bluuebunny/crossref_metadata_2025 huggingface dataset:
Rear Surface Passivation for Ink‐Based, Submicron CuIn(S, Se)2 Solar Cells
Authors: Suresh Sunil , Gidey Abraha T. , Chowdhury Towhid H. , Rondiya Sachin R. , Tao Li , Liu Jian , Vermang Bart , Uhl Alexander R.
Published: January 2024

A N, N‐dimethylformamide and thiourea‐based route is developed to fabricate submicron (0.55 and 0.75 µm) thick CuIn(S,Se)2 (CISSe) thin films for photovoltaic applications, addressing challenges of material usage, throughput, and manufacturing costs. However, reducing the absorber film thickness below 1 µm in a regular CISSe solar cell decreases the device efficiency due to losses at the highly‐recombinative, and mediocre‐reflective Mo/CISSe rear interface. For the first time, to mitigate the rear recombination losses, a novel rear contacting structure involving a surface passivation layer and point contact openings is developed for solution processed CISSe films and demonstrated in tangible devices. An atomic layer deposited Al2O3 film is employed to passivate the Mo/CISSe rear surface while precipitates formed via chemical bath deposition of CdS are used to generate nanosized point openings. Consequently, Al2O3 passivated CISSe solar cells show an increase in the open‐circuit voltage (VOC) and short‐circuit current density when compared to reference cells with equivalent absorber thicknesses. Notably, a VOC increase of 59 mV contributes to active area efficiencies of 14.2% for rear passivated devices with 0.75 µm thick absorber layers, the highest reported value for submicron‐based solution processed, low bandgap CISSe solar cells.
Inundation and nutrient assessment of farmed prairie potholes during a cropping season with high precipitation
Authors: Tirtalistyani Rose , Rempe Isaac , Long Leigh Ann , Soupir Michelle , Kaleita Amy , Nahkala Brady
Published: January 2024

Enclosed topographical depressions that retain water intermittently are abundant across the prairie pothole region of the United States. These depressional wetlands (potholes) are located at local minimum elevations with small contributing micro‐watersheds. These features are often located in areas where the primary land use is row crop agriculture; thus subsurface tile drainage has been implemented to improve crop production and field accessibility. However, even with drainage improvements, farmed potholes still tend to retain water during high precipitation periods. This study monitored 10 farmed potholes in 2018, a year with 32% more precipitation than the 30‐year average. Potholes were inundated between 12% and 81% of the monitored growing season; the highest inundation percentage occurred in a pothole without surface intakes. Nutrient concentrations in 2018 were lower on average than previously reported for the same potholes, possibly due to higher precipitation and less fertilizer applied because most of the potholes were in soybeans rather than corn. Total nitrogen and nitrate‐N median concentrations were 16.71 and 14.82 mg N L−1 lower (p‐value < 0.0001) during the early season (May 15–July 7) than concentrations in 2016–2017. Total phosphorus and dissolved reactive P median concentrations, conversely, were slightly but significantly lower during the late season (July 8–November 1) with 0.15 and 0.13 mg P L−1 difference (p‐value < 0.01), respectively. Observed DRP concentrations increased by 63% during multiday inundation periods. Our monitoring results suggest during seasons of heavy precipitation, farmed potholes might act as hotspots, contributing elevated levels of P to downstream waters.
Helicene‐type β‐isoindigo‐based boron‐dipyrromethene analogs with strong near‐infrared chiroptical activity
Authors: Chen Ziwei , Ni Zhigang , Chen Xing‐Yu , Xu Yongqiang , Yu Chunyan , Wang SiSi , Wang Xiao‐Ye , Lu Hua
Published: January 2024

Near‐infrared (NIR) chiroptical response has been less explored because it is challenging to achieve both chirality and NIR absorption/emission. Herein, we describe the design of heterohelicene‐type β‐isoindigo‐based boron‐dipyrromethene (BODIPY) analogs (β‐IBs), which shift the absorption peak to 800 nm and produce significant Cotton effects (127.8 M−1 cm−1) and absorbance dissymmetry factors (|gabs| = 3.5 × 10−3). The luminescence dissymmetry factor (glum) and circularly polarized luminescence (CPL) brightness (BCPL) of up to 1.24 × 10−3 and 1.78 M−1 cm−1 were realized beyond 800 nm. These β‐IBs are the first examples of helicene‐type compounds with the highest gabs in the NIR region and CPL beyond 800 nm. Theoretical calculations demonstrate that the strong chiroptical activities are triggered by their large transition magnetic dipole moments. This study not only provides a new approach to the synthesis of a larger variety of unprecedented helicene‐type BODIPY analogs but also demonstrates excellent NIR chiroptical properties.
Data‐driven decision‐focused surrogate modeling
Authors: Gupta Rishabh , Zhang Qi
Published: January 2024

We introduce the concept of decision‐focused surrogate modeling for solving computationally challenging nonlinear optimization problems in real‐time settings. The proposed data‐driven framework seeks to learn a simpler, for example, convex, surrogate optimization model that is trained to minimize the decision prediction error, which is defined as the difference between the optimal solutions of the original and the surrogate optimization models. The learning problem, formulated as a bilevel program, can be viewed as a data‐driven inverse optimization problem to which we apply a decomposition‐based solution algorithm from previous work. We validate our framework through numerical experiments involving the optimization of common nonlinear chemical processes such as chemical reactors, heat exchanger networks, and material blending systems. We also present a detailed comparison of decision‐focused surrogate modeling with standard data‐driven surrogate modeling methods and demonstrate that our approach is significantly more data‐efficient while producing simple surrogate models with high decision prediction accuracy.
c.202_204del in NUP214 causes late onset form of febrile encephalopathy
Authors: Farooqui Sheeba , Narayanan Dhanya Lakshmi , Mascarenhas Selinda , do Rosario Michelle C. , Nair Karthik Vijay , Periyasamy Radhakrishnan , Shukla Anju
Published: January 2024

Nucleoporins (NUPs) are a group of transporter proteins that maintain homeostasis of nucleocytoplasmic transport of proteins and ribonucleic acids under physiological conditions. Biallelic pathogenic variants in NUP214 are known to cause susceptibility to acute infection‐induced encephalopathy‐9 (IIAE9, MIM#618426), which is characterized by severe and early‐onset febrile encephalopathy causing neuroregression, developmental delay, microcephaly, epilepsy, ataxia, brain atrophy, and early death. NUP214‐related IIAE9 has been reported in eight individuals from four distinct families till date. We identified a novel in‐frame deletion, c.202_204del p.(Leu68del), in NUP214 by exome sequencing in a 20‐year‐old male with episodic ataxia, seizures, and encephalopathy, precipitated by febrile illness. Neuroimaging revealed progressive cerebellar atrophy. In silico predictions show a change in the protein conformation that may alter the downstream protein interactions with the NUP214 N‐terminal region, probably impacting the mRNA export. We report this novel deletion in NUP214 as a cause for a late onset and less severe form of IIAE9.
Vertical climbing in free‐ranging bonobos: An exploratory study integrating locomotor performance and substrate compliance
Authors: Druelle François , Leti Innocent , Bokika Ngawolo Jean‐Christophe , Narat Victor
Published: January 2024

Objectives

Ecological factors and body size shape animal movement and adaptation. Large primates such as bonobos excel in navigating the demanding substrates of arboreal habitats. However, current approaches lack comprehensive assessment of climbing performance in free‐ranging individuals, limiting our understanding of locomotor adaptations. This study aims to explore climbing performance in free‐ranging bonobos and how substrate properties affect their behavior.

Methods

We collected data on the climbing performance of habituated bonobos, Pan paniscus, in the Bolobo Territory, Democratic Republic of Congo. We analyzed 46 climbing bouts (12 ascents, 34 descents) while moving on vertical substrates of varying diameter and compliance levels. This study assessed the average speed, peak acceleration, resting postures, and transitions between climbing and other locomotor modes.

Results

During climbing sequences and transitions, bonobos mitigate speed variations. They also exhibit regular pauses during climbing and show higher speeds during descent in contrast to their ascent. Regarding the influence of substrate properties, bonobos exhibit higher speed when ascending on thin and slightly flexible substrates, while they appear to achieve higher speeds when descending on large and stiff substrates, by using a “fire‐pole slide” submode.

Discussion

Bonobos demonstrate remarkable abilities for negotiating vertical substrates and substrate properties influence their performance. Our results support the idea that bonobos adopt a behavioral strategy that aligns with the notion of minimizing costs. Overall, the adoption of high velocities and the use of low‐cost resting postures may reduce muscle fatigue. These aspects could represent important targets of selection to ensure ecological efficiency in bonobos.
Stabilisierung von Acenen: Geländerpentacene
Authors: Ludwig Philipp , Rominger Frank , Freudenberg Jan , Bunz Uwe H. F.
Published: January 2024

Wir berichten über aus Pentacen‐5,7,12,14‐tetraon synthetisierte, lösliche, tetrakisbiphenylylsubstituierte Pentacene bestehend aus sp2‐Kohlenstoffen. Intramolekulare Yamamoto‐Kupplung zweier Tetrakis(chlorbiphenylyl)pentacenen führt zu helikalen, zweifach überbrückten Pentacenen, bei denen die Quaterphenyleneinheiten die Pentacene solubilisieren und ihre zentrale Anthraceneinheit in einem noch nie dagewesenen Maße abschirmen. Die kreuzweise verbrückten Pentacene trotzen (Photo‐)Oxidation und Diels–Alder‐Reaktionen, sie sind weniger reaktiv als TIPS‐ethinyliertes Pentacen. Eine Erweiterung dieses Konzeptes könnte den Zugang zu den größeren Acenen ermöglichen.
Exploring the Fate of Copper Ions in the Synthesis of Graphdiyne
Authors: Zhang Lu , Li Junfang , Wei Guoying , Yang Haifeng , Bai Hua , Xi Guangcheng
Published: January 2024

Copper is a crucial catalyst in the synthesis of graphdiyne (GDY). However, as catalysts, the final fate of the copper ions has hardly been concerned, which are usually treated as impurities. Here, it is observed that after simple washing with water and ethanol, GDY still contains a certain amount of copper ions, and demonstrated that the copper ions are adsorbed at the atomic layers of GDY. Furthermore, we transformed in situ the copper ions into ultrathin Cu nanocrystals, and the obtained Cu/GDY hybrids can be generally converted into a series of metal/GDY hybrid materials, such as Ag/GDY, Au/GDY, Pt/GDY, Pd/GDY, and Rh/GDY. The Cu/GDY hybrids exhibit extraordinary surface enhanced Raman scattering effect and can be applied in pollutant efficient enrichment and detection.
Guest‐Facilitated Heteroleptic Assembly of Helical Anionocages Enables Reversible Chirality Modulation
Authors: Wang Shanshan , Ye Xuanli , Yang Zaiwen , Li Anyang , Sheng Xinsong , Wang Qiangqiang , Jia Chuandong
Published: January 2024

We report a novel strategy for reversible modulation of the supramolecular chirality based on guest‐facilitated heteroleptic assembly of helical anionocages. Two triple‐stranded helical anionocages including a chiral cage 1 (A2L13) and a crown ether functionalized achiral cage 2 (A2L23) were synthesized by anion coordination of bis‐monourea‐based ligands and PhPO32−. Both cages exhibited favorable binding with tetraethylammonium TEA+ and cobaltocenium Cob+ (endo‐guest, bound in the cavity). Additionally, cage 2 could reversibly release and recapture the guests through binding the exo‐guest potassium ions (K+) in the crown ethers and subsequent removal of the K+ by [2,2,2]‐cryptand. The circular dichroism (CD) spectrum of cage 1 was not significantly affected by guest encapsulation or mixing with the “empty” cage 2. However, in the presence of both cage 2 and an endo‐guest/exo‐guest, the Cotton effects were reversed at 391 nm and significantly enhanced at 310 nm. This observation was attributed to the guest‐facilitated formation of heteroleptic cages that enabled effective chirality transfer from the chiral to the achiral ligands. The CD changes induced by K+ could be fully reversed by removing it with [2,2,2]‐cryptand. Sequential addition and removal of K+ allowed reversible modulation of the chirality for at least 10 cycles without significant attenuation.
Suppressing Exciton‐Vibration Coupling to Prolong Exciton Lifetime of Nonfullerene Acceptors Enables High‐Efficiency Organic Solar Cells
Authors: Zhu Yufan , He Dan , Wang Chong , Han Xiao , Liu Zesheng , Wang Ke , Zhang Jianqi , Shen Xingxing , Li Jie , Lin Yuze , Wang Chunru , He Yuehui , Zhao Fuwen
Published: January 2024

The limited exciton lifetime (τ, generally <1 ns) leads to short exciton diffusion length (LD) of organic semiconductors, which is the bottleneck issue impeding the further improvement of power conversion efficiencies (PCEs) for organic solar cells (OSCs). However, efficient strategies to prolong intrinsic τ are rare and vague. Herein, we propose a facile method to efficiently reduce vibrational frequency of molecular skeleton and suppress exciton‐vibration coupling to decrease non‐radiative decay rate and thus prolong τ via deuterating nonfullerene acceptors. The τ remarkably increases from 0.90 ns (non‐deuterated L8‐BO) to 1.35 ns (deuterated L8‐BO‐D), which is the record for organic photovoltaic materials. Besides, the inhibited molecular vibration improves molecular planarity of L8‐BO‐D for enhanced exciton diffusion coefficient. Consequently, the LD increases from 7.9 nm (L8‐BO) to 10.7 nm (L8‐BO‐D). The prolonged LD of L8‐BO‐D enables PM6 : L8‐BO‐D‐based bulk heterojunction OSCs to acquire higher PCEs of 18.5 % with more efficient exciton dissociation and weaker charge carrier recombination than PM6 : L8‐BO‐based counterparts. Moreover, benefiting from the prolonged LD, D18/L8‐BO‐D‐based pseudo‐planar heterojunction OSCs achieve an impressive PCE of 19.3 %, which is among the highest values. This work provides an efficient strategy to increase the τ and thus LD of organic semiconductors, boosting PCEs of OSCs.
Tandem Nitrate‐to‐Ammonia Conversion on Atomically Precise Silver Nanocluster/MXene Electrocatalyst
Authors: Liu Lin , Zheng Su‐Jun , Chen Hong , Cai Jinmeng , Zang Shuang‐Quan
Published: January 2024

Electrocatalytic reduction of nitrate (NO3RR) to synthesize ammonia (NH3) provides a competitive manner for carbon neutrality and decentralized NH3 synthesis. Atomically precise nanoclusters, as an advantageous platform for investigating the NO3RR mechanisms and actual active sites, remain largely underexplored due to the poor stability. Herein, we report a (NH4)9[Ag9(mba)9] nanoclusters (Ag9 NCs) loaded on Ti3C2 MXene (Ag9/MXene) for highly efficient NO3RR performance towards ambient NH3 synthesis with improved stability in neutral medium. The composite structure of MXene and Ag9 NCs enables a tandem catalysis process for nitrate reduction, significantly increasing the selectivity and FE of NH3. Besides, compared with individual Ag9 NCs, Ag9/MXene has better stability with the current density performed no decay after 108 hours of reaction. This work provides a strategy for improving the catalytic activity and stability of atomically precise metal NCs, expanding the mechanism research and application of metal NCs.
Lateral Heterometal Junction Rectifier Fabricated by Sequential Transmetallation of Coordination Nanosheet**
Authors: Tan Choon Meng , Fukui Naoya , Takada Kenji , Maeda Hiroaki , Selezneva Ekaterina , Bourgès Cédric , Masunaga Hiroyasu , Sasaki Sono , Tsukagoshi Kazuhito , Mori Takao , Sirringhaus Henning , Nishihara Hiroshi
Published: January 2024

Heterostructures of two‐dimensional materials realise novel and enhanced physical phenomena, making them attractive research targets. Compared to inorganic materials, coordination nanosheets have virtually infinite combinations, leading to tunability of physical properties and are promising candidates for heterostructure fabrication. Although stacking of coordination materials into vertical heterostructures is widely reported, reports of lateral coordination material heterostructures are few. Here we show the successful fabrication of a seamless lateral heterojunction showing diode behaviour, by sequential and spatially limited immersion of a new metalladithiolene coordination nanosheet, Zn3BHT, into aqueous Cu(II) and Fe(II) solutions. Upon immersion, the Zn centres in insulating Zn3BHT are replaced by Cu or Fe ions, resulting in conductivity. The transmetallation is spatially confined, occurring only within the immersed area. We anticipate that our results will be a starting point towards exploring transmetallation of various two‐dimensional materials to produce lateral heterojunctions, by providing a new and facile synthetic route.
Hydrophilic Cocrystals with Water Switched Luminescence
Authors: Gao Lei , Baryshnikov Glib V. , Ali Amjad , Kuklin Artem , Qian Cheng , Zhang Xianrui , Chen Fengkun , Yi Tao , Wu Hongwei
Published: January 2024

Utilizing water molecules to regulate the luminescence properties of solid materials is highly challenging. Herein, we develop a strategy to produce water‐triggered luminescence‐switching cocrystals by coassembling hydrophilic donors with electron‐deficient acceptors, where 1,2,4,5‐Tetracyanobenzene (TCNB) was used as the electron acceptor and pyridyl benzimidazole derivatives were used as the electron donors enabling multiple hydrogen‐bonds. Two cocrystals, namely 2PYTC and 4PYTC were obtained and showed heat‐activated emission, and such emission could be quenched or weakened by adding water molecules. The cocrystal structure exhibited the donor molecule that can form multiple hydro bonds with water and acceptor molecules due to the many nitrogen atoms of them. The analyses of the photophysical data, powder X‐ray diffraction, and other data confirmed the reversible fluorescence “on‐off” effects were caused by eliminating and adding water molecules in the crystal lattice. The density functional theory calculations indicate that the vibration of the O‐H bond of water molecules in the cocrystal can absorb the excitation energy and suppress fluorescence. Furthermore, the obtained cocrystals also showed temperature, humidity, and H+/NH4+ responsive emission behavior, which allows their applications as thermal and humidity sensors, and multiple information encryptions. This research paves the way for preparing intelligent hydrophilic organic cocrystal luminescent materials.
A new Schiff‐base complex of palladium nanoparticles on modified boehmite with di(pyridin‐2‐yl)methanone as a robust, reusable, and selective nanocatalyst in the C‐C coupling reaction
Authors: Tahmasbi Bahman , Darabi Mitra , Nikoorazm Mohsen
Published: January 2024

Boehmite is one of the stable phases of alumina that is easily available, and it also has a variety of applications. Therefore in this work, for preparation of AlOOH, Sodium hydroxide (NaOH) solutions was added to aluminum nitrate nonahydrate (Al(NO3)3.9H2O) solution. Then, the surface of AlOOH was modified with (3‐aminopropyl)triethoxysilane (APTES), due to high condensation of hydroxyl groups on its surface. Then, di(pyridin‐2‐yl)methanone (di(PM)) was immobilized on the surface of modified AlOOH toward synthesis of immobilized Schiff‐base on AlOOH (di(PM)@AlOOH) as a heterogeneous Schiff‐base ligand. Finally, a palladium complex was immobilized on its surface (Pd‐di(PM)@AlOOH) as a reusable, practical, and novel nanocatalyst. Pd‐di(PM)@AlOOH was characterized by thermogravimetric analysis (TGA) analysis, Fourier‐transform infrared spectroscopy (FT‐IR), transmission electron microscopy (TEM), scanning electron microscope (SEM) imaging, energy‐dispersive X‐ray spectroscopy (EDS) analysis, wavelength‐dispersive X‐ray spectroscopy (WDX) analysis, and inductively coupled plasma (ICP) analysis. After the characterization of Pd‐di(PM)@AlOOH, its performance was used as a highly practical, stable, retrievable, and hybrid organic–inorganic catalyst in the C‐C coupling of the Suzuki reaction. The hot filtration study of Pd‐di(PM)@AlOOH revealed that it acts heterogeneously in the Suzuki reaction. We found that this catalyst can be recycled for five runs without palladium leaching, as studied by hot filtration test and ICP analysis.
Synthesis, Photophysical Properties and Self‐Assembly of a Tetraphenylethylene‐Naphthalene Diimide Donor‐Acceptor Molecule
Authors: Bhusanur Dnyaneshwar I. , More Kerba S. , Al Kobaisi Mohammad , Singh Prabhat K. , Bhosale Sidhanath V. , Bhosale Sheshanath V.
Published: January 2024

The development of new π‐conjugated molecular structures with controlled self‐assembly and distinct photophysical properties is crucial for advancing applications in optoelectronics and biomaterials. This study introduces the synthesis and detailed self‐assembly analysis of tetraphenylethylene (TPE) functionalized naphthalene diimide (NDI), a novel donor‐acceptor molecular structure referred to as TPE‐NDI. The investigation specifically focuses on elucidating the self‐assembly behavior of TPE‐NDI in mixed solvents of varying polarities, namely chloroform: methylcyclohexane (CHCl3: MCH) and chloroform: methanol (CHCl3: MeOH). Employing a several analytical methodologies, including UV‐Vis absorption and fluorescence emission spectroscopy, scanning electron microscopy (SEM), X‐ray diffraction (XRD), and dynamic light scattering (DLS), these self‐assembled systems have been comprehensively examined. The results reveal that TPE‐NDI manifests as distinct particles in CHCl3: MCH (fMCH=90 %), while transitioning to flower‐like assemblies in CHCl3: MeOH (fMeOH=90 %). This finding underscores the critical role of solvent polarity in dictating the morphological characteristics of TPE‐NDI self‐assembled aggregates. Furthermore, the study proposes a molecular packing mechanism, based on SEM data, offering significant insights into the design and development of functional supramolecular systems. Such advancements in understanding the molecular self‐assembly new π‐conjugated molecular structures are anticipated to pave the way for novel applications in material science and nanotechnology.
Optimal maintenance policy for imperfect production systems using reliability function and defect rate
Authors: Ho Jyh‐Wen , Huang Yeu‐Shiang , Huang Peng‐Tsi
Published: January 2024

This study examines how a manufacturer can improve the robustness of an imperfect production system by implementing maintenance activities, which can be measured in terms of system reliability and product failure rate. A two‐dimensional maintenance policy comprising system reliability and the product defect rate is proposed to assess maintenance activity costs. The optimal thresholds of the two dimensions are analyzed to investigate the trade‐off between cost and system quality. A numerical example is provided to verify the proposed model's effectiveness. The results showed that the less stable the system, the greater the total costs incurred; therefore, lower stringent thresholds may be set to prevent frequent maintenance. Moreover, a sensitivity analysis is performed to investigate the essential parameters that significantly affect maintenance decisions. The results showed that the thresholds of the reliability function and defect rate significantly impact total costs. Any inaccurate assessment of system usage could lead to incorrect estimations and a substantial increase in cost.
Selection and Characterization of DNA Aptamers for Cytidine and Uridine
Authors: Gu Lide , Zheng Jiajie , Zhang Yao , Wang Deli , Liu Juewen
Published: January 2024

Cytidine and uridine are two essential pyrimidine ribonucleotides, and accurate detection of these nucleosides holds significant biological importance. While many aptamers were reported to bind purines, little success was achieved for pyrimidine binding. This study employs the library‐immobilization capture‐SELEX technique to isolate aptamers capable of selectively binding to cytidine and uridine. First, a selection was performed using a mixture of cytidine and uridine as the target. This selection led to the isolation of a highly selective aptamer for cytidine with a dissociation constant (Kd) of 0.9 μM as determined by isothermal titration calorimetry (ITC). In addition, a dual‐recognition aptamer was also discovered, which exhibited selective binding to both cytidine and uridine. Subsequently, a separate selection was carried out using uridine as the sole target, and the resulting uridine aptamer displayed a Kd of 4 μM based on a thioflavin T fluorescence assay and a Kd of 102 μM based on ITC. These aptamers do not have a strict requirement of metal ions for binding, and they showed excellent selectivity since no binding was observed with their nucleobases or nucleotides. This study has resulted three aptamers for pyrimidines, which can be employed in biosensors and DNA switches.
Knockdown of fat mass and obesity alleviates the ferroptosis in Parkinson's disease through m6A‐NRF2‐dependent manner
Authors: Pang Pengfei , Zhang Shirong , Fan Xinxin , Zhang Shitao
Published: January 2024

Emerging evidence has suggested that N6‐methyladenosine (m6A) regulates the pathology of Parkinson's disease (PD). Nevertheless, the function of demethylase fat mass and obesity (FTO) associated pathogenesis is still not fully elucidated. Here, this research findings revealed that m6A‐modification was decreased in PD models, meanwhile, the FTO level upregulated in the PD models. Functionally, in N‐methyl‐4‐phenylpyridinium (MPP+) treated SH‐SY5Y cells, the ferroptosis significantly upregulated and FTO silencing mitigated the ferroptosis phenotype. Moreover, in silico assays indicated that nuclear factor erythroid 2‐related factor‐2 (NRF2) acted as the target of FTO, and FTO demethylated the m6A modification from NRF2 mRNA. Furthermore, FTO impaired the NRF2 mRNA stability via m6A‐dependent pathway. Thus, our findings illustrated an important role of FTO on PD through m6A‐NRF2‐ferroptosis manner. Taken together, the study revealed the potential function of FTO on PD nervous system diseases.
Cavernous hemangioma of corpus imitating endometrial polyp in a young non‐pregnant woman: A case report study
Authors: Emami Ali , Bahadoran Ensiyeh , SamieeRad Fatemeh
Published: January 2024

Key Clinical Message

Cavernous hemangiomas are rare and have various non‐specific clinical presentations, such as menorrhagia. It can mimic different diseases such as endometrial polyps. Pathologists and gynecologists should be aware of performing histopathological examinations of this neoplasm for accurate diagnosis and to avoid unwarranted therapeutic interventions.

Internal genital tract hemangiomas are rare and can be divided into capillary and cavernous. We present a rare case of cavernous hemangioma (CH) of the corpus in a young, non‐pregnant woman. The patient was a 28‐year‐old woman who had complained of menorrhagia for 2.5 years. Sonography showed a hypoechoic intramural area measuring 35 × 23 mm. Histomorphology revealed neoplastic proliferation of dilated thin‐walled arteries of various sizes within the myometrium. Due to the variable clinical presentations of CH, histopathological examination should be performed for an accurate diagnosis. It is a rare entity and we recommend training pathologists and gynecologists on this neoplasm for accurate diagnosis and to avoid unwarranted therapeutic interventions.
Palmar papules as a manifestation of cutaneous oxalosis in primary hyperoxaluria: A case report and review of the literature
Authors: Alabdullah Hadi , Soqia Jameel , Douri Thaer
Published: January 2024

Key Clinical Message

Cutaneous oxalosis is a rare manifestation of systemic oxalosis, typically associated with primary or secondary hyperoxaluria. We present a rare case of a 23‐year‐old female diagnosed with primary hyperoxaluria and end‐stage renal disease, who presented with papules on the palms without any vascular complications. The skin can be affected by oxalate deposition, resulting in various manifestations such as vascular complications or calcified nodules. In our case, the patient had primary hyperoxaluria and end‐stage renal disease but exhibited atypical features of cutaneous oxalosis. Histopathology confirmed the presence of oxalate crystals in the dermis, subcutis, and medium‐sized arteries. The mechanism of oxalate deposition in this case remains unclear. This case underscores the importance of considering cutaneous oxalosis in the differential diagnosis of patients with renal failure and skin lesions, and highlights the variability of clinical presentations in primary hyperoxaluria.
Trimetallic PdRhPt Porous Nanooctahedra as Highly Active and Cost‐Effective Electrocatalysts for Ethanol Electrooxidation
Authors: Qian Hehe , Su Yuetan , Mi Ji , Guo Yongsheng , Yang Kun , Fang Wenjun , Weng Xiaole
Published: January 2024

The development of highly active and cost‐effective electrocatalysts for the ethanol oxidation reaction (EOR) is imperative for the prospective application of direct ethanol fuel cells (DEFCs). In this study, we successfully synthesized porous octahedral nanoarchitectures comprising Pd, Rh, and Pt, through a straightforward one‐step co‐reduction aided by additional Ag precursors and other surface capping agents. The in‐situ galvanic replacement played a pivotal role in shaping hollow structures within the prepared PdRhPt porous octahedra, designated as PdRhPt‐POct. By strategically employing both composition and structure engineering, PdRhPt‐POct exhibited remarkably enhanced activity and stability toward EOR. Specifically, the mass activity of PdRhPt‐POct, reaching 8.11 A mg−1Pd+Pt, surpassed that of the majority of state‐of‐the‐art EOR electrocatalysts, owing to increased efficiency in C−C bond breaking and enhanced anti‐poisoning properties. This work introduces new prospects for designing and producing unique hollow‐structured multi‐metal nanocrystals as high‐performance EOR catalysts.
Deciphering Nitroaromatics Reduction: Theoretical Insights into Dioxomolybdenum Catalysis with Biomass‐Derived Pinacol
Authors: Kiriakidi Sofia , Silva López Carlos , Sanz Roberto , Faza Olalla Nieto
Published: January 2024

Density Functional Theory is used to unravel the mechanism of the nitrobenzene to aniline reduction, catalyzed by dioxomolybdenum (VI) dichloride. The use of pinacol as an oxoaccepting reagent and the production of only acetone and water as byproducts, signals a novel and environmentally friendly way to add value to the oxygen‐rich biomass‐derived polyols. The reaction proceeds through three consecutive cycles, each one responsible for one of the three reductive steps needed to yield aniline from nitrobenzene, with nitrosobenzene and hydroxylamine as intermediates. Each cycle regenerates the catalyst and releases one water and two acetone molecules. The mechanism involves singlet/triplet state crossings, a crucial feature in polyoxomolibdate catalyzed processes. The role of the Mo‐coordinated water as the provider of the mysterious protons needed to reduce the nitro group, was revealed. The disclosure of this challenging mechanism and its rate limiting step can contribute to the design of more effective Mo(VI) catalysts.
Conformational Preferences at the Glycosidic Linkage of Saccharides in Solution as Deduced from NMR Experiments and MD Simulations: Comparison to Crystal Structures
Authors: Dorst Kevin M. , Widmalm Göran
Published: January 2024

Glycans are central to information content and regulation in biological systems. These carbohydrate molecules are active either as oligo‐ or polysaccharides, often in the form of glycoconjugates. The monosaccharide entities are joined by glycosidic linkages and stereochemical arrangements are of utmost importance in determining conformation and flexibility of saccharides. The conformational preferences and population distributions at the glycosidic torsion angles φ and ψ have been investigated for O‐methyl glycosides of three disaccharides where the substitution takes place at a secondary alcohol, viz., in α‐l‐Fucp‐(1→3)‐β‐d‐Glcp‐OMe, α‐l‐Fucp‐(1→3)‐α‐d‐Galp‐OMe and α‐d‐Glcp‐(1→4)‐α‐d‐Galp‐OMe, corresponding to disaccharide structural elements present in bacterial polysaccharides. Stereochemical differences at or adjacent to the glycosidic linkage were explored by solution state NMR spectroscopy using one‐dimensional 1H,1H‐NOESY NMR experiments to obtain transglycosidic proton‐proton distances and one‐ and two‐dimensional heteronuclear NMR experiments to obtain 3JCH transglycosidic coupling constants related to torsion angles φ and ψ. Computed effective proton‐proton distances from molecular dynamics (MD) simulations showed excellent agreement to experimentally derived distances for the α‐(1→3)‐linked disaccharides and revealed that for the bimodal distribution at the ψ torsion angle for the α‐(1→4)‐linked disaccharide experiment and simulation were at variance with each other, calling for further force field developments. The MD simulations disclosed a highly intricate inter‐residue hydrogen bonding pattern for the α‐(1→4)‐linked disaccharide, including a nonconventional hydrogen bond between H5′ in the glucosyl residue and O3 in the galactosyl residue, supported by a large downfield 1H NMR chemical shift displacement compared to α‐d‐Glcp‐OMe. Comparison of population distributions of the glycosidic torsion angles φ and ψ in the disaccharide entities to those of corresponding crystal structures highlighted the potential importance of solvation on the preferred conformation.
Synthesis of the Reducing‐end Hexasaccharide Fragment of Marine Lipopolysaccharide Axinelloside A
Authors: Zhang Haoliang , Zeng Changgen , Zhu Qian , Zhu Dapeng , Yu Biao
Published: January 2024

Chemical synthesis of an orthogonally protected hexasaccharide relevant to the reducing‐end half of axinelloside A, a highly sulfated marine lipopolysaccharide, is disclosed. The synthesis features preparation of the scyllo‐inositol unit via a Ferrier‐type‐II rearrangement, construction of the 1,2‐cis‐glycosidic bonds via remote participation, and concise [2+2+2] assembly via Au(I)‐catalyzed glycosylation.
Colorectal cancer screening at age 45 years in Israel: Cost‐effectiveness and global implications
Authors: Half Elizabeth E. , Levi Zohar , Mannalithara Ajitha , Leshno Moshe , Ben‐Aharon Irit , Abu‐Freha Naim , Silverman Barbara , Ladabaum Uri
Published: January 2024

Background

Colorectal cancer (CRC) incidence at ages <50 years is increasing worldwide. Screening initiation was lowered to 45 years in the United States. The cost‐effectiveness of initiating CRC screening at 45 years in Israel was assessed with the aim of informing national policy and addressing internationally relevant questions.

Methods

A validated CRC screening model was calibrated to Israeli data and examined annual fecal immunochemical testing (FIT) or colonoscopy every 10 years from 45 to 74 years (FIT45‐74 or Colo45‐74) versus from 50 to 74 years (FIT50‐74 or Colo50‐74). The addition of a fourth colonoscopy at 75 years was explored, subanalyses were performed by sex/ethnicity, and resource demands were estimated.

Results

FIT50‐74 and Colo50‐74 reduced CRC incidence by 57% and 70% and mortality by 70% and 77%, respectively, versus no screening, with greater absolute impact in Jews/Other versus Arabs but comparable relative impact. FIT45‐74 further reduced CRC incidence and mortality by an absolute 3% and 2%, respectively. With Colo45‐74 versus Colo50‐74, CRC cases and deaths increased slightly as three colonoscopies per lifetime shifted to 5 years earlier but mean quality‐adjusted life‐years gained (QALYGs) per person increased. FIT45‐74 and Colo45‐74 cost 23,800–53,900 new Israeli shekels (NIS)/QALYG and 110,600–162,700 NIS/QALYG, with the lowest and highest values among Jewish/Other men and Arab women, respectively. A fourth lifetime colonoscopy cost 48,700 NIS/QALYG. Lowering FIT initiation to 45 years with modest participation required 19,300 additional colonoscopies in the first 3 years.

Conclusions

Beginning CRC screening at 45 years in Israel is projected to yield modest clinical benefits at acceptable costs per QALYG. Despite different estimates by sex/ethnicity, a uniform national policy is favored. These findings can inform Israeli guidelines and serve as a case study internationally.
Phase 2 trial of tremelimumab in patients with metastatic urothelial cancer previously treated with programmed death 1/programmed death ligand 1 blockade
Authors: Miller Eric J. , Rose Tracy L. , Maughan Benjamin L. , Milowsky Matthew I. , Bilen Mehmet A. , Carthon Bradley C. , Gao Xin , Rapisuwon Suthee , Zhao Qianqian , Yu Menggang , Agarwal Neeraj , Galsky Matthew D.
Published: January 2024

Introduction

Programmed death 1 (PD‐1)/programmed death ligand 1 (PD‐L1) blockade has changed the landscape of treatment for metastatic urothelial cancer, but single‐agent cytotoxic T‐lymphocyte–associated protein 4 (CTLA‐4) blockade in metastatic urothelial cancer has been underexplored. A prior phase 2 trial of tremelimumab in PD‐1/PD‐L1–blockade naive patients with metastatic urothelial cancer revealed activity comparable to that observed with PD‐1/PD‐L1 blockade raising the hypothesis that these classes of immune checkpoint inhibitors might be non‐cross‐resistant.

Methods

The current phase 2 trial treated patients with PD‐1/PD‐L1 blockade‐resistant metastatic urothelial cancer with single‐agent tremelimumab (750 mg intravenously every 28 days for up to 7 cycles). The primary end point was objective response rate.

Results

Twenty‐six patients were enrolled and 24 patients were evaluable for response. The objective response rate was 8.3%, composed of a total of two partial responses that lasted 10.9 and 24.0 months. Stable disease was observed in another 20.8% of patients, with a median duration of stable disease of 5.4 months. Diarrhea occurred in 15 patients (58%), elevated hepatic transaminases occurred in seven patients (27%), and adrenal insufficiency occurred in two patients (8%); one patient died after experiencing immune‐related hepatitis.

Conclusions

High dose CTLA‐4 blockade in patients with PD‐1/PD‐L1–resistant metastatic urothelial cancer has modest activity and is associated with treatment‐related toxicity similar to prior reports.
A Novel Rhodamine‐Phenolphthalein Architecture for Selective Mercury Ion Detection in Aqueous Media
Authors: Hussein Abdullah Saleh , Lafzi Ferruh , Bayindir Sinan , Kilic Haydar , Toprak Mahmut
Published: January 2024

In this study, the primary objective is to synthesize a novel fluorescent Rh‐PP‐Rh compound and explore its extensive range of photochemical behaviors. Initially, the synthesis of the novel Rh‐PP‐Rh was carried out for this purpose. Subsequently, UV‐Vis and fluorescence spectroscopy were employed to investigate the interactions between Rh‐PP‐Rh and a diverse array of ions in aqueous solvent systems. Through fluorescence and UV‐Vis studies, it was observed that Rh‐PP‐Rh demonstrated turn‐on sensor properties in the presence of Hg2+ ions. Furthermore, the limits of detection (LOD) and association constant (Ka) values for Rh‐PP‐Rh/Hg2+ were determined as 334 nM and 9.13×1011 M−2, respectively. Additionally, the reversible studies demonstrated a switchable on/off response upon alternate addition of HgCl2 and [Bu4N]F to Rh‐PP‐Rh. These findings suggest that the probe Rh‐PP‐Rh also possesses specific sensor properties for F− ions in the presence of mercury. In addition, the investigation encompassed an assessment of the visual analysis of the color alterations of Rh‐PP‐Rh both on filter paper and in an EtOH/H2O solution. The findings demonstrated that Rh‐PP‐Rh can be successfully utilized in solutions containing mercury, as it generates significant color transformations.
Challenges in Developing Perovskite Nanocrystals for Commercial Applications
Authors: Zhang Xiaoyu , Huang Qianqian , Yin Wenxu , Zheng Weitao
Published: January 2024

Zero‐dimensional lead halide perovskite nanocrystals (NCs) exhibit size‐dependent bandgap and carrier confinement compared to bulk counterparts due to the quantum confinement effect, making them essential for achieving wide‐color‐gamut displays, studying excitonic spin relaxation, and constructing superlattices. Despite their promising potential, they face a variety of technical bottlenecks, such as insufficient color reproducibility, limited large‐scale production, low stability, and toxicity. An outline of a research roadmap is provided in the review, which highlights key challenges in developing perovskite NCs for commercial applications.
Maternal oxytocin treatment at birth increases epigenetic age in male offspring
Authors: Danoff Joshua S. , Carter C. Sue , Gordevičius Juozas , Milčiūtė Milda , Brooke Robert T. , Connelly Jessica J. , Perkeybile Allison M.
Published: January 2024

Exogenous oxytocin is widely used to induce or augment labor with little understanding of the impact on offspring development. In rodent models, including the prairie vole (Microtus ochrogaster), it has been shown that oxytocin administered to mothers can affect the nervous system of the offspring with long‐lasting behavioral effects especially on sociality. Here, we examined the hypothesis that perinatal oxytocin exposure could have epigenetic and transcriptomic consequences. Prairie voles were exposed to exogenous oxytocin, through injections given to the mother just prior to birth, and were studied at the time of weaning. The outcome of this study revealed increased epigenetic age in oxytocin‐exposed animals compared to the saline‐exposed group. Oxytocin exposure led to 900 differentially methylated CpG sites (annotated to 589 genes), and two CpG sites (two genes) remained significantly different after correction for multiple comparisons. Differentially methylated CpG sites were enriched in genes known to be involved in regulation of gene expression and neurodevelopment. Using RNA‐sequencing, we also found 217 nominally differentially expressed genes (p < .05) in nucleus accumbens, a brain region involved in reward circuitry and social behavior; after corrections for multiple comparisons, six genes remained significantly differentially expressed. Finally, we found that maternal oxytocin administration led to widespread alternative splicing in the nucleus accumbens. These results indicate that oxytocin exposure during birth may have long‐lasting epigenetic consequences. A need for further investigation of how oxytocin administration impacts development and behavior throughout the life span is supported by these outcomes.
Effects of time spent in pregnancy or brooding on immunocompetence
Authors: Revathi Venkateswaran Vandana , Gokhale Chaitanya S. , Mangel Marc , Eliassen Sigrunn
Published: January 2024

Sexes of a species may show different characteristics beyond the differences in their sexual organs and such sexual dimorphism often occurs in the level of immune response when exposed to pathogens (immunocompetence). In general, females have increased longevity relative to males, which is associated with higher immunocompetence. However, males have higher immunocompetence in some species, such as pipefishes and seahorses. Experimental evidence suggests that this could be because males, rather than females, carry fertilized eggs to birth in these species. This observation suggests that an increase in immunocompetence may be related to the level of parental investment and not to a particular sex. We use state‐dependent life‐history theory to study optimal investment in offspring production relative to parent immunocompetence, varying the relative time that a parent spends in brooding or pregnancy within a breeding cycle. When offspring is dependent on a parent's survival for a large part of the breeding cycle, we predict higher investments in immunity and longer life expectancies.
Phosphate Triester Hydrolysis by Mononuclear Iron(III) Complexes: The Role of Benzimidazole in the Second Coordination Sphere
Authors: Luiz Edinara , Farias Giliandro , Alzamora Mariella , Sánchez Dalber R. , Xavier Fernando R. , Peralta Rosely A.
Published: January 2024

Over the years, phosphate ester hydrolysis catalyzed by coordination compounds has attracted extensive research on developing new bioinspired compounds. However, the literature lacks sufficient examples displaying activity toward phosphate triesters specifically, limiting the understanding of efficient strategies for the hydrolysis of this compound hydrolysis. Herein, we report preparing and characterizing three mononuclear iron(III) complexes (1, 2, and 3) and their hydrolase‐like activity. Complexes 2 and 3 have benzimidazole (BIMZ) moieties and were strategically designed to separate the BIMZ moiety from the first coordination sphere, and complex 1 (without BIMZ) was used as a reference. Several techniques provided structural information, including spectrophotometry, spectrometry, electrochemistry, elemental analysis, and 57Fe Mossbauer. Density functional theory (DFT) revealed distorted octahedral geometries due to the presence of the BIMZ groups. These groups also directly affected the protonation equilibria and catalytic activity. The phosphate triester diethyl‐2,4‐dinitrophenylphosphate (DEDNPP) hydrolysis was enhanced at least 27 times compared to the uncatalyzed reaction, with complexes 2 and 3, thus showing higher catalytic rates (kcat). Moreover, a longer carbon chain led to a higher hydrolysis rate but less interaction with substrate. These findings provide background for further investigations and the development of efficient catalysts for agrochemical degradation.
Actinide Triamidoamine (TrenR) Chemistry: Uranium and Thorium Derivatives Supported by a Diphenyl‐tert‐Butyl‐Silyl‐Tren Ligand
Authors: Du Jingzhen , Gregson Matthew , Wooles Ashley J. , Liddle Stephen T.
Published: January 2024

We report the synthesis and characterisation of thorium(IV), uranium(III), and uranium(IV) complexes supported by a sterically demanding triamidoamine ligand with N‐diphenyl‐tert‐butyl‐silyl substituents. Treatment of ThCl4(THF)3.5 or UCl4 with [Li3(TrenDPBS)] (TrenDPBS={N(CH2CH2NSiPh2But)3}3−) afforded [An(TrenDPBS)Cl] (An=Th, 1Th; U, 1U). Complexes 1An react with benzyl potassium to afford the cyclometallates (TrenDPBScyclomet) [An{N(CH2CH2NSiPh2But)2(CH2CH2NSiPhButC6H4)}] (An=Th, 2Th; U, 2U). Treatment of 1An with sodium azide affords [An(TrenDPBS)N3] (An=Th, 3Th; U, 3U). Reaction of 3Th with potassium graphite affords 2Th. In contrast, 3Th reacts with cesium graphite to afford the doubly‐cyclometallated (TrenDPBSd‐cyclomet) ate complex [Th{N(CH2CH2NSiPh2But)(CH2CH2NSiPhButC6H4)}2Cs(THF)3] (4). In contrast to 3Th, reaction of 3U with potassium graphite produces the uranium(III) complex [U(TrenDPBS)] (5), and 5 can also be prepared by reaction of potassium graphite with 1U. The loss of azide instead of conversion to nitrides contrasts to prior work when the silyl group is iso‐propyl silyl, underscoring how ligand substituents profoundly drive the reaction chemistry. Several complexes exhibit T‐shaped meta‐C−H⋅⋅⋅phenyl and staggered parallel π–π‐stacking interactions, demonstrating subtle weak interactions that drive ancillary ligand geometries. Compounds 1An–3An, 4, and 5 have been variously characterised by single crystal X‐ray diffraction, multi‐nuclear NMR spectroscopy, infrared spectroscopy, UV/Vis/NIR spectroscopy, and elemental analyses.