bluuebunny/crossref_metadata_2025 huggingface dataset:
Toward High Thermoelectric Performance of Thiophene and Ethylenedioxythiophene (EDOT) Molecular Wires
Authors: Famili Marjan , Grace Iain M. , Al‐Galiby Qusiy , Sadeghi Hatef , Lambert Colin J.
Published: October 2017

The design of thermoelectric materials for the efficient conversion of waste heat into electricity requires simultaneous tuning of their electrical and thermal conductance. A comparative theoretical study of electron and phonon transport in thiophene and ethylenedioxythiophene (EDOT) based molecular wires is performed. It is shown that modifying thiophene by substituting ethylenedioxy enhances the thermoelectric figure of merit ZT for molecules of the same length. Furthermore, it is demonstrated that the electrical conductance of EDOT‐based wires decays more slowly with length than that of thiophene‐based wires and that their thermal conductance is lower. The room‐temperature ZT of undoped EDOT is found to be rather low. However, doping of EDOT by the electron acceptor tolunenesulfunate increases the Seebeck coefficient and electrical conductance, while decreasing the thermal conductance, leading to a thermoelectric figure of merit as high as ZT = 2.4.
Composite Colloidal Gels Made of Bisphosphonate‐Functionalized Gelatin and Bioactive Glass Particles for Regeneration of Osteoporotic Bone Defects
Authors: Diba Mani , Camargo Winston A. , Brindisi Mariateresa , Farbod Kambiz , Klymov Alexey , Schmidt Stephan , Harrington Matthew J. , Draghi Lorenza , Boccaccini Aldo R. , Jansen John A. , van den Beucken Jeroen J. J. P. , Leeuwenburgh Sander C. G.
Published: October 2017

Injectable composite colloidal gels are developed for regeneration of osteoporotic bone defects through a bottom‐up assembly from bisphosphonate‐functionalized gelatin and bioactive glass particles. Upon bisphosphonate functionalization, gelatin nanoparticles show superior adhesion toward bioactive glass particles, resulting in elastic composite gels. By tuning their composition, these composite colloidal gels combine mechanical robustness with self‐healing ability. The composite colloidal gels support cell proliferation and differentiation in vitro without requiring any osteogenic supplement. In vivo evaluation of the composite colloidal gels reveals their capacity to support the regeneration of osteoporotic bone defects. Furthermore, the bisphosphonate modification of gelatin induces a therapeutic effect on the peri‐implantation region by enhancing the bone density of the osteoporotic bone tissue. Consequently, these composite colloidal gels offer new therapeutic opportunities for treatment of osteoporotic bone defects.
Tunable Near‐Infrared Organic Nanowire Nanolasers
Authors: Wang Xuedong , Li Zhi‐Zhou , Zhuo Ming‐Peng , Wu Yishi , Chen Shuo , Yao Jiannian , Fu Hongbing
Published: October 2017

Organic semiconductor nanowires have inherent advantages, such as amenability to low‐cost, low‐temperature processing, and inherent four‐level energy systems, which will significantly contribute to the organic solid‐state lasers (OSSLs) and miniaturized laser devices. However, the realization of near‐infrared (NIR) organic nanowire lasers is always a big challenge due to the difficultly in fabrication of organic nanowires with diameters of ≈100 nm and material issues such as low photoluminescence quantum efficiency in the red‐NIR region. What is more, the achievement of wavelength‐tunable OSSLs has also encountered enormous challenge. This study first demonstrates the 720 nm NIR lasing with a low lasing threshold of ≈1.4 µJ cm−2 from the organic single‐crystalline nanowires, which are self‐assembled from small organic molecules of (E)‐3‐(4‐(dimethylamino)‐2‐methoxyphenyl)‐1‐(1‐hydroxynaphthalen‐2‐yl)prop‐2‐en‐1‐one through a facile solution‐phase growth method. Notably, these individual nanowires' Fabry–Pérot cavity can alternatively provide the red‐NIR lasing action at 660 or 720 nm from the 0–1 or 0–2 radiative transition channels, and the single (660 or 720 nm)/dual‐wavelength (660 and 720 nm) laser action can be achieved by modulating the length of these organic nanowires due to the intrinsic self‐absorption. These easily‐fabricated organic nanowires are natural laser sources, which offer considerable promise for coherent light devices integrated on the optics microchip.
Spiro‐Bridged Ladder‐Type Oligo(para‐phenylene)s: Fine Tuning Solid State Structure and Optical Properties
Authors: Kobin Björn , Schwarz Jutta , Braun‐Cula Beatrice , Eyer Moritz , Zykov Anton , Kowarik Stefan , Blumstengel Sylke , Hecht Stefan
Published: October 2017

A set of ladder‐type quaterphenyls with an incremental number of spiro‐bifluorene units in the bridge positions as well as an in‐plane bent quaterphenyl carrying all bridges on one and the same side of the ribbon are synthesized and characterized. While spiro‐bifluorene substituents lead to bathochromically shifted maxima in the UV–vis absorption spectra, this effect can be compensated by in‐plane bending. The influence of different deposition techniques on the solid state structure is analyzed by X‐ray diffraction of single crystals obtained by crystallization from solution as well as sublimation. An increasing number of spiro‐bifluorene substituents are found to aid thin‐film formation.
Organ‐On‐A‐Chip Platforms: A Convergence of Advanced Materials, Cells, and Microscale Technologies
Authors: Ahadian Samad , Civitarese Robert , Bannerman Dawn , Mohammadi Mohammad Hossein , Lu Rick , Wang Erika , Davenport‐Huyer Locke , Lai Ben , Zhang Boyang , Zhao Yimu , Mandla Serena , Korolj Anastasia , Radisic Milica
Published: October 2017

Significant advances in biomaterials, stem cell biology, and microscale technologies have enabled the fabrication of biologically relevant tissues and organs. Such tissues and organs, referred to as organ‐on‐a‐chip (OOC) platforms, have emerged as a powerful tool in tissue analysis and disease modeling for biological and pharmacological applications. A variety of biomaterials are used in tissue fabrication providing multiple biological, structural, and mechanical cues in the regulation of cell behavior and tissue morphogenesis. Cells derived from humans enable the fabrication of personalized OOC platforms. Microscale technologies are specifically helpful in providing physiological microenvironments for tissues and organs. In this review, biomaterials, cells, and microscale technologies are described as essential components to construct OOC platforms. The latest developments in OOC platforms (e.g., liver, skeletal muscle, cardiac, cancer, lung, skin, bone, and brain) are then discussed as functional tools in simulating human physiology and metabolism. Future perspectives and major challenges in the development of OOC platforms toward accelerating clinical studies of drug discovery are finally highlighted.
Planar‐Structure Perovskite Solar Cells with Efficiency beyond 21%
Authors: Jiang Qi , Chu Zema , Wang Pengyang , Yang Xiaolei , Liu Heng , Wang Ye , Yin Zhigang , Wu Jinliang , Zhang Xingwang , You Jingbi
Published: October 2017

Low temperature solution processed planar‐structure perovskite solar cells gain great attention recently, while their power conversions are still lower than that of high temperature mesoporous counterpart. Previous reports are mainly focused on perovskite morphology control and interface engineering to improve performance. Here, this study systematically investigates the effect of precise stoichiometry, especially the PbI2 contents on device performance including efficiency, hysteresis and stability. This study finds that a moderate residual of PbI2 can deliver stable and high efficiency of solar cells without hysteresis, while too much residual PbI2 will lead to serious hysteresis and poor transit stability. Solar cells with the efficiencies of 21.6% in small size (0.0737 cm2) and 20.1% in large size (1 cm2) with moderate residual PbI2 in perovskite layer are obtained. The certificated efficiency for small size shows the efficiency of 20.9%, which is the highest efficiency ever recorded in planar‐structure perovskite solar cells, showing the planar‐structure perovskite solar cells are very promising.
Realization of High‐Performance Screen‐Printed Flexible Thermoelectric Generator by Improving Contact Characteristics
Authors: Kim Yong Jun , Kim Sun Jin , Choi Hyeongdo , Kim Choong Sun , Lee Gyusoup , Park Sang Hyun , Cho Byung Jin
Published: October 2017

To fabricate a flexible thermoelectric generator (f‐TEG) that can be applied to curvilinear surfaces such as the human body, the screen‐printing technique is a practical method for forming the thermoelectric (TE) elements. One of the main obstacles to fabricating high‐performance screen‐printed f‐TEGs is the high contact resistance. In this work, the output power of a screen‐printed f‐TEG is increased by 80% through engineering of the contact and its formation process. Reduction ambient annealing is a process that removes the surface oxides while modulating the tellurium (Te) concentration on the surface, easily forming a favorable intermetallic compound at the contact interface. The wetting angle of the solder is also drastically reduced by applying an anti‐diffusion bilayer. Using these methods, the specific contact resistivity (ρC) is reduced from 8.2 to 3.3 × 10−6 Ω cm−2 and 75 to 4.7 × 10−6 Ω cm−2 for p‐ and n‐type TE material respectively. The device figure of merit measured for one leg is increased from 0.301 to 0.595 and 0.247 to 0.481 for p‐ and n‐type respectively. The improved contact characteristics result in an increase in the output power of the complete module (a 72‐couple f‐TEG) from 0.25 to 0.4 W at a temperature difference of 40K.
Manipulating Superparamagnetic Microparticles with an Electromagnetic Needle
Authors: Cenev Zoran , Zhang Hongbo , Sariola Veikko , Rahikkala Antti , Liu Dongfei , Santos Hélder A. , Zhou Quan
Published: October 2017

Selective, precise, and high‐throughput manipulation of individual superparamagnetic microparticles has profound applications in performing location‐tailored in vitro biomedical studies. The current techniques for manipulation of microparticles allow only a single particle in the manipulation workspace, or simultaneous transportation of multiple microparticles in batches. In this work, a method based on a robotized electromagnetic needle for manipulation of individual superparamagnetic microparticles within a microparticle population is introduced. By automatically controlling the highly localized magnetic field of the needle, a single microparticle is selectively picked when its neighboring particle is few micrometers away. Supported by the nanometer resolution of the robotic positioner, particles are placed at sub‐micrometer precision. This manipulation technique allows the creating of arbitrary patterns, sorting of microparticles based on size and morphology, and transporting of individual microparticles in 3D space. Therefore, this approach has the potential to enable more deterministic and quantitative microanalysis and microsynthesis using superparamagnetic microparticles.
Monitoring Personalized Learning Curves for Emergency Ultrasound With Risk‐adjusted Learning‐curve Cumulative Summation Method
Authors: Peyrony Olivier , Legay Léa , Morra Ivonne , Verrat Anne , Milacic Hélène , Franchitti Jessica , Amami Jihed , Gillet Ariane , Azarnoush Kouchiar , Elezi Arben , Bragança Adélia , Taboulet Pierre , Bourrier Pierre , Fontaine Jean‐Paul , Resche‐Rigon Matthieu
Published: October 2017

Background

Ultrasound (US) has been a regular practice in emergency departments for several decades. Thus, train our students to US is of prime interest. Because US image acquisition ability can be very different from a patient to another (depending on image quality), it seems relevant to adapt US learning curves (LCs) to patient image quality using tools based on cumulative summation (CUSUM) as the risk‐adjusted LC CUSUM (RLC).

Objectives

The aim of this study was to monitor LC of medical students for the acquisition of abdominal emergency US views and to adapt these curves to patient image quality using RLC.

Methods

We asked medical students to perform abdominal US examinations with the acquisition of 11 views of interest on emergency patients after a learning session. Emergency physicians reviewed the student examinations for validation. LCs were plotted and the student was said proficient for a specific view if his LC reached a predetermined limit fixed by simulation.

Results

Seven students with no previous experience in US were enrolled. They performed 19 to 50 examinations of 11 views each. They achieve proficiency for a median of 9 (6–10) views. Aorta and right pleura views were validated by seven students; inferior vena cava, right kidney, and bladder by six; gallbladder and left kidney by five; portal veins and portal hilum by four; and subxyphoid and left pleura by three. The number of US examinations required to reach proficiency ranged from five to 41 depending on the student and on the type of view. LC showed that students reached proficiency with different learning speeds.

Conclusions

This study suggests that, when monitoring LCs for abdominal emergency US, there is some heterogeneity in the learning process depending on the student skills and the type of view. Therefore, rules based on a predetermined number of examinations to reach proficiency are not satisfactory.
A Convenient Method for the Direct Acquisition of Kinetic Rate Data for Catalytic Organic Reactions by Gas Uptake Measurements
Authors: Wang Yu‐Jie , Li Wei‐Tang , Jiao Lei
Published: October 2017

Kinetics studies play an indispensable role in determining the mechanism of many catalytic organic reactions. In this context, real‐time rate data, rather than concentration data, have proved particularly valuable for mechanistic analysis. However, methods that can directly yield rate data of sufficiently high quality are still limited. In this paper, a convenient method for the direct measurement of rate profiles of homogeneous catalytic organic reactions that involve a gaseous reactant is described. By integrating a high‐precision pressure controller and an accurate mass flow meter, real‐time rate profiles of catalytic reactions on a research laboratory scale at isobaric conditions could be acquired. The method is precise, easy to implement for most organic chemists, and can produce kinetic data of comparable or even superior quality to established kinetic methods, such as ReactIR. The potential of this method in kinetics studies was demonstrated by the study of the initial rate and reaction progress kinetic analysis of several aerobic oxidation reactions.
Temperature‐Controlled Base‐Promoted Cyclization for the Synthesis of 2‐Amino‐4H‐benzo[d][1,3]thiazin‐4‐ones and 2‐Thioxo‐4(3H)‐quinazolinones
Authors: Zhou Zhi‐Wen , Jia Feng‐Cheng , Xu Cheng , Jiang Shi‐Fen , Wu Yan‐Dong , Wu An‐Xin
Published: October 2017

A base‐promoted and highly selective temperature‐dependent tandem oxidation/decarboxylative cyclization of isothiocyanates and isatins has been developed. This method allows the chemodivergent synthesis of 4H‐benzo[d][1,3]thiazin‐4‐ones and 2‐thioxo‐2,3‐dihydroquinazolin‐4(1H)‐ones in moderate to high yields.
Activation and Deactivation of Gold/Ceria–Zirconia in the Low‐Temperature Water–Gas Shift Reaction
Authors: Carter James H. , Liu Xi , He Qian , Althahban Sultan , Nowicka Ewa , Freakley Simon J. , Niu Liwei , Morgan David J. , Li Yongwang , Niemantsverdriet J. W. (Hans) , Golunski Stanislaw , Kiely Christopher J. , Hutchings Graham J.
Published: October 2017

Gold (Au) on ceria–zirconia is one of the most active catalysts for the low‐temperature water–gas shift reaction (LTS), a key stage of upgrading H2 reformate streams for fuel cells. However, this catalyst rapidly deactivates on‐stream and the deactivation mechanism remains unclear. Using stop–start scanning transmission electron microscopy to follow the exact same area of the sample at different stages of the LTS reaction, as well as complementary X‐ray photoelectron spectroscopy, we observed the activation and deactivation of the catalyst at various stages. During the heating of the catalyst to reaction temperature, we observed the formation of small Au nanoparticles (NPs; 1–2 nm) from subnanometer Au species. These NPs were then seen to agglomerate further over 48 h on‐stream, and most rapidly in the first 5 h when the highest rate of deactivation was observed. These findings suggest that the primary deactivation process consists of the loss of active sites through the agglomeration and possible dewetting of Au NPs.
Ynamide Preactivation Allows a Regio‐ and Stereoselective Synthesis of α,β‐Disubstituted Enamides
Authors: Baldassari Lucas L. , de la Torre Aurélien , Li Jing , Lüdtke Diogo S. , Maulide Nuno
Published: October 2017

A novel ynamide preactivation strategy enables the use of otherwise incompatible reagents and allows preparation of α,β‐disubstituted enamides with high regio‐ and stereoselectivity. Mechanistic analysis reveals the intermediacy of a triflate‐bound intermediate as a solution‐stable, effective keteniminium reservoir, whilst still allowing subsequent addition of organometallic reagents.
Ferrocene‐substituted bis(ethynyl)anthracene compounds as anticancer agents
Authors: Singh Ajeet , Kumari Pratibha , Raghuvanshi Abhinav , Mobin Shaikh M. , Mathur Pradeep
Published: October 2017

Three compounds (1–3) were synthesized, where ethynylferrocene is substituted at different positions of anthracene and anthraquinone, and their biological properties were investigated. Compounds 1–3 were characterized using NMR and mass spectroscopies and confirmed by their single‐crystal X‐ray structure. They were also characterized from electronic and photophysical properties. All three crystal structures were optimized using density functional theory calculations. The presence of C–H⋅⋅⋅π interactions in 1–3 leads to the formation of two‐ and three‐dimensional networks. The bioactivity of 1–3 was expressed by molecular docking with various cancerous proteins, which participated in progression of cancer. Compound 2 displayed the best interaction with cancer‐related Aurora A protein in terms of both binding energy (−10.61 kcal mol−1) as well as inhibition constant (16.74 nM). The molecular docking result also coincides with cytotoxicity on cancer cell lines (A375, HeLa) and DNA/protein binding affinity.
Novel water soluble bis(μ‐chloro) bridged Cu(II) binuclear and mononuclear complexes: Synthesis, characterization and biological evaluation
Authors: Thirunavukkarasu Thangavel , Puschmann H. , Sparkes H.A. , Natarajan Karuppannan , Gnanasoundari V.G.
Published: October 2017

A water soluble chloro bridged binuclear copper(II) complex (3) and mononuclear complex (4) have been synthesized from chloro substituted 2‐oxo‐1,2‐dihydroquinolin‐3‐yl‐methylene‐2 hydroxybenzohydrazide 1 and 2 and CuCl2·2H2O. The structures of the complexes have been determined by single crystal X‐ray diffraction. The binding interactions of the ligands and complexes with CT‐DNA and protein have been evaluated by absorption and emission spectroscopic method. CT‐DNA and ethidium bromide (EB) competitive studies revealed that the compounds could interact with CT‐DNA through intercalation binding mode. Interactions of the compounds with BSA were also studied by UV−visible, fluorescence and synchronous fluorescence spectroscopic methods which showed that the compounds had a strong binding affinity with BSA through static quenching process. The cytotoxic effect of the compounds examined on cancer cell lines, such as A549 (lung cancer) and MCF7 (breast cancer) cell lines showed that all four compounds exhibited substantial cytotoxic activity.
Design, Synthesis, and Screening of Triazolopyrimidine–Pyrazole Hybrids as Potent Apoptotic Inducers
Authors: Kamal Raj , Kumar Vipan , Kumar Ravinder , Bhardwaj Jitender K. , Saraf Priyanka , Kumari Priya , Bhardwaj Vikas
Published: October 2017

An efficient synthesis of novel 3‐(3‐aryl‐1‐phenyl‐1H‐pyrazol‐4‐yl)‐5,7‐dimethyl‐[1,2,4]triazolo[4,3‐a]‐pyrimidines was accomplished by the oxidation of pyrimidinylhydrazones by using organoiodine(III) reagent. All new triazolopyrimidine derivatives bearing the pyrazole scaffold were screened to evaluate them as a reproductive toxicant in the testicular germ cells of goat (Capra hircus). This study aimed at assessing the cytological and biochemical changes in testicular germ cells after the exposure to triazolopyrimidines in a dose‐ and time‐dependent manner. Histomorphological analysis, fluorescence assays, apoptosis quantification, and terminal deoxynucleotidyl transferase dUTP‐mediated nick‐end labeling (TUNEL) assays were performed to determine cytological changes, whereas thiobarbituric acid‐reactive substance (TBARS) and ferric reducing antioxidant power (FRAP) assays were carried out to measure the oxidative stress in triazolopyrimidines treated germ cells. The parallel use of these methods enabled us to determine the role of triazolopyrimidines in inducing apoptosis as a consequence of cytogenetic damage and oxidative stress generated in testicular germ cells of goat.
Altered Electroencephalography Spectral Profiles in Rats with Different Patterns of Experimental Brain Dysplasia
Authors: Kielbinski Michal , Setkowicz Zuzanna , Gzielo Kinga , Węglarz Władysław , Janeczko Krzysztof
Published: October 2017

BACKGROUND

Malformations of cortical development, such as focal cortical dysplasia, are commonly associated with intractable epilepsy. Multiple animal models were created in attempts to recapitulate features of human malformations of cortical development. These manipulations give rise to various focal or diffuse anatomical abnormalities, accompanied by altered susceptibility to epileptic seizures. Both in humans and in models of dysplasia, the question of timing of the initiating insult is important.

METHODS

Here, we used a rat model of cerebral dysplasia elicited by prenatal irradiation at gestational days (E) 13, 15, 17, or 19. Previous results suggest these animals are characterized by different patterns of dysplasia as well as different reactivity to seizurogenic stimuli in several seizure models. Rats were implanted with telemetric electroencephalography (EEG) transmitters. We compared EEG data from freely moving animals with anatomical observations obtained with MRI, as well as Western blotting and immunohistochemistry.

RESULTS

We performed spectral analyses of EEG signal, revealing differential regulation of specific bands (including delta, theta, alpha‐beta, gamma) in animals with different patterns of dysplasia. Relative contribution of low‐frequency activity in delta band is the lowest in E15 and the highest in E19. Conversely, higher frequency bands, corresponding to alpha/beta and gamma components, are reduced in E15 versus E19. This is accompanied by altered expression of glial markers in the E19 group.

CONCLUSION

To our knowledge, this constitutes the first quantitative description of power spectral properties in this experimental model, providing insight into mechanisms underlying the anatomical and electrophysiological abnormalities associated with brain dysplasia of different types. Birth Defects Research, 110:303–316, 2018. © 2017 Wiley Periodicals, Inc.
Enhanced pyruvate production in Candida glabrata by carrier engineering
Authors: Luo Zhengshan , Liu Song , Du Guocheng , Xu Sha , Zhou Jingwen , Chen Jian
Published: October 2017

Pyruvate is an important organic acid that plays a key role in the central metabolic pathway. Manipulating transporters is an efficient strategy to enhance production of target organic acids and a means to understand the effects of altered intracellular pyruvate content on global metabolic networks. Efforts have been made to manipulate mitochondrial pyruvate carrier (MPC) to transport pyruvate into different subcellular compartments in Candida glabrata to demonstrate the effects of the subcellular distribution of pyruvate on central carbon metabolism. By increasing the mitochondrial pyruvate content through enhancing the rate of pyruvate transport into mitochondria, a high central carbon metabolism rate, specific growth rate and specific pyruvate production rate were obtained. Comparing the intracellular pyruvate content of engineered and control strains showed that higher intracellular pyruvate levels were not conducive to improving pyruvate productivity or central carbon metabolism. Plasma membrane expression of MPCs significantly increased the expression levels of key rate‐limiting glycolytic enzymes. Moreover, pyruvate production of CGΔura3‐Sp‐MPC1, CGΔura3‐Sp‐MPC2, and CGΔura3‐Sp‐MPC1‐Sp‐MPC2 increased 134.4%, 120.3%, and 30.0%, respectively. In conclusion, lower intracellular pyruvate content enhanced central carbon metabolism and provided useful clues for improving the production of other organic acids in microorganisms.
Impact of marital status at diagnosis on survival and its change over time between 1973 and 2012 in patients with nasopharyngeal carcinoma: a propensity score‐matched analysis
Authors: Xu Cheng , Liu Xu , Chen Yu‐Pei , Mao Yan‐Ping , Guo Rui , Zhou Guan‐Qun , Tang Ling‐Long , Lin Ai‐Hua , Sun Ying , Ma Jun
Published: October 2017

The impact of marital status at diagnosis on survival outcomes and its change over time in patients with nasopharyngeal carcinoma (NPC) are unclear. The Surveillance, Epidemiology, and End Results (SEER) database was used to identify patients diagnosed with NPC in the United States from 1973 to 2012. A primary comparison (married vs. unmarried) was implemented with 1:1 propensity score matching. Secondary comparisons were performed individually between three unmarried subgroups (single, separated/divorced, widowed) and married group. The effect of marital status on cause‐specific survival (CSS) and overall survival (OS) were evaluated using univariate/multivariate analysis. Moreover, we investigated the change over time (1973–2012) in the effect of marital status on NPC survival. Married patients had better 5‐year CSS/OS than unmarried patients (61.1% vs. 52.6%, P < 0.001; 55.6% vs. 45.3%, P < 0.001, respectively). In multivariate analysis, unmarried patients had significantly poorer CSS/OS than married patients (adjusted hazard ratio [aHR] = 1.35, P < 0.001; aHR = 1.40, P < 0.001, respectively). The survival benefit of being married was only detected in non‐Hispanic white and Chinese American patients. Single, separated/divorced, and widowed patients had significantly poorer CSS/OS than married patients (aHR = 1.37 and 1.37; 1.46 and 1.42; 1.43 and 1.48, respectively; all P < 0.001). The change over time in the effect of marital status on survival was more stable in male than female. The strength of the negative effect of separated/divorced and widowed status showed a downward and upward trend, respectively. Gender difference in the adverse effect of single status on NPC survival became smaller over time. Only non‐Hispanic white and Chinese American patients with NPC obtain survival benefits from married status. Single and widowed patients are regarded as high‐risk population
A Flexible Polyphosphate‐Driven Regeneration System for Coenzyme A Dependent Catalysis
Authors: Mordhorst Silja , Maurer Alice , Popadić Désirée , Brech Johanna , Andexer Jennifer N.
Published: October 2017

Coenzyme A (CoA) is a common cofactor in biochemical reactions, and CoA‐dependent enzymes catalyze essential steps in anabolism and catabolism. This complex molecule also plays an important role in the synthesis of many high‐value products, such as synthetic antibiotics, vitamins, pheromones, and biopolymers. Nevertheless, the synthetic potential for biocatalytic processes cannot be fully exploited owing to the lack of an efficient regeneration system. Here, we report an acyl‐CoA regeneration system with integrated adenosine triphosphate (ATP) regeneration that is based on inexpensive polyphosphate as the single energy source. In the four‐enzyme cascade, two cofactors, acyl‐CoA and ATP, are each regenerated up to 2000 times. The applicability for different acyl donors and acceptors is shown by HPLC analysis. Owing to its flexibility toward virtually all relevant substrates, the system has the potential to make CoA‐dependent reactions more accessible for chemical synthesis in vitro.
Spectroelectrochemical Investigation of the Charge Carrier Kinetics of Gold‐Decorated Cadmium Chalcogenide Nanorods
Authors: Miethe Jan F. , Lübkemann Franziska , Poppe Jan , Steinbach Frank , Dorfs Dirk , Bigall Nadja C.
Published: October 2017

The interfacial transfer of charge carriers across the semiconductor nanoparticle/electrolyte boundary is an elementary process for applications such as photoelectrochemical sensing and photocatalysis. This mechanism is investigated for systems based on complex shaped semiconductor and metal‐semiconductor nano‐heteroparticles. In the present work the influence of the presence of a CdSe domain within the CdS nanorod as well as the influence of gold domain decoration is investigated spectroelectrochemically. Therefore, the mentioned nanoparticles are linked to transparent indium tin oxide (ITO) glass slides via (3‐mercaptopropyl)trimethoxysilane (MPTMS). This preparation yields sub‐monolayers of the particles. External photocurrent quantum efficiency spectra are measured in the range from λ=350–650 nm. Intensity‐modulated photocurrent spectroscopy (IMPS) and electrochemical impedance spectroscopy (EIS) measurements are applied to the samples in order to reveal and explain the differences of the electrochemical kinetics between the four different particle types (CdS, CdSe/CdS, CdS−Au, and CdSe/CdS−Au nanorods). We demonstrate that the presence of gold domains affects the carrier dynamics of various involved processes. An equivalent circuit model is derived and fitted to the impedance data to explain changes of the kinetics in the system.
Model Macrocyclic Ligands for Proof‐of‐Concept Mechanistic Studies in Transition‐Metal Catalysis
Authors: Ribas Xavi , Devillard Marc
Published: October 2017

In this Concept article, we will scrutinize different approaches devoted to the mechanistic understanding of catalytic processes, paying special attention to the successful use of triazamacrocyclic aryl‐halide or arene‐containing substrates used for Cu‐, Ag‐, Au‐, Co‐ and Ni‐catalysis. The importance of designing model substrate platforms to unravel mechanistic details at a molecular level of C−C or C‐heteroatom bond‐forming processes catalyzed by transition metals will be highlighted. This fundamental mechanistic knowledge will serve as a foundation for the catalyst design for a desired transformation.
Inside Cover: Effect of Brønsted/Lewis Acid Ratio on Conversion of Sugars to 5‐Hydroxymethylfurfural over Mesoporous Nb and Nb‐W Oxides (Chin. J. Chem. 10/2017)
Authors: Guo Bin , Ye Lin , Tang Gangfeng , Zhang Li , Yue Bin , Tsang Shik Chi Edman , He Heyong
Published: October 2017

The inside cover picture shows the excellent catalytic performance of mesoporous Nb and Nb‐W oxides catalysts for the conversion of glucose to 5‐hydroxymethylfurfural. The catalytic activity and selectivity for all Nb‐W oxides vary according to the ratio of Brønsted to Lewis acid sites. The highest HMF selectivity of 52% was achieved over Nb7W3 oxide catalyst. More details are discussed in the article by He et al. on page 1529–1539.

image
Patterns of BAP1 protein expression provide insights into prognostic significance and the biology of uveal melanoma
Authors: Farquhar Neil , Thornton Sophie , Coupland Sarah E , Coulson Judy M , Sacco Joseph J , Krishna Yamini , Heimann Heinrich , Taktak Azzam , Cebulla Colleen M , Abdel‐Rahman Mohamed H , Kalirai Helen
Published: October 2017

Uveal melanoma (UM) is a rare aggressive intraocular tumour with a propensity for liver metastases, occurring in ∼50% of patients. The tumour suppressor BAP1 is considered to be key in UM progression. Herein, we present the largest study to date investigating cellular expression patterns of BAP1 protein in 165 UMs, correlating these patterns to prognosis. Full clinical, histological, genetic, and follow‐up data were available for all patients. BAP1 gene sequencing was performed on a subset of 26 cases. An independent cohort of 14 UMs was examined for comparison. Loss of nuclear BAP1 (nBAP1) protein expression was observed in 54% (88/165) UMs. nBAP1 expression proved to be a significant independent prognostic parameter: it identified two subgroups within monosomy 3 (M3) UM, which are known to have a high risk of metastasis. Strikingly, nBAP1‐positiveM3 UMs were associated with prolonged survival compared to nBAP1‐negative M3 UMs (Log rank, p = 0.014). nBAP1 protein loss did not correlate with a BAP1 mutation in 23% (6/26) of the UMs analysed. Cytoplasmic BAP1 protein (cBAP1) expression was also observed in UM: although appearing ‘predominantly diffuse’ in most nBAP1‐negative UM, a distinct ‘focal perinuclear’ expression pattern – localized immediately adjacent to the cis Golgi – was seen in 31% (18/59). These tumours tended to carry loss‐of‐function BAP1 mutations. Our study demonstrates loss of nBAP1 expression to be the strongest prognostic marker in UM, confirming its importance in UM progression. Our data suggest that non‐genetic mechanisms account for nBAP1 loss in a small number of UMs. In addition, we describe a subset of nBAP1‐negative UM, in which BAP1 is sequestered in perinuclear bodies, most likely within Golgi, warranting further mechanistic investigation.
Standard of nearly zero energy buildings in Germany
Authors: Schöndube Tim , Carrigan Svenja , Schoch Torsten , Kornadt Oliver
Published: October 2017

The European Union intends to reduce the energy consumption in the building sector. The European Directive 2010/31/EU requires the definition of national standards for nearly zero energy buildings. This article presents a research study supported as part of the research initiative “Zukunft Bau” of the Federal Ministry for the Environment, Nature Conservation, Building and Nuclear Safety for the definition of a nearly zero energy building standard for new buildings in Germany. First, the methodology is discussed, then the first results of a variant study on a model building are presented and discussed.
Ecosystem regime shifts disrupt trophic structure
Authors: Hempson Tessa N. , Graham Nicholas A. J. , MacNeil M. Aaron , Hoey Andrew S. , Wilson Shaun K.
Published: October 2017

Regime shifts between alternative stable ecosystem states are becoming commonplace due to the combined effects of local stressors and global climate change. Alternative states are characterized as substantially different in form and function from pre‐disturbance states, disrupting the delivery of ecosystem services and functions. On coral reefs, regime shifts are typically characterized by a change in the benthic composition from coral to macroalgal dominance. Such fundamental shifts in the benthos are anticipated to impact associated fish communities that are reliant on the reef for food and shelter, yet there is limited understanding of how regime shifts propagate through the fish community over time, relative to initial or recovery conditions. This study addresses this knowledge gap using long‐term data of coral reef regime shifts and recovery on Seychelles reefs following the 1998 mass bleaching event. It shows how trophic structure of the reef fish community becomes increasingly dissimilar between alternative reef ecosystem states (regime‐shifted vs. recovering) with time since disturbance. Regime‐shifted reefs developed a concave trophic structure, with increased biomass in base trophic levels as herbivorous species benefitted from increased algal resources. Mid trophic level species, including specialists such as corallivores, declined with loss of coral habitat, while biomass was retained in upper trophic levels by large‐bodied, generalist invertivores. Recovering reefs also experienced an initial decline in mid trophic level biomass, but moved toward a bottom‐heavy pyramid shape, with a wide range of feeding groups (e.g., planktivores, corallivores, omnivores) represented at mid trophic levels. Given the importance of coral reef fishes in maintaining the ecological function of coral reef ecosystems and their associated fisheries, understanding the effects of regime shifts on these communities is essential to inform decisions that enhance ecological resilience and economic sustainability.
The modeled cost‐effectiveness of family‐based and adolescent‐focused treatment for anorexia nervosa
Authors: Le Long Khanh‐Dao , Barendregt Jan J. , Hay Phillipa , Sawyer Susan M. , Hughes Elizabeth K. , Mihalopoulos Cathrine
Published: October 2017

Background

Anorexia nervosa (AN) is a prevalent, serious mental disorder. We aimed to evaluate the cost‐effectiveness of family‐based treatment (FBT) compared to adolescent‐focused individual therapy (AFT) or no intervention within the Australian healthcare system.

Method

A Markov model was developed to estimate the cost and disability‐adjusted life‐year (DALY) averted of FBT relative to comparators over 6 years from the health system perspective. The target population was 11–18 year olds with AN of relatively short duration. Uncertainty and sensitivity analyses were conducted to test model assumptions. Results are reported as incremental cost‐effectiveness ratios (ICER) in 2013 Australian dollars per DALY averted.

Results

FBT was less costly than AFT. Relative to no intervention, the mean ICER of FBT and AFT was $5,089 (95% uncertainty interval (UI): dominant to $16,659) and $51,897 ($21,591 to $1,712,491) per DALY averted. FBT and AFT are 100% and 45% likely to be cost‐effective, respectively, at a threshold of AUD$50,000 per DALY averted. Sensitivity analyses indicated that excluding hospital costs led to increases in the ICERs but the conclusion of the study did not change.

Conclusion

FBT is the most cost‐effective among treatment arms, whereas AFT was not cost‐effective compared to no intervention. Further research is required to verify this result.
The cost‐effectiveness of cognitive behavioral therapy for bulimia nervosa in the Australian context
Authors: Le Long Khanh‐Dao , Hay Phillipa , Wade Tracey , Touyz Stephen , Mihalopoulos Cathrine
Published: October 2017

Objective

This study was to model the cost‐effectiveness of specialist‐delivered cognitive behavioral therapy for bulimia nervosa (CBT‐BN) compared to no intervention within the Australian context.

Method

An illness‐death model was developed to estimate the cost per disability‐adjusted life‐year (DALY) averted of CBT‐BN over 2 years from the healthcare perspective. Target population was adults aged 18–65 years with BN. Results are reported as incremental cost‐effectiveness ratios (ICER) in 2013 Australian dollars per DALY averted. Uncertainty and sensitivity analyses were conducted to test the robustness of results.

Results

Primary analysis indicated that CBT‐BN was associated with greater DALY averted (0.10 DALY per person) and higher costs ($1,435 per person) than no intervention, resulting the mean ICER of $14,451 per DALY averted (95% uncertainty interval [UI]: $8,762 to $35,650). Uncertainty analysis indicated CBT‐BN is 99% likely to be cost‐effective at a threshold of $50,000 per DALY averted. Including the patients' time and travel costs resulted in the mean ICER of $18,858 per DALY averted (95% UI: $11,235 to $46,026). Sensitivity analysis indicated the intervention was not cost‐effective if over 80% people discontinued treatment. Other analyses including a reduced time horizon, increased remission rates, and 4‐month effect size of CBT‐BN increases the ICERs but these ICERs remained well below under a threshold of $50,000 per DALY averted.

Conclusion

This study has demonstrated that CBT‐BN for adults with BN is a cost‐effective treatment intervention. Further research is required to investigate the practicability of CBT‐ED and the cost‐effectiveness of other formats of CBT‐BN delivery.
Resin monoterpene defenses decline within three widespread species of pine (Pinus) along a 1530‐m elevational gradient
Authors: Ferrenberg Scott , Langenhan Joseph M. , Loskot Steven A. , Rozal Leonardo M. , Mitton Jeffry B.
Published: October 2017

The elevational gradient in plant defense (EGPD) hypothesis posits that natural enemy pressures increase alongside temperature across elevational climatic gradients, thereby selecting for enhanced defenses at lower elevations while leaving plants less defended at higher elevations. Phylogenetically constrained tests of this hypothesis are uncommon, with tests focused on defenses of mature trees in natural settings being exceedingly rare. In the absence of this information, predicting the spatiotemporal dynamics of forest pests that preferentially attack mature trees is rendered more difficult. Tree properties such as age, growth rate, and size have all been correlated with levels of tree defenses against insect pests. Thus, we sought to disentangle the interacting influences of these properties from possible elevational climatic effects on monoterpene concentrations, diversity, and intraspecific dissimilarity of constitutive resin within three widespread pines (Pinus contorta, Pinus ponderosa, and Pinus flexilis) across a 1530‐m elevational transect in the Rocky Mountains, Colorado, USA. Overall, we found some support for the EGPD hypothesis within all three of the pine species studied. However, while elevation and tree properties were strong predictors of the variation in monoterpene concentration and moderate predictors of variation in diversity and dissimilarity in P. contorta, they were a relatively weak set of predictors in P. ponderosa and P. flexilis. Significant, (negative) elevational effects were found for total monoterpene concentration in P. contorta and monoterpene diversity in P. ponderosa, while elevation had a significant negative effect on monoterpene concentration and diversity, and a positive effect on dissimilarity in P. flexilis. Nevertheless, tree age, size, and/or growth measures had significant influences on one or more monoterpene measures in all three of the pine species indicating a need to parse effects of these factors within studies of tree defenses across environmental gradients. Our results offer some support for the EGPD hypothesis while suggesting the presence of a variable hierarchy of drivers of pine defense and resistance across congeners in shared environments—a situation that presents challenges for predicting spatiotemporal patterns in secondary chemistry across species from a common set of potential drivers.
Synthesis of Spiro[2.2]pentanes and Spiro[2.3]hexanes Employing the Me3Al/CH2I2 Reagent
Authors: Ramazanov Ilfir R. , Kadikova Rita N. , Zosim Tat'yana P. , Dzhemilev Usein M. , de Meijere Armin
Published: October 2017

Substituted alkylidenecyclopropanes reacted with 5 equivalents each of Me3Al and CH2I2 at room temperature in hexane to give 1‐mono‐ and 1,1‐disubstituted spiro[2.2]pentanes in high yields. Surprisingly, the same reaction with substituted alkylidenecyclopropanes in CH2Cl2 afforded exclusively 1,1‐disubstituted spiro[2.3]hexanes. The transformation of 1,1‐diphenylspiro[2.2]pentane into 1,1‐diphenylspiro[2.3]hexane was studied with the use of CD2I2 and a plausible mechanism was suggested. The reaction of substituted alkylidenecyclobutanes with the Me3Al/CH2I2 reagent in CH2Cl2 gave only 1,1‐disubstituted spiro[2.3]hexanes.
Synthesis of Benzo[k]fluoranthene Derivatives through Diels–Alder Reaction of 1,3‐Diarylbenzo[c]furans
Authors: Karunakaran Jayachandran , Mohanakrishnan Arasambattu K.
Published: October 2017

Diels–Alder reaction of symmetrical/unsymmetrical benzo[c]furans with acenaphthylene in xylenes at reflux temperatures followed by p‐toluenesulfonic acid‐mediated epoxide cleavage and dehydration furnished diaryl/heteroaryl‐substituted benzo[k]fluoranthenes. This strategy could be successfully applied to the synthesis of dimeric and trimeric benzo[k]fluoranthenes. Functionalization of representative benzo[k]fluoranthene derivatives was also performed. UV/Visible, emission and electrochemical properties of representative fluoranthene derivatives are also reported.
Direct Synthesis of Symmetric Diarylethynes from Calcium Carbide and Arylboronic Acids/Esters
Authors: Fu Rugang , Li Zheng
Published: October 2017

A new methodology for the direct synthesis of symmetric diarylethynes from the reactions of calcium carbide with arylboronic acids/esters is described. Various symmetric diarylethynes were generated from the corresponding arylboronic acids/esters in satisfactory yield by using a palladium catalyst. The advantages of this protocol include the use of a readily available and easy‐to‐handle acetylene source, and a simple work‐up procedure.
Association of insomnia severity with well‐being, quality of life and health care costs: A cross‐sectional study in older adults with chronic pain (PainS65+)
Authors: Dragioti E. , Bernfort L. , Larsson B. , Gerdle B. , Levin L.Å.
Published: October 2017

Background

Insomnia is one of the most common complaints in chronic pain. This study aimed to evaluate the association of insomnia with well‐being, quality of life and health care costs.

Methods

The sample included 2790 older individuals (median age = 76; interquartile range [IQR] = 70–82) with chronic pain. The participants completed a postal survey assessing basic demographic data, pain intensity and frequency, height, weight, comorbidities, general well‐being, quality of life and the insomnia severity index (ISI). Data on health care costs were calculated as costs per year (€ prices) and measured in terms of outpatient and inpatient care, pain drugs, total drugs and total health care costs.

Results

The overall fraction of clinical insomnia was 24.6% (moderate clinical insomnia: 21.9% [95% CI: 18.8–23.3]; severe clinical insomnia: 2.7% [95% CI: 1.6–3.2]). Persons who reported clinical insomnia were more likely to experience pain more frequently with higher pain intensity compared to those reported no clinically significant insomnia. Mean total health care costs were € 8469 (95% CI: €4029‐€14,271) for persons with severe insomnia compared with € 4345 (95% CI: €4033‐€4694) for persons with no clinically significant insomnia. An association between severe insomnia, well‐being, quality of life, outpatient care, total drugs costs and total health care costs remained after controlling for age, sex, pain intensity, frequency, body mass index and comorbidities using linear regression models.

Conclusions

Our results determine an independent association of insomnia with low health‐related quality of life and increased health care costs in older adults with chronic pain.

Significance

The concurrence and the severity of insomnia among older adults with chronic pain were associated with decreased well‐being and quality of life, and increased health care costs to society.
Polyacrylonitrile Nanoparticle‐Derived Hierarchical Structure for CO2 Capture
Authors: Beltzung Anna , Klaue Antoine , Colombo Claudio , Wu Hua , Storti Giuseppe , Morbidelli Massimo
Published: October 2017

The production of porous clusters by controlled aggregation of polyacrylonitrile nanoparticles and thermal treatment, and their application to CO2 capture are reported. The synthesis of the primary particles by emulsion polymerization exhibits good reproducibility and is easy to scale up. The subsequent gelation of the produced latexes (controlled destabilization by salt addition) results in the formation of macroporous monoliths of nanoparticles with a mean pore diameter of 100 nm. A carefully assessed thermal treatment is applied to the dried monolith after grinding. The produced porous clusters are processed with three high‐temperature steps: oxidation, stabilization, and pyrolysis. The latter allows for the creation of micropores in the initially non‐porous nanoparticles, thus enabling access to the remaining nitrogen‐bearing species present in the pyrolyzed polymer. The relative contributions of the remaining nitrogen‐bearing species and of the micropores are elucidated by applying different oxidation temperatures. In particular, the fraction of the pores with diameter smaller than 0.7 nm is decisive in determining the final capture ability. After a treatment including oxidation at 240 °C, stabilization at 350 °C, and pyrolysis at 900 °C, the best reported material shows an average CO2 adsorption capacity of 3.56±0.17 mol (CO2) kg−1 at 0 °C and 1 atm.