bluuebunny/crossref_metadata_2025_split huggingface dataset:
Reactivity and Stability of Glucosinolates and Their Breakdown Products in Foods
Authors: Hanschen Franziska S. , Lamy Evelyn , Schreiner Monika , Rohn Sascha 
Published: August 2014

AbstractThe chemistry of glucosinolates and their behavior during food processing is very complex. Their instability leads to the formation of a bunch of breakdown and reaction products that are very often reactive themselves. Although excessive consumption of cabbage varieties has been thought for long time to have adverse, especially goitrogenic effects, nowadays, epidemiologic studies provide data that there might be beneficial health effects as well. Especially Brassica vegetables, such as broccoli, radish, or cabbage, are rich in these interesting plant metabolites. However, information on the bioactivity of glucosinolates is only valuable when one knows which compounds are formed during processing and subsequent consumption. This review provides a comprehensive, in‐depth overview on the chemical reactivity of different glucosinolates and breakdown products thereof during food preparation.
Metal‐Free CH Bond Activation of Branched Aldehydes with a Hypervalent Iodine(III) Catalyst under Visible‐Light Photolysis: Successful Trapping with Electron‐Deficient Olefins
Authors: Moteki Shin A. , Usui Asuka , Selvakumar Sermadurai , Zhang Tiexin , Maruoka Keiji 
Published: August 2014

AbstractDirect acyl radical formation of linear aldehydes (RCH2‐CHO) and subsequent hydroacylation with electron‐deficient olefins can be effected with various types of metal and nonmetal catalysts/reagents. In marked contrast, however, no successful reports on the use of branched aldehydes have been made thus far because of their strong tendency of generating alkyl radicals through the facile decarbonylation of acyl radicals. Here, use of a hypervalent iodine(III) catalyst under visible light photolysis allows a mild way of generating acyl radicals from various branched aldehydes, thereby giving the corresponding hydroacylated products almost exclusively. Another characteristic feature of this approach is the catalytic use of hypervalent iodine(III) reagent, which is a rare example on the generation of radicals in hypervalent iodine chemistry.
A Multivalent Ligand for the Mannose‐6‐Phosphate Receptor for Endolysosomal Targeting of an Activity‐Based Probe
Authors: Hoogendoorn Sascha , van Puijvelde Gijs H. M. , Kuiper Johan , van der Marel Gijs A. , Overkleeft Herman S. 
Published: August 2014

AbstractThe ubiquitously expressed mannose‐6‐phosphate receptors (MPRs) are a promising class of receptors for targeted compound delivery into the endolysosomal compartments of a variety of cell types. The development of a synthetic, multivalent, mannose‐6‐phosphate (M6P) glycopeptide‐based MPR ligand is described. The conjugation of this ligand to fluorescent DCG‐04, an activity‐based probe for cysteine cathepsins, enabled fluorescent readout of its receptor‐targeting properties. The resulting M6P‐cluster–BODIPY–DCG‐04 probe was shown to efficiently label cathepsins in cell lysates as well as in live cells. Furthermore, the introduction of the 6‐O‐phosphates leads to a completely altered uptake profile in COS and dendritic cells compared to a mannose‐containing ligand. Competition with mannose‐6‐phosphate abolished all uptake of the probe in COS cells, and we conclude that the mannose‐6‐phosphate cluster targets the MPR and ensures the targeted delivery of cargo bound to the cluster into the endolysosomal pathway.
Mild ArI‐Catalyzed C(sp2)H or C(sp3)H Functionalization/CO Formation: An Intriguing Catalyst‐Controlled Selectivity Switch
Authors: Wang Xueqiang , Gallardo‐Donaire Joan , Martin Ruben 
Published: August 2014

AbstractA tandem C(sp2)H and C(sp3)H functionalization/CO bond formation catalyzed by iodine(III) reagents generated in situ has been developed. The method shows wide scope under mild conditions and exhibits an unprecedented selectivity profile that can be switched depending on the catalyst employed.
Comparison of the pomegranate seed oil organogels of carnauba wax and monoglyceride
Authors: Öğütcü Mustafa , Yılmaz Emin 
Published: August 2014

ABSTRACTThe aims of this study were to prepare organogels from pomegranate seed oil (PO) with carnauba wax (CW) and monoglyceride (MG), compare the organogels with a commercial margarine (CM) and evaluate 3 months storage stability. At 3% organogelator addition, no gels were formed, while at 7 and 10% additions, the oil binding capacities increased and were always higher in CW organogels, with crystal formation times of 8.0 to 14.0 min. Solid fat content (SFC) of the CW organogels varied between 2.96 and 8.71% at 20°C, while MG gels had 2.89–9.43%, and CM had 29.73% SFC. The peak melting temperatures of the CW organogels ranged from 74.73 to 75.74°C and MG organogels ranged from 11.09 to 50.63°C, whereas CM product exhibited 45.92°C peak melting temperature. The hardness of CW organogels was higher than that of MG organogels. The organogels showed potential as spreadable products. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41343.
Ultrasonic welding of plasticized PLA films
Authors: Stoehr Neda , Baudrit Benjamin , Haberstroh Edmund , Nase Michael , Heidemeyer Peter , Bastian Martin 
Published: August 2014

ABSTRACTPoly(lactic acid) (PLA) is a commercially available biobased material that has become an ideal material in packaging applications because of its low toxicity along with its environmentally friendly characteristics. Unfortunately, PLA is rigid and brittle. These characteristics impede its wide application. The flexibility of PLA can be improved by plasticization. In addition, welding polymer films is essential in the packaging production. Therefore, the weldability by means of ultrasonic welding of the neat and with polyethylene glycol plasticized PLA films was analyzed in this study. Moreover, the study examines the influence of the material composition on the processing window, that is, the range of welding parameters which could be used to weld films efficiently, and on the weld quality. This research showed that all examined films can be welded by ultrasonic welding. Furthermore, it was discovered that the addition of a plasticizer has a strong influence on the processing window and on the weld quality. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41351.
Nitrogen pollution negatively affects Stratiotes aloides in Central‐Eastern Europe. Implications for translocation actions
Authors: Abeli Thomas , Rossi Graziano , Smolders Alfons J. P. , Orsenigo Simone 
Published: August 2014

ABSTRACTThe preliminary evaluation of threats and the possibility of their removal or mitigation is a key issue for a successful translocation. Here, the possibility to reintroduce Stratiotes aloides in Italy where it had become extinct about 25 years ago was investigated by studying the difference in water quality in sites where the species currently exists in Europe, where the species has recently disappeared (extinct) and in proposed translocation sites.Sediment pore‐water samples and surface water samples were collected in 18 localities in The Netherlands, Germany, Hungary, Italy and Romania, representing six European river basins.The high concentrations of surface water inorganic nitrogen (especially nitrates) were identified as the likely cause of decline of S. aloides in central‐eastern Europe and the cause of extinction of the species in Italy.The proposed translocation sites are more similar to current conditions of extinct sites than current sites of occurrence of S. aloides, affecting the possibility of successfully reintroducing the species at the southern edge of its European range. Increasing concentration of nitrates in other parts of the species range might further decrease the species abundance. Copyright © 2014 John Wiley & Sons, Ltd.
Exfoliation of Graphite into Graphene in Polar Solvents Mediated by Amphiphilic Hexa‐peri‐hexabenzocoronene
Authors: Kabe Ryota , Feng Xinliang , Adachi Chihaya , Müllen Klaus 
Published: August 2014

AbstractA water‐soluble surfactant consisting of hexa‐peri‐hexabenzocoronene (HBC) as hydrophobic aromatic core and hydrophilic carboxy substituents was synthesized. It exhibited a self‐assembled nanofiber structure in the solid state. Profiting from the π interactions between the large aromatic core of HBC and graphene, the surfactant mediated the exfoliation of graphite into graphene in polar solvents, which was further stabilized by the bulky hydrophilic carboxylic groups. A graphene dispersion with a concentration as high as 1.1 mg L−1 containing 2–6 multilayer nanosheets was obtained. The lateral size of the graphene sheets was in the range of 100–500 nm based on atomic force microscope (AFM) and transmission electron microscope (TEM) measurements.
Excellent Capacitive Performance of a Three‐Dimensional Hierarchical Porous Graphene/Carbon Composite with a Superhigh Surface Area
Authors: Li Xue Jin , Xing Wei , Zhou Jin , Wang Gui Qiang , Zhuo Shu Ping , Yan Zi Feng , Xue Qing Zhong , Qiao Shi Zhang 
Published: August 2014

AbstractThree‐dimensional hierarchical porous graphene/carbon composite was successfully synthesized from a solution of graphene oxide and a phenolic resin by using a facile and efficient method. The morphology, structure, and surface property of the composite were investigated intensively by a variety of means such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), N2 adsorption, Raman spectroscopy, and Fourier transform infrared spectroscopy (FTIR). It is found that graphene serves as a scaffold to form a hierarchical pore texture in the composite, resulting in its superhigh surface area of 2034 m2g−1, thin macropore wall, and high conductivity (152 S m−1). As evidenced by electrochemical measurements in both EMImBF4 ionic liquid and KOH electrolyte, the composite exhibits ideal capacitive behavior, high capacitance, and excellent rate performance due to its unique structure. In EMImBF4, the composite has a high energy density of up to 50.1 Wh kg−1 and also possesses quite stable cycling stability at 100 °C, suggesting its promising application in high‐temperature supercapacitors. In KOH electrolyte, the specific capacitance of this composite can reach up to an unprecedented value of 186.5 F g−1, even at a very high current density of 50 A g−1, suggesting its prosperous application in high‐power applications.
Unexpected Self‐Assembly of a Homochiral Metallosupramolecular M4L4 Catenane
Authors: Hovorka Rainer , Meyer‐Eppler Georg , Piehler Torsten , Hytteballe Sophie , Engeser Marianne , Topić Filip , Rissanen Kari , Lützen Arne 
Published: August 2014

AbstractTwo enantiomerically pure 9,9′‐spirobifluorene‐based bis(pyridine) ligands 1 and 2 were prepared to study their self‐assembly behavior upon coordination to cis‐protected palladium(II) ions. Whereas the sterically more demanding ligand, 2, gave rise to the expected dinuclear metallosupramolecular M2L2 rhombi, the sterically less demanding ligand, 1, acts as a template to give rise to a homochiral metallosupramolecular M4L4 catenane.
Diphenylprolinol Silyl Ether Catalyzed Asymmetric Michael Reaction of Nitroalkanes and β,β‐Disubstituted α,β‐Unsaturated Aldehydes for the Construction of All‐Carbon Quaternary Stereogenic Centers
Authors: Hayashi Yujiro , Kawamoto Yuya , Honda Masaki , Okamura Daichi , Umemiya Shigenobu , Noguchi Yuka , Mukaiyama Takasuke , Sato Itaru 
Published: August 2014

AbstractThe asymmetric Michael reaction of nitroalkanes and β,β‐disubstituted α,β‐unsaturated aldehydes was catalyzed by diphenylprolinol silyl ether to afford 1,4‐addition products with an all‐carbon quaternary stereogenic center with excellent enantioselectivity. The reaction is general for β‐substituents such as β‐aryl and β‐alkyl groups, and both nitromethane and nitroethane can be employed. The addition of nitroethane is considered a synthetic equivalent of the asymmetric Michael reaction of ethyl and acetyl substituents by means of radical denitration and Nef reaction, respectively. The short asymmetric synthesis of (S)‐ethosuximide with a quaternary carbon center was accomplished by using the present asymmetric Michael reaction as the key step. The reaction mechanism that involves the E/Z isomerization of α,β‐unsaturated aldehydes, the retro‐Michael reaction, and the different reactivity between nitromethane and nitroethane is discussed.
Asymmetric Organocatalyzed Michael Addition of Nitromethane to a 2‐Oxoindoline‐3‐ylidene Acetaldehyde and the Three One‐Pot Sequential Synthesis of (−)‐Horsfiline and (−)‐Coerulescine
Authors: Mukaiyama Takasuke , Ogata Kento , Sato Itaru , Hayashi Yujiro 
Published: August 2014

Abstract(−)‐Horsfiline and (−)‐coerulescine were synthesized through three one‐pot operations in 33 and 46 % overall yield, respectively. Key to the success was the efficient use of a diarylprolinol silyl ether to catalyze the asymmetric Michael addition of nitromethane to a 2‐oxoindoline‐3‐ylidene acetaldehyde. This allowed the all‐carbon quaternary, spirocyclic carbon stereocenter to be constructed in good yield with excellent enantioselectivity.
Covalent Bond or Noncovalent Bond: A Supramolecular Strategy for the Construction of Chemically Synthesized Vaccines
Authors: Gao Yue , Sun Zhan‐Yi , Huang Zhi‐Hua , Chen Pu‐Guang , Chen Yong‐Xiang , Zhao Yu‐Fen , Li Yan‐Mei 
Published: August 2014

AbstractA novel noncovalent strategy to construct chemically synthesized vaccines has been designed to trigger a robust immune response and to dramatically improve the efficiency of vaccine preparation. Glycosylated MUC1 tripartite vaccines were constructed through host–guest interactions with cucurbit[8]uril. These vaccines elicited high levels of IgG antibodies that were recognized by transformed cells and induced the secretion of cytokines. The antisera also mediated complement‐dependent cytotoxicity. This noncovalent strategy with good suitability, scalability, and feasibility can be applied as a universal strategy for the construction of chemically synthesized vaccines.
Dispersion Interaction Stabilizes Sterically Hindered Double Fullerenes
Authors: Zhang Jun , Dolg Michael 
Published: August 2014

AbstractBy state‐of‐the‐art quantum chemical methods, we show that for bulky functional groups like cyclohexane, [20]fullerene, dodecahedrane, and C60, the attractive dispersion interaction can have a greater impact on stereochemistry than the repulsive steric effect, making the compact isomer the more stable one. In particular, for the double C60 adduct of pentacene 1, the syn isomer should be the main product instead of the anti one inferred in the original synthesis experiment (Y. Murata et al., J. Org. Chem.­ 1999, 64, 3483). With and without dispersion interactions taken into account, the Gibbs energy difference ΔG(syn−anti) is −6.36 and +1.15 kcal mol−1, respectively. This study reminds us that dispersion interactions as well as electrostatic or hyperconjugation effects, etc. can lead to some unusual stereochemical phenomena.
Theoretical Studies on the Reactions of 1,1,2,2,3,3,4‐Heptafluorocyclopentane with Hydroxyl and Hydrogen Free Radicals
Authors: Lu Dayong , Chao Mingyong , Zhou Xiaomeng 
Published: August 2014

Abstract1,1,2,2,3,3,4‐Heptafluorocyclopentane (F7A) has considerable potential to be a new halon replacement due to its environmental friendliness and low‐toxicity. However, the reaction processes of F7A with hydroxyl and hydrogen free radicals, which are of great importance for investigating its fire suppression mechanisms, are still unclear. In this paper, ab inito and density functional theory are used to deduce the possible reaction pathways for the reactions of F7A with hydroxyl and hydrogen free radicals at the CCSD/cc‐pVDZ//B3LYP/6‐311++G (d,p) level of theory. Two distinct reaction pathways including ten elementary reaction channels for F7A with hydroxyl free radical, and five distinct reaction pathways including twenty elementary reaction channels for F7A with hydrogen free radical are investigated. The geometries, vibrational frequencies and reaction energy barriers are also determined. Based on the calculated results, the possible reaction mechanisms are proposed and discussed. The most feasible reaction channel for F7A with hydroxyl free radical is that leads to CH(OH)CH2(CF2)3+·F, and the most feasible reaction channel for F7A with hydrogen free radical is that leads to (CF2)3CH2CH·+HF. The study is helpful to further study its fire suppression mechanisms and promote it to be a new generation of halon replacement.
Enantioselective Construction of Functionalized Thiochromans via Squaramide‐Catalyzed Asymmetric Cascade Sulfa‐Michael/Michael Addition
Authors: Yang Yi , Du Daming 
Published: August 2014

AbstractAn efficient enantioselective cascade sulfa‐Michael/Michael addition reaction of trans‐3‐(2‐mercaptophenyl)‐2‐propenoic acid ethyl ester with nitroalkenes catalyzed by a chiral squaramide catalyst was disclosed. This cascade reaction afforded thiochroman derivatives with three contiguous stereocenters in high yields (up to 94%), excellent diastereoselectivities (up to >25:1 dr) and enantioselectivities (up to 99% ee).
Deammoniative Condensation of Primary Allylic Amines with Nonallylic Amines
Authors: Wang Yong , Li Manbo , Ma Xiantao , Liu Congrong , Gu Yonghong , Tian Shi‐Kai 
Published: August 2014

AbstractAn unprecedented deammoniative condensation reaction of primary allylic amines with nonallylic amines has been developed through CN bond cleavage. In the presence of 5 mol% palladium diacetate, 10 mol% 1,4‐bis(diphenylphosphino)butane (dppb), and 5 mol% p‐toluenesulfonic acid (TsOH), a range of α‐unbranched primary allylic amines smoothly underwent deammoniative condensation with nonallylic amines in an α‐selective fashion to give structurally diverse secondary and tertiary amines in good to excellent yields and E selectivity. Replacing dppb with racemic 2,2′‐bis(diphenylphosphino)‐1,1′‐binaphthyl (BINAP) permitted the deammoniative condensation of enantioenriched α‐chiral primary allylic amines with nonallylic amines to proceed with complete retention of configuration. Electrospray ionization (ESI) mass spectrometric analysis of the reaction mixture permitted the identification of some π‐allylpalladium intermediates, and plausible mechanisms have been proposed to account for the regioselectivity and stereospecificity of the deammoniative condensation reaction.
The changing landscape of phase II/III metastatic NSCLC clinical trials and the importance of biomarker selection criteria
Authors: Gentzler Ryan D. , Yentz Sarah E. , Johnson Melissa L. , Rademaker Alfred W. , Patel Jyoti D. 
Published: August 2014

ABSTRACTOver the last decade, new cytotoxic treatments and targeted therapies have altered treatment paradigms for patients with metastatic non‐small cell lung cancer (NSCLC). We sought to analyze the impact of histology and biomarker selection criteria on outcomes of clinical trials in metastatic NSCLC reported over the last decade at the American Society of Clinical Oncology (ASCO) Annual Meeting. Data were collected from ASCO abstracts of Phase II–IV clinical trials for patients with metastatic NSCLC from 2004–2014. 770 of 2,989 identified metastatic NSCLC category abstracts met selection criteria. Despite a decline in the number of abstracts from 107 to 46 abstracts annually over this period, the proportion of trials with positive progression free survival (PFS) and overall survival (OS) outcomes has increased significantly. Trials with histology selection (6%) or molecular biomarker (15%) criteria were more likely to result in an improvement in PFS than those without selection criteria (21% vs. 8%, p = 0.0001 and 31% vs. 10%, p < 0.0001, respectively). These data demonstrate profound changes in the clinical trial landscape over the last 10 years with significantly increasing proportion of trials with positive outcomes. These changes are likely attributed to the use of histology and biomarker selection criteria in clinical trial design. Cancer 2014;120:3853–3858. © 2014 American Cancer Society.
Gel‐Derived Cation–π Stacking Films of Carbon Nanotube–Graphene Complexes as Oxygen Cathodes
Authors: Zhang Tao , Matsuda Hirofumi , Zhou Haoshen 
Published: August 2014

AbstractA key challenge in processing carbon nanotubes and their composites for large‐scale applications is aggregation. Cation–π stacking interactions have been discovered to disperse heavily entangled single‐walled carbon nanotube (SWNT) bundles in ionic liquids (ILs). In this work, we found that a dispersible, silky single‐layer graphene (SLG) can be readily gathered together to form a crosslinked gel after entrapping sufficient IL molecular via the likely noncovalent interaction. By incorporating the dispersed SWNTs into the gathered SLG gel synchronously, we prepared solid, finely crosslinked SWNTs–SLG films, assisted by an avenue of 2‐step extraction to remove the IL completely. The gel‐derived SWNTs–SLG complex film was applied as a support material of oxygen cathodes for Li–O2 batteries. It exhibited a remarkable improved cycleability in comparison to made of SWNTs and SLG alone due to the finely crosslinked feature. Decorated SWNTs and SLG can also form gel‐derived complexes via the same process to construct support–catalyst complexes. A SWNTs–SLG film loaded with Ru nanoparticles exhibited not only catalytic effects, but also the ability to suppress the side reactions, and hence stabilized the whole Li–O2 battery. Our research introduces a gel‐derived, high‐dispersed processing of carbon nanotube‐graphene complexes and demonstrates their favorable applications on Li–O2 batteries.
Synthesis of Metforminium(2+) Decavanadates – Crystal Structures and Solid‐State Characterization
Authors: Sánchez‐Lombardo Irma , Sánchez‐Lara Eduardo , Pérez‐Benítez Aarón , Mendoza Ángel , Bernès Sylvain , González‐Vergara Enrique 
Published: August 2014

AbstractThree new compounds were formed between decavanadate and diprotonated metformin (H2Metf) at different pH values and in the presence or absence of ammonium cations, namely, [H2Metf]3[V10O28]·8H2O (1), [H2Metf]2[NH4]2[V10O28]·10H2O (2), and [H2Metf]2[NH4]2[V10O28]·4H2O (3). We present their spectroscopic, thermal, and single‐crystal X‐ray diffraction characterization. The solid‐state structure of 1 shows that the three H2Metf2+ dications that counterbalance the charge of the decavanadate anion are in the close vicinity of the latter, as a result of the strong Coulombic forces that arise from the ionic charges. The replacement of one metforminium(2+) cation by two ammonium cations results in two hydrates 2 and 3, which differ only in their water content. Although 2 and 3 crystallize in the same centrosymmetric space group as 1, a remarkable difference for 2 and 3 is that the [V10O28]6– anion is placed on an inversion center, which is not the case for 1.
Organocatalytic Oxidation of Secondary Alcohols Using 1,2‐Di(1‐naphthyl)‐1,2‐ethanediamine (NEDA)
Authors: Al‐Hunaiti Afnan , Räisänen Minna , Pihko Petri , Leskelä Markku , Repo Timo 
Published: August 2014

AbstractDiamine, 1,2‐di(1‐naphthyl)‐1,2‐ethanediamine (NEDA), efficiently catalyzes the oxidation of alcohols by using TBHP as an oxidant. Notably, secondary benzyl alcohols are oxidized in almost quantitative yields, and the catalyst also displays high activity towards even hindered cycloaliphatic secondary alcohols. With enantiopure (R,R)‐NEDA, oxidative kinetic resolution can be realized and depending on the alcohol ee up to 99 % are achieved.