bluuebunny/crossref_metadata_2025 huggingface dataset:
Side Chain Engineering on Medium Bandgap Copolymers to Suppress Triplet Formation for High‐Efficiency Polymer Solar Cells
Authors: Xue Lingwei , Yang Yankang , Xu Jianqiu , Zhang Chunfeng , Bin Haijun , Zhang Zhi‐Guo , Qiu Beibei , Li Xiaojun , Sun Chenkai , Gao Liang , Yao Jia , Chen Xiaofeng , Yang Yunxu , Xiao Min , Li Yongfang
Published: August 2017

Suppression of carrier recombination is critically important in realizing high‐efficiency polymer solar cells. Herein, it is demonstrated difluoro‐substitution of thiophene conjugated side chain on donor polymer can suppress triplet formation for reducing carrier recombination. A new medium bandgap 2D‐conjugated D–A copolymer J91 is designed and synthesized with bi(alkyl‐difluorothienyl)‐benzodithiophene as donor unit and fluorobenzotriazole as acceptor unit, for taking the advantages of the synergistic fluorination on the backbone and thiophene side chain. J91 demonstrates enhanced absorption, low‐lying highest occupied molecular orbital energy level, and higher hole mobility, in comparison with its control polymer J52 without fluorination on the thiophene side chains. The transient absorption spectra indicate that J91 can suppress the triplet formation in its blend film with n‐type organic semiconductor acceptor m‐ITIC (3,9‐bis(2‐methylene‐(3‐(1,1‐dicyanomethylene)‐indanone)‐5,5,11,11‐tetrakis(3‐hexylphenyl)‐dithieno[2,3‐d:2,3′‐d′]‐s‐indaceno[1,2‐b:5,6‐b′]‐dithiophene). With these favorable properties, a higher power conversion efficiency of 11.63% with high VOC of 0.984 V and high JSC of 18.03 mA cm−2 is obtained for the polymer solar cells based on J91/m‐ITIC with thermal annealing. The improved photovoltaic performance by thermal annealing is explained from the morphology change upon thermal annealing as revealed by photoinduced force microscopy. The results indicate that side chain engineering can provide a new solution to suppress carrier recombination toward high efficiency, thus deserves further attention.
Batch Fabrication of Metasurface Holograms Enabled by Plasmonic Cavity Lithography
Authors: Liu Liqin , Zhang Xiaohu , Zhao Zeyu , Pu Mingbo , Gao Ping , Luo Yunfei , Jin Jinjin , Wang Changtao , Luo Xiangang
Published: August 2017

Metasurface holograms consisting of nanostructures have shown great promise for various applications due to their unique capability of shaping light. Usually, they are fabricated by point‐by‐point scanning method, such as focused ion beam and electron beam lithography, which would greatly hamper their applications due to the high cost and low yield. In this work, plasmonic cavity lithography is proposed to fabricate metasurface holograms. The lithography system consists of Cr mask and plasmonic cavity that compose of 20 nm Ag/30 nm photoresist/50 nm Ag, where an air separation layer exists between them to avoid contamination and damage of mask patterns. The simulated results show that the cavity can effectively amplify the evanescent waves and modulate the electric field components on imaging plane, resulting in greatly improved resolution and fidelity compared to near field and superlens lithography. In experiments, the Au metaholograms are fabricated by the proposed lithography method and following etching processes. Furthermore, the designed holographic image of character “E” is successfully observed with the fabricated hologram. This approach is believed to open up a batch fabrication way for reproducing many copies of a metasurface hologram.
Risk factor for permanent stoma and incontinence quality of life after sphincter‐preserving surgery for low rectal cancer without a diverting stoma
Authors: Miura Takuya , Sakamoto Yoshiyuki , Morohashi Hajime , Yoshida Tatsuya , Sato Kentaro , Hakamada Kenichi
Published: August 2017

The goal of the present study was to evaluate permanent stoma formation and defecation function in long‐term follow up after surgery for low rectal cancer without a diverting stoma. Subjects were 275 patients who underwent sphincter‐preserving surgery for low rectal cancer between 2000 and 2012. Clinical outcomes were evaluated and defecation function was assessed based on a questionnaire survey, using Wexner and modified fecal incontinence quality of life (mFIQL) scores. Incidence of anastomotic leakage was 21.8%, and surgery‐related death as a result of anastomotic leakage occurred in one male patient. Median follow‐up period was 4.9 years and permanent stoma formation rate was 16.7%. Anastomotic leakage was an independent predictor of permanent stoma formation (odds ratio [OR] 5.86, P<0.001). Age <65 years (OR 1.99, P=0.001) and male gender (OR 4.36, P=0.026) were independent predictors of anastomotic leakage. A permanent stoma was formed as a result of poor healing of anastomotic leakage in 29.6% of males, but in no females. Defecation function was surveyed in 27 and 116 patients with and without anastomotic leakage, respectively. These groups had no significant differences in median follow‐up period (63.5 vs 63 months), Wexner scores (quartile) (6 (2.5‐9) vs 6 (3‐11)), and mFIQL scores (26.1 (4.8‐64.2) vs 23.8 (5.9‐60.7). Defecation function associated with anastomotic leakage showed no significant dependence on gender or resection procedure. Sphincter‐preserving surgery without a diverting stoma may be indicated for females with low rectal cancer. In this procedure, male gender is a risk factor for anastomotic leakage and subsequent formation of a permanent stoma in one in three patients.
Encephalopathy caused by novel mutations in the CMP‐sialic acid transporter, SLC35A1
Authors: Ng Bobby G. , Asteggiano Carla G. , Kircher Martin , Buckingham Kati J. , Raymond Kimiyo , Nickerson Deborah A. , Shendure Jay , Bamshad Michael J. ,   University of Washington Center for Mendelian Genomics, Ensslen Matthias , Freeze Hudson H.
Published: August 2017

Transport of activated nucleotide‐sugars into the Golgi is critical for proper glycosylation and mutations in these transporters cause a group of rare genetic disorders termed congenital disorders of glycosylation. We performed exome sequencing on an individual with a profound neurological presentation and identified rare compound heterozygous mutations, p.Thr156Arg and p.Glu196Lys, in the CMP‐sialic acid transporter, SLC35A1. Patient primary fibroblasts and serum showed a considerable decrease in the amount of N‐ and O‐glycans terminating in sialic acid. Direct measurement of CMP‐sialic acid transport into the Golgi showed a substantial decrease in overall rate of transport. Here we report the identification of the third patient with CMP‐sialic acid transporter deficiency, who presented with severe neurological phenotype, but without hematological abnormalities.
Selen und Selenocystein in der Proteinchemie
Authors: Mousa Reem , Notis Dardashti Rebecca , Metanis Norman
Published: August 2017

Selenocystein, das selenhaltige Analogon des Cysteins, ist die 21. proteinogene Aminosäure. Seit ihrer Entdeckung vor beinahe fünfzig Jahren ist ihre Rolle biologischen Systemen intensiv untersucht worden, in nichtnatürlichen noch häufiger als in natürlichen. Die Chemie des Selenocysteins hat aufgrund der hohen Reaktivität der Verbindung und des daraus resultierenden Potentials für diverse Anwendungen, z. B. in der chemischen Modifizierung, der chemische Protein(semi)synthese oder der Proteinfaltung, viel Aufmerksamkeit auf dem Gebiet der chemischen Biologie auf sich gezogen. In diesem Kurzaufsatz richten wir den Fokus auf die Chemie des Selens und des Selenocysteins sowie deren Nutzen in der Proteinchemie.
Das Aufrollen von Oligophenylenen zu Nanographenen durch einen HF‐Reißverschluss
Authors: Steiner Ann‐Kristin , Amsharov Konstantin Y.
Published: August 2017

Die intramolekulare Aryl‐Aryl‐Kupplung ist die Schlüsselumwandlung in der rationalen Synthese von Nanographenen und Nanobändern. In dieser Hinsicht erwies sich die C‐F‐Bindungsaktivierung als eine vielseitige Alternative, die die Synthese mehrerer einzigartiger Kohlenstoff‐basierter Nanostrukturen ermöglicht. Hier beschreiben wir eine beispiellos anspruchsvolle Transformation, die zeigt, dass die C‐F‐Bindungsaktivierung durch Aluminiumoxid eine hochwirksame Domino‐C‐C‐Bindungsbildung ermöglicht. Trotz der flexiblen Struktur der Oligophenylen‐basierten Vorstufen gelingt ein effizienter regioselektiver Aufbau der Zielstrukturen. Die Fluorpositionen in der Vorstufe geben eindeutig das “Reißverschluss‐Programm” vor, welches zu einem Aufrollen von linearen Oligophenylenketten um einen Phenylrest führt und die gewünschten Nanographene ergibt. Das hoch effiziente Verfahren ist attraktiv für die Synthese nichtsubstituierter Nanographenen, die durch alternative Methoden in reiner Form schwer zugänglich sind.
Because the Light is Better Here: Correlation‐Time Analysis by NMR Spectroscopy
Authors: Smith Albert A. , Ernst Matthias , Meier Beat H.
Published: August 2017

Relaxation data in NMR spectra are often used for dynamics analysis, by modeling motion in the sample with a correlation function consisting of one or more decaying exponential terms, each described by an order parameter, and a correlation time. This method has its origins in the Lipari–Szabo model‐free approach, which originally considered overall tumbling plus one internal motion and was later expanded to several internal motions. Considering several of these cases in the solid state it is found that if the real motion is more complex than the assumed model, model fitting is biased towards correlation times where the relaxation data are most sensitive. This leads to unexpected distortions in the resulting dynamics description. Therefore dynamics detectors should be used, which characterize different ranges of correlation times and can help in the analysis of protein motion without assuming a specific model of the correlation function.
Rocking‐Chair Ammonium‐Ion Battery: A Highly Reversible Aqueous Energy Storage System
Authors: Wu Xianyong , Qi Yitong , Hong Jessica J. , Li Zhifei , Hernandez Alexandre S. , Ji Xiulei
Published: August 2017

Aqueous rechargeable batteries are promising solutions for large‐scale energy storage. Such batteries have the merit of low cost, innate safety, and environmental friendliness. To date, most known aqueous ion batteries employ metal cation charge carriers. Here, we report the first “rocking‐chair” NH4‐ion battery of the full‐cell configuration by employing an ammonium Prussian white analogue, (NH4)1.47Ni[Fe(CN)6]0.88, as the cathode, an organic solid, 3,4,9,10‐perylenetetracarboxylic diimide (PTCDI), as the anode, and 1.0 m aqueous (NH4)2SO4 as the electrolyte. This novel aqueous ammonium‐ion battery demonstrates encouraging electrochemical performance: an average operation voltage of ca. 1.0 V, an attractive energy density of ca. 43 Wh kg−1 based on both electrodes’ active mass, and excellent cycle life over 1000 cycles with 67 % capacity retention. Importantly, the topochemistry results of NH4+ in these electrodes point to a new paradigm of NH4+‐based energy storage.
Polysulfid‐Koordinationscluster der Lanthanoide
Authors: Ma Ying‐Zhao , Bestgen Sebastian , Gamer Michael T. , Konchenko Sergey N. , Roesky Peter W.
Published: August 2017

Die Reaktion von [(DippForm)2Ln(thf)2] mit einem Überschuss an elementaren Schwefel führt in Toluol zur Bildung der dreikernigen Polysulfid‐Koordinationscluster [(DippForm)3Ln3S12] (Ln=Sm, Yb; DippForm=N,N′‐bis(2,6‐diisopropylphenyl)‐formamidinat). Dies sind die ersten f‐Element‐Koordinationscluster (LnnSx) mit einer größeren Polysulfideinheit (n und x>2). Die Bildung dieser Spezies kann über die reduktive Spaltung von Cyclooctaschwefel (S8) mittels zweiwertiger Lanthanoide erklärt werden.
Photoaktivierung von Cerdioxid: die Rolle von Defekten
Authors: Yang Chengwu , Yu Xiaojuan , Pleßow Philipp N. , Heißler Stefan , Weidler Peter G. , Nefedov Alexei , Studt Felix , Wang Yuemin , Wöll Christof
Published: August 2017

Die Photoreaktivität von Cerdioxid, einem photochemisch inaktiven Oxid mit großer Bandlücke, lässt sich durch die Erzeugung von O‐Leerstellen deutlich steigern. Zur Klärung des Mechanismus wurde die UV‐induzierte Zersetzung von N2O an Einkristall‐Modellsystemen dieses Materials mithilfe von IRRAS untersucht. In Verbindung mit theoretischen Erkenntnissen bestätigen die IRRAS‐Daten, dass eine Reduzierung der Cerdioxid‐(110)‐Oberfläche zu einer hohen Photoreaktivität führt. An der (111)‐Oberfläche sind dagegen keine solchen Effekte zu beobachten. Der Tieftemperatur‐Photoabbau von N2O erfolgt hauptsächlich an O‐Leerstellen an der (110)‐Oberfläche. An diesen Defekten verkleinern die elektronenreichen Cerkationen die große Bandlücke (ca. 6 eV) lokal erheblich. Die Quanteneffizienz der stark reduzierten (110)‐Oberflächen von Cerdioxid beim Photoabbau von N2O ist erstaunlich hoch. Der Wert von 0.03 % ist vergleichbar mit dem Wirkungsgrad, der für die Photooxidation von CO an Rutil‐Titandioxid‐(110) beobachtet wurde.
H2S‐Activable MOF Nanoparticle Photosensitizer for Effective Photodynamic Therapy against Cancer with Controllable Singlet‐Oxygen Release
Authors: Ma Yu , Li Xiangyuan , Li Aijie , Yang Peng , Zhang Caiyun , Tang Bo
Published: August 2017

Photodynamic therapy (PDT) has emerged as an important minimally invasive tumor treatment technology. The search for an effective photosensitizer to realize selective cancer treatment has become one of the major foci in recent developments of PDT technology. Controllable singlet‐oxygen release based on specific cancer‐associated events, as another major layer of selectivity mode, has attracted great attention in recent years. Here, for the first time, we demonstrated that a novel mixed‐metal metal–organic framework nanoparticle (MOF NP) photosensitizer can be activated by a hydrogen sulfide (H2S) signaling molecule in a specific tumor microenvironment for PDT against cancer with controllable singlet‐oxygen release in living cells. The effective removal of tumors in vivo further confirmed the satisfactory treatment effect of the MOF NP photosensitizer.
Regioselektive para‐Carboxylierung von Catecholen mit einer Prenylflavin‐abhängigen Decarboxylase
Authors: Payer Stefan E. , Marshall Stephen A. , Bärland Natalie , Sheng Xiang , Reiter Tamara , Dordic Andela , Steinkellner Georg , Wuensch Christiane , Kaltwasser Susann , Fisher Karl , Rigby Stephen E. J. , Macheroux Peter , Vonck Janet , Gruber Karl , Faber Kurt , Himo Fahmi , Leys David , Pavkov‐Keller Tea , Glueck Silvia M.
Published: August 2017

Die Verwendung von CO2 als Kohlenstoffquelle in der Synthese organischer Verbindungen entspricht den aktuellen Bemühungen für eine nachhaltigere Produktion von Chemikalien. Wir beschreiben hier die enzymkatalysierte para‐Carboxylierung von Catecholen durch eine 3,4‐Dihydroxybenzoesäure‐Decarboxylase (AroY) aus der UbiD‐Enzymfamilie. Die Kristallstrukturen und experimentelle Daten zeigen, dass dieses Enzym ein erst kürzlich entdecktes prenyliertes Flavin als Cofaktor benötigt (prFMN) und oxidative Prozesse zur Bildung der katalytisch aktiven prFMNiminium‐Spezies führen. Diese Studie beschreibt die In‐vitro‐Rekonstitution und Aktivierung dieser prFMN‐abhängigen Enzyme, welche die direkte Carboxylierung von aromatischen Catecholen unter milden Bedingungen katalysieren. Ein Reaktionsmechanismus für den reversiblen Carboxylierungsprozess über ein Intermediat mit einfach kovalent gebundener Chinoidform des Substrats wird vorgeschlagen, der sich von dem 1,3‐Cycloadditionsmechanismus in verwandten Enzymen unterscheidet.
Stereoselective Synthesis of Z Fluoroalkenes through Copper‐Catalyzed Hydrodefluorination of gem‐Difluoroalkenes with Water
Authors: Hu Jiefeng , Han Xiaowei , Yuan Yu , Shi Zhuangzhi
Published: August 2017

A copper catalytic system was established for the stereoselective hydrodefluorination of gem‐difluoroalkenes through C−F activation to synthesize various Z fluoroalkenes. H2O is used as the hydrogen source for the fluorine acceptor moiety. This mild catalytic system shows good‐functional group compatibility, accepting a range of carbonyls as precursors to the gem‐difluoroalkenes, including aliphatic, aromatic, and α,β‐unsaturated aldehydes and even ketones. It serves as a powerful synthetic method for the late‐stage modification of complex compounds.
Wellenlängenselektive freie radikalische Photopolymerisation zur einfachen Herstellung von Sternpolymeren
Authors: Eibel Anna , Fast David E. , Sattelkow Jürgen , Zalibera Michal , Wang Jieping , Huber Alex , Müller Georgina , Neshchadin Dmytro , Dietliker Kurt , Plank Harald , Grützmacher Hansjörg , Gescheidt Georg
Published: August 2017

Sternpolymere finden zunehmende Bedeutung auf den schnell wachsenden Gebieten der Nanotechnologie und der Lebenswissenschaften, unter anderem in den Bereichen diagnostische Bildgebung, Gewebezüchtung und gezielte Wirkstoff‐Freisetzung. Hier wird über eine effiziente Methode zur Synthese von wellenlängenselektiven multifunktionellen Photoinitiatoren (PIs) berichtet, die aus einer Bisacylphosphanoxid(BAPO)‐ und einer α‐Hydroxyketon‐Einheit bestehen. Diese photoaktiven Gruppen werden bei drei unterschiedlichen Wellenlängen selektiv angeregt und aktiviert. Dies ermöglicht die Herstellung von ABC‐Miktoarm‐Sternpolymeren mithilfe einer einfachen, hochselektiven und robusten radikalischen Polymerisation. Die Photochemie dieser neuartigen Initiatoren und die Möglichkeiten ihrer Anwendbarkeit wurden mit einer Reihe spektroskopischer Methoden detailliert untersucht.
Preorganization and Cooperation for Highly Efficient and Reversible Capture of Low‐Concentration CO2 by Ionic Liquids
Authors: Huang Yanjie , Cui Guokai , Zhao Yuling , Wang Huiyong , Li Zhiyong , Dai Sheng , Wang Jianji
Published: August 2017

A novel strategy based on the concept of preorganization and cooperation has been designed for a superior capacity to capture low‐concentration CO2 by imide‐based ionic liquids. By using this strategy, for the first time, an extremely high gravimetric CO2 capacity of up to 22 wt % (1.65 mol mol−1) and excellent reversibility (16 cycles) have been achieved from 10 vol. % of CO2 in N2 when using an ionic liquid having a preorganized anion. Through a combination of quantum‐chemical calculations and spectroscopic investigations, it is suggested that cooperative interactions between CO2 and multiple active sites in the preorganized anion are the driving force for the superior CO2 capacity and excellent reversibility.
Ultrafast Charge Transfer and Upconversion in Zinc β‐Tetraaminophthalocyanine‐Functionalized PbS Nanostructures Probed by Transient Absorption Spectroscopy
Authors: Lauth Jannika , Grimaldi Gianluca , Kinge Sachin , Houtepen Arjan J. , Siebbeles Laurens D. A. , Scheele Marcus
Published: August 2017

We functionalize PbS nanocrystals with the organic semiconductor Zn β‐tetraaminophthalocyanine to design a nanostructured solid‐state material with frequent organic–inorganic interfaces. By transient absorption and fluorescence spectroscopy, we investigate the optoelectronic response of this hybrid material under near‐infrared excitation to find efficient charge transfer from the nanocrystals to the molecules. We demonstrate that the material undergoes cooperative sensitization of two nanocrystals followed by photon upconversion and singlet emission of the organic semiconductor. The upconversion efficiency resembles that of comparable systems in solution, which we attribute to the large amount of interfaces present in this solid‐state film. We anticipate that this synthetic strategy has great prospects for increasing the open‐circuit voltage in PbS nanocrystal‐based solar cells.
Polysulfide Coordination Clusters of the Lanthanides
Authors: Ma Ying‐Zhao , Bestgen Sebastian , Gamer Michael T. , Konchenko Sergey N. , Roesky Peter W.
Published: August 2017

The reaction of [(DippForm)2Ln(thf)2] with an excess of elemental sulfur in toluene resulted in the formation of the trinuclear polysulfide coordination clusters [(DippForm)3Ln3S12] (Ln=Sm, Yb; DippForm=N,N′‐bis(2,6‐diisopropylphenyl)formamidinate). These are the first f element coordination clusters (LnnSx) with a larger polysulfide unit (n and x>2). The formation of the coordination clusters can be rationalized by the reductive cleavage of S8 with divalent lanthanides.
Reply to “Photoredox Catalysis: The Need to Elucidate the Photochemical Mechanism”
Authors: Ghosh Indrajit , Bardagi Javier I. , König Burkhard
Published: August 2017

Spectroscopic measurements and estimated thermodynamic values are important tools for the investigation of photocatalytic reaction mechanisms. However, data derived under idealized conditions fail to capture the complexity of reaction mixtures in preparative organic synthesis.
Constructing a Strongly Absorbing Low‐Bandgap Polymer Acceptor for High‐Performance All‐Polymer Solar Cells
Authors: Zhang Zhi‐Guo , Yang Yankang , Yao Jia , Xue Lingwei , Chen Shanshan , Li Xiaojun , Morrison William , Yang Changduk , Li Yongfang
Published: August 2017

All‐polymer solar cells (all‐PSCs) offer unique morphology stability for the application as flexible devices, but the lack of high‐performance polymer acceptors limits their power conversion efficiency (PCE) to a value lower than those of the PSCs based on fullerene derivative or organic small molecule acceptors. We herein demonstrate a strategy to synthesize a high‐performance polymer acceptor PZ1 by embedding an acceptor–donor–acceptor building block into the polymer main chain. PZ1 possesses broad absorption with a low band gap of 1.55 eV and high absorption coefficient (1.3×105 cm−1). The all‐PSCs with the wide‐band‐gap polymer PBDB‐T as donor and PZ1 as acceptor showed a record‐high PCE of 9.19 % for the all‐PSCs. The success of our polymerization strategy can provide a new way to develop efficient polymer acceptors for all‐PSCs.
Regioselective para‐Carboxylation of Catechols with a Prenylated Flavin Dependent Decarboxylase
Authors: Payer Stefan E. , Marshall Stephen A. , Bärland Natalie , Sheng Xiang , Reiter Tamara , Dordic Andela , Steinkellner Georg , Wuensch Christiane , Kaltwasser Susann , Fisher Karl , Rigby Stephen E. J. , Macheroux Peter , Vonck Janet , Gruber Karl , Faber Kurt , Himo Fahmi , Leys David , Pavkov‐Keller Tea , Glueck Silvia M.
Published: August 2017

The utilization of CO2 as a carbon source for organic synthesis meets the urgent demand for more sustainability in the production of chemicals. Herein, we report on the enzyme‐catalyzed para‐carboxylation of catechols, employing 3,4‐dihydroxybenzoic acid decarboxylases (AroY) that belong to the UbiD enzyme family. Crystal structures and accompanying solution data confirmed that AroY utilizes the recently discovered prenylated FMN (prFMN) cofactor, and requires oxidative maturation to form the catalytically competent prFMNiminium species. This study reports on the in vitro reconstitution and activation of a prFMN‐dependent enzyme that is capable of directly carboxylating aromatic catechol substrates under ambient conditions. A reaction mechanism for the reversible decarboxylation involving an intermediate with a single covalent bond between a quinoid adduct and cofactor is proposed, which is distinct from the mechanism of prFMN‐associated 1,3‐dipolar cycloadditions in related enzymes.
Preparation of an organic–inorganic hybrid based on synergy of Brønsted and Lewis acid centres as heterogeneous magnetic nanocatalyst for ultrafast synthesis of acetaminophen
Authors: Kooti M. , Nasiri E.
Published: August 2017

A heterogeneous nanocatalyst based on a Cu(II) complex containing phosphotungstic acid and N/O‐donor ligands supported on cobalt ferrite nanoparticles was successfully prepared. The synthesized nanocatalyst was characterized using various techniques. The magnetic nanocatalyst was examined as an efficient and synergistic catalyst for ultrafast synthesis of acetaminophen at room temperature and under solventless conditions. The examined synergistic nanocatalyst, which has both Lewis and Brønsted acidic sites, could be easily separated from the reaction system and reused several times without significant loss of its activity. The synthesized acetaminophen was also fully characterized.
Iminophosphine palladium catalysts for Suzuki carbonylative coupling reaction
Authors: Yılmaz Mustafa Kemal , Keleş Hülya , İnce Simay , Keleş Mustafa
Published: August 2017

Three iminophosphine ligands having soft phosphorus and hard nitrogen atoms and their Pd(II) complexes were synthesized and characterized using 1H NMR, 13C NMR, 31P NMR and Fourier transform infrared spectroscopic techniques. Also, electrochemical properties of the iminophosphines and their Pd(II) complexes were investigated in acetonitrile–tetrabutylammonium perchlorate solution with cyclic and square wave voltammetry techniques. All Pd(II) complexes were evaluated as catalysts for carbonylative cross‐coupling reactions of aryl iodides with phenylboronic acid. The Suzuki carbonylation of aryl iodides at 80 °C under balloon pressure of carbon monoxide in the presence of K2CO3 as a base was examined, and good to high conversions and excellent selectivities were obtained.
Microstructural and mechanical property evolutions of shape memory polyurethane during a thermodynamic cycle
Authors: Shi Shuang , Shen Dongya , Xu Tao
Published: August 2017

To better understand the shape memory behaviors of synthesized shape memory polyurethane (SMPU) sealant with a tailored transition temperature (Tt) for concrete pavement joints, the thermal and dynamic mechanical properties of SMPU were first characterized to determine the shape memory switching temperature of SMPU. Then the microstructural and mechanical property evolutions of SMPU in the original, programmed, and recovered states during a five‐step thermodynamic cycle were discussed, respectively. The results indicate that the tailored Tt of prepared SMPU can be used as the shape memory switching temperature to match its working temperature. Further, the programming causes the phase separation in SMPU, leading to an obvious anisotropy. The SMPU has satisfactory shape memory performance. The orientation of molecular chains in soft segments is confirmed along the stretching direction. The oriented molecular chains can restore to the naturally curled state during the free recovery. Finally, the programming improves the mechanical properties of SMPU. The recovered SMPU shows a slight decrease in mechanical properties because of the partially impaired crystal structures and broken molecular segments during the programming and recovery. It is concluded that the synthesized SMPU with the specially tailored Tt is suitable to use as a sealant of concrete pavement joints. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45703.
Assessing the importance of net colour as a seabird bycatch mitigation measure in gillnet fishing
Authors: Hanamseth Roshan , Barry Baker G. , Sherwen Sally , Hindell Mark , Lea Mary‐Anne
Published: August 2017

Gillnets are used widely in fisheries throughout the world and known to cause the death of thousands of seabirds each year. Currently few practical or technical options are available to fishers for preventing seabird mortalities.

The ability of little penguins (Eudyptula minor) to differentiate between different coloured netting materials was tested under controlled conditions to ascertain if changes in gillnet colour could facilitate a potential mitigation measure by improving visibility of nets.

The study involved a repeated‐measures design with penguins exposed to variously coloured mono‐filament threads creating a gillnet mimic. The gillnet mimic was made up of gillnet material configured as a series of vertical lines 25 mm apart stretched tightly across a stainless steel frame that measured 1160 mm × 1540 mm and divided into two equal panel areas. The panels were placed in a large tank within an enclosure that housed 25 penguins. Penguins were able to readily access the tank and swim freely. The frame was always introduced into the tank with one panel containing a gillnet mimic, and the other panel left empty as a control.

Gillnet filament colours tested were clear, green and orange. Orange coloured monofilament lines resulted in lower collision rates (5.5%), while clear and green monofilament lines resulted in higher rates of collision (35.9% and 30.8%, respectively).

These results suggest that orange‐coloured lines were more apparent to the birds. Constructing nets of orange‐coloured material may be effective in reducing bycatch in gillnets set in shallow waters and high light levels where seabirds are able to identify fine colour differences.

Further testing under experimental conditions, accompanied with at‐sea trials to verify effectiveness in varied light conditions is warranted, together with an assessment of the effect of gillnet colour on catch efficiency of target species.
Re‐introduction of structurally complex wood jams promotes channel and habitat recovery from overwidening: Implications for river conservation
Authors: Harvey Gemma L. , Henshaw Alexander J. , Parker Chris , Sayer Carl D.
Published: August 2017

Large wood is a powerful geomorphic agent in rivers, providing important habitat functions for a range of aquatic organisms, but has been subject to a long history of removal.

Internationally, approaches to river restoration are increasingly incorporating large wood features, but generally favour simple flow deflectors (e.g. single logs, stripped of branches and anchored in place) over more complex structures that more accurately mimic natural wood jams.

This paper explores channel response to wood‐based restoration of an overwidened lowland chalk stream that incorporated whole felled trees. Hydraulics, sediment, topography and vegetation data were assessed for a 3 year period for two restored reaches: an upstream reach where pre‐restoration baseline data were obtained, and a downstream reach restored before data collection.

Where pre‐restoration data were available, the introduction of wood jams generated sediment deposition within jams leading to the development of vegetated marginal ‘benches’ and bed scour in adjacent areas of flow convergence. Patterns were less clear in the downstream reach, where restoration design was less ambitious and outcomes may have been affected by subsequent restoration work upstream.

The results indicate that reintroduction of large wood (whole trees), can promote channel and habitat recovery from overwidening in lowland rivers, creating important ecological benefits through the provision of structurally complex marginal habitat and associated food resources. Longer‐term assessments are required to establish whether the trajectories of change are persistent.

The work emphasizes the effectiveness of restoration approaches that aim to ‘work with nature’. The ambitious design, incorporating structurally complex wood jams, was also low‐cost, using materials available from the river corridor (existing riparian trees). Furthermore, ecosystem engineering effects were amplified by the colonization of wood jams by aquatic vegetation. The approach should, therefore, be transferable to other lowland rivers, subject to wider catchment constraints.
Oued Bouhlou: A new hope for the Moroccan pearl mussel
Authors: Sousa Ronaldo , Teixeira Amílcar , Santos André , Benaissa Hassan , Varandas Simone , Ghamizi Mohamed , Prié Vincent , Froufe Elsa , Lopes‐Lima Manuel
Published: August 2017

The freshwater pearl mussel Margaritifera marocana (Pallary, ) is an endemic species of Morocco being listed as critically endangered and it stands among the world's 100 most threatened species. An extensive survey was performed in the Sebou basin (total area of approximately 40,000 km2), covering 26 different sites. Margaritifera marocana was found only in four sites limited to a small tributary (Oued (=River) Bouhlou).

This population has a very restricted distribution (no more than 4 km of river length) but appears stable with recent recruitment, since small specimens were found.

Genetic analyses were performed, showing that this population has a similar diversity to that found in the River Laabid (Oum Er Rbia basin), but represents a distinct conservation unit that should be managed independently.

Although this study adds a new population to the current known distribution of M. marocana, urgent conservation measures (e.g. extension of the Tazzekka National Park; better management of river flow; increase of the riparian vegetation in some stretches; establishment of national and international legislation, and engagement of local citizens) are needed given the species' restricted distribution, its rarity, and the numerous threats that impair its future survival.
Earliest Phase of Systemic Sclerosis Typified by Increased Levels of Inflammatory Proteins in the Serum
Authors: Cossu Marta , van Bon Lenny , Preti Carlo , Rossato Marzia , Beretta Lorenzo , Radstake Timothy R. D. J.
Published: August 2017

Objective

Patients with definite systemic sclerosis (SSc) who lack fibrotic features can be stratified into an intermediate stage of disease severity between preclinical/earlySSc (EaSSc) and fibrotic subsets (limited cutaneousSSc [lcSSc] and diffuse cutaneousSSc [dcSSc]). The aim of the present study was to molecularly characterize nonfibroticSSc and EaSSc on the basis of a broad panel of serum markers of inflammation and tissue damage, in order to increase the knowledge of the pathophysiologic mechanisms underlyingSSc progression before the development of fibrosis.

Methods

An 88‐plex immunoassay was performed in serum samples from a discovery cohort composed of 21 patients with EaSSc (meeting the LeRoy and Medsger criteria), 15 with nonfibroticSSc (meeting the American College of Rheumatology/European League Against Rheumatism 2013 classification criteria, without skin or lung fibrosis), and 11 healthy controls. Analyte concentrations that were consistently significantly different at the exploratoryPvalue threshold of 0.1 were selected for replication analysis in a larger group composed of 47 patients with EaSSc, 48 with nonfibroticSSc, and 43 healthy controls, as well as 51 patients with lcSSc and 35 with dcSSc. The value of the replicated molecules in predictingSSc progression (at a family‐wise error rate of 0.05) was tested.

Results

Based on the results of the explorative analysis, 16 molecules were selected for testing in the replication set. The results showed thatCXCL10,CXCL11, tumor necrosis factor receptor typeII(TNFRII), and chitinase 3–like protein 1 levels were significantly increased in patients with EaSSc and those with nonfibroticSSc as compared to healthy controls. The disease in patients with high concentrations ofCXCL10 andTNFRIIwas also characterized by a faster rate of progression from EaSSc and from nonfibroticSSc to worse disease stages.

Conclusion

SSc patients with preclinical/earlySSc and those with established, yet nonfibrotic, disease exhibit clear molecular alterations that are associated with faster rates of disease evolution. These data open novel avenues for disease interception inSSc.
Lupus‐Associated Functional Polymorphism in PNP Causes Cell Cycle Abnormalities and Interferon Pathway Activation in Human Immune Cells
Authors: Ghodke‐Puranik Yogita , Dorschner Jessica M. , Vsetecka Danielle M. , Amin Shreyasee , Makol Ashima , Ernste Floranne , Osborn Thomas , Moder Kevin , Chowdhary Vaidehi , Eliopoulos Elias , Zervou Maria I. , Goulielmos George N. , Jensen Mark A. , Niewold Timothy B.
Published: August 2017

Objective

Systemic lupus erythematosus (SLE) is frequently characterized by activation of the type I interferon (IFN) pathway. We previously observed that a missense single‐nucleotide polymorphism (rs1049564) in the purine nucleoside phosphorylase (PNP) gene was associated with high levels of IFN in SLE. PNP is a key enzyme involved in purine metabolism. In this study, we performed functional follow‐up of this polymorphism in human cells.

Methods

Type I IFN was measured in patient sera, using a reporter cell assay. Structural modeling of the PNP variant was performed using PyMOL software. PNP messenger RNA (mRNA) and protein levels and type I IFN–induced gene expression were measured in lymphoblastoid cell lines with known PNP rs1049564 genotypes. The cell cycle was assayed using flow cytometry.

Results

Structural modeling indicated no major disruption in folding related to rs1049564. We observed that homozygous rs1049564 TT lymphoblastoid cells had decreased PNP mRNA expression and protein levels, and that cells with the TT genotype had reduced PNP enzymatic activity even when the amount of PNP was controlled. Cells with the TT genotype had a 2‐fold increase in S‐phase block as compared with cells with the homozygous CC phenotype. The S‐phase block could be pharmacologically reversed with hypoxanthine and adenosine, supporting the notion that relative PNP deficiency is the cause of the S‐phase block. Type I IFN–induced transcripts were increased in a dose‐response manner related to the rs1049564 T allele, at both baseline and after type I IFN stimulation.

Conclusion

The PNP rs1049564 T allele is a loss‐of‐function variant that induces S‐phase block and IFN pathway activation in lymphocytes. The S‐phase block could be rescued in our in vitro experiments, suggesting the potential for personalized treatment.
Transparent Substrates Prepared From Different Amorphous Polymers Can Directly Modulate Primary Human B cell functions
Authors: Roch Toralf , Hahne Stefanie , Kratz Karl , Ma Nan , Lendlein Andreas
Published: August 2017

Manipulation of B cell functions such as antibody and cytokine secretion, is of clinical and biotechnological interest and can be achieved by soluble ligands activating cell surface receptors. Alternatively, the exposure to suitable solid substrates would offer the possibility to transiently induced cell signaling, since the signaling is interrupted when the cells are removed from the substrate. Cell/substrate interactions are mediated by physical valences such as, hydrogen bonds or hydrophobic forces on the substrate surface. Therefore, in this study B cells were cultivated on polymeric substrates, differing in their chemical composition and thus their capacity to undergo physical interactions. Activated B cells cultivated on polystyrene (PS) showed an altered cytokine response indicated by increased IL‐10 and decreased IL‐6 secretion. Interestingly, B cells cultivated on polyetherurethane (PEU), which has among all tested polymers the highest potential to form strong hydrogen bonds showed an impaired activation, which could be restored by re‐cultivation on tissue culture polystyrene. The results indicate that B cell behavior can transiently be manipulated solely by interacting with polymeric surface, which could be explained by receptor activation mediated by physical interaction with the substrate or by altering the availability of the soluble stimulatory reagents by adsorption processes.
Neoadjuvant chemotherapy for initially unresectable intrahepatic cholangiocarcinoma
Authors: Le Roy B , Gelli M , Pittau G , Allard M -A , Pereira B , Serji B , Vibert E , Castaing D , Adam R , Cherqui D , Sa Cunha A
Published: August 2017

Background

Locoregional extension of intrahepatic cholangiocarcinoma (ICC) at the time of diagnosis results in a low resectability rate and poor prognosis. The aim of this retrospective study was to assess the efficacy of neoadjuvant chemotherapy for locally advanced ICC.

Methods

All consecutive patients with ICC between 2000 and 2013 were included prospectively in a single-centre database and analysed retrospectively. Patients with locally advanced ICC considered as initially unresectable received primary chemotherapy, followed by surgery in those with secondary resectability. Results of patients who underwent surgery for locally advanced ICC were compared with those of patients with initially resectable ICC treated by surgery alone.

Results

A total of 186 patients were included in the study. Of 74 patients with locally advanced ICC, 39 (53 per cent) underwent secondary resection after a median of six chemotherapy cycles. Patients in this group were younger (P = 0·030) and had more advanced disease than those who had surgery alone, and presented more frequently with lymphadenopathy (P = 0·010) and vascular invasion (P = 0·010). Postoperative morbidity and mortality were no different between the groups. The median survival of patients who had surgery after chemotherapy was 24·1 months, and that of patients who had surgery alone was 25·7 months (P = 0·391).

Conclusion

Patients with locally advanced ICC treated by surgery following neoadjuvant chemotherapy had similar short- and long-term results to patients with initially resectable ICC who had surgery alone. Neoadjuvant chemotherapy as a first-line treatment for locally advanced ICC may be an effective downstaging option, facilitating secondary resectability in patients with initially unresectable disease.
An Aptamer‐based Self‐Catalytic Colorimetric Assay for Carcinoembryonic Antigen
Authors: Zou Mingjing , Wang Shuyu
Published: August 2017

We report a visualization assay for carcinoembryonic antigen (CEA). The assay was prepared based on target‐specific recognition, aptamer‐based DNAzyme self‐catalysis, and colorimetric reaction. Aptamer of CEA was gathered at the surface of magnetic beads for sandwiched co‐conjugate when CEA was added. The second aptamer (Apt2) on the beads was folded into G‐quadruplex by KCl to make G‐quadruplex‐hemin DNAzyme with hemin. Apt2‐based DNAzyme catalyzed H2O2‐mediated oxidation of 3,3′,5,5′‐tetramethylbenzidine, resulting in color changes and significant increase in absorption intensity at 450 nm (ΔA450nm). Yellow products can be observed with naked eyes when over 1.0 ng/mL CEA was added and there was a linear correlation between ΔA450 nm and CEA concentrations in the range of 0.1–8.0 ng/mL with the detection limit of 0.06 ng/mL. The proposed method was then used to determine CEA in human serum from healthy people and tumor patients, revealing a correlation with data from the electrochemiluminescent immunoassay. Owing to its simplicity, selectivity, and low‐cost, this method is a promising candidate for detecting CEA and clinical diagnosis of cancer.
BF2‐Complexes of Carbazole–Benzimidazole Conjugates: Synthesis, Structures, and Spectroscopic Properties
Authors: Dutta Ranjan , Firmansyah Dikhi , Yoo Jaeduk , Kumar Ravi , Mulugeta Endale , Jo Hongil , Ok Kang Min , Lee Chang‐Hee
Published: August 2017

A series of carbazole–benzimidazole conjugates and corresponding BF2‐complexes (BODIPYs) are synthesized and characterized. Carbazole–benzimidazole conjugates are synthesized by the condensation of 1‐formyl carbazole and phenylene diamines in good yields. Various substituents are introduced into the benzimidazole moiety and subsequent reaction with BF3•Et2O afforded the BF2‐complexes in moderate to good yield. The structural and photophysical properties of the synthesized fluorophores are investigated with various spectroscopic techniques such as UV/Vis and fluorescence spectroscopy, cyclic voltammetry and X‐ray crystallography.
The crisis intervention team (CIT) model: An evidence‐based policing practice?
Authors: Watson Amy C. , Compton Michael T. , Draine Jeffrey N.
Published: August 2017

As academic researchers, we are often asked to opine on whether the Crisis Intervention Team model (CIT) is an evidence‐based practice (EBP) or evidence‐based policing. Our answer is that it depends on how you define evidence‐based practice and what outcome you are interested in. In this commentary, we briefly describe the CIT model, examine definitions of evidence‐based practice and evidence‐based policing, and then summarize the existing research on what is known about the effectiveness of CIT to date. We conclude that CIT can be designated an EBP for officer‐level cognitive and attitudinal outcomes, but more research is needed to determine if CIT can be designated an EBP for other outcomes. Using an evidence‐based practice process approach, CIT may also be a justified strategy for many communities. Future directions to inform the field are discussed.
“Life's hurried tangled road”: A therapeutic jurisprudence analysis of why dedicated counsel must be assigned to represent persons with mental disabilities in community settings
Authors: Lynch Alison J. , Perlin Michael L.
Published: August 2017

The right to counsel is a fundamental right for individuals facing criminal processes and involuntary civil commitment. However, individuals with serious mental illnesses are subject to many community proceedings (e.g., being taken by law enforcement to a crisis drop‐off center) where counsel is not available. We argue that, unless meaningful counsel is provided in such situations, the cycle of arrest, hospitalization, and stays in the community will continue for these individuals, who are among some of the most disenfranchised citizens in the nation and are often without any meaningful voice.
Media Coverage, Public Awareness and State Intervention in Child Abuse in China – An Analysis of High‐Profile Cases
Authors: Qiao Dong Ping , Whittaker Andrew Jonathan , Zhang Tong
Published: August 2017

Key Practitioner Messages

Child abuse is a complex social problem that is often deeply rooted in the cultural, economic and social practices of the country in which it exists.

Child abuse in China is understood as deliberate and harmful acts, while many Western societies also include acts of omission such as neglect.

There is a complex relationship between public awareness, media coverage and state intervention.

‘A complex relationship between public awareness, media coverage and state intervention’
RGS3 inhibits TGF‐β1/Smad signalling in adventitial fibroblasts
Authors: Xu Fang , Liu Ying , Shi Lei , Cai Hongjing , Liu Wei , Hu Yejia , Li Yuling , Yuan Wendan
Published: August 2017

Recent evidence suggests that adventitial fibroblasts (AFs) are crucially implicated in atherosclerosis. However, the mechanisms by which AFs are dysfunctional and contribute to atherosclerosis remain unclear. This study aimed to investigate the role of regulator of G‐protein signalling 3 (RGS3) in the regulation of AFs using apoE knockout mouse as the model. Pathological changes in aortic arteries of apoE knockout mice fed with hyperlipid diet were examined by Movat staining. The expression of RGS3, α‐SMA, TGF‐β1, Smad2, and Smad3 in the adventitia was detected by immunohistochemistry. Adventitial fibroblasts were isolated from aortic arteries of apoE knockout mice and infected with RGS3 overexpression lentivirus or empty lentivirus. The expression of RGS3, α‐SMA, TGF‐β1, Smad2, and Smad3 in AFs was detected by real‐time polymerase chain reaction and Western blot analysis. We found that hyperlipidic diet caused significant aortic intima thickening and atherosclerotic plaques in 15‐week‐old apoE knockout mice. Compared to wild‐type mice, RGS3 expression was lower while α‐SMA, TGF‐β1, Smad2, and Smad3 expression was higher in the adventitia of apoE knockout mice. In addition, lentivirus mediated overexpression of RGS3 caused decreased expression of α‐SMA, TGF‐β1, Smad2, and Smad3 in AFs derived from apoE(−/−) mice. In conclusion, these results suggest that RGS3 may provide protection against pathological changes of AFs and the development of atherosclerosis by inhibiting TGF‐β1/Smad signalling. RGS3 may be a potential therapeutic target for atherosclerosis.