bluuebunny/crossref_metadata_2025 huggingface dataset:
Interface‐Assisted Sign Inversion of Magnetoresistance in Spin Valves Based on Novel Lanthanide Quinoline Molecules
Authors: Bedoya‐Pinto Amilcar , Miralles Sara G. , Vélez Saül , Atxabal Ainhoa , Gargiani Pierluigi , Valvidares Manuel , Casanova Fèlix , Coronado Eugenio , Hueso Luis E.
Published: October 2017

Molecules are proposed to be an efficient medium to host spin‐polarized carriers, due to their weak spin relaxation mechanisms. While relatively long spin lifetimes are measured in molecular devices, the most promising route toward device functionalization is to use the chemical versatility of molecules to achieve a deterministic control and manipulation of the electron spin. Here, by combining magnetotransport experiments with element‐specific X‐ray absorption spectroscopy, this study shows the ability of molecules to modify spin‐dependent properties at the interface level via metal–molecule hybridization pathways. In particular, it is described how the formation of hybrid states determines the spin polarization at the relevant spin valve interfaces, allowing the control of macroscopic device parameters such as the sign and magnitude of the magnetoresistance. These results consolidate the application of the spinterface concept in a fully functional device platform.
Vacancy‐Controlled Contact Friction in Graphene
Authors: Gajurel Prakash , Kim Mina , Wang Qiang , Dai Weitao , Liu Haitao , Cen Cheng
Published: October 2017

Defects‐controlled friction in graphene is of technological importance in many applications, but the underlying mechanism remains a subject of debate. Here it is shown that, during the controlled oxidation in oxygen plasma and subsequent reduction induced by high‐energy photons, the contact friction in chemical vapor deposition grown graphene is dominantly determined by the vacancies formed instead of the bonding with add‐atoms. This effect is attributed to the vacancy‐enhanced out‐of‐plane deformation flexibility in graphene, which tends to produce large puckering of graphene sheet near the contact edge and thus increases the effective contact area. Modified graphene with large contact friction has a large density of defects, but remains a good electrical conductor, in which the carrier transport is strongly affected by quantum localization effects even at room temperature. It is also found that the oxidation process in graphene is substrate‐sensitive. Comparing to monolayer graphene on SiO2 substrate, the oxidation process progresses much faster when the substrate is SrTiO3, while bilayer graphene exhibits great oxidation resistance on both substrates. The collection of observations provides important information for tailoring the mechanical, electrical, and chemical properties of graphene through selected defects and substrates.
Highly Periodic Metal Dichalcogenide Nanostructures with Complex Shapes, High Resolution, and High Aspect Ratios
Authors: Jang Sungwoo , Kim Seon Joon , Koh Hyeong‐Jun , Jang Doo Hyung , Cho Soo‐Yeon , Jung Hee‐Tae
Published: October 2017

The development of high resolution, high aspect ratio metal dichalcogenide nanostructures is one of the most important issues in 2D material researchers due to the potential to exploit their properties into high performance devices. In this study, for the first time a way of fabricating metal dichalcogenide nanostructures with high resolution (<50 nm scale) and high aspect ratios (>120) by chemical vapor deposition assisted secondary sputtering phenomenon is reported. This approach can universally synthesize various types of metal dichalcogenides including MoS2, WS2, and SnS2, implying the possibility for further utilization with selenides and tellurides. Also, this method can produce highly periodic complex patterns such as hole–cylinder, concentric rings, and line patterns, which are unprecedented in previous reports. The feature size and aspect ratio of the metal dichalcogenide structures can be manipulated by controlling the dimensions of the photoresist prepatterns, while the pattern resolution and layer orientation can be manipulated by controlling the thickness of the deposited metal film. It is demonstrated that nanostructures with high resolution and high aspect ratio significantly improve gas‐sensing properties compared with previous metal dichalcogenide films. It is believed that the method can be a foundation for synthesizing various materials with complex patterns for future applications.
Hierarchically Porous Carbon Photonic Structures
Authors: Gil‐Herrera Luz Karime , Pariente Jose Angel , Gallego‐Gómez Francisco , Gándara Felipe , Juárez Beatriz H. , Blanco Álvaro , López Cefe
Published: October 2017

Hierarchically porous carbon holds promise for many applications involving not only electrical, catalytic, power storage and related functionalities but, despite absorption in the visible and near‐infrared, also optical and sensing uses are envisaged. In this paper, the self‐assembly of heterogeneous core–shell and hollow carbon spheres based on polystyrene cores, their optical properties and their response to humidity are described. The remarkable high quality of the crystals permits to exploit their singular optical properties among which a very high sensitivity to adsorption of guest materials stands out. In this regard, an original characterization of the system response is performed by means of the photonic bandgap variation with the relative gas pressure. Controlled pyrolysis enables to create and tune the features of the porosity brought about by degassing and the restructuring of the carbon lattice. Functionality associated with diverse pore populations reveals sensitivity to diverse ranges of humidity owing to selective adsorption of water in different size pores.
Mercury‐Mediated Organic Semiconductor Surface Doping Monitored by Electrolyte‐Gated Field‐Effect Transistors
Authors: Zhang Qiaoming , Leonardi Francesca , Casalini Stefano , Mas‐Torrent Marta
Published: October 2017

Surface doping allows tuning the electronic structure of semiconductors at near‐surface regime and is normally accomplished through the deposition of an ultrathin layer on top or below the host material. Surface doping is particularly appealing in organic field‐effect transistors (OFETs) where charge transport takes place at the first monolayers close to the dielectric surface. However, due to fabrication restrictions that OFET architecture imparts, this is extremely challenging. Here, it is demonstrated that mercury cations, Hg2+, can be exploited to control doping levels at the top surface of a thin film of a p‐type organic semiconductor blended with polystyrene. Electrolyte‐ or water‐gated field‐effect transistors, which have its conductive channel at the top surface of the organic thin film, turn out to be a powerful tool for monitoring the process. A positive shift of the threshold voltage is observed in the devices upon Hg2+ exposure. Remarkably, this interaction has been proved to be specific to Hg2+ with respect to other divalent cations and sensitive down to nanomolar concentrations. Hence, this work also opens new perspectives for employing organic electronic transducers in portable sensors for the detection of an extremely harmful water pollutant without the need of using specific receptors.
Hydrogen‐Bonding‐Assisted Intermolecular Charge Transfer: A New Strategy to Design Single‐Component White‐Light‐Emitting Materials
Authors: Xie Zongliang , Huang Qiuyi , Yu Tao , Wang Leyu , Mao Zhu , Li Wenlang , Yang Zhan , Zhang Yi , Liu Siwei , Xu Jiarui , Chi Zhenguo , Aldred Matthew P.
Published: October 2017

This study reveals the mechanism of the dual‐emission properties for asymmetrical diphenylsulfone and diphenylketone derivatives. A series of asymmetrical diphenylketone and diphenylsulfone derivatives with dual‐emission properties are designed and synthesized. By single crystal structure analyses, various photophysical studies, and 2D 1H–1H NOSEY NMR studies, the lower energy emission bands in the dual‐emission spectra are successfully assigned to hydrogen‐bonding‐assisted intermolecular charge transfer emission. The emission properties of these compounds can easily be tuned in both solid state and solution state by destroying or strengthening the intermolecular hydrogen bonding. In addition, thermally activated delayed fluorescence characteristics for the intermolecular charge transfer emissions are also observed. The control of the intermolecular and intramolecular charge transfers serves as the basis for the generation of the white‐light emission. For compound CPzPO, nearly pure white‐light emission with CIE coordinates of (0.31, 0.32) is easily achieved by precipitation from dichloromethane and hexane mixed solvent system. These results clearly give an insight into the dual‐emission properties and provide a rational strategy for the design and synthesis of single‐component white‐light‐emitting materials and mechanoresponsive light‐emitting materials.
Perfluoroaryl‐Elemental Sulfur SNAr Chemistry in Covalent Triazine Frameworks with High Sulfur Contents for Lithium–Sulfur Batteries
Authors: Je Sang Hyun , Kim Hyeon Jin , Kim Jiheon , Choi Jang Wook , Coskun Ali
Published: October 2017

In order to address the challenges associated with lithium–sulfur batteries with high energy densities, various approaches, including advanced designs of sulfur composites, electrolyte engineering, and functional separators, are lately introduced. However, most approaches are effective for sulfur cathodes with limited sulfur contents, i.e., <80 wt%, imposing a significant barrier in realizing high energy densities in practical cell settings. Here, elemental sulfur‐mediated synthesis of a perfluorinated covalent triazine framework (CTF) and its simultaneous chemical impregnation with elemental sulfur via SNAr chemistry are demonstrated. SNAr chemistry facilitates the dehalogenation and nucleophilic addition reactions of perfluoroaryl units with nucleophilic sulfur chains, achieving a high sulfur content of 86 wt% in the resulting CTF. The given sulfur‐impregnated CTF, named SF‐CTF, exhibits a specific capacity of 1138.2 mAh g−1 at 0.05C, initial Coulombic efficiency of 93.1%, and capacity retention of 81.6% after 300 cycles, by utilizing homogeneously distributed sulfur within the micropores and nitrogen atoms of triazine units offering high binding affinity toward lithium polysulfides.
Bioinspired Nanocomposite Hydrogels with Highly Ordered Structures
Authors: Zhao Ziguang , Fang Ruochen , Rong Qinfeng , Liu Mingjie
Published: October 2017

In the human body, many soft tissues with hierarchically ordered composite structures, such as cartilage, skeletal muscle, the corneas, and blood vessels, exhibit highly anisotropic mechanical strength and functionality to adapt to complex environments. In artificial soft materials, hydrogels are analogous to these biological soft tissues due to their “soft and wet” properties, their biocompatibility, and their elastic performance. However, conventional hydrogel materials with unordered homogeneous structures inevitably lack high mechanical properties and anisotropic functional performances; thus, their further application is limited. Inspired by biological soft tissues with well‐ordered structures, researchers have increasingly investigated highly ordered nanocomposite hydrogels as functional biological engineering soft materials with unique mechanical, optical, and biological properties. These hydrogels incorporate long‐range ordered nanocomposite structures within hydrogel network matrixes. Here, the critical design criteria and the state‐of‐the‐art fabrication strategies of nanocomposite hydrogels with highly ordered structures are systemically reviewed. Then, recent progress in applications in the fields of soft actuators, tissue engineering, and sensors is highlighted. The future development and prospective application of highly ordered nanocomposite hydrogels are also discussed.
Structure Formation in Soft‐Matter Solutions Induced by Solvent Evaporation
Authors: Zhou Jiajia , Man Xingkun , Jiang Ying , Doi Masao
Published: October 2017

Solvent evaporation in soft‐matter solutions (solutions of colloidal particles, polymers, and their mixtures) is an important process in material making and in the printing and coating industries. The solvent‐evaporation process determines the structure of materials and strongly affects their performance. Solvent evaporation involves many physicochemical processes: flow, diffusion, crystallization, gelation, glass transition, etc. and is quite complex. Here, recent progress in this important process is reported, with a special focus on theoretical and simulation studies.
Gold Nanobipyramid‐Enhanced Hydrogen Sensing with Plasmon Red Shifts Reaching ≈140 nm at 2 vol% Hydrogen Concentration
Authors: Yip Hang Kuen , Zhu Xingzhong , Zhuo Xiaolu , Jiang Ruibin , Yang Zhi , Wang Jianfang
Published: October 2017

Plasmonic sensors that make use of localized surface plasmon resonance provide an excellent platform for hydrogen sensing. In this work, large plasmonic red shifts are obtained on (Au nanobipyramid core)@(Pd shell) bimetallic nanostructures for hydrogen sensing. Au nanobipyramid@Pd nanostructures with different shell thicknesses are synthesized by varying the Pd precursor amount. The Au nanobipyramid@Pd nanostructures with thicker Pd shells are found to exhibit larger responses to hydrogen. The maximal plasmonic red shift reaches 97 nm at 4 vol% hydrogen concentration. The shell morphology of the Au nanobipyramid@Pd nanostructures is further optimized to improve the hydrogen sensing performance. With the optimized nanostructures, the maximal plasmonic red shift is improved to ≈140 nm at 2 vol% hydrogen concentration. Compared with the Au nanobipyramid@Pd nanostructures, Au nanobipyramid/AgPd nanostructures show smaller plasmonic red shifts under the same conditions. The highly enhanced plasmonic shifts and sensitivity to hydrogen make our Au nanobipyramid@Pd nanostructures highly promising for the development of optical hydrogen sensing devices.
Palladium‐Catalyzed Three‐Component Tandem Reaction for One‐pot Highly Stereoselective Synthesis of (Z)‐α‐Hydroxymethyl Allylic Sulfones
Authors: Hou Yunlei , Shen Qi , Li Zefei , Chen Shaowei , Zhao Yanfang , Qin Mingze , Gong Ping
Published: October 2017

A novel method is reported for the stereoselective synthesis of highly functionalized allyl aryl sulfones. This protocol is based on a Pd‐catalyzed three‐component tandem reaction of sulfonyl hydrazides and aryl iodides with allenes and exhibits high (Z)‐selectivity, good yields, minimal waste, ample product scope, and operational simplicity.

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Stereoelectroencephalography and surgical outcome in polymicrogyria‐related epilepsy: A multicentric study
Authors: Maillard Louis Georges , Tassi Laura , Bartolomei Fabrice , Catenoix Hélène , Dubeau François , Szurhaj William , Kahane Philippe , Nica Anca , Marusic Petr , Mindruta Ioana , Chassoux Francine , Ramantani Georgia
Published: October 2017

Objective

We aimed to (1) assess the concordance between various polymicrogyria (PMG) types and the associated epileptogenic zone (EZ), as defined by stereoelectroencephalography (SEEG), and (2) determine the postsurgical seizure outcome in PMG‐related drug‐resistant epilepsy.

Methods

We retrospectively analyzed 58 cases: 49 had SEEG and 39 corticectomy or hemispherotomy.

Results

Mean age at SEEG or surgery was 28.3 years (range, 2–50). PMG was bilateral in 9 (16%) patients and unilateral in 49, including 17 (29%) unilobar, 12 (21%) multilobar, 15 (26%) perisylvian, and only 5 (9%) hemispheric. Twenty‐eight (48%) patients additionally had schizencephaly, heterotopia, or focal cortical dysplasia. The SEEG‐determined EZ was fully concordant with the PMG in only 8 (16%) cases, partially concordant in 74%, and discordant in 10%. The EZ included remote cortical areas in 21 (43%) cases and was primarily localized in those in 5 (10%), all related to the mesial temporal structures. All but 1 PMG patient with corticectomy or hemispherotomy had a unilateral PMG. At last follow‐up (mean, 4.6 years; range, 1–16), 28 (72%) patients remained seizure free. Shorter epilepsy duration to surgery was an independent predictor of seizure freedom.

Interpretation

PMG‐related drug‐resistant epilepsy warrants a comprehensive presurgical evaluation, including SEEG investigations in most cases, given that the EZ may only partially overlap with the PMG or include solely remote cortical areas. Seizure freedom is feasible in a large proportion of patients. PMG extent should not deter from exploring the possibility of epilepsy surgery. Our data support the early consideration of epilepsy surgery in this patient group. Ann Neurol 2017;82:781–794
Stimulation of the mesencephalic locomotor region for gait recovery after stroke
Authors: Fluri Felix , Malzahn Uwe , Homola György A. , Schuhmann Michael K. , Kleinschnitz Christoph , Volkmann Jens
Published: October 2017

Objective

One‐third of all stroke survivors are unable to walk, even after intensive physiotherapy. Thus, other concepts to restore walking are needed. Because electrical stimulation of the mesencephalic locomotor region (MLR) is known to elicit gait movements, this area might be a promising target for restorative neurostimulation in stroke patients with gait disability. The present study aims to delineate the effect of high‐frequency stimulation of the MLR (MLR‐HFS) on gait impairment in a rodent stroke model.

Methods

Male Wistar rats underwent photothrombotic stroke of the right sensorimotor cortex and chronic implantation of a stimulating electrode into the right MLR. Gait was assessed using clinical scoring of the beam‐walking test and video‐kinematic analysis (CatWalk) at baseline and on days 3 and 4 after experimental stroke with and without MLR‐HFS.

Results

Kinematic analysis revealed significant changes in several dynamic and static gait parameters resulting in overall reduced gait velocity. All rats exhibited major coordination deficits during the beam‐walking challenge and were unable to cross the beam. Simultaneous to the onset of MLR‐HFS, a significantly higher walking speed and improvements in several dynamic gait parameters were detected by the CatWalk system. Rats regained the ability to cross the beam unassisted, showing a reduced number of paw slips and misses.

Interpretation

MLR‐HFS can improve disordered locomotor function in a rodent stroke model. It may act by shielding brainstem and spinal locomotor centers from abnormal cortical input after stroke, thus allowing for compensatory and independent action of these circuits. Ann Neurol 2017;82:828–840
Microporous Cyclic Titanium‐Oxo Clusters with Labile Surface Ligands
Authors: Zhao Chaowei , Han Ying‐Zi , Dai Shuqi , Chen Xumao , Yan Juanzhu , Zhang Weijie , Su Haifeng , Lin Shuichao , Tang Zichao , Teo Boon K. , Zheng Nanfeng
Published: October 2017

By using ethylene glycol and monocarboxylic acid as surface ligands, a series of cyclic Ti‐oxo clusters (CTOC) with permanent microporosity are successfully synthesized. With a cyclic {Ti32O16} backbone made of eight connected Ti4 tetrahedral cages that are arranged in a zigzag fashion, the clusters have a “donut” shape with an inner diameter of 8.3 Å, outer diameter of 26.9 Å and height of 10.4 Å. While both inner and outer walls of the “donut” clusters are modified by double‐deprotonated ethylene glycolates, their upper and lower surfaces are bound by carboxylates and mono‐deprotonated ethylene glycolates. The clusters are readily packed into one‐dimensional tubes which are further arranged in two different modes into crystalline microporous solids with surface areas over 660 m2 g−1, depending on the surface carboxylates. The solid with olefin‐bearing carboxylates exhibits a superior CO2 adsorption capacity of 40 cm3 g−1 at 273 K under 1 atm. Moreover, the mono‐deprotonated ethylene glycolates on the clusters are demonstrated to be highly exchangeable by other alcohols, providing a nice platform for creating microporous solids or films with a wide variety of surface functionalities.
Understanding LiOH Chemistry in a Ruthenium‐Catalyzed Li–O2 Battery
Authors: Liu Tao , Liu Zigeng , Kim Gunwoo , Frith James T. , Garcia‐Araez Nuria , Grey Clare P.
Published: October 2017

Non‐aqueous Li–O2 batteries are promising for next‐generation energy storage. New battery chemistries based on LiOH, rather than Li2O2, have been recently reported in systems with added water, one using a soluble additive LiI and the other using solid Ru catalysts. Here, the focus is on the mechanism of Ru‐catalyzed LiOH chemistry. Using nuclear magnetic resonance, operando electrochemical pressure measurements, and mass spectrometry, it is shown that on discharging LiOH forms via a 4 e− oxygen reduction reaction, the H in LiOH coming solely from added H2O and the O from both O2 and H2O. On charging, quantitative LiOH oxidation occurs at 3.1 V, with O being trapped in a form of dimethyl sulfone in the electrolyte. Compared to Li2O2, LiOH formation over Ru incurs few side reactions, a critical advantage for developing a long‐lived battery. An optimized metal‐catalyst–electrolyte couple needs to be sought that aids LiOH oxidation and is stable towards attack by hydroxyl radicals.
‘Somebody Else's Roadmap’: Lived Experience of Maudsley and Family‐based Therapy for Adolescent Anorexia Nervosa
Authors: Conti Janet , Calder Jamie , Cibralic Sara , Rhodes Paul , Meade Tanya , Hewson Daphne
Published: October 2017

The Maudsley and more recent family‐based therapy manualised approaches are positioned by some as the gold standard, evidence‐based therapy for adolescent anorexia nervosa (AN). However, a significant proportion of adolescents and their families either discontinue this therapy and/or find that it simply does not work for them. These adolescents and families are under‐represented in the literature on therapeutic interventions for adolescent AN. This paper begins to address this gap with an in‐depth qualitative case study that explores the lived experience of Maudsley family therapy (MFT)/family‐based therapy (FBT) for one female adolescent (age 14 years) and her family over the period of 3 years (ages 11–14). Although initially handing over the responsibility for her eating was comforting and reinstated a sense of control in the family system, these experiences were not maintained. When she did not progress past the first phase of FBT, she and her family experienced the approach as blaming. She felt silenced and family alliances were weakened. This paper analyses how the family members negotiated and preserved their identities within this disabling context.
Facile synthesis of extremely biocompatible double‐network hydrogels based on chitosan and poly(vinyl alcohol) with enhanced mechanical properties
Authors: Pourjavadi Ali , Tavakoli Elham , Motamedi Anahita , Salimi Hamid
Published: October 2017

An easy and ecofriendly method for designing double‐network (DN) hydrogels based on chitosan and poly(vinyl alcohol) (PVA) with high mechanical performance is described. When covalent bonds in the networks are used as crosslinking agents in the achievement of a higher mechanical strength, the irreversible deformation of these hydrogels after a large force is applied is still one of the most important obstacles. To overcome this problem, we used physical crosslinking for both networks. The mechanical strength, surface morphology, and cytotoxicity of the films were studied by tensile testing, scanning electron microscopy analysis, and an MTT assay. The synthesized chitosan–PVA DN hydrogels showed a large improvement in the tensile strength to 11.52 MPa with an elongation of 265.6%. The surface morphologies of the films demonstrated the effective interactions between the two networks and a suitable porosity. Also, because of the use of a natural polymer and honey as a plasticizer, the cell culture indicated that the synthesized DN hydrogels had good biocompatibility (with 327.49 ± 11.22% viability) and could be used as capable biomaterials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45752.
pH‐sensitive polymeric particles as smart carriers for rebar inhibitors delivery in alkaline condition
Authors: Feng Lijuan , Yang Huaiyu , Dong Xiqing , Lei Haibo , Chen Di
Published: October 2017

The waste problem of the rebar inhibitors is very serious due to that it is a long time before they can exert their best effect in the concrete and they are kept losing all the time. However, there is still no effective solution to alleviate such situation. Meanwhile, drug delivery control technology based on environmental sensitive polymers has been successfully applied in biomedical fields. Thus, poly(acrylic acid)–acrylamide was synthesized as smart carrier for controlling rebar inhibitors delivery in concrete. Dipotassium hydrogen phosphate as model drug was encapsulated inside the polymeric particles via a self‐assembly process. The pH‐responsive activities of the polymeric particles were estimated by monitoring their swelling performances in solutions of different pH values and the drug delivery control characteristics were studied in simulated concrete pore solutions. The results indicate the polymeric particles deserve network structures with high porosity and exhibit excellent pH‐responsive activities, which can perform as perfect intelligent carriers whereas the releasing of the inhibitors follows the first‐order kinetic law. The work suggests a new application field of drug delivery control technology. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45886.
The First Record of Incidences of Ankylosis in Seven Triplefin Fishes (Pisces: Tripterygiidae) from New Zealand
Authors: Jawad Laith A.
Published: October 2017

Different cases of vertebral ankylosis were examined in seven tripterygiid species obtained from waters around New Zealand. The skeletal deformities observed are located in the caudal region of the vertebral column. Those occurred in Forsterygion nigripenne, Matanui bathytaton and in one specimen of Ruanoho whero were severe cases. The mechanism of the formation of vertebral ankylosis and the causes behind such anomaly were discussed. Further studies are needed to relate specific pollutants with the observed types of deformities. Anat Rec, 2017. © 2017 Wiley Periodicals, Inc. Anat Rec, 301:39–45, 2018. © 2017 Wiley Periodicals, Inc.
Proposal for biorefineries based on mixed cultures for lignocellulosic biofuel production: a techno‐economic analysis
Authors: Valdez‐Vazquez Idania , Sanchez Arturo
Published: October 2017

An innovative conceptual design is introduced for lignocellulosic‐based biochemical platform biorefineries using three mixed‐culture bioprocesses that sequentially disintegrate each polysaccharide fraction into different target biofuels: hydrogen, methane, and fuel butanol. This mixed‐culture biorefinery circumvents the use of corrosive chemicals, energy‐demanding pre‐treatments, costly enzymes, separate units for saccharification and fermentation, steam for sterilization, and expensive steel bioreactors. The concept mimics bioprocesses occurring in nature to degrade complex substrates. A techno‐economic analysis of these biorefineries is carried out focusing on the impact of residence times (8–120 h) and butanol titers (10–20 g/L) of the production of acetone‐butanol‐ethanol (ABE) on the total production costs (TPC) of butanol. The design includes electricity‐steam cogeneration from gaseous biofuels and lignin, as well as solvent purification. Simulation results show that the highest butanol titer impacts TPC to a greater extent than the lowest residence time. TPC range from US$1.04 to US$1.27 per liter of butanol in facilities with 20 g/L of butanol irrespective of residence time. The end‐use energy ratio for all facilities was close to 2 or higher. These biorefineries display lower energy consumption and environmental impacts than conventional second‐generation lignocellulosic biofuels biorefineries, and its cost structure is determined by the substrate similar to bioprocesses with mature technology. Finally, this study provides an insight to the advancements made in realizing viable mixed‐culture fermentations for different fields of biotechnology and therefore might be encouraging for further studies of lignocellulosic biorefineries based on mixed cultures. © 2017 Society of Chemical Industry and John Wiley & Sons, Ltd
Animal Models in Translational Research: Rosetta Stone or Stumbling Block?
Authors: Bolker Jessica A.
Published: October 2017

Leading animal models are powerful tools for translational research, but they also present obstacles. Poorly conducted preclinical research in animals is a common cause of translational failure, but even when such research is well‐designed and carefully executed, challenges remain. In particular, dominant models may bias research directions, elide essential aspects of human disease, omit important context, or subtly shift research targets. Recognizing these stumbling blocks can help us find ways to avoid them: employing a wider range of models, incorporating more realistic environmental conditions, better aligning studies between animals and patients, and focusing on human biology and therapeutic goals. Such changes are costly; but insisting it would be impractical or unrealistic to change strategies offers no way out of the current impasse. Rather, we must acknowledge the obstacles as well as the advantages presented by core models, and direct some of our investments in translational research toward getting around them.
Highly Efficient Oxidation of Amines to Aldehydes with Flow‐based Biocatalysis
Authors: Contente Martina L. , Dall'Oglio Federica , Tamborini Lucia , Molinari Francesco , Paradisi Francesca
Published: October 2017

The front cover artwork for Issue 20/2017 is a collaboration between the University of Nottingham (UK) and the University of Milan (Italy). The image shows the ease of production of a range of aldehydes in continuous flow through an efficient enzymatic oxidation with minimal waste and in an environmentally friendly manner. See the Full Paper itself at https://doi.org/10.1002/cctc.201701147.
Issues and Current Trends of Hollow‐Fiber Mixed‐Matrix Membranes for CO2Separation from N2and CH4
Authors: Mubashir Muhammad , Fong Yeong Yin , Leng Chew Thiam , Keong Lau Kok
Published: October 2017

To control CO2emission from industries, membrane technology is preferred over conventional technologies due to its numerous advantages including reliability, operational simplicity, and low capital cost. Hollow‐fiber mixed‐matrix membranes (HFMMMs) exhibit great potential for CO2separation. Various inorganic fillers were incorporated into different types of polymeric materials for fabrication of HFMMMs. This review focuses on the performance and issues of HFMMMS based on various materials for CO2/CH4and CO2/N2separation. Major features are reflected in the following three aspects: comprehensive study on the performance of HFMMMs for CO2/N2and CO2/CH4separation, issues with the fabrication of HFMMMs in CO2/N2and CO2/CH4separation, and prediction of transport models for HFMMMs in gas separation.
Hybrid central composite design for simultaneous optimization of removal of methylene blue and alizarin red S from aqueous solutions using Vitis tree leaves
Authors: Bagtash Maryam , Zolgharnein Javad
Published: October 2017

Vitis tree leaves powder was used for efficient removal of dyes (eg, alizarin red and methylene blue) from water samples in binary batch systems. The influence of various parameters such as initial pH, initial dye concentration, and sorbent mass on the biosorption process was investigated. Statistical experimental design was utilized to optimize this biosorption process. A regression model was derived using a response surface methodology through performing the 416B model of hybrid central composite design. Model adequacy was checked by means of tests such as analysis of variance, a lack of fit test, and residual distribution consideration. The proposed quadratic model resulted from the hybrid design approach fitted very well to the experimental data. The optimal conditions for dye biosorption were as follows: pH = 3.0, sorbent mass = 0.05 g, initial alizarin red concentration (CAR) = 999.6 mg L−1 and initial methylene blue concentration (CMB) = 878.5 mg L−1. Evaluation of biosorption data with Langmuir and Freundlich isotherms shows that the Langmuir model indicated the best fit to the equilibrium data with maximum adsorption capacity of 66.4 and 53.5 mg g−1 in single system and 54.6 and 43.9 mg g−1 in binary system for AR and MB, respectively. Moreover, kinetics of the biosorption process was also investigated.
Recent Progress in the Surface Modification of Photoelectrodes toward Efficient and Stable Overall Water Splitting
Authors: Kaneko Hiroyuki , Minegishi Tsutomu , Domen Kazunari
Published: October 2017

Photoelectrochemical (PEC) water splitting using a combination of a photocathode and photoanode is one of the most promising methods of producing hydrogen from water employing sunlight. Recent reports have shown that surface modification of the photoelectrodes dramatically improves their PEC performance. Bare photoelectrodes often exhibit insufficient depletion regions, undesired surface states and/or degradation due to photocorrosion. It has been demonstrated that surface modifications can tune the flat‐band potentials, band‐edge potentials, surface states and chemical stabilities of these electrodes and thus improve quantum efficiency, onset potential and durability. This review describes in detail the various surface modification materials that have been developed to date, and the functions of these modifiers. This information is expected to provide guidelines for the future development of photoelectrodes capable of highly efficient and stable PEC water splitting.
Recent Advances in Functional Polymer Decorated Two‐Dimensional Transition‐Metal Dichalcogenides Nanomaterials for Chemo‐Photothermal Therapy
Authors: Zhang Aitang , Li Aihua , Zhao Wei , Liu Jingquan
Published: October 2017

Novel nanomaterials and advanced nanotechnologies continue to promote the fast development of new approaches for efficient tumor therapy. As an alternative choice to various traditional therapies, non‐invasive photothermal therapy (PTT) has attracted significant attention mainly due to its low cost, highly localizing, specific tumor treatment and minimal side effects on healthy tissues. PTT induced by photo‐absorbing agents which can absorb and convert the external NIR laser into heat to ablate tumors. Plenty of studies have shown the significant potential of PTT to treat tumors in future practical applications. However, PTT alone usually could not eradicate tumors considering the intensity of laser gradual attenuates in biological tissues and the heat generated tends to distribute inhomogeneous within tumors tissues. Combination of chemotherapy with photothermal therapy into one system for tumor therapy is an effective strategy to further improve the therapy efficiency. In this Minireview, we focus on the recent advances in constructing PTT therapeutic and multi‐model combination therapeutic via integrating nanomaterials and functional polymers.
Head‐to‐Tail Cyclic Peptide Inhibitors of the Interaction between Human von Willebrand Factor and Collagen
Authors: Guarracino Danielle A. , Oldfield Alexis , Gentile Kayla , Martin Sara , Nguyen Dylan , Barreto Gianna , Kouba Christopher
Published: October 2017

The development of peptide‐based therapeutics is on the rise, with macrocyclic compounds providing the added stability and drug‐like characteristics sought after. Currently, therapies and preventatives for pathogenic thrombosis target platelet interactions at the site of the clot and have many complications. Herein we describe novel cyclic peptides as moderate inhibitors of the protein–protein interaction between von Willebrand factor (vWF) and collagen that initiates blood clot formation. We based our designs on two known disulfide‐containing, peptide‐based inhibitors of the vWF–collagen interaction. Replacing the disulfide with a head‐to‐tail cyclization strategy confers remarkable stability to the peptides when treated with a panel of proteases. Our peptides also showed moderate activity in our developed fluorescently linked immunosorbent assay (FLISA), similar to the most active disulfide‐containing peptide. These peptides provide a springboard for future advances in exceptionally stable, active cyclic peptides as drugs.
Synthesis and Biological Evaluation of Stilbene Analogues as Hsp90 C‐Terminal Inhibitors
Authors: Byrd Katherine M. , Kent Caitlin N. , Blagg Brian S. J.
Published: October 2017

The design, synthesis, and biological evaluation of stilbene‐based novobiocin analogues is reported. Replacement of the biaryl amide side chain with a triazole side chain produced compounds that exhibited good antiproliferative activities. Heat shock protein 90 (Hsp90) inhibition was observed when N‐methylpiperidine was replaced with acyclic tertiary amines on the stilbene analogues that also contain a triazole‐derived side chain. These studies revealed that ≈24 Å is the optimal length for compounds that exhibit good antiproliferative activity as a result of Hsp90 inhibition.
Comparative Molecular Dynamics Simulation of Aggregating and Non‐Aggregating Inhibitor Solutions: Understanding the Molecular Basis of Promiscuity
Authors: Ghattas Mohammad A. , Bryce Richard A. , Al Rawashdah Sara , Atatreh Noor , Zalloum Waleed A.
Published: October 2017

The presence of false positives in enzyme inhibition assays is a common problem in early drug discovery, especially for compounds that form colloid aggregates in solution. The molecular basis of these aggregates could not be thoroughly explored because of their transient stability. In this study we conducted comparative molecular dynamics (MD) simulations of miconazole, a strong aggregator, and fluconazole, a known non‐aggregator. Interestingly, miconazole displays full aggregation within only 50 ns, whilst fluconazole shows no aggregation over the 500 ns simulation. The simulations indicate that the center of the aggregate is densely packed by the hydrophobic groups of miconazole, whereas polar and nonpolar groups comprise the surface to form a micelle‐like colloid. The amphiphilic moment and planar nature of the miconazole structure appear to promote its aggregating behavior. The simulations also predict rapid aggregate formation for a second known promiscuous inhibitor, nicardipine. Thus, MD appears to be a useful tool to characterize aggregate‐prone inhibitors at molecular‐level detail and has the potential to provide useful information for drug discovery and formulation design.
The relationship between physical and psychological symptoms and health care utilization in hospitalized patients with advanced cancer
Authors: Nipp Ryan D. , El‐Jawahri Areej , Moran Samantha M. , D'Arpino Sara M. , Johnson P. Connor , Lage Daniel E. , Wong Risa L. , Pirl William F. , Traeger Lara , Lennes Inga T. , Cashavelly Barbara J. , Jackson Vicki A. , Greer Joseph A. , Ryan David P. , Hochberg Ephraim P. , Temel Jennifer S.
Published: October 2017

BACKGROUND

Patients with advanced cancer often experience frequent and prolonged hospitalizations; however, the factors associated with greater health care utilization have not been described. We sought to investigate the relation between patients' physical and psychological symptom burden and health care utilization.

METHODS

We enrolled patients with advanced cancer and unplanned hospitalizations from September 2014‐May 2016. Upon admission, we assessed physical (Edmonton Symptom Assessment System [ESAS]) and psychological symptoms (Patient Health Questionnaire 4 [PHQ‐4]). We examined the relationship between symptom burden and healthcare utilization using linear regression for hospital length of stay (LOS) and Cox regression for time to first unplanned readmission within 90 days. We adjusted all models for age, sex, marital status, comorbidity, education, time since advanced cancer diagnosis, and cancer type.

RESULTS

We enrolled 1,036 of 1,152 (89.9%) consecutive patients approached. Over one‐half reported moderate/severe fatigue, poor well being, drowsiness, pain, and lack of appetite. PHQ‐4 scores indicated that 28.8% and 28.0% of patients had depression and anxiety symptoms, respectively. The mean hospital LOS was 6.3 days, and the 90‐day readmission rate was 43.1%. Physical symptoms (ESAS: unstandardized coefficient [B], 0.06; P < .001), psychological distress (PHQ‐4 total: B, 0.11; P = .040), and depression symptoms (PHQ‐4 depression: B, 0.22; P = .017) were associated with longer hospital LOS. Physical (ESAS: hazard ratio, 1.01; P < .001), and anxiety symptoms (PHQ‐4 anxiety: hazard ratio, 1.06; P = .045) were associated with a higher likelihood for readmission.

CONCLUSIONS

Hospitalized patients with advanced cancer experience a high symptom burden, which is significantly associated with prolonged hospitalizations and readmissions. Interventions are needed to address the symptom burden of this population to improve health care delivery and utilization. Cancer 2017;123:4720‐4727. © 2017 American Cancer Society.
Histological outcomes of anal high‐grade cytopredictions
Authors: Roberts Jennifer Margaret , Jin Fengyi , Poynten Isobel Mary , Law Carmella , Templeton David James , Thurloe Julia Kathleen , Garland Suzanne Marie , Grulich Andrew Edwin , Farnsworth Annabelle , Hillman Richard John ,   on behalf of the Study of the Prevention of Anal Cancer Study Team
Published: October 2017

BACKGROUND

Longitudinal studies of histological outcomes after anal cytological screening in men who have sex with men (MSM) are rare. This study measured the positive predictive values (PPVs) of each level of baseline cytological abnormality in MSM in Sydney, Australia, over a 12‐month period.

METHODS

The Study of the Prevention of Anal Cancer is a 3‐year prospective study of the natural history of anal human papillomavirus infection in MSM at least 35 years old. For each participant with a baseline cytological abnormality, the worst histology was recorded at the baseline high‐resolution anoscopy and at 6 and 12 months. PPVs for a histological high‐grade squamous intraepithelial lesion (HSIL) diagnosis were calculated for each level of baseline cytological abnormality at each time point.

RESULTS

Among 424 men who completed 3 visits, the PPV of a cytological HSIL increased from 71.6% at the baseline to 86.4% at 6 months and to 92.6% at 12 months (P < .001). For cytological atypical squamous cells, cannot rule out high‐grade squamous intraepithelial lesion (ASC‐H), the PPV increased from 51.5% at the baseline to 69.7% at 6 months and to 75.8% at 12 months (P = .004). At each time point, the PPV of a cytological HSIL was significantly higher than the PPV of ASC‐H. The PPV of low‐grade cytology reports was significantly lower than the PPV of ASC‐H at each time point.

CONCLUSIONS

In a cohort of MSM, a baseline histological HSIL diagnosis after an HSIL cytoprediction is high, and it increases with further examinations over the course of 12 months. Lower levels of cytological abnormalities have significantly lower PPVs. These data can inform patient management and the quality assessment of each aspect of the screening pathway. Cancer Cytopathol 2018;126:136‐44. © 2017 American Cancer Society.
The Anaclitic–Introjective Depression Assessment: Development and preliminary validity of an observer‐rated measure
Authors: Rost Felicitas , Luyten Patrick , Fonagy Peter
Published: October 2017

Background

The two‐configurations model developed by Blatt and colleagues offers a comprehensive conceptual and empirical framework for understanding depression. This model suggests that depressed patients struggle, at different developmental levels, with issues related to dependency (anaclitic issues) or self‐definition (introjective issues), or a combination of both.

Aims

This paper reports three studies on the development and preliminary validation of the Anaclitic–Introjective Depression Assessment, an observer‐rated assessment tool of impairments in relatedness and self‐definition in clinical depression based on the item pool of the Shedler–Westen Assessment Procedure.

Method

Study 1 describes the development of the measure using expert consensus rating and Q‐methodology. Studies 2 and 3 report the assessment of its psychometric properties, preliminary reliability, and validity in a sample of 128 patients diagnosed with treatment‐resistant depression.

Results

Four naturally occurring clusters of depressed patients were identified using Q‐factor analysis, which, overall, showed meaningful and theoretically expected relationships with anaclitic/introjective prototypes as formulated by experts, as well as with clinical, social, occupational, global, and relational functioning.

Conclusion

Taken together, findings reported in this paper provide preliminary evidence for the reliability and validity of the Anaclitic–Introjective Depression Assessment, an observer‐rated measure that allows the detection of important nuanced differentiations between and within anaclitic and introjective depression.
Ligand‐Controlled Electrodeposition of Highly Intrinsically Active and Optically Transparent NiFeOxHy Film as a Water Oxidation Electrocatalyst
Authors: Lee Husileng , Wu Xiujuan , Yang Xiaonan , Sun Licheng
Published: October 2017

A highly intrinsically active and optically transparent NiFeOxHy water oxidation catalyst was prepared by electrodeposition of [Ni(C12‐tpen)](ClO4)2 complex (Ni−C12). This NiFeOxHy film has a current density of 10 mA cm−2 with an overpotential (η) of only 298 mV at nanomolar concentration and the current density of 10 mA cm−2 remains constant over 22 h in 1 m KOH. The extremely high turnover frequency of 0.51 s−1 was obtained with η of 300 mV. More importantly, such outstanding activity and transparency (optical loss <0.5 %) of the NiFeOxHy film are attributed to a ligand effect of the dodecyl substituent in Ni−C12, which enables its future application in solar water splitting.
Trends and uncertainties in budburst projections of Norway spruce in Northern Europe
Authors: Olsson Cecilia , Olin Stefan , Lindström Johan , Jönsson Anna Maria
Published: October 2017

Budburst is regulated by temperature conditions, and a warming climate is associated with earlier budburst. A range of phenology models has been developed to assess climate change effects, and they tend to produce different results. This is mainly caused by different model representations of tree physiology processes, selection of observational data for model parameterization, and selection of climate model data to generate future projections. In this study, we applied (i) Bayesian inference to estimate model parameter values to address uncertainties associated with selection of observational data, (ii) selection of climate model data representative of a larger dataset, and (iii) ensembles modeling over multiple initial conditions, model classes, model parameterizations, and boundary conditions to generate future projections and uncertainty estimates. The ensemble projection indicated that the budburst of Norway spruce in northern Europe will on average take place 10.2 ± 3.7 days earlier in 2051–2080 than in 1971–2000, given climate conditions corresponding to RCP 8.5. Three provenances were assessed separately (one early and two late), and the projections indicated that the relationship among provenance will remain also in a warmer climate. Structurally complex models were more likely to fail predicting budburst for some combinations of site and year than simple models. However, they contributed to the overall picture of current understanding of climate impacts on tree phenology by capturing additional aspects of temperature response, for example, chilling. Model parameterizations based on single sites were more likely to result in model failure than parameterizations based on multiple sites, highlighting that the model parameterization is sensitive to initial conditions and may not perform well under other climate conditions, whether the change is due to a shift in space or over time. By addressing a range of uncertainties, this study showed that ensemble modeling provides a more robust impact assessment than would a single phenology model run.