bluuebunny/crossref_metadata_2025 huggingface dataset:
Compositional Effects of Large Graphene Oxide Sheets on the Spinnability and Properties of Polyurethane Composite Fibers
Authors: Seyedin Shayan , Razal Joselito M. , Innis Peter C. , Jalili Rouhollah , Wallace Gordon G.
Published: January 2016

Recent advances in wearable electronics, technical textiles, and wearable strain sensing devices have resulted in extensive research on stretchable electrically conductive fibers. Addressing these areas require the development of efficient fiber processing methodologies that do not compromise the mechanical properties of the polymer (typically an elastomer) when nanomaterials are added as conductive fillers. It is highly desirable that the addition of conductive fillers provides not only electrical conductivity, but that these fillers also enhance the stiffness, strength, stretchability, and toughness of the polymer. Here, the compatibility of polyurethane (PU) and graphene oxide (GO) is utilized for the study of the properties of elastomeric conductive fibers prepared by wet‐spinning. The GO‐reinforced PU fibers demonstrate outstanding mechanical properties with a 200‐fold and a threefold enhancement in Young's modulus and toughness, respectively. Postspinning thermal annealing of the fibers results in electrically conductive fibers with a low percolation threshold (≈0.37 wt% GO). An investigation into optimized fiber's electromechanical behavior reveals linear strain sensing abilities up to 70%. Results presented here provide practical insights on how to simultaneously maintain or improve electrical, mechanical, and electromechanical properties in conductive elastomer fibers.
Lasing Emission from Plasmonic Nanodome Arrays
Authors: Wu Hsin‐Yu , Liu Longju , Lu Meng , Cunningham Brian T.
Published: January 2016

Plasmonic nano‐dome arrays (PNDA) have been previously studied as chemical and biological sensors. The present study reports large‐area plasmonic lasing from the PNDA structures with liquid‐phase gain materials to provide optical gain. The PDNA structure consists of a 2D array of nanoposts, fabricated inexpensively using a nanoreplica molding process, with silicon dioxide and gold thin‐film coatings to produce the dome‐shaped surface profile. Covered with a dye‐doped solution, the PDNA structures can generate lasing emission when they are optically pumped above the lasing threshold. The lasing emission is enabled by energy coupling from the photoexcited dye molecules to the hybridized plasmon mode supported by the PDNA oscillator. Two PDNA lasers with array periods of 400 and 450 nm are fabricated and characterized. Plasmonic resonant modes of the PDNA lasers are numerically studied to illustrate the underlying lasing mechanism. The emission characteristics, including lasing wavelength, linewidth, threshold, beam divergence, and radiation angle, are presented in the paper. The PNDA laser represents a new path for plasmonic lasing in the near‐infrared region with potential applications that include integrated photonic circuits, optical communications, and high‐performance biosensors.
Solvent‐Mediated Dimension Tuning of Semiconducting Oxide Nanostructures as Efficient Charge Extraction Thin Films for Perovskite Solar Cells with Efficiency Exceeding 16%
Authors: Wu Wu‐Qiang , Huang Fuzhi , Chen Dehong , Cheng Yi‐Bing , Caruso Rachel A.
Published: January 2016

The recent surge in efficiency and progress of organohalide perovskite solar cells (PSCs) has been significant. The PSC performance is significantly influenced by nanostructuring as this varies the intrinsic optical, electrical, and electrochemical properties. Diverse TiO2 electron transport layers (ETLs) are solvothermally grown on the transparent conducting oxide substrate with different dimensionalities, 0D nanoparticles (TNP), 1D nanowires (TNW) to 2D nanosheets (TNS), by varying the organic solvent used. These layers feature enhanced optical transparency (≈2%–5% transmittance improvement compared to pristine fluorine doped tin oxide, FTO, glass) minimizing light absorption losses. PSCs constructed using 1D TNW or 2D TNS yield enhanced photovoltaic performance compared to the 0D TNP counterparts. This is a result of i) improved infiltration of the perovskite in the porous TNW or TNS network and ii) facilitated electron transport and charge extraction at the TNW/perovskite or TNS/perovskite interfaces, thus reduced interfacial recombination loss. Employing a bilayered ETL film consisting of a self‐assembled TiO2 blocking layer and a subsequent TNW active layer, produces PSC devices with an efficiency exceeding 16%. This bilayered ETL film can simultaneously block the photogenerated holes and enhance electron ­extraction, therefore improving PSC performance.
A novel treatment adjunct for aspirin exacerbated respiratory disease: the low‐salicylate diet: a multicenter randomized control crossover trial
Authors: Sommer Doron D. , Rotenberg Brian W. , Sowerby Leigh J. , Lee John M. , Janjua Arif , Witterick Ian J. , Monteiro Eric , Gupta Michael K. , Au Michael , Nayan Smriti
Published: January 2016

Background

Aspirin‐exacerbated respiratory disease (AERD) is a clinical triad consisting of aspirin/acetylsalicylic acid (ASA) sensitivity, bronchial asthma, and nasal polyposis. Although respiratory reactions following ingestion of ASA and other nonsteroidal anti‐inflammatory drugs (NSAIDs) are considered a hallmark of the condition, respiratory inflammation persists despite patients’ avoidance of NSAIDs. Treatment of this condition remains challenging and includes both medical and surgical options.

Methods

A prospective crossover single‐blind multicenter study involving 4 tertiary rhinology care centers (n = 30) was conducted in which patients were randomized to start with either 6 weeks of a regular diet or 6 weeks of a low‐salicylate diet and then crossed‐over for a total study duration of 12 weeks. Patients were evaluated at baseline, 6 weeks (at crossover) and 12 weeks using subjective measures (22‐item Sino‐Nasal Outcome Test‐22 [SNOT‐22], Nasal Sinus Symptom Scale [NSSS], and 7‐item Asthma Control Questionnaire [ACQ‐7]) and objective outcome instruments (Perioperative Sinus Evaluation [POSE] and Lund‐Kennedy Endoscopic Score [LKES]).

Results

Data was analyzed for 30 patients. Wilcoxon rank sum tests determined that patients had improvement in their median difference in scores, which were all statistically significant, when they followed the low‐salicylate diet compared to their regular diet: SNOT‐22: 15 (95% confidence interval [CI], 10 to 23.25), p < 0.001; NSSS: 3 (95% CI, 1.75 to 4), p < 0.001; ACQ‐7: 4.5 (95% CI, 1.5 to 8.5), p < 0.001; POSE 6 (95% CI, 2.5 to 10), p < 0.001; and LKES: 2.5 (95% CI, 1.5 to 4), p < 0.001).

Conclusion

The low‐salicylate diet may offer a novel treatment adjunct to the current management of AERD. Clinically and statistically significant improvements on both subjective and objective outcome measures were noted for the upper and lower respiratory tracts.
Frontal sinus surgery and sinus distribution of nasal irrigation
Authors: Barham Henry P. , Ramakrishnan Vijay R. , Knisely Anna , Do Timothy Quy‐Phong , Chan Lyndon S. , Gunaratne Dakshika A. , Weston Jared D. , Seneviratne Sheran , Marcells George N. , Sacks Raymond , Harvey Richard J.
Published: January 2016

Background

Effective mucus lavage and delivery of topical pharmaceuticals are central to successful management of chronic rhinosinusitis (CRS). The frontal sinus remains difficult to penetrate with topical therapies. This study evaluates the benefit of Draf III frontal dissection compared to traditional Draf IIa for distribution of topical therapies.

Methods

Fresh human cadaver heads were dissected sequentially with Draf IIa frontal sinusotomy and then Draf III procedures. Each cavity was irrigated with pediatric (120 mL) and adult (240 mL) irrigation bottles with 1/1000 10% fluorescein‐labeled free water in 2 fixed positions (vertex and Frankfort horizontal). An endoscope at a fixed position within the frontal sinus recorded frontal sinus and frontal recess penetration. The images then underwent blinded evaluation of fluid distribution scored as 0 to 4 (nasal cavity only, frontal recess, medial one‐half, lateral one‐half, and lavage). Ordinal distribution score was analyzed with Kendall's tau‐b.

Results

Eight specimens (age 76 ± 11.2 years; 50% female) were assessed. Draf III was superior to Draf IIa in ability to achieve frontal sinus distribution of irrigation (90.6% vs 50.1%, p < 0.001). Vertex head position improved distribution (90.6% vs 50.1%, p < 0.001), was synergistic with Draf III (100% with 87.5% lavage, p < 0.001), but was unable to overcome Draf IIa (81.2% with 25% lavage, p < 0.001). Irrigation volume trended toward improved distribution with larger volume irrigations.

Conclusion

Successful treatment of sinonasal disease may require postoperative delivery of topical therapies. Draf III frontal sinusotomy achieves superior topical access, and access to the frontal sinus with Draf IIa appears limited, despite large volumes and positioning.
Baseline clinical characteristics predict follow‐up clinic attendance in patients undergoing endoscopic sinus surgery for chronic rhinosinusitis
Authors: Lal Devyani , B. Golisch Kimberly , Chang Yu‐Hui , A. Rank Matthew
Published: January 2016

Background

The objective of this work was to describe the association between baseline clinical characteristics and attendance at follow‐up visits after endoscopic sinus surgery (ESS).

Methods

A retrospective review of chronic rhinosinusitis (CRS) patients electing ESS at a tertiary‐care center (2011‐2013) was conducted. Baseline characteristics were studied for association with clinic attendance at 3, 6, 12, and 24 months post‐ESS.

Results

We identified 268 patients. Significant decline occurred in the number of patients following up after ESS (3 months: 246 patients [92%]; 6 months: 145 [54%]; 12 months: 94 [35%]; and 24 months: 90 [34%]). Older patients were more likely to follow up at 3 months (mean age 55.7 vs 48.4 years, p = 0.04) and 6 months (57.5 vs 52.3 years; p = 0.01) post‐ESS. Those with higher preoperative sinus computed tomography (CT) (Lund‐Mackay) scores were more likely to follow at 6 months (11.8 vs 10.3, p = 0.01), 12 months (12.6 vs 10.3, p < 0.001), and 24 months (12.2 vs 10.5, p = 0.01). At 12 months having asthma (p = 0.03), previous ESS (p = 0.04), nasal polyps (p < 0.0001), allergic fungal sinusitis (AFS) (p = 0.002), and granulomatosis with polyangiitis (GPA) (p = 0.01) were associated with clinic attendance. At 24 months asthma status (p = 0.003), previous ESS (p = 0.002), AFS (p = 0.04), GPA (p = 0.001), and aspirin‐exacerbated respiratory disease (AERD) (p = 0.006) were associated with higher attendance. Geographical proximity did not impact attendance.

Conclusion

The sharpest decline in patient follow‐up occurred between 3–6 months after ESS. Higher preoperative sinus CT scores, previous ESS, presence of asthma, and diagnosis of recalcitrant CRS subtype (nasal polyps, AERD, AFS, GPA) were factors associated with increased long‐term attendance.
Vitamin D deficiency is associated with increased human sinonasal fibroblast proliferation in chronic rhinosinusitis with nasal polyps
Authors: Carroll William W. , Schlosser Rodney J. , O'Connell Brendan P. , Soler Zachary M. , Mulligan Jennifer K.
Published: January 2016

Background

Vitamin D3 (VD3) is a steroid hormone with known antiproliferative properties. Patients with chronic rhinosinusitis with nasal polyps (CRSwNP) have been shown to be VD3‐deficient. Moreover, VD3 deficiency is associated with worse disease in patients with CRSwNP. One cell type thought to play a role in chronic rhinosinusitis (CRS) is the human sinonasal fibroblast (HSNF). The aim of this study was to investigate VD3 deficiency and HSNF proliferation in CRSwNP.

Methods

Blood and sinus tissue explants were collected at the time of surgery from patients with CRSwNP (n = 15). Control subjects (n = 12) were undergoing surgery for cerebrospinal fluid leak repair or to remove non–hormone‐secreting pituitary tumors. Ex vivo HSNF proliferation was analyzed with flow cytometry using expression of fibroblast‐specific protein (FSP) and the proliferation marker Ki67. Plasma levels of 25‐hydroxyvitamin D3 (25VD3) were measured by enzyme‐linked immunosorbent assay. In vitro analysis of HSNF proliferation after treatment with calcitriol (1,25VD3) was performed using carboxyfluorescein succinimidyl ester (CFSE) and analyzed with flow cytometry.

Results

In CRSwNP patients there was an inverse correlation between 25VD3 and proliferating HSNFs (p = 0.0135). This correlation was not seen for control patients (p = 0.3869). In vitro analysis showed that HSNFs from patients with CRSwNP had a higher proliferation index at baseline than HSNFs from control patients (p < 0.01). When treated with 1,25VD3, there was a significant decrease in HSNF proliferation index in patients with CRSwNP (p < 0.01), but not control patients.

Conclusion

VD3 deficiency is associated with increased HSNF proliferation in CRSwNP. Further investigation into how HSNFs and VD3 impact CRSwNP pathophysiology is warranted.
An alien fish threatens an endangered parasitic bivalve: the relationship between brook trout (Salvelinus fontinalis) and freshwater pearl mussel (Margaritifera margaritifera) in northern Europe
Authors: Salonen Jouni K. , Marjomäki Timo J. , Taskinen Jouni
Published: January 2016

Host–parasite interactions may play a significant role in biological invasions: for example, an invader may benefit from lower infectivity by native parasites in competition against the native hosts (‘enemy release hypothesis’).

The invasive North American brook trout (Salvelinus fontinalis) is replacing the native salmonid hosts of the freshwater pearl mussel (FPM,Margaritifera margaritifera) in northern Europe, but the suitability of brook trout as a host for FPM is poorly known. In this study its suitability was investigated using an array of laboratory and field experiments, and several FPM populations from a catchment in northern Finland. The occurrence of brook trout in FPM rivers in the area was also studied.

There were differences with respect to numbers and size of FPM larvae among the fish exposed to FPM, but generally brook trout was an unsuitable host or was clearly a poorer host for FPM than the native European salmonids, brown trout (Salmo trutta) or Atlantic salmon (Salmo salar). However, in one river a few FPM glochidia remained encysted in wild brook trout for at least 9 months, suggesting successful development – the first observation of its kind in Europe.

A tendency was found for higher occurrence of brook trout in brown trout rivers with FPM than in brown trout rivers without FPM, being consistent with the enemy release hypothesis: as FPM infection is costly to the host, a higher glochidial load in brown trout may offer a competitive advantage to brook trout in FPM rivers.

Generally, these results indicate that northern European FPM populations cannot typically use brook trout as their host fish. Therefore, the invasion and dispersal of brook trout, potentially leading to the disappearance of native salmonids, should also be considered as a potential threat to the endangered FPM populations.

Copyright © 2016 John Wiley & Sons, Ltd.
Cranial Suture Closure in Domestic Dog Breeds and Its Relationships to Skull Morphology
Authors: Geiger Madeleine , Haussman Sinah
Published: January 2016

Bulldog‐type brachycephalic domestic dog breeds are characterized by a relatively short and broad skull with a dorsally rotated rostrum (airorhynchy). Not much is known about the association between a bulldog‐type skull conformation and peculiar patterns of suture and synchondrosis closure in domestic dogs. In this study, we aim to explore breed‐specific patterns of cranial suture and synchondrosis closure in relation to the prebasial angle (proxy for airorhynchy and thus bulldog‐type skull conformation) in domestic dogs. For this purpose, we coded closure of 18 sutures and synchondroses in 26 wolves, that is, the wild ancestor of all domestic dogs, and 134 domestic dogs comprising 11 breeds. Comparisons of the relative amount of closing and closed sutures and synchondroses (closure scores) in adult individuals showed that bulldog‐type breeds have significantly higher closure scores than non‐bulldog‐type breeds and that domestic dogs have significantly higher closure scores than the wolf. We further found that the prebasial angle is significantly positively correlated with the amount of closure of the basispheno‐presphenoid synchondrosis and sutures of the nose (premaxillo‐nasal and maxillo‐nasal) and the palate (premaxillo‐maxillary and interpalatine). Our results show that there is a correlation between patterns of suture and synchondrosis closure and skull shape in domestic dogs, although the causal relationships remain elusive. Anat Rec, 299:412–420, 2016. © 2016 Wiley Periodicals, Inc.
The Digestive Tract and Derived Primordia Differentiate by Following a Precise Timeline in Human Embryos Between Carnegie Stages 11 and 13
Authors: Ueno Saki , Yamada Shigehito , Uwabe Chigako , Männer Jörg , Shiraki Naoto , Takakuwa Tetsuya
Published: January 2016

The precise mechanisms through which the digestive tract develops during the somite stage remain undefined. In this study, we examined the morphology and precise timeline of differentiation of digestive tract‐derived primordia in human somite‐stage embryos. We selected 37 human embryos at Carnegie Stage (CS) 11–CS13 (28–33 days after fertilization) and three‐dimensionally analyzed the morphology and positioning of the digestive tract and derived primordia in all samples, using images reconstructed from histological serial sections. The digestive tract was initially formed by a narrowing of the yolk sac, and then several derived primordia such as the pharynx, lung, stomach, liver, and dorsal pancreas primordia differentiated during CS12 (21–29 somites) and CS13 (≥ 30 somites). The differentiation of four pairs of pharyngeal pouches was complete in all CS13 embryos. The respiratory primordium was recognized in ≥ 26‐somite embryos and it flattened and then branched at CS13. The trachea formed and then elongated in ≥ 35‐somite embryos. The stomach adopted a spindle shape in all ≥ 34‐somite embryos, and the liver bud was recognized in ≥ 27‐somite embryos. The dorsal pancreas appeared as definitive buddings in all but three CS13 embryos, and around these buddings, the small intestine bent in ≥ 33‐somite embryos. In ≥ 35‐somite embryos, the small intestine rotated around the cranial‐caudal axis and had begun to form a primitive intestinal loop, which led to umbilical herniation. These data indicate that the digestive tract and derived primordia differentiate by following a precise timeline and exhibit limited individual variations. Anat Rec, 299:439–449, 2016. © 2016 Wiley Periodicals, Inc.
The Peridural Membrane of the Human Spine is Well Innervated
Authors: Bosscher Hemmo A. , Heavner James E. , Grozdanov Petar , Warraich Irfan A. , Wachtel Mitchell S. , Dertien Janet
Published: January 2016

There is evidence that low back pain may originate from a peridural membrane (PDM) at the inferior and medial aspect of neural foramen of the lumbar spine. The objective of this investigation was to determine if this membrane contains neural elements suggestive of sensory innervation with nociceptive function. Spines of four embalmed and three non‐embalmed human cadavers were dissected using a sagittal approach to the neural foramen. Seventeen samples of the peridural membrane overlying the neural foramen were collected for immunohistochemistry (IHC) examination by light microscopy and transmission electron microscopy (TEM). Chromagin tagged antibodies to protein gene product 9.5 (PGP9.5) and S‐100, and fluorescent antibodies to substance P and calcitonin gene related peptide (CGRP) were used to label neural structures in tissue sections cut from paraffin embedded blocks. This approach allows good visualization of all neural elements, small sensory, and nociceptive nerve fibers in particular. Neural elements were found in all samples. Marked presence of small nerve fibers was observed in 12 of 15 samples. IHC and TEM evaluation revealed myelinated as well as unmyelinated fibers in the peridural membrane. CGRP and substance P immunoreactive fibers indicative of nociceptive function were abundant. These findings confirm and expand evidence that the peridural membrane in human is well innervated and contains sensory nociceptive nerve fibers suggestive of a nociceptive function of the membrane. Anat Rec, 299:484–491, 2016. © 2016 Wiley Periodicals, Inc.
The effect of personalization provider characteristics on privacy attitudes and behaviors: An Elaboration Likelihood Model approach
Authors: Kobsa Alfred , Cho Hichang , Knijnenburg Bart P.
Published: January 2016

Many computer users today value personalization but perceive it in conflict with their desire for privacy. They therefore tend not to disclose data that would be useful for personalization. We investigate how characteristics of the personalization provider influence users' attitudes towards personalization and their resulting disclosure behavior. We propose an integrative model that links these characteristics via privacy attitudes to actual disclosure behavior. Using the Elaboration Likelihood Model, we discuss in what way the influence of the manipulated provider characteristics is different for users engaging in different levels of elaboration (represented by the user characteristics of privacy concerns and self‐efficacy). We find particularly that (a) reputation management is effective when users predominantly use the peripheral route (i.e., a low level of elaboration), but much less so when they predominantly use the central route (i.e., a high level of elaboration); (b) client‐side personalization has a positive impact when users use either route; and (c) personalization in the cloud does not work well in either route. Managers and designers can use our results to instill more favorable privacy attitudes and increase disclosure, using different techniques that depend on each user's levels of privacy concerns and privacy self‐efficacy.
On a new multivariate IFR ageing notion based on the standard construction
Authors: Arriaza A. , Belzunce F. , Mulero J. , Suárez‐Llorens A.
Published: January 2016

Many criteria of ageing for random variables or vectors have been proposed in the literature over many years. For instance, a random variable is increasing in failure rate (IFR) if, and only if, it can be ordered with an exponentially distributed random variable in the classical univariate convex transform order. A new multivariate generalization of the convex transform order has recently been proposed in the literature. In this work, we propose a new multivariate IFR notion for multivariate distributions based on comparisons in this new order with a properly defined exponentially distributed random vector. Properties, applications, and illustrations of this new notion are given as well. Copyright © 2016 John Wiley & Sons, Ltd.
Self‐Sacrificial Template‐Directed Synthesis of Metal–Organic Framework‐Derived Porous Carbon for Energy‐Storage Devices
Authors: Ding Bing , Wang Jie , Chang Zhi , Xu Guiyin , Hao Xiaodong , Shen Laifa , Dou Hui , Zhang Xiaogang
Published: January 2016

Metal–organic framework (MOF)‐derived carbon materials exhibit large surface areas, but dominant micropore characteristics and uncontrollable dimensions. Herein, we propose a self‐sacrificial template‐directed synthesis method to engineer the porous structure and dimensions of MOF‐derived carbon materials. A porous zinc oxide (ZnO) nanosheet solid is selected as the self‐sacrificial template and two‐dimensional (2D) nanostructure‐directing agent to prepare 2D ZIF‐8‐derived carbon nanosheets (ZCNs). The as‐prepared ZCN materials exhibit a large surface area with hierarchical porosity. These intriguing features render ZCN materials advanced electrode materials for electrochemical energy‐storage devices, demonstrating large ion‐accessible surface area and high ion‐/electron‐transport rates. This self‐sacrificial template‐directed synthesis method offers new avenues for rational engineering of the porous structure and dimensions of MOF‐derived porous carbon materials, thus exploiting their full potential for electrochemical energy‐storage devices.
Nitrogen‐Doped Hollow Amorphous Carbon Spheres@Graphitic Shells Derived from Pitch: New Structure Leads to Robust Lithium Storage
Authors: Ma Qingtao , Wang Luxiang , Xia Wei , Jia Dianzeng , Zhao Zongbin
Published: January 2016

Nitrogen‐doped mesoporous hollow carbon spheres (NHCS) consisting of hybridized amorphous and graphitic carbon were synthesized by chemical vapor deposition with pitch as raw material. Treatment with HNO3 vapor was performed to incorporate oxygen‐containing groups on NHCS, and the resulting NHCS‐O showed excellent rate capacity, high reversible capacity, and excellent cycling stability when tested as the anode material in lithium‐ion batteries. The NHCS‐O electrode maintained a reversible specific capacity of 616 mAh g−1 after 250 cycles at a current rate of 500 mA g−1, which is an increase of 113 % compared to the pristine hollow carbon spheres. In addition, the NHCS‐O electrode exhibited a reversible capacity of 503 mAh g−1 at a high current density of 1.5 A g−1. The superior electrochemical performance of NHCS‐O can be attributed to the hybrid structure, high N and O contents, and rich surface defects.
The Nature of Activated Non‐classical Hydrogen Bonds: A Case Study on Acetylcholinesterase–Ligand Complexes
Authors: Berg Lotta , Mishra Brijesh Kumar , Andersson C. David , Ekström Fredrik , Linusson Anna
Published: January 2016

Molecular recognition events in biological systems are driven by non‐covalent interactions between interacting species. Here, we have studied hydrogen bonds of the CH⋅⋅⋅Y type involving electron‐deficient CH donors using dispersion‐corrected density functional theory (DFT) calculations applied to acetylcholinesterase–ligand complexes. The strengths of CH⋅⋅⋅Y interactions activated by a proximal cation were considerably strong; comparable to or greater than those of classical hydrogen bonds. Significant differences in the energetic components compared to classical hydrogen bonds and non‐activated CH⋅⋅⋅Y interactions were observed. Comparison between DFT and molecular mechanics calculations showed that common force fields could not reproduce the interaction energy values of the studied hydrogen bonds. The presented results highlight the importance of considering CH⋅⋅⋅Y interactions when analysing protein–ligand complexes, call for a review of current force fields, and opens up possibilities for the development of improved design tools for drug discovery.
The Synthesis of Organic Molecules of Intrinsic Microporosity Designed to Frustrate Efficient Molecular Packing
Authors: Taylor Rupert G. D. , Bezzu C. Grazia , Carta Mariolino , Msayib Kadhum J. , Walker Jonathan , Short Rhys , Kariuki Benson M. , McKeown Neil B.
Published: January 2016

Efficient reactions between fluorine‐functionalised biphenyl and terphenyl derivatives with catechol‐functionalised terminal groups provide a route to large, discrete organic molecules of intrinsic microporosity (OMIMs) that provide porous solids solely by their inefficient packing. By altering the size and substituent bulk of the terminal groups, a number of soluble compounds with apparent BET surface areas in excess of 600 m2 g−1 are produced. The efficiency of OMIM structural units for generating microporosity is in the order: propellane>triptycene>hexaphenylbenzene>spirobifluorene>naphthyl=phenyl. The introduction of bulky hydrocarbon substituents significantly enhances microporosity by further reducing packing efficiency. These results are consistent with findings from previously reported packing simulation studies. The introduction of methyl groups at the bridgehead position of triptycene units reduces intrinsic microporosity. This is presumably due to their internal position within the OMIM structure so that they occupy space, but unlike peripheral substituents they do not contribute to the generation of free volume by inefficient packing.
Synthesis of Optically Active, X‐Shaped, Conjugated Compounds and Dendrimers Based on Planar Chiral [2.2]Paracyclophane, Leading to Highly Emissive Circularly Polarized Luminescence
Authors: Gon Masayuki , Morisaki Yasuhiro , Sawada Risa , Chujo Yoshiki
Published: January 2016

Optically active, Fréchet‐type dendrimers containing an emissive X‐shaped π‐electron system as the core unit were synthesized. Gram‐scale optical resolution and transformations of 4,7,12,15‐tetrasubstituted [2.2]paracyclophanes were also carried out. The high‐generation dendrons effectively absorbed UV light and transferred energy to the core, resulting in high photoluminescence (PL) from the core. In addition, the dendrons sufficiently isolated the emissive X‐shaped conjugated core and bright emission was observed from both thin films and solutions. Intense circularly polarized luminescence (CPL) was observed from the thin film. The dendrimer films exhibited excellent optical properties, such as large molar extinction coefficients, high fluorescence quantum efficiencies, intense PL and CPL, and large CPL dissymmetry factors.
Stereo‐ and Regioselective Synthesis of Tricyclic Spirolactones by Diastereoisomeric Differentiation of a Collective Key Precursor
Authors: Valerio Viviana , Mostinski Yelena , Kotikalapudi Ramesh , Tsvelikhovsky Dmitry
Published: January 2016

A general, parallel, and collective synthesis of 5/5/5‐ and 5/5/6‐ring fusion topologies of tricyclic spiranoid lactones through the controlled cyclizations of easily accessible, common key precursors is described. The rapid composition of key cycloalkyl methylene precursors yielded an assembly of bicyclic diastereoisomeric iodolactones, which were individually converted into a wide range of tricyclic, angularly fused spiranoid lactones in a regioselective and stereodirected fashion through the diastereoisomeric differentiation of a collective key precursor. The critical stereochemical assignment of the bicyclic starting materials, as well as the tricyclic targets, was confirmed by X‐ray crystal structure determination.
Syntheses of Platinum–Sulindac Complexes and Their Nanoparticles as Targeted Anticancer Drugs
Authors: Hwu Jih Ru , Tsay Shwu‐Chen , Chuang Kao Shu , Kapoor Mohit , Lin Jia Yu , Yeh Chen‐Sheng , Su Wu‐Chou , Wu Ping‐Ching , Tsai Tsung‐Lin , Wang Pei‐Wen , Shieh Dar‐Bin
Published: January 2016

Platinum(II)–sulindac complexes [{η2‐C5H4SN(O)}Pt(DMSO){O(C=O)Sulindac}], [{η2‐C5H4SN(O)}PtCl{(S=O)Sulindac}], [{η2‐C5H4SN(O)}PtCl{(S=O)Sulindac–succinimide}], and [{η2‐C5H4SN(O)}PtCl{(S=O)Sulindac–thymidine}] were synthesized that exhibited IC50 values of 2.9–4.8 μm against human oral cancer cells OECM1. The poly(lactic‐co‐glycolic acid) (PLGA) encapsulated [{η2‐C5H4SN(O)}PtCl{(S=O)Sulindac}] also showed cytotoxic activity although less potent than the pristine species.
Production of synthetic fuels by high‐temperature co‐electrolysis of carbon dioxide and steam with Fischer‐Tropsch synthesis
Authors: Frost Lyman , Elangovan Elango , Hartvigsen Joseph
Published: January 2016

Numerous entities are currently involved in the production of synthetic fuels using various feedstock options including natural gas, refuse derived fuel, landfill gas, anaerobic digester gas, coal, and mixtures of these inputs. Current world‐class FT plants (∼15 900 m3/d or 100 000 barrels per day) require large deposits of natural gas (i.e. ∼1.78 m3/L/d or 10 MSCF/BPD means gas sources that can provide ∼10 billion m3 per year for plant lifetime). Modular Fischer‐Tropsch (FT) reactors currently under development have some unique features that reduce cost and provide the ability to utilize sources of natural gas, biomass, or other under‐utilized sources of energy that would otherwise not be developed. The current Ceramatec modular FT reactor operates with a fixed bed size of 10 cm diameter using an internal heat transfer structure to keep axial and radial temperature variation to < 10 °C. The internal heat transfer media avoids the traditional problem with fixed bed reactors of heat removal from highly exothermic reactions. These reactors can also be used to mitigate the current concern with emissions of carbon dioxide when used in conjunction with high‐temperature co‐electrolysis (HTCE) of carbon dioxide and water to produce synthesis gas and subsequently synthetic fuels. When combined with a non‐carbon source of electricity such as wind, solar, biomass gasification, or anaerobic digester gas, it is possible to store intermittent sources of electricity as liquid fuels for later use. The HTCE generally operates at a voltage of 1.32 V and a current density of ∼300 mA/cm2.
Chronic medical conditions in adult survivors of retinoblastoma: Results of the Retinoblastoma Survivor Study
Authors: Friedman Danielle Novetsky , Chou Joanne F. , Oeffinger Kevin C. , Kleinerman Ruth A. , Ford Jennifer S. , Sklar Charles A. , Li Yuelin , McCabe Mary S. , Robison Leslie L. , Marr Brian P. , Abramson David H. , Dunkel Ira J.
Published: January 2016

BACKGROUND

Limited data are available regarding long‐term morbidity in adult survivors of retinoblastoma (Rb).

METHODS

The Retinoblastoma Survivor Study is a retrospective cohort of adult survivors of Rb diagnosed between 1932 and 1994. Participants completed a comprehensive questionnaire adapted from the Childhood Cancer Survivor Study surveys. Chronic conditions were classified using the National Cancer Institute's Common Terminology Criteria for Adverse Events (version 4.03). Multivariate Poisson regression was used to compare survivors of Rb with 2377 non‐Rb controls, consisting of the Childhood Cancer Survivor Study sibling cohort and survivors with bilateral versus unilateral disease.

RESULTS

Survivors of Rb (53.6% with bilateral disease) and non‐Rb controls had a mean age of 43.3 years (standard deviation, 11 years) and 37.6 years (SD, 8.6 years), respectively, at the time of study enrollment. At a median follow‐up of 42 years (range, 15‐75 years), 86.6% of survivors of Rb had at least 1 condition and 71.1% had a severe/life‐threatening (grade 3‐4) condition. The adjusted relative risk (RR) of a chronic condition in survivors compared with non‐Rb controls was 1.4 (95% confidence interval [95% CI], 1.3‐1.4; P<.01); for a grade 3 to 4 condition, the RR was 7.6 (95% CI, 6.4‐8.9; P<.01). Survivors were at an excess risk regardless of laterality. After stratifying by laterality and excluding ocular conditions and second malignant neoplasms (SMNs), only those with bilateral disease were found to be at an increased risk of any nonocular, non‐SMN condition (RR, 1.2; 95% CI, 1.1‐1.2) and for grade 3 to 4 nonocular, non‐SMN conditions (RR, 1.7; 95% CI, 1.2‐2.5).

CONCLUSIONS

Survivors of Rb have an increased risk of chronic conditions compared with non‐Rb controls. After excluding ocular conditions and SMNs, this excess risk was found to persist only for those with bilateral disease. Cancer 2016;122:773–781. © 2016 American Cancer Society.
Excited‐State Proton Transfer and Intramolecular Charge Transfer in 1,3‐Diketone Molecules
Authors: Savarese Marika , Brémond Éric , Adamo Carlo , Rega Nadia , Ciofini Ilaria
Published: January 2016

The photophysical signature of the tautomeric species of the asymmetric (N,N‐dimethylanilino)‐1,3‐diketone molecule are investigated using approaches rooted in density functional theory (DFT) and time‐dependent DFT (TD‐DFT). In particular, since this molecule, in the excited state, can undergo proton transfer reactions coupled to intramolecular charge transfer events, the different radiative and nonradiative channels are investigated by making use of different density‐based indexes. The use of these tools, together with the analysis of both singlet and triplet potential energy surfaces, provide new insights into excited‐state reactivity allowing one to rationalize the experimental findings including different behavior of the molecule as a function of solvent polarity.
The Effect of Exciton‐Delocalizing Thiols on Intrinsic Dual Emitting Semiconductor Nanocrystals
Authors: Jethi Lakshay , Mack Timothy G. , Krause Michael M. , Drake Sebastian , Kambhampati Patanjali
Published: January 2016

The emissive properties of thiol‐capped CdSe nanocrystals (NCs) with intrinsic dual emission are investigated through temperature‐dependent photoluminescence (PL) measurements. We demonstrate the influence of thiols on the relative PL intensities of the core and surface emissive states, as well as on the observed Stokes shifts. A redshift of both the core and surface PL in comparison with phosphonate‐capped NCs is consistent with recent work exploring the effect of thiols as excitonic hole‐delocalizing ligands. This observation is consistent with prior reports suggesting that surface excitons originate from electrons bound to cadmium trap states.
Quinones as Reversible Electron Relays in Artificial Photosynthesis
Authors: Rodenberg Alexander , Orazietti Margherita , Mosberger Mathias , Bachmann Cyril , Probst Benjamin , Alberto Roger , Hamm Peter
Published: January 2016

We explore the potential of various hydroquinone/quinone redox couples as electron relays in a homogenous water reduction system between a Re‐based photosensitizer and a sacrificial electron donor [tris‐(2‐carboxyethyl)‐phosphine, TCEP]. By using transient IR spectroscopy, flash photolysis as well as stopped‐flow techniques covering timescales from picoseconds to 100 ms, we determine quenching rates and cage escape yields, the kinetics of the follow‐up chemistry of the semiquinone, the recombination rates, as well as the re‐reduction rates by TCEP. The overall quantum yield of hydrogen production is low, and we show that the limiting factors are the small cage escape yields and, more importantly, the slow regeneration rate by TCEP in comparison to the undesired charge recombination with the reduced water reduction catalyst.
Controlled Synthesis of Recyclable, Porous FMO/C@TiO2 Core–Shell Nanofibers with High Adsorption and Photocatalysis Properties for the Efficient Treatment of Dye Wastewater
Authors: Chen Dezhi , Liu Caixia , Chen Suhua , Shen Weisong , Luo Xubiao , Guo Lin
Published: January 2016

One‐dimensional magnetite/manganese iron oxide modified by carbon coating and with TiO2 nanoparticles into core–shell composite nanofibers (FMO/C@TiO2) with porous structure were fabricated using organometallic compounds as templates. The structure and physicochemical properties of the as‐obtained composite nanofibers were characterized by a series of techniques, including X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, nitrogen adsorption–desorption isotherms, X‐ray photoelectron spectroscopy and UV/Vis diffuse reflectance. The results demonstrate that the one‐dimensional core–shell structure was formed by coating TiO2 nanoparticles onto a substrate of FMO/C nanofibers. The porous nanostructures and photoresponse range of the composite nanofibers can be controlled by varying the proportion of both template and titanium source. The resultant composite nanofibers exhibited highly efficient removal of dye from wastewater by combining adsorption and photocatalysis processes. In addition, the composite nanofibers are superparamagnetic, and can be recovered by magnet easily with almost no decline in the removal efficiency. The facile synthesis strategy used here might provide a universal and efficient method to fabricate one‐dimensional magnetic nanocomposites with porous structures for various functional applications.
Developing Emotion‐Based Case Formulations: A Research‐Informed Method
Authors: Pascual‐Leone Antonio , Kramer Ueli
Published: January 2016

Objectives

New research‐informed methods for case conceptualization that cut across traditional therapy approaches are increasingly popular. This paper presents a trans‐theoretical approach to case formulation based on the research observations of emotion.

Methods

The sequential model of emotional processing (Pascual‐Leone & Greenberg, 2007) is a process research model that provides concrete markers for therapists to observe the emerging emotional development of their clients. We illustrate how this model can be used by clinicians to track change and provides a ‘clinical map,’ by which therapist may orient themselves in‐session and plan treatment interventions.

Results

Emotional processing offers as a trans‐theoretical framework for therapists who wish to conduct emotion‐based case formulations. First, we present criteria for why this research model translates well into practice. Second, two contrasting case studies are presented to demonstrate the method.

Conclusions

The model bridges research with practice by using client emotion as an axis of integration.

Key Practitioner Message

Process research on emotion can offer a template for therapists to make case formulations while using a range of treatment approaches. The sequential model of emotional processing provides a ‘process map’ of concrete markers for therapists to (1) observe the emerging emotional development of their clients, and (2) help therapists develop a treatment plan. Copyright © 2016 John Wiley & Sons, Ltd.
Short‐Term Cognitive–Behavioural Group Treatment for Hoarding Disorder: A Naturalistic Treatment Outcome Study
Authors: Moulding Richard , Nedeljkovic Maja , Kyrios Michael , Osborne Debra , Mogan Christopher
Published: January 2016

The study aim was to test whether a 12‐week publically rebated group programme, based upon Steketee and Frost's Cognitive Behavioural Therapy‐based hoarding treatment, would be efficacious in a community‐based setting. Over a 3‐year period, 77 participants with clinically significant hoarding were recruited into 12 group programmes. All completed treatment; however, as this was a community‐based naturalistic study, only 41 completed the post‐treatment assessment. Treatment included psychoeducation about hoarding, skills training for organization and decision making, direct in‐session exposure to sorting and discarding, and cognitive and behavioural techniques to support out‐of‐session sorting and discarding, and nonacquiring. Self‐report measures used to assess treatment effect were the Savings Inventory—Revised (SI‐R), Savings Cognition Inventory, and the Depression, Anxiety and Stress Scales. Pre‐post analyses indicated that after 12 weeks of treatment, hoarding symptoms as measured on the SI‐R had reduced significantly, with large effect sizes reported in total and across all subscales. Moderate effect sizes were also reported for hoarding‐related beliefs (emotional attachment and responsibility) and depressive symptoms. Of the 41 participants who completed post‐treatment questionnaires, 14 (34%) were conservatively calculated to have clinically significant change, which is considerable given the brevity of the programme judged against the typical length of the disorder. The main limitation of the study was the moderate assessment completion rate, given its naturalistic setting. This study demonstrated that a 12‐week group treatment for hoarding disorders was effective in reducing hoarding and depressive symptoms in an Australian clinical cohort and provides evidence for use of this treatment approach in a community setting. Copyright © 2016 John Wiley & Sons, Ltd.

Key Practitioner Message

A 12‐week group programme delivered in a community setting was effective for helping with hoarding symptoms with a large effect size.

Hoarding beliefs (emotional attachment and responsibility) and depression were reduced, with moderate effect sizes.

A third of all participants who completed post‐treatment questionnaires experienced clinically significant change.

Suggests that hoarding CBT treatment can be effectively translated into real‐world settings and into a brief 12‐session format, albeit the study had a moderate assessment completion rate.
A distributed detection and prevention scheme from malicious nodes in vehicular networks
Authors: Bouali Tarek , Senouci Sidi‐Mohammed , Sedjelmaci Hichem
Published: January 2016

Vehicular environments still remain vulnerable to various potential attacks because of continuous interactions and information exchange between vehicles despite the deployment of authentication techniques by communication standards. Therefore, an authenticated node with a certificate could initiate an attack while complying with implemented protocols. Some mechanisms were proposed to enhance communication technologies, but none of them was able to anticipate nodes' behavior. They also mismanage oscillating vehicles, because they evict them automatically after misbehaving. In this paper, we propose a preventive mechanism, namely, Intrusion Prevention and Detection System (IPDS), able to predict vehicles behavior. This mechanism is based on a Kalman filter to predict the future vehicles' behavior and classify them into three categories (white, gray, and black) based on their expected trustworthiness. The main concerns of this work are to prevent from various attacks, namely, DoS, false alert, and Sybil, and deal with oscillating vehicles. Therefore, IPDS treats these latter in a different way where they are introduced into a gray list and used for routing purposes until they persist in their attacks. Simulations performed using ns3 simulator highlight IPDS accuracy regarding the detection rate of malicious nodes and its good impact on the network applications performances. Copyright © 2016 John Wiley & Sons, Ltd.
Patterns of hybridization among cutthroat trout and rainbow trout in northern Rocky Mountain streams
Authors: McKelvey Kevin S. , Young Michael K. , Wilcox Taylor M. , Bingham Daniel M. , Pilgrim Kristine L. , Schwartz Michael K.
Published: January 2016

Introgressive hybridization between native and introduced species is a growing conservation concern. For native cutthroat trout and introduced rainbow trout in western North America, this process is thought to lead to the formation of hybrid swarms and the loss of monophyletic evolutionary lineages. Previous studies of this phenomenon, however, indicated that hybrid swarms were rare except when native and introduced forms of cutthroat trout co‐occurred. We used a panel of 86 diagnostic, single nucleotide polymorphisms to evaluate the genetic composition of 3865 fish captured in 188 locations on 129 streams distributed across western Montana and northern Idaho. Although introgression was common and only 37% of the sites were occupied solely by parental westslope cutthroat trout, levels of hybridization were generally low. Of the 188 sites sampled, 73% contained ≤5% rainbow trout alleles and 58% had ≤1% rainbow trout alleles. Overall, 72% of specimens were nonadmixed westslope cutthroat trout, and an additional 3.5% were nonadmixed rainbow trout. Samples from seven sites met our criteria for hybrid swarms, that is, an absence of nonadmixed individuals and a random distribution of alleles within the sample; most (6/7) were associated with introgression by Yellowstone cutthroat trout. In streams with multiple sites, upstream locations exhibited less introgression than downstream locations. We conclude that although the widespread introduction of nonnative trout within the historical range of westslope cutthroat trout has increased the incidence of introgression, sites containing nonadmixed populations of this taxon are common and broadly distributed.