bluuebunny/crossref_metadata_2025 huggingface dataset:
Experimental Spin State Determination of Iron(II) Complexes by Hirshfeld Atom Refinement
Authors: Brüx Daniel , Ebel Ben , Pelzer Niklas , Kalf Irmgard , Kleemiss Florian
Published: December 2024

In this study, we present the first experimental determination of the spin state of transition metal complexes by using Hirshfeld Atom Refinement. For the demonstration, the two iron(II) complexes, (NH4)2Fe(SO4)2 ⋅ 6 H2O and lFe(pic)3jCl2 ⋅ EtOH were investigated. The method involves the refinement using wavefunctions of different spin multiplicity and comparison against experimental diffraction data by means of refinement indicators and residual electron density. Our results show a clear distinction between high‐spin and low‐spin configurations, even for compounds with spin‐crossover behavior. The presented work demonstrates the potential of Hirshfeld Atom Refinement for the experimental determination of spin states in transition metal complexes.
Photocatalytic Multiple Deuteration of Polyethylene Glycol Derivatives Using Deuterium Oxide
Authors: Ogasahara Riku , Mae Miyu , Matsuura Keisuke , Yoshimura Sota , Ishimoto Takayoshi , Udagawa Taro , Harada Kazuo , Fujioka Hiroyoshi , Kamiya Mako , Asada Rio , Uchiyama Hiromasa , Tozuka Yuichi , Akai Shuji , Sawama Yoshinari
Published: December 2024

Deuterated molecules are of growing interest because of the specific characteristics of deuterium, such as stronger C−D bonds being stronger than C−H bonds. Polyethylene glycols (PEGs) are widely utilized in scientific fields (e. g., drug discovery and material sciences) as linkers and for the improvement of various properties (solubility in water, stability, etc.) of mother compounds. Therefore, deuterated PEGs can be used as novel tools for drug discovery. Although the H/D exchange reaction (deuteration) is a powerful and straightforward method to produce deuterated compounds, the deuteration of PEGs bearing many unactivated C(sp3)−H bonds has not been developed. Herein, we report the photocatalytic deuteration of multiple sites of PEGs using tetra‐n‐butylammonium decatungstate (TBADT) and D2O as an inexpensive deuterium source. This deuteration can be adapted to PEG derivatives bearing various substituents ((hetero)aryl, benzoyl, alkyl, etc.). The deuteration efficiencies of the α‐oxy C(sp3)−H bonds at the terminal positions of the PEGs were strongly influenced by the substituents. These reactivities were elucidated by density functional theory calculations of the reaction barriers towards the formation of radical intermediates, induced by the excited state of TBADT and the PEG substrate. In addition, the applicability of deuterated PEGs to internal standard experiments and Raman spectroscopy was demonstrated.
MOF Derived Cobalt Ferrite Cubic Rod‐Like Materials for Highly Efficient Electrochemical Simultaneous Detection of Multiple Heavy Metal Ions
Authors: Guo Jieli , Ye Mengli , Xing Xiujing , Lv Yaokang , Xiong Wei , Li Hao
Published: December 2024

A series of CoFe2O4 materials derived from metal‐organic framework were successfully constructed by the solvent‐thermal method. The morphology of a typical sample CoFe2O4‐1 was mostly in the form of a cubic rod‐like structure with a size distribution of 3.2±0.2 μm, while a small amount of the structure presented hexagonal shape with uniform size dispersion. The XPS characterization results confirmed that the CoFe2O4‐1 material contained Co3+ (Co2+/Co3+=0.98), and the redox reaction between Co2+ and Fe3+ produced more Fe2+ (Fe2+/Fe3+=1.63), leading to the production of more OV on the surface of the CoFe2O4‐1 material (OV%=0.34), thereby facilitating the efficient adsorption of the efficient adsorption of heavy metal ions (HMIs). CoFe2O4‐1/GCE as a typical electrode presented excellent performance for the detection of multiple HMIs. The results should be attributed to the good electrical conductivity and large electrochemically active surface area of CoFe2O4‐1/GCE, accelerating the transport of ions and charges in the system. Interestingly, there are interaction mechanisms between the HMIs when performing simultaneous detection, suggesting the detection of target ions can be facilitated by adding additional ions. This study provides new research insights for the development of highly sensitive electrochemical sensors for real‐time environmental monitoring.
Elucidating the High Affinity Copper(II) Complexation by the Iron Chelator Deferasirox Provides Therapeutic and Toxicity Insight
Authors: Orta Rivera Aixa M. , Landrau Correa Luis A. , Schiavone‐Chamorro Selene L. , Rankins Moriana , Pérez Otero Mariela V. , Benjamín‐Rivera Josué A. , Vega Aponte José A. , Ebenki Valerie B. , Vargas Figueroa Adriana I. , Astashkin Andrei V. , Fernández‐Vega Lauren , Tinoco Arthur D.
Published: December 2024

Tinoco A‐Team Deferasirox (Def), an orally administered iron‐chelating drug, has drawn significant interest in repurposing for anticancer application due to the elevated Fe demand by cancer cells. But there are also concerns about its severe off target health effects. Herein Cu(II) binding is studied as a potential off target interaction. The aqueous solution stability and speciation of the ternary complex Cu(Def)(pyridine) was studied by UV‐Vis and EPR spectroscopy, ESI‐mass spectrometry, and cyclic voltammetry under physiologically relevant conditions. The complex is observed to be a redox active, mononuclear Cu(II) complex in square planar geometry. UV‐Vis spectroscopy demonstrates that at pH 7.4 the complex is quite stable (ϵ337nm=10,820 M−1 cm−1) with a log K=16.65±0.1. Cu scavenging from the Cu transporters ceruloplasmin and albumin was also studied. Def does not inhibit ceruloplasmin activity but forms a ternary Cu(II) complex at the bovine serum albumin ATCUN site. Cu(Def)(py) displays potent but nonselective cytotoxicity against A549 cancer and MRC‐5 noncancer lung cells but the potency of the ternary protein complex was more moderate. This work elucidates potential Def toxicity from Cu complexation in the body but also cytotoxic synergy between the metal and chelator that informs on new drug design directions.
The Competition Between Cation‐Anion and Cation‐Triglyme Interaction in Solvate Ionic Liquids Probed by Far Infrared Spectroscopy and Molecular Dynamics Simulations
Authors: Kristin Philipp Jule , Fumino Koichi , Appelhagen Andreas , Paschek Dietmar , Ludwig Ralf
Published: December 2024

Glyme‐based electrolyte solutions provide new concepts for developing suitable lithium‐ion batteries. The so‐called solvate ionic liquids (SILs) are promising electrolytes. They are most efficient in equimolar mixtures of lithium bis(trifluoromethanesulfonyl)imide ([Li][NTf2]) and glyme, wherein the [Li]+ cation is supposedly fully solvated by glyme molecules. Here, we performed far (FIR) and mid (MIR) infrared spectroscopy for probing the solvation and local structures around the [Li]+ ions. In particular, we studied the competition between the triglyme molecule (G3) and the salt anions for the coordination to the lithium cations with increasing [Li][NTf2] concentration. The formation of nano structures in the [Li][NTf2]:G3 mixtures is discussed in terms of contact (CIP) and solvent‐separated (SIP) ion pairs in solution. At low salt concentrations, the [Li]+ cations are solvated by two triglyme molecules resulting in SIPs only. With increasing salt concentration, [Li]+ is predominantly solvated by one triglyme molecule as [Li(triglyme)1]+ but still remains in contact to one of the four oxygen atoms of the [NTf2]− anion. Molecular dynamics (MD) simulations provide a molecular picture of the [Li][NTf2]:G3 mixtures that supports the conclusions drawn from the experimental findings.
Unraveling Phenanthrenoid Dimerization in Juncus acutus: A DFT‐guided Exploration of Radical‐Coupling Reaction Mechanisms
Authors: Coppola Federico , Cimino Paola , Rega Nadia , Zuppolini Simona , Di Fabio Giovanni , Zarrelli Armando
Published: December 2024

Juncus acutus is a plant found near ponds and brackish marshes, producing secondary metabolites like phenanthrenoid dimers with antibacterial, antioxidant, and anti‐inflammatory activities. Despite this, little is known about the detailed mechanisms behind their dimerization reactions. In this study, we used Density Functional Theory to explore the reaction mechanisms of phenanthrene and dihydrophenanthrene species in radical coupling, both in gas‐phase and solution. The dimerization reactions, initiated by the OH radical, result in the formation of two phenanthrenoid dimers (homodimer and heterodimer). The OH radical abstracts a hydrogen atom from the hydroxyl group, leading to the formation of radicals and water. Our analysis of electronic spin density highlighted the preferred reactive sites that drive regioselective dimer formation. Furthermore, the study identifies a triplet π‐π stacked intermediate preceding the diketone formation on the singlet potential energy surface, revealing a two‐state reactivity mechanism. The diketone dimers are then converted via a water‐mediated keto‐enol tautomerization into their dienolic forms, completing the reaction pathway. This work offers insights into the complex dimerization processes of phenanthrenoids in nature, using computational methods to shed light on poorly understood molecular mechanisms in plant organisms.
Reactions of Unsymmetric Chiral Dialdehydes with Lysine: Regio‐ and Enantioselective Macrocyclization and Fluorescent Sensing
Authors: Mao Yifan , Li Yichen , Davis Stephanie , Pu Lin
Published: December 2024

Three BINOL‐based unsymmetric chiral dialdehydes, (S)‐4, (S)‐5, and (S)‐6, each containing a salicylaldehyde moiety and an ortho‐, meta‐ or para‐substituted benzaldehyde unit, are synthesized and used to react with the enantiomers of an unsymmetric chiral diamine, lysine. These reactions represent the first examples of regioselective as well as enantioselective reactions of an unsymmetric chiral dialdehyde with an unsymmetric chiral diamine to generate unsymmetric chiral macrocycles. The addition of Zn2+ can further enhance the selectivity for the macrocycle formation. Compounds (S)‐4 and (S)‐5 are found to exhibit chemoselective and enantioselective fluorescent recognition of lysine in the presence of Zn2+.
Recent Development of DNA‐based Biohybrid Systems Driven by Light
Authors: Pastorel Zachary , Zanzi Juliette , Canac Yves , Baslé Olivier , Smietana Michael
Published: December 2024

Photochemistry has provided a powerful alternative to generate reactive intermediates under mild reaction conditions and photobiocatalysis is currently widely applied in organic synthesis. While enzyme‐based photocatalysis has attracted a lot of attention, light‐driven DNA‐based biohybrid systems are also increasingly being applied to a large variety of applications from molecular imaging to enantioselective catalysis, and other fields such as DNA‐encoded libraries (DELs). This review gives insights into these research fields by classifying the existing light‐driven DNA‐based biohybrid systems developed to date.
Preparation and Physicochemical Properties of Inorganic Solidified Foam for Forest Fire
Authors: You Bo , Zeng Lei , Shi Yu , Yang Ming , Gao Ke , Gong Zhe , Xu Meifeng
Published: December 2024

To optimize the performance of inorganic solidified foam and apply it effectively in forest fire fighting, three different ionic surfactants were combined with four viscosity‐increasing foam stabilizers. Then, the ratio of inorganic solidified foam was changed to investigate the effects of four factors, namely, water–binder ratio, quick‐setting agent dosing, fly ash dosing, and foam dosing, on the foaming multiple and stability of the inorganic solidified foam. Finally, the fluidity and adhesion ability of the inorganic solidified foam were tested with different quick‐setting agent dosages and foam dosages, and the optimal working condition range of the inorganic solidified foam was determined based on the test results. The results showed that when SDS:APG = 7:1, the foaming multiples of the foam were higher and it could reach 52.5 times when the surfactant content in the solution was 1.2 wt%; among the four viscosity‐increasing stabilizers, the stabilizing effect of xanthan gum was the best. The inorganic solidified foam exhibits an extended foaming time when utilizing a water–binder ratio of 0.45 and a fly ash dosage of 0.5. To ensure optimal mobility and a specific adhesion thickness, it is recommended to maintain a foam dosage of 6 V or higher, with mobility falling within the 11–13 range. The preferred ratio for creating inorganic solidified foam involves a water–binder ratio of 0.45, a 0.6 wt% dosage of accelerating agent, a 0.5 fly ash content, and a foam mixing of 7 V.
A dataset of tracked mesoscale precipitation systems in the tropics
Authors: Russell James , Rajagopal Manikandan , Veals Peter , Skok Gregor , Zipser Edward , Tinoco‐Morales Michell
Published: December 2024

Mesoscale Convective Systems (MCSs) are often quantified via surface‐based radar network, geostationary satellite, or low earth orbit satellite observations. However, each of these has drawbacks for detecting cloud systems such as a lack of global coverage, a lack of variables to quantify deep convective cloud and precipitation properties, and a lack of continuous observations of individual MCSs, respectively. To generate a dataset of tropical Tracked IMERG Mesoscale Precipitation Systems (TIMPS), we use the Forward in Time tracking algorithm to track precipitation systems in the Integrated Multi‐satellitE Retrievals for the Global Precipitation Mission (IMERG). IMERG is a global gridded precipitation product that incorporates observations from a constellation of satellites with passive microwave sensors and other sources, allowing the TIMPS dataset to have continuous temporal precipitation information for MCSs in a global tropical strip with data every 30 min in time and 0.1° in space. TIMPS are provided in a publicly available data base with a variety of variables including MCS size, motion, and precipitation properties, estimations of MCS life cycle stages, and their proximity to the nearest tropical cyclone. By combining the TIMPS dataset with the University of Washington Convective Features database, we also provide snapshots of information from more spatially detailed space‐borne radar coverage. The TIMPS dataset provides the means for detailed long‐term and large‐scale study of MCSs in all regions of the tropics with applications such as composite studies of MCS life cycles and the evaluation of model performance.
Racial Disparities in Perioperative Outcomes for Patients With Head and Neck Cancer
Authors: Fereydooni Soraya , Valdez Caroline , Williams Lauren C. , Verma Avanti , Judson Benjamin
Published: December 2024

Objective

To characterize the perioperative complications after ablative and reconstructive surgery in patients with head and neck cancer (HNC) based on race.

Methods

We conducted a retrospective study of the 2015–2020 National Surgical Quality Improvement Program Database. We compared the perioperative outcomes between White, Asian, Black, Native Hawaiian or Pacific Islander, and American Indian or Alaskan Native patients with bivariate analysis. Multivariate logistic regression assessed the independent association of race with perioperative complications.

Results

Black patients experienced longer surgeries (aβ, 43; 95% CI, 33, 53), longer hospital stays (aβ, 1.6 [95% CI, 1.1–2.1]), and were less likely to be discharged home (aOR, 0.64; [95% CI, 0.54, 0.76]). Black patients also had higher major complications risk (aOR, 1.38; [95% CI, 1.13–1.67]) with the most common being reintubation/ventilation (Black, 4.4% vs. White 2.7%; p = 0.003) and sepsis/septic shock (Black, 3.4% vs. White 1.8%; p = < 0.001). Black patients had higher reoperation rates (aOR, 1.33; [95% CI, 1.12–1.56]) with incision and drainage of abscess and hematoma, exploration of postoperative hemorrhage, thrombosis or infection, or surgical debridement being the top reasons for reoperation. Concordantly, they were at higher risk of postoperative transfusion (Black, 18%; White, 7.2%; p = < 0.001) and wound dehiscence (Black, 4.1%; White, 2.1%; p = < 0.001).

Conclusion

There is evidence of racial disparities in HNC surgery perioperatively. Black patients face an increased risk of major complications, reoperation, extended hospital stay, and non‐home discharge. Developing a comprehensive surgical database with more social determinants of health variables and using a socioecological framework of health can help us identify contributors to these disparities and design high‐leverage solutions.
A hitchhiker's guide to single‐cell epigenomics: Methods and applications for cancer research
Authors: Moreno‐Gonzalez Marta , Sierra Isabel , Kind Jop
Published: December 2024

Genetic mutations are well known to influence tumorigenesis, tumor progression, treatment response and relapse, but the role of epigenetic variation in cancer progression is still largely unexplored. The lack of epigenetic understanding in cancer evolution is in part due to the limited availability of methods to examine such a heterogeneous disease. However, in the last decade the development of several single‐cell methods to profile diverse chromatin features (chromatin accessibility, histone modifications, DNA methylation, etc.) has propelled the study of cancer epigenomics. In this review, we detail the current landscape of single‐omic and multi‐omic single‐cell methods with a particular focus on the examination of histone modifications. Furthermore, we provide recommendations on both the application of these methods to cancer research and how to perform initial computational analyses. Together, this review serves as a referential framework for incorporating single‐cell methods as an important tool for tumor biology.
Bond Losses in Post‐Auction Resale Markets: Causes and Consequences
Authors: Barbosa Klenio , De Silva Dakshina G. , Yang Liyu , Yoshimoto Hisayuki
Published: December 2024

This paper examines the primary‐dealers' returns in post‐auction resale markets for treasury bonds, assesses the prevalence of losses and gains and their consequences for the financial sector. Using a novel database that tracks more than 2350 primary‐to‐secondary transactions, we find that bond losses for primary‐dealers are pervasive and were severe during the financial crisis. Our results indicate that liquidity constraint is a major source of the bond losses. We also find that financial sector value is correlated with these losses. Using an alternating market experiment, we show that primary‐to‐secondary losses are higher under discriminatory auctions as compared to uniform auctions.
Is Fintech Good for Bank Performance? The Case of Mobile Money in the East African Community
Authors: Ky Serge Stéphane , Rugemintwari Clovis , Sauviat Alain
Published: December 2024

Mobile money, a technology‐driven innovation in financial services, has profoundly penetrated the financial landscape in Sub‐Saharan Africa, including banks. Yet, besides anecdotal evidence, little is known about whether mobile money adoption enhances or worsens bank performance. Combining hand‐collected data with balance sheet data from the Bureau Van Djik (BvD) Bankscope and Bankfocus databases for a panel of 141 banks over the period 2009–2018, we find a strong positive and significant relationship between the time elapsed since banks' involvement in mobile money and their performance considering bank profitability, efficiency, and stability. In further investigations, we explore possible channels by showing how bank size, deposit collection and diversification levels alter such an association. Our results are robust to using instrumental variables, controlling for bank and macro level confounding factors, bank fixed effects and considering alternative measures of bank performance and bank‐MNO partnerships. Overall, our findings highlight the bright side of cooperation between banks and mobile network operators in the provision of mobile money.
28‐Day Repeated Dose Toxicity and Toxicokinetics Study on Dihydroartemisinin (DHA) in SD Rats
Authors: Jian Yang  , Yue Peng  , Qiao Hongqun 
Published: December 2024

Dihydroartemisinin (DHA) is an effective antimalarial drug with potential antitumor efficacy, yet toxicological information is limited. The present study was designed to evaluate the potential toxicity of oral DHA. DHA was administered orally by gavage to SD rats at doses of 0, 25, 50, and 75/60 mg/kg b.w./day for 28 days, followed by a 4‐week recovery period. Concomitant toxicokinetics was also evaluated. Due to potential toxicity affecting survival, only the female top dose was adjusted from 75 to 60 mg/kg on study day 14 (D14). Female rats in the low‐dose group and male rats in the low‐ and medium‐dose groups did not show any signs of toxicity. In contrast, male rats in the high‐dose group and female rats in the medium‐ and high‐dose groups showed significant toxic effects, including weight loss, hair loss, and gastrointestinal reactions (soft stools, perianal dirt, and fecal abnormalities). At the end of administration, female rats in the 75/60 (dose‐adjusted) mg/kg dose group had significantly higher reticulocytes (Ret% and RETIC) and alanine aminotransferase (ALT), increased liver weights, and significantly lower hemoglobin (HGB). In addition, histopathology showed mild vacuolation of hepatocytes. These findings suggest that female rats have a greater toxic response than males, and toxicokinetics further demonstrate this sex difference. However, the toxic effects of DHA were reversed at the end of the 4‐week recovery period. Therefore, the liver was identified as the primary target organ. The no‐observed‐adverse‐effect‐level (NOAEL) was 25 and 50 mg/kg b.w./day in female and male rats, respectively.
Ghost Peaks of Aromatic Metabolites Induced by Corona Discharge Artifacts in LC‐ESI‐MS/MS
Authors: Hongo Yayoi , Fukuyama Daisuke , Chen Lee Chuin , Sekimoto Kanako , Watanabe Hiroshi
Published: December 2024

LC‐ESI‐MS/MS is a preferred method for detecting and identifying metabolites, including those that are unpredictable from the genome, especially in basal metazoans like Cnidaria, which diverged earlier than bilaterians and whose metabolism is poorly understood. However, the unexpected appearance of a “ghost peak” for dopamine, which exhibited the same m/z value and MS/MS product ion spectrum during an analysis of Nematostella vectensis, a model cnidarian, complicated its accurate identification. Understanding the mechanism by which “ghost peaks” appear is crucial to accurately identify the monoamine repertoire in early animals so as to avoid misassignments. Verification experiments showed that in‐source oxidation of tyramine, which produced an intense signal, was responsible for this “ghost peak.” This artifact commonly occurs among aromatic compounds with high signal intensities and appears at the same m/z as their respective in vivo oxidized metabolites. In metabolomics, spectra contain diverse signals from complex biological mixtures, making it difficult to recognize artifact peaks. To prevent misassignments, despite +16 Da differences, adequate chromatographic separation of metabolites from their respective in vivo oxidation precursors is necessary. Whereas both electrolysis and gas‐phase corona discharge can cause in‐source oxidation in ESI, corona discharge proved to be the dominant factor. Additionally, the presence of multiple oxygen atom sources was suggested by the voltage‐dependent mass shift of +16 Da to +18 Da of the “ghost peak” when using 18O‐labeled water as a solvent. Accurate metabolite identification using LC‐ESI‐MS/MS requires accounting for in‐source products that can mimic in vivo products.
Identifying Rare Alleles Affecting Seed Coat and Hilum Color in Soybean (Glycine max) Using Applied Genomics
Authors: Kaňovská Ivana , Biová Jana , Slivková Jana , Bilyeu Kristin , Škrabišová Mária
Published: December 2024

Breeding programs are often constrained by the genetic diversity of the parental lines, even though these lines can be a rare source of unique alleles not found elsewhere. Therefore, identifying these rare alleles is crucial for keeping them in the breeding programs while introducing new genetic resources. The growing amount of whole genome sequenced data has made Genome‐wide Association Study (GWAS) dominant in investigations to find causal genes for all crops, including legumes. However, GWAS often fails to predict more than one causative mutation (CM) in multiple alleles of a single causal gene. Consequently, multiple alleles complicate breeding when not recognized by a single associated marker, which typically identifies only the most frequent CM and discriminates against the others. In this work, we focus on adopting recent applied genomics methods to identify multiple independent alleles and rare alleles in soybean as a model for other legumes. We predicted, identified, and confirmed a new and extremely rare CM for the loss of black pigmentation in the soybean seed coat and hilum color R gene, the Q25fs. The deletion of eight bases leads to a frameshift, a premature stop codon, and a truncated, nonfunctional protein. Our results also suggest a possibly new gene or an allele of the seed coat color inhibitor I gene. Using a soybean model, we demonstrate how applied genomics methods can accelerate pre‐breeding, and additionally, we discuss the potential for adopting these methods for application to other legumes.
QCL‐Based Cryogen‐Free THz Optical Wireless Communication Link
Authors: Sorgi Alessia , Meucci Marco , Umair Muhammad A. , Cappelli Francesco , Toci Guido , De Natale Paolo , Viti Leonardo , Ferrari Andrea C. , Vitiello Miriam S. , Consolino Luigi , Catani Jacopo
Published: December 2024

The increased demand for high‐speed (terabit‐per‐second) wireless data transmission has driven the shift of the frequency carrier from ubiquitous radio frequency systems toward the 1–5 THz range, triggering a new interest for THz quantum cascade laser (QCL)‐based free‐space optical (FSO) links. As compared to standard telecom‐band FSO links, platforms based on THz frequency sources are inherently robust against Rayleigh scattering. Atmospheric absorption, mainly due to water vapor, limits the achievable link distance range, but at the same time, it shifts channel security on the physical layer. THz QCL‐based FSO links are reported with setups requiring cryogenic cooling, seriously limiting their development for mass applications. Here, a cryogen‐free, transportable THz FSO communication system is presented relying on a directly modulated 2.83 THz QCL transmitter, hosted in a closed‐cycle Stirling cryocooler, and exploiting a room‐temperature graphene‐based receiver, implementing a binary on‐off keying modulation scheme with Manchester encoding. Power‐versus‐distance measurements and communication tests are performed, and propose a propagation model to extrapolate the performances of the THz link in an optimized configuration. This approach reduces complexity and costs, as compared to the state‐of‐the‐art THz FSO links, and paves the way for the deployment of optical wireless communication systems exploiting the 1–5 THz frequency range.
3D deuterium metabolic imaging (DMI) of the human liver at 7 T using low‐rank and subspace model‐based reconstruction
Authors: Nam Kyung Min , Gursan Ayhan , Lee Nam G. , Klomp Dennis W. J. , Wijnen Jannie P. , Prompers Jeanine J. , Hendriks Arjan D. , Bhogal Alex A.
Published: December 2024

Purpose

To implement a low‐rank and subspace model‐based reconstruction for 3D deuterium metabolic imaging (DMI) and compare its performance against Fourier transform‐based (FFT) reconstruction in terms of spectral fitting reliability.

Methods

Both reconstruction methods were applied on simulated and experimental DMI data. Numerical simulations were performed to evaluate the effect of increasing acceleration factors. The impact on spectral fitting results, SNR, and the overall normalized root mean square error (NRMSE) compared to ground‐truth data were calculated. A comparative analysis was performed on DMI data acquired from the human liver, including both natural abundance and post‐deuterated glucose intake data at 7 T.

Results

Simulation showed the Cramer‐Rao lower bound [%] of water, glucose, sum of glutamate and glutamine (Glx), and lipid signals for the low‐rank and subspace model‐based reconstruction at R = 1.0 was 12.4, 14.7, 17.3, and 11.0 times lower than FFT. At R = 1.1, NRMSE was 1.4%, 1.3%, 0.8%, and 4.2% lower for the water, glucose, Glx, and lipid, respectively, compared to FFT. However, the NRMSE of the Glx and lipid increased by 0.4% and 3.2% at R = 1.3. For the in vivo DMI experiment, SNR was 2.5–3.0 times higher compared to FFT. The fitted amplitude of water and glucose peaks showed Cramer‐Rao lower bound [%] values that were approximately 2.3 times lower than FFT.

Conclusion

Simulations and in vivo experiments on the human liver demonstrate that low‐rank and subspace model‐based reconstruction with undersampled data mitigates noise and enhances spectral fitting quality.
Electrospun Nanofibers of Polyvinyl Alcohol Loaded With Carvacrol Nano‐Emulsions Toward Antioxidant, Antimicrobial, and Controlled‐Release Applications
Authors: Yang Sijia , Liu Yuxin , Xu Hang , Wu Ke , Li Shujing
Published: December 2024

Antibacterial composite films are commonly used in food packaging. However, most of these packaging materials are prepared from petroleum‐based polymers and has generated grand challenges to the global environment due to the abuse of these non‐biodegradable packaging materials. In this study, carvacrol (Car) was used to form highly stable nano‐emulsions, followed by electrospinning with the polyvinyl alcohol (PVA) solution to prepare bio‐functional nanofiber membranes (PVA‐Car‐NEs‐NF). Meaningfully, the PVA‐Car‐NEs‐NF can still maintain filamentary structure similar to the undoped PVA‐NF membrane confirmed by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) further demonstrated the interfacial interaction between carvacrol and PVA molecules. As a consequence, the PVA‐Car‐NEs‐NF demonstrated a modest release rate of carvacrol invitro with controlled release behavior. Moreover, the antioxidant capacity of PVA‐Car‐NEs‐NF towards scavenging the free radical 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) progressively increased as the increasing carvacrol concentration, and the maximal clearance rate reached 52.56% ± 2.50% at a carvacrol concentration of 2.0 mg/mL. Additionally, PVA‐Car‐NEs‐NF also exhibited enhanced antimicrobial activity against Escherichia coli (E. coli), Staphylococcus aureus (S. aureus), and Candida albicans (C. albicans), while the inhibitory effect was positively dependent on the carvacrol content, thus greatly improving their utilization efficacy and provides the potential application of carvacrol for food, medicine, and cosmetic‐related fields.
Das Stadtklima: Herausforderung im Klimawandel: Leben auf der Wärmeinsel
Authors: Halbig Guido W.
Published: December 2024

Damit Städte weiterhin lebenswert bleiben, müssen sie ihren Beitrag zur Reduktion der Treibhausgas‐Emissionen leisten. Zusätzlich sind Anpassungsmaßnahmen an den Klimawandel erforderlich. Dazu zählen Verschattungen durch Bäume, Entsiegelung von Flächen und Schwammstadt‐Konzepte. Die Klimatologie unterstützt die Stadtplanung dabei mit wissenschaftlichen Erkenntnissen zum aktuellen und zukünftigen Stadtklima. Sie entwickelt auch Stadtklima‐Modelle, die Stadtplanern kostenfrei zur Verfügung stehen. Solche Modelle berücksichtigen wesentliche Wechselwirkungen zwischen Mensch, Stadtkörper und der belebten städtischen Umwelt, inklusive Pflanzen‐ und Tierwelt.
Patient‐Reported Worst‐Case Scenarios in Advanced Cancer: Presence, Contents, and Predictors
Authors: Arch Joanna J. , Kirk Mackenzie H. , Finkelstein Lauren B.
Published: December 2024

Background

Advancements in precision oncology have led to a growing community of adults with advanced cancer who live longer but face prognostic uncertainty, with corresponding fears of the future. Their worst future fears related to cancer remain understudied, hindering support efforts.

Aims

This study aimed to characterize the presence, content, and predictors of imagined future worst‐case scenarios related to cancer (WCS) among distressed adults with advanced cancer.

Methods

Two hundred fifteen distressed adults with advanced solid tumor cancer (mixed type) responded to survey questions regarding the presence (Yes/No) of a WCS related to cancer and if yes, to briefly describe it. Mixed methods were used to assess WCS prevalence, thematic content, and sociodemographic, psychological, and medical predictors.

Results

Two thirds (66.5%) of advanced cancer survivors endorsed having a WCS. Content reflected four major themes of Death (52.2%), Suffering and Deterioration (47.1%), Cancer Progression and Future Uncertainty (28.7%), and Concern about Family (18.4%). WCS often contained more than one major theme, further distinguished by additional themes and sub‐themes that revealed distinct fears. Higher anxiety and lower life meaning/peace predicted the presence of a WCS whereas sociodemographic characteristics, depression, time since diagnosis, and physical symptom burden did not. Younger age and living with children predicted a WCS focused on loved ones.

Conclusions

WCS are prevalent and diverse in content among distressed adults with advanced cancer. Assessing WCS offers a quick and straightforward way to solicit advanced cancer survivors' most intense fears about the future with cancer, thereby facilitating patient‐provider communication and support efforts.
Photocurrent Nanoscopy in the Near Field: A Comparative Study of Different Atomic Force Microscopy Tips in Relation to Their Optical Performance
Authors: Dai Dinghe , Siebenkotten Dario , Šobáň Zbyněk , Girnghuber Anna , Krzysteczko Patryk , Hoehl Arne , Wunderlich Jörg , Kästner Bernd
Published: December 2024

Photocurrent is a critical observable in a wide range of physical processes across different length scales, serving as a valuable tool for the characterization of semiconductors or two‐dimensional materials. Recently, photocurrent mapping, particularly when combined with magnetothermal transport effects, such as the anomalous Nernst effect (ANE), has been used to image magnetic domains and domain walls. To gain access to photocurrents on the nanoscale, this effect is combined with infrared scattering‐type scanning near‐field optical microscopy, in which strong field enhancement is created at the apex of an atomic force microscopy (AFM) tip, which serves as the confined illumination source creating localized temperature gradients through light absorption in the sample, which can be exploited for ANE detection. Herein, ANE photocurrents generated in a cobalt–iron–boron channel and the optical scattering are compared between various AFM tips, revealing significantly differing behavior for different tips. To gain insight into the origin of these differences, the measurements are further compared to finite element method simulations of tips with varied tip apex radii.
Conjugated Phthalocyanine‐Based Mesoporous Covalent Organic Frameworks for Efficient Anodic Lithium Storage
Authors: Jiang Rong , Wang Xiaoyang , Zhi Qianjun , Liu Zhixin , Yang Xiya , Li Chunli , Xu Qianqian , Zhan Xiaoning , Wang Kang , Zhang Lijuan , Jiang Jianzhuang , Feng Yongjun
Published: December 2024

Organic anode materials have been recognized as promising candidates for low‐cost and sustainable lithium‐ion batteries (LIBs), which however suffer from the inferior cycling stability and low conductivity with unsatisfactory LIBs performance. Herein, two conjugated phthalocyanine‐based covalent organic frameworks (COFs), namely CoPc‐Ph‐COF and CoPc‐3Ph‐COF, are synthesized by the nucleophilic substitution reaction of hexafluorophthalocyanine cobalt (II) (CoPcF16) with 1,2,4,5‐tetrahydroxybenzene and 9,10‐dimethyl‐2,3,6,7‐tetrahydroxyanthracene, respectively. Powder X‐ray diffraction and electron microscopy analysis reveal the crystalline porous structure of both COFs with a pore size of 1.6‐2.4 nm, enabling facile ion transportation. Immersion experiments demonstrate the excellent stability of both COFs. I–V curve measurement discloses the superb conductivity of both COFs due to their fully π‐conjugated frameworks. These merits, in combination with their N‐rich skeleton, endow the two COFs with excellent anodic Li+ storage performance in terms of high specific capacities, superb rate performance, and good cycling stability. In particular, CoPc‐3Ph‐COF suggests a large reversible capacity of 1086 mA h g−1 at 100 mA g−1, superior to most reported organic LIBs anodes, exhibiting its promising application in high‐performance LIBs.
Photo‐Cross‐linked DNA Structures Greatly Improves Their Serum Nuclease Resistances and Gene Knock‐In Efficiencies
Authors: Li Zhigang , Ma Youwei , Li Chengxu , Xiao Shiyan , Liang Haojun
Published: December 2024

The stabilization and structural integrity of DNA architectures remain significant challenges in their biomedical applications, particularly when inserting functional units into the genome using long single‐stranded DNA (lssDNA). To address these challenges, a site‐specific photo‐cross‐linking method is employed. Single‐stranded oligonucleotides, containing one or two photosensitive cyanovinylcarbazole nucleoside (CNVK) molecules, are precisely incorporated and cross‐linked at the specific sites of ssDNA through base‐pairing, followed by rapid UV irradiation at 365 nm. This interstrand photo‐cross‐linking improves the thermal stability of DNA duplexes and allows this study to afford a tetrahedral DNA nanostructure in a yield of >94%. Most importantly, the photo‐cross‐linked DNA architectures exhibit high resistances against serum degradation, especially prevent digestion of exonuclease III (exo III), which is common in conventional lambda‐processing method. Meanwhile, this photo‐cross‐linking treatment can significantly improve the knock‐in (KI) efficiencies of lssDNA in different cells including 293T, K562, and HepG2, approximately three to eightfold those of the uncross‐linked lssDNA, and remain a low cytotoxicity. Given the significantly enhanced nuclease resistance in serum and improved KI efficiencies, this study anticipates that this photo‐cross‐linking method will become a valuable tool in technologically advanced biomedical applications, such as nanotechnology and nucleic acid therapy.
Mitigating Passivation Layer Damage and Lowering Contact Resistivity of TOPcon Solar Cells Through Low PbO Content Ag Paste
Authors: Chen Sheshicheng , Guo Cuiwen , Feng Jiwei , Zhang Xiaopeng , An Ruihao , Liu Zunke , Du Haojiang , Gou Yangyang , Xiao Chuanxiao , Liu Wei , Yang Jie , Xu Menglei , Tan Ying , Gu Zhijie , Qiao Yifan , Li Changzhi , Yang Zhenhai , Zeng Yuheng , Zhang Weiming , Ye Jichun
Published: December 2024

The development of front‐side pastes suitable for devices with high sheet resistance such as tunnel oxide passivated contact (TOPCon), is of great significance but remains a considerable challenge. The optimization of the Ag‐Si contact interface is crucial for enhancing contact and improving the efficiency of these devices. This work investigates the front‐side Ag pastes with low Al content (<2 wt.%) and different frit compositions for TOPCon. It is found that the paste with low‐addition frit effectively prevents excessive etching of passivation layers and minimizes additional damage to boron emitters while ensuring favorable contact. Meanwhile, the lowly FT (fire through) paste promotes Ag nanoparticles with larger particle sizes and higher quantities in the interfacial glass, thereby enhancing the conductivity of the interfacial glass and reducing contact resistivity. A low contact resistivity of ≈1 mΩ·cm2 and superior photovoltaic conversion efficiency of 25.19% are achieved on TOPCon with a sheet resistance of ≈350 Ω/□. This work demonstrates the application potential of Ag‐Al paste with low Al content suitable for high sheet resistance emitters by modulating the Ag‐Si interface structure. The coupling between microstructure and device performance is elucidated offering an innovative approach for developing silver paste suitable for high sheet resistance TOPCon.
Metamorphic Testing on Scientific Programs for Solving Second‐Order Elliptic Differential Equations
Authors: Yan Shiyu , Zhu Hong
Published: December 2024

Practical problems in scientific computation that solve differential equations rarely have explicit exact solutions. Therefore, verifying the correctness of such programs has long been a challenge due to the difficulty of producing expected outputs on test cases. In this paper, the principles of metamorphic testing are applied to verify programs that solve second‐order elliptic differential equations. We present a testing process specifically tailored for the verification testing of scientific computation programs and integrate it to the process of developing scientific software. Unlike existing approaches, we formally derive metamorphic relations from the numerical models of differential equations built in development process of scientific computing programs. The experimental results clearly show that our approach is effective in detecting faults commonly found in scientific computing programs. It outperforms the fault detecting ability of the trend method, which is a traditional testing method for scientific software.
Time as a Weapon: Women, Temporal Experience, and Resistance in a Central New York Jail
Authors: Friday Gabreélla
Published: December 2024

Time is a social construct often weaponized against marginalized people via waiting, imprisonment, and other forms of social control. In prisons, the length of one's sentence is something to be passed, overcome, or defeated. This paper seeks to understand how incarcerated women in jails—associated with awaiting sentencing or short sentences—experience time in the United States. Moreover, how do minoritized women experience and resist the time of imprisonment in such liminal spaces? I utilized participant observation, semi‐structured interviews, and visitations—in‐person and virtually—with women in a county jail. Their narratives elucidate that time was weaponized against them at three levels: (1) imprisonment itself, (2) through local and facility policies, and (3) via the manipulation of time by facility actors. Moreover, the women articulated how the weaponization of time was exacerbated for minoritized women and women who questioned their mistreatment. Finally, despite this weaponization, the women resisted the jail's temporal regime via intrapersonal tactics and interpersonal organizing. This was done in symbolic and meaningful ways tied to their intimate and embodied familiarity with jail time structures. They also resisted in substantive ways, alongside a community organization, which culminated in mutual aid programs, solidarity protests, and exposure of abuses in the jail.
Advanced neutralization technique for the treatment of highly acidic wastewater from steel rolling mills of western Rajasthan
Authors: Tatiya Shreyansh , Maurya Shiwangi , Pandey Mohit , Bhattacharya Shantanu
Published: December 2024

In this study, we developed an economical treatment process for highly acidic effluents from steel rolling mills containing toxic heavy metals. Our method involves a pH‐dependent approach using mining waste and hydrated lime. The treatment occurs in two steps: First, metal oxides precipitate at pH 3–3.5 using mining waste, followed by lime precipitation at pH 9–9.5. The process, completed in less than 6 h without heavy machinery, reduces sludge formation by extracting high‐purity gypsum, a valuable industrial product. Water quality posttreatment matches local groundwater standards. Compared to conventional methods like common effluent treatment plant (CETP) in Jodhpur, India, our approach reduces operational costs by over 58%. In this study, we also characterized the by‐product formed, that is, gypsum using various characterization tools and performed a detailed cost analysis.

Practitioner Points

A quick, efficient, and economical treatment process for extremely acidic (pH ~ 1) wastewater from steel industries.

Stepwise treatment strategy without involving heavy machinery or high manpower.

Processed water quality closely resembles groundwater with all the major heavy metals been removed.

Sludge quantity reduced by regeneration of pure gypsum (96% purity).

Reduced the overall operation cost of effluent treatment by 58%.
Navigating the Complexities of the OTC Medicine Ecosystem
Authors: Caratti Elena
Published: December 2024

The previous chapters have analysed the difficulties a patient may face in purchasing a medicine, even though supported by the prescription and the information he or she may receive, in written or verbal form, from the doctor during the examination and from the pharmacist during dispensing of the medicine. However, some medicines do not need to be prescribed by the doctor but can be purchased independently by the patient. In these cases, even more so than in the case of medicines dispensed on prescription, it is necessary for the information accompanying the medicine to be comprehensive, understandable and to make certain information available to the patient before the medicine is purchased. This is the case here with over-the-counter analgesics.
The In-Home Place of Medications: Perspectives of Domestication
Authors: Pizzocaro Silvia
Published: December 2024

Starting from the relevance of observing people’s behaviors with common types of medicines, this contribution is intended to pinpoint some notes that revolve around in-home medication. What is proposed is a reflection on medicines as tangible, concrete devices that materialize the meaning of medication in the prosaic in-home dimension. While literature mainly intends the domestication of pharmaceutical consumption as either the pharmaceuticalization of daily life, or the domestication of usage, here we will use the term ‘domestication’ to mean the latter only. This perspective tries to highlight some traits of the use of medicines within the in-home spaces of everyday life, among ordinary things. It also looks at people’s real behaviors with medications to let habits, routines, and even rituals emerge. Against the background of these study interests, the consideration is posed that a substantial percentage of medication non-compliances, inconveniences, even errors and/or difficulties may be caused not only by lack of info-communicative aspects, but by the deficiencies of still ameliorable user-centered qualities of medicines themselves. These are deficiencies that may variably concern the usable properties of medicines as commodities (shape, size, proportions, annex co-products for intake or dosage) and the traits of that peculiar relation between users and medication use which may disorient the user, favoring or—conversely—hindering access or correct use, reducing but also potentially inducing possible errors. The framework within which in-home medication is approached here advocates the relevance of those disciplinary contributions stemming from studies in product design, product affordance, product-user cognition and interaction, accessibility, and usability design. Meant as a theoretical contribution, this reflection partly reviews some consolidated studies conducted in the anthropology of pharmaceuticals, while integrating inputs derived from person-centered care literature.