bluuebunny/crossref_metadata_2025 huggingface dataset:
Integrated Micro/Nanoengineered Functional Biomaterials for Cell Mechanics and Mechanobiology: A Materials Perspective
Authors: Shao Yue , Fu Jianping
Published: December 2013

The rapid development of micro/nanoengineered functional biomaterials in the last two decades has empowered materials scientists and bioengineers to precisely control different aspects of the in vitro cell microenvironment. Following a philosophy of reductionism, many studies using synthetic functional biomaterials have revealed instructive roles of individual extracellular biophysical and biochemical cues in regulating cellular behaviors. Development of integrated micro/nanoengineered functional biomaterials to study complex and emergent biological phenomena has also thrived rapidly in recent years, revealing adaptive and integrated cellular behaviors closely relevant to human physiological and pathological conditions. Working at the interface between materials science and engineering, biology, and medicine, we are now at the beginning of a great exploration using micro/nanoengineered functional biomaterials for both fundamental biology study and clinical and biomedical applications such as regenerative medicine and drug screening. In this review, an overview of state of the art micro/nanoengineered functional biomaterials that can control precisely individual aspects of cell‐microenvironment interactions is presented and they are highlighted them as well‐controlled platforms for mechanistic studies of mechano‐sensitive and ‐responsive cellular behaviors and integrative biology research. The recent exciting trend where micro/nanoengineered biomaterials are integrated into miniaturized biological and biomimetic systems for dynamic multiparametric microenvironmental control of emergent and integrated cellular behaviors is also discussed. The impact of integrated micro/nanoengineered functional biomaterials for future in vitro studies of regenerative medicine, cell biology, as well as human development and disease models are discussed.
A Unique Route to Tetrasubstituted Propargylic Amines by Catalytic Markovnikov Hydroamination–Alkynylation
Authors: Pierce Conor J. , Yoo Hoseong , Larsen Catharine H.
Published: December 2013

Tetrasubstituted propargylic amines are not accessible from ketones under the many catalytic conditions reported for the synthesis of trisubstituted propargylic amines by reacting an aldehyde with an amine and alkyne. The first tandem Markovnikov hydroamination–alkynylation provides direct access to tetrasubstituted propargylic amines from an amine and alkyne via an unusual route involving no carbonyl compounds. A simple copper salt enables both catalytic cycles without ligands, promoters, co‐catalysts, solvents, or by‐products.

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Erythropoiesis‐driven regulation of hepcidin in human red cell disorders is better reflected through concentrations of soluble transferrin receptor rather than growth differentiation factor 15
Authors: Fertrin Kleber Yotsumoto , Lanaro Carolina , Franco‐Penteado Carla Fernanda , de Albuquerque Dulcinéia Martins , de Mello Mariana Rezende Bandeira , Pallis Flávia Rubia , Bezerra Marcos André Cavalcanti , Hatzlhofer Betania Lucena Domingues , Olbina Gordana , Olalla Saad Sara Terezinha , da Silva Araújo Aderson , Westerman Mark , Costa Fernando Ferreira
Published: December 2013

Growth differentiation factor 15 (GDF‐15) is a bone marrow‐derived cytokine whose ability to suppress iron regulator hepcidin in vitro and increased concentrations found in patients with ineffective erythropoiesis (IE) suggest that hepcidin deficiency mediated by GDF‐15 may be the pathophysiological explanation for nontransfusional iron overload. We aimed to compare GDF‐15 production in anemic states with different types of erythropoietic dysfunction. Complete blood counts, biochemical markers of iron status, plasma hepcidin, GDF‐15, and known hepcidin regulators [interleukin‐6 and erythropoietin (EPO)] were measured in 87 patients with red cell disorders comprising IE and hemolytic states: thalassemia, sickle cell anemia, and cobalamin deficiency. Healthy volunteers were also evaluated for comparison. Neither overall increased EPO, nor variable GDF‐15 concentrations correlated with circulating hepcidin concentrations (P = 0.265 and P = 0.872). Relative hepcidin deficiency was found in disorders presenting with concurrent elevation of GDF‐15 and soluble transferrin receptor (sTfR), a biomarker of erythropoiesis, and sTfR had the strongest correlation with hepcidin (rS = −0.584, P < 0.0001). Our data show that high concentrations of GDF‐15 in vivo are not necessarily associated with pathological hepcidin reduction, and hepcidin deficiency was only found when associated with sTfR overproduction. sTfR elevation may be a necessary common denominator of erythropoiesis‐driven mechanisms to favor iron absorption in anemic states and appears a suitable target for investigative approaches to iron disorders. Am. J. Hematol. 89:385–390, 2014. © 2013 Wiley Periodicals, Inc.
Study on the binding of chlorogenic acid to pepsin by spectral and molecular docking
Authors: Zeng Hua‐jin , Liang Hui‐li , You Jing , Qu Ling‐bo
Published: December 2013

The interaction of pepsin with chlorogenic acid (CHA) was investigated using fluorescence, UV/vis spectroscopy and molecular modeling methods. Stern–Volmer analysis indicated that the fluorescence quenching of pepsin by CHA resulted from a static mechanism, and the binding constant was 1.1846 × 105 and 1.1587 × 105 L/mol at 288 and 310 K, respectively. The distance between donor (pepsin) and acceptor (CHA) was calculated to be 2.39 nm and the number of binding sites for CHA binding on pepsin was ~ 1. The results of synchronous fluorescence and three‐dimensional fluorescence showed that binding of CHA to pepsin could induce conformational changes in pepsin. Molecular docking experiments found that CHA bonded with pepsin in the area of the hydrophobic cavity with Van der Waals' forces or hydrogen bonding interaction, which were consistent with the results obtained from the thermodynamic parameter analysis. Furthermore, the binding of CHA can inhibit pepsin activity in vitro. Copyright © 2013 John Wiley & Sons, Ltd.
Modulation of CD14 and TLR4⋅MD‐2 Activities by a Synthetic Lipid A Mimetic
Authors: Cighetti Roberto , Ciaramelli Carlotta , Sestito Stefania Enza , Zanoni Ivan , Kubik Łukasz , Ardá‐Freire Ana , Calabrese Valentina , Granucci Francesca , Jerala Roman , Martín‐Santamaría Sonsoles , Jiménez‐Barbero Jesus , Peri Francesco
Published: December 2013

Monosaccharide lipid A mimetics based on a glucosamine core linked to two fatty acid chains and bearing one or two phosphate groups have been synthesized. Compounds 1 and 2, each with one phosphate group, were practically inactive in inhibiting LPS‐induced TLR4 signaling and cytokine production in HEK‐blue cells and murine macrophages, but compound 3, with two phosphate groups, was found to be active in efficiently inhibiting TLR4 signal in both cell types. The direct interaction between compound 3 and the MD‐2 coreceptor was investigated by NMR spectroscopy and molecular modeling/docking analysis. This compound also interacts directly with the CD14 receptor, stimulating its internalization by endocytosis. Experiments on macrophages show that the effect on CD14 reinforces the activity on MD‐2⋅TLR4 because compound 3's activity is higher when CD14 is important for TLR4 signaling (i.e., at low LPS concentration). The dual targeting of MD‐2 and CD14, accompanied by good solubility in water and lack of toxicity, suggests the use of monosaccharide 3 as a lead compound for the development of drugs directed against TLR4related syndromes.
Small bowel obstruction
Authors: Saurabh Shireesh , Singh Namrata
Published: December 2013

Key Clinical Message

Gallstone ileus is a rare complication of cholelithiasis, but an established cause of mechanical small bowel obstruction in elderly patients. It is associated with high morbidity and mortality as most patients are elderly with multiple comorbidities. Surgery of choice is enterolithotomy.
Organo‐Gallium/Indium Chalcogenide Complexes of Copper(I): Molecular Structures and Thermal Decomposition to Ternary Semiconductors
Authors: Kluge Oliver , Biedermann Ralf , Holldorf Joscha , Krautscheid Harald
Published: December 2013

Several organo‐gallium/indium chalcogenide complexes of copper(I), stabilized by trialkylphosphines, were isolated, structurally characterized by using single‐crystal X‐ray diffraction, and investigated in thermolysis experiments. The syntheses with [E(Me3Si)2] (E=S, Se) as a starting material and a chalcogen source involve the elimination of volatile silyl acetate, silyl ethers, and methane from copper(I) acetate, and Group 13 metal trimethyl compounds, respectively. Chalcogenide complexes, according to the general formulas [(R3PCu)4(MeM)4E6] (1–6) and [(R3PCu)6(MeM)4M4S13] (7–9; with R=alkyl and M=Ga, In), and mixed chalcogenide–phenylchalcogenolate complexes [(iPr3PCuEPh)3(MeGaE)4] (10, 11) were isolated. The heavy atom cores of 1–6 consist of an octahedron of chalcogen atoms, interpenetrated by a cube of metal atoms. Depending on the steric demand of the phosphine ligands, two constitutions are observed; the metal atoms of the same element either forming tetrahedra, or parallelograms, respectively. This constitutional isomerism is further investigated by quantum chemical calculations. Complexes 7–9 contain a central sulfur atom, surrounded by two interpenetrating tetrahedra of Group 13 metal atoms, an octahedron of copper atoms, and an icosahedron of twelve outer sulfur atoms; the heavy atom framework of 10 and 11 is a “cut‐out” of this structure. Thermolysis experiments include thermogravimetry measurements and subsequent Rietveld phase analysis of the residues by using powder X‐ray diffraction. The homologous compounds 1, 3, 4, and 6 yield the respective crystalline ternary semiconductor material CuME2 at temperatures below 300 °C. Partial release of Me3M during the thermolysis process results in excess copper in the residue and therefore in small amounts of additional binary copper chalcogenide phases or metallic CuM alloys. Compound 8 produces nanocrystalline CuGaS2 at about 300 °C.
Synthesis of Mesoporous Platinum–Copper Films by Electrochemical Micelle Assembly and Their Electrochemical Applications
Authors: Li Cuiling , Yamauchi Yusuke
Published: December 2013

We have electrochemically synthesized mesoporous platinum–copper films with various compositions in an aqueous surfactant solution. By tuning the composition ratios of the platinum and copper sources in the precursor solutions, mesoporous bimetallic films with copper contents that dramatically change from 0 to 70 mol % can be successfully prepared. The obtained bimetallic films possess uniformly sized mesopores over the entire area. These mesoporous platinum–copper films are electrochemically active and show composition‐dependent catalytic activity and stability for the methanol oxidation reaction. The bimetallic mesoporous films are a promising new class of electrocatalyst for the future.
ChemInform Abstract: Subsolidus Phase Relationships and Photocatalytic Properties in the Ternary System TiO2—Bi2O3—V2O5 .
Authors: Lv Peiwen , Zheng Meng , Wang Xian , Huang Feng
Published: December 2013

Samples for a systematic study of the TiO2—Bi2O3—V2O5 subsolidus system are prepared by calcination of pellets of mixtures of the binary oxides (550—850 °C, 3 d).
ChemInform Abstract: Microwave‐Assisted Carbohydrohalogenation of First‐Row Transition‐Metal Oxides (M: V, Cr, Mn, Fe, Co, Ni, Cu) with the Formation of Element Halides.
Authors: Berger Matthias , Neumeyer Felix , Auner Norbert
Published: December 2013

Anhydrous transition metal chlorides and bromides MyXz (M: V, Cr, Mn, Fe, Co, Ni, Cu; X: Cl, Br) are synthesized in quantitative yields in a one‐step reaction of the metal oxides, graphite, and flowing HX under microwave irradiation (quartz‐tubes, 1000—1400 °C, 15 min).
ChemInform Abstract: High‐Pressure Synthesis, Crystal Structures, and Properties of ScRhO3 and InRhO3 Perovskites.
Authors: Belik Alexei A. , Matsushita Yoshitaka , Tanaka Masahiko , Takayama‐Muromachi Eiji
Published: December 2013

The title compounds are prepared from stoichiometric mixtures of In2O3 or Sc2O3 and Rh2O3 (Au capsules, 6 GPa, 1500 K, 2 h).
ChemInform Abstract: Asymmetric Copper‐Catalyzed Diels—Alder Reaction Revisited: Control of the Structure of Bis(oxazoline) Ligands.
Authors: Le Maux Paul , Dorcet Vincent , Simonneaux Gerard
Published: December 2013

Bisoxazolines bearing an ethanoanthracene backbone are reinvestigated as ligands in Cu‐catalyzed Diels—Alder reactions.
ChemInform Abstract: Alkene Chemoselectivity in Ruthenium‐Catalyzed Z‐Selective Olefin Metathesis.
Authors: Cannon Jeffrey S. , Grubbs Robert H.
Published: December 2013

This method yields E,Z‐dienes from dienes and terminal alkenes or internal Z‐alkenes with high chemoselectivity (with regard to the diene substrate) and complete stereoselectivity.
ChemInform Abstract: Highly Efficient Dynamic Kinetic Resolution of Secondary Aromatic Alcohols Using a Low‐Cost Solid Super Acid as a Racemization Catalyst.
Authors: Xu Gang , Wang Liang , Chen Yongjun , Cheng Yongmei , Wu Jianping , Yang Lirong
Published: December 2013

The dynamic kinetic resolution of alcohols (I) with 4‐chlorophenyl valerate as acyl donor proceeds in the presence of Novozym 435 and sulfated TiO2 as nano solid super acidic racemization catalyst.
ChemInform Abstract: Iodobenzene‐Catalyzed Deprotection of Hydrazones Using m‐Chloroperbenzoic Acid.
Authors: Jia Xiao‐Chuan , Li Jing , Yu Zhi‐Rui , Wang Yu‐Hu , Zhou Lei , Yu Yan‐Yan
Published: December 2013

This deprotection method tolerates a variety of functional groups.
ChemInform Abstract: Ruthenium‐Catalyzed Reductive Deamination and Tandem Alkylation of Aniline Derivatives.
Authors: Koreeda Tetsuro , Kochi Takuya , Kakiuchi Fumitoshi
Published: December 2013

These two new catalytic reactions proceed via oxidative addition of the C‐N‐bonds, followed by a β‐hydride elimination process from the ruthenium amide species.
ChemInform Abstract: Tandem Oxidative Amidation of Benzyl Alcohols with Amine Hydrochloride Salts Catalyzed by Iron Nitrate.
Authors: Ghosh Subhash Chandra , Ngiam Joyce S. Y. , Seayad Abdul M. , Tuan Dang Thanh , Johannes Charles W. , Chen Anqi
Published: December 2013

A two‐step one‐pot process is developed to allow a tandem oxidative amidation of benzyl alcohols with amine hydrochloride salts to yield secondary and tertiary benzamides under mild conditions.
ChemInform Abstract: Development of One‐Pot Synthesis of α‐Hydroxy α‐Trifluoromethyl Amides.
Authors: Meng Zhaoyang , Butcher William E.
Published: December 2013

A general and efficient one‐pot three‐step approach is developed to synthesize α‐hydroxy‐α‐trifluoromethyl amides from reactive aromatic halides, methyl trifluoropyruvate, and primary and secondary amines.
ChemInform Abstract: The Ru‐Catalyzed Alkylative Dearyloxylation of L‐Type 2‐Aryloxyethanols.
Authors: Weickmann Daniel , Plietker Bernd
Published: December 2013

The coupling of the two hydrogen‐autotransfer processes of dearyloxylation and subsequent dehydrative α‐alkylation using primary alcohols allows for the alkylative dearyloxylation of various lignin‐type model compounds.
ChemInform Abstract: Enantioselective One‐Pot Catalytic Synthesis of 4,5‐Epoxy‐3‐alkanols and 1‐Phenyl‐2,3‐epoxy‐1‐alkanols from α,β‐Unsaturated Aldehydes.
Authors: Infante Rebeca , Hernandez Yulan , Nieto Javier , Andres Celia
Published: December 2013

One‐pot asymmetric ethylation/epoxidation, and an unprecedented arylation/epoxidation of wide range of trisubstituted α,β‐unsaturated aldehydes is presented obtaining the title products including new enantioenriched compounds.
ChemInform Abstract: Halogen—Metal Exchange Reactions of Bromoaryl‐Substituted β‐Lactams.
Authors: Geherty Maryll , Melnyk James , Chomsky Keith , Hunt David A.
Published: December 2013

Successful halogen‐metal exchange reactions of the title compounds are described without ring‐opening of the lactam core.
ChemInform Abstract: Organocatalyzed Formal [2 + 2] Cycloaddition of Ketimines with Allenoates: Facile Access to Azetidines with a Chiral Tetrasubstituted Carbon Stereogenic Center.
Authors: Takizawa Shinobu , Arteaga Fernando Arteaga , Yoshida Yasushi , Suzuki Michitaka , Sasai Hiroaki
Published: December 2013

The title reaction is highly E‐selective and provides azetidines in good yields with high enantioselectivities.
ChemInform Abstract: An Atom‐Economic Route to Thiophenes and 2,2′‐Bithiophenes by Intramolecular Transannulation of gem‐Dialkylthio Enynes.
Authors: Fang Guichun , Li Jichun , Wang Yeming , Gou Mingyu , Liu Qun , Li Xingqi , Bi Xihe
Published: December 2013

This novel, simple, and highly efficient method allows the synthesis of different functionalized thiophenes and bithiophenes.
ChemInform Abstract: Enantioselective Merger of Aminocatalysis with π‐Lewis Acid Metal Catalysis: Asymmetric Preparation of Carbo‐ and Heterocycles.
Authors: Praveen Chandrasekaran , Montaignac Benjamin , Vitale Maxime R. , Ratovelomanana‐Vidal Virginie , Michelet Veronique
Published: December 2013

The catalytic system is applied to the preparation of indanes with poor enantioselectivities and a wide range of pyrrolidines.
ChemInform Abstract: Synthesis of 2‐Substituted Pyrrolidines from Nitriles.
Authors: Ramachandran P. Veeraraghavan , Mitsuhashi Wataru , Nicponski Daniel R.
Published: December 2013

An operationally simple six‐step procedure is presented for the conversion of nitriles into pyrrolidines via reduction, allylation, hydroboration, oxidation, chlorination, and cyclization.
ChemInform Abstract: Enantioselective Cyanoethoxycarbonylation of Isatins Promoted by a Lewis Base—Broensted Acid Cooperative Catalyst.
Authors: Ogura Yoshihiro , Akakura Matsujiro , Sakakura Akira , Ishihara Kazuaki
Published: December 2013

This is the first enantioselective cyanoethoxycarbonylation of isatins using a simple protocol employing a Lewis base/Broensted acid cooperative catalyst.
ChemInform Abstract: Reaction of Two Differently Functionalized Oxiranes with Nickel Perchlorate: A Modular Entry to Highly Substituted 1,3‐Dioxolanes.
Authors: Chen Zuliang , Xiao Yuanjing , Zhang Junliang
Published: December 2013

An alternative route for the synthesis of the title compounds by using oxiranes instead of aldehydes is presented via sequential Meinwald rearrangement and cycloaddition.
ChemInform Abstract: Convenient One‐Pot Three‐Component Synthesis of Trifluoromethylated Tetrahydrobenzo[g]chromene Derivatives (IV)
Authors: Duan Yijun , Wang Xu , Xu Xiaoling , Kang Zhangping , Zhang Min , Song Liping , Deng Hongmei
Published: December 2013

(18 examples).
ChemInform Abstract: Cobalt‐Catalyzed C—H Bond Functionalizations with Aryl and Alkyl Chlorides.
Authors: Punji Benudhar , Song Weifeng , Shevchenko Grigory A. , Ackermann Lutz
Published: December 2013

The title reaction proceeds under ambient temperature and low catalyst loading with excellent chemo‐ and site‐selectivities for a broad substrate scope.
ChemInform Abstract: Catalytic Asymmetric Allylic Alkylation of 3‐Arylated Piperidin‐2‐ones.
Authors: Michon Christophe , Bethegnies Aurelien , Capet Frederic , Roussel Pascal , de Filippis Arnault , Gomez‐Pardo Domingo , Cossy Janine , Agbossou‐Niedercorn Francine
Published: December 2013

The enantioenriched products (III) are useful intermediates for the synthesis of neurokinin antagonists.
ChemInform Abstract: One‐Pot Synthesis of Optically Enriched 2‐Piperidinones from Aliphatic Aldehydes and Cyanoacrylamides.
Authors: Kang Tai‐Ran , et al. et al.
Published: December 2013

The newly developed title reaction includes an organocatalytic Michael addition followed by an intramolecular hemiaminalization.
ChemInform Abstract: Isocyanide Cyclization Reactions: 4‐Methylene‐4H‐benzo[d][1,3]oxazine, 3‐Benzyl‐4‐methylene‐3,4‐dihydroquinazolines and 3‐(4‐Benzyl)‐3H‐quinazolin‐4‐ones — Experiment and Theory.
Authors: Neue Benedikt , Reiermann Ralph , Froehlich Roland , Wibbeling Birgit , Bergander Klaus , Wuerthwein Ernst‐Ulrich
Published: December 2013

The unexpected formation of the new class of heterocycles (III) and their oxidation products from the easily accessible starting material (I) is presented.
ChemInform Abstract: Generation of Low‐Valent Alkoxy Niobium from Nb(OEt)5 and Grignard Reagents and Their Use as Catalysts in the Cyclotrimerization of Isocyanates.
Authors: Ozaki Makoto , Obora Yasushi , Tada Yusuke , Ishii Yasutaka
Published: December 2013

Furthermore, the title reagents can be used for the allylation reaction of 4‐octyne.
ChemInform Abstract: Gold(I)‐Catalyzed Benz[c]azepin‐4‐ol Synthesis by Intermolecular [5 + 2] Cycloaddition.
Authors: Iqbal Nassem , Fiksdahl Anne
Published: December 2013

Au‐mediated coupling of phenylpropargyl acetals and esters with benzaldimines allows a new access to biologically important benzacepinols.
ChemInform Abstract: A Catalyst‐Free, Three‐Component Decarboxylative Coupling of Amino Acids with Aldehydes and H‐Dialkylphosphites for the Synthesis of α‐Aminophosphonates.
Authors: Kaboudin Babak , Karami Leila , Kato Jun‐ya , Aoyama Hiroshi , Yokomatsu Tsutomu
Published: December 2013

Transition metal‐free decarboxylative coupling of proline with aldehydes and dialkyl phosphites offers a direct synthesis of aminophosphonates.
ChemInform Abstract: Cytotoxic ent‐Kaurane Diterpenoids from Isodon nervosus.
Authors: Gao You‐Heng , Wei Zhi‐Xiong , Cheng Yi , Wang Teng‐Hua , Ni Lin , Zhou Xiao‐Hong , Zhang Li‐Yuan
Published: December 2013

The diterpenoids rabdonervosins G‐J [(I) ‐ (IV)] are isolated from the leaves and stems of title plant.
ChemInform Abstract: Unusual Nor‐Sesquiterpene Lactone from the Fruits of Illicium henryi.
Authors: Liu Ji‐Feng , Wang Ya‐Feng , Bi Ya‐Ping , Li Hui‐Juan , Jia Lu , Bi Yue‐Feng , Zhang Yan‐Bing
Published: December 2013

Henrylactones F (I) and G (II) as well as anislactone B (III) are isolated from the title fruit.
ChemInform Abstract: Metathesis Reactions: Recent Trends and Challenges
Authors: Deraedt Christophe , d'Halluin Martin , Astruc Didier
Published: December 2013

Review: 273 refs.
ChemInform Abstract: Oxidative Dehydrogenation of Ethane: Common Principles and Mechanistic Aspects
Authors: Gaertner Christian , van Veen Andre C. , Lercher Johannes A.
Published: December 2013

Review: 182 refs.
ChemInform Abstract: Be Squared: Expanding the Horizon of Squaric Acid‐Mediated Conjugations
Authors: Wurm Frederik R. , Klok Harm‐Anton
Published: December 2013

Review: overview of the well‐established squaric acid diester mediated coupling reactions for glycoconjugates and recent advances to expand this very versatile reaction protocol to the modification of peptides and proteins; 101 refs.
ChemInform Abstract: ′Upenamide: Trials and Tribulations
Authors: Unsworth William P. , Taylor Richard J. K.
Published: December 2013

Review: 64 refs.
ChemInform Abstract: Nitrogenase: A General Hydrogenator of Small Molecules
Authors: Dance Ian
Published: December 2013

Review: 150 refs.
ChemInform Abstract: Fermentative Hydrogen Production ‐ Process Design and Bioreactors
Authors: Waligorska Malgorzata
Published: December 2013

Review: 76 refs.
Small‐Angle Neutron Scattering Studies of Hemoglobin Confined Inside Silica Tubes of Varying Sizes
Authors: Mandal Soumit S. , Cristiglio Viviana , Lindner Peter , Bhattacharyya Aninda J.
Published: December 2013

In addition to the chemical nature of the surface, the dimensions of the confining host exert a significant influence on confined protein structures; this results in immense biological implications, especially those concerning the enzymatic activities of the protein. This study probes the structure of hemoglobin (Hb), a model protein, confined inside silica tubes with pore diameters that vary by one order of magnitude (≈20–200 nm). The effect of confinement on the protein structure is probed by comparison with the structure of the protein in solution. Small‐angle neutron scattering (SANS), which provides information on protein tertiary and quaternary structures, is employed to study the influence of the tube pore diameter on the structure and configuration of the confined protein in detail. Confinement significantly influences the structural stability of Hb and the structure depends on the Si‐tube pore diameter. The high radius of gyration (Rg) and polydispersity of Hb in the 20 nm diameter Si‐tube indicates that Hb undergoes a significant amount of aggregation. However, for Si‐tube diameters greater or equal to 100 nm, the Rg of Hb is found to be in very close proximity to that obtained from the protein data bank (PDB) reported structure (Rg of native Hb=23.8 Å). This strongly indicates that the protein has a preference for the more native‐like non‐aggregated state if confined inside tubes of diameter greater or equal to 100 nm. Further insight into the Hb structure is obtained from the distance distribution function, p(r), and ab initio models calculated from the SANS patterns. These also suggest that the Si‐tube size is a key parameter for protein stability and structure.
The importance of rare species: a trait‐based assessment of rare species contributions to functional diversity and possible ecosystem function in tall‐grass prairies
Authors: Jain Meha , Flynn Dan F.B. , Prager Case M. , Hart Georgia M. , DeVan Caroline M. , Ahrestani Farshid S. , Palmer Matthew I. , Bunker Daniel E. , Knops Johannes M.H. , Jouseau Claire F. , Naeem Shahid
Published: December 2013

The majority of species in ecosystems are rare, but the ecosystem consequences of losing rare species are poorly known. To understand how rare species may influence ecosystem functioning, this study quantifies the contribution of species based on their relative level of rarity to community functional diversity using a trait‐based approach. Given that rarity can be defined in several different ways, we use four different definitions of rarity: abundance (mean and maximum), geographic range, and habitat specificity. We find that rarer species contribute to functional diversity when rarity is defined by maximum abundance, geographic range, and habitat specificity. However, rarer species are functionally redundant when rarity is defined by mean abundance. Furthermore, when using abundance‐weighted analyses, we find that rare species typically contribute significantly less to functional diversity than common species due to their low abundances. These results suggest that rare species have the potential to play an important role in ecosystem functioning, either by offering novel contributions to functional diversity or via functional redundancy depending on how rare species are defined. Yet, these contributions are likely to be greatest if the abundance of rare species increases due to environmental change. We argue that given the paucity of data on rare species, understanding the contribution of rare species to community functional diversity is an important first step to understanding the potential role of rare species in ecosystem functioning.
In Situ Synthesis of ZnMn2O4–ZnO–C and ZnMn2O4–C Nanohybrids as High Performance Lithium‐Ion Battery Anodes
Authors: Li Guangda , Wang Yuyan , Yang Lishan , Ma Wanyong , Wang Meng
Published: December 2013

ZnMn2O4–ZnO–C nanohybrids have been synthesized by means of a simple carbonthermal reduction reaction between ZnMnO3 and acetylene black. ZnMn2O4–C nanohybrids are obtained by further washing with NaOH solution. The reversible discharge capacity of the ZnMn2O4–ZnO–C nanohybrids can reach 620 mA h g–1 at a current density of 100 mA g–1 and 520 mA h g–1 at 800 mA g–1 after 100 cycles. More importantly, ZnMn2O4–C shows better conductivity along with better rate performance after the removal of ZnO. The as‐prepared ZnMn2O4–C nanohybrids show a high specific capacity of approximately 750 mA h g–1 at a current density of 100 mA g–1 after 100 cycles and excellent rate performance. The reaction involved in the discharge/charge processes are discussed on the basis of ex situ high‐resolution transmission of the electrode materials. The conclusions will be of benefit in the design and exploration of future binary transition‐metal oxide anode materials for lithium‐ion batteries.
Direct Reactions of Iodine‐Activated Rare‐Earth Metals with Phenols of Varying Steric Bulk
Authors: Deacon Glen B. , Hamidi Shima , Junk Peter C. , Kelly Rory P. , Wang Jun
Published: December 2013

Sonication of rare‐earth metals activated by iodine with 2,6‐di‐tert‐butyl‐4‐methylphenol (HOdbmp), 2,6‐diphenylphenol (HOdpp) and mesitol (HOmes) in acetonitrile or tetrahydrofuran (thf) yielded [La(Odbmp)3(NCMe)2], [Eu(Odbmp)2(thf)3], [Ln(Odpp)3(thf)2] (Ln = La, Nd), [Eu(Odpp)2(dme)2] (after workup with 1,2‐dimethoxyethane), [Ln2(Omes)6(thf)4] (Ln = La, Nd), [Y(Omes)3(thf)3] and [Eu3(Omes)6(thf)6] in reactions controlled both by the bulk of the phenol and of the metal. It was noteworthy that EuII complexes were obtained under the conditions used. The method offers a general, environmentally friendly, metal‐based route to rare‐earth phenolates with prospects for wide application. Some comparison reactions of Ln metals with Hg(C6F5)2 and the phenols were also carried out and the additional complex [Eu(Odpp)3(dme)] was isolated. Structures of the new low‐coordinate complexes [La(Odbmp)3(NCMe)2]·2MeCN, [Eu(Odpp)2(dme)2] and [Eu(Odpp)3(dme)], and a new polymorph of [Eu(Odbmp)2(thf)3]·thf, were determined.
Structural correlates of subjective and objective memory performance in multiple sclerosis
Authors: Pardini Matteo , Bergamino Maurizio , Bommarito Giulia , Bonzano Laura , Luigi Mancardi Gian , Roccatagliata Luca
Published: December 2013

Subjective and objective memory deficits represent a frequent and ill‐understood aspect of multiple sclerosis (MS), and a significant cause of disability and quality of life reduction. The aim of the study is to verify the role of hippocampal and temporal associative fibers' damage in MS‐related memory complaints. To reach this aim, 25 patients with low disability relapsing‐remitting MS and 19 healthy controls were included in the study. All subjects underwent 3D T1 structural imaging and Diffusion Tensor Imaging. Additionally, MS patients underwent neuropsychological evaluation of objective (Selective Reminding Test and Spatial Recall Test) and of subjective (Perceived Deficit Questionnaire, Retrospective and Prospective Memory Subscales) memory deficits. Normalized hippocampal volume (NHV) and mean Fractional Anisotropy (FA) for the uncinate fasciculus (UF) and for the ventral division of the cingulum bundle (VCB) were calculated for all subjects. We showed that, compared to controls, MS subjects presented with reduced right NHV and with reduced mean FA bilaterally in the UF and the VCB. In the MS group, verbal memory scores correlated with left NHV, spatial memory scores correlated with right NHV, while perceived retrospective and prospective memory deficits correlated with left VCB and left UF mean FA respectively. Our data confirm an early involvement of memory‐related brain structures in MS patients. Our data suggest that verbal and nonverbal memory as well as perceived retrospective and prospective memory deficits are related to alterations of discrete anatomical structures in the low‐disability phase of MS. © 2013 Wiley Periodicals, Inc.
Comparison of optimized long echo time STEAM and PRESS proton MR spectroscopy of lipid olefinic protons at 3 Tesla
Authors: Bingölbali Ayhan , Fallone B. Gino , Yahya Atiyah
Published: December 2013

Purpose

To investigate the response of lipid olefinic protons (≈ 5.35 ppm) as a function of STEAM (Stimulated Echo Acquisition Mode) mixing time (TM), and echo time (TE), to find values that resolve the olefinic resonance from water in vivo while retaining sufficient olefinic signal.

Materials and Methods

PRESS (Point RESolved Spectroscopy) and STEAM experiments with varying timing parameters (TE and also TM for STEAM) were conducted on nine oils (almond, canola, cod liver, corn, linseed, peanut, sesame, sunflower, and walnut oil), and on vertebral bone marrow in vivo at 3 Tesla (T). Olefinic and methylene (methyl + methylene in vivo) peak areas were measured.

Results

Optimal STEAM parameters were found to be TM = 20 ms and TE = 100 ms. The STEAM olefinic/methylene area ratios (ranging between 0.1 and 0.4) calculated for each oil correlated well with ratios deduced from oil compositions in the literature (R2 = 0.975). The optimized STEAM sequence resolved the olefinic peak from water in vivo and yielded on average 1.91 times more olefinic signal compared with a previously optimized PRESS (TE = 200 ms) sequence tailored for the same purpose. Olefinic/(methyl + methylene) area ratios obtained with optimized STEAM and PRESS in vivo were linearly correlated (R2 = 0.972).

Conclusion

A STEAM sequence with TE = 100 ms and TM = 20 ms provides an alternative to the previously optimized PRESS (TE = 200 ms) sequence for determining relative amounts of lipid unsaturation at 3T.J. Magn. Reson. Imaging 2013. © 2013 Wiley Periodicals, Inc. J. Magn. Reson. Imaging 2015;41:481–486.© 2013 Wiley Periodicals, Inc.
Glucocorticoids in laryngology: A review
Authors: Rafii Benjamin , Sridharan Shaum , Taliercio Salvatore , Govil Nandini , Paul Benjamin , Garabedian Michael J. , Amin Milan R. , Branski Ryan C.
Published: December 2013

Objectives/Hypothesis

To provide the otolaryngologist an evidence‐based sound review of glucocorticoid use for laryngeal pathology.

Study Design

Review of contemporary peer‐reviewed literature as well as review articles.

Methods

A review of the literature regarding glucocorticoids as a therapeutic intervention for the treatment of benign laryngeal pathology and laryngeal manifestations of systemic disease was performed. Review included both systemic administration as well as local injection.

Results

Glucocorticoids, administered in the critical care setting for planned extubation, markedly reducing the risk of reintubation and remain a rudimentary pharmacologic adjunct in laryngeal manifestations of common autoimmune and inflammatory disorders. Intralesional injection has reduced the rate of surgical intervention for benign inflammatory primary laryngeal pathology.

Conclusions

Glucocorticoids are effective in the treatment of a number of laryngeal pathologies, through both systemic and intralesional administration. However, a clear consensus for utilization of glucocorticoids in the treatment of specific laryngeal disorders has yet to be published.

Level of Evidence

Laryngoscope, 124:1668–1673, 2014
Periodic solutions for fourth‐order nonlinear functional difference equations
Authors: Liu Xia , Zhang Yuanbiao , Shi Haiping , Deng Xiaoqing
Published: December 2013

By using the critical point method, some new criteria are obtained for the existence and multiplicity of periodic solutions for fourth‐order nonlinear functional difference equations. The proof is based on the linking theorem in combination with variational technique. Recent results in the literature are generalized and significantly improved. Copyright © 2013 John Wiley & Sons, Ltd.
H‐reflexes reduce fatigue of evoked contractions after spinal cord injury
Authors: Bergquist Austin J. , Wiest Matheus J. , Okuma Yoshino , Collins David F.
Published: December 2013

Introduction: Neuromuscular electrical stimulation (NMES) over a muscle belly (mNMES) generates contractions predominantly through M‐waves, while NMES over a nerve trunk (nNMES) can generate contractions through H‐reflexes in people who are neurologically intact. We tested whether the differences between mNMES and nNMES are present in people with chronic motor‐complete spinal cord injury and, if so, whether they influence contraction fatigue. Methods: Plantar‐flexion torque and soleus electromyography were recorded from 8 participants. Fatigue protocols were delivered using mNMES and nNMES on separate days. Results: nNMES generated contractions that fatigued less than mNMES. Torque decreased the least when nNMES generated contractions, at least partly through H‐reflexes (n = 4 participants; 39% decrease), and torque decreased the most when contractions were generated through M‐waves, regardless of NMES site (nNMES 71% decrease, n = 4; mNMES, 73% decrease, n = 8). Conclusions: nNMES generates contractions that fatigue less than mNMES, but only when H‐reflexes contribute to the evoked contractions. Muscle Nerve 50:224–234, 2014
Explicit strategies for incompressible fluid‐structure interaction problems: Nitsche type mortaring versus Robin–Robin coupling
Authors: Burman Erik , Fernández Miguel A.
Published: December 2013

We discuss explicit coupling schemes for fluid‐structure interaction problems where the added mass effect is important. In this paper, we show the close relation between coupling schemes by using Nitsche's method and a Robin–Robin type coupling. In the latter case, the method may be implemented either using boundary integrals of the stresses or the more conventional discrete lifting operators. Recalling the explicit method proposed in Comput. Methods Appl. Mech. Engrg. 198(5‐8):766–784, 2009, we make the observation that this scheme is stable under a hyperbolic type CFL condition, but that optimal accuracy imposes a parabolic type CFL conditions because of the splitting error. Two strategies to enhance the accuracy of the coupling scheme under the hyperbolic CFL‐condition are suggested, one using extrapolation and defect‐correction and one using a penalty‐free non‐symmetric Nitsche method. Finally, we illustrate the performance of the proposed schemes on some numerical examples in two and three space dimensions. Copyright © 2013 John Wiley & Sons, Ltd.
Human adipocyte extracellular vesicles in reciprocal signaling between adipocytes and macrophages
Authors: Kranendonk Mariëtte E.G. , Visseren Frank L.J. , van Balkom Bas W.M. , Nolte‐'t Hoen Esther N.M. , van Herwaarden Joost A. , de Jager Wilco , Schipper Henk S. , Brenkman Arjan B. , Verhaar Marianne C. , Wauben Marca H.M. , Kalkhoven Eric
Published: December 2013

Objective

Extracellular vesicles (EVs) released by human adipocytes or adipose tissue (AT)‐explants play a role in the paracrine interaction between adipocytes and macrophages, a key mechanism in AT inflammation, leading to metabolic complications like insulin resistance (IR) were determined.

Methods

EVs released from in vitro differentiated adipocytes and AT‐explants ex vivo were characterized by electron microscopy, Western blot, multiplex adipokine‐profiling, and quantified by flow cytometry. Primary monocytes were stimulated with EVs from adipocytes, subcutaneous (SCAT) or omental‐derived AT (OAT), and phenotyped. Macrophage supernatant was subsequently used to assess the effect on insulin signaling in adipocytes.

Results

Adipocyte and AT‐derived EVs differentiated monocytes into macrophages characteristic of human adipose tissue macrophages (ATM), defined by release of both pro‐ and anti‐inflammatory cytokines. The adiponectin‐positive subset of AT‐derived EVs, presumably representing adipocyte‐derived EVs, induced a more pronounced ATM‐phenotype than the adiponectin‐negative AT‐EVs. This effect was more evident for OAT‐EVs versus SCAT‐EVs. Furthermore, supernatant of macrophages pre‐stimulated with AT‐EVs interfered with insulin signaling in human adipocytes. Finally, the number of OAT‐derived EVs correlated positively with patients HOMA‐IR.

Conclusions

A possible role for human AT‐EVs in a reciprocal pro‐inflammatory loop between adipocytes and macrophages, with the potential to aggravate local and systemic IR was demonstrated.
Succinonitrile‐based solid‐state electrolytes for dye‐sensitised solar cells
Authors: Byrne Owen , Coughlan Aoife , Surolia Praveen K. , Thampi K. Ravindranathan
Published: December 2013

Succinonitrile (SCN), a solid ion conductor (10−4 to 10−3 S/cm) in solid form at room temperature, is mixed with either 1,2‐dimethyl‐3‐propylimidazoliuum iodide or 1‐butyl‐3‐methyl imidazolium iodide ionic liquids for forming a solid plastic phase electrolyte for use in dye‐sensitised solar cell (DSSC). Cells containing these two electrolytes showed best energy conversion efficiencies of 6.3% and 5.6%, respectively. The commonly used DSSC electrolyte additives inhibit the formation of the SCN plastic phase. However, for the first time, an SCN‐additive (additive = guanidinium thiocyanate) electrolyte composition is reported here, which remains as a solid at room temperatures. By using these new solid electrolytes, a simple and rapid single‐step filling procedure for making solid‐state DSSC is outlined. This process, which reduces the required manufacturing steps from four to one, is most suitable for continuous, high‐throughput, commercial DSSC manufacturing lines. These new electrolytes have been tested under low incident light levels (200 lx) to investigate their suitability for indoor DSSC applications. Copyright © 2013 John Wiley & Sons, Ltd.
Structure‐guided analysis of catalytic specificity of the abundantly secreted chitosanase SACTE_5457 from Streptomyces sp. SirexAA‐E
Authors: Takasuka Taichi E. , Bianchetti Christopher M. , Tobimatsu Yuki , Bergeman Lai F. , Ralph John , Fox Brian G.
Published: December 2013

SACTE_5457 is secreted by Streptomyces sp. SirexAA‐E, a highly cellulolytic actinobacterium isolated from a symbiotic community composed of insects, fungi, and bacteria. Here we report the 1.84 Å resolution crystal structure and functional characterization of SACTE_5457. This enzyme is a member of the glycosyl hydrolase family 46 and is composed of two α‐helical domains that are connected by an α‐helical linker. The catalytic residues (Glu74 and Asp92) are separated by 10.3 Å, matching the distance predicted for an inverting hydrolysis reaction. Normal mode analysis suggests that the connecting α‐helix is flexible and allows the domain motion needed to place active site residues into an appropriate configuration for catalysis. SACTE_5457 does not react with chitin, but hydrolyzes chitosan substrates with an ∼4‐fold improvement in kcat/KM as the percentage of acetylation and the molecular weights decrease. Analysis of the time dependence of product formation shows that oligosaccharides with degree of polymerization <4 are not hydrolyzed. By combining the results of substrate docking to the X‐ray structure and end‐product analysis, we deduce that SACTE_5457 preferentially binds substrates spanning the −2 to +2 sugar binding subsites, and that steric hindrance prevents binding of N‐acetyl‐d‐glucosamine in the +2 subsite and may weakly interfere with binding of N‐acetyl‐d‐glucosamine in the +1 subsites. A proposal for how these constraints account for the observed product distributions is provided. Proteins 2014; 82:1245–1257. © 2013 Wiley Periodicals, Inc.
Highly stable amorphous indium‐zinc‐oxide thin‐film transistors with back‐channel wet‐etch process
Authors: Luo Dongxiang , Li Min , Xu Miao , Pang Jiawei , Zhang Yanli , Wang Lang , Tao Hong , Wang Lei , Zou Jianhua , Peng Junbiao
Published: December 2013

The stabilities of amorphous indium‐zinc‐oxide (IZO) thin film transistors (TFTs) with back‐channel‐etch (BCE) structure are investigated. A molybdenum (Mo) source/drain electrode was deposited on an IZO layer and patterned by hydrogen peroxide (H2O2)‐based etchants. Then, after etching the Mo layer, SF6 plasma with direct plasma mode was employed and optimized to improve the bias stress stability. Scanning electron microscopy and X‐ray photoelectron spectroscopic analysis revealed that the etching residues were removed efficiently by the plasma treatment. The modified BCE‐ TFTs showed only threshold voltage shifts of 0.25 V and –0.20 V under positive/negative bias thermal stress (P/NBTS, VGS = ±30 V, VDS = 0 V and T = 60 °C) after 12 hours, respectively. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
A New Phenolic Component from Triticum aestivum Sprouts and its Effects on LPS‐Stimulated Production of Nitric oxide and TNF‐α in RAW 264.7 Cells
Authors: Luyen Bui Thi Thuy , Tai Bui Huu , Thao Nguyen Phuong , Cha Ji Yun , Lee Young Mi , Kim Young Ho
Published: December 2013

An unusual new phenolic component, triticumoside (1), and eight known compounds, isoorientin (2), isoscoparin (3), (2R)‐2‐O‐β‐D‐glucopyranosyloxy‐4,7‐dimethoxy‐2H‐1,4‐benzoxazin‐3(4H)‐one (4), adenosine (5), β‐sitosterol (6), daucosterol (7), 6′‐O‐linolenoyl daucosterol (8), α‐tocopherol (9), were isolated from Triticum aestivum sprouts. The hybrid structure of 1, which is a hybrid between a flavone and a polyoxygenated benzene, is rarely found in natural sources. In addition, the effects of these compounds on LPS‐induced NO and TNF‐α production in RAW 264.7 cells were evaluated. At a concentration of 2.0 μM, compounds 2–4 significantly inhibited the production of both NO and TNF‐α. Compound 1 exhibited inhibitory activity on the secretion of TNF‐α at concentrations as low as 2.0 μM, but it did not reduce NO levels at any of the tested concentrations. Copyright © 2013 John Wiley & Sons, Ltd.
Flavonoids from Sophora moorcroftiana and their Synergistic Antibacterial Effects on MRSA
Authors: Wang Shuang‐Ying , Sun Zhong‐Lin , Liu Tao , Gibbons Simon , Zhang Wen‐Ju , Qing Mu
Published: December 2013

Synergy is now a widely recognized approach that has direct applicability for new pharmaceuticals. The ethanolic extract of the aerial parts of the herb Sophora moorcroftiana showed significant antibacterial activity against drug‐resistant Staphylococcus aureus, and its minimum inhibitory concentration (MIC) was 8 µg/mL. In a phytochemical study of the extract, five flavonoids were obtained. However, the isolates exhibited antibacterial activity in the range of 32–128 µg/mL, which was weaker than the extract. In combination with antibiotics, the antibacterially inactive compound genistein (1) and diosmetin (4) showed significant synergistic activity against drug‐resistant S. aureus. In combination with norfloxacin, genistein (1) reduced the MIC to 16 µg/mL and showed synergy against strain SA1199B with a fractional inhibitory concentration index (FICI) of 0.38. With the antibiotics norfloxacin, streptomycin and ciprofloxacin, diosmetin (4) showed synergy against SA1199B, RN4220 and EMRSA‐15, with FICI values of 0.38, 0.38 and 0.09, respectively. In an efflux experiment to elucidate a plausible mechanism for the observed synergy, genistein showed marginal inhibition of the NorA efflux protein. Copyright © 2013 John Wiley & Sons, Ltd.
Hyperoside Regulates the Level of Thymic Stromal Lymphopoietin through Intracellular Calcium Signalling
Authors: Han Na‐Ra , Go Ji‐Hyun , Kim Hyung‐Min , Jeong Hyun‐Ja
Published: December 2013

Hyperoside (HYP) is the principle active component of Crataegus pinnatifida. Thymic stromal lymphopoietin (TSLP) plays a vital role in the pathogenesis of allergic reactions. Here, we investigated how HYP regulates the levels of TSLP in a human mast cell line, HMC‐1 cells. We analyzed the levels of TSLP by treatment with HYP in phorbol myristate acetate plus calcium ionophore A23187‐stimulated HMC‐1 cells with ELISA and a polymerase chain reaction analysis. We also analyzed the pathway that HYP regulates TSLP by measuring the level of fluorescent intracellular calcium and using a Western blot analysis. HYP decreased the level of intracellular calcium in stimulated HMC‐1 cells. It also significantly decreased the production and mRNA expression of TSLP in stimulated HMC‐1 cells. It significantly decreased the levels of receptor‐interacting protein 2 and active caspase‐1 in stimulated HMC‐1 cells. HYP significantly decreased the translocation of NF‐κB into the nucleus and degradation of IκBα in the cytoplasm in stimulated HMC‐1 cells. Furthermore, it significantly decreased the production and mRNA expression of interleukin‐1β and interleukin‐6 in stimulated HMC‐1 cells. Taken together, our findings establish HYP as a potential agent for the treatment of allergic reactions. Copyright © 2013 John Wiley & Sons, Ltd.