bluuebunny/crossref_metadata_2025 huggingface dataset:
Symmetriebruch in chiralen ionischen Flüssigkeiten: Nachweis durch vibratorisch‐optische Aktivität
Authors: Oulevey Patric , Luber Sandra , Varnholt Birte , Bürgi Thomas
Published: August 2016

Ionische Flüssigkeiten (ILs) erfreuen sich in Syntheselaboren und in der Industrie großer Beliebtheit. Ihre Zusammensetzung aus geladenen Ionen verleiht den ILs ein komplexes und zu einem großen Teil noch unerforschtes Verhalten. Chirale ILs (CILs) bergen ein hohes Potential beim Einsatz als Lösungsmittel für enantioselektive Synthesen. Chiroptische Messmethoden ermöglichen wegen ihrer Empfindlichkeit für die molekulare Konformation, die Struktur solcher CILs zu erforschen. Die Messung der Raman‐optischen Aktivität ist eine geeignete Methode, Aminosäure‐basierte CILs (Gegenion: 1‐Ethyl‐3‐methylimidazolium, achiral) zu untersuchen. Mithilfe theoretischer Methoden konnte nun belegt werden, dass auch das achirale Gegenion in der Gegenwart der (chiralen) Aminosäuren eine im Mittel chirale Konformation einnimmt. Diese Erkenntnis zeigt, dass bei der Entwicklung neuer CILs für die Verwendung in asymmetrischen Reaktionen auch die Struktur des achiralen Gegenions sorgfältig ausgewählt werden muss.
Symmetry Breaking in Chiral Ionic Liquids Evidenced by Vibrational Optical Activity
Authors: Oulevey Patric , Luber Sandra , Varnholt Birte , Bürgi Thomas
Published: August 2016

Ionic liquids (ILs) are receiving increasing interest for their use in synthetic laboratories and industry. Being composed of charged entities, they show a complex and widely unexplored dynamic behavior. Chiral ionic liquids (CILs) have a high potential as solvents for use in asymmetric synthesis. Chiroptical methods, owing to their sensitivity towards molecular conformation, offer unique possibilities to study the structure of these chiral ionic liquids. Raman optical activity proved particularly useful to study ionic liquids composed of amino acids and the achiral 1‐ethyl‐3‐methylimidazolium counterion. We could substantiate, supported by selected theoretical methods, that the achiral counterion adopts an overall chiral conformation in the presence of chiral amino acid ions. These findings suggest that in the design of chiral ionic liquids for asymmetric synthesis, the structure of the achiral counter ion also has to be carefully considered.
MOF‐5‐Polystyrene: Direct Production from Monomer, Improved Hydrolytic Stability, and Unique Guest Adsorption
Authors: Gamage Nipuni‐Dhanesha H. , McDonald Kyle A. , Matzger Adam J.
Published: August 2016

An unprecedented mode of reactivity of Zn4O‐based metal–organic frameworks (MOFs) offers a straightforward and powerful approach to polymer‐hybridized porous solids. The concept is illustrated with the production of MOF‐5‐polystyrene wherein polystyrene is grafted and uniformly distributed throughout MOF‐5 crystals after heating in pure styrene for 4–24 h. The surface area and polystyrene content of the material can be fine‐tuned by controlling the duration of heating styrene in the presence of MOF‐5. Polystyrene grafting significantly alters the physical and chemical properties of pristine MOF‐5, which is evident from the unique guest adsorption properties (solvatochromic dye uptake and improved CO2 capacity) as well as the dramatically improved hydrolytic stability of composite. Based on the fact that MOF‐5 is the best studied member of the structure class, and has been produced at scale by industry, these findings can be directly leveraged for a range of current applications.
Energetic 4,4′‐Oxybis[3,3′‐(1‐hydroxytetrazolyl)]furazan and Its Salts
Authors: Tang Yongxing , He Chunlin , Imler Gregory H. , Parrish Damon A. , Shreeve Jean'ne M.
Published: August 2016

Energetic compounds that incorporate multiple nitrogen‐rich heterocycles are of great interest for high‐density energetic materials. A facile synthetic strategy to combine an oxy bridge and furazan groups, as well as tetrazole‐ols, into a molecule (5) was found. Some energetic salts based on 5 were prepared by neutralization. All of the compounds were fully characterized. Additionally, the structure of 7 has been elucidated by single‐crystal XRD analysis. Physicochemical and energetic properties were also studied; these show that these newly designed energetic salts exhibit good thermal stabilities. Hydroxylammonium salt (6) has a detonation performance and sensitivities comparable with those of 1,3,5‐trinitroperhydro‐1,3,5‐triazine (RDX).
Continuous Fractional‐Order Sliding PI Control for Nonlinear Systems Subject to Non‐Differentiable Disturbances
Authors: Muñoz‐Vázquez A. J. , Parra‐Vega V. , Sánchez‐Orta A.
Published: August 2016

Aiming at designing a robust controller to withstand a class of continuous, but not necessarily differentiable, disturbances, such as Hölder type, a continuous and chattering‐free sliding mode control is proposed. The key idea is a judicious synthesis of a resetting memory principle for the differintegral operators to show that a sliding mode is induced, and sustained, in finite‐time, to guarantee asymptotic tracking. The closed‐loop system achieves exact rejection of Hölder disturbances even in case of uncertain flow, but assuming certain knowledge of the input matrix. Furthermore, it is shown that our methodology generalizes continuous high‐oder sliding mode schemes by using an integral action of fractional‐order. A representative simulation study is discussed to show the feasibility of the proposal.
A dual control approach for repeated anticipatory traffic control with estimation of network flow sensitivity
Authors: Huang Wei , Viti Francesco , Tampère Chris M. J.
Published: August 2016

This paper investigates a strategic signal control, which anticipates travelers' route choice response and determines signal timings to optimize network‐wide objectives. In general traffic assignment models are used for anticipating this route choice response. However, model‐reality mismatch usually brings suboptimal solutions to the real system. A repeated anticipatory control resolves the suboptimality and addresses the modeling error by learning from information on model bias. This paper extends the repeated control approach and focuses on the estimation of flow sensitivity as well as its influence on control, which is a crucial issue in implementation of model bias correction. The main objective of this paper is first to analyze the estimation error in the real flow derivative that is estimated from noisy measurements. A dual control method is then presented, improving both optimization objective function and derivative estimation during the control process. The proposed dual algorithm is tested on a simple network as well as on a midsize network. Numerical examples confirm the reliable performance of the new reality‐tracking control strategy and its ability to identify (local) optimal solutions on real traffic networks. Copyright © 2016 John Wiley & Sons, Ltd.
The pharmacokinetics of propofol in ICU patients undergoing long‐term sedation
Authors: Smuszkiewicz Piotr , Wiczling Paweł , Przybyłowski Krzysztof , Borsuk Agnieszka , Trojanowska Iwona , Paterska Marta , Matysiak Jan , Kokot Zenon , Grześkowiak Edmund , Bienert Agnieszka
Published: August 2016

The aim of this study was to characterize the pharmacokinetics (PK) of propofol in ICU patients undergoing long‐term sedation and to assess the influence of routinely collected covariates on the PK parameters. Propofol concentration–time profiles were collected from 29 patients. Non‐linear mixed‐effects modelling in NONMEM 7.2 was used to analyse the observed data. The propofol pharmacokinetics was best described with a three‐compartment disposition model. Non‐parametric bootstrap and a visual predictive check were used to evaluate the adequacy of the developed model to describe the observations. The typical value of the propofol clearance (1.46 l/min) approximated the hepatic blood flow. The volume of distribution at steady state was high and was equal to 955.1 l, which is consistent with other studies involving propofol in ICU patients. There was no statistically significant covariate relationship between PK parameters and opioid type, SOFA score on the day of admission, APACHE II, predicted death rate, reason for ICU admission (sepsis, trauma or surgery), gender, body weight, age, infusion duration and C‐reactive protein concentration. The population PK model was developed successfully to describe the time‐course of propofol concentration in ICU patients undergoing prolonged sedation. Despite a very heterogeneous group of patients, consistent PK profiles were observed. Copyright © 2016 John Wiley & Sons, Ltd.
A short‐term extremely low frequency electromagnetic field exposure increases circulating leukocyte numbers and affects HPA‐axis signaling in mice
Authors: de Kleijn Stan , Ferwerda Gerben , Wiese Michelle , Trentelman Jos , Cuppen Jan , Kozicz Tamas , de Jager Linda , Hermans Peter W. M. , Verburg‐van Kemenade B. M. Lidy
Published: August 2016

There is still uncertainty whether extremely low frequency electromagnetic fields (ELF‐EMF) can induce health effects like immunomodulation. Despite evidence obtained in vitro, an unambiguous association has not yet been established in vivo. Here, mice were exposed to ELF‐EMF for 1, 4, and 24 h/day in a short‐term (1 week) and long‐term (15 weeks) set‐up to investigate whole body effects on the level of stress regulation and immune response. ELF‐EMF signal contained multiple frequencies (20–5000 Hz) and a magnetic flux density of 10 μT. After exposure, blood was analyzed for leukocyte numbers (short‐term and long‐term) and adrenocorticotropic hormone concentration (short‐term only). Furthermore, in the short‐term experiment, stress‐related parameters, corticotropin‐releasing hormone, proopiomelanocortin (POMC) and CYP11A1 gene‐expression, respectively, were determined in the hypothalamic paraventricular nucleus, pituitary, and adrenal glands. In the short‐term but not long‐term experiment, leukocyte counts were significantly higher in the 24 h‐exposed group compared with controls, mainly represented by increased neutrophils and CD4 ± lymphocytes. POMC expression and plasma adrenocorticotropic hormone were significantly lower compared with unexposed control mice. In conclusion, short‐term ELF‐EMF exposure may affect hypothalamic‐pituitary‐adrenal axis activation in mice. Changes in stress hormone release may explain changes in circulating leukocyte numbers and composition. Bioelectromagnetics. 37:433–443, 2016. © 2016 The Authors. Bioelectromagnetics Published by Wiley Periodicals, Inc.
Calmodulin EF‐hand peptides as Ca2+‐switchable recognition tags
Authors: Oku Akihiko , Imanishi Miki , Noshiro Daisuke , Murayama Tomo , Takeuchi Toshihide , Nakase Ikuhiko , Futaki Shiroh
Published: August 2016

Calmodulin is a representative calcium‐binding protein comprised of four Ca2+‐binding motifs with a helix‐loop‐helix structure (EF‐hands). In this study, we clarified the potential of peptide segments derived from the third and fourth EF‐hands (EF3 and EF4) to act as recognition tags. Through an analysis of the mode of disulfide formation among cysteines inserted at the N‐ or C‐terminus of these peptide segments, EF3 and EF4 peptides were suggested to form a heterodimer with a topology similar to that in the wild‐type protein. Heterodimer formation was shown to be a function of the Ca2+ concentration, suggesting that these structures may be used as Ca2+‐switchable recognition tags. An example of an “EF‐tag” system involving the membrane fusion of liposomes decorated with EF3 and EF4 peptides is presented. © 2016 Wiley Periodicals, Inc. Biopolymers (Pept Sci), 2016.
Randomized clinical trial of the use of glyceryl trinitrate patches to aid arteriovenous fistula maturation
Authors: Field M , McGrogan D , Marie Y , Joinson M , Andujar C , Dutton M , Krishnan H , Hodson J , van Dellen D , Inston N G
Published: August 2016

Background

Arteriovenous fistulas are critical for haemodialysis, but maturation rates remain poor. Experimental and anecdotal evidence has supported the use of transdermal glyceryl trinitrate (GTN) patches. The aim of this RCT was to determine whether use of a GTN patch aids arteriovenous fistula maturation.

Methods

Patients referred for arteriovenous fistula formation were eligible. The GTN or placebo patch was applied immediately after surgery and left in situ for 24 h. The primary outcome measure was the change in venous diameter at 6 weeks after fistula formation. The secondary outcome measure was clinical fistula patency at 6 weeks.

Results

Of 200 patients recruited (533 screened), 101 were randomized to the placebo group and 99 to the GTN group. Of these, 81 and 86 respectively completed surgery, and had follow-up data available at 6 weeks. Improvements in venous diameter were similar in the two groups: mean(s.d.) increase 2·3(1·9) mm in the placebo group compared with 2·2(1·8) mm in the GTN group (P = 0·704). The fistula failure rate did not differ significantly between the two groups: 23 per cent for placebo and 28 per cent for GTN (P = 0·596).

Conclusion

GTN transdermal patches used for 24 h after surgery did not improve arteriovenous fistula maturation. Registration number: NCT01685710 (http://www.clinicaltrials.gov).
An efficient method for the application of PHA‐poor solvents to extract polyhydroxybutyrate from Cupriavidus necator
Authors: Aramvash Asieh , Gholami‐Banadkuki Narges , Seyedkarimi Mansooreh‐Sadat
Published: August 2016

There are many published studies presenting ethanol and acetone as PHAs‐poor solvents, where these two solvents are shown to dissolve <2% (w/v) of PHAs at low temperatures. In this study, the suitability of ethanol and acetone for the recovery of PHB at different temperatures (from room temperature to near boiling point) in Cupriavidus necator was investigated. Experiments were performed using response surface methodology to examine the effects of different temperatures and heating incubation times on recovery percentage using the two solvents. The highest recovery percentage (92.3%) and product purity (up to 99%) were obtained with ethanol‐assisted extraction at 76°C for 32 min of incubation time. Under these conditions the extracted PHB exhibited a molecular mass of 1.2 × 106. The present strategy showed that at temperatures near its boiling point, ethanol, as a nonhalogenated solvent, represents a good alternative to halogenated solvents, like chloroform, when PHB recovery is concerned. DSC analysis showed good thermal properties for ethanol‐ and acetone‐extracted biopolymers. GC and 1H NMR analysis confirmed the extracted biopolymer to be polyhydroxybutyrate of good purity. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:1480–1486, 2016
Mechanism of Error‐Free Bypass of the Environmental Carcinogen N‐(2′‐Deoxyguanosin‐8‐yl)‐3‐aminobenzanthrone Adduct by Human DNA Polymerase η
Authors: Patra Amritraj , Politica Dustin A. , Chatterjee Arindom , Tokarsky E. John , Suo Zucai , Basu Ashis K. , Stone Michael P. , Egli Martin
Published: August 2016

The environmental pollutant 3‐nitrobenzanthrone produces bulky aminobenzanthrone (ABA) DNA adducts with both guanine and adenine nucleobases. A major product occurs at the C8 position of guanine (C8‐dG‐ABA). These adducts present a strong block to replicative polymerases but, remarkably, can be bypassed in a largely error‐free manner by the human Y‐family polymerase η (hPol η). Here, we report the crystal structure of a ternary Pol⋅DNA⋅dCTP complex between a C8‐dG‐ABA‐containing template:primer duplex and hPol η. The complex was captured at the insertion stage and provides crucial insight into the mechanism of error‐free bypass of this bulky lesion. Specifically, bypass involves accommodation of the ABA moiety inside a hydrophobic cleft to the side of the enzyme active site and formation of an intra‐nucleotide hydrogen bond between the phosphate and ABA amino moiety, allowing the adducted guanine to form a standard Watson–Crick pair with the incoming dCTP.
The potential role of HER2 upregulation in metastatic breast cancer to the uterus: a case report
Authors: Moey Melissa Y. Y. , Hassan Omer A. , Papageorgiou Christos N. , Schnepp Stephanie L. , Hoff John T.
Published: August 2016

Key Clinical Message

Abnormal uterine bleeding in a patient on maintenance hormonal therapy for breast cancer should raise concern for endometrial abnormalities including rare uterine metastasis from the breast. Hormonal receptor profile changes in metastatic lesions favoring human epidermal growth factor receptor 2 (HER2) overexpression may be involved in the pathogenesis of metastasis to the uterus.
Common electrocardiogram variations pre‐ and post‐marathon
Authors: Martin‐Beaulieu John P. , Myrick Karen M. , Martin Thomas , Pata Rachel W. , Feinn Richard S.
Published: August 2016

Key Clinical Message

Electrocardiographic changes can be present in marathon runners. These findings may be misinterpreted as malignant by healthcare providers. For example, incomplete right bundle branch block, early ventricular repolarization, and left ventricular hypertrophy by voltage criteria alone are quite common in athletes, yet considered benign.
Facile Preparation of Poly(3,4‐ethylenedioxythiophene)/MnO2 Composite Electrodes for Efficient Supercapacitors
Authors: Gao Xue , Dong Bin , Chen Si , Chen Buxin , Xiao Xinyu , Zhou Jingbo , Su Xin , Zou Dechun
Published: August 2016

An innovative method to prepare poly(3,4‐ethylenedioxythiophene) (PEDOT)/MnO2 composite electrodes without adding any binder, conductive agent, or catalyst is reported. The preparation process for the supercapacitor electrodes is facile and involves simple spin coating and in situ polymerization of vacuum‐deposited 2,5‐dibromo‐3,4‐ethylenedioxythiophene. A uniform and stable PEDOT/MnO2 composite thin film is obtained after the in situ synthesis of the PEDOT thin film on the surface of the MnO2 nanoparticles with strong adhesion. The PEDOT/MnO2 supercapacitor electrodes exhibit excellent performance with a high specific capacitance of 575.0 F g−1 at a current density of 8 A g−1. The symmetrical supercapacitor offers an energy density of 14.6 Wh kg−1 with a high power density of 1365 Wh kg−1. Moreover, the PEDOT/MnO2 supercapacitor electrodes can be prepared from flexible substrates, of which the specific capacitance still reaches 352.9 F g−1 at a current density of 5 A g−1. The preparation method should facilitate the use of the multicomponent composite in further energy‐storage applications as well as in many other related fields.
Water Formation for the Metalation of Porphyrin Molecules on Oxidized Cu(111)
Authors: Verdini Alberto , Shinde Prashant , Montanari Gian Luca , Suran‐Brunelli Simone Tommaso , Caputo Marco , Di Santo Giovanni , Pignedoli Carlo A. , Floreano Luca , Passerone Daniele , Goldoni Andrea
Published: August 2016

Herein the formation of water molecules in the intermediate step of the redox reaction of porphyrins self‐metalation on O/Cu(111) is demonstrated. Photoemission measurements show that the temperature on which porphyrins pick‐up a substrate metal atom on O/Cu(111) is reduced by about 185±15 K with respect to the pure Cu(111). DFT calculations clearly indicate that the formation of a water molecule is less expensive than the formation of H2 on the O/Cu(111) substrate and, in some cases, it can be also exothermic.
Hydrazones as Singular Reagents in Asymmetric Organocatalysis
Authors: de Gracia Retamosa María , Matador Esteban , Monge David , Lassaletta José M. , Fernández Rosario
Published: August 2016

This Minireview summarizes strategies and developments regarding the use of hydrazones as reagents in asymmetric organocatalysis, their distinct roles in nucleophile–electrophile, cycloaddition, and cyclization reactions. The key structural elements governing the reactivity of these reagents in a preferred pathway will be discussed, as well as their different interactions with organocatalysts, leading to diverse activation modes. Along these studies, the synthetic equivalence of N‐monoalkyl, N,N‐dialkyl, and N‐acyl hydrazones with several synthons is also highlighted. Emphasis is also put on the mechanistic studies performed to understand the observed reactivities. Finally, the functional group transformations performed from the available products has also been analyzed, highlighting the synthetic value of these methodologies, which served to access numerous families of valuable multifunctional compounds and nitrogen‐containing heterocycles.
5‐(2‐Mercaptoethyl)‐1H‐tetrazole: Facile Synthesis and Application for the Preparation of Water Soluble Nanocrystals and Their Gels
Authors: Voitekhovich Sergei V. , Wolf André , Guhrenz Chris , Lyakhov Alexander S. , Ivashkevich Ludmila S. , Adam Marion , Gaponik Nikolai , Kaskel Stefan , Eychmüller Alexander
Published: August 2016

A facile method for the preparation of the novel capping ligand 5‐(2‐mercaptoethyl)‐1H‐tetrazole for the stabilization of water‐soluble nanocrystals was developed. This effective synthetic procedure is based on the cycloaddition of sodium azide to 3,3′‐dithiobis(propionitrile) followed by the reductive cleavage of a S−S bond with triphenylphosphine. The structure of the synthesized compound was confirmed by single‐crystal X‐ray analysis. A target tetrazole was successfully applied for the direct aqueous synthesis of CdTe and Au nanocrystals. CdTe nanocrystals capped with 5‐(2‐mercaptoethyl)‐1H‐tetrazole were found to reveal high photoluminescence efficiencies (up to 77 %). Nanocrystals capped with this tetrazole ligand are able to build 3D structures in a metal‐ion‐assisted gelation process in aqueous solution. Critical point drying of the as‐formed hydrogels allowed the preparation of the corresponding aerogels, while preserving the mesoporous structure.
Synthesis, Properties, and Two‐Dimensional Adsorption Characteristics of [6]Hexahelicene‐7‐carboxylic acid
Authors: van der Meijden Maarten W. , Balandina Tatyana , Ivasenko Oleksandr , De Feyter Steven , Wurst Klaus , Kellogg Richard M.
Published: August 2016

A convergent synthesis of racemic [6]hexahelicene‐7‐carboxylic acid by cross‐coupling of a bicyclic and a tricyclic component is described. A metal‐catalyzed ring‐closure is also a fundamental component of the synthetic approach. Scanning tunneling microscopy (STM) measurements of the racemate self‐assembled on Au(111) at liquid–solid interface revealed the formation of ordered racemic 2D crystals.
Nanoconfinement Inside Molecular Metal Oxide Clusters: Dynamics and Modified Encapsulation Behavior
Authors: Wang Zhe , Daemen Luke L. , Cheng Yongqiang , Mamontov Eugene , Bonnesen Peter V. , Hong Kunlun , Ramirez‐Cuesta Anibal J. , Yin Panchao
Published: August 2016

Invited for the cover of this issue are Panchao Yin and collaborators at Oak Ridge National Laboratory. The image depicts a 2.9 nm molybdenum oxide molecular cluster for the size‐selective encapsulation of small alkane molecules. Read the full text of the article at 10.1002/chem.201603239.
How do you write and present research well? 19–emulate articles in high impact factor journals
Authors: Patience Gregory S. , Patience Christian A. , Bertrand François , Patience Paul A. , Boffito Daria C.
Published: August 2016

Identify WoS's top 5 Chemical Engineering journals based on the number of citations over the last 25 years.[1,2]

Process Biochemistry

Chemical Engineering Science

Energy & Environmental Science

Progress in Energy and Combustion Science

AIChE Journal 5—13 207 citations

Industrial & Engineering Chemistry Research

Applied Catalysis B: Environmental 4—16 636 citations

Journal of Membrane Science 3—21 511 citations

Catalysis Today 2—29 312 citations

Journal of Catalysis 1—39 249 citations

Canadian Journal of Chemical Engineering
Percutaneous Coronary Intervention for Bifurcation: How Can We Outperform the Provisional Strategy?
Authors: Ng Andrew Kei‐Yan , Jim Man‐Hong
Published: August 2016

In the era of drug‐eluting stents, the provisional stenting strategy has been established as the default strategy in percutaneous coronary intervention for bifurcation lesions. However, emerging evidence shows that, in selected situations, the complex strategy of stenting both vessels regardless could reduce side‐branch restenosis without penalty. In particular, the double kissing crush technique has been proven to outperform the provisional strategy and other complex strategies in randomized trials. In this review, we present the evidence comparing the 2 strategies and individual stenting techniques and discuss the roles of other optimization techniques such as final kissing balloon inflation, proximal optimization technique, intravascular ultrasonography, and optical coherence tomography. Finally, we suggest a practical approach for choosing the optimal strategy for intervention with coronary bifurcation lesions.
Magnetically Alignable Bicelles with Unprecedented Stability Using Tunable Surfactants Derived from Cholic Acid
Authors: Matsui Ryoichi , Uchida Noriyuki , Ohtani Masataka , Yamada Kuniyo , Shigeta Arisu , Kawamura Izuru , Aida Takuzo , Ishida Yasuhiro
Published: August 2016

Five novel surfactants were prepared by modifying the three hydroxy groups of sodium cholate with triethylene glycol chains endcapped with an amide (SC‐C1, SC‐nC4, and SC‐nC5) or a carbamoyl group (SC‐OnC4 and SC‐OtC4). The phase behavior of aqueous mixtures of these surfactants with 1,2‐dimyristoyl‐sn‐glycero‐3‐phosphatidylcholine (DMPC) was systematically studied by 31P NMR spectroscopy. The surfactants endcapped with carbamate groups (SC‐OnC4 and SC‐OtC4) formed magnetically alignable bicelles over unprecedentedly wide ranges of conditions, in terms of temperature (from 21–23 to >90 °C), lipid/surfactant ratio (from 5 to 8), total lipid content (5–20 wt %), and lipid type [DMPC, 1,2‐dilauroyl‐sn‐glycero‐3‐phosphatidylcholine (DLPC), or 1‐palmitoyl‐2‐oleoyl‐sn‐glycero‐3‐phosphatidylcholine (POPC)]. In conjunction with appropriate phospholipids, the carbamate‐endcapped surfactants afforded unique bicelles, characterized by exceptional thermal stabilities (from 0 to >90 °C), biomimetic lipid compositions (DMPC/POPC=25:75 to 50:50), and extremely large 2H quadrupole splittings (up to 71 Hz).
Additive‐Free Transparent Triarylamine‐Based Polymeric Hole‐Transport Materials for Stable Perovskite Solar Cells
Authors: Matsui Taisuke , Petrikyte Ieva , Malinauskas Tadas , Domanski Konrad , Daskeviciene Maryte , Steponaitis Matas , Gratia Paul , Tress Wolfgang , Correa‐Baena Juan‐Pablo , Abate Antonio , Hagfeldt Anders , Grätzel Michael , Nazeeruddin Mohammad Khaja , Getautis Vytautas , Saliba Michael
Published: August 2016

Triarylamine‐based polymers with different functional groups were synthetized as hole‐transport materials (HTMs) for perovskite solar cells (PSCs). The novel materials enabled efficient PSCs without the use of chemical doping (or additives) to enhance charge transport. Devices employing poly(triarylamine) with methylphenylethenyl functional groups (V873) showed a power conversion efficiency of 12.3 %, whereas widely used additive‐free poly[bis(4‐phenyl)(2,4,6‐trimethylphenyl)amine] (PTAA) demonstrated 10.8 %. Notably, devices with V873 enabled stable PSCs under 1 sun illumination at maximum power point tracking for approximately 40 h at room temperature, and in the dark under elevated temperature (85 °C) for more than 140 h. This is in stark contrast to additive‐containing devices, which degrade significantly within the same time frame. The results present remarkable progress towards stable PSC under real working conditions and industrial stress tests.
Oxidative Direct Arylation Polymerization Using Oxygen as the Sole Oxidant: Facile, Green Access to Bithiazole‐Based Polymers
Authors: Guo Qiang , Wu Di , You Jingsong
Published: August 2016

The most appealing oxidant, molecular oxygen, is employed for the first time as the sole oxidant in the transition metal‐catalyzed oxidative direct arylation polymerization (C−H/C−H‐type DArP), which eliminates by‐product formation of stoichiometric metal salts except for water . Compared to conventional approaches, other than the avoidance of an end‐capping procedure, the current protocol is remarkably advanced in the aspect of eco‐friendliness, step‐ and cost‐economy, and, of special significance, the purity of polymer products. As illustrative examples, six 5,5′‐bithiazole‐based polymers are synthesized using this new method, demonstrating higher number‐average molecular weight (Mn up to 33 700) in better yields (up to 93 %) through only one step. The evolution of C−H/C−H‐type DArP from heavy metal salts to O2 alone as the oxidant could solve the problem of metal residues in polymers, which is considered harmful to the performance of devices.
Facile Preparation of Flavinium Organocatalysts
Authors: Arakawa Yukihiro , Oonishi Takahiro , Kohda Takahiro , Minagawa Keiji , Imada Yasushi
Published: August 2016

We developed a safe, simple, inexpensive, and environmentally benign method for preparing N(5)‐ethylated flavinium organocatalysts without using hazardous reagents or inert conditions as previously required. 5‐Ethyl‐3‐methyllumiflavinium cation was prepared from its reduced form by NaNO2‐free aerobic oxidation, which was subsequently extracted onto commercial cation‐exchange resins under NaClO4‐free conditions. The resulting resin‐immobilized flavinium salts were found to be effective organocatalysts for aerobic oxidation reactions.
3D Graphene Aerogels Decorated with Cobalt Phosphide Nanoparticles as Electrocatalysts for the Hydrogen Evolution Reaction
Authors: Zhang Xueping , Han Yujie , Huang Liang , Dong Shaojun
Published: August 2016

The development of non‐precious‐metal hydrogen evolution reaction (HER) electrocatalysts with high activity and excellent durability in acidic media is of significant importance for renewable energy research. We report a novel electrocatalyst based on a three‐dimensional (3D) graphene aerogel decorated with cobalt phosphide nanoparticles (CoP/GA). The material has a unique hierarchical porous structure with CoP nanoparticles encapsulated uniformly within the graphene sheets. The optimized catalyst shows superior activity, with an overpotential of only 121 mV at 10 mA cm−2, a Tafel slope of 50 mV dec−1, and an exchange current density of 0.105 mA cm−2, and it maintains its catalytic activity for at least 13 h. More importantly, this work provides a versatile way for the rational design and fabrication of 3D graphene‐based multifunctional composite materials.
Tailored Combination of Low Dimensional Catalysts for Efficient Oxygen Reduction and Evolution in Li–O2 Batteries
Authors: Yoon Ki Ro , Kim Dae Sik , Ryu Won‐Hee , Song Sung Ho , Youn Doo‐Young , Jung Ji‐Won , Jeon Seokwoo , Park Yong Joon , Kim Il‐Doo
Published: August 2016

Invited for this month′s cover are the groups of Il‐Doo Kim at Korea Advanced Institute of Science and Technology and Yong Joon Park at Kyonggi University. The image shows that an electric vehicle supported by Li–O2 batteries based on combined catalytic reactions is running on a graphene road. The Communication itself is available at 10.1002/cssc.201600341.
Boost student success with text messaging
Authors: Hope Joan
Published: August 2016

CHICAGO — Many admissions offices use text messaging to engage with prospective students. It can also be useful for boosting retention and GPAs by engaging enrolled students.
Collaborate across campus for successful initiatives
Authors: Hope Joan
Published: August 2016

James W. Dean Jr., executive vice chancellor and provost at the University of North Carolina at Chapel Hill, enjoys the broad scope of his job. “It's almost easier to list the things I'm not responsible for,” he said.
Synthesis, Structure, and Gas‐Phase Fragmentation of Trinuclear Mo3S4 Clusters Bearing Aminophosphine Ligands: A Combined Experimental and Theoretical Study
Authors: Beltrán Tomás F. , Safont Vicent S. , Llusar Rosa
Published: August 2016

Aminophosphine [Mo3S4X3(edpp)3]+ cluster complexes, 1+ (X = Cl) and 2+ (X = Br) {edpp = (2‐aminoethyl)diphenylphosphine} have been quantitatively prepared by treating the [Mo3S7X6]2– anion with the edpp ligand in a one‐pot synthetic procedure. Alternatively, complexes 1+ and 2+ can be synthesized using polymeric {Mo3S7X4}n phases as metal precursors. Their crystal structures show the incomplete cubane‐type Mo3S4 cluster core as well as the formation of a unique isomer in which the nitrogen atoms of the amino group and the halide atoms are located above the trimetallic plane. Gas‐phase reactivity studies on complexes 1+ and 2+ show the subsequent elimination of neutral HX (X = Cl, Br) molecules under collision induced dissociation (CID) conditions. The fragmentation pattern of 1+ and 2+ in combination with gas‐phase DFT calculations are contrary to the general ideas involving the hemilabile character of the aminophosphine ligands and give support to the formation of unsaturated molybdenum/imine Mo=NH species. On the basis of DFT calculations, two competitive mechanisms involving a proton transfer from the amino group to a halide ligand attached to the geminal or to the vicinal molybdenum center are proposed. The first mechanism, which is a proton transfer within the nitrogen and halogen atoms bound to the same metal atom, is energetically favored from a theoretical point of view.
Oxidized Styrylruthenium–Ferrocene Conjugates: From Valence Localization to Valence Tautomerism
Authors: Hassenrück Christopher , Mücke Philipp , Scheck Johanna , Demeshko Serhiy , Winter Rainer F.
Published: August 2016

We report on ferrocenyl–styrylruthenium conjugates Fc–C6H4–CH=CH–Ru(CO)(PiPr3)2(L) in which the electron density at the alkenylruthenium site is modified by the variation of the coligand L [L = Cl, acetylacetonate (acac), hexafluoroacetylacetonate (hfac), or dipivaloylmethane (dpvm); Fc = ferrocenyl]. Crystallographic studies on three derivatives provide snapshots of the conformational degrees of freedom for rotation around the vinyl–phenylene and phenylene–ferrocenyl linkages. All four complexes undergo two consecutive, reversible one‐electron oxidations, the potentials of which depend on the ligand L. On the basis of IR spectroelectrochemistry results, the first oxidations of the less electron‐rich chlorido and hfac complexes are biased strongly towards the ferrocenyl site. However, the radical cation of the acac complex exists as two equilibrating valence tautomers (VTs) Fc+–C6H4–CH=CH–{Ruacac} ⇌ Fc–[C6H4–CH=CH–{Ruacac}]+ [{Ruacac} = Ru(CO)(PiPr3)2(acac)], in which the positive charge is either localized at the ferrocenyl site or delocalized over the styrylruthenium moiety. Variable‐temperature electron paramagnetic resonance (EPR) and Mössbauer spectroscopy reveal that the ferrocenium valence tautomer dominates at low temperature. A marked solvent dependence on the position and relative intensities of the separate Ru(CO) bands in the IR spectra reveals environmental effects on the relative stabilities of the two VTs, whereas the strong negative solvatochromism of the prominent near‐IR band of the radical cation of the acac complex argues for a sizable (intervalence) charge‐transfer component of the underlying excitation.
Evolution of endogenous enzyme activities and virgin olive oil characteristics during Chétoui and Chemlali olive ripening
Authors: Hachicha Hbaieb Rim , Kotti Faten , Vichi Stefania , Gargouri Mohamed
Published: August 2016

The composition and biochemical characteristics of olive fruits, mainly olive enzymes system, are crucial in determining the final quality of virgin olive oil (VOO). Thus, olives endogenous olive enzyme activities were studied during Chétoui and Chemlali olive ripening. The compositional quality of the corresponding VOO was also studied. Peroxidase (POX) and β‐glucosidase activities increased during olives ripening. However, polyphenoloxidase activity decreased slowly. Moreover, the POX enzyme appears to play an essential role in determining VOO total phenol amounts, as the decrease in phenol content registered during olive ripening coincided with the increase in POX activity. A positive correlation between oil antioxidant activity and the total phenol content was established for both the olive cultivars studied. With regard to pigments, chlorophyll content was much higher than that of carotenoids in both Chétoui and Chemlali oils. Moreover, different trends in chlorophyll and carotenoid contents were observed, depending on the olive cultivar. Concerning volatile compounds, our results showed that the highest content of total C6, C5 LOX compounds, and pentene dimers was observed at a RI of approximately 3 for both cultivars. However, C6 alcohols and total C5 compounds decreased in Chétoui and Chemlali oils, respectively, during olive ripening.

Practical applications: Volatile and phenolic compounds play an important role in determining VOO quality. However, these compounds were affected by numerous factors, such as, endogenous olive enzyme activities. Monitoring these enzymes activities (peroxidase, polyphenoloxidase, and β‐glucosidase) during olive fruits ripening by a simple spectrophotometric assay could be useful to establish an optimum harvesting date for each olive cultivar and their possible correlation with VOO total phenol amount.

Evolution of endogenous olive enzyme activities (POX, peroxidase; PPO, polyphenoloxidase; and β‐glucosidase) during Chétoui (●) and Chemlali (○) olive ripening.
Facile Entry to 3,4‐Dihydro‐1H‐pyrrolo[2,1‐c][1,4]oxazines through the oxa‐Pictet–Spengler Reaction
Authors: Reddy Chada Raji , Burra Amarender Goud , Singarapu Kiran K. , Grée René
Published: August 2016

An intermolecular approach to the construction of 3,4‐dihydro‐1H‐pyrrolo[2,1‐c][1,4]oxazines is reported for the first time using the oxa‐Pictet–Spengler reaction. The method involves a sequence of carbon–carbon‐ and carbon–oxygen‐bond formation between a substituted 2‐(1H‐pyrrol‐1‐yl)ethan‐1‐ol and an aldehyde/ketone. p‐Toluenesulfonic acid (pTSA) was identified as a suitable catalyst to promote the reaction. The method provides a one‐step conversion of various aldehydes/ketones into the corresponding 3,4‐dihydro‐1H‐pyrrolo[2,1‐c][1,4]oxazines.
Syn‐convergence exhumation of continental crust: evidence from structural and metamorphic analysis of the Monte Cecu area, Alpine Corsica (Northern Corsica, France)
Authors: Di Rosa Maria , De Giorgi Alberto , Marroni Michele , Vidal Olivier
Published: August 2016

In the Corsica Island, a stack of metamorphic continental units derived from the European continental margin is thrust over a pre‐Alpine basement during the convergence‐related processes in the Late Eocene–Early Miocene time span. The Piedigriggio‐Prato Unit is representative of these units. Its tectono‐metamorphic history has been reconstructed by an integrated approach, ranging from map‐ to meso‐ and microscopic scale analyses. This unit is characterized by a polyphase deformation history that consists of three deformation phases developed under retrograde metamorphism ranging from blueschist to sub‐greenschist facies metamorphic conditions. At the map‐scale, the Piedigriggio‐Prato Unit is characterized by km‐size isoclinal folds deformed by open to closed recumbent folds producing Type 3 fold interference pattern. The features of the deformations and the P–T conditions suggest that the first two phases were acquired during the ductile extrusion of the Piedigriggio‐Prato Unit. Before the Early Miocene, the gravitational collapse of over‐thickened continental crust produced vertical shortening and the consequently recumbent F3 folds. The exhumation history of the Piedigriggio‐Prato Unit can be viewed as representative for the exhumation of a continental crust fragment during the transition from the continental subduction to the continental collision. Copyright © 2016 John Wiley & Sons, Ltd.
Phase II organ‐preservation trial: Concurrent cisplatin and radiotherapy for advanced laryngeal cancer after response to docetaxel, cisplatin, and 5‐fluorouracil–based induction chemotherapy
Authors: Popovtzer Aron , Burnstein Hanna , Stemmer Salomon , Limon Dror , Hili Ohad , Bachar Gideon , Sopov Vladamir , Feinmesser Raphael , Groshar David , Shvero Jacob
Published: August 2016

Background

The optimal treatment for locally advanced laryngeal cancer remains controversial. The purpose of this trial was to determine if the response to induction chemotherapy could select patients for organ preservation protocols, and improve larynx‐preservation rates without compromising overall survival (OS).

Methods

The cohort comprised 12 patients with T3 disease and 14 with T4. Induction chemotherapy consisted of docetaxel, cisplatin, and 5‐fluorouracil (TPF). Response to the first cycle was determined by examination and positron emission tomography (PET)‐CT. Responders (>50% tumor reduction) underwent chemoradiation, whereas nonresponders underwent laryngectomy.

Results

Eighty‐three percent of the patients had a response and 17% had stable or progressive disease. At 2 years, the median OS was 80%, the larynx‐preservation rate was 83%, and the disease‐specific survival rate was 86%. Response to a single TPF cycle was associated with 2‐year OS (92% vs 50%; p = .02). The T classification was not predictive of survival.

Conclusion

Response to a single TPF‐based cycle may identify patients with advanced laryngeal cancer who are amenable to organ preservation treatment. © 2016 Wiley Periodicals, Inc. Head Neck 39: 227–233, 2017
The epidemiology of metastases in neuroendocrine tumors
Authors: Riihimäki Matias , Hemminki Akseli , Sundquist Kristina , Sundquist Jan , Hemminki Kari
Published: August 2016

The epidemiology of metastases in neuroendocrine tumors (NETs) is virtually unknown. The present novel approach took use of two nationwide Swedish registers to assess the distribution of metastatic sites in comparison to adenocarcinoma. 7,334 patients with NET were identified from the Swedish Cancer Registry. Metastatic sites were identified from the National Patient and Cause of Death Registries. Sites of metastasis were investigated depending on the primary site of NET. The metastatic potential of NET was assessed. The liver was the most common site of metastasis (82% of patients with metastases), and the small intestine was the most common source of NET metastases. Of all patients with metastatic lung NETs, 66% had liver metastases, whereas the corresponding number for adenocarcinoma of lung was only 20%. The risk of metastasis was highest if the primary was in the small intestine or pancreatohepatobiliary tract, whereas it was lower with appendiceal and rectal NET. Men had more bone metastases compared to women. Patients with metastatic NET had worse prognosis if the primary site was unknown (11 months, 9% of NET patients) compared to those whose primary was known (19 months). The metastatic potential of NETs varies profoundly depending on the primary site. NETs show a clear preference to metastasize to the liver. Surveillance of liver metastases may enable earlier diagnosis and treatment. In liver metastases from NET, the small intestine should be suspected as the primary site, whereas the lung should be suspected in nervous system metastases of NET origin.
EATING AND FEEDING DISORDERS IN THE FIRST FIVE YEARS OF LIFE: REVISING THE DC:0–3R DIAGNOSTIC CLASSIFICATION OF MENTAL HEALTH AND DEVELOPMENTAL DISORDERS OF INFANCY AND EARLY CHILDHOOD AND RATIONALE FOR THE NEW DC:0–5 PROPOSED CRITERIA
Authors: Keren Miri
Published: August 2016

Problems of eating and feeding are one of the most common reasons of referral to pediatric and infant mental health clinics. This article is drawn from work done by the ZERO TO THREE Task Force developing the DC:0–5 Diagnostic Classification of Mental Health and Developmental Disorders of Infancy and Early Childhood, specifically dealing with eating disorders in the first 5 years of life. The proposed changes come from both reviewing major studies and reviews published in the last 10 years and reports from clinicians collected through surveys commissioned by the Task Force. The main changes that are proposed include changes in terminology, such as Eating Disorders instead of Feeding Behavior Disorders, as well as focusing on the child's observed eating symptoms rather than on classifying the eating problems by inferred etiologies. Another major change relates to the differentiation between eating disorders that are observed beyond any specific caregiver–child relationship context and those that are confined to one specific relationship. A new category, Overeating Disorder, has been added, as it has been increasingly recognized as a significant and not rare clinical condition. Two illustrative cases are described. The proposed changes in the classification of eating disorders in the first 5 years of life are intended to encourage both clinicians and researchers to study these important disorders in young children.
SYMPTOM PRESENTATIONS AND CLASSIFICATION OF AUTISM SPECTRUM DISORDER IN EARLY CHILDHOOD: APPLICATION TO THE DIAGNOSTIC CLASSIFICATION OF MENTAL HEALTH AND DEVELOPMENTAL DISORDERS OF INFANCY AND EARLY CHILDHOOD (DC:0–5)
Authors: Soto Timothy , Giserman Kiss Ivy , Carter Alice S.
Published: August 2016

Over the past 5 years, a great deal of information about the early course of autism spectrum disorder (ASD) has emerged from longitudinal prospective studies of infants at high risk for developing ASD based on a previously diagnosed older sibling. The current article describes early ASD symptom presentations and outlines the rationale for defining a new disorder, Early Atypical Autism Spectrum Disorder (EA‐ASD) to accompany ASD in the new revision of the ZERO TO THREE Diagnostic Classification of Mental Health and Developmental Disorders of Infancy and Early Childhood (DC:0–5) (in press) alternative diagnostic classification manual. EA‐ASD is designed to identify children who are 9 to 36 months of age presenting with a minimum of (a) two social‐communication symptoms and (b) one repetitive and restricted behavior symptom as well as (c) evidence of impairment, with the intention of providing these children with appropriately tailored services and improving the likelihood of optimizing their development.
The Millennium Peak in Club Convergence: A New Look at Distributional Changes in The Wealth of Nations
Authors: Krause Melanie
Published: August 2016

This paper proposes an easy‐to‐use nonparametric indicator for club convergence, or convergence within clusters of countries: it measures whether the modes of the gross domestic product (GDP) per capita distribution become more pronounced over time. Relying on changes in the critical bandwidth for unimodality, the indicator is a dynamic extension of concepts from often‐used multimodality tests. Its evolution suggests the new empirical result of a ‘millennium peak’ in club convergence in the worldwide GDP per capita distribution. The club convergence movements of the 1980s and 1990s, when groups of poor and rich countries converged to two separate points, was followed by a de‐clubbing movement after the turn of the millennium. Copyright © 2016 John Wiley & Sons, Ltd.