bluuebunny/crossref_metadata_2025_split huggingface dataset:
β-Functionalized palladium(II) porphyrins: Facile synthesis, structural, spectral, and electrochemical redox properties
Authors: Rathi Pinki , Prakash Kamal , Sankar Muniappan 
Published: November 2022

Two [Formula: see text]-substituted Pd(II) porphyrins, (PdTPP(NO[Formula: see text]Ph2 and PdTPP(Ph)[Formula: see text], were synthesized and characterized by various spectroscopic techniques, and their spectral and electrochemical redox properties were investigated with respect to PdTPP. The single-crystal X-ray structure of PdTPP(NO[Formula: see text]-Ph2 revealed saddle-shape conformation of the macrocyclic core of porphyrin. DFT studies revealed nonplanar saddle shape conformation of PdTPP(Ph)4 with an average deviation of [Formula: see text]-pyrrole carbon atoms from the porphyrin mean plane ([Formula: see text]C[Formula: see text] = ± 0.751 Å) and also 24 core atoms ([Formula: see text]24 = ± 0.368 Å) as compared to PdTPP(NO[Formula: see text]Ph2 ([Formula: see text]C[Formula: see text] = 0.649 Å and [Formula: see text]24 = ± 0.317 Å) due to more [Formula: see text]-pyrrole substitution. Both PdTPP(NO[Formula: see text]Ph2 and PdTPP(Ph)4 exhibited 13-19 nm and 49-59 nm red-shift in the Soret and Q[Formula: see text] bands as compared to PdTPP, respectively. PdTPP(NO[Formula: see text]Ph2 exhibited a very high dipole moment (7.32 D) as compared to PdTPP(Ph)4 (0.239 D) due to the “push-pull” effect of electron donor (phenyl) and acceptor (-NO[Formula: see text] groups at the [Formula: see text]-pyrrole positions of the macrocycle. The redox potentials of PdTPP(NO[Formula: see text]Ph2 anodically shifted ([Formula: see text]E = 0.2-0.4V) as compared to PdTPP and PdTPP(Ph)4 due to the presence of [Formula: see text]-phenyl groups and the strong electron-withdrawing effect of the nitro group. Hence the HOMO-LUMO energy gap of PdTPP(NO[Formula: see text]Ph2 decreased by 0.20 V and 0.28 V as compared to PdTPP(Ph)4 and PdTPP, respectively.
Detecting Liver Cancer Using Cell-Free DNA Fragmentomes
Authors: Foda Zachariah H. , Annapragada Akshaya V. , Boyapati Kavya , Bruhm Daniel C. , Vulpescu Nicholas A. , Medina Jamie E. , Mathios Dimitrios , Cristiano Stephen , Niknafs Noushin , Luu Harry T. , Goggins Michael G. , Anders Robert A. , Sun Jing , Meta Shruti H. , Thomas David L. , Kirk Gregory D. , Adleff Vilmos , Phallen Jillian , Scharpf Robert B. , Kim Amy K. , Velculescu Victor E. 
Published: November 2022

AbstractLiver cancer is a major cause of cancer mortality worldwide. Screening individuals at high risk, including those with cirrhosis and viral hepatitis, provides an avenue for improved survival, but current screening methods are inadequate. In this study, we used whole-genome cell-free DNA (cfDNA) fragmentome analyses to evaluate 724 individuals from the United States, the European Union, or Hong Kong with hepatocellular carcinoma (HCC) or who were at average or high-risk for HCC. Using a machine learning model that incorporated multifeature fragmentome data, the sensitivity for detecting cancer was 88% in an average-risk population at 98% specificity and 85% among high-risk individuals at 80% specificity. We validated these results in an independent population. cfDNA fragmentation changes reflected genomic and chromatin changes in liver cancer, including from transcription factor binding sites. These findings provide a biological basis for changes in cfDNA fragmentation in patients with liver cancer and provide an accessible approach for noninvasive cancer detection.Significance:There is a great need for accessible and sensitive screening approaches for HCC worldwide. We have developed an approach for examining genome-wide cfDNA fragmentation features to provide a high-performing and cost-effective approach for liver cancer detection.See related commentary Rolfo and Russo, p. 532.This article is highlighted in the In This Issue feature, p. 517
Nucleosome Patterns in Circulating Tumor DNA Reveal Transcriptional Regulation of Advanced Prostate Cancer Phenotypes
Authors: De Sarkar Navonil , Patton Robert D. , Doebley Anna-Lisa , Hanratty Brian , Adil Mohamed , Kreitzman Adam J. , Sarthy Jay F. , Ko Minjeong , Brahma Sandipan , Meers Michael P. , Janssens Derek H. , Ang Lisa S. , Coleman Ilsa M. , Bose Arnab , Dumpit Ruth F. , Lucas Jared M. , Nunez Talina A. , Nguyen Holly M. , McClure Heather M. , Pritchard Colin C. , Schweizer Michael T. , Morrissey Colm , Choudhury Atish D. , Baca Sylvan C. , Berchuck Jacob E. , Freedman Matthew L. , Ahmad Kami , Haffner Michael C. , Montgomery R. Bruce , Corey Eva , Henikoff Steven , Nelson Peter S. , Ha Gavin 
Published: November 2022

Abstract

Advanced prostate cancers comprise distinct phenotypes, but tumor classification remains clinically challenging. Here, we harnessed circulating tumor DNA (ctDNA) to study tumor phenotypes by ascertaining nucleosome positioning patterns associated with transcription regulation. We sequenced plasma ctDNA whole genomes from patient-derived xenografts representing a spectrum of androgen receptor active (ARPC) and neuroendocrine (NEPC) prostate cancers. Nucleosome patterns associated with transcriptional activity were reflected in ctDNA at regions of genes, promoters, histone modifications, transcription factor binding, and accessible chromatin. We identified the activity of key phenotype-defining transcriptional regulators from ctDNA, including AR, ASCL1, HOXB13, HNF4G, and GATA2. To distinguish NEPC and ARPC in patient plasma samples, we developed prediction models that achieved accuracies of 97% for dominant phenotypes and 87% for mixed clinical phenotypes. Although phenotype classification is typically assessed by IHC or transcriptome profiling from tumor biopsies, we demonstrate that ctDNA provides comparable results with diagnostic advantages for precision oncology.

Significance:
This study provides insights into the dynamics of nucleosome positioning and gene regulation associated with cancer phenotypes that can be ascertained from ctDNA. New methods for classification in phenotype mixtures extend the utility of ctDNA beyond assessments of somatic DNA alterations with important implications for molecular classification and precision oncology.
This article is highlighted in the In This Issue feature, p. 517
Early Catheter Ablation Versus Initial Medical Therapy for Ventricular Tachycardia Storm
Authors: Huang Kaimin , Bennett Richard G. , Campbell Timothy , Lee Vickie , Turnbull Samual , Chik William W.B. , El-Sokkari Ihab , Hallani Hisham , Dieleman Jan , Kruit Natalie , Eslick Adam , Priestley Mark , Burgess David , Thomas Stuart P. , Denniss A. Robert , Chow Clara K. , Kumar Saurabh 
Published: November 2022

Background:
Ventricular tachycardia (VT) storm is associated with significantly increased morbidity, mortality, and exponential healthcare utilization. Although catheter ablation (CA) may be curative, there are limited data directly comparing outcomes of early CA with initial medical therapy.

Methods:
We compared outcomes of patients presenting with VT storm treated with initial CA versus those treated with initial medical therapy during their first storm presentation in an observational study. Retrospective data from the host institution from January 2014 to April 2020 of 129 patients with their first VT storm presentation were analyzed (58 underwent initial CA, 71 underwent treatment with initial medical therapy). Outcomes were compared in follow-up.

Results:

Median time to initial CA was 6 days. Over a median follow-up of 702 days, patients who underwent initial CA compared with those treated with initial medical therapy had significantly less: (i) VA recurrence (43% versus 92%;
P
=0.002); (ii) VT storm recurrence (28% versus 73%;
P
<0.001); (iii) composite end point of death, heart transplant, VT storm recurrence, and VT-related hospitalization (47% versus 89%;
P
=0.002); (iv) iatrogenic complications (at 12 months: 17% versus 45%;
P
<0.001); (v) cardiovascular-related hospitalizations (50% versus 89%;
P
=0.01); (vi) total number of hospitalizations (median 1 versus 4;
P
<0.001); and (vi) cumulative days in hospital (median 0.5 versus 18;
P
<0.001). There were no intraprocedural deaths in patients treated with early CA.

Conclusion:
In an observational setting in which patients presenting with storm, early CA appears superior to initial medical therapy in terms of VT recurrence, storm recurrence, iatrogenic complications, cardiovascular hospitalizations, and cumulative days in hospital in follow-up.
Rorty and the Question of Normativity: Replies to Commentators on Reconstructing Pragmatism
Authors: Voparil Chris 
Published: November 2022

Abstract
This response to insightful commentaries on my book, from Richard Shusterman, Susan Dieleman, Raff Donelson, and Colin Koopman, takes up the recurring theme of the nature of normativity on a Rortyan view. To frame my individual replies, I revisit the Davidsonian account of epistemic interaction that influences Rorty’s mature view and suggest that the norms implicit in Davidsonian triangulation are insufficient to support Rorty’s antiauthoritarianism in ethics and epistemology. To address the resulting question of how to account for norms of responsibility and obligation within Rorty’s thought, I highlight key strands of the pragmatic tradition, originating with Peirce but extending through James, Addams, and Dewey, that Rorty reconstructs in the process of developing the full implications of prioritizing democracy over philosophy.
On the Legal Regime of Waters Off the Disputed Territories in the Eastern Mediterranean
Authors: Caligiuri Andrea 
Published: November 2022

Abstract
This paper analyses how the legal status of the disputed territories of Northern Cyprus and the Gaza Strip affects the legal regime of waters off their coasts. For both situations, the analysis focuses on the following fundamental issues: the legal regime of maritime disputed territories; the maritime delimitation disputes between each disputed territory and States with opposite or adjacent coasts; and the legal regime of natural resources of the waters off the coasts of a disputed territory. In particular, the legal opinions expressed by Turkish Republic of Northern Cyprus and the State of Palestine are scrutinized, offering an assessment in the light of the relevant rules of the law of the sea and other pertinent rules of international law.
The Legal Regime Governing Mediterranean Fisheries: The General Fisheries Commission for the Mediterranean of the FAO and the Added-Value of Article XIV Bodies
Authors: Ferri Nicola 
Published: November 2022

Abstract
The impact that the progressive development of public international law as relating to fisheries has had on the evolution of the role of Regional Fisheries Management Organizations (RFMOs) is fairly well-known, having periodically attracted interest from public international law scholars and practitioners. There are some instances though where this development has not been the sole factor leading to the emergence of decision-making by RFMOs on the management of fisheries found in marine waters worldwide. The RFMOs family is broad and heterogeneous, also encompassing some organizations which belong to the institutional setting of the Food and Agriculture Organization of the United Nations (FAO). The General Fisheries Commission for the Mediterranean (GFCM) is one of those FAO RFMOs.
Established in 1949 through an international agreement adopted pursuant to Article XIV of the FAO Constitution, the GFCM is the RFMO currently exercising regulatory powers to ensure the sustainability of Mediterranean fisheries. Its institutional belonging to the FAO is key to understanding that throughout its seventy years of existence the GFCM has not been responsive only to the progressive development of public international law as relating to fisheries, like all other RFMOs. The story of its evolution and, consequently, that of the legal regime governing Mediterranean fisheries, is deeply intertwined with developments that took place within the FAO’s administrative framework. This piece will briefly detail these developments, trying to shed light on the fact that the internal decisions taken by the FAO to enable bodies established under Article XIV of the FAO Constitution to exercise their regulatory powers have been, in the specific case of the GFCM, as decisive as the progressive development of public international law relating to fisheries; not only in bringing about the legal regime governing Mediterranean fisheries, but also in ultimately ensuring that this regime is as effective as that implemented by other RFMOs established independently of the FAO.
Italy’s Implementation of the Rome Statute of the International Criminal Court and its Amendments: Unresolved Issues
Authors: Mancini Marina 
Published: November 2022

Abstract
The present article investigates whether the international crimes listed in the Rome Statute of the International Criminal Court and its amendments are punished under Italian law and, if not, what changes to domestic law are necessary so that perpetrators can be prosecuted before the Italian courts. To this end, firstly, it recalls Italy’s efforts to enact ad hoc legislation implementing the Statute. Secondly, it scrutinizes the existing Italian legislation on international crimes and identifies gaps and inconsistencies with the Statute. Finally, it considers the recent Government’s initiative for adopting a code of international crimes. The author finds that the Italian legislation does not provide a proper legal basis for the prosecution of most of the aforementioned international crimes and advocates a major legislative effort to make all of them prosecutable before the domestic courts.
The New Italian Law Against Investment in Antipersonnel Mines and Cluster Munitions: Achievements and Loopholes
Authors: Rossi Pierfrancesco 
Published: November 2022

Abstract
This contribution analyses the key legal issues raised by Law No. 220 of 9 December 2021, the new Italian law against investment in anti-personnel mines and cluster munitions and submunitions. Law No. 220 targets firms in any way involved in the production of these weapons with a total investment ban and provides effective means of enforcing the prohibition upon financial intermediaries. This signals that Italy subscribes to a broad and progressive interpretation of its international obligations under the Mine Ban Treaty and the Convention on Cluster Munitions. At the same time, though, the resulting legal regime also presents some inexplicable gaps with regard to penalties for the financing of firms involved in anti-personnel mines. It is argued here that these gaps create problems of compatibility with the Mine Ban Treaty and raise concerns of constitutionality with respect to Articles 3 and 117(1) of the Italian Constitution. Such issues may not be resoved by the Constitutional Court and should therefore be promptly addressed by Parliament.
The Song Resistance Movement, 1276–1279: An Episode in Chinese Regional History
Authors: Buell Paul D. 
Published: November 2022

Abstract
The final years of the Mongol conquest of Song China, 1276 to 1279, were intensely eventful and fateful. In this short span of time the Song lost three emperors and all of its territory, and the largest land-based empire the world has ever known reached its fullest extent in the wake of a massive battle on the seas off the coast of Guangdong in March 1279. The fighting during these years was largely riparian and littoral, with Song and Mongol (Yuan) warships engaging in intense clashes and suffering horrendous casualties. The Song resistance movement that developed after the withdrawal of the Song royal family in 1276 was valiant and dogged in its struggle against the Mongol juggernaut but ultimately ineffectual because it was waged against spectacularly superior tactics. In southern China, particularly Fujian, Guangdong, and Guangxi, the Song resistance helped Sinicize the once-largely unassimilated and isolated southeast, and many families to this day in the region point with pride to their valiant forebears. Sun Yat-sen was himself a successor to the Song resistance movement.
The Role of the Gulf of California in the North American Monsoon
Authors: Johnson Benjamin O. , Delworth Thomas L. 
Published: November 2022

Abstract
The role of the Gulf of California (GoC) in the North American monsoon (NAM) is investigated using a global climate model with 50-km horizontal atmospheric resolution and prescribed SSTs. Specifically, two 135-yr simulations are compared to quantify the influence of the GoC on the NAM: in the first simulation a realistic representation of the GoC is incorporated, while in the second simulation the GoC is replaced with land surface. The results suggest that the GoC has a significant impact on circulation, with cooler surface air temperatures and lower surface friction allowing for south-southeasterly surface flow along the entire length of the GoC, in turn increasing low-level moisture fluxes into the NAM region. Cooler air over the GoC also leads to lower heights at 700–500 hPa, with a corresponding cyclonic moisture flux anomaly, further increasing moisture fluxes into the NAM region. Correspondingly, precipitation is substantially higher over the NAM region and even east of the Continental Divide in areas such as New Mexico and the U.S. Great Plains. July/August precipitation with a realistic GoC is generally 25%–50% greater in northwestern Mexico than the land-filled case, with precipitation 50% greater in much of the southwestern United States. Due to enhanced surface evaporation, areas with increased precipitation also tend to have lower surface temperatures, higher sea level pressure, and lower mid- to upper-tropospheric heights, thus altering the large-scale circulation. These results highlight the importance of the GoC in the NAM and demonstrate the necessity of resolving the GoC in climate simulations.

Significance Statement
This paper seeks to improve our understanding of the North American monsoon, an important moisture source in the relatively arid region of northwest Mexico and the Southwest United States. Specifically, we investigate the role of the Gulf of California: a long, narrow sea surrounded by elevated topography within the North American monsoon region, oriented roughly southeast–northwest. The results suggest the Gulf of California is an important component of the North American monsoon system. We find that the Gulf of California acts to enhance moisture transports into the North American monsoon, leading to substantially higher precipitation over a large region. Therefore, the Gulf of California should be carefully considered in climate simulations and future projections, especially given it is often not well resolved.
Oxidative damage induced by combined exposure of titanium dioxide nanoparticles and cypermethrin in rats for 90 days
Authors: Zhong Mingqing , Zhang Ruoyu , He Xianzhi , Fu Yu , Cao Yuqing , Li Yuanyuan , Zhai Qingfeng 
Published: November 2022

Titanium dioxide nanoparticles (TiO2NPs) and cypermethrin (CPM) are widely used in various fields, and they can enter the environment in different ways. Combined exposure of TiO2NPs and CPM may increase the accumulation of pollutants in organisms and affect human health. This study was undertaken to evaluate the oxidative and inflammatory parameters associated with the combined exposure of TiO2NPs and CPM in rats. Twenty-four healthy male adult SD rats were randomly divided into four groups. The first group served as the control, while groups 2, 3, and 4 were treated with TiO2NPs (450 mg/m3); CPM (6.67 mg/m3) or combined exposure of TiO2NPs and CPM by inhalation for 90 days. We investigated the oxidative damage induced through combined exposure of TiO2NPs and CPM in rats by evaluating hematology of the rats and determining the blood biochemical index. Our results demonstrated that inhalation of TiO2NPs and CPM increased the levels of oxidative stress markers such as malondialdehyde and alkaline phosphatase in the serum of rats. These were accompanied by a decreased glutathione peroxidase and total superoxide dismutase levels. Furthermore, the level of glutathione peroxidase was further decreased while malondialdehyde was increased in the combined exposure of TiO2NPs and CPM. Interestingly, pathological sections showed that different degrees of tissue injury could be seen in the liver and lung tissues of each exposure group. In summary, the combined exposure of TiO2NPs and CPM can cause increased oxidative damage in rats and damage the tissue structure of the liver and lung.
Beyond entrepreneurship, raising broad academic professionals: Work-based learning in science from the employer’s perspective
Authors: Grooters Saskia , Zaal Emma , Gerkema Menno 
Published: November 2022

The need for employees in the exact and natural sciences sector with both work experience and academic qualifications, especially combined with an entrepreneurial mindset, is rising. The University of Groningen offers an alternative Master’s program entitled Science, Business and Policy (SBP). SBP combines entrepreneurship education with the integration of a disciplinary science domain and thereby prepares students in science advising. This includes a work placement of 6 months, provided by companies, policy organisations and NGOs. To examine the impact of work placements from the perspective of the employer, this article analyses 20 semi-structured interviews with providers of placements. The results show that employers judge students who have undertaken a work placement as attractive future employees, and the quality of science advice given by students is seen as high. From a work floor perspective, work placements are a strong component in the optimal education of future employees. Integrating academic theory and experience in practice contributes to the employability of science students. The impact of work placements goes further than employability, since employers also indicate a direct effect on work dynamics and see the direct impact of advice reports in their organisation. The work-based learning approach chosen to achieve this specific entrepreneurship education fits the need of industry and other non-academic employers.
The evaluation of an inorganic-organic poly(carborane-siloxane-arylacetylene) hybrid resin system
Authors: Monzel William Jacob , Berglund Kyle , Kolel-Veetil Manoj , Simone Davide , Gibson Thao 
Published: November 2022

The realization of aerospace vehicle technologies demanding extreme service conditions is facilitated by the development of materials with greater oxidative stability at high temperatures. Thermal performance of polymer composites can be increased by incorporating a hybrid (organic-inorganic) resin as a thermal barrier coating. One such resin system, meta-poly (carborane-siloxane-arylacetylene) ( m-PCSAA), developed by the U.S. Naval Research Laboratory, shows potential for such application and is further investigated in this work. The resin has a low viscosity (0.1 Pa s) with large processing window (2.5 h) from 100°C to 230°C. These processing characteristics are advantageous for infusion processes or the inclusion of fillers for coating applications. Curing was accomplished in two stages, corresponding to two exothermic reactions. After the first curing stage, the resin exhibits elastomeric behavior, and after the second curing stage is rigid with a high glass transition temperature (∼330°C). The materials exhibited high char yields (89%) in air at 1000°C and may be useful in space or for attritable technology. No cracks were observed during long-term service at 288°C, but significant degradation and cracking were observed after aging at 316°C. The materials exhibited high coefficients of thermal expansion; 186.9 and 168.6 μm/(m∙°C) after first and second curing stage respectively. Similar to epoxies and polyimides, the resin acquired up to 3% moisture at 70°C and 85% relative humidity.