bluuebunny/crossref_metadata_2025_split huggingface dataset:
Learning From Vitamin B12‐Mediated Reactions: Cobalt(III)−Carbon‐Assisted Catalytic C−H Difluoroacylation of (Hetero)Arenes through Controlled‐Potential Electrolysis
Authors: Hossain Md. Jakir , Ono Toshikazu , Yano Yoshio , Hisaeda Yoshio 
Published: March 2019

AbstractThe synthesis of difluoromethylated (CF2R) (R=H, alkyl/aryl, CO2R, etc.) compounds has received considerable attention in recent years. In this study, the cobalt(III)−carbon‐mediated catalytic C−H difluoroacylation of unactivated arenes and heteroarenes using BrCF2CO2Et is reported. This catalytic cycle is based on a valence change of the cobalt catalyst, a naturally derived vitamin B12 derivative, driven by controlled‐potential electrolysis at −0.8 V vs. Ag/AgCl under visible‐light irradiation in dimethyl sulfoxide. A broad substrate scope is demonstrated, and two compounds were characterized according to their X‐ray crystal structures. Mechanistic studies showed that the reaction proceeds through a radical pathway mediated by homolytic cleavage of the cobalt(III)–carbon bond. A turnover number of more than 100 was observed, owing to the inherent stability of the vitamin B12 framework. This naturally derived catalytic system has potential applications in medicinal chemistry and materials science.
Vibrational Fingerprinting of Defects Sites in Thin Films of Zeolitic Imidazolate Frameworks
Authors: Weckhuysen Bert M. , Öztürk Zafer , Brand Rogier P. , Boereboom Jelle M. , Meirer Florian 
Published: March 2019

AbstractSurface‐mounted metal–organic frameworks (SURMOFs) are crystalline films of MOFs and have garnered a great deal of attention in the past years. So far, thin‐film MOF research has been mainly focused on the synthesis and the exploration of potential applications of these materials, while a detailed understanding of their growth is still lacking. In this report evidence is provided for the inter‐grown nature of surface‐mounted thin films of Zn‐ZIF‐8 (SURZIF‐8; ZIF=zeolitic imidazolate framework). Two distinct SURZIF‐8 thin films have been made through layer‐by‐layer (LBL) growth after applying 20 and 50 LBL cycles. They have been characterized with atomic force microscopy (AFM) and Raman micro‐spectroscopy. A detailed analysis of the Raman mapping data, inter alia using principal component analysis (PCA), revealed the existence of phase boundaries within the 20‐cycle thin film, while the 50‐cycle thin film is chemically more homogeneous. To further analyze these chemical heterogeneities, density functional theory (DFT) calculations were performed of three theoretical models providing spectroscopic fingerprints of the molecular vibrations associated with the Zn‐ZIF‐8 thin films. Based on these calculations and the experimental data distinct vibrational markers indicative for the presence of defects sites were identified.
Polyoxometalate‐Based Photochromic Supramolecular Hydrogels with Highly Ordered Spherical and Cylindrical Micellar Nanostructures
Authors: Sun Na , Wu Aoli , Yu Yang , Gao Xinpei , Zheng Liqiang 
Published: March 2019

AbstractPolyoxometalates (POMs) have attracted much attention in the field of photochromic materials. However, POM‐based photochromic supramolecular hydrogels with high transparency and good photochromic properties are seldom reported. In this work, a homogenous, optically transparent, injectable, and photochromic supramolecular hydrogel was fabricated through the coassembly of ammonium heptamolybdate (Mo7) and an imidazolium‐based zwitterionic amphiphile (3‐(1‐hexadecyl‐3‐imidazolio)propanesulfonate (C16IPS)). The balance between electrostatic attraction and repulsion of Mo7 clusters and zwitterionic amphiphiles enables them to coassemble into a homogenous and transparent supramolecular hydrogel. By adjusting the molar ratio of C16IPS/Mo7, ordered spherical micelle‐based hydrogels and aligned wormlike micelle‐based hydrogels can be obtained. The incorporation of Mo7 into hydrogels endows these hydrogels with excellent photochromic properties. Specifically, after coassembly with C16IPS, the photochromic ability of hydrogels is significantly enhanced compared with that of a pure aqueous solution of Mo7. These hydrogels exhibit great potential applications as photochromic materials for the recording of rewritable information.
A C4N4 Diaminopyrimidine Fluorophore
Authors: Noda Hidetoshi , Asada Yasuko , Maruyama Tatsuro , Takizawa Naoki , Noda Nobuo N. , Shibasaki Masakatsu , Kumagai Naoya 
Published: March 2019

AbstractInvited for the cover of this issue is the group of Masakatsu Shibasaki and Naoya Kumagai at the Institute of Microbial Chemistry (BIKAKEN), Tokyo. The image depicts the C4N4 unit, which harvests photoenergy and radiates a varied palette of lights. Read the full text of the article at 10.1002/chem.201900467.
Gold‐Catalyzed Cyclisation by 1,4‐Dioxidation
Authors: Claus Vanessa , Molinari Lise , Büllmann Simon , Thusek Jean , Rudolph Matthias , Rominger Frank , Hashmi A. Stephen K. 
Published: March 2019

AbstractAmide‐substituted diynes were cyclized in the presence of a cationic gold catalyst and an external nucleophile leading to 1‐indenones and 1‐iminoindenones. The electron‐donating features of the nitrogen atom enable the formation of a reactive ketene iminium ion, which can be trapped by either diphenyl sulfoxide or anthranil as nucleophiles in a subsequent oxidation step, providing substituted inden‐1‐on‐3‐carboxamides.
Development of Novel Amides as Noncovalent Inhibitors of Immunoproteasomes
Authors: Ettari Roberta , Cerchia Carmen , Maiorana Santina , Guccione Manuela , Novellino Ettore , Bitto Alessandra , Grasso Silvana , Lavecchia Antonio , Zappalà Maria 
Published: March 2019

AbstractThe development of immunoproteasome‐selective inhibitors is a promising strategy for treating hematologic malignancies, autoimmune and inflammatory diseases. In this context, we report the design, synthesis, and biological evaluation of a new series of amide derivatives as immunoproteasome inhibitors. Notably, the designed compounds act as noncovalent inhibitors, which might be a promising therapeutic option because of the lack of drawbacks and side effects associated with irreversible inhibition. Among the synthesized compounds, we identified a panel of active inhibitors with Ki values in the low micromolar or sub‐micromolar ranges toward the β5i and/or β1i subunits of immunoproteasomes. One of the active compounds was shown to be the most potent and selective inhibitor with a Ki value of 21 nm against the single β1i subunit. Docking studies allowed us to determine the mode of binding of the molecules in the catalytic site of immunoproteasome subunits.
Automatic mapping of atrial fiber orientations for patient‐specific modeling of cardiac electromechanics using image registration
Authors: Hoermann Julia M. , Pfaller Martin R. , Avena Linda , Bertoglio Cristóbal , Wall Wolfgang A. 
Published: March 2019

AbstractKnowledge of appropriate local fiber architecture is necessary to simulate patient‐specific electromechanics in the human heart. However, it is not yet possible to reliably measure in vivo fiber directions especially in human atria. Thus, we present a method that defines the fiber architecture in arbitrarily shaped atria using image registration and reorientation methods based on atlas atria with fibers predefined from detailed histological observations. Thereby, it is possible to generate detailed fiber families in every new patient‐specific geometry in an automated, time‐efficient process. We demonstrate the good performance of the image registration and fiber definition on 10 differently shaped human atria. Additionally, we show that characteristics of the electrophysiological activation pattern that appear in the atlas atria also appear in the patients' atria. We arrive to analogous conclusions for coupled electro‐mechano‐hemodynamical computations.
Procedures for sensor nodes operation in the secured domain
Authors: Furtak Janusz , Zieliński Zbigniew , Chudzikiewicz Jan 
Published: March 2019

SummaryCurrently, the networks of mobile sensor nodes, which are IoT components, are increasingly a source of data for building situational awareness. Such networks can be a source of data for critical infrastructure systems if, in addition to the timeliness (freshness) of the data, it will also be possible to ensure the reliability of these data. Such requirements are met by a secure domain of sensor nodes, in which all sensor nodes are authenticated, sensitive data is stored in protected resources of sensor nodes, and data exchange in the domain and outside the domain is cryptographically protected. This paper presents the concept of a safe domain of sensor nodes for IoT and describes the data structures necessary to ensure security in the domain and the way of protecting the resources of each node. Particular attention was paid to the procedure of preparing a sensor node for work in a secured domain of sensor nodes.
Cosolvent and Crowding Effects on the Temperature‐ and Pressure‐Dependent Dissociation Process of the α/β‐Tubulin Heterodimer
Authors: Schummel Paul Hendrik , Anders Christian , Jaworek Michel W. , Winter Roland 
Published: March 2019

AbstractTubulin is one of the main components of the cytoskeleton of eukaryotic cells. The formation of microtubules depends strongly on environmental and solution conditions, and has been found to be among the most pressure sensitive processes in vivo. We explored the effects of different types of cosolvents, such as trimethylamine‐N‐oxide (TMAO), sucrose and urea, and crowding agents to mimic cell‐like conditions, on the temperature and pressure stability of the building block of microtubules, i. e. the α/β‐tubulin heterodimer. To this end, fluorescence and FTIR spectroscopy, differential scanning and pressure perturbation calorimetry as well as fluorescence anisotropy and correlation spectroscopies were applied. The pressure and temperature of dissociation of α/β‐tubulin as well as the underlying thermodynamic parameters upon dissociation, such as volume and enthalpy changes, have been determined for the different solution conditions. The temperature and pressure of dissociation of the α/β‐tubulin heterodimer and hence its stability increases dramatically in the presence of TMAO and the nanocrowder sucrose. We show that by adjusting the levels of compatible cosolutes and crowders, cells are able to withstand deteriorating effects of pressure even up to the kbar‐range.
Efficient Visible‐Light‐Driven Hydrogen Generation on g‐C3N4 Coupled with Iron Phosphide
Authors: Sun Zhichao , Fujitsuka Mamoru , Shi Chuan , Zhu Mingshan , Wang Anjie , Majima Tetsuro 
Published: March 2019

AbstractTransition metal phosphides as promising noble metal free cocatalysts are gaining increasing interest for hydrogen generation and other energy conversion reactions. The present study reports a new Fe2P/g‐C3N4 hybrid for efficient photocatalytic hydrogen generation by water splitting under visible light irradiation. The H2 production rate obtained using this system is approximately 15 times higher than that obtained using pure g‐C3N4, and is comparable with that of Pt/g‐C3N4 under the same conditions. According to detailed studies using UV/Vis diffuse reflectance and photoluminescence spectroscopies as well as photoelectrochemical measurements, the reason for the high efficiency of the Fe2P/g‐C3N4 hybrid is due to a highly effective separation and low recombination rate of photogenerated electrons and holes rather than absorption under visible light. The present study reports a promising non‐toxic photocatalyst with low cost and high natural abundance for improving photocatalytic H2 generation.
Photoswitchable Affinity Reagents: Computational Design and Efficient Red‐Light Switching
Authors: Yasuike Nobuo , Blacklock Kristin M. , Lu Huixin , Jaikaran Anna S. I. , McDonald Sherin , Uppalapati Maruti , Khare Sagar D. , Woolley G. Andrew 
Published: March 2019

AbstractPhoto‐controlled affinity reagents seek to provide modular spatiotemporal control of bioactivity by conferring photo‐switchability of function on an affinity reagent scaffold. Herein we used Rosetta‐based computational methods to screen for sites on the Fynomer affinity reagent structure for attachment of photoswitchable cross‐linkers. Both established UV‐based cross‐linkers (azobenzene‐iodoacetamide (IAC)) and an azonium‐based efficient red‐light‐switchable cross‐linker, piperazino‐tetra‐ortho‐methoxy azobenzene (PIP), were then tested experimentally. Several sites compatible with Fynomer function were identified, including sites showing rapid (<10 s) red light (633 nm) modulation of function. Although a range of overall target binding affinities were observed, the degree of photo‐switchability of Fynomer function was generally small (<twofold). Computational models suggest that local flexibility limits the degree of switching seen in these designs.
Expression and role of regulator of G‐protein signaling 5 in squamous cell carcinoma of the tongue
Authors: Abe Yushi , Ogasawara Sachiko , Akiba Jun , Naito Yoshiki , Kondo Reiichiro , Nakamura Ken , Kusukawa Jingo , Yano Hirohisa 
Published: March 2019

AbstractRegulator of G‐protein signaling (RGS) 5 acts as a GTPase‐activating protein to negatively regulate G‐protein signaling. RGS5 is reportedly related to the invasion and metastasis of cancers, such as nonsmall lung cancer and hepatocellular carcinoma. We examined RGS5 expression and its relationship with invasion in squamous cell carcinoma (SCC) of the tongue. For immunohistochemical analysis of RGS5, we used SCC tissues of the tongue obtained from 43 patients. We examined the relationship between RGS5 expression in the deepest point of invasion and clinicopathological features. Because the invasion and metastasis of cancers are related to epithelial‐mesenchymal transition (EMT), we carried out staining for N‐cadherin, vimentin, and E‐cadherin to examine the relationship between EMT and RGS5. RGS5 expression in the deepest point of invasion in SCC of the tongue was observed in 32 cases (75%). Immunohistochemical analysis revealed a significant correlation between RGS5 expression in the aggressive invasion pattern, invasion depth, and lymphovascular invasion. Kaplan–Meier analysis revealed that high RGS5 expression was associated with postoperative early lymph node metastasis. Further, a significant positive correlation was observed between RGS5 and N‐cadherin (P = 0.0003) and vimentin (P < 0.0001). In contrast, E‐cadherin and RGS5 or vimentin were significantly negatively correlated (P < 0.0001–0.005). The findings indicate that RGS5 expression is related to tumor invasion and EMT in SCC of the tongue and that RGS5 may predict postoperative early lymph node metastasis. Therefore, RGS5 may be a useful prognostic biomarker of the surgically resected SCC and a potential target of molecular therapy for treating SCC of the tongue.
Acantholysis may precede elevation of circulating anti‐desmoglein 3 antibody levels in pemphigus vulgaris presenting with desquamative gingivitis
Authors: Endo Hiroyasu , Rees Terry D. , Niwa Hideo , Kuyama Kayo , Oshima Maya , Serizawa Tae , Tanaka Shigeo , Komiya Masamichi , Ito Takanori 
Published: March 2019

AbstractPemphigus vulgaris (PV) is an autoimmune, blistering disease that affects the mucosa and skin. The current theory favors the concept that anti‐desmoglein (Dsg) 3 autoimmunity is the only pathogenic event needed to induce acantholysis. However, a few cases of active PV in the oral cavity had no detectable anti‐Dsg 3 antibody. The aim of this study was to evaluate the differences in clinical and laboratory findings, whether or not the anti‐Dsg 3 antibodies were present. This study was based on a retrospective review of 10 PV cases. The evaluation of the circulating autoantibody titers to Dsg 3 was conducted by using enzyme‐linked immunosorbent assay (ELISA). An index value of 20 or more was used as the cutoff for a positive reaction. Only five of the 10 PV cases had a positive Dsg 3 ELISA. There were no differences in clinical, cytological, histopathological, and direct immunofluorescence findings, whether or not the anti‐Dsg 3 antibodies were present. Of the five patients with a negative reaction at the time of diagnosis, the Dsg 3 ELISA became positive in the follow‐up period in three cases. In the remaining two cases, the Dsg 3 ELISA was consistently negative for 18 months. Dsg 3 ELISA was negative early in some PV cases. Therefore, PV acantholysis may precede the elevation of circulating anti‐Dsg 3 antibody levels. The diagnosis of PV should be considered based on comprehensive clinical, histopathological, and immunofluorescent criteria.
Solar Cells Sensitized with Porphyrin Dyes Containing Oligo(Ethylene Glycol) Units: A High Efficiency Beyond 12 %
Authors: Lu Yunyue , Liu Qingyun , Luo Jiaxin , Wang Bo , Feng Tong , Zhou Xiaoyi , Liu Xinyu , Xie Yongshu 
Published: March 2019

AbstractA series of new porphyrin dyes (XW42–XW44) containing oligo(ethylene glycol) units have been designed and synthesized. Two triethylene glycol units were introduced into the phenothiazine moiety of XW42, whereas diethylene glycol (DEG) and ethylene glycol chains were introduced to afford XW43 and XW44, respectively. Interestingly, the efficiencies of the DSSCs were clearly dependent on the chain lengths. Among the three dyes, XW42 and XW43 exhibited relatively high open‐circuit voltages of 751 and 750 mV, respectively, and XW43 exhibited the highest efficiency of 10.32 % owing to the presence of the DEG chains with suitable lengths and excellent ability to trap Li+. Furthermore, through a combined coadsorption and cosensitization approach, the efficiencies were dramatically enhanced. As a result, a highest efficiency of 12.10 % was obtained for the XW43+chenodeoxycholic acid+PT‐C6 (a metal‐free organic dye) system, which ranks among the highest efficiencies of cells based on the traditional iodine electrolyte.
Can we condition native plants to increase drought tolerance and improve restoration success?
Authors: Valliere Justin M. , Zhang Jacqueline , Sharifi M. Rasoul , Rundel Phillip W. 
Published: March 2019

AbstractA common method in ecological restoration is the transplanting of nursery‐grown seedlings to the field and, with proper resources, this technique can be highly successful. However, stressors such as drought may negatively impact plant performance and restoration success, especially in dryland ecosystems. Furthermore, increasing environmental change may hamper the ability of practitioners to restore native vegetation. A growing body of research suggests that exposing plants to a stressor may improve tolerance to subsequent stress events later in life. We sought to understand if such a phenomenon could be exploited in order to improve plant drought‐tolerance and aid native plant restoration in southern California. In a multi‐phase experiment, we first exposed seedlings of native perennials to episodic drought and then later compared the response of these plants to a second drought event to that of well‐watered controls. We also transplanted replicates of both treatments to a restoration site in the field to test whether exposure to drought as a seedling could improve plant performance. Plant species responded to drought differently, with species exhibiting the full range of positive, neutral, and negative responses to temporal variability in water stress. However, some species appeared to benefit from drought preconditioning, exhibiting greater growth and increased water‐use efficiency compared to well‐watered plants. This suggests that simple applications of stress treatments could improve plant growth and stress tolerance, but the success of this method is likely very species specific. Restoration practitioners should consider conducting pilot studies with target plant species to better understand if this technique could assist in achieving restoration goals.
Optimizing treatment outcomes in adolescents with eating disorders: The potential role of cognitive behavioral therapy
Authors: Craig Mirin , Waine Joanne , Wilson Scott , Waller Glenn 
Published: March 2019

AbstractObjectiveWhile family‐based treatment (FBT) is the leading psychological therapy for adolescents with eating disorders, it is not universally effective or suitable. This study considered the effectiveness of cognitive‐behavioral therapy for eating disorders (CBT‐ED) in adolescent cases where FBT was not fully effective or where it was not applicable to the individual case.MethodA transdiagnostic case series of 54 adolescents with eating disorders (52% with anorexia nervosa; 31% with atypical anorexia nervosa) were offered CBT‐ED following previous treatment using FBT or following FBT being judged inappropriate. Pre‐post outcomes were assessed using standardized measures of eating attitudes and clinical impairment, and weight change was measured for the patients with anorexia nervosa.ResultsThe rate of attrition was similar to that found in other CBT‐ED studies (38.9% of patients who started CBT‐ED; 59.3% of those offered CBT‐ED). The patients showed positive outcomes on all measures, regardless of whether they had previously been treated with FBT. Effect sizes were moderate to large. Severity and duration of the eating disorder were unrelated to outcomes.DiscussionCBT‐ED merits consideration as a second‐line approach for adolescents with eating disorders when FBT has not been effective or could not be applied. There is no evidence that previous failure to benefit from FBT impairs outcome from subsequent CBT‐ED, and severity and duration of the eating disorder did not influence outcome. Treatment matching for adolescents with eating disorders might consider the role of previous treatment outcomes and family availability in determining optimum treatment strategies for individuals.
Postglacial colonization history reflects in the genetic structure of natural populations of Festuca rubra in Europe
Authors: von Cräutlein Maria , Leinonen Päivi H. , Korpelainen Helena , Helander Marjo , Väre Henry , Saikkonen Kari 
Published: March 2019

AbstractWe conducted a large‐scale population genetic survey of genetic diversity of the host grass Festuca rubra s.l., which fitness can be highly dependent on its symbiotic fungus Epichloë festucae, to evaluate genetic variation and population structure across the European range. The 27 studied populations have previously been found to differ in frequencies of occurrence of the symbiotic fungus E. festucae and ploidy levels. As predicted, we found decreased genetic diversity in previously glaciated areas in comparison with nonglaciated regions and discovered three major maternal genetic groups: southern, northeastern, and northwestern Europe. Interestingly, host populations from Greenland were genetically similar to those from the Faroe Islands and Iceland, suggesting gene flow also between those areas. The level of variation among populations within regions is evidently highly dependent on the postglacial colonization history, in particular on the number of independent long‐distance seed colonization events. Yet, also anthropogenic effects may have affected the population structure in F. rubra. We did not observe higher fungal infection rates in grass populations with lower levels of genetic variability. In fact, the fungal infection rates of E. festucae in relation to genetic variability of the host populations varied widely among geographical areas, which indicate differences in population histories due to colonization events and possible costs of systemic fungi in harsh environmental conditions. We found that the plants of different ploidy levels are genetically closely related within geographic areas indicating independent formation of polyploids in different maternal lineages.