bluuebunny/crossref_metadata_2025 huggingface dataset:
Morphological features and crystallization behavior of the conductive composites of poly(trimethylene terephthalate)/graphene nanosheets
Authors: Huang Chien‐Lin , Wang Yu‐Jyun , Fan Yang‐Chun
Published: February 2016

Poly(trimethylene terephthalate) (PTT) composites filled with well‐dispersed graphene nanosheets (GNSs) were prepared through a coagulation method. The effects of increased GNS concentration on variations in the structure and properties of the PTT matrix, such as its electrical conductivity, crystallization kinetics, melting behavior, and crystal morphology, were investigated. Several analytical techniques were used, including electrical conductivity measurement, differential scanning calorimetry, Fourier transform infrared spectroscopy, wide‐angle X‐ray diffraction, polarized light microscopy, transmission electron microscopy (TEM), and thermo‐gravimetric analysis (TGA). Electrical conductivity increased from 1.8 × 10−17S/cm for neat PTT to 0.33 ± 0.23 S/cm for PTT/GNS composites with 2.97 vol % GNS content. Percolation scaling laws were applied, and then threshold concentration and exponent were determined. In the case wherein liquid nitrogen was used to quench the melt, a mesomorphic phase was formed despite the extremely short crystallization time after adding high GNS contents. PTT crystallization rate increased with the gradual addition of GNSs. The enhanced crystallization kinetics was attributed to the high nucleation ability of GNSs to induce epitaxially grown lamellae on their surfaces, as revealed by TEM. PTT nuclei were randomly developed on the GNS surface to form the lamellae. However, crystallinity reached its maximum value near the electrical percolation threshold because the PTT chain mobility was confined after the GNS–GNS network formed. The growth of PTT banded spherulites in the bulk was still observed for composites with high GNS content, and TGA results revealed that the GNS‐filled PTT composites had excellent thermal stability. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2016,133, 43419.
A Reset‐Time Dependent Approach for Stability Analysis of Nonlinear Reset Control Systems
Authors: Ghaffari Valiollah , Karimaghaee Paknosh , Khayatian Alireza
Published: February 2016

A reset mechanism in controller can affect the stability property of a closed loop control system. In a simple word, there are stable reset control systems with unstable base‐systems and also unstable reset systems with stable base‐systems. The Lyapunov stability theory is a strong tool to investigate the stability of a nonlinear system. In this paper, based on the well‐known Lyapunov stability concept, some stability conditions for nonlinear reset control systems are addressed. These conditions are dependent on the reset‐times and hence the reset‐time intervals are explicitly emerged in the stability conditions. Some applications of these results are used in numerical examples to show the effectiveness of the proposed approach.
On an Optimized Fuzzy Supervized Multiphase Guidance Law
Authors: Rezaee Mohsen , Seyedtabaii Saeed
Published: February 2016

Proportional navigation (PN) is an effective guidance law in chasing a constant speed target. However, intercepting a maneuvering target requires extra provisions to contain target acceleration. This is observed in the next generation of guidance laws, namely augmented proportional navigation (APN) and the optimal guidance law (OGL). The other advanced guidance method is integral sliding mode (ISM), which exhibits superb low miss distance (MD), but unfortunately at the cost of disappointing effective lateral acceleration (Ceff), higher than the modest level that APN and OGL demand. Reducing both MD and Ceff can be achieved using a multiphase algorithm. A setup of APN, OGL and ISM is proposed to integrate the strength of each and overcome their weaknesses. Hybrid algorithm smooth management is conducted by an optimally tuned fuzzy supervisory controller. The results indicate that in facing a constant acceleration target, an APN‐ISM twin yields the best results, while in case of a constant jerk target an APN‐OGL‐ISM triplet renders excellent interception. Miss distance as low as 0.012m can be achieved with significantly lower control effort than required by ISM alone. The simulations results confirm the conclusions and illustrate the capacity of the algorithm in combating maneuvering targets.
Formlogik an Brücken – Teil 1
Authors: Kleiser Michael
Published: February 2016

Brücken mit kurzen und mittleren Spannweiten werden in den letzten Jahren durchwegs als integrale Bauwerke ohne Fugen und Lager konzipiert. Das zugrunde liegende statische System des Rahmens erfordert ein differenziertes konzeptionelles Vorgehen nicht nur in statisch‐konstruktiven, sondern auch in ästhetischen Belangen. Es werden Anregungen zur Formbildung aufgezeigt, die der innewohnenden Absicht der Bauweise in der entsprechenden Ausformung Geltung verschaffen. Viele Beispiele im Infrastrukturbau zeigen jedoch noch immer Brückentypen, die statisch konstruktiv integral berechnet und konstruktiv ausgebildet sind, jedoch das äußere Erscheinungsbild einer gelagerten bzw. gefügten Brücke vermitteln. Auch vielen Ingenieuren ist der essenzielle Zusammenhang zwischen der rationalen statisch‐konstruktiven Lösung und dem formalen Ausdruck vielfach zu wenig bewusst. Um zu ganzheitlichen und authentischen Entwürfen zu gelangen, muss eine Kohärenz zwischen der Form der Brücke und dem ihr zugrunde liegenden statischen System erkennbar sein. Ziel ist es, Ingenieure von einer ingenieurtechnischen zu einer erweiterten ingeniösen Herangehensweise zu ermutigen, die auch die aus dem statischen System heraus entwickelten formgebenden Aspekte berücksichtigt und letztendlich in der Gesamtheit zu ästhetisch befriedigenden Ergebnissen führen soll. In diesem ersten Aufsatz werden konzeptionelle Überlegungen zur Formbildung im Bereich der Brückenenden erläutert, die die integrale Bauweise auf Basis hergeleiteter Funktionseinheiten reflektieren.

Form logic on bridges (Part 1) – Considerations on authentic shaping of integral bridge ends

In recent years bridges with short and medium spans have been designed as integral structures without expansion joints and bearings. The structural system is based on the frame system and requires a differentiated conceptual approach not only in structural but also in aesthetic concerns. In this paper form suggestions are introduced, which provide the inherent intention of the integral structure to the viewer. However, many bridges within the infrastructure are calculated and structurally designed as monolithic structures but have a visual appearance of conventional supported and assembled bridges. Moreover, many engineers are not sufficiently aware of the essential correlation between the rational structural design and its formal expression. In order to achieve holistic and authentic designs, a coherence between the form of the bridge and its underlying structural system must be perceptible. The aim is to encourage engineers from the pure engineer‐technical to an extended ingenious approach that considers form aspects which are developed based on the structural system and ultimately leads to aesthetically satisfactory results. In this first paper, conceptual form considerations for integral bridge ends are discussed, which are based on derived functional units and reflect the integral structural system.
Grünbrückenkonstruktion aus Fertigteil‐Bogensegmenten
Authors: Suffner Andrea , Schulze Torsten
Published: February 2016

Aufgabe der Grünbrücken ist eine Wiedervernetzung von Lebensräumen, um die Zerschneidungswirkung von Verkehrswegen zu kompensieren.

Aus ihrer Funktion heraus sind Grünbrücken in der Regel in ökologisch sensiblen Gebieten erforderlich, die sich im Umkreis stark befahrener Verkehrswege befinden.

Die Errichtung einer Grünbrücke bedeutet im Gegensatz zu ihrem Schutzziel einerseits einen starken Eingriff in gerade diesen sensiblen, oftmals geschützten Raum und andererseits eine Beeinträchtigung des Verkehrs der betroffenen Verkehrswege während der Bauzeit. Der Entwurf und der Bau eines Bauwerks in diesem Spannungsfeld werden im Folgenden beschrieben.

Green bridges from prefabricated arch‐segments

Green bridges aim at relinking habitats to compensate for the dissection effect of traffic routes. Resulting from this function, green bridges are usually needed in ecologically sensitive areas, which are situated in the vicinity of highly frequented traffic routes. Contrary to its protective purpose, the construction of a green bridge on the one hand represents a drastic intervention into these delicate, mostly protected areas and on the other hand a disturbance of traffic on the concerned routes. Considering this area of conflict, the design and construction of a green bridge are described below.
Längskraftabtragung auf Eisenbahnbrücken
Authors: Wenner Marc , Lippert Peter , Plica Sebastian , Marx Steffen
Published: February 2016

Beim Entwurf von Eisenbahnbrücken spielt die Wechselwirkung zwischen Gleis und Bauwerk eine maßgebende Rolle. Durch die lückenlose Verlegung der Schiene über längere Tragwerke führen Bewegungen des Überbaus infolge Temperatur, Langzeitverhalten des Betons sowie vertikaler und horizontaler Verkehrslasten zu einer zusätzlichen Beanspruchung der ohnehin schon stark belasteten Schiene. Zur Gewährleistung der Betriebssicherheit müssen daher die in der Schiene auftretenden Kräfte begrenzt werden. Das zu verwendende Rechenmodell sowie die zu führenden Nachweise und die dazugehörigen Grenzwerte sind europaweit im Eurocode EN 1991‐2, Kapitel 6.5.4 geregelt. In Deutschland gilt zusätzlich die DB‐Richtlinie 804.3401. In der praktischen Anwendung kommt es jedoch immer wieder zu Fragen hinsichtlich des Hintergrunds der Modellannahmen sowie der Herkunft der Grenzwerte und der fallbezogenen Anpassung derselben. Die aktuellen Regelungen sind geprägt durch eine lange historische Entwicklung, die vorrangig auf Untersuchungen in Deutschland basiert. Im folgenden Teil 1 des Beitrags sollen die Geschichte des lückenlosen Gleises und die Entwicklung der Betrachtung des Zusammenwirkens zwischen Schiene und Brücke vorgestellt werden. Zusätzlich werden das Modell und die Annahmen, auf denen es beruht, präsentiert. Im Teil 2 werden dann die Hintergründe des Nachweises und der zugehörigen, im Regelwerk verankerten Grenzwerte erläutert.

Track‐bridge‐interaction – Part 1: historical development and model

In order to guarantee improved driving dynamics and comfort for railway passengers, it is common today to weld rails to a continuously track. However, viaducts constitute singularities in the railway substructure. Under thermal variations, creep, shrinkage, train passage and braking, the bridge structure deforms and leads to additional solicitation of the rail. The track‐bridge interaction becomes a decisive criterion in railway bridge design. The forces in the rail must be limited in order to guarantee the safety of the traffic. The calculation model as well as the verification schema is regulated in the Eurocode EN 1991‐2, chapter 6.5.4 and in Germany additionally in the Richtlinie 804. However, the backgrounds of the model assumptions and of the stress limits, which are necessary for the understanding of the calculations, are very poor documented. In the part 1 of this article, the history of the continuous welded rail and the development of the investigation of track‐bridge interaction effects will be presented. Additionally, the model as well as the assumptions for the calculation will be presented. In the part 2, the backgrounds of the verification procedure and of its limits will be explained.
Zur praktischen Anwendung des Sicherheitskonzepts nach EC3 bei der Bemessung von Tragseilen
Authors: Gugeler Jochen
Published: February 2016

Das Sicherheitskonzept der DIN EN 1993‐1‐11 für die Bemessung und Konstruktion von Zuggliedern aus Stahl führt gegenüber den bisherigen Regelungen bei Seiltragwerken, die gegen Steifigkeit vorgespannt werden, zu deutlich größeren und damit unwirtschaftlicheren Querschnitten von Seilen und Anschlussdetails. Im folgenden Artikel soll deshalb hinterfragt werden, ob die gewählten Bemessungsansätze für diesen Typ von vorgespannten Seiltragwerken sinnvoll und notwendig sind.

Some remarks concerning the application of the safety concept according to EC3 for the design of steel cables

Compared with the former regulations for cable structures that are prestressed against stiffness, the safety concept of DIN EN 1993‐1‐11 for design and construction of steel tension members results in larger and less economic cross sections for cables and clamps. The following text debates the question whether the use of this design concept is reasonable for all types of cable structures.
Congenital anomalies of the kidney and the urinary tract: A murmansk county birth registry study
Authors: Postoev Vitaly A. , Grjibovski Andrej M. , Kovalenko Anton A. , Anda Erik Eik , Nieboer Evert , Odland Jon Øyvind
Published: February 2016

BACKGROUND

Congenital anomalies of the kidney and the urinary tract (CAKUTs) are relatively common birth defects. The combined prevalence in Europe was 3.3 per 1000 in 2012. The risk factors for these anomalies are not clearly identified. The aims of our study were to calculate the birth prevalences of urinary malformations in Murmansk County during 2006 to 2011 and to investigate related prenatal risk factors.

METHODS

The Murmansk County Birth Registry was the primary source of information and our study included 50,936 singletons in the examination of structure, prevalence and proportional distribution of CAKUTs. The multivariate analyses of risk factors involved 39,322 newborns.

RESULTS

The prevalence of CAKUTs was 4.0 per 1000 newborns (95% confidence interval [CI], 3.4–4.5) and did not change during the study period. The most prevalent malformation was congenital hydronephrosis (14.2% of all cases). Diabetes mellitus or gestational diabetes (odds ratio [OR] = 4.77; 95% CI, 1.16–19.65), acute infections while pregnant (OR = 1.83; 95% CI, 1.14–2.94), the use of medication during pregnancy (OR = 2.03; 95% CI, 1.44–2.82), and conception during the summer (OR = 1.75; 95% CI 1.15–2.66) were significantly associated with higher risk of CAKUTs.

CONCLUSION

The overall fourfold enhancement of the occurrence of urinary malformations in Murmansk County for the 2006 to 2011 period showed little annual dependence. During pregnancy, use of medications, infections, pre‐existing diabetes mellitus, or gestational diabetes were associated with increased risk of these anomalies, as was conception during summer. Our findings have direct applications in improving prenatal care in Murmansk County and establishing targets for prenatal screening and women's consultations. Birth Defects Research (Part A) 106:185–193, 2016. © 2016 Wiley Periodicals, Inc.
Multiway analysis applied to time‐resolved chemiluminescence for simultaneous determination of paracetamol and codeine in pharmaceuticals
Authors: Mokhtari Ali , Jafari Delouei Nastaran , Keyvanfard Mohsen , Abdolhosseini Mohammad
Published: February 2016

This method is based on the enhancing effect of codeine (COD) and paracetamol (PAR) on the chemiluminescence (CL) reaction of Ru(phen)32+ with Ce(IV). In the batch mode, COD gives a relatively sharp peak with the highest CL intensity at 4.0 s, whereas the maximum CL intensity of the PAR appears at ~60 s after injection of Ce(IV) solution. Whole CL time profiles allowed use of the time‐resolved CL data in combination with multiway calibration techniques, as multiway partial least squares (N‐PLS), for the quantitative determination of both COD and PAR in binary mixtures. In this work, we found that the impact of Ce(IV) concentration on the CL intensity was different for COD and PAR. Therefore, a Ce(IV) concentration mode was added to the time and sample modes to obtain 3D data. The percent relative standard deviation (%RSD) values for 10 determinations of 1.0 × 10−5 mol/L of COD and 1.0 × 10−4 mol/L of PAR were 6.1% and 8.7%, respectively. The limit of detection (LOD) values (S/N = 3) were 0.9 × 10−8 mol/L and 1.0 × 10−6 mol/L for COD and PAR, respectively. The proposed method was successfully applied to the determination of PAR and COD in commercial pharmaceutical formulations. Acceptable recoveries (90–110%) were obtained for the quantification of these drugs in the real samples. Copyright © 2016 John Wiley & Sons, Ltd.
Luminescence properties of novel deep‐red‐emitting Ca3Al2Ge2O10:Cr3+ phosphors
Authors: Bai Qiongyu , Wang Zhijun , Li Panlai , Li Ting , Xu Shuchao , Yang Zhiping
Published: February 2016

Ca3Al2Ge2O10:Cr3+ phosphors were prepared by a high‐temperature solid‐state method, and their luminescence properties were investigated. Under excitation at 550 nm, Ca3Al2Ge2O10:Cr3+ phosphors exhibited a broad red emission band at 697 nm in the range 650–750 nm that was caused by the 2E→4A2 transition of Cr3+. For the 697 nm emission peak, emission intensity reached a maximum at x = 0.07, and there was concentration quenching of Cr3+ in Ca3Al2Ge2O10; the corresponding concentration quenching mechanism was analysed. Under excitation at 262 nm, the Ca3Al2Ge2O10:Cr3+ phosphor showed a weakly broad emission band in the range 350–600 nm that was caused by intrinsic defects (V′′Ca and V′′O). Copyright © 2016 John Wiley & Sons, Ltd.
Invited review: MnmE, a GTPase that drives a complex tRNA modification reaction
Authors: Fislage Marcus , Wauters Lina , Versées Wim
Published: February 2016

MnmE is a multi‐domain GTPase that is conserved from bacteria to man. Together with its partner protein MnmG it is involved in the synthesis of a tRNA wobble uridine modification. The orthologues of these proteins in eukaryotes are targeted to mitochondria and mutations in the encoding genes are associated with severe mitochondrial diseases. While classical small GTP‐binding proteins are regulated via auxiliary GEFs and GAPs, the GTPase activity of MnmE is activated via potassium‐dependent homodimerization of its G domains. In this review we focus on the catalytic mechanism of GTP hydrolysis by MnmE and the large scale conformational changes that are triggered throughout the GTPase cycle. We also discuss how these conformational changes might be used to drive and tune the complex tRNA modification reaction. © 2016 Wiley Periodicals, Inc. Biopolymers 105: 568–579, 2016.
Diminished oligomerization in the synthesis of new anti‐angiogenic cyclic peptide using solution instead of solid‐phase cyclization
Authors: Rubio Sandra , Clarhaut Jonathan , Péraudeau Elodie , Vincenzi Marian , Soum Claire , Rossi Filomena , Guillon Jean , Papot Sébastien , Ronga Luisa
Published: February 2016

The design and synthesis of novel peptides that inhibit angiogenesis is an important area for anti‐angiogenic drug development. Cyclic and small peptides present several advantages for therapeutic application, including stability, solubility, increased bio‐availability and lack of immune response in the host cell. We describe here the synthesis and biological evaluations of a new cyclic peptide analog of CBO‐P11: cyclo(RIKPHE), designated herein as CBO‐P23M, a hexamer peptide encompassing residues 82 to 86 of VEGF which are involved in the interaction with VEGF receptor‐2. CBO‐P23M was prepared using in solution cyclization, therefore reducing the peptide cyclodimerization occurred during solid‐phase cyclization. The cyclic dimer of CBO‐P23M, which was obtained as the main side product during synthesis of the corresponding monomer, was also isolated and investigated. Both peptides markedly reduce VEGF‐A‐induced phosphorylation of VEGFR‐2 and Erk1/2. Moreover, they exhibit anti‐angiogenic activity in an in vitro morphogenesis study. Therefore CBO‐P23M and CBO‐P23M dimer appear as attractive candidates for the development of novel angiogenesis inhibitors for the treatment of cancer and other angiogenesis‐related diseases. © 2016 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 106: 368–375, 2016.
miR‐708/LSD1 axis regulates the proliferation and invasion of breast cancer cells
Authors: Ma Lin , Ma Shan , Zhao Guimei , Yang Longqiu , Zhang Peng , Yi Qingting , Cheng Shuguang
Published: February 2016

Breast cancer is one of the most common malignant tumors in women worldwide. The microRNAs (miRNAs) are small, noncoding RNAs that regulate various biological processes, including breast cancer. miR‐708 played an important role in a variety of cancers. However, its involvement in breast cancer remains largely unclear. In this study, we found that forced the expression of miR‐708 in breast cancer cell lines decreased cell proliferation and invasion, whereas inhibition of miR‐708 increased cell growth and invasion. miR‐708 could directly target the LSD1 3′UTR to downregulate the expression. Further studies suggested that inhibition of LSD1 could phenocopied function of the miR‐708 overexpression in MDA‐MB‐231 cells .Overexpression of LSD1 could counteract the effects of miR‐708 on the proliferation and invasion. Taken together, the results indicate that miR‐708 may function as a tumor suppressor gene in breast cancer development, and miR‐708/LSD1 axis may be a therapeutic intervention in breast cancer in the future.
Heterotopic pregnancy with natural conception; a rare event that is still being misdiagnosed: a case report
Authors: Fatema Nishat , Al Badi Muna Mubarak , Rahman Mahin , Elawdy Mohamed M.
Published: February 2016

Key Clinical Message

Simultaneous presence of intra‐ and extra‐uterine pregnancies have been known as heterotopic pregnancy (HP); the condition which is extremely rare with natural conception. Our aim is to increase the obstetrician's awareness to increase the level of positive outcome in such rare events.
Bipolar Electrochemical Approach with a Thin Layer of Supporting Electrolyte towards the Growth of Self‐Organizing TiO2 Nanotubes
Authors: Saqib Muhammad , Lai Jianping , Zhao Jianming , Li Suping , Xu Guobao
Published: February 2016

The front cover artwork is provided by the group of Prof. Guobao Xu at State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences (http://people.gucas.ac.cn/∼guobaoxu?language=en). The image shows the bipolar electrochemical approach with a thin layer of supporting electrolyte towards the growth of self‐organizing TiO2 nanotubes in a horizontal direction for single and multiple samples in a single wireless run with tunable diameters. Read the full text of the Communication at 10.1002/celc.201500182.
Synthesis and Photophysical Studies of Calixarene‐Based Alkynylplatinum(II) Terpyridine Complexes with Various Receptor Sites for Colorimetric and Luminescence Sensing of Anions
Authors: Hau Franky Ka‐Wah , Lo Hiu‐Suet , Yam Vivian Wing‐Wah
Published: February 2016

A series of mononuclear and dinuclear platinum(II) terpyridine complexes with amide‐, sulfonamide‐, and urea‐containing ligands (1–9) has been successfully designed and synthesized, and their photophysical and anion‐binding properties have been studied. The anion‐binding properties of the complexes were studied by electronic absorption, emission, and 1H NMR spectroscopy. Upon the binding with anions, the dinuclear complexes 1–3 exhibit large electronic absorption and emission spectral changes, while for the mononuclear analogues 4–6 much smaller spectral changes were observed. Interesting colorimetric responses towards different anions were observed in dinuclear complexes 1–3. Dinuclear complexes 7–9 are found to be insensitive to anion‐binding, which could be attributed to the presence of intramolecular Pt⋅⋅⋅Pt interactions and/or π–π stacking in the complexes that led to the reduced anion‐binding affinity.
Construction of a 2D Graphene‐Like MoS2/C3N4 Heterojunction with Enhanced Visible‐Light Photocatalytic Activity and Photoelectrochemical Activity
Authors: Yan Jia , Chen Zhigang , Ji Haiyan , Liu Zheng , Wang Xin , Xu Yuanguo , She Xiaojie , Huang Liying , Xu Li , Xu Hui , Li Huaming
Published: February 2016

A novel graphene‐like MoS2/C3N4 (GL‐MoS2/C3N4) composite photocatalyst has been synthesized by a facile ethylene glycol (EG)‐assisted solvothermal method. The structure and morphology of this GL‐MoS2/C3N4 photocatalyst have been investigated by a wide range of characterization methods. The results showed that GL‐MoS2 was uniformly distributed on the surface of GL‐C3N4 forming a heterostructure. The obtained composite exhibited strong absorbing ability in the ultraviolet (UV) and visible regions. When irradiated with visible light, the composite photocatalyst showed high activity superior to those of the respective individual components GL‐MoS2 and GL‐C3N4 in the degradation of methyl orange. The enhanced photocatalytic activity of the composite may be attributed to the efficient separation of electron–hole pairs as a result of the matching band potentials between GL‐MoS2 and GL‐C3N4. Furthermore, a photocatalytic mechanism for the composite material has been proposed, and the photocatalytic reaction kinetics has been measured. Moreover, GL‐MoS2/C3N4 could serve as a novel sensor for trace amounts of Cu2+ since it exhibited good selectivity for Cu2+ detection in water.
Non‐Thermal Plasma in Contact with Water: The Origin of Species
Authors: Gorbanev Yury , O'Connell Deborah , Chechik Victor
Published: February 2016

Non‐thermal atmospheric pressure plasma has attracted considerable attention in recent years due to its potential for biomedical applications. Determining the mechanism of the formation of reactive species in liquid treated with plasma is thus of paramount importance for both fundamental and applied research. In this work, the origin of reactive species in plasma‐treated aqueous solutions was investigated by using spin‐trapping, hydrogen and oxygen isotopic labelling and electron paramagnetic resonance (EPR) spectroscopy. The species originating from molecules in the liquid phase and those introduced with the feed gas were differentiated by EPR and 1H NMR analysis of liquid samples. The effects of water vapour and oxygen admixtures in the feed gas were investigated. All the reactive species detected in the liquid samples were shown to be formed largely in the plasma gas phase. It is suggested that hydrogen peroxide (determined by UV/Vis analysis) is formed primarily in the plasma tube, whereas the radical species ⋅OOH, ⋅OH and ⋅H are proposed to originate from the region between the plasma nozzle and the liquid sample.
Regioselective Synthesis of Quinazolinone‐/Phenanthridine‐Fused Heteropolycycles by Pd‐Catalyzed Direct Intramolecular Aerobic Oxidative C−H Amination from Aromatic Strained Amides
Authors: Banerji Biswadip , Bera Suvankar , Chatterjee Satadru , Killi Sunil Kumar , Adhikary Saswati
Published: February 2016

A new route for the expedient synthesis of specific regioisomer of quinazolinone‐ and phenanthridine‐fused heterocycles through a palladium‐catalyzed regioselective intramolecular oxidative C−H amination from cyclic strained amides of aromatic amido–amidine systems (quinazolinones) has been developed. The amine functionalization of an aromatic C−H bond from a strained amide nitrogen involved in aromaticity has been a challenging work so far. The fusion of two heterocyclic cores, quinazolinone and phenanthridine, can occur in two different ways (linear and angular), but under the conditions reported here, only linear type isomer is exclusively produced. This approach provides a variety of substituted quinazolinone‐ and phenanthridine‐fused derivatives in moderate to excellent yields. Moreover, such fused molecules show excellent fluorescent properties and have great potential to be a new type of fluorophores for the use in medicinal and material science.
Optimal ATRP‐Made Soluble Polymer Supports for Phosphoramidite Chemistry
Authors: Oswald Laurence , Al Ouahabi Abdelaziz , Charles Laurence , Lutz Jean‐François
Published: February 2016

Soluble polystyrene supports with optimal molecular structures for iterative phosphoramidite chemistry were prepared by atom‐transfer radical polymerization (ATRP) and subsequent chain‐end modification steps. The controlled radical polymerization of styrene was first performed in the presence of an 9‐fluorenylmethoxycarbonyl (Fmoc)‐protected amino‐functional ATRP initiator. Soluble supports of different molecular weight were prepared. Size‐exclusion chromatography and NMR analysis indicated formation of well‐defined polymers with controlled chain lengths and narrow dispersity. After synthesis, the bromo ω end group of the ATRP polymer was removed by dehalogenation in the presence of tributyltin hydride, and the Fmoc protecting group of the α moiety was subsequently cleaved with piperidine. The resulting α‐primary amine was afterwards treated with a linker containing a carboxyl group, a cleavable ester site, and a dimethoxytrityl‐protected hydroxyl group to afford ideal soluble supports for phosphoramidite chemistry. NMR analysis indicated that these chain‐end modifications were quantitative. The supports were tested for the synthesis of a non‐natural sequence‐defined oligophosphates. High‐resolution ESI‐MS analysis of the cleaved oligomers indicated formation of uniform species, and thus confirmed the efficiency of the ATRP‐made soluble polymer supports. In addition, the synthesis of a thymidine‐loaded soluble support was achieved.
Fused π‐Extended Truxenes via a Threefold Borylation as the Key Step
Authors: Zhang Gang , Rominger Frank , Mastalerz Michael
Published: February 2016

On the basis of a threefold borylated truxene, which is accessible in high yields by iridium‐catalyzed borylation under CH‐activation, fused π‐extended truxenes have been synthesized by a two‐step method of first Suzuki–Miyaura cross‐coupling reaction and subsequent condensation reaction. The mild condensation method tolerates the presence of a variety of functional groups, such as nitro, fluoro, or carboxyl moieties. Furthermore, by using this approach, N‐ and S‐heteroarene analogues become accessible for the first time, as well as larger structures that represent derivatives of precursors for fullerene C60 or buckybowls. The attached tert‐butyl groups make all derivatives sufficiently soluble to allow full spectroscopic and electrochemical investigations. Postfunctionalization of selected derivatives for further synthetic applications of the compounds is also presented.
Design and Synthesis of Novel Chiral Dirhodium(II) Carboxylate Complexes for Asymmetric Cyclopropanation Reactions
Authors: Adly Frady G. , Gardiner Michael G. , Ghanem Ashraf
Published: February 2016

A novel approach to the design of dirhodium(II) tetracarboxylates derived from (S)‐amino acid ligands is reported. The approach is founded on tailoring the steric influences of the overall catalyst structure by reducing the local symmetry of the ligand's N‐heterocyclic tether. The application of the new approach has led to the uncovering of [Rh2(S‐tertPTTL)4] as a new member of the dirhodium(II) family with extraordinary selectivity in cyclopropanation reactions. The stereoselectivity of [Rh2(S‐tertPTTL)4] was found to be comparable to that of [Rh2(S‐PTAD)4] (up to >99 % ee), with the extra benefit of being more synthetically accessible. Correlations based on X‐ray structures to justify the observed enantioinduction are also discussed.
Trichloromethylthiolation of N‐Heterocycles: Practical and Completely Regioselective
Authors: Ernst Johannes B. , Rühling Andreas , Wibbeling Birgit , Glorius Frank
Published: February 2016

The first trichloromethylthiolation of a broad range of indoles and pyrroles is reported employing bench‐stable N‐trichloromethylthiosaccharin as reagent. This methodology is highly regioselective, exhibits high functional group tolerance, and provides access to two previously unknown classes of potentially bioactive compounds.
Rosetta detektiert organische Moleküle
Authors: Feil Sylvia
Published: February 2016

Kometen geben Einblicke in die Entstehungszeit des Sonnensystems vor rund 4,5 Milliarden Jahren. Ausgewertet wurden nun die ersten Tage des Landers Philae auf dem Kern des Kometen 67P/Churyumov‐Gerasimenko. Die Ergebnisse der Rosetta‐Mission zeigen, dass organische Moleküle, die Zucker und Aminosäuren bilden können, im Kometen enthalten sind.
Validation of immunocytochemistry as a morphomolecular technique
Authors: Maxwell Perry , Salto‐Tellez Manuel
Published: February 2016

Immunocytochemistry (ICC) is a long‐established means for clinical laboratories to investigate material for which it is difficult to obtain tissue samples. Unlike immunohistochemistry (IHC), the cells do not retain surrounding tissue environment/architecture. This can be of benefit in that fixation is often immediate and rapid, protecting the cells. Although fixation is frequently observed as the main preanalytic variable of test quality, all cytology preanalytic factors should be identified and controlled. In addition, the validation of ICC should take the same rigorous approach that other molecular pathology techniques follow. A three‐step validation protocol is offered here. The end result is a comprehensive, morphomolecular approach to ICC, with an emphasis on therapeutic ICC. Cancer Cytopathol 2016;124:540‐5. © 2016 American Cancer Society.
Charged Inorganic Nanowire‐Directed Mineralization of Amorphous Calcium Carbonate
Authors: Liu Yang‐Yi , Liu Lei , Xue Lei , Mao Li‐Bo , Gao Huai‐Ling , Xu Liang , Yu Shu‐Hong
Published: February 2016

Charged inorganic nanowires (e.g., tellurium nanowires, TeNWs), analogous to supramolecular templates, have been used to direct the mineralization of uniform amorphous calcium carbonate (ACC) shells on their surfaces. The role of surface charges of TeNWs, mixed solvent ratio, and the diameter of the TeNWs is discussed, and the formation mechanism of ACC‐coated tellurium nanowires (ACC@TeNWs) is elucidated. This charged‐nanowire‐directed mineralization process represents a new approach that could be extended for the synthesis of other amorphous inorganic nanostructures in the future.
Excited‐State Deactivation of Adenine by Electron‐Driven Proton‐Transfer Reactions in Adenine–Water Clusters: A Computational Study
Authors: Wu Xiuxiu , Karsili Tolga N. V. , Domcke Wolfgang
Published: February 2016

The reactivity of photoexcited 9H‐adenine with hydrogen‐bonded water molecules in the 9H‐adenine–(H2O)5 cluster is investigated by using ab initio electronic structure methods, focusing on the photoreactivity of the three basic sites of 9H‐adenine. The energy profiles of excited‐state reaction paths for electron/proton transfer from water to adenine are computed. For two of the three sites, a barrierless or nearly barrierless reaction path towards a low‐lying S1–S0 conical intersection is found. This reaction mechanism, which is specific for adenine in an aqueous environment, can explain the substantially shortened excited‐state lifetime of 9H‐adenine in water. Depending on the branching ratio of the nonadiabatic dynamics at the S1–S0 conical intersection, the electron/proton transfer process can enhance the photostability of 9H‐adenine in water or can lead to the generation of adenine‐H⋅ and OH⋅ free radicals. Although the branching ratio is yet unknown, these findings indicate that adenine might have served as a catalyst for energy harvesting by water splitting in the early stages of the evolution of life.
Wholly Synthetic Molecular Machines
Authors: Cheng Chuyang , Stoddart J. Fraser
Published: February 2016

The past quarter of a century has witnessed an increasing engagement on the part of physicists and chemists in the design and synthesis of molecular machines de novo. This minireview traces the development of artificial molecular machines from their prototypes in the form of shuttles and switches to their emergence as motors and pumps where supplies of energy in the form of chemical fuel, electrochemical potential and light activation become a minimum requirement for them to function away from equilibrium. The challenge facing this rapidly growing community of scientists and engineers today is one of putting wholly synthetic molecules to work, both individually and as collections. Here, we highlight some of the recent conceptual and practical advances relating to the operation of wholly synthetic rotary and linear motors.
Optimal synchronization of two different in‐commensurate fractional‐order chaotic systems with fractional cost function
Authors: Behinfaraz Reza , Badamchizadeh Mohammadali
Published: February 2016

This article investigates the optimal synchronization of two different fractional‐order chaotic systems with two kinds of cost function. We use calculus of variations for minimizing cost function subject to synchronization error dynamics. We introduce optimal control problem to solve fractional Euler–Lagrange equations. Optimal control signal and minimum time of synchronization are obtained by proposed method. Examples show the optimal synchronization of two different systems with two different cost functions. First, we use an ordinary integer cost function then we use a fractional‐order cost function and comparing the results. Finally, we suggest a cost function which has the optimal solution of this problem, and we can extend this solution to solve other synchronization problems. © 2016 Wiley Periodicals, Inc. Complexity 21: 401–416, 2016
Design of Highly Selective Platinum Nanoparticle Catalysts for the Aerobic Oxidation of KA‐Oil using Continuous‐Flow Chemistry
Authors: Gill Arran M. , Hinde Christopher S. , Leary Rowan K. , Potter Matthew E. , Jouve Andrea , Wells Peter P. , Midgley Paul A. , Thomas John M. , Raja Robert
Published: February 2016

Highly active and selective aerobic oxidation of KA‐oil to cyclohexanone (precursor for adipic acid and ɛ‐caprolactam) has been achieved in high yields using continuous‐flow chemistry by utilizing uncapped noble‐metal (Au, Pt & Pd) nanoparticle catalysts. These are prepared using a one‐step in situ methodology, within three‐dimensional porous molecular architectures, to afford robust heterogeneous catalysts. Detailed spectroscopic characterization of the nature of the active sites at the molecular level, coupled with aberration‐corrected scanning transmission electron microscopy, reveals that the synthetic methodology and associated activation procedures play a vital role in regulating the morphology, shape and size of the metal nanoparticles. These active centers have a profound influence on the activation of molecular oxygen for selective catalytic oxidations.
Hydrogen from Water over Openly‐Structured Graphitic Carbon Nitride Polymer through Photocatalysis
Authors: Huang Zhijun , Li Fengbo , Chen Bingfeng , Yuan Guoqing
Published: February 2016

Openly‐structured g‐C3N4 microspheres (CNMS) are developed through a well‐controlled strategy. These materials have unique features of open 3 D structure, ordered hierarchical porosity, and improved optical and electronic properties. Hydrogen evolution from water is performed under a 300 W Xe lamp with a cut‐off filter (λ>420 nm) and Pt nanoparticles are used as the co‐catalyst (3.0 wt %). The catalyst prepared at 600 °C (CNMS‐600) has a hydrogen evolution rate (HER) of 392 μmol h−1 (apparent quantum yield, AQY=6.3 %) at 420 nm. This value is higher than that of g‐C3N4 nanosheets prepared through thermal oxidation, liquid exfoliation, or chemical exfoliation. The HER value is only 27 μmol h−1 (AQY=0.43 %) at 420 nm for bulk g‐C3N4 from melamine. The evolution of openly‐structured CNMS was investigated by TEM, FTIR, and XRD. The improved optical and electronic properties were demonstrated through UV/Vis absorption spectra, valence‐band X‐ray photoelectron spectroscopy, photoluminescence spectroscopy, electron paramagnetic resonance spectroscopy, and electrochemical impedance spectroscopy.
Metal‐free Nanoporous Carbon as a Catalyst for Electrochemical Reduction of CO2 to CO and CH4
Authors: Li Wanlu , Seredych Mykola , Rodríguez‐Castellón Enrique , Bandosz Teresa J.
Published: February 2016

S‐doped and dual S,N‐doped polymer‐derived carbons were studied as electrocatalysts for the reduction of CO2. Higher Faradaic efficiencies for conversion to CO and CH4 were obtained for S,N‐doped carbon than its S‐doped counterpart. The former showed a maximum Faradaic efficiency of 11.3 % for CO and 0.18 % for CH4 formation. The S,N‐nanoporous carbon was better at decreasing the overpotential of the reduction process. The pyridinic nitrogen groups were found to be actively participating in binding CO2. The quaternary nitrogen and thiophenic groups were also involved in the reduction process. It is proposed that the positively charged sites on the carbon atoms, adjacent to pyridinic nitrogen, stabilize the CO2.− and COOH* intermediates, promoting the formation of CO. The surface basicity of the catalysts improved the CO2 reduction selectivity when competing with H2 evolution. N2 adsorption measurements suggested that ultra‐micropores enhance the reduction of CO2 to CH4.
Comprehensive Insights into the Reactivity of Electrolytes Based on Sodium Ions
Authors: Eshetu Gebrekidan Gebresilassie , Grugeon Sylvie , Kim Huikyong , Jeong Sangsik , Wu Liming , Gachot Gregory , Laruelle Stephane , Armand Michel , Passerini Stefano
Published: February 2016

We report a systematic investigation of Na‐based electrolytes that comprise various NaX [X=hexafluorophosphate (PF6), perchlorate (ClO4), bis(trifluoromethanesulfonyl)imide (TFSI), fluorosulfonyl‐(trifluoromethanesulfonyl)imide (FTFSI), and bis(fluorosulfonyl)imide (FSI)] salts and solvent mixtures [ethylene carbonate (EC)/dimethyl carbonate (DMC), EC/diethyl carbonate (DEC), and EC/propylene carbonate (PC)] with respect to the Al current collector stability, formation of soluble degradation compounds, reactivity towards sodiated hard carbon (Nax‐HC), and solid–electrolyte interphase (SEI) layer formation. Cyclic voltammetry demonstrates that the stability of Al is highly influenced by the nature of the anions, solvents, and additives. GC–MS analysis reveals that the formation of SEI telltales depends on the nature of the linear alkyl carbonates and the battery chemistry (Li+ vs. Na+). FTIR spectroscopy shows that double alkyl carbonates are the main components of the SEI layer on Nax‐HC. In the presence of Na salts, EC/DMC and EC/DEC presented a higher reactivity towards Nax‐HC than EC/PC. For a fixed solvent mixture, the onset temperature follows the sequence NaClO4<NaFTFSI<NaPF6<NaTFSI<NaFSI, and the total heat generated increases in the order NaFSI<NaTFSI<NaClO4<NaPF6<NaFTFSI.
Metal‐Free Chemoselective Oxidative Dehomologation or Direct Oxidation of Alcohols: Implication for Biomass Conversion
Authors: Kim Sun Min , Shin Hun Yi , Kim Dong Wan , Yang Jung Woon
Published: February 2016

Invited for this month′s cover is the group of Jung Woon Yang at the Department of Energy Science, Sungkyunkwan University (SKKU). The image shows how simple base and molecular dioxygen can play a role in the cleavage of lignin model compound for the production of phenol and benzoic acid. The Communication itself is available at 10.1002/cssc.201501359.
Might macronutrient requirements influence grizzly bear–human conflict? Insights from nutritional geometry
Authors: Coogan Sean C. P. , Raubenheimer David
Published: February 2016

Knowledge of carnivore nutritional requirements offers a potentially powerful aid for conservation and management strategies, yet has received little attention. We discuss how nutritional ecology, nutritional geometry, and the concept of macronutrient (protein, lipid, and carbohydrate) balance can be used to further our understanding of behavioral regulatory mechanisms that may influence food‐related human–wildlife conflict, focusing on North American grizzly bears (Ursus arctos). We propose that the macronutrient preferences of omnivorous grizzly bears are a strong driver of their conflict with humans due to nutrient‐specific foraging behavior, which we predict will be particularly noticeable during periods in which “key” natural foods high in lipid or carbohydrate are limiting. We demonstrate how nutritional geometry can be used to investigate the concept of nutrient balance by integrating recent research on the macronutrient selection of the grizzly bear with nutritional estimates of potentially consumed anthropogenic foods. Our geometric analysis utilizing right‐angled mixture triangles suggested that anthropogenic foods offer grizzly bears nonprotein energy sources that may allow them to optimize macronutrient intake. This macronutrient‐focused approach gives rise to fundamentally different predictions (and potentially management strategies) than the conventional food and energy‐focused approaches. This article also provides insight into food‐related conflict among other bear and carnivore species, and human–carnivore conflict more generally, by outlining a nutritionally explicit predictive framework for understanding the potentially volatile interface between anthropogenic environments and the behavior of wild animals.
Public lands and private waters: scarce mesic resources structure land tenure and sage‐grouse distributions
Authors: Donnelly J. P. , Naugle D. E. , Hagen C. A. , Maestas J. D.
Published: February 2016

Water scarcity in semiarid environments provides a model system to evaluate the role of mesic resources in structuring the distribution and abundance of wildlife. We used remote sensing and point process analyses to evaluate spatio–temporal variability in limited mesic resources in relation to greater sage‐grouse (Centrocercus urophasianus) distributions in Oregon, California, and northwest Nevada, USA, 1984–2011. We then link population distribution to changes in resource availability over time, space, and land tenure. Despite encompassing only 2.4% of landscape area, mesic sites influenced sage‐grouse breeding distributions as evidenced by significantly shorter lek to mesic resource distances in observed (5.3 km) vs. predicted (8.2 km) values. Population abundance increased with proximity to mesic sites. Lag effects evident in abundance and proximity trends of mesic resources suggest a level of drought tolerance that moderated climatic variability. Mesic abundance and proximity remained relatively stable during the study period in comparison to more dynamic climatic patterns. Drought effects were most pronounced during multiyear events as evidenced by the 1987–1992 period that decreased mesic abundance >25% and approximately doubled mean lek to mesic resource distances (4.8–8.3 km). In our study area, 75% of all mesic resources were in private ownership, where the predominant land use is livestock ranching. Results suggest a holistic conservation strategy inclusive of private and public lands is needed to ensure sage‐grouse habitat requisites are met throughout the life cycle of this landscape species.