bluuebunny/crossref_metadata_2025_split huggingface dataset:
Au–Ag Nanoflower Catalysts with Clean Surfaces for Alcohol Oxidation
Authors: Imura Yoshiro , Akiyama Ryota , Furukawa Shinya , Kan Ryota , Morita‐Imura Clara , Komatsu Takayuki , Kawai Takeshi 
Published: January 2019

AbstractShape‐controlled metal nanocrystals, such as nanowires and nanoflowers, are attractive owing to their potentially novel catalytic properties and bimetallic nanocrystals composed of two distinct metals are expected to act as highly active catalysts. However, their catalytic activities are limited because of the capping agents adsorbed on the metal surfaces, which are necessary for the preparation and dispersion of these nanocrystals in solvents. Therefore, the preparation of bimetallic shape‐controlled noble metal nanocrystals with clean surfaces, devoid of almost all capping agents, are expected to have high catalytic activity. Herein, we report the preparation of bimetallic Au–Ag nanoflowers using melamine as the capping agent. The bimetallic Au–Ag nanoflowers with a clean surface were subsequently obtained by a support and extraction method. The bimetallic nanoflowers with a clean surface were then used for the aerobic oxidation of 1‐phenylethyl alcohol and they exhibited high rates for the formation of acetophenone compared to Au nanoflowers and spherical nanoparticles with almost the same size and Au/Ag ratio. We also show that Au–Ag nanoflowers containing only 1 % Ag (Au99–Ag1NFs) exhibit the highest rate of acetophenone formation among Au–Ag nanoflowers with different Au/Ag ratios owing to an increase in the electron density of the Au atoms that act as active sites for the oxidation of 1‐phenylethyl alcohol.
Removal of Oil Spills through a Self‐Propelled Smart Device
Authors: Ju Guannan , Yang Xiao , Li Lin , Cheng Mengjiao , Shi Feng 
Published: January 2019

AbstractOil/water separation through superhydrophobic/superoleophilic materials has attracted considerable interest over the past decades; however, dealing with oil spills on broad waters through an active way remains a challenge. Herein, we report a self‐propelled smart device driven by the decomposition of hydrogen peroxide that can spontaneously move on the water surface and collect floating oil droplets inside with superhydrophobic and superoleophilic properties. Moreover, the self‐propelled smart device exhibits excellent stability and high efficiency for oil/water separation. We believe this study may provide a promising strategy for fabricating smart aquatic devices that have potential applications in water remediation.
Intramolecular Metal⋅⋅⋅π‐Arene Interactions in Neutral and Cationic Main Group Compounds
Authors: Schwamm Ryan J. , Fitchett Christopher M. , Coles Martyn P. 
Published: January 2019

AbstractThe role of intramolecular metal⋅⋅⋅π‐arene interactions has been investigated in the solid‐state structures of a series of main group compounds supported by the bulky amide ligands, [N(tBuAr≠)(SiR3)]− (tBuAr≠=2,6‐(CHPh2)2‐4‐tBuC6H2, R=Me, Ph). The lithium and potassium amide salts showed different patterns of solvation and demonstrated that the SiPh3 substituent is able to be involved in stabilizing the electrophilic metal. These group 1 metal compounds served as ligand transfer reagents to access a series of bismuth(III) halides. Chloride extraction from Bi(N{tBuAr≠}{SiPh3})Cl2 using AlCl3 afforded the 1:1 salt [Bi(N{tBuAr≠}{SiPh3})Cl][AlCl4]. This was accompanied by a significant rearrangement of the stabilizing π‐arene contacts in the solid‐state. Attempted preparation of the corresponding tetraphenylborate salt resulted in phenyl‐transfer and generation of the neutral Bi(N{tBuAr≠}{SiPh3})(Ph)Cl.
Neutral and Negatively Charged Phosphate Modifications Altering Thermal Stability, Kinetics of Formation and Monovalent Ion Dependence of DNA G‐Quadruplexes
Authors: Su Yongdong , Fujii Hirofumi , Burakova Ekaterina A. , Chelobanov Boris P. , Fujii Masayuki , Stetsenko Dmitry A. , Filichev Vyacheslav V. 
Published: January 2019

AbstractThe effect of phosphate group modifications on formation and properties of G‐quadruplexes (G4s) has not been investigated in detail. Here, we evaluated the structural, thermodynamic and kinetic properties of the parallel G‐quadruplexes formed by oligodeoxynucleotides d(G4T), d(TG4T) and d(TG5T), in which all phosphates were replaced with N‐methanesulfonyl (mesyl) phosphoramidate or phosphoryl guanidine groups resulting in either negatively charged or neutral DNA sequences, respectively. We established that all modified sequences were able to form G‐quadruplexes of parallel topology; however, the presence of modifications led to a decrease in thermal stability relative to unmodified G4s. In contrast to negatively charged G4s, assembly of neutral G4 DNA species was faster in the presence of sodium ions than potassium ions, and was independent of the salt concentration used. Formation of mixed G4s composed of both native and neutral G‐rich strands has been detected using native gel electrophoresis, size‐exclusion chromatography and ESI‐MS. In summary, our results indicate that the phosphate modifications studied are compatible with G‐quadruplex formation, which could be used for the design of biologically active compounds.
Guest Solvent‐dependence of the Nanomechanical Response in Substituted Dihydropyrimidinone Crystals
Authors: Bhandary Subhrajyoti , Rani Gulshan , Mangalampalli S. R. N. Kiran , Rao G. B. Dharma , Ramamurty Upadrasta , Chopra Deepak 
Published: January 2019

AbstractThe nanomechanical responses of two crystalline phases of a dihydropyrimidine analogue (1) were similar irrespective of the presence (or absence) of the guest solvent. In contrast, the mechanical responses of two differently solvated forms of the second related (2) crystals were significantly different. These contrasting behaviors are rationalized in terms of intermolecular interactions and energy distributions.
Feasibility and efficiency of concurrent chemoradiotherapy with a single agent or double agents vs radiotherapy alone for elderly patients with esophageal squamous cell carcinoma: Experience of two centers
Authors: Huang Chunyue , Zhu Yujia , Li Qiwen , Zhang Wenwen , Liu Hui , Zhang Weijun , Hu Yonghong , Yuan Yawei , Liu Mengzhong 
Published: January 2019

AbstractThe incidence of elderly patients with esophageal cancer (OC) is increasing as the population ages. Until now, the treatment strategy in these patients has been unclear. The aim of our study was to assess the efficiency and tolerance of treatment with radiotherapy alone (RT alone), single‐agent‐based concurrent chemoradiotherapy (CCRT‐1), or double‐agent‐based concurrent chemoradiotherapy (CCRT‐2) in elderly patients (≥65 years) with OC. A total of 271 patients with OC aged 65 years or older were included in this study. The median overall survival (OS), median progression‐free survival (PFS), overall response rate (ORR), disease control rate (DCR), and treatment‐related toxicities were assessed. The median OS time for all patients was 23.6 ± 2.3 months, with 2‐year survival rates of 48.0 ± 3.0%. The median PFS time was 13.6 ± 1.3 months with the 2‐year PFS rate was 33.0 ± 4.0%. Among patients who received CCRT‐1, better OS, and PFS were found in patients who received docetaxel than in patients received fluorouracil and platinum. In a subgroup analysis, 118 patients who underwent RT alone had a median OS time of 15.6 ± 1.9 months and median PFS time of 10.4 ± 0.9 months. The median OS time of patients who received CCRT‐1 was 28.8 ± 10.1 months compared with 27.8 ± 2.5 months for the patients treated with CCRT‐2 (P = 0.537). The similar results were observed for median PFS, with 16.5 ± 3.2 months in the CCRT‐1 group and 17.0 ± 2.0 months in the CCRT‐2 group (P = 0.321). Grade ≥3 leukocytopenia and grade ≥2 weight loss during treatment occurred in 40.6% and 17.9% of patients, respectively, in the CCRT‐2 group, which was higher than that observed in the CCRT‐1 group. Our results suggested that CCRT could be considered as an acceptable treatment for elderly patients with OC. The CCRT‐1 group presented with a lower incidence of treatment toxicities but comparable survival outcomes, compared to the CCRT‐2 group. Docetaxel was superior to fluorouracil and platinum in terms of OS.
Tumor‐infiltrating CD8+ T‐cell density is an independent prognostic marker for oral squamous cell carcinoma
Authors: Shimizu Shota , Hiratsuka Hiroyoshi , Koike Kazushige , Tsuchihashi Kei , Sonoda Tomoko , Ogi Kazuhiro , Miyakawa Akira , Kobayashi Junichi , Kaneko Takeshi , Igarashi Tomohiro , Hasegawa Tadashi , Miyazaki Akihiro 
Published: January 2019

AbstractBackgroundThe presence of tumor‐infiltrating lymphocytes (TILs) is associated with improved survival in head and neck squamous cell carcinoma. However, the prognostic value of TILs remains unclear in oral squamous cell carcinoma (OSCC).MethodsWe evaluated the associations between tumor‐infiltrating CD8+ T‐cell density and survival in five distinct compartments in 139 OSCC cases.ResultsThere was a significant association between increased tumor‐infiltrating CD8+ T cells and their distribution. High parenchymal CD8+ T‐cell density at the invading tumor edge was associated with improved overall survival (OS) and disease‐specific survival (DSS; P < 0.01 and P < 0.01, respectively). High stromal CD8+ T‐cell density at the tumor periphery was also associated with improved recurrence‐free survival (RFS; P < 0.01). Cox regression analysis revealed that high stromal CD8+ T‐cell density at the tumor periphery and high parenchymal CD8+ T‐cell density at the invading edge were independent prognostic makers (hazard ratio: 0.38 and 0.19, 95% confidence interval, 0.18‐0.80 and 0.05‐0.72, P = 0.01 and 0.01, respectively) for RFS and OS, respectively.ConclusionsAssessment of CD8+ T cells at the parenchyma of the invading edge and peripheral stroma provides an indicator of tumor recurrence and prognosis.
“Not just another meta‐analysis”: Sources of heterogeneity in psychosocial treatment effect on cancer survival
Authors: Mirosevic Spela , Jo Booil , Kraemer Helena C. , Ershadi Mona , Neri Eric , Spiegel David 
Published: January 2019

AbstractBackgroundCurrently, there are eight meta‐analyses that address the question whether psychosocial intervention can prolong survival with widely disparate conclusions. One reason for inconsistent findings may be the methods by which previous meta‐analyses were conducted.MethodsDatabases were searched to identify valid randomized controlled trials that compared psychosocial intervention with usual care. Hazard ratios (HRs) and their confidence intervals were pooled to estimate the strength of the treatment effect on survival time, and z‐tests were performed to assess possible heterogeneity of effect sizes associated with different patient and treatment characteristics.ResultsTwelve trials involving 2439 cancer patients that met screening criteria were included. The overall effect favored the treatment group with a HR of 0.71 (95% Cl 0.58‐0.88; P = 0.002). An effect size favoring treatment group was observed in studies sampling lower vs higher percentage of married patients’ (NNT = 4.3 vs NNT = 15.4), when Cognitive‐Behavioral Therapy was applied at early vs late cancer stage (NNT = 2.3 vs NNT = −28.6), and among patients’ older vs younger than 50 (NNT = 4.2 vs NNT = −20.5).ConclusionsPsychosocial interventions may have an important effect on survival. Reviewed interventions appear to be more effective in unmarried patients, patients who are older, and those with an early cancer stage who attend CBT. Limitations of previous meta‐analysis are discussed.
The prognostic impact of programmed cell death 1 and its ligand and the correlation with epithelial‐mesenchymal transition in thymic carcinoma
Authors: Funaki Soichiro , Shintani Yasushi , Fukui Eriko , Yamamoto Yoko , Kanzaki Ryu , Ose Naoko , Kanou Takashi , Minami Masato , Mori Eiichi , Okumura Meinoshin 
Published: January 2019

AbstractBackgroundThe significance of epithelial‐mesenchymal transition (EMT) and immune checkpoint proteins in thymic carcinoma remains unknown. We examined the clinical significance of EMT, tumor‐infiltrating lymphocytes expressing the immune checkpoint protein, programmed cell death 1 (PD‐1 + TILs), and the expression of PD‐1 ligand 1 (PD‐L1) in thymic carcinoma (TC). We also investigated the relationships between these immune checkpoint proteins and the EMT status and examined the impact of induction chemotherapy on patients with tumors that express these proteins.MethodsThe relationship between PD‐1 + TILs/PD‐L1 and clinicopathological findings including EMT was investigated by immunohistochemistry (IHC) of surgically resected samples from 43 patients with TC. In 15 patients receiving induction therapy (IT), those factors were compared before and after IT.ResultsWith IHC, 26 cases (60.5%) were positive for PD‐L1, and 19 cases were positive for PD‐1 + TILs (44.2%). The disease‐free survival rate in patients showing EMT and who were PD‐1/PD‐L1 positive was significantly worse compared to negative cases (EMT; P = 0.0095, PD‐1; P = 0.001, PD‐L1; P = 0.0037). We found a significant relationship between PD‐L1 and EMT status (P = 0.01). In patients who received IT, PD‐L1 increased, and the change was strongly correlated with EMT status (P = 0.01).ConclusionEpithelial‐mesenchymal transition, PD‐L1, and PD‐1 + TILs have prognostic impact, and PD‐L1 is correlated with EMT status. PD‐L1 expression after IT was significantly higher compared to before IT and was correlated with the EMT change. Thus, PD‐L1 may be upregulated during EMT, and anti‐PD‐1/PD‐L1 immunotherapy may provide reliable treatment of TC in combination with chemotherapy.
Next‐generation sequencing in precision oncology: Patient understanding and expectations
Authors: Roberts J. Scott , Gornick Michele C. , Le Lan Q. , Bartnik Natalie J. , Zikmund-Fisher Brian J. , Chinnaiyan Arul M. ,   for the MI‐ONCOSEQ Study team
Published: January 2019

AbstractBackgroundImplementation of precision oncology interventions poses several challenges to informed consent and patient education. This study assessed cancer patients’ understanding, expectations, and outcomes regarding participation in research examining the impact of matched tumor and germline sequencing on their clinical care.MethodsA total of 297 patients (mean age: 59 years; 50% female; 96% white) with refractory, metastatic cancer were surveyed, including 217 who completed surveys both before and after undergoing integrated whole exome and transcriptome sequencing as part of a larger clinical research study.ResultsAt baseline, the vast majority of patients expected to receive several potential direct benefits from study participation, including written reports of sequencing findings (88%), greater understanding of the causes of their cancer (74%), and participation in clinical trials for which sequencing results would make them eligible (84%). In most cases, these benefits were not realized by study completion. Despite explanations from study personnel to the contrary, most participants (67%‐76%) presumed that incidental germline sequencing findings relevant to noncancerous health conditions (eg, diabetes) would automatically be disclosed to them. Patients reported low levels of concern about study risks at baseline and low levels of regret about study participation at follow‐up.ConclusionsFindings suggest that cancer patients participating in precision oncology intervention research have largely unfulfilled expectations of direct benefits related to their study participation. Increased focus on patient education to supplement the informed consent process may help manage patients’ expectations regarding the extent and likelihood of benefits received as a result of undergoing genomic sequencing.
Toxicity and Sublethal Effects of Phthalides Analogs to Rhyzopertha dominica
Authors: Farias Elizeu S. , Araújo Tamíris A. , Resende Gabriela C. , Campos Júlia N. D. , Pimentel Mirian F. , Alvarenga Elson S. , Picanço Marcelo C. 
Published: January 2019

AbstractPhthalides and their precursors have demonstrated a large variety of biological activities. Eighteen phthalides were synthesized and tested on the stored grain pest Rhyzopertha dominica. In the screening bioassay, compounds rac‐(2R,2aS,4R,4aS,6aR,6bS,7R)‐7‐bromohexahydro‐2,4‐methano‐1,6‐dioxacyclopenta[cd]pentalen‐5(2H)‐one (15) and rac‐(3R,3aR,4R,7S,7aS)‐3‐(propan‐2‐yloxy)hexahydro‐4,7‐methano‐2‐benzofuran‐1(3H)‐one (17) showed mortality similar to the commercial insecticide, Bifenthrin® (≥90 %). The time (LT50) and dose (LD50) necessary to kill 50 % of the R. dominica population were determined for the most efficacious phthalides 15 and 17. Compound 15 presented the lowest LD50 (1.97 μg g−1), being four times more toxic than Bifenthrin® (LD50=9.11 μg g−1). Both compounds presented an LT50 value equal to 24 h. When applied at a sublethal dose, both phthalides (especially compound 15), reduced the emergence of the first progeny of R. dominica. These findings highlight the potential of phthalides 15 and 17 as precursors for the development of insecticides for R. dominica control.
Prospection of Enzyme Modulators in Aqueous and Ethanolic Extracts of Lippia sidoides Leaves: Genotoxicity, Digestion, Inflammation, and Hemostasis
Authors: Aparecida Braga Mariana , Silva de Abreu Tatiane , Cardoso Trento Marcus Vinicius , Henrique Andrade Machado Gustavo , Lopes Silva Pereira Luciana , Assaid Simão Anderson , Marcussi Silvana 
Published: January 2019

AbstractThe aqueous and ethanolic extracts of Lippia sidoides Cham. were chemically characterized and tested for their action on enzymes involved in processes such as inflammation, blood coagulation, and digestion. Both extracts potentiated the activity of phospholipases A2 present in the venom of Bothrops atrox in 12 % and completely inhibited the hemolysis induced by B. jararacussu and B. moojeni venoms in the proportions between 1 : 0.5 and 1 : 5 (venom/extracts (w/w)). They inhibited the thrombolysis induced by B. moojeni (10 to 25 %), potentiated the thrombolysis induced by the Lachesis muta muta venom (30 to 80 %), prolonged the coagulation time induced by B. moojeni and L. muta muta venoms, and presented antigenotoxic action. Both extracts reduced the activity of α‐glycosidases, the aqueous extract inhibited lipases, and the ethanolic extract inhibited α‐amylases. The results demonstrate the modulatory action of the extracts on proteases, phospholipases, and digestive enzymes. In addition, the rich phenolic composition of these extracts highlights their potential for nutraceutical use.
Chromane Enantiomers from the Flower Buds of Tussilago farfara L. and Assignments of Their Absolute Configurations
Authors: Sun Jia , Yu Jin‐Hai , Zhang Jun‐Sheng , Song Xiu‐Qing , Bao Jie , Zhang Hua 
Published: January 2019

AbstractFourteen chromane derivatives of seven pairs of enantiomers (1–14) have been obtained from the ethanolic extract of the flower buds of Tussilago farfara L. Their structures with absolute configurations have been elucidated by detailed spectroscopic analyses, chemical methods, and particularly comparison of experimental ECD spectra with theoretically computed ones. Biological evaluations revealed that they did not show cytoprotective, antimicrobial, and α‐glucosidase inhibitory activities.
Hidden Specificities in Enzyme Catalysis: Structural Basis of Substrate Structure‐Selectivity Relationship of a Ketoreductase
Authors: Häckh Matthias , Lucas Xavier , Marolt Marija , Leadlay Peter F. , Müller Michael , Günther Stefan , Lüdeke Steffen 
Published: January 2019

AbstractEnzymes often convert both physiological and non‐physiological substrates with high stereoselectivity; yet, for some enzymes, opposite product chirality is observed. A possible explanation is the existence of hidden specificities becoming apparent when non‐physiological substrates confer different substrate–enzyme interactions than the physiological substrate. To test this hypothesis, a series of α‐methylated β‐keto esters were converted with Tyl‐KR1, a ketoreductase from polyketide synthesis in Streptomyces fradiae. The conversions of six substrates with different physicochemical properties exhibited enantioselectivities ranging from 84 % ee for R,R to 84 % ee for S,S, yet high and uniform diastereoselectivity (anti, d.r.>9:1). The exchange of a single atom, namely an oxygen ester instead of a thioester, led to almost complete loss of enantioselectivity (<5 % ee). An additional S,S‐selective binding mode as a hidden specificity in Tyl‐KR1 has been identified through molecular modeling and site‐directed mutagenesis.
Congenital fistula of the fourth branchial arch: Report of case with long‐lasting misdiagnosis
Authors: Stadler Thomas M. , Morand Grégoire B. , Schmid Stephan , Broglie Martina A. 
Published: January 2019

Key Clinical MessageFourth branchial arch anomalies are extremely rare. The anatomic course of the fourth branchial arch fistula usually determines the delay in diagnosis. High clinical suspicion should be given to reoccurring neck infections in infants and young adults. Diagnosis is obtained by direct laryngoscopy.
Cobalt Nanoparticles Embedded in N‐Doped Porous Carbon Derived from Bimetallic Zeolitic Imidazolate Frameworks for One‐Pot Selective Oxidative Depolymerization of Lignin
Authors: Sun Kangkang , Chen Shujie , Zhang Jiawei , Lu Guo‐Ping , Cai Chun 
Published: January 2019

AbstractCobalt nanoparticles embedded in N‐doped porous carbon (Co@CN) were prepared by the pyrolysis of bimetallic zeolitic imidazolate frameworks (BMZIFs) based on ZIF‐8 and ZIF‐67. The catalyst shows excellent catalytic efficiency in one‐pot selective oxidative cleavage of different linkages like β‐O‐4, a‐O‐4 and β‐1 in organosolv lignin and lignin model compounds in the presence of oxygen (ambient pressure) under mild conditions (383 K). Compared with traditional supported catalyst, the catalyst gives a highly hollow structure, which favored the adsorption of substrates and oxygen. The uniform cobalt nanoparticles surrounded by N‐doped graphitic structures and the strong electron transfer from graphitic nitrogen to Co NPs make it hard to be oxidized prior to use and higher catalytic reactivity. Moreover, the catalyst can be easily recovered by magnetic force after the reaction, and reused after reduction for five times without an obvious change in yields.
Manganese‐Catalyzed C−H Olefination Reactions
Authors: Hu Yuanyuan , Wang Congyang 
Published: January 2019

AbstractOlefins are essential building blocks in organic synthesis, the access to which from simple C−H substrates through catalysis of transition metals, in particular the earth's abundant ones meets the requirements of green and sustainable chemistry. Manganese‐catalyzed C−H olefination reactions have emerged as an efficient approach to olefins in recent years, complementary to traditional olefin synthesis. Varieties of alkynes, alkenes, allenes as well as alcohols are successfully applied to the Mn‐catalyzed reactions with C−H substrates, providing multisubstituted olefins bearing varied functional groups. This minireview presents great progresses newly achieved on manganese‐catalyzed C−H olefination reactions.