bluuebunny/crossref_metadata_2025 huggingface dataset:
Mechanical properties of epoxy resins reinforced with synthetic boehmite (AlOOH) nanosheets
Authors: Wu Zhanjun , Zhuo Qin , Sun Tao , Wang Zhi
Published: September 2014

In this article, sheet boehmite (AlOOH), which was synthesized via a facile and environmental friendly method, was used as reinforcing agent to toughen Bisphenol A epoxy resin. The result of X–ray Diffraction (XRD) and IR spectrum indicated that the as–synthesized product was pure crystalline and high purity AlOOH. The effects of sheet AlOOH on the mechanical properties of AlOOH/epoxy nanocomposites were investigated. The results indicated that the introduction of AlOOH significantly improved the mechanical properties of epoxy resin. Compared with neat epoxy resin, the tensile strength and the fracture toughness (KIC) of the AlOOH/epoxy nanocomposites filled with 4 wt % AlOOH increased by 24.2% and 28.7%, respectively, while the flexural strength increased from 40.92 to 50.00 MPa. From Scanning Electron Microscope (SEM), a phase‐separated morphology and plenty of cervices and river branches were observed in the fractured surfaces of composites. With the increase of sheet AlOOH content, river‐shaped cracks became more and more intensive. Overall, the addition of sheet AlOOH is shown as a promising method for mechanical properties enhancement of epoxy matrix. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41409.
Electrolytically exfoliated graphene–polylactide‐based bioplastic with high elastic performance
Authors: Sriprachuabwong Chakrit , Duangsripat Sorawit , Sajjaanantakul Komkrit , Wisitsoraat Anurat , Tuantranont Adisorn
Published: September 2014

This work reports an innovative way to prepare biopolymer composite by incorporating graphene (GP) synthesized from electrolytic exfoliation into biodegradable polymer blend (polylactide/epoxidized palm oil: PLA/EPO) based on melt‐blending method and studies their physical properties for food packaging and related applications. Multilayer GP structure synthesized by electrolytic exfoliation is confirmed by transmission electron microscopy and Raman spectroscopy, whereas homogeneous GP incorporation in PLA/EPO is verified by scanning electron microscopy and X‐ray diffraction. From thermogravimetric analysis and heat deformation temperature (HDT) studies, the decomposition and HDTs of PLA/EPO/GP composites are higher than those of PLA/EPO but are lower than those of pristine PLA and tend to decrease with increasing GP content because of thermal conductivity effect. From standard tensile test, loading of GP in PLA/EPO at an optimal concentration of 0.6 wt % results in higher elongation at break by as much as 52%. The observed additional elongation under a given tension and the corresponding lower tensile strength/Young's modulus may be attributed to lower binding force of materials in the composite because of the presence of relatively weak GP–PLA/EPO interfaces. Moreover, oxygen permeability is found to decrease with increasing GP contents and oxygen permeability is reduced by 40.33% at the GP loading concentration of 0.6 wt %. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41439.
The Nightmare for Aboriginal People and its Relation to Dreamtime
Authors: Lord Alderdice John
Published: September 2014

Using his experience of applying “large group” psychology to analyzing and intervening in violent political conflicts in many parts of the world, the author describes his observations from a brief engagement with some Australian Aboriginal people and those who are trying to help them. He concludes that the way in which Aboriginal culture views existence, in particular its concepts of time, space and the symbolic, is a major contributor to their difficulties in challenging and coming to terms with the majority culture. He proposes that simply continuing to provide material resources to improve Aboriginal well‐being will not be effective, and that a conservation approach to Aboriginal culture may doom Aboriginal people to continuing misery and untimely deaths. A process of psychosocial engagement is proposed that requires a preparedness to change perspectives on both sides to address the long‐term problems of historically disturbed relationships between indigenous and colonizing peoples. Copyright © 2014 John Wiley & Sons, Ltd.
Australian Reconciliation from a US and New Zealand Perspective
Authors: Twemlow Stuart W.
Published: September 2014

This paper provides a perspective from two cultures and suggests ways to improve relationships between the Australian White fellas and First Nation (Aboriginal) populations. Several differences are highlighted especially the lack of formal protracted wars with the natives that characterized most other countries in the setting up of the British Empire. It is suggested that a great deal more work needs to be done with the way First Nation people were seen as non‐human until 1970, a topic that seems either talked out or denied depending on whom you talk to. Modern efforts focus on positive and collaborative ways to remedy the problems from those who stand firmly in both camps. Its seems to this writer that more needs to be known about the elder, the dream world and other levels of consciousness that influence the transmission of essential knowledge. With some hesitation I have gone along with the idea of making Western suggestions, but I know what I would rather have. Copyright © 2014 John Wiley & Sons, Ltd.
Radical Doubt and Radical Hope. The Eye of the Storm and then alakenhe it Rains
Authors: Nathan Pamela
Published: September 2014

In this paper I provide a glimpse of work of the two‐year partnership between the Central Australian Aboriginal Congress Aboriginal Corporation CAACAC based in Alice Springs – a large health organization with five remote health satellite services – and Creating a Safe Supportive Environment (CASSE) – a small psychoanalytic non‐voluntary organization focusing on violence and underlying trauma in Aboriginal communities. The project is called Kurunna Mwarre – Make My Spirit Inside Me Good. I hope to demonstrate the potential role of psychoanalysis in experiencing and being present during the emotional storms of a people in traumatic collision, catastrophic change and uncharted territories. The racial divide and cultural contact giving rise to violence and trauma is the eye of the thundering storm. I also hope to demonstrate the capacity of Aboriginal people to transform the stormy ruptures to provide a living continuity in being over time and into the future. Copyright © 2014 John Wiley & Sons, Ltd.
Psychoanalytic Reflections on an Experience of Australian Aboriginal Culture
Authors: Keogh Timothy
Published: September 2014

The paper represents reflections on the experience of a week spent as part of the Scientific Advisory Committee of CASSE (Creating a Safe Supportive Environment), as a guest of the Central Australian Aboriginal Congress Aboriginal Corporation (CAACAC). The reflections were based on a methodology of “psychoanalytic observation” processed with reference to the ideas of Bion, Ogden, Bolognini, Fairbairn and Scharff and Scharff. A key reflection concerned the significance of the rupture of the traditional cultural container to the current provision of mental health services. A further reflection was on the importance of the functioning of the CASSE/CAACAC reconciliation‐based partnership and how this might be enhanced by integrating Scharff and Scharff's (1991) dyadic version of Fairbairn's “Endopsychic Model” and Bion's concept of the container–contained relationship into a theoretical framework about its functioning. At the level of delivery of mental health services the importance of a focus on the commonalities between the Aboriginal and psychoanalytic worldviews is stressed. Copyright © 2014 John Wiley & Sons, Ltd.
Towards Vaporized Molecular Discrimination: A Quartz Crystal Microbalance (QCM) Sensor System Using Cobalt‐Containing Mesoporous Graphitic Carbon
Authors: Tang Jing , Torad Nagy L. , Salunkhe Rahul R. , Yoon Jang‐Hee , Al Hossain Md Shahriar , Dou Shi Xue , Kim Jung Ho , Kimura Tatsuo , Yamauchi Yusuke
Published: September 2014

A recent study on nanoporous carbon based materials (J. Am. Chem. Soc.­ 2012, 134, 2864) showed that the presence of abundant graphitized sp2 carbon species in the frameworks led to higher affinity for aromatic hydrocarbons than their aliphatic analogues. Herein, improved understanding of the sensitive and selective detection of aromatic substances by using mesoporous carbon (MPC)‐based materials, combined with a quartz crystal microbalance (QCM) sensor system, was obtained. MPCs were synthesized by direct carbonization of mesoporous polymers prepared from resol through a soft templating approach with Pluronic F127. The carbon‐based frameworks can be graphitized through the addition of a cobalt source to the precursor solution, according to the catalytic activity of the cobalt nanoparticles formed during the carbonization process. From the Raman data, the degree of the graphitization was clearly increased by increasing the cobalt content and elevating the carbonization temperature. From a QCM study, it was proved that the highly graphitized MPCs exhibited a higher affinity for aromatic hydrocarbons than their aliphatic analogues. By increasing the degree of graphitization in the carbon‐based pore walls, the MPCs showed both larger adsorption uptake and faster sensor response towards toxic benzene and toluene vapors.
Synthesis of a Large‐Sized Mesoporous Phosphosilicate Thin Film through Evaporation‐Induced Polymeric Micelle Assembly
Authors: Li Yunqi , Bastakoti Bishnu Prasad , Imura Masataka , Suzuki Norihiro , Jiang Xiangfen , Ohki Shinobu , Deguchi Kenzo , Suzuki Madoka , Arai Satoshi , Yamauchi Yusuke
Published: September 2014

A triblock copolymer, poly(styrene‐b‐2‐vinyl pyridine‐b‐ethylene oxide) (PS‐b‐P2VP‐b‐PEO) was used as a soft template to synthesize large‐sized mesoporous phosphosilicate thin films. The kinetically frozen PS core stabilizes the micelles. The strong interaction of the inorganic precursors with the P2VP shell enables the fabrication of highly robust walls of phosphosilicate and the PEO helps orderly packing of the micelles during solvent evaporation. The molar ratio of phosphoric acid and tetraethyl orthosilicate is crucial to achieve the final mesostructure. The insertion of phosphorus species into the siloxane network is studied by 29Si and 31P MAS NMR spectra. The mesoporous phosphosilicate films exhibit steady cell adhesion properties and show great promise as excellent materials in bone‐growth engineering applications.
Precompensated Second Order Repetitive Control of an Active Filter Under Varying Network Frequency
Authors: Ramos Germán A. , Costa‐Castelló Ramon , Olm Josep M.
Published: September 2014

Network frequency variations cause a dramatic performance decay in repetitive controller‐based shunt active power filters. This problem may be solved by adapting the sampling period in order to keep the ratio between the network period and the sampling period at a constant value. However, these changes may yield closed‐loop instability. The introduction of a precompensator that forces the plant to remain invariant despite sampling rate changes allows the use of standard LTI methods in control design and stability analysis as well. Moreover, in order to improve robustness in the face of network frequency estimation uncertainty and sampling time quantization, the regular repetitive controller is replaced by a high order one. Experimental results show the validity of the proposal.
A membrane stirrer for product recovery and substrate feeding
Authors: Femmer T. , Carstensen F. , Wessling M.
Published: September 2014

During fermentation processes, in situ product recovery (ISPR) using submerged membranes allows a continuous operation mode with effective product removal. Continuous recovery reduces product inhibition and organisms in the reactor are not exposed to changing reaction conditions. For an effective in situ product removal, submerged membrane systems should have a sufficient large membrane area and an anti‐fouling concept integrated in a compact device for the limited space in a lab‐scale bioreactor. We present a new membrane stirrer with integrated filtration membranes on the impeller blades as well as an integrated gassing concept in an all‐in‐one device. The stirrer is fabricated by rapid prototyping and is equipped with a commercial micromesh membrane. Filtration performance is tested using a yeast cell suspension with different stirring speeds and aeration fluxes. We reduce membrane fouling by backflushing through the membrane with the product stream. Biotechnol. Bioeng. 2015;112: 331–338. © 2014 Wiley Periodicals, Inc.
Interleukin‐4 receptor alpha overexpression in human bladder cancer correlates with the pathological grade and stage of the disease
Authors: Joshi Bharat H. , Leland Pamela , Lababidi Samir , Varrichio Frederick , Puri Raj K.
Published: September 2014

Previously, we have demonstrated that interleukin‐4 receptor α (IL‐4Rα) is overexpressed on a variety of human cancers and can serve as target for IL‐4 immunotoxin comprised of IL‐4 and a mutated Pseudomonas exotoxin. However, its expression and association with grade and clinical stage of bladder cancer has not been studied. IL‐4Rα expression was examined in human bladder cancer cell lines, mouse xenografts, and biopsy specimens at mRNA and protein levels by real‐time RT‐PCR and IHC/ISH techniques. We also examined the effect of IL‐4 on proliferation and invasion of bladder carcinoma cell lines. For tissue microarray (TMA) results, we analyzed the precision data using exact binomial proportion with exact two‐sided P‐values. We used Cochran–Armitage Statistics with exact two‐sided P‐values to examine the trend analysis of IL‐4Rα over grade or stage of the bladder cancer specimens. The influence of age and gender covariates was also analyzed using multiple logistic regression models. IL‐4Rα is overexpressed in five bladder cancer cell lines, while normal bladder and human umbilical vein cell lines (HUVEC) expressed at low levels. Two other chains of IL‐4 receptor complex, IL‐2RγC and IL‐13Rα1, were absent or weakly expressed. IL‐4 modestly inhibited the cell proliferation, but enhanced cell invasion of bladder cancer cell lines in a concentration‐dependent manner. Bladder cancer xenografts in immunodeficient mice also maintained IL‐4Rα overexpression in vivo. Analysis of tumor biopsy specimens in TMAs revealed significantly higher IL‐4Rα immunostaining (≥2+) in Grade 2 (85%) and Grade 3 (97%) compared to Grade 1 tumors (0%) (P ≤ 0.0001). Similarly, 9% stage I tumors were positive for IL‐4Rα (≥2+) compared to 84% stage II (P ≤ 0.0001) and 100% stages III–IV tumors (P ≤ 0.0001). IL‐13Rα1 was also expressed in tumor tissues but at low levels and it did not show any correlation with the grade and stage of disease. However, the IL‐2RγC was not expressed. Ten normal bladder specimens demonstrated ≤1+ staining for IL‐4Rα and IL‐13Rα1 and no staining for IL‐2RγC. These results demonstrate that IL‐4Rα is overexpressed in human bladder cancer, which correlates with advanced grade and stage of the disease. Thus, IL‐4Rα may be a bladder tumor‐associated protein and a prognostic biomarker.
BACE1 RNA interference improves spatial memory and attenuates Aβburden in a streptozotocin‐induced tau hyperphosphorylated rat model
Authors: Yu Chun‐Jiang , Liu Wei , Chen Hong‐Yuan , Wang Li , Zhang Zhi‐Ren
Published: September 2014

Both senile plaques and intracellular neurofibrillary tangles are important pathological characteristics in Alzheimer's disease. However, the relationship between Aβdeposition and tau hyperphosphorylation is unknown. In this study, the increased levels of full‐length amyloid precursor protein (APP), APP C‐terminal fragment (β‐CTF) and BACE1 were found in streptozotocin‐induced tau hyperphosphorylation models by quantitative polymerase chain reaction, Western blotting and immunohistochemistry methods. In the previous studies, few strategies focusing on inhibitingβ‐secretase (BACE1) in a tau hyperphosphorylation model were utilized. Here, BACE1 RNAi was used to treat the streptozotocin‐induced tau hyperphosphorylation animal models. BACE1 RNAi treatment improved the behavioural ability of animal models and reduced the amount of Aβ1‐40 and Aβ1‐42, accompanied by decreasing the levels of BACE1 andβ‐CTF. Our results demonstrated that neurological defects and neurotoxic fragments, including Aβandβ‐CTF, were eliminated by BACE1 RNAi in the tau hyperphosphorylated model, implying the efficiency and safety of BACE1RNAi treatment against Alzheimer's disease. Copyright © 2014 John Wiley & Sons, Ltd.
PNA‐Encoded Synthesis (PES) of a 10 000‐Member Hetero‐Glycoconjugate Library and Microarray Analysis of Diverse Lectins
Authors: Novoa Alexandre , Machida Takuya , Barluenga Sofia , Imberty Anne , Winssinger Nicolas
Published: September 2014

Identification of selective and synthetically tractable ligands to glycan‐binding proteins is important in glycoscience. Carbohydrate arrays have had a tremendous impact on profiling glycan‐binding proteins and as analytical tools. We report a highly miniaturized synthetic format to access nucleic‐acid‐encoded hetero‐glycoconjugate libraries with an unprecedented diversity in the combinations of glycans, linkers, and capping groups. Novel information about plant and bacterial lectin specificity was obtained by microarray profiling, and we show that a ligand identified on the array can be converted to a high‐affinity soluble ligand by straightforward chemistry.
A Simple Fragment of Cyclic Acyldepsipeptides Is Necessary and Sufficient for ClpP Activation and Antibacterial Activity
Authors: Carney Daniel W. , Compton Corey L. , Schmitz Karl R. , Stevens Julia P. , Sauer Robert T. , Sello Jason K.
Published: September 2014

The development of new antibacterial agents, particularly those with unique biological targets, is essential to keep pace with the inevitable emergence of drug resistance in pathogenic bacteria. We identified the minimal structural component of the cyclic acyldepsipeptide (ADEP) antibiotics that exhibits antibacterial activity. We found that N‐acyldifluorophenylalanine fragments function via the same mechanism of action as ADEPs, as evidenced by the requirement of ClpP for the fragments' antibacterial activity, the ability of fragments to activate Bacillus subtilis ClpP in vitro, and the capacity of an N‐acyldifluorophenylalanine affinity matrix to capture ClpP from B. subtilis cell lysates. N‐acyldifluorophenylalanine fragments are much simpler in structure than the full ADEPs and are also highly amenable to structural diversification. Thus, the stage has been set for the development of non‐peptide activators of ClpP that can be used as antibacterial agents.
The Importance of Catalyst Wettability
Authors: Wang Liang , Xiao Feng‐Shou
Published: September 2014

The contribution of catalyst wettability for catalytic performance has been ignored for a long time. In this Concept, we have briefly summarized recent works on the importance of catalyst wettability for improving catalytic activity, product selectivity, and catalyst stability. Suitable catalyst wettability is favourable for several reasons: 1) to enrich the reactants, leading to enhancement of the catalytic activity; 2) to inhibit side‐reactions, giving desirable products; 3) to reduce the poisoning of active sites and damage to catalyst framework, resulting in an increase of catalyst stability. These advantages of suitable catalyst wettability will be very important for designing and developing novel heterogeneous catalysts in the future.
Synthesis of Mono‐ and Dihydroxylated Amino Acids with New α‐Ketoglutarate‐Dependent Dioxygenases: Biocatalytic Oxidation of CH Bonds
Authors: Baud Damien , Saaidi Pierre‐Loïc , Monfleur Adam , Harari Marine , Cuccaro Julien , Fossey Aurélie , Besnard Marielle , Debard Adrien , Mariage Aline , Pellouin Virginie , Petit Jean‐Louis , Salanoubat Marcel , Weissenbach Jean , de Berardinis Véronique , Zaparucha Anne
Published: September 2014

Iron(II)/α‐ketoacid‐dependent oxygenases (αKAOs) are enzymes that mainly catalyse hydroxylation reaction. By using a genomic approach combining sequence comparison and protein‐domain sharing, a set of 131 αKAO enzymes was prepared. The screening of various substrates revealed five new αKAOs. Four αKAOs were found to be active towards L‐lysine, L‐ornithine and L‐arginine with total regio‐ and stereoselectivities and yielding the corresponding 3‐ or 4‐hydroxyamino acids. The enzymatic cascade reaction with two stereoselective regiodivergent αKAOs enabled the synthesis of 3,4‐dihydroxy‐L‐lysine.
Selective Hydrogenation of Phenol to Cyclohexanone in Water over Pd@N‐Doped Carbon Derived from Ionic‐Liquid Precursors
Authors: Xu Xuan , Li Haoran , Wang Yong
Published: September 2014

In this report, a kind of mesoporous N‐doped carbon (CN‐x) derived from N‐containing ionic‐liquid (IL) precursors were synthesized, and Pd@CN‐x prepared by a simple ultrasound‐assisted method showed higher catalytic activity for the selective hydrogenation of phenol and its derivatives under mild reaction conditions in water than commercial Pd@C and other common Pd heterogeneous catalysts. The catalytic activities of Pd@CN‐x derived from different ILs were different, and further study into the influencing factors, including physical properties, N species of CN‐x, and Pd status of Pd@CN‐x, were performed.
Graphene Oxide: An Efficient Acid Catalyst for Alcoholysis and Esterification Reactions
Authors: Zhu Shanhui , Chen Chengmeng , Xue Yanfeng , Wu Jianbing , Wang Jianguo , Fan Weibin
Published: September 2014

Evidence is presented for graphene oxide (GO), prepared by modified Hummers method, as a highly active, selective and reusable solid‐acid catalyst for the production of alkyl levulinates via alcoholysis or esterification. 95.5 % yield of ethyl levulinate was achieved by GO in furfuryl alcohol alcoholysis. Moreover, the surface SO3H groups were identified as the primary active sites, while the surface carboxyl groups worked synergistically to adsorb furfuryl alcohol.
New Layered Proton‐Conducting Oxides LixAl0.6Co0.4O2 and LixAl0.7Co0.3O2
Authors: Lan Rong , Tao Shanwen
Published: September 2014

Single‐phase layered oxides with nominal composition LiAl0.6Co0.4O2 and LiAl0.7Co0.3O2 were synthesised and tested as electrolytes for H2/air fuel cells. The maximum current and power densities of 382 mA cm−2 and 108 mW cm−2, respectively, were achieved at 650 °C when a 0.70 mm‐thick LiAl0.6Co0.4O2 pellet was used as the electrolyte. The ionic conductivity of LiAl0.7Co0.3O2 was 4.0×10−2 S cm−1 at 725 °C, which was derived from the series resistance of the impedance spectra of the H2/air fuel cells. For LiAl0.6Co0.4O2, the highest ionic conductivity was 7.7×10−2 S cm−1, observed at 625 °C. In the LiAl1−yCoyO2 series, the proton conductivity and working temperature of the materials are closely related to the composition. It is essential to integrate the multivalent element into the layered‐oxide lattice to achieve high proton conductivity, as the proton conduction is a coherent effect between the reduction of the multivalent element, such as cobalt, and the insertion of protons.
Robust Inclusion Complexes of Crown Ether Fused Tetrathiafulvalenes with Li+@C60 to Afford Efficient Photodriven Charge Separation
Authors: Supur Mustafa , Kawashima Yuki , Larsen Karina R. , Ohkubo Kei , Jeppesen Jan O. , Fukuzumi Shunichi
Published: September 2014

Inclusion complexes of benzo‐ and dithiabenzo‐crown ether functionalized monopyrrolotetrathiafulvalene (MPTTF) molecules were formed with Li+@C60 (1⋅Li+@C60 and 2⋅Li+@C60). The strong complexation has been quantified by high binding constants that exceed 106 M−1 obtained by UV/Vis titrations in benzonitrile (PhCN) at room temperature. On the basis of DFT studies at the B3LYP/6‐311G(d,p) level, the orbital interactions between the crown ether moieties and the π surface of the fullerene together with the endohedral Li+ have a crucial role in robust complex formation. Interestingly, complexation of Li+@C60 with crown ethers accelerates the intersystem crossing upon photoexcitation of the complex, thereby yielding 3(Li+@C60)*, when no charge separation by means of 1Li+@C60* occurs. Photoinduced charge separation by means of 3Li+@C60* with lifetimes of 135 and 120 μs for 1⋅Li+@C60 and 2⋅Li+@C60, respectively, and quantum yields of 0.82 in PhCN have been observed by utilizing time‐resolved transient absorption spectroscopy and then confirmed by electron paramagnetic resonance measurements at 4 K. The difference in crown ether structures affects the binding constant and the rates of photoinduced electron‐transfer events in the corresponding complex.
PMLABe Diol Synthesized by Ring‐Opening Polymerization of Racemic Benzyl β‐Malolactonate Initiated by Rare‐Earth Trisborohydride Complexes: An Experimental and DFT Study
Authors: Jaffredo Cédric G. , Schmid Matthias , del Rosal Iker , Mevel Teddy , Roesky Peter W. , Maron Laurent , Guillaume Sophie M.
Published: September 2014

Polymer diols are a class of polymeric building blocks of high interest for the synthesis of complex macromolecular edifices. Rare‐earth borohydride complexes are known as efficient initiators for the ring‐opening polymerization (ROP) of cyclic esters, directly affording α,ω‐dihydroxy‐telechelic polyesters. Here, were report the direct synthesis of poly(benzyl β‐malolactonate) (PMLABe) diols, from the ROP of racemic (benzyl β‐malolactonate) (rac‐MLABe), a valuable and renewable monomer, initiated by the homoleptic [Ln(BH4)3(thf)3] (Ln=La, Nd, and Sm) complexes. These initiators enabled the controlled ROP of this β‐lactone, affording well‐defined syndiotactic‐enriched (Pr≈0.83) PMLABes (Mn up to 21 300 g mol−1, ÐM≈1.5) as evidenced by size exclusion chromatography, 1H and 13C NMR spectroscopy, and MALDI‐ToF mass spectrometry analyses. The first and second insertions of rac‐MLABe, as assessed by DFT calculations, revealed more favorable stationary front‐side than migratory back‐side insertions, the thermodynamically and kinetically competitive ROP on two distinct arms with that on a one arm‐only, and the thermodynamically slightly favored formation of syndiotactic‐enriched PMLABes.
Making Fast Photoswitches Faster—Using Hammett Analysis to Understand the Limit of Donor–Acceptor Approaches for Faster Hemithioindigo Photoswitches
Authors: Maerz Benjamin , Wiedbrauk Sandra , Oesterling Sven , Samoylova Elena , Nenov Artur , Mayer Peter , de Vivie‐Riedle Regina , Zinth Wolfgang , Dube Henry
Published: September 2014

Hemithioindigo (HTI) photoswitches have a tremendous potential for biological and supramolecular applications due to their absorptions in the visible‐light region in conjunction with ultrafast photoisomerization and high thermal bistability. Rational tailoring of the photophysical properties for a specific application is the key to exploit the full potential of HTIs as photoswitching tools. Herein we use time‐resolved absorption spectroscopy and Hammett analysis to discover an unexpected principal limit to the photoisomerization rate for donor‐substituted HTIs. By using stationary absorption and fluorescence measurements in combination with theoretical investigations, we offer a detailed mechanistic explanation for the observed rate limit. An alternative way of approaching and possibly even exceeding the maximum rate by multiple donor substitution is demonstrated, which give access to the fastest HTI photoswitch reported to date.
Conformational Control of Oligo(p‐phenyleneethynylene)s with Intrinsic Substituent Electronic Effects: Origin of the Twist in Pentiptycene‐Containing Systems
Authors: Lin Che‐Jen , Kundu Sandip Kumar , Lin Cheng‐Kai , Yang Jye‐Shane
Published: September 2014

Dependence of the backbone planarity of oligo(p‐phenyleneethynylene)s (OPEs) on the intrinsic electronic character of substituents and on the nature of the solvent has been experimentally demonstrated with a series of center‐symmetrical five‐ring systems, pentiptycene‐pentiptycene‐arene‐pentiptycene‐pentiptycene, differing in the substituents on the central arene. In frozen 2‐methyltetrahydrofuran (MTHF), the adjacent pentiptycene units prefer to be in a mutually twisted orientation when the substituents are electron‐withdrawing (F and amido), resulting in a TPPT or TTTT conformation, whereas a planarized PPPP backbone is favored in the case of electron‐donating substituents (alkyl and alkoxy). The propensity to adopt the PPPP form is generally enhanced by replacing MTHF with either methylcyclohexane or mixed ethanol/methanol as solvent. These observations reveal that the twist between adjacent pentiptycene units in OPEs is a consequence of the electronic rather than steric effects of iptycenyl substituents. The electronic effect of iptycenyl substituents is manifested in decreased phenylene π polarizability as the net effect of both electron‐donating hyperconjugation and an electron‐withdrawing inductive effect. Variable‐temperature electronic absorption and emission spectroscopies are the critical tools for this work. Our findings provide important guidelines for conformational and electronic engineering of OPEs and for the design of novel iptycene‐based organic electronic materials.
Cationic Copper(I) Complexes as Highly Efficient Catalysts for Single and Double A3‐Coupling Mannich Reactions of Terminal Alkynes: Mechanistic Insights and Comparative Studies with Analogous Gold(I) Complexes
Authors: Grirrane Abdessamad , Álvarez Eleuterio , García Hermenegildo , Corma Avelino
Published: September 2014

Cationic CuL complexes (L=Buchwald‐type phosphane) with N co‐ligands have been characterised by structural and spectroscopic properties. These copper(I) complexes are extremely active catalysts, far more active than analogous gold(I) complexes, to promote the single and double A3 coupling of terminal alkynes, pyrrolidine and formaldehyde. The activity data show the possible ways in which the solvent can influence the catalytic performance by limiting complex solubility, by solvent decomposition or instability of the copper(I) redox state. Isolation of copper(I) complexes that are likely to be the key catalytic species has allowed light to be shed on the reaction mechanism.
Copper‐Catalyzed Mild Nitration of Protected Anilines
Authors: Hernando Elier , Castillo Rafael R. , Rodríguez Nuria , Gómez Arrayás Ramón , Carretero Juan C.
Published: September 2014

A practical copper‐catalyzed direct nitration of protected anilines, by using one equivalent of nitric acid as the nitrating agent, has been developed. This procedure features mild reaction conditions, wide structural scope (with regard to both N‐protecting group and arene substitution), and high functional‐group tolerance. Dinitration with two equivalents of nitric acid is also feasible.
Gallium‐Assisted Transfer Hydrogenation of Alkenes
Authors: Michelet Bastien , Bour Christophe , Gandon Vincent
Published: September 2014

We report a rare case of alkene transfer hydrogenation using a main‐group compound instead of a transition‐metal complex as catalyst. We disclosed that 1,4‐cyclohexadiene can be used as H2 surrogate towards olefin reduction in the presence of [IPrGaCl2][SbF6]. Hydrogenative cyclizations have also been carried out because this cationic gallium complex is also a potent hydroarylation catalyst.
Asymmetric Hetero‐Diels–Alder Reaction of Danishefsky’s Diene with α‐Ketoesters and Isatins Catalyzed by a Chiral N,N′‐Dioxide/Magnesium(II) Complex
Authors: Zheng Jianfeng , Lin Lili , Fu Kai , Zhang Yulong , Liu Xiaohua , Feng Xiaoming
Published: September 2014

A highly enantioselective hetero‐Diels–Alder reaction of Danishefsky’s diene with α‐ketoesters and isatins has been realized by using a chiral N,N′‐dioxide/MgII complex. In the presence of only 0.1–0.5 mol % catalyst, a series of substrates were transformed into the corresponding tetrasubstituted 2,3‐dihydropyran‐4‐ones in up to 99 % yield and more than 99 % ee in two hours.
One‐Pot Synthesis of Highly Fluorescent Pyrido[1,2‐a]indole Derivatives through CH/NH Activation: Photophysical Investigations and Application in Cell Imaging
Authors: Samala Srinivas , Pallavi Pragyan , Kumar Ravi , Arigela Rajesh K , Singh Gajendra , Ampapathi Ravi Sankar , Priya Amulya , Datta Sunando , Patra Abhijit , Kundu Bijoy
Published: September 2014

We describe a straightforward strategy for the synthesis of strongly fluorescent pyridoindoles by Pd‐catalyzed oxidative annulations of internal alkynes with C‐3 functionalized indoles through CH/NH bond activation in a one‐pot tandem process. Mechanistic investigations reveal the preferential activation of NH indole followed by CH activation during the cyclization process. Photophysical properties of pyridoindoles exhibited the highest fluorescence quantum yield of nearly 80 %, with emission color varying from blue to green to orange depending on the substructures. Quantum mechanical calculations provide insights into the observed photophysical properties. The strong fluorescence of the pyrido[1,2‐a]indole derivative has been employed in subcellular imaging, which demonstrates its localization in the cell nucleus.
Angular‐Resolved Magnetometry Beyond Triclinic Crystals Part II: Torque Magnetometry of Cp*ErCOT Single‐Molecule Magnets
Authors: Perfetti Mauro , Cucinotta Giuseppe , Boulon Marie‐Emmanuelle , El Hallak Fadi , Gao Song , Sessoli Roberta
Published: September 2014

The experimental investigation of the molecular magnetic anisotropy in crystals in which the magnetic centers are symmetry related, but do not have a parallel orientation has been approached by using torque magnetometry. A single crystal of the orthorhombic organometallic Cp*ErCOT [Cp*=pentamethylcyclopentadiene anion (C5Me5−); COT=cyclooctatetraenedianion (C8H82−)] single‐molecule magnet, characterized by the presence of two nonparallel families of molecules in the crystal, has been investigated above its blocking temperature. The results confirm an Ising‐type anisotropy with the easy direction pointing along the pseudosymmetry axis of the complex, as previously suggested by out‐of‐equilibrium angular‐resolved magnetometry. The use of torque magnetometry, not requiring the presence of magnetic hysteresis, proves to be even more powerful for these purposes than standard single‐crystal magnetometry. Furthermore, exploiting the sensitivity and versatility of this technique, magnetic anisotropy has been investigated up to 150 K, providing additional information on the crystal‐field splitting of the ground J multiplet of the ErIII ion.
Nickel(II)–Lanthanide(III) Magnetic Exchange Coupling Influencing Single‐Molecule Magnetic Features in {Ni2Ln2} Complexes
Authors: Ahmed Naushad , Das Chinmoy , Vaidya Shefali , Langley Stuart K. , Murray Keith S. , Shanmugam Maheswaran
Published: September 2014

Four isostructural [Ni2Ln2(CH3CO2)3(HL)4(H2O)2]3+(Ln3+=Dy (1), Tb (2), Ho (3) or Lu (4)) complexes and a dinuclear [NiGd(HL)2(NO3)3] (5) complex are reported (where HL=2‐methoxy‐6‐[(E)‐2′‐hydroxymethyl‐phenyliminomethyl]‐phenolate). For compounds 1–3 and 5, the Ni2+ ions are ferromagnetically coupled to the respective lanthanide ions. The ferromagnetic coupling in 1 suppresses the quantum tunnelling of magnetisation (QTM), resulting in a rare zero dc field Ni–Dy single‐molecule magnet, with an anisotropy barrier Ueff of 19 K.
Palladium‐Catalysed Direct Cross‐Coupling of Organolithium Reagents with Aryl and Vinyl Triflates
Authors: Vila Carlos , Hornillos Valentín , Giannerini Massimo , Fañanás‐Mastral Martín , Feringa Ben L.
Published: September 2014

A palladium‐catalysed cross‐coupling of organolithium reagents with aryl and vinyl triflates is presented. The reaction proceeds at 50 or 70 °C with short reaction times, and the corresponding products are obtained with moderate to high yields, with a variety of alkyl and (hetero)aryl lithium reagents.
Silaproline Helical Mimetics Selectively Form an All‐trans PPII Helix
Authors: Martin Charlotte , Legrand Baptiste , Lebrun Aurélien , Berthomieu Dorothée , Martinez Jean , Cavelier Florine
Published: September 2014

The polyproline II helix (PPII) is increasingly recognized as an important element in peptide and protein structures. The discovery of pertinent PPII peptidomimetics is of great interest to tune physical properties of the targeted structure. A series of silaproline oligomers from dimer to pentamer were synthesized. CD studies, NMR spectroscopy and molecular modeling revealed that the ribbon preferentially populates the polyproline type II secondary structure in both [D]chloroform and [D4]MeOH. The characteristics of this new lipophilic PPII‐like helix were determined.
Reversible pH‐ and Photocontrollable Carbohydrate‐Based Surfactants
Authors: Tabor Rico F. , Tan David D. , Han Sean S. , Young Scott A. , Seeger Zoe L. E. , Pottage Matthew J. , Garvey Christopher J. , Wilkinson Brendan L.
Published: September 2014

The parallel synthesis and properties of a library of photoswitchable surfactants comprising a hydrophobic butylazobenzene tail‐group and a hydrophilic carbohydrate head‐group, including the first surfactants to exhibit dual photo‐ and pH‐responsive behavior, is reported. This new generation of surfactants shows varying micelle morphologies, photocontrollable surface tension, and pH‐induced aggregation and adsorption.
ChemInform Abstract: Vanadium Sandwich Complexes with Boroxine and Boronyl Boroxine Ligands.
Authors: Li Da‐Zhi , Zhang Shi‐Guo , Liu Jun‐jie , Tang Cui
Published: September 2014

The geometric, electronic, and magnetic properties of the complexes B3O3X3V (C3v), [B3O3X3]2V (D3d), and [B3O3X3]3V2 (X: H, BO) are investigated by DFT calculations.
ChemInform Abstract: Dimanganese(II) Hydroxide Vanadate, Mn2(OH)[VO4].
Authors: Sun Kewen , Moeller Angela
Published: September 2014

The title compound is prepared by hydrothermal reaction of H2V3O8 and Mn(OAc)2 in the presence of LiCl (pH 9.1 adjusted with NH3, autoclave, 493 K, 3 d).
ChemInform Abstract: Thortveitite‐Type Tm2Si2O7.
Authors: Kahlenberg Volker , Aichholzer Paul
Published: September 2014

Single crystals of Tm2Si2O7 are obtained via flux synthesis in the system SiO2—Tm2O3—LiF with a molar ratio of Si:Tm = 4:1 at ambient pressure (sealed Pt tube, 1373 K, 2 h).
ChemInform Abstract: Highly Distorted Uranyl Ion Coordination and One/Two‐Dimensional Structural Relationship in the Ba2[UO2(TO4)2] (T: P, As) System: An Experimental and Computational Study.
Authors: Wu Shijun , Kowalski Piotr M. , Yu Na , Malcherek Thomas , Depmeier Wulf , Bosbach Dirk , Wang Shuao , Suleimanov Evgeny V. , Albrecht‐Schmitt Thomas E. , Alekseev Evgeny V.
Published: September 2014

α‐Ba2[UO2(PO4)2] (I) and β‐Ba2[UO2(PO4)2] (II) are prepared by H3BO3/B2O3 flux reactions using stoichiometric amounts of BaCO3, BPO4, and UO2(NO3)2 (Pt crucible, 1.
ChemInform Abstract: CaMg2P6O3N10 — A Quinary Oxonitridophosphate with an Unprecedented Tetrahedra Network Structure Type.
Authors: Marchuk Alexey , Neudert Lukas , Oeckler Oliver , Schnick Wolfgang
Published: September 2014

Colorless crystals of the title compound are prepared from stoichiometric mixtures of Ca(N3)2, Mg3N2, P3N5, and PON with catalytic amounts of NH4Cl as mineralizer (Walker‐type multi‐anvil assembly, 8 GPa, 1100 °C, 1 h).
ChemInform Abstract: A Novel Vanadosilicate with Hexadeca‐Coordinated Cs+ Ions as a Highly Effective Cs+ Remover.
Authors: Datta Shuvo Jit , Moon Won Kyung , Choi Do Young , Hwang In Chul , Yoon Kyung Byung
Published: September 2014

The mixed‐valent vanadosilicate K4.6{(VIVO)0.8 (VVO)1.2H2O}2 {Si12O32 [Cs(H2O)4]}·xH2O is obtained by partial oxidation of Na7{(VIVO)2H2O}2 {Si12O32 [Cs(H2O)4]}·xH2O with Br2 in an organic solvent (not specified) followed by cation exchange using a KCl solution (80 °C, 6 h).
ChemInform Abstract: Non‐Covalent Immobilization of Rare Earth Heterobimetallic Frameworks and Their Reactivity in an Asymmetric Michael Addition.
Authors: Robinson Jerome R. , Yadav Jagjit , Fan Xinyuan , Stanton Gretchen R. , Schelter Eric J. , Pericas Miquel A. , Walsh Patrick J.
Published: September 2014

A non‐covalent binding strategy for immobilization of Shibasaki′s REMB framework is developed.
ChemInform Abstract: C3‐Symmetric Cinchonine‐Squaramide‐Catalyzed Asymmetric Chlorolactonization of Styrene‐Type Carboxylic Acids with 1,3‐Dichloro‐5,5‐dimethylhydantoin: An Efficient Method to Chiral Isochroman‐1‐ones.
Authors: Han Xin , Dong Chune , Zhou Hai‐Bing
Published: September 2014

The nature of substrates plays an important role in the chlorolactonization reactions.
ChemInform Abstract: Organocatalytic Stereoselective Synthesis of Acyclic γ‐Nitrothioesters with All‐Carbon Quaternary Stereogenic Centers.
Authors: Arakawa Yukihiro , Fritz Sven P. , Wennemers Helma
Published: September 2014

Synthetically versatile acyclic γ‐nitrothioesters bearing an all‐carbon quaternary stereocenter are obtained from α‐substituted monothiomalonates (MTM) with high stereoselectivity.
ChemInform Abstract: Solvent‐Free Diels—Alder Reactions Catalyzed by FeCl3 on Aerosil® Silica.
Authors: Donatoni Maria C. , Junior Gilmar A. B. , de Oliveira Kleber T. , Ando Romulo A. , Brocksom Timothy J. , Dos Santos Alcindo A.
Published: September 2014

A mild and solvent free protocol using FeCl3 supported on aerosil silica as catalyst allows the preparation of Diels—Alder cycloadducts from p‐benzoquinones and simple dienes in high yields.
ChemInform Abstract: Synthesis and Antioxidant Activity of 5‐Hydroxycoumarans, 6‐Hydroxychromanes and Sulfur‐Containing Derivatives on Their Base.
Authors: Yagunov S. E. , Khol'shin S. V. , Kandalintseva N. V. , Prosenko A. E.
Published: September 2014

Several hydroxycoumarans (II) and hydroxychromanes (III) are prepared and used as starting material for the synthesis of the corresponding long‐chained thioethers.
ChemInform Abstract: Pd‐Catalyzed Nucleophilic Fluorination of Aryl Bromides.
Authors: Lee Hong Geun , Milner Phillip J. , Buchwald Stephen L.
Published: September 2014

The explored fluorination reaction is applicable to a wide scope of aryl and heteroaryl bromides and iodides to give high yields and proceeds without significant formation of side products.
ChemInform Abstract: cis‐Specific Hydrofluorination of Alkenylarenes under Palladium Catalysis Through an Ionic Pathway.
Authors: Emer Enrico , Pfeifer Lukas , Brown John M. , Gouverneur Veronique
Published: September 2014

The cis‐specific hydrofluorination proceeds through sequential H‐ and F+ addition and is distinct from known hydrofluorinations involving radical intermediates.
ChemInform Abstract: Stereoselective Silylcupration of Conjugated Alkynes in Water at Room Temperature.
Authors: Linstadt Roscoe T. H. , Peterson Carl A. , Lippincott Daniel J. , Jette Carina I. , Lipshutz Bruce H.
Published: September 2014

Optimized conditions allow the silylcupration of various electron‐deficient alkynes to give the corresponding products with high E‐selectivity.
ChemInform Abstract: An Effective Activation of Palladium Phosphine Complexes in Aqueous Phase Reactions of Hetero‐Aromatic Boronic Acids with Aryl Halides.
Authors: Bumagin N. A. , Veselov I. S. , Belov D. S.
Published: September 2014

The Suzuki reaction proceeds quantitatively in aqueous medium within short reaction times using palladium complexes as catalysts.
ChemInform Abstract: A Practical Procedure for Iron‐Catalyzed Cross‐Coupling Reactions of Sterically Hindered Aryl‐Grignard Reagents with Primary Alkyl Halides.
Authors: Sun Chang‐Liang , Krause Helga , Fuerstner Alois
Published: September 2014

The use of an iron phosphine complex as catalyst renders possible the cross‐coupling of sterically hindered arylmagnesium halides with primary alkyl halides and tosylates.
ChemInform Abstract: Flow‐Based, Cerium Oxide Enhanced, Low‐Level Palladium Sonogashira and Heck Coupling Reactions by Perovskite Catalysts.
Authors: Battilocchio Claudio , Bhawal Benjamin N. , Chorghade Rajeev , Deadman Benjamin J. , Hawkins Joel M. , Ley Steven V.
Published: September 2014

A low‐level palladium perovskite catalyst deposited on cerium oxide is efficiently employed for Pd‐catalyzed Sonogashira and Heck cross‐coupling reactions under continuous flow conditions.
ChemInform Abstract: Bioreductions Catalyzed by an Alcohol Dehydrogenase in Non‐Aqueous Media.
Authors: Kara Selin , Spickermann Dominik , Weckbecker Andrea , Leggewie Christian , Arends Isabel W. C. E. , Hollmann Frank
Published: September 2014

Long reaction times are required since only low conversions are observed after 24 h, albeit high enantioselectivity is determined already at that time.
ChemInform Abstract: Regioisomeric Allene Dimer Formation by the Reaction of Tetraarylbutatrienes with Tetracyanoethene.
Authors: Ueta Shoko , Hida Kazuo , Nishiuchi Masaki , Kawamura Yasuhiko
Published: September 2014

The allene dimers are stable in nonpolar solvents, but they converts to bicyclic systems (VI) in MeOH.
ChemInform Abstract: Catalyst‐Free Synthesis of Skipped Dienes from Phosphorus Ylides, Allylic Carbonates, and Aldehydes via a One‐Pot SN2′ Allylation—Wittig Strategy.
Authors: Xu Silong , Zhu Shaoying , Shang Jian , Zhang Junjie , Tang Yuhai , Dou Jianwei
Published: September 2014

The regioselective title reaction of stabilized phosphorus ylides with aliphatic and aromatic aldehydes as well as in situ generated ketenes [from (XV)] affords highly functionalized skipped dienes and synthetically important homoallylic allenoates with flexible substitution pattern.
ChemInform Abstract: Rh(III)‐ and Ir(III)‐Catalyzed C—H Alkynylation of Arenes under Chelation Assistance.
Authors: Xie Fang , Qi Zisong , Yu Songjie , Li Xingwei
Published: September 2014

An efficient, mild, and ortho selective Rh‐ and Ir‐catalyzed C—H alkynylation of diversified arenes using hypervalent iodine‐alkyne reagents is developed.
ChemInform Abstract: Direct Reductive Alkylation of Amine Hydrochlorides with Aldehyde Bisulfite Adducts.
Authors: Barniol‐Xicota Marta , Turcu Andreea L. , Codony Sandra , Escolano Carmen , Vazquez Santiago
Published: September 2014

The starting materials are prepared from the corresponding aldehydes by adding sodium bisulfite.
ChemInform Abstract: Enantioselective Synthesis of α‐Trifluoromethyl Arylmethylamines by Ruthenium‐Catalyzed Transfer Hydrogenation Reaction.
Authors: Dai Xiaoyang , Cahard Dominique
Published: September 2014

A bifunctional catalyst generated in situ from a ruthenium complex, chiral amine alcohol and isopropyl alcohol renders possible the transfer hydrogenation of ketimines (I) in excellent yields with high enantioselectivities.
ChemInform Abstract: An Easy Access to Tertiary Amides from Aldehydes and N,N‐Dialkylchlorothiophosphoramidates.
Authors: Pathak Uma , Bhattacharyya Shubhankar , Pandey Lokesh Kumar , Mathur Sweta , Jain Rajeev
Published: September 2014

The reaction of benzaldehyde with 2‐methylpiperidine does not give the desired product.
ChemInform Abstract: Regioselective Hydroacylation of 1,3‐Dienes by Cobalt Catalysis.
Authors: Chen Qing‐An , Kim Daniel K. , Dong Vy M.
Published: September 2014

Aromatic aldehydes give the 1,4‐hydroacylation products as the major isomer, while the 1,2‐addition products are mainly obtained by using aliphatic aldehydes.
ChemInform Abstract: Efficient and Selective Nitrile Hydration Reactions in Water Catalyzed by an Unexpected Dimethylsulfinyl Anion Generated in situ from CsOH and DMSO.
Authors: Chen Haonan , Dai Wujie , Chen Yi , Xu Qing , Chen Jianhui , Yu Lei , Zhao Yajuan , Ye Mingde , Pan Yuanjiang
Published: September 2014

The reaction is conducted under environmentally benign conditions.
ChemInform Abstract: Enantioselective Cyanosilylation of Aldehydes Catalyzed by Novel Camphor Derived Schiff Bases‐Titanium(IV) Complexes.
Authors: Blocka Ewelina , Bosiak Mariusz J. , Welniak Miroslaw , Ludwiczak Agnieszka , Wojtczak Andrzej
Published: September 2014

A series of camphor derived Schiff bases is designed and their utility as chiral ligands in the Ti(OiPr)4‐catalyzed cyanosilylation of a variety of aldehydes is demonstrated.
ChemInform Abstract: Terminal Aryl Alkenes and Alkynes as Arylcarboxy Surrogates Toward o‐Benzoxylation of 2‐Phenylpyridine Catalyzed by Copper.
Authors: Rout Saroj Kumar , Guin Srimanta , Gogoi Anupal , Majji Ganesh , Patel Bhisma K.
Published: September 2014

Styrenes possessing strongly electron‐withdrawing groups such es meta‐NO2 fail to give the corresponding ortho‐benzylated products.