bluuebunny/crossref_metadata_2025 huggingface dataset:
Bioactive Seed Layer for Surface‐Confined Self‐Assembly of Peptides
Authors: Vigier‐Carrière Cécile , Garnier Tony , Wagner Déborah , Lavalle Philippe , Rabineau Morgane , Hemmerlé Joseph , Senger Bernard , Schaaf Pierre , Boulmedais Fouzia , Jierry Loïc
Published: July 2015

The design and control of molecular systems that self‐assemble spontaneously and exclusively at or near an interface represents a real scientific challenge. We present here a new concept, an active seed layer that allows to overcome this challenge. It is based on enzyme‐assisted self‐assembly. An enzyme, alkaline phosphatase, which transforms an original peptide, Fmoc‐FFY(PO42−), into an efficient gelation agent by dephosphorylation, is embedded in a polyelectrolyte multilayer and constitutes the “reaction motor”. A seed layer composed of a polyelectrolyte covalently modified by anchoring hydrogelator peptides constitutes the top of the multilayer. This layer is the nucleation site for the Fmoc‐FFY peptide self‐assembly. When such a film is brought in contact with a Fmoc‐FFY(PO42−) solution, a nanofiber network starts to form almost instantaneously which extents up to several micrometers into the solution after several hours. We demonstrate that the active seed layer allows convenient control over the self‐assembly kinetics and the geometric features of the fiber network simply by changing its peptide density.
Cobalt(II)‐Catalyzed CH Alkynylation/Annulation with Terminal Alkynes: Selective Access to 3‐Methyleneisoindolin‐1‐one
Authors: Zhang Lin‐Bao , Hao Xin‐Qi , Liu Zhan‐Jiang , Zheng Xin‐Xiang , Zhang Shou‐Kun , Niu Jun‐Long , Song Mao‐Ping
Published: July 2015

A highly efficient cobalt(II)‐catalyzed alkynylation/annulation of terminal alkynes assisted by an N,O‐bidentate directing group is described. This protocol is characterized by wide substrate scope utilizing cheap cobalt catalysts, and offers a new approach to 3‐methyleneisoindolin‐1‐one, which can be converted into an oxadiazine salt in one step. Moreover, the directing group could be removed in three steps.
Development of novel polar thermoplastic vulcanizates based on ethylene acrylic elastomer and polyamide 12 with special reference to heat and oil aging
Authors: Reffai Syed Ismail Syed Mohammed , Chatterjee Tuhin , Naskar Kinsuk
Published: July 2015

Thermoplastic vulcanizates (TPVs) based on ethylene acrylic elastomer (AEM) and polyamide 12 (PA12) have been developed by the dynamic vulcanization process, in which selective cross‐linking of the elastomer phase (AEM) during melt mixing with the thermoplastic phase (PA12) has been carried out simultaneously. TPVs at varied blend ratios (50 : 50, 60 : 40, 70 : 30) of AEM/PA12 were prepared at 185°C at a rotor speed of 80 rpm up to 5 min of mixing. Di‐(2‐tert‐butyl peroxy isopropyl) benzene (DTBPIB) was chosen as the suitable cross‐linking peroxide to carry out the dynamic vulcanization. Morphology study reveals the development of continuous agglomerate of rubber network in case of all the TPVs took place and the average dimension of the rubber particles are in the range of 30–40 nm. TPV based on 50 : 50 AEM/PA12 shows better physicomechanical properties, thermal stability, and dynamic mechanical behavior among all the TPVs. For aging test, TPVs were exposed to air, ASTM oil 2 and 3. Air aging tests were carried out in hot air oven for 72 h at 125°C, while the oil aging tests were carried out after immersion of the samples into the oils in an aging oven. After aging, there are only slight deterioration of physicomechanical properties of the TPVs. Particularly in case of 50 : 50 blend of AEM/PA12, the retention of the properties even after aging was found excellent. The recyclability of these new TPVs is also found to be excellent leading to find potential application in automotives. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42655.
Composition‐Dependent Reaction Pathways and Hydrogen Storage Properties of LiBH4/Mg(AlH4)2 Composites
Authors: Pang Yuepeng , Liu Yongfeng , Zhang Xin , Li Qian , Gao Mingxia , Pan Hongge
Published: July 2015

Herein, an initial attempt to understand the relationships between hydrogen storage properties, reaction pathways, and material compositions in LiBH4–x Mg(AlH4)2 composites is demonstrated. The hydrogen storage properties and the reaction pathways for hydrogen release from LiBH4–x Mg(AlH4)2 composites with x=1/6, 1/4, and 1/2 were systematically investigated. All of the composites exhibit a four‐step dehydrogenation event upon heating, but the pathways for hydrogen desorption/absorption are varied with decreasing LiBH4/Mg(AlH4)2 molar ratios. Thermodynamic and kinetic investigations reveal that different x values lead to different enthalpy changes for the third and fourth dehydrogenation steps and varied apparent activation energies for the first, second, and third dehydrogenation steps. Thermodynamic and kinetic destabilization caused by the presence of Mg(AlH4)2 is likely to be responsible for the different hydrogen desorption/absorption performances of the LiBH4–x Mg(AlH4)2 composites.
Conjugated Oligomers and Polymers Sheathed with Designer Side Chains
Authors: Pan Chengjun , Zhao Chunhui , Takeuchi Masayuki , Sugiyasu Kazunori
Published: July 2015

Conjugated polymers (CPs) are often referred to as molecular wires because of their quasi one‐dimensional electronic wavefunctions delocalized along the polymer chains. However, in the solid state, CPs tend to self‐assemble through π‐stacking, which greatly attenuates the one‐dimensional nature. By molecular design, CPs can be molecularly insulated just like electric power cords, resulting in so‐called “insulated” molecular wires (IMWs). In this Focus Review, we will discuss their unique photophysical, electronic, and mechanical properties which originate from the absence of π‐stacking.
RhIII‐Catalyzed C−H Olefination of Benzoic Acids under Mild Conditions using Oxygen as the Sole Oxidant
Authors: Jiang Quandi , Zhu Changlei , Zhao Huaiqing , Su Weiping
Published: July 2015

Phthalide skeletons have been synthesized for the first time through a RhIII‐catalyzed C−H olefination of benzoic acids under mild conditions using oxygen as the sole oxidant. Aromatic acids bearing a variety of functional groups could react with diverse alkenes to afford the desired cyclized lactones or uncyclized alkenylarenes in moderate‐to‐excellent yields.
Simultaneous Target Flying Mode Identification and Altitude Estimation in Bistatic T/R‐R HFSWR
Authors: Zhao Kongrui , Yu Changjun , Zhou Gongjian , Quan Taifan
Published: July 2015

High frequency surface wave radar (HFSWR) cannot detect target altitude directly and is unable to identify flight mode. Assuming that the estimation and identification processes are mutually dependent, an integrated method called simultaneous identification and estimation (SIE) is proposed by applying a two‐level multiple model approach to the flight mode probability mass function (pmf) and state probability density function (pdf) simultaneously. The SIE involves two altitude estimation mode‐conditioned model sets, which are established utilizing the variation property of the propagation attenuation at different flight modes. The multiple model approach incorporated in SIE is different from the traditional interacting multiple model (IMM). It is applied at two levels: within each mode‐conditioned estimation model set and across all the mode‐conditioned estimation model sets. Simulations and real trials demonstrate the performance of the proposed SIE method.
GRB‐selected galaxies through cosmic time
Authors: Krühler T.
Published: July 2015

To use the luminous gamma‐ray bursts and their afterglows as messengers from the early Universe has been advocated ever since the discovery of the cosmological nature of the GRB phenomenon in the late nineties. It took, however, until the advent of Swift to detect high‐redshift GRBs in significant numbers, and to provide the localization capabilities to enable statistical samples of GRBs free of selection biases and complete in redshift. I will present and discuss some of the recent progress in the field, with an emphasize on new results derived from sample studies and their implications for the nature of GRBs and their host galaxies. I will particularly focus on observations made with the seven‐channel imager GROND and X‐shooter, an optical/NIR echelle spectrograph mounted at the Very Large Telescope since 2009. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
TANAMI: Multiwavelength and multimessenger observations of active galaxies
Authors: Kadler M. , Ojha R. , TANAMI Collaboration
Published: July 2015

Extragalactic jets launched from the immediate vicinity of supermassive black holes in radio‐loud active galactic nuclei (AGN) are key objects in modern astronomy and astroparticle physics. AGN jets carry a fraction of the total gravitational energy released during the accretion of matter onto supermassive black holes and are prime suspects as possible sources of ultrahigh‐energy cosmic rays and the recently detected extraterrestrial neutrinos at PeV energies. TANAMI (Tracking Active galactic Nuclei with Austral Milliarcsecond Interferometry) is a multiwavelength program monitoring AGN jets of the southern sky. It combines high‐resolution imaging and spectral monitoring at radio wavelengths with higher‐frequency observations at IR, optical/UV, X‐ray, and γ‐ray energies. We review recent results of the TANAMI program, highlighting AGN candidate neutrino‐emitters in the error circles of the IceCube PeV neutrino events. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Life cycle assessment of an integrated forest biorefinery: hot water extraction process case study
Authors: Gilani Banafsheh , Stuart Paul R.
Published: July 2015

The environmental footprint of bioproducts depends on the performance and implementation strategy of the biorefinery processes through which they are produced. Life cycle assessment (LCA) studies are categorized into two general types: attributional and consequential. The consequential life cycle assessment (CLCA) method illustrates the change of flows to and from environment, resulting from different potential decisions. Depending on the analysis goal,CLCAis known to be the proper approach to address the environmental analysis of integrated biorefineries with multiple bioproducts.

In this study, anLCAof hot water extraction‐based biorefinery strategy was performed, including five production pathways. Defined process options consisted of an extraction of hemicellulose to produce (i) biogas, (ii) hemicellulose for animal feed, (iii) hemicellulose forC5‐sugars, (iv)C5‐sugars, and (v) furfural. Except for the “biogas”, acetate salt was the by‐product of all the process options. ConsequentialLCAresults proved that the bark consumption, chemicals, and bioproducts transportation have significant environmental impacts. ‘Hemicellulose forC5‐sugars’ and ‘C5‐sugars’ outperformed other alternative options with a greenhouse gas reduction of 80% and 68%, respectively. Also, normalized results of these two options presented remarkable improvement of more than three times in human health impacts in comparison to existing process at the case study mill. © 2015 Society of Chemical Industry and John Wiley & Sons, Ltd
The Bioenergy Debate
Authors: Cozier Muriel
Published: July 2015

A multinational effort to establish the viability and efficacy of bioenergy has led to the publication of an in‐depth report which aims to bring some consensus to the bioenergy debate. Here Biofuels, Bioproducts and Biorefining (Biofpr) looks at some of the findings. © 2015 Society of Chemical Industry and John Wiley & Sons, Ltd
Reproductive and Developmental Toxicity of Orally Administered Botanical Composition, UP446‐Part III: Effects on Fertility and Early Embryonic Development to Implantation in Sprague Dawley Rats
Authors: Yimam Mesfin , Lee Young‐Chul , Hyun Eu‐Jin , Jia Qi
Published: July 2015

In recent years, high prevalence of adverse effects associated to the use of traditional medicines during pregnancy is becoming alarming due to the self‐medication of oral supplements by expecting mothers without supervision. Many expectant mothers use alternative and complementary medicines as a supplement to conventional pregnancy management with an inherent belief of considering herbal remedies as harmless. To the contrary, herbal remedies could incur a potential teratogenic risk both to the child bearing mother and the developing fetuses when consumed before or at the time of gestation. Here, we describe the potential adverse effects of orally administered UP446, a standardized bioflavonoid composition from the roots of Scutellaria baicalensis and the heartwoods of Acacia catechu, on fertility and early embryonic development to implantation in Sprague Dawley rats at doses of 250, 500, and 1000 mg/kg. Besides body weight and food consumption, reproductive functions, sperm motility and morphology, estrus cycle, and fertility rate were monitored. There were no statistically significant differences in reproductive function in all UP446 treated groups in both genders. Test substance impacts on reproductive parameters were very minimal. Neither sperm motility nor morphology was affected as a result of oral UP446 administrations in males. There were no treatment‐related effects on estrus cycle stages in females. No significant changes in necropsy or histopathology were observed for all the groups. Therefore, the no observed adverse effect level (NOAEL) of UP446 was considered to be 1000 mg/kg, the highest dose tested, in both genders
A single cell culture system using lectin‐conjugated magnetite nanoparticles and magnetic force to screen mutant cyanobacteria
Authors: Arai Sayuri , Okochi Mina , Shimizu Kazunori , Hanai Taizo , Honda Hiroyuki
Published: July 2015

Cyanobacteria can be utilized as a potential biocatalyst for the production of biofuels and biochemicals directly from CO2. Useful mutants of cyanobacteria, which can grow rapidly or are resistant to specific metabolic products, are essential to improve the productivity of biofuels. In this study, we developed a single cell culture system to effectively screen mutant cyanobacteria using magnetite nanoparticles and magnetic force. Lens culinaris Agglutinin (LCA) was selected as a lectin, which binds to the surface of Synechococcus elongatus PCC7942 cells and the LCA‐conjugated magnetite cationic liposomes (MCLs) were developed for magnetic labeling of PCC7942 cells. The MCL‐labeled PCC7942 cells were magnetically patterned at a single cell level by using 6,400 iron pillars of the pin‐holder device. The device enabled 1,600 single cells to be arrayed in one square centimeter. We cultured the patterned cells in liquid medium and achieved higher colony‐forming ratio (78.4%) than that obtained using conventional solid culture method (4.8%). Single cells with different properties could be distinguished in the single cell culture system depending on their growth. Furthermore, we could selectively pick up the target cells and subsequently perform efficient isolation culture. The ratio of successful isolation culture using the developed method was 13 times higher than that of the conventional methods. Thus, the developed system would serve as a powerful tool for screening mutant cyanobacteria. Biotechnol. Bioeng. 2016;113: 112–119. © 2015 Wiley Periodicals, Inc.
Neural basis of motivational approach and withdrawal behaviors in neurodegenerative disease
Authors: Shinagawa Shunichiro , Babu Adhimoolam , Sturm Virginia , Shany‐Ur Tal , Toofanian Ross Parnian , Zackey Diana , Poorzand Pardis , Grossman Scott , Miller Bruce L. , Rankin Katherine P.
Published: July 2015

Introduction

The Behavioral Inhibition System (BIS) and the Behavioral Activation System (BAS) have been theorized as neural systems that regulate approach/withdrawal behaviors. Behavioral activation/inhibition balance may change in neurodegenerative disease based on underlying alterations in systems supporting motivation and approach/withdrawal behaviors, which may in turn be reflected in neuropsychiatric symptoms.

Method

A total of 187 participants (31 patients diagnosed with behavioral variant of FTD [bvFTD], 13 semantic variant of primary progressive aphasia [svPPA], 14 right temporal variant FTD [rtFTD], 54 Alzheimer's disease [AD], and 75 older healthy controls [NCs]) were included in this study. Changes in behavioral inhibition/activation were measured using the BIS/BAS scale. We analyzed the correlation between regional atrophy pattern and BIS/BAS score, using voxel‐based morphometry (VBM).

Results

ADs had significantly higher BIS scores than bvFTDs and NCs. bvFTDs activation‐reward response (BAS‐RR) was significantly lower than ADs and NCs, though their activation‐drive (BAS‐D) was significantly higher than in ADs. Both AD and rtFTD patients had abnormally low activation fun‐seeking (BAS‐FS) scores. BIS score correlated positively with right anterior cingulate and middle frontal gyrus volume, as well as volume in the right precentral gyrus and left insula/operculum.

Conclusions

AD, bvFTD, and rtFTD patients show divergent patterns of change in approach/withdrawal reactivity. High BIS scores correlated with preservation of right‐predominant structures involved in task control and self‐protective avoidance of potentially negative reinforcers. Damage to these regions in bvFTD may create a punishment insensitivity that underlies patients’ lack of self‐consciousness in social contexts.
Factors Associated with Delays of Days to Decades to Criminal Prosecutions of Child Sexual Abuse
Authors: Connolly Deborah A. , Chong Kristin , Coburn Patricia I. , Lutgens Danyael
Published: July 2015

Until the latter part of the 20th century, legal doctrines made it almost impossible to successfully prosecute in criminal court a case involving child sexual abuse (CSA), whether the complaint was timely or delayed. Many English‐speaking countries have abrogated most formal legal barriers to prosecuting CSA cases, and courts are faced with the singular challenge of adjudicating sexual offenses against children that are reported to have happened years or decades earlier. We conducted analyses of 4,237 criminal complaints of CSA heard in Canadian criminal courts. There were several differences between timely and delayed prosecutions that led us to conclude that delayed prosecutions of CSA are common and due, in part, to the nature of the offense. Offense duration was associated with longer delays to prosecution. When the accused had access to the child through his position in the community, length of delay to prosecution was very long, particularly for male complainants. More research is needed on delayed CSA prosecutions, particularly given an apparent trend for jurisdictions to abolish barriers to criminal prosecutions of CSA that occurred years or decades earlier. Copyright © 2015 John Wiley & Sons, Ltd.
Pegylated liposomal mitomycin C prodrug enhances tolerance of mitomycin C: a phase 1 study in advanced solid tumor patients
Authors: Golan Talia , Grenader Tal , Ohana Patricia , Amitay Yasmine , Shmeeda Hilary , La‐Beck Ninh M. , Tahover Esther , Berger Raanan , Gabizon Alberto A.
Published: July 2015

Mitomycin C (MMC) has potent cytotoxicity but cumulative toxicity limits widespread use. In animals, pegylated liposomal mitomycin C lipid‐based prodrug (PL‐MLP) was well tolerated and more effective than free MMC. We evaluated PL‐MLP in patients with advanced cancer. Twenty‐seven patients were treated in escalating dose cohorts of 0.5–3.5 mg/kg (equivalent to 0.15–1.03 mg/kg MMC) every 4 weeks for up to 12 cycles, unless disease progression or unacceptable toxicity occurred. Pharmacokinetics were assessed during cycles 1 and 3. Per protocol maximum tolerated dose was not reached at 3.5 mg/kg. However, prolonged thrombocytopenia developed after repeated doses of 3 mg/kg or cumulative doses of 10–12 mg/kg. Dose‐related grade 3 or higher adverse events included fatigue, anemia, and decreased platelets. Cmax and AUC0‐∞ increased linearly over the dose range 0.5–2.0 mg/kg, and greater than linearly from 2.5 to 3.5 mg/kg; there were no significant differences in clearance of MLP between cycles 1 and 3. Median t1/2 was 23 h among dose cohorts, with no trend by dose or cycle. One patient had a partial response. Stable disease was observed in 10 patients across all dose levels. PL‐MLP has a long circulation time, was well tolerated, and can be administered to heavily pretreated patients at a single dose of 3.0 mg/kg and cumulative dose of 10–12 mg/kg before development of prolonged thrombocytopenia; this is nearly threefold the equivalent dose of MMC tolerated historically. This formulation may be active in a variety of tumor types and is better tolerated than free MMC.
Follow practical strategies for leading the way out of a rut
Authors: McCarthy Claudine
Published: July 2015

KEVIN STEELE, DIRECTOR OF ATHLETICS, MIDAMERICA NAZARENE UNIVERSITY
Practice strategies to successfully lead your athletics department through change
Authors: Hope Joan
Published: July 2015

Change is a constant at many colleges and universities. But what does it take to lead change?
Review court ruling on captioning at university football stadiums, basketball arenas and on athletics websites
Authors: Charmatz Marc
Published: July 2015

A Maryland federal court held that it wouldn't be a fundamental alteration for a university to provide captioning at football stadiums and basketball arenas and on athletics websites, but that factual issues existed as to whether providing captioning would be an undue burden on the university. Innes v. The Board of Regents of the University System of Maryland, Civil Action No. DKC 13‐2800, will now go to trial.
Bag‐1 promotes cell survival through c‐Myc‐mediated ODC upregulation that is not preferred under apoptotic stimuli in MCF‐7 cells
Authors: Ozfiliz Pelin , Kizilboga Tugba , Demir Salih , Alkurt Gizem , Palavan‐Unsal Narçin , Arisan Elif Damla , Dinler‐Doganay Gizem
Published: July 2015

Bag‐1, Bcl‐2 associated athanogene‐1, is a multifunctional protein that can regulate a wide variety of cellular processes: proliferation, cell survival, transcription, apoptosis and motility. Bag‐1 interacts with various targets in the modulation of these pathways; yet molecular details of Bag‐1's involvement in each cellular event are still unclear. We first showed that forced Bag‐1 expression promotes cell survival and prevents drug‐induced apoptosis in MCF‐7 breast cancer cells. Increased mRNA expressions of c‐myc protooncogene and ornithine decarboxylase (ODC), biosynthetic enzyme of polyamines, were detected in Bag‐1L+ cells, and western blots against the protein product of c‐Myc and ODC confirmed these findings. Once ODC, a c‐Myc target, gets activated, polyamine biosynthesis increases. We observed enhanced polyamine content in the Bag‐1L+ cells. On the contrary, when polyamine catabolic mechanisms were investigated, Bag‐1 silencing suppressed biosynthesis of polyamines because of the downregulation of ODC and upregulation of PAO. Exposure of cells to apoptotic inducers enhances the cell death mechanism by producing toxic products such as H2O2 and aldehydes. Bag‐1L+ cells prevented drug‐induced PAO activation leading to a decrease in H2O2 production following cisplatin or paclitaxel treatment. In this line, our results suggested that Bag‐1 indirectly affects cell survival through c‐Myc activated signalling that causes elevation of ODC levels, leading to an increase of the polyamine content. Copyright © 2015 John Wiley & Sons, Ltd.
Hydroxybenzaldoximes Are D‐GAP‐Competitive Inhibitors of E. coli 1‐Deoxy‐D‐Xylulose‐5‐Phosphate Synthase
Authors: Bartee David , Morris Francine , Al‐khouja Amer , Freel Meyers Caren L.
Published: July 2015

1‐Deoxy‐D‐xylulose 5‐phosphate (DXP) synthase is the first enzyme in the methylerythritol phosphate pathway to essential isoprenoids in pathogenic bacteria and apicomplexan parasites. In bacterial pathogens, DXP lies at a metabolic branch point, serving also as a precursor in the biosynthesis of vitamins B1 and B6, which are critical for central metabolism. In an effort to identify new bisubstrate analogue inhibitors that exploit the large active site and distinct mechanism of DXP synthase, a library of aryl mixed oximes was prepared and evaluated. Trihydroxybenzaldoximes emerged as reversible, low‐micromolar inhibitors, competitive against D‐glyceraldehyde 3‐phosphate (D‐GAP) and either uncompetitive or noncompetitive against pyruvate. Hydroxybenzaldoximes are the first class of D‐GAP‐competitive DXP synthase inhibitors, offering new tools for mechanistic studies of DXP synthase and a new direction for the development of antimicrobial agents targeting isoprenoid biosynthesis.
Tuning of the Temperature Window for Unit‐Cell and Pore‐Size Enlargement in Face‐Centered‐Cubic Large‐Mesopore Silicas Templated by Swollen Block Copolymer Micelles
Authors: Li Yingyu , Yi Jinhui , Kruk Michal
Published: July 2015

The unit‐cell size and pore diameter as functions of temperature are investigated in the syntheses of FDU‐12 silicas with face‐centered cubic structure templated by Pluronic (PEO‐PPO‐PEO) block copolymer micelles swollen by toluene. The temperature range in which the unit‐cell size and pore size strongly increase as temperature decreases is correlated with the critical micelle temperature (CMT) of the surfactant. While Pluronic F127 affords a wide range of unit‐cell parameters (28–51 nm) and pore diameters (16–32 nm), it renders moderately enlarged pore sizes at 25 °C. The use of Pluronic F108 with higher CMT affords FDU‐12 with very large unit‐cell size (∼49 nm) and large pore diameter (27 nm) at 23 °C. Large unit‐cell size (40–41 nm) and pore size (22 nm) were obtained even at 25 °C. The application of Pluronics F87 and F88 with much smaller molecular weights and higher CMTs also allows one to synthesize FDU‐12 with quite large unit‐cell parameters and pore sizes at room temperature. The present work demonstrates that one can judiciously select Pluronic surfactants with appropriate CMT to shift the temperature range in which the pore diameter is readily tunable.
Organometallic Probe for the Electronics of Base‐Stabilized Group 11 Metal Cations
Authors: Braunschweig Holger , Ewing William C. , Kramer Thomas , Mattock James D. , Vargas Alfredo , Werner Christine
Published: July 2015

A number of trimetalloborides have been synthesized through the reactions of base‐stabilized coinage metal chlorides with a dimanganaborylene lithium salt in the hope of using this organometallic platform to compare and evaluate the electronics of these popular coinage metal fragments. The adducts of CuI, AgI, and AuI ions, stabilized by tricyclohexylphosphine (PCy3), N‐1,3‐bis(4‐methylphenyl)imidazol‐2‐ylidene (ITol), or 1‐(2,6‐diisopropylphenyl)‐3,3,5,5‐tetramethylpyrrolidin‐2‐ylidene (CAAC), with [{Cp(CO)2Mn}2B]− were studied spectroscopically, structurally, and computationally. The geometries of the adducts fall into two classes, one symmetric and one asymmetric, each relying on the combined characteristics of both the metal and ligand. The energetic factors proposed as the causes of the structural differences were investigated by ETS‐NOCV (extended transition state‐natural orbitals for chemical valence) analysis, which showed the final geometry to be controlled by the competition between the tendency of the coinage metal to adopt a higher or lower coordination number and the willingness of the cationic fragment to participate in back‐bonding interactions.
Combined Experimental and Simulation Studies Suggest a Revised Mode of Action of the Anti‐Alzheimer Disease Drug NQ‐Trp
Authors: Berthoumieu Olivia , Nguyen Phuong H. , Castillo‐Frias Maria P. del , Ferre Sabrina , Tarus Bogdan , Nasica‐Labouze Jessica , Noël Sabrina , Saurel Olivier , Rampon Claire , Doig Andrew J. , Derreumaux Philippe , Faller Peter
Published: July 2015

Inhibition of the aggregation of the monomeric peptide β‐amyloid (Aβ) into oligomers is a widely studied therapeutic approach in Alzheimer’s disease (AD). Many small molecules have been reported to work in this way, including 1,4‐naphthoquinon‐2‐yl‐L‐tryptophan (NQ‐Trp). NQ‐Trp has been reported to inhibit aggregation, to rescue cells from Aβ toxicity, and showed complete phenotypic recovery in an in vivo AD model. In this work we investigated its molecular mechanism by using a combined approach of experimental and theoretical studies, and obtained converging results. NQ‐Trp is a relatively weak inhibitor and the fluorescence data obtained by employing the fluorophore widely used to monitor aggregation into fibrils can be misinterpreted due to the inner filter effect. Simulations and NMR experiments showed that NQ‐Trp has no specific “binding site“‐type interaction with mono‐ and dimeric Aβ, which could explain its low inhibitory efficiency. This suggests that the reported anti‐AD activity of NQ‐Trp‐type molecules in in vivo models has to involve another mechanism. This study has revealed the potential pitfalls in the development of aggregation inhibitors for amyloidogenic peptides, which are of general interest for all the molecules studied in the context of inhibiting the formation of toxic aggregates.
Silanization‐Based Zeolite Crystallization: Participation Degree and Pathway
Authors: Yan Yueer , Azhati Arepati , Guo Xiao , Zhang Yahong , Tang Yi
Published: July 2015

A clear and deep understanding of zeolite crystallization with the addition of organosilane is desirable for the reasonable design and preparation of hierarchical zeolites. Herein, the effects of different organosilanes on zeolite crystallization were systematically studied. It was found that organosilane plays the role of an inhibitor in the silanization‐based zeolite preparation, and this inhibition effect was determined by its participation degree. An organosilane with a high participation degree can result in the prolongation of nucleation and growth periods of zeolite as well as the variation of product properties. More importantly, a dynamic participation pathway of organosilane is proposed, that is, the growth of zeolite is accompanied by the continuous removal of organosilane, leading to an increase of product crystallinity as well as the decrease of mesoporosity. This study gives a new insight into the role that organosilane plays in zeolite crystallization, which will help to direct the rational selection of organosilane and design of crystallization condition for the optimal synthesis of hierarchical zeolites.
An Azine‐Linked Covalent Organic Framework: Synthesis, Characterization and Efficient Gas Storage
Authors: Li Zhongping , Zhi Yongfeng , Feng Xiao , Ding Xuesong , Zou Yongcun , Liu Xiaoming , Mu Ying
Published: July 2015

A azine‐linked covalent organic framework, COF‐JLU2, was designed and synthesized by condensation of hydrazine hydrate and 1,3,5‐triformylphloroglucinol under solvothermal conditions for the first time. The new covalent organic framework material combines permanent micropores, high crystallinity, good thermal and chemical stability, and abundant heteroatom activated sites in the skeleton. COF‐JLU2 possesses a moderate BET surface area of over 410 m2 g−1 with a pore volume of 0.56 cm3 g−1. Specifically, COF‐JLU2 displays remarkable carbon dioxide uptake (up to 217 mg g−1) and methane uptake (38 mg g−1) at 273 K and 1 bar, as well as high CO2/N2 (77) selectivity. Furthermore, we further highlight that it exhibits a higher hydrogen storage capacity (16 mg g−1) than those of reported COFs at 77 K and 1 bar.
Experimental and Theoretical Studies on the Magnetic Anisotropy in Lanthanide(III)‐Centered Fe3Ln Propellers
Authors: Rigamonti Luca , Nava Andrea , Boulon Marie‐Emmanuelle , Luzon Javier , Sessoli Roberta , Cornia Andrea
Published: July 2015

Compounds [Fe3Ln(tea)2(dpm)6] (Fe3Ln; Ln= Tb–Yb, H3tea=triethanolamine, Hdpm=dipivaloylmethane) were synthesized as lanthanide(III)‐centered variants of tetrairon(III) single‐molecule magnets (Fe4) and isolated in crystalline form. Compounds with Ln=Tb–Tm are isomorphous and show crystallographic threefold symmetry. The coordination environment of the rare earth, given by two tea3− ligands, can be described as a bicapped distorted trigonal prism with D3 symmetry. Magnetic measurements showed the presence of weak ferromagnetic Fe⋅⋅⋅Ln interactions for derivatives with Tb, Dy, Ho, and Er, and of weak antiferromagnetic or negligible coupling in complexes with Tm and Yb. Alternating current susceptibility measurements showed simple paramagnetic behavior down to 1.8 K and for frequencies reaching 10000 Hz, despite the easy‐axis magnetic anisotropy found in Fe3Dy, Fe3Er, and Fe3Tm by single‐crystal angle‐resolved magnetometry. Relativistic quantum chemistry calculations were performed on Fe3Ln (Ln=Tb–Tm): the ground J multiplet of Ln3+ ion is split by the crystal field to give a ground singlet state for Tb and Tm, and a doublet for Dy, Ho, and Er with a large admixture of mJ states. Gyromagnetic factors result in no predominance of gz component along the threefold axis, with comparable gx and gy values in all compounds. It follows that the environment provided by the tea3− ligands, though uniaxial, is unsuitable to promote slow magnetic relaxation in Fe3Ln species.
A Highly K+‐Selective Two‐Photon Fluorescent Probe
Authors: Schwarze Thomas , Riemer Janine , Eidner Sascha , Holdt Hans‐Jürgen
Published: July 2015

A highly K+‐selective two‐photon fluorescent probe for the in vitro monitoring of physiological K+ levels in the range of 1–100 mM is reported. The two‐photon excited fluorescence (TPEF) probe shows a fluorescence enhancement (FE) by a factor of about three in the presence of 160 mM K+, independently of one‐photon (OP, 430 nm) or two‐photon (TP, 860 nm) excitation and comparable K+‐induced FEs in the presence of competitive Na+ ions. The estimated dissociation constant (Kd) values in Na+‐free solutions (KdOP=(28±5) mM and KdTP=(36±6) mM) and in combined K+/Na+ solutions (KdOP=(38±8) mM and KdTP=(46±25) mM) reflecting the high K+/Na+ selectivity of the fluorescent probe. The TP absorption cross‐section (σ2PA) of the TPEF probe+160 mM K+ is 26 GM at 860 nm. Therefore, the TPEF probe is a suitable tool for the in vitro determination of K+.
A Stable Polyoxometalate‐Pillared Metal–Organic Framework for Proton‐Conducting and Colorimetric Biosensing
Authors: Zhou En‐Long , Qin Chao , Huang Peng , Wang Xin‐Long , Chen Wei‐Chao , Shao Kui‐Zhan , Su Zhong‐Min
Published: July 2015

A stable metal–organic framework pillared by Keggin‐type polyoxometalate, Cu6(Trz)10(H2O)4[H2SiW12O40]⋅8 H2O (Trz=1,2,4‐triazole) (1), has been prepared under hydrothermal condition. The 2D layer structure with a 22‐member ring was formed by Cu2+ ions, which are connected with each other via the Trz ligands on the ab plane. Thus, the 2D layers are further interconnected through Keggin polyoxoanions to generate a 3D porous network with a small 1D channel. Moreover, the presence of polyoxoanions make it exhibit selective adsorption of water and proton‐conducting properties. Additionally it showed efficient intrinsic peroxidase‐like activity, providing a simple and sensitive colorimetric assay to detect H2O2.
Origin of Orthogonality of Strain‐Promoted Click Reactions
Authors: Wagner Johannes A. , Mercadante Davide , Nikić Ivana , Lemke Edward A. , Gräter Frauke
Published: July 2015

Site‐specific labeling of biomolecules is rapidly advancing due to the discovery of novel mutually orthogonal reactions. Quantum chemistry studies have also increased our understanding of their relative rates, although these have until now been based on highly simplified reactants. Here we examine a set of strain‐promoted click‐type cycloaddition reactions of n‐propyl azide, 3‐benzyl tetrazine and 3‐benzyl‐6‐methyl tetrazine with cyclooctenes/ynes, in which we aim to address all relevant structural details of the reactants. Our calculations have included the obligatory handles used to attach the label and biomolecule as these can critically influence the stereochemistry and electron demand of the reaction. We systematically computed orbital gaps, activation and distortion energies using density functional theory and determined experimental rates for validation. Our results challenge the current paradigm of the inverse electron demand for this class of reactions. We found that the ubiquitous handles, when next to the triple bond of cyclooctynes, can switch the Diels–Alder type ligations to normal electron demand, a class we term as SPINEDAC reactions. Electron donating substituents on tetrazine can enhance normal demand but also increase distortion penalties. The presence and isomeric configuration of handles thus determine the reaction speed and regioselectivity. Our findings can be directly utilized in engineering genuine cycloaddition click chemistries for biological labeling.
Charged Porous Polymers using a Solid CO Cross‐Coupling Reaction
Authors: Zhang Pengfei , Jiang Xueguang , Wan Shun , Dai Sheng
Published: July 2015

Herein, we report a green, fast, efficient mechanochemical strategy for charged porous polymers (CPPs). A cationic CPP with basic anions and an anionic CPP with Li+ cations were fabricated by solid grinding under solvent‐free conditions. Compared with solution‐based synthesis, mechanochemical grinding can shorten the reaction time from dozens of hours to several minutes (60–90 min) to form polymers possessing a high molecular mass and low polydispersity. During the construction of CPPs, a Pd‐catalyzed solid polycondensation based on unactivated organic linkers was introduced. In particular, CPPs with basic phenolic or proline anions showed good activity and stability in SO2 capture, and Li+‐functionalized CPPs can be post‐modified to CPPs with other metal ions by ion exchange, highlighting the tailorable feature of ionic‐modified CPPs.
D3h‐Symmetric Porphyrin‐Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One‐Nanometer‐Sized Cavity
Authors: Ohkoda Yohei , Asaishi Akane , Namiki Tomoya , Hashimoto Tomoaki , Yamada Midori , Shirai Koichiro , Katagami Yuta , Sugaya Tomoaki , Tadokoro Makoto , Satake Akiharu
Published: July 2015

The one‐step synthesis of D3h‐symmetric cyclic porphyrin trimers 1 composed of three 2,2′‐[4,4′‐bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel‐mediated reductive coupling of meso‐5,15‐bis(6‐chloro‐4‐methoxycarbonylpyrid‐2‐yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin oligomers, an extremely specific separation was observed only for cyclic trimers 1 when using columns of silica gel modified with pyrenylethyl, cyanopropyl, and other groups. Structural analysis of cyclic trimers 1 was carried out by means of NMR spectroscopy and X‐ray crystallography. Treatment of an η3‐allylpalladium complex with a cyclic trimer gave a tris(palladium) complex containing three η3‐allylpalladium groups inside the space, which indicated that the bipyridyl moieties inside the ring could work as bidentate metalloligands.
Donor–Acceptor Heterojunction Configurations Based on DNA–Multichromophore Arrays
Authors: Nakamura Mitsunobu , Tsuto Koji , Jomura Ayumi , Takada Tadao , Yamana Kazushige
Published: July 2015

Multichromophore arrays of bis(2‐thienyl)diketopyrrolopyrrole (DPP) and naphthalenediimide (NDI) with two ZnII‐cyclens were constructed using thymidine DNA as a scaffold through the binding of the ZnII‐cyclens with thymine bases. We demonstrate photocurrent generation in a donor–acceptor heterojunction configuration consisting of the DPP (donor) and NDI (acceptor) arrays co‐immobilized on an Au electrode. The co‐immobilized electrode exhibited good photocurrent responses because of the efficient charge separation between the DPP and NDI arrays. In contrast, an immobilized electrode consisting of randomly assembled DPP‐NDI arrays generated no photocurrent response because DPP formed ground‐state charge‐transfer complexes with NDI in the randomly assembled arrays. Therefore, our approach to generate donor–acceptor heterojunctions based on DNA–multichromophore arrays is a useful method to efficiently generate photocurrent.
Asymmetric Total Synthesis of (−)‐Englerin A through Catalytic Diastereo‐ and Enantioselective Carbonyl Ylide Cycloaddition
Authors: Hanari Taiki , Shimada Naoyuki , Kurosaki Yasunobu , Thrimurtulu Neetipalli , Nambu Hisanori , Anada Masahiro , Hashimoto Shunichi
Published: July 2015

An asymmetric total synthesis of the guaiane sesquiterpene (−)‐englerin A, a potent and selective inhibitor of the growth of renal cancer cell lines, was accomplished. The basis of the approach is a highly diastereo‐ and enantioselective carbonyl ylide cycloaddition with an ethyl vinyl ether dipolarophile under catalysis by dirhodium(II) tetrakis[N‐tetrachlorophthaloyl‐(S)‐tert‐leucinate], [Rh2(S‐TCPTTL)4], to construct the oxabicyclo[3.2.1]octane framework with concomitant introduction of the oxygen substituent at C9 on the exo‐face. Another notable feature of the synthesis is ruthenium tetraoxide‐catalyzed chemoselective oxidative conversion of C9 ethyl ether to C9 acetate.
Construction of a Near‐Infrared Fluorescent Turn‐On Probe for Selenol and Its Bioimaging Application in Living Animals
Authors: Chen Hua , Dong Baoli , Tang Yonghe , Lin Weiying
Published: July 2015

As selenocysteine (Sec) carries out the majority of the functions of the various Se‐containing species in vivo, it is of high importance to develop reliable and rapid assays with biocompatibility to detect Sec. Herein, an NIR fluorescent turn‐on probe for highly selective detection of selenol was designed and synthesized. The probe exhibits large turn‐on signal upon treatment with selenocysteine (R‐SeH), and it was further demonstrated that the new NIR fluorescent probe can be employed to image selenol in living animals.
ChemInform Abstract: Tuning the Magnetic Properties of New Layered Iron Chalcogenides (BaF)2Fe2‐xQ3 (Q: S, Se) by Changing the Defect Concentration on the Iron Sublattice.
Authors: Sturza Mihai , Allred Jared M. , Malliakas Christos D. , Bugaris Daniel E. , Han Fei , Chung Duck Young , Kanatzidis Mercouri G.
Published: July 2015

Single‐phase (BaF)2Fe2‐xQ3 (Q: S, Se; x = 0, 0.1, 0.2, 0.3) are prepared by solid state reaction of stoichiometric amounts of BaS, BaSe, BaF2, Fe, S, and Se (graphite crucible inside evacuated silica tube, 850 °C, 12 h).
ChemInform Abstract: Acid‐Stable Peroxoniobophosphate Clusters to Make Patterned Films.
Authors: Son Jung‐Ho , Park Deok‐Hie , Keszler Douglas A. , Casey William H.
Published: July 2015

(Me4N)5 [HNb4P2O14(O2)4] ·9H2O (I) is prepared by hydrothermal reaction of Nb2O5, Me4NOH, and H3PO4 (autoclave, 130 °C, 16 h) followed by addition of 30% aq.
ChemInform Abstract: Asymmetric Hydroamination Catalyzed by a New Chiral Zirconium System: Reaction Scope and Mechanism.
Authors: Zhou Xiaoguang , Wei Bing , Sun Xiu‐Li , Tang Yong , Xie Zuowei
Published: July 2015

New chiral zirconium systems catalyze the asymmetric hydroamination/cyclization of primary aminoalkenes affording five‐ and six‐membered N‐heterocyclic amines with up to 94% e.e.
ChemInform Abstract: Aqueous Enantioselective Aldol Reaction of Methyl‐ and Phenylglyoxal Organocatalyzed by N‐Tosyl‐(Sa)‐binam‐L‐prolinamide.
Authors: Moles Fernando J. N. , Guillena Gabriela , Najera Carmen
Published: July 2015

Chiral γ‐oxo‐β‐hydroxycarbonyl compounds and ε‐oxo‐δ‐hydroxy‐α,β‐unsaturated esters are synthesized by aldol reactions of methylglyoxal (I) under aqueous conditions or phenylglyoxal monohydrate with ketones or aldehydes.
ChemInform Abstract: Intermolecular Carbene S—H Insertion Catalyzed by Engineered Myoglobin‐Based Catalysts.
Authors: Tyagi Vikas , Bonn Rachel B. , Fasan Rudi
Published: July 2015

Engineered variants of sperm whale myoglobin are found to efficiently catalyze C—S bond forming transformation across a diverse set of aryl and alkyl mercaptan substrates and α‐diazoester carbene donors, providing high conversions (60—99%) and catalytic turnover numbers.
ChemInform Abstract: Synthesis of a Heterogeneous Artificial Metallolipase with Chimeric Catalytic Activity
Authors: Filice M. , Romero O. , Gutierrez‐Fernandez J. , de las Rivas B. , Hermoso J. A. , Palomo J. M.
Published: July 2015

A new solid‐phase strategy using lipase as a biomolecular scaffold to produce a large amount of Cu2+‐metalloenzyme is presented.
ChemInform Abstract: Transition‐Metal‐Catalyzed Intramolecular Cyclization of Amido(hetero)arylboronic Acid Aldehydes to Isoquinolinones and Derivatives.
Authors: Marques C. S. , Peixoto D. , Burke A. J.
Published: July 2015

The efficient metal‐catalyzed intramolecular cyclization of amidoarylboronic acid aldehydes (I), (III), (V) is the key step in the simple three step synthesis of a library of chiral isoquinolinone derivatives with aryl (II), pyridyl (IV), and thiophene (VI) cores.
ChemInform Abstract: Rh2(esp)2‐Catalyzed Allylic and Benzylic Oxidations.
Authors: Wang Yi , Kuang Yi , Wang Yuanhua
Published: July 2015

The reaction is performed with remarkably low catalyst loading.
ChemInform Abstract: A Tuned Bicyclic Proazaphosphatrane for Catalytically Enhanced N‐Arylation Reactions with Aryl Chlorides.
Authors: Kim So Han , Kim Min , Verkade John G. , Kim Youngjo
Published: July 2015

An efficient Pd‐catalyzed process for the Buchwald type amination of aryl chlorides with primary and secondary aliphatic and aromatic amines is described using a new and electron‐rich proazaphosphatrane (PPT) as ligand.
ChemInform Abstract: A Baker—Venkataraman Retro‐Claisen Cascade Delivers a Novel Alkyl Migration Process for the Synthesis of Amides.
Authors: Ameen Dana , Snape Timothy J.
Published: July 2015

If water is not strictly excluded the initially formed Baker—Venkataraman rearrangement products of substrates (I) undergo retro‐Claisen rearrangement to form amides (II).
ChemInform Abstract: Cu‐Catalyzed Asymmetric Addition of sp2‐Hybridized Zirconium Nucleophiles to Racemic Allyl Bromides.
Authors: Sidera Mireia , Fletcher Stephen P.
Published: July 2015

Alkenylzirconium nucleophiles generated in situ by the hydrozirconation of terminal alkynes undergo dynamic kinetic asymmetric allylic alkenylation with racemic allyl bromides to give enantioenriched products.
ChemInform Abstract: Palladium‐Catalyzed Regio‐ and Stereoselective Cross‐Addition of Terminal Alkynes to Ynol Ethers and Synthesis of 1,4‐Enyn‐3‐ones.
Authors: Hari Babu Madala , Dwivedi Vikas , Kant Ruchir , Sridhar Reddy Maddi
Published: July 2015

The title reaction proceeds in a highly regio‐ and stereoselective manner.
ChemInform Abstract: Copper‐Catalyzed ortho‐Halogenation of Arenes and Heteroarenes Directed by a Removable Auxiliary.
Authors: Li Bo , Liu Bin , Shi Bing‐Feng
Published: July 2015

The new method is scalable and tolerates a broad range of functional groups and heteroarenes, providing an efficient access to chlorinated arenes and heteroarenes.
ChemInform Abstract: Regioselective Nitration of Phenols and Phenyl Ethers Using Aluminium Nitrate on Silica as a Nitrating System.
Authors: Patil Mahadeo R. , Mohite Pravinkumar H. , Shisodia Suresh , Keri Rangappa S.
Published: July 2015

The reported methodology shows a considerable enhancement in the reaction rate along with a high ortho‐selectivity, excellent yields and ease of operation.
ChemInform Abstract: Cation‐Triggered Switchable Asymmetric Catalysis with Chiral Aza‐CrownPhos.
Authors: Ouyang Guang‐Hui , He Yan‐Mei , Li Yong , Xiang Jun‐Feng , Fan Qing‐Hua
Published: July 2015

The catalytic activity of a novel aza‐crown‐phosphoramidite ligand is switched on by the interaction with sodium ions.
ChemInform Abstract: Palladium‐Catalyzed Regioselective Synthesis of Oxygenated Biphenyls.
Authors: Chittimalla Santhosh Kumar , Kuppusamy Rajesh , Akavaram Naresh
Published: July 2015

The title compounds are easily obtained by Pd‐catalyzed Michael addition reaction of arylboronic acids to cyclohexa‐2,4‐dienones.
ChemInform Abstract: A Facile Synthesis of Novel Pyridone‐Anellated Spirooxindolepyrrolidines via 1,3‐Dipolar Cycloaddition.
Authors: Al‐As'ad Randa M. , El‐Abadelah Mustafa M. , Sabri Salim S. , Zahra Jalal A. , Awwadi Firas F. , Voelter Wolfgang
Published: July 2015

of N‐methylmaleimide as 1,3‐dipolarophile and the appropriate azomethine ylide generated in situ via decarboxylative condensation reaction of α‐amino acids with pyridine‐anellated isatin