bluuebunny/crossref_metadata_2025_split huggingface dataset:
Electron Tunneling Rates in Respiratory Complex I Are Tuned for Efficient Energy Conversion
Authors: de Vries Simon , Dörner Katerina , Strampraad Marc J. F. , Friedrich Thorsten 
Published: January 2015

AbstractRespiratory complex I converts the free energy of ubiquinone reduction by NADH into a proton motive force, a redox reaction catalyzed by flavin mononucleotide(FMN) and a chain of seven iron–sulfur centers. Electron transfer rates between the centers were determined by ultrafast freeze‐quenching and analysis by EPR and UV/Vis spectroscopy. The complex rapidly oxidizes three NADH molecules. The electron‐tunneling rate between the most distant centers in the middle of the chain depends on the redox state of center N2 at the end of the chain, and is sixfold slower when N2 is reduced. The conformational changes that accompany reduction of N2 decrease the electronic coupling of the longest electron‐tunneling step. The chain of iron–sulfur centers is not just a simple electron‐conducting wire; it regulates the electron‐tunneling rate synchronizing it with conformation‐mediated proton pumping, enabling efficient energy conversion. Synchronization of rates is a principle means of enhancing the specificity of enzymatic reactions.
Asymmetric Total Synthesis of (−)‐Lundurine B and Determination of Its Absolute Stereochemistry
Authors: Nakajima Masaya , Arai Shigeru , Nishida Atsushi 
Published: January 2015

AbstractA total synthesis of the Kopsia tenuis alkaloid (−)‐lundurine B has been achieved. A quaternary chiral carbon has been created by an asymmetric deprotonation using a symmetric spiro cyclohexanone intermediate with a chiral lithium amide. The hexacyclic skeleton was sequentially constructed through metal‐mediated reactions. The absolute stereochemistry of intermediate 5 has been unambiguously established by X‐ray crystallographic analysis. This is the first description of the absolute stereochemistry of Kopsia tenuis alkaloids based on chemical synthesis.
Stigma by Association Among Family Members of People with a Mental Illness: A Qualitative Analysis
Authors: van der Sanden Remko L. M. , Bos Arjan E. R. , Stutterheim Sarah E. , Pryor John B. , Kok Gerjo 
Published: January 2015

AbstractPeople with mental illness are not the sole recipients of stigmatisation; their immediate family members may be subjected to stigma by association. Through semi‐structured interviews, we investigated experiences of stigma by association among 23 immediate family members of people with mental illness. Participants reported experiencing stigma by association from community members, mental health professionals, and civil servants. Familial relationship, co‐residence, and the gender of participants appeared to play a role in their stigma experiences; parents and spouses reported different manifestations of stigma by association than siblings and children, participants who lived together with their family member with mental illness reported increased experiences of stigma by association, and in contrast to male participants, female participants reported others thinking they are overprotective and as such perpetuated, maintained, or sustained their family members' mental illness. The relevance of these factors points to the need for tailored education and emotional support provision to family members of people with mental illness. Moreover, in‐service training for mental health professionals should include the development of relevant social skills that enable the recognition of familial relationships and roles, and family members' fears, concerns, and problems. Copyright © 2014 John Wiley & Sons, Ltd.
Epimerization at C‐3′′ in Butirosin Biosynthesis by an NAD+‐Dependent Dehydrogenase BtrE and an NADPH‐Dependent Reductase BtrF
Authors: Takeishi Ryohei , Kudo Fumitaka , Numakura Mario , Eguchi Tadashi 
Published: January 2015

AbstractButirosin is an aminoglycoside antibiotic consisting two epimers at C‐3′′ of ribostamycin/xylostasin with a unique 4‐amino‐2‐hydroxybutyrate moiety at C‐1 of the aminocyclitol 2‐deoxystreptamine (2DOS). To date, most of the enzymes encoded in the biosynthetic gene cluster for butirosin, from the producing strain Bacillus circulans, have been characterized. A few unknown functional proteins, including nicotinamide adenine dinucleotide cofactor‐dependent dehydrogenase/reductase (BtrE and BtrF), are supposed to be involved in the epimerization at C‐3′′ of butirosin B/ribostamycin but remain to be characterized. Herein, the conversion of ribostamycin to xylsostasin by BtrE and BtrF in the presence of NAD+ and NADPH was demonstrated. BtrE oxidized the C‐3′′ of ribostamycin with NAD+ to yield 3′′‐oxoribostamycin. BtrF then reduced the generated 3′′‐oxoribostamycin with NADPH to produce xylostasin. This reaction step was the last piece of butirosin biosynthesis to be described.
The “Chimney approach” for transcatheter aortic valve implantation: A strategy for trans axillarian bareback approach in patients with no other access options
Authors: Biasco L. , De Backer O. , Holme S. , Søndergaard L. , Jönsson A. 
Published: January 2015

Aimto describe the procedural steps and to report the short term follow up of our initial experience with an axillarian bareback Dacron graft based technique that could potentially reduce the rate of vascular and ischemic complications during transcatheter aortic valve implantation in patients with contraindications to trans‐femoral approach and with patent left internal mammary arterial graft to left anterior descending coronary artery (LIMA‐LAD) or small caliber axillarian/subclavian arteries.Methods and ResultsFour patients were treated with TAVI implantation with a trans axillarian bareback approach. Three out of four had a patent LIMA‐LAD graft. In three patients, femoral approach was not considered as an option for the presence of diffuse peripheral vascular disease, while in one for the small caliber of iliac‐femoral arteries. All procedures were performed under general anaesthesia. No procedural complications occurred.ConclusionsIn this initial experience, the axillarian bareback approach technique allowed a safe and successful TAVI implant in a subgroup of patients with a high risk of procedural complications due to the presence of a patent LIMA‐LAD or vessels of small caliber. Considering the increasing number of patients referred for TAVI, in the next future the axillarian bareback approach could represent a safer alternative to direct cannulation in patients with severe aortic stenosis with no other access options. © 2015 Wiley Periodicals, Inc.
Comparison of the boomerang wire vascular access management system versus manual compression alone during percutaneous diagnostic and interventional cardiovascular procedures: The boomerang™ wire vascular access management trial II
Authors: Goswami Nilesh J. , Smalling Ronnie G. , Sinha Shantanu , Gammon Roger S. , Ramaiah Venkatesh G. 
Published: January 2015

ObjectivesTo evaluate the use of the Boomerang™ Wire as an adjunct to manual compression (MC) in patients requiring diagnostic (Dx) or interventional (Ix) percutaneous procedures.BackgroundMC remains the standard of care for closure of femoral artery access sites. Adjunctive use of a device to facilitate closure, reduce time to hemostasis (TTH) and ambulation (TTA) without increasing complication rates could reduce costs and hospital resource demands.MethodsThe Boomerang™ Trial was a prospective, multicenter, randomized, controlled trial comparing use of the Boomerang™ wire, (Cardiva Medical, Sunnyvale, CA) in conjunction with MC versus MC alone to achieve hemostasis in Dx and Ix patients undergoing percutaneous procedures requiring femoral artery access. Endpoints included TTH, TTA, major, and minor access‐site related complications. Subjects were randomized 3:1, Boomerang versus MC.ResultsNo minor or major device‐related adverse events were reported. Nondevice related complication rates were 3 (0.9%) in the Boomerang arm (n = 327) and 1 (0.8%) in MC arm (n = 123). Mean TTH for Boomerang vs. MC was 11.2 ± 4.3 vs. 23.2 ± 11 min for Dx (P < 0.0001) and 13.9 ± 5.4 vs. 38.4 ± 57.3 min for Ix patients (P < 0.0001). Mean TTA for Boomerang vs. MC was 3.3 ± 3.0 vs. 4.5 ± 2.0 hr (P < 0.0001)for Dx and 5.4 ± 3.3 vs. 6.8 ± 3.2 hr (P < 0.0001) for Ix patients.ConclusionsBoomerang™ use, in conjunction with MC, was associated with low rates of complications and demonstrated that Boomerang™ as an adjunct to MC can significantly decrease TTH and TTA after both Dx and Ix procedures. © 2015 Wiley Periodicals, Inc.
Copper‐Catalyzed Tandem Asymmetric Borylation of β‐Chloroalkyl Aryl Ketones and Related Compounds
Authors: Jiang Quanbin , Guo Tenglong , Yu Zhengkun 
Published: January 2015

AbstractThe Cu‐catalyzed, one‐pot tandem (asymmetric) borylation of β‐chloroalkyl aryl ketones via the in situ generated acyclic enones with bis(pinacolato)diboron was achieved efficiently to reach up to 97 % yield and 99 % enantioselectivity for the formal sp3 CCl borylation products. The present methodology provides an efficient alternative route to (chiral) alkylboron compounds.
In Situ Fluorescence Microscopy Study of the Interfacial Inhomogeneity of DNA Mixed Self‐Assembled Monolayers at Gold Electrodes
Authors: Meunier Anne , Triffaux Eleonore , Bizzotto Dan , Buess‐Herman Claudine , Doneux Thomas 
Published: January 2015

AbstractMixed self‐assembled monolayers composed of a fluorescently labeled DNA and a mercaptobutanol diluent immobilized on gold electrodes were characterized by electrochemical measurements coupled with in situ fluorescence microscopy. The reductive desorption of the self‐assembled monolayers was monitored in real time through variations in the capacitance and fluorescence intensity. Desorption occurred in several steps, which was related to substrate crystallinity. Fluorescence microscopy revealed the presence of spatial heterogeneities in the form of highly fluorescent aggregates that remained at the electrode surface even after a reductive desorption step. This in situ electrofluorescence microscopy technique is useful to optimize the formation of the mixed layer to obtain a homogeneous distribution of the probes, which thus improves the efficiency of the recognition process in the development of biosensors.
A Qualitative Exploration of the Use of Attachment Theory in Adult Psychological Therapy
Authors: Burke Eilish , Danquah Adam , Berry Katherine 
Published: January 2015

There is a growing interest into how attachment theory can inform psychotherapeutic practice with adults. This study aimed to explore how a group of therapists with an interest in attachment theory use it in their work with adult clients. A cross‐sectional qualitative design was adopted. Sampling, data collection and analysis procedures were guided by grounded theory principles. Semi‐structured telephone interviews were conducted with 12 therapists from a variety of training backgrounds. Data were coded and developed into thematic categories. Six primary themes were identified to describe how attachment theory influenced the clinical practice of the sample through the following: (i) complementing other therapeutic models; (ii) providing a framework to understand the development of clients' mental health problems; (iii) working with different attachment styles; (iv) thinking about the therapeutic relationship as an attachment relationship; (iv) influencing the different stages of the therapeutic process; and (vi) influencing clinical service design and delivery. It is concluded that attachment theory can play a significant role in influencing the practice of therapists and can be usefully adopted to complement therapeutic processes irrespective of the therapist's dominant clinical orientation. Further research is needed to explore the views of clinicians from different theoretical orientations and to investigate the security of the client–therapist attachment within the context of therapeutic change processes. Copyright © 2015 John Wiley & Sons, Ltd.Key Practitioner Message

Attachment theory may have implications for practice across a range of different types of therapy and may help therapists to bridge apparent differences between modality‐specific formulation and techniques.
Attachment theory can be used to understand the development of mental health problems. Therapists should assess and formulate clients' attachment styles, and these formulations should guide therapeutic approaches.
Attachment theory provides a comprehensive framework for facilitating the therapist's attentiveness to relational issues and use of the therapeutic relationship as a fulcrum for change.
The principles of attachment theory can be used to inform all stages of the therapeutic process, as well as the design and delivery of mental health services.
Defoliation effects of Diorhabda carinulata on tamarisk evapotranspiration and groundwater levels
Authors: Sueki Sachiko , Acharya Kumud , Huntington Justin , Liebert Ryan , Healey John , Jasoni Richard , Young Michael 
Published: January 2015

AbstractDiorhabda carinulata (northern tamarisk beetle) has been released in the western United States as a biological control agent for the invasive plant Tamarix spp. (tamarisk). A few studies have been conducted analysing the effects of beetle defoliation on tamarisk water consumption, but predefoliation and post‐defoliation comparison based on field data is scarce. The question of whether beetles substantially alter tamarisk water consumption is still open for discussion. In this study, an eddy covariance station and groundwater monitoring well were installed in a tamarisk stand along the Virgin River near Mesquite, NV, in 2010 to observe the impacts of tamarisk defoliation on evapotranspiration (ET) and groundwater levels. ET was calculated using the eddy covariance method and the White method and supported by Landsat remote sensing estimates. Data collected in 2010 established a baseline since the beetles arrived at the site in late 2010 and started feeding on foliage causing tamarisk trees to turn to brown during 2011. Repeated defoliations in 2011 and 2012 show that post‐defoliation ET values and magnitude of diurnal groundwater‐level fluctuations decreased compared with the predefoliation values. Estimated annual ET and annual average daily groundwater fluctuations were reduced by 18% and 35%, respectively. However, the magnitude of effects of defoliation was dependent on the growth stage of tamarisk at the time of defoliation. Also, ET recovered within a month as tamarisk established new leaves. Results from this study suggest that long‐term changes in ET are highly dependent on repeated defoliation occurrences over several years. Copyright © 2015 John Wiley & Sons, Ltd.
Short‐term high altitude exposure at 3454 m is well tolerated in patients with stable heart failure
Authors: Schmid Jean‐Paul , Nobel Daniel , Brugger Nicolas , Novak Jan , Palau Patricia , Trepp Anja , Wilhelm Matthias , Saner Hugo 
Published: January 2015

AimsHigh altitude exposure for the purpose of tourism is very popular in mountainous regions and is considered to be safe for patients with stable CAD and preserved LV function. The purpose of this study was to evaluate the haemodynamic response to exercise and electrical stability by Holter monitoring in patients with chronic heart failure (HF) and an EF <40%.Methods and resultsWe studied 29 HF patients with a peak VO2 >50% of the predicted (25 men, age 60.0 ± 8.9 years, EF 28.8 ± 5.4%) at 540 and 3454 m after an ascent using public transport. Assessments of exercise capacity (cardiopulmonary exercise test), haemodynamic response (inert gas rebreathing system), and susceptibility to arrhythmias (Holter ECG recording) were performed. None of the patients (19 with ischaemic heart disease, 11 with an implantable cardioverter defibrillator) had to return prematurely to the lowland site. Two patients presented symptoms of mild mountain sickness, and one patient developed a self‐limited ventricular tachycardia during maximal exercise at high altitude. Mean peak VO2 at the lowland site was 18.5 ± 3.6 mL/min/kg and decreased by 22.2% (P < 0.001) at high altitude. Mean resting heart rate increased from 74.3 ± 12.3 to 83.3 ± 13.4 b.p.m., P < 0.001. No statistically significant difference in premature ventricular contractions (92 ± 150/h at 540 m vs. 111 ± 196/h at 3454 m, P = 0.284) was noted.ConclusionPatients with stable chronic HF and a peak VO2 >50% of the predicted tolerate a short exposure to an altitude of 3454 m well, even during exercise. However, it cannot be excluded that the susceptibility to ventricular tachyarrhythmias during exercise is increased in some subjects.
3D Microporous Lanthanide–Organic Frameworks Constructed from Left‐ and Right‐Handed Helical Chains: Synthesis, Crystal Structure, and Tunable Photo­luminescence
Authors: Huo Rui , Li Xia , Ma Dou 
Published: January 2015

AbstractNew lanthanide–organic frameworks, [Ln2(2,6‐NDS)3(IP)(H2O)4]·H2O {Ln = Sm (1), Eu (2), Tb (3); 2,6‐NDS = 2,6‐Anaphthalenedisulfonate, IP = 1H‐imidazo[4,5‐f][1,10]‐phenanthroline}, were synthesized and characterized. These complexes are isostructural and have three‐dimensional structures (3D) composed of a pair of entanglement double helixes. The structure is an open framework with rhombic channels filled with uncoordinated water molecules. The photoluminescence properties of the SmIII complex (1) and EuIII/TbIII‐doped complex were explored by adjusting the excitation wavelengths. Interestingly, SmIII complex 1 generated a white‐light emission, whereas the EuIII/TbIII‐doped complex (Tb0.95Eu0.05) allowed the realization of white‐light emission under broad UV wavelengths. An energy transfer for TbIII 5D4→EuIII 5D0 was observed.
Two Rearrangement Pathways in the Geminal Acylation of 2‐Methoxyoxazolidines Leading to Substituted 1,4‐Oxazines
Authors: Moulins Jonathan R. , Hughes Jeremy A. , Doyle Lauren E. , Cameron T. Stanley , Burnell D. Jean 
Published: January 2015

AbstractLewis acid‐mediated geminal acylation of 2‐methoxyoxazolidines with five‐ or six‐membered acyloins followed by heterocyclization afforded 1,4‐oxazines fused to cyclopentenone or cyclohexenone rings. Overall yields ranged from 30 to 73 %. The position of the carbonyl group in the products depended on whether or not water was present during the ring‐expanding acyl migration step. The route lacking water during the acyl migration step was best conducted in one pot. The addition of water effected cleavage of a silyloxy group in the intermediate during the initial Mukaiyama aldol reaction prior to the acyl migration.
Elucidating the Structural Isomerism of Fluorescent Strigolactone Analogue CISA‐1
Authors: Goossens Hannelore , Heugebaert Thomas S. A. , Dereli Busra , Van Overtveldt Melissa , Karahan Ozlem , Dogan Ilknur , Waroquier Michel , Van Speybroeck Veronique , Aviyente Viktorya , Catak Saron , Stevens Christian V. 
Published: January 2015

AbstractThe synthesis of a new potent strigolactone analogue (CISA‐1), resulting in the formation of two interconverting structural isomers, which could not be identified, was recently reported. In the present study, a combined computational and experimental approach is used to identify the exact nature of these structural isomers. Although standard experimental techniques could not be used to determine the identity of the isomers, chromatographic methods excluded E/Z isomerisation. Computational 1H NMR chemical shift values and DFT calculations on interconversion barriers strongly suggest that the CISA‐1 isomers were interconverting (Z)‐configured atropisomers.
Diastereodivergent Pictet–Spengler Cyclization of Bicyclic N‐Acyliminium Ions: Controlling a Quaternary Stereocenter
Authors: de Carné‐Carnavalet Benoît , Krieger Jean‐Philippe , Folléas Benoît , Brayer Jean‐Louis , Demoute Jean‐Pierre , Meyer Christophe , Cossy Janine 
Published: January 2015

AbstractThe diastereoselectivity of the Pictet–Spengler cyclization of bicyclic N‐acyliminium ions that contain a 3‐azabicyclo[n.3.0]alkane core and an electron‐rich π‐nucleophilic moiety, such as an indol‐2‐yl, indol‐3‐yl, 1‐methylpyrrol‐2‐yl, or 3,5‐dimethoxyphenyl group, was examined. The N‐acyliminium ions were generated by protonation of the corresponding enamides or hemiaminals, which were derived from imides. Control of the quaternary stereocenter created at the newly formed ring junction was achieved in a diastereodivergent manner by fine‐tuning the reaction conditions, which determined whether the reaction proceeded under kinetic or thermodynamic control. Mechanistic studies indicated that a retro‐Pictet–Spengler reaction pathway is involved in the equilibration process.
Capacity investigation of on–off keying in noncoherent channel settings at low SNR
Authors: Zhang Peng , Willems Frans M. J. , Huang Li 
Published: January 2015

AbstractOn–off keying (OOK) has repossessed much new research interest to realize green communication for establishing autonomous sensor networks. To realize ultra‐low power wireless design, we investigate the minimum energy per bit required for reliable communication of using OOK in a noncoherent channel setting where envelope detection is applied at the receiver. By defining different OOK channels with average transit power constraints, the achievability of the Shannon limit for both cases of using soft and hard decisions at the channel output is evaluated based on the analysis of the capacity per unit‐cost at low signal‐to‐noise ratio. We demonstrate that in phase fading using hard decisions cannot destroy the capacity only if extremely asymmetric OOK inputs are used with a properly chosen threshold. The corresponding pulse‐position modulation scheme is explicitly studied and demonstrated to be a Shannon‐type solution. Moreover, we also consider a slow Rayleigh fading scenario where the transmitter and receiver have no access to channel realizations. Throughput per unit‐cost results are developed to explore the tradeoff between power efficiency and channel quality for noncoherent OOK using soft and hard decisions. Copyright © 2015 John Wiley & Sons, Ltd.
A hybrid phase field multiple relaxation time lattice Boltzmann method for the incompressible multiphase flow with large density contrast
Authors: Shao J. Y. , Shu C. 
Published: January 2015

AbstractA hybrid phase field multiple relaxation time lattice Boltzmann method (LBM) is presented in this paper for simulation of multiphase flows with large density contrast. In the present method, the flow field is solved by a lattice Boltzmann equation. Concurrently, the interface of two fluids is captured by solving the macroscopic Cahn‐Hilliard equation using the upwind scheme. To be specific, for simulation of the flow field, an lattice Boltzmann equation (LBE) model developed in Shao et al. (Physical Review E, 89 (2014), 033309) for consideration of density contrast in the momentum equation is used. Moreover, in the present work, the multiple relaxation time collision operator is applied to this LBE to enable simulation of problems with large viscosity contrast or high Reynolds number. For the interface capturing, instead of solving another set of LBE as in many phase field LBMs, the macroscopic Cahn‐Hilliard equation is directly solved by using a weighted essentially non‐oscillatory scheme. In this way, the present hybrid phase field LBM shares full advantages of the phase field LBM while enhancing numerical stability. The ability of the present method to simulate multiphase flow problems with large density contrast is demonstrated by several numerical examples. Copyright © 2015 John Wiley & Sons, Ltd.