bluuebunny/crossref_metadata_2025_split huggingface dataset:
Interplay of Structure, Charge‐Carrier Localization and Dynamics in Copper‐Silver‐Bismuth‐Halide Semiconductors
Authors: Buizza Leonardo R. V. , Sansom Harry C. , Wright Adam D. , Ulatowski Aleksander M. , Johnston Michael B. , Snaith Henry J. , Herz Laura M. 
Published: October 2021

AbstractSilver‐bismuth based semiconductors represent a promising new class of materials for optoelectronic applications because of their high stability, all‐inorganic composition, and advantageous optoelectronic properties. In this study, charge‐carrier dynamics and transport properties are investigated across five compositions along the AgBiI4–CuI solid solution line (stoichiometry Cu4x(AgBi)1−xI4). The presence of a close‐packed iodide sublattice is found to provide a good backbone for general semiconducting properties across all of these materials, whose optoelectronic properties are found to improve markedly with increasing copper content, which enhances photoluminescence intensity and charge‐carrier transport. Photoluminescence and photoexcitation‐energy‐dependent terahertz photoconductivity measurements reveal that this enhanced charge‐carrier transport derives from reduced cation disorder and improved electronic connectivity owing to the presence of Cu+. Further, increased Cu+ content enhances the band curvature around the valence band maximum, resulting in lower charge‐carrier effective masses, reduced exciton binding energies, and higher mobilities. Finally, ultrafast charge‐carrier localization is observed upon pulsed photoexcitation across all compositions investigated, lowering the charge‐carrier mobility and leading to Langevin‐like bimolecular recombination. This process is concluded to be intrinsically linked to the presence of silver and bismuth, and strategies to tailor or mitigate the effect are proposed and discussed.
A Structured Phase Change Material with Controllable Thermoconductive Highways Enables Unparalleled Electricity via Solar‐Thermal‐Electric Conversion
Authors: Zhang Yongzheng , Wu Kai , Fu Qiang 
Published: October 2021

AbstractA solar thermoelectric generator (STEG) that harvests solar energy and converts it into electricity based on the fundamentals of the Seebeck effect is a promising alternative to photovoltaic technologies. The combination of a phase change material (PCM) with STEG further enables stable and durable energy output despite the variations of solar radiation flux. However, the widespread promotion of STEG is still impeded by its restricted output electricity (<50 W m−2), attributed to the undesirable thermal management in PCMs. Herein, an ingenious phase change composite, with the typical conformation of circular truncated cone and embedded with the actinomorphic arrangement of polybenzobisoxazole fibers, is tailored by a mold processing strategy. The fibrous crystals in organic fibers offer temperature‐resistance thermal highways during the charging/discharging processes, while their actinomorphic configuration facilitates a controllable thermo‐conductive behavior. These structural features render concentrated thermal energy to be efficiently stored in the PCM and maximally discharged into the thermoelectric system. A record‐breaking power density as high as 198.70 W m−2 can be achieved in this powerful STEG via real‐environment solar‐thermal‐electric conversion, a value comparable to that of some commercial photovoltaic devices. This work opens up opportunities for durable and giant electricity supply from clean solar energy during real‐time STEG applications.
An Approach to Quantify the Negative Capacitance Features in a Triple‐Cation based Perovskite Solar Cells
Authors: Dhifaoui Hassen , Hemasiri Naveen Harindu , Aloui Walid , Bouazizi Abdelaziz , Kazim Samrana , Ahmad Shahzada 
Published: October 2021

AbstractUnderstanding the device kinetics occurring in the bulk and at the charge selective interfaces is vital for optimizing the performance of perovskite solar cells (PSCs) and their development. Planar PSCs are studied with and without hole transport layer (HTL) and power conversion efficiency of 16.23% is measured with poly(3‐hexylthiophene) [P3HT] as HTL, while the PSCs without HTL show significant hysteresis. A comprehensive electrical response of the PSCs is investigated. The bias‐dependent electrochemical impedance spectroscopy (EIS) reveals the appearance of the negative capacitance in the low‐frequency regime. The modification of the low‐frequency PSCs response accompanied by a further decrease in recombination resistance is due to the interfacial interactions between the migrating ions and the metal contact. The doped and undoped P3HT layers impede this interaction which explains the absence of the negative capacitance at lower applied voltages. The investigation provides an understanding of the physical processes behind the negative capacitance.
Dielectric Metasurfaces for Complete Control of Phase, Amplitude, and Polarization
Authors: Wu Tong , Zhang Xueqian , Xu Quan , Plum Eric , Chen Kaiji , Xu Yuehong , Lu Yongchang , Zhang Huifang , Zhang Ziying , Chen Xieyu , Ren Guanhua , Niu Li , Tian Zhen , Han Jiaguang , Zhang Weili 
Published: October 2021

AbstractThe achievable functionalities of metasurfaces are mainly determined by the capability of their unit cells to control the local electromagnetic responses. To realize full control over light, it is highly desired to find a kind of unit cell that can achieve complete control of the phase, amplitude, and polarization, which remains a big challenge and cannot be fully replaced with iteration algorithms. Here, such control is achieved by exploiting interference in a dielectric unit cell composed of multiple meta‐atoms, namely, a meta‐molecule. This strategy provides sufficient effective geometric degrees of freedom within the meta‐molecule to enable full control over its optical properties, as is demonstrated here with a complete meta‐molecule database. As a proof‐of‐concept demonstration, polarization‐independent, polarization‐dependent, and vectorial meta‐holograms are proposed and experimentally characterized. High imaging quality is achieved in both the measured intensity and phase distributions. This is allowed by the ability of the meta‐molecules to fully record the information of the target images. This strategy opens a direct way toward optical devices with various desirable functionalities.
DNA Aptamer–Cyanine Complexes as Generic Colorimetric Small‐Molecule Sensors
Authors: Alkhamis Obtin , Canoura Juan , Bukhryakov Konstantin V. , Tarifa Anamary , DeCaprio Anthony P. , Xiao Yi 
Published: October 2021

AbstractAptamers are promising biorecognition elements for sensors. However, aptamer‐based assays often lack the requisite levels of sensitivity and/or selectivity because they typically employ structure‐switching aptamers with attenuated affinity and/or utilize reporters that require aptamer labeling or which are susceptible to false positives. Dye‐displacement assays offer a label‐free, sensitive means for overcoming these issues, wherein target binding liberates a dye that is complexed with the aptamer, producing an optical readout. However, broad utilization of these assays has been limited. Here, we demonstrate a rational approach to develop colorimetric cyanine dye‐displacement assays that can be broadly applied to DNA aptamers regardless of their structure, sequence, affinity, or the physicochemical properties of their targets. Our approach should accelerate the development of mix‐and‐measure assays that could be applied for diverse analytical applications.
Dynamischer Austausch von Substituenten in einem präbiotischen Organokatalysator: Erste Schritte auf dem Weg zu einem evolutionären System
Authors: Closs Anna C. , Bechtel Maximilian , Trapp Oliver 
Published: October 2021

AbstractAlle evolutionsbiologischen Prozesse führen zu einer Veränderung der vererbbaren Merkmale über nachfolgende Generationen hinweg. Die in der DNA kodierte genetische Information wird durch Mutation der Basensequenz verändert, selektiert und vererbt. Während dies auf der biologischen Ebene gut verstanden wird, ist eine evolutionäre Veränderung auf der molekularen Ebene kleiner organischer Moleküle unbekannt, stellt aber eine wichtige Voraussetzung für die Entstehung von Leben dar. In dieser Arbeit stellen wir eine Klasse von präbiotischen Imidazolidin‐4‐thion‐Organokatalysatoren vor, die ihre Zusammensetzung dynamisch ändern können und möglicherweise in der Lage sind, ein evolutionäres System zu bilden. Diese Katalysatoren funktionalisieren ihre Bausteine und passen sich durch Mutation ihrer eigenen Struktur dynamisch an ihre (selbst modifizierte) Umgebung an. Abhängig von den Umgebungsbedingungen zeigen sie eine ausgeprägte und gegensätzliche Selektivität bei ihrer Bildung. Bemerkenswerterweise können die bevorzugt gebildeten Spezies mit unterschiedlichen katalytischen Eigenschaften verbunden sein, die mehrere Wege für den Übergang von abiotischer Materie zu funktionellen Biomolekülen ermöglichen.
Visible Light Induced Brønsted Acid Assisted Pd‐Catalyzed Alkyl Heck Reaction of Diazo Compounds and N‐Tosylhydrazones
Authors: Zhang Ziyan , Kvasovs Nikita , Dubrovina Anastasiia , Gevorgyan Vladimir 
Published: October 2021

AbstractA mild visible light‐induced palladium‐catalyzed alkyl Heck reaction of diazo compounds and N‐tosylhydrazones is reported. A broad range of vinyl arenes and heteroarenes with high functional group tolerance, as well as a range of different diazo compounds, can efficiently undergo this transformation. This method features Brønsted acid‐assisted generation of hybrid palladium C(sp3)‐centered radical intermediate, which allowed for new selective C−H functionalization protocol.
Synthesis of (±)‐Setigerumine I: Biosynthetic Origins of the Elusive Racemic Papaveraceae Isoxazolidine Alkaloids**
Authors: Serna Ana V. , Kürti László , Siitonen Juha H. 
Published: October 2021

AbstractThe biosynthetic origins of the structurally related racemic isoxazolidine Papaveraceae alkaloids Setigerumine I, Dactylicapnosinine and Dactylicapnosine have remained elusive since their original isolation over two decades ago. Herein we report the first biosynthetic hypothesis for their formation and, inspired by it, the first synthesis of (±)‐Setigerumine I with accompanying computational rationale. Based on the results, these isoxazolidine alkaloids arise from racemizing oxidative rearrangements of prominent isoquinoline alkaloids Noscapine and Hydrastine. The key steps featured in this synthesis are a room temperature Cope elimination and a domino oxidation/inverse‐electron demand 1,3‐dipolar cycloaddition of an axially chiral, yet configurationally unstable, intermediate. The work opens this previously inaccessible family of natural products for biological studies.
Enhancement of SNAr reactions by CH3SO3− ionic liquid and organic solvent dimethylformamide as bifunctional organocatalysts: A mechanistic study
Authors: Oh Young‐Ho , Lee Sungyul 
Published: October 2021

AbstractQuantum chemical analysis is presented for the mechanism of SNAr reaction of p‐fluoronitrobenzene and p‐anisidine promoted by [C4C1im][CH3SO3] and by dimethylformamide (DMF), experimentally observed by Welton and co‐workers (Org. Lett. 2007, 9, 5247–5250). We find that [C4C1im]+ assists the detachment of the fluoride leaving group, while [CH3SO3]− supplies partial negative charge to the nucleophile NH2 to enhance the reactivity. We also show the moderate yield (22.1%) in DMF can also be understood by considering the solvent molecule as a bifunctional organocatalyst. The calculated Gibbs free energies of activation are in excellent agreement with the experimental observations.
Tuning Ruthenium Carbene Complexes for Selective P−H Activation through Metal‐Ligand Cooperation
Authors: Feichtner Kai‐Stephan , Scharf Lennart T. , Scherpf Thorsten , Mallick Bert , Boysen Nils , Gessner Viktoria H. 
Published: October 2021

AbstractThe use of iminophosphoryl‐tethered ruthenium carbene complexes to activate secondary phosphine P−H bonds is reported. Complexes of type [(p‐cymene)‐RuC(SO2Ph)(PPh2NR)] (with R = SiMe3 or 4‐C6H4−NO2) were found to exhibit different reactivities depending on the electronics of the applied phosphine and the substituent at the iminophosphoryl moiety. Hence, the electron‐rich silyl‐substituted complex undergoes cyclometallation or shift of the imine moiety after cooperative activation of the P−H bond across the M=C linkage, depending on the electronics of the applied phosphine. Deuteration experiments and computational studies proved that cyclometallation is initiated by the activation process at the M=C bond and triggered by the high electron density at the metal in the phosphido intermediates. Consistently, replacement of the trimethylsilyl (TMS) group by the electron‐withdrawing 4‐nitrophenyl substituent allowed the selective cooperative P−H activation to form stable activation products.
Resound Trial: A phase 2 study of regorafenib in patients with thymoma (type B2‐B3) and thymic carcinoma previously treated with chemotherapy
Authors: Perrino Matteo , De Pas Tommaso , Bozzarelli Silvia , Giordano Laura , De Vincenzo Fabio , Conforti Fabio , Digiacomo Nunzio , Cordua Nadia , D'Antonio Federica , Borea Federica , Santoro Armando , Zucali Paolo Andrea 
Published: October 2021

BackgroundAngiogenesis has an important role in thymic epithelial tumors (TETs). Regorafenib inhibits vascular endothelial growth factor receptors (VEGFRs), platelet‐derived growth factor receptor β (PDGFR‐β), and fibroblast growth factor receptors (FGFRs). This study explored the activity of regorafenib as monotherapy in patients with advanced or recurrent B2‐B3 thymoma (T) and thymic carcinoma (TC) previously treated with platinum‐containing chemotherapy.MethodsA Fleming single‐arm, single‐stage, phase 2 trial to evaluate the activity of regorafenib (160 mg once a day by mouth for 3 weeks on/1 week off) was planned. The study was designed to reject the null hypothesis of an 8‐week progression‐free survival (PFS) rate ≤25% with a type I error of 0.10 and a statistical power of 80% at the alternative hypothesis of an 8‐week PFS rate of ≥50% (≥8 of 19 evaluable patients progression‐free at 2 months).ResultsFrom June 2016 to November 2017, 19 patients were enrolled (11T/8TC). We observed partial response (PR) in 1 patient (1T) (5.3%), stable disease (SD) in 14 patients (9T/5TC) (73.7%), and progressive disease in 2 patients (1T/1TC) (10.5%), with a disease control rate of 78.9%. According to Choi‐criteria, 13 patients (68.4%) achieved PR, and 2 patients SD (10.5%). The median PFS was 9.6 months whereas median overall survival was 33.8 months. The 8‐week PFS rate was 78.9% (15 of 19 patients). Grade 3‐4 treatment‐related adverse events were observed in 10 patients (52.6%).ConclusionsThe primary end point of this study was reached. The high rate of PR (Choi‐criteria) suggests antitumor activity of regorafenib in TETs. On the basis of survival outcomes, the efficacy of regorafenib should be further evaluated in larger studies.
Biologics update: IL‐23 inhibitors
Authors: Hong Julie , Hadeler Edward , Mosca Megan , Chung Mimi , Yeroushalmi Samuel , Hakimi Marwa , Liao Wilson , Bhutani Tina 
Published: October 2021

AbstractIntroductionIL‐23 inhibitors have shown long‐term efficacy and safety for the treatment of moderate‐to‐severe plaque psoriasis in adults. Guselkumab has also been approved to treat psoriatic arthritis while tildrakizumab and risankizumab are currently under investigation for treating psoriatic arthritis. The goal of this paper is to review and highlight the most current benefits and potential adverse events of IL‐23 inhibitors for psoriasis treatment.MethodsA literature search was performed using the MEDLINE (PubMed), Embase, PsycINFO, and Web of Science databases. Only Phase III and Phase IV clinical studies were reviewed for the purpose of this paper.ResultsClinical studies have shown IL‐23 inhibitors demonstrate superior efficacy compared to IL‐12/23 inhibitors and TNF‐a inhibitors. Adverse events with IL‐23 inhibitors are minimal, and the most common side effect is increased risk of infection.ConclusionTildrakizumab, risankizumab, and guselkumab are IL‐23 inhibitors that are approved for the treatment of moderate‐to‐severe psoriasis. Multiple head‐to‐head trials have demonstrated long‐term efficacy and safety of IL‐23 inhibitors, compared to IL‐17 inhibitors, which have demonstrated short‐term efficacy.
Biologics update: IL‐17 inhibitors
Authors: Sheth Samip , Wu Jashin J. , Han George Z. 
Published: October 2021

AbstractIntroductionPsoriasis is an immune‐mediated, multifactorial, systemic disease that has undergone a translational research revolution in the past two decades. As our understanding of the pathogenesis of psoriasis has improved, the interleukin‐17 (IL‐17) pathway has been elucidated as a key driver of chronic inflammation in psoriasis, which contributes to disease onset and progression. Biologic therapies targeting IL‐17 and its receptor have been developed to attenuate the IL‐17 pathway in patients with moderate‐to‐severe plaque psoriasis. This review includes a discussion on the IL‐17 pathway and biologics targeting IL‐17 in clinical trials and practice for the treatment of psoriasis.ObjectivesThe primary objective of this manuscript is to present safety and efficacy data from clinical trials released in 2018–2021 on IL‐17 therapies for the treatment of psoriasis. An update on the IL‐17 pathway will also be presented to inform the therapeutic development of IL‐17 biologics.MethodsReview of randomized controlled trials on the efficacy and safety of current and upcoming IL‐17 biologics via an electronic literature search on PubMed, The Cochrane Library, and ClinicalTrials.gov.ResultsA total of five IL‐17 biologics were included: secukinumab, ixekizumab, broadalumab, ustekinumab, and sonelokimab. The latest clinical trial safety and efficacy data are presented.ConclusionThe introduction of biologic IL‐17 therapies into clinical practice has ushered in a new era of treatment for psoriasis. With a greater understanding of the IL‐17 pathway and new IL‐17 biologics in clinical trials, physicians, and patients will have a greater number of options for more aggressive, targeted management of psoriasis.
Insulin action and secretion independent of traditional risk factors predict new‐onset type 2 diabetes in Iraqi and Swedish born citizens – The MEDIM cohort study
Authors: Pikkemaat Miriam , Larsson Lönn Sara , Bennet Louise 
Published: October 2021

AbstractAimsOur aim was to study the incidence of type 2 diabetes in a population‐based cohort of Swedish and Iraqi born individuals, focussing on traditional risk factors, insulin action, insulin secretion and ethnicity.Materials and MethodsThe cohort consisted of 1164 Iraqi and 693 Swedish‐born citizens. We investigated the association between new‐onset type 2 diabetes and the predictors including lifestyle factors, metabolic risk markers, country of birth, insulin sensitivity and secretion assessed by Matsuda index with Cox regression.ResultsEighty‐nine individuals were diagnosed with type 2 diabetes with a mean follow‐up of 7.5 years. Both lower insulin sensitivity (ISI, HR 0.02 [0.01–0.08]) as well as insulin secretion (CIR, HR 0.13 [0.07–0.24]) at baseline predicted type 2 diabetes onset, independent of traditional risk factors. Our results were not modified by country of birth. Regarding traditional risk factors, WHR (1.05 [1.00–1.09]), blood glucose (3.27 [2.35–4.55]), LDL/HDL (1.46 [1.20–1.78]) and diastolic blood pressure (1.04 [1.00–1.07]) predicted diabetes incidence in the full model.ConclusionsBoth impaired insulin sensitivity index and corrected insulin response predicted type 2 diabetes onset, independent of traditional risk factors. We conclude that insulin secretion and action might be useful additional predictors for type 2 diabetes in populations of European and Middle Eastern ethnicities.
Diverse demographic factors influence apparent juvenile survival in a migratory songbird
Authors: White Emma M. , Perlut Noah G. , Travis Steven E. , Strong Allan M. 
Published: October 2021

AbstractTo better understand the dynamics of avian populations and their role in population trends, we require an in‐depth understanding of the factors influencing the survival of adults and juveniles. However, assessing survival in juveniles is often challenging, especially in small, migratory species where individuals typically disperse from the study area and are not available for recapture in subsequent years. Bobolinks (Dolichonyx oryzivorus) are a long‐distance migrant that exhibits natal philopatry in at least one population, allowing for more comprehensive juvenile survival analyses than in many other long‐distance avian migrants. Using a 17‐yr dataset from two sites representing a Vermont population of Bobolinks, we used Program MARK to assess factors influencing apparent juvenile survival, including factors related to nesting timing, nest attempt number, the philopatric behaviors of relatives, body mass, brood size, and agricultural management scheme. Our top models indicated that nest attempt number and whether or not a nest mate also survived and returned to breed locally were important factors explaining variation in apparent survival in juvenile Bobolinks. Specifically, juveniles from first nest attempts that fledged earlier in the season, with siblings that did not survive and return to breed locally, showed higher apparent survival. Factors such as site and the philopatric behavior of females associated with nests also appeared in top‐ranking models, while factors such as body mass and brood size did not. These results indicate the importance of providing high‐quality breeding habitat to birds early in the season when juvenile survival is greatest and indicate that individuals may be utilizing inbreeding avoidance strategies. These results provide new insight into the ecological and agricultural management factors influencing survival in migratory species that use managed habitats and underscore the importance of integrating juvenile survival data into current management schemes to better support this and other declining species.