bluuebunny/crossref_metadata_2025 huggingface dataset:
Mitigation implications of an ice‐free summer in the Arctic Ocean
Authors: González‐Eguino Mikel , Neumann Marc B. , Arto Iñaki , Capellán‐Perez Iñigo , Faria Sérgio H.
Published: January 2017

The rapid loss of sea ice in the Arctic is one of the most striking manifestations of climate change. As sea ice melts, more open water is exposed to solar radiation, absorbing heat and generating a sea‐ice–albedo feedback that reinforces Arctic warming. Recent studies stress the significance of this feedback mechanism and suggest that ice‐free summer conditions in the Arctic Ocean may occur faster than previously expected, even under low‐emissions pathways. Here we use an integrated assessment model to explore the implications of a potentially rapid sea‐ice‐loss process. We consider a scenario leading to a full month free of sea ice in September 2050, followed by three potential trajectories afterward: partial recovery, stabilization, and continued loss of sea ice. We analyze how these scenarios affect the efforts to keep global temperature increase below 2°C. Our results show that sea‐ice melting in the Arctic requires more stringent mitigation efforts globally. We find that global CO2 emissions would need to reach zero levels 5–15 years earlier and that the carbon budget would need to be reduced by 20%–51% to offset this additional source of warming. The extra mitigation effort would imply an 18%–59% higher mitigation cost to society. Our results also show that to achieve the 1.5°C target in the presence of ice‐free summers negative emissions would be needed. This study highlights the need for a better understanding of how the rapid changes observed in the Arctic may impact our society.
White matter predicts functional connectivity in premanifest Huntington's disease
Authors: McColgan Peter , Gregory Sarah , Razi Adeel , Seunarine Kiran K. , Gargouri Fatma , Durr Alexandra , Roos Raymund A. C. , Leavitt Blair R. , Scahill Rachael I. , Clark Chris A. , Tabrizi Sarah J. , Rees Geraint ,   and the Track On‐HD Investigators
Published: January 2017

Objectives

The distribution of pathology in neurodegenerative disease can be predicted by the organizational characteristics of white matter in healthy brains. However, we have very little evidence for the impact these pathological changes have on brain function. Understanding any such link between structure and function is critical for understanding how underlying brain pathology influences the progressive behavioral changes associated with neurodegeneration. Here, we demonstrate such a link between structure and function in individuals with premanifest Huntington's.

Methods

Using diffusion tractography and resting state functional magnetic resonance imaging to characterize white matter organization and functional connectivity, we investigate whether characteristic patterns of white matter organization in the healthy human brain shape the changes in functional coupling between brain regions in premanifest Huntington's disease.

Results

We find changes in functional connectivity in premanifest Huntington's disease that link directly to underlying patterns of white matter organization in healthy brains. Specifically, brain areas with strong structural connectivity show decreases in functional connectivity in premanifest Huntington's disease relative to controls, while regions with weak structural connectivity show increases in functional connectivity. Furthermore, we identify a pattern of dissociation in the strongest functional connections between anterior and posterior brain regions such that anterior functional connectivity increases in strength in premanifest Huntington's disease, while posterior functional connectivity decreases.

Interpretation

Our findings demonstrate that organizational principles of white matter underlie changes in functional connectivity in premanifest Huntington's disease. Furthermore, we demonstrate functional antero–posterior dissociation that is in keeping with the caudo–rostral gradient of striatal pathology in HD.
Challenges of Spinel Li4Ti5O12 for Lithium‐Ion Battery Industrial Applications
Authors: Yuan Tao , Tan Zhuopeng , Ma Chunrong , Yang Junhe , Ma Zi‐Feng , Zheng Shiyou
Published: January 2017

Rechargeable lithium‐ion batteries (LIBs) offer the advantages of having great electrical energy storage and increased continuous and pulsed power output capabilities, which enable their applications in grid energy storage and electric vehicles (EVs). For safety, high power and durability considerations, spinel Li4Ti5O12 is one of the most appealing potential candidate as an anode material for power LIBs due to its excellent cycling stability and thermal stability. However, there are still a number of challenges remaining for Li4Ti5O12 battery applications. Herein, an updated overview of the latest advances in Li4Ti5O12 research is provided and key challenges for its future development (i.e., fast‐charging, specific capacity, swelling, interface chemistry, matching cathode and electrolyte as well as batteries design and manufacturing) are highlighted.
Highly efficient and reversible CO2 capture by tunable anion‐functionalized macro‐porous resins
Authors: He Xi , Mei Ke , Dao Rina , Cai Jingsong , Lin Wenjun , Kong Xueqian , Wang Congmin
Published: January 2017

Anion functionalized strategy has been proposed for the synthesis of macro‐porous resins [IRA‐900][An] through the neutral reaction of the basic resin [IRA‐900][OH] with the corresponding donors. Combining CO2 adsorption results and FT‐IR, solid‐state 13C NMR characterization as well as quantum chemical calculations, chemical adsorption mechanism was verified and tunable capture of CO2 was realized. Among them, the anion functionalized resin [IRA‐900][Triz] exhibits an extremely high adsorption capacity (4.02 mmol g−1 at 25°C, 0.15 bar), outperforming many other good adsorbents. Finally, we discuss the thermostability and recycling stability of [IRA‐900][Triz], which shows a great potential in the industrial capture of CO2. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3008–3015, 2017
Elevated tricuspid regurgitant jet velocity, reduced forced expiratory volume in 1 second, and mortality in adults with sickle cell disease
Authors: Chaturvedi Shruti , Labib Ghafuri Djamila , Kassim Adetola , Rodeghier Mark , DeBaun Michael R.
Published: January 2017

Cardiopulmonary disease is the leading cause of mortality in adults with sickle cell disease (SCD). Elevated tricuspid regurgitant jet velocity (TRJV) and reduced forced expiratory volume in 1 second (FEV1) %predicted are associated with early mortality in SCD; however their relationship and combined effect on survival is unknown. We investigated the relationship between TRJV and FEV1 %predicted, and their combined effect on mortality, in a retrospective cohort of 189 adults with SCD who underwent both pulmonary function testing and echocardiography. Nineteen (9.9%) of 189 patients died over a median follow‐up of 1.4 years; cardiopulmonary disease was the major cause of death in 52.6%. FEV1%predicted was negatively associated with TRJV (Spearman rho, −0.34, P < 0.001). Individuals with FEV1%predicted ≤70% were more likely to have an elevated TRJV ≥2.5 m/second, compared to those with FEV1%predicted >70% [45.8% versus 17.1%; odds ratio (OR) 4.1 (95% Confidence interval ([CI] 2.1–8.0); P = 0.001]. In a multivariable cox regression model, the combination of TRJV ≥2.5 m/second and FEV1%predicted ≤70% predicted earlier mortality [hazard ratio (HR) 4.97 (95% CI 1.30‐18.91; P = 0.019)] after adjusting for age, sex, and nephropathy. Both FEV1 %predicted ≤70% and TRJV ≥2.5 m/second were independently associated with nephropathy [OR 4.48 (95% CI 1.51–13.31); P = 0.004] and [OR 3.27 (95% CI 1.19–9.00); P = 0.017], respectively. In conclusion, pulmonary and cardiac impairment are associated with, and contribute to mortality in SCD. Therapies aimed at improving reduced FEV1%predicted and elevated TRJV could improve survival in patients with SCD. Am. J. Hematol. 92:125–130, 2017. © 2016 Wiley Periodicals, Inc.
Association of cardiorespiratory fitness and adiposity with inflammatory biomarkers in young adults
Authors: Park Eunduck , Meininger Janet C. , Kang Duck‐Hee , Gabriel Kelley Pettee , Padhye Nikhil S.
Published: January 2017

Objectives

Cardiorespiratory fitness (fitness) has been inversely associated with inflammation, but whether the association is attributed to fitness itself or lower levels of adiposity remains uncertain in young adults. The purpose of this study was to determine the association of fitness and adiposity with inflammation in young adults.

Methods

A cross‐sectional study was conducted with 88 participants aged 20–34 years. Fitness was assessed by a submaximal treadmill walking test. Adiposity was assessed by body mass index (BMI) and waist circumference (WC). Inflammation was measured by plasma C‐reactive protein (CRP), interleukin‐6 (IL‐6), and tumor necrosis factor‐alpha (TNF‐α) levels using immunoassays. Biological data were log10 transformed. A separate multiple regression analysis was conducted with each inflammatory biomarker as a dependent variable. Covariates (sex, oral contraceptive use, and education level) were adjusted.

Results

Fitness was inversely associated with log10 CRP after adjustment for covariates but not after adjusting for BMI or WC. Fitness was inversely associated with log10 IL‐6 after adjustment for WC and covariates (β = −0.341, P = .049) but not after adjusting for BMI. Fitness × WC interaction (partial eta2 = 0.056, P = .033) indicated that high fitness was more strongly associated with low log10 IL‐6 in young adults with high WC than those with low WC.

Conclusions

Although adiposity has a stronger association than fitness with CRP and IL‐6, higher levels of fitness could be essential for maintaining low levels of IL‐6, especially in the presence of high levels of central adiposity.
Nutritional, inflammatory, and ecological correlates of maternal retinol allocation to breast milk in agro‐pastoral Ariaal communities of northern Kenya
Authors: Fujita Masako , Lo Yun‐Jia , Brindle Eleanor
Published: January 2017

Objectives

Vitamin A (VA) is an essential micronutrient required for a range of biological functions throughout life. VA deficiency (VAD) claims an estimated 1 million preschool children's lives annually. Human milk is enriched with VA (retinol) from the maternal blood, which originates from the hepatic reserve and dietary intake. Secreting retinol into milk will benefit the nursing infant through breast milk, but retaining retinol is also important for the maternal health. Previous studies found that the public health intervention of high‐dose VA supplementation to lactating mothers did not significantly lower child mortality. The World Health Organization (WHO) recently acknowledged that our understanding about the principle of VA allocation within the maternal system and the secretion into milk is too incomplete to devise an effective intervention.

Methods

We present a secondary analysis of data collected among lactating mothers in VAD endemic northern Kenya (n = 171), examining nutritional, inflammatory, and ecological factors that might associate with maternal retinol allocation. Regression models were applied using the outcome milk‐retinol allocation index: milk retinol/(milk retinol + serum retinol).

Results

Ten percent of the sample was identified as VAD. The average milk retinol concentration was 0.1 μmo/L, grossly below what is considered minimally necessary for an infant (1 μmol/L). VAD mothers and mothers with inflammation did not seem to compromise their milk retinol even though their serum retinol was lower than non‐VAD and noninflammation mothers. Breast milk fat concentration positively correlated with milk retinol but not with serum retinol.

Conclusions

This exploratory study contributes toward an understanding of maternal retinol allocation.
Water‐Soluble Pyrrolo[3,2‐b]pyrroles: Synthesis, Luminescence and Two‐Photon Cellular Imaging Properties
Authors: Santra Mithun , Jun Yong Woong , Bae Juryang , Sarkar Sourav , Choi Wanuk , Gryko Daniel T. , Ahn Kyo Han
Published: January 2017

Water‐soluble, quadrupolar (A‐π‐D‐π‐A) pyrrolo[3,2‐b]pyrrole dyes have been prepared, and their photophysical properties, including solid‐state fluorescence, are characterized. Analysis of packing patterns of the para analogue in single crystal shows negligible π–π interactions between molecular planes in stacked layers, resulting in no fluorescence quenching in the aggregate state. One of the dyes is used for fluorescence imaging of cells by confocal and two‐photon microscopy, showing potential applicability of such dyes as bioimaging agents.
Vocal repertoire of free‐ranging black howler monkeys’ (Alouatta pigra): Call types, contexts, and sex‐related contributions
Authors: Briseño‐Jaramillo Margarita , Biquand Véronique , Estrada Alejandro , Lemasson Alban
Published: January 2017

Alouatta species utter the most powerful primate vocalizations in the Neotropics and are well‐known for their loud and long‐lasting male howling bouts. However, the diversity of acoustic structures used in these howling bouts, as well as in non‐howling contexts, and the relative contribution of the different group members to the entire vocal repertoire, needed to be explored further. This report provides the first detailed description of the vocal repertoire of black howler monkeys (Alouatta pigra), focusing on acoustic structures and contexts of emission of both loud and soft calls as well as on the contribution rate of males and females to the different call types. Three free‐ranging social groups of black howler monkeys living in Palenque National Park, Mexico were monitored. We identified twelve acoustically discriminable call types, eight described previously and four described here for the first time. A few call types were systematically emitted either isolated or during howling bouts, but most of them could be heard in both calling contexts. Three call types were emitted only by females and two only by males. Adult males’ call rates (for the seven shared call types) were higher than those of females but only when considering calls emitted within howling bouts. Our contextual analysis enabled us to divide call types into potential functional categories, according to their degree of contribution, to intra‐group versus inter‐group interactions and to neutral‐positive versus negative situations. We then discussed how socio‐ecological factors, notably sex differences in social behaviors, may explain the variability found in the vocal repertoire of this species and compared our findings with the literature on other primate species.
Synthesis and investigation of dual pH‐ and temperature‐responsive behaviour of poly[2‐(dimethylamino)ethyl methacrylate]‐grafted gold nanoparticles
Authors: Mohammadi Maryam , Salami‐Kalajahi Mehdi , Roghani‐Mamaqani Hossein , Golshan Marzieh
Published: January 2017

Gold nanoparticles (AuNPs) were synthesized by reduction of chloroauric acid (HAuCl4) aqueous solution with hydrazine monohydrate. The AuNPs were immediately treated with cysteamine to obtain amine‐functionalized nanoparticles (Au‐NH2). The reaction of Au‐NH2 with epichlorohydrin and subsequent treatment with sodium hydroxide gave epoxidized AuNPs (Au‐EP). Then, thiol‐capped AuNPs (Au‐SH) were synthesized by reaction of Au‐EP with cysteamine. A ‘grafting to’ approach was utilized to graft bromine‐terminated poly(N,N′‐dimethylaminoethyl methacrylate), synthesized via aqueous atom transfer radical polymerization, with various molecular weights (6280, 25 800, 64 200 and 87 600 g mol−1) onto Au‐SH to obtain Au‐P1, Au‐P2, Au‐P3 and Au‐P4 samples, respectively. All samples were exposed to temperature and pH variations, and Z‐average diameter was monitored using dynamic light scattering. According to the results, polymer‐grafted nanoparticles collapsed at lower temperatures with increasing solution pH for all molecular weight ranges due to deprotonation of tertiary amine groups. However, higher molecular weight polymers were more sensitive to pH variation especially in alkaline media. Also, a high degree of agglomeration was observed for Au‐P4 nanoparticles in alkaline media on increasing the temperature to 55 and 65 °C.
A simulation approach to achieve the best miscible enrichment in gas flooding and chemical injection process for enhanced oil recovery
Authors: Salari Sardari F. , Khorsand Movaghar M.R.
Published: January 2017

The effect of injected gas composition (as minimum miscible enrichment) on minimum miscibility pressure (MMP) and respective oil recovery has been studied through numerical slim tube simulation on a wide range of gas compositions. An initial comparative study on the performances of representative equations of state for predicting MMP in slim tube simulations has proven Peng–Robinson equation of state to provide results with better agreement with experimental data. Different injection scenarios are then designed to understand the effects of varying percentages of each component (like CO2) into the injected gas mixture on MMP. MMP decreased when the concentration of CO2 and intermediate components (C2–C6) increased. It was also found that when C7+ content in the injected gas increased, recovery factor decreased significantly. Further investigations on the effect of adding benzene, toluene, and xylene as chemicals into the injected gas (in slim tube simulations) also prove that addition of these aromatics can obviously improve oil recovery and decrease MMP and toluene gives the better results in comparison with the other ones. © 2017 Curtin University of Technology and John Wiley & Sons, Ltd.
Down‐regulation of a chitin synthase a gene by RNA interference enhances pathogenicity of Beauveria bassiana ANU1 against Spodoptera exigua (HÜBNER)
Authors: Lee Jung‐Bok , Kim Hyun Soo , Park Youngjin
Published: January 2017

Chitin synthase (CHS) is an important enzymatic component, which is required for chitin formation in the cuticles and cuticular linings of other tissues in insects. CHSs have been divided into two classes, classes A and B, based on their amino acid sequence similarities and functions. Class A CHS (CHS‐A) is specifically expressed in the epidermis and related ectodermal cells such as tracheal cells, while class B CHS (CHS‐B) is expressed in gut epithelial cells that produce peritrophic matrices. In this study, we cloned the CHS‐A gene from the beet armyworm, Spodoptera exigua (SeCHS‐A). The SeCHS‐A contains an open reading frame of 4,698 nucleotides, encoding a protein of 1,565 amino acids with a predicted molecular mass of approximately 177.8 kDa. The SeCHS‐A mRNA was expressed in all developmental stages and specifically in the epidermis and tracheae tissue by quantitative real‐time‐PCR analysis. Expression of SeCHS‐A gene was suppressed by feeding double‐stranded RNA (dsCHS‐A, 400 ng/larva) in the third instar larvae of S. exigua. Suppression of the SeCHS‐A gene expression significantly increased 35% of mortality on pupation of S. exigua. Also, the third instar larvae fed with dsCHS‐A significantly increased susceptibility to entomopathogenic fungi, Beauveria bassiana ANU1 at 3 days after treatment. These results suggest that the SeCHS‐A gene plays an important role in development of S. exigua and RNA interference may apply to effective pest control with B. bassiana.
Design, Synthesis, and Biological Evaluation of Novel Quinazoline Clubbed Thiazoline Derivatives
Authors: Ali Zulphikar , Akhtar Md J. , Siddiqui Anees A. , Khan Ahsan A. , Haider Md R. , Yar Mohammad S.
Published: January 2017

A novel series of quinazoline clubbed thiazoline derivatives was rationally designed and synthesized. The newly synthesized compounds were evaluated for in vitro dipeptidyl peptidase IV (DPP‐4) inhibitory activity. Compounds that showed good to moderate activity were compared using linagliptin as standard. Compound 4x (IC50 = 1.12 nM) exhibited the most promising results. The special chemical feature of compound 4x also imparts good inhibition selectivity for DPP‐4 over DPP‐8/9. Moreover, docking of compound 4x into the active site of DPP‐4 illustrates its possible binding interactions.
Effect of Heat Treatment on the Nitrogen Content and Its Role on the Carbon Dioxide Adsorption Capacity of Highly Ordered Mesoporous Carbon Nitride
Authors: Lakhi Kripal S. , Park Dae‐Hwan , Joseph Stalin , Talapaneni Siddulu N. , Ravon Ugo , Al‐Bahily Khalid , Vinu Ajayan
Published: January 2017

Mesoporous carbon nitrides (MCNs) with rod‐shaped morphology and tunable nitrogen contents have been synthesized through a calcination‐free method by using ethanol‐washed mesoporous SBA‐15 as templates at different carbonization temperatures. Carbon tetrachloride and ethylenediamine were used as the sources of carbon and nitrogen, respectively. The resulting MCN materials were characterized with low‐ and high‐angle powder XRD, nitrogen adsorption, high‐resolution (HR) SEM, HR‐TEM, elemental analysis, X‐ray photoelectron spectroscopy, and X‐ray absorption near‐edge structure techniques. The carbonization temperature plays a critical role in controlling not only the crystallinity, but also the nitrogen content and textural parameters of the samples, including specific surface area and specific pore volume. The nitrogen content of MCN decreases with a concomitant increase in specific surface area and specific pore volume, as well as the crystallinity of the samples, as the carbonization temperature is increased. The results also reveal that the structural order of the materials is retained, even after heat treatment at temperatures up to 900 °C with a significant reduction of the nitrogen content, but the structure is partially damaged at 1000 °C. The carbon dioxide adsorption capacity of these materials is not only dependent on the textural parameters, but also on the nitrogen content. The MCN prepared at 900 °C, which has an optimum BET surface area and nitrogen content, registers a carbon dioxide adsorption capacity of 20.1 mmol g−1 at 273 K and 30 bar, which is much higher than that of mesoporous silica, MCN‐1, activated carbon, and multiwalled carbon nanotubes.
PEG‐Induced Synthesis of Coordination‐Polymer Isomers with Tunable Architectures and Iodine Capture
Authors: Zhao Si‐Si , Chen Li , Zheng Xiaohua , Wang Lei , Xie Zhigang
Published: January 2017

Controllable synthesis of coordination polymer (CP) isomers and revealing their structure–property relationships remain enormous challenges. Three new supramolecular isomers have been synthesized by tuning the poly(ethylene glycol) (PEG) content in the feed. These supramolecular isomers have the same framework formula of [Cu2I2(tppe)] and different architectures from the classical 2D stacking framework to a 3D entangled system with the coexistence of interpenetration and polycatenation, and a 3D topological framework. Interestingly, these CPs could be utilized for capturing iodine molecules. According to multiple complementary experiments and crystallographic analyses, iodine capture is mainly based on halogen‐bond interactions in the inorganic {Cu2I2} building blocks of the framework. The present study describes a structure–property relationship in supramolecular isomerism with distinct topological structures.
The Influence of Board Composition on Sustainable Development Disclosure
Authors: Jizi Mohammad
Published: January 2017

Despite knowing the potential effect of social reporting on firms' continuity, there is limited research into the influence of the composition of boards of directors on CSR disclosure. This paper adds to the emerging CSR literature empirical evidence by examining how board composition relates to a firm's social and environmental disclosure as well as the implementation of social policies. Using a sample of FTSE 350 firms for the period 2007–2012, the results show that higher board independence facilitates the conveying of firms' good citizenship image through enhancing societal conscience. The results also show that female participation on boards is favorably affecting CSR engagement and reporting as well as the establishment of ethical policies. Hence, the research suggests that boards with higher female participation and independence boost the legitimacy of CSR reporting. Board gender diversity and independence facilitates directing part of the firm's scarce resources toward value maximizing social projects and subsequent reporting on these. Copyright © 2017 John Wiley & Sons, Ltd and ERP Environment
Exploring the Framework Development Status for Sustainability in Supply Chain Management: A Systematic Literature Synthesis and Future Research Directions
Authors: Ansari Zulfiquar N. , Kant Ravi
Published: January 2017

The need to integrate environmental and social aspects into the supply chain has created a debate amongst academicians and researchers on two topics: sustainability and the supply chain. A large number of journals and special volumes are publishing research that carries out a case study or survey, develops a mathematical model or builds a conceptual model/framework on sustainable supply chain management (SSCM). However, classified analysis of articles that develop a framework on SSCM has not been carried out by any researcher. The study thus aims to review SSCM framework articles to identify the major contributions and gaps. A total of 92 framework articles on SSCM from the sample of 349 over a period of 19 years (1998–2016) are structurally analyzed to meet the objectives. The selected literature is categorized by novel or adapted framework, source of framework, framework verification, method used for framework verification and identifying the constructs/elements that build the structural framework. Analyzing the literature sample using these categories reveals that framework development in the context of SSCM is still an area with ample future opportunities. The findings of the study are especially interesting for academicians and practitioners to investigate the critical gaps in the field of sustainable supply chain management frameworks (SSCMFs). Copyright © 2017 John Wiley & Sons, Ltd and ERP Environment
Electrochemical Generation of Excited Intramolecular Charge‐Transfer States
Authors: Kapturkiewicz Andrzej
Published: January 2017

Excited intramolecular charge‐transfer states have been attracting significant attention in recent decades, as they are crucial for different optoelectronic applications including the construction of efficient organic light‐emitting devices. This possibility arises from the unique combination of the electrochemical and photophysical properties characterizing organic A−D molecules, which contain the linked electron‐donating D and electron‐accepting A subunits. For the same reasons, the A−D molecules are excellent luminophores that can be effectively excited in electrochemically generated chemiluminescence processes. This Review provides an overview of the current achievements in this particularly exciting field.
Anion‐Templated Nanosized Silver Alkynyl Clusters: Cluster Engineering and Solution Behavior
Authors: Zhang Shan‐Shan , Su Hai‐Feng , Wang Zhi , Wang Lina , Zhao Quan‐Qin , Tung Chen‐Ho , Sun Di , Zheng Lan‐Sun
Published: January 2017

Assembly of nanosized polynuclear metal clusters from simple building blocks usually involves complicated self‐organization processes and thus is a long‐standing challenge. Here, we demonstrate the controllable assembly, single‐crystal structures and solution behaviors of four molecular assemblies based on nanosized silver alkynyl clusters, formulated as {[(CrO4)2Cl@Ag42(PhC≡C)34(CF3COO)2]⋅CF3COO} (1), {(NH4)[(CrO4)2Cl@Ag42(PhC≡C)34(CrO4)(H2O)2]⋅2BF4⋅CH3OH}n (2), [(CrO4)@Ag22(PhC≡C)16(CF3SO3)4]n (3), and {[(CrO4)2@Ag31(PhC≡C)22(CF3SO3)4]⋅CF3SO3⋅2CH3OH⋅H2O}n (4). In the presence of concomitant CrO42− and Cl− templates, we could isolate a discrete cluster 1 and a polymeric chain‐like compound 2 by using different silver salts. Both 1 and 2 have a similar 42‐metallic cage, which traps two CrO42− and one Cl− as anion templates. Using sole CrO42− template, 3 and 4 were simultaneously isolated in a one‐pot reaction. Both of them are 1D chain structures based on single CrO42− templated Ag18 and double CrO42− templated Ag30 clusters, respectively. HR‐ESI‐MS was used to study the solution behaviors of 1–4. This work has the following purposes: i) it presents the cluster engineering concept used in the assembly of polynuclear silver alkynyl clusters; ii) it exemplifies template effects from hetero and homo anions; and iii) it provides a controllable way to achieve assembly of silver alkynyl clusters.
Light‐Controlled Reversible Modulation of Frontier Molecular Orbital Energy Levels in Trifluoromethylated Diarylethenes
Authors: Herder Martin , Eisenreich Fabian , Bonasera Aurelio , Grafl Anna , Grubert Lutz , Pätzel Michael , Schwarz Jutta , Hecht Stefan
Published: January 2017

Among bistable photochromic molecules, diarylethenes (DAEs) possess the distinct feature that upon photoisomerization they undergo a large modulation of their π‐electronic system, accompanied by a marked shift of the HOMO/LUMO energies and hence oxidation/reduction potentials. The electronic modulation can be utilized to remote‐control charge‐ as well as energy‐transfer processes and it can be transduced to functional entities adjacent to the DAE core, thereby regulating their properties. In order to exploit such photoswitchable systems it is important to precisely adjust the absolute position of their HOMO and LUMO levels and to maximize the extent of the photoinduced shifts of these energy levels. Here, we present a comprehensive study detailing how variation of the substitution pattern of DAE compounds, in particular using strongly electron‐accepting and chemically stable trifluoromethyl groups either in the periphery or at the reactive carbon atoms, allows for the precise tuning of frontier molecular orbital levels over a broad energy range and the generation of photoinduced shifts of more than 1 eV. Furthermore, the effect of different DAE architectures on the transduction of these shifts to an adjacent functional group is discussed. Whereas substitution in the periphery of the DAE motif has only minor implications on the photochemistry, trifluoromethylation at the reactive carbon atoms strongly disturbs the isomerization efficiency. However, this can be overcome by using a nonsymmetrical substitution pattern or by combination with donor groups, rendering the resulting photoswitches attractive candidates for the construction of remote‐controlled functional systems.
The Nature of Metal–Metal Interactions in Dimeric Hydrides and Halides of Group 11 Elements in the Light of High Level Relativistic Calculations
Authors: Dem'yanov Piotr I. , Polestshuk Pavel M. , Kostin Vladimir V.
Published: January 2017

The titular calculations show that charges at metal atoms M are apparently the main factor governing the nature of M⋅⋅⋅M interactions in two‐nuclear coinage‐metal complexes, and there are certain critical values of positive charges on M atoms, on exceeding which the pair‐wise M⋅⋅⋅M interactions and/or the binding between M atoms in such complexes become repulsive despite negative formation energies of such complexes, short M–M internuclear distances, and the existence of a bond critical point (BCP) between M atoms.
Selective Electrochemical Bleaching of the Outer Leaflet of Fluorescently Labeled Giant Liposomes
Authors: Perez Jimenez Ana Isabel , Challier Lylian , Aït‐Yahiatène Eric , Delacotte Jérôme , Labbé Eric , Buriez Olivier
Published: January 2017

Electrochemistry and confocal fluorescence microscopy were successfully combined to selectively bleach and monitor the fluorescence of NBD (7‐nitrobenz‐2‐oxa‐1,3‐diazole)‐labeled phospholipids of giant liposomes. Three types of giant unilamellar vesicles have been investigated, the fluorescent phospholipids being localized either mainly on their outer‐, inner‐, or both inner/outer leaflets. We established that only the fluorescent lipids incorporated in the outer leaflet of the vesicles underwent electrochemical bleaching upon reduction. The relative fluorescence intensity decay was quantified all along the electrochemical extinction through an original fluorescence loss in electrobleaching (FLIE) assay. As expected, the reorganization of the fluorescent phospholipids followed diffusion‐driven dynamics. This was also evidenced by comparison with fluorescence loss in photobleaching (FLIP) and the corresponding numerical model. The value of the lateral diffusion coefficient of phospholipids was found to be similar to that obtained by other methods reported in the literature. This versatile and selective bleaching procedure appears reliable to explore important biological and pharmacological issues.
Oxygen Delivery as a Limiting Factor in Modelling Dicopper(II) Oxidase Reactivity
Authors: Gülzow Jana , Hörner Gerald , Strauch Peter , Stritt Anika , Irran Elisabeth , Grohmann Andreas
Published: January 2017

Deprotonation of ligand‐appended alkoxyl groups in mononuclear copper(II) complexes of N,O ligands L1 and L2, gave dinuclear complexes sharing symmetrical Cu2O2 cores. Molecular structures of these mono‐ and binuclear complexes have been characterized by XRD, and their electronic structures by UV/Vis, 1H NMR, EPR and DFT; moreover, catalytic performance as models of catechol oxidase was studied. The binuclear complexes with anti‐ferromagnetically coupled copper(II) centers are moderately active in quinone formation from 3,5‐di‐tert‐butyl‐catechol under the established conditions of oxygen saturation, but are strongly activated when additional dioxygen is administered during catalytic turnover. This unforeseen and unprecedented effect is attributed to increased maximum reaction rates vmax, whereas the substrate affinity KM remains unaffected. Oxygen administration is capable of (partially) removing limitations to turnover caused by product inhibition. Because product inhibition is generally accepted to be a major limitation of catechol oxidase models, we think that our observations will be applicable more widely.
Synthesis of 2,2,2,‐Trichloroethyl Aryl‐ and Vinyldiazoacetates by Palladium‐Catalyzed Cross‐Coupling
Authors: Fu Liangbing , Mighion Jeffrey D. , Voight Eric A. , Davies Huw M. L.
Published: January 2017

An efficient and convenient synthesis of 2,2,2‐trichloroethyl (TCE) aryl‐ and vinyldiazoacetates was achieved by palladium‐catalyzed cross‐coupling reactions between TCE diazoacetates and aryl or vinyl iodides. The broad substrate scope allows for rapid and facile formation of TCE aryl‐ and vinyldiazoacetates, which recently have emerged as versatile reagents for rhodium‐carbene chemistry.
N‐Heterocyclic Carbene‐Catalyzed Intramolecular Nucleophilic Substitution: Enantioselective Construction of All‐Carbon Quaternary Stereocenters
Authors: Zhao Ming , Chen Jie , Yang Hui , Zhou Ling
Published: January 2017

An efficient enantioselective N‐heterocyclic carbene (NHC)‐catalyzed intramolecular SN2′ nucleophilic substitution of aldehydes with (E/Z)‐trisubstituted allylic bromides was accomplished. A range of enantioenriched chromanones bearing an all‐carbon quaternary stereocenter at the C3 position were prepared with up to 97 % yield and 98 % enantiomeric excess. The resulting vinyl and carbonyl groups in these products can be transformed into a variety of synthetically important building blocks.
Unprecedented Access to β‐Arylated Selenophenes through Palladium‐Catalysed Direct Arylation
Authors: Skhiri Aymen , Salem Ridha Ben , Soulé Jean‐François , Doucet Henri
Published: January 2017

Several reported methods allow access to α‐arylated selenophenes, whereas the synthesis of β‐arylated selenophenes remains very challenging. Here, the Pd‐catalysed coupling of benzenesulfonyl chlorides with selenophenes affording regiospecific β‐arylated selenophenes is reported. The reaction proceeds with easily accessible catalyst, base and substrates, and tolerates a variety of substituents both on the benzene and selenophene moieties. This transformation allows the programmed synthesis of polyarylated selenophenes with potential applications in pharmaceutical and materials chemistry, as the installation of aryl groups at the desired positions can be achieved.
Mechanistic Studies of Cyclohexene Oxide/CO2 Copolymerization by a Chromium(III) Pyridylamine‐Bis(Phenolate) Complex
Authors: Devaine‐Pressing Katalin , Kozak Christopher M.
Published: January 2017

Chromium(III) chlorido amine‐bis(phenolate) complexes paired with nucleophilic co‐catalysts are a promising family of catalysts for the copolymerization of CO2 and epoxides to selectively produce polycarbonates with a very high degree of carbonate linkages. Single‐component catalyst systems can be prepared, where the neutral nucleophile, 4‐dimethylaminopyridine (DMAP), is coordinated to the metal site to provide a stable octahedral CrIII complex. These complexes possess the potential for both anionic (from the chlorido ligand) or neutral (DMAP) nucleophilic epoxide ring‐opening during the proposed rate‐determining initiation step. Concentration effect studies support a first‐order dependence of the polymerization rate on the concentration of single‐component catalyst. End‐group analysis of polycarbonates by MALDI‐TOF MS indicate the presence of predominantly DMAP‐initiated chains as well as the occurrence of chain‐transfer events resulting in ether linkages, likely from the presence of cyclohexene diol formed by the reaction of cyclohexene oxide and adventitious water.
Xenopus egg extract to study regulation of genome‐wide and locus‐specific DNA replication
Authors: Raspelli Erica , Falbo Lucia , Costanzo Vincenzo
Published: January 2017

Faithful DNA replication, coupled with accurate repair of DNA damage, is essential to maintain genome stability and relies on different DNA metabolism genes. Many of these genes are involved in the assembly of replication origins, in the coordination of DNA repair to protect replication forks progression in the presence of DNA damage and in the replication of repetitive chromatin regions. Some DNA metabolism genes are essential in higher eukaryotes, suggesting the existence of specialized mechanisms of repair and replication in organisms with complex genomes. The impact on cell survival of many of these genes has so far precluded in depth molecular analysis of their function. The cell‐free Xenopus laevis egg extract represents an ideal system to overcome survival issues and to facilitate the biochemical study of replication‐associated functions of essential proteins in vertebrate organisms. Here, we will discuss how Xenopus egg extracts have been used to study cellular and molecular processes, such as DNA replication and DNA repair. In particular, we will focus on innovative imaging and proteomic‐based experimental approaches to characterize the molecular function of a number of essential DNA metabolism factors involved in the duplication of complex vertebrate genomes.
What we can learn from a tadpole about ciliopathies and airway diseases: Using systems biology in Xenopus to study cilia and mucociliary epithelia
Authors: Walentek Peter , Quigley Ian K.
Published: January 2017

Over the past years, the Xenopus embryo has emerged as an incredibly useful model organism for studying the formation and function of cilia and ciliated epithelia in vivo. This has led to a variety of findings elucidating the molecular mechanisms of ciliated cell specification, basal body biogenesis, cilia assembly, and ciliary motility. These findings also revealed the deep functional conservation of signaling, transcriptional, post‐transcriptional, and protein networks employed in the formation and function of vertebrate ciliated cells. Therefore, Xenopus research can contribute crucial insights not only into developmental and cell biology, but also into the molecular mechanisms underlying cilia related diseases (ciliopathies) as well as diseases affecting the ciliated epithelium of the respiratory tract in humans (e.g., chronic lung diseases). Additionally, systems biology approaches including transcriptomics, genomics, and proteomics have been rapidly adapted for use in Xenopus, and broaden the applications for current and future translational biomedical research. This review aims to present the advantages of using Xenopus for cilia research, highlight some of the evolutionarily conserved key concepts and mechanisms of ciliated cell biology that were elucidated using the Xenopus model, and describe the potential for Xenopus research to address unresolved questions regarding the molecular mechanisms of ciliopathies and airway diseases.
Xenopus as a model for studies in mechanical stress and cell division
Authors: Stooke‐Vaughan Georgina A. , Davidson Lance A. , Woolner Sarah
Published: January 2017

We exist in a physical world, and cells within biological tissues must respond appropriately to both environmental forces and forces generated within the tissue to ensure normal development and homeostasis. Cell division is required for normal tissue growth and maintenance, but both the direction and rate of cell division must be tightly controlled to avoid diseases of over‐proliferation such as cancer. Recent studies have shown that mechanical cues can cause mitotic entry and orient the mitotic spindle, suggesting that physical force could play a role in patterning tissue growth. However, to fully understand how mechanics guides cells in vivo, it is necessary to assess the interaction of mechanical strain and cell division in a whole tissue context. In this mini‐review we first summarise the body of work linking mechanics and cell division, before looking at the advantages that the Xenopus embryo can offer as a model organism for understanding: (1) the mechanical environment during embryogenesis, and (2) factors important for cell division. Finally, we introduce a novel method for applying a reproducible strain to Xenopus embryonic tissue and assessing subsequent cell divisions.
TALENs and CRISPR/Cas9 fuel genetically engineered clinically relevant Xenopus tropicalis tumor models
Authors: Naert Thomas , Van Nieuwenhuysen Tom , Vleminckx Kris
Published: January 2017

The targeted nuclease revolution (TALENs, CRISPR/Cas9) now allows Xenopus researchers to rapidly generate custom on‐demand genetic knockout models. These novel methods to perform reverse genetics are unprecedented and are fueling a wide array of human disease models within the aquatic diploid model organism Xenopus tropicalis (X. tropicalis). This emerging technology review focuses on the tools to rapidly generate genetically engineered X. tropicalis models (GEXM), with a focus on establishment of genuine genetic and clinically relevant cancer models. We believe that due to particular advantageous characteristics, outlined within this review, GEXM will become a valuable alternative animal model for modeling human cancer. Furthermore, we provide perspectives of how GEXM will be used as a platform for elucidation of novel therapeutic targets and for preclinical drug validation. Finally, we also discuss some future prospects on how the recent expansions and adaptations of the CRISPR/Cas9 toolbox might influence and push forward X. tropicalis cancer research.
From questions to answers: Examining the role of pediatric surveillance units in eating disorder research
Authors: Katzman Debra K. , Madden Sloane , Nicholls Dasha , Mawjee Karizma , Norris Mark L.
Published: January 2017

Pediatric Surveillance Units (PSUs) provide a unique model for the study of pediatric eating disorders (EDs). Australia, Britain, and Canada have surveillance programs that have generated valuable epidemiological and clinical data on early‐onset eating disorders (EOED). The PSUs represent an important collaborative tool that has helped shape our understanding of EOEDs and offers potential to contribute to decisions regarding health resource allocation and public health policy. This paper reviews the role of PSUs as a unique model to study pediatric EDs and its success in translating the knowledge generated by these programs into improving the health of children and adolescents with EDs worldwide.
Incremental validity of weight suppression in predicting clinical impairment in bulimic syndromes
Authors: Hagan Kelsey E. , Clark Kelsey E. , Forbush Kelsie T.
Published: January 2017

Research has shown that weight suppression (WS; the difference between a person's highest and current body weight in pounds) is a robust predictor of weight gain and eating‐disorder (ED) symptoms among individuals with bulimic syndromes. Given the important prognostic role that WS plays in ED course and outcome, we hypothesized that WS would represent a clinically useful indicator of impairment for bulimic syndromes. We further posited that WS would demonstrate incremental validity above‐and‐beyond other proposed indicators in explaining clinical impairment in bulimic syndromes. Participants were community‐recruited adults (N = 101; 80.2% female) with full‐threshold (n = 51) or subthreshold (n = 50) bulimia nervosa. Other indicators of impairment included body mass index, frequency of inappropriate compensatory behaviors, lifetime history of any internalizing disorder, and multiple purging. Clinical impairment was assessed with the clinical impairment assessment (CIA). Hierarchical linear regression tested whether WS added to the explanation of CIA score variance above‐and‐beyond other indicators of bulimic‐syndrome impairment. WS was significantly associated with clinical impairment (p = .011), but did not demonstrate incremental validity over other independent variables in predicting CIA scores. WS explained an additional 1.7% of the variance in CIA scores above‐and‐beyond other variables and the independent effect of WS on CIA scores represented a medium‐sized effect (Cohen's d = 0.521). Results suggested that WS may be an indicator of ED‐related clinical impairment. Inquiring about WS could be an informative component of routine bulimic‐syndrome assessment, given that WS explains some of the variance in clinical impairment in bulimic syndromes.
An N‐Heterocyclic‐Carbene–Tetracyanoethylene Zwitterion: Experimental and Theoretical Study on Its Formation and Reactivity
Authors: Song Hayoung , Kim Youngsuk , Park Junbeom , Ko Young Ho , Kim Kimoon , Lee Eunsung
Published: January 2017

The direct addition of tetracyanoethylene (TCNE) to the carbene center of 1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene (IPr) was successfully demonstrated. The IPr–TCNE adduct, that is, zwitterion 1, clearly differs from the typical [2+1]‐cycloaddition products obtained from the reaction of carbenes with olefins. The results obtained from experimental and theoretical studies suggest that adduct 1 disassembles into IPr and TCNE, which is followed by the addition of IPr to the nitrile carbon atom of TCNE and subsequent isomerization into a thermodynamically more stable singlet nitrene intermediate. This intermediate is then captured by an additional molecule of TCNE to afford another heterocycle. This study reveals a unique example of the reactivity between N‐heterocyclic carbenes and olefins.
Synthesis of bare and functionalized porous adsorbent materials for CO2 capture
Authors: Olajire Abass A.
Published: January 2017

The ever‐increasing demand for nanostructured composite materials and sustainable processes for next generation CO2 capture technologies has necessitated the need to develop novel and cost‐effective synthetic routes for CO2 adsorbents based on amine and ionic liquid functionalized porous adsorbent materials with improved physico‐chemical properties. The most obvious option is modification of the synthesized porous adsorbent materials by the incorporation of organic functional molecules into the pore structures of support materials, giving place to hybrid materials that combine the properties of both composites. These hybrid materials will be of great potential for practical applications, especially for post‐combustion CO2 capture, owing to the increase in CO2 capturing ability and selectivity to CO2 compared to other gases in the flue gas stream. This paper reviews the diverse synthesis routes of bare porous materials and rich functionalities of porous adsorbent materials which will allow further post‐modification to improve their performance in CO2 capture and increase their CO2/N2 and CO2/CH4 selectivity ratios. © 2017 Society of Chemical Industry and John Wiley & Sons, Ltd.