bluuebunny/crossref_metadata_2025 huggingface dataset:
Chain‐Length Dependence of the Optical Activity of Helical Triptycene‐Based π‐Conjugated Ladder Polymers
Authors: Ammenhäuser Robin , Lupton John M. , Scherf Ullrich
Published: October 2023

Helical ladder polymers are designed by connecting planar indenofluorene chromophores by chiral triptycene linkers. The resulting hexagonal helices exhibit a substantial degree of homoconjugation across the triptycene knots, with saturation above ≈20 repeat units. The chiroptical anisotropy values gabs = Δε/ε of the lower‐energy lobes of the red‐most couplets in the circular dichroism (CD) spectra arise from the π−π* transition of the planar indenofluorene chromophores and increase almost sevenfold when going from a model dimer to the corresponding polymeric helical ladder structures. This increase represents a signature of “chiral amplification” that is observed at the molecular, single‐chain level. Here, the incorporated chiral linker units determine the chiroptical properties of the helical polymer chain, with chiral interactions arising across many achiral indenofluorene building blocks (>12). This behavior is observed for a fully covalently bound single polymer chain, in contrast to the more commonly studied supramolecular assemblies of appropriate chiral molecules.
Nanoprobes for PET/MR Imaging
Authors: Liu Huanhuan , Wang Runze , Gao Haiyan , Chen Lijuan , Li Xiaochen , Yu Xuan , Wu Yaping , Bai Yan , Wei Wei , Wang Meiyun
Published: October 2023

The development of clinical imaging techniques significantly improves diagnostic accuracy and provides guidance for personalized treatment of individuals. However, every single imaging modality has its distinct drawbacks that cannot fully fulfil the diagnosis requirement. Thus, rational combination of different imaging modalities can achieve more comprehensive information of disease and in this way provide better personalized treatment strategy. The hybrid PET/MRI has drawn increasing attention since its first clinical application. Imaging probes play an essential role in achieving qualified figures with accurate information of diseases. The application of nanotechnology promotes the development of versatile molecular probes for PET/MRI technique. Though there is an emerging clinical requirement, only a small number of multimodal PET/MRI probes have been investigated in preclinical research. Thus, this review tries to thoroughly summarize the nano‐sized PET/MRI probes on their design, preparation and biological application. By discussing the strength and limitations of these current available PET/MRI multimodal probes, this work aims to figure out the further research direction and promote the possible clinic translation of the novel PET/MRI probes.
Abnormal Photocurrent in Semiconductor p‐n Heterojunctions: Toward Multifunctional Photoelectrochemical‐Type Photonic Devices and Beyond
Authors: Fathabadi Milad , Zhao Songrui
Published: October 2023

Semiconductor p‐n heterojunctions are important building blocks for modern electronic and photonic devices. Further combining semiconductor p‐n heterojunctions with light and electrolyte environment, interesting photoelectrochemical (PEC) phenomena can occur, which enriches the design principles of multifunctional devices. In fact, recent years have witnessed the emergence of PEC‐type photonic devices. For PEC‐type photonic devices, a key to realize multifunctionality is to control the photocurrent polarity of the photoelectrode. In this study, an abnormal photocurrent is reported from p‐InGaN/n‐GaN nanowire heterojunctions under a blue light illumination: although n‐GaN is transparent to the blue light (and thus optical absorption mainly occurs in p‐InGaN) and p‐InGaN in principle can only give negative PEC photocurrent, the detailed experiments show that positive PEC photocurrent can be generated from the p‐InGaN segment due to the existence of the built‐in electric field at the p‐n junction. This study shows a new route to control the photocurrent polarity in a semiconductor p‐n heterojunction photoelectrode. This unveiled role of the built‐in electric field is expected to impact the design of emerging PEC‐type photonic devices, as well as other novel photonic and electronic devices based on semiconductor nanowire p‐n heterojunctions.
Taming Active‐Ion Crosstalk by Targeted Ion Sifter Toward High‐Voltage Lithium Metal Batteries
Authors: Feng Yang , Zhong Beidou , Zhang Ruochen , Yu Jiangtao , Huang Zhenheng , Huang Yangqi , Wu Zhonghan , Fan Yanpeng , Tian Jing , Xie Weiwei , Zhang Kai
Published: October 2023

Lithium metal batteries (LMBs), based on high‐voltage (HV) LiNixCoyMnzO2 (NCM, x+y+z = 1) materials, exhibit great potential for next‐generation electric vehicle (EV) cells. Nevertheless, the inevitable dissolution and shuttle of transition metal (TM) ions from NCM cathodes poses a threat to the electrochemical sustainability of LMBs, especially at high voltage and high temperatures. Herein, ethylene diamine tetraacetic acid (EDTA)‐grafted MOF‐808 is proposed to serve as a multifunctional ion‐selective separator coating, in which EDTA molecules play a targeted ion sifter role in restricting active‐ion crosstalk. Judicious characterizations and theoretical calculations reveal that the separator coating effectively captures the TM‐ions in the electrolyte and thus ensures stable Li deposition without dendrites. As a result, the 4.5 V NCM622//Li cell with the ion‐selective separator achieves a high‐capacity retention over 1000 cycles with a high Coulombic efficiency of 99.68%, and its cycling stability at 55 °C is also upgraded. This crosstalk‐taming strategy offers fresh insight into constructing long‐life HV‐LMBs.
Bio‐Inspired Sandwich‐Structured All‐Day‐Round Solar Evaporator for Synergistic Clean Water and Electricity Generation
Authors: Niu Ran , Ren Jiaxin , Koh Junqiang Justin , Chen Ling , Gong Jiang , Qu Jinping , Xu Xiaodong , Azadmanjiri Jalal , Min Jiakang
Published: October 2023

The integration of solar‐driven interfacial evaporation and electricity co‐generation is considered a promising approach to simultaneously alleviate freshwater scarcity and the energy crisis. However, affected by intermittent solar irradiation/uncontrollable weather, the overall performance of solar‐driven evaporation in the real world is greatly reduced. Herein, inspired by antifreeze proteins in beetles that survive in extreme climates, all‐weather solar‐driven interfacial evaporators with a sandwich structure are designed. The top and bottom layers composed of MnO2‐modified cotton cloth are used for photothermal conversion and water transport, meanwhile, the middle layer made of a phase change microcapsule/hydrogel composite serves for heat storage and release. Under 1 kW m−2 irradiation, the evaporator exhibits a high evaporation rate of 2.67 kg m−2 h−1 and an efficiency of 89.5%. In the dark, the heat released from the phase change layer supports an evaporation rate of 0.43 kg m−2 h−1, 3.6 times that of pure water. Additionally, assembled with a thermoelectric module, the hybrid device achieves a stable output electricity power of 0.42 W m−2 under 1‐sun illumination and a prolonged output for 30 min in the dark. This work provides a novel approach for full‐time solar‐powered steam‐electricity co‐generation and a proof of concept for biomimetic steam generation/heat management integration.
Organic Eutectic Salts‐Assisted Direct Lithium Regeneration for Extremely Low State of Health Ni‐Rich Cathodes
Authors: Liu Xue , Wang Renheng , Liu Shaoqing , Pu Junhan , Xie Honggui , Wu Mingli , Liu Dongming , Li Yun , Liu Jianwen
Published: October 2023

Currently, the concept of direct regeneration has garnered considerable attention from the public due to its minimal environmental impact, high economic value, and stable performance of recycled materials. In this study, an organic lithium salt‐assisted eutectic salts direct regeneration (OAER) is proposed for replenishing lithium in an extremely low state of health Ni‐rich cathode (Low SOH NCM). The OAER method capitalizes on the favorable inherent properties of eutectic salts; moreover, the reactions of organic lithium salt create an oxidation environment and vacancies. By employing OAER, Low SOH NCM are able to be recovered, which originally has a capacity of only 46.8 mAh g−1, to 155.5 mAh g−1 with a capacity retention of 95.6% after 100 cycles. Notably, this performance is substantially higher than that achieved through conventional and purely eutectic salt regeneration methods and even slightly surpasses the current commercial NCM material. Considering the economic and environmental benefits of the OAER approach, it demonstrates potential for direct regeneration of Low SOH NCM and exhibits competitiveness for industrial applications.
Associations between land bank ownership and stewardship of vacant properties and crime, violence, and youth victimization in Flint, MI
Authors: Bushman Gregory , Kondo Michelle C. , Rupp Laney A. , Hohl Bernadette C. , Gong Catherine H. , Zimmerman Marc A.
Published: October 2023

Land banks across the United States are managing expanding vacant property inventories. By maintaining vacant properties and engaging residents in the process, land banks facilitate processes integral to building safe neighborhoods and may play a role in violence prevention. Using generalized additive mixed model regression, adjusted for spatial and temporal dependencies, we examined whether land bank ownership and stewardship of vacant properties in Flint, Michigan were associated with trends in serious, violent, and firearm‐involved crime, between 2015 and 2018. We tested for differences in trends in crime density between properties owned by the Genesee County Land Bank Authority (GCLBA; n = 7151) and comparison properties not owned by the land bank (n = 6,245). In addition, we tested for differences in crime density trends between vacant properties that received different levels of land bank stewardship, including biannual mowing, GCLBA standard stewardship, and GCLBA‐sponsored community‐engaged stewardship. We found that GCLBA ownership was associated with net declines in densities of all types of crime and violence, over time, relative to properties not owned by the GCLBA. When we distinguished between levels of stewardship, we found that GCLBA stewardship, both with and without community engagement, was associated with net declines in serious and violent crime relative to comparison properties. Only community‐engaged GCLBA stewardship was associated with declines in firearm‐involved crime and firearm‐involved crime with a youth victim over time, relative to comparison properties. Land bank stewardship of vacant properties may be protective against crime, violence, and youth victimization in legacy cities like Flint, MI that experience high rates of vacant properties and violent crime.
Structural barriers explain the link between negative community re‐entry experiences and motives for illegal behavior in street‐identified Black men and women
Authors: Bounoua Nadia , Sadeh Naomi , Payne Yasser A. , Hitchens Brooklynn K.
Published: October 2023

This study examines how the re‐entry process is related to structural barriers in the community and to motives for engaging in illegal behavior—two key risk factors for recidivism. We analyzed survey data collected on perceptions of community re‐entry, employment opportunities, neighborhood violence, and illegal behavior motives from 379 formerly incarcerated and street‐identified Black‐American community members residing in Wilmington, Delaware (Mage = 32.3/8.9 years old; 77.0% men; 100% Black) by employing Street Participatory Action Research (Street PAR) methodology. We found that negative perceptions of re‐entry correlated positively with (i) hardship caused by structural barriers in the community, specifically blocked employment opportunities and neighborhood violence, and (ii) motives for engaging in illegal behavior. Notably, the link between negative perceptions of re‐entry and motives for illegal behavior became significantly weaker when the influence of structural barriers on these individual‐level factors was included in a multivariate model. Results suggest negative views of the re‐entry process reflect the resource‐scarce and stressful environments people are living in, and structural barriers can account for the relationship between negative re‐entry experiences and why individuals are motivated to engage in illegal behavior. Findings underscore the importance of improving the economic conditions of communities with high numbers of returning citizens.
The prognostic contribution of CBL, NRAS, KRAS, RUNX1, and TP53 mutations to mutation‐enhanced international prognostic score systems (MIPSS70/plus/plus v2.0) for primary myelofibrosis
Authors: Loscocco Giuseppe G. , Rotunno Giada , Mannelli Francesco , Coltro Giacomo , Gesullo Francesca , Pancani Fabiana , Signori Leonardo , Maccari Chiara , Esposito Maria , Paoli Chiara , Vannucchi Alessandro M. , Guglielmelli Paola
Published: October 2023

Contemporary risk models in primary myelofibrosis (PMF) include the mutation (MIPSS70) and mutation/karyotype enhanced (MIPSS70 plus/v2.0) international prognostic scoring systems. High molecular risk (HMR) mutations incorporated in one or both of these models include ASXL1, SRSF2, EZH2, IDH1/2, and U2AF1Q157; the current study examines additional prognostic contribution from more recently described HMR mutations, including CBL, NRAS, KRAS, RUNX1, and TP53. In a cohort of 363 informative cases (median age 58 years; 60% males), mutations included JAK2 61%, CALR 24%, MPL 6%, ASXL1 29%, SRSF2 10%, U2AF1Q157 5%, EZH2 10%, IDH1/2 4%, TP53 5%, CBL 5%, NRAS 7%, KRAS 4%, and RUNX1 4%. At a median follow‐up of 4.6 years, 135 (37%) deaths and 42 (11.6%) leukemic transformations were recorded. Univariate analysis confirmed significant survival impact from the original MIPSS70/plus/v2.0 HMR mutations as well as CBL (HR 2.8; p < .001), NRAS (HR 2.4; p < .001), KRAS (HR 2.1; p = .01), and TP53 (HR 2.4; p = .004), but not RUNX1 mutations (HR 1.8; p = .08). Multivariate analysis (MVA) that included both the original and more recently described HMR mutations confirmed independent prognostic contribution from ASXL1 (HR 1.8; p = .007), SRSF2 (HR 4.3; p < .001), U2AF1Q157 (HR 2.9, p = .004), and EZH2 (HR 2.4; p < .001), but not from IDH1/2 (p = .3), TP53 (p = .2), CBL (p = .3), NRAS (p = .8) or KRAS (p = .2) mutations. The lack of additional prognostic value from CBL, NRAS, KRAS, RUNX1, and TP53 was further demonstrated in the setting of (i) MVA of mutations and karyotype, (ii) MVA of MIPSS70/plus/v2.0 composite scores and each one of the recently described HMR mutations, except TP53, and iii) modified MIPSS70/plus/plus v2.0 that included CBL, NRAS, KRAS, and TP53 as part of the HMR constituency, operationally referred to as “HMR+” category. Furthermore, “HMR+” enhancement of MIPSS70/plus/plus v2.0 did not result in improved model performance, as measured by C‐statistics. We conclude that prognostic integrity of MIPSS70/plus/plus v2.0, as well as their genetic components, was sustained and their value not significantly upgraded by the inclusion of more recently described HMR mutations, including CBL, NRAS, KRAS, and RUNX1. Additional studies are needed to clarify the apparent additional prognostic value of TP53 mutation and its allelic state.
Endovascular Thrombectomy for a Progressive Stroke Patient With a High‐Burden Carotid Free‐Floating Thrombus
Authors: Hou Zhikai , Cui Rongrong , Yu Ying , Ma Ning
Published: October 2023

Carotid free‐floating thrombus (FFT) is a rare cause of acute ischemic events. The optimal management of carotid FFT remains unclear. The optimal and individualized management of carotid FFT should be determined based on the underlying etiology, clinical manifestation, and imaging characteristics. we reported a case with endovascular thrombectomy for a progressive stroke patient with a high‐burden carotid free‐floating thrombus. ANN NEUROL 2024;95:362–364
Subrutilan – Ein Hexacyclisches Sesterterpen aus Streptomyces subrutilus
Authors: Gu Binbin , Goldfuss Bernd , Schnakenburg Gregor , Dickschat Jeroen S.
Published: October 2023

Die Untersuchung einer Terpensynthase aus Streptomyces subrutilus führte zur Identifizierung des hexacyclischen Sesterterpens Subrutilan sowie von acht pentacyclischen Nebenprodukten. Subrutilan stellt den ersten Fall eines gesättigten Sesterterpenkohlenwasserstoffs dar. Seine Struktur einschließlich der absoluten Konfiguration wurde durch Röntgenstrukturanalyse und stereoselektive Deuterierung eindeutig bestimmt. Der Cyclisierungsmechanismus zu Subrutilan und seinen Nebenprodukten wurde durch Isotopenmarkierungsexperimente und DFT‐Rechnungen detailliert untersucht. Die Subrutilan‐Synthase (SrS) wandelte auch (2Z)‐GFPP in ein Hauptprodukt um. Weitere Verbindungen wurden aus den Substratanaloga (7R)‐6,7‐Dihydro‐GFPP und (2Z,7R)‐6,7‐Dihydro‐GFPP mit blockierter Reaktivität in der C6−C7‐Bindung erhalten. Interessanterweise verlaufen die frühen Schritte der Cyclisierungskaskade mit (2Z)‐GFPP und den gesättigten Substratanaloga analog zu denen von GFPP, doch dann kommt es zu Abweichungen vom natürlichen Cyclisierungsmodus.
Synthesis and properties of bisphenol‐Z polycarbonate via melt transesterification
Authors: Han Yiming , Zhang Yaqi , Long Xin , Bai Wei , Wang Qingyin , Wang Gongying
Published: October 2023

Polycarbonate (PC) is a thermoplastic engineering plastic with excellent properties, and its excellent dielectric properties have broad application prospects in the field of electronics. In this paper, bisphenol Z (BPZ) and diphenyl carbonate (DPC) are used as raw materials to synthesize special polycarbonate (BPZ‐PC) by melt transesterification. The effects of catalyst type, catalyst dosage, molar ratio of raw materials, transesterification reaction time and vacuum degree, polycondensation reaction temperature and time on the molecular weight of the product are investigated, and the optimal reaction conditions are obtained. The chemical structure of the product is verified by FTIR, 1H‐NMR and 13C‐NMR spectra tests. The thermal properties, mechanical properties, optical properties and dielectric properties of BPZ‐PC are evaluated. Therefore, due to its excellent performance, BPZ‐PC, a high‐performance low‐dielectric polycarbonate, can be widely used in high‐frequency communication, microelectronics, and aerospace industries.
Alternative conservation outcomes from aquatic fauna translocations: Losing and saving the Running River rainbowfish
Authors: Moy Karl , Schaffer Jason , Hammer Michael P. , Attard Catherine R. M. , Beheregaray Luciano B. , Duncan Richard , Lintermans Mark , Brown Culum , Unmack Peter J.
Published: October 2023

The translocation of species outside their natural range is a threat to aquatic biodiversity globally, especially freshwater fishes, as most are not only susceptible to predation and competition but readily hybridize with congeners.

Running River rainbowfish (RRR, Melanotaenia sp.) is a narrow‐ranged, small‐bodied freshwater fish that recently became threatened and was subsequently listed as Critically Endangered, owing to introgressive hybridization and competition following the translocation of a congeneric species, the eastern rainbowfish (Melanotaenia splendida).

To conserve RRR, wild fish were taken into captivity, genetically confirmed as pure representatives, and successfully bred. As the threat of introgression with translocated eastern rainbowfish could not be mitigated, a plan was devised to translocate captive raised RRR into unoccupied habitats within their native catchment, upstream of natural barriers. The translocation plan involved careful site selection and habitat assessment, predator training (exposure to predators prior to release), soft release (with a gradual transition from captivity to nature), and post‐release monitoring, and this approach was ultimately successful.

Two populations of RRR were established in two previously unoccupied streams above waterfalls with a combined stream length of 18 km. Post‐release monitoring was affected by floods and low sample sizes, but suggested that predation and time of release are important factors to consider in similar conservation recovery programmes for small‐bodied, short‐lived fishes.
Strategies on aroma formation in Chardonnay sparkling base wine: Different Saccharomyces cerevisiae strains, co‐inoculation with Torulaspora delbrueckii and utilization of bentonite
Authors: Hickert Lilian Raquel , Cattani Andressa , Manfroi Luciano , Wagner Roger , Furlan Junior Mendes , Sant'Anna Voltaire
Published: October 2023

The worldwide production of sparkling wines has been growing annually, driven by a market demand for high quality and more complex products. The present study aimed to evaluate the fermentation of Chardonnay must using two different Saccharomyces cerevisiae yeasts, either alone (from commercial brands A and B) or in combination with Torulaspora delbrueckii (ScA + Td and ScB + Td, respectively), as well as the addition of bentonite to the fermentation with ScA (ScA + Ben), to investigate their impact on aroma formation in sparkling base wine. Enological parameters, volatile composition, and sensory profile were evaluated. The results showed notable differences in total sulfur dioxide and volatile acidity among the S. cerevisiae strains. Moreover, the esters ethyl acetate, isoamyl acetate, hexyl acetate, and phenethyl acetate showed significant differences among treatments. Esters are recognized for their contribution to fruity and floral aromas, making them an essential part of the aromatic profile of wines. The descriptive analysis revealed that ScB + Td had the highest intensity of floral and tropical fruit notes, as well as aromatic clarity. The use of bentonite did not affect the aromatic composition or sensory profile of the wine. Therefore, the co‐inoculation of S. cerevisiae with T. delbrueckii can lead to a base wine with a higher intensity of important volatile compounds and sensory attributes, providing an important alternative to produce winery products with a more complex aroma profile.
Phenolic Acid Derivatives from Ficus esquiroliana Levl. and Their Anti‐Inflammatory Effects
Authors: Dai De‐Cai , Xu Xue‐Feng , Yan Hao , Zhang Yu
Published: October 2023

One new mesomer, ficusnaph A (1), two new phenolic acid derivatives, ficusnaphs B and C (2 and 3) together with three known biogenetically related polysubstituted naphthalene derivatives (4–6) were isolated from the stems of Ficus esquiroliana Levl. The structures of these compounds were elucidated using comprehensive spectroscopic methods. Compounds 1–6 were evaluated the inhibitory activities against the nitric oxide (NO) production induced by lipopolysaccharide (LPS) in mouse macrophage RAW264.7 cells in vitro. Compounds 1 and 2 showed significant inhibitory activity with the IC50 value of 3.12±0.14 and 7.66±0.18 μM, respectively.
Unusual manifestation of cystic mycetoma lesions: A case report
Authors: Abdallah Alaa Tajeldeen Habeeb , Abdelkhalig Rami Elsiddig , Hamid Elwasila , Ahmed Ayman , Siddig Emmanuel Edwar
Published: October 2023

Key Clinical Message

This case presents an atypical cystic presentation of mycetoma without sinuses or discharge. Awareness of these variations is crucial for accurate diagnosis and timely intervention, highlighting the need for healthcare professionals to consider diverse manifestations of mycetoma.

Mycetoma is a chronic and debilitating infectious disease characterized by localized swellings and granulomatous lesions. It primarily affects individuals in tropical and subtropical regions and is caused by certain fungi or bacteria. While mycetoma typically presents with sinuses and discharge, this case report presents a unique cystic presentation without these features. The patient, a 12‐year‐old female from Sudan, presented with a painless swelling on the dorsum of her right foot. Physical examination revealed a round, non‐tender, and fluctuant mass. Histopathological examination confirmed actinomycetoma caused by Streptomyces somaliensis. The patient was successfully treated with a combination of antibiotherapy. This atypical presentation underscores the need for healthcare professionals to consider uncommon variations of mycetoma for accurate diagnosis and management.
Recurrent laryngeal lymphangiomatosis in a patient with Proteus syndrome: A case report
Authors: Sauter Christina , Kolb Veronika , Bosch Nikolaus , Hornberger Cornelia , Plinkert Peter Karl , Hohenberger Ralph
Published: October 2023

Key Clinical Message

Proteus syndrome is a rare genetic disease characterized by an asymmetrical growth of individual parts of the body and has only been described in single cases. This patient presented with recurrent manifestations of a laryngeal and hypopharyngeal lymphangioma, which were treated with laser surgery, systemic therapy, and sclerotherapy. The reported data depict the diagnosis and treatment in the department of otorhinolaryngology, head and neck surgery of the university hospital Heidelberg from 2019 until May 2023. The recurrent endoscopy of the upper airway was performed using a flexible HD‐endoscope and the Visera Elite video tower from Olympus, Hamburg. The 29‐year old female patient initially presented in February 2019 with stridor and exertional dyspnea due to a lymphatic malformation of the left larynx and hypopharynx. In April 2019 there was no improvement by sclerotherapy with Picibanil, so that systemic therapy with the PIK3CA inhibitor alpelisib was initiated (03–07/2020) and discontinued due to a high side effect profile. In the course of 2021–2023, three microlaryngoscopies with laser surgical resection and renewed sclerotherapy of the lymphangioma with Picibanil were carried out due to fluctuating findings. After these interventions a stable disease could be established until May 2023. Laser surgical therapy is currently described as the therapy of choice in lymphangiomas in the head and neck region and also showed the highest effectiveness in our patient. In case of airway obstruction in particular, it can bring rapid symptom relief. Alternatively, and with a lower surgical risk, local improvements have been reported by sclerotherapy, which was less effective in the presented case. Rare syndromic diseases require multidisciplinary collaboration. In the case of laryngeal lymphangiomatosis, other treatment options should be considered in addition to surgical excision, especially in the case of recurrence.
Copper‐Catalyzed Asymmetric Radical 1,2‐Alkylesterification of 1,3‐Dienes with Cycloalkyl Hydroperoxides and Acids
Authors: Li Tian‐Tian , Cheng Ying , Xiao Wen‐Jing , Shi De‐Qing , Chen Jia‐Rong
Published: October 2023

Transition‐metal‐catalyzed radical relay cross‐coupling reactions of 1,3‐dienes have recently emerged as one of the most powerful methods for construction of structurally diverse allylic compound in a single chemical step. However, there still has been limited success in expanding substrate scope of radical precursors and coupling partners, as well as exploring catalytic asymmetric variants. Herein, we report a copper‐catalyzed enantioselective three‐component 1,2‐alkylesterification of 1,3‐dienes using cycloalkyl hydroperoxides as the carbonyl‐containing alkyl radical sources and carboxylic acids as O‐nucleophiles under mild and redox‐neutral conditions. This protocol features broad substrate scope and good functional group tolerance with respect to each component, providing practical access to a variety of distally keto‐functionalized allylic esters with high enantioselectivity. Mechanistic studies suggest the involvement of a sequential radical relay and C−O cross‐coupling in this three‐component radical reaction.
A Sustainable Ruthenium(III) Chloride Catalyzed Alcohol Oxidation
Authors: Nunheim Nelly F. , Thiel Werner R.
Published: October 2023

Systematic optimization of the ruthenium‐catalyzed oxidation of alcohols withtert‐butyl hydroperoxide (TBHP) as the oxidizing agent was carried out. This resulted in the development of a sustainable protocol with a water/tert‐butanol mixture as the solvent and an optimum use of the oxidizing agent by continuous addition with a syringe pump. The protocol is applicable for a broad variety of substrates. High yields of ketones and aldehydes are accessible.
Patented Technology Innovation Portfolio in Producing Biofuel Using the Theory of Inventive Problem Solving (TRIZ) Methodology
Authors: Abdul Rahim Zulhasni , Iqbal Muhammad Saqib
Published: October 2023

Ethanol is produced from biomass through pyrolysis, a technology creating business prospects for biofuels. The power may be utilized in turbines, engines, boilers, manufacturing, and energy production. Two of the numerous benefits of pyrolysis technology are low operational costs and simple liquid fuel storage and transportation. The theory of inventive problem solving (TRIZ) approach of systematic innovation is compatible with patent database analysis to produce innovations used for this study. The development of biofuel pyrolysis technology can benefit from the systematic innovation provided by the TRIZ framework. Patent portfolio analysis can profit from TRIZ's unique perspective due to its utilization of three essential indicators. The first metric examines the evolution of patented technology over the previous two decades and offers recommendations for advancing the sector. Patent‐protected scientific research and technology applications give essential insight into and foresight of future technological breakthroughs in various industries.
Removal of Reactive Red120 from Aqueous Solutions by Graphene Oxide/Zirconium Oxide Nanocomposites
Authors: Anakli Duygu , Erşan Mehtap
Published: October 2023

A graphene oxide/zirconium oxide (GO/ZrO2) nanocomposite was developed and evaluated for the efficient removal of Reactive Red120 (RR120) dye. The characterization of the GO/ZrO2 nanocomposite was carried out by Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), Raman spectroscopy, Brunauer‐Emmett‐Teller (BET), field emission scanning electron microscopy (FESEM), and energy dispersive X‐ray (EDX) spectroscopy. Box‐Behnken design (BBD) was used as a statistical optimization to evaluate the effects of adsorption parameters, including adsorbent concentration, RR120 amount, and removal time. The study describes the GO/ZrO2 nanocomposite adsorbent, which has a potential application in the treatment of anionic dye‐contaminated water.
Fischer‐Tropsch Synthesis by a Cobalt‐Based Carbon Aerogel Catalyst
Authors: Haghighi Farzad , Ahmadpour Ali , Nakhaei Pour Ali
Published: October 2023

Carbon aerogel (CA) as a novel catalyst support in Fischer‐Tropsch synthesis (FTS) was synthesized by polymerization of a resorcinol‐formaldehyde (RF) precursor through an ambient pressure drying route. The cobalt‐doped CA was synthesized by three main strategies: (a) impregnation of the metal precursor on the CA (Co‐CA‐I), (b) carbonization of cobalt‐doped organic RF aerogel (Co‐CA‐II), and (c) addition of the cobalt precursor to the RF mixture (Co‐CA‐III). The pores and cobalt particle size increased in the order of Co‐CA‐I > Co‐CA‐II > Co‐CA‐III and cobalt particles wrapped between the graphite layers when cobalt was added to the RF mixture. The CA as the catalyst support presented high CO conversion and high stability under FTS conditions. The CH4 selectivity increased by reducing the size of the cobalt particles. Hydrogen spillover from the support to metallic particles was observed in the case of Co‐CA‐I and Co‐CA‐III catalysts. This phenomenon improved the reducibility and also resulted in higher hydrogenated products being produced.
Adsorption of Model Polyfluoroalkyl Substances on Gold Electrodes for Electroanalytical Applications
Authors: Wang Xin , Ham Seokgyun , Zhang Hongwei , Wang Yun , Qiao Rui
Published: October 2023

Electrochemical methods can detect trace amounts of perfluoroalkyl and polyfluoroalkyl substances (PFAS) in the environment to help their management. PFAS adsorption on electrodes is an essential step in these methods, but is poorly understood. Here, we study the adsorption of perfluorooctanoic acid (PFOA), a model PFAS molecule, on gold substrates using metadynamics and equilibrium molecular dynamics simulations. The two‐dimensional free energy landscape obtained from metadynamics reveals that a PFOA molecule can adsorb on a neutral gold surface with the lowest free energy of −83.9 kJ/mol by adopting a co‐planar orientation, indicating a strong enrichment of PFOA occurs near the electrode. Spontaneous adsorption in other configurations, e. g., only a PFOA molecule‘s head attaches to the electrode, also occurs. However, a PFOA molecule generally must overcome energy barriers to become adsorbed. We show that energetic effects, particularly those associated with van der Waals PFOA‐gold interactions, are the primary driver for PFOA adsorption, and entropic effects associated with interfacial water molecules are the secondary driver. The implications of these results for the electrochemical detection and analysis of PFAS molecules are discussed.
Numerical simulation and structure optimization of spiral wound heat exchanger with novel spacing bars
Authors: Duan Xudong , Zhou Aimin , Xiao Juan , Wang Simin , Wen Jian
Published: October 2023

Spiral wound heat exchangers are widely used in industrial production for their advantages, such as large heat transfer areas and compact structures. However, their compact design also poses significant difficulties for numerical simulation and experimental research. The spacing bar between tube bundles has an essential impact on the performance of wound tube heat exchangers. This paper presents a new type of spacing bar vertically installed on the core barrel of the spiral wound heat exchanger to enhance the comprehensive heat transfer performance. A numerical model of a new type of wrapped tube heat exchanger has been constructed, which agrees with experimental results. Under the same working conditions, the comprehensive heat transfer performance on the shell side of the spiral wound heat exchanger with new spacing bars is increased by 7.4%–10.5% compared with the traditional structure. On this basis, the influence of the new spacing bar's structural parameters on the heat exchanger's performance was studied, and the empirical correlation between the structural parameters and operating conditions of the new spacing bar and the performance of the heat exchanger was fitted. The research results have guiding significance for the design of spiral wound heat exchangers.
Discovery of ICOS‐Targeted Small Molecules Using Pharmacophore‐Based Screening
Authors: Calvo‐Barreiro Laura , Talagayev Valerij , Pach Szymon , Abdel‐Rahman Somaya A. , Wolber Gerhard , Gabr Moustafa T.
Published: October 2023

There are currently no small molecules clinically approved as immune checkpoint modulators. Besides possessing oral bioavailability, cell‐penetrating capabilities and enhanced tumor penetration compared to monoclonal antibodies (mAbs), small molecules are amenable to pharmacokinetic optimization, which allows adopting flexible dosage regimens that may avoid immune‐related adverse events associated with mAbs. The interaction of inducible co‐stimulator (ICOS) with its ligand (ICOS‐L) plays key roles in T‐cell differentiation and activation of T‐cell to B‐cell functions. This study represents the development and validation of a virtual screening strategy to identify small molecules that bind a novel druggable binding pocket in human ICOS. We used a lipophilic canyon in the apo‐structure of ICOS and the ICOS/ICOS‐L interface individually as templates for molecular dynamics simulation to generate 3D pharmacophores subsequently used for virtual screening campaigns. Our strategy was successful finding a first‐in‐class small molecule ICOS binder (5P, KD value=108.08±26.76 μM) and validating biophysical screening platforms for ICOS‐targeted small molecules. We anticipate that future structural optimization of 5P will result in the discovery of high affinity chemical ligands for ICOS.
Early relapse within 18 months is a powerful dynamic predictor for prognosis and could revise static risk distribution in multiple myeloma
Authors: Yan Wenqiang , Xu Jingyu , Fan Huishou , Li Lingna , Cui Jian , Du Chenxing , Deng Shuhui , Sui Weiwei , Xu Yan , Hao Mu , Anderson Kenneth C. , Zou Dehui , Qiu Lugui , An Gang
Published: October 2023

Background

The duration of response to treatment is a major prognostic factor, and early relapse (ER) strongly predicts inferior survival in multiple myeloma (MM). However, the definitions of ER in MM vary from study to study and how to dynamically integrate risk distribution is still unsolved.

Methods

This study evaluated these ER definitions and further investigated the underlying relationship with static risk distribution in 629 newly diagnosed MM (NDMM) patients from the National Longitudinal Cohort of Hematological Diseases in China (NCT04645199).

Results

These data indicated that early relapse within 18 months (ER18) after initial treatment was the best time point for identifying early progression and dynamic high‐risk in MM. The ER18 population (114 of 587, 19.4%) presented with more aggressive biologic features and the inferior response to treatment compared to a reference cohort (p < .001), with a significantly short median overall survival (OS) of 28.9 months. Multivariate analyses confirmed the most significant prognostic value of ER18 on OS in the context of International Staging System stage, elevated lactate dehydrogenase, thrombocytopenia, cytogenetic abnormalities, and treatment (hazard ratio, 4.467; p < .001). The authors also described the specific transitions from static risk profile to dynamic risk distribution and then constructed a mixed‐risk‐pattern to identify four novel populations with distinct survival (p < .001). Additionally, the authors proposed a second‐state model that predicts dynamic risk changes, enabling a complementary role to the Revised International Staging System model in facilitating individualized systematic treatment.

Conclusions

Collectively, this study concludes that ER18 is a simple and dynamic prognostic predictor in MM. In addition to static risk assessment, dynamic risk plays an important role in survival prediction.
Photoluminescence Properties of Graphene Oxide in Non‐Aqueous Solvents
Authors: Pandit Souvik , Bhattacharjee Sanyukta , Seth Debabrata
Published: October 2023

Detailed attention to the interaction between graphene oxide (GO) and various organic fluorophores has been documented in literature as a result of which the impact of GO on the photophysical properties of the fluorophores is well known to the scientific community. However, the photoluminescence (PL) properties of GO in polar aprotic solvents are yet to be established. In this article, the PL properties of GO in polar aprotic solvents using various spectroscopic techniques have been reported. n‐π* transition due to the C=O bonds in the sp3 hybrid regions and π‐π* transition due to C=C bonds in the sp2 hybrid are prominent in GO. The presence of quasi‐molecules within sp2‐sp3 domains acts as PL centers located in the sp3 matrixes of GO are responsible for the PL properties. This study showcases the presence of multiple emissive states of GO in polar aprotic solvents and conveys the fact that the PL properties of GO are very much wavelength‐dependent.
KDM6A promotes hepatocellular carcinoma progression and dictates lenvatinib efficacy by upregulating FGFR4 expression
Authors: Guo Wenyun , Li Songling , Qian Yifei , Li Linfeng , Wang Fan , Tong Yu , Li Qianyu , Zhu Zijun , Gao Wei‐Qiang , Liu Yanfeng
Published: October 2023

Background

Hepatocellular carcinoma (HCC) is one of the major causes of death from cancer and has a very poor prognosis with few effective therapeutic options. Despite the approval of lenvatinib for the treatment of patients suffering from advanced HCC, only a small number of patients can benefit from this targeted therapy.

Methods

Diethylnitrosamine (DEN)‐CCL4 mouse liver tumour and the xenograft tumour models were used to evaluate the function of KDM6A in HCC progression. The xenograft tumour model and HCC cell lines were used to evaluate the role of KDM6A in HCC drug sensitivity to lenvatinib. RNA‐seq and ChIP assays were conducted for mechanical investigation.

Results

We revealed that KDM6A exhibited a significant upregulation in HCC tissues and was associated with an unfavourable prognosis. We further demonstrated that KDM6A knockdown remarkably suppressed HCC cell proliferation and migration in vitro. Moreover, hepatic Kdm6a loss also inhibited liver tumourigenesis in a mouse liver tumour model. Mechanistically, KDM6A loss downregulated the FGFR4 expression to suppress the PI3K–AKT–mTOR signalling pathway, leading to a glucose and lipid metabolism re‐programming in HCC. KDM6A and FGFR4 levels were positively correlated in HCC specimens and mouse liver tumour tissues. Notably, KDM6A knockdown significantly inhibited the efficacy of lenvatinib therapy in HCC cells in vitro and in vivo.

Conclusions

Our findings revealed that KDM6A promoted HCC progression by activating FGFR4 expression and may be an essential molecule for influencing the efficacy of lenvatinib in HCC therapy.
Identification of an APOE ε4–specific blood‐based molecular pathway for Alzheimer's disease risk
Authors: Tao Qiushan , Zhang Chao , Mercier Gustavo , Lunetta Kathryn , Ang Ting Fang Alvin , Akhter‐Khan Samia , Zhang Zhengrong , Taylor Andrew , Killiany Ronald J. , Alosco Michael , Mez Jesse , Au Rhoda , Zhang Xiaoling , Farrer Lindsay A. , Qiu Wendy Wei Qiao ,   for the Alzheimer's Disease Neuroimaging Initiative
Published: October 2023

INTRODUCTION

The precise apolipoprotein E (APOE) ε4‐specific molecular pathway(s) for Alzheimer's disease (AD) risk are unclear.

METHODS

Plasma protein modules/cascades were analyzed using weighted gene co‐expression network analysis (WGCNA) in the Alzheimer's Disease Neuroimaging Initiative study. Multivariable regression analyses were used to examine the associations among protein modules, AD diagnoses, cerebrospinal fluid (CSF) phosphorylated tau (p‐tau), and brain glucose metabolism, stratified by APOE genotype.

RESULTS

The Green Module was associated with AD diagnosis in APOE ε4 homozygotes. Three proteins from this module, C‐reactive protein (CRP), complement C3, and complement factor H (CFH), had dose‐dependent associations with CSF p‐tau and cognitive impairment only in APOE ε4 homozygotes. The link among these three proteins and glucose hypometabolism was observed in brain regions of the default mode network (DMN) in APOE ε4 homozygotes. A Framingham Heart Study validation study supported the findings for AD.

DISCUSSION

The study identifies the APOE ε4–specific CRP–C3–CFH inflammation pathway for AD, suggesting potential drug targets for the disease.

Highlights

Identification of an APOE ε4 specific molecular pathway involving blood CRP, C3, and CFH for the risk of AD.

CRP, C3, and CFH had dose‐dependent associations with CSF p‐Tau and brain glucose hypometabolism as well as with cognitive impairment only in APOE ε4 homozygotes.

Targeting CRP, C3, and CFH may be protective and therapeutic for AD onset in APOE ε4 carriers.
Day‐flying lepidoptera larvae have a poorer ability to thermoregulate than adults
Authors: Ashe‐Jepson Esme , Hayes Matthew P. , Hitchcock Gwen E. , Wingader Keira , Turner Edgar C. , Bladon Andrew J.
Published: October 2023

Changes to ambient temperatures under climate change may detrimentally impact small ectotherms that rely on their environment for thermoregulation; however, there is currently a limited understanding of insect larval thermoregulation. As holometabolous insects, Lepidoptera differ in morphology, ecology and behaviour across the life cycle, and so it is likely that adults and larvae differ in their capacity to thermoregulate. In this study, we investigated the thermoregulatory capacity (buffering ability) of 14 species of day‐flying Lepidoptera, whether this is influenced by body length or gregariousness, and whether it differs between adult and larval life stages. We also investigated what thermoregulation mechanisms are used: microclimate selection (choosing locations with a particular temperature) or behavioural thermoregulation (controlling temperature through other means, such as basking). We found that Lepidoptera larvae differ in their buffering ability between species and body lengths, but gregariousness did not influence buffering ability. Larvae are worse at buffering themselves against changes in air temperature than adults. Therefore Lepidoptera may be more vulnerable to adverse temperature conditions during their larval life stage. Adults and larvae rely on different thermoregulatory mechanisms; adults primarily use behavioural thermoregulation, whereas larvae use microclimate selection. This implies that larvae are highly dependent on the area around their foodplant for effective thermoregulation. These findings have implications for the management of land and species, for example, highlighting the importance of creating and preserving microclimates and vegetation complexity surrounding Lepidoptera foodplants for larval thermoregulation under future climate change.
Policy feedback and the enforcement of international wildlife treaties in Germany
Authors: Gabehart Kayla M. , Fullerton Allegra H. , Stefes Christoph H.
Published: October 2023

Laws are only as good as their enforcement. International treaties are no exception. We investigate how Germany implements international wildlife protection treaties, namely the International Trade in Endangered Species of Wild Fauna and Flora and the Bern Convention. We find that Germany's federal system allows for uneven enforcement of national legislation across the 16 federal states. We utilize Policy Feedback Theory as a theoretical lens to examine how federalism (re‐)produces different enforcement regimes. We rely on qualitative analysis of interviews of German street‐level bureaucrats, government officials, and NGO representatives. We find that macrolevel context impacts how institutions enforce wildlife protection policies. Particularly, Germany's federal structure permits either centralized, decentralized, or cooperative arrangements that result in differences in resources, affecting the ways bureaucrats view their roles and responsibilities. These resource and interpretive effects further feedback into the contextual structure of the federal enforcement system.
Potentilla thuringiaca Bernh. ex Link in Germany—A polyploid enigma
Authors: Gregor Thomas , Korsch Heiko , Paule Juraj
Published: October 2023

Plants in German states Thuringia and Bavaria previously thought to belong to Potentilla thuringiaca belong to at least three different taxa. Most populations in Thuringia and Bavaria are rather uniform and have a ploidy of 2n = 10x. These populations belong to P. thuringiaca as originally described. A lectotype and an epitype are designated for P. thuringiaca. In an isolated range in Eastern Thuringia, we found octoploids (2n = 8x), which are characterized mainly by a higher number of flowering stems. These populations are described as Potentilla saalae T. Gregor & Korsch. Decaploid (2n = 10x) plants from a very small range in the Bavarian Rhoen with more rounded central leaves are probably of independent origin. The relationship of German P. thuringiaca populations to those in the Alps, the Balkans, the Carpathians, and Eastern Europe is unresolved.