bluuebunny/crossref_metadata_2025_split huggingface dataset:
Dual‐Band Chiral Nonlinear Metasurface Supported by Quasibound States in the Continuum
Authors: Liu Qing‐Song , Chao Ming‐Hao , Zhang Wen‐Jing , Song Guo‐Feng 
Published: September 2022

AbstractThis paper presents an all‐dielectric chiral metasurface composed of an array of two‐layer distorted square structures with nanoholes. This metasurface can simultaneously generate dual‐band opposite chiral responses, which can be attributed to the bound states in the continuum (BICs) and the distorted chiral structure. By combining the BICs with chirality, a dual‐band chiral nonlinear metasurface and a chiral‐sensing method are proposed. The simulated results show that the third harmonic generation (THG) conversion efficiency can reach the order of 10−4 for two peaks with a peak‐pump intensity of approximately 5.3 GW cm−2 in the near‐infrared region. Moreover, the third‐harmonic circular dichroism for each peak can reach up to 0.99 and ‐0.94, respectively. Furthermore, it is theoretically demonstrated that this metasurface can be used for chiral sensing with high sensitivities. These results provide new insights for linear and nonlinear spin‐dependent applications.
4′‐SCF3‐Labeling Constitutes a Sensitive 19F NMR Probe for Characterization of Interactions in the Minor Groove of DNA
Authors: Li Qiang , Trajkovski Marko , Fan Chaochao , Chen Jialiang , Zhou Yifei , Lu Kuan , Li Hongjun , Su Xuncheng , Xi Zhen , Plavec Janez , Zhou Chuanzheng 
Published: September 2022

AbstractFluorinated nucleotides are invaluable for 19F NMR studies of nucleic acid structure and function. Here, we synthesized 4′‐SCF3‐thymidine (T
) and incorporated it into DNA by means of solid‐phase DNA synthesis. NMR studies showed that the 4′‐SCF3 group exhibited a flexible orientation in the minor groove of DNA duplexes and was well accommodated by various higher order DNA structures. The three magnetically equivalent fluorine atoms in 4′‐SCF3‐DNA constitute an isolated spin system, offering high 19F NMR sensitivity and excellent resolution of the positioning of T
within various secondary and tertiary DNA structures. The high structural adaptability and high sensitivity of T
make it a valuable 19F NMR probe for quantitatively distinguishing diverse DNA structures with single‐nucleotide resolution and for monitoring the dynamics of interactions in the minor groove of double‐stranded DNA.
Maximized Green Photoluminescence in Tb‐Based Metal–Organic Framework via Pressure‐Treated Engineering
Authors: Wang Yixuan , Yang Xinyi , Liu Chuang , Liu Zhaodong , Fang Qianrong , Bai Fuquan , Wang Shiping , Hou Xuyuan , Feng Bingtao , Chen Banglin , Zou Bo 
Published: September 2022

AbstractLanthanide metal–organic frameworks are of great interest in the development of photoluminescence (PL) materials owing to their structural tunability and intrinsic features of lanthanide elements. However, there exists some limitations arising from poor matching with metal ions, thereby exhibiting a weak ligand‐to‐metal energy transfer (LMET) process. Here we demonstrate a pressure‐treated strategy for achieving high PL performance in green‐emitting Tb(BTC)(H2O)6. The PL quantum yield of pressure‐treated sample increased from 50.6 % to 90.4 %. We found that the enhanced hydrogen bonds locked the conjugated configuration formed by two planes of carboxyl group and benzene ring, enabling the promoted intersystem crossing to effectively drive LMET. Moreover, the optimized singlet and triplet states also validated the facilitated LMET process. This work opens the opportunity of structure optimization to improve PL performance in MOFs by pressure‐treated engineering.
Catalytic Multicomponent Synthesis ofC‐Acyl Glycosides by Consecutive Cross‐Electrophile Couplings
Authors: Jiang Yi , Yang Kai , Wei Yi , Wang Quanquan , Li Shi‐Jun , Lan Yu , Koh Ming Joo 
Published: September 2022

AbstractC‐Acyl glycosides are versatile intermediates to natural products and medicinally relevant entities. Conventional cross‐coupling strategies to secure these molecules often relied on two‐component manifolds in which a glycosyl precursor is coupled with an acyl donor (pre‐synthesized or generated in situ) under transition metal or dual catalysis to forge a C−C bond. Here, we disclose a three‐component Ni‐catalyzed reductive regime that facilitates the chemoselective union of glycosyl halides, organoiodides and commercially available isobutyl chloroformate as a CO surrogate. The method tolerates multiple functionalities and the resulting products are obtained in high diastereoselectivities. Theoretical calculations provide a mechanistic rationale for the unexpectedly high chemoselectivity of sequential cross‐electrophile couplings. This approach enables the expeditious assembly of difficult‐to‐synthesizeC‐acyl glycosides, as well as late‐stage keto‐glycosylation of oligopeptides.
Palladium‐Catalyzed Transient Chirality Transfer and Atroposelective C‐H Functionalization to Access Quaternary Stereocenters
Authors: Han Lu‐Lu , Cui Yu‐Ming , Yang Qin , Fang Li‐Lei , Xu Li‐Wen 
Published: September 2022

AbstractAlthough palladium‐catalyzed asymmetric C−H functionalization and Heck reactions represents one of the most important synthetic strategies for the construction of quaternary stereocenters, developing the enantioselective version of PdII‐catalyzed carbopalladation‐initiated cascade reactions still remains a formidable challenge. Herein, an unprecedent enantioselective [3+2] annulation of oxime ethers and alkynes has been developed, providing both spiro and nonspiro indenes bearing all‐carbon quaternary stereocenters in good yields (up to 98 %) with excellent enantioselectivities (up to >99 % ee). This annulation is accomplished by merging the PdII‐catalyzed atroposelective C−H activation/double carbopalladation and the transient axial‐to‐central chirality transfer process, constituting the first successful example of catalytic chirality transfer strategy involving axially chiral styrene intermediate.
Chrom/Photoredox‐dualkatalysierte Synthese von α‐benzylischen Alkoholen, Isochromanonen, 1,2‐Oxyalkoholen und 1,2‐Thioalkoholen
Authors: Dutta Subhabrata , Erchinger Johannes E. , Schäfers Felix , Das Ankita , Daniliuc Constantin G. , Glorius Frank 
Published: September 2022

AbstractIn diesem Artikel wird eine allgemeine Cr/Photoredox‐katalysierte Synthesestrategie für den Zugang zu α‐benzylischen Alkoholen, Isochromanonen, Oxyalkoholen und Thioalkoholen vorgestellt. Da die Alkylierung von Aldehyden eine wichtige C−C‐Bindungsbildungsreaktion darstellt, ermöglicht die Entwicklung kompetenter katalytischer Systeme die Darstellung dekorierter Alkoholmotive. Angesichts der Herausforderungen, die mit der klassischen Organometallchemie verbunden sind, wird hier die Strategie der dualen Katalyse angewandt, um diverse Alkoholmotive auf milde und effiziente Weise zu erzeugen. Die Verschmelzung von Photokatalyse und Chromchemie wurde gewählt, um eine Umgebung von geringer Basizität und damit hoher Chemoselektivität zu schaffen. Mit Alkylsilanen als Kupplungspartner bietet sich ein breites Substratspektrum mit einer ausgezeichneten Toleranz gegenüber funktionellen Gruppen und leichter Skalierbarkeit. Die Anwendung auf biologisch relevante Moleküle und die Produktdiversifizierung unterstützen den synthetischen Nutzen dieser Methode.
Photoresponsive dissipative Makrocyclen unter Verwendung von mit sichtbarem Licht schaltbaren Azobenzolen
Authors: Nieland Esther , Voss Jona , Mix Andreas , Schmidt Bernd M. 
Published: September 2022

AbstractMit sichtbarem Licht lassen sich dynamische, kovalente Iminverbindungen aus dem Gleichgewicht bringen. Wir haben einen fluorierten Azobenzol‐Baustein untersucht, der bei Bestrahlung zuverlässig eine geometrische Isomerie eingeht. Der Baustein wurde in Kombination mit zwei verschiedenen Aminen, Ethylendiamin undR,R‐1,2‐Diaminocyclohexan, verwendet, um eine Bibliothek von Imin‐Makrocyclen zu erstellen. Während mit dem einfachen Amin ein polymerer Zustand und ein definierter schalenförmiger Makrocyclus erhalten werden kann, ermöglicht das chirale Amin den Zugang zu einem großen Netzwerk von Makrocyclen, die sowohl eine Isomerisierung als auch eine Interkonversion zwischen verschiedenen makrocyclischen Spezies durchlaufen, wodurch die Anzahl der an der Cyclo‐Oligomerisierung beteiligten Monomere kontrolliert werden kann. Diese Prozesse wurden mittels1H‐ und19F‐DOSY NMR, MALDI‐MS‐Messungen und UV/Vis‐Spektroskopie untersucht.
Photoresponsive Dissipative Macrocycles Using Visible‐Light‐Switchable Azobenzenes
Authors: Nieland Esther , Voss Jona , Mix Andreas , Schmidt Bernd M. 
Published: September 2022

AbstractVisible light can be used to shift dynamic covalent imine assemblies out of equilibrium. We studied a fluorinated azobenzene building block that reliably undergoes geometric isomerism upon irradiation. The building block was used in combination with two different amines, ethylenediamine andR,R‐1,2‐diaminocyclohexane, to create a library of imine macrocycles. Whereas the simple amine can be used to access a polymeric state and a defined bowl‐shaped macrocycle, the chiral amine gives access to a rich network of macrocycles that undergo both isomerisation as well as interconversion between different macrocyclic species, thereby allowing for control over the number of monomers involved in the cyclo‐oligomerization;1H‐ and19F‐DOSY NMR, MALDI‐MS measurements, and UV/Vis spectroscopy were used to study the processes.
Comparative study of elliptical fin microchannel over oblique micro‐fin heat sinks
Authors: Mahesh Pallikonda , Kumar Kupireddi Kiran , Balasubramanian Karthik , Chandramohan V. P. , Lee Poh Seng , Kong Chui Chee 
Published: September 2022

AbstractIn the present paper, the effect of elliptical fin and its orientation were computationally examined by considering equivalent fin cross‐sectional area and height of oblique fin to enhance thermal performance. A total of seven distinctly oriented elliptical fin microchannel models were developed and analyzed using finite volume method for velocity range of 0.2 to 0.9 m/s at constant heat flux of 65 W/cm2. The results showed that the elliptical fin microchannel model reduced pressure drop significantly and consumed less pumping power than the oblique fin microchannel model. It was also found that the average Nusselt number initially increases with decreasing elliptical fin orientation angle and then it rapidly decreases on further reduction of orientation angle beyond 4°. The optimal performance factor for a 4° elliptical fin was 1.21, with only a 6.5% penalty in wall temperature at Re 436. Furthermore, the maximum pumping power reduction of 41.4% was found for the 4° elliptical fin microchannel model with a 2.3% increase in Nusselt number. Hence, for the same pumping power, the 4° elliptical fin microchannel model performs better than oblique fin microchannel.
Polymerization of Bio‐Derived Conjugated Dienes with Rare‐Earth‐Metal Complexes
Authors: You Fen , Shi Wenyu , Yan Xuyang , Wang Xiaoyu , Shi Xiaochao 
Published: September 2022

AbstractThe reliance of both our life and industry on fossil resource and the alarming accumulation of polymeric materials in the environment have presented huge challenges to sustainable society. Nowadays, utilization of renewable monomers as building blocks for polymeric materials has emerged as a hot topic and increasingly gained attention from chemists. As a class of biomass with abundance and low cost, terpenes are typical hydrocarbon‐rich natural compounds, and some of them, such as myrcene and farnesene, are inherently suitable for coordination polymerization. In this review, we focus on the rare‐earth metal catalyzed highly regio‐ and stereoselective polymerization of bio‐based conjugated dienes, especially the ones from terpene‐derived compounds with or without modifications. This review also discusses the future direction on the modification of these bio‐based conjugated dienes.
Predefined‐time control for Euler–Lagrange systems with model uncertainties and actuator faults
Authors: Wang Wencong , Hou Mingshan , Feng Dan , Liu Bojun 
Published: September 2022

SummaryA novel adaptive predefined‐time tracking control algorithm is proposed for the Euler–Lagrange systems (ELSs) with model uncertainties and actuator faults. Compared with traditional finite‐time and fixed‐time studies, the system output tracking error under the proposed predefined‐time controller converges to a small neighborhood of zero in finite time, whose upper bound is exactly a design parameter in the control algorithm. For the uncertain model, radial‐based function neural network (RBFNN) is utilized to approximate the continuous uncertain dynamics. To deal with the actuator faults, an adaptive control law is involved in the fault‐tolerant controller. In order to achieve the predefined‐time bounded, a novel predefined‐time sliding mode surface is designed. It is proved that the tracking error vector trajectory of closed‐loop system is semi‐globally uniformly ultimately predefined‐time bounded, and the upper bounds of both the system settling time and the corresponding output tracking error can be adjusted with a simple parameter. Simulation examples finally demonstrate the effectiveness of the proposed control algorithm.
Measures of tonic and phasic activity of the locus coeruleus—norepinephrine system in children with autism spectrum disorder: An event‐related potential and pupillometry study
Authors: Kim Yesol , Kadlaskar Girija , Keehn Rebecca McNally , Keehn Brandon 
Published: September 2022

AbstractA growing body of research suggests that locus coeruleus‐norepinephrine (LC‐NE) system may function differently in individuals with autism spectrum disorder (ASD). Understanding the dynamics of both tonic (resting pupil diameter) and phasic (pupil dilation response [PDR] and event‐related potential [ERP]) indices may provide meaningful insights about the nature of LC‐NE function in ASD. Twenty‐four children with ASD and 27 age‐ and nonverbal‐IQ matched typically developing (TD) children completed two experiments: (1) a resting eye‐tracking task to measure tonic pupil diameter, and (2) a three‐stimulus oddball paradigm to measure phasic responsivity using PDR and ERP. Consistent with prior reports, our results indicate that children with ASD exhibit increased tonic (resting pupil diameter) and reduced phasic (PDR and ERP) activity of the LC‐NE system compared to their TD peers. For both groups, decreased phasic responsivity was associated with increased resting pupil diameter. Lastly, tonic and phasic LC‐NE indices were primarily related to measures of attention‐deficit/hyperactivity disorder (ADHD), and not ASD, symptomatology. These findings expand our understanding of neurophysiological differences present in ASD and demonstrate that aberrant LC‐NE activation may be associated with atypical arousal and decreased responsivity to behaviorally‐relevant information in ASD.
Optimal Stein‐type goodness‐of‐fit tests for count data
Authors: Weiß Christian H. , Puig Pedro , Aleksandrov Boris 
Published: September 2022

AbstractCommon count distributions, such as the Poisson (binomial) distribution for unbounded (bounded) counts considered here, can be characterized by appropriate Stein identities. These identities, in turn, might be utilized to define a corresponding goodness‐of‐fit (GoF) test, the test statistic of which involves the computation of weighted means for a user‐selected weight function f. Here, the choice of f should be done with respect to the relevant alternative scenario, as it will have great impact on the GoF‐test's performance. We derive the asymptotics of both the Poisson and binomial Stein‐type GoF‐statistic for general count distributions (we also briefly consider the negative‐binomial case), such that the asymptotic power is easily computed for arbitrary alternatives. This allows for an efficient implementation of optimal Stein tests, that is, which are most powerful within a given class of weight functions. The performance and application of the optimal Stein‐type GoF‐tests is investigated by simulations and several medical data examples.
Increased lncRNA AFAP1‐AS1 expression predicts poor prognosis in gastric cancer: Evidence from published studies and followed up verification
Authors: Duan Fujiao , Li Yilin , Feng Yajing , Niu Guanghui , Chai Junhui , Wang Kaijuan 
Published: September 2022

AbstractAimThe purpose of this study was to clarify the influence of long non‐coding RNA actin fiber‐associated protein‐1 antisense RNA 1 (lncRNA AFAP1‐AS1) on the prognosis of gastric cancer (GC).MethodsBased on meta‐analysis, the association between the expression of AFAP1‐AS1 and the prognosis of GC was estimated. GC tissue and non‐cancer tissues from 136 patients were determined by quantitative real‐time reverse transcription polymerase chain reaction (qRT‐PCR) and verified by Gene Expression Profiling Interactive Analysis (GEPIA). Kaplan–Meier and Cox proportional hazards models were conducted to analyze the correlation between AFAP1‐AS1 expression and GC prognosis.ResultsThe pooled analysis from five studies revealed that the AFAP1‐AS1 expression was significantly associated with GC overall survival (hazard ratio (HR) = 2.49 and 95% confidence interval (95% CI): 2.02–3.08, p  <  0.001). Compared with non‐cancer tissues, AFAP1‐AS1 expression level of GC tissues were significantly upregulated (p  <  0.001), which was confirmed by the results of GEPIA. The area under the receiver‐operating characteristic (ROC) curve was 0.893, and the high expression of AFAP1‐AS1 was correlated with poor prognosis in patients with GC (p = 0.005). Clinical grade (HR = 1.912, 95% CI: 1.246–2.934, p = 0.003), pathologic tumor node metastasis (pTNM) (HR = 2.393, 95% CI: 1.431–4.033, p = 0.001), log odds of positive lymph nodes (LODDS) (HR = 2.910, 95% CI: 1.787–4.793, p  <  0.001) and AFAP1‐AS1 expression (HR = 2.393, 95% CI: 1.869–3.064, p  <   0.001) were independent prognostic factors for GC revealed by multivariate Cox‐regression analysis.ConclusionThis study demonstrated that the AFAP1‐AS1 may be a novel biomarker for the diagnosis and prognosis of GC.
Red Phosphorus/P25 Nanophotosensitizers Coated with Platelet Membrane for Enhancing Cancer Cells Photodynamic Therapy
Authors: Chen Jingying , Liu Jiaxiu , Lin Xitong , Zhu Yukun , Tang Hua , Ye Wanneng , Zhang Shuchao 
Published: September 2022

AbstractPhotodynamic therapy (PDT), which uses targeted photosensitizing drugs, has been regarded as a promising method for cancer therapy. In the present study, photosensitizer red phosphorus modified P25 nanophotosensitizers (P25‐RP) were generated, which were coated with platelet membrane (P25‐RP@PLT) extracted from platelet rich plasma. The biocompatibility of P25‐RP was demonstrated by cell counting kit‐8 (CCK‐8) and optical microscope assay, more than 93 % cells in the concentration of 100 μg/ml of P25‐RP suspension after co‐incubation for 24 h were still kept alive. The antitumor performance of P25‐RP@PLT was evaluated via CCK‐8 assay, flow cytometry and fluorescence staining of live/dead cells. The experiment results showed that P25‐RP@PLT could ablate 55 % malignant tumor cells upon laser irradiation within 5 min, which was 10 % higher than P25‐RP alone against cancer cells. Mechanistically, the cancer cell toxicity of P25‐RP@PLT nanophotosensitizers was attributed to its heterojunction structure that broadens the absorption spectra, whereas PLT membrane coating technology allows for immune escape and selective adhesion capacity to cancer cells. This work provided a novel pathway on the design of novel visible‐light‐driven photosensitizer for cancer therapy.
Immunological Modulation and Control of Parasitaemia by Ayahuasca Compounds: Therapeutic Potential for Chagas's Disease
Authors: Katchborian‐Neto Albert , Santos Mário Ferreira Conceição , Vilas‐Boas Diego Fernandes , dos Santos Elda Gonçalves , Veloso Márcia Paranho , Bueno Paula Carolina Pires , Caldas Ivo Santana , Soares Marisi Gomes , Dias Danielle Ferreira , Chagas‐Paula Daniela Aparecida 
Published: September 2022

AbstractAyahuasca is a psychoactive and psychedelic decoct composed mainly of Banisteriopsis caapi and Psychotria viridis plant species. The beverage is rich in alkaloids and it is ritualistically used by several indigenous communities of South America as a natural medicine. There are also reports in the literature indicating the prophylaxis potential of Ayahuasca alkaloids against internal parasites. In the present study, Ayahuasca exhibited moderate in vitro activity against Trypanosoma cruzi trypomastigotes (IC50 95.78 μg/mL) compared to the reference drug benznidazole (IC50 2.03 μg/mL). The β‐carboline alkaloid harmine (HRE), isolated from B. caapi, was considered active against the trypomastigotes forms (IC50 6.37), and the tryptamine N, N‐dimethyltryptamine (DMT), isolated from P. viridis was also moderately active with IC50 of 21.02 μg/mL. Regarding the in vivo evaluations, no collateral effects were observed. The HRE alone demonstrated the highest trypanocidal activity in a dose‐responsive manner (10 and 100 mg/kg). The Ayahuasca and the association between HRE and DMT worsened the parasitaemia, suggesting a modulation of the immunological response during the T. cruzi infection, especially by increasing total Immunoglobulin (IgG) and IgG1 antibody levels. The in silico molecular docking revealed HRE binding with low energy at two sites of the Trypanothione reductase enzyme (TR), which are absent in humans, and thus considered a promissory target for drug discovery. In conclusion, Ayahuasca compounds seem to not be toxic at the concentrations of the in vivo evaluations and can promote trypanocidal effect in multi targets, including control of parasitaemia, immunological modulation and TR enzymatic inhibition, which might benefit the treatments of patients with Chagas’ disease. Moreover, the present study also provides scientific information to support the prophylactic potential of Ayahuasca against internal parasites.
Chemical Recycling for Plastic Waste: Status and Perspectives
Authors: Maisels Arkadi , Hiller Andreas , Simon Franz‐Georg 
Published: September 2022

AbstractIndustrial‐scale mechanical recycling of plastics has been established for years, but has technical and economic limits. Chemical recycling processes lead back to monomers or to the raw materials, so that in the end new goods can be produced for all areas of application of plastics. The variety of chemical recycling processes is large. The capacities of the plants are still low today. The profitability of the plants is strongly influenced by the price of oil; the profitability limit is currently between 50 and 60 US $ per barrel.
Competitive Options for Bio‐Syngas in High‐Temperature Heat Demand Sectors: Projections until 2050
Authors: Mutlu Özge , Jordan Matthias , Zeng Thomas , Lenz Volker 
Published: September 2022

AbstractGermany aims to accomplish climate neutrality by 2045. Thus, it is important to take actions, especially to decarbonize the industrial heat sector. In this study, competitive options for bio‐syngas as substitute for natural gas in the German industry sectors with high‐temperature heat demand were projected until 2050 by integrating selected gasification technologies into the existing BenOpt (BioENergyOPTimisation) model for energy system modeling. The results showed that the integration of heat production from selected technologies is still not competitive for large‐scale applications, but other existing biomass technologies have the potential to become competitive. Methanation can be a possible option to tailor bio‐syngas quality for specific high‐temperature industrial applications.