bluuebunny/crossref_metadata_2025 huggingface dataset:
An Enantiospecific Synthesis of Jiadifenolide
Authors: Siler David A. , Mighion Jeffrey D. , Sorensen Erik J.
Published: April 2014

A Robinson annulation, van Leusen homologation, and a desymmetrizing CH oxidation enabled an enantiospecific synthesis of the neurotrophic natural product jiadifenolide. From a pulegone‐derived building block, a key propellane intermediate was constructed through the use of simple reagents in a highly diastereoselective fashion. A short series of oxidations of this tricylic framework allowed progression to the natural product.
Organokatalytische atropselektive Aldolkondensation: Synthese axial‐chiraler Biaryle durch Arenbildung
Authors: Link Achim , Sparr Christof
Published: April 2014

Axial‐chirale Verbindungen sind in der modernen Synthesechemie von zentraler Bedeutung und für die Arzneimittelentwicklung unentbehrlich. Der Zugang zu Atropisomeren in reiner Form erweist sich jedoch oft als sehr aufwendig. Hier zeigen wir eine atropselektive Synthesemethode, welche die stereochemische Information eines sekundären Amin‐Organokatalysators effizient in die axiale Chiralität von tri‐ortho‐substituierten Biarylen überträgt. Die beschriebene Aldolkondensationskaskade führt während der Dehydratisierung zur Arenbildung und somit zu hoch enantiomerenangereicherten Binaphthylderivaten. Der grundlegende Reaktionsablauf ist mit der aromatischen Polyketid‐Biosynthese verwandt.
anti‐Markovnikov Hydroamination of Alkenes Catalyzed by a Two‐Component Organic Photoredox System: Direct Access to Phenethylamine Derivatives
Authors: Nguyen Tien M. , Manohar Namita , Nicewicz David A.
Published: April 2014

Disclosed herein is a general catalytic system for the intermolecular anti‐Markovnikov hydroamination of alkenes. By using an organocatalytic photoredox system, α‐ and β‐substituted styrenes as well as aliphatic alkenes undergo anti‐Markovnikov hydroamination. Heterocyclic amines were also successfully employed as nitrogen nucleophiles, thus providing a direct route to heterocyclic motifs common in medicinal agents.
Nonenzymatic Rubylation and Ubiquitination of Proteins for Structural and Functional Studies
Authors: Singh Rajesh K. , Sundar Adithya , Fushman David
Published: April 2014

Uncovering the mechanisms that allow conjugates of ubiquitin (Ub) and/or Ub‐like (UBL) proteins such as Rub1 to serve as distinct molecular signals requires the ability to make them with native connectivity and defined length and linkage composition. A novel, effective, and affordable strategy for controlled chemical assembly of fully natural UBL–Ub, Ub–UBL, and UBL–UBL conjugates from recombinant monomers is presented. Rubylation of Ub and Rub1 and ubiquitination of Rub1 was achieved without E2/E3 enzymes. New residue‐specific information was obtained on the interdomain contacts in naturally‐occurring K48‐linked Rub1–Ub and Ub–Rub1, and K29‐linked Rub1–Ub heterodimers, and their recognition by a K48‐linkage‐specific Ub receptor. The disassembly of these heterodimers by major deubiquitinating enzymes was examined and it was discovered that some deubiquitinases also possess derubylase activity. This unexpected result suggests possible crosstalk between Ub and Rub1/Nedd8 signaling pathways.
Tetravinylethylene
Authors: Lindeboom Erik J. , Willis Anthony C. , Paddon‐Row Michael N. , Sherburn Michael S.
Published: April 2014

The first four‐fold cross coupling reaction involving alkenic partners leads to the title hydrocarbon on multi‐gram scale in one step from commercially available precursors. In stark contrast to its close structural relatives, tetravinylethylene is a remarkably robust, bench‐stable compound. The π‐bond rich hydrocarbon is shown to undergo one‐pot sequences of pericyclic reactions leading to the formation of complex systems with four new rings, seven CC bonds and ten stereocenters with a very high level of stereoselectivity. Insights into the reactivity of this and related systems is provided using the accurate composite ab initio MO G4(MP2) method.
Intramolecular Metal‐Free Oxidative Aryl–Aryl Coupling: An Unusual Hypervalent‐Iodine‐Mediated Rearrangement of 2‐Substituted N‐Phenylbenzamides
Authors: Shang Siyun , Zhang‐Negrerie Daisy , Du Yunfei , Zhao Kang
Published: April 2014

Hypervalent‐iodine‐mediated oxidative coupling of the two aryl groups in either 2‐acylamino‐N‐phenyl‐benzamides or 2‐hydroxy‐N‐phenylbenzamides, with concomitant insertion of the ortho‐substituted N or O atom into the tether, has been described for the first time. This unusual metal‐free rearrangement reaction involves an oxidative C(sp2)C(sp2) aryl–aryl bond formation, cleavage of a C(sp2)C(O) bond, and a lactamization/lactonization. Furthermore, unsymmetrical diaryl compounds can be easily obtained by removing the tether within the cyclized product.
Pullulan Encapsulation of Labile Biomolecules to Give Stable Bioassay Tablets
Authors: Jahanshahi‐Anbuhi Sana , Pennings Kevin , Leung Vincent , Liu Meng , Carrasquilla Carmen , Kannan Balamurali , Li Yingfu , Pelton Robert , Brennan John D. , Filipe Carlos D. M.
Published: April 2014

A simple and inexpensive method is reported for the long‐term stabilization of enzymes and other unstable reagents in premeasured quantities in water‐soluble tablets (cast, not compressed) made with pullulan, a nonionic polysaccharide that forms an oxygen impermeable solid upon drying. The pullulan tablets dissolve in aqueous solutions in seconds, thereby facilitating the easy execution of bioassays at remote sites with no need for special reagent handling and liquid pipetting. This approach is modular in nature, thus allowing the creation of individual tablets for enzymes and their substrates. Proof‐of‐principle demonstrations include a Taq polymerase tablet for DNA amplification through PCR and a pesticide assay kit consisting of separate tablets for acetylcholinesterase and its chromogenic substrate, indoxyl acetate, both of which are highly unstable. The encapsulated reagents remain stable at room temperature for months, thus enabling the room‐temperature shipping and storage of bioassay components.
Accelerating Diffusion‐Ordered NMR Spectroscopy by Joint Sparse Sampling of Diffusion and Time Dimensions
Authors: Urbańczyk Mateusz , Koźmiński Wiktor , Kazimierczuk Krzysztof
Published: April 2014

Diffusion‐ordered multidimensional NMR spectroscopy is a valuable technique for the analysis of complex chemical mixtures. However, this method is very time‐consuming because of the costly sampling of a multidimensional signal. Various sparse sampling techniques have been proposed to accelerate such measurements, but they have always been limited to frequency dimensions of NMR spectra. It is now revealed how sparse sampling can be extended to diffusion dimensions.
Direct Umpolung of Glycals and Related 2,3‐Unsaturated N‐Acetylneuraminic Acid Derivatives Using Samarium Diiodide
Authors: Le Tien Xuan , Papin Caroline , Doisneau Gilles , Beau Jean‐Marie
Published: April 2014

The umpolung of glycals with samarium diiodide offers a simple route to novel carbohydrate‐derived nucleophilic reagents in a single step using a readily available reductant. The corresponding allyl samarium reagent that arises from the hexose series reacts with ketones at the C3 position with high stereoselectivity; carbon–carbon bond formation takes place only anti to the substituent at the C4 position of the dihydropyran ring. For the sialic acid series, the completely regio‐ and stereoselective coupling process of the samarium reagent occurs at the anomeric carbon atom and provides a new approach to the α‐C‐glycosides of N‐acetyl neuraminic acid.
Reversible Click Reactions with Boronic Acids to Build Supramolecular Architectures in Water
Authors: Arzt Matthias , Seidler Christiane , Ng David Y. W. , Weil Tanja
Published: April 2014

The interaction of boronic acids with various bifunctional reagents offers great potential for the preparation of responsive supramolecular architectures. Boronic acids react with 1,2‐diols yielding cyclic boronate esters that are stable at pH>7.4 but can be hydrolyzed at pH<5.0. The phenylboronic acid (PBA)–salicylhydroxamic acid (SHA) system offers ultra‐fast reaction kinetics and high binding affinities. This Focus Review summarizes the current advances in exploiting the bioorthogonal interaction of boronic acids to build pH‐responsive supramolecular architectures in water.
Synthesis, Crystal Packing, and Ambipolar Carrier Transport Property of Twisted Dibenzo[g,p]chrysenes
Authors: Ueda Yasuyuki , Tsuji Hayato , Tanaka Hideyuki , Nakamura Eiichi
Published: April 2014

A versatile method for the synthesis of dibenzo[g,p]chrysene (DBC) derivatives based on regio‐ and stereoselective stannyllithiation to diarylacetylenes is described. This method affords a variety of DBCs possessing both electron‐donating and electron‐withdrawing functional groups. These twisted molecules take brickwork packing structures in single crystals. Thus, ambipolar carrier transport properties with mobility values of up to 10−3 cm2 V−1 s−1 in the amorphous state were achieved. Functional groups on DBC frameworks are considered to increase carrier mobility through the enhancement of intermolecular interactions in the brickwork packing structures.
Experimental and theoretical study of mechanoluminescence and lyoluminescence of Li3PO4: RE (RE=Dy and Tb) phosphors
Authors: Sahu A. K. , Kadukar Monali R. , Chowdhary P. S. , Nayar V. , Dhoble S. J.
Published: April 2014

Li3PO4 phosphors prepared by solid‐state diffusion technique and lyoluminescence (LL) as well as mechanoluminescence (ML) studies are reported. Dy‐ and Tb‐activated phosphors show dosimetric characteristics using LL and ML techniques. The energy levels and hence trapping and detrapping of charge carriers in the material can be studied using ML. Li3PO4 phosphor can be used in the dosimetric applications for ionizing radiation. By using the LL technique, the LL characteristics of Li3PO4 may be useful for high radiation doses. We also report a more detailed theoretical understanding of the mechanism of LL and ML. Copyright © 2014 John Wiley & Sons, Ltd.
Characterization of an anthraquinone fluor from the bioluminescent, pelagic polychaete Tomopteris
Authors: Francis Warren R. , Powers Meghan L. , Haddock Steven H. D.
Published: April 2014

Tomopteris is a cosmopolitan genus of polychaetes. Many species produce yellow luminescence in the parapodia when stimulated. Yellow bioluminescence is rare in the ocean, and the components of this luminescent reaction have not been identified. Only a brief description, half a century ago, noted fluorescence in the parapodia with a remarkably similar spectrum to the bioluminescence, which suggested that it may be the luciferin or terminal light‐emitter. Here, we report the isolation of the fluorescent yellow–orange pigment found in the luminous exudate and in the body of the animals. Liquid chromatography‐mass spectrometry revealed the mass to be 270 m/z with a molecular formula of C15H10O5, which ultimately was shown to be aloe‐emodin, an anthraquinone previously found in plants. We speculate that aloe‐emodin could be a factor for resonant‐energy transfer or the oxyluciferin for Tomopteris bioluminescence. © 2014 The Authors. Luminescence published by John Wiley & Sons Ltd.
Prediction of IgG1 aggregation in solution
Authors: Ojala Frida , Degerman Marcus , Hansen Thomas Budde , Broberg Hansen Ernst , Nilsson Bernt
Published: April 2014

Interest in monoclonal antibody aggregation is increasing as aggregates of biopharmaceuticals can cause an immunogenic response when injected into the body. In this work, a stoichiometric reaction model from concentration–time data is developed to predict the dimer ratio in stored antibody solutions over time. IgG1 was incubated at pH from 4.5 to 5.5, salt concentrations from 100 to 600 mmol/kg and protein concentrations of 10.6–26.3 g/L; samples were taken at intervals of 20 min to 5 h over time periods from 4 h to 7.6 days, and analyzed with size‐exclusion chromatography. The experiments showed the formation of dimers from monomers, but no higher order aggregates. Dilution of samples containing dimers led to the reversal of the dimerization reaction. Measurements of the concentrations of each component were made by fitting exponentially modified Gaussian peaks to the chromatograms used to measure the concentrations of the different forms of protein. This stoichiometric reaction model was able to predict the formation of dimers by the antibody studied. The equilibrium constant was found to be dependent on the salt concentration, and the kinetic constant showed a dependence on the pH of the solution. The prediction of the aggregation leads to a possibility of optimizing the conditions in order to prevent the dimer formation and to maximize the monomer concentration.
Risk factors for bleeding in hepatocellular adenoma
Authors: Bieze M , Phoa S S K S , Verheij J , van Lienden K P , van Gulik T M
Published: April 2014

Background

Hepatocellular adenoma (HCA) is a benign hepatic lesion that may be complicated by bleeding, although the risk of bleeding is ill-defined. The aim of this study was to assess risk factors for bleeding in patients diagnosed with HCA.

Methods

Patients with HCA were included prospectively from January 2008 to July 2012. Patient characteristics were noted. Patients underwent dynamic magnetic resonance imaging (MRI) and/or computed tomography (CT) at presentation and during follow-up. Lesion characteristics on (follow-up) imaging were noted, and bleeding was graded as intratumoral (grade I), intrahepatic (grade II) or extrahepatic (grade III). The standard of reference for diagnosis was histopathology, or dynamic MRI and/or CT findings. Possible risk factors were included if mentioned in literature (lesion size, body mass index), or based on clinical experience (lesion location, visible vessels on imaging).

Results

A total of 45 patients (median age 39 (range 22–60) years; 44 women) with 195 lesions (median size 24 (10–250) mm) were evaluated. Bleeding occurred in 29 patients (64 per cent) and in 42 lesions (21·5 per cent) with a median size of 62 (10–160) mm. Size was a risk factor for bleeding (P < 0·001), with an increased number of bleeding events in lesions of 35 mm or more. Exophytic lesions (protruding from liver) had more bleeding (16 of 24, 67 per cent) than intrahepatic (9 of 82, 11 per cent) or subcapsular (17 of 89, 19 per cent) lesions (P < 0·001). Lesions in segments II and III had more bleeds than those in the right liver (11 of 32 versus 31 of 163; P = 0·049), as did lesions in which peripheral or central arteries were visualized on imaging (10 of 13 versus 32 of 182 lesions with no visible vascularization; P < 0·001).

Conclusion

Risk factors for bleeding of HCA include diameter of 35 mm or more, visualization of lesional arteries, location in the left lateral liver, and exophytic growth.
Randomized clinical trial comparing Nordic pole walking and a standard home exercise programme in patients with intermittent claudication
Authors: Spafford C , Oakley C , Beard J D
Published: April 2014

Background

This was a randomized clinical trial to determine whether Nordic pole walking (NPW) is more effective in improving walking distance than a standard home exercise programme (HEP) in patients with intermittent claudication.

Methods

Fifty-two patients with stable claudication were allocated randomly to a standard HEP or NPW group, and asked to complete three 30-min walks per week for 12 weeks. Claudication distance (CD) and maximum walking distance (MWD) were measured at 0 (baseline), 4, 8 and 12 weeks. Patients in the NPW group were tested with (NPW+) and without (NPW–) poles.

Results

For NPW+, CD increased immediately from a median (range) of 124 (71–248) m to 148 (116–426) m, and MWD from 248 (149–900) to 389 (194–1099) m (P = 0·004 and P < 0·001 respectively). By 12 weeks, CD had further increased to 199 (118–550) m and MWD had more than doubled to 538 (250–1750) m (P < 0·001 and P = 0·001). For NPW–, CD at 12 weeks had increased significantly to 151 (100–328) m and MWD to 400 (200–900) m (P < 0·001 and P = 0·006 respectively). At 12 weeks the changes in the standard HEP group were not significant, despite excellent compliance: CD from 107 (56–332) to 153 (59–321) m and MWD from 355 (92–600) to 334 (149–874) m (P = 0·030 and P = 0·260 respectively).

Conclusion

A 12-week exercise programme using Nordic poles significantly improved walking distance in claudicants compared with a standard HEP. Registration number: ISRCTN78168304 (http://www.controlled-trials.com).
Determination of 10‐chloromethyl‐11‐demethyl‐12‐oxo‐calanolide A in rat plasma using liquid chromatography–tandem mass spectrometry and its application to pharmacokinetics
Authors: Sheng Li , Zhang Qinghao , Liu Zhihao , Liu Xin , Wang Baolian , Chen Hui , Li Yan
Published: April 2014

A rapid and specific liquid chromatography–tandem mass spectrometry for the quantitation of 10‐chloromethyl‐11‐demethyl‐12‐oxo‐calanolide A (F18), a small‐molecule nonnucleoside reverse transcriptase inhibitor, was developed and validated in rat plasma. F18 was monitored by positive electrospray ionization in the selected reaction monitoring mode. The standard curve was linear over the range of 2–1000 ng/mL. The method was used to determine the plasma concentration of F18 after a single oral dose of 50 mg/kg in rats. Copyright © 2014 John Wiley & Sons, Ltd.
Palladium‐Catalyzed Silver‐Mediated α‐Arylation of Acetic Acid: A New Approach for the α‐Arylation of Carbonyl Compounds
Authors: Wu Guo‐Jie , Guan Jing , Han Fu‐She , Zhao Yu‐Long
Published: April 2014

A new approach for the α‐arylation of acetic acid through Pd‐catalyzed silver‐mediated direct CH arylation of acetic acid with aryl iodides was developed. This protocol provided a straightforward method for the synthesis of a diverse set of α‐phenylacetic acids.
Multivalency by Self‐Assembly: Binding of Concanavalin A to Metallosupramolecular Architectures Decorated with Multiple Carbohydrate Groups
Authors: Chmielewski Michał J. , Buhler Eric , Candau Jean , Lehn Jean‐Marie
Published: April 2014

Multiplication of functional units through self‐assembly is a powerful way to new properties and functions. In particular, self‐organization of components decorated with recognition groups leads to multivalent entities, amenable to strong and selective binding with multivalent targets, such as protein receptors. Here we describe an efficient, supramolecular, one‐pot valency multiplication process proceeding through self‐organization of monovalent components into well‐defined, grid‐shaped [2×2] tetranuclear complexes bearing eight sugar residues for multivalent interaction with the tetrameric lectin, concanavalin A (Con A). The grids are stable in water under physiological pH at a relatively high concentration, but dissociate readily at slightly more acidic pH or upon dilution below a certain threshold, in a type of on–off behavior. The carbohydrate‐decorated grids interact strongly and selectively with Con A forming triply supramolecular bio‐hybrid polymeric networks, which lead to a highly specific phase‐separation and quasi‐quantitative precipitation of Con A out of solution. Dramatic effects of valency number on agglutination properties were demonstrated by comparison of grids with divalent carbohydrates of covalent and non‐covalent (L‐shaped, mononuclear zinc complex) scaffolds. The results presented here provide prototypical illustration of the power of multivalency generation by self‐assembly leading to defined arrays of functional groups and binding patterns.
pH‐Controlled Multiple Chiral Inversion That Induces Molecular Dimerization in a Gold(I)–Cobalt(III) Coordination System with L‐Cysteinate
Authors: Lee Pei‐Shan , Igashira‐Kamiyama Asako , Kuwamura Naoto , Yoshinari Nobuto , Konno Takumi
Published: April 2014

Herein, a unique coordination system that exhibits multiple chiral inversions and molecular dimerization in response to a subtle pH change is reported. Treatment of (Δ)2‐H3[Au3Co2(L‐cys)6] (H3[1 a]) with [Co3(aet)6](NO3)3 (aet=2‐aminoethanethiolate) in water at pH 7 gave a 1:1 complex salt of [Co3(aet)6]3+ and [1 a]3−, retaining the AuI3CoIII2 structure and chiral configurations of [1 a]3−. Similar treatment at pH 9 led to not only the inversion of all of the chiral CoIII and S centers but also the dimerization of [1 a]3−, giving a 2:1 complex salt of [Co3(aet)6]3+ and (Λ)4(R)12‐[Au6Co4(L‐cys)12]6− ([2]6−). When dissociated from [Co3(aet)6]3+ in solution, [2]6− was converted to (Λ)2(R)6‐[Au3Co2(L‐cys)6]3− ([1 b]3−) with retention of the chiral configurations.
Comparative Binding of Endocrine Disrupting Compounds and Pharmaceuticals with Polydopamine‐ and Polypyrrole‐coated Magnetic Nanoparticles
Authors: Miah Musharraf , Iqbal Zafar , Lai Edward P.C.
Published: April 2014

Global concern about pharmaceutical and endocrine disrupting compounds in water resources is at its most intense due to their adverse effects on human health and environmental sustainability. Polydopamine‐coated magnetic nanoparticles (MNPs@PDA) and polypyrrole‐coated magnetic nanoparticles (MNPs@PPy) were successfully synthesized with strong magnetic attraction for easy separation. Their binding efficiencies with bisphenol A (BPA), metformin (MF), naphthalene acetic acid (NAA), phenformin (PF), quinine sulfate (QS), and triclosan (TC) in water were determined using capillary electrophoresis with UV detection. At a concentration of 200 mg mL−1, the binding efficiencies of MNPs@PPy were found to be 99 ± 1% BPA, 34 ± 4% MF, 39 ± 6% NAA, 99 ± 1% PF, 98 ± 2% QS, and 99 ± 1% TC, whereas MNPs@PDA afforded 65 ± 5% BPA, 14 ± 6% MF, 21 ± 4% NAA, 99 ± 1% PF, 94 ± 2% QS, and 92 ± 3% TC. Hence, both MNPs@PDA and MNPs@PPy have a high capacity for efficient removal of aromatic compounds from water.
Effect of Natural Zeolite Application on Nitrite Concentrations in Rape (Brassica campestris L.) in Pb‐Contaminated Soils in Peri‐Urban Areas
Authors: Shi Wei‐yu , Li Hua , Du Sheng , Chen Yiping , Wang Kaibo
Published: April 2014

Peri‐urban soils are polluted by lead (Pb) due to urban development in China. Natural zeolites have been widely used for remediating heavy metals in soils, but the effects of natural zeolite application on nitrite concentration in rape have not been studied. Pot experiments were carried out to investigate using a random complete block design. Zeolite application and Pb contaminants in soil caused significant decreases in nitrite concentrations in rape. Chlorophyll a (Chl‐a), chlorophyll b (Chl‐b), and chlorophyll a + b (Chl‐a + b) in rape decreased as levels of Pb contamination increased. Pb contamination reduced the photosynthetic activity of rape, and appears to limit the transformation of nitrate to nitrite, but pose food risk. Zeolite application caused a significant increase in soil pH, with a variation range of 0.5. The increase in soil pH reduced nitrite accumulation in soil by enhancing activity of ammonia‐oxidizing bacteria. The content of soil aggregates >0.25 and >2.00 mm all increased in response to the application of zeolite. Increases in soil aggregates could effectively control excessive release of nitrogen (N) accumulated in soils, which would reduce uptake of N by plants. These results indicate that the application of zeolite is an eco‐friendly and effective way to improve the quality of rape growing in peri‐urban areas.
Optimizing high performance computing workflow for protein functional annotation
Authors: Stanberry Larissa , Rekepalli Bhanu , Liu Yuan , Giblock Paul , Higdon Roger , Montague Elizabeth , Broomall William , Kolker Natali , Kolker Eugene
Published: April 2014

Functional annotation of newly sequenced genomes is one of the major challenges in modern biology. With modern sequencing technologies, the protein sequence universe is rapidly expanding. Newly sequenced bacterial genomes alone contain over 7.5 million proteins. The rate of data generation has far surpassed that of protein annotation. The volume of protein data makes manual curation

infeasible, whereas a high compute cost limits the utility of existing automated approaches. In this work, we present an improved and optmized automated workflow to enable large‐scale protein annotation. The workflow uses high performance computing architectures and a low complexity classification algorithm to assign proteins into existing clusters of orthologous groups of proteins. On the basis of the Position‐Specific Iterative Basic Local Alignment Search Tool the algorithm ensures at least 80% specificity and sensitivity of the resulting classifications. The workflow utilizes highly scalable parallel applications for classification and sequence alignment. Using Extreme Science and Engineering Discovery Environment supercomputers, the workflow processed 1,200,000 newly sequenced bacterial proteins. With the rapid expansion of the protein sequence universe, the proposed workflow will enable scientists to annotate big genome data. Copyright © 2014 John Wiley & Sons, Ltd.
The Process of Seeking Psychotherapy and Its Impact on Therapy Expectations and Experiences
Authors: Elliott Katherine P. , Westmacott Robin , Hunsley John , Rumstein‐McKean Orly , Best Marlene
Published: April 2014

Seeking psychotherapy can be conceptualized as having three stages: deciding that therapy might help, deciding to seek therapy and contacting a therapist. The present study examined the duration and difficulty of clients' decisions to seek psychotherapy and whether these experiences were predictive of expected difficulty and commitment to the therapy process. One‐hundred and fifty‐five adults seeking individual psychological services from a university training clinic were assessed before intake; 107 of these participants also completed measures between the third and fourth therapy sessions and at post‐therapy. Deciding that therapy might help was reported to be the most difficult step and took the longest, with each subsequent step becoming easier and briefer. At each step, the more difficult the decision, the more time participants took to make it. Higher distress was associated with more difficulty in deciding that therapy might help and deciding to seek therapy. Duration and difficulty of decisions to seek therapy were positively correlated with expectations of difficulty in therapy as measured prior to treatment and following the third session but were not associated with participants' commitment to therapy. The implications of these results for clinicians and mental health services are discussed. Copyright © 2014 John Wiley & Sons, Ltd.

Key Practitioner Message

The most difficult and time‐consuming step for those who seek mental health services is recognizing that their distressing experiences are connected to mental health; clinicians may aid this challenge by providing information on the nature of mental disorders and common symptoms of emotional distress on websites or through other means (e.g., physicians' waiting rooms and advertising campaigns).

The next most difficult and time‐consuming step for those who seek mental health services is deciding that psychotherapy may help; by providing easily accessible information (e.g., on websites) about what psychotherapy entails, including clinicians' expectations of clients and the benefits/challenges of therapy, potential clients may be able to progress through this step more rapidly and with less difficulty.

Clients' expectations of the value of psychotherapy and their commitment to engage in therapy do not appear to be affected by how long it took, or how difficult it was, to obtain psychotherapy.

Factors such as forming a strong therapeutic alliance and providing support and guidance during the initial sessions of therapy may be more important in helping potential clients commit to therapy than what they experienced in their efforts to receive psychotherapy.
Are Dyslexic Children Sensitive to the Morphological Structure of Words When They Read? The Case of Dyslexic Readers of French
Authors: Berthiaume Rachel , Daigle Daniel
Published: April 2014

Typically, research has cited a deficient use of word recognition procedures mainly caused by a phonological deficit as the source of dyslexic students' reading difficulties. However, recent studies have shown that morphological processing also plays an important part in reading. In the present study, sensitivity to the morphological structure of words was assessed with a plausibility judgment task, where participants determined which of two pseudo‐words most resembled a real word in French, and with a decomposition task requiring participants to extract the base forms of morphologically complex words. Dyslexic participants (DYS, n = 26) aged 9–12 years were matched to 26 participants of the same chronological age (CA) and 30 younger participants of the same reading age (RA). Overall, the decomposition task was less successful at demonstrating morphological knowledge than the plausibility judgment task. Results indicate that dyslexic participants demonstrated some morphological sensitivity, particularly on the plausibility task, but were outperformed by both control groups on both tasks. Performance on morphological tasks was significantly correlated to reading comprehension scores. More research needs to be carried out to better comprehend the effects of task characteristics on dyslexic participants' success and before claiming a different or deviant developmental path for morphological knowledge. Copyright © 2014 John Wiley & Sons, Ltd.
Structural and Physical Properties of (EDO‐TTF‐Cl)2XF6 (X = As, Sb): Geometrical Aspects for Monosubstituted EDO‐TTF (EDO‐TTF = 4,5‐ethylenedioxytetrathiafulvalene)
Authors: Ishikawa Manabu , Nakano Yoshiaki , Uruichi Mikio , Otsuka Akihiro , Yakushi Kyuya , Yamochi Hideki
Published: April 2014

Compounds of the formula (EDO‐TTF‐Cl)2XF6 (EDO‐TTF‐Cl = 4‐chloro‐4′,5′‐ethylenedioxytetrathiafulvalene, X = As, Sb) were prepared to examine the substituent size effect on the packing structure of the donor molecules. In these salts, a head‐to‐tail type donor stacking was observed. Although the AsF6 salt is a quasi‐one‐dimensional dimer Mott insulator, the SbF6 salt shows quasi‐one‐dimensional metallic behavior. Detailed crystal structure analyses revealed the correlation between the anion size and the intermolecular slipping among the donor molecules. The donor morphology, which plays an important role in the overlapping mode selectivity, is characterized by the magnitude and configuration of the out‐of‐plane substituent size.
3D/3D Hetero‐Interpenetrating Diamondoid Framework and Homo‐Interpenetrating pcu Network by a One‐Pot Reaction
Authors: Guo Xiang‐Guang , Yang Wen‐Bin , Wu Xiao‐Yuan , Lin Lang , Lu Can‐Zhong
Published: April 2014

Two new metal–organic frameworks (MOFs) with novel architectures, namely, [Co2(NDC)2(H2MDP)2][(Co(NDC)(H2MDP)] (1) and [Co(NDC)(H2MDP)0.5] (2) were synthesized through a one‐pot reaction. The metal to ligand ratio was found to influence the formation of the two compounds, and their pure phases were successfully obtained only by adjusting the molar ratios of Co/H2NDC/H2MDP to be 1:1:1 and 2:2:1, respectively [H2NDC = 1,4‐naphthalenedicarboxylic acid, H2MDP = methylenebis(3,5‐dimethylpyrazole)]. X‐ray crystallographic analyses showed that 1 crystallizes as a racemic twin and features an interesting threefold 3D/3D hetero‐interpenetrating diamondoid framework with left‐handed and right‐handed helical chains, whereas 2 displays a 3D twofold homo‐interpenetrating pcu network constructed from paddle‐wheel secondary building units and H2MDP pillars in a trans conformation. The one‐pot synthesis of two or more MOFs with hetero‐interpenetration and homo‐interpenetration has been rarely reported.
Inclusion complexes of astaxanthin with hydroxypropyl‐β‐cyclodextrin: Parameters optimization, spectroscopic profiles, and properties
Authors: Dong Shengzhao , Huang Yi , Zhang Rui , Lian Zhongshuai , Wang Shihui , Liu Yun
Published: April 2014

Inclusion complexes of astaxanthin with hydroxypropyl‐β‐cyclodextrin (HPCD) were systematically investigated from several aspects of processing optimization by RSM, spectroscopic profiles of UV, FT‐IR, and TG/DTA, and properties of water solubility, storage stability, 1,1‐diphenyl‐2‐picrylhydrazyl (DPPH) radical scavenging activity, and reducing power. The results showed that the optimal preparation conditions of inclusion complexes were: 500:1 of HPCD/astaxanthin mass ratio, 49.58°C of temperature and 25 mg/mL of HPCD concentration. Under the optimized conditions, inclusion rate of 30.4 ± 1.3% was achieved. Spectroscopic profiles revealed that the hexatomic ring of the astaxanthin molecules was partly included into the HPCD cavities and the starting decomposition temperature of astaxanthin increased by about 50°C due to the protection of HPCD. The storage stability of inclusion complexes was enhanced at the temperatures of 4, 25, 37, and 50°C in dark and light storage conditions. The reducing power and DPPH radical scavenging activities of inclusion complexes were much higher than those of pure astaxanthin, and the inclusion complexes showed good water solubility with high concentration up to 50 mg/mL. In conclusion, the optimized parameters and monitoring procedure by TGA, UV, FT‐IR, and HPLC are useful to conduct the inclusion complexes preparation with good properties, which are helpful for its applications in food and feed industries as an antioxidant additive.

Practical applications: (i) The operational parameters of inclusion complexes were optimized and monitored by TGA, UV, FT‐IR, and HPLC, which is useful to conduct the inclusion complexes preparation with good properties; (ii) The properties of inclusion complexes were elucidated such as water solubility, storage stability, DPPH radical scavenging activity, and reducing power, which are helpful for its applications in food and feed industries as an antioxidant additive.

Inclusion complexes of astaxanthin with hydroxypropyl‐β‐cyclodextrin (HPCD) were systematically investigated from several aspects of processing optimization by RSM, spectroscopic profiles of UV, FT‐IR, and TG/DTA, and properties of water solubility, storage stability, DPPH radical scavenging activity, and reducing power. The results are useful to conduct the inclusion complexes preparation with good properties and helpful for its applications in food and feed industries as an antioxidant additive.
Synthesis and Characterization of Bisumanenylidene
Authors: Amaya Toru , Ito Takanori , Hirao Toshikazu
Published: April 2014

Bisumanenylidene, consisting of two sumanene components bridged by a double bond, was synthesized by McMurry coupling of monooxosumanene. Calculations and low‐temperature 1H NMR spectroscopy experiments suggest that bisumanenylidene is likely to be dominantly present in the C2h symmetric structure rather than the C2 symmetric one. Evidence for the extension of π conjugation in bisumanenylidene was shown by absorption and emission spectroscopy.
A Glassy Carbon Electrode Modified with LangmuirBlodgett Film Composed of DNA and Polyaniline for the Sensitive Determination of Salbutamol
Authors: Zou Lina , Li Yinfeng , Cao Shaokui , Ye Baoxian
Published: April 2014

A composite LangmuirBlodgett film prepared from DNA and polyaniline was deposited on the surface of a glassy carbon electrode (GCE) to give a new voltammetric sensor for the β2‐agonist salbutamol (SAL). Cyclic voltammetry and electrochemical impedance spectroscopy were employed to study the characteristic of the modified electrode. The electrochemistry of SAL at the modified electrode was investigated at pH 6.8 by cyclic voltammetry and differential pulse anodic voltammetry. The oxidation of SAL at this electrode is an adsorption‐controlled irreversible process. A sensitive electroanalytical method for determination of SAL was worked out that displays high precision and good reproducibility. The method was applied to quantify SAL in tablets with satisfactory results.
Series expansion of complex ground amplifications with a sequence of simple transfer functions
Authors: Goto Hiroyuki
Published: April 2014

Amplification of earthquake ground motions at actual deposit sites is an important factor to consider when assessing the risk of an earthquake disaster. In order to identify the amplification properties, several preprocessings such as the Fourier transform are required. I propose a series expansion of the amplification with simple ground transfer functions as a new preprocessing. I define a sequence of transfer functions based on a two‐layered structure excluding an internal damping and a function space spanned by the set of the functions. I mathematically prove that the function space is equal to L2 space. This indicates that all the functions belonging to L2 space, that is, an arbitrary ground amplification, have a unique series expansion. This expansion is applied to the physics‐based decomposition of the amplification. Some numerical examples indicate that the similarity between a target complex structure and a simple model is measured by the absolute value of each coefficient in the series expansion. Copyright © 2014 John Wiley & Sons, Ltd.
Generalized force vectors for multi‐mode pushover analysis of torsionally coupled systems
Authors: Kaats𝚤z Kaan , Sucuoğlu Halûk
Published: April 2014

A generalized multi‐mode pushover analysis procedure was developed for estimating the maximum inelastic seismic response of symmetrical plan structures under earthquake ground excitations. Pushover analyses are conducted with story‐specific generalized force vectors in this procedure, with contributions from all effective modes.

Generalized pushover analysis procedure is extended to three‐dimensional torsionally coupled systems in the presented study. Generalized force distributions are expressed as the combination of modal forces to simulate the instantaneous force distribution acting on the system when the interstory drift at a story reaches its maximum value during seismic response. Modal contributions to the generalized force vectors are calculated by a modal scaling rule, which is based on the complete quadratic combination. Generalized forces are applied to the mass centers of each story incrementally for producing nonlinear static response. Maximum response quantities are obtained when the individual frames attain their own target interstory drift values in each story. The developed procedure is tested on an eight‐story frame under 15 ground motions, and assessed by comparing the results obtained from nonlinear time history analysis. The method is successful in predicting the torsionally coupled inelastic response of frames responding to large interstory drift demands. Copyright © 2014 John Wiley & Sons, Ltd.
Stair evacuation of people with mobility impairments
Authors: Kuligowski Erica , Peacock Richard , Wiess Emily , Hoskins Bryan
Published: April 2014

This paper presents data on the movement speeds of occupants with various types of mobility impairments evacuating two residential facilities for older adults located on the East Coast of the USA with the goal of better understanding of behavior and movement speeds during stairwell evacuation with and without assistance. The building populations who took part in the current study comprised a diverse array of older adults and disabled residents descending the stairwells by the following methods: self‐evacuation without assistance, assistance using a cane, assistance from another occupant or firefighter, or assistance using a stair chair. Movement data of these specific groups were compared and contrasted with other data collected on mobility‐impaired individuals. In the current study, the National Institute of Standards and Technology observed overall average speeds of 0.31 ± 0.16 m/s (with individual speeds ranging from 0.07 to 0.91 m/s), which in some cases, approximate the speeds of disabled people and older adults found in earlier studies, and in other cases are slower than those observed in previous studies. Slower speeds reported here may have resulted from observing a wider variety of mobility impairments (because one of the buildings observed was an assisted‐living facility) and from evacuation assistance provided by untrained populations. These data provide an adequate confirmation of exiting literature values typically used for disabled movement speeds in addition to updated values for future analyses. Copyright © 2014 John Wiley & Sons, Ltd.
Objective assessment of attention in delirium: a narrative review
Authors: Tieges Zoë , Brown Laura J. E. , MacLullich Alasdair M. J.
Published: April 2014

Objective

Inattention is a core feature of delirium, and valid assessment of attention is central to diagnosis. Methods of measuring attention in delirium can be divided into two broad categories: (i) objective neuropsychological testing; and (ii) subjective grading of behaviour during interview and clinical examination. Here, we review and critically evaluate studies of objective neuropsychological testing of attention in delirium. We examine the implications of these studies for delirium detection and monitoring in clinical practice and research, and how these studies inform understanding of the nature of attentional deficits in delirium.

Methods

Searches of MEDLINE and ISI Web of Knowledge databases were performed to identify studies in which objective tests of attention had been administered to patients with delirium, who had been diagnosed using DSM or ICD criteria.

Results

Sixteen publications were identified. The attention tests administered in these studies were grouped into the following categories: measures of attention span, vigilance tests, other pen‐and‐paper tests (e.g. Trail Making Test) and computerised tests of speeded reaction, vigilance and sustained attention. Patients with delirium showed deficits on all tasks, although most tasks were not considered pure measures of attention. Five papers provided data on differential diagnosis from dementia. Cancellation tests, spatial span tests and computerised tests of sustained attention discriminated delirium from dementia. Five studies presented reliability or validity statistics.

Conclusions

The existing evidence base on objective assessment of attention in delirium is small. Objective testing of attention is underdeveloped but shows considerable promise in clinical practice and research. Copyright © 2014 John Wiley & Sons, Ltd.
The Effectiveness of Recruitment Advertisements and Recruitment Websites: Indirect and Interactive Effects on Applicant Attraction
Authors: Baum Matthias , Kabst Rüdiger
Published: April 2014

This study compares the effect of printed recruitment advertisements and recruitment websites on applicant attraction and shows how these recruitment activities interact with one another. Our results indicate that websites have a significantly stronger impact on applicant attraction than printed advertisements. We show that websites and printed recruitment advertisements have an indirect effect on applicant attraction that is mediated by employer knowledge. Furthermore, printed advertisements supplement the positive effects of websites and, thus, the simultaneous use of multiple recruitment activities directly influences applicant attraction. © 2014 Wiley Periodicals, Inc.
[18F]DPA‐C5yne, a novel fluorine‐18‐labelled analogue of DPA‐714: radiosynthesis and preliminary evaluation as a radiotracer for imaging neuroinflammation with PET
Authors: Médran‐Navarrete Vincent , Bernards Nicholas , Kuhnast Bertrand , Damont Annelaure , Pottier Géraldine , Peyronneau Marie‐Anne , Kassiou Michael , Marguet Frank , Puech Frédéric , Boisgard Raphaël , Dollé Frédéric
Published: April 2014

DPA‐C5yne, the lead compound of a novel series of DPA‐714 derivatives in which the fluoroethoxy chain linked to the phenylpyrazolopyrimidine scaffold has been replaced by a fluoroalkyn‐1‐yl moiety, is a high affinity (Ki: 0.35 nM) and selective ligand targeting the translocator protein 18 kDa. In the present work, DPA‐C5yne was labelled with no‐carrier‐added [18F]fluoride based on a one‐step tosyloxy‐for‐fluorine nucleophilic substitution reaction, purified by cartridge and HPLC, and formulated as an i.v. injectable solution using a TRACERLab FX N Pro synthesizer. Typically, 4.3–5.2 GBq of [18F]DPA‐C5yne, ready‐to‐use, chemically and radiochemically pure (> 95%), was obtained with specific radioactivities ranging from 55 to 110 GBq/µmol within 50–60 min, starting from a 30 GBq [18F]fluoride batch (14–17%). LogP and LogD of [18F]DPA‐C5yne were measured using the shake‐flask method and values of 2.39 and 2.51 were found, respectively. Autoradiography studies performed on slices of ((R,S)‐α‐amino‐3‐hydroxy‐5‐methyl‐4‐isoxazolopropionique (AMPA)‐lesioned rat brains showed a high target‐to‐background ratio (1.9 ± 0.3). Selectivity and specificity of the binding for the translocator protein was demonstrated using DPA‐C5yne (unlabelled), PK11195 and Flumazenil (central benzodiazepine receptor ligand) as competitors. Furthermore, DPA‐C5yne proved to be stable in plasma at 37°C for at least 90 min.
Empowering Corporate Social Responsibility in Chinese Nongovernmental Organizations
Authors: Yang Jan , Webber Jon
Published: April 2014

One must overcome multiple barriers to develop viable corporate social responsibility (CSR) programs for nongovernmental organizations (NGOs) headquartered in Beijing, China. Our qualitative, collective case study follows up on Yu and Webber's () research, which explored how a Chinese nongovernmental organization in Guangzhou, Guangdong province developed corporate social responsibility in the country's socioeconomic and political context. The 15 participants in the current study were chosen because of their association with the China CSR Map, Syn Tao project and their willingness to be interviewed. Participants identified economic, legal, ethical, and philanthropic responsibilities as key categories for CSR consideration within the framework of consumers, employees, government, and other stakeholder interest. The authors’ findings offer insights into the factors pertaining to the development of a viable CSR program in China's political context. China CSR Map, Syn Tao identified its key stakeholders and suggested that governmental leaders create a set of CSR standards to discipline Chinese companies’ behaviors toward achieving the goals of building a harmonious society and a beautiful China.
De novo Stage IV breast cancer: Breast conserving resection of the primary tumor?
Authors: Khan Seema Ahsan
Published: April 2014

Multiple retrospective reviews completed over the past decade suggest a survival advantage with resection of the intact primary tumor in women with metastatic breast cancer. However, these reviews are not without bias, and recently completed randomized trials do not support a significant survival benefit, although local control benefits may exist. Completion of ongoing trials is needed to reach a definitive conclusion regarding the merit of primary tumor resection for local control and survival. J. Surg. Oncol. 2014 110:51–57. © 2014 Wiley Periodicals, Inc.
A stress and displacement discontinuity element method for elastic transversely anisotropic rock
Authors: Bobet A. , García Marín V.
Published: April 2014

The paper presents closed‐form solutions for stress and displacement influence functions for stress discontinuity (SD) and displacement discontinuity (DD) elements, for a two‐dimensional plane‐strain elastic, transversely anisotropic medium. The solutions for SD elements are based on Kelvin's problem and for DD elements on the concept of dipoles. Stress and displacement influence functions are derived for the following elements: constant SD, linear SD, constant DD, linear DD, square root DD, parabolic DD, constant DD surface, and linear DD surface elements. The formulations are incorporated into FROCK, a hybridized boundary element method code, and are validated by providing comparisons between the results from FROCK and the finite element code ABAQUS. A limited parametric analysis shows the effects of slight anisotropy on the stress field around the tip of a crack and of the orientation of the crack with respect to the axes of elastic symmetry. Copyright © 2014 John Wiley & Sons, Ltd.