bluuebunny/crossref_metadata_2025 huggingface dataset:
Root and Pattern in Semitic – and Beyond
Authors: Faust Noam , Lampitelli Nicola
Published: October 2023

Root‐and‐pattern morphology (R&P), a central feature of Semitic languages, refers to the combination of two types of morphs: (i) roots that are never surface‐true, pronounceable sequences, and (ii) prosodically‐determined templates, with arbitrary prosody and melody. This combination makes these languages typological outliers, of relevance to determining the range of possible rationales in morphological systems. This entry surveys work on several formal aspects of R&P morphology, from approaches that merely formalize the relation between these two types of morphological entities, to approaches that attempt to bring the data closer to more concatenative, universal principles. The second part of the entry illustrates how both templaticity and internal changes occur outside this language family; and yet, none of the cases surveyed qualifies as involving R&P morphology.
Syncretism
Authors: Hein Johannes , Weisser Philipp
Published: October 2023

This entry presents and discusses various patterns of syncretism, understood to be morphological markers that have a common form but serve different functions. The delineation of different syncretisms will largely be based on the theoretical concepts that have been employed to describe them. In this vein, we distinguish elsewhere syncretisms, natural‐class syncretisms based on cross‐classification and subclassification, directional syncretisms, and morphomic syncretisms. The entry concludes with a brief discussion of the broader impact that the research on syncretism has on our conception of grammar.
Word‐Internal Inflection
Authors: Punske Jeffrey
Published: October 2023

This entry examines phenomena related to word‐internal inflection. In particular, it looks at apparent counter‐examples to Greenberg's Universal 28, which states that inflection must always occur outside of derivation, and compound‐internal inflection. It examines how different morphological models define inflection and derivation and how models capture the distributional facts related to inflection.
Development of Flexible Rare Earth–Fe–B Rubber Magnets toward Efficient Utilization of Ce, La, and Y Elements
Authors: Zhou Bang , Huang Weisen , Fan Wenbing , Zhang Hongrui , Yu Hongya , Long Kewen , Liu Zhongwu
Published: October 2023

The microstructure, magnetic properties, corrosion and aging resistance, and mechanical properties of Nd–Fe–B, (Nd, La, Ce)–Fe–B, and (Ce, La, Y)–Fe–B rubber magnets have been investigated. For Nd–Fe–B magnets, increasing particle size and filling ratio of magnetic particles not only improves the overall magnetic properties but also increases the tensile strength. Using the Nd26.4Fe67.6Co5B powder with particle size of 75–106 μm and filling ratio of 90%, the optimum magnetic properties with the coercivity Hcj = 738.2 kA m−1, remanence Jr = 0.51 T, and maximum energy product (BH)max = 43.5 kJ m−3 are obtained. The magnet also exhibits an enhanced tensile strength of 4.52 MPa owing to its compact and uniform microstructure. In addition, the magnetic properties of Hcj = 518 kA m−1, Jr = 0.34 T, and (BH)max = 20.6 kJ m−3 are obtained in the partial high‐abundance (Nd, La, Ce)–Fe–B rubber magnet, which is superior to some of commercial Nd–Fe–B rubber magnets. For full high‐abundance (Ce, La, Y)–Fe–B magnet, these values are 320 kA m−1, 0.27 T, and 10.5 kJ m−3, respectively. Despite its lower magnetic properties than Nd‐based rubber magnets, (Ce, La, Y)–Fe–B rubber magnet exhibits a competitive advantage over the Nd‐containing magnets in terms of corrosion resistance and aging resistance performance. Moreover, (Ce, La, Y)–Fe–B magnet shows a tensile strength of 7.86 MPa, which is nearly 74.2% and 56.8% higher than the Nd–Fe–B and (Nd, La, Ce)–Fe–B rubber magnets. The present results indicate that the Ce, La, and Y elements can be reasonably selected to manufacture flexible rare earths–Fe–B rubber magnets with a high performance/cost ratio and good performance stability.
Cucurbit[7]uril‐Mediated Organ‐Specific Delivery of Ultrasmall NIR‐II Luminescent Gold Nanocarriers for Therapy of Acute Kidney Injury
Authors: He Kui , Ding Yuan‐Fu , Zhao Zhipeng , Liu Ben , Nie Wenyan , Luo Xiaoxi , Yu Hua‐Zhong , Liu Jinbin , Wang Ruibing
Published: October 2023

The design of nanocarriers that selectively target the liver or kidney is a significant challenge in drug delivery due to the diverse physiological structures and inherent characteristics, as well as their distinct requirements for nanocarriers. Herein, a strategy to synthesize a series of second near‐infrared region (NIR‐II) emitting gold nanocarriers for fine‐tuning liver or kidney‐specific delivery via altering their surface chemistry using cucurbit[7]uril (CB[7]) and Cys‐Arg‐Gly‐Asp (CRGD) peptide is reported. Accordingly, it shows that ultrasmall nanocarriers can facilitate kidney‐targeted delivery in cisplatin‐induced acute kidney injury (AKI) mice, which significantly boosted the accumulation of dexamethasone (DXM) loaded onto the nanocarriers at the site of injured kidneys, thereby achieving improved therapeutic results. Thus, this organ‐specific delivery strategy holds tremendous promise for improving drug delivery efficiency and providing new perspectives and methods for personalized treatments.
Bulk In Situ Reconstruction of Heterojunction Perovskite Enabling Stable Solar Cells Over 24% Efficiency
Authors: Hou Shanyue , Ma Zhu , Li Yanlin , Du Zhuowei , Chen Yi , Yang Junbo , You Wei , Yang Qiang , Yu Tangjie , Huang Zhangfeng , Li Guomin , Wang Haoyu , Liu Qianyu , Yan Guangyuan , Li Haimin , Huang Yuelong , Zhang Wenhua , Abdi‐Jalebi Mojtaba , Ou Zeping , Sun Kuan , Su Rong , Long Wei
Published: October 2023

Heterojunction perovskite solar cells combine the stability of 2D perovskites and the high efficiency of 3D perovskites, making them an excellent photovoltaic candidate. While heterojunctions with intermixed or gradient perovskites can reduce surface recombination, the aggregation and phase distribution of 2D perovskite induce transport losses, thereby limiting device fill factors. Accordingly, a bulk in situ reconstruction (BISR) strategy is proposed to induce the reconstruction of 3D perovskites on a minim self‐assembled 2D crystal seed, forming heterojunction perovskite that runs through the entire active layer. This facilitates charge extraction, relieves tensile stress, and avoids the decomposition of perovskite on grain boundaries. As a result, the best‐performing heterojunction perovskite solar cells show a high‐power conversion efficiency (PCE) of 24.06% with 82.9% FF for the small‐area device (0.105 cm2) and a superior PCE of 19.2% for the large‐area module (5 × 5 cm2). Importantly, the unencapsulated device shows dramatically improved operational stability, maintaining 87% of its initial efficiency after 8000 h of storage under ambient atmosphere at room temperature. This work provides an effective and simple approach to establish heterojunction perovskite to simultaneously boost the efficiency and stability of PSCs.
Digital Mechanical Metamaterial: Encoding Mechanical Information with Graphical Stiffness Pattern for Adaptive Soft Machines
Authors: Choe Jun Kyu , Yi Jiyoon , Jang Hanhyeok , Won Heejae , Lee Suwoo , Lee Hajun , Jang Yeonwoo , Song Hyeonseo , Kim Jiyun
Published: October 2023

Inspired by the adaptive features exhibited by biological organisms like the octopus, soft machines that can tune their shape and mechanical properties have shown great potential in applications involving unstructured and continuously changing environments. However, current soft machines are far from achieving the same level of adaptability as their biological counterparts, hampered by limited real‐time tunability and severely deficient reprogrammable space of properties and functionalities. As a steppingstone toward fully adaptive soft robots and smart interactive machines, an encodable multifunctional material that uses graphical stiffness patterns is introduced here to in situ program versatile mechanical capabilities without requiring additional infrastructure. Through independently switching the digital binary stiffness states (soft or rigid) of individual constituent units of a simple auxetic structure with elliptical voids, in situ and gradational tunability is demonstrated here in various mechanical qualities such as shape‐shifting and ‐memory, stress–strain response, and Poisson's ratio under compressive load as well as application‐oriented functionalities such as tunable and reusable energy absorption and pressure delivery. This digitally programmable material is expected to pave the way toward multienvironment soft robots and interactive machines.
Growth, Distribution, and Photosynthesis of Chlamydomonas Reinhardtii in 3D Hydrogels
Authors: Oh Jeong‐Joo , Ammu Satya , Vriend Vivian Dorine , Kieffer Roland , Kleiner Friedrich Hans , Balasubramanian Srikkanth , Karana Elvin , Masania Kunal , Aubin‐Tam Marie‐Eve
Published: October 2023

Engineered living materials (ELMs) are a novel class of functional materials that typically feature spatial confinement of living components within an inert polymer matrix to recreate biological functions. Understanding the growth and spatial configuration of cellular populations within a matrix is crucial to predicting and improving their responsive potential and functionality. Here, this work investigates the growth, spatial distribution, and photosynthetic productivity of eukaryotic microalga Chlamydomonas reinhardtii (C. reinhardtii) in three‐dimensionally shaped hydrogels in dependence of geometry and size. The embedded C. reinhardtii cells photosynthesize and form confined cell clusters, which grow faster when located close to the ELM periphery due to favorable gas exchange and light conditions. Taking advantage of location‐specific growth patterns, this work successfully designs and prints photosynthetic ELMs with increased CO2 capturing rate, featuring high surface to volume ratio. This strategy to control cell growth for higher productivity of ELMs resembles the already established adaptations found in multicellular plant leaves.
Charge Dispersion Strategy for High‐Performance and Rain‐Proof Triboelectric Nanogenerator
Authors: Sun Qizeng , Ren Guozhang , He Shunhao , Tang Biao , Li Yijia , Wei Yuewen , Shi Xuewen , Tan Shenxing , Yan Ren , Wang Kaili , Yu Liuyingzi , Wang Junjie , Gao Kun , Zhu Chengcheng , Song Yaxin , Gong Zhongyan , Lu Gang , Huang Wei , Yu Hai‐Dong
Published: October 2023

Triboelectric nanogenerator (TENG) is becoming a sustainable and renewable way of energy harvesting and self‐powered sensing because of low cost, simple structure, and high efficiency. However, the output current of existing TENGs is still low. It is proposed that the output current of TENGs can be dramatically improved if the triboelectric charges can distribute inside the triboelectric layers. Herein, a novel single‐electrode conductive network‐based TENG (CN‐TENG) is developed by introducing a conductive network of multiwalled carbon nanotubes in dielectric triboelectric layer of thermoplastic polyurethane (TPU). In this CN‐TENG, the contact electrification‐induced charges distribute on both the surface and interior of the dielectric TPU layer. Thus, the short‐circuit current of CN‐TENG improves for 100‐fold, compared with that of traditional dielectric TENG. In addition, this CN‐TENG, even without packing, can work stably in high‐humidity environments and even in the rain, which is another main challenge for conventional TENGs due to charge leakage. Further, this CN‐TENG is applied for the first time, to successfully distinguish conductive and dielectric materials. This work provides a new and effective strategy to fabricate TENGs with high output current and humidity‐resistivity, greatly expanding their practical applications in energy harvesting, movement sensing, human–machine interaction, and so on.
Band Structure Engineering and Orbital Orientation Control Constructing Dual Active Sites for Efficient Sulfur Redox Reaction
Authors: Lao Zhoujie , Han Zhiyuan , Ma Jiabin , Zhang Mengtian , Wu Xinru , Jia Yeyang , Gao Runhua , Zhu Yanfei , Xiao Xiao , Yu Kuang , Zhou Guangmin
Published: October 2023

The kinetics difference among multistep electrochemical processes leads to the accumulation of soluble polysulfides and thus shuttle effect in lithium−sulfur (Li−S) batteries. While the interaction between catalysts and representative species has been reported, the root of the kinetics difference, interaction change among redox reactions, remains unclear, which significantly impedes the catalysts design for Li−S batteries. Here, this work deciphers the interaction change among electrocatalytic sulfur reactions, using tungsten disulfide (WS2) a model system to demonstrate the efficiency of modifying electrocatalytic selectivity via dual‐coordination design. Band structure engineering and orbital orientation control are combined to guide the design of WS2 with boron dopants and sulfur vacancies (B−WS2−x), accurately modulating interaction with lithium and sulfur sites in polysulfide species for relatively higher interaction with short‐chain polysulfides. The modified interaction trend is experimentally confirmed by distinguishing the kinetics of each electrochemical reaction step, indicating the effectiveness of the designed strategy. An Ah‐level pouch cell with B−WS2−x delivers a gravimetric energy density of up to 417.6 Wh kg−1 with a low electrolyte/sulfur ratio of 3.6 µL mg−1 and negative/positive ratio of 1.2. This work presents a dual‐coordination strategy for advancing evolutionarily catalytic activity, offering a rational strategy to develop effective catalysts for practical Li−S batteries.
Activation and Stabilization of Mn‐Based Positive Electrode Materials by Doping Nonmetallic Elements
Authors: Mahara Yuji , Oka Hideaki , Nonaka Takamasa , Kosaka Satoru , Takahashi Naoko Takechi , Kondo Yasuhito , Makimura Yoshinari
Published: October 2023

Disordered rock‐salt (DRS) type active materials are highly significant because of their large reversible capacities, which are due to their unique Li+ diffusion pathway and the redox capabilities of cationic transition metals (TMs) and anionic O ions. Loosely crystalline DRS materials have weak covalent bonds between TMs and O, increasing the O redox contribution and thereby enhancing their capacities. In this study, Mn‐based positive electrode materials with DRS structures are activated and stabilized by mechanochemical doping of nonmetallic elements P and B into interstitial sites. Synthesized Li0.90Mn0.84P0.04O2 (LMPO5) exhibits an initial discharge capacity of 346 mAh g−1 (1050 Wh kg−1) during charging/discharging. Li0.91Mn0.83B0.10O2 (LMBO5) has a moderately expanded lattice size, which facilitates high‐capacity retention during cycling (≈284 mAh g−1 at the 30th cycle). The structural properties of the synthesized active materials are extensively characterized. By introducing nonmetallic elements into the interstitial sites of Mn‐based materials, inexpensive, high‐capacity, and long‐cycling/calendar‐life Co/Ni‐free monometallic positive electrode materials may be further developed.
Single‐dose rituximab plus glucocorticoid versus cyclophosphamide plus glucocorticoid in patients with newly diagnosed acquired hemophilia A: A multicenter, open‐label, randomized noninferiority trial
Authors: Wang PanJing , Zhou Rongfu , Xue Feng , Zhou Hu , Bai Jie , Wang Xianghua , Ma Yueshen , Song Zhen , Chen Yunfei , Liu Xiaofan , Fu Rongfeng , Sun Ting , Ju Mankai , Dai Xinyue , Dong Huan , Yang Renchi , Liu Wei , Zhang Lei
Published: October 2023

Acquired hemophilia A (AHA) is a rare but serious bleeding disorder. Randomized controlled trial (RCT) comparing the efficacy of immunosuppression therapy for AHA lacks. We conducted the first multicenter RCT aiming to establish whether the single‐dose rituximab combination regimen was noninferior to the cyclophosphamide combination regimen. From 2017 to 2022, 63 patients with newly diagnosed AHA from five centers were randomly assigned 1:1 to receive glucocorticoid (methylprednisolone 0.8 mg/kg per day for the first 3 weeks and then tapered) plus single‐dose rituximab (375 mg/m2; n = 31) or plus cyclophosphamide (2 mg/kg per day until inhibitor becomes negative, for a maximum of 5 weeks; n = 32). The primary outcome was complete remission (CR, defined as FVIII activity ≥50 IU/dL, FVIII inhibitor undetectable, immunosuppression tapered and no bleeding for 24 h without bypassing agents) rate measured within 8 weeks. The noninferiority margin was an absolute difference of 20%. Twenty‐four (77.4%) patients in the rituximab group and 22 (68.8%) patients in the cyclophosphamide group achieved CR, which showed the noninferiority of the single‐dose rituximab‐based regimen (absolute difference = −8.67%, lower limit of the 95% confidence interval = −13.11%; Pnoninferiority = 0.005). No difference was found in the incidence of treatment‐related adverse events. Single‐dose rituximab plus glucocorticoid regimen showed similar efficacy and safety, without a reported risk of secondary malignancies or reproductive toxicity seen in cyclophosphamide, it might be recommended as a first‐line therapy for AHA, especially in China where there is a young age trend in AHA patients. This trial was registered at ClinicalTrials.gov as #NCT03384277.
Noise intensity modulates the responses of mantled howler monkeys to anthropophony
Authors: Dias Pedro A. D. , Gómez Espinosa Eugenia Eréndira , Chavira Ramírez David Roberto , Rangel Negrín Ariadna
Published: October 2023

Anthropogenic noise is a major global pollutant but its effects on primates are poorly understood, limiting our ability to develop mitigation actions that favor their welfare and conservation. In this study, we used an experimental approach to determine the impact of variation in noise intensity on mantled howler monkeys (Alouatta palliata). We conducted the study at Los Tuxtlas (México), where we studied the physiological stress (proxied via fecal glucocorticoid metabolites, fGCM) and behavioral responses of 16 males. We played back chainsaw noise at two intensities (40 and 80 dB) and used days in which groups were not exposed to noise as matched controls. With increased noise intensity fGCM increased, vigilance and vocalizations were longer, and vigilance, vocalizations, and flight occurred quicker. Physiological and behavioral responses occurred even after low‐intensity noise playbacks (i.e., 40 dB). Therefore, noise intensity is a significant factor explaining the responses of mantled howler monkeys to anthropogenic noise. These results imply that management actions aimed at eradicating anthropogenic noise are required for the conservation and welfare of mantled howler monkeys at Los Tuxtlas.
The Sporadic Early‐onset Alzheimer's Disease Signature Of Atrophy: Preliminary Findings From The Longitudinal Early‐onset Alzheimer's Disease Study (LEADS) Cohort
Authors: Touroutoglou Alexandra , Katsumi Yuta , Brickhouse Michael , Zaitsev Alexander , Eckbo Ryan , Aisen Paul , Beckett Laurel , Dage Jeffrey L. , Eloyan Ani , Foroud Tatiana , Ghetti Bernardino , Griffin Percy , Hammers Dustin , Jack Clifford R. , Kramer Joel H. , Iaccarino Leonardo , Joie Renaud La , Mundada Nidhi S , Koeppe Robert , Kukull Walter A. , Murray Melissa E. , Nudelman Kelly , Polsinelli Angelina J. , Rumbaugh Malia , Soleimani‐Meigooni David N. , Toga Arthur , Vemuri Prashanthi , Atri Alireza , Day Gregory S. , Duara Ranjan , Graff‐Radford Neill R. , Honig Lawrence S. , Jones David T. , Masdeu Joseph C. , Mendez Mario F. , Musiek Erik , Onyike Chiadi U. , Riddle Meghan , Rogalski Emily , Salloway Stephen , Sha Sharon , Turner R. Scott , Wingo Thomas S. , Wolk David A. , Womack Kyle , Carrillo Maria C. , Rabinovici Gil D. , Apostolova Liana G. , Dickerson Bradford C. ,   the LEADS Consortium
Published: October 2023

INTRODUCTION

Magnetic resonance imaging (MRI) research has advanced our understanding of neurodegeneration in sporadic early‐onset Alzheimer's disease (EOAD) but studies include small samples, mostly amnestic EOAD, and have not focused on developing an MRI biomarker.

METHODS

We analyzed MRI scans to define the sporadic EOAD‐signature atrophy in a small sample (n = 25) of Massachusetts General Hospital (MGH) EOAD patients, investigated its reproducibility in the large longitudinal early‐onset Alzheimer's disease study (LEADS) sample (n = 211), and investigated the relationship of the magnitude of atrophy with cognitive impairment.

RESULTS

The EOAD‐signature atrophy was replicated across the two cohorts, with prominent atrophy in the caudal lateral temporal cortex, inferior parietal lobule, and posterior cingulate and precuneus cortices, and with relative sparing of the medial temporal lobe. The magnitude of EOAD‐signature atrophy was associated with the severity of cognitive impairment.

DISCUSSION

The EOAD‐signature atrophy is a reliable and clinically valid biomarker of AD‐related neurodegeneration that could be used in clinical trials for EOAD.

Highlights

We developed an early‐onset Alzheimer's disease (EOAD)–signature of atrophy based on magnetic resonance imaging (MRI) scans.

EOAD signature was robustly reproducible across two independent patient cohorts.

EOAD signature included prominent atrophy in parietal and posterior temporal cortex.

The EOAD‐signature atrophy was associated with the severity of cognitive impairment.

EOAD signature is a reliable and clinically valid biomarker of neurodegeneration.
Expression and prognosis of inducible T‐cell co‐stimulator and its ligand in Chinese stage I–III lung adenocarcinoma patients
Authors: Zhan Xiao‐Kai , Liu Xi‐Kun , Zhang Sen , Chen Hong
Published: October 2023

Background

Immunotherapy has become the fastest‐adopting treatment paradigm for lung cancer with improved survival. By binding with its ligand (inducible T‐cell co‐stimulator and its ligand [ICOSL]), an inducible T‐cell co‐stimulator (ICOS) could contribute to reversing immunosuppression and improving immune response and thus be a potential target for cancer immunotherapy.

Methods

We selected 54 formalin‐fixed, paraffin‐embedded tumor tissues from cases with stage I–III lung adenocarcinoma cancer. Immunohistochemical expression of ICOS and ICOSL was evaluated. The correlation with clinical parameters in Chinese patients was also compared with TCGA results.

Results

The positive rates of ICOS and ICOSL were 68% and 81.5%, respectively, in lung tumor tissues. Of these, 9 cases had a low expression of ICOS, and 22 cases had a high expression of ICOS; ICOSL expression was low in 20 cases and high in 24 cases. According to the International Association for the Study of Lung Cancer (8th edition), phase I lesions were detected in 21 cases, phase II lesions in 15 cases, and phase III lesions in 18 cases. The median survival time of all patients was 44.5 months, and the median disease‐free survival was 32 months. Univariate analysis showed that the factors significantly associated with overall survival were tumor size, regional lymph node involvement, stage, and expression level of ICOS/ICOSL. Survival analysis using log‐rank test indicated that the lower ICOS+ cell infiltration may predict poor prognosis, whereas lower ICOSL protein expression may be associated with better prognosis, but ICOSL data need further validation in larger samples due to inconsistency in TCGA mRNA prediction.

Conclusion

ICOS/ICOSL might be associated with prognosis of lung cancer, and ICOS and its ligand may be potential therapeutic targets in non‐small cell lung cancer.
A Class of Activatable NIR‐II Photoacoustic Dyes for High‐Contrast Bioimaging
Authors: Li Jiangfeng , Wang Jiangyan , Xu Lizhen , Chi Hanwen , Liang Xing , Yoon Juyoung , Lin Weiying
Published: October 2023

Photoacoustic (PA) imaging is emerging as one of the important non‐invasive imaging techniques in biomedical research. Small molecule‐ second near‐infrared window (NIR‐II) PA dyes combined with imaging data can provide comprehensive and in‐depth in vivo physiological and pathological information. However, the NIR‐II PA dyes usually exhibit “always‐on” properties due to the lack of a readily optically tunable group, which hinders the further applications in vivo. Herein, a novel class of dyes GX have been designed and synthesized as an activatable NIR‐II PA platform, in which the absorption/emission wavelength of GX‐5 extends up to 1082/1360 nm. Importantly, the GX dyes have a strong tissue penetration depth and high‐resolution for the mouse vasculature structures in NIR‐II PA 3D imaging and high signal‐to‐noise ratio in NIR‐II fluorescence (FL) imaging. Furthermore, to demonstrate the applicability of GX dyes, the first NIR‐II PA probe GX‐5‐CO activated by carbon monoxide (CO) was engineered and employed to reveal the enhancement of the CO levels in the hypertensive mice by high‐contrast NIR‐II PA and FL imaging. We expect that many derivatives of GX dyes will be developed to afford versatile NIR‐II PA platforms for designing a wide variety activatable NIR‐II PA probes as biomedical tools.
Aryne‐Enabled C−N Arylation of Anilines
Authors: Sephton Thomas , Charitou Anastasios , Trujillo Cristina , Large Jonathan M. , Butterworth Sam , Greaney Michael F.
Published: October 2023

Anilines are potentially high‐value arylating agents, but are limited by the low reactivity of the strong C−N bond. We show that the reactive intermediate benzyne can be used to both activate anilines, and set‐up an aryl transfer reaction in a single step. The reaction does not require any transition metal catalysts or stoichiometric organometallics, and establishes a metal‐free route to valuable biaryl products by functionalizing the aniline C−N bond.
Ligand‐Enabled Double γ‐C(sp3)−H Functionalization of Aliphatic Acids: One‐Step Synthesis of γ‐Arylated γ‐Lactones
Authors: Hoque Md. Emdadul , Yu Jin‐Quan
Published: October 2023

γ‐methylene C(sp3)−H functionalization of linear free carboxylic acids remains a significant challenge. Here in we report a Pd(II)‐catalyzed tandem γ‐arylation and γ‐lactonization of aliphatic acids enabled by a L,X‐type CarboxPyridone ligand. A wide range of γ‐arylated γ‐lactones are synthesized in a single step from aliphatic acids in moderate to good yield. Arylated lactones can readily be converted into disubstituted tetrahydrofurans, a prominent scaffold amongst bioactive molecules.
Effect of Ni loading onto Pt (Pt‐Ni/C) electrocatalysts for PEM fuel cell: A study of ORR activity, stability, and temperature effect
Authors: Polagani Rajesh Kumar , Suryawanshi Prashant L. , Chinthala Mahendra , Annamareddy Sri Hari Kumar , Nasani Narendar , Sonawane Shirish H.
Published: October 2023

Pt is a noble metal when alloyed with transition metals like Ni onto the carbon support, minimizes the cost and increases the oxygen reduction reaction (ORR) activity and stability of Pt‐Ni/C electrocatalyst in a low‐temperature proton exchange membrane (LTPEM) fuel cell. A simple sonochemical‐based synthesis of Pt‐Ni/C bimetallic nanoparticles is carried out through varying amounts of Ni and Pt precursors. The various combinations of Pt and Ni metal (50:50, 75:25, and 83:17) nanoparticles were uniformly distributed on a carbon support. The shifting of 2θ values to higher levels in XRD patterns confirmed the alloy formation between Pt and Ni. The carbon (60 wt. %) supported Pt and Ni (40 wt. %) electrocatalyst ink is coated on a carbon paper which acts as a gas diffusion layer (GDL). The electrocatalytic performance of Pt‐Ni/C was evaluated in the PEM fuel cell using an electrochemical test station. The best performance was observed with the Pt: Ni (83:17) coated electrocatalyst, which delivered 0.162 W/cm2 power at 0.45 V. Also, the PEM fuel cell performance was enhanced by increasing the single cell's operating temperature.
Water lead levels in Massachusetts schools and early education and childcare facilities
Authors: Amery Liam , Tobiason John , Kumpel Emily
Published: October 2023

Exposure to lead through drinking water is of concern for children, particularly at schools and early education and care facilities (EECFs), where they spend much of their time. We use lead and copper data from monitoring in schools and EECFs in Massachusetts (USA) and create risk indices based on the percentage of fixtures in a school above three water lead level (WLL) thresholds (15, 5, and 1 ppb) to model which building characteristics, water source, and water treatment practices are associated with a school exceeding these thresholds. Local building characteristics had larger effects than information about the public water supplier (PWS), and buildings built from 1950 to 1980 were most at risk. Daily flushing and fixture replacement often decreased elevated WLLs, and water coolers had lower WLLs than other fixtures. These findings highlight the value of WLL monitoring programs and can be used to prioritize future investment in monitoring and remediation.
Über die katalytische Ammoniakoxydation an oxydischen Kontakten und der stationäre Zustand der Oxydkontakte
Authors: Krauss Walther
Published: October 2023

In einer früheren Arbeit1) wurde die katalytische Oxydation des Ammoniaks an Oxyden untersucht, wobei besonders das Temperaturgebiet und die Kontakte Beachtung fanden, die zu N2O führen. Es sollte Aufschluß über die Reaktionen des Primärproduktes NH3O mit Sauerstoffatomen und Molekülen erhalten werden. Gleichzeitig wollten wir Anhaltspunkte gewinnen für die Bedingungen, unter denen Oxydkontakte die N2O‐Bildung katalysieren. Im folgenden soll über einige weitere während des Krieges im physikalisch‐chemischen Institut der Universität Berlin durchgeführten Versuche berichtet werden.
Theorie der Röntgenstreuung an statistisch ungeordneten linearen Gittern. Rückschlüsse auf die Feinstruktur hochpolymerer Stoffe
Authors: Hosemann Rolf
Published: October 2023

Um die Streueffekte an hochpolymeren Stoffen zu erklären, genügen weder die bestehenden Modelle realer Kristalle noch die der Flüssigkeitsunordnung. Es wird darum, zunächst für den eindimensionalen Fall, ein Gitter einer ganz bestimmten idealen Unordnung untersucht, für das die exakten Streuformeln leicht anzugeben sind. Dieses Gitter liefert, wie verlangt, Kristallreflexe und Flüssigkeitsinterferenzen mit allen möglichen Zwischenstufen. Auch ein dreidimensionales Gittermodell wird, zunächst nur skizzenhaft, diskutiert und eine Reihe von Folgerungen für den feinstrukturellen Aufbau der hochpolymeren Stoffe gezogen.
Kathodische Grenzströme in geschmolzenen Salzen
Authors: Drossbach Paul , Petrick Paul
Published: October 2023

Es werden die kathodischen Grenzstromdichten bei der Elektrolyse von PbCl2, CdCl2, NiCl2, CuCl und AgCl in geschmolzenen Mischungen mit KCl+LiCl experimentell bestimmt.
Zur Theorie der Wanderungsvorgänge in Flüssigkeiten
Authors: Wirtz K.
Published: October 2023

Sowohl Platzwechsel relativ zu den nächsten Nachbarn als auch viskose Prozesse in der weiteren Umgebung liefern Anteile zur Wanderungsgeschwindigkeit (Diffusion, Ionenbeweglichkeit usw.) von molekularen Teilchen in Flüssigkeiten. Eine Analyse dieser Anteile wird versucht, und vom Standpunkt dieser Analyse werden einige Wanderungsgesetze (Stokessches Gesetz, Rieckesches Gesetz) für Moleküle diskutiert. Es zeigt sich, daß eine Gültigkeit derartiger Näherungen nur in Grenzfällen erwartet werden kann.
Die Kinetik der photochemischen Reduktion des Thionins
Authors: Pestemer M.
Published: October 2023

Die Abhängigkeit der Ausbleichgeschwindigkeit des Thionins von der Konzentration der zugesetzten Akzeptoren (Elektronendonatoren), als welche Anethol, Allylthioharnstoff und Diäthylallylthioharnstoff eingesetzt wurden, einerseits, von der Wasserstoffionenkonzentration andererseits, bestätigt ein einfaches Reaktionsschema, nach welchem der erste auf den Primärakt folgende Schritt der Photoreduktion der Übergang eines Elektrons und nicht eines H‐Atoms vom Akzeptor zum angeregten Farbstoffkation ist.
Über die UV‐Absorption hochkonzentrierter Phenollösungen sowie reinen flüssigen und festen Phenols
Authors: Von Keussler V.
Published: October 2023

Infolge der großen Stärke der Lichtabsorption im UV war es bisher nicht möglich, Absorptionsmessungen an hochkonzentrierten Lösungen in diesem Gebiet auszuführen. Es wurde daher eine Spezialküvette für extrem dünne Flüssigkeitsschichten konstruiert. Der Abstandsring wurde auf eines der mit hoher Präzision plangeschliffenen dichten Küvettenfenster aus Homosilquarz durch Aufdampfen von Aluminium im Hochvakuum erzeugt. Die Plattenabstände können aus der Lage der infolge von Reflexion an den Innenwänden bei leerem Gefäß entstehenden Interferenzstreifen im Spektrum sehr genau bestimmt werden. Plattenabstände bis zu 0,34 μ wurden hergestellt.

Mit Hilfe dieser Spezialküvette wurden Absorptionsmessungen an der Bandenfolge 2800–2550 Å des Phenols bei hochkonzentrierten Lösungen in Cyclohexan und Tetrachlorkohlenstoff sowie bei reinem flüssigen und festen Phenol ausgeführt. Es wurde festgestellt, daß mit zunehmender Konzentration eine starke Verbreiterung der Banden stattfindet und die Struktur der Bandenfolge verwaschen wird. Gleichzeitig erfolgt eine Verschiebung der gegenüber dem Gaszustande nach niederen Frequenzen verlagerten Bandenmaxima in entgegengesetztem Sinne. Beim Erstarren des flüssigen Phenols werden die Banden wieder wesentlich schärfer und verschieben sich nach niederen Frequenzen.

Es wird gezeigt, daß die Intensitätsverteilungskurven bei mittlerer Konzentration durch Superposition zweier Kurven dargestellt werden können, von denen die eine der Absorption des monomeren, die andere der des assoziierten Phenols entspricht. Aus dem Verhältnis der Ordinatenmaßstäbe, in denen diese beiden Kurven zu zeichnen sind, kann der Grad der Assoziation bestimmt werden. Letzterer stimmt bei Tetrachlorkohlenstoff als Lösungsmittel mit dem aus IR‐Messungen gewonnenen Wert überein, während bei Phenol in Cyclohexan die Assoziation größer ist. Die gewonnenen Ergebnisse führen auf Grund der herrschenden Vorstellungen über die Natur der Wasserstoffbrückenbindung zu der Schlußfolgerung, daß die Störung der Banden auf Deformation der Elektronenwolke (Verlagerung des einsamen Elektronenpaares) zurückzuführen ist. Das Schärferwerden der Banden beim Übergang zu festem Phenol wird durch Aufhebung der Möglichkeit gegenseitiger Bewegungen der Bestandteile des Moleküls des Assoziats und zunehmender Ordnung infolge Kristallisation erklärt.
Über die Absorptionsspektren polarisierter organischer Moleküle und deren Gesetzmäßigkeiten I. Diphenylpolyene
Authors: Krauss Walther , Grund Harald
Published: October 2023

Es wird gezeigt, daß bei der Anlagerung von elektrophilen Reagenzien (im wesentlichen Metallhalogenide) an Verbindungen mit Konjuenbindungen Primärkomplexe entstehen, deren Absorptionsmaxima in gesetzmäßiger Weise mit der Zahl der Konjuenbindungen nach Rot verschoben werden. Die Geschwindigkeit der Bildung der Primärkomplexe steigt mit der Zahl der Konjuenbindungen. Die Untersuchungen wurden durchgeführt im wesentlichen mit Diphenylpolyenen. Weiterhin wurde gezeigt, daß die Metallhalogenide allein nicht in der Lage sind, eine C=C‐Bindung bzw. eine Carbonylbindung zu polarisieren. Hierzu bedarf es eines Kokatalysators, der mit dem Metallhalogenid eine polare Verbindung ergibt. Ohne Kokatalysator tritt hier nur eine dielektrische Polarisation ein, deren Rotverschiebung wesentlich geringer ist als die für die Primärkomplexe gefundene Verschiebung.
Differential role of potential stressors, underlying degradation mechanism, characterization of degradants using LC–MS/MS, and establishment of a stability‐indicating analytical method for duvelisib
Authors: Tapkir Nikita Tanaji , Sahu Amit Kumar , Rajput Niraj , Jadav Tarang , Sengupta Pinaki
Published: October 2023

Duvelisib (DUV) was first approved globally in 2018. An extensive literature search revealed that the differential role of a potential degradation medium in altering the shelf‐life of DUV due to its exposure during storage has not been identified till date. Moreover, its degradation impurities and degradation mechanism are not known. In addition, no analytical method has been reported for the quantification of DUV in the presence of its degradation impurities. Therefore, the aim of this study was to identify the impact of different potential degradation media on the stability of DUV, establish the degradation mechanism, and identify its major degradation impurities. The aim was also to establish a stability‐indicating analytical method for the quantification of DUV in the presence of its degradation impurities. This study is the first to report the structure of degradation impurities and the step‐by‐step degradation mechanism of DUV. This information will be useful for the scientific community and manufacturers in optimizing the formulation parameters and/or storage conditions. The validated method can be employed for analysis of stability study and routine quality control samples of newer DUV formulations in pharmaceutical industries. The identified impurities may serve as impurity standards for specifying their limits in the drug after required qualification studies.
Factors influencing cognitive function in patients with Huntington's disease from China: A cross‐sectional clinical study
Authors: Cheng Yang‐Fan , Liu Kun‐Cheng , Yang Tian‐Mi , Xiao Yi , Jiang Qi‐Rui , Huang Jing‐Xuan , Zhang Sirui , Wei Qian‐Qian , Ou Ru‐Wei , Li Chun‐Yu , Gu Xiao‐Jing , Burgunder Jean‐Marc , Shang Hui‐Fang
Published: October 2023

Background and aim

Huntington's disease (HD) is an autosomal dominant inherited neurodegenerative disorder caused by CAG repeats expansion. Cognitive decline contributes to the loss of daily activity in manifest HD. We aimed to examine the cognition status in a Chinese HD cohort and explore factors influencing the diverse cognitive domains.

Methods

A total of 205 participants were recruited in the study with the assessment by neuropsychological batteries, including the mini–mental state examination (MMSE), Stroop test, symbol digit modalities test (SDMT), trail making test (TMT), verbal fluency test (VFT), and Hopkins verbal learning test–revised, as well as motor and psychiatric assessment. Pearson correlation and multiple linear regression models were applied to investigate the correlation.

Results

Only 41.46% of patients had normal global function first come to our center. There was a significantly difference in MMSE, Stroop test, SDMT, TMT, and VFT across each stage of HD patients (p < .05). Apathy of PBA‐s was correlated to MMSE, animal VFT and Stroop‐interference tests performance. Severity of motor symptoms, functional capacity, age, and age of motor symptom onset were correlated to all neuropsychological scores, whereas education attainment and diagnostic delay were correlated to most neuropsychological scores except TMT. Severity of motor symptoms, functional capacity, and education attainment showed independent predicting effect (p < .05) in diverse cognitive domains.

Conclusion

Cognitive impairment was very common in Chinese HD patients at the first visit and worse in the patients in advanced phase. The severity of motor symptoms and functional capacity were correlated to the diverse cognitive domains.
Static magnetic field assisted thawing improves cryopreservation of mouse whole ovaries
Authors: Zhang Liyuan , Chi Mengqiao , Cheng Yue , Chen Zhongrong , Cao Yunxia , Zhao Gang
Published: October 2023

Ovarian tissue cryopreservation is considered to be the only means to preserve fertility for prepubertal girls and women whose cancer treatment cannot be postponed. However, ovarian tissues are inevitably damaged by oxidative stress during cryopreservation, which threatens follicle survival and development, and thus affects female fertility. Therefore, reducing tissue oxidative stress injury is one of the major challenges to achieving efficient cryopreservation of ovarian tissues, especially for whole ovaries. Here, we proposed a new method to improve the antioxidant capacity of whole ovaries during cryopreservation, static magnetic field assisted thawing. The results demonstrated that the antioxidant capacity of the ovarian tissue was significantly improved by static magnetic field treatment. In addition, ovarian tissue allograft transplantation was carried out, which successfully achieved vascular regeneration and maintained follicular development. The findings of this study not only provide a new reference for the preservation of female fertility, but also is a major step forward in the cryopreservation of tissues and organs. It will have good application prospects in the field of assisted reproduction and cryo‐biomedicine.
Asymmetric [3+n]‐Cycloaddition Reactions of Donor‐Acceptor Cyclopropanes
Authors: Bao Ming , Doyle Michael P.
Published: October 2023

[3+n]‐Cycloaddition reactions that employ donor‐acceptor cyclopropanes using either chiral catalysts and racemic cyclopropanes or achiral catalysts and chiral, non‐racemic, cyclopropanes have become useful transformations for the construction of carbocyclic and heterocyclic compounds, with both processes offering mechanistic and structural advantages in ring formation. Although the vast majority of asymmetric cycloaddition reactions of donor‐acceptor cyclopropanes have been performed with racemic cyclopropane compounds catalyzed by Lewis acids with chiral ligands, optically active cyclopropane compounds can serve the same role using Lewis acids without chiral ligands. This review covers the use of chiral catalysts with racemic donor‐acceptor cyclopropanes and the use of chiral non‐racemic donor‐acceptor cyclopropanes with achiral Lewis acid catalysts.
Nucleophilicity of 4‐(Alkylthio)‐3‐imidazoline Derived Enamines
Authors: Hensinger Magenta J. , Eitzinger Andreas , Trapp Oliver , Ofial Armin R.
Published: October 2023

Imidazolidine‐4‐thiones (ITOs) are cyclic, secondary amines that were considered as potential prebiotic organocatalysts for light‐driven α‐alkylations of aldehydes by bromoacetonitrile (BAN). Recent studies showed that the initially supplied ITOs represent the pre‐catalyst because they undergo S‐alkylation with BAN to give 4‐(alkylthio)‐3‐imidazolines (TIMs). Given that the same reagent mix that undergoes light‐driven α‐alkylations is also effective in the dark, we synthesized ten ITO‐ or TIM‐derived enamines of aldehydes and characterized their nucleophilic reactivities by kinetic studies in acetonitrile. The experimental second‐order rate constants k2 for reactions of enamines with benzhydrylium ions (reference electrophiles) were evaluated by the Mayr‐Patz equation, lg k2(20 °C)=sN(N+E). The determined nucleophilicities N (and sN) reveal the reactivity profiles of these enamines under prebiotically relevant conditions as well as their potential for use in organocatalytic synthesis.
Provider motivations and barriers to cancer clinical trial screening, referral, and operations: Findings from a survey
Authors: Durden Kelly , Hurley Patricia , Butler Dorothy L. , Farner Amy , Shriver Sharon P. , Fleury Mark E.
Published: October 2023

Background

Provider and institutional practices have been shown to have a large impact on cancer clinical trial enrollment. Understanding provider perspectives on screening for trial eligibility is necessary to improve enrollment.

Methods

A questionnaire about incentives, barriers, process tools, and infrastructure related to opening trials and referring patients to onsite and offsite trials was administered to diverse stakeholders, including professional societies, advocacy organizations, and industry networks. Descriptive statistics were used to summarize findings.

Results

Overall, 693 responses were received, primarily from physicians (42.7%) and nurses (35.6%) employed at hospital health systems (43.7%) and academic centers (36.5%). Approximately half (49.2%) screened all patients for onsite clinical trials with screening typically done by manual chart review (81.9%). The greatest incentive reported for offering trials was providing the best treatment options for patients (67.7%). Contracting and paperwork (48.5%) were the greatest barriers to opening more onsite trials. Offsite referrals were rare.

Conclusions

Screening for trial eligibility is a largely manual and ad hoc process, with screening and referral to offsite trials occurring infrequently. Administrative and infrastructure barriers commonly prevent sites from opening more onsite trials. These findings suggest that automated trial screening tools built into workflows that screen in a site‐agnostic manner could result in more frequent trial eligibility screening, especially for offsite trials. With recent momentum, in part in response to the COVID‐19 pandemic, to improve clinical trial efficiencies and broaden access and participant diversity, implementing tools to improve screening and referral processes is timely and essential.

Plain Language Summary

There are many factors that contribute to low adult enrollment in cancer clinical trials, but previous research has indicated that provider and institutional barriers are the largest contributors to low cancer clinical trial enrollment.

In this survey, we sought to gain insight into cancer clinical trial enrollment practices from the perspective of health care providers such as physicians and nurses. We found that only approximately half of respondents indicated their institution systematically screens their patients for clinical trials and this process is manual and time consuming. Furthermore, we found that providers infrequently search for and refer patients to clinical trials at other sites.

Creating better screening methods could improve enrollment in clinical trials.
Rotational Transitions in the N2+ Ion Induced by Collisions with Helium Atoms in Cold Helium Plasmas. A Quasiclassical Trajectory Study
Authors: Paláček Stanislav , Kalus René , Gadéa Florent Xavier , Benhenni Malika , Leininger Thierry , Yousfi Mohammed
Published: October 2023

Cross‐sections of state‐to‐state rotational transitions in electronically ground‐state 14
(X2
) ions induced by collisions with 4He atoms have been calculated using a quasiclassical trajectory method and a set of artificial neural networks representing the
/He potential energy surface. The training points for the neural networks have been calculated at a MCSCF (multi‐configuration self‐consistent field)/aug‐cc‐pVQZ level. A broad range of the
/He collision energy has been considered (
 eV) and the efficiency of vibrational transitions in the
ion has also been analyzed. It has been found that vibrational transitions are negligible with respect to rotational transitions up to
 eV and that above this energy, both rotational and vibrational transitions in
are marginal in the
/He collisions.
Corporate integrity culture on environmental, social, and governance (ESG) performance
Authors: Bao Xin , Sun Baiqing , Han Meini , Mai Qiang , Lin Han
Published: October 2023

Recent research has viewed desirable environmental performance as the proxy of corporate integrity culture. Based on the stakeholder theory, we extend this literature by examining whether the corporate integrity culture is associated with environmental, social, and governance (ESG) performance among China A‐listed firms. We first build the integrity culture dictionary by the word embedding model. We also absorb the social influence into the integrity dictionary and identify corporate integrity culture through textual analysis. The results show that corporate integrity culture is positively associated with ESG performance. This research further discloses that this relationship is from both an indirect of integrity on green innovation and a direct effect of integrity in signaling internal stakeholders' behavioral integrity and verifying integrity culture to external stakeholders. Overall, the empirical evidence further enriches our understanding of the relationship between ESG performance and corporate integrity culture in China.
Yale modifies mental health policies
Authors: Charmatz Marc
Published: October 2023

A Connecticut federal court has approved a settlement agreement between Yale University and Elis For Rachael, Inc., a Connecticut corporation and individual Yale students and alumni, which includes changes in the mental health policies of Yale College and training. Elis For Rachael, Inc., et al. v. Yale University et al,, Case No. 3:22‐cv‐01517‐MPS (D. Conn. Aug. 28, 2023).