bluuebunny/crossref_metadata_2025 huggingface dataset:
Controlling three‐dimensional ice template via two‐dimensional surface wetting
Authors: Yang Miao , Wu Jingjun , Bai Hao , Xie Tao , Zhao Qian , Wong Tuck‐Whye
Published: September 2016

Significance

Directional freezing (DF) is a fast, scalable, and environmental friendly technique for fabricating monoliths with long‐range oriented pores, which can be applied toward a wide variety of materials. However, the pore size is typically larger than 20 μm and cannot be spatially controlled, which prevent the technique from being used more widely. In this work, effect of wettability of the freezing substrate on the pore size of monolithic polyethylene glycol cryogels is studied. Smaller pores can be generated via more hydrophilic substrates, and tubular pores smaller 5 μm can be created using a poly(vinyl alcohol) coated copper substrate. A numerical fitting between water contact angle of the substrates and pore size is then obtained. Moreover, pore size can be locally varied duplicating wetting patterns of the substrates. The concept of using two dimensional patterns to build monoliths with three dimensional microstructures can probably be extended to other material systems. DF is an effecient and scalable processing method for fabricating materials with long‐range oriented pores. However, the smallest pore feature size reported is around 20 µm, which is in many cases too large for application such as separation and catalysis. We show here, with exemplary cryogels, that both spatial control and feature size reduction (by one order of magnitude) can be realized in DF by controlling the wettability of the ice growth substrate. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4186–4192, 2016
Mathematical modelling and experimental validation of a novel periodic flow crystallization using MSMPR crystallizers
Authors: Su Qinglin , Rielly Chris D. , Powell Keddon A. , Nagy Zoltan K.
Published: September 2016

The challenges of insufficient residence time for crystal growing and transfer line blockage in conventional continuous mixed‐suspension mixed‐product removal (MSMPR) operations are still not well addressed. Periodic flow crystallization is a novel method whereby controlled periodic disruptions are applied to the inlet and outlet flows of an MSMPR crystallizer to increase its residence time. A dynamic model of residence time distribution in an MSMPR crystallizer was first developed to demonstrate the periodic flow operation. Besides, process models of periodic flow crystallizations were developed with an aim to provide a better understanding and improve the performance of the periodic flow operation, wherein the crystallization mechanisms and kinetics of the glycine‐water system were estimated from batch cooling crystallization experiments. Experiments of periodic flow crystallizations were also conducted in single‐/three‐stage MSMPR crystallizers to validate the process models and demonstrate the advantages of using periodic flow operation in MSMPR stages. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1313–1327, 2017
Stratification of unresponsive patients by an independently validated index of brain complexity
Authors: Casarotto Silvia , Comanducci Angela , Rosanova Mario , Sarasso Simone , Fecchio Matteo , Napolitani Martino , Pigorini Andrea , G. Casali Adenauer , Trimarchi Pietro D. , Boly Melanie , Gosseries Olivia , Bodart Olivier , Curto Francesco , Landi Cristina , Mariotti Maurizio , Devalle Guya , Laureys Steven , Tononi Giulio , Massimini Marcello
Published: September 2016

Objective

Validating objective, brain‐based indices of consciousness in behaviorally unresponsive patients represents a challenge due to the impossibility of obtaining independent evidence through subjective reports. Here we address this problem by first validating a promising metric of consciousness—the Perturbational Complexity Index (PCI)—in a benchmark population who could confirm the presence or absence of consciousness through subjective reports, and then applying the same index to patients with disorders of consciousness (DOCs).

Methods

The benchmark population encompassed 150 healthy controls and communicative brain‐injured subjects in various states of conscious wakefulness, disconnected consciousness, and unconsciousness. Receiver operating characteristic curve analysis was performed to define an optimal cutoff for discriminating between the conscious and unconscious conditions. This cutoff was then applied to a cohort of noncommunicative DOC patients (38 in a minimally conscious state [MCS] and 43 in a vegetative state [VS]).

Results

We found an empirical cutoff that discriminated with 100% sensitivity and specificity between the conscious and the unconscious conditions in the benchmark population. This cutoff resulted in a sensitivity of 94.7% in detecting MCS and allowed the identification of a number of unresponsive VS patients (9 of 43) with high values of PCI, overlapping with the distribution of the benchmark conscious condition.

Interpretation

Given its high sensitivity and specificity in the benchmark and MCS population, PCI offers a reliable, independently validated stratification of unresponsive patients that has important physiopathological and therapeutic implications. In particular, the high‐PCI subgroup of VS patients may retain a capacity for consciousness that is not expressed in behavior. Ann Neurol 2016;80:718–729
Specifically neuropathic Gaucher's mutations accelerate cognitive decline in Parkinson's
Authors: Liu Ganqiang , Boot Brendon , Locascio Joseph J. , Jansen Iris E. , Winder‐Rhodes Sophie , Eberly Shirley , Elbaz Alexis , Brice Alexis , Ravina Bernard , van Hilten Jacobus J. , Cormier‐Dequaire Florence , Corvol Jean‐Christophe , Barker Roger A. , Heutink Peter , Marinus Johan , Williams‐Gray Caroline H. , Scherzer Clemens R. ,   for the International Genetics of Parkinson Disease Progression (IGPP) Consortium
Published: September 2016

Objective

We hypothesized that specific mutations in the β‐glucocerebrosidase gene (GBA) causing neuropathic Gaucher's disease (GD) in homozygotes lead to aggressive cognitive decline in heterozygous Parkinson's disease (PD) patients, whereas non‐neuropathic GD mutations confer intermediate progression rates.

Methods

A total of 2,304 patients with PD and 20,868 longitudinal visits for up to 12.8 years (median, 4.1) from seven cohorts were analyzed. Differential effects of four types of genetic variation in GBA on longitudinal cognitive decline were evaluated using mixed random and fixed effects and Cox proportional hazards models.

Results

Overall, 10.3% of patients with PD and GBA sequencing carried a mutation. Carriers of neuropathic GD mutations (1.4% of patients) had hazard ratios (HRs) for global cognitive impairment of 3.17 (95% confidence interval [CI], 1.60–6.25) and a hastened decline in Mini–Mental State Exam scores compared to noncarriers (p = 0.0009). Carriers of complex GBA alleles (0.7%) had an HR of 3.22 (95% CI, 1.18–8.73; p = 0.022). By contrast, the common, non‐neuropathic N370S mutation (1.5% of patients; HR, 1.96; 95% CI, 0.92–4.18) or nonpathogenic risk variants (6.6% of patients; HR, 1.36; 95% CI, 0.89–2.05) did not reach significance.

Interpretation

Mutations in the GBA gene pathogenic for neuropathic GD and complex alleles shift longitudinal cognitive decline in PD into “high gear.” These findings suggest a relationship between specific types of GBA mutations and aggressive cognitive decline and have direct implications for improving the design of clinical trials. Ann Neurol 2016;80:674–685
Regulierbare Sonden mit direktem Fluoreszenzsignal für das konstitutive und das Immunoproteasom
Authors: Dubiella Christian , Cui Haissi , Groll Michael
Published: September 2016

Reaktive Elektrophile werden häufig für die Hemmung von Proteasen genutzt. Insbesondere die Aktivität von Inhibitoren gegen das Proteasom – ein zentraler Regulator des Zellüberlebens und ein klinisch genutzter Angriffspunkt für Medikamente – hängt von der entsprechenden Kopfgruppe ab. Hier zeigen wir, dass diese Reaktivität in peptidischen Sulfonsäureestern durch Variation der Abgangsgruppe (AG) einstellbar ist. Tatsächlich korrelierte die Wirksamkeit der Inhibitoren mit dem pKS‐Wert der verwendeten AG. Der Einsatz von Fluorophoren als AG ermöglicht zudem das Design von Sonden, die ein stöchiometrisches Fluoreszenzsignal während der Bindung an das Proteasom erzeugen und damit direkt deren Inaktivierung mit einem Messwert verknüpfen. Dieses Prinzip könnte auch für weitere, auf Sulfonylfluoriden basierende Inhibitoren anwendbar sein und das Design von empfindlichen Sonden für enzymatische Studien ermöglichen.
Stereocontrolled Syntheses of Seven‐Membered Carbocycles by Tandem Allene Aziridination/[4+3] Reaction
Authors: Gerstner Nels C. , Adams Christopher S. , Tretbar Maik , Schomaker Jennifer M.
Published: September 2016

A tandem allene aziridination/[4+3]/reduction sequence converts simple homoallenic sulfamates into densely functionalized aminated cycloheptenes, where the relative stereochemistry at five contiguous asymmetric centers can be controlled through the choice of the solvent and the reductant. The products resulting from this chemistry can be readily transformed into complex molecular scaffolds which contain up to seven contiguous stereocenters.
Comparing the 2,2′‐Biphenylenedithiophosphinate Binding of Americium with Neodymium and Europium
Authors: Cross Justin N. , Macor Joseph A. , Bertke Jeffery A. , Ferrier Maryline G. , Girolami Gregory S. , Kozimor Stosh A. , Maassen Joel R. , Scott Brian L. , Shuh David K. , Stein Benjamin W. , Stieber S. Chantal E.
Published: September 2016

Advancing our understanding of the minor actinides (Am, Cm) versus lanthanides is key for developing advanced nuclear‐fuel cycles. Herein, we describe the preparation of (NBu4)Am[S2P(tBu2C12H6)]4 and two isomorphous lanthanide complexes, namely one with a similar ionic radius (i.e., NdIII) and an isoelectronic one (EuIII). The results include the first measurement of an Am−S bond length, with a mean value of 2.921(9) Å, by single‐crystal X‐ray diffraction. Comparison with the EuIII and NdIII complexes revealed subtle electronic differences between the complexes of AmIII and the lanthanides.
Transition‐Metal‐Free Synthesis of N‐Hydroxy Oxindoles by an Aza‐Nazarov‐Type Reaction Involving Azaoxyallyl Cations
Authors: Ji Wenzhi , Liu Yahu A. , Liao Xuebin
Published: September 2016

A novel transition‐metal‐free method to construct N‐hydroxy oxindoles by an aza‐Nazarov‐type reaction involving azaoxyallyl cation intermediates is described. A variety of functional groups were tolerated under the weak basic reaction conditions and at room temperature. A one‐pot process was also developed to make the reaction even more practical. This method provides alternative access to oxindoles and their biologically active derivatives.
Use of a Catalytic Chiral Leaving Group for Asymmetric Substitutions at sp3‐Hybridized Carbon Atoms: Kinetic Resolution of β‐Amino Alcohols by p‐Methoxybenzylation
Authors: Kuroda Yusuke , Harada Shingo , Oonishi Akinori , Kiyama Hiroki , Yamaoka Yousuke , Yamada Ken‐ichi , Takasu Kiyosei
Published: September 2016

A catalytic strategy was developed for asymmetric substitution reactions at sp3‐hybridized carbon atoms by using a chiral alkylating agent generated in situ from trichloroacetimidate and a chiral phosphoric acid. The resulting chiral p‐methoxybenzyl phosphate selectively reacts with β‐amino alcohols rather than those without a β‐NH functionality. The use of an electronically and sterically tuned chiral phosphoric acid enables the kinetic resolution of amino alcohols through p‐methoxybenzylation with good enantioselectivity.
Bismuth Complexes in Phenylazomethine Dendrimers: Controllable Luminescence and Emission in the Solid State
Authors: Kambe Tetsuya , Watanabe Aiko , Imaoka Takane , Yamamoto Kimihisa
Published: September 2016

Dendritic phosphors were obtained by the stepwise integration of BiCl3 in phenylazomethine dendrimers. The bismuth‐coordinated phenylazomethines displayed photoluminescence at 500–800 nm, and the intensity could be tuned by changing the stoichiometry of BiCl3 and the dendrimer. This phosphor did not show serious luminescence quenching even though the local concentration of BiCl3 in the dendrimer was as high as 20 M, and luminescence was also observed in the solid state. The absorption and emission properties could be reversibly switched by addition of a Lewis base or under electrochemical redox control, which induced the reversible complexation of BiCl3 in the dendrimer.
(5,6‐Dihydro‐1,4‐dithiin‐2‐yl)methanol as a Versatile Allyl‐Cation Equivalent in (3+2) Cycloaddition Reactions
Authors: Hullaert Jan , Winne Johan M.
Published: September 2016

The title heterocyclic alcohol readily generates a sulfur‐substituted allylic cation upon simple treatment with a protic acid, thus facilitating a synthetically useful stepwise (3+2) cycloaddition reaction pathway with a range of conjugated‐olefin‐type substrates. The introduction of an allyl fragment in this way provided rapid access to a variety of cyclopentanoid scaffolds. The cyclic nature of the cation precursor alcohol was shown to be instrumental for efficient cycloaddition reactions to take place, thus indicating an attractive strategy for controlling the reactivity of heteroatom‐substituted allyl cations. The formal cycloaddition reaction is highly regio‐ and stereoselective and was also used for a short total synthesis of the natural product cuparene in racemic form through a cycloaddition–hydrodesulfurization sequence.
Elastomeric foam prepared by supercritical carbon dioxide
Authors: Meng Linghan , Liu Hongsheng , Yu Long , Khalid Saud , Chen Ling , Jiang Tianyu , Li Qiaoling
Published: September 2016

Biodegradable elastomer poly[(1,4‐butylene terephthalate)‐co‐(1,4‐butylene adipate)] foam was successfully prepared using supercritical CO2. The elastomer foam has closed and uniform cell structure with density about 90 g/L. Narrow size distribution with average cell diameter 32 μm were obtained. The foamed balls show rubbery properties and can recover well (>90%) to their original shape quickly after releasing press stress. Cell growth needs to take place at melting state where the migration and orientation of polymer chains are permanently kept without remained force of springback. Some unique phenomena were observed during foaming the elastomer: post‐expansion (about 40%) was obtained after removing the foamed samples from a cylinder mold, which results in forming a ball rather than a cylinder like the mold. This phenomenon was explained by the lower glass transition temperature of the elastomer, in which residual CO2 foam continuously in the room temperature; and “memory” of internal strength. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44354.
Anisotropies and the thermoelectric properties of semiconducting polymers
Authors: Patel Shrayesh N. , Chabinyc Michael L.
Published: September 2016

In this article, we present a review of the thermoelectric properties of semiconducting polymers. Organic semiconductors have emerged as promising materials for the capture of low‐grade waste heat and for local temperature control. The thermoelectric performance of a material is dictated by its electrical conductivity, thermopower, and thermal conductivity. The role of processing methods, particularly of alignment methods, on the electrical properties of polymers are described in the context of their thermoelectric properties. We review recent work on understanding the anisotropy of the thermal conductivity of polymers and present an outlook for future research directions toward improved organic thermoelectrics. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44403
Studies of nanocomposites based on carbon nanomaterials and RTV silicone rubber
Authors: Kumar Vineet , Lee Dong‐Joo
Published: September 2016

The mechanical and electrical properties were investigated for nanocomposites based on carbon nanotubes (CNTs) and conductive carbon black (CB). Solution room‐temperature‐vulcanized silicone rubber was used as a matrix. Vulcanizates based on CNTs and CB was prepared by solution mixing. With the addition of 2 phr of CNTs to the rubber matrix, the Young's modulus increased by 272% and reached as high as ∼706% at 8 phr, whereas the modulus increased only 125% for CB specimens at 10 phr. Similarly, the electrical properties at 5 phr content of CNT were ∼0.7 kΩ against ∼0.9 kΩ at 20 phr CB. The Kraus plot from equilibrium swelling tests shows that the high properties for CNT specimens are due to high polymer–filler interfacial interactions, the small particle size that improves the distribution of the filler in a highly exfoliated state, and high electrical connective networks among the filler particles. These improvements can especially influence medical products such as feeding tubes, seals and gaskets, catheters, respiratory masks and artificial muscles. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44407.
Porosity, mechanical properties, and damping ratio of particulate‐filled polymer composite for precision machine tools
Authors: Yin Jicai , Zhang Jianhua , Zhang Yi , Wang Wenqiang
Published: September 2016

Particulate‐filled polymer composites (PFPC) have received a great deal of attention in the field of precision machine tools because of their excellent vibration‐alleviating property. However, applications of PFPC in the field of precision machine tools are restricted by its limited mechanical strength. The pores in PFPC are one of the key influences on its mechanical properties, such that the porosity determines the overall mechanical properties of the PFPC directly. In this paper, the relationship between porosity and mechanical properties (compressive strength, flexural strength, elasticity modulus) and damping ratio of PFPC was studied systematically. A strong correlation between the porosity and the mechanical properties and damping ratio of PFPC was found. The results show that the mechanical properties (damping ratio) of PFPC deteriorated (increased) dramatically with increasing porosity. An empirical formula was proposed for the relation between the porosity and the mechanical properties (and damping ratio) of PFPC. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44435.
Preparation and properties of reactive polyurethane polyacrylate blends based on carbonyl‐hydrazide reaction
Authors: Chai Guang , Sun Dongcheng
Published: September 2016

A new reactive polyurethane/polyacrylate (PU/PA) blend was developed by mixing a core–shell polyacrylate latex containing keto groups in shell layer and a polyurethane dispersion incorporating multiple hydrazide groups which was synthesized by introducing the poly‐hydrazide groups into the end of the vinyl‐terminated polyurethane chains. Fourier transform infrared (FTIR) spectroscopy and gel permeation chromatography (GPC) results indicated that poly‐hydrazide groups had been incorporated in the polyurethane chains. Transmission electron microscopy (TEM) micrograph revealed that polyacrylate particles had a clear core–shell structure. The results of FTIR, scanning electron microscopy (SEM), and differential scanning calorimetry (DSC) indicated that the crosslinking reaction between two polymer systems had happened and crosslinking structure could effectively improve the compatibility between PA and PU. Thermogravimetric analysis (TGA) and mechanical tests results suggested that crosslinking structure could enhance the thermal stability and mechanical properties of blends. The influence of the PA content and the n(CO)/n(NHNH2) ratio on the hardness, water resistance, solvent resistance, and gel fraction of the blend films were comprehensively studied. The optimal PA content and n(CO)/n(NHNH2) ratio was 30% and 1.5:1 in this experiment, respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44443.
Effect of surface properties of polysulfone support on the performance of thin film composite polyamide reverse osmosis membranes
Authors: Ehsan Yakavalangi Mohammad , Rimaz Sajjad , Vatanpour Vahid
Published: September 2016

In this work, influence of initial conditions and surface characteristics of porous support layer on structure and performance of a thin film composite (TFC) polyamide reverse osmosis (RO) membrane was investigated. The phase inversion method was used for casting of polysulfone (PSf) supports and interfacial polymerization was used for coating of polyamide layer over the substrates. The effect of PSf concentrations that varied between 16 wt % and 21 wt %, and kind of the solvent (DMF and NMP) used for preparation of initial casting solution were investigated on the properties of the final RO membranes. SEM imaging, surface porosity, mean pore radius, and pure water flux analysis were applied for characterization of the supports. The substrate of the membrane, which synthesized with 18 wt % of PSf showed the most porosity and the synthesized RO membrane had the lowest salt rejection. In case of the solvents, the membranes synthesized with DMF presented better separation performance that can be attributed to their lower thickness and sponge‐like structure. The best composition of support for TFC RO membranes reached 16 wt % PSf in DMF solvent. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44444.
The Thr–His Connection on the Distal Heme of Catalase‐Related Hemoproteins: A Hallmark of Reaction with Fatty Acid Hydroperoxides
Authors: Mashhadi Zahra , Newcomer Marcia E. , Brash Alan R.
Published: September 2016

This review focuses on a group of heme peroxidases that retain the catalase fold in structure, yet show little or no reaction with hydrogen peroxide. Instead of having a role in oxidative defense, these enzymes are involved in secondary metabolite biosynthesis. The prototypical enzyme is catalase‐related allene oxide synthase, an enzyme that converts a specific fatty acid hydroperoxide to the corresponding allene oxide (epoxide). Other catalase‐related enzymes form allylic epoxides, aldehydes, or a bicyclobutane fatty acid. In all catalases (including these relatives), a His residue on the distal face of the heme is absolutely required for activity. Its immediate neighbor in sequence as well as in 3 D space is conserved as Val in true catalases and Thr in the fatty acid hydroperoxide‐metabolizing enzymes. Thr–His on the distal face of the heme is critical in switching the substrate specificity from H2O2 to fatty acid hydroperoxide.
Lewis Acid Sites Stabilized Nickel Catalysts for Dry (CO2) Reforming of Methane
Authors: Ni Jun , Zhao Jia , Chen Luwei , Lin Jianyi , Kawi Sibudjing
Published: September 2016

Strong Lewis acid species [Al–F] were synthesized on a series of Al2O3‐supported Ni catalysts modified with (0, 1, 5, and 10 wt.%) of KF to investigate the electronic and anchoring effect of [Al–F] on Ni catalysts in terms of catalytic activity, stability, and carbon resistance during dry reforming of methane (DRM) reaction. With the aids of XRD analysis, X‐ray photoelectron spectroscopy, H2 temperature‐programmed reduction, and in situ diffuse reflectance infrared Fourier transform spectroscopy analyses, it was found that the activity and stability of KF‐modified catalysts in the reaction was directly associated to the presence of [Al–F] sites. The [Al–F] Lewis acid sites not only stabilized the metal Ni from high‐temperature sintering after reaction of 200 h through an enhanced metal–support interaction, but also reduced the electron density of Ni metal, which alleviated the fast decomposition of CH4 and subsequent carbon deposition on catalysts. Balancing the rates for CH4 dissociation and carbon removal would be promising steps in the design of active and stable Ni‐based catalysts.
Rim, Side Arms, and Cavity: Three Sites for the Recognition of Anions by Tetraazolium Resorcinarene Cavitands
Authors: Ruiz‐Botella Sheila , Vidossich Pietro , Ujaque Gregori , Peris Eduardo
Published: September 2016

Two tetrabenzoimidazolium‐resorcinarene cavitands were prepared and used for the recognition of chloride, bromide, iodide, cyanide, nitrate, perchlorate, hexanoate, benzenesulfonate, and p‐toluenesulfonate. Binding affinities of the two cavitands were determined by 1H NMR titration and computational analysis. The observed spectral changes were related to specific interaction sites, which were supported by the computational studies. In the case of the C2−H tetrabenzoimidazolium‐resorcinarene, the recognition region of the inorganic anions and hexanoate was located at the rim of the cavitand, although chloride and bromide also interacted with the aromatic C−H bonds located between adjacent arms of the cavitand. By contrast, the recognition of the two anions with an aromatic ring (benzenesulfonate and p‐toluenesulfonate) results from encapsulation of the aromatic part of the anions inside the hydrophobic cavity of the host. In the case of the C2−Me tetrabenzoimizazolium‐resorcinarene receptor, the ability of the molecule to bind all inorganic anions and hexanoate was suppressed, but the receptor maintained its ability to strongly bind benzenesulfonate and p‐toluenesulfonate. This is interpreted in terms of suppression of the ability of the cavitand to form hydrogen bonds at the rim of the molecule due to replacement of the C2−H proton by a methyl group, while the hydrophobic pocket of the molecule maintains its binding abilities.
Electrochemical Synthesis and Catalytic Properties of Encapsulated Metal Clusters within Zeolitic Imidazolate Frameworks
Authors: Wang Pengyuan , Liu Jia , Liu Chuanfang , Zheng Bin , Zou Xiaoqin , Jia Mingjun , Zhu Guangshan
Published: September 2016

It is very interesting and also a big challenge to encapsulate metal clusters within microporous solids to expand their application diversity. For this target, herein, we present an electrochemical synthesis strategy for the encapsulation of noble metals (Au, Pd, Pt) within ZIF‐8 cavities. In this method, metal precursors of AuCl42−, PtCl62−, and PdCl42− are introduced into ZIF‐8 crystals during the concurrent crystallization of ZIF‐8 at the anode. As a consequence, very small metal clusters with sizes around 1.2 nm are obtained within ZIF‐8 crystals after hydrogen reduction; these clusters exhibit high thermal stability, as evident from the good maintenance of their original sizes after a high‐temperature test. The catalytic properties of the encapsulated metal clusters within ZIF‐8 are evaluated for CO oxidations. Because of the small pore window of ZIF‐8 (0.34 nm) and the confinement effect of small pores, about 80 % of the metal clusters (fractions of 0.74, 0.77, and 0.75 for Au, Pt, and Pd in ZIF‐8, respectively) retain their catalytic activity after exposure to the organosulfur poison thiophene (0.46 nm), which is in contrast to their counterparts (fractions of 0.22, 0.25, and 0.20 for Au, Pt, and Pd on the SiO2 support). The excellent performances of metal clusters encapsulated within ZIF‐8 crystals give new opportunities for catalytic reactions.
N‐Heterocyclic Olefin–Carbon Dioxide and –Sulfur Dioxide Adducts: Structures and Interesting Reactivity Patterns
Authors: Finger Lars H. , Guschlbauer Jannick , Harms Klaus , Sundermeyer Jörg
Published: September 2016

Depending on the amount of methanol present in solution, CO2 adducts of N‐heterocyclic carbenes (NHCs) and N‐heterocyclic olefins (NHOs) have been found to be in fully reversible equilibrium with the corresponding methyl carbonate salts [EMIm][OCO2Me] and [EMMIm][OCO2Me]. The reactivity pattern of representative 1‐ethyl‐3‐methyl‐NHO–CO2 adduct 4 has been investigated and compared with the corresponding NHC–CO2 zwitterion: The protonation of 4 with HX led to the imidazolium salts [NHO–CO2H][X], which underwent decarboxylation to [EMMIm][X] in the presence of nucleophilic catalysts. NHO–CO2 zwitterion 4 can act as an efficient carboxylating agent towards CH acids such as acetonitrile. The [EMMIm] cyanoacetate and [EMMIm]2 cyanomalonate salts formed exemplify the first C−C bond‐forming carboxylation reactions with NHO‐activated CO2. The reaction of the free NHO with dimethyl carbonate selectively led to methoxycarbonylated NHO, which is a perfect precursor for the synthesis of functionalized ILs [NHO–CO2Me][X]. The first NHO‐SO2 adduct was synthesized and structurally characterized; it showed a similar reactivity pattern, which allowed the synthesis of imidazolium methyl sulfites upon reaction with methanol.
The population impact of human papillomavirus/cytology cervical cotesting at 3‐year intervals: Reduced cervical cancer risk and decreased yield of precancer per screen
Authors: Silver Michelle I. , Schiffman Mark , Fetterman Barbara , Poitras Nancy E. , Gage Julia C. , Wentzensen Nicolas , Lorey Thomas , Kinney Walter K. , Castle Philip E.
Published: September 2016

BACKGROUND

The objective of cervical screening is to detect and treat precancer to prevent cervical cancer mortality and morbidity while minimizing overtreatment of benign human papillomavirus (HPV) infections and related minor abnormalities. HPV/cytology cotesting at extended 5‐year intervals currently is a recommended screening strategy in the United States, but the interval extension is controversial. In the current study, the authors examined the impact of a decade of an alternative, 3‐year cotesting, on rates of precancer and cancer at Kaiser Permanente Northern California. The effect on screening efficiency, defined as numbers of cotests/colposcopy visits needed to detect a precancer, also was considered.

METHODS

Two cohorts were defined. The “open cohort” included all women screened at least once during the study period; > 1 million cotests were performed. In a fixed “long‐term screening cohort,” the authors considered the cumulative impact of repeated screening at 3‐year intervals by restricting the cohort to women first cotested in 2003 through 2004 (ie, no women entering screening later were added to this group).

RESULTS

Detection of cervical intraepithelial neoplasia 3/adenocarcinoma in situ (CIN3/AIS) increased in the open cohort (2004‐2006: 82.0/100,000 women screened; 2007‐2009: 140.6/100,000 women screened; and 2010‐2012: 126.0/100,000 women screened); cancer diagnoses were unchanged. In the long‐term screening cohort, the detection of CIN3/AIS increased and then decreased to the original level (2004‐2006: 80.5/100,000 women screened; 2007‐2009: 118.6/100,000 women screened; and 2010‐2012: 84.9./100,000 women screened). The number of cancer diagnoses was found to decrease. When viewed in terms of screening efficiency, the number of colposcopies performed to detect a single case of CIN3/AIS increased in the cohort with repeat screening.

CONCLUSIONS

Repeated cotesting at a 3‐year interval eventually lowers population rates of precancer and cancer. However, a greater number of colposcopies are required to detect a single precancer. Cancer 2016;122:3682‐6. © 2016 American Cancer Society.
Testing and referral patterns in the years surrounding the US Preventive Services Task Force recommendation against prostate‐specific antigen screening
Authors: Hutchinson Ryan , Akhtar Abdulhadi , Haridas Justin , Bhat Deepa , Roehrborn Claus , Lotan Yair
Published: September 2016

BACKGROUND

Since the US Preventive Services Task Force (USPSTF) recommended against prostate‐specific antigen (PSA) screening, there have been conflicting reports regarding the impact on the behavior of providers. This study analyzed real‐world data on PSA ordering and referral practices in the years surrounding the recommendation.

METHODS

A whole‐institution sample of entered PSA orders and urology referrals was obtained from the electronic medical record. The study was performed at a tertiary referral center with a catchment in the southern United States. PSA examinations were defined as screening when they were ordered by providers with appointments in internal medicine, family medicine, or general internal medicine. Linear and quadratic regression analyses were performed, and joinpoint regression was used to assess for trend inflection points.

RESULTS

Between January 2010 and July 2015, there were 275,784 unique ambulatory visits for men. There were 63,722 raw PSA orders, and 54,684 were evaluable. Primary care providers ordered 17,315 PSA tests and 858 urology referrals. The number of PSA tests per ambulatory visit, the number of referrals per ambulatory visit, the age at the time of the urology referral, and the proportion of PSA tests performed outside the recommended age range did not significantly change. The PSA value at the time of referral increased significantly (P = .022). Joinpoint analysis revealed no joinpoints in the analysis of total PSA orders, screening PSA tests, or examinations per 100 visits.

CONCLUSIONS

In the years surrounding the USPSTF recommendation, PSA behavior did not change significantly. Patients were referred at progressively higher average PSA levels. The implications for prostate cancer outcomes from these trends warrant further research into provider variables associated with actual PSA utilization. Cancer 2016;122:3785–3793. © 2016 American Cancer Society.
Association between access to accelerated partial breast irradiation and use of adjuvant radiotherapy
Authors: Wang Elyn H. , Park Henry S. , Rutter Charles E. , Gross Cary P. , Soulos Pamela R. , Yu James B. , Evans Suzanne B.
Published: September 2016

BACKGROUND

The current study was performed to determine whether access to facilities performing accelerated partial breast irradiation (APBI) is associated with differences in the use of adjuvant radiotherapy (RT).

METHODS

Using the National Cancer Data Base, the authors performed a retrospective study of women aged ≥50 years who were diagnosed with early‐stage breast cancer between 2004 and 2013 and treated with breast‐conserving surgery (BCS). Facilities performing APBI in ≥10% of their eligible patients within a given year were defined as APBI facilities whereas those not performing APBI were defined as non‐APBI facilities. All other facilities were excluded. The authors identified independent factors associated with RT use using multivariable logistic regression with clustering in the overall sample as well as in subsets of patients with standard‐risk invasive cancer, low‐risk invasive cancer, and ductal carcinoma in situ.

RESULTS

Among 222,544 patients, 76.6% underwent BCS plus RT and 23.4% underwent BCS alone. The likelihood of RT receipt in the overall sample did not appear to differ significantly between APBI and non‐APBI facilities (adjusted odds ratio [AOR], 1.02; P = .61). Subgroup multivariable analysis demonstrated that among patients with standard‐risk invasive cancer, there was no association between evaluation at an APBI facility and receipt of RT (AOR, 0.98; P = .69). However, patients with low‐risk invasive cancer were found to be significantly more likely to receive RT (54.4% vs 59.5%; AOR, 1.22 [P<.001]), whereas patients with ductal carcinoma in situ were less likely to receive RT (56.9% vs 55.3%; AOR, 0.89 [P = .04]) at APBI facilities.

CONCLUSIONS

Patients who were eligible for observation were more likely to receive RT in APBI facilities but no difference was observed among patients with standard‐risk invasive cancer who would most benefit from RT. Cancer 2017;123:502–511. © 2016 American Cancer Society.
Herringbone Pattern and CH–π Bonding in the Crystal Architecture of Linear Polycyclic Aromatic Hydrocarbons
Authors: Guijarro Albert , Vergés José A. , San‐Fabián Emilio , Chiappe Guillermo , Louis Enrique
Published: September 2016

The herringbone pattern is a pervasive structural motive found in most molecular crystals involving aromatic compounds. A plot of the experimental sublimation enthalpies of members of increasing size of the acene, phenacene and p‐phenyl families versus the number of carbons uncovers a linear relationship between the two magnitudes, suggesting a major role of CH–π bonding. In this work we undertake the task of evaluating the relevance of the edge‐to‐face interaction (or CH–π bond) in the overall reticular energy of the crystal, to quantitatively assess the importance of this structural element. Following a heuristic approach, we considered the series of acenes, phenacenes and p‐phenyls and analyzed the edge‐to‐face interaction between the molecules as they occur in the experimental crystal network. Isolation of the relevant molecular dimers allows to incorporate some of the most sophisticated tools of quantum chemistry and get a reliable picture of the isolated bond. When compared to the experimental sublimation energy, our results are conclusive: this sole interaction is the largest contribution to the lattice energy, and definitively dictates the crystal architecture in all the studied cases. Elusive enough, the edge‐to‐face interaction is mainly dominated by correlation interactions, specifically in the form of dispersion and, to a less extent, of charge‐transfer terms. A suggestive picture of the bond has been obtained by displaying the differences in local electron densities calculated by either correlated or non‐correlated methods.
What are People's Experiences of a Novel Cognitive Behavioural Therapy for Bipolar Disorders? A Qualitative Investigation with Participants on the TEAMS Trial
Authors: Joyce Emmeline , Tai Sara , Gebbia Piersanti , Mansell Warren
Published: September 2016

Background

Psychological interventions for bipolar disorders typically produce mixed outcomes and modest effects. The need for a more effective intervention prompted the development of a new cognitive behavioural therapy, based on an integrative cognitive model (‘Think Effectively About Mood Swings’ [TEAMS] therapy). Unlike previous interventions, TEAMS addresses current symptoms and comorbidities, and helps clients achieve long‐term goals. A pilot randomized controlled trial (the TEAMS trial) of the therapy has recently concluded. This study explored participants' experiences of TEAMS, recommendations for improvement and experiences of useful changes post‐therapy.

Methods

Fourteen TEAMS therapy participants took part in semi‐structured interviews. Their accounts were analysed using interpretative thematic analysis. Two researchers coded the dataset independently. Member checks were conducted of the preliminary themes.

Results

Two overarching themes; ‘useful elements of therapy’ and ‘changes from therapy’ encompassed 12 emerging subthemes. Participants appreciated having opportunities to talk and described the therapy as person‐centred and delivered by caring, approachable and skilled therapists. Some recommended more sessions than the 16 provided. Helpful therapeutic techniques were reported to be, normalization about moods, methods to increase understanding of moods, relapse‐prevention, reappraisal techniques and metaphors. However, some did not find therapeutic techniques helpful. Post‐therapy, many reported changes in managing mood swings more effectively and in their thinking (although some participants reported changes in neither). Many described increased acceptance of themselves and of having bipolar disorder, increased productivity and reduced anxiety in social situations.

Conclusions

The present study evaluates participants' therapy experiences in detail, including aspects of therapy viewed as helpful, and meaningful post‐therapy outcomes. Copyright © 2016 John Wiley & Sons, Ltd.

Key Practitioner Message

This is the first paper to qualitatively explore people's experiences of individual psychotherapy for bipolar disorders. It highlights elements of psychotherapy described as particularly helpful or unhelpful and the clinical changes viewed as most impactful.

Participants reported benefitting in a number of ways from TEAMS therapy. They valued learning to reappraise and problem‐solve situations and manage moods.

Participants identified TEAMS techniques as helpful, such as exploring advantages and disadvantages of moods, and building healthy self‐states.
Strontium titanate: From symmetry changes to functionality
Authors: Stöcker Hartmut , Hanzig Juliane , Zschornak Matthias , Mehner Erik , Jachalke Sven , Richter Carsten , Hanzig Florian , Meutzner Falk , Leisegang Tilmann , Meyer Dirk C.
Published: September 2016

Pure strontium titanate exhibits a cubic perovskite‐type structure at room temperature, but many approaches to break this high degree of symmetry are accessible. The present review summarizes some possible methods by discussing the effects of stoichiometry variation, ion implantation, temperature treatment and external electric fields. Since oxygen vacancies are the most prominent and most mobile defect species in strontium titanate, they play a crucial role also for structural changes due to external influences. Possible functionalities range from tuning of permittivity, band gap and conductivity to field‐induced structure changes, which lead to applications as solid‐state battery or switchable pyroelectric.
Water Oxidation by Size‐Selected Co27 Clusters Supported on Fe2O3
Authors: Pellin Michael J. , Riha Shannon C. , Tyo Eric C. , Kwon Gihan , Libera Joseph A. , Elam Jeffrey W. , Seifert Soenke. , Lee Sungsik , Vajda Stefan
Published: September 2016

The complexity of the water oxidation reaction makes understanding the role of individual catalytic sites critical to improving the process. Here, size‐selected 27‐atom cobalt clusters (Co27) deposited on hematite (Fe2O3) anodes were tested for water oxidation activity. The uniformity of these anodes allows measurement of the activity of catalytic sites of well‐defined nuclearity and known density. Grazing incidence X‐ray absorption near‐edge spectroscopy (GIXANES) characterization of the anodes before and after electrochemical cycling demonstrates that these Co27 clusters are stable to dissolution even in the harsh water oxidation electrochemical environment. They are also stable under illumination at the equivalent of 0.4 suns irradiation. The clusters show turnover rates for water oxidation that are comparable or higher than those reported for Pd‐ and Co‐based materials or for hematite. The support for the Co27 clusters is Fe2O3 grown by atomic layer deposition on a Si chip. We have chosen to deposit a Fe2O3 layer that is only a few unit cells thick (2 nm), to remove complications related to exciton diffusion. We find that the electrocatalytic and the photoelectrocatalytic activity of the Co27/Fe2O3 material is significantly improved when the samples are annealed (with the clusters already deposited). Given that the support is thin and that the cluster deposition density is equivalent to approximately 5 % of an atomic monolayer, we suggest that annealing may significantly improve the exciton diffusion from the support to the catalytic moiety.
A reporting system for endometrial cytology: Cytomorphologic criteria—Implied risk of malignancy
Authors: Margari Niki , Pouliakis Abraham , Anoinos Dionysios , Terzakis Emmanouil , Koureas Nikolaos , Chrelias Charalampos , Marios Makris George , Pappas Assimakis , Bilirakis Evripidis , Goudeli Christina , Damaskou Vasileia , Papantoniou Nicolaos , Panayiotides Ioannis , Karakitsos Petros
Published: September 2016

Background

There have been various attempts to assess endometrial lesions on cytological material obtained via direct endometrial sampling. The majority of efforts focus on the description of cytological criteria that lead to classification systems resembling histological reporting formats. These systems have low reproducibility, especially in cases of atypical hyperplasia and well differentiated carcinomas. Moreover, they are not linked to the implied risk of malignancy.

Methods

The material was collected from women examined at the outpatient department of four participating hospitals. We analyzed 866 consecutive, histologically confirmed cases. The sample collection was performed using the EndoGyn device, and processed via Liquid Based Cytology, namely ThinPrep technique. The diagnostic categories and criteria were established by two cytopathologists experienced in endometrial cytology; performance of the proposed reporting format was assessed on the basis of histological outcome; moreover, the implied risk of malignancy was calculated.

Results

The proposed six diagnostic categories are as follows: (i) nondiagnostic or unsatisfactory; (ii) without evidence of hyperplasia or malignancy; (iii) atypical cells of endometrium of undetermined significance; (iv) atypical cells of endometrium of low probability for malignancy; (v) atypical cells of endometrium of high probability for malignancy; and (vi) malignant. The risk of malignancy was 1.42% ± 0.98%, 44.44% ± 32.46% (nine cases), 4.30% ± 4.12%, 89.80% ± 8.47%, and 97.81% ± 2.45%, respectively.

Conclusion

We propose a clinically oriented classification scheme consisting of diagnostic categories with well determined criteria. Each diagnostic category is linked with an implied risk of malignancy; thus, clinicians may decide on patient management and eventually reduce unnecessary interventional diagnostic procedures. Diagn. Cytopathol. 2016;44:888–901. © 2016 Wiley Periodicals, Inc.
Resource partitioning between sympatric seabird species increases during chick‐rearing
Authors: Barger Christopher P. , Young Rebecca C. , Will Alexis , Ito Motohiro , Kitaysky Alexander S.
Published: September 2016

Partitioning of resources by competing species of seabirds may increase during periods of food shortages and elevated energy demands. Here, we examined whether food resource partitioning (differential use of foraging habitat or the consumption of different prey species) between common murres (COMU, Uria aalge) and thick‐billed murres (TBMU, U. lomvia) breeding on the same colony in the Bering Sea increases with a predictable increase in energy demands between the incubation and chick‐rearing stages of reproduction. We assessed the seasonal dynamics of food availability via corticosterone (CORT) levels and examined adult diet (via stable isotope analysis of nitrogen and carbon, SI) and chick diets (based on nest observations). We compared chick provisioning patterns and examined the characteristics of parental foraging habitat via deployment of bird‐borne temperature‐depth recorders. We found that CORT levels remained low and similar between the species and reproductive stages, reflecting relatively stable and favorable foraging conditions for both murre species during the study period. Comparisons of SI between murres and their potential prey indicated that diets were similar between the species during incubation and diverged during chick‐rearing. Chick‐rearing common and thick‐billed murres also used different foraging habitats, as reflected in travel distances to foraging areas and sea surface temperature distributions of their foraging dives. TBMUs performed shorter foraging trips, deeper dives and delivered squid to their chicks, while COMUs foraged farther from the colony, performed shallower dives, and delivered fish species to their chicks. These results suggest that food resource partitioning between murre species increased during chick‐rearing under favorable foraging conditions. Whether the dietary segregation reflected species‐specific differences in adults' foraging efficiency, differences in chicks' dietary requirements, or was a way of reducing competition remains unknown. Regardless of the causal mechanism(s), food resource partitioning might ameliorate interspecific competition between sympatrically breeding birds during periods of increased energy demands.