bluuebunny/crossref_metadata_2025 huggingface dataset:
Dopant‐Free Spiro‐Triphenylamine/Fluorene as Hole‐Transporting Material for Perovskite Solar Cells with Enhanced Efficiency and Stability
Authors: Wang Ya‐Kun , Yuan Zhong‐Cheng , Shi Guo‐Zheng , Li Yong‐Xi , Li Qian , Hui Fei , Sun Bao‐Quan , Jiang Zuo‐Quan , Liao Liang‐Sheng
Published: January 2016

Chemical doping is often used to enhance electric conductivity of the conjugated molecule as hole‐transporting material (HTM) for the application in optoelectronics. However, chemical dopants can promote ion migration at the electrical field, which deteriorates the device efficiency as well as increases the fabrication cost. Here, two star HTMs, namely 2,2′,7,7′‐tetrakis(N,N‐di‐p‐methoxyphenyl‐amine) 9,9′‐spirobifluorene (Spiro‐OMeTAD) and poly(triarylamine) are subjeted to chemical combination to yield dopant‐free N2,N2,N2′,N2′,N7,N7,N7′,N7′‐octakis(4‐methoxyphenyl)‐10‐phenyl‐10H‐spiro[acridine‐9,9′‐fluorene]‐2,2′,7,7′‐tetraamine (SAF‐OMe). The power conversion efficiencies (PCEs) of 12.39% achieved by solar cells based on pristine, dopant‐free SAF‐OMe are among the highest reported for perovskite solar cells and are even comparable to devices based on chemically doped Spiro‐OMeTAD (14.84%). Moreover, using a HTM comprised of SAF‐OMe with an additional dopant results in a record PCE of 16.73%. Compared to Spiro‐OMeTAD‐based devices, SAF‐OMe significantly improves stability.
An Interface Engineered Multicolor Photodetector Based on n‐Si(111)/TiO2 Nanorod Array Heterojunction
Authors: Ji Tao , Liu Qian , Zou Rujia , Sun Yangang , Xu Kaibing , Sang Liwen , Liao Meiyong , Koide Yasuo , Yu Li , Hu Junqing
Published: January 2016

A multicolor photodetector based on the heterojunction of n‐Si(111)/TiO2 nanorod arrays responding to both ultraviolet (UV) and visible light is developed by utilizing interface engineering. The photodetector is fabricated via a consecutive process including chemical etching, magnetron sputtering, hydrothermal growth, and assembling. Under a small reverse bias (from 0 to ≈−2 V), only the photogenerated electrons in TiO2 are possible to tunnel through the low barrier of ΔEC, and the device only responses to UV light; as the reverse bias increases, the photogenerated holes in Si also begin to tunnel through the high barrier of ΔEV. As a result, the device is demonstrated to have the capacity to detect both UV and visible lights, which is useful in the fields of rapid detection and multicolor imaging. It has been also observed that the crystal orientation of Si affects the characteristics of bias‐controlled spectral response of the n‐Si/TiO2 heterojunctions.
Large Area Artificial Spin Ice and Anti‐Spin Ice Ni80Fe20 Structures: Static and Dynamic Behavior
Authors: Zhou Xue , Chua Geng‐Li , Singh Navab , Adeyeye Adekunle O.
Published: January 2016

Artificial spin ice has been the subject of extensive investigation in the last few years due to advances in nanotechnology and characterization techniques. So far, most of the studies have been limited to local probe of small area magnetic elements due to limitations with lithographic techniques used. In this study, large area spin ice and anti‐spin ice Ni80Fe20 structures with three lattice configurations have been fabricated using deep ultraviolet lithography at 193 nm exposure wavelength. The static and dynamic properties are systematically characterized using vibrating sample magnetometer, magnetic force microscopy, and broadband ferromagnetic resonance spectroscopy. Intriguing static and dynamic behaviors are observed due to the geometrical arrangement of the nanomagnets in the lattice. When the nanomagnets are saturated at high field, multiple resonance peaks whose frequencies are strongly dependent on the orientation of the applied magnetic field are observed. The experimental results are in qualitative agreement with the micromagnetic simulations. These findings may find application in the design of magnetically controlled tunable microwave filters.
Engineering Metallic Nanoparticles for Enhancing and Probing Catalytic Reactions
Authors: Collins Gillian , Holmes Justin D.
Published: January 2016

Recent developments in tailoring the structural and chemical properties of colloidal metal nanoparticles (NPs) have led to significant enhancements in catalyst performance. Controllable colloidal synthesis has also allowed tailor‐made NPs to serve as mechanistic probes for catalytic processes. The innovative use of colloidal NPs to gain fundamental insights into catalytic function will be highlighted across a variety of catalytic and electrocatalytic applications. The engineering of future heterogenous catalysts is also moving beyond size, shape and composition considerations. Advancements in understanding structure‐property relationships have enabled incorporation of complex features such as tuning surface strain to influence the behavior of catalytic NPs. Exploiting plasmonic properties and altering colloidal surface chemistry through functionalization are also emerging as important areas for rational design of catalytic NPs. This news article will highlight the key developments and challenges to the future design of catalytic NPs.
New Developments in Smart Bandage Technologies for Wound Diagnostics
Authors: McLister Anna , McHugh Jolene , Cundell Jill , Davis James
Published: January 2016

The pH of wound fluid has long been recognized as an important diagnostic for assessing wound condition, but as yet there are few technological options available to the clinician. The availability of sensors that can measure wound pH, either in the clinic or at home could significantly improve clinical outcome – particularly in the early identification of complications such as infection. New material designs and electrochemical research strategies that are being targeted at wound diagnostics are identified and a critical overview of emerging research that could be pivotal in setting the direction for future devices is provided.
High‐Performance Hole Transport and Quasi‐Balanced Ambipolar OFETs Based on D–A–A Thieno‐benzo‐isoindigo Polymers
Authors: James David Ian , Wang Suhao , Ma Wei , Hedström Svante , Meng Xiangyi , Persson Petter , Fabiano Simone , Crispin Xavier , Andersson Mats R. , Berggren Magnus , Wang Ergang
Published: January 2016

Two new conjugated polymers are synthesized based on a novel donor–acceptor–acceptor (D–A–A) design strategy with the intention of attaining lower lowest unoccupied molecular obital levels compared to the normally used D–A strategy. By coupling two thieno‐benzo‐isoindigo units together via the phenyl position to give a new symmetric benzene‐coupled di‐thieno‐benzo‐isoindigo (BdiTBI) monomer as an A–A acceptor and thiophene (T) or bithiophene (2T) as a donor, two new polymers PT‐BdiTBI and P2T‐BdiTBI are synthesized via Stille coupling. The two polymers are tested in top gate and top contact field effect transistors, which exhibit balanced ambipolar charge transport properties with poly(methyl methacrylate) as dielectric and a high hole mobility up to 1.1 cm2 V–1 s–1 with poly(trifluoroethylene) as dielectric. The polymer films are investigated using atomic force microscopy, which shows fibrous features due to their high crystallinity as indicated by grazing incidence wide‐angle X‐ray scattering. The theoretical calculations agree well with the experimental data on the energy levels. It is demonstrated that the D–A–A strategy is very effective for designing low band gap polymers for organic electronic applications.
Outstanding Low Temperature Thermoelectric Power Factor from Completely Organic Thin Films Enabled by Multidimensional Conjugated Nanomaterials
Authors: Cho Chungyeon , Wallace Kevin L. , Tzeng Ping , Hsu Jui‐Hung , Yu Choongho , Grunlan Jaime C.
Published: January 2016

In an effort to create a paintable/printable thermoelectric material, comprised exclusively of organic components, polyaniline (PANi), graphene, and double‐walled nanotube (DWNT) are alternately deposited from aqueous solutions using the layer‐by‐layer assembly technique. Graphene and DWNT are stabilized with an intrinsically conductive polymer, poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). An 80 quadlayer thin film (≈1 μm thick), comprised of a PANi/graphene‐PEDOT:PSS/PANi/DWNT‐PEDOT:PSS repeating sequence, exhibits unprecedented electrical conductivity (σ ≈ 1.9 × 105 S m−1) and Seebeck coefficient (S ≈ 120 μV K−1) for a completely organic material. These two values yield a thermoelectric power factor (PF = S
2
σ
−1) of 2710 μW m−1 K−2, which is the highest value ever reported for a completely organic material and among the highest for any material measured at room temperature. These outstanding properties are attributed to the highly ordered structure in the multilayer assembly. This water‐based thermoelectric nanocomposite is competitive with the best inorganic semiconductors (e.g., bismuth telluride) at room temperature and can be applied as a coating to any flexible surface (e.g., fibers in clothing). For the first time, there is a real opportunity to harness waste heat from unconventional sources, such as body heat, to power devices in an environmentally‐friendly way.
Therapeutically targeting SELF‐reinforcing leukemic niches in acute myeloid leukemia: A worthy endeavor?
Authors: Bernasconi Paolo , Farina Mirko , Boni Marina , Dambruoso Irene , Calvello Celeste
Published: January 2016

A tight relationship between the acute myeloid leukemia (AML) population and the bone marrow (BM) microenvironment has been convincingly established. The AML clone contains leukemic stem cells (LSCs) that compete with normal hematopoietic stem cells (HSCs) for niche occupancy and remodel the niche; whereas, the BM microenvironment might promote AML development and progression not only through hypoxia and homing/adhesion molecules, but also through genetic defects. Although it is still unknown whether the niche influences treatment results or contains any potential target for treatment, this dynamic AML‐niche interaction might be a promising therapeutic objective to significantly improve the AML cure rate. Am. J. Hematol. 91:507–517, 2016. © 2016 Wiley Periodicals, Inc.
Diversity and severity of adverse reactions to quinine: A systematic review
Authors: Liles Nathan W. , Page Evaren E. , Liles Amber L. , Vesely Sara K. , Raskob Gary E. , George James N.
Published: January 2016

Quinine is a common cause of drug‐induced thrombocytopenia and the most common cause of drug‐induced thrombotic microangiopathy. Other quinine‐induced systemic disorders have been described. To understand the complete clinical spectrum of adverse reactions to quinine we searched 11 databases for articles that provided sufficient data to allow evaluation of levels of evidence supporting a causal association with quinine. Three reviewers independently determined the levels of evidence, including both immune‐mediated and toxic adverse reactions. The principal focus of this review was on acute, immune‐mediated reactions. The source of quinine exposure, the involved organ systems, the severity of the adverse reactions, and patient outcomes were documented. One hundred‐fourteen articles described 142 patients with definite or probable evidence for a causal association of quinine with acute, immune‐mediated reactions. These reactions included chills, fever, hypotension, painful acral cyanosis, disseminated intravascular coagulation, hemolytic anemia, thrombocytopenia, neutropenia, acute kidney injury, rhabdomyolysis, liver toxicity, cardiac ischemia, respiratory failure, hypoglycemia, blindness, and toxic epidermal necrolysis. One hundred‐two (72%) reactions were caused by quinine pills; 28 (20%) by quinine‐containing beverages; 12 (8%) by five other types of exposures. Excluding 41 patients who had only dermatologic reactions, 92 (91%) of 101 patients had required hospitalization for severe illness; 30 required renal replacement therapy; three died. Quinine, even with only minute exposure from common beverages, can cause severe adverse reactions involving multiple organ systems. In patients with acute, multi‐system disorders of unknown origin, an adverse reaction to quinine should be considered. Am. J. Hematol. 91:461–466, 2016. © 2016 Wiley Periodicals, Inc.
CLTC as a clinically novel gene associated with multiple malformations and developmental delay
Authors: DeMari Joseph , Mroske Cameron , Tang Sha , Nimeh Joseph , Miller Ryan , Lebel Robert R.
Published: January 2016

Diagnostic exome sequencing has recently emerged as an invaluable tool in determining the molecular etiology of cases involving dysmorphism and developmental delay that are otherwise unexplained by more traditional methods of genetic testing. Our patient was large for gestational age at 35 weeks, delivered to a 27‐year‐old primigravid Caucasian whose pregnancy was complicated by preeclampsia. Neonatal period was notable for hypoglycemia, apnea, bradycardia, hyperbilirubinemia, grade I intraventricular hemorrhage, subdural hematoma, laryngomalacia, hypotonia, and feeding difficulties. The patient had numerous minor dysmorphic features. At three and a half years of age, she has global developmental delays and nystagmus, and is being followed for a mediastinal neuroblastoma that is currently in remission. Karyotype and oligo‐microarray were normal. Whole‐exome, next generation sequencing (NGS) coupled to bioinformatic filtering and expert medical review at Ambry Genetics revealed 14 mutations in 9 genes, and these genes underwent medical review. A heterozygous de novo frameshift mutation, c.2737_2738dupGA p.D913Efs*59, in which two nucleotides are duplicated in exon 17 of the CLTC gene, results in substitution of glutamic acid for aspartic acid at position 913 of the protein, as well as a frame shift that results in a premature termination codon situated 58 amino acids downstream. Clathrin Heavy Chain 1 (CHC1) has been shown to play an important role in the brain for vesicle recycling and neurotransmitter release at pre‐synaptic nerve terminals. There is also evidence implicating it in the proper development of the placenta during the early stages of pregnancy. The CLTC alteration identified herein is likely to provide an explanation for the patient's adverse phenotype. Ongoing functional studies will further define the impact of this alteration on CHC1 function and consequently, human disease. © 2016 Wiley Periodicals, Inc.
Use of metaphors about exome and whole genome sequencing
Authors: Nelson Sarah C. , Crouch Julia M. , Bamshad Michael J. , Tabor Holly K. , Yu Joon‐Ho
Published: January 2016

Clinical and research uses of exome and whole genome sequencing (ES/WGS) are growing rapidly. An enhanced understanding of how individuals conceptualize and communicate about sequencing results is needed to ensure effective, mutual exchange of information between care providers and patients and between researchers and participants. Focus groups and interviews participants were recruited to discuss their attitudes and preferences for receiving hypothetical results from ES/WGS. African Americans were intentionally oversampled. We qualitatively analyzed participants’ speech to identify unsolicited metaphorical language pertaining to genes and health, and grouped these occurrences into metaphorical concepts. Participants compared genetic information to physical objects including tools, weapons, contents of boxes, and formal documents or reports. These metaphorical concepts centered on several key themes, including locus of control; containment versus release of information; and desirability, usability, interpretability, and ownership of genetic results. Metaphorical language is often used intentionally or unintentionally in discussions about receiving results from ES/WGS in both clinical and research settings. Awareness of the use of metaphorical language and attention to its varied meanings facilitates effective communication about return of ES/WGS results. In turn, both should foster shared and informed decision‐making and improve the translation of genetic information by clinicians and researchers. © 2016 Wiley Periodicals, Inc.
Consequences of a male takeover on mating skew in wild Sanje mangabeys
Authors: Fernández David
Published: January 2016

Among primate species living in multimale‐multifemale groups, the number of receptive females may determine the rank of the lowest male that copulates (priority of access model, or PoA [Altmann SA. 1962. A field study of the sociobiology of rhesus monkeys, Macaca mulatta. Annals of the New York Academy of Sciences 102:338–435]). Factors, such as temporary instability in the hierarchy and female behavior can, however, affect high‐ranking males’ ability to monopolize females, reducing mating skew and causing the hierarchy to depart from predictions of PoA. Here, I use behavioral data collected over a 22‐month period on a wild group of Sanje mangabeys (Cercocebus sanjei) to examine the effect of a takeover by two immigrating males who became α and β in the hierarchy, and of female behavior on male mating skew. Data on male agonistic interactions were collected on nine males using ad libitum observations, while information on male mating success (i.e., daily proportion of ejaculatory copulations with the focal female) was collected through focal follows of 12 sexually receptive females. Before the takeover, the hierarchy was stable and highly skewed, with the α‐male monopolizing up to 75% of copulations. At this time, however, mating skew did not follow the predictions of PoA. During the takeover, from the time one of the newly immigrant males replaced the α until the second immigrant male became the new β, the stability of the hierarchy dropped significantly and mating was no longer skewed. Accordingly, the top two ranking males at that time (i.e., the new α and former β) accounted for only 33% of copulations. After the takeover, rank stability increased, and mating skew followed the PoA. Female mating solicitations also had a significant positive effect on male mating success, and may have contributed to the deviation from the PoA. This study demonstrates that temporary rank instability decreases high‐ranking males’ ability to monopolize copulations, causing a departure from the predictions of the PoA. Am. J. Primatol. 79:e22532, 2017. © 2016 Wiley Periodicals, Inc.
Quantifying soluble carbohydrates in tropical leaves using a portable mid‐infrared sensor: Implications for primate feeding ecology
Authors: Dunham Noah T. , Kane Erin E. , Rodriguez‐Saona Luis E.
Published: January 2016

Identifying the nutritional composition of food items has significant ramifications for primate feeding ecology, which, in turn, influences investigations of primate sociality, cognition, and conservation. The aim of our study was to analyze water soluble carbohydrate (WSC) concentrations in the leaves of trees common to the Diani Forest of Kenya. Many of these leaves are consumed by black and white colobus monkeys (Colobus angolensis palliatus). We assessed whether the infrared spectral data collected using a portable spectrometer can be used to accurately predict WSC concentrations. WSC content was first quantified using the phenol–sulfuric acid method for young and mature leaves of 24 species and ranged from 1.15% to 9.16% dry weight. Spectral data were recorded with a spectrometer equipped with an attenuated total reflectance accessory (Agilent Cary 630) and analyzed using partial least squares regression. The spectral region from 1600 cm−1 to 1000 cm−1 gave unique polysaccharide bands associated with carboxyl, acetyl, and glycosidic linkages of sugar residues. The multivariate analysis gave excellent performance parameters with correlation coefficient (r2) of 0.95 and standard error of cross‐validation of 0.6% WSC. We found that IR spectroscopy provides a rapid and accurate technique for analyzing WSC concentrations and offers primatologists many advantages over wet chemistry methods for analyzing nutritional composition. Am. J. Primatol. 78:701–706, 2016. © 2016 Wiley Periodicals, Inc.
Experimental and Computational Analysis of the Solvent‐Dependent O2/Li+‐O2− Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium–Oxygen Batteries
Authors: Kwabi David G. , Bryantsev Vyacheslav S. , Batcho Thomas P. , Itkis Daniil M. , Thompson Carl V. , Shao‐Horn Yang
Published: January 2016

Understanding and controlling the kinetics of O2 reduction in the presence of Li+‐containing aprotic solvents, to either Li+‐O2− by one‐electron reduction or Li2O2 by two‐electron reduction, is instrumental to enhance the discharge voltage and capacity of aprotic Li‐O2 batteries. Standard potentials of O2/Li+‐O2− and O2/O2− were experimentally measured and computed using a mixed cluster‐continuum model of ion solvation. Increasing combined solvation of Li+ and O2− was found to lower the coupling of Li+‐O2− and the difference between O2/Li+‐O2− and O2/O2− potentials. The solvation energy of Li+ trended with donor number (DN), and varied greater than that of O2− ions, which correlated with acceptor number (AN), explaining a previously reported correlation between Li+‐O2− solubility and DN. These results highlight the importance of the interplay between ion–solvent and ion–ion interactions for manipulating the energetics of intermediate species produced in aprotic metal–oxygen batteries.
Durch Nichtedelmetallsalze ausgelöste Friedel‐Crafts‐artige intermolekulare C‐H‐Silylierung von elektronenreichen Arenen
Authors: Yin Qin , Klare Hendrik F. T. , Oestreich Martin
Published: January 2016

Es wird über eine elektrophile aromatische Substitution (SEAr) mit einem katalytisch erzeugten Siliciumelektrophil berichtet. Bei Aktivierung mit NaBArF4 wirkt im Grunde jedes käufliche Nichtedelmetallsalz als Initiator/Katalysator. Die auf diese Weise gebildete Lewis‐Säure vermittelt dann die SEAr von elektronenreichen Arenen mit Hydrosilanen, nicht aber mit Halogensilanen. Diese neue C‐H‐Silylierung ist für FeCl2/NaBArF4 optimiert und erbringt gute Ausbeuten bei Katalysatorbeladungen von lediglich 0.5 Mol‐%. Die Vorgehensweise ist denkbar einfach und kommt typischen Friedel‐Crafts‐Reaktionsvorschriften nahe, bei denen keine zusätzliche Base zum Abfangen der freigesetzten Protonen vonnöten ist.
Chiral Phosphoric Acid Catalyzed Kinetic Resolution of Indolines Based on a Self‐Redox Reaction
Authors: Saito Kodai , Akiyama Takahiko
Published: January 2016

A strategy for oxidative kinetic resolution of racemic indolines was developed, employing salicylaldehyde derivative as the pre‐resolving reagent and chiral phosphoric acid as the catalyst. The iminium intermediate, formed by the condensation reaction of an enantiomer of indoline with salicylaldehyde derivative, was hydrogenated by the same enantiomer of indoline to afford another enantiomer of indoline by a self‐redox mechanism. The oxidative kinetic resolution of 2‐aryl‐substituted indolines proceeded to give enantiomers in good yields with excellent enantioselectivities.
Porous Organic Polymer Films with Tunable Work Functions and Selective Hole and Electron Flows for Energy Conversions
Authors: Gu Cheng , Huang Ning , Chen Youchun , Zhang Huanhuan , Zhang Shitong , Li Fenghong , Ma Yuguang , Jiang Donglin
Published: January 2016

Organic optoelectronics are promising technologies for energy conversion. However, the electrode interlayer, a key material between active layers and conducting electrodes that controls the transport of charge carriers in and out of devices, is still a chemical challenge. Herein, we report a class of porous organic polymers with tunable work function as hole‐ and electron‐selective electrode interlayers. The network with organoborane and carbazole units exhibits extremely low work‐function‐selective electron flow; while upon ionic ligation and electro‐oxidation, the network significantly increases the work function and turns into hole conduction. We demonstrate their outstanding functions as anode and cathode interlayers in energy‐converting solar cells and light‐emitting diodes.
Überwindung von Phasentransportlimitierungen in der Umsetzung lipophiler Oleoverbindungen in wässrigen Medien – ein temperaturgesteuerter Ansatz
Authors: Gaide Tom , Dreimann Jens M. , Behr Arno , Vorholt Andreas J.
Published: January 2016

In dieser Forschungsarbeit wird ein neues Verfahrenskonzept zur Katalysatorabtrennung von Übergangsmetallkomplexen bei der Synthese mittelpolarer Produkte mit neu entwickelten wässrigen thermomorphen Mehrkomponenten‐Lösungsmittelsystemen vorgestellt. Ein Schwerpunkt der Prozessentwicklung liegt in der Nutzung von “grünen” Lösungsmitteln (1‐Butanol und Wasser) zur Hydroformylierung des biobasierten Substrats 10‐Undecensäuremethylester. Nach der erfolgreichen Entwicklung eines zweiphasigen Reaktionssystems im Labormaßstab wurde die Reaktion in eine kontinuierlich betriebene Anlage überführt, in der die Robustheit des neuen wässrigen Katalysatorrecyclingkonzepts demonstriert wird.
A General Strategy for the Nickel‐Catalyzed C−H Alkylation of Anilines
Authors: Ruan Zhixiong , Lackner Sebastian , Ackermann Lutz
Published: January 2016

The C−H alkylation of aniline derivatives with both primary and secondary alkyl halides was achieved with a versatile nickel catalyst of a vicinal diamine ligand. Step‐economic access to functionalized 2‐pyrimidyl anilines, key structural motifs in anticancer drugs, is thus provided. The C−H functionalization proceeded through facile C−H activation and SET‐type C−X bond cleavage with the assistance of a monodentate directing group, which could be removed in a traceless fashion.
Single‐Molecule Nanocatalysis Shows In Situ Deactivation of Pt/C Electrocatalysts during the Hydrogen‐Oxidation Reaction
Authors: Zhang Yuwei , Chen Tao , Alia Shaun , Pivovar Bryan S. , Xu Weilin
Published: January 2016

By coupling a Pt‐catalyzed fluorogenic reaction with the Pt‐electrocatalyzed hydrogen‐oxidation reaction (HOR), we combine single‐molecule fluorescence microscopy with traditional electrochemical methods to study the real‐time deactivation kinetics of a Pt/C electrocatalyst at single‐particle level during electrocatalytic hydrogen‐oxidation reaction. The decay of the catalytic performance of Pt/C could be mainly attributed to the electrocatalysis‐induced etching or dissolution of Pt nanoparticles. Spontaneous regeneration of activity and incubation period of the Pt electrocatalyst were also observed at single‐particle level. All these new insights are practically useful for the understanding and rational design of highly efficient electrocatalysts for application in fuel cells.
Reductive Cyclopropanations Catalyzed by Dinuclear Nickel Complexes
Authors: Zhou You‐Yun , Uyeda Christopher
Published: January 2016

Dinuclear Ni complexes supported by naphthyridine‐diimine (NDI) ligands catalyze the reductive cyclopropanation of alkenes with CH2Cl2 as the methylene source. The use of mild terminal reductants (Zn or Et2Zn) confers significant functional‐group tolerance, and the catalyst accommodates structurally and electronically diverse alkenes. Mononickel catalysts bearing related N chelates afford comparatively low cyclopropane yields (≤20 %). These results constitute an entry into catalytic carbene transformations from oxidized methylene precursors.
Enzyme Selectivity Fine‐Tuned through Dynamic Control of a Loop
Authors: Vögeli Beat , Bibow Stefan , Chi Celestine N.
Published: January 2016

Allostery has been revealed as an essential property of all proteins. For enzymes, shifting of the structural equilibrium distribution at one site can have substantial impacts on protein dynamics and selectivity. Promising sites of remotely shifting such a distribution by changing the dynamics would be at flexible loops because relatively large changes may be achieved with minimal modification of the protein. A ligand‐selective change of binding affinity to the active site of cyclophilin is presented involving tuning of the dynamics of a highly flexible loop. Binding affinity is increased upon substitution of double Gly to Ala at the hinge regions of the loop. Quenching of the motional amplitudes of the loop slightly rearranges the active site. In particular, key residues for binding Phe60 and His126 adopt a more fixed orientation in the bound protein. Our system may serve as a model system for studying the effects of various time scales of loop motion on protein function tuned by mutations.
Dendrite‐Free Nanocrystalline Zinc Electrodeposition from an Ionic Liquid Containing Nickel Triflate for Rechargeable Zn‐Based Batteries
Authors: Liu Zhen , Cui Tong , Pulletikurthi Giridhar , Lahiri Abhishek , Carstens Timo , Olschewski Mark , Endres Frank
Published: January 2016

Metallic zinc is a promising anode material for rechargeable Zn‐based batteries. However, the dendritic growth of zinc has prevented practical applications. Herein it is demonstrated that dendrite‐free zinc deposits with a nanocrystalline structure can be obtained by using nickel triflate as an additive in a zinc triflate containing ionic liquid. The formation of a thin layer of Zn–Ni alloy (η‐ and γ‐phases) on the surface and in the initial stages of deposition along with the formation of an interfacial layer on the electrode strongly affect the nucleation and growth of zinc. A well‐defined and uniform nanocrystalline zinc deposit with particle sizes of about 25 nm was obtained in the presence of NiII. Further, it is shown that the nanocrystalline Zn exhibits a high cycling stability even after 50 deposition/stripping cycles. This strategy of introducing an inorganic metal salt in ionic liquid electrolytes can be considered as an efficient way to obtain dendrite‐free zinc.
A Bis(Diphosphanyl N‐Heterocyclic Carbene) Gold Complex: A Synthon for Luminescent Rigid AuAg2 Arrays and Au5 and Cu6 Double Arrays
Authors: Ai Pengfei , Mauro Matteo , De Cola Luisa , Danopoulos Andreas A. , Braunstein Pierre
Published: January 2016

A mononuclear bis(NHC)/AuI (NHC=N‐heterocyclic carbene) cationic complex with a rigid bis(phosphane)‐functionalized NHC ligand (PCNHCP) was used to construct linear Au3 and Ag2Au arrays, a Au5 cluster with two intersecting crosslike Au3 arrays, and an unprecedented Cu6 complex with two parallel Cu3 arrays. The impact of metallophilic interactions on photoluminescence was studied experimentally.
Overcoming Phase‐Transfer Limitations in the Conversion of Lipophilic Oleo Compounds in Aqueous Media—A Thermomorphic Approach
Authors: Gaide Tom , Dreimann Jens M. , Behr Arno , Vorholt Andreas J.
Published: January 2016

A new process concept has been developed for recycling transition‐metal catalysts in the synthesis of moderately polar products via aqueous thermomorphic multicomponent solvent systems. This work focuses on the use of “green” solvents (1‐butanol and water) in the hydroformylation of the bio‐based substrate methyl 10‐undecenoate. Following the successful development of a biphasic reaction system on the laboratory scale, the reaction was transferred to a continuously operated miniplant to demonstrate the robustness of this innovative recycling concept for homogenous catalysts.
The Largest Metalloid Group 14 Cluster, Ge18[Si(SiMe3)3]6: An Intermediate on the Way to Elemental Germanium
Authors: Kysliak Oleksandr , Schrenk Claudio , Schnepf Andreas
Published: January 2016

The oxidation of [Ge9(Hyp)3]− (Hyp=Si(SiMe3)3) with an FeII salt leads to Ge18(Hyp)6 (1), the largest Group 14 metalloid cluster that has been structurally characterized to date. The arrangement of the 18 germanium atoms in 1 shows similarities to that found in the solid‐state structure Ge(cF136). Furthermore, 1 can be described as a macropolyhedral cluster of two Ge9 units. Quantum‐chemical calculations further hint at a strained arrangement so that 1 can be considered as a first trapped intermediate on the way from Ge9 units to elemental germanium with the clathrate‐II structure (Ge(cF136)).
Silver‐Mediated Intermolecular 1,2‐Alkylarylation of Styrenes with α‐Carbonyl Alkyl Bromides and Indoles
Authors: Ouyang Xuan‐Hui , Song Ren‐Jie , Hu Ming , Yang Yuan , Li Jin‐Heng
Published: January 2016

A new iron‐facilitated silver‐mediated radical 1,2‐alkylarylation of styrenes with α‐carbonyl alkyl bromides and indoles is described, and two new C−C bonds were generated in a single step through a sequence of intermolecular C(sp3)−Br functionalization and C(sp2)−H functionalization across the alkenes. This method provides an efficient access to alkylated indoles with broad substrate scope and excellent selectivity.
New palladium(II)–N‐heterocyclic carbene complexes containing benzimidazole‐2‐ylidene ligand derived from menthol: synthesis, characterization and catalytic activities
Authors: Kılınçarslan Rafet , Emin Günay M. , Fırıncı Rukiye , Denizaltı Serpil , Çetinkaya Bekir
Published: January 2016

A new series of sterically hindered ligands containing (1R,2S,4R)‐(+)‐menthoxymethyl group attached to benzimidazole‐based N‐heterocyclic carbene (NHC), palladium–bis‐NHC complexes and (κ2‐C,N)‐palladacyclic NHC complexes have been synthesized and characterized using appropriate spectroscopic techniques. Catalytic performance of the palladium complexes has been investigated for allylic alkylation, Suzuki and Heck carbon–carbon coupling reactions. These complexes smoothly catalyse the carbon–carbon bond formation reactions. Copyright © 2016 John Wiley & Sons, Ltd.
Effects of plasticization and hydrostatic pressure on tensile properties ofPMMAunder compressed carbon dioxide and nitrogen
Authors: Taguchi Tomoaki , Saito Hiromu
Published: January 2016

We investigated the stress−strain behavior of PMMA films under compressed CO2and N2. The elongation at break increased and the stress decreased with increasing CO2pressure at pressures above 3 MPa, indicating that the tensile property changed from brittle to ductile under compressed CO2. In contrast, the material property became more brittle under compressed CO2at pressures below 2 MPa and under compressed N2. By depressurizing the compressed gas and excluding the hydrostatic pressure, the property of the gas‐absorbed specimen changed from brittle to ductile. These results suggest that deformability by molecular orientation is enhanced by the plasticizing effect caused by a large amount of absorbed gas while it is suppressed by the effect of hydrostatic pressure caused by a small amount of absorbed gas. Conversely, the elastic modulus decreased under both compressed CO2and N2, but the decrease under CO2was much larger than that under N2, suggesting that distortion in the elastic region is dominated by the plasticization effect. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2016,133, 43431.
Linking the biology and ecology of key herbivorous unicornfish to fisheries management in the Pacific
Authors: Ford Amanda K. , Bejarano Sonia , Marshell Alyssa , Mumby Peter J.
Published: January 2016

Naso lituratus (orangespine unicornfish) and Naso unicornis (bluespine unicornfish) are widespread species that are heavily targeted in many nearshore fisheries of Pacific Island countries. In addition to providing a critical food and income source, both species fulfil critical ecological functions in the top‐down control of coral reef macroalgae; particularly fleshy brown algae (i.e. Sargassum spp.) which can out‐compete and smother corals.

Despite heavy long‐term harvesting, there are currently very limited species‐specific management measures. This review assesses the biology and ecology of both species, and combines this with the current status of the fisheries in the Pacific, and proposes realistic ecosystem‐based species‐specific fisheries policies.

Although unicornfish populations have displayed continuing resilience to heavy fishing pressure, reports of declining stocks combined with a range of life‐history traits (i.e. longevity, habitat‐specificity, easily targeted aggregations), indicate that both species are vulnerable to overexploitation. Modern day common fishing practices such as scuba and night‐time spearfishing are intensifying their exploitation.

The most effective management measure would be fishing effort constraints, including banning modern and unsustainable methods. However, owing to enforcement limitations in Pacific Islands, the most practical approach to management would include a combination of management tools, including periodic sales bans around identified spawning times (i.e. Hawaii; May–June), and size/catch limits.

Furthermore, home range data suggest that even with limited knowledge, small MPAs (<1 km2) in structurally complex areas using natural boundaries should accommodate the movement patterns of both species and provide sufficient protection; although MPAs of > 10 km linear distance are recommended for N. lituratus.

This comprehensive review confirms the pressing need for implementation of the aforementioned management practices to protect these species in regions where they are heavily targeted, and prevent the impairment of their critical ecological function and importance as a food and income source.

Copyright © 2016 John Wiley & Sons, Ltd.
Maternal metabolic risk factors for autism spectrum disorder—An analysis of electronic medical records and linked birth data
Authors: Connolly Natalia , Anixt Julia , Manning Patty , Ping‐I Lin Daniel , Marsolo Keith A. , Bowers Katherine
Published: January 2016

Past studies have suggested that conditions experienced by women during pregnancy (e.g. obesity and gestational diabetes mellitus (GDM)) may be associated with having a child with autism spectrum disorder (ASD). Our objective was to compare mothers who had a child diagnosed with ASD to mothers of children with a non‐ASD developmental disorder (DD) or without any reported DD (controls). To accomplish the objective we collected medical record data from patients who resided in the Cincinnati Children's Hospital Medical Center's (CCHMC) primary catchment area and linked those data to data from birth certificates (to identify risk factors). Two comparison groups were analyzed; one with DD; and the other, controls without a reported ASD or DD. Descriptive statistics and regression analyses evaluated differences. Differences were greater comparing mothers of ASD to controls than comparing ASD to DD. Maternal obesity and GDM were associated with a statistically significant approximately 1.5‐fold increased odds of having a child with an ASD. For mothers with both GDM and obesity, the association was twofold for having a child with ASD compared with controls. Maternal obesity and GDM might be associated with an increased risk of ASD in the offspring; however, no difference in risk of ASD according to BMI and GDM was seen when comparing to DD. Autism Res 2016, 9: 829–837,. © 2016 International Society for Autism Research, Wiley Periodicals, Inc.
Factors associated with sinus bradycardia during crizotinib treatment: a retrospective analysis of two large‐scale multinational trials (PROFILE 1005 and 1007)
Authors: Ou Sai‐Hong Ignatius , Tang Yiyun , Polli Anna , Wilner Keith D. , Schnell Patrick
Published: January 2016

Decreases in heart rate (HR) have been described in patients receiving crizotinib. We performed a large retrospective analysis of HR changes during crizotinib therapy. HRs from vital‐sign data for patients with anaplastic lymphoma kinase (ALK)‐positive nonsmall cell lung cancer enrolled in PROFILE 1005 and the crizotinib arm of PROFILE 1007 were analyzed. Sinus bradycardia (SB) was defined as HR <60 beats per minute (bpm). Magnitude and timing of HR changes were assessed. Potential risk factors for SB were investigated by logistic regression analysis. Progression‐free survival (PFS) was evaluated according to HR decrease by <20 versus ≥20 bpm within the first 50 days of starting treatment. For the 1053 patients analyzed, the mean maximum postbaseline HR decrease was 25 bpm (standard deviation 15.8). Overall, 441 patients (41.9%) had at least one episode of postbaseline SB. The mean precrizotinib treatment HR was significantly lower among patients with versus without postbaseline SB (82.2 bpm vs. 92.6 bpm). The likelihood of experiencing SB was statistically significantly higher among patients with a precrizotinib treatment HR <70 bpm. PFS was comparable among patients with or without HR decrease of ≥20 bpm within the first 50 days of starting crizotinib. Decrease in HR is very common among patients on crizotinib. The likelihood of experiencing SB was statistically significantly higher among patients with a precrizotinib treatment HR <70 bpm. This is the first large‐scale report investigating the association between treatment with a tyrosine kinase inhibitor and the development of bradycardia. HRs should be closely monitored during crizotinib treatment.
Pd/C as an Efficient and Reusable Catalyst for the Selective N‐Alkylation of Amines with Alcohols
Authors: Liu Xiang , Hermange Philippe , Ruiz Jaime , Astruc Didier
Published: January 2016

An efficient Pd/C‐catalyzed synthesis of secondary amines involving C−N bond formation was achieved from amines and alcohols with H2O as the only byproduct. This common, green, commercial, and cheap catalyst was recycled five times in this sustainable, simple, and economic procedure.
Waste Lard Methanolysis Catalyzed by KOH at Moderate Temperatures
Authors: Stojković Ivan J. , Banković‐Ilić Ivana B. , Veličković Ana V. , Avramović Jelena M. , Stamenković Olivera S. , Povrenović Dragan S. , Veljković Vlada B.
Published: January 2016

The KOH‐catalyzed methanolysis of waste lard from piglet roasting in a moderate temperature range was investigated in order to establish the reaction kinetics. For comparison, lard and thermally treated lard were also included in the study. All three reactions occurred via a pseudo‐homogeneous regime where the chemical reaction controlled the overall process kinetics. A simple kinetic model comprising the irreversible pseudo‐first‐order reaction was demonstrated for all three fatty feedstocks. The reaction rate constant increases with raising the fatty acid unsaturation degree. The final products satisfied the EN 14214 biodiesel standard specifications.
CO2 Capture Performance of Calcium‐Based Sorbents in the Presence of SO2 under Pressurized Carbonation
Authors: Chen Huichao , Zhao Changsui
Published: January 2016

In order to understand the effect of SO2 on the CO2 capture performance under pressurized carbonation conditions, tests by orthogonal design were carried out in a calcination/pressurized carbonation reactor system. The effects of variables such as carbonation temperature, carbonation pressure, SO2 concentration, CO2 concentration, and the number of cycles on carbonation and sulfation were investigated. A range method was employed for analysis. Phase structure and scanning electron microscopy images were measured as supplement for a reaction study. Temperature increase enhanced the SO2 capture, leading to a rapid decay in CO2 uptake. The carbonation pressure had a stronger effect on the CO2 uptake than the temperature. SO2 uptake increased rapidly with increasing pressure while CO2 uptake decreased.
Concentration Distribution of Droplets in a Liquid‐Liquid Hydrocyclone and its Application
Authors: Qian Peng , Ma Ji , Liu Yi , Yang Xuejin , Zhang Yanhong , Wang Hualin
Published: January 2016

The concentration distribution of droplets in liquid‐liquid hydrocyclones was studied using a phase Doppler particle analyzer. The effect of cone angle and inlet flow flux on the concentration distribution of droplets was determined. The cone angle of the hydrocyclone obviously influenced the maximum droplet concentration, especially that in the cone section. The hydrocyclone with a cone angle of 6° presented the best separation result. A higher inlet flow rate enhanced the separation of droplets from the water. The concentration profiles at five different axial heights presented a parabola law pattern in the radial direction. The optimized hydrocyclone was applied for the dewatering of vinyl chloride monomer (VCM). The amount of residual water could be greatly reduced.
Structure of Amido Pyridinium Betaines: Persistent Intermolecular C−H⋅⋅⋅N Hydrogen Bonding in Solution
Authors: Thatcher Robert J. , Johnson David G. , Slattery John M. , Douthwaite Richard E.
Published: January 2016

A hydrogen bond of the type C−H⋅⋅⋅X (X=O or N) is known to influence the structure and function of chemical and biological systems in solution. C−H⋅⋅⋅O hydrogen bonding in solution has been extensively studied, both experimentally and computationally, whereas the equivalent thermodynamic parameters have not been enumerated experimentally for C−H⋅⋅⋅N hydrogen bonds. This is, in part, due to the lack of systems that exhibit persistent C−H⋅⋅⋅N hydrogen bonds in solution. Herein, a class of molecule based on a biologically active norharman motif that exhibits unsupported intermolecular C−H⋅⋅⋅N hydrogen bonds in solution has been described. A pairwise interaction leads to dimerisation to give bond strengths of about 7 kJ mol−1 per hydrogen bond, which is similar to chemically and biologically relevant C−H⋅⋅⋅O hydrogen bonding. The experimental data is supported by computational work, which provides additional insight into the hydrogen bonding by consideration of electrostatic and orbital interactions and allowed a comparison between calculated and extrapolated NMR chemical shifts.
The Bond Order of C2 from a Strictly N‐Representable Natural Orbital Energy Functional Perspective
Authors: Piris Mario , Lopez Xabier , Ugalde Jesus M.
Published: January 2016

The bond order of the ground electronic state of the carbon dimer has been analyzed in the light of natural orbital functional theory calculations carried out with an approximate, albeit strictly N‐representable, energy functional. Three distinct solutions have been found from the Euler equations of the minimization of the energy functional with respect to the natural orbitals and their occupation numbers, which expand upon increasing values of the internuclear coordinate. In the close vicinity of the minimum energy region, two of the solutions compete around a discontinuity point. The former, corresponding to the absolute minimum energy, features two valence natural orbitals of each of the following symmetries, σ, σ*, π and π*, and has three bonding interactions and one antibonding interaction, which is very suggestive of a bond order large than two but smaller than three. The latter, features one σ–σ* linked pair of natural orbitals and three degenerate pseudo‐bonding like orbitals, paired each with one triply degenerate pseudo‐antibonding orbital, which points to a bond order larger than three. When correlation effects, other than Hartree–Fock for example, between the paired natural orbitals are accounted for, this second solution vanishes yielding a smooth continuous dissociation curve. Comparison of the vibrational energies and electron ionization energies, calculated on this curve, with their corresponding experimental marks, lend further support to a bond order for C2 intermediate between acetylene and ethylene.