bluuebunny/crossref_metadata_2025 huggingface dataset:
Modal Adjectives
Authors: Oltra‐Massuet Isabel , Castroviejo Elena
Published: October 2023

Modal adjectives pose wide‐ranging questions for the architecture of grammar, because they involve aspects of morphology, syntax and semantics and thus they are a good testing ground to investigate the ways in which these modules interact or how they are constrained, especially in relation to morphosyntactic decomposition, passive and middle voice, types of modality and the notions of stativity and eventivity. They raise further specific questions for syntactic categorization and category change, the nature of non‐verbal semantic modality, the relationship between the syntactic subcategorization properties of the base and those of the modal adjective, or how morphological processes influence the syntactic and semantic properties of adjectives. Some of the main challenges raised by modal adjectives across different languages are reviewed, mainly (i) their modal semantics, in relation to the different root modal interpretations available in the verbal domain, suggesting a neat classification that distinguishes the various dynamic, priority and dispositional/willingness interpretations available; and (ii) their morphosyntactic properties, especially in relation to their (non)‐eventive properties and the typology of ‐bleadjectives they give rise to.
Rich Agreement and Verb Movement
Authors: Koeneman Olaf , Tvica Seid , Zeijlstra Hedde
Published: October 2023

In this entry we provide an overview of the alleged correlation between the finite verb and the properties of the inflection of the verb. Specifically, it has been attested that in languages where the verb exhibits little or no inflectional morphology, no elements can intervene between the verb and the direct object (in discourse‐neutral contexts). In contrast, such intervention effects have been abundantly attested in languages where the verb exhibits a sufficiently ‘rich’ morphology. This led to the hypothesis that verb movement is triggered by rich inflectional morphology. Thus far this relation between the syntax and the morphology of the finite verb has been addressed in great detail primarily for Germanic and related languages, but more recently the research has extended beyond them. We will review the empirical claims that led to the hypothesis, as well as their theoretical implications. In addition, we will evaluate the empirical facts in a number of non‐Germanic and non‐Indo‐European languages and address the issues that arise in them. We will see that the hypothesis has not been fully confirmed or rejected yet, partly because, even though it is superficially far‐reaching, there often are particular, language‐specific properties and confounding effects that make its straightforward evaluation impossible.
Suspended Affixation
Authors: Yoon James Hye Suk
Published: October 2023

This entry surveys the properties of suspended affixation, where an affix attached to one conjunct in a coordinate structure scopes over all conjuncts. After surveying the documented properties of suspended affixation, a critical evaluation of proposed analyses is provided and questions for further exploration are identified.
Synthetic versus Analytic Expressions
Authors: Acedo‐Matellán Víctor
Published: October 2023

A single semantic representation can be expressed via one word, in a synthetic expression, or via multiple words, in an analytic expression. Similarly, the notions of synthetic and analytic can be related to how features are expressed in morphemes: they can be encoded either in one single morpheme or in several morphemes. Pairs of related synthetic and analytic expressions are found abundantly both within and across languages, which explains why the synthetic–analytic difference has been exploited by scholars since the seventeenth century to define linguistic typologies and phases of diachronic change. Within generative‐transformational grammar, the synthetic–analytic connection finds a parallel in multi stratality. All major generative models map a basically analytic representation onto one that contains some degree of syntheticity. In the latest, minimalist instantiations, different mechanisms are devised to produce a packaging of features into morphemes and of morphemes into words. Moreover, these models have produced a bunch of successful predictions about the universal constraints on the synthetic versus analytic realization of linguistic expressions.
Commissioning of Mobius3D/FX for patient‐specific quality assurance: The CUIMC—NewYork Presbyterian Hospital experience
Authors: Li Fiona , Price Michael
Published: October 2023

Purpose

To present the process undertaken by our institute in commissioning Mobius3D (M3D) for patient‐specific quality assurance.

Method

168 plans were randomly selected to compare dose distribution measured with ArcCheck and dose calculated from M3D, both compared against the treatment planning system (TPS). The gamma criteria for measurement and M3D are 3%/2 mm with 10% and 50% dose thresholds, respectively. The effect of tissue inhomogeneity was investigated on 11 plans by recalculating the dose in M3D on a homogeneous phantom. Tolerance and action limits were established following the AAPM Task Group 218 recommendations.

Results

The M3D showed high variability in gamma passing rate compared to the measurement. Twenty‐three out of 168 plans had false negative dose comparisons. These plans fall under high tissue inhomogeneity like lung and metal implants, small field targets, and breast plans planned with high energy. One false negative case (0.6%) was observed. A single tolerance limit of 91% and 92% gamma passing rate for the M3D and measurement‐based PSQA were established, respectively. Against the expectation, recalculating plans on the homogeneous phantom in M3D did not necessarily increase the gamma passing rate. These plans have a duty cycle >4.2, and the small field sizes combined with differences in slice thickness contributed to observed dose differences in the homogeneous phantom comparisons.

Conclusion

Following the commissioning, M3D is adopted in our institute. Currently, the gamma criteria used for measurement and M3D are 3%/2 mm, 40% dose threshold, with gamma passing rates of 92% and 95%, respectively. A higher passing rate for M3D is adopted until more data is available. The combined effect of plan modulation, the field sizes, the tissue inhomogeneity, the dose algorithm, and the volume averaging effect from differences in slice thickness can contribute to the differences in dose in M3D and TPS.
Introduction of Heavy Micro‐Titanium‐Carbide Particles into Zn–Ni Coatings on Steel During In Situ Brush Electroplating
Authors: Guo Wei , Shen Kangning , Wang Chen , Zhang Jinmeng , Li Jiaqing , Zhang Hao , Shen Shaobo
Published: October 2023

The heavy micro‐titanium‐carbide (TiC) particles are first introduced into brush‐electroplated Zn–Ni coating (TiC‐0 coating) by using some surfactants here. The effect of TiC concentration of brush‐electroplating solution on the properties of Zn–Ni–TiC coatings is investigated. It is found that the coating hardness and corrosion resistance are enhanced significantly due to the co‐deposition of TiC and an optimal coating with a thickness of 71 μm and adhesive strength of 37.2 MPa is obtained when TiC concentration was 40 (g L−1) (TiC‐40 coating). The pencil hardness of TiC‐0 and TiC‐40 is 2 H and 5 H, respectively. The corrosion resistance time to hot NH4NO3 solution (or inferred neutral salt spray) of TiC‐0 and TiC‐40 are 40 and 240 min (or 321 and 1995 h), respectively. Many pores appear on the coating due to the incomplete overlap of many batch layers. The TiC content is the factor dominating the coating hardness and corrosion resistance by changing the structure, contact angle, and pore diameter of coating, thereby changing the linear polar resistance Rp from potentiodynamic polarization curves, charge‐transfer resistance Rct or |Z|0.01 Hz, or polarization resistance from electrochemical impedance spectroscopy. The content of Zn–Ni alloy is the factor dominating the adhesive strength of Zn–Ni–TiC coating.
A Novel Method for Preparing Intermetallics/Superalloy Dissimilar Materials Using Current Sintering of Metallic Powders
Authors: Ning Hanwei , Wang Dongjun , Qin Shaohua , Zhao Jie , Wei Wenqing , Liu Ze , Liu Gang
Published: October 2023

Herein, a novel method is proposed to prepare the multimaterial composite component for aerospace applications using the current sintering. Two representative high‐temperature structural materials, the new potential intermetallic NiAl and the widely used Ni‐based superalloy K4202, have been employed to achieve the target. As shown by the results, a clean interface with almost no defects is successfully obtained in NiAl/K4202 alloy. Nevertheless, the existence of a continuous Cr(Mo) phase along the region leads to an insufficient bonding ability. To optimize the interfacial microstructure, a Ni foil is employed as the interlayer. The results indicate that the interlayer can hinder the intense diffusion of elements and prevent the abnormal growth of Cr(Mo) phases, which result in a considerable improvement of interfacial properties.
Photoinduced Nonvolatile Memory Transistor Based on Lead‐Free Perovskite Incorporating Fused π‐Conjugated Organic Ligands
Authors: Zhang Fan , Shao Mingchao , Wang Chengyu , Wen Wei , Shi Wenkang , Qin Mingcong , Huang Haojie , Wei Xiaofang , Guo Yunlong , Liu Yunqi
Published: October 2023

Perovskites field‐effect transistors (PeFETs) have been intensively investigated for their application in detector and synapse. However, synapse based on PeFETs is still very difficult to integrate excellent charge carrier transporting ability, photosensitivity, and nonvolatile memory effects into one device, which is very important for developing bionic electronic devices and edge computing. Here, two‐dimensional (2D) perovskites are synthesized by incorporating fused π‑conjugated pyrene‐O‐ethyl‐ammonium (POE) ligands and a systematic study is conducted to obtain enhanced performance and reliable PeFETs. The optimized (POE)2SnI4 transistors display the hole mobility over 0.3 cm2 V−1 s−1, high repeatability, and operational stability. Meanwhile, the derived photo memory devices show remarkable photoresponse, with a switching ratio higher than 105, high visible light responsivity (>4 × 104 A W−1), and stable storage‐erase cycles, as well as competitive retention performance (104 s). The photoinduced memory behavior can be benefiting from the insulating nature of quantum‐well in 2D perovskite under dark and its excellent light sensitivity. The excellent photo memory behaviors have been maintained after 40 days in a N2 atmosphere. Finally, a 2D perovskite‐only transistors with a multi‐level memory behavior (16 distinct states) is described by controlling incident light pulse. This work provides broader attention toward 2D perovskite and optoelectronic application.
Cd‐Free Pure Sulfide Kesterite Cu2ZnSnS4 Solar Cell with Over 800 mV Open‐Circuit Voltage Enabled by Phase Evolution Intervention
Authors: Wang Ao , Huang Jialiang , Cong Jialin , Yuan Xiaojie , He Mingrui , Li Jianjun , Yan Chang , Cui Xin , Song Ning , Zhou Shujie , Green Martin A , Sun Kaiwen , Hao Xiaojing
Published: October 2023

The Cd‐free Cu2ZnSnS4 (CZTS) solar cell is an ideal candidate for producing low‐cost clean energy through green materials owing to its inherent environmental friendliness and earth abundance. Nevertheless, sulfide CZTS has long suffered from severe open‐circuit voltage (VOC) deficits, limiting the full exploitation of performance potential and further progress. Here, an effective strategy is proposed to alleviate the nonradiative VOC loss by manipulating the phase evolution during the critical kesterite phase formation stage. With a Ge cap layer on the precursor, premature CZTS grain formation is suppressed at low temperatures, leading to fewer nucleation centers at the initial crystallization stage. Consequently, the CZTS grain formation and crystallization are deferred to high temperatures, resulting in enhanced grain interior quality and less unfavorable grain boundaries in the final film. As a result, a champion efficiency of 10.7% for Cd‐free CZTS solar cells with remarkably high VOC beyond 800 mV (63.2% Schockley–Queisser limit) is realized, indicating that nonradiative recombination is effectively inhibited. This strategy may advance other compound semiconductors seeking high‐quality crystallization.
A Dynamically Stable Mixed Conducting Interphase for All‐Solid‐State Lithium Metal Batteries
Authors: Li Shuai , Yang Shi‐Jie , Liu Gui‐Xian , Hu Jiang‐Kui , Liao Yu‐Long , Wang Xi‐Long , Wen Rui , Yuan Hong , Huang Jia‐Qi , Zhang Qiang
Published: October 2023

All‐solid‐state lithium (Li) metal batteries (ASSLMBs) employing sulfide solid electrolytes have attracted increasing attention owing to superior safety and high energy density. However, the instability of sulfide electrolytes against Li metal induces the formation of two types of incompetent interphases, solid electrolyte interphase (SEI) and mixed conducting interphase (MCI), which significantly blocks rapid Li‐ion transport and induces uneven Li deposition and continuous interface degradation. In this contribution, a dynamically stable mixed conducting interphase (S‐MCI) is proposed by in situ stress self‐limiting reaction to achieve the compatibility of Li metal with composite sulfide electrolytes (Li6PS5Cl (LPSCl) and Li10GeP2S12 (LGPS)). The rational design of composite electrolytes utilizes the expansion stress induced by the electrolyte decomposition to in turn constrain the further decomposition of LGPS. Consequently, the S‐MCI inherits the high dynamical stability of LPSCl‐derived SEI and the lithiophilic affinity of Li–Ge alloy in LGPS‐derived MCI. The Li||Li symmetric cells with the protection of S‐MCI can operate stably for 1500 h at 0.5 mA cm−2 and 0.5 mAh cm−2. The Li||NCM622 full cells present stable cycling for 100 cycles at 0.1 C with a high‐capacity retention of 93.7%. This work sheds fresh insight into constructing electrochemically stable interphase for high‐performance ASSLMBs.
A Lithium Intrusion‐Blocking Interfacial Shield for Wide‐Pressure‐Range Solid‐State Lithium Metal Batteries
Authors: Hu Xia , Yu Jiahao , Wang Yao , Guo Weiqian , Zhang Xiang , Armand Michel , Kang Feiyu , Wang Guoxiu , Zhou Dong , Li Baohua
Published: October 2023

Lithium garnets are considered as promising solid‐state electrolytes for next‐generation solid‐state Li metal batteries (SSLBs). However, the Li intrusion driven by external stack pressure triggers premature of Li metal batteries. Herein, for the first time, an in situ constructed interfacial shield is reported to efficiently inhibit the pressure‐induced Li intrusion in SSLBs. Theoretical modeling and experimental investigations reveal that high‐hardness metallic Mo nanocrystals inside the shield effectively suppress Li dendrite growth without alloy hardening‐derived interfacial contact deterioration. Meanwhile the electrically insulated Li2S as a shield component considerably promotes interfacial wettability and hinders Li dendrite penetration into the bulk of garnet electrolyte. Interfacial shield‐protected Li6.4La3Zr1.4Ta0.6O12 (LLZTO)‐based cells exhibit significantly enhanced cyclability without short circuits under conventional pressures of ≈0.2 MPa and even at high pressure of up to 70 MPa; which is the highest endurable stack pressure reported for SSLBs using garnet electrolytes. These key findings are expected to promote the wide‐pressure‐range applications of SSLBs.
Targeting DNA Damage and Repair Machinery via Delivering WEE1 Inhibitor and Platinum (IV) Prodrugs to Stimulate STING Pathway for Maximizing Chemo‐Immunotherapy in Bladder Cancer
Authors: Wang Wenkuan , Yang Feiya , Zhang Lingpu , Wang Mingshuai , Yin Lu , Dong Xiying , Xiao Haihua , Xing Nianzeng
Published: October 2023

Both cisplatin‐based chemotherapy and immune checkpoint blockers (ICBs)‐based immunotherapy are the first‐line treatments for patients with advanced bladder cancer. Cancer cells can develop resistance to cisplatin through extensive DNA repair, while a low response rate to ICBs is mostly due to the presence of an immunosuppressive microenvironment and low PD‐L1 expression. Herein, a glutathione (GSH)‐responsive nanoparticle (NP2) loaded with cisplatin prodrug (Pt (IV)) and WEE1 inhibitor (MK1775) is designed. NP2 can be triggered by GSH in cancer cells, and the released MK1775 can inhibit the activity of WEE1 protein, which ultimately increases DNA damage by cisplatin. Genome‐wide RNA sequencing first reveals that NP2 can inhibit DNA repair machinery by interfering with the cell cycle and significantly activate the stimulator of interferon genes pathway. Tumor growth is significantly inhibited by NP2 in vivo. As innate and adaptive immune responses are stimulated, the immunosuppressive microenvironment is modified, and the “immune cold tumor” is transformed into an “immune hot tumor". In addition, NP2 can upregulate PD‐L1 expression in tumor cells, thereby increasing the response rate of PD‐L1 monoclonal antibody (αPD‐L1) and eliciting long‐term immune responses in both primary and metastatic tumors.
A Promising Optical Bio‐Interface: Graded‐Index Hydrogel Fiber
Authors: Zhuo Xuan , Han Yaning , Bian Yinxu , Xu Anni , Shen Hua
Published: October 2023

Light in human‐machine interactions requires a bio‐friendly, efficient, and stable optical bio‐interface. Optical hydrogel fibers (HFs) with excellent biocompatibility will advance next‐generation implantable optical bio‐interfaces. However, the efficiency of HFs is limited by high optical attenuation. Moreover, the stability of implanted HFs is degraded by refraction leakage due to contact with high‐refractive‐index (RI) tissue and bending losses due to in vivo motion or organ micro‐stress. Here, a graded‐index hydrogel fiber (GIHF) is created for high‐performance, anti‐interference optical bio‐interface. The gradient RI of GIHF provides a “self‐focusing” ability to confine the light field, achieving a high transmittance and resistance to stress bending and interference of high‐RI tissue. Additionally, GIHF with optimized RI distribution is fabricated by a projection‐suspended photocuring (PSP) 3D printing method. The optical loss (0.25 dB cm−1), tissue‐contact transmittance (98%), and bending loss (0.24 dB per 90°) of the developed GIHF indicate that it outperforms other HFs. The GIHF optical bio‐interface is used to guide sufficient light to excite fluorescence in phantom brain, and the fluorescence signal is stable under multi‐frequency vibration. It paves the way for advances in optogenetics and brain‐machine interfaces (BMI).
Development of a Hibernation‐Inspired Preservation Strategy to Enhance the Clinical Translation of Photosynthetic Biomaterials
Authors: Corrales‐Orovio Rocío , Castillo Valentina , Rozas Pablo , Schenck Thilo L. , Egaña José Tomás
Published: October 2023

Photosynthetic biomaterials have emerged as a promising approach for delivering oxygen and other bioactive molecules in several biomedical applications. This technology is based on the use of standard biomaterials loaded with photosynthetic cells for the controlled release of oxygen at the target site. However, as well as for other cell‐based approaches, a main drawback for their clinical translation is the low shelf‐life of living materials. Here, the potential of inducing a dormant hibernation‐inspired state to preserve photosynthetic biomaterials for clinical applications is explored. First, a protocol to preserve microalgae Chlamydomonas reinhardtii is optimized and then applied to photosynthetic scaffolds, showing that the viability and functionality of the biomaterial is preserved for up to 6 weeks. To evaluate the clinical viability of this approach, both fresh and preserved photosynthetic scaffolds are implanted in a full‐skin defect mouse model. The safety of this approach is evaluated and confirmed by several means, including clinical parameters, histological assays, and local and systemic molecular analysis. Altogether, for the first time the successful preservation of photosynthetic biomaterials through a hibernation‐inspired strategy is described here, which could have a tremendous impact for the clinical translation of these materials as well as other photosynthetic therapies.
Deciphering the Functional Long Non‐Coding RNAs Derived from MicroRNA Loci
Authors: Li Weiqian , Huo Yue , Ren Yue , Han Chenxi , Li Shuo , Wang Kangning , He Manman , Chen Yiying , Wang Yanran , Xu Lingjie , Guo Yuehong , Si Yanmin , Gao Yufeng , Xu Jiayue , Wang Xiaoshuang , Ma Yanni , Yu Jia , Wang Fang
Published: October 2023

Albeit the majority of eukaryotic genomes can be pervasively transcribed to a diverse population of lncRNAs and various subtypes of lncRNA are discovered. However, the genome‐wide study of miRNA‐derived lncRNAs is still lacking. Here, it is reported that over 800 miRNA gene‐originated lncRNAs (molncRNAs) are generated from miRNA loci. One of them, molnc‐301b from miR‐301b and miR‐130b, functions as an “RNA decoy” to facilitate dissociation of the chromatin remodeling protein SMARCA5 from chromatin and thereby sequester transcription and mRNA translation. Specifically, molnc‐301b attenuates erythropoiesis by mitigating the transcription of erythropoietic and translation‐associated genes, such as GATA1 and FOS. In addition, a useful and powerful CRISPR screen platform to characterize the biological functions of molncRNAs at large‐scale and single‐cell levels is established and 29 functional molncRNAs in hematopoietic cells are identified. Collectively, the focus is on miRNA‐derived lncRNAs, deciphering their landscape during normal hematopoiesis, and comprehensively evaluating their potential roles.
Programmable and Reversible Integrin‐Mediated Cell Adhesion Reveals Hysteresis in Actin Kinetics that Alters Subsequent Mechanotransduction
Authors: Zhang Zheng , Zhu Hongyuan , Zhao Guoqing , Miao Yunyi , Zhao Lingzhu , Feng Jinteng , Zhang Huan , Miao Run , Sun Lin , Gao Bin , Zhang Wencheng , Wang Zheng , Zhang Jianfang , Zhang Ying , Guo Hui , Xu Feng , Lu Tian Jian , Genin Guy M. , Lin Min
Published: October 2023

Dynamically evolving adhesions between cells and extracellular matrix (ECM) transmit time‐varying signals that control cytoskeletal dynamics and cell fate. Dynamic cell adhesion and ECM stiffness regulate cellular mechanosensing cooperatively, but it has not previously been possible to characterize their individual effects because of challenges with controlling these factors independently. Therefore, a DNA‐driven molecular system is developed wherein the integrin‐binding ligand RGD can be reversibly presented and removed to achieve cyclic cell attachment/detachment on substrates of defined stiffness. Using this culture system, it is discovered that cyclic adhesion accelerates F‐actin kinetics and nuclear mechanosensing in human mesenchymal stem cells (hMSCs), with the result that hysteresis can completely change how hMSCs transduce ECM stiffness. Results are dramatically different from well‐known results for mechanotransduction on static substrates, but are consistent with a mathematical model of F‐actin fragments retaining structure following loss of integrin ligation and participating in subsequent repolymerization. These findings suggest that cyclic integrin‐mediated adhesion alters the mechanosensing of ECM stiffness by hMSCs through transient, hysteretic memory that is stored in F‐actin.
Fully Integrated Ultrathin Solid Immersion Grating Microspectrometer for Handheld Visible and Near‐Infrared Spectroscopic Applications
Authors: Park Jung‐Woo , Jeon Jaehun , Kim Gi Beom , Jeong Ki‐Hun
Published: October 2023

Despite advances in microfabrication, compact spectrometers still face challenges in shrinking their size without sacrificing optical performance. Here,  the solid immersion grating microspectrometer (SIG‐µSPEC) for high spectral resolution in a broad operational wavelength range is reported. The spectroscopic module incorporates a silicon microslit, index‐matched lens, plane mirrors, solid immersion grating (SIG), and a CMOS line sensor within a small form factor. The SIG facilitates high angular dispersion of light on a planar focal plane, resulting in an average spectral resolution of 5.8 nm, with over 76% maximum sensitivity from 400 to 800 nm. SIG‐µSPEC measures the spectral reflectance of fruits at different ripening stages, clearly revealing changes in the chlorophyll absorption band. The measured spectrum is further utilized for the precise prediction of the soluble solid content (SSC) levels, achieving a high correlation (R2 = 0.91) and a ratio of prediction‐to‐deviation of 2.36. This compact microspectrometer holds the potential for precise and non‐invasive spectral analysis across point‐of‐care fields.
Homozygous deletion of the DSG3 terminal exon associated with acantholytic blistering of the oral and laryngeal mucosa
Authors: Jiang Nan , Sewell Taylor B. , Kowalski Theresa L. , Rekab Aisha , Hills Susannah , Fazlollahi Ladan , Lauren Christine T. , Morel Kimberly , Mehta Lakshmi , Liao Jun
Published: October 2023

We report a novel homozygous 49.6 kb deletion of chromosome 18q12.1 involving the last exon of DSG3 in dizygotic twins with phenotype consistent with acantholytic blistering of the oral and laryngeal mucosa (ABOLM). The twin siblings presented predominantly with friability of the laryngeal and respiratory mucosa. This is only the second report in the literature of this unusual autosomal recessive blistering disorder. The diagnosis explains the mucosal phenotype of a pemphigus‐like disorder without evidence of autoimmune dysfunction. The exclusion of an autoimmune basis has management implications. The deletion also involved the DSG2 gene, which is associated with arrhythmogenic right ventricular dysplasia (ARVD). The affected siblings and heterozygous parents do not show any cardiac phenotype at this time. Functional studies would further clarify how deletions resulting in loss of function of DSG3 may cause the reported phenotypes of DSG3‐related ABOLM.
Palladium Encapsulated by an Oxygen‐Saturated TiO2 Overlayer for Low‐Temperature SO2‐Tolerant Catalysis during CO Oxidation
Authors: Chen Jingkun , Su Yuetan , Meng Qingjie , Qian Hehe , Shi Le , Darr Jawwad A. , Wu Zhongbiao , Weng Xiaole
Published: October 2023

The development of oxidation catalysts that are resistant to sulfur poisoning is crucial for extending the lifespan of catalysts in real‐working conditions. Herein, we describe the design and synthesis of oxide‐metal interaction (OMI) catalyst under oxidative atmospheres. By using organic coated TiO2, an oxide/metal inverse catalyst with non‐classical oxygen‐saturated TiO2 overlayers were obtained at relatively low temperature. These catalysts were found to incorporate ultra‐small Pd metal and support particles with exceptional reactivity and stability for CO oxidation (under 21 vol % O2 and 10 vol % H2O). In particular, the core (Pd)‐shell (TiO2) structured OMI catalyst exhibited excellent resistance to SO2 poisoning, yielding robust CO oxidation performance at 120 °C for 240 h (at 100 ppm SO2 and 10 vol % H2O). The stability of this new OMI catalyst was explained through density functional theory (DFT) calculations that interfacial oxygen atoms at Pd−O−Ti sites (of oxygen‐saturated overlayers) serve as non‐metal active sites for low‐temperature CO oxidation, and change the SO2 adsorption from metal(d)‐to‐SO2(π*) back‐bonding to much weaker σ(Ti−S) bonding.
CycloSiFA: The Next Generation of Silicon‐Based Fluoride Acceptors for Positron Emission Tomography (PET)
Authors: Mawick Matthias , Jaworski Carolin , Bittermann Jens , Iovkova Ljuba , Pu Yinglan , Wängler Carmen , Wängler Björn , Jurkschat Klaus , Krause Norbert , Schirrmacher Ralf
Published: October 2023

The ring‐opening Si‐fluorination of a variety of azasilole derivatives cyclo‐1‐(iPr2Si)−4‐X−C6H3−2‐CH2NR (4: R=2,6‐iPr2C6H3, X=H; 4 a: R=2,4,6‐Me3C6H2, X=H; 9: R=2,6‐iPr2C6H3, X=tBuMe2SiO; 10: R=2,6‐iPr2C6H3, X=OH; 13: R=2,6‐iPr2C6H3, X=HCCCH2O; 22: R=2,6‐iPr2C6H3, X=tBuMe2SiCH2O) with different 19F‐fluoride sources was studied, optimized and the experience gained was used in a translational approach to create a straightforward 18F‐labelling protocol for the azasilole derivatives [18F]6 and [18F]14. The latter constitutes a potential clickable CycloSiFA prosthetic group which might be used in PET tracer development using Cu‐catalysed triazole formation. Based on our findings, CycloSiFA has the potential to become a new entry into non‐canonical labelling methodologies for radioactive PET tracer development.
Effect of sintering on processability vis‐a‐vis microcellular foaming of ultrahigh molecular weight polyethylene
Authors: Shandilya Prashant Mani , Ghosh Anup K.
Published: October 2023

Processing of ultrahigh molecular weight polyethylene (UHMWPE) involves sintering due to its high melt strength and no flowability above melting temperature. Variations in compression molding pressure during sintering lead to chain rearrangement at the sintered interphase and the boundary, affecting foamability. UHMWPE particles are sintered using compression molding; samples are prepared at two different pressures: UHPE‐HP (80 bar) and UHPE‐LP (40 bar) at 180°C. The sintering phenomenon of UHMWPE particles is observed through an optical microscope, and their effect on foaming was observed. UHPE‐HP foams are systematically studied to obtain the foaming window. Increasing foaming pressure (80–120 bar) made UHPE‐HP foams softer (0.350–0.219 g/cm3) with varying average cell size (26.37–46.1 μm) and foam cell density (3.98 × 107–1.06 × 108 cells/cm3), and compression modulus decreased from 9 to 5.4 MPa. DMA results showed a strong dependence of stiffness on crystallinity, and foamed samples exhibit higher stiffness than their unfoamed counterpart. The storage modulus for foamed samples decreases with increase in the gas content. The UHPE‐LP foam is relatively softer, with a lower foam density (0.233 g/cm3), a higher expansion ratio, bigger average foam cells (35.13 μm), and lower foam cell density (9.33 × 107 cells/cm3). This is due to constrained crystallinity at the interphase and pre‐existing cavities, favoring the foaming.
Synthesis, polymerization and thermal properties of bio‐based benzoxazine resins containing imide or amide functionality
Authors: Chen Qian , Ren Dayong , Sheng Weichen , Zhang Kan
Published: October 2023

Two novel bio‐based benzoxazine monomers containing imide or amide group (HPIDD‐fa and HPBA‐fa) were synthesized from raw materials of benzoyl chloride/phthalic anhydride, tyramine, furfurylamine and paraformaldehyde via a two‐step reaction. Fourier transform infrared spectroscopy (FT‐IR), proton and carbon nuclear magnetic resonance (NMR) spectroscopies were performed to characterize the structures of the benzoxazine monomers. The curing behavior was investigated by using differential scanning calorimetry (DSC) and in situ FT‐IR, and the DSC results indicate that the peak curing temperatures of HPIDD‐fa and HPBA‐fa are centered at 248.5 and 230.1°C, respectively. In addition, thermogravimetric analysis (TGA) suggests that the newly developed bio‐based benzoxazine‐derived polybenzoxazines present excellent thermal stability with Td10 (temperature at 10% weight loss) of 385 and 368°C for poly(HPIDD‐fa) and poly(HPBA‐fa), respectively. The current investigation suggests that our newly obtained bio‐based thermosetting resins are promising materials for high‐tech applications.
Janus POSS‐based hydrogel electrolytes with highly stretchable and low‐temperature resistant performances for all‐in‐one supercapacitors
Authors: Fan Kaiqi , Liu Sen , Feng Wenbo , Yang Wentong , Peng Jiwei , Liu Ruixue , Fang Shaoming , Zhang Xiaojing
Published: October 2023

Conductive hydrogels can be utilized in the field of flexible supercapacitors due to their stretchable properties and high ionic conductivity. However, many of the conductive hydrogels lose their stretchability and conductivity at subzero temperatures. Herein, a novel Janus POSS‐based hydrogel electrolyte that shows excellent flexibility and ionic conductivity at low temperatures is designed and prepared by the copolymerization of acrylamide and a water‐soluble Janus‐type polyhedral oligomeric silsesquioxane (AS‐POSS) containing sodium sulfonate groups and double bonding groups. The sodium sulfonate groups of AS‐POSS and LiCl endow the hydrogel electrolyte with excellent anti‐freezing ability. Simultaneously, the double bonding groups of AS‐POSS enable a successful POSS crosslinking in the polymer network, resulting in a highly stretchable hydrogel electrolyte (1445%) with high ionic conductivity (0.067 S cm−1) at −20°C. Thereafter, the all‐in‐one flexible supercapacitor is prepared by in‐situ polymerization of aniline. Based on the exceptional anti‐freezing properties of the Janus POSS‐based hydrogel electrolyte, the all‐in‐one supercapacitor exhibits stable electrochemical performance (>90% capacitance retained under deformation at −20°C) and excellent cycling stability (only 19.7% capacitance decay over 2000 charge/discharge cycles at −20°C) at low temperatures. The Janus POSS‐based hydrogel electrolyte is expected to be a promising gel electrolyte for an all‐in‐one supercapacitor that resists freezing.
Meßmethoden der Polarisationsspannungen. III
Authors: Piontelli R. , Bertocci U. , Bianchi G. , Guerci C. , Poli G.
Published: October 2023

Es werden die verschiedenen Methoden zur Messung von Polarisationsspannungen an Hand der allgemein üblichen Apparaturen besprochen sowie deren Stromspeisungs‐ und Registriereinrichtungen. Es wurde die Überlegenheit der direkten Methode festgestellt. Die Stromspeisung erfolgt mit Rechteckimpulsen. Der sich während einer Impulslänge ergebende Spannungsverlauf an der Elektrode wird hierbei mit einem Kathodenstrahloszillographen verfolgt.

Es wird eine Polarisationszelle mit zur Elektrode frontal ansetzender Sonde mit seitlicher Öffnung beschrieben; die Rührung des Elektrolyten erfolgte durch Umlauf desselben. Ferner wird eine Apparatur zur Erzeugung von Rechteckimpulsen und zur Messung der Polarisationsspannung beschrieben, die in diesem Laboratorium entwickelt und erfolgreich angewandt wurde und die den obengenannten Bedingungen genügt.

Es werden einige Oszillogramme gezeigt, die mit dieser Apparatur erhalten wurden und aus denen Vorzüge und Grenzen der Leistung der Anlage hervorgehen.
Feste Gashydrate. V Die Bindungsenergien
Authors: v. Stackelberg M.
Published: October 2023

Es äßt sich zeigen, daß die einfachen Gas‐ und Flüssigkeitshydrate insofern ideale Käfigverbindungen sind, als zwischen den Hydratbildnermolekeln M und den Wassermolekeln der diese einschließenden Hohlraum‐wände nur van der Waalssche Kräfte wirksam werden. Die Bildungswärmen der Gas‐und Flüssigkeitshydrate sind dementsprechend gleich den Verfestigungswärmen ihrer Komponenten. Das Fehlen spezifischer chemischer Bindungskräfte macht eine Berechnung der Tension der Hydrate aus der Siedetemperatur des Hydratbildners möglich. Zudem ergibt diese Berechnung in Übereinstimmung mit der Erfahrung, daß nur

Stoffe mit Siedetemperaturen unter 60° C Hydrate des hier behandelten Typs bilden können. Im Gegensatz zu diesen Verhältnissen bei den einfachen Gashydraten tritt bei den H2S‐Doppelhydraten eine zusätzliche spezifische Bindungsenergie von bis zu 20 kcal je Mol M · 2H2S · 17H2O auf. Die Natur dieser zusätzlichen Energie ist noch unklar.

Die stabilisierende Wirkung der „Hilfsgase”︁ bei Mischhydraten ist von anderer Art, aber ebenfalls noch nicht befriedigend deutbar.
Die Gefrierpunktserniedrigung geschmolzener Elektrolyte bei Zusatz fremder Salze II. Mitteilung: Der Molekularzustand von geschmolzenem LiSO4
Authors: Kordes Ernst , Ziegler Günther , Proeger Hans‐Jürgen
Published: October 2023

Aus der Lage des Eutektikums in den binären Systemen von Li2SO2 mit SrSO4, BaSO4 bzw, PbSO4, aus der Gefrierpunktserniedrigung von Li2SO4 durch kleine Zusätze von Sulfaten anderer Metalle und aus der Gefrierpunktserniedrigung von KNO3 durch kleine Zusätze von Li2SO4 wird auf folgende Dissoziations‐verhältnisse von Li2SO4 in Elektrolytschmelzen geschlossen:

magnified image

Durch Überführungsmessungen wird das Vorhandensein von Li‐ und SO4‐haltigen komplexen Anionen und Kationen im geschmolzenen reinen Li2SO4 bestätigt.
Beiträge zur Elektrochemie des Niobs 1. Die Reduktion aus salzsauren Lösungen
Authors: Cozzi D. , Vivarelli S.
Published: October 2023

Die Reduktion salzsaurer Lösungen von Nb(V) wird auf polarographischem Wege an einer Quecksilberkathode mit großer Oberfläche verfolgt. Es wird nachgewiesen, daß bei der Reduktion in salzsaurer Lösung Nb (IV) gebildet wird, das in Nb (V) und Nb(III) disproportioniert. Die Reduktion kommt mit der Bildung von Nb (III) zum Abschluß. In Anwesenheit von Äthylenglykol, bei Konzentrationen von 10 bis 20 Vol.‐%, verläuft die Disproportionierung langsamer. Auch unter diesen Bedingungen führt die Reduktion zu Nb (IV), das jedoch weiter zu Nb (II) reduziert werden kann. Infolge der Einwirkung von Nb (IV) auf Nb (II) endet die Reduktion (auch in Anwesenheit von Glykol) mit der Bildung von Nb (III). Weiter wurde das Normalpotential von Nb(V)/Nb(IV) mit und ohne Glykolzusatz gemessen.
Separation of lithium isotopes by countercurrent‐exchange‐electrolysis
Authors: Arkenbout G. J. , Boerboom A. J. H. , Smit W. M.
Published: October 2023

The separation of the lithium isotopes by countercurrent‐exchange‐electrolysis was investigated. In this process the separation is based on an exchange between a lithium amalgam and a solution of a lithium salt, transported in countercurrent through a column. It appeared possible to obtain a satisfactory countercurrent transport in a packed column. Sand with a particle size between 0.35 and 0.5 mm was found to be a suitable packing material. The reflux at the bottom of a column, where the lithium is transported from the amalgam to the electrolyte solution (anodic reflux) was realized by a continous method based on exchange‐electrolysis. The cathodic reflux is obtained by evaporating the solvent dimethyl formamide, transferring the lithium chloride into water and electrolyzing the lithium chloride solution in water. Experiments carried out during 20 to 40 hours in an exchange‐column with a length of 1 to 2 m resulted in an increase of lithium‐6 content from 7.5 to 13% at the bottom of the column and a decrease of lithium‐6 content from 7.5 to 5.3% at the top of the column.
Die Bestimmung von Gleichgewichtskonstanten aus kinetischen Messungen
Authors: Kohler Gerold , Wendt Hartmut
Published: October 2023

Gleichgewichtskonstanten wie z. B. die Komplexkonstante für die Bildung des inner‐sphere‐Komplexes von Metallkomplexen \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm K}_{\rm i} {\rm =}\frac{{{\rm [MeX]}}}{{{\rm MeH}_{\rm 2} {\rm OX}}} $\end{document} oder die Hydratationskonstante von Carbonylverbindungen \documentclass{article}\pagestyle{empty}\begin{document}$ K_{\rm H} {\rm = }\frac{{{\rm [R}_{\rm 1} {\rm R}_{\rm 2} {\rm C(OH)}_{\rm 2} {\rm]}}}{{{\rm [R}_{\rm 1} {\rm R}_{\rm 2} {\rm C = O]}}}, $\end{document}
die mit statischen Messungen nur schwierig oder prinzipiell nicht bestimmt werden können, lassen sich mit Hilfe der Drucksprungmethode nicht nur durch Relaxationszeitmessungen bestimmen. Die Auswertung der Amplituden der Relaxationsoszillogramme bietet eine weitere Möglichkeit zur Bestimmung oder Abschätzung derartiger Gleichgewichtskonstanten. Auf diese Weise wurde die Konstante Ki für folgende Komplexe bestimmt: VOSO4, BeSO4 und FeCl2+.

Außerdem wurde die Hydratationskonstante des Ninhydrins (die zweite Hydratationskonstante des Triketoindans) bestimmt und das Reaktionsvolumen der Hydratation abgeschatzt. Die entwickelte Methode eignet sich besonders zur Bestimmung der Hydratationskonstanten von α‐Keto‐Carbonsäuren und anderer saurer Carbonylverbindungen, bei denen die Hydratation eine merkliche Änderung der Azidität bewirkt und deren Hydratation so schnell erfolgt, daß eine anderweitige Bestimmung der Hydratationskonstanten ausgeschlossen erscheint.
Über das Wärmeleitvermögen von organischen Reaktorkühlmitteln im flüssigen und dampfförmigen Zustand
Authors: Reiter F. W.
Published: October 2023

Es wird berichtet über Wärmeleitfahigkeitsmessungen an flüssigem Diphenyl, o‐, m‐, p‐Terphenyl und Mischungen hiervon bis in die Nähe des normalen Siedepunktes, an gesättigten Dämpfen von Diphenyl, o‐, m‐, und p‐Terphenyl bis zu Dampfdrucken von 2–3 Atmosphären und an flüssigem und gesättigtem dampfförmigem Benzol bis in die Nähe des kritischen Punktes.

Die Bestimmungen wurden nach der stationären Hitzdrahtmethode durchgeführt. Der experimentelle Fehler wird auf 2% geschätzt. Eine Darstellung in reduzierten Einheiten zeigt, daß für die Wärmeleitfähigkeit der gesättigten Dämpfe der hier untersuchten Stoffe das Theorem der übereinstimmenden Zustande sehr gut erfüllt ist, während dies für den flüssigen Zustand nicht der Fall ist.
Austauschstromdichten und Reaktionsmechanismen der Sauerstoffelektrode
Authors: Hamann Karl H.
Published: October 2023

Die kathodische Reduktion des Sauerstoffes vollzieht sich in zwei Stufen unter Aufnahme von jeweils zwei Elektronen. Die Reduktion des Zwischenproduktes H2O2 ist so stark gehemmt, daß im allgemeinen nur die erste Stufe für den Stromfluß bestimmend ist.

Die somit vorliegende Sauerstoff‐Peroxid‐Elektrode stellt eine Zweifachredoxelektrode mit den Austauschstromdichtenjo, OX undjo,red dar. Die Berechnung der Austauschstromdichten aus den Stromdichte‐Spannungs‐Kurven ergab, daß im gesamten pH‐Bereich jo, OX ≪ jo, red ist, d.h., die Aufnahme des ersten Elektrons ist für die Reduktion des Sauerstoffes zu H2O2 geschwindigkeitsbestimmend. Die Abhängigkeit der Austausch‐stromdichtejo, OX vom pH‐Wert zeigt sowohl an blankem als auch an platiniertem Platin im Neutralbereich ein ausgeprägtes Minimum und einen exponentiellen Anstieg zu zwei etwa gleich hohen Maxima im stark sauren und im stark alkalischen Gebiet.

Der Versuch einer Bestimmung der Reaktionsmechanismen der Sauerstoff‐Peroxid‐Elektrode aus den gewonnenen experimentellen Daten führte im sauren Bereich zu den beiden ersten Teilschritten:
Die kathodische Reduktion von Cu‐I‐oxid‐Elektroden als Beispiel für den Mechanismus der Reduktion eines Halbleiter‐Kristalls
Authors: Schöppel H. R. , Gerischer H.
Published: October 2023

An Einkristallen des p‐Leiters Cu‐I‐oxid wurde die kathodische Reduktion des Kristallgitters im Kontakt mit einem Elektrolyten untersucht. Es zeigt sich, daß in Einklang mit theoretischen Überlegungen die Reduktion der Halbleiteroberfläche zu metallischem Kupfer nur unter Verbrauch von Leitungselektronen abläuft.
Doppelresonanz‐Methoden
Authors: Möbius K.
Published: October 2023

Doppelresonanz‐Methoden in der Molekülspektroskopie, bei denen die Probe resonanzhaft mit zwei Strahlungsfeldern bestrahlt wird, überstreichen den gesamten Spektralbereich vom Radiofrequenzgebiet über das Mikrowellen‐, Infrarot‐, Sichtbare bis ins UV‐Gebiet. Die Mehrzahl dieser Methoden zeichnet sich gegenüber den entsprechenden Einfachresonanzen durch 1. Verbesserung der spektralen Auflösung und/oder durch 2. Verbesserung der Nachweisempfindlichkeit aus. Die Auflösung wird durch Einführung zusätzlicher Auswahlregeln, die Nachweisempfindlichkeit durch “Quantentransformation” gesteigert. Häufig beruht der Doppelresonanzeffekt auf einer beobachtbaren Intensitätsänderung einer Linie, während das zweite Strahlungsfeld die entsprechenden Besetzungszahlen ändert. Voraussetzung dafür ist, daß die Energieniveaus, zwischen denen Beobachtungs‐ und Pumpübergänge induziert werden, genügend gut miteinander kommunizieren, indem sie gemeinsam Energieniveaus haben oder durch Relaxationsübergange oder durch die Strahlungsfelder verkoppelt werden. Diese gemeinsamen Gesichtspunkte der Doppelresonanz‐Methoden werden an Beispielen aus der NMR (INDOR, Torrey‐Oszillationen), EPR (ELDOR, ENDOR, ODMR) und Mikrowellen‐Rotationsspektroskopie (MODOR) diskutiert.
I and Thou? Challenges to dialogical pedagogy in a diverse London secondary school
Authors: Soye Emma
Published: October 2023

A growing body of literature suggests that ‘intercultural education’ is an important tool for transformative learning about oneself and the other. Yet little is known about the challenges and opportunities of intercultural education in practice, particularly in light of an increasing focus in Western education policy on testing and standardisation. This article uses ethnographic and focus group research in an ethnically diverse secondary school in East London to empirically explore the opportunities and challenges of intercultural education in practice. It highlights similarities between the concept of intercultural education and Martin Buber's theory of the ‘I−Thou’ encounter, suggesting that this dialogical relation has the potential to transform stereotypes and develop personhood. The research findings show how teachers at the East London secondary school employed dialogical techniques to encourage critical perspectives among their students and to cultivate their trust, a key element of I−Thou encounter. The findings also, however, draw attention to the deleterious impact of the marketised education paradigm on the dialogical relation, demonstrating how a policy focus on attainment and the narrow national curriculum limit opportunities for dialogue in the classroom and erode trust between teacher and student. The article argues that there is a clear and urgent imperative for change within the Western education system if Buber's dialogical pedagogy is to bear fruit and transformative learning is to take place.
Catechol‐Amyloid Interactions
Authors: Le Nghia T. K. , Kang Eun Joo , Park Ji Hun , Kang Kyungtae
Published: October 2023

This review introduces multifaceted mutual interactions between molecules containing a catechol moiety and aggregation‐prone proteins. The complex relationships between these two molecular species have previously been elucidated primarily in a unidirectional manner, as demonstrated in cases involving the development of catechol‐based inhibitors for amyloid aggregation and the elucidation of the role of functional amyloid fibers in melanin biosynthesis. This review aims to consolidate scattered clues pertaining to catechol‐based amyloid inhibitors, functional amyloid scaffold of melanin biosynthesis, and chemically designed peptide fibers for providing chemical insights into the role of the local three‐dimensional orientation of functional groups in manifesting such interactions. These orientations may play crucial, yet undiscovered, roles in various supramolecular structures.
Controllable Structural Transformation of Non‐Porous Propyl‐Malonate Hexakis[60]fullerene by Chloroform Uptake/Release
Authors: Fernández‐Bartolomé Estefanía , Santos José , Rodriguez‐Sánchez Eider , Sañudo E. Carolina , Martín Nazario , Sánchez Costa José
Published: October 2023

The design of dynamic structures with high recognition host‐guest materials capable to host selectively small volatile molecules is an emergent field of research with both fundamental and applied implications. The challenge of exploring novel materials with advanced functionalities has led to the development of dynamic crystalline structures promoted by soft interactions. Here, a new pure organic dynamic framework based on hexakis[60]fullerene that are held together by weak van der Waals interactions is described. This crystalline structure is capable of absorbing and releasing chloroform, through internal structural reorganization. This research provides new insight into the design of organic molecular crystals for selective adsorption applications.