bluuebunny/crossref_metadata_2025 huggingface dataset:
Embraces are lateralized in spider monkeys (Ateles fusciceps rufiventris)
Authors: Boeving Emily R. , Belnap Starlie C. , Nelson Eliza L.
Published: March 2017

Side biases observed in behavior are thought to reflect underlying asymmetric brain function or hemispheric specialization. Previous work in multiple species identified left side biases (associated with the right hemisphere) for processing social behavior. In highly social species such as primates, many behaviors may be categorized as social, yet differences between such behaviors have not been examined as a test of asymmetric brain function. Using Colombian spider monkeys (Ateles fusciceps rufiventris), we observed lateral positioning during two types of behaviors widely categorized as social affiliative: embracing and grooming, and identified a left bias for embracing, but not grooming. Our findings partially support prior research in hemispheric specialization, but suggest that there may be differences between social behaviors that drive specialization. We discuss these results in light of current theory on hemispheric specialization and highlight differences between embracing and grooming.
Vitamin D status in wild toque macaques (Macaca sinica) in Sri Lanka
Authors: Power Michael L. , Dittus Wolfgang P. J.
Published: March 2017

The vitamin D receptor is found on most cells, including active immune cells, implying that vitamin D has important biological functions beyond calcium metabolism and bone health. Although captive primates should be given a dietary source of vitamin D, under free‐living conditions vitamin D is not a required nutrient, but rather is produced in skin when exposed to UV‐B light. The circulating level of 25 hydroxyvitamin D (25‐OH‐D) considered adequate for humans is a topic of current controversy. Levels of circulating 25‐OH‐D sufficient for good health for macaques and other Old World anthropoids are assumed to be the same as human values, but data from free‐living animals are scant. This study reports values for 25‐OH‐D and the active vitamin D metabolite, 1,25‐dihydroxyvitamin D (1,25[OH]2 D) for wild, forest‐ranging toque macaques (Macaca sinica) in Sri Lanka. Plasma samples were obtained from eight adult males, seven juvenile males, six young nulliparous females, nine adult females not pregnant or lactating, eleven lactating adult females, and four pregnant females. Mean values for the complete sample were 61.3 ± 4.0 ng/ml for 25‐OH‐D and 155.6 ± 8.7 pg/ml for 1,25[OH]2 D. There were no significant differences for either metabolite among age and sex classes, nor between lactating and non‐reproductive females. Values from the literature for circulating 25‐OH‐D in captive macaques are three times higher than those found in this wild population, however, 1,25[OH]2 D values in captive animals were similar to the wild values. The data from this study indicate that anthropoid primates exposed to extensive sunlight will have circulating values of 25‐OH‐D generally above 30 ng/ml, providing some support for the Endocrine Society recommendations for humans. Current dietary vitamin D supplementation of captive macaques likely exceeds requirement. This may affect metabolism and immune function, with possible consequences for macaque health and biomedical research results.
Stable carbon, oxygen, and nitrogen, isotope analysis of plants from a South Asian tropical forest: Implications for primatology
Authors: Roberts Patrick , Blumenthal Scott A. , Dittus Wolfgang , Wedage Oshan , Lee‐Thorp Julia A.
Published: March 2017

Stable isotope analysis of primate tissues in tropical forest contexts is an increasingly popular means of obtaining information about niche distinctions among sympatric species, including preferences in feeding height, forest canopy density, plant parts, and trophism. However, issues of equifinality mean that feeding height, canopy density, as well as the plant parts and plant species consumed, may produce similar or confounding effects. With a few exceptions, researchers have so far relied largely on general principles and/or limited plant data from the study area as references for deducing the predominant drivers of primate isotope variation. Here, we explore variation in the stable carbon (δ13C), nitrogen (δ15N), and oxygen (δ18O) isotope ratios of 288 plant samples identified as important to the three primate species from the Polonnaruwa Nature Sanctuary, Sri Lanka, relative to plant part, season, and canopy height. Our results show that plant part and height have the greatest effect on the δ13C and δ18O measurements of plants of immediate relevance to the primates, Macaca sinica, Semnopithecus priam thersites, and Trachypithecus vetulus, living in this monsoonal tropical forest. We find no influence of plant part, height or season on the δ15N of measured plants. While the plant part effect is particularly pronounced in δ13C between fruits and leaves, differential feeding height, and plant taxonomy influence plant δ13C and δ18O differences in addition to plant organ. Given that species composition in different regions and forest types will differ, the results urge caution in extrapolating general isotopic trends without substantial local baselines studies.
How do rivers, geographic distance, and dispersal behavior influence genetic structure in two sympatric New World monkeys?
Authors: Lecompte Emilie , Bouanani Mohand‐Ameziane , de Thoisy Benoît , Crouau‐Roy Brigitte
Published: March 2017

Dispersal, one of the major factors affecting the gene flow between populations, shapes the spatial distribution of genetic diversity within species.Alouatta macconnelliandSaguinus midasare two Neotropical monkey species that sympatrically inhabit the Guiana shield in northern Amazonia and are likely to differ in their dispersal behavior and vagility. We took advantage of their sympatry to investigate, over a fine geographical scale (∼50 km long), the relationship between spatial genetic structure, on the one hand, and geographical features and the species’ dispersal behavior on the other. A total of 84A. macconnelliindividuals from 25 social units and 76S. midasindividuals from 19 social units were genotyped for nine microsatellite markers. Both species displayed high genetic diversity and allelic richness. However, patterns of genetic structure differed between the two species. InA. macconnelli, no genetic substructuring was observed, while inS. midaswe detected significant structuring, but this structuring was not correlated with geographical features, such as the location of individuals relative to the river and/or the distance between them. Instead, the geographical distribution of genetic variation observed for each species is predominantly explained by each species’ dispersal pattern. We identified bisexual dispersal for both species, but with significant differences, either in the distance or in the rate of dispersal, between species and sexes. Genetic relatedness within social units was higher inS.midasthan inA. macconnelli: gene flow between social units seems limited inS.midas, especially for females, while high dispersal characterizesA. macconnelli, where females seem to disperse at lower rate but at a longer distance than males.
Second‐to‐fourth digit ratio (2D:4D) is unrelated to measures of somatic reproductive effort among young men from Cebu, the Philippines
Authors: Georgiev Alexander V. , Ryan Calen P. , Gettler Lee T. , McDade Thomas W. , Kuzawa Christopher W.
Published: March 2017

Objectives

A low second‐to‐fourth (2D:4D) digit ratio, a retrospective marker of high prenatal androgens, predicts increased investment in costly sexually dimorphic traits in men in some studies, although results are mixed. Here we test the hypothesis that the association of low 2D:4D ratios with increased muscularity and decreased adiposity depends on current testosterone (T) levels, such that digit ratio will be a particularly strong predictor of outcomes among men exhibiting a mating‐effort‐oriented endocrinological profile (high T). We also test the association between 2D:4D and somatic traits independently of T.

Materials and methods

We related 2D:4D digit ratios, and their interaction with T, to handgrip strength, lean mass, arm muscle area, and skinfold thickness in a sample of young, childess men (20–22 y) from Cebu, Philippines (N = 623).

Results

Digit ratio did not significantly predict men's T‐dependent somatic traits. Interactions between 2D:4D and morning T, similarly, did not predict male muscularity or adiposity. Although two of the interactions were significant or marginally significant (p < .1), after adjusting for multiple testing the evidence in support of our hypothesis was weak.

Discussion

We found no evidence that 2D:4D predicted measures of somatic reproductive effort in this sample of young men from Cebu, who as a group could be considered mostly mating‐oriented. These relationships were also not contingent upon, or stronger, when considering the moderating effect of concurrent T levels. In this sample, 2D:4D was therefore either a poor proxy of prenatal androgen exposure or prenatal androgens had limited influence on adult somatic outcomes.
The dawn of dentistry in the late upper Paleolithic: An early case of pathological intervention at Riparo Fredian
Authors: Oxilia Gregorio , Fiorillo Flavia , Boschin Francesco , Boaretto Elisabetta , Apicella Salvatore A. , Matteucci Chiara , Panetta Daniele , Pistocchi Rossella , Guerrini Franca , Margherita Cristiana , Andretta Massimo , Sorrentino Rita , Boschian Giovanni , Arrighi Simona , Dori Irene , Mancuso Giuseppe , Crezzini Jacopo , Riga Alessandro , Serrangeli Maria C. , Vazzana Antonino , Salvadori Piero A. , Vandini Mariangela , Tozzi Carlo , Moroni Adriana , Feeney Robin N. M. , Willman John C. , Moggi‐Cecchi Jacopo , Benazzi Stefano
Published: March 2017

Objectives

Early evidence for the treatment of dental pathology is found primarily among food‐producing societies associated with high levels of oral pathology. However, some Late Pleistocene hunter‐gatherers show extensive oral pathology, suggesting that experimentation with therapeutic dental interventions may have greater antiquity. Here, we report the second earliest probable evidence for dentistry in a Late Upper Paleolithic hunter‐gatherer recovered from Riparo Fredian (Tuscany, Italy).

Materials and Methods

The Fredian 5 human consists of an associated maxillary anterior dentition with antemortem exposure of both upper first incisor (I1) pulp chambers. The pulp chambers present probable antemortem modifications that warrant in‐depth analyses and direct dating. Scanning electron microscopy, microCT and residue analyses were used to investigate the purported modifications of external and internal surfaces of each I1.

Results

The direct date places Fredian 5 between 13,000 and 12,740 calendar years ago. Both pulp chambers were circumferentially enlarged prior to the death of this individual. Occlusal dentine flaking on the margin of the cavities and striations on their internal aspects suggest anthropic manipulation. Residue analyses revealed a conglomerate of bitumen, vegetal fibers, and probable hairs adherent to the internal walls of the cavities.

Discussion

The results are consistent with tool‐assisted manipulation to remove necrotic or infected pulp in vivo and the subsequent use of a composite, organic filling. Fredian 5 confirms the practice of dentistry—specifically, a pathology‐induced intervention—among Late Pleistocene hunter‐gatherers. As such, it appears that fundamental perceptions of biomedical knowledge and practice were in place long before the socioeconomic changes associated with the transition to food production in the Neolithic.
Many‐body localization from the perspective of Integrals of Motion
Authors: Rademaker Louk , Ortuño Miguel , Somoza Andres M.
Published: March 2017

We study many‐body localization (MBL) from the perspective of integrals of motion (IOMs). MBL can be understood phenomenologically through the existence of macroscopically many localized IOMs. We develop a systematic procedure based on IOM to calculate many‐body quantities. Displacement transformations made clear that any operator can be expanded in 1‐,2‐ ... n‐particles terms. We use this property to develop a systematic procedure to approximately calculate IOMs and many‐body quantities. We characterize the decay with distance of the IOM's and their interactions through effective localization lengths. For all values of disorder the typical IOMs are localized, suggesting the importance of rare fluctuations in understanding the MBL‐to‐ergodic transition.

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Stereoselective Catalytic Synthesis of Active Pharmaceutical Ingredients in Homemade 3D‐Printed Mesoreactors
Authors: Rossi Sergio , Porta Riccardo , Brenna Davide , Puglisi Alessandra , Benaglia Maurizio
Published: March 2017

3D‐printed flow reactors were designed, fabricated from different materials (PLA, HIPS, nylon), and used for a catalytic stereoselective Henry reaction. The use of readily prepared and tunable 3D‐printed reactors enabled the rapid screening of devices with different sizes, shapes, and channel dimensions, aimed at the identification of the best‐performing reactor setup. The optimized process afforded the products in high yields, moderate diastereoselectivity, and up to 90 % ee. The method was applied to the continuous‐flow synthesis of biologically active chiral 1,2‐amino alcohols (norephedrine, metaraminol, and methoxamine) through a two‐step sequence combining the nitroaldol reaction with a hydrogenation. To highlight potential industrial applications of this method, a multistep continuous synthesis of norephedrine has been realized. The product was isolated without any intermediate purifications or solvent switches.
Enantioselective Palladium‐Catalyzed Carbonylative Carbocyclization of Enallenes via Cross‐Dehydrogenative Coupling with Terminal Alkynes: Efficient Construction of α‐Chirality of Ketones
Authors: Yang Bin , Qiu Youai , Jiang Tuo , Wulff William D. , Yin Xiaopeng , Zhu Can , Bäckvall Jan‐E.
Published: March 2017

An enantioselective PdII/Brønsted acid‐catalyzed carbonylative carbocyclization of enallenes ending with a cross‐dehydrogenative coupling (CDC) with a terminal alkyne was developed. VAPOL phosphoric acid was found as the best co‐catalyst among the examined 28 chiral acids, for inducing the enantioselectivity of α‐chiral ketones. As a result, a number of chiral cyclopentenones were easily synthesized in good to excellent enantiomeric ratio with good yields.
Highly Selective Synthesis of cis‐Enediynes on a Ag(111) Surface
Authors: Wang Tao , Lv Haifeng , Fan Qitang , Feng Lin , Wu Xiaojun , Zhu Junfa
Published: March 2017

Cis‐enediyne‐type compounds have received much attention as potent antitumor antibiotics. The conventional synthesis of cis‐enediynes in solution typically involves multiple steps and various side reactions. For the first time, selective one‐step synthesis of cis‐enediyne from a single reactant is reported on a Ag(111) surface with a yield up to 90 %. High selectivity for the formation of cis‐enediyne originates from the steric effect posed by weak intermolecular interactions, which protect the cis‐enediyne from further reaction. A series of comparative experiments and DFT‐based transition‐state calculations support the findings. The described synthetic approach for directing reaction pathways on‐surface may illuminate potential syntheses of other unstable organic compounds.
Oxygen‐Containing Amorphous Cobalt Sulfide Porous Nanocubes as High‐Activity Electrocatalysts for the Oxygen Evolution Reaction in an Alkaline/Neutral Medium
Authors: Cai Pingwei , Huang Junheng , Chen Junxiang , Wen Zhenhai
Published: March 2017

A novel OER electrocatalyst, namely oxygen‐incorporated amorphous cobalt sulfide porous nanocubes (A‐CoS4.6O0.6 PNCs), show advantages over the benchmark RuO2 catalyst in alkaline/neutral medium. Experiments combining with calculation demonstrate that the desirable O* adsorption energy, associated with the distorted CoS4.6O0.6 octahedron structure and the oxygen doping, contribute synergistically to the outstanding electrocatalytic activity.
Some divalent metal(II) complexes of novel potentially tetradentate Schiff base N,N′‐bis(2‐carboxyphenylimine)‐2,5‐thiophenedicarboxaldhyde: Synthesis, spectroscopic characterization and bioactivities
Authors: Abdel Aziz Ayman A. , El‐Sayed Ibrahim S.A. , Khalil Mostafa M.H.
Published: March 2017

A novel tetradentate dianionic Schiff base ligand, N,N′‐bis(2‐carboxyphenylimine)‐2,5‐thiophenedicarboxaldhyde (H2L) and some first row d‐transition metal chelates (Co(II), Cu(II), Ni(II) and Zn(II)) were synthesized and characterized using various physicochemical and spectroscopic methods. The spectroscopic data suggested that the parent Schiff base ligand coordinates through both deprotonated carboxylic oxygen and imine nitrogen atoms. The free Schiff base and its metal chelates were screened for their antimicrobial activities for various pathogenic bacteria and fungi using the agar well diffusion method. The antibacterial and antifungal activities of all the newly synthesized compounds are significant compared to the standard drugs ciprofloxacin and nystatin. The antioxidant activities of the compounds were determined by reduction of 1,1‐diphenyl‐2‐picrylhydrazyl and compared with that of vitamin C as a standard. DNA binding ability of the novel Schiff base and its complexes was investigated using absorption spectroscopy, fluorescence spectroscopy, viscosity measurements and thermal denaturation. The obtained results clearly demonstrate that the binding affinity with calf thymus DNA follows the order: Cu(II) complex > Ni(II) complex > Zn(II) complex > Co(II) complex >H2L. Furthermore, the DNA cleavage activity of the newly synthesized ligand and its metal complexes was investigated using supercoiled plasmid DNA (pUC18) gel electrophoresis.
Synthesis and use of dioxime ligands for treatment of leukemia and colon cancer cells
Authors: Babahan Ilknur , Özmen Ali , Aslan Kadir
Published: March 2017

Two new vicinal dioxime ligands containing thiosemicarbazone units (L1H2 and L2H2) were synthesized and characterized using 1H NMR, 13C NMR, heteronuclear multiple quantum correlation, mass, infrared and UV–visible spectroscopies, elemental analysis and magnetic susceptibility measurements. In addition, homotrinuclear nickel(II), copper(II) and cobalt(II) complexes with a metal‐to‐ligand ratio of 3:2 for L1H2 and L2H2 were prepared. Synthesis of nickel(II) complex containing a BF2+ bridge was carried out using a precursor hydrogen‐bridged nickel(II) complex via the template effect. All metal–ligand complexes were tested against two human cancer cell lines (HL‐60 and HT‐29) for their antiproliferative and apoptotic activities. The results showed that [Co(L2H)2(H2O)2] and [Ni(L2H)2] exhibited the strongest antiproliferative activity with IpC50 values ranging between 5 and 10 μM, while [Co(L2H)2(H2O)2] and [Ni(L2H)2] both induced necrosis of HT‐29 cells and 60 and 65% apoptosis in HL‐60 cells, respectively.
Preparation and characterization of cyclohexandiamine/Fe3O4/ZnO core/shell nanomagnetic composite as a novel reusable catalyst and its application for the diastereoselective synthesis of β‐lactams via the asymmetric Kinugasa reaction
Authors: Safaei‐Ghomi Javad , Zahedi Safura
Published: March 2017

A novel magnetic composite catalyst has been prepared by immobilizing a chiral diamine on core/shell Fe3O4/ZnO. This new catalyst was characterized using X‐ray diffraction, energy‐dispersive X‐ray analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis and vibrating sample magnetometry. The performance of the catalyst was investigated in the asymmetric Kinugasa reaction and confirmed to be efficient in the synthesis of β‐lactam derivatives under mild conditions.
Plasmonic Ag/AgCl‐modified bismuth subcarbonate with enhanced visible light photocatalytic activity
Authors: An Yanting , Cao Wenrong , Zhou Yuanyuan , Chen Lifang , Qi Zhiwen
Published: March 2017

Plasmonic Ag/AgCl‐modified bismuth subcarbonate (Bi2O2CO3) composites were prepared by a multistep process with hydrothermal, deposition, and photoreduction in the absence of organic capping agents. The properties of the obtained Ag/AgCl/Bi2O2CO3 samples were characterized using X‐ray diffraction, field emission scanning electron microscopy and X‐ray photoelectron, UV–visible diffuse reflectance, and photoluminescence spectroscopies. The results reveal that Ag/AgCl nanoparticles are dispersed on the Bi2O2CO3 surface to achieve plasmonic Ag/AgCl/Bi2O2CO3. The Ag/AgCl/Bi2O2CO3 nanocomposites show improved rhodamine B (RhB) adsorption capacity and photocatalytic activity compared with pure Bi2O2CO3 and Ag/AgCl. In addition, the Ag/AgCl/Bi2O2CO3 composite with 20 wt% Ag/AgCl exhibits the highest photocatalytic activity and remains stable for the photodegradation of RhB under visible light. The enhanced photocatalytic activity of Ag/AgCl/Bi2O2CO3 may be attributed to the surface plasmon resonance effect of in situ generated Ag nanoparticles and synergistic effect of Ag/AgCl and Bi2O2CO3, which increase the separation efficiency of photogenerated electron–hole pairs under visible light irradiation.
Preparation of chitosan–graphene nanosheet composites with enhanced electrochemical and mechanical properties
Authors: Wu Guangyu , Huang Jianguo , Li Weidong
Published: March 2017

In this study, we proposed an alternative way to produce graphene nanosheet (GNS)/chitosan (CS) composites. Graphite‐intercalating compounds (GICs) were prepared by graphite and m‐chloroperbenzion acid (M‐CPBA) as starting materials. The GNS–CS composites were produced through the mixing of the GICs into CS and the removal of impurities in the final step. X‐ray diffraction, atomic force microscopy, and transmission and scanning electron microscopy analyses showed that graphite could be effectively exfoliated by an intercalating agent (M‐CPBA) and the GNSs were homogeneously dispersed into the CS matrix. Furthermore, we demonstrated that the electrochemical behavior and mechanical properties of the GNS–CS composites were significantly improved with a low level of GNSs in CS. The redox peak current increased 509%, and the modulus and hardness of the GNS–CS composites increased by 2.7 and 0.15 GPa, respectively, when the GNSs addition was 0.6 wt %. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45104.
Bio‐based flexible polyurethane foams derived from succinic polyol: Mechanical and acoustic performances
Authors: Oliviero Maria , Verdolotti Letizia , Stanzione Mariamelia , Lavorgna Marino , Iannace Salvatore , Tarello Maurizio , Sorrentino Andrea
Published: March 2017

Polyurethane foams have widespread applications as temperature insulators, sound barriers and shock absorbers. The market requests for these materials growth annually and its production pose serious environmental problems. In this article, several polyurethane foams compositions are obtained by partially replacing a conventional synthetic polyol with a new bio‐polyol made from succinic acid. The effects of water content, carbon black addition and bio‐succinic polyol replacement on foam properties are investigated. Results show that the addition of bio‐succinic polyol significantly changes the foam morphology leading to both an increase of the interconnectivity and an enhancement of mechanical properties. Furthermore, the addition of carbon black modifies the cell morphology and increases the foam density; consequently, an improvement in sound insulation performance at high frequency values is recorded. Due to this peculiar combination of mechanical and acoustic properties, the produced bio‐foams may be considered as potential substitutes of conventional flexible polyurethane foams to reduce vibrations, noise pollution, and consequently increase comfort in automobile and aircraft industries. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45113.
Intuitive Understanding of σ Delocalization in Loose and σ Localization in Tight Helical Conformations of an Oligosilane Chain
Authors: Jovanovic Milena , Antic Dean , Rooklin David , Bande Annika , Michl Josef
Published: March 2017

Conformational effects on the σ‐electron delocalization in oligosilanes are addressed by Hartree–Fock and time‐dependent density functional theory calculations (B3LYP, 6‐311G**) at MP2 optimized geometries of permethylated uniformly helical linear oligosilanes (all‐ω‐SinR2n+2) up to n=16 and for backbone dihedral angles ω=55–180°. The extent of σ delocalization is judged by the partition ratio of the highest occupied molecular orbital and is reflected in the dependence of its shape and energy and of UV absorption spectra on n. The results agree with known spectra of all‐transoid loose‐helix conformers (all‐[±165]‐SinMe2n+2) and reveal a transition at ω≈90° from the “σ‐delocalized” limit at ω=180° toward and close to the physically non‐realizable “σ‐localized” tight‐helix limit ω=0 with entirely different properties. The distinction is also obtained in the Hückel Ladder H and C models of σ delocalization. An easy intuitive way to understand the origin of the two contrasting limits is to first view the linear chain as two subchains with alternating primary and vicinal interactions (σ hyperconjugation), one consisting of the odd and the other of the even σ(SiSi) bonds, and then allow the two subchains to interact by geminal interactions (σ conjugation).
How positive and negative contact relate to attitudes towards Roma: Comparing majority and high‐status minority perspectives
Authors: Visintin Emilio Paolo , Green Eva G.T. , Pereira Adrienne , Miteva Polimira
Published: March 2017

Intergroup contact scholars have recently called for analyzing the effects of negative intergroup contact. In response to this call, we examined the correlates of positive and negative contact with one of the most stigmatized ethnic minorities, that is, Roma. We conducted a study in Bulgaria considering the point of view of the ethnic Bulgarian majority (n = 516) and of Bulgarian Turks (n = 274), an ethnic minority with higher status compared to Roma. Regression analyses showed that positive contact was associated with reduced prejudice and more support for pro‐Roma policies, while negative contact revealed the opposite pattern. These associations did not differ between ethnic Bulgarians and Bulgarian Turks. Moreover, positive and negative intergroup emotions mediated the relationships between positive and negative contact on the one hand and prejudice and policy support on the other. Our study highlights the importance of emotional processes involved in positive and negative intergroup contact experiences and encourages future research to analyze how absolute versus relative status differences shape the effects of positive and negative contact in complex hierarchical societies.
Tuning Hole and Electron Transfer from Photoexcited CdSe Quantum Dots to Phenol Derivatives: Effect of Electron‐Donating and ‐Withdrawing Moieties
Authors: Debnath Tushar , Sebastian Deepa , Maiti Sourav , Ghosh Hirendra N.
Published: March 2017

Charge‐transfer processes from photoexcited CdSe quantum dots (QDs) to phenol derivatives with electron‐ donating (4‐methoxy) and ‐withdrawing (4‐nitro) moieties have been demonstrated by using steady‐state and time‐ resolved emission and femtosecond transient absorption spectroscopy. Steady‐state and time‐resolved emission studies suggest that in the presence of both 4‐nitrophenol (4NP) and 4‐methoxyphenol (4MP) CdSe QDs luminescence is quenched. Stern–Volmer analysis suggests both static and dynamic mechanisms are active for both the QD/phenol composites. Cyclic voltammetric analysis recommends that photoexcited CdSe QDs can donate electrons to 4NP and holes to 4MP. To reconfirm both electron‐ and hole‐transfer mechanisms, CdSe/CdS quasi‐type II and CdSe/CdTe type II core–shell nanocrystals were synthesized and photoluminescence quenching was monitored in the absence and presence of both 4NP and 4MP, for which hole and electron transfer were systematically restricted. Results suggest that indeed electron and hole transfer take place from photoexcited CdSe to 4NP and 4MP, respectively. To monitor the charge‐transfer dynamics in both systems on an early timescale, femtosecond transient absorption spectroscopic techniques have been employed. Electron and hole transfer and charge‐recombination dynamics are discussed and the effect of electron‐donating and ‐withdrawing groups has been demonstrated.
Multimetallic and Mixed Environment Iridium(III) Complexes: A Modular Approach to Luminescence Tuning Using a Host Platform
Authors: Pritchard Victoria E. , Rota Martir Diego , Zysman‐Colman Eli , Hardie Michaele J.
Published: March 2017

Mononuclear and trinuclear bis‐cyclometallated IrIII complexes of the host ligands tris(4‐[4′‐methyl‐2,2′‐bipyridyl]methyl)cyclotriguaiacylene (L1) and tris(4‐(4′‐methyl‐2,2′‐ bipyridyl)carboxy)cyclotriguaiacylene (L2) have been prepared. Complexes [{Ir(ppy)2}3(L1)](PF6)3 (1.1), [{Ir(ppy)2}(L1)](PF6)3 (1.2), [{Ir(ppy)2}3(L2)](PF6)3 (2.1) and [{Ir(ppy)2}(L2)](PF6)3 (2.2) (where ppy=phenylpyridinato) showed distinct photophysical properties depending on the L ligand. Complexes featuring the L1 ligand were comparatively blue‐shifted in solution, with longer lifetimes and higher quantum yields. The mixed bis‐cyclometallated IrIII complexes [{Ir(ppy)2}{Ir(dFppy)2}2(L1)](PF6)3 (1.3), [{Ir(ppy)2}{Ir(dFppy)2}2(L2)](PF6)3 (2.3), [{Ir(ppy)2}2{Ir(dFppy)2}(L1)](PF6)3 (1.4) and [{Ir(ppy)2}2{Ir(dFppy)2}(L2)](PF6)3 (2.4) (where dFppy=2,4‐difluorophenylpyrinato) were also synthesised. Steady‐state and time‐resolved spectroscopy, along with electrochemical investigations, show that the Ir(III) chromophores within these mixed Ir‐environment species behave as isolated centres, with no energy transfer or electronic communication between them.
A Simple Tetraminocalix[4]arene as a Highly Efficient Catalyst under “On‐Water” Conditions through Hydrophobic Amplification of Weak Hydrogen Bonds
Authors: De Rosa Margherita , La Manna Pellegrino , Soriente Annunziata , Gaeta Carmine , Talotta Carmen , Hickey Neal , Geremia Silvano , Neri Placido
Published: March 2017

The simple tetraminocalix[4]arene 1, which contains weak H‐bond‐donor NH2 groups, is reported to be a highly efficient organocatalyst for the Vinylogous Mukaiyama Aldol Reaction (VMAR) of 2‐(trimethylsilyloxy)furan 5 with α‐ketoesters 6 a–l under “on‐water” conditions owing to the hydrophobic amplification of weak H‐bond interactions. The catalytic efficiency of calixarene catalyst 1 was shown to be closely related to its recognition abilities towards the reactants 5 and 6 through a multipoint recognition model. The proposed model provided good explanations for the differences on the reaction rate acceleration and on the stereoselectivity observed with different substrates.
An Untrodden Path: Versatile Fabrication of Self‐Supporting Polymer‐Stabilized Percolation Membranes (PSPMs) for Gas Separation
Authors: Friebe Sebastian , Mundstock Alexander , Schneider Daniel , Caro Jürgen
Published: March 2017

The preparation and scalability of zeolite or metal organic framework (MOF) membranes remains a major challenge, and thus prevents the application of these materials in large‐scale gas separation. Additionally, several zeolite or MOF materials are quite difficult or nearly impossible to grow as defect‐free layers, and require expensive macroporous ceramic or polymer supports. Here, we present new self‐supporting zeolite and MOF composite membranes, called Polymer‐Stabilized Percolation Membranes (PSPMs), consisting of a pressed gas selective percolation network (in our case ZIF‐8, NaX and MIL‐140) and a gas‐impermeable infiltrated epoxy resin for cohesion. We demonstrate the performance of these PSPMs by separating binary mixtures of H2/CO2 and H2/CH4. We report the brickwork‐like architecture featuring selective percolation pathways and the polymer as a stabilizer, compare the mechanical stability of said membranes with competing materials, and give an outlook on how economic these membranes may become.
Direct Noncovalent Activation of α,β‐Unsaturated Aldehydes for the Stereodivergent Synthesis of Substituted Cyclohexenes
Authors: Xie Ji‐Kang , Wang Yang , Lin Jun‐Bing , Ren Xiao‐Rui , Xu Peng‐Fei
Published: March 2017

HOMO‐raising noncovalent activation of α‐aryl α,β‐unsaturated aldehydes using a bifunctional Brønsted base catalyst is achieved. The catalytically generated dienolate intermediate undergoes all‐carbon [4+2] cyclizations with nitroolefins, leading to chiral cyclohexenes with four contiguous stereocenters in high yields and with excellent enantioseletivity. Furthermore, the diastereodivergent synthesis of the products is realized by introducing a second steric control to the bifunctional catalyst; 4 isomers out of 16 possible stereoisomers of the products were selectively produced by simple use of two catalysts and their (pseudo)enantiomers. The results presented here provide new insights into the remote activation of the carbonyl functionality as well as the stereodivergent synthesis of complex chiral molecules with multiple stereocenters.
Edge Engineering of MoS2 Nanoribbons as High Performance Electrode Material for Na‐ion Battery: A First‐Principle Study
Authors: Wang Jianbin , Zhao Qing , Chen Jun
Published: March 2017

Substantial effort has been made to search for electrode materials of Na‐ion batteries with high energy/power density. The application of S‐saturated zigzag MoS2 nanoribbons (MoS2NRs) for Na‐ion batteries has been explored through density function theory (DFT). The theoretical maximum specific capacity reaches 386.4 mAh•g−1 via double‐side and special edge adsorption mode. The electronic structure reveals that there exists charge transfer between Na and MoS2NRs. The diffusion barrier on MoS2NRs (0.17 eV) is much lower than that of bulk MoS2 (1.15 eV), indicating an excellent diffusion kinetics. In addition, the S‐edge in MoS2NRs plays a key role. Firstly, the Mo edge was half saturated by S, which helps to stabilize the MoS2NRs as well as offer more intercalation sites for Na. On the other hand, Na migrates much faster on the S edge route in MoS2NRs. Our computational results show that S‐saturated MoS2NRs exhibit a great potential as electrode materials for Na‐ion batteries with high performance.
Construction of Redox Responsive Vesicles Based on a Supra‐Amphiphile for Enzyme Confinement
Authors: Pan Tiezheng , Zou Huixin , Sun Hongcheng , Liu Yao , Liu Shengda , Luo Quan , Dong Zeyuan , Xu Jiayun , Liu Junqiu
Published: March 2017

Redox responsive vesicles were constructed based on self‐assembly of a supra‐amphiphile built by the host‐ guest interaction between β‐cyclodextrin and a ferrocene derivative. The structure and destruction‐reconstruction reversibility of the “smart” vesicles were clearly characterized by electron microscopy and dynamic light scattering. Notably, these vesicles were proved to be capable of controlled release function and bringing protease resistance to the enzyme, showing great biocompatibility and promising applications.
Clinical features of Bim deletion polymorphism and its relation with crizotinib primary resistance in Chinese patients with ALK/ROS1 fusion‐positive non–small cell lung cancer
Authors: Zhang Limin , Jiang Tao , Li Xuefei , Wang Yan , Zhao Chao , Zhao Sha , Xi Lei , Zhang Shijia , Liu Xiaozhen , Jia Yijun , Yang Hui , Shi Jinpeng , Su Chunxia , Ren Shengxiang , Zhou Caicun
Published: March 2017

BACKGROUND

The authors' previous study demonstrated that the B‐cell chronic lymphocytic leukemia/lymphoma (Bcl‐2)‐like 11 (BCL2L11) (Bim) deletion polymorphism was associated with poor clinical response to epidermal growth factor receptor (EGFR) tyrosine kinase inhibitors in patients with non–small cell lung cancer (NSCLC) with EGFR mutations. The objective of the current study was to investigate the impact of the Bim deletion polymorphism among patients with anaplastic lymphoma kinase (ALK)‐positive or ROS proto‐oncogene 1, receptor tyrosine kinase (ROS1)‐positive NSCLC who were treated with crizotinib.

METHODS

A total of 55 patients with ALK‐positive NSCLC and 14 patients with ROS1‐positive NSCLC who were treated with crizotinib were enrolled into the current study. The Bim deletion polymorphism was analyzed by polymerase chain reaction. The clinical features of the Bim deletion polymorphism and its impact on the effect of crizotinib were investigated.

RESULTS

The Bim deletion polymorphism was present in 9 of 69 patients with ALK‐positive or ROS1‐positive NSCLC (13.0%). There were no differences noted with regard to clinicopathological features between patients with and without the Bim deletion polymorphism. Patients with the Bim deletion polymorphism had a significantly shorter progression‐free survival (PFS) and lower objective response rate compared with those without (median PFS, 182 days vs 377 days [P = .008]) (objective response rate, 44.4% vs 81.7% [P =.041]) in all populations. The significant difference in PFS was observed in patients with ALK‐positive NSCLC (83 days vs 305 days [P =.0304]) compared with those with ROS1‐positive NSCLC (218 days vs not reached [P =.082]). Multivariate analysis indicated that the Bim deletion polymorphism was an independent predictive factor for patients with ALK‐positive NSCLC who were treated with crizotinib (hazard ratio, 4.786 [P =.006]).

CONCLUSIONS

The Bim deletion polymorphism was found to be associated with poor clinical response to crizotinib in patients with ALK fusion‐positive NSCLC. Cancer 2017;123:2927–35. © 2017 American Cancer Society.
Management of stage III colon cancer in the elderly: Practice patterns and outcomes in the general population
Authors: Merchant Shaila J. , Nanji Sulaiman , Brennan Kelly , Karim Safiya , Patel Sunil V. , Biagi James J. , Booth Christopher M.
Published: March 2017

BACKGROUND

Clinical trials have established surgical resection and adjuvant chemotherapy (ACT) as the standard management for stage III colon cancer; however, the extent to which these results apply to elderly patients in routine practice is unclear. This article describes the management and outcomes of elderly patients with stage III colon cancer.

METHODS

All cases of surgically resected colon cancer from 2002 to 2008 were identified with the population‐based Ontario Cancer Registry. Pathology reports were obtained for a random sample (25% of all cases); those with stage III disease constituted the study population. The utilization of ACT, cancer‐specific survival (CSS), and overall survival (OS) in elderly patients (≥70 years) and nonelderly patients (<70 years) were compared.

RESULTS

The study population included 2920 patients, and 1521 (52%) were elderly. The 30‐ and 90‐day mortality rates increased with advanced age: <70 years, 2% and 5%; 70 to 74 years, 3% and 7%; 75 to 79 years, 5% and 8%, and ≥80 years, 9% and 16% (P < .001). ACT was delivered to 48% of elderly patients and to 81% of younger patients (P < .001). Factors independently associated with ACT utilization among the elderly were a younger age (P < .001), male sex (P = .041), and no comorbidities (P = .001). Among elderly patients, ACT was associated with improved CSS (hazard ratio [HR], 0.73; 95% confidence interval [CI], 0.60‐0.88) and OS (HR, 0.71; 95% CI, 0.60‐0.83); however, the magnitude of the benefit was smaller for elderly patients than younger patients (HR for CSS, 0.53; 95% CI, 0.42‐0.67; HR for OS 0.56; 95% CI, 0.45‐0.69).

CONCLUSIONS

Half of elderly patients with stage III colon cancer do not receive ACT. Although the effect size is smaller than that in younger patients, ACT is associated with improved long‐term survival. Cancer 2017;123:2840–49. © 2017 American Cancer Society.
7‐year follow‐up after stereotactic ablative radiotherapy for patients with stage I non–small cell lung cancer: Results of a phase 2 clinical trial
Authors: Sun Bing , Brooks Eric D. , Komaki Ritsuko U. , Liao Zhongxing , Jeter Melenda D. , McAleer Mary F. , Allen Pamela K. , Balter Peter A. , Welsh James D. , O'Reilly Michael S , Gomez Daniel , Hahn Stephen M. , Roth Jack A. , Mehran Reza J. , Heymach John V. , Chang Joe Y.
Published: March 2017

BACKGROUND

The authors evaluated the efficacy, patterns of failure, and toxicity of stereotactic ablative radiotherapy (SABR) for patients with medically inoperable, clinical stage I non–small cell lung cancer (NSCLC) in a prospective clinical trial with 7 years of follow‐up. Clinical staging was performed according to the seventh edition of the American Joint Committee on Cancer TNM staging system.

METHODS

Eligible patients with histologically confirmed NSCLC of clinical stage I as determined using positron emission tomography staging were treated with SABR (50 grays in 4 fractions). The primary endpoint was progression‐free survival. Patients were followed with computed tomography and/or positron emission tomography/computed tomography every 3 months for the first 2 years, every 6 months for the next 3 years, and then annually thereafter.

RESULTS

A total of 65 patients were eligible for analysis. The median age of the patients was 71 years, and the median follow‐up was 7.2 years. A total of 18 patients (27.7%) developed disease recurrence at a median of 14.5 months (range, 4.3‐71.5 months) after SABR. Estimated incidences of local, regional, and distant disease recurrence using competing risk analysis were 8.1%, 10.9%, and 11.0%, respectively, at 5 years and 8.1%, 13.6%, and 13.8%, respectively, at 7 years. A second primary lung carcinoma developed in 12 patients (18.5%) at a median of 35 months (range, 5‐67 months) after SABR. Estimated 5‐year and 7‐year progression‐free survival rates were 49.5% and 38.2%, respectively; the corresponding overall survival rates were 55.7% and 47.5%, respectively. Three patients (4.6%) experienced grade 3 treatment‐related adverse events. No patients developed grade 4 or 5 adverse events (toxicity was graded according to the National Cancer Institute Common Terminology Criteria for Adverse Events [version 3.0]).

CONCLUSIONS

With long‐term follow‐up, the results of the current prospective study demonstrated outstanding local control and low toxicity after SABR in patients with clinical stage I NSCLC. Regional disease recurrence and distant metastases were the dominant manifestations of failure. Surveillance for second primary lung carcinoma is recommended. Cancer 2017;123:3031–39. © 2017 American Cancer Society.
Are Various σ‐Hole Bonds Steered by the Same Mechanisms?
Authors: Grabowski Sławomir J. , Sokalski W. Andrzej
Published: March 2017

Representative Lewis acid–Lewis base complexes linked by tetrel, pnicogen, chalcogen, and halogen bonds have been studied within the quantum theory of atoms in molecules (QTAIM) approach and the hybrid variation‐perturbation theory (HVPT) to analyze possible relationships between these σ‐hole dimers. Results obtained at the MP2/aug‐cc‐pVTZ level indicate numerous correlations similar to hydrogen‐bonded systems.
Replacing Two Chlorido Ligands by a Bipyridine Ligand in Ruthenium Nitrosyl Complexes with NO‐Release Capabilities: A Comparative Study
Authors: Enriquez‐Cabrera Alejandro , Sasaki Isabelle , Bukhanko Valerii , Tassé Marine , Mallet‐Ladeira Sonia , Lacroix Pascal G. , Barba‐Barba Rodrigo M. , Ramos‐Ortiz Gabriel , Farfán Norberto , Voitenko Zoia , Malfant Isabelle
Published: March 2017

[RuII(FT)(bipy)(NO)][PF6]3 [FT is the electron‐rich 4′‐(2‐fluorenyl)‐2,2′:6′,2′′‐terpyridine ligand and bipy is 2,2′‐bipyridine] is synthesized and characterized. It crystallizes in the triclinic P1 space group [a = 9.5362(2) Å, b = 10.3946(4) Å, c = 22.5701(8) Å, α = 94.7400(10)°, β = 94.9400(10)°, γ = 101.0680(10)]. A photochemical study is presented in comparison with that of the parents cis(Cl,Cl)‐[RuII(FT)Cl2(NO)][PF6] and trans(Cl,Cl)‐[RuII(FT)Cl2(NO)][PF6]. The three derivatives release nitric oxide (·NO) under irradiation at λ = 405 nm with respective quantum yields of 0.06, 0.31, and 0.10. Their two‐photon absorption (TPA) cross‐sections (σTPA) were investigated by the Z‐scan technique on related derivatives in which two hexyl chains were introduced to improve their solubility while their spectroscopic properties remained almost unaffected. The resulting σTPA values of 100 GM at λ = 800 nm are in the window of transparency for human tissues, and the bipyridine‐based complex exhibits a slight tendency for higher efficiency. The replacement of the [RuII(Cl)2(NO)] core by [RuII(bipy)(NO)] provides a much simpler synthesis, and the TPA‐induced ·NO‐release capabilities are in the same range of magnitude. Therefore, it is envisioned that ·NO donors of greater complexity with several metal centers could be investigated in future.
Towards New Tricyclic Motifs: Intramolecular C–H Arylation as the Key Step in a Formal [3+3] Cyclocondensation Strategy
Authors: Vrijdag Johannes L. , De Ruysscher Dries , De Borggraeve Wim M.
Published: March 2017

Tricyclic scaffolds structurally related to the well‐known benzodiazepine class of drugs show diverse biological activities strikingly different from those of their benzodiazepine counterparts. Interested by this scaffold‐hopping perspective, we previously developed a continuous‐flow method for the conversion of benzodiazepinediones into oxazoloquinolinones. Attempted extension of this synthetic route to the corresponding oxazolonaphthyridinone scaffolds met with limited success, however. This encouraged us to develop a different approach to pyridine‐based tricyclic motifs. In line with our interest in scaffold hopping, in this paper we describe a general, convergent [3+3] cyclocondensation approach to [1,3]oxazolo[4,5‐c]‐1‐naphthyridin‐4(5H)‐ones. The key synthetic steps in this approach are: (1) the construction of an amide linkage connecting two peripheral heterocycles; and (2) a palladium‐catalysed intramolecular C–H arylation to complete the tricyclic scaffold.
Silver‐Mediated Synthesis of 4H‐Benzoxazin‐4‐ones by Intramolecular Decarboxylative O‐Acylation Reactions with α‐Oxocarboxylic Acid
Authors: Bharathimohan Kuppusamy , Ponpandian Thanasekaran , Jafar Ahamed A.
Published: March 2017

The first example of an intramolecular decarboxylative acylation reaction for the synthesis of 4H‐benzoxazin‐4‐one derivatives has been described. The silver‐mediated reaction has a broad substrate scope and provides a mild and rapid approach to the corresponding products in high yields.