bluuebunny/crossref_metadata_2025_split huggingface dataset:
Treatment modalities in sinonasal undifferentiated carcinoma: an analysis from the national cancer database
Authors: Khan Mohemmed N. , Konuthula Neeraja , Parasher Arjun , Genden Eric M. , Miles Brett A. , Govindaraj Satish , Iloreta Alfred M. 
Published: October 2016

BackgroundSinonasal undifferentiated carcinoma (SNUC) is a rare, aggressive malignancy of unknown etiology with a poor overall prognosis. Its relative rarity has made it difficult to determine the impact of different treatment modalities on survival.MethodsRetrospective study of cases in the National Cancer Data Base (NCDB). NCDB cases that were diagnosed as having SNUC between January 1, 2004, and December 31, 2013 were included in the analysis. Outcomes of patients treated with surgery followed adjuvant chemoradiotherapy were compared with definitive chemoradiotherapy.Results A 5‐year survival rate of 42.2% was observed in the 460 patients in the analysis. American Joint Committee on Cancer (AJCC) clinical staging data were available for 304 patients. Of these patients, 60.2% had advanced tumors (AJCC stage 3 or 4). Surgery followed by adjuvant chemoradiotherapy was associated with better survival than definitive chemoradiotherapy (55.8% vs 42.6%, p = 0.007) in the study population. However, in late‐stage tumors, there was no difference in survival between the 2 treatment groups (p = 0.22). For late‐stage tumors, the time to initiation of adjuvant therapy was 49.2 ± 5.1 days for the surgery plus adjuvant therapy group as compared with 25.9 ± 2.6 days in the definitive chemoradiotherapy group (p < 0.0001), yet this did not appear to affect outcomes. No differences in age, gender, race, Charlson‐Deyo score, facility type (academic vs nonacademic), or radiation dose were found between the 2 treatment groups (p > 0.05). Margin status played a critical role in the success of surgical resection, as no patients with positive margin status receiving adjuvant therapy survived to 5 years.ConclusionSurgery may play a role in a multimodality approach to treatment of late‐stage SNUC if the tumor is amenable to surgical resection and negative margins can be reliably obtained. However, in cases where there may be difficulty obtaining negative margins, or this is considered unlikely preoperatively, surgical resection does not appear to provide any additional survival benefit.
Die Erschließung von Wirkstoffmetaboliten durch übergangsmetallkatalysierte C‐H‐Oxidation: die Leber als Inspiration für die Synthese
Authors: Genovino Julien , Sames Dalibor , Hamann Lawrence G. , Touré B. Barry 
Published: October 2016

AbstractKönnen klassische und moderne C‐H‐Oxidationsreaktionen Biotransformationen bei der Synthese von Wirkstoffmetaboliten ergänzen? Wir haben versucht, bei einer Durchsicht der Literatur eine Antwort auf diese wichtige Frage für die Praxis der pharmazeutischen Industrie zu finden. Solche Metaboliten werden während aller Phasen der Wirkstoffsuche und ‐entwicklung benötigt; ihre Synthese ist jedoch noch immer ein ungelöstes Problem. Dieser Aufsatz stellt relevante Anwendungen von chemischen C‐H‐Oxidationen, Elektrochemie und Mikrofluidiktechniken auf Wirkstoff‐Grundgerüste vor, mit denen Metaboliten zugänglich gemacht werden sollen, und fasst vielversprechende Reaktionen für diesen Zweck zusammen. Wo es möglich oder passend ist, wird der Vergleich zur Biotransformation gezogen. So haben wir versucht, bestehende Lücken zu finden, um weitere Aktivitäten auf diesem wichtigen Forschungsfeld anzuspornen.
Synthesis of Highly Selective Submicromolar Microcystin‐Based Inhibitors of Protein Phosphatase (PP)2A over PP1
Authors: Fontanillo Miriam , Zemskov Ivan , Häfner Maximilian , Uhrig Ulrike , Salvi Francesca , Simon Bernd , Wittmann Valentin , Köhn Maja 
Published: October 2016

AbstractResearch and therapeutic targeting of the phosphoserine/threonine phosphatases PP1 and PP2A is hindered by the lack of selective inhibitors. The microcystin (MC) natural toxins target both phosphatases with equal potency, and their complex synthesis has complicated structure–activity relationship studies in the past. We report herein the synthesis and biochemical evaluation of 11 MC analogues, which was accomplished through an efficient strategy combining solid‐ and solution‐phase approaches. Our approach led to the first MC analogue with submicromolar inhibitory potency that is strongly selective for PP2A over PP1 and does not require the complex lipophilic Adda group. Through mutational and structural analyses, we identified a new key element for binding, as well as reasons for the selectivity. This work gives unprecedented insight into how selectivity between these phosphatases can be achieved with MC analogues.
Dynamic Odd–Even Effect in Liquid n‐Alkanes near Their Melting Points
Authors: Yang Ke , Cai Zhikun , Jaiswal Abhishek , Tyagi Madhusudan , Moore Jeffrey S. , Zhang Yang 
Published: October 2016

Abstractn‐Alkanes are the textbook examples of the odd–even effect: The difference in the periodic packing of odd‐ and even‐numbered n‐alkane solids results in odd–even variation of their melting points. However, in the liquid state, in which this packing difference is not obvious, it seems natural to assume that the odd–even effect does not exist, as supported by the monotonic dependence of the boiling points of n‐alkanes on the chain length. Herein, we report a surprising odd–even effect in the translational diffusional dynamic properties of n‐alkanes in their liquid states. To measure the dynamics of the molecules, we performed quasi‐elastic neutron scattering measurements near their melting points. We found that odd‐numbered n‐alkanes exhibit up to 30 times slower dynamics than even‐numbered n‐alkanes near their respective melting points. Our results suggest that, although n‐alkanes are the simplest hydrocarbons, their dynamic properties are extremely sensitive to the number of carbon atoms.
High‐Density Liquid‐Crystalline Polymer Brushes Formed by Surface Segregation and Self‐Assembly
Authors: Mukai Koji , Hara Mitsuo , Nagano Shusaku , Seki Takahiro 
Published: October 2016

AbstractHigh‐density polymer brushes on substrates exhibit unique properties and functions stemming from the extended conformations due to the surface constraint. To date, such chain organizations have been mostly attained by synthetic strategies of surface‐initiated living polymerization. We show herein a new method to prepare a high‐density polymer brush architecture using surface segregation and self‐assembly of diblock copolymers containing a side‐chain liquid‐crystalline polymer (SCLCP). The surface segregation is attained from a film of an amorphous base polymer (polystyrene, PS) containing a minor amount of a SCLCP‐PS diblock copolymer upon annealing above the glass‐transition temperature. The polystyrene portion of the diblock copolymer can work as a laterally mobile anchor for the favorable self‐assembly on the polystyrene base film.
Enantioselective Dearomative [3+2] Cycloaddition Reactions of Benzothiazoles
Authors: Wang Dong‐Chao , Xie Ming‐Sheng , Guo Hai‐Ming , Qu Gui‐Rong , Zhang Meng‐Cheng , You Shu‐Li 
Published: October 2016

AbstractA highly enantioselective dearomative [3+2] cycloaddition of benzothiazole has been successfully developed. A wide range of benzothiazoles and cyclopropane‐1,1‐dicarboxylates are suitable substrates for this reaction. The desired hydropyrrolo[2,1‐b]thiazole compounds were obtained in excellent enantioselectivity and yields (up to 97 % ee and 97 % yield). With the same catalytic system, a highly efficient kinetic resolution of 2‐substituted cyclopropane‐1,1‐dicarboxylates was also realized.
Access to Acyclic Z‐Enediynes by Alkyne Trimerization: Cooperative Bimetallic Catalysis Using Air as the Oxidant
Authors: Lee Jin Tu Danence , Zhao Yu 
Published: October 2016

AbstractPresented herein is a mild, operationally simple, mix‐and‐go procedure for the synthesis of acyclic trisubstituted Z‐enediynes, from readily available terminal alkynes, in good yields. This method stems from a serendipitous discovery, and makes use of cooperative palladium/copper bimetallic catalysis and air as an oxidant to effect an intriguing alkyne trimerization to yield the valuable Z‐enediyne moiety.
Non‐Porous Iron(II)‐Based Sensor: Crystallographic Insights into a Cycle of Colorful Guest‐Induced Topotactic Transformations
Authors: Rodríguez‐Jiménez Santiago , Feltham Humphrey L. C. , Brooker Sally 
Published: October 2016

AbstractMaterials capable of sensing volatile guests at room temperature by an easily monitored set of outputs are of great appeal for development as chemical sensors of small volatile organics and toxic gases. Herein the dinuclear iron(II) complex, [FeII2(L)2(CH3CN)4](BF4)4⋅2 CH3CN (1) [L=4‐(4‐methylphenyl)‐3‐(3‐pyridazinyl)‐5‐pyridyl‐4H‐1,2,4‐triazole], is shown to undergo reversible single‐crystal‐to‐single‐crystal (SCSC) transformations upon exposure to vapors of different guests: 1 (MeCN)⇌2 (EtOH)→3 (H2O)⇌1 (MeCN). Whilst 1 and 2 remain dimetallic, SCSC to 3 involves conversion to a 1D polymeric chain (due to a change in L bridging mode), which, remarkably, can undergo SCSC de‐polymerization, reforming dimetallic 1. Additionally, SC‐XRD studies of two ordered transient forms, 1TF3 and 2TF3, confirm that guest exchange occurs by diffusion of the new guests into the non‐porous lattices as the old guests leave. These reversible SCSC events also induce color and magnetic responses. Indeed dark red 1 is spin crossover active (T1/2↓ 356 K; T1/2↑ 369 K), whilst orange 2 and yellow 3 remain high spin.
Recognition‐Mediated Hydrogel Swelling Controlled by Interaction with a Negative Thermoresponsive LCST Polymer
Authors: Belal Khaled , Stoffelbach François , Lyskawa Joël , Fumagalli Matthieu , Hourdet Dominique , Marcellan Alba , Smet Lieselot De , de la Rosa Victor R. , Cooke Graeme , Hoogenboom Richard , Woisel Patrice 
Published: October 2016

AbstractMost polymeric thermoresponsive hydrogels contract upon heating beyond the lower critical solution temperature (LCST) of the polymers used. Herein, we report a supramolecular hydrogel system that shows the opposite temperature dependence. When the non‐thermosesponsive hydrogel NaphtGel, containing dialkoxynaphthalene guest molecules, becomes complexed with the tetra cationic macrocyclic host CBPQT4+, swelling occurred as a result of host–guest complex formation leading to charge repulsion between the host units, as well as an osmotic contribution of chloride counter‐ions embedded in the network. The immersion of NaphtGel in a solution of poly(N‐isopropylacrylamide) with tetrathiafulvalene (TTF) end groups complexed with CBPQT4+ induced positive thermoresponsive behaviour. The LCST‐induced dethreading of the polymer‐based pseudorotaxane upon heating led to transfer of the CBPQT4+ host and a concomitant swelling of NaphtGel. Subsequent cooling led to reformation of the TTF‐based host–guest complexes in solution and contraction of the hydrogel.
Highly Efficient Cooperative Catalysis by CoIII(Porphyrin) Pairs in Interpenetrating Metal–Organic Frameworks
Authors: Lin Zekai , Zhang Zhi‐Ming , Chen Yu‐Sheng , Lin Wenbin 
Published: October 2016

AbstractA series of porous twofold interpenetrated In‐CoIII(porphyrin) metal–organic frameworks (MOFs) were constructed by in situ metalation of porphyrin bridging ligands and used as efficient cooperative catalysts for the hydration of terminal alkynes. The twofold interpenetrating structure brings adjacent CoIII(porphyrins) in the two networks parallel to each other with a distance of about 8.8 Å, an ideal distance for the simultaneous activation of both substrates in alkyne hydration reactions. As a result, the In‐CoIII(porphyrin) MOFs exhibit much higher (up to 38 times) catalytic activity than either homogeneous catalysts or MOF controls with isolated CoIII(porphyrin) centers, thus highlighting the potential application of MOFs in cooperative catalysis.
Time‐Resolved In Situ X‐ray Diffraction Reveals Metal‐Dependent Metal–Organic Framework Formation
Authors: Wu Yue , Henke Sebastian , Kieslich Gregor , Schwedler Inke , Yang Miaosen , Fraser Duncan A. X. , O'Hare Dermot 
Published: October 2016

AbstractVersatility in metal substitution is one of the key aspects of metal‐organic framework (MOF) chemistry, allowing properties to be tuned in a rational way. As a result, it important to understand why MOF syntheses involving different metals arrive at or fail to produce the same topological outcome. Frequently, conditions are tuned by trial‐and‐error to make MOFs with different metal species. We ask: is it possible to adjust synthetic conditions in a systematic way in order to design routes to desired phases? We have used in situ X‐ray powder diffraction to study the solvothermal formation of isostructural M2(bdc)2dabco (M=Zn, Co, Ni) pillared‐paddlewheel MOFs in real time. The metal ion strongly influences both kinetics and intermediates observed, leading in some cases to multiphase reaction profiles of unprecedented complexity. The standard models used for MOF crystallization break down in these cases; we show that a simple kinetic model describes the data and provides important chemical insights on phase selection.
Experimental investigation of the effects of crosslinking processes on the swelling and hygroscopic performances of a poly(vinyl alcohol) membrane
Authors: Gao Ying , Ye Hong , Wang Liwei , Liu Minghou 
Published: October 2016

ABSTRACTPoly(vinyl alcohol) (PVA) membranes crosslinked with L‐malic acid were prepared, and the effects of the heat‐treatment temperature and crosslinker concentration on their swelling and hygroscopic performances were investigated. Both the swelling and hygroscopic performances of the PVA membranes decreased with increasing heat‐treatment temperature; while the former decreased, the latter increased with increasing crosslinker concentration. The PVA membranes were characterized with differential scanning calorimetry (DSC), acid–base titration, and Fourier transform infrared spectrometry. The DSC results indicated that there was freezing and nonfreezing water in the swollen membranes, whereas there was only nonfreezing water in the moistened membranes. In addition, acid–base titration analysis revealed that both increased heat‐treatment temperature and increased crosslinker concentration increased the bilateral ester group levels (crosslinking degree) and decreased the content of freezing water. By contrast, the content of hydrophilic groups decreased and increased with increasing heat‐treatment temperature and crosslinker concentration, respectively; this resulted in decreased and increased levels of nonfreezing water, respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2017,134, 44481.
Catalytically enhanced organic transistors for in vitro toxicology monitoring through hydrogel entrapment of enzymes
Authors: Strakosas Xenofon , Huerta Miriam , Donahue Mary J. , Hama Adel , Pappa Anna‐Maria , Ferro Magali , Ramuz Marc , Rivnay Jonathan , Owens Roisin M. 
Published: October 2016

ABSTRACTThe regulation of cell metabolism is important for cell function and viability. In the presence of toxic compounds or pathogens, cell metabolism can change drastically because of excess stress on the cell. The monitoring of key metabolites, such as glucose and lactate, can provide insight into cellular function and can be used as a tool for toxicology studies. The development of enzymatic sensors based on organic electrochemical transistors (OECTs) was demonstrated in this study through the immobilization of enzymes in a photocrosslinkable hydrogel, which was, in turn, tethered to the platinum‐modified gate of a planar OECT. The resulting sensors exhibited high stability, sensitivity, and selectivity. The sensing of relevant metabolites in complex media collected from live kidney epithelial cells was performed. As a proof of the principle, the monitoring of glucose and lactate was also performed from cells treated with cisplatin, a known nephrotoxicant. The glucose and lactate monitoring show that the metabolism of cells was significantly altered by the presence of cisplatin. These findings support the monitoring of cell metabolism as a good approach for toxicology studies. They also illustrate the need for the development of enzymatic sensors that can be used in situ to monitor cell viability and function. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44483.
Effects of hydrosilyl monomers on the performance of polysiloxane encapsulant/phosphor blend based hybrid white‐light‐emitting diodes
Authors: Chang Chi‐Jung , Lai Chun‐Feng , Chiou Wei‐Yung , Reddy P. Madhusudhana , Su Min‐Ju 
Published: October 2016

ABSTRACTPolysiloxane‐based encapsulants were prepared by a hydrosilylation reaction of methacryl polyhedral oligomeric silsesquioxane and different hydrosilyl monomers. With the wavelength conversion method, white‐light‐emitting diodes (WLEDs) were produced by the application of a thermally cured polysiloxane encapsulant/phosphor composite as a wavelength converter on blue‐light‐emitting InGaN diodes. The color rendering index, the Commission Internationale de l'Éclairage coordinates, correlated the color temperature, and the luminous efficacy of the WLEDs with different encapsulants were evaluated. The effects of the chemical structures of hydrosilyl monomers on the optical, mechanical, and thermal resistance properties of the encapsulants, together with the performance of the WLEDs, were investigated. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44524.
Noise Induced DNA Damage Within the Auditory Nerve
Authors: Guthrie O'neil W. 
Published: October 2016

ABSTRACTAn understanding of the molecular pathology that underlies noise induced neurotoxicity is a prerequisite to the design of targeted therapies. The objective of the current experiment was to determine whether or not DNA damage is part of the pathophysiologic sequela of noise induced neurotoxicity. The experiment consisted of 41 hooded Long‐Evans rats (2 month old males) that were randomized into control and noise exposed groups. Both the control and the noise group followed the same time schedule and therefore started and ended the experiment together. The noise dose consisted of a 6000 Hz noise band at 105 dB SPL. Temporal bones from both groups were harvested, and immunohistochemistry was used to identify neurons with DNA damage. Quantitative morphometric analyses was then employed to determine the level of DNA damage. Neural action potentials were recorded to assess the functional impact of noise induced DNA damage. Immunohistochemical reactions revealed that the noise exposure precipitated DNA damage within the nucleus of auditory neurons. Quantitative morphometry confirmed the noise induced increase in DNA damage levels and the precipitation of DNA damage was associated with a significant loss of nerve sensitivity. Therefore, DNA damage is part of the molecular pathology that drives noise induced neurotoxicity. Anat Rec, 300:520–526, 2017. © 2016 Wiley Periodicals, Inc.
The development of methods for the detection of Salmonella in chickens by a combination of immunomagnetic separation and PCRs
Authors: Dai Fengying , Zhang Miao , Xu Dixin , Yang Yin , Wang Jiaxiao , Li Mingzhen , Du Meihong 
Published: October 2016

AbstractMicro‐ and nanoimmunomagnetic beads (MIMBs and NIMBs) used for immunomagnetic separation (IMS) with PCR were studied for the rapid detection of Salmonella. The capture efficiency of the two different IMBs was evaluated by a conventional plate counting method, and the binding pattern was studied using scanning electron microscopy. The specificity of the IMBs was tested with Salmonella, Shigella flexneri, enterohemorrhagic Escherichia coli O157:H7, and Listeria monocytogenes. By comparing the pre‐enrichment IMS and the IMS enrichment steps with a 5.5‐H enrichment time, this study developed a rapid and sensitive method for the detection of Salmonella in chicken. The method was implemented by IMS enrichment and PCR with MIMBs and NIMBs, with a total analysis time of 8 H. We showed that the method was sensitive based on NIMBs with a detection limit of 10° CFU for Salmonella in 25 g of chicken.
Targeted modification of plant genomes for precision crop breeding
Authors: Hilscher Julia , Bürstmayr Hermann , Stoger Eva 
Published: October 2016

AbstractThe development of gene targeting and gene editing techniques based on programmable site‐directed nucleases (SDNs) has increased the precision of genome modification and made the outcomes more predictable and controllable. These approaches have achieved rapid advances in plant biotechnology, particularly the development of improved crop varieties. Here, we review the range of alterations which have already been implemented in plant genomes, and summarize the reported efficiencies of precise genome modification. Many crop varieties are being developed using SDN technologies and although their regulatory status in the USA is clear there is still a decision pending in the EU. DNA‐free genome editing strategies are briefly discussed because they also present a unique regulatory challenge. The potential applications of genome editing in plant breeding and crop improvement are highlighted by drawing examples from the recent literature.
Identification of peptide sequences that selectively bind to pentaerythritol trinitrate hemisuccinate‐a surrogate of PETN, via phage display technology
Authors: Kubas George , Rees William , Caguiat Jonathan , Asch David , Fagan Diana , Cortes Pedro 
Published: October 2016

AbstractThe present research investigates the identification of amino acid sequences that selectively bind to a pentaerythritol tetranitrate (PETN) explosive surrogate. Through the use of a phage display technique and enzyme‐linked immunosorbent assays (ELISA), a peptide library was tested against pentaerythritol trinitrate hemisuccinate (PETNH), a surrogate of PETN, to screen for those with amino acids having affinity toward the explosive. The results suggest that the library contains peptides selective to PETNH. Following three rounds of panning, clones were picked and tested for specificity toward PETNH. ELISA results from these samples show that each phage clone has some level of selectivity for binding to PETNH. The peptides from these clones have been sequenced and shown to contain certain common amino acid segments among them. This work represents a technological platform for identifying amino‐acid sequences selective toward any bio‐chem analyte of interest.
A parallel stranded G‐quadruplex composed of threose nucleic acid (TNA)
Authors: Liao Jen‐yu , Anosova Irina , Bala Saikat , Van Horn Wade D. , Chaput John C. 
Published: October 2016

AbstractG‐rich sequences can adopt four‐stranded helical structures, called G‐quadruplexes, that self‐assemble around monovalent cations like sodium (Na+) and potassium (K+). Whether similar structures can be formed from xeno‐nucleic acid (XNA) polymers with a shorter backbone repeat unit is an unanswered question with significant implications on the fold space of functional XNA polymers. Here, we examine the potential for TNA (α‐l‐threofuranosyl nucleic acid) to adopt a four‐stranded helical structure based on a planar G‐quartet motif. Using native polyacrylamide gel electrophoresis (PAGE), circular dichroism (CD) and solution‐state nuclear magnetic resonance (NMR) spectroscopy, we show that despite a backbone repeat unit that is one atom shorter than the backbone repeat unit found in DNA and RNA, TNA can self‐assemble into stable G‐quadruplex structures that are similar in thermal stability to equivalent DNA structures. However, unlike DNA, TNA does not appear to discriminate between Na+ and K+ ions, as G‐quadruplex structures form equally well in the presence of either ion. Together, these findings demonstrate that despite a shorter backbone repeat unit, TNA is capable of self‐assembling into stable G‐quadruplex structures.