058.
2. Y. Xu, C. He, F. Liu, M. Jiao, S. F. Yang, J. Mater. Chem. 2011, 21, 13538-13545.
3. Y. Xu, J. Guo, T. Wei, X. Chen, Q. Yang, S. F. Yang, Nanoscale
2013, 5, 1993-2001.
4. Y. Xu, X. Chen, F. P. Liu, X. Chen, J. H. Guo, S. F. Yang, Mater. Horiz. 2014, 2, 411-418.
5. J. H. Wu, X. J. Zhu, Y. Guan, Y. J. Wang, F. Jin, R. N. Guan, F. P. Liu, M. Q. Chen, Y. C. Tian, S. F. Yang, Angew. Chem. Int. Ed.
2019, 58, 11350-11354.
(Invited) Electrochemical Generation of Wavy Carbon Nanostructures from Curved Polyaromatic Hydrocarbons
Authors: Marcaccio Massimo , Valenti Giovanni , Paolucci Francesco 
Published: May 2020

Carbon nanostructures, such as nanotubes and graphenes, represent a very promising class of new materials in the field of nanotechnology. In principle, graphenes could be obtained following a bottom-up approach by synthesizing large polycyclic aromatic hydrocarbons (nanographenes) starting from suitable precursors. Their subsequent intermolecular condensation into progressively more extended structures can produce macroscopic graphene films.
Amongst the polycyclic aromatic hydrocarbons, Corannulene is a bowl-shaped species recalling the fullerene surface. It is particularly intriguing, for its unique redox and luminescent properties, to develop new materials. The electrochemical reduction and oxidation processes have been reinvestigated in our lab over a large range of experimental conditions.
Concerning the oxidation, it is completely irreversible and this brings about a rapid fouling and passivation of the electrode surface. The adoption of suitable solvents and electrolytes, with very high oxidation resistance and low nucleophilicity, allowed to explore the reactivity of the electrogenerated corannulene carbocations.
The interesting redox, spectroelectrochemical, luminescence and electrochemiluminesce properties of corannulene and derivative species, together with the structure of their electrochemically generated films, will be discussed.
Cumulative Burden of Financial Hardship From Medical Bills Across the Spectrum of Diabetes Mellitus and Atherosclerotic Cardiovascular Disease Among Non‐Elderly Adults in the United States
Authors: Mszar Reed , Grandhi Gowtham R. , Valero‐Elizondo Javier , Caraballo César , Khera Rohan , Desai Nihar , Virani Salim S. , Blankstein Ron , Blaha Michael J. , Nasir Khurram 
Published: May 2020

Background

Atherosclerotic cardiovascular disease (
ASCVD
) has a strong association with diabetes mellitus (
DM
), accounting for approximately two thirds of deaths in this patient population. Many individuals with
ASCVD
and
DM
are vulnerable to financial hardship associated with treatment‐related expenses. Therefore, we examined the burden of financial hardship from medical bills across the spectrum of
ASCVD
status with and without
DM
.

Methods and Results

Using data from the National Health Interview Survey from 2013 to 2017, we used logistic regression analysis to examine the association of
ASCVD
and
DM
status with financial hardship and an inability to pay medical bills from a representative sample of non‐elderly adults in the United States. Our study population consisted of 121 672 individuals. Approximately 3.1% of the weighted population had
ASCVD
, 5.6% had
DM
, and 1.3% had both
ASCVD
and
DM
. Nearly 50% of individuals with
ASCVD
and
DM
reported financial hardship from medical bills (23% being unable to pay medical bills at all), whereas ≈28% of those with neither
ASCVD
nor
DM
reported financial hardship from medical bills (8% being unable to pay medical bills at all). Individuals with concurrent
ASCVD
and
DM
had the highest relative odds of expressing an inability to pay at all when compared with those with neither condition (odds ratio, 2.69; 95%
CI
, 2.21–3.28).

Conclusions

Individuals with concurrent
ASCVD
and
DM
are at a disproportionately high risk of being unable to pay their medical bills. The findings provide strong evidence for developing more effective public health policies that protect vulnerable populations from financial hardship.
Combined in-person and tele-delivered mobile school clinic: A novel approach for improving access to healthcare during school hours
Authors: Nelson Rachel , Bhattacharya Syamal D , Hart Sharon 
Published: May 2020

Aims We report a novel pilot project that allows access to healthcare for children and staff at school via a mobile clinic or telemedicine portal connected to the mobile clinic. The objectives of this pilot project were (a) to perform physicals for children not attached to a primary care physician; (b) to provide medical consultations and treatment for acute illnesses of students and staff, and (c) to lower absenteeism rates among students and staff. Methods In 2013, Ronald McDonald House Charities, a non-profit organization, partnered with Children’s Hospital of Erlanger to provide a mobile clinic trademarked Ronald McDonald Care Mobile utilising a large, box-style truck equipped with examination rooms and a telemedicine portal. Initially, starting with three elementary schools in Bradley County, Tennessee, USA, the programme rapidly expanded to include schools in five other participating Tennessee counties. Only three schools in Bradley County have the option of in-person visits. All other schools access care via telemedicine portals. Funding is provided through multiple grants and community partners. If a student does have insurance, the insurance carrier is billed for the visit, but students without insurance are treated free of charge. Prior to the 2018–2019 school year, only limited data were collected. Results Our first goal was to perform physicals for children not attached to a primary care physician. During the 2018–2019 school year, 28 patients presented for a well-child check. However, 16 of these (57%) did not have a primary care physician. Of note, 19% of students presenting for any complaint did not have a primary care physician on file (172 students). All well-child checks were performed in-person on the Care Mobile. Our second goal was to provide medical consultations and treatment for acute illnesses. A total of 1446 persons were seen for sick visits. Of these, 424 were telemedicine visits (352 students and 72 staff), while 1022 were in-person visits. The five most common diagnoses that the nurse practitioner managed during the 2018–2019 school year included acute pharyngitis, acute upper respiratory infection, streptococcal pharyngitis, fever and acute maxillary sinusitis. Finally, our third goal was to lower absenteeism rates. There were 1446 sick person visits (1253 students and 193 staff). Twenty-two per cent of the students (276 persons) returned to class while 74% (142 persons) of staff returned to work. Conclusion The mobile/telemedicine health clinic is a novel innovation to increase access to acute care and reduce school absenteeism among both students and staff, potentially saving schools hundreds to thousands of dollars.
Medical Assistance in Dying: A Review of Canadian Regulatory Documents
Authors: Villeneuve Michael J. 
Published: May 2020

After years of heated debate about the issue, medical assistance in dying (MAiD) was legalized in Canada in 2016. Canada became the first jurisdiction where MAiD may be delivered by nurse practitioners as well as physicians. Experience has revealed significant public demand for the service, and Canadians expect nurses to advocate for safe, high-quality, ethical practice in this new area of care. Pesut et al. offer a superb analysis of the related Canadian nursing regulatory documents and the challenges in creating a harmonized approach that arise in a federation where the Criminal Code is a federal entity and the regulation of health care providers and delivery of care fall under provincial and territorial legislation. Organizations like the Canadian Nurses Association contribute to the development of good legislation by working with partners to present evidence to help legislators consider impacts on public health, health care, and providers. Nursing regulators across Canada responded quickly to the unfolding policy landscape as the federal legislation evolved and will face that task again: In February 2020, the federal government tabled legislation to relax conditions related to MAiD requests that will force regulators and professional associations back to public advocacy and legislative tables. The success of the cautious approach exercised by nursing bodies throughout this journey should continue to reassure Canadians that their high trust in the profession is well placed.
COVID-19 Impact Among Spine Surgeons in Latin America
Authors: Guiroy Alfredo , Gagliardi Martín , Coombes Nicolas , Landriel Federico , Zanardi Carlos , Willhuber Gastón Camino , Guyot Juan Pablo , Valacco Marcelo 
Published: May 2020

Study Design: Cross-sectional study. Objective: The aim of this study was to evaluate the impact of the COVID-19 outbreak in spine surgeons in Latin America. Methods: A questionnaire was sent to Latin American spine surgeons from April 4 to 6, 2020. Surgeon characteristics were recorded. The impact of COVID-19 on economic well-being, work, and mental health were also determined. All variables were compared and analyzed. Results: Two hundred four surgeons answered the complete survey; most of them were male (96.6%), the average age was 47.7 years; 58.8% (n = 120) were orthopedic surgeons and 41.2% (n = 84) were neurosurgeons. The majority of the respondents were from Argentina (59.8%, n = 122), followed by Brazil (17.2%, n = 35), Chile (6.4%, n = 13), and Mexico (5.9%, n = 12). Most of the surgeons reported performing emergency procedures only during the pandemic (76.5%, n = 156). Half used telemedicine or online consultation modalities (54.4%, n = 111). The average concern about the financial situation due to the pandemic was 7.53 in a scale of 1 to 10 (10 being the worst scenario). Twenty-two percent (n = 45) of the surgeons had a score over 10 in the Patient Health Questionnaire (PHQ-9; scores higher than 10 needs referral to confirm depression diagnosis). Young age and neurosurgery as a specialty were associated with higher PHQ-9 scores. Conclusions: COVID-19 has an impact in the daily working practice and financial situation of spine surgeons in Latin America. The long-term psychological impact should be taken into consideration to avoid a heavier burden for health care providers.
Two distinct prognostic groups in advanced-stage Hodgkin lymphoma revealed by the presence and site of bulky disease
Authors: Qi Shunan , Milgrom Sarah , Dabaja Bouthaina , Tsang Richard , Levis Mario , Ricardi Umberto , Lopez-Alonso Rebecca , Dann Eldad J. , Ng Andrea , Yahalom Joachim 
Published: May 2020

Abstract
Controversy exists regarding the definition and prognostic significance of bulk in advanced-stage (stage III/IV) Hodgkin lymphoma (ASHL), and bulk location (mediastinum vs other sites) further complicated the setting. This retrospective, multi-institutional study comprised 814 ASHL patients between 2000 and 2010 and aimed to evaluate the significance of bulk in ASHL. End points of interest included progression-free survival (PFS) and overall survival (OS). Covariates included maximum diameter and the site of bulky disease. SmoothHR and Kaplan-Meier analyses were used to assess for an association of PFS and OS with covariates. In the exploratory cohort (n = 683), maximum diameter had no association with PFS and a complex, U-shaped association with all-cause mortality on smoothHR analysis. Using 5 cm as a cutoff for bulk, Kaplan-Meier analyses confirmed the smoothHR results. The site of bulk was incorporated to divide patients into 2 groups. The mediastinal bulk (MB) type had more favorable characteristics than the nonbulky/non-MB (NB/NMB) type on age, histology, and bone marrow involvement (P &lt; .001). The MB type was associated with better OS than the NB/NMB-type on univariable analysis (5-year OS, 92% vs 86%; HR, 0.53; 95% confidence interval, 0.34-0.84; P = .007). These findings persisted in the subgroup treated with chemotherapy alone and were confirmed in an independent validation cohort (n = 131). Our findings indicate that mediastinal bulk was associated with more favorable disease characteristics and improved OS in ASHL, and may be a surrogate of a more favorable biology.
Myelodysplastic syndrome unrelated to lentiviral vector in a patient treated with gene therapy for sickle cell disease
Authors: Hsieh Matthew M. , Bonner Melissa , Pierciey Francis John , Uchida Naoya , Rottman James , Demopoulos Laura , Schmidt Manfred , Kanter Julie , Walters Mark C. , Thompson Alexis A. , Asmal Mohammed , Tisdale John F. 
Published: May 2020

Key Points
Ability to accurately attribute adverse events post–gene therapy is required to describe the benefit-risk of these novel treatments. A SCD patient developed myelodysplastic syndrome post-LentiGlobin treatment; we show how insertional oncogenesis was excluded as the cause.