bluuebunny/crossref_metadata_2025_split huggingface dataset:
Photo‐induced Desulfurative Processes for Carbon Radical Generation
Authors: Geniller Lilian , Taillefer Marc , Jaroschik Florian , Prieto Alexis 
Published: July 2023

AbstractThiols constitute an important family among sulfur‐containing compounds, with well‐established applications in various fields ranging from medicine to material science. For instance, thiol residues are good hydrogen donors which reduce radical species in biological or chemical processes. However, even though the S−H bond activation of thiols for providing access to thiyl radicals has been largely studied, desulfurative processes affording carbon‐based radicals by C−S bond activation have been less explored. In recent years, photoredox catalysis has become the prevalent method for the generation of radicals under soft reaction conditions from readily available starting materials under visible light. In this context, recent studies have been devoted to the development of photocatalytic procedures aiming at the desulfurization of thiol derivatives leading to new C−H, C−C or C‐Het bond formation reactions. This review will cover the synthetic methodologies and strategies for photo‐mediated desulfurization of native thiols, thioethers, sulfonium salts and xanthates to access new organic compounds. This emerging field is especially interesting for new transformations of cysteine and peptide derivatives.
Surface Modification of ITO with N‐Heterocyclic Carbene Precursors Results in Electron Selective Contacts in Organic Photovoltaic Devices
Authors: Das Mowpriya , Kohlstädt Markus , Enders Maria , Burger Stephan , Sasmal Himadri Sekhar , Zimmermann Birger , Schäfer Andreas , Tyler Bonnie J. , Arlinghaus Heinrich F. , Krossing Ingo , Würfel Uli , Glorius Frank 
Published: July 2023

AbstractSurface modification of indium tin oxide (ITO) electrodes with organic molecules is known to tune their work function which results in higher charge carrier selectivity in corresponding organic electronic devices and hence influences the performance of organic solar cells. In recent years, N‐heterocyclic carbenes (NHCs) have also been proven to be capable to modify the work function of metals and semimetals compared to the unfunctionalized surface via the formation of strong covalent bonds. In this report, we have designed and performed the modification of the ITO surface with NHC by using the zwitterionic bench stable IPr‐CO2 as the NHC precursor, applied via spin coating. Upon modification, the work function of ITO electrodes was reduced significantly which resulted in electron selective contacts in corresponding organic photovoltaic devices. In addition, various characterization techniques and analytical methods are used to elucidate the nature of the bound species and the corresponding binding mechanism of the material to the ITO surface.
Hexakis‐TIPS‐Alkynylated Nonacenes: Persistent and Processible
Authors: Zeitter Nico , Hippchen Nikolai , Weidlich Anna , Jäger Patrick , Ludwig Philipp , Rominger Frank , Dreuw Andreas , Freudenberg Jan , Bunz Uwe H. F. 
Published: July 2023

AbstractFour substituted nonacenes were prepared and characterized by UV‐vis and EPR spectroscopy and X‐ray crystallography. The compounds are the most stable and soluble nonacenes to date – due to six strategically placed triisopropylsilyl(TIPS)‐ethynyl groups. They are stable for several weeks in the solid state. In dilute solution their half‐life is 5–9 h. Crystal structure analyses of two nonacenes prove their structures. A nonacene derivative was tested in a solution‐processed transistor and exhibits ambipolar charge transport (μe=0.007 cm2/Vs; μh=0.023 cm2/Vs).
Iron‐Catalyzed Amide Bond Formation from Carboxylic Acids and Isocyanates†
Authors: Zi Lingjian , Zhang Jing 
Published: July 2023

Comprehensive SummaryWe describe an iron‐catalyzed amide bond formation from readily available carboxylic acids and isocyanates. This method utilizes an abundant and biocompatible iron catalyst and easily accessible starting materials, generates CO2 as the only byproduct, and features broad substrate scopes with good functional group compatibility. Therefore, it provides a cost‐effective and practical protocol to access a diverse variety of amides.
Cobalt Hydroxide Spindle Nanosheet Amorphous Electrocatalysts via In‐Situ Fast Reduction Release/Oxidization Mechanistic Method for Efficient Overall Water Electrolysis
Authors: Ashok Venkatachalam , Sangamithirai Muthukumaran , Vijayarangan Murugan , Gayathri Arunagiri , Jayabharathi Jayaraman 
Published: July 2023

AbstractWater electrolysis focused with electricity or sunlight is one of the sustainable methods to produce hydrogen; this helps to address the global energy demand whereas sluggish OER and HER kinetic barriers hamper this process. Here, we report an earth abundant Co(OH)2 spindle nanosheet electrocatalyst synthesized via surfactant with boron‐assisted release/oxidize mechanistic process and employed it as a bifunctional electrocatalyst (OER/HER) with small overpotential (258 mV/156 mV), low Tafel slope (78 mV dec−1/71 mV dec−1), higher turnover frequency (0.235 s−1/0.100 s−1) and low charge transfer resistance (4.7 Ω). The higher electrochemical active surface area (45 cm2) of the catalyst exploits the potential electrocatalyst nature with overall cell voltage 1.64 V at 10 mA cm−2.
Refined fiber inulin promotes inflammation‐associated colon tumorigenesis by modulating microbial succinate production
Authors: Tian Sangshan , Paudel Devendra , Hao Fuhua , Neupane Rabin , Castro Rita , Patterson Andrew D. , Tiwari Amit K. , Prabhu K. Sandeep , Singh Vishal 
Published: July 2023

AbstractBackground and AimThere is an increased risk of colon cancer associated with inflammatory bowel disease (IBD). Dietary fibers (DFs) naturally present in vegetables and whole grains offer numerous beneficial effects on intestinal health. However, the effects of refined DFs on intestinal health remain unclear. Therefore, we elucidated the impact of the refined DF inulin on colonic inflammation and tumorigenesis.MethodsFour‐week‐old wild‐type (WT) mice were fed diets containing insoluble DF cellulose (control) or refined DF inulin for 4 weeks. A subgroup of mice was then switched to drinking water containing dextran sulfate sodium (DSS, 1.4% wt/vol) for colitis induction. In another subgroup of mice, colitis‐associated colorectal cancer (CRC) was initiated with three 7‐day alternate cycles of DSS following an initial dose of mutagenic substance azoxymethane (AOM; 7.5 mg/kg body weight; i.p.). Post 7 weeks of AOM treatment, mice were euthanized and examined for CRC development.ResultsMice consuming inulin‐containing diet exhibited severe colitis upon DSS administration, as evidenced by more body weight loss, rectal bleeding, and increased colonic inflammation than the DSS‐treated control group. Correspondingly, histological analysis revealed extensive disruption of colon architecture and massive infiltration of immune cells in the inulin‐fed group. We next examined the effect of inulin on CRC development. Surprisingly, significant mortality (~50%) was observed in the inulin‐fed but not in the control group during the DSS cycle. Consequently, the remaining inulin‐fed mice, which completed the study exhibited extensive colon tumorigenesis. Immunohistochemical characterization showed comparatively high expression of the cell proliferation marker Ki67 and activation of the Wnt signaling in tumor sections obtained from the inulin‐fed group. Gut microbiota and metabolite analysis revealed expansion of succinate producers and elevated cecal succinate in inulin‐fed mice. Human colorectal carcinoma cells (HCT116) proliferated more rapidly when supplemented with succinate in an inflamed environment, suggesting that elevated luminal succinate may contribute to tumorigenesis.ConclusionsOur study uncovers that supplementation of diet with refined inulin induces abnormal succinate accumulation in the intestinal lumen, which in part contributes to promoting colon inflammation and tumorigenesis.
Shattering versus metastability in spin glasses
Authors: Arous Gérard Ben , Jagannath Aukosh 
Published: July 2023

AbstractOur goal in this work is to better understand the relationship between replica symmetry breaking, shattering, and metastability. To this end, we study the static and dynamic behaviour of spherical pure p‐spin glasses above the replica symmetry breaking temperature . In this regime, we find that there are at least two distinct temperatures related to non‐trivial behaviour. First we prove that there is a regime of temperatures in which the spherical p‐spin model exhibits a shattering phase. Our results holds in a regime above but near . We then find that metastable states exist up to an even higher temperature as predicted by Barrat–Burioni–Mézard which is expected to be higher than the phase boundary for the shattering phase . We develop this work by first developing a Thouless–Anderson–Palmer decomposition which builds on the work of Subag. We then present a series of questions and conjectures regarding the sharp phase boundaries for shattering and slow mixing.
Integration of Cobalt Phthalocyanine, Acetylene Black and Cu2O Nanocubes for Efficient Electroreduction of CO2 to C2H4
Authors: Liu Jilin , Yu Kai , Qiao Zhiyuan , Zhu Qianlong , Zhang Hong , Jiang Jie 
Published: July 2023

AbstractSuppressing side reactions and simultaneously enriching key intermediates during CO2 reduction reaction (CO2RR) has been a challenge. Here, we propose a tandem catalyst (Cu2O NCs‐C‐Copc) consisting of acetylene black, cobalt phthalocyanine (Copc) and cuprous oxide nanocubes (Cu2O NCs) for efficient CO2‐to‐ethylene conversion. Density‐functional theory (DFT) calculation combined with experimental verification demonstrated that Copc can provide abundant CO to nearby copper sites while acetylene black successfully reduces the formation energies of key intermediates, leading to enhanced C2H4 selectivity. X‐ray photoelectron spectroscopy (XPS) and potentiostatic tests indicated that the catalytic stability of Cu2O NCs‐C‐Copc was significantly enhanced compared with Cu2O NCs. Finally, the industrial application prospect of the catalyst was evaluated using gas diffusion electrolyzers. The
of Cu2O NCs‐C‐Copc can reach to 58.4 % at −1.1 V vs. RHE in 0.1 M KHCO3 and 70.3 % at −0.76 V vs. RHE in 1.0 M KOH. This study sheds new light on the design and development of highly efficient CO2RR tandem catalytic systems.
A novel time delay‐based phase‐locked loop with improved anti‐harmonic interference performance for grid synchronization
Authors: An Dingguo , Yuan Lifen , Cheng Zhen , He Yigang , Yin Baiqiang , Li Bing 
Published: July 2023

SummaryThe time delay unit‐based PLLs (TD‐PLLs) are widely used in grid synchronization in single‐phase power systems. However, the TD‐PLL is vulnerable to frequency variations and harmonic disturbances, leading to grid synchronization failures. Analysis shows that the performance degradation is due to the inability to obtain the variation of the input signal frequency. This paper proposes a new time delay‐based phase‐locked loop called immune to double frequency component TD‐PLL (IDFC‐TD‐PLL) based on a feedback structure to accurately capture the variation of input signal frequency, which can improve the dynamic performance and the performance against harmonic interference. Simulations and experiments have evaluated the performance of the proposed phase‐locked loop, demonstrating its superior accuracy and dynamic performance compared to the phase‐locked loops referred in the paper.
Low‐dose decitabine promotes M2 macrophage polarization in patients with primary immune thrombocytopenia via enhancing KLF4 binding to PPARγ promoter
Authors: Shao Xia , Xu Pengcheng , Ji Lili , Wu Boting , Zhan Yanxia , Zhuang Xibing , Ou Yang , Hua Fanli , Sun Lihua , Li Feng , Wang Xiangdong , Chen Hao , Cheng Yunfeng 
Published: July 2023

BackgroundThe first‐line therapy is effective for the treatment of primary immune thrombocytopenia (ITP); however, maintaining the long‐term responses remains challenging. Low‐dose decitabine (DAC) has been adopted to treat refractory ITP, while its role in macrophage polarization has not been fully understood. We aimed to investigate the mechanistic role of DAC in M2 macrophage polarization and evaluated its therapeutic effect in ITP.MethodsThe M2 monocytes were identified by flow cytometry from peripheral blood mononuclear cells in healthy controls (HCs) and ITP patients. The expression of PPARγ, Arg‐1, DNMT3b and NLRP3, together with IL‐10 plasma levels was measured to examine its function. Bisulfite‐sequencing PCR was used to evaluate the methylation status of PPARγ promoter, and the binding affinity of KLF4 was measured by Cut&Tag. A sh‐PPARγ THP‐1 cell line was created to verify if low‐dose DAC‐modulated M2 macrophage polarization was PPARγ‐dependent. The passive ITP models were used to investigate the therapeutic effects of low‐dose DAC and its role in modulating polarization and immunomodulatory function of macrophages. NLRP3 inflammasome and reactive oxygen species were also tested to understand the downstream of PPARγ.ResultsThe M2 monocytes with impaired immunoregulation were observed in ITP. After high‐dose dexamethasone (HD‐DXM) treatment, M2 monocytes increased significantly with the elevated expression of PPARγ, Arg‐1 and IL‐10 in CR patients. Low‐dose DAC promoted M2 macrophage polarization in a PPARγ‐dependent way via demethylating the promoter of PPARγ, especially the KLF4 binding sites. Low‐dose DAC alleviated ITP mice by restoring the M1/M2 balance and fine‐tuning immunomodulatory function of macrophages. The downstream of the PPARγ modulation of M2 macrophage polarization might physiologically antagonize NLRP3 inflammasome.ConclusionsLow‐dose DAC promoted M2 macrophage polarization due to the demethylation within the promoter of PPARγ, thus enhanced the KLF4 binding affinity in ITP.
Gut instinct: Sex differences in the gut microbiome are associated with changes in adolescent nociception following maternal separation in rats
Authors: Salberg Sabrina , Macowan Matthew , Yamakawa Glenn R. , Beveridge Jaimie K. , Noel Melanie , Marsland Benjamin J. , Mychasiuk Richelle 
Published: July 2023

AbstractAdolescent chronic pain is a growing public health epidemic. Our understanding of its etiology is limited; however, several factors can increase susceptibility, often developing in response to an acute pain trigger such as a surgical procedure or mild traumatic brain injury (mTBI), or an adverse childhood experience (ACE). Additionally, the prevalence and manifestation of chronic pain is sexually dimorphic, with double the rates in females than males. Despite this, the majority of pre‐clinical pain research focuses on males, leaving a gap in mechanistic understanding for females. Given that emerging evidence has linked the gut microbiome and the brain–gut–immune axis to various pain disorders, we aimed to investigate sex‐dependent changes in taxonomic and functional gut microbiome features following an ACE and acute injury as chronic pain triggers. Male and female Sprague Dawley rat pups were randomly assigned to either a maternal separation (MS) or no stress paradigm, then further into a sham, mTBI, or surgery condition. Chronically, the von Frey test was used to measure mechanical nociception, and fecal samples were collected for 16S rRNA sequencing. Animals in the surgery group had an increase in pain sensitivity when compared to mTBI and sham groups, and this was complemented by changes to the gut microbiome. In addition, significant sex differences were identified in gut microbiome composition, which were exacerbated in response to MS. Overall, we provide preliminary evidence for sex differences and ACE‐induced changes in bacterial composition that, when combined, may be contributing to heterogeneity in pain outcomes.
Application to several suspected poisoning cases of a validated analytical method for the determination of muscarine in human biological matrices using liquid chromatography with high‐resolution mass spectrometry detection
Authors: Flament Estelle , Gaulier Jean‐Michel , Paret Nathalie , Jarrier Nathalie , Bruneau Chloé , Creusat Gaelle , Guitton Jérôme , Gaillard Yvan 
Published: July 2023

AbstractDespite prevention efforts, many cases of mushroom poisoning are reported around the world every year. Among the different toxins implicated in these poisonings, muscarine may induce parasympathetic neurological damage. Muscarine poisonings are poorly reported in the current literature, implying a lack of available data on muscarine concentrations in human matrices. A validated liquid chromatography with high‐resolution mass spectrometry detection (Orbitrap technology) method was developed to determine muscarine concentrations in human urine, plasma, and whole blood samples. Muscarine was determined using 100 μL of biological fluids, and precipitation was used for sample preparation. Liquid chromatography‐mass spectrometry was performed using an Accucore Phenyl‐X analytical column with the electrospray source in positive ion mode. Muscarine was quantitated in parallel reaction monitoring (PRM) mode with D9‐muscarine as the internal standard. The method was validated successfully over the concentration range 0.1–100 μg/L for plasma and whole blood and 1–100 μg/L for urine, with acceptable precision and accuracy (<13.5%), including the lower limit of quantification. Ten real cases of suspected muscarine poisoning were successfully confirmed with this validated method. Muscarine concentrations in these cases ranged from 0.12 to 14 μg/L in whole blood, <LOQ to 43 μg/L in plasma, and <LOQ to 1537 μg/L in urine. This work provides a tool of choice for the diagnosis of muscarine poisoning when mushrooms are not available for identification, as well as the possibility of determining toxins in the blood, which is an important step toward understanding the pharmacokinetics of the mycotoxin.
Monitoring of phosphatidylethanol in dried blood spots and of ethyl glucuronide in hair over 6 months of alcohol consumption
Authors: Herzog Josefine , Skopp Gisela , Musshoff Frank 
Published: July 2023

AbstractThe aim of this study was to monitor seven phosphatidylethanol (PEth) homologues in dried blood spots (DBS) and ethyl glucuronide in hair (EtGH) over a 6‐month period of drinking while documenting the daily drinks (amount and type) of alcohol via app. A total of 23 volunteers (12 males and 11 females) aged 19–54 years were enrolled. At four‐weekly intervals, capillary blood to create DBS and after 3 and 6 months, respectively, a strand of hair (proximal, 3 cm) was collected. Analyses of EtGH and PEth homologues were performed using liquid chromatography–tandem mass spectrometry. All participants consumed alcohol during the 6 months. Only one participant tested negative for both PEth and EtGH. Eight participants had PEth 16:0/18:1 concentrations between 20 and <210 ng/mL (mean: 45.6 ng/mL) but EtGH concentrations below 5 pg/mg. PEth 16:0/18:1 concentrations between 20 and <210 ng/mL and EtGH concentrations between 5 and <30 pg/mg were assigned to eight subjects, uniformly matching them in the category of socially accepted drinking behavior. Four test subjects exceeded the cutoff for social drinking behavior in both PEth 16:0/18:1 (mean: 528 ng/mL) and EtGH (mean: 84.5 pg/mg). Two participants exceeded the threshold for PEth 16:0/18:1 of 210 ng/mL in blood but remained below 30 pg EtG/mg hair. PEth showed a higher detection rate for alcohol consumption than EtGH did. Moreover, PEth concentrations reacted quickly to changes in drinking behavior, whereas EtGH concentrations remained similar over time.
Screen use while eating is associated with lower intuitive eating and higher disordered eating in Chinese adult men and women
Authors: He Jinbo , Fu Yuru , Cui Shuqi , Barnhart Wesley R. , Zhang Xinyi , Han Jiayi , Wang Yitong , Ganson Kyle T. , Nagata Jason M. 
Published: July 2023

AbstractObjectiveWe aimed to explore the potential associations between screen use while eating and intuitive eating and disordered (thinness‐oriented and muscularity‐oriented) eating behaviors.MethodsAnalyses included 600 Chinese adults (50% women; Mage = 30.67, SD = 8.08) recruited online. The use of four major screen devices was captured, including cell phones, tablets, computers, and TVs. Three types of eating behaviors were examined, namely intuitive eating, thinness‐oriented disordered eating, and muscularity‐oriented disordered eating. Pearson correlation and hierarchical regression analyses were conducted separately for men and women to examine the sex‐specific associations between screen use while eating and intuitive eating, thinness‐oriented disordered eating, and muscularity‐oriented disordered eating.ResultsIn both men and women, more screen use while eating was significantly associated with lower intuitive eating, higher thinness‐oriented disordered eating, and higher muscularity‐oriented disordered eating, above and beyond total screen time and social media use.DiscussionWe found preliminary evidence for the significant links between screen use while eating and intuitive eating and disordered eating. Given the global increases in screen use, continued research is warranted to further explore the role of screen use while eating in the development and maintenance of intuitive eating and disordered eating.Public SignificanceMuch remains unknown regarding screen use while eating and eating behaviors. We found that in both Chinese men and women, more screen use while eating was significantly and uniquely associated with lower intuitive eating, higher thinness‐oriented disordered eating, and higher muscularity‐oriented disordered eating. Findings highlight the importance of incorporating screen use while eating in future research on intuitive eating and disordered eating.
Temporal resolution of birth rate analysis in zooplankton and its implications for identifying strong interactions in ecology
Authors: Polishchuk Leonard V. , Kasparson Anna A. 
Published: July 2023

AbstractExpanding on Haeckel's classical definition, ecology can be defined as the study of strong and weak interactions between the organism and the environment, hence the need for identifying strong interactions as major drivers of population and community dynamics. The solution to this problem is facilitated by the fact that the frequency distribution of interaction strengths is highly skewed, resulting in few or, according to Liebig's law of the minimum, just one strong interaction. However, a single strong interaction often remains elusive. One of the reasons may be that, due to the ever‐present dynamics of ecological systems, a single strong interaction is likely to exist only on relatively short time intervals, so methods with sufficient temporal resolution are required. In this paper, we study the temporal resolution of contribution analysis of birth rate in zooplankton, a method to assess the relative strength of bottom‐up (food) versus top‐down (predation) effects. Birth rate is estimated by the Edmondson–Paloheimo model. Our test system is a population of the cladoceran Bosmina longirostris inhabiting a small northern lake with few planktivorous predators, and thus likely controlled by food. We find that the method's temporal resolution in detecting bottom‐up effects corresponds well to the species' generation time, and the latter seems comparable to the lifetime of a single strong interaction. This enables one to capture a single strong interaction “on the fly,” right during its time of existence. We suggest that this feature, the temporal resolution of about the lifetime of a single strong interaction, may be a generally desirable property for any method, not only the one studied here, intended to identify and assess strong interactions. Success in disentangling strong interactions in ecological communities, and thus solving one of the key issues in ecology, may critically depend on the temporal resolution of the methods used.