bluuebunny/crossref_metadata_2025_split huggingface dataset:
Disulfides and Boryl Sulfides Serve as both Initiators and Precatalysts in Radical Reductions of Halides by an N‐Heterocyclic Carbene⋅Borane
Authors: Pan Xiangcheng , Lalevée Jacques , Lacôte Emmanuel , Curran Dennis P. 
Published: November 2013

AbstractDiphenyl disulfide (PhSSPh), a typical boryl monosulfide (diiPr‐Imd‐BH2SPh) and a typical boryl bis‐sulfide [diMe‐Imd‐BH(SPh)2] all serve as both initiators and precatalysts in the reduction of alkyl and aryl halides by readily available 1,3‐dimethylimidazol‐2‐ylidene⋅borane (diMe‐Imd‐BH3). The reactions are suggested to occur by a polarity reverse catalysis mechanism where in situ generated thiophenol is the active catalyst.magnified image
A rural community's involvement in the design and usability testing of a computer‐based informed consent process for the personalized medicine research project
Authors: Mahnke Andrea N. , Plasek Joseph M. , Hoffman David G. , Partridge Nathan S. , Foth Wendy S. , Waudby Carol J. , Rasmussen Luke V. , McManus Valerie D. , McCarty Catherine A. 
Published: November 2013

AbstractMany informed consent studies demonstrate that research subjects poorly retain and understand information in written consent documents. Previous research in multimedia consent is mixed in terms of success for improving participants' understanding, satisfaction, and retention. This failure may be due to a lack of a community‐centered design approach to building the interventions. The goal of this study was to gather information from the community to determine the best way to undertake the consent process. Community perceptions regarding different computer‐based consenting approaches were evaluated, and a computer‐based consent was developed and tested. A second goal was to evaluate whether participants make truly informed decisions to participate in research. Simulations of an informed consent process were videotaped to document the process. Focus groups were conducted to determine community attitudes towards a computer‐based informed consent process. Hybrid focus groups were conducted to determine the most acceptable hardware device. Usability testing was conducted on a computer‐based consent prototype using a touch‐screen kiosk. Based on feedback, a computer‐based consent was developed. Representative study participants were able to easily complete the consent, and all were able to correctly answer the comprehension check questions. Community involvement in developing a computer‐based consent proved valuable for a population‐based genetic study. These findings may translate to other types of informed consents, including those for trials involving treatment of genetic disorders. A computer‐based consent may serve to better communicate consistent, clear, accurate, and complete information regarding the risks and benefits of study participation. Additional analysis is necessary to measure the level of comprehension of the check‐question answers by larger numbers of participants. The next step will involve contacting participants to measure whether understanding of what they consented to is retained over time. © 2013 Wiley Periodicals, Inc.
Social conditions for people with Down syndrome: A register‐based cohort study in Denmark
Authors: Zhu Jin Liang , Obel Carsten , Hasle Henrik , Rasmussen Sonja A. , Li Jiong , Olsen Jørn 
Published: November 2013

AbstractToday, most persons with Down syndrome (DS) survive into middle age, but information on their social conditions as adults is limited. We addressed this knowledge gap using data from national registers in Denmark. We identified a national cohort of 1,998 persons with DS who were born between 1968 and 2007 (1,852 with standard trisomy 21, 80 with Robertsonian translocations and 66 with mosaicism) using the Danish Cytogenetic Register. We followed this cohort from 1980 to 2007. Information on social conditions (education, employment, source of income, marital status, etc.) was obtained by linkages to national registers, including the Integrated Database for Longitudinal Labor Market Research. For those aged 18 and older, more than 80% of persons with DS attended 10 years of primary school, with about 2% completing secondary or post‐secondary education. About 4% obtained a full‐time job, whereas the remaining mainly received public support from the government. Only a few (1–2%) of persons with DS were married or had a child. No significant differences in these social conditions were seen between males and females. More persons with mosaic DS attended secondary or post‐secondary education, had a full‐time job, were married, or had a child (18%, 28%, 15%, and 7%, respectively), compared with persons with standard DS (1%, 2%, 1%, and 1%, respectively). These data may provide families with better insight into social conditions and society with a better understanding of the social support needed for persons with DS. © 2013 Wiley Periodicals, Inc.
Highly Stereoselective Recognition and Deracemization of Amino Acids by Supramolecular Self‐Assembly
Authors: So Soon Mog , Moozeh Kimia , Lough Alan J. , Chin Jik 
Published: November 2013

AbstractThe highly stereoselective supramolecular self‐assembly of α‐amino acids with a chiral aldehyde derived from binol and a chiral guanidine derived from diphenylethylenediamine (dpen) to form the imino acid salt is reported. This system can be used to cleanly convert D‐amino acids into L‐amino acids or vice versa at ambient temperature. It can also be used to synthesize α‐deuterated D‐ or L‐amino acids. A crystal structure of the ternary complex together with DFT computation provided detailed insight into the origin of the stereoselective recognition of amino acids.
Tunable Visible and Near‐IR Photoactivation of Light‐Responsive Compounds by Using Fluorophores as Light‐Capturing Antennas
Authors: Shell Thomas A. , Shell Jennifer R. , Rodgers Zachary L. , Lawrence David S. 
Published: November 2013

AbstractAlthough the corrin ring of vitamin B12 is unable to efficiently absorb light beyond 550 nm, it is shown that commercially available fluorophores can be used as antennas to capture long‐wavelength light to promote scission of the CoC bond at wavelengths up to 800 nm. The ability to control the molecular properties of bioactive species with long visible and near‐IR light has implications for drug delivery, nanotechnology, and the spatiotemporal control of cellular behavior.
Gold Carbenoids: Lessons Learnt from a Transmetalation Approach
Authors: Seidel Günter , Gabor Barbara , Goddard Richard , Heggen Berit , Thiel Walter , Fürstner Alois 
Published: November 2013

AbstractCarbophilic catalysts that are based on AuI allow a host of different nucleophiles to be added across various π systems.1–3 Although many of these reactions are thought to proceed via gold carbenoids, the challenge to observe and characterize these putative intermediates has basically been unmet.4 The current mechanistic interpretation therefore largely relies on indirect evidence and computational data, some of which are subject to debate.5 In an attempt to fill this gap, we pursued a potential route to gold carbenoids by formal transmetalation of chromium or tungsten Fischer carbene complexes with [LAu]+. Whereas this transformation proceeds with exceptional ease as long as a stabilizing heteroelement is present on the carbene center, it stops half‐way in its absence. Rather unusual bimetallic arrays are formed, which allow the charge density to delocalize over several positions. The obvious difficulty of releasing an “unstabilized” gold carbenoid has potential mechanistic implications for the understanding of π‐acid catalysis in general.
Thermal stability of cocured blends of vinyl trimethoxysilane and aryl acetylene resins with different posttreatments
Authors: Wu Yongsheng , Yu Ruobing , Hu Lin , Li Qianqian , Zhu Changjin 
Published: November 2013

ABSTRACTPoly(aryl acetylene) (PAA) modified by vinyl trimethoxysilane (VTMS) was successfully prepared from a blend of diethynyl benzene (DEB) and VTMS. Scanning electron microscopy and Fourier transform infrared spectroscopy investigations showed that VTMS was copolymerized with DEB. Thermogravimetric analysis revealed that PAA modified by VTMS had a better thermooxidation stability than PAA. Through the application of postirradiation and posthydrolysis, the thermal stability in nitrogen and in air of PAA modified by VTMS was greatly improved. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40158.
Influence of rare earth elements (Y, Gd and Lu) on the luminescent properties of green phosphor ZnMoO4:Tb3+
Authors: Xu Y. , Yang W. , Li X. , Li W. , Ju X. 
Published: November 2013

ABSTRACT(Zn,Lnx)MoO4:Tb3+ (Ln = Y3+, Gd3+ and Lu3+) were prepared using the co‐precipitation method. Phase impurity, morphology and composition were investigated by power X‐ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The experimental results show that crystal structure is not destroyed after doping an appropriate amount of Y3+, Gd3+ and Lu3+. EDS analysis reveals that Y, Gd and Lu have been successfully doped into ZnMoO4. In addition, the morphology of the phosphors is notably improved, exhibiting homogeneous dispersion morphology and irregular shapes of particle size ~ 0.5–1 µm. The luminescent intensity of (Zn,Lnx)MoO4:Tb3+ (Ln = Y3+, Gd3+ and Lu3+) phosphor is obviously higher than that of ZnMoO4:Tb3+ phosphor. The energy transfer process between trivalent rare earth ions indicates that the inert earth ions can act as an energy bridge from MoO42‐ to Tb3+. Copyright © 2013 John Wiley & Sons, Ltd.
Semisynthetic model calibration for monitoring glucose in mammalian cell culture with in situ near infrared spectroscopy
Authors: Milligan Michael , Lewin‐Koh Nicholas , Coleman Daniel , Arroyo Adeyma , Saucedo Victor 
Published: November 2013

ABSTRACTNear infrared (NIR) spectroscopy has the capability of providing real‐time, multi‐analyte monitoring of the complex reaction mixture associated with cell culture processes. However, the development of robust models to predict the concentration of key analytes has proven difficult. In this study, a modeling methodology using semisynthetic process samples was used to predict glucose concentrations in Chinese Hamster Ovary (CHO) cell culture processes. Partial Least Squares (PLS) regression models were built from in situ NIR spectra, and glucose levels between 4.0 and 14.0 g/L. Two models were constructed. The “standard model” used data provided by cell culture production process samples. The “full model” included the data provided from both cell culture production process samples and semisynthetic samples. The semisynthetic samples were generated by titrating cell culture samples with target viable cell density (VCD) and lactate levels to defined glucose concentrations. The robustness of each model was gauged by predicting glucose in a subsequent cell culture process utilizing a media formulation and cell line not contained in the calibration data sets. The “full model” generated glucose predictions with a root mean square error of prediction (RMSEP) of 0.99 g/L while the “standard model” provided glucose predictions with a RMSEP of 2.26 g/L. The modeling approach utilizing semisynthetic samples proved to be faster development and more effective than using just standard cell culture processes. Biotechnol. Biotechnol. Bioeng. 2014;111: 896–903. © 2013 Wiley Periodicals, Inc.
Ultra scale‐down characterization of the impact of conditioning methods for harvested cell broths on clarification by continuous centrifugation—Recovery of domain antibodies from rec E. coli
Authors: Chatel Alex , Kumpalume Peter , Hoare Mike 
Published: November 2013

ABSTRACTThe processing of harvested E. coli cell broths is examined where the expressed protein product has been released into the extracellular space. Pre‐treatment methods such as freeze–thaw, flocculation, and homogenization are studied. The resultant suspensions are characterized in terms of the particle size distribution, sensitivity to shear stress, rheology and solids volume fraction, and, using ultra scale‐down methods, the predicted ability to clarify the material using industrial scale continuous flow centrifugation. A key finding was the potential of flocculation methods both to aid the recovery of the particles and to cause the selective precipitation of soluble contaminants. While the flocculated material is severely affected by process shear stress, the impact on the very fine end of the size distribution is relatively minor and hence the predicted performance was only diminished to a small extent, for example, from 99.9% to 99.7% clarification compared with 95% for autolysate and 65% for homogenate at equivalent centrifugation conditions. The lumped properties as represented by ultra scale‐down centrifugation results were correlated with the basic properties affecting sedimentation including particle size distribution, suspension viscosity, and solids volume fraction. Grade efficiency relationships were used to allow for the particle and flow dynamics affecting capture in the centrifuge. The size distribution below a critical diameter dependant on the broth pre‐treatment type was shown to be the main determining factor affecting the clarification achieved. Biotechnol. Bioeng. 2014;111: 913–924. © 2013 The Authors. Biotechnology and Bioengineering Published by Wiley Periodicals, Inc.
Model‐based estimation of optimal temperature profile during simultaneous saccharification and fermentation of Arundo donax
Authors: Mutturi Sarma , Lidén Gunnar 
Published: November 2013

ABSTRACTA kinetic model fitted to enzymatic hydrolysis of Arundo donax was coupled to a fermentation kinetic model derived from simultaneous saccharification and fermentation (SSF) experiments at different temperatures for the determination of optimal temperature profile (between 36 and 45°C) using iterative dynamic programming (IDP). A sensitivity analysis of enzyme kinetic model not only facilitated model reduction in terms of number of parameters, but also enabled artifacts from parameter estimations to be identified. In separate fermentation experiments conducted at 35, 40, 45, and 50°C using ∼40 g/L background glucose in fiber‐free liquid fraction of Arundo it was found that growth was possible at 40°C, but the fermentation capacity was completely lost after 12 h at 50°C. The final ethanol concentration obtained after 120 h in isothermal SSF experiments at 36, 39, 42, and 45°C were 10.6, 13.7, 14.2, and 12.5 g/L, respectively. The predicted optimal temperature profile in SSF determined by iterative dynamic programming was (i) gradual decrease from 40 to 37.5°C until 16 h, (ii) a linear increase upto 45°C until 80 h, and (iii) gradual decrease by 1°C until 120 h. Experimental results were in good agreement with the model predictions. The ethanol concentration after 72 h obtained in the optimal case was 13.6 g/L in comparison to 9.1, 12.2, 12.6, and 11.6 g/L for ISO‐SSF at 36, 39, 42, and 45°C, respectively. Moreover this value was 95.8% of the final value achieved at the end of 120 h, indicating that the process times could be significantly shortened by using non‐isothermal SSF. Biotechnol. Biotechnol. Bioeng. 2014;111: 866–875. © 2013 Wiley Periodicals, Inc.
Spectrum of oesophageal perforations and their influence on management
Authors: Wahed S , Dent B , Jones R , Griffin S M 
Published: November 2013

Abstract

Background
Oesophageal perforations are associated with high mortality and morbidity rates. A spectrum of aetiologies and clinical presentations has resulted in a variety of operative and non-operative management strategies. This analysis focused on the impact of these strategies in a single specialist centre.

Methods
All patients with oesophageal perforation managed in a single oesophagogastric unit in the UK between January 2002 and December 2012 were identified. Gastric perforations and anastomotic leaks were excluded. Data were verified using an endoscopy database, electronic and paper records. Aetiology of perforation, management and outcomes were analysed.

Results
There were 101 adult patients with oesophageal perforation. Complete records were not available for five patients and they were excluded from the analysis. The median age was 69·5 years. Thoracic perforations were present in 84 per cent of patients. There were 51 spontaneous perforations, 41 iatrogenic and four related to foreign bodies. Oesophageal malignancy was present in 11 patients. Forty-four patients were managed surgically, 47 without operation and five patients were considered unfit for active treatment. The in-hospital mortality rate for treated patients was 24 per cent and median length of hospital stay was 31·5 days.

Conclusion
The management of oesophageal perforation requires specialist multidisciplinary input. It is best provided in an environment familiar with the range of treatment modalities. Management decisions should be guided primarily by the degree of contamination rather than the aetiology of the defect. The routine use of stents is unproven and controversial.
Inducible gene deletion in the entire cardiac conduction system using Hcn4‐CreERT2 BAC transgenic mice
Authors: Wu Meng , Peng Siwu , Zhao Yong 
Published: November 2013

SummaryDevelopmental defects and disruption of molecular pathways of the cardiac conduction system (CCS) can cause life‐threatening cardiac arrhythmias. Despite decades of effort, knowledge about the development and molecular control of the CCS remains primitive. Mouse genetics, complementary to other approaches such as human genetics, has become a key tool for exploring the developmental processes of various organs and associated diseases. Genetic analysis using mouse models will likely provide great insights about the development of the CCS, which can facilitate the development of novel therapeutic strategies to treat arrhythmias. To enable genetic studies of the CCS, CCS‐associated Cre mouse models are essential. However, existing mouse models with Cre activity reported in the CCS have various limitations such as Cre leak, haploinsufficiency, and inadequate specificity of the Cre activity. To circumvent those limitations, we successfully generated Hcn4‐CreERT2 bacterial artificial chromosome (BAC) transgenic mice using BAC recombineering in which Cre activity was specifically detected in the entire CCS after tamoxifen induction. Our Hcn4‐CreERT2 BAC transgenic line will be an invaluable genetic tool with which to dissect the developmental control of CCS and arrhythmias. genesis 52:134–140. © 2013 Wiley Periodicals, Inc.
Coupled numerical–analytical approach to landscape evolution modeling
Authors: Goren Liran , Willett Sean D. , Herman Frédéric , Braun Jean 
Published: November 2013

ABSTRACTThe Earth's topography is shaped by surface processes that operate on various scales. In particular, river processes control landscape dynamics over large length scales, whereas hillslope processes control the dynamics over smaller length scales. This scale separation challenges numerical treatments of landscape evolution that use space discretization. Large grid spacing cannot account for the dynamics of water divides that control drainage area competition, and erosion rate and slope distribution. Small grid spacing that properly accounts for divide dynamics is computationally inefficient when studying large domains. Here we propose a new approach for landscape evolution modeling that couples irregular grid‐based numerical solutions for the large‐scale fluvial dynamics and continuum‐based analytical solutions for the small‐scale fluvial and hillslope dynamics. The new approach is implemented in the landscape evolution model DAC (divide and capture). The geometrical and topological characteristics of DAC's landscapes show compatibility with those of natural landscapes. A comparative study shows that, even with large grid spacing, DAC predictions fit well an analytical solution for divide migration in the presence of horizontal advection of topography. In addition, DAC is used to study some outstanding problems in landscape evolution. (i) The time to steady‐state is investigated and simulations show that steady‐state requires much more time to achieve than predicted by fixed area calculations, due to divides migration and persistent reorganization of low‐order streams. (ii) Large‐scale stream captures in a strike‐slip environment are studied and show a distinct pattern of erosion rates that can be used to identify recent capture events. (iii) Three tectono‐climatic mechanisms that can lead to asymmetric mountains are studied. Each of the mechanisms produces a distinct morphology and erosion rate distribution. Application to the Southern Alps of New Zealand suggests that tectonic advection, precipitation gradients and non‐uniform tectonic uplift act together to shape the first‐order topography of this mountain range. Copyright © 2014 John Wiley & Sons, Ltd.
NHS arm's length bodies and regulatory networks in England: quantitative analysis
Authors: McManus Richard 
Published: November 2013

SUMMARYHealth regulation is an area of English public policy that involves a plethora of different bodies operating independently of one another with the purported aim of monitoring standards, ensuring minimum standards are met and providing assurance for the public and government. The purpose of this research is to ascertain as well as possible whether regulation generally is having a positive effect on service provision as well as what the relationship between the data collected by these bodies is. The rationale for testing whether the effect of regulation is positive is obvious; it costs money, time and effort, so does it work? The rationale for testing the relationships is that providers who score well on quality measures should also be experiencing fewer deaths compared with what would be expected. They should also be the providers who are performing well in terms of finances and governance. If there is no relationship between these data sets, then surely something is going wrong; that is, does the various regulatory monitoring and scrutiny actually measure what it sets out to measure? Copyright © 2013 John Wiley & Sons, Ltd.