bluuebunny/crossref_metadata_2025_split huggingface dataset:
Pentafluoro(aryl)‐λ6‐tellanes and Tetrafluoro(aryl)(trifluoromethyl)‐λ6‐tellanes: From SF5 to the TeF5 and TeF4CF3 Groups
Authors: Bornemann Dustin , Pitts Cody Ross , Ziegler Carmen J. , Pietrasiak Ewa , Trapp Nils , Kueng Sebastian , Santschi Nico , Togni Antonio 
Published: June 2019

AbstractThe TeF5 group is significantly underexplored as a highly fluorinated substituent on an organic framework, despite it being a larger congener of the acclaimed SF5 group. In fact, only one aryl‐TeF5 compound (phenyl‐TeF5) has been reported to date, synthesized using XeF2. Our recently developed mild TCICA/KF approach to oxidative fluorination provides an affordable and scalable alternative to XeF2. Using this method, we report a scope of extensively characterized aryl‐TeF5 compounds, along with the first SC‐XRD data on this compound class. The methodology was also extended to the synthesis and structural study of heretofore unknown aryl‐TeF4CF3 compounds. Additionally, preliminary reactivity studies unveiled some inconsistencies with previous literature regarding phenyl‐TeF5. Although our studies conclude that the arene‐based TeF5 (and TeF4CF3) group is not quite as robust as the SF5 group, we find that the TeF5 group is more stable than previously thought, thus opening a door to explore new applications of this motif.
3D printing of shape memory poly(d,l‐lactide‐co‐trimethylene carbonate) by direct ink writing for shape‐changing structures
Authors: Wan Xue , Wei Hongqiu , Zhang Fenghua , Liu Yanju , Leng Jinsong 
Published: June 2019

ABSTRACTFour‐dimensional (4D) printing of shape memory materials has attracted increasing interests for personalized structures. In this study, a biocompatible poly(d,l‐lactide‐co‐trimethylene carbonate) (PLMC) is utilized to fabricate 4D shape‐changing structures with customized geometries through direct ink writing. The printed objects show shape transformations at different dimensions under thermal programming. The influence of the printing parameters on the properties including rheological, solvent evaporation, and static mechanical behavior are systematically investigated. A printing map is further depicted to achieve high‐quality printing with high viscous ink flowed from micronozzle to construct various structures. The printed structures in one‐dimensional, two‐dimensional, and three‐dimensional (3D) exhibit shape‐changing behavior with fast response around body temperature. The fast responsive time shows potential in the field of surgical suture (4 s), nonwoven fabric (3 s), and self‐expandable stent (35 s). The feasibility of 3D printing of PLMC opens the way for applications in shape‐changing devices with small diameter. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 48177.
Connective Tissue Ultrastructure: A Direct Comparison between Conventional Specimen Preparation and High‐Pressure Freezing/Freeze‐Substitution
Authors: Keene Douglas R. , Tufa Sara F. 
Published: June 2019

ABSTRACTIt is generally agreed within the microscopy community that the quality of ultrastructure within the connective tissue matrix resulting from high‐pressure freezing followed by freeze‐substitution (HPF/FS) far exceeds that gained following the “conventional” preparation method, which includes aqueous fixation, dehydration, and embedding. Exposure to cryogen at high pressure is the only cryopreservation method capable of vitrifying tissue structure to a depth exceeding 200 μm. Cells within connective tissues prepared by HPF/FS are universally larger, filling the commonly seen void at the juncture between cell and matrix. Without significant shrinkage of cells and the coincident extraction of the cytosolic components, well‐resolved organelles are less clustered within an expanded cytosol. Much of the artifact from “conventional” methods occurs as large space filling and also smaller fibril‐associated proteoglycans are extracted during fixation. However, the visualization of some matrix features by electron microscopy is actually dependent on the collapse or extraction of these “masking” components. Herein, we argue that an impression of ultrastructure within commonly studied matrices, in particular skin, is best gained following the evaluation of both conventional preparations and tissue prepared by HPF/FS. Anat Rec, 2019. © 2019 American Association for Anatomy
Stability/activity features of the main enzyme components of rohapect 10L
Authors: Dal Magro Lucas , Kornecki Jakub F. , Klein Manuela P. , Rodrigues Rafael C. , Fernandez‐Lafuente Roberto 
Published: June 2019

AbstractRohapect 10L is an enzyme cocktail commercialized for juice clarification. Here, we characterized the activity and stability of five enzymatic activities present in this cocktail: total pectinase (PE), polygalacturonase (PG), pectin lyase (PL), pectin methyl esterase (PME), and total cellulase (CE) activities. All these enzyme activities have the maximum activity and stability at pH 4, conditions near those found in most fruit juices. However, if the enzymes need to be handled under different conditions (e.g., to immobilize them), their stability becomes extremely low in some cases, just at pH values slightly higher than the optimal one. For example, at pH 10 only CE was reasonably stable at 25°C, while many other enzyme activities were rapidly almost inactivated, even at 4°C. For these cases, different additives were evaluated, and we found that polyethylene glycol was positive or very positive for all enzyme stabilities, allowing keeping reasonable activities after several hours at pH 10 and 25°C. Another additive, that is, dextran, has a small positive effect for PE, PG, and CE, and a very positive effect for PL, albeit significantly destabilizing PME. Thus, the handling and use of this extract requires some care when is performed out of optimal conditions.
Retracted: Long noncoding RNA NORAD is upregulated in epithelial ovarian cancer and its downregulation suppressed cancer cell functions by competing with miR‐155‐5p
Authors: Tong Lingling , Ao Yu , Zhang Hejia , Wang Kun , Wang Yunyun , Ma Qingjie 
Published: June 2019

AbstractPurposeIn the present study, we evaluated the expression and function of human long noncoding RNA (lncRNA) activated by DNA damage (NORAD) in human epithelial ovarian cancer (EOC).MethodsNORAD expression was evaluated by qRT‐PCR in EOC cell lines and in situ EOC clinical samples. Lentivirus‐mediated NORAD downregulation was conducted in OVCAR‐3 and ES‐2 cells, and its effect on cancer cell proliferation, bufalin chemoresistance, cell‐cycle transition in vitro, and xenotransplantation in vivo were examined, respectively. The likelihood of an lncRNA‐microRNA (miRNA) signaling pathway was examined by probing the possible downstream competing target of NORAD, hsa‐miR‐155‐5p. Moreover, hsa‐miR‐155‐5p was knocked down in NORAD‐downregulated EOC cells to functionally evaluate the correlation between NORAD and hsa‐miR‐155‐5p in EOC.ResultsWe found that NORAD was substantially upregulated in both EOC cell lines and human tumors. In OVCAR‐3 and ES‐2 cells, lentivirus‐mediated NORAD downregulation had significant anticancer effects, as it suppressed cell proliferation, decreased bufalin chemoresistance, arrested cell‐cycle transition, and inhibited xenograft growth. Also, hsa‐miR‐155‐5p was confirmed to be the competing target of NORAD in EOC, and its knockdown in OVCAR‐3 and ES‐2 cells reversed the NORAD downregulation‐induced anticancer functions.ConclusionsNORAD is upregulated in EOC. Inhibition of NORAD, possibly through endogenously competing against hsa‐miR‐155‐5p, can be a new tumor‐suppressing strategy in EOC.
Competition Between Intra‐ and Intermolecular Hydrogen Bonding:o‐Anisic Acid⋅⋅⋅Formic Acid Heterodimer
Authors: Macario Alberto , Blanco Susana , Thomas Javix , Xu Yunjie , López Juan Carlos 
Published: June 2019

AbstractFour conformers of the heterodimero‐anisic acid–formic acid, formed in a supersonic expansion, have been probed by Fourier transform microwave spectroscopy. Two of these forms have the typical double intermolecular hydrogen‐bond cyclic structure. The other two show theo‐anisic acid moiety bearing atrans‐COOH arrangement supported by an intramolecular O−H⋅⋅⋅O bond to the neighbor methoxy group. In these conformers, formic acid interacts witho‐anisic acid mainly through an intermolecular O−H⋅⋅⋅O hydrogen bond either to the O−H or to the C=O moieties, reinforced by other weak interactions. Surprisingly, the most abundant conformer in the supersonic expansion is the complex in which theo‐anisic acid is intransarrangement with the formic acid interacting with the O−H group. Such atrans‐COOH arrangement in which the intramolecular hydrogen bond dominates over the usually observed double intermolecular hydrogen bond interaction has never been observed previously in an acid–acid dimer.
Isostructural NiII Metal–Organic Frameworks (MOFs) for Efficient Electrocatalysis of Oxygen Evolution Reaction and for Gas Sorption Properties
Authors: Konavarapu Satyanarayana K. , Ghosh Debanjali , Dey Avishek , Pradhan Debabrata , Biradha Kumar 
Published: June 2019

AbstractDesign and synthesis of stable, active and cost‐effective electrocatalyst for water splitting applications is an emerging area of research, given the depletion of fossil fuels. Herein, two isostructural NiII redox‐active metal–organic frameworks (MOFs) containing flexible tripodal trispyridyl ligand (L) and linear dicarboxylates such as terephthalate (TA) and 2‐aminoterphthalate (H2NTA) are studied for their catalytic activity in oxygen evaluation reaction (OER). The 2D‐layered MOFs form 3D hydrogen bonded frameworks containing one‐dimensional hydrophilic channels that are filled with water molecules. The electrochemical studies reveal that MOFs display an efficient catalytic activity towards oxygen evolution reaction in alkaline conditions with an overpotential as low as 356 mV. Further, these 2D‐MOFs exhibit excellent ability to adsorb water vapor (180–230 cc g−1 at 273 K) and CO2 (33 cc g−1 at 273 K). The presence of hydrophilic functionality in the frameworks was found to significantly enhance the electrocatalytic activity as well as H2O sorption.
Nanoscale Effects in One‐Dimensional Columnar Supramolecular Ferroelectrics
Authors: Anetai Hayato , Sambe Kohei , Takeda Takashi , Hoshino Norihisa , Akutagawa Tomoyuki 
Published: June 2019

AbstractOrganic ferroelectrics have been actively developed with the goal of fabricating environmentally friendly and low‐cost memory devices. The remanent polarization of hydrogen‐bonded organic ferroelectrics approaches that of the inorganic ones. Nanoscale fabrication of organic ferroelectrics is an essential aspect of high‐density memory devices. A pyrene derivative with four tetradecylamide (−CONHC14H29) chains (1) formed an amide‐type N−H⋅⋅⋅O hydrogen‐bonded one‐dimensional (1D) column, which demonstrated ferroelectricity in the discotic hexagonal columnar (Colh) liquid crystalline phase through the inversion of the orientation of the hydrogen‐bonded chains. On the contrary, similar chiral pyrene derivatives bearing 3,7‐dimethyl‐1‐octhylamide chains (S‐2 and R‐2) did not indicate the Colh phase and ferroelectricity. Homogeneous mixed liquid crystals (1)1−x(S‐2)x (i.e., between the ferroelectric 1 and the non‐ferroelectric S‐2) enable the control of the nanoscale aggregation state of the organic ferroelectrics, resulting in a nanoscale effect of the 1D supramolecular ferroelectrics. Ferroelectric mixed liquid crystals (1)1−x(S‐2)x were observed at x≦0.03, where one S‐2 molecule was inserted after every thirty‐three 1 molecule in the mixed liquid crystal (1)33(S‐2). An average (1)34 length of approximately 12 nm was required to maintain the 1D ferroelectricity, which was similar to the nanoscale limit of inorganic ferroelectrics, such as hafnium oxide thin film (≈15 nm).
Tuning Chemical and Physical Properties of Phosphorus Corroles for Advanced Applications
Authors: Chen Qiu‐Cheng , Xiao Zi‐Ye , Fite Shachar , Mizrahi Amir , Fridman Natalia , Zhan Xuan , Keisar Or , Cohen Yair , Gross Zeev 
Published: June 2019

AbstractAlthough the affinity of metallocorroles to axial ligands is quite low, this is not the case when the chelated element is phosphorus. This work is hence focused on the mechanism of ligand exchange of six‐coordinate phosphorus corroles as a tool for affecting their chemical and physical properties. These fundamental investigations allowed for the development of facile methodologies for the synthesis of a large series of complexes and the establishment of several new structure/activity profiles that may be used to understand and predict spectroscopic features and for tailor‐made modification of photophysical and electrochemical properties. This is exemplified by the facile access to complexes with terminal groups that are of large potential for practical applications based on click chemistry, optical imaging, and surface science.
Increased β‐endorphin and autotaxin in patients with prurigo
Authors: Ishikawa Takahiro , Hashimoto Takashi , Munetsugu Takichi , Yokozeki Hiroo , Satoh Takahiro 
Published: June 2019

AbstractObjectivesPrurigo is a treatment‐resistant inflammatory disease of unknown etiology. Persistent and severe itch is a major and important clinical symptom, but pathological mechanisms and/or actual mediators for itch in prurigo remain to be defined.MethodsWe investigated blood levels of β‐endorphin, dynorphin A, and autotaxin in adult patients with prurigo (n = 18), including prurigo nodularis, prurigo chronica multiformis, and other forms. Patients with hemodialysis, hepatic dysfunction, and pregnancy were excluded. Immunofluorescence staining for β‐endorphin and autotaxin in lesional skin was also performed. In addition, β‐endorphin and autotaxin synthesis of cultured epidermal keratinocytes in response to several cytokine stimulation was assessed in vitro.ResultsBlood levels of β‐endorphin were higher in patients with prurigo than in control subjects (n = 20), while dynorphin A levels were comparable in the two groups. Blood autotaxin levels also were increased in patients with prurigo compared to control subjects. On the one hand, epidermal expression of β‐endorphin was increased in skin lesions of prurigo chronica multiformis, but not in prurigo nodularis. On the other hand, enhanced expression of autotaxin was observed in the epidermis in both prurigo nodularis and prurigo chronica multiformis. In vitro studies showed that β‐endorphin‐expressing epidermal keratinocytes increased following stimulation with TNF‐α, interleukin‐31, and/or IFN‐γ. Autotaxin was also detected in the cytoplasm of cultured epidermal keratinocytes. The fraction of autotaxin‐expressing cells increased when stimulated with TNF‐α and/or interleukin‐31.ConclusionsImbalance of opioid receptor signals and/or the autotaxin‐lysophosphatidic acid axis may contribute, at least in part, to the pathogenesis and intractable pruritus in some of the patients with prurigo.
Conservative management of low‐risk prostate cancer among young versus older men in the United States: Trends and outcomes from a novel national database
Authors: Mahal Amandeep R. , Butler Santino , Franco Idalid , Muralidhar Vinayak , Larios Dalia , Pike Luke R. G. , Zhao Shuang G. , Sanford Nina N. , Dess Robert T. , Feng Felix Y. , D’Amico Anthony V. , Spratt Daniel E. , Yu James B. , Nguyen Paul L. , Rebbeck Timothy R. , Mahal Brandon A. 
Published: June 2019

BackgroundManagement for men aged ≤55 years with low‐risk prostate cancer (LRPC) is debated given quality‐of‐life implications with definitive treatment versus the potential missed opportunity for cure with conservative management. The objective of this study was to define rates of conservative management for LRPC and associated short‐term outcomes in young versus older men in the United States.MethodsThe nonpublic Surveillance, Epidemiology, and End Results Prostate with Active Surveillance/Watchful Waiting (AS/WW) Database identified 50,302 men who were diagnosed with LRPC from 2010 through 2015. AS/WW rates in the United States were stratified by age (≤55 vs ≥56 years). Prostate cancer‐specific mortality and overall mortality were defined by initial management type (AS/WW vs definitive treatment [referent]) and age.ResultsAS/WW utilization increased from 8.61% (2010) to 34.56% (2015) among men aged ≤55 years (P for trend <0.001) and from 15.99% to 43.81% among men aged ≥56 years (P for trend <.001). Among patients who had ≤2 positive biopsy cores, AS/WW rates increased from 12.90% to 48.78% for men aged ≤55 years and from 21.85% to 58.01% for men aged ≥56 years. Among patients who had ≥3 positive biopsy cores, AS/WW rates increased from 3.89% to 22.45% for men aged ≤55 years and from 10.05% to 28.49% for men aged ≥56 years (all P for trend <.001). Five‐year prostate cancer‐specific mortality rates were <0.30% across age and initial management type subgroups.ConclusionsAS/WW rates quadrupled for patients aged ≤55 years from 2010 to 2015, with favorable short‐term outcomes. These findings demonstrate the short‐term safety and increasing acceptance of AS/WW for both younger and older patients. However, there are still higher absolute rates of AS/WW in older patients (P < .001), suggesting some national ambivalence toward AS/WW in younger patients.
Phase 2 study of pembrolizumab and circulating biomarkers to predict anticancer response in advanced, unresectable hepatocellular carcinoma
Authors: Feun Lynn G. , Li Ying‐Ying , Wu Chunjing , Wangpaichitr Medhi , Jones Patricia D. , Richman Stephen P. , Madrazo Beatrice , Kwon Deukwoo , Garcia‐Buitrago Monica , Martin Paul , Hosein Peter J. , Savaraj Niramol 
Published: June 2019

BackgroundCheckpoint inhibitors have shown modest activity in patients with advanced hepatocellular carcinoma (HCC). Herein, the authors report a prospective single‐institution clinical/translational phase 2 study of pembrolizumab in patients with advanced HCC and circulating biomarkers closely related to response.MethodsPembrolizumab was administered at a dose of 200 mg intravenously every 3 weeks among patients who may have developed disease progression while receiving, were intolerant of, or refused sorafenib. The circulating levels of cytokines, chemokines, programmed cell death protein 1 (PD‐1), programmed death–ligand 1 (PD‐L1), and PD‐L2 were correlated with response, tumor PD‐L1 expression, and other clinicopathological features.ResultsA total of 29 patients were treated and 28 patients were evaluable for response. The most common laboratory grade 3/4 adverse events were increases in aspartate aminotransferase and/or alanine aminotransferase and serum bilirubin, which for the most part were reversible. In terms of efficacy, one patient achieved a complete response and 8 patients achieved partial responses for an overall response rate of 32%. Four other patients had stable disease. The median progression‐free survival was 4.5 months and the median overall survival was 13 months. Response did not correlate with prior sorafenib therapy, PD‐L1 tumor staining, or a prior history of hepatitis. Correlative studies revealed that high baseline plasma TGF‐β levels (≥200 pg/mL) significantly correlated with poor treatment outcomes after pembrolizumab. Tumor PD‐L1 and plasma PD‐L1/PD‐1 levels were associated with plasma IFN‐γ or IL‐10.ConclusionsPembrolizumab was found to demonstrate activity in patients with advanced HCC. Toxicity generally was tolerable and reversible. A set of immunological markers in blood plasma as well as PD‐L1 staining indicated that baseline TGF‐β could be a predictive biomarker for response to pembrolizumab.
Enhanced data security in MANET using trust‐based Bayesian statistical model with RSSI by AOMDV
Authors: Sadayan Geetha , Ramaiah Karthiyayini 
Published: June 2019

SummaryA Mobile Ad‐hoc Network (MANET) is a form of mobile node which is known for its random movement and communication to other nodes without the need for any infrastructure. The Bayesian statistical model helps a routing protocol in MANET in getting a high mobility trusted node that relies on the outcome of the prediction. Fuzzy logic has been of immense use for trust in the calculation of RSSI value that helps finding a reliable and trusted route from source to destination. This innovative proposal that uses fuzzy logic in AOMDV is referred to as the Fuzzy trust with RSSI in Ad hoc On‐demand Multipath Distance Vector (FT‐AOMDV). It is known for its help in finding a reliable path in mobile Ad Hoc Networks. Simulation was conducted using a NS‐2 network simulator under various scenarios that include varying node speeds and varying malicious nodes for the evaluation of the efficiency of the protocols. Metrics that include delivery ratio, end‐to‐end delay, routing packet overhead, and throughput have been used in the comparison of FT‐AOMDV with AOMDV, TB‐AOMDV1, and TB‐AOMDV2.
Coaxial Electrospinning Formation of Complex Polymer Fibers and their Applications
Authors: Han Daewoo , Steckl Andrew J. 
Published: June 2019

AbstractThe formation of fibers by electrospinning has experienced explosive growth in the past decade, recently reaching 4,000 publications and 1,500 patents per year. This impressive growth of interest is due to the ability to form fibers with a variety of materials, which lend themselves to a large and rapidly expanding set of applications. In particular, coaxial electrospinning, which forms fibers with multiple core−sheath layers from different materials in a single step, enables the combination of properties in a single fiber that are not found in nature in a single material. This article is a detailed review of coaxial electrospinning: basic mechanisms, early history and current status, and an in‐depth discussion of various applications (biomedical, environmental, sensors, energy, catalysis, textiles). We aim to provide readers who are currently involved in certain aspects of coaxial electrospinning research an appreciation of other applications and of current results.
Photocatalytic Oxygenation Reactions Using Water and Dioxygen
Authors: Fukuzumi Shunichi , Lee Yong‐Min , Nam Wonwoo 
Published: June 2019

AbstractWater (H2O) is the most environmentally benign reductant and is oxidized to evolve dioxygen (O2)—the greenest oxidant—in photosystem II. This Minireview focuses on photocatalytic oxygenation of substrates with H2O as an oxygen source and O2 as an oxidant. Metal complexes can be oxidized by two molecules of one‐electron oxidants with H2O to produce high‐valent metal–oxo complexes, which act as active oxidants for oxygenating organic substrates. When an appropriate oxidant is employed for the substrate oxidation, the reduced oxidant can be oxidized by dioxygen to regenerate the oxidant when water and dioxygen are used as an oxygen source and an oxidant, respectively. Photoinduced electron transfer from a substrate (S) to the excited state of complex [(L)MIII]+ produces a substrate radical cation (S.+), accompanied by the regeneration of [(L)MII]. S.+ then reacts with H2O to produce an OH adduct radical that is oxidized by [(L)MIII]+ to yield an oxygenated product (SO), in which the oxygen atom originates from H2O, accompanied by regeneration of [(L)MII]. Photocatalytic oxidation of H2O by O2 to produce H2O2 is combined with the catalytic oxygenation of substrates with H2O2 to produce the oxygenated products, in which the oxygen atom originates from O2 at the beginning but later from water. This Minireview provides a promising strategy for oxygenation of substrates by using H2O as an oxygen source and O2 as the greenest oxidant.
Preface to Special Issue of ChemSusChem: Sustainable Organic Synthesis
Authors: Beller Matthias , Shi Feng , Stahl Shannon S. 
Published: June 2019

AbstractIn this Editorial, Guest Editors Matthias Beller, Feng Shi, and Shannon Stahl introduce the Special Issue of ChemSusChem on Sustainable Organic Synthesis, discussing the importance of advances in the sustainability of synthetic organic processes in both academic and industrial settings, and laying out the scope of the Special Issue.