bluuebunny/crossref_metadata_2025 huggingface dataset:
General Formation of MS (M = Ni, Cu, Mn) Box‐in‐Box Hollow Structures with Enhanced Pseudocapacitive Properties
Authors: Yu Xin‐Yao , Yu Le , Shen Laifa , Song Xiaohui , Chen Hongyu , Lou Xiong Wen (David)
Published: September 2014

Complex hollow structures of metal sulfides could be promising materials for energy storage devices such as supercapacitors and lithium‐ion batteries. However, it is still a great challenge to fabricate well‐defined metal sulfides hollow structures with multi‐shells, hierarchical architectures, and non‐spherical shape. In this work, a template‐engaged strategy is developed to synthesize hierarchical NiS box‐in‐box hollow structures with double‐shells. The NiS box‐in‐box hollow structures constructed by ultrathin nanosheets are evaluated as electrode materials for supercapacitors. As expected, the NiS box‐in‐box hollow structures exhibit excellent rate performance and impressive cycling stability due to their unique nano‐architecture. More importantly, the synthetic method can be easily extended to synthesize other transition metal sulfides box‐in‐box hollow structures. For example, we have also successfully synthesized similar CuS and MnS box‐in‐box hollow structures. The present work makes a significant contribution to the design and synthesis of transition metal sulfides hollow structures with non‐spherical shape and complex architecture, as well as their potential applications in electrochemical energy storage.
Wideband Omnidirectional Polarization‐Insensitive Light Absorbers Made with 1D Silicon Gratings
Authors: Yoon Jae Woong , Lee Kyu Jin , Wu Wenhua , Magnusson Robert
Published: September 2014

Photonic resonance in lossy films with 1D periodicity is generally associated with narrow spectral, angular, and polarization‐selective absorption. Contrarily, in this paper a 1D amorphous Si grating structure is demonstrated that efficiently absorbs fully hemispherical unpolarized light in the entire visible spectral domain. The absorber provides a broad spectral continuum of densely populated resonant photonic states as well as a cooperating wide‐angular antireflection effect, resulting in the observed broadband, omnidirectional, and polarization‐insensitive light absorption. The absorber performance is experimentally verified with precise fabrication and conical input beam spectral analysis. The absorber's fundamental mechanisms, explained in detail, are applicable to other semiconducting materials including GaAs, Ge, and SiC. These materials provide the absorber design with potential impact on practical device applications including near/mid/long infrared detectors and stray background rejection surfaces for imaging and spectroscopy.
Second‐Order Nonlinear Optical Switch of a New Hydrogen‐Bonded Supramolecular Crystal with a High Laser‐Induced Damage Threshold
Authors: Sun Zhihua , Li Shenhui , Zhang Shuquan , Deng Feng , Hong Maochun , Luo Junhua
Published: September 2014

Organic nonlinear optical (NLO) materials are anticipated as the competitive successors to inorganic compounds in the highly controllable photonic devices. Here, a new supramolecular crystal, bis(imidazolium hydrochlorate) dihydrate 18‐crown‐6 (1), behaves as a potential modulator of quadratic NLO responses. It is found that (1) possesses a superior NLO switching‐contrast of up to ∼12, a remarkable switching reversibility, and a quite high laser‐induced damage threshold (up to ∼8.9 GW/cm2), which may guarantee its device application. In addition, mechanism studies reveal that both the freezing of thermally activated molecular vibrations and atomic displacements are greatly contributive to its NLO switching. Such an exceptional coupling in (1) is distinguishing from the prevenient order–disorder transition and much superior to the chemical changes of other NLO switches. It is believed that the findings provide a concrete example of a solid‐state NLO switch and will urge further development of these desirable devices, as well as to establish new design strategies.
Integrated Design of Organic Hole Transport Materials for Efficient Solid‐State Dye‐Sensitized Solar Cells
Authors: Xu Bo , Tian Haining , Lin Lili , Qian Deping , Chen Hong , Zhang Jinbao , Vlachopoulos Nick , Boschloo Gerrit , Luo Yi , Zhang Fengling , Hagfeldt Anders , Sun Licheng
Published: September 2014

A series of triphenylamine‐based small molecule organic hole transport materials (HTMs) with low crystallinity and high hole mobility are systematically investigated in solid‐state dye‐sensitized solar cells (ssDSCs). By using the organic dye LEG4 as a photosensitizer, devices with X3 and X35 as the HTMs exhibit desirable power conversion efficiencies (PCEs) of 5.8% and 5.5%, respectively. These values are slightly higher than the PCE of 5.4% obtained by using the state‐of‐the‐art HTM Spiro‐OMeTAD. Meanwhile, transient photovoltage decay measurement is used to gain insight into the complex influences of the HTMs on the performance of devices. The results demonstrate that smaller HTMs induce faster electron recombination in the devices and suggest that the size of a HTM plays a crucial role in device performance, which is reported for the first time.
PTCH1 expression at diagnosis predicts imatinib failure in chronic myeloid leukaemia patients in chronic phase
Authors: Alonso‐Dominguez Juan M. , Grinfeld Jacob , Alikian Mary , Marin David , Reid Alistair , Daghistani Mustafa , Hedgley Corinne , O'Brien Stephen , Clark Richard E. , Apperley Jane , Foroni Letizia , Gerrard Gareth
Published: September 2014

The tyrosine kinase inhibitor (TKI) imatinib has revolutionized the management of chronic myeloid leukaemia (CML). However, around 25% of patients fail to sustain an adequate response. We sought to identify gene‐expression biomarkers that could be used to predict imatinib response. The expression of 29 genes, previously implicated in CML pathogenesis, were measured by TaqMan Low Density Array in 73 CML patient samples. Patients were divided into low and high expression for each gene and imatinib failure (IF), probability of achieving CCyR, progression free survival and CML related OS were compared by Kaplan–Meier and log‐rank. Results were validated in a second cohort of 56 patients, with a further technical validation using custom gene‐expression assays in a conventional RT‐qPCR in a sub‐cohort of 37 patients. Patients with low PTCH1 expression showed a worse clinical response for all variables in all cohorts. PTCH1 was the most significant predictor in the multivariate analysis compared with Sokal, age and EUTOS. PTCH1 expression assay showed the adequate sensitivity, specificity and predictive values to predict for IF. Given the different treatments available for CML, measuring PTCH1 expression at diagnosis may help establish who will benefit best from imatinib and who is better selected for second generation TKI. Am. J. Hematol. 90:20–26, 2015. © 2014 Wiley Periodicals, Inc.
The Collision Auto Repair Safety Study (CARSS): A health and safety intervention
Authors: Parker David L. , Bejan Anca , Brosseau Lisa M. , Skan Maryellen , Xi Min
Published: September 2014

Background

Collision repair employs approximately 205,500 people in 33,400 shops. Workers are exposed to a diverse array of chemical, physical, and ergonomic hazards.

Methods

CARSS was based on a random and purposeful sample. Baseline and one baseline and one‐year evaluations consisted of 92 questions addressing issues, such as Right‐to‐Know, fire protection, painting‐related hazards, ergonomics, electrical safety, and personal protective equipment. Owners received a report and selected at least 30% of items found deficient for remediation. In‐person and web‐based services were provided.

Results

Forty‐nine shops were evaluated at baseline and 45 at follow‐up. At baseline, 54% of items were present. This improved to 71% at follow‐up (P < 0.0001). Respiratory protection improved 37% (P < 0.0001) and Right‐to‐Know training increased 30% (P < 0.0001). Owners completed 61% of items they selected for remediation.

Conclusions

Small businesses' interventions should address the lack of personnel and administrative infrastructure. Tailored information regarding hazards and easy‐to‐use training and administrative programs overcome many barriers to improvement. Am. J. Ind. Med. 58:88–100, 2015. © 2014 Wiley Periodicals, Inc.
Informed consent for exome sequencing research in families with genetic disease: The emerging issue of incidental findings
Authors: Bergner Amanda L. , Bollinger Juli , Raraigh Karen S. , Tichnell Crystal , Murray Brittney , Blout Carrie Lynn , Telegrafi Aida Bytyci , James Cynthia A.
Published: September 2014

Genomic sequencing technology is increasingly used in genetic research. Studies of informed consent for exome and genome sequencing (ES/GS) research have largely involved hypothetical scenarios or healthy individuals enrolling in population‐based studies. Studies have yet to explore the consent experiences of adults with inherited disease. We conducted a qualitative interview study of 15 adults recently enrolled in a large‐scale ES/GS study (11 affected adults, four parents of affected children). Our study had two goals: (1) to explore three theoretical barriers to consent for ES/GS research (interpretive/technical complexity, possibility of incidental findings, and risks of loss of privacy); and (2) to explore how interviewees experienced the consent process. Interviewees could articulate study goals and processes, describe incidental findings, discuss risks of privacy loss, and reflect on their consent experience. Few expected the study would identify the genetic cause of their condition. All elected to receive incidental findings. Interviewees acknowledged paying little attention to potential implications of incidental findings in light of more pressing goals of supporting research regarding their own medical conditions. Interviewees suggested that experience living with a genetic condition prepared them to adjust to incidental findings. Interviewees also expressed little concern about loss of confidentiality of study data. Some experienced the consent process as very long. None desired reconsent prior to return of study results. Families with inherited disease likely would benefit from a consent process in which study risks and benefits were discussed in the context of prior experiences with genetic research and genetic disease. © 2014 Wiley Periodicals, Inc.
Disruption of the ARID1B and ADAMTS6 loci due to a t(5;6)(q12.3;q25.3) in a patient with developmental delay
Authors: Malli Theodora , Duba Hans‐Christoph , Erdel Martin , Marschon Renate , Kranewitter Wolfgang , Deutschbauer Sabine , Kralik Johanna , Diel Evita , Güenther Barbara , Mueller Doris , Webersinke Gerald
Published: September 2014

Here, we report on a male patient with developmental delay, speech impairment, mild dysmorphic features, and borderline intellectual disability, bearing a de novo balanced t(5;6)(q11;q25.3). By combining FISH and long distance inverse PCR, we identified two genes, ADAMTS6 and ARID1B, which were disrupted at the translocation breakpoints. Due to the opposing transcriptional directions of the two genes, no fusion transcripts could be formed. ADAMTS6 on chromosome 5 encodes a zinc metalloprotease. To date, there has been no information about the substrates and the exact role of this enzyme protein. ARID1B on chromosome 6 is involved in chromatin remodeling and transcriptional activation and is known to play a role in neural development. To our knowledge, this is the fourth translocation involving ARID1B reported in association with intellectual disability. ARID1B haploinsufficiency has already been described in patients with intellectual disabilities with or without corpus callosum abnormalities, Coffin–Siris syndrome and autism (OMIM 614562 and OMIM 614556). A review of patients with ARID1B mutations reveals their broad phenotypic variability. The phenotype of the present patient is of the mildest described to date and further underscores this observation. We conclude that the most prominent and consistent clinical findings in patients with ARID1B haploinsufficiency are developmental delay, speech impairment and intellectual disability and propose that patients with unresolved genetic background and these clinical findings should be considered for ARID1B mutation screening. © 2014 Wiley Periodicals, Inc.
Direct Synthesis of Boron‐Protected Alkenyl‐ and Alkylborons via Copper‐Catalyzed Formal Hydroboration of Alkynes and Alkenes
Authors: Yoshida Hiroto , Takemoto Yuki , Takaki Ken
Published: September 2014

Formal hydroboration of internal alkynes proceeds regio‐ and stereoselectively by the use of a diboron reagent masked with 1,8‐diaminonaphthalene (dan) in the presence of readily available [(Ph3P)3CuCl], leading to direct formation of diverse B‐protected alkenylborons in high yield. The B(dan) moiety can also be efficiently installed into the CC double bond of alkenes to afford the respective alkylborons.
A Method for Evaluating the Level of Soluble β‐Amyloid(1–40/1–42) in Alzheimer’s Disease Based on the Binding of Gelsolin to β‐Amyloid Peptides
Authors: Yu Yanyan , Zhang Lin , Li Chenglin , Sun Xiaoyu , Tang Daoquan , Shi Guoyue
Published: September 2014

In the present work, a new electrochemical strategy for the sensitive and specific detection of soluble β‐amyloid Aβ(1–40/1–42) peptides in a rat model of Alzheimer’s disease (AD) is described. In contrast to previous antibody‐based methods, β‐amyloid(1–40/1–42) was quantified based on its binding to gelsolin, a secretory protein present in the cerebrospinal fluid (CSF) and plasma. The level of soluble β‐amyloid peptides in the CSF and various brain regions were found with this method to be lower in rats with AD than in normal rats.
Ein selbstorganisierter supramolekularer ternärer Komplex zur magnetischen Trennung von Proteinen
Authors: Samanta Avik , Ravoo Bart Jan
Published: September 2014

Für die Proteomik ist die einfache und effiziente Isolierung von Proteinen aus einer Mischung essenziell. Wir beschreiben hier einen supramolekularen Ansatz, um selektiv Proteine aus einer Proteinmischung einzufangen und mithilfe eines Magnetfeldes auszufällen. Dies geschieht durch die Bildung eines multivalenten selbstorganisierten Komplexes aus einer verdünnten Lösung der folgenden drei Komponenten: Cyclodextrin‐beschichtete magnetische Nanopartikel, Adamantan‐ und Kohlenhydrat‐funktionalisierte nichtkovalente Vernetzer und Lectine. Der selbstorganisierte ternäre Komplex wird im Magnetfeld ausgefällt und kann durch die Zugabe eines konkurrierenden Bindungspartners leicht wieder in Lösung gebracht werden. Wir zeigen, dass dieser supramolekulare Ansatz zur Aufreinigung von Proteinen mithilfe magnetischer Extraktion hoch selektiv und effizient erfolgt.
Polymer‐Induced Surface Modifications of Pd‐based Thin Films Leading to Improved Kinetics in Hydrogen Sensing and Energy Storage Applications
Authors: Ngene Peter , Westerwaal Ruud J. , Sachdeva Sumit , Haije Wim , de Smet Louis C. P. M. , Dam Bernard
Published: September 2014

The catalytic properties of Pd alloy thin films are enhanced by a thin sputtered PTFE coating, resulting in profound improvements in hydrogen adsorption and desorption in Pd‐based and Pd‐catalyzed hydrogen sensors and hydrogen storage materials. The remarkably enhanced catalytic performance is attributed to chemical modifications of the catalyst surface by the sputtered PTFE leading to a possible change in the binding strength of the intermediate species involved in the hydrogen sorption process.
Selektive Inhibition des Immunoproteasoms durch ligandeninduzierte Vernetzung des katalytischen Zentrums
Authors: Dubiella Christian , Cui Haissi , Gersch Malte , Brouwer Arwin J. , Sieber Stephan A. , Krüger Achim , Liskamp Rob M. J. , Groll Michael
Published: September 2014

Das Konzept der Proteasom‐Inhibition zählt zu den jüngsten Errungenschaften der Blutkrebstherapie und stellt eine vielversprechende Strategie zur Regulierung von Autoimmunerkrankungen dar. Diese Arbeit beschreibt die selektive Hemmung der katalytischen β5‐Untereinheit des Immunoproteasoms durch peptidische Sulfonylfluoride, die nur geringen zytotoxischen Effekt haben. Strukturelle und massenspektrometrische Analysen offenbarten einen neuartigen Inhibitionsmechanismus, der zu einer Umpolung und irreversiblen Vernetzung des proteasomalen aktiven Zentrums führt. Hierdurch identifizierten wir die Sulfonylfluorid‐Kopfgruppe für die Weiterentwicklung von Immunoproteasom‐spezifischen Verbindungen und ihren möglichen Einsatz zur Behandlung von Autoimmunerkrankungen.
Directional Photomanipulation of Breath Figure Arrays
Authors: Wang Wei , Du Can , Wang Xiaofan , He Xiaohua , Lin Jiaping , Li Lei , Lin Shaoliang
Published: September 2014

Porous polymeric films are of paramount importance in many areas of modern science and technology. However, processing methods typically based on direct writing, imprint, and lithography techniques have low throughput and are often limited to specific fabricated shapes. Herein, we demonstrate the directional photomanipulation of breath figure arrays (BFAs) formed by an azobenzene‐containing block copolymer to address the aforementioned problems. Under the irradiation of linearly polarized light, the round pores in the BFAs were converted to rectangular, rhombic, and parallelogram‐shaped pores in 30 min, due to the anisotropic mass migration based on the photo‐reconfiguration of the azobenzene units. Through a secondary irradiation after rotating the sample by 90°, the transformed pores were apparently recovered. Therefore, this non‐contacted, directional photomanipulation technique in conjunction with breath figure processing opens a new route to nano/microporous films with finely tuned features.
Atomic Layer Deposition Overcoating: Tuning Catalyst Selectivity for Biomass Conversion
Authors: Zhang Hongbo , Gu Xiang‐Kui , Canlas Christian , Kropf A. Jeremy , Aich Payoli , Greeley Jeffrey P. , Elam Jeffrey W. , Meyers Randall J. , Dumesic James A. , Stair Peter C. , Marshall Christopher L.
Published: September 2014

The terraces, edges, and facets of nanoparticles are all active sites for heterogeneous catalysis. These different active sites may cause the formation of various products during the catalytic reaction. Here we report that the step sites of Pd nanoparticles (NPs) can be covered precisely by the atomic layer deposition (ALD) method, whereas the terrace sites remain as active component for the hydrogenation of furfural. Increasing the thickness of the ALD‐generated overcoats restricts the adsorption of furfural onto the step sites of Pd NPs and increases the selectivity to furan. Furan selectivities and furfural conversions are linearly correlated for samples with or without an overcoating, though the slopes differ. The ALD technique can tune the selectivity of furfural hydrogenation over Pd NPs and has improved our understanding of the reaction mechanism. The above conclusions are further supported by density functional theory (DFT) calculations.
Chiral Palladacycle Catalysts Generated on a Single‐Handed Helical Polymer Skeleton for Asymmetric Arylative Ring Opening of 1,4‐Epoxy‐1,4‐dihydronaphthalene
Authors: Yamamoto Takeshi , Akai Yuto , Suginome Michinori
Published: September 2014

Post‐polymerization CH activation of poly(quinoxaline‐2,3‐diyl)‐based helically chiral phosphine ligands (PQXphos) with palladium(II) acetate afforded chiral phosphapalladacycles quantitatively. In situ generated palladacycles exhibited enantioselectivities up to 94 % ee in the palladium‐catalyzed asymmetric ring‐opening arylation of 1,4‐epoxy‐1,4‐dihydronaphthalenes with arylboronic acids.
[2+2]‐Photocycloaddition von 3‐Alkenyloxy‐2‐cycloalkenonen: enantioselektive Lewis‐Säure‐Katalyse und Ringerweiterung
Authors: Brimioulle Richard , Bach Thorsten
Published: September 2014

Durch Verwendung substöchiometrischer Mengen (50 Mol‐%) einer chiralen Lewis‐Säure ist es gelungen, die intramolekulare [2+2]‐Photocycloaddition der Titelverbindungen mit hoher Enantioselektivität (bis zu 94 % ee) zu realisieren. Die resultierenden tricyclischen Produkte unterziehen sich im sauren Milieu einer Ringerweiterungsreaktion, in deren Verlauf der Cyclobutanring gespalten wird und racemisierungsfrei anellierte Sieben‐ oder Achtringe gebildet werden. Die Ringerweiterung kann unter BF3‐Katalyse mit einer diastereoselektiven Reduktion (Triethylsilan) oder Allylübertragung (Allyltrimethylsilan) kombiniert werden (48–87 % Ausbeute).
Ultrahigh Energy Density Realized by a Single‐Layer β‐Co(OH)2 All‐Solid‐State Asymmetric Supercapacitor
Authors: Gao Shan , Sun Yongfu , Lei Fengcai , Liang Liang , Liu Jiawei , Bi Wentuan , Pan Bicai , Xie Yi
Published: September 2014

A conceptually new all‐solid‐state asymmetric supercapacitor based on atomically thin sheets is presented which offers the opportunity to optimize supercapacitor properties on an atomic level. As a prototype, β‐Co(OH)2 single layers with five‐atoms layer thickness were synthesized through an oriented‐attachment strategy. The increased density‐of‐states and 100 % exposed hydrogen atoms endow the β‐Co(OH)2 single‐layers‐based electrode with a large capacitance of 2028 F g−1. The corresponding all‐solid‐state asymmetric supercapacitor achieves a high cell voltage of 1.8 V and an exceptional energy density of 98.9 Wh kg−1 at an ultrahigh power density of 17 981 W kg−1. Also, this integrated nanodevice exhibits excellent cyclability with 93.2 % capacitance retention after 10 000 cycles, holding great promise for constructing high‐energy storage nanodevices.
Bowl‐like SnO2@Carbon Hollow Particles as an Advanced Anode Material for Lithium‐Ion Batteries
Authors: Liang Jin , Yu Xin‐Yao , Zhou Han , Wu Hao Bin , Ding Shujiang , Lou Xiong Wen (David)
Published: September 2014

Despite the great advantages of hollow structures as electrodes for lithium‐ion batteries, one apparent common drawback which is often criticized is their compromised volumetric energy density due to the introduced hollow interior. Here, we design and synthesize bowl‐like SnO2@carbon hollow particles to reduce the excessive hollow interior space while retaining the general advantages of hollow structures. As a result, the tap density can be increased about 30 %. The as‐prepared bowl‐like SnO2@carbon hollow particles with conformal carbon support exhibit excellent lithium storage properties in terms of high capacity, stable cyclability and excellent rate capability.
A Carbene‐Rich but Carbonyl‐Poor [Ir6(IMe)8(CO)2H14]2+ Polyhydride Cluster as a Deactivation Product from Catalytic Glycerol Dehydrogenation
Authors: Campos Jesús , Sharninghausen Liam S. , Crabtree Robert H. , Balcells David
Published: September 2014

The title cluster, a deactivation product in the catalytic dehydrogenation of glycerol, was characterized by XRD, DFT calculations, HRMS, FTIR spectroscopy, and NMR spectroscopy. Experimental/computational studies located the 14 H ligands, and all 1H and 13C{1H} NMR resonances were assigned. The structure contains an unprecedented Ir6H14 core with two CO and eight IMe ligands.
Processive Catalysis
Authors: van Dongen Stijn F. M. , Elemans Johannes A. A. W. , Rowan Alan E. , Nolte Roeland J. M.
Published: September 2014

Nature’s enzymes are an ongoing source of inspiration for scientists. The complex processes behind their selectivity and efficiency is slowly being unraveled, and these findings have spawned many biomimetic catalysts. However, nearly all focus on the conversion of small molecular substrates. Nature itself is replete with inventive catalytic systems which modify, replicate, or decompose entire polymers, often in a processive fashion. Such processivity can, for example, enhance the rate of catalysis by clamping to the polymer substrate, which imparts a large effective molarity. Reviewed herein are the various strategies for processivity in nature’s arsenal and their properties. An overview of what has been achieved by chemists aiming to mimic one of nature’s greatest tricks is also included.
Magnetic Separation of Proteins by a Self‐Assembled Supramolecular Ternary Complex
Authors: Samanta Avik , Ravoo Bart Jan
Published: September 2014

The easy and effective separation of proteins from a mixture is crucial in proteomics. A supramolecular method is described to selectively capture and precipitate one protein from a protein mixture upon application of a magnetic field. A multivalent complex self‐assembles in a dilute aqueous solution of three components: magnetic nanoparticles capped with cyclodextrin, non‐covalent cross‐linkers with an adamantane and a carbohydrate moiety, and lectins. The self‐assembled ternary complex is precipitated in a magnetic field and readily redispersed with the aid of a non‐ionic surfactant and competitive binding agents. This strategy to purify proteins by supramolecular magnetic precipitation is highly selective and efficient.
Restraint of the Differentiation of Mesenchymal Stem Cells by a Nonfouling Zwitterionic Hydrogel
Authors: Bai Tao , Sun Fang , Zhang Lei , Sinclair Andrew , Liu Sijun , Ella‐Menye Jean‐Rene , Zheng Ying , Jiang Shaoyi
Published: September 2014

The success of human mesenchymal stem cell (hMSC) therapies is largely dependent on the ability to maintain the multipotency of cells and control their differentiation. External biochemical and biophysical cues can readily trigger hMSCs to spontaneously differentiate, thus resulting in a rapid decrease in the multipotent cell population and compromising their regenerative capacity. Herein, we demonstrate that nonfouling hydrogels composed of pure poly(carboxybetaine) (PCB) enable hMSCs to retain their stem‐cell phenotype and multipotency, independent of differentiation‐promoting media, cytoskeletal‐manipulation agents, and the stiffness of the hydrogel matrix. Moreover, encapsulated hMSCs can be specifically induced to differentiate down osteogenic or adipogenic pathways by controlling the content of fouling moieties in the PCB hydrogel. This study examines the critical role of nonspecific interactions in stem‐cell differentiation and highlights the importance of materials chemistry in maintaining stem‐cell multipotency and controlling differentiation.
Selective Transcription of an Unnatural Naphthyridine:Imidazopyridopyrimidine Base Pair Containing Four Hydrogen Bonds with T7 RNA Polymerase
Authors: Nomura Yusaku , Kashiwagi Satoshi , Sato Kousuke , Matsuda Akira
Published: September 2014

The naphthyridine:imidazopyridopyrimidine base pair is the first base pair containing four hydrogen bonds that can be replicated selectively and efficiently by the use of DNA polymerases. Herein we describe the synthesis of naphthyridine‐C‐ribonucleoside 5′‐triphosphate (rNaTP) and transcription reactions catalyzed by T7 RNA polymerase with rNaTP and template DNA containing imidazopyridopyrimidine. The transcription reaction was also applied to a longer transcript containing part of the human c‐Ha‐Ras gene.
Selective Inhibition of the Immunoproteasome by Ligand‐Induced Crosslinking of the Active Site
Authors: Dubiella Christian , Cui Haissi , Gersch Malte , Brouwer Arwin J. , Sieber Stephan A. , Krüger Achim , Liskamp Rob M. J. , Groll Michael
Published: September 2014

The concept of proteasome inhibition ranks among the latest achievements in the treatment of blood cancer and represents a promising strategy for modulating autoimmune diseases. In this study, we describe peptidic sulfonyl fluoride inhibitors that selectively block the catalytic β5 subunit of the immunoproteasome by inducing only marginal cytotoxic effects. Structural and mass spectrometric analyses revealed a novel reaction mechanism involving polarity inversion and irreversible crosslinking of the proteasomal active site. We thus identified the sulfonyl fluoride headgroup for the development and optimization of immunoproteasome selective compounds and their possible application in autoimmune disorders.
Preparation of a low‐phosphorous terpolymer as a scale, corrosion inhibitor, and dispersant for ferric oxide
Authors: Chen Yiyi , Zhou Yuming , Yao Qingzhao , Bu Yunyun , Wang Huchuan , Wu Wendao , Sun Wei
Published: September 2014

A novel low‐phosphorus terpolymer, used as scale, corrosion inhibitor, and dispersant for iron oxide, was prepared through free‐radical polymerization reaction of acrylic acid (AA), oxalic acid‐allypolyethoxy carboxylate (APEM), and phosphorous acid (H3PO3) in water with redox system of hypophosphorous and ammonium persulfate as initiator. Structure of the synthesized AA‐APEM‐H3PO3 terpolymer was characterized by Fourier transform infrared spectrometer and 1H‐NMR. The polymer possesses excellent scale inhibition performance for CaCO3, outstanding ability to disperse ferric oxide, and good corrosion inhibition properties. The study showed that AA‐APEM‐H3PO3 exhibited excellent ability to control calcium carbonate scale, with approximately 90.16% CaCO3 inhibition at a level of 8 mg/L AA‐APEM‐H3PO3. The data of the light transmittance showed that, compared to hydrolyzed polymaleic acid and polyepoxysuccinic acid, AA‐APEM‐H3PO3 had superior ability to control iron ions scaling. The light transmittance of the solution was about 24.1% in the presence of the terpolymer when the dosage was 8 mg/L. Moreover, the corrosion inhibition efficiency could reach up to 79.77% at a dosage of 30 mg/L, with ethylene diamine tetra methylene phosphonic acid just 39.62%. Scanning electronic microscopy, transmission electron microscope, and X‐ray powder diffraction analysis were used to investigate the effect of AA‐APEM‐H3PO3 on morphology of calcium carbonate scale. The low‐phosphorous terpolymer has also been proven to be effective inhibitor of calcium carbonate even at increasing solution temperature, pH, and Ca2+ concentration. The proposed inhibition mechanism suggests the surface complexation and chelation between the functional groups P(O) (OH)2, COOH and Ca2+, with polyethylene glycol segments increasing its solubility in water. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41447.
Electrical, mechanical, structural, and thermal behaviors of polymeric gel electrolyte membranes of poly(vinylidene fluoride‐co‐hexafluoropropylene) with the ionic liquid 1‐butyl‐3‐methylimidazolium tetrafluoroborate plus lithium tetrafluoroborate
Authors: Shalu  , Chaurasia Sujeet Kumar , Singh Rajendra Kumar , Chandra Suresh
Published: September 2014

Polymeric gel electrolyte membranes based on the polymer poly(vinylidene fluoride‐co‐hexafluoropropylene) [P(VdF–HFP)] with different weight percentages of the ionic liquid (IL) 1‐butyl‐3‐methylimidazolium tetrafluoroborate plus 0.3M lithium tetrafluoroborate (LiBF4) salt were prepared and characterized by scanning electron microscopy, X‐ray diffraction, differential scanning calorimetry, thermogravimetric analysis, Fourier transform infrared (FTIR) spectroscopy, complex impedance spectroscopy, pulse echo techniques, and Vickers hardness (H) testing. After the incorporation of the IL plus the salt solution in the P(VdF–HFP) polymer, the melting temperature, glass‐transition temperature (Tg), degree of crystallinity, thermal stability, elastic modulus (E), and hardness (H) gradually decreased with increasing content of the IL–salt solution as a result of complexation between the P(VdF–HFP) and IL. This was confirmed by FTIR spectroscopy. A part of the IL and LiBF4 were found to remain uncomplexed as well. The ionic conductivity (σ) of the polymeric gel membranes was found to increase with increasing concentration of the IL–salt solution. The temperature‐dependent σs of these polymeric gel membranes followed an Arrhenius‐type thermally activated behavior. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41456.
Sugarcane bagasse ash as a reinforcing filler in thermoplastic elastomers: Structural and mechanical characterizations
Authors: Ozório Maiza da Silva , Reis Elton Aparecido Prado dos , Teixeira Silvio Rainho , Bellucci Felipe Silva , Job Aldo Eloizo
Published: September 2014

The incorporation of residues as reinforcing fillers in polymer composites has emerged as a viable solution, enabling improvements in the mechanical properties of these materials, and has also resulted in a reduction in the cost of the final product. In this work, sugarcane bagasse ash (SBA) was used as a reinforcing filler in comparison with commercial silica (CS) in thermoplastic elastomers prepared from the compatibility of low‐density polyethylene (LDPE) with natural rubber (NR). The composites were obtained by a physical mixture of LDPE and NR with different proportions of CS and SBA using a Haake rotational rheometer. The samples were analyzed by Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and tensile testing. The results show that SBA has similar properties to CS, thus making its use feasible as a reinforcing filler in thermoplastic elastomers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41466.
Mitochondria as a Target in the Therapeutic Properties of Curcumin
Authors: Trujillo Joyce , Granados‐Castro Luis Fernando , Zazueta Cecilia , Andérica‐Romero Ana Cristina , Chirino Yolanda Irasema , Pedraza‐Chaverrí José
Published: September 2014

Curcumin, a phenolic compound extracted from Curcuma longa, is commonly used in Asia as a spice and pigment and has several biological functions, particularly antioxidant properties. It has been reported that curcumin exhibits bifunctional antioxidant properties related to its capability to react directly with reactive oxygen species (ROS) and also to its ability to induce the expression of cytoprotective and antioxidant proteins through the transcription factor nuclear factor‐erythroid‐2‐related factor 2 (Nrf2). Recently, it has been postulated that the mitochondrial function and metabolism are associated with Nrf2 and that curcumin has shown activities against mitochondrial dysfunction. The damage in mitochondria has been implicated in the pathogenesis of diseases like diabetes, cancer, aging, and neurodegenerative disorders. This review focuses on some of the most recent findings of curcumin properties that suggest a close relationship of this antioxidant with the mitochondrial function.
Rewritable Multilevel Memory Performance of a Tetraazatetracene Donor–Acceptor Derivative with Good Endurance
Authors: Wang Chengyuan , Hu Benlin , Wang Jiangxin , Gao Junkuo , Li Gang , Xiong Wei‐Wei , Zou Binghua , Suzuki Mitsuharu , Aratani Naoki , Yamada Hiroko , Huo Fengwei , Lee Pooi See , Zhang Qichun
Published: September 2014

A new tetraazatetracene derivative, 2,3‐[4,4′‐bis(N,N‐diphenylamino)benzyl]‐5,12‐bis[(triisopropylsilyl)ethynyl]‐1,4,6,11‐tetraazatetracene (TPAs‐BTTT), displays rewritable multilevel memory behavior, which is probably induced by multielectron intramolecular charge transfer (CT).
How does oncogene transformation render tumor cells hypersensitive to nutrient deprivation?
Authors: Leprivier Gabriel , Sorensen Poul H.
Published: September 2014

Oncogene activation leads to cellular transformation by deregulation of biological processes such as proliferation and metabolism. Paradoxically, this can also sensitize cells to nutrient deprivation, potentially representing an Achilles' heel in early stage tumors. The mechanisms underlying this phenotype include loss of energetic and redox homeostasis as a result of metabolic reprogramming, favoring synthesis of macromolecules. Moreover, an emerging mechanism involving the deregulation of mRNA translation elongation through inhibition of eukaryotic elongation factor 2 kinase (eEF2K) is presented. The potential consequences of eEF2K deregulation leading to cell death under nutrient depletion are discussed. Finally, the relevance of eEF2K as a master regulator of the response to nutrient deprivation in vivo, and its potential exploitation for therapeutic targeting of cancers, are elaborated. Overall, a better understanding of the adaptive mechanisms allowing tumors to circumvent oncogene‐induced hypersensitivity to nutrient deprivation is a promising avenue for uncovering novel therapeutic targets in cancers.
Preparation of pH‐stimuli‐responsive PEG–TGA/TGH‐capped CdTe QDs and their application in cell labeling
Authors: Du Yan , Yang Dongzhi , Sun Shian , Zhao Ziming , Tang Daoquan
Published: September 2014

A pH‐sensitive and double functional nanoprobe was designed and synthesized in a water‐soluble system using thioglycolic acid (TGA) and mercapto‐acetohydrazide (TGH) as the stabilizers. TGA is biocompatible because the carboxyl group is easily linked to biological macromolecules. At the same time, the hydrazide on TGH reacts with the aldehyde on poly(ethylene glycol) (PEG) and forms a hydrazone bond. The hydrazone bond ruptured at specific pH values and exhibited pH‐stimuli‐responsive characteristics. As an optical imaging probe, the PEG–TGA/TGH‐capped CdTe quantum dots (QDs) had high quality, with a fluorescence efficiency of 25–30%, and remained stable for at least five months. This pH‐responsive factor can be used for the effective release of CdTe QDs under the acidic interstitial extracellular environment of tumor cells. This allows the prepared pH‐stimuli‐responsive nanoprobes to show fluorescence signals for use in cancer cell imaging. Copyright © 2014 John Wiley & Sons, Ltd.
Occipital neuralgia: Anatomic considerations
Authors: Cesmebasi Alper , Muhleman Mitchel A. , Hulsberg Paul , Gielecki Jerzy , Matusz Petru , Tubbs R. Shane , Loukas Marios
Published: September 2014

Occipital neuralgia is a debilitating disorder first described in 1821 as recurrent headaches localized in the occipital region. Other symptoms that have been associated with this condition include paroxysmal burning and aching pain in the distribution of the greater, lesser, or third occipital nerves. Several etiologies have been identified in the cause of occipital neuralgia and include, but are not limited to, trauma, fibrositis, myositis, fracture of the atlas, and compression of the C‐2 nerve root, C1‐2 arthrosis syndrome, atlantoaxial lateral mass osteoarthritis, hypertrophic cervical pachymeningitis, cervical cord tumor, Chiari malformation, and neurosyphilis. The management of occipital neuralgia can include conservative approaches and/or surgical interventions. Occipital neuralgia is a multifactorial problem where multiple anatomic areas/structures may be involved with this pathology. A review of these etiologies may provide guidance in better understanding occipital neuralgia. Clin. Anat. 28:101–108, 2015. © 2014 Wiley Periodicals, Inc.
Delivery of Antibody Mimics into Mammalian Cells via Anthrax Toxin Protective Antigen
Authors: Liao Xiaoli , Rabideau Amy E. , Pentelute Bradley L.
Published: September 2014

Antibody mimics have significant scientific and therapeutic utility for the disruption of protein–protein interactions inside cells; however, their delivery to the cell cytosol remains a major challenge. Here we show that protective antigen (PA), a component of anthrax toxin, efficiently transports commonly used antibody mimics to the cytosol of mammalian cells when conjugated to the N‐terminal domain of LF (LFN). In contrast, a cell‐penetrating peptide (CPP) was not able to deliver any of these antibody mimics into the cell cytosol. The refolding and binding of a transported tandem monobody to Bcr‐Abl (its protein target) in chronic myeloid leukemia cells were confirmed by co‐immunoprecipitation. We also observed inhibition of Bcr‐Abl kinase activity and induction of apoptosis caused by the monobody. In a separate case, we show disruption of key interactions in the MAPK signaling pathway after PA‐mediated delivery of an affibody binder that targets hRaf‐1. We show for the first time that PA can deliver bioactive antibody mimics to disrupt intracellular protein–protein interactions. This technology adds a useful tool to expand the applications of these modern agents to the intracellular milieu.
Multicomponent Approach to Silica‐Grafted Peptide Catalysts: A 3 D Continuous‐Flow Organocatalytic System with On‐line Monitoring of Conversion and Stereoselectivity
Authors: Scatena Gabriel S. , de la Torre Alexander F. , Cass Quezia B. , Rivera Daniel G. , Paixão Márcio W.
Published: September 2014

The derivatization of organocatalysts with functional appendages suitable to anchor onto solid supports is usually achieved by stepwise syntheses. As an alternative to such a strategy, this work describes a one‐pot approach to silylated prolyl‐peptide catalysts by a multicomponent reaction that enables the simultaneous incorporation of the catalytic and the heterogenizable (triethoxysilane) moieties. A microreactor with high catalytic efficacy and reproducibly in the conjugate addition of aldehydes to nitroolefins was obtained by grafting onto HPLC‐grade silica (10 μm) and packing into a column with a selected catalyst. A 3 D continuous‐flow system that includes the on‐line monitoring of the reaction outcome was set up. For that, the microreactor was coupled to a chromatographic column for the separation of the remaining substrates from the Michael adduct in the second dimension, followed by a chiral polysaccharide column for the analysis of conversion and stereoselectivity. This approach represents a new instrumental setup that combines the advantages of multidimensional chromatography and flow catalysis.
Niobium Peroxide‐Catalyzed Selective Epoxidation of Allylic Alcohols
Authors: Chen Chen , Zhao Xiuge , Chen Jizhong , Hua Li , Zhang Ran , Guo Li , Song Baoning , Gan Huimei , Hou Zhenshan
Published: September 2014

Modified niobium peroxides were prepared and used for catalyzing the epoxidation of allylic alcohols with hydrogen peroxide in the absence of any other solvent under ice bath conditions. Niobium peroxides modified with ionic liquid‐type 1‐dodecyl‐3‐methylimidazolium hydroxide or conventional tetradecyl trimethyl ammonium hydroxide surfactants demonstrated excellent yields (80–99 %) for the epoxidation of allylic alcohols to their epoxides even if the reaction was performed without any other solvent at 0 °C for 0.5 h. The catalyst characterization demonstrated that the surfactant molecules were anchored on the surface of the niobium catalyst by weak noncovalent interactions. Compared with niobium peroxides, the modified amphiphilic catalysts allowed easier accessibility to hydrophobic substrates and thus demonstrated high reaction rate and excellent recyclability for the epoxidation under mild conditions.
Biohydrogen for a New Generation of H2/O2 Biofuel Cells: A Sustainable Energy Perspective
Authors: de Poulpiquet Anne , Ranava David , Monsalve Karen , Giudici‐Orticoni Marie‐Thérèse , Lojou Elisabeth
Published: September 2014

Among sustainable alternatives to fossil fuel, proton exchange membrane fuel cells are promising devices that deliver electricity from hydrogen and oxygen, producing only water. The transformation of the fuel and oxidant however relies on rare‐metal catalysts. H2/O2 enzymatic biofuel cells thus emerge as sustainable biotechnological devices in which chemical catalysts are replaced by hydrogenases at the anode and multicopper oxidases at the cathode. This review discusses the recent breakthroughs and the limitations in all the components of H2/O2 biofuel cells: 1) Catalytic mechanisms involved in multicopper oxidases and hydrogenases, in addition to the new potential of enzymes from the biodiversity pool, which exhibit outstanding properties. 2) The molecular basis for oriented enzyme immobilization on the electrochemical interfaces as a prerequisite for a fast direct electron‐transfer rate. 3) The requirement for 3D networks to enhance current densities. 4) The production of H2 from biomass. 5) The history of H2/O2 biofuel cells and recent devices, which also highlights the remaining issues that will allow the use of such devices in low‐power applications.
Direct Catalytic Addition of Alkylnitriles to Aldehydes by Transition‐Metal/NHC Complexes
Authors: Sureshkumar Devarajulu , Ganesh Venkataraman , Kumagai Naoya , Shibasaki Masakatsu
Published: September 2014

Direct catalytic addition of alkylnitriles to aldehydes allows for an atom‐economical access to β‐hydroxynitriles under proton transfer conditions. Direct use of alkylnitriles as pronucleophiles has been hampered due to their low acidity resulting in an inability to generate α‐cyano carbanions in a catalytic manner. A transition metal/N‐heterocyclic carbene (NHC) complex prepared from [{Rh(OMe)(cod)}2] and an imidazolium‐based carbene was identified as an effective catalyst to promote the reaction with as little as 1.25 mol % of catalyst loading. The corresponding Rh complex, derived from chiral triazolium salt, rendered the reaction enantioselective, albeit with moderate enantioselectivity.
Structure Sensitivity in the Decomposition of Ethylene Carbonate on Si Anodes
Authors: Rohrer Jochen , Kaghazchi Payam
Published: September 2014

The interaction of ethylene carbonate (EC) with Si surfaces is studied by density functional theory. The results show a strong structure sensitivity in the adsorption of EC on Si surfaces. While the adsorbed EC molecule readily decomposes on the Li/Si(111) surface, it does not dissociate on the Li/Si(100) and Li/Si(110) surfaces. On Si(111), the O atom at the top of EC is detached from the EC molecule and binds to the Li adatom, forming LiO molecules. The mechanism of EC decomposition is the transfer of 2.4 electrons from the surface to the EC molecule, as well as the formation of a covalent bond between the Li adatom and the EC molecule. This result shows that in lithium‐ion batteries with Si anodes, dissociation of the solvent and formation of a solid electrolyte interphase layer start as soon as the Li atoms cover the anode surface.
Magnetic Fe3O4 Nanoparticle‐Supported Phosphotungstic Acid as a Recyclable Catalyst for the Kabachnik–Fields Reaction of Isatins, Imines, and Aldehydes under Solvent‐Free Conditions
Authors: Nazish Mohd , Saravanan S. , Khan Noor‐ul H. , Kumari Prathibha , Kureshy Rukhsana I. , Abdi Sayed H. R. , Bajaj Hari C.
Published: September 2014

Magnetic‐nanoparticle‐supported phosphotungstic acid has been used to efficiently catalyze the hydrophosphonylation reaction of isatins, imines, and aldehydes using dimethyl and diethyl phosphite as a nucleophile to give the corresponding α‐hydroxy and α‐amino phosphonates in excellent yields for a wide range of substrates. The reaction conditions were simple, green, and efficient. The catalyst was recycled up to five times with retention of its activity. Based on the NMR spectroscopy studies, a probable catalytic cycle was proposed.
Thin‐Film Silicon for Flexible Metal–Air Batteries
Authors: Garamoun Ahmed , Schubert Markus B. , Werner Jürgen H.
Published: September 2014

Due to its high energy density, theoretical studies propose silicon as a promising candidate material for metal–air batteries. Herein, for the first time, experimental results detail the use of n‐type doped amorphous silicon and silicon carbide as fuel in Si–air batteries. Thin‐film silicon is particularly interesting for flexible and rolled batteries with high specific energies. Our Si–air batteries exhibit a specific capacity of 269 Ah kg−1 and an average cell voltage of 0.85 V at a discharge current density of 7.9 μA cm−2, corresponding to a specific energy of 229 Wh kg−1. Favorably in terms of safety, low concentrated alkaline solution serves as electrolyte. Discharging of the Si–air cells continues as long as there is silicon available for oxidation.