bluuebunny/crossref_metadata_2025 huggingface dataset:
Do Student Evaluations of University Reflect Inaccurate Beliefs or Actual Experience? A Relative Rank Model
Authors: Brown Gordon D. A. , Wood Alex M. , Ogden Ruth S. , Maltby John
Published: June 2014

It was shown that student satisfaction ratings are influenced by context in ways that have important theoretical and practical implications. Using questions from the UK's National Student Survey, the study examined whether and how students' expressed satisfaction with issues such as feedback promptness and instructor enthusiasm depends on the context of comparison (such as possibly inaccurate beliefs about the feedback promptness or enthusiasm experienced at other universities) that is evoked. Experiment 1 found strong effects of experimentally provided comparison context—for example, satisfaction with a given feedback time depended on the time's relative position within a context. Experiment 2 used a novel distribution‐elicitation methodology to determine the prior beliefs of individual students about what happens in universities other than their own. It found that these beliefs vary widely and that students' satisfaction was predicted by how they believed their experience ranked within the distribution of others' experiences. A third study found that relative judgement principles also predicted students' intention to complain. An extended model was developed to show that purely rank‐based principles of judgement can account for findings previously attributed to range effects. It was concluded that satisfaction ratings and quality of provision are different quantities, particularly when the implicit context of comparison includes beliefs about provision at other universities. Quality and satisfaction should be assessed separately, with objective measures (such as actual times to feedback), rather than subjective ratings (such as satisfaction with feedback promptness), being used to measure quality wherever practicable. © 2014 The Authors. Journal of Behavioral Decision Making published by John Wiley & Sons Ltd.
The unintended consequences of targeting: young people's lived experiences of social and emotional learning interventions
Authors: Evans Rhiannon , Scourfield Jonathan , Murphy Simon
Published: June 2014

In the past twenty years there has been a proliferation of targeted school‐based social and emotional learning (SEL) interventions. However, the lived experience of young peoples’ participation is often elided, while the potential for interventions to confer unintended and even adverse effects remains under‐theorised and empirically under‐explored. This paper reports findings from a qualitative case study of students’ participation in a targeted SEL intervention, the Student Assistance Programme. Data was generated with four secondary schools in Wales, with 41 students (age 12–14) taking part in the study. Findings indicate that students’ identification for participation in the intervention and their reaction to the group composition may lead to harmful effects. Four iatrogenic processes were identified: (1) identification may be experienced as negative labelling resulting in rejection of the school (2) the label of SEL failure may serve as a powerful form of intervention capital, being employed to enhance students’ status amongst peers. Possession of this capital is contingent on continued resistance of the intervention (3) targeting of discrete friendship groups may lead to the construction of intervention ‘outsiders’ as students seek safety through the reification of pre‐exiting relationships (4) students may seek to renegotiate positioning within targeted friendships groups by ‘bragging’ about and reinforcing anti‐school activities, leading to deviancy amplification.
Conformational preferences of peptide–peptoid hybrid oligomers
Authors: Butterfoss Glenn L. , Drew Kevin , Renfrew P. Douglas , Kirshenbaum Kent , Bonneau Richard
Published: June 2014

Peptomers are oligomeric molecules composed of both α‐amino acids and N‐substituted glycine monomers, thus creating a hybrid of peptide and peptoid units. Peptomers have been used in several applications such as antimicrobials, protease inhibitors, and antibody mimics. Despite the considerable promise of peptomers as chemically diverse molecular scaffolds, we know little about their conformational tendencies. This lack of knowledge limits the ability to implement computational approaches for peptomer design. Here we computationally evaluate the local structural propensities of the peptide–peptoid linkage. We find some general similarities between the peptide residue conformational preferences and the Ramachandran distribution of residues that precede proline in folded protein structures. However, there are notable differences. For example, several β‐turn motifs are disallowed when the i+2 residue is also a peptoid monomer. Significantly, the lowest energy geometry, when dispersion forces are accounted for, corresponds to a “cis‐Pro touch‐turn” conformation, an unusual turn motif that has been observed at protein catalytic centers and binding sites. The peptomer touch‐turn thus represents a useful design element for the construction of folded oligomers capable of molecular recognition and as modules in the assembly of structurally complex peptoid–protein hybrid macromolecules. © 2014 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 102: 369–378, 2014.
Host cell pigmentation in Scenedesmus dimorphus as a beacon for nascent parasite infection
Authors: Collins Aaron M. , Jones Howland D.T. , McBride Robert C. , Behnke Craig , Timlin Jerilyn A.
Published: June 2014

Biofuels derived from the mass cultivation of algae represent an emerging industry that aims to partially displace petroleum based fuels. Outdoor, open‐pond, and raceway production facilities are attractive options for the mass culture of algae however, this mode of cultivation leaves the algae susceptible to epidemics from a variety of environmental challenges. Infestations can result in complete collapse of the algal populations and destruction of their valuable products making it paramount to understand the host–pathogen relationships of known algal pests in order to develop mitigation strategies. In the present work, we characterize the spatial‐temporal response of photosynthetic pigments in Scenedesmus dimorphus to infection from Amoeboaphelidium protococcarum, a destructive endoparasite, with the goal of understanding the potential for early detection of infection via host pigment changes. We employed a hyperspectral confocal fluorescence microscope to quantify these changes in pigmentation with high spatial and spectral resolution during early parasite infection. Carotenoid abundance and autofluorescence increased within the first 24 h of infection while chlorophyll emission remained constant. Changes in host cell photosynthesis and bulk chlorophyll content were found to lag behind parasite replication. The results herein raise the possibility of using host–cell pigment changes as indicators of nascent parasite infection. Biotechnol. Bioeng. 2014;111: 1748–1757. © 2014 Wiley Periodicals, Inc.
Characterization and quantitative amino acids analysis of analgesic peptides in cinobufacini injection by size exclusion chromatography, matrix‐assisted laser desorption/ionization time of flight mass spectrometry and gas chromatography mass spectrometry
Authors: Wu Xu , Si Nan , Bo Gao , Hu Hao , Yang Jian , Bian Baolin , Zhao Hai Yu , Wang Hongjie
Published: June 2014

Cinobufacini injection that comes from the water extract of Bufo bufo gargarizans Cantor skin is widely used for cancer treatment in China. Peptide is one of its major types of constituents, however the biological effects and content of this injection are little reported. In present study, the analgesic effect of peptides was determined and evaluated by in‐vivo models. To characterize and quantitatively analyze these peptides, a reliable and efficient method combining size exclusion chromatography and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry with amino acid analysis was developed. The peptides presented as a series of analogs with similar molecular weights mostly ranging from 2 to 8 kDa. The amino acid analysis by gas chromatography mass spectrometry (GC‐MS) was developed to determine both free and combined amino acids (FAA and CAA) in cinobufacini injection. This method achieved good linearity (R2, 0.9909–0.9999) and low limit of detection and quantification. FAA and CAA samples were efficiently analyzed by modified Phenomenex EZ: faast procedure. For the sample analysis, the method showed good repeatability (relative standard deviation, RSD ≤ 10%). For most FAA and CAA the mean recoveries were >80% with RSD <10%. The GC‐MS based method is useful for quality assurance of both FAA and CAA in cinobufacini injection. Copyright © 2014 John Wiley & Sons, Ltd.
UPLC‐MS/MS determination of voriconazole in human plasma and its application to a pharmacokinetic study
Authors: Wang Zhe , Huang Cheng‐ke , Sun Wei , Xiao Cui , Wang Zeng‐shou
Published: June 2014

A sensitive and rapid ultra performance liquid chromatography tandem mass spectrometry (UPLC‐MS/MS) method was developed to determine voriconazole in human plasma. Sample preparation was accomplished through a simple one‐step protein precipitation with methanol. Chromatographic separation was carried out on an Acquity UPLC BEH C18 column using an isocratic mobile phase system composed of acetonitrile and water containing 1% formic acid (45:55, v/v) at a flow rate of 0.50 mL/min. Mass spectrometric analysis was performed using a QTrap5500 mass spectrometer coupled with an electrospray ionization source in the positive ion mode. The multiple reaction monitoring transitions of m/z 351.0 → 281.5 and m/z 237.1 → 194.2 were used to quantify voriconazole and carbamazepine (internal standard), respectively. The linearity of this method was found to be within the concentration range of 2.0–1000 ng/mL with a lower limit of quantification of 2.0 ng/mL. Only 1.0 min was needed for an analytical run. This fully validated method was successfully applied to the pharmacokinetic study after oral administration of 200 mg voriconazole to 20 Chinese healthy male volunteers. Copyright © 2014 John Wiley & Sons, Ltd.
Target cell extraction coupled with LC‐MS/MS analysis for screening potential bioactive components in Ginkgo biloba extract with preventive effect against diabetic nephropathy
Authors: Qiu Jing‐ying , Chen Xu , Zheng Xiao‐xiao , Jiang Xiang‐lan , Yang Dong‐zhi , Yu Yan‐yan , Du Qian , Tang Dao‐quan , Yin Xiao‐xing
Published: June 2014

A rapid and useful approach for screening potential bioactive components in Ginkgo biloba extract (GBE) with preventive effect against diabetic nephropathy (DN) was developed using mesangial cells extraction coupled with high‐performance liquid chromatography tandem mass spectrometry (LC‐MS/MS) analysis. Mesangial cells were first divided into two groups according to their treatments with high glucose or high glucose plus GBE. After incubation for 4, 8, 12, 16, 24 and 48 h, the cells were harvested and extracted with 40% acetic acid in water before LC‐MS/MS analysis. Then, 19 compounds and five metabolites were found to selectively combine with mesangial cells. Notably, compounds including quercetin and rutin were identified or tentatively characterized according to the results of retention time and MS spectra, which is highly consistent with our previous reports that quercetin and rutin are potent protective agents against glomerulosclerosis in DN. Therefore, all these results indicate that target cell extraction coupled with LC‐MS/MS analysis can be successfully applied for predicting the bioactive components in GBE with preventive effect against DN. Copyright © 2014 John Wiley & Sons, Ltd.
Simultaneous determination of linarin, naringenin and formononetin in rat plasma by LC‐MS/MS and its application to a pharmacokinetic study after oral administration of Bushen Guchi Pill
Authors: Guo Panpan , Dong Lihua , Yan Wenying , Wei Jianceng , Wang Chunying , Zhang Zijian
Published: June 2014

A sensitive and reproducible liquid chromatography tandem mass spectrometry (LC‐MS/MS) method was developed and validated for the simultaneous determination of linarin, naringenin and formononetin in rat plasma after addition of sulfamethoxazole as the internal standard (IS). Separation was carried out on a Diamonsil C18 column (150 × 4.6 mm, 5 µm) with liner gradient elution using methanol (A) and 0.5‰ formic acid aqueous solution (B). Detection was performed on a triple‐quadrupole linear ion trap mass spectrometer with the negative ion electrospray ionization in multiple‐reaction monitoring (MRM) mode. The MRM transitions were m/z 591.2 → 283.2, 271.0 → 150.9, 266.9 → 252.0 and 252.0 → 155.9 for linarin, naringenin, formononetin and IS, respectively. All analytes showed good linearity within the concentration range (r > 0.9973). The lower limits of quantitation of linarin, naringenin and formononetin were 0.64, 1.07 and 1.04 ng/mL, respectively. Intra‐day and inter‐day precisions of the investigated components exhibited an RSD within 9.96%, and the accuracy (relative error) ranged from −11.25 to 9.38% at all quality control levels. The developed method was successfully applied to a pharmacokinetic study of linarin, naringenin and formononetin in rats after oral administration of Bushen Guchi Pill. Copyright © 2014 John Wiley & Sons, Ltd.
Synthesis of Heterocycles through Transition‐Metal‐Catalyzed Isomerization Reactions
Authors: Ishoey Mette , Nielsen Thomas E.
Published: June 2014

Metal‐catalyzed isomerization of N‐ and O‐allylic systems is emerging as an effective method to form synthetically useful iminium and oxocarbenium intermediates. In the presence of tethered nucleophiles, several recent examples illuminate this approach as a powerful strategy for the synthesis of structurally complex and diverse heterocycles. In this Concept article, we attempt to cover this area of research through a selection of recent versatile examples.
Direct Enantioselective Three‐Component Synthesis of Optically Active Propargylamines in Water
Authors: Ohara Mutsuyo , Hara Yoshichika , Ohnuki Tohru , Nakamura Shuichi
Published: June 2014

An enantioselective three‐component reaction of aldehydes, amines, and alkynes in water by using a bis(imidazoline)–CuI catalysts having a hydrophobic substituent and sodium dodecyl sulfate as a surfactant was developed. The reaction was applied to a broad range of aldehydes and alkynes to give optically active propargylamines with excellent yields (up to 99 %) and enantiomeric excesses (up to 99 % ee).
Polydopamine—An Organocatalyst Rather than an Innocent Polymer
Authors: Mrówczyński Radosław , Bunge Alexander , Liebscher Jürgen
Published: June 2014

Polydopamine (PDA) is easily available by oxidation of dopamine and is widely used for persistent coatings of various materials. It is hitherto considered to be inert in many interesting biomedical and other applications. Results presented here, reveal an unexpected behavior of polydopamine as an organocatalyst in direct aldol reactions under mild conditions. Evidence was found for dual catalysis making use of amino and phenolic hydroxy groups found in PDA. Thus scientists must be aware that PDA is not an innocent polymer and can cause unwanted side effects in important applications, such as in biomedicine or as supports in catalysis.
Hydrophobic Modification of Pd/SiO2@Single‐Site Mesoporous Silicas by Triethoxyfluorosilane: Enhanced Catalytic Activity and Selectivity for One‐Pot Oxidation
Authors: Nakatsuka Kazuki , Mori Kohsuke , Okada Shusuke , Ikurumi Shohei , Kamegawa Takashi , Yamashita Hiromi
Published: June 2014

To enhance the catalytic activity in a selective one‐pot oxidation using in‐situ generated H2O2, a hydrophobically modified core–shell catalyst was synthesized by means of a simple silylation reaction using the fluorine‐containing silylation agent triethoxyfluorosilane (TEFS, SiF(OEt)3). The catalyst consisted of a Pd‐supported silica nanosphere and a mesoporous silica shell containing isolated TiIV and F ions bonded with silicon (SiF bond). Structural analyses using XRD and N2 adsorption–desorption suggested that the mesoporous structure and large surface area of the mesoporous shells were retained even after the modification. During the one‐pot oxidation of sulfide, catalytic activity was enhanced significantly by increasing the amount of fluorine in the shell. A hydrophobic surface enhanced adsorption of the hydrophobic reactant into the mesopore, while the less hydrophobic oxygenated products efficiently diffused into the outside of the shell, which improved the catalytic activity and selectivity. In addition, the present methodology can be used to enhance the catalytic activity and selectivity in the one‐pot oxidation of cyclohexane by using an Fe‐based core–shell catalytic system.
The Photo‐Nazarov Reaction: Scope and Application
Authors: Cai Shujun , Xiao Zheming , Shi Yingbo , Gao Shuanhu
Published: June 2014

The reaction conditions and scope of the photo‐Nazarov reaction of aryl vinyl ketones were investigated. In contrast to the conventional acid‐catalyzed methods, this photolytic electrocyclization proceeds in the neutral or basic conditions. Irradiating substrates bearing various aromatic rings, acid‐sensitive groups, cyclohexenyl, cycloheptenyl, and unsaturated pyran with UV‐light (254 nm) smoothly yielded hexahydrofluorenones and related structures. This photo‐Nazarov reaction could also be applicable to the substrates carrying β‐alkyl groups on the enone, which gave corresponding polycyclic rings containing quaternary centers. These photo‐electrocyclized products may prove useful for synthesizing a variety of natural products and their derivatives. Further application of this mild photo‐Nazarov reaction in the synthesis of taiwaniaquinol B was achieved.
Metal‐Free Stabilization of Monomeric Antimony(I): A Carbene‐Supported Stibinidene
Authors: Dorsey Christopher L. , Mushinski Ryan M. , Hudnall Todd W.
Published: June 2014

A diamidocarbene was coordinated to an antimony(III) dichloride Lewis acid. Subsequent reduction with magnesium gave a monomeric, formally antimony(I) fragment that is supported by the diamidocarbene. Spectroscopic, crystallographic, and computational analyses demonstrated that the carbene ligand engages the antimony(I) center in π‐backbonding resulting in a short (2.068(7) Å) SbC interaction that is comparable to those observed in known stibaalkenes.
ChemInform Abstract: Self‐Assembly and Photocatalytic Hydrogen Evolution of a Niobium‐Containing Polyoxometalate.
Authors: Yang Zhao‐Xia , Huang Peng , Zhao Liang , Zhang Min , Zhang Yu‐Teng , Su Zhong‐Min
Published: June 2014

Cs19K2 [Nb4O6 (SiW9Nb3O40)4] Cl·27H2O is hydrothermally synthesized from a mixture of Cs8H[SiW9(NbO2)3O37], KCl, HCl, and H2O (autoclave, pH 2, 160 °C, 3 d, 76% yield).
ChemInform Abstract: Iron‐Catalyzed Reductive Cyclization of 1,6‐Enynes.
Authors: Lin Aijun , Zhang Zhi‐Wei , Yang Jiong
Published: June 2014

A FeCl2‐catalyzed cyclization of 1,6‐enynes (I) and (III) is developed using a unique combination of Et2Zn and MgBr2·OEt2 as reagent for the in‐situ‐generation of the catalytically active species.
ChemInform Abstract: Enantioselective Synthesis of α‐Halo‐α‐alkylmalonates via Phase‐Transfer Catalytic α‐Alkylation.
Authors: Hong Suckchang , Kim Minsik , Jung Myunggi , Ha Min Woo , Lee Myungmo , Park Yohan , Kim Mi‐hyun , Kim Taek‐Soo , Lee Jihoon , Park Hyeung‐geun
Published: June 2014

This method gives also access to the precursor of Welch′s HIV‐1 protease inhibitor (VI).
ChemInform Abstract: Synthesis of Bis(halovinyl)benzenes by Catalytic Olefination.
Authors: Muzalevskiy V. M. , Shikhaliev N. G. , Magerramov A. M. , Gurbanova N. V. , Geydarova S. D. , Balenkova E. S. , Shastin A. V. , Nenajdenko V. G.
Published: June 2014

The catalytic olefination of hydrazines of terephthalic (I) and isoterephthalic (XI) aldehydes with several polyhaloalkanes is studied.
ChemInform Abstract: Synthesis of 1‐Haloethenamides from Ynamide Through Halotrimethylsilane‐Mediated Hydrohalogenation.
Authors: Ohashi Kazuhiro , Mihara Shigenori , Sato Akihiro H. , Ide Masataka , Iwasawa Tetsuo
Published: June 2014

The reaction is initiated by HX which is prepared in‐situ from halotrimethylsilane and water.
ChemInform Abstract: Highly Enantioselective Rh‐Catalyzed Alkenylation of Imines: Synthesis of Chiral Allylic Amines via Asymmetric Addition of Potassium Alkenyltrifluoroborates to N‐Tosyl Imines.
Authors: Gopula Balraj , Chiang Chien‐Wei , Lee Way‐Zen , Kuo Ting‐Shen , Wu Ping‐Yu , Henschke Julian P. , Wu Hsyueh‐Liang
Published: June 2014

For the first time, simple N‐tosyl aryl aldimines are used as substrates in the rhodium catalyzed 1,2‐addition reaction with alkenylboron nucleophiles.
ChemInform Abstract: One‐Pot Three‐Component Sulfone Synthesis Exploiting Palladium‐Catalyzed Aryl Halide Aminosulfonylation.
Authors: Richards‐Taylor Charlotte S. , Blakemore David C. , Willis Michael C.
Published: June 2014

The title reaction combines aryl‐ or alkenyl iodides (I) and (IV) with a sulfonyl unit and an electrophilic coupling fragment, such as alkyl halides or electron‐poor arenes, e.g. (VIII), to provide the corresponding sulfone products (III), (V), (VII), and (IX) in good to high yields.
ChemInform Abstract: Chlorotrimethylsilane (TMSCl): An Efficient Silicon‐Based Lewis Acid Mediator in Allylic Alkylation Using a Diethylzinc Reagent.
Authors: Deng Wen‐Hui , Ye Fei , Bai Xing‐Feng , Li Li , Song Tao , Wei Yun‐Long , Xu Li‐Wen
Published: June 2014

Allylic alkylation of 1,3‐diaryl‐2‐propenyl acetates leads to 1,3‐diarylpent‐1‐enes without any enantiomeric excess.
ChemInform Abstract: Studies Towards the Total Synthesis of Hygrocins A and B.
Authors: Rasapalli Sivappa , Jarugumilli Gopalakrishna , Yarrapothu Gangadhara Rao , Ijaz Hamza , Golen James A. , Williard Paul G.
Published: June 2014

Compound (I) is successfully synthesized, which represents the western segment of the title compounds.
ChemInform Abstract: Synthesis and Antiproliferative Evaluation of Amide‐Containing Anthraquinone, Xanthone, and Carbazole.
Authors: Chen Li‐Chai , Juang Shin‐Hun , Chang Ken‐Ming , Tzeng Cherng‐Chyi , Chen Jih‐Jung , Chen I‐Li , Wang Tai‐Chi
Published: June 2014

The synthesized compounds are screened for their in vitro antiproliferative activities against some human cancer cell lines.
ChemInform Abstract: Novel Stereoselective Synthesis of Spiroketal Structure Using Pd(II)‐Catalyst.
Authors: Miyazawa Masahiro , Eizawa Toru , Yoshihara Shoko , Hatanaka Akinori , Yokoyama Hajime , Hirai Yoshiro
Published: June 2014

A highly stereoselective palladium(II)‐catalyzed intramolecular cyclization of 1,11‐dihydroxyundec‐9‐en‐5‐one derivatives via unstable hemiacetal intermediates is reported.
ChemInform Abstract: Palladium‐Catalyzed Unactivated C(sp3)—H Bond Activation and Intramolecular Amination of Carboxamides: A New Approach to β‐Lactams.
Authors: Sun Wen‐Wu , Cao Pei , Mei Ren‐Qiang , Li Yue , Ma Yuan‐Liang , Wu Bin
Published: June 2014

The described intramolecular C‐N bond formation process is compatible with a broad range of functional groups and is successfully applied in the synthesis of fused ring systems, which is rarely achieved by other methodologies.
ChemInform Abstract: Benzenesulfonyl Chlorides: New Reagents for Access to Alternative Regioisomers in Palladium‐Catalyzed Direct Arylations of Thiophenes.
Authors: Yuan Kedong , Doucet Henri
Published: June 2014

The Pd‐catalyzed coupling of benzenesulfonyl chlorides (II) with thiophene derivatives, such as (I), (IV), and (VI) allows regioselective access to β‐arylated thiophenes (III), (V), and (VII), respectively.
ChemInform Abstract: Complementary Stereochemical Outcomes in Proline‐Based Self‐Regenerations of Stereocenters.
Authors: Knight Brian J. , Stache Erin E. , Ferreira Eric M.
Published: June 2014

Stereoselective alkylation of proline‐based amino amides is described.
ChemInform Abstract: Ylide Mediated Carbonyl Homologations for the Preparation of Isatin Derivatives.
Authors: Lollar Christina T. , Krenek Katherine M. , Bruemmer Kevin J. , Lippert Alexander R.
Published: June 2014

The reaction proceeds via the in situ generated sulfur ylide intermediates.
ChemInform Abstract: Towards a Facile and Convenient Synthesis of Highly Functionalized Indole Derivatives Based on Multi‐Component Reactions.
Authors: Neochoritis Constantinos G. , Doemling Alexander
Published: June 2014

A novel indole isocyanide (IV) is synthesized through accelerated Leuckart—Wallach reaction and subsequently employed in important multi‐component reactions leading to potential bioactive compounds.
ChemInform Abstract: Regioselective Synthesis of 1,3,5‐Trisubstituted Pyrazoles from N‐Alkylated Tosylhydrazones and Terminal Alkynes.
Authors: Kong Yuanfang , Tang Meng , Wang Yun
Published: June 2014

This efficient protocol can be applied to a wide range of substrates and tolerating a variety of substituents, including both electron‐donating and ‐withdrawing groups.
ChemInform Abstract: Expedient Synthesis of α‐Heteroaryl Piperidines Using a Pd‐Catalyzed Suzuki Cross‐Coupling—Reduction Sequence.
Authors: Hesp Kevin D. , Fernando Dilinie P. , Jiao Wenhua , Londregan Allyn T.
Published: June 2014

The method provides a robust strategy towards α‐azine piperidines which are not accessible using standard approaches like reduction of 2‐aryl pyridines.
ChemInform Abstract: Samarium(III)‐Catalyzed C(sp3)—H Bond Activation: Synthesis of Indolizines via C—C and C—N Coupling Between 2‐Alkylazaarenes and Propargylic Alcohols.
Authors: Wang Xu , Li Shen‐yan , Pan Ying‐ming , Wang Heng‐shan , Liang Hong , Chen Zhen‐feng , Qin Xiao‐huan
Published: June 2014

The reaction proceeds under solvent‐free conditions and tolerates a wide range of functional groups.
ChemInform Abstract: Metal Modified SSA as a Heterogeneous Catalyst to Promote the Cyclocondesation of O‐Aminobenzonitriles with Cycloketones in Water.
Authors: Zhang Li Jun , Yu Jian Ling , Wang Wei Li , Li Heng , Xu Dan Dan , Bi Ya Dong , Liu Fu De
Published: June 2014

A novel solid catalyst based on silica sulfuric acid (SSA) is prepared.
ChemInform Abstract: Reaction of Hexafluoro‐N‐(4‐N,N‐dialkylaminophenyl)‐1,4‐naphthoquinon‐4‐imines with Primary Amines.
Authors: Ektova L. V. , Bukhtoyarova A. D. , Chuikov I. P. , Beregovaya I. V.
Published: June 2014

The reaction of hexafluoro‐N‐imines (I) with primary amines (II) affords amino‐substituted compounds (III) and the corresponding cyclized products (IV).
ChemInform Abstract: Copper‐Catalyzed Trifluoromethylselenolation of Aryl and Alkyl Halides: The Silver Effect in Transmetalation.
Authors: Chen Chaohuang , Hou Chuanqi , Wang Yuguang , Hor T. S. Andy , Weng Zhiqiang
Published: June 2014

The presented method is applicable to a broad range of aryl, heteroaryl, and alkyl halides giving high yields and is compatible with a high number of functional groups.
ChemInform Abstract: (.+‐.)‐Paeoveitol, a Pair of New Norditerpene Enantiomers from Paeonia veitchii.
Authors: Chen Ji‐Jun , et al. et al.
Published: June 2014

(.+‐.)‐Paeoveitol is isolated and resolved by chiral HPLC.
ChemInform Abstract: Synthesis, Structure and Inhibitory Activity of a Stereoisomer of Oseltamivir Carboxylate.
Authors: Sartori Andrea , et al. et al.
Published: June 2014

The first total synthesis of 4‐epi‐oseltamivir carboxylate (I) is described.
ChemInform Abstract: Total Synthesis, Stereochemical Assignment, and Biological Activity of All Known (‐)‐Trigonoliimines.
Authors: Han Sunkyu , Morrison Karen C. , Hergenrother Paul J. , Movassaghi Mohammad
Published: June 2014

Full details of the enantioselective total syntheses of all known (‐)‐trigonoliimine alkaloids already shortly reported in 2011 (see CI 2011‐50‐182) are given that had enabled the revision of the absolute stereochemistry of trigonoliimine A (Ia), B (Ib), and C (II).
ChemInform Abstract: Asymmetric Synthesis of (+)‐(S)‐Massoia Lactone (III), Pheromone of Idea leuconoe. Formal Total Synthesis of Valilactone and Lachnelluloic Acid (II).
Authors: Mineeva I. V.
Published: June 2014

An asymmetric synthesis is presented for lactone (I) which contains the cyclic scaffold of valilactone.
ChemInform Abstract: Carbamidocyclophanes F and G with anti‐Mycobacterium tuberculosis Activity from the Cultured Freshwater Cyanobacterium Nostoc sp.
Authors: Luo Shangwen , Kang Hahk‐Soo , Krunic Aleksej , Chlipala George E. , Cai Geping , Chen Wei‐Lun , Franzblau Scott G. , Swanson Steven M. , Orjala Jimmy
Published: June 2014

Carbamidocyclophane F (Ia) shows a potent anti‐Mycobacterium tuberculosis activity in the microplate Alamar blue assay and low‐oxygen‐recovery assay with MIC values of 0.8 and 5.4 μM, respectively.
ChemInform Abstract: Coibacins A and B: Total Synthesis and Stereochemical Revision.
Authors: Carneiro Vania M. T. , Avila Carolina M. , Balunas Marcy J. , Gerwick William H. , Pilli Ronaldo A.
Published: June 2014

Coibacin A (I) is prepared in 12 steps and 3.4% overall yield.
ChemInform Abstract: Study on Chemical Stabilization in Arsenic Contaminated Soil: A Review
Authors: Li Y. , Tang J. X. , Zhang T. , Lian M. H. , Tian X. Z.
Published: June 2014

Review: 17 refs.
ChemInform Abstract: The Electrochemical Reduction Processes of Solid Compounds in High Temperature Molten Salts
Authors: Xiao Wei , Wang Dihua
Published: June 2014

Review: tutorial review; 50 refs.
ChemInform Abstract: State of the Art and Perspectives in the “Molecular Approach” Towards Well‐Defined Heterogeneous Catalysts
Authors: Conley Matthew P. , Coperet Christophe
Published: June 2014

Review: 110 refs.
ChemInform Abstract: Electrophilic Activation of Allenenes and Allenynes: Analogies and Differences Between Broensted and Lewis Acid Activation
Authors: Caneque T. , Truscott F. M. , Rodriguez R. , Maestri G. , Malacria M.
Published: June 2014

Review: 50 refs.
ChemInform Abstract: Mechanistic Insights into the Gold Chemistry of Allenes.
Authors: Yang Weibo , Hashmi A. Stephen K.
Published: June 2014

Review: 42 refs.
ChemInform Abstract: Allene Ether Nazarov Cyclization
Authors: Tius Marcus A.
Published: June 2014

Review: [59 refs.
ChemInform Abstract: Heterometallic Complexes, Tandem Catalysis and Catalytic Cooperativity
Authors: Mata Jose A. , Hahn F. Ekkehardt , Peris Eduardo
Published: June 2014

Review: [36 refs.
ChemInform Abstract: Sulfur‐Containing Derivatives of Mono‐ and Bicyclic Natural Monoterpenoids
Authors: Ishmuratov G. Yu. , Yakovleva M. P. , Tukhvatshin V. S. , Talipov R. F. , Nikitina L. E. , Artemova N. P. , Startseva V. A. , Tolstikov A. G.
Published: June 2014

Review: 102 refs.
ChemInform Abstract: Catalytic, Asymmetric, Intramolecular Carbon‐Hydrogen Insertion
Authors: Doyle Michael P. , Liu Yu , Ratnikov Maxim
Published: June 2014

Review: 339 refs.
ChemInform Abstract: Oxetane Synthesis Through the Paterno—Buchi Reaction
Authors: D'Auria Maurizio , Racioppi Rocco
Published: June 2014

Review: 263 refs.
ChemInform Abstract: Metal Promoted Charge and Hapticities of Phosphines: The Uniqueness of Carboranylphosphines
Authors: Popescu Adrian R. , Teixidor Francesc , Vinas Clara
Published: June 2014

Review: 231 refs.
ChemInform Abstract: Recent Progress in Metal—Organic Complexes for Optoelectronic Applications
Authors: Xu Hui , Chen Runfeng , Sun Qiang , Lai Wenyong , Su Qianqian , Huang Wei , Liu Xiaogang
Published: June 2014

Review: [202 refs.
ChemInform Abstract: Fiber Based Structured Materials for Catalytic Applications
Authors: Reichelt Erik , Heddrich Marc P. , Jahn Matthias , Michaelis Alexander
Published: June 2014

Review: 212 refs.
ChemInform Abstract: Advances in Radical Probe Mass Spectrometry for Protein Footprinting in Chemical Biology Applications
Authors: Maleknia Simin D. , Downard Kevin M.
Published: June 2014

Review: 50 refs.
Low‐Temperature Synthesis of Crystalline Inorganic/Metallic Nanocrystal‐Halloysite Composite Nanotubes
Authors: Li Cuiping , Wang Jiaqiang , Feng Siquan , Liu Zan
Published: June 2014

We have demonstrated a facile approach for the low‐temperature synthesis of crystalline inorganic/metallic nanocrystal‐halloysite composite nanotubes by employing the bulk controlled synthesis of inorganic/metallic nanocrystals on halloysite nanotubes. The halloysite clay nanotubes can adsorb the target precursor and induce inorganic/metallic nanocrystals to grow in situ. The crystalline phase and morphology of the composite clay nanotubes is tunable. By simply tuning the acidity of the titania sol, the crystalline titania‐clay nanotubes with tunable crystalline phases of anatase, a mixture of anatase and rutile or rutile are achieved. The approach is general and has been extended to synthesize the representative perovskite oxide (barium and strontium titanate)‐halloysite composite nanotubes. Metallic nickel nanocrystal can also be grown on the surface of halloysite nanotubes at low temperature. The traditional thermal treatment for crystallite transformation is not required, thus intact contour of halloysite nanotubes and the crystallinity structure of halloysite nanotubes can be guaranteed. The combined properties from inorganic/metallic nanocrystal (high refractive index, high dielectric constant and catalytic ability) and the halloysite clay nanotubes are promising for applications such as photonic crystals, high‐k‐gate dielectrics, photocatalysis and purification.
Synthesis and Insecticidal Evaluation of Novel Phthalic Diamides Containing 1,2,3‐Triazoles via Click Reaction
Authors: Chen Yinbo , Xiao Youxin , Shao Xusheng , Xu Xiaoyong , Li Zhong
Published: June 2014

A series of novel phthalic diamide derivatives containing 1,2,3‐triazole moiety were synthesized using one‐pot click chemistry approach and characterized by 1H NMR and HRMS. The insecticidal activity against armyworm (Mythimna separata), Tetranychu scinnabarinus and cowpea aphid (Aphis craccivora) was evaluated. Compounds 4II‐a and 4II‐i showed 50% insecticidal activity against armyworm (Mythimna separata) at the concentration of 4 mg/L and one‐third of the compounds had moderate activity against Tetranychus cinnabarinus at 500 mg/L.
Activation of nuclear factor κB pathway and downstream targets survivin and livin by SHARPIN contributes to the progression and metastasis of prostate cancer
Authors: Zhang Yiming , Huang Hai , Zhou Huimin , Du Tao , Zeng Lexiang , Cao Yi , Chen Jieqing , Lai Yiming , Li Jin , Wang Ganping , Guo Zhenghui
Published: June 2014

BACKGROUND

Nuclear factor κB (NFκB) signaling is strongly associated with tumor progression, and studies have shown that SHANK‐associated RH domain interacting protein (SHARPIN) is crucial for NFκB pathway activation. However, the expression and functions of SHARPIN in prostate cancer (PCa) have not yet been defined.

METHODS

The expression of SHARPIN in PCa cell lines and tissues was evaluated with western blotting, quantitative real‐time polymerase chain reaction, and immunohistochemistry. After SHARPIN was silenced in the PCa cell lines, western blots were used to confirm that SHARPIN physically associated with components of the NFκB pathway and the downstream targets (survivin and livin). The functions of SHARPIN in cell proliferation, migration, and invasion in vitro were measured with 5‐(3‐carboxymethoxyphenyl)‐2‐(4,5‐dimenthylthiazoly)‐3‐(4‐sulfophenyl)tetrazolium, inner salt (MTS), Transwell, and invasion assays, respectively. Flow cytometry was employed to evaluate cell apoptosis. Furthermore, tumorigenesis in vivo was examined with tumorigenicity assays.

RESULTS

SHARPIN expression was upregulated in PCa cell lines and tissues. The knockdown of SHARPIN or incubation with Bay 11‐7082 (an NFκB inhibitor) led to dramatically decreased levels of phosphorylated IκBα and phosphorylated p65 in comparison with the control group. Downregulation of survivin and livin due to SHARPIN inhibition was attributable to transcriptional repression (P < .05). Decreases in cell viability, migration, invasion, and survival with a higher sensitivity to docetaxel in vitro and with repressed tumorigenesis in vivo were observed upon SHARPIN silencing, and this was consistent with the results from inhibition of the NFκB pathway and its downstream targets.

CONCLUSION

The current study demonstrates that overexpression of SHARPIN promotes activation of the NFκB pathway and downstream targets survivin and livin, which potentially contributes to PCa development. Cancer 2014;120:3208–3218. ©2014 American Cancer Society.
Uterine sarcoma dissemination during myomectomy: If not “acceptable collateral damage,” is it possible to mitigate the risk?
Authors: Judson Ian R. , Miah Aisha B.
Published: June 2014

Uterine sarcomas are rare, but benign leiomyomas (fibroids) are extremely common and frequently require surgery: either hysterectomy or myomectomy. A rare but potentially devastating consequence of myomectomy is inadvertent incomplete resection of a uterine sarcoma, resulting in tumor dissemination and a worse prognosis. The authors discuss the acceptable level of risk and how such a risk could be mitigated.
Retrospective cohort study evaluating the impact of intraperitoneal morcellation on outcomes of localized uterine leiomyosarcoma
Authors: George Suzanne , Barysauskas Constance , Serrano César , Oduyebo Titilope , Rauh‐Hain Jose A. , Del Carmen Marcela G. , Demetri George D. , Muto Michael G.
Published: June 2014

BACKGROUND

Uterine leiomyosarcoma (ULMS) is identified in 0.1% to 0.2% of hysterectomy specimens of presumed leiomyoma. To date, there is no preoperative technique that reliably differentiates ULMS from uterine leiomyoma. Increasing use of minimally invasive approaches for the management of leiomyomas may result in inadvertently morcellated ULMS with resultant intraperitoneal dissemination of tumor. The objective of this study was to assess the impact of intraperitoneal morcellation on the outcomes of patients with ULMS.

METHODS

In this retrospective cohort study, all patients with ULMS who attended the authors' institutions from 2007 to 2012 were reviewed. Demographics and outcomes were compared between those who underwent morcellation or total abdominal hysterectomy (TAH) as their first surgery for uterus‐limited ULMS.

RESULTS

In total, 58 patients were identified, including 39 who underwent TAH and 19 who underwent intraperitoneal morcellation. Intraperitoneal morcellation was associated with a significantly increased risk of abdominal/pelvic recurrences (P = .001) and with significantly shorter median recurrence‐free survival (10.8 months vs 39.6 months; P = .002). A multivariate adjusted model demonstrated a >3 times increased risk of recurrence associated with morcellation (hazard ratio, 3.18; 95% confidence interval, 1.5‐6.8; P = .003).

CONCLUSIONS

Intraperitoneal morcellation of presumed leiomyoma worsens the outcomes of women with ULMS. Because there are no reliable preoperative techniques to distinguish ULMS from benign leiomyoma, all efforts to minimize intraperitoneal uterine morcellation should be considered. [See editorial on pages 000‐000, this issue.] Cancer 2014;120:3154–3158. © 2014 American Cancer Society.
Ion Pairing in Protic Ionic Liquids Probed by Far‐Infrared Spectroscopy: Effects of Solvent Polarity and Temperature
Authors: Fumino Koichi , Fossog Verlaine , Stange Peter , Wittler Kai , Polet Wigbert , Hempelmann Rolf , Ludwig Ralf
Published: June 2014

The cation–anion and cation–solvent interactions in solutions of the protic ionic liquid (PIL) [Et3NH][I] dissolved in solvents of different polarities are studied by means of far infrared vibrational (FIR) spectroscopy and density functional theory (DFT) calculations. The dissociation of contact ion pairs (CIPs) and the resulting formation of solvent‐separated ion pairs (SIPs) can be observed and analyzed as a function of solvent concentration, solvent polarity, and temperature. In apolar environments, the CIPs dominate for all solvent concentrations and temperatures. At high concentrations of polar solvents, SIPs are favored over CIPs. For these PIL/solvent mixtures, CIPs are reformed by increasing the temperature due to the reduced polarity of the solvent. Overall, this approach provides equilibrium constants, free energies, enthalpies, and entropies for ion‐pair formation in trialkylammonium‐containing PILs. These results have important implications for the understanding of solvation chemistry and the reactivity of ionic liquids.
Self‐Organization of Polar Porphyrinoids
Authors: Babu Sukumaran Santhosh , Bonifazi Davide
Published: June 2014

This Minireview focuses on the very recent developments in the field of porphyrin‐based self‐assembled nanomaterials with a particular focus on the use of tetrapyrrolic macrocycles bearing amphiphilic and ionic functionalities. As one of the most studied molecular materials, the importance of porphyrin‐derived nanomaterials has attracted wide interest in many applications like catalysis, photodynamic therapy, and organic solar cells to name a few. By using key examples that have recently appeared in the literature, the discussion unfolds through two sections: amphiphilic and ionic assemblies. Although it focuses on the nanostructuring methodologies used to obtain organized materials, the discussion will also target the physical characterization of the functional materials for their implementation in prototypes.
A piggyBac transposon‐ and gateway‐enhanced system for efficient BAC transgenesis
Authors: Zhao Liang , Ng Ee Ting , Koopman Peter
Published: June 2014

Background: Bacterial artificial chromosomes (BACs) have become increasingly popular vectors for making transgenic mice, as they are able to carry large genomic DNA fragments that in many cases are needed to reproduce the endogenous gene expression pattern. However, the efficiency of BAC transgenesis is generally low, and gene transfer to BAC vectors by recombination‐mediated engineering (recombineering) is time‐consuming and technically demanding. Results and Conclusions: We present an enhanced system, comprising a BAC vector retrofitted with piggyBac DNA transposon elements and attL (Gateway) docking sites, that obviates these problems. Using this system, a gene‐of‐interest (such as a reporter gene) is transferred to the vector in a one‐step in vitro reaction, and piggyBac transposition mediates transgene integration at high efficiency when microinjected into mouse zygotes with piggyBac transposase mRNA. We establish proof‐of‐principle for this system using a Wilms tumour‐1 (Wt1) BAC to drive expression of an mCherry‐2A‐EGFP (RG) reporter gene, which yielded transgenic mice at a frequency of 33%, and recapitulated endogenous WT1 expression in developing gonads, kidneys and heart. The system we describe is applicable to any BAC transgenesis strategy. Developmental Dynamics 243:1086–1094, 2014. © 2014 Wiley Periodicals, Inc.
Application of FT‐NIR spectroscopy in assessment of used frying fats and oils*
Authors: Gertz Christian , Behmer Dagmar
Published: June 2014

NIR spectroscopy (NIRS) was used to develop a fast and cost‐effective method to assess the quality of deep‐frying oil. A large number of fresh, used and discarded oils, used in fast food units, restaurants, fisheries, bakeries, and other frying industries, were analyzed for relevant parameters of thermo‐oxidative fat degradation such as total polar compounds (TPC), di‐ and polymerized tri‐acylglycerols (DPTG), anisidine value (AnV) and acid value (AV) using the standard DGF methods. Additionally, the fatty acid composition, including trans fatty acids, iodine value (IV) and the contents of monomeric oxidized tri‐acylglycerols (MonoxTG) were determined to describe the nutritional value of fried food. MonoxTG is a mixture of oxidized triglycerides of different molecular weight forming two groups separated in GPC. It is suggested to call them total oxidized products (TOP) as both groups of monomeric oxidized TAGs characterize, objectively and reliably, the whole spectrum of oxidized products in a used frying oil in contrast to AnV. Typical concentrations of this group of oxidized monomeric tri‐acylglycerols (TOP) in frying oils are 3 up to 15%. High calibration accuracy was obtained for all NIRS determinations. All methods were validated using test set validations. Partial least squares regression (PLS) was used to correlate spectral data with TPC, TOP, DPTG, AV, and AnV. High calibration accuracy was obtained for the NIR determination of all parameters analyzing used frying oils. For the TPC, the coefficient of determination R2 was 97.6 with an RMSEP of 1.56% over a range from 2.0 to 50.3%. Also DPTG was predicted successfully with R2 = 99.4 and RMSEP = 0.47% (0–31.3%). The AnV was measured over a broad range of 0.1 to 173 with R2 = 95.7 and RMSEP = 6.8. For acidity expressed as AV covering a wide range from 0 to 5.7 the R2 value was 97.4% with an RMSEP of 0.17%. A new parameter to monitor the degree of oxidation (TOP) has shown an R2 = 96.8 and RMSEP = 0.57%

Practical applications: NIRS is a useful tool for monitoring the thermo‐oxidative changes in used frying fats and oils during the frying process. This helps to optimize the frying process and to improve the quality of the food to be fried. From the results obtained in this study, it can be deduced that the determination of the TPC is not sufficient. The determination of all oxidized monomeric triglycerides TOP provide better information of those compounds which are discussed to have a detrimental effect to human health.
Fatty acid alterations in oils and fats during heating and frying*
Authors: Brühl Ludger
Published: June 2014

Oils and fats degrade during the frying process and many reactions with numerous fatty acid alteration products have been examined. The geometrical isomerisation of double bonds leads to the formation of trans fatty acids. At frying temperatures also conjugated double bond systems are detected. The reaction of oxygen with unsaturated fatty acids results in hydroperoxides, which immediately degrade in further radical reactions at frying temperature. A set of oxygenated fatty acids has been detected including epoxy‐, keto‐ and hydroxyl fatty acids. Another route leads to β‐scission at the carbonyl‐ or the alkyl side of the oxygen bearing carbon atom in the fatty acid chain. In this case short chain fatty acids, aldehydic, keto, and hydroxyl acids appear together with volatile compounds. Also the formation of cyclic and furan fatty acids was detected. As a reaction between fatty acids also dimeric and polymerised fatty acids can be observed. Taking into account the different amounts of these fatty acid degradation products the physiological relevance has to be discussed. Due to high concentrations of dimeric and polymerised molecules these substances can lower significantly the digestibility of fried foods, while oxidised fatty acid monomers are readily absorbed and raise concern about their effect on lipid metabolism. These two different effects of altered TAGs and fatty acids have to be considered separately.