bluuebunny/crossref_metadata_2025 huggingface dataset:
Deuteration‐Induced Energy Level Structure Reconstruction of Carbon Dots for Enhancing Photoluminescence
Authors: Yao Zimin , Wen Xiaokun , Hong Xia , Tao Ran , Yin Feifei , Cao Shuo , Yan Jiayi , Wang Kexin , Wang Jiwei
Published: May 2024

Constrained by a limited understanding of the structure and luminescence mechanisms of carbon dots (CDs), achieving precise enhancement of their photoluminescence (PL) performance without altering the emission wavelength and color remains a challenge. In this work, a deuterated CD is first achieved by simply replacing the reaction solvent from H2O to D2O. The substitution of D atoms for H atoms is not limited on the surface but also within the internal structure of CDs. Deuteration affects the formation of the π‐conjugated network structure by altering the content of sp2 carbon and sp3 carbon, ultimately inducing a reconstruction for energy level structure of CDs. Both the intrinsic state and surface state emission, including quantum yield, emission intensity and lifetime, are significantly enhanced after deuteration. It benefits from the reduction in non‐radiative transitions, since the lowered vibrational frequencies of D atoms and optimized local energy level distribution in CDs structure. The deuterated CDs are applied in the fabrication of white‐light‐emitting diodes to show their application potential. This work provides a highly versatile route for improving and controlling photoluminescence performance of CDs and has opportunities to guide the development of CDs for practical applications.
Polydopamine Nanoparticles as Mimicking RPE Melanin for the Protection of Retinal Cells Against Blue Light‐Induced Phototoxicity
Authors: Kwon Yong‐Su , Munsoor Julie , Kaufmann Mary , Zheng Min , Smirnov Alex I. , Han Zongchao
Published: May 2024

Exposure of the eyes to blue light can induce the overproduction of reactive oxygen species (ROS) in the retina and retinal pigment epithelium (RPE) cells, potentially leading to pathological damage of age‐related macular degeneration (AMD). While the melanin in RPE cells absorbs blue light and prevents ROS accumulation, the loss and dysfunction of RPE melanin due to age‐related changes may contribute to photooxidation toxicity. Herein, a novel approach utilizing a polydopamine‐replenishing strategy via a single‐dose intravitreal (IVT) injection is presented to protect retinal cells against blue light‐induced phototoxicity. To investigate the effects of overexposure to blue light on retinal cells, a blue light exposure Nrf2‐deficient mouse model is created, which is susceptible to light‐induced retinal lesions. After blue light irradiation, retina degeneration and an overproduction of ROS are observed. The polydopamine‐replenishing strategy demonstrated effectiveness in maintaining retinal structural integrity and preventing retina degeneration by reducing ROS production in retinal cells and limiting the phototoxicity of blue light exposure. These findings highlight the potential of polydopamine as a simple and effective replenishment for providing photoprotection against high‐energy blue light exposure.
Solar‐Driven Biomass Reforming for Hydrogen Generation: Principles, Advances, and Challenges
Authors: Pan Hu , Li Jinglin , Wang Yangang , Xia Qineng , Qiu Liang , Zhou Baowen
Published: May 2024

Hydrogen (H2) has emerged as a clean and versatile energy carrier to power a carbon‐neutral economy for the post‐fossil era. Hydrogen generation from low‐cost and renewable biomass by virtually inexhaustible solar energy presents an innovative strategy to process organic solid waste, combat the energy crisis, and achieve carbon neutrality. Herein, the progress and breakthroughs in solar‐powered H2 production from biomass are reviewed. The basic principles of solar‐driven H2 generation from biomass are first introduced for a better understanding of the reaction mechanism. Next, the merits and shortcomings of various semiconductors and cocatalysts are summarized, and the strategies for addressing the related issues are also elaborated. Then, various bio‐based feedstocks for solar‐driven H2 production are reviewed with an emphasis on the effect of photocatalysts and catalytic systems on performance. Of note, the concurrent generation of value‐added chemicals from biomass reforming is emphasized as well. Meanwhile, the emerging photo‐thermal coupling strategy that shows a grand prospect for maximally utilizing the entire solar energy spectrum is also discussed. Further, the direct utilization of hydrogen from biomass as a green reductant for producing value‐added chemicals via organic reactions is also highlighted. Finally, the challenges and perspectives of photoreforming biomass toward hydrogen are envisioned.
Decoding the algorithmic operations of Australia's National Disability Insurance Scheme
Authors: van Toorn Georgia , Carney Terry
Published: May 2024

In recent years, Australia has embarked on a digital transformation of its social services, with the primary goal of creating user‐centric services that are more attentive to the needs of citizens. This article examines operational and technological changes within Australia's National Disability Insurance Scheme (NDIS) as a result of this comprehensive government digital transformation strategy. It discusses the effectiveness of these changes in enhancing outcomes for users of the scheme. Specifically, the focus is on the National Disability Insurance Agency's (NDIA) use of algorithmic decision support systems to aid in the development of personalised support plans. This administrative process, we show, incorporates several automated elements that raise concerns about substantive fairness, accountability, transparency and participation in decision making. The conclusion drawn is that algorithmic systems exercise various forms of state power, but in this case, their subterranean administrative character positions them as “algorithmic grey holes”—spaces effectively beyond recourse to legal remedies and more suited to redress by holistic and systemic accountability reforms advocated by algorithmic justice scholarship.
Cyclometalated half‐sandwich iridium complexes: Synthesis, characterization, and catalytic activity in preparation of esters from halides by using formate as both CO source and coupling partner
Authors: Gao Song , Cao Chuan‐Qi , Luo Yu‐Zhou , Yao Zi‐Jian
Published: May 2024

A highly efficient carbonylation of aryl halides using half‐sandwich iridium catalysis was developed, providing a new avenue for synthesizing carboxylic ester derivatives and yielding consistently impressive results. These iridium complexes demonstrated remarkable catalytic performance in the coupling reaction using phenyl formate derivatives as the source of CO, phenol, and aryl halides as the starting material in the presence of air and possessed good air and moisture stability properties. Ester products with different substituents were synthesized at low reaction temperatures without the need for an inert atmosphere, leading to high yields. The broad substrate scope, impressive catalytic activity, and mild reaction conditions suggest promising industrial applications for this catalytic system. The desired metal complexes 1–4 have been well proven by attenuated total reflectance‐Fourier transform infrared (ATR‐FTIR), nuclear magnetic resonance (NMR), and elemental analysis (EA). The molecular structure of the cyclometalated iridium complexes 2 and 3 was proven through X‐ray crystallography. Additionally, the possible mechanism of this Ir‐catalyzed process is further supported by the density functional theory (DFT) study.
Transforming histology students from passive lecture listeners into active lecture learners
Authors: Hortsch Michael
Published: May 2024

Traditional academic lectures have long been criticized as providing a passive learning environment to students. Often, they do not capture the audience's attention, resulting in learners being distracted or bored and thereby reducing their learning efficacy. Consequently, they are being abandoned by many schools and universities as an educational modus or modified into more learner‐centered experiences. This descriptive article outlines a strategy of inserting active learning PowerPoint slides into traditional histology lectures. Suggestions and advice for adding or improving existing active learning slides are being offered to readers, who are planning to modify their own lecture presentations. The author's experience of using this formative assessment strategy with different types of histology learners is also discussed.
Structural‐Change‐Induced Two‐Stage Redox Behavior of Pentacenebisquinodimethane with Tricolor Chromism
Authors: Ishigaki Yusuke , Mizuno Shin‐ichi , Harimoto Takashi , Shimajiri Takuya , Suzuki Takanori
Published: May 2024

Tricolor electrochromism was realized through the interconversion among the neutral (yellow), dicationic (green), and tetracationic (blue) states, even though only one kind of chromophore is generated upon oxidation. Both dicationic and tetracationic states were isolated as stable salts, and their different colors come from the effective inter‐chromophore interaction only in the tetracationic state but not in the dicationic state. Despite the negligible Coulombic repulsion in the tetracationic state with four cyanine‐type chromophores, pentacenebisquinodimethane undergoes stepwise two‐stage two‐electron oxidation when radical‐stabilizing 5‐(4‐octyloxyphenyl)‐2‐thienyl groups are attached on the exomethylene bonds. A contribution from the biradical form only in the neutral state but not in the dicationic state is the reason for the observed negative cooperativity during the electrochemical oxidation.
Safety of urethral preservation using urethral frozen section analysis in radical cystectomy
Authors: Hattori Yuto , Nagoshi Akihiko , Fujiwara Tasuku , Kambe Takanari , Mine Yuta , Hagimoto Hiroki , Abe Yohei , Yamashita Daisuke , Tsutsumi Naofumi , Shibasaki Noboru , Yamasaki Toshinari , Kawakita Mutsushi
Published: May 2024

Background

The objective of this study is to assess whether urethral preservation can be performed safely using frozen section analysis (FSA) of the urethral stump on urethral recurrence after radical cystectomy.

Methods

Between June 2012 and July 2022, we investigated consecutive male patients who underwent urethral FSA during radical cystectomy for urothelial carcinoma. For FSA‐abnormal cases, urethrectomy was performed, and for FSA‐normal cases, the urethra was preserved. The diagnostic accuracy of FSA was assessed in comparison with the pathological findings of the permanent sections of the same tissue. Postoperatively, computed tomography and urinary cytology were performed as routine surveillance of recurrence.

Results

Of the 77 patients included in this study, three patients with abnormal FSA underwent concurrent urethrectomy. The negative predictive value of urethral FSA was 100%. With a median postoperative follow‐up of 38 months (interquartile ranges 21–71), no urethral recurrence was observed.

Conclusions

FSA may be useful in determining the indication for urethrectomy.
Listening to young children with disabilities: Experiences of quality in mainstream primary education
Authors: Gulliver Katherine
Published: May 2024

All children should have access to quality education through a child‐centred pedagogy. An inclusive, child‐centred pedagogy uses a strength‐based view of children that recognises each child as unique and competent, providing children with multiple opportunities to explore and learn at their own pace. However, competing tensions in mainstream primary education in England can impact this through a performative school culture that focusses on progress and attainment rather than the successful inclusion of all children including those with disabilities. This adult‐centric view of education quality does not consider children's experiences of what happens in mainstream primary education, through their perspectives. The research described here uses methodology that actively listens to young children with developmental disabilities themselves to understand what is important and valuable to them. Four case studies present children's experience of education in different English primary schools, using a range of photography activities, guided tours and interviews. Methods illicit rich detail and novel understandings of experiences from the views of young children with developmental disabilities, whose voices have tended to be excluded from research. The study demonstrates ways in which young children can develop self‐advocacy through opportunities to share their voice and understanding of education. Findings reveal the significance of children's involvement in the different spaces and objects associated with experiencing mainstream education, and the different types of pedagogy found in education that may or may not offer opportunities for self‐advocacy for children with developmental disabilities.
A Bayesian hierarchical hidden Markov model for clustering and gene selection: Application to kidney cancer gene expression data
Authors: Chekouo Thierry , Mukherjee Himadri
Published: May 2024

We introduce a Bayesian approach for biclustering that accounts for the prior functional dependence between genes using hidden Markov models (HMMs). We utilize biological knowledge gathered from gene ontologies and the hidden Markov structure to capture the potential coexpression of neighboring genes. Our interpretable model‐based clustering characterized each cluster of samples by three groups of features: overexpressed, underexpressed, and irrelevant features. The proposed methods have been implemented in an R package and are used to analyze both the simulated data and The Cancer Genome Atlas kidney cancer data.
Solvent stabilizing effects on the order–disorder transition of schizophyllan in aqueous mixtures of carboxylic acids
Authors: Yoshiba Kazuto , Yasuda Yota , Sato Mana , Matsuda Yasuhiro
Published: May 2024

Schizophyllan is a triple helical β‐1,3‐D‐glucan, and shows the cooperative order–disorder transition in the aqueous solution at the triple helix state. In this paper, the solvent stabilizing effects of two carboxylic acids, acetic acid and citric acid, on the cooperative order–disorder transition of aqueous schizophyllan solution were investigated from DSC and SEC‐MALS measurements. The transition temperature (Tr) was shifted to higher temperature with increasing the molar fraction of carboxylic acid in the mixture (x). The transition enthalpy (ΔHr) was increased with increasing x. These solvent stabilizing effects indicate that these carboxylic acid molecules were selectively associated with the branched side chains of schizophyllan to stabilize the ordered state. The composition dependencies of Tr and ΔHr were analyzed by the linear cooperative transition theory to estimate the association parameters between the side chains and carboxylic acid. The theoretical parameters obtained were compared with those for the other active substances for the transition to discuss the molecular interactions between the triple helix and carboxylic acid.
Spectroscopic characterization and pharmacokinetic evaluation of amorphous solid dispersions of glibenclamide for bioavailability enhancement in Wistar rats
Authors: Mir Khalid Bashir , Abrol Vidushi , Singh Nasseb , Khan Nisar A. , Dar Alamgir A. , Alahmadi Tahani Awad , Ansari Mohammad Javed
Published: May 2024

Oral bioavailability of glibenclamide (Glb) was appreciably improved by the formation of an amorphous solid dispersion with Poloxamer‐188 (P‐188). Poloxamer‐188 substantially enhanced the solubility and thereby the dissolution rate of the biopharmaceutics classification system (BCS) class II drug Glb and simultaneously exhibited a better stabilizing effect of the amorphous solid dispersion prepared by the solvent evaporation method. The physical state of the dispersed Glb in the polymeric matrix was characterized by differential scanning calorimetry, X‐ray diffraction, scanning electron microscope and Fourier transform infrared studies. In vitro drug release in buffer (pH 7.2) revealed that the amorphous solid dispersion at a Glb–P‐188 ratio of 1:6 (SDE4) improved the dissolution of Glb by 90% within 3 h. A pharmacokinetic study of the solid dispersion formulation SDE4 in Wistar rats showed that the oral bioavailability of the drug was greatly increased as compared with the market tablet formulation, Daonil®. The formulation SDE4 resulted in an AUC0–24h ~2‐fold higher. The SDE4 formulation was found to be stable during the study period of 6 months.
De‐NeRF: Ultra‐high‐definition NeRF with deformable net alignment
Authors: Hou Jianing , Zhang Runjie , Wu Zhongqi , Meng Weiliang , Zhang Xiaopeng , Guo Jianwei
Published: May 2024

Neural Radiance Field (NeRF) can render complex 3D scenes with viewpoint‐dependent effects. However, less work has been devoted to exploring its limitations in high‐resolution environments, especially when upscaled to ultra‐high resolution (e.g., 4k). Specifically, existing NeRF‐based methods face severe limitations in reconstructing high‐resolution real scenes, for example, a large number of parameters, misalignment of the input data, and over‐smoothing of details. In this paper, we present a novel and effective framework, called De‐NeRF, based on NeRF and deformable convolutional network, to achieve high‐fidelity view synthesis in ultra‐high resolution scenes: (1) marrying the deformable convolution unit which can solve the problem of misaligned input of the high‐resolution data. (2) Presenting a density sparse voxel‐based approach which can greatly reduce the training time while rendering results with higher accuracy. Compared to existing high‐resolution NeRF methods, our approach improves the rendering quality of high‐frequency details and achieves better visual effects in 4K high‐resolution scenes.
PR3D: Precise and realistic 3D face reconstruction from a single image
Authors: Huang Zhangjin , Wu Xing
Published: May 2024

Reconstructing the three‐dimensional (3D) shape and texture of the face from a single image is a significant and challenging task in computer vision and graphics. In recent years, learning‐based reconstruction methods have exhibited outstanding performance, but their effectiveness is severely constrained by the scarcity of available training data with 3D annotations. To address this issue, we present the PR3D (Precise and Realistic 3D face reconstruction) method, which consists of high‐precision shape reconstruction based on semi‐supervised learning and high‐fidelity texture reconstruction based on StyleGAN2. In shape reconstruction, we use in‐the‐wild face images and 3D annotated datasets to train the auxiliary encoder and the identity encoder, encoding the input image into parameters of FLAME (a parametric 3D face model). Simultaneously, a novel semi‐supervised hybrid landmark loss is designed to more effectively learn from in‐the‐wild face images and 3D annotated datasets. Furthermore, to meet the real‐time requirements in practical applications, a lightweight shape reconstruction model called fast‐PR3D is distilled through teacher–student learning. In texture reconstruction, we propose a texture extraction method based on face reenactment in StyleGAN2 style space, extracting texture from the source and reenacted face images to constitute a facial texture map. Extensive experiments have demonstrated the state‐of‐the‐art performance of our method.
A double‐layer crowd evacuation simulation method based on deep reinforcement learning
Authors: Zhang Yong , Yang Bo , Zhu Jianlin
Published: May 2024

Existing crowd evacuation simulation methods commonly face challenges of low efficiency in path planning and insufficient realism in pedestrian movement during the evacuation process. In this study, we propose a novel crowd evacuation path planning approach based on the learning curve–deep deterministic policy gradient (LC‐DDPG) algorithm. The algorithm incorporates dynamic experience pool and a priority experience sampling strategy, enhancing convergence speed and achieving higher average rewards, thus efficiently enabling global path planning. Building upon this foundation, we introduce a double‐layer method for crowd evacuation using deep reinforcement learning. Specifically, within each group, individuals are categorized into leaders and followers. At the top layer, we employ the LC‐DDPG algorithm to perform global path planning for the leaders. Simultaneously, at the bottom layer, an enhanced social force model guides the followers to avoid obstacles and follow the leaders during evacuation. We implemented a crowd evacuation simulation platform. Experimental results show that our proposed method has high path planning efficiency and can generate more realistic pedestrian trajectories in different scenarios and crowd sizes.
The therapeutic potential of isosakuranetin against perfluorooctane sulfonate instigated cardiac toxicity via modulating Nrf‐2/Keap‐1 pathway, inflammatory, apoptotic, and histological profile
Authors: Ijaz Muhammad Umar , Shahid Humna , Hayat Muhammad Faisal , Khan Hammad Ahmad , Al‐Ghanim Khalid A. , Riaz Mian Nadeem
Published: May 2024

Perfluorooctane sulfonate (PFOS) is a pervasive organic toxicant that damages body organs, including heart. Isosakuranetin (ISN) is a plant‐based flavonoid that exhibits a broad range of pharmacological potentials. The current investigation was conducted to evaluate the potential role of ISN to counteract PFOS‐induced cardiac damage in rats. Twenty‐four albino rats (Rattus norvegicus) were distributed into four groups, including control, PFOS (10 mg/kg) intoxicated, PFOS + ISN (10 mg/kg + 20 mg/kg) treated, and ISN (20 mg/kg) alone supplemented group. It was revealed that PFOS intoxication reduced the expressions of Nrf‐2 and its antioxidant genes while escalating the expression of Keap‐1. Furthermore, PFOS exposure reduced the activities of glutathione reductase (GSR), superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx), glutathione S‐transferase (GST), Heme oxygenase‐1 (HO‐1) and glutathione (GSH) contents while upregulating the levels of reactive oxygen species (ROS) and malondialdehyde (MDA). Besides, PFOS administration upregulated the levels of creatine kinase‐MB (CK‐MB), troponin I, creatine phosphokinase (CPK), and lactate dehydrogenase (LDH). Moreover, the levels of tumor necrosis factor‐alpha (TNF‐α), nuclear factor kappa‐B (NF‐κB), interleukin‐6 (IL‐6), and interleukin‐1β (IL‐1β) were increased after PFOS intoxication. Additionally, PFOS exposure downregulated the expression of Bcl‐2 while upregulating the expressions of Bax and Caspase‐3. Furthermore, PFOS administration disrupted the normal architecture of cardiac tissues. Nonetheless, ISN treatment remarkably protected the cardiac tissues via regulating aforementioned dysregulations owing to its antioxidative, anti‐inflammatory, and antiapoptotic properties.
Single‐cell and bulk RNA‐sequencing reveals mitosis‐involved gene HAUS1 is a promising indicator for predicting prognosis and immune responses in prostate adenocarcinoma (PRAD)
Authors: Liu Shiwei , Yu Yang , Xu Jie , Wang Yi , Li Deng
Published: May 2024

It was imperative to identify latent biomarkers pertinent to malignancies, given the pivotal role targeted molecular therapies play in tumor treatment investigations. This study aimed to assess the validity of HAUS1 as an indicator for survival prognosis and immune responses in prostate adenocarcinoma (PRAD) via single‐cell and bulk RNA‐sequencing. Related data on HAUS1 expression in PRAD were obtained from online databases, followed by comprehensive analyses to delineate its associations with survival prognosis, implicated pathways, and immune responses. Besides, the expression pattern of HAUS1 in PRAD was also verified in vitro, by using qRT‐PCR, Western blot analysis, and immunohistochemistry. We found HAUS1 was downregulated in PRAD compared with normal tissues, as verified in vitro by qRT‐PCR, Western blot, and immunohistochemistry (p < 0.05). Single‐cell RNA‐sequencing analysis indicated that HAUS1 had relatively higher expressions in B cells, Mono/Macro cells, and Endothelial cells compared with other cell types. Cox regression analysis revealed HAUS1 could serve as an independent indicator for the overall survival prognosis of PRAD (p < 0.05). Spearman correlation analyses revealed HAUS1 was closely related to the tumor microenvironment, immune cell infiltration levels, immune checkpoints, and immune cell pathways (p < 0.05). Furthermore, HAUS1 expression was found to be closely related to the immunotherapeutic response of patients receiving clinical intervention (p < 0.05). Collectively, our findings underscored the significant role of HAUS1 in PRAD prognosis and immune response, thereby presenting a novel and promising avenue for investigating the clinical utility of immunotherapy in PRAD.
Frailty and transcatheter valve intervention: A narrative review
Authors: Kempton Hannah , Hall Rachael , Hungerford Sara L. , Hayward Christopher S. , Muller David W. M.
Published: May 2024

Frailty is a common clinical syndrome that portends poor peri‐procedural outcomes and increased mortality following transcatheter valve interventions. We reviewed frailty assessment tools in transcatheter intervention cohorts to recommend a pathway for preprocedural frailty assessment in patients referred for transcatheter valve procedures, and evaluated current evidence for frailty interventions and their efficacy in transcatheter intervention. We recommend the use of a frailty screening instrument to identify patients as frail, with subsequent referral for comprehensive geriatric assessment in these patients, to assist in selecting appropriate patients and then optimizing them for transcatheter valve interventions. Interventions to reduce preprocedural frailty are not well defined, however, data from limited cohort studies support exercise‐based interventions to increase functional capacity and reduce frailty in parallel with preprocedural medical optimization.
Over 2000 gallstones of varying sizes and types during a cholecystectomy
Authors: Mohammadi Sardo Hamzeh , Pourfridoni Mohammad
Published: May 2024

Key Clinical Message

This rare case highlights the number of over 2000 mixed gallstones, which shows the importance of thorough evaluation in patients with RUQ pain to identify underlying conditions and associated complications.
Multiple Pathways in the Triplet States Population for a Naphthalenediimide‐C60 Dyad
Authors: Ye Kaiyue , Carbonera Donatella , Liao Sheng , Zhang Xue , Chen Xi , Xiao Xiao , Zhao Jianzhang , Shanmugam Muralidharan , Li Mingde , Barbon Antonio
Published: May 2024

The link of an antenna dye with an electron spin converter, in this case naphthalenediimide and C60, produces a system with a rich photophysics including the detection of more than one triplet state on the long timescale (tens of μs). Beside the use of optical spectroscopies in the ns and in the fs time scale, we used time‐resolved Electron Paramagnetic Resonance (TREPR) to study the system evolution following photoexcitation. TREPR keeps track of the formation path of the triplet states through specific spin polarization patterns observed in the spectra. The flexibility of the linker and solvent polarity play a role in favouring either electron transfer or energy transfer processes.
peri‐Benzo‐Diindenotetracenyl: Helically π‐Extended Allyl Radical with Robust Stability
Authors: Hamamoto Hodaka , Shimizu Daiki , Matsuda Kenji
Published: May 2024

Here is described the synthesis and characterization of a stable hydrocarbon radical, peri‐benzo‐diindenotetracenyl, with a helical structure. Although the helical π‐radical has no peripheral substituents, it was stable in the solid and solutions. According to the X‐ray diffraction analysis and quantum chemical calculations, the radical was best described as an allyl radical fused by five Clar's sextets. The optically resolved enantiomers exhibited mirror image CD spectra with |gCD| of 2.4×10−4 at 522 nm. The racemization barrier was determined to be 95.9 kJ/mol at 298 K, which is compatible with that of [5]helicene (108 kJ/mol).
Thiocarbonyl Pseudohalides – The Curious Case of Thiocarbonyl Dithiocyanate
Authors: Pfeiffer Jonathan , Günther Hennes , Fuzon Patrick , Weigend Florian , Tambornino Frank
Published: May 2024

Thiocarbonyl dithiocyanate (1) and chlorothiocarbonyl thiocyanate (2) were synthesized from thiophosgene and ammonium or silver thiocyanate, respectivley. Their crystal structures show syn‐anti (1) and syn (2) conformations, which were confirmed in the bulk phases by powder X‐ray diffraction, vibrational spectroscopy and DFT calculations. Further calculations explain the isolation of the kinetic reaction products by a lower transition states opposed to the thermodynamic reaction products. Reaction of 1 with ethanol gave a dithiobiuret derivative (3). In a proof‐of‐principle study we show that it in turn can be used for the complexation of nickel to yield (4).
Unravelling the Role of Structural Factors in the Luminescence Properties of Persulfurated Benzenes
Authors: Fermi Andrea , D'Agostino Simone , Dai Yasi , Brunetti Filippo , Negri Fabrizia , Gingras Marc , Ceroni Paola
Published: May 2024

Room temperature phosphorescence rarely occurs from pure organic molecules, especially in the solid‐state. A strategy for the design of highly emissive organic phosphors is still hard to predict, thus impeding the development of new functional materials with the desired optical properties. Herein, we analyze a family of alkyl and aryl‐substituted persulfurated benzenes, the latter representing a class of organic solid‐state triplet emitters able to show very high emission quantum yield at room temperature. In this work, we correlate structural parameters with the photophysical properties observed in different experimental conditions (diluted solution, crystalline and amorphous phase at RT and low temperature). Our results, corroborated by a detailed computational analysis, indicate a close relationship between the luminescence properties and i) the nature of the substituents on the persulfurated core, ii) the adopted conformations in the solid state, both in crystalline and amorphous phases. These factors contribute to characterize the lowest‐energy lying excited‐state, its deactivation pathways, the phosphorescence lifetime and quantum yield. These findings provide a useful roadmap for the development of highly performing purely organic solid‐state emitters based on the persulfurated benzene platform.
1,4‐Pyrazolyl‐Containing SAFit‐Analogues are Selective FKBP51 Inhibitors With Improved Ligand Efficiency and Drug‐Like Profile
Authors: Buffa Vanessa , Meyners Christian , Sugiarto Wisely Oki , Bauder Michael , Gaali Steffen , Hausch Felix
Published: May 2024

The FK506 binding protein 51 (FKBP51) is an appealing drug target due to its role in several diseases such as depression, anxiety, chronic pain and obesity. Towards this, selectivity versus the close homolog FKBP52 is essential. However, currently available FKBP51‐selective ligands such as SAFit2 are too large and lack drug‐like properties. Here, we present a structure activity relationship (SAR) analysis of the pipecolic ester moiety of SAFit1 and SAFit2, which culminated in the discovery of the 1,4‐pyrazolyl derivative 23 d, displaying a binding affinity of 0.077 μM for FKBP51, reduced molecular weight (541.7 g/mol), lower hydrophobicity (cLogP=3.72) and higher ligand efficiency (LE=0.25). Cocrystal structures revealed the importance of the 1,4‐ and 1,3,4‐ substitution patterns of the pyrazole ring versus the 1,4,5 arrangement.
An OpenMP‐based breadth‐first search implementation using the bag data structure
Authors: Gonzaga de Oliveira S. L. , Santana M. I. , Brandão D. N. , Osthoff C.
Published: May 2024

The breadth‐first search procedure is an algorithm that traverses the vertices of a graph, determining the distance from each vertex to the initial vertex. The distance is infinite for a non‐reachable vertex from the starting vertex. Despite having an efficient serial version, this important algorithm is irregular, making its effective parallel implementation a daunting task. This paper shows the results of an OpenMP‐based implementation of the breadth‐first search procedure using the bag data structure. Furthermore, the code relied on the C++ programming language. This paper reimplements an existing proposal coded using the Cilk++ programming language. The experiments relied on 32 strongly connected graphs and 31 disconnected graphs in executions performed on two machines. The first machine contained 28 cores and two threads per core. The second machine comprised 48 processing cores, with hyperthreading disabled. Regarding the serial version, the parallel implementation yielded a speedup of up to 20× when using 28 processing cores and up to 25× when using 56 threads in tests performed on a machine with the first generation of Intel® Xeon® Scalable processors. Furthermore, the new parallel implementation yielded speedups of up to 45× when using 48 cores in experiments performed on a machine with the second generation of Intel® Xeon® Scalable processors.
Theoretical Investigation on the Reversible Photoswitch Mechanism of Benzylidene–Oxazolone System
Authors: Geng Xuehui , Wang Jiangyue , Liu Yuxuan , Yan Wenhui , Xu Zhijie , Chen Junsheng , Zhao Li
Published: May 2024

The design and application of molecular photoswitches have attracted much attention. Herein, we performed a detailed computational study on the photoswitch benzylidene–oxazolone system based on static electronic structure calculations and on‐the‐fly excited‐state dynamic simulations. For the Z and E isomer, we located six and four minimum energy conical intersections (MECIs) between the first excited state (S1) and the ground state (S0), respectively. Among them, the relaxation pathway driven by ring‐puckering motion is the most competitive channel with the photoisomeization process, leading to the low photoisomerization quantum yield. In the dynamic simulations, about 88 % and 66 % trajectories decay from S1 to S0 for Z and E isomer, respectively, within the total simulation time of ~2 ps. The photoisomeization quantum yields obtained in our study (0.20 for Z→E and 0.12 for E→Z) agree well with the experimental measured values (0.25 and 0.11), even though the number of trajectories is limited to 50. Our study sheds light on the complexity of the benzylidene–oxazolone system ′s deactivation process and the competitive mechanisms among different reaction channels, which provides theoretical guidance for further design and development of benzylidene–oxazolone based molecular photoswitches.
A Stable Perovskite Sensitized Photonic Crystal P−N Junction with Enhanced Photoelectrochemical Hydrogen Production
Authors: Nwaji Njemuwa , Kang Hyojin , Bayissa Gicha Birhanu , Osial Magdalena , Vapaavuori Jaana , Lee Jaebeom , Giersig Michael
Published: May 2024

The slow photon effect in inverse opal photonic crystals represents a promising approach to manipulate the interactions between light and matter through the design of material structures. This study introduces a novel ordered inverse opal photonic crystal (IOPC) sensitized with perovskite quantum dots (PQDs), demonstrating its efficacy for efficient visible‐light‐driven H2 generation via water splitting. The rational structural design contributes to enhanced light harvesting. The sensitization of the IOPC with PQDs improves optical response performance and enhances photocatalytic H2 generation under visible light irradiation compared to the IOPC alone. The designed photoanode exhibits a photocurrent density of 3.42 mA cm−2 at 1.23 V vs RHE. This work advances the rational design of visible light‐responsive photocatalytic heterostructure materials based on wide band gap metal oxides for photoelectrochemical applications.
A case of metastatic HPV‐related cervical small cell neuroendocrine carcinoma with varying cytomorphology found in cytological specimens of a solid organ transplant recipient
Authors: Fasanya‐Maku Henrietta , Petty Danielle , Knapik Jaquelyn , Leon Marino , Gonsalves Catherine
Published: May 2024

Small cell neuroendocrine carcinoma (NEC) of the cervix is a rare gynecological malignancy, constituting 2%–5% of all such cases. As high‐risk Human Papilloma Virus (HR‐HPV) infections contribute to 85% of these tumors, small cell NEC poses a significant risk for solid organ transplant recipients, increasing their risk of progressive disease. We present a case of an uterine cervix small cell NEC with metastasis to the bladder and pleural cavities in a 53‐year‐old woman with a past medical history of kidney transplantation, who presented with abnormal uterine bleeding. The initial liquid preparation (ThinPrep) cytology stained with Papanicolaou (Pap) showed an adenocarcinoma not otherwise specified. At the time of diagnosis, the patient had diffusely metastatic disease. A subsequent uterine cervix biopsy was consistent with a small cell NEC. Despite treatment with chemotherapy, the patient's condition deteriorated, evidenced by a worsening right‐sided pleural effusion one‐month postdiagnosis. A pleural effusion showed a tumor with glandular features, with immunohistochemistry suggestive of metastatic adenocarcinoma. HR HPV E6/E7 RNA in situ hybridization (ISH) was positive. Bladder washing showed cytopathologic findings consistent with bladder involvement by small cell carcinoma. The patient's lesions in both urine and pleural fluids showed distinct cytomorphology. Within a year of diagnosis, the patient was declared deceased. This case highlights the existence of carcinoma admixed with NEC tumor, such as an HPV associated adenocarcinoma admixed with a NEC and underscores the elevated risk of HPV‐related genital lesions in renal transplant patients. In patients with a history of solid organ transplant or other immunosuppressive conditions, there is an increased necessity for enhanced surveillance and appropriate cancer screening.
Harnessing open science practices to teach ecology and evolutionary biology using interactive tutorials
Authors: Griffith Jory E. , Houghton Elizabeth , Slein Margaret A. , Fraser Franco Maxime , Chávez Jhoan , Forsythe Amy B. , Glynn Victoria M. , Katkov Egor , Palmier Kirsten M. , Sang Zihaohan , Trejo‐Pérez Rolando , Wiley Bryn , Sunday Jennifer M. , Bernhardt Joey R.
Published: May 2024

Open science skills are increasingly important for a career in ecology and evolutionary biology (EEB) as efforts to make data and analyses publicly available continue to become more commonplace. While learning core concepts in EEB, students are also expected to gain skills in conducting open science to prepare for future careers. Core open science skills like programming, data sharing, and practices that promote reproducibility can be taught to undergraduate students alongside core concepts in EEB. Yet, these skills are not always taught in biology undergraduate programs, and a major challenge in developing open science skills and learning EEB concepts simultaneously is the high cognitive load associated with learning multiple disparate concepts at the same time. One solution is to provide students with easily digestible, scaffolded, pre‐formatted code in the form of vignettes and interactive tutorials. Here, we present six open source teaching tutorials for undergraduate students in EEB. These tutorials teach fundamental ecological concepts, data literacy, programming (using R software), and analysis skills using publicly available datasets while introducing students to open science concepts and tools. Spanning a variety of EEB topics and skill levels, these tutorials serve as examples and resources for educators to integrate open science tools, programming, and data literacy into teaching EEB at the undergraduate level.
Woodland caribou calving fidelity: Spatial location, habitat, or both?
Authors: Walker P. D. , Rodgers A. R. , Shuter J. , Fryxell J. M. , Merrill E. H.
Published: May 2024

Individuals that isolate themselves to give birth can use more than one strategy in choosing birth sites to maximize reproductive success. Previous research has focused on the consistency in the use of the same birth‐site across years (i.e., spatial fidelity), but individuals alternatively may use similar habitat conditions across years (i.e., habitat fidelity). Using GPS telemetry, we determined whether woodland caribou expressed spatial or habitat fidelity during calving, and evaluated intrinsic and extrinsic factors associated with expressing either type of fidelity. We identified 56 individuals with ≥2 putative birth events, via a movement‐based model, across northern Ontario between 2010 and 2014. Individuals were classified as expressing (1) spatial fidelity by comparing sequential calving locations to a random spatial distribution of available calving locations, (2) habitat fidelity using a logistic use model compared to a null (intercept only) model, (3) no fidelity (neither criterion met), or (4) both spatial and habitat fidelity (both criteria met). Across all individuals, 37% expressed no fidelity (36 of 98), 15% expressed only spatial fidelity (15 of 99), 35% expressed only habitat fidelity (34 of 98), and 14% expressed both spatial and habitat fidelity (14 of 98). Older individuals were more likely to express spatial fidelity, whereas lower availability of upland and lowland conifer forests without linear features increased the probability an individual expressed habitat fidelity. Our results indicate that managing for caribou calving needs to consider protecting both specific, known birthing sites, but also broad‐scale areas of preferred habitat for calving. Understanding the mechanisms that influence caribou expressing calving fidelity, and associated fitness costs, is crucial for the conservation of the species.
Phenotypic plasticity in the sailfin molly III: Geographic variation in reaction norms of growth and maturation to temperature and salinity
Authors: Travis Joseph , Trexler Joel C.
Published: May 2024

Phenotypic plasticity, the ability of a single genotype to produce different phenotypes under different environmental conditions, plays a profound role in several areas of evolutionary biology. One important role is as an adaptation to a variable environment. While plasticity is extremely well documented in response to many environmental factors, there is controversy over how much of that plasticity is adaptive. Evidence is also mixed over how often conspecific populations display qualitative differences in the nature of plasticity. We present data on the reaction norms of growth and maturation to variation in temperature and salinity in male and female sailfin mollies (Poecilia latipinna) from three locally adjacent populations from South Carolina (SC). We compare these reaction norms to those previously reported in locally adjacent populations from north Florida (NF). In general, patterns of plasticity in fish from SC were similar to those in fish from NF. The magnitude of plasticity differed; fish from SC displayed less plasticity than fish from NF. This was because SC fish grew faster and matured earlier at the lower temperatures and salinities compared to NF fish. This is a countergradient pattern of variation, in which SC fish grew faster and matured earlier in conditions that would otherwise slow growth and delay maturity. Among fish from both regions, males were much less plastic than females, especially for length at maturity. While there was no detectable heterogeneity among populations from NF, males from one of the SC populations, which is furthest from the other two, displayed a qualitatively different response in age at maturity to temperature variation than did males from the other two SC populations. The pattern of population variation in plasticity within and among regions suggests that gene flow, which diminishes with distance in sailfin mollies, plays a critical role in constraining divergence in norms of reaction.
Sulthiame use in children with pharmacoresistant epilepsies: A retrospective study
Authors: Laliberté Alexandra , Berrahmoune Saoussen , Myers Kenneth A.
Published: May 2024

Objective

This retrospective study aimed to assess the efficacy and tolerability of sulthiame as an add‐on treatment in children with pharmacoresistant epilepsies.

Methods

All patients with epilepsy who received sulthiame at Montreal Children's Hospital over an 11‐year period were included. Medical charts were reviewed, and extracted data included patient age and sex, seizure types, epilepsy syndrome, electroencephalography (EEG) reports, brain imaging reports, antiseizure treatments trialed, starting and final dose of sulthiame, duration of sulthiame treatment, adverse events attributed to sulthiame, and seizure frequency before and after sulthiame treatment. EEG studies were also analyzed and spike–wave index (SWI) in the first 10 min of sleep was calculated.

Results

Sixteen patients were included, all of whom had pharmacoresistant epilepsies (mean of 9.9 trials of other antiseizure treatments). Six had genetic diagnoses, four had in utero/perinatal acquired brain injury, one had a suspected focal cortical dysplasia, and five were idiopathic. Ten patients had developmental and epileptic encephalopathy with spike–wave activation in sleep, three had Lennox–Gastaut syndrome, and one each had sleep‐related hyperkinetic epilepsy, self‐limited epilepsy with centrotemporal spikes, and mixed generalized and multifocal epilepsy. Of the 12 patients with uncontrolled seizures at the time of sulthiame initiation, 4 had improvement in seizure frequency, including 2 who became seizure free. Eight patients had EEG data available that allowed calculation of sleep SWI; from this group, SWI decreased from 81.1% +/− 17.6% to 45.1% +/− 36.5% (p = .007). The most common adverse events reported were somnolence/drowsiness, aggression, and increased seizure frequency. Of the patients with genetic etiologies, significant positive responses were seen in patients with pathogenic variants in NDUFS1 and SATB1.

Significance

These data demonstrate the therapeutic potential of sulthiame, even in patients with highly pharmacoresistant epilepsy. Improvements may be seen in both seizure frequency and sleep SWI.