bluuebunny/crossref_metadata_2025_split huggingface dataset:
Diversifying Nanoparticle Superstructures and Functions Enabled by Translative Templating from Supramolecular Polymerization
Authors: Liu Jiaming , Liu Rongjuan , Li Hui , Zhang Fenghua , Yao Qingyuan , Wei Jingjing , Yang Zhijie 
Published: February 2022

AbstractBiology exploits a transcription–translation approach to deliver structural information from DNA to the protein‐building machines with high precision. Here, we show how the structural information of small synthetic molecules could be used to guide the assembly of inorganic nanoparticles into diversified yet long‐range ordered superstructures, enabling the information transfer across four or five orders of magnitude in length scale. We designed three perylene diimide (PDI) based isomers differing by their site‐specific substitutions of the methyl group, which were able to supramolecularly polymerize into diverse structures. Importantly, coassembly of these PDI isomers with nanoparticles (NPs) could produce diverse long‐range ordered nanoparticle superstructures, including one‐dimensional NPs chains, double helical NPs assemblies and two‐dimensional NPs superlattices. Equally important, we demonstrate that the information originated from small molecules could diversify the functions of the self‐assembled nanocomposites.
Discovery of Two Polymorphs of TiP4N8Synthesized from Binary Nitrides
Authors: Eisenburger Lucien , Weippert Valentin , Paulmann Carsten , Johrendt Dirk , Oeckler Oliver , Schnick Wolfgang 
Published: February 2022

AbstractTiP4N8was obtained from the binary nitrides TiN and P3N5upon addition of NH4F as a mineralizer at 8 GPa and 1400 °C. An intricate interplay of disorder and polymorphism was elucidated by in situ temperature‐dependent single‐crystal X‐ray diffraction, STEM‐HAADF, and the investigation of annealed samples. This revealed two polymorphs, which consist of dense networks of PN4tetrahedra (degree of condensationκ=0.5) and either augmented triangular TiN7prisms or triangular TiN6prisms for α‐ and β‐TiP4N8, respectively. The structures of TiP4N8exhibit body‐centered tetragonal (bct) framework topology. DFT calculations confirm the measured band gaps of α‐ and β‐TiP4N8(1.6–1.8 eV) and predict the thermochemistry of the polymorphs in agreement with the experiments.
Aktivierung eines biomimetischen [FeFe]‐Hydrogenase‐Komplexes für die H2‐Produktion mit sichtbarem Licht**
Authors: Buday Philipp , Kasahara Chizuru , Hofmeister Elisabeth , Kowalczyk Daniel , Farh Micheal K. , Riediger Saskia , Schulz Martin , Wächtler Maria , Furukawa Shunsuke , Saito Masaichi , Ziegenbalg Dirk , Gräfe Stefanie , Bäuerle Peter , Kupfer Stephan , Dietzek‐Ivanšić Benjamin , Weigand Wolfgang 
Published: February 2022

AbstractInspiriert von dem aktiven Zentrum der natürlichen [FeFe]‐Hydrogenasen haben wir eine kompakte und edelmetallfreie Dyade aus Photosensibilisator (PS) und Katalysator (CAT) entwickelt, die bei Bestrahlung mit sichtbarem Licht Wasserstoff generiert.PS‐CATist ein prototypischer [FeFe]‐Hydrogenase‐Modellkomplex, der π‐konjugierte Oligothiophene als Sammeleinheit für Licht nutzt.PS‐CATund seine Wechselwirkung mit dem Opferdonor 1,3‐Dimethyl‐2‐phenylbenzimidazolin wurden mittels stationärer und zeitaufgelöster Spektroskopie untersucht, verbunden mit elektrochemischen Methoden und photokatalytischen Untersuchungen mit sichtbarem Licht. Über EPR‐Spektroskopie während der Photokatalyse (operando) wurde die Bildung einer aktiven [FeIFe0]‐Spezies sichtbar, die, in Übereinstimmung mit theoretischen Berechnungen, mutmaßlich für die effektive Katalyse (TON≈210) verantwortlich ist.
A Dual pH‐ and Light‐Responsive Spiropyran‐Based Surfactant: Investigations on Its Switching Behavior and Remote Control over Emulsion Stability
Authors: Reifarth Martin , Bekir Marek , Bapolisi Alain M. , Titov Evgenii , Nußhardt Fabian , Nowaczyk Julius , Grigoriev Dmitry , Sharma Anjali , Saalfrank Peter , Santer Svetlana , Hartlieb Matthias , Böker Alexander 
Published: February 2022

AbstractA cationic surfactant containing a spiropyran unit is prepared exhibiting a dual‐responsive adjustability of its surface‐active characteristics. The switching mechanism of the system relies on the reversible conversion of the non‐ionic spiropyran (SP) to a zwitterionic merocyanine (MC) and can be controlled by adjusting the pH value and via light, resulting in a pH‐dependent photoactivity: While the compound possesses a pronounced difference in surface activity between both forms under acidic conditions, this behavior is suppressed at a neutral pH level. The underlying switching processes are investigated in detail, and a thermodynamic explanation based on a combination of theoretical and experimental results is provided. This complex stimuli‐responsive behavior enables remote‐control of colloidal systems. To demonstrate its applicability, the surfactant is utilized for the pH‐dependent manipulation of oil‐in‐water emulsions.
On‐Surface Synthesis of [3]Radialenes via [1+1+1] Cycloaddition
Authors: Li Deng‐Yuan , Wang Ying , Hou Xiao‐Yu , Ren Yin‐Ti , Kang Li‐Xia , Xue Fu‐Hua , Zhu Ya‐Cheng , Liu Jian‐Wei , Liu Mengxi , Shi Xing‐Qiang , Qiu Xiaohui , Liu Pei‐Nian 
Published: February 2022

Abstract[3]Radialenes are the smallest carbocyclic structures with unusual topologies and cross‐conjugated π‐electronic structures. Here, we report a novel [1+1+1] cycloaddition reaction for the synthesis of aza[3]radialenes on the Ag(111) surface, where the steric hindrance of the chlorine substituents guides the selective and orientational assembling of the isocyanide precursors. By combining scanning tunneling microscopy, non‐contact atomic force microscopy, and time‐of‐flight secondary ion mass spectrometry, we determined the atomic structure of the produced aza[3]radialenes. Furthermore, two reaction pathways including synergistic and stepwise are proposed based on density functional theory calculations, which reveal the role of the chlorine substituents in the activation of the isocyano groups via electrostatic interaction.
A Metal‐Ion‐Incorporated Mussel‐Inspired Poly(Vinyl Alcohol)‐Based Polymer Coating Offers Improved Antibacterial Activity and Cellular Mechanoresponse Manipulation
Authors: Gao Lingyan , Hou Yong , Wang Haojie , Li Mingjun , Ma Linjie , Chu Zhiqin , Donskyi Ievgen S. , Haag Rainer 
Published: February 2022

AbstractCobalt (CoII) ions have been an attractive candidate for the biomedical modification of orthopedic implants for decades. However, limited research has been performed into how immobilized CoII ions affect the physical properties of implant devices and how these changes regulate cellular behavior. In this study we modified biocompatible poly(vinyl alcohol) with terpyridine and catechol groups (PVA‐TP‐CA) to create a stable surface coating in which bioactive metal ions could be anchored, endowing the coating with improved broad‐spectrum antibacterial activity against Escherichia coli and Staphylococcus aureus, as well as enhanced surface stiffness and cellular mechanoresponse manipulation. Strengthened by the addition of these metal ions, the coating elicited enhanced mechanosensing from adjacent cells, facilitating cell adhesion, spreading, proliferation, and osteogenic differentiation on the surface coating. This dual‐functional PVA‐TP‐CA/Co surface coating offers a promising approach for improving clinical implantation outcomes.
Salt‐Stabilized Silylzinc Pivalates for Nickel‐Catalyzed Carbosilylation of Alkenes
Authors: Wang Jixin , Duan Zhili , Liu Xingchen , Dong Shoucheng , Chen Kaixin , Li Jie 
Published: February 2022

AbstractWe herein report the preparation of solid and salt‐stabilized silylzinc pivalates from the corresponding silyllithium reagents via transmetalation with Zn(OPiv)2. These resulting organosilylzinc pivalates show enhanced air and moisture stability and unique reactivity in the silylative difunctionalization of alkenes. Thus, a practical chelation‐assisted nickel‐catalyzed regioselective alkyl and benzylsilylation of alkenes has been developed, which provides an easy method to access alkyl silanes with broad substrate scope and wide functional group compatibility. Kinetic experiments highlight that the OPiv‐coordination is crucial to improve the reactivity of silylzinc pivalates. Furthermore, late‐stage functionalizations of druglike molecules and versatile modifications of the products illustrate the synthetical utility of this protocol.
Study on adsorption characteristics optimization of vertical radial flow adsorber
Authors: Xu Pan , Wen Jian , Zhao Xin , Wang Simin , Li Ke , Li Yanzhong 
Published: February 2022

AbstractIn view of high energy consumption, poor flow uniformity, and short adsorption period in the actual work of vertical radial flow adsorber, computational fluid dynamics (CFD) technology and multiobjective genetic algorithm (MOGA) are used to optimize its structure. Through response surface analysis, it is found that the main structural parameters affecting adsorber performance are adsorption layer length and central channel diameter. The effect analysis of characteristic structural parameters and the calculation of multiobjective optimization show that the optimized structure has the ratio of horizontal to vertical of adsorption layer about 0.29 and the area ratio of central channel to annular channel about 0.67. Compared with the original structure, the optimized structure is reduced by 9.57% on pressure drop, increased by 0.86% on flow uniformity, and increased by 17.04% on breakthrough time. The data points on the response surface are used to fit the correlation of adsorber performance and the fitting degrees are 99.7% and 99.3%, respectively, which provided a theoretical reference for the optimal design of vertical radial flow adsorber.
Effects of nano‐TiO2 on the structure and properties of composite materials constructed from eggshell powder/poly(butyleneadipate‐co‐terephthalate)
Authors: Xu Dan , Xiong Zhouyi , Xia Changxing , Xiong Hanguo 
Published: February 2022

AbstractIn the present work, the effects of nano‐TiO2 on the properties and structure of eggshell powder/poly(butyleneadipate‐co‐terephthalate) (PBAT) composites were comprehensively explored. The results showed that nano‐TiO2 could promote the tensile strength and water resistance of the composite material, as well as reduce the light transmittance. Nano‐TiO2 reacted with PBAT to form the C‐O‐Ti bonds, resulted in enhanced structure stability of the composite material. Nano‐TiO2 served as the nanoscale filler to improve the internal compatibility of the composites through hydrogen bonds. Besides, the crystallization performance of the polymer system was also altered by nano‐TiO2 incorporation. These changes in structure promoted the thermal stability and surface hydrophobicity. Finally, the antibacterial test was performed, and the nanocomposite material containing nano‐TiO2 exhibited excellent antibacterial properties. This research provides a novel strategy for constructing an eggshell powder/PBAT/nano‐TiO2 nanocomposite biodegradable plastic that could be used for the development of antibacterial materials.
Cerebellar demyelination and neurodegeneration associated with mTORC1 hyperactivity may contribute to the developmental onset of autism‐like neurobehavioral phenotype in a rat model
Authors: Kútna Viera , O'Leary Valerie Bríd , Hoschl Cyril , Ovsepian Saak V. 
Published: February 2022

AbstractThe cerebellum hosts more than half of all neurons of the human brain, with their organized activity playing a key role in coordinating motor functions. Cerebellar activity has also been implicated in the control of speech, communication, and social behavior, which are compromised in autism spectrum disorders (ASD). Despite major research advances, there is a shortage of mechanistic data relating cellular and molecular changes in the cerebellum to autistic behavior. We studied the impact of tuberous sclerosis complex 2 haploinsufficiency (Tsc2+/−) with downstream mTORC1 hyperactivity on cerebellar morphology and cellular organization in 1, 9, and 18 m.o. Eker rats, to determine possible structural correlates of an autism‐like behavioural phenotype in this model. We report a greater developmental expansion of the cerebellar vermis, owing to enlarged white matter and thickened molecular layer. Histochemical and immunofluorescence data suggest age‐related demyelination of central tract of the vermis, as evident from reduced level of myelin‐basic protein in the arbora vitae. We also observed a higher number of astrocytes in Tsc2+/− rats of older age while the number of Purkinje cells (PCs) in these animals was lower than in wild‐type controls. Unlike astrocytes and PCs, Bergmann glia remained unaltered at all ages in both genotypes, while the number of microglia was higher in Tsc2+/− rats of older age. The convergent evidence for a variety of age‐dependent cellular changes in the cerebellum of rats associated with mTORC1 hyperactivity, thus, predicts an array of functional impairments, which may contribute to the developmental onset of an autism‐like behavioral phenotype in this model.Lay SummaryThis study elucidates the impact of constitutive mTORC1 hyperactivity on cerebellar morphology and cellular organization in a rat model of autism and epilepsy. It describes age‐dependent degeneration of Purkinje neurons, with demyelination of central tract as well as activation of microglia, and discusses the implications of these changes for neuro‐behavioral phenotypes. The described changes provide new indications for the putative mechanisms underlying cerebellar impairments with their age‐related onset, which may contribute to the pathobiology of autism, epilepsy, and related disorders.
Large‐Scale Synthesis of Nanostructured Carbon‐Ti4O7 Hollow Particles as Efficient Sulfur Host Materials for Multilayer Lithium‐Sulfur Pouch Cells
Authors: Mei Shilin , Siebert Andreas , Xu Yaolin , Quan Ting , Garcia‐Diez Raul , Bär Marcus , Härtel Paul , Abendroth Thomas , Dörfler Susanne , Kaskel Stefan , Lu Yan 
Published: February 2022

AbstractApplications of advanced cathode materials with well‐designed chemical components and/or optimized nanostructures promoting the sulfur redox kinetics and suppressing the shuttle effect of polysulfides are highly valued. However, in the case of actual lithium‐sulfur (Li−S) batteries under practical working conditions, one long‐term obstacle still exists, which is mainly due to the difficulties in massive synthesis of such nanomaterials with low cost and ease of control on the nanostructure. Herein, we develop a facile synthesis of carbon coated Ti4O7 hollow nanoparticles (C−Ti4O7) using spherical polymer electrolyte brush as soft template, which is scalable via utilizing a minipilot reactor. The C−Ti4O7 hollow nanoparticles provide strong chemical adsorption to polysulfides through the large polar surface and additional physical confinement by rich micro‐ & mesopores and have successfully been employed as an efficient sulfur host for multilayer pouch cells. Besides, the sluggish kinetics of the sulfur and lithium sulfide redox mechanism can be improved by the highly conductive Ti4O7 via catalyzation of the conversion of polysulfides. Consequently, the C−Ti4O7 based pouch cell endows a high discharge capacity of 1003 mAh g−1 at 0.05 C, a high‐capacity retention of 83.7 % after 100 cycles at 0.1 C, and a high Coulombic efficiency of 97.5 % at the 100th cycle. This work proposes an effective approach to transfer the synthesis of hollow Ti4O7 nanoparticles from lab‐ to large‐scale production, paving the way to explore a wide range of advanced nanomaterials for multilayer Li−S pouch cells.
Comparing stimulus equivalence‐based instruction to self‐study of videos to teach examples of sign language to adults
Authors: Longo Angelina , Reeve Kenneth F. , Jennings Adrienne M. , Vladescu Jason C. , Reeve Sharon A. , Colasurdo Christopher R. 
Published: February 2022

AbstractThe current study compared equivalence‐based instruction (EBI) to self‐study of American Sign Language (ASL) videos to teach eight 3‐member classes of signs with 24 college students. Four of the equivalence classes consisted of verbs (i.e., throw, touch, blow, spin) and four classes were object nouns (i.e., truck, dollar, egg, ball). Each class consisted of (a) a picture corresponding to the targeted sign, (b) a video clip depicting the sign's topography, and (c) a printed corresponding word. Pretests and posttests assessed the degree to which participants (a) showed emergence of classes during match‐to‐sample (MTS) tests, (b) could sign both single words and verb‐noun pairs (i.e., speaker tasks), and (c) could comply with signed requests consisting of ASL verb‐noun pairs (i.e., listener tasks). EBI consisted of training the AB relation (picture to video clip) followed by tests of all possible derived relations. The AC relation (picture to printed word) was not trained because it was assumed to be present in the participants' repertoires. Self‐study consisted of viewing video clips of the eight ASL signs simultaneously presented with the printed word. The MTS posttest showed equivalence classes emerged for all participants from both EBI and self‐study groups. In addition, all EBI participants met passing criterion for emitting all single signs, all verb‐noun sign pairs, and they complied with all listener tasks. In contrast, only 4 of 12 participants from the self‐study group emitted the single signs. After re‐exposure to self‐study, most participants then passed all posttests. These results are important because they demonstrate recombinative generalization of ASL signs, which increases the utility of ASL skills.
Engineering Corynebacterium glutamicum for synthesis of poly(3‐hydroxybutyrate) from lignocellulose biomass
Authors: Jin Ci , Li Jing , Huang Zhen , Han Xushen , Bao Jie 
Published: February 2022

AbstractLignocellulose is the only feasible carbohydrates feedstock for commercial scale and carbon neutral production of poly(3‐hydroxybutyrate) (PHB) biopolymer by its great abundance and availability. Microbial cell factories for fermentative PHB synthesis are highly restricted by the growth suppression of inhibitors from lignocellulose pretreatment. This study targeted a potential PHB‐producing cell factory Corynebacterium glutamicum owing to its strong inhibitors tolerance. A systematic metabolic engineering was conducted starting with the stable PHB synthesis pathway construction from glucose and xylose, followed by the enhancement of PHB synthesis on PHA synthase activity and stability, cell morphology modification, and growth factors regulation. The relocation of the PHA synthase on the cell membrane guided by secrete signal peptides and cell membrane display motifs increased the PHB content by 2.4 folds. Excessive nitrogen preferentially promoted the PHB synthesis capacity and resulted in the PHB content increased by 13.3 folds. Modification of the genes responsible for cell division changed the cell morphology but the cell size was not enlarged to a PHB accumulation favorable environment. The metabolic engineering of C. glutamicum resulted in a high fermentative production of PHB using wheat straw as feedstock. This study provided an important microbial cell factory choice for PHB production using lignocellulose feedstock.
UPLC–MS/MS method for the determination of voriconazole plasma concentration from pediatric patients with hematologic tumors: An application toward personalized therapy
Authors: Wen Zhi‐peng , Zhang Hong , Li Qin , Hu Chu‐jiao , Yang Cheng‐li , Fan Xing‐hua , Zheng Zhi‐chang , Li Ming , Tan Lin , Tan Rong , Xia Bin‐yi , Ji Jing , Bai Yang , Yang Yi , Zheng Xiao‐li , Yang Ji‐hong 
Published: February 2022

AbstractUntreated invasive fungal infection is one of the important risk factors affecting the prognosis of pediatric patients with hematologic tumors. Voriconazole (VOR) is the first‐line antifungal drug for the treatment of Aspergillus infections. In order to reduce the risk of adverse drug reactions while producing an ideal antifungal effect, therapeutic drug monitoring was performed to maintain the VOR plasma concentration in a range of 1,000–5,500 ng/ml. In the present study, a reliable, accurate, sensitive and quick ultra‐high performance liquid chromatograph–tandem mass spectrometry (UPLC–MS/MS) method was developed for the determination of the VOR level. Protein precipitation was performed using acetonitrile, and then the chromatographic separation was carried out by UPLC using a C18 column with the gradient mobile phases comprising 0.1% methanoic acid in acetonitrile (A) and 0.1% methanoic acid in water (B). In the selective reaction monitor mode, the mass spectrometric detection was carried out using an TSQ Endura triple quadruple mass spectrometer. The performance of this UPLC–MS/MS method was validated as per the National Medical Products Administration for Bioanalytical Method Validation. Additionally, the plasma concentrations of VOR in pediatric patients with hematologic tumors were detected using this method, and the analyzed results were used for personalized therapy.
Carcinosarcoma is an aggressive subtype of bladder cancer: A population‐based study
Authors: Liu Lin , Zhu Jinglan , Tian Yun 
Published: February 2022

AbstractBackgroundCase reports of bladder carcinosarcoma (BCS) indicate high rates of recurrence and metastasis and poor prognosis. However, the differences in clinicopathologic characteristics and prognosis between BCS and conventional bladder cancer histologies (transitional cell carcinoma [TCC], squamous cell carcinoma [SCC] and adenocarcinoma [AC]) have not been fully clarified in a large study. Therefore, we conducted a large population‐based study to further investigate these differences.Patients and methodsInformation on patients with BCS and conventional bladder cancer (TCC, SCC or AC) was extracted from the Surveillance, Epidemiology, and End Results database. Categorical variables were compared using Pearson's chi‐squared test or Fisher's exact test. Survival analysis was carried out using the Kaplan–Meier method, and differences in survival were assessed using the log‐rank test. Propensity score matching analysis was conducted to calibrate the differences between the baseline characteristics, after which Cox regression analysis was applied to calculate the hazard ratios and 95% confidence intervals of BCS compared to other subtypes. Subgroup analysis and related interaction were tested to evaluate the consistency and heterogeneity of results.ResultsWe enrolled 152 patients with BCS and 180,196 patients with TCC, SCC or AC. Our results showed that BCS was associated with poor differentiation, advanced stage and an unfavourable overall survival and cancer‐specific survival. BCS had a worse prognosis than TCC and AC, but no statistically significant difference in survival was noted between BCS and SCC.ConclusionsBCS is a more aggressive bladder cancer than TCC and AC but is comparable to SCC. These findings broaden our understanding of BCS and may be helpful in clinical practice.
Accelerated silicosis and silico‐tuberculosis: A difficult diagnosis
Authors: Khemakhem Rim , Moussa Nedia , Kotti Amina , Feki Wiem , Mnif Zeineb , Feki Walid , Kammoun Samy 
Published: February 2022

AbstractIt is well established that exposure to respirable crystalline silica is associated with higher mortality. Such exposures are associated with an increased risk of silico‐tuberculosis, silicosis, and other respiratory morbidities. We report two cases of accelerated silicosis, complicated with pulmonary tuberculosis and pulmonary infection.