bluuebunny/crossref_metadata_2025 huggingface dataset:
Control of Light‐Promoted [2+2] Cycloaddition Reactions by a Remote Ancillary Regulatory Group That Is Covalently Attached to Rhenium Rectangles
Authors: Lu Zong‐Zhan , Lee Chung‐Chou , Velayudham Murugesan , Lee Li‐Wei , Wu Jing‐Yun , Kuo Ting‐Shen , Lu Kuang‐Lieh
Published: October 2012

The high‐yielding self‐assembly of three neutral rhenium(I) rectangles, [Re2(CO)6(L)(bpe)]2 (1 a, L=2,2′‐biimidazolate (biim); 1 b, L=2,2′‐bisbenzimidazolate (bbim); 1 c, L=2,2′‐bis(4,5‐dimethylimidazolate) (bdmim); bpe=trans‐1,2‐bis(4‐pyridyl)ethylene), under hydrothermal conditions is described. The rectangles were structurally characterized by spectroscopic techniques and further confirmed by single‐crystal X‐ray diffraction. Upon irradiation with a Hg lamp at 365 nm, the bpe ligands of rectangles 1 a and 1 b underwent [2+2] photocycloaddition reactions to produce [{(Re(CO)3)2L}2(4,4′‐tpcb)2] (2 a, L=biim; 2 b, L=bbim; 4,4′‐tpcb=1,2,3,4‐tetrakis(4‐pyridyl)cyclobutane) through a single‐crystal‐to‐single‐crystal (SCSC) transformation. However, rectangle 1 c, which contained methyl groups on the 2,2′‐biimidazolate ligand, failed to undergo cycloaddition, even after prolonged irradiation. This result indicates that the light‐induced cycloaddition reaction can be preferentially controlled by the remote regulatory substituents, which are attached onto the same backbone of the rectangle complex. This transformation is the first reported utilization of a remote ancillary regulatory ligand that is covalently attached onto a coordination compound to control the [2+2] cycloaddition reaction.
Mechanistic Investigation of the Ruthenium–N‐Heterocyclic‐Carbene‐Catalyzed Amidation of Amines with Alcohols
Authors: Makarov Ilya S. , Fristrup Peter , Madsen Robert
Published: October 2012

The mechanism of the ruthenium–N‐heterocyclic‐carbene‐catalyzed formation of amides from alcohols and amines was investigated by experimental techniques (Hammett studies, kinetic isotope effects) and by a computational study with dispersion‐corrected density functional theory (DFT/M06). The Hammett study indicated that a small positive charge builds‐up at the benzylic position in the transition state of the turnover‐limiting step. The kinetic isotope effect was determined to be 2.29(±0.15), which suggests that the breakage of the CH bond is not the rate‐limiting step, but that it is one of several slow steps in the catalytic cycle. Rapid scrambling of hydrogen and deuterium at the α position of the alcohol was observed with deuterium‐labeled substrates, which implies that the catalytically active species is a ruthenium dihydride. The experimental results were supported by the characterization of a plausible catalytic cycle by using DFT/M06. Both cis‐dihydride and trans‐dihydride intermediates were considered, but when the theoretical turnover frequencies (TOFs) were derived directly from the calculated DFT/M06 energies, we found that only the trans‐dihydride pathway was in agreement with the experimentally determined TOFs.
Supramolecular Polymerization at Low Monomer Concentrations: Enhancing Intermolecular Interactions and Suppressing Cyclization by Rational Molecular Design
Authors: Liu Yiliu , Fang Ruochen , Tan Xinxin , Wang Zhiqiang , Zhang Xi
Published: October 2012

We present the construction of long‐chain water‐soluble supramolecular polymers at low monomer concentrations. Naphthalene‐based host‐enhanced π–π interactions, which possess high binding constants, were used as the driving force of supramolecular polymerization. A monomer, DNDAB, with a rigid, bulky 1,4‐diazabicyclo[2.2.2]octane‐1,4‐diium linker was designed. The design of the monomer structure strongly influenced the efficiency of the supramolecular polymerization. The rigid, bulky linker in DNDAB effectively eliminates cyclization, promoting the formation of long‐chain supramolecular polymers at low monomer concentrations. In contrast, a reference monomer containing a flexible linker (DNPDN) only forms oligomers owing to cyclization.
Correlation of Electrocardiographic Changes and Myocardial Fibrosis in Patients With Hypertrophic Cardiomyopathy Detected by Cardiac Magnetic Resonance Imaging
Authors: Song Bong Gun , Yang Hyun Suk , Hwang Hweung Kon , Kang Gu Hyun , Park Yong Hwan , Chun Woo Jung , Oh Ju Hyeon
Published: October 2012

Background:

Despite several electrophysiologic and pathologic studies, the cause of electrocardiographic (ECG) changes in patients with hypertrophic cardiomyopathy (HCM) remains unclear. Late gadolinium enhancement (LGE) cardiovascular magnetic resonance (CMR) imaging can detect myocardial fibrosis. We aimed to assess the relationship between ECG findings and LGE in such patients.

Hypothesis:

Myocardial LGE may be associated with ECG changes in HCM.

Methods:

Seventy consecutive patients with HCM (mean age, 55.5 ± 10.7 years; 47 males) underwent CMR and 12‐lead ECG. The subjects were divided into 3 groups according to the type of hypertrophy: the asymmetric septal hypertrophy group (ASH group, n = 31), the apical hypertrophy group (AP group, n = 22), and concentric hypertrophy group (CH group, n = 17). The transmural and segmental extent, pattern, and location of myocardial LGE were assessed and analyzed in relation to ECG changes.

Results:

All of the subjects showed some degree of LGE on CMR. The AP group showed significantly higher prevalence of negative T‐wave (P = 0.028) and deep negative T‐wave inversion (P = 0.001) than the ASH and CH groups. The total volume of LGE did not show any significant association with ECG changes. LGE detected at the interventricular septum was associated with increased QRS duration (P = 0.009) and was found in 94% of the ASH group, 59% of the AP group, and 77% of the CH group. LGE at the apex of the heart was present in 32% of the ASH group, 73% of the AP group, and 35% of the CH group and was also associated with negative T‐wave (P = 0.006) and deep negative T‐wave inversion (P = 0.018). Multifocal LGE lesions were associated with increased QRS duration (P = 0.039) as opposed to single nodular or patchy pattern of presence.

Conclusions:

The location of myocardial LGE in HCM shows significant association with various ECG changes. This may be useful information for initially evaluating subjects with HCM and adds pathophysiological insight into understanding ECG changes in myocardial diseases that cannot be explained otherwise. Clin. Cardiol. 2011 DOI: 10.1002/clc.22062

The authors have no funding, financial relationships, or conflicts of interest to disclose.
Outcomes Associated With Warfarin Use in Older Patients With Heart Failure and Atrial Fibrillation and a Cardiovascular Implantable Electronic Device: Findings From the ADHERE Registry Linked to Medicare Claims
Authors: Hess Paul L. , Greiner Melissa A. , Fonarow Gregg C. , Klaskala Winslow , Mills Roger M. , Setoguchi Soko , Al‐Khatib Sana M. , Hernandez Adrian F. , Curtis Lesley H.
Published: October 2012

Background:

Warfarin use and associated outcomes in patients with heart failure and atrial fibrillation and a cardiovascular implantable electronic device have not been described previously.

Hypothesis:

We hypothesized that warfarin is underused and is associated with lower risks of mortality, thromboembolic events, and myocardial infarction.

Methods:

Using data from a clinical registry linked with Medicare claims, we examined warfarin use at discharge and 30‐day and 1‐year Kaplan‐Meier estimates of all‐cause mortality and cumulative incidence rates of mortality, thromboembolic events, myocardial infarction, and bleeding events in patients 65 years or older, with a history of atrial fibrillation and a cardiovascular implantable electronic device admitted with heart failure between 2001 and 2006, who were naïve to anticoagulation therapy at admission. We compared outcomes between patients who were or were not prescribed warfarin at discharge and tested associations between treatment and outcomes.

Results:

Of 2586 eligible patients in 252 hospitals, 2049 were discharged without a prescription for warfarin. At 1 year, the group discharged without warfarin had a higher mortality rate after discharge (37.4% vs 28.8%; P < 0.001) but similar rates of thromboembolism, myocardial infarction, and bleeding events. After adjustment, treatment with warfarin was associated with lower risk of all‐cause death 1 year after discharge (hazard ratio: 0.76, 95% confidence interval: 0.63–0.92).

Conclusions:

Among older patients with heart failure and atrial fibrillation and a cardiovascular implantable electronic device, 4 of 5 were discharged without a prescription for warfarin. Warfarin nonuse was associated with a higher risk of death 1 year after discharge. Clin. Cardiol. 2011 DOI: 10.1002/clc.22064

Damon M. Seils, MA, Duke University, assisted with manuscript preparation. Mr. Seils did not receive compensation for his assistance apart from his employment at the institution where the study was conducted.

This study was supported by a research agreement between Duke University and Janssen Pharmaceuticals.

The authors have no other funding, financial relationships, or conflicts of interest to disclose.
The Speedup‐Test: a statistical methodology for programme speedup analysis and computation
Authors: Touati Sid‐Ahmed‐Ali , Worms Julien , Briais Sébastien
Published: October 2012

In the area of high‐performance computing and embedded systems, numerous code optimisation methods exist to accelerate the speed of the computation (or optimise another performance criteria). They are usually experimented by doing multiple observations of the initial and the optimised execution times of a programme in order to declare a speedup. Even with fixed input and execution environment, programme execution times vary in general. Hence, different kinds of speedups may be reported: the speedup of the average execution time, the speedup of the minimal execution time, the speedup of the median and others. Many published speedups in the literature are observations of a set of experiments. To improve the reproducibility of the experimental results, this article presents a rigorous statistical methodology regarding programme performance analysis. We rely on well‐known statistical tests (Shapiro–Wilk's test, Fisher's F‐test, Student's t‐test, Kolmogorov–Smirnov's test and Wilcoxon–Mann–Whitney's test) to study if the observed speedups are statistically significant or not. By fixing 0 < α < 1 a desired risk level, we are able to analyse the statistical significance of the average execution time as well as the median. We can also check if , the probability that an individual execution of the optimised code is faster than the individual execution of the initial code. In addition, we can compute the confidence interval of the probability to obtain a speedup on a randomly selected benchmark that does not belong to the initial set of tested benchmarks. Our methodology defines a consistent improvement compared with the usual performance analysis method in high‐performance computing. We explain in each situation the hypothesis that must be checked to declare a correct risk level for the statistics. The Speedup‐Test protocol certifying the observed speedups with rigorous statistics is implemented and distributed as an open source tool based on R software. Copyright © 2012 John Wiley & Sons, Ltd.
Distribution of random streams for simulation practitioners
Authors: Hill David R. C. , Mazel Claude , Passerat‐Palmbach Jonathan , Traore Mamadou K.
Published: October 2012

There is an increasing interest in the distribution of parallel random number streams in the high‐performance computing community particularly, with the manycore shift. Even if we have at our disposal statistically sound random number generators according to the latest and thorough testing libraries, their parallelization can still be a delicate problem. Indeed, a set of recent publications shows it still has to be mastered by the scientific community. With the arrival of multi‐core and manycore processor architectures on the scientist desktop, modelers who are non‐specialists in parallelizing stochastic simulations need help and advice in distributing rigorously their experimental plans and replications according to the state of the art in pseudo‐random numbers parallelization techniques. In this paper, we discuss the different partitioning techniques currently in use to provide independent streams with their corresponding software. In addition to the classical approaches in use to parallelize stochastic simulations on regular processors, this paper also presents recent advances in pseudo‐random number generation for general‐purpose graphical processing units. The state of the art given in this paper is written for simulation practitioners. Copyright © 2012 John Wiley & Sons, Ltd.
GPU‐based acceleration of bio‐inspired motion estimation model
Authors: Ayuso F. , Botella G. , García C. , Prieto M. , Tirado F.
Published: October 2012

In this paper, we describe the specific and efficient implementation of a gradient‐based optical flow model. This scheme was particularized using a validated neuromorphic motion estimation system for the robust extraction of image velocity. This model contains many characteristics that enhanced the capability when compared with other optical flow gradient family algorithms. Our implementation was performed using specific graphic processing units designed in an ad hoc framework for this model, which could be reused in several low‐level machine‐vision approaches. Observed performance results indicate that these accelerators be highly recommended. Furthermore, the throughput obtained in comparison with a general CPU was analyzed for the accurateness of a system built with regard to other optical flow systems. Additionally, several visual examples, commonly used for testing motion estimation sequences, were shown to reveal implementation behavior features. Copyright © 2012 John Wiley & Sons, Ltd.
Kinetically Controlled Formation of Formamide Trimer from First Principles
Authors: Szyja Bartłomiej M. , Antoniou Anna , Doltsinis Nikos L.
Published: October 2012

The formation of formamide trimers was simulated using Car–Parrinello molecular dynamics. A variety of different initial setups were compared to study the effects of spatial arrangement, concentration, and temperature on the trimer product distribution. A total of nine different trimer species were obtained by simulation. Although a triangular initial arrangement of the three monomers is found to favour a less energetically stable chain‐like product at high concentration, the more compact global minimum structure is expected to be the most abundant species overall in experiment. This is because there is evidence of a low activation barrier for conversion of the chain‐like trimer to the lowest‐energy structure. For one, this process is observed upon increasing the length of the trajectories. Furthermore, a slight rise in temperature drastically reduces the number of chain‐like trimers. With regard to the intermolecular forces driving the aggregation dynamics, dispersion corrections to the underlying density functional theory description have a strong effect on the product distribution, again favouring the global minimum species. Certain local minimum structures are significantly destabilised relative to the global minimum by dispersion correction while the relative energies of the majority of species are practically unchanged.
Hierarchical Composite of Ag/AgBr Nanoparticles Supported on Bi2MoO6 Hollow Spheres for Enhanced Visible‐Light Photocatalytic Performance
Authors: Tian Guohui , Chen Yajie , Meng Xiangying , Zhou Juan , Zhou Wei , Pan Kai , Tian Chungui , Ren Zhiyu , Fu Honggang
Published: October 2012

The fabrication of multicomponent composite systems may provide benefits in terms of charge separation and the retardation of charge pair recombination. For this purpose, a hierarchical Ag/AgBr/Bi2MoO6 composite was fabricated by using prepared hierarchical floriated Bi2MoO6 hollow spheres as a supporting material. The interleaved nanoflakes assembled in the hierarchical floriated Bi2MoO6 hollow spheres contributed to the stable deposition of Ag/AgBr nanoparticles and the formation of effective nanojunctions, which led to the low recombination rates of the photoinduced electron–hole pairs. The presence of double visible‐light‐active components in the Ag/AgBr/Bi2MoO6 nanojunction system further broadened the visible‐light photoresponse range. As a result, the hierarchical Ag/AgBr/Bi2MoO6 composite exhibited a higher photocatalytic activity than both photocatalysts containing single visible‐light‐active components and crushed Ag/AgBr/Bi2MoO6 nanoparticles for the degradation of alizarin red S (ARS) and phenol. X‐ray photoelectron spectroscopy (XPS) analyses indicated that both AgBr and Ag0 components coexist in the system, and the as‐prepared composite is relatively stable. The improved photoinduced charge‐transfer properties of the hierarchical Ag/AgBr/Bi2MoO6 composite were investigated by using the transient photovoltage (TPV) technique.
Recall of Threat and Submissiveness in Childhood and Psychopathology: The Mediator Effect of Self‐Criticism
Authors: Castilho Paula , Pinto‐Gouveia José , Amaral Vânia , Duarte Joana
Published: October 2012

Research has robustly shown that early negative parenting experiences are associated with psychopathology and self‐criticism in adulthood. This study investigates recall of personal feelings of perceived threat and subordination in childhood and its relation to psychopathology. In addition, we explore the mediator role of self‐criticism in this association. A sample of 193 subjects from the general population completed self‐report questionnaires measuring the study variables. The mediator analyses suggested that the impact of submissiveness experiences in childhood on depression and anxiety is mediated by self‐criticism. Our findings highlight the route through which the recall of personal feelings of perceived involuntary subordination to parents contributes to depression and anxiety in adulthood. Copyright © 2012 John Wiley & Sons, Ltd.

Key Practitioner Message

Although the relation between early experiences of abuse and later psychological problems is now well established, there has been less study on subtler forms of threat and subordinate behaviour in childhood. Given ours and previous findings, therapists should be aware of, and prone to explore, these early experiences.

Most studies exploring early negative experiences mainly refer to attachment theory‐related constructs (e.g., attachment style). We also highlight the importance of noting rank structure and rank style in the family.

Self‐criticism seems to be a key process in the relation between early aversive experiences of subordination and psychopathology.

Given the idea that self‐reassuring operates through a different affect system, helping people develop inner warmth and compassion for the self may be important to counteract feelings of self‐hatred and self‐attack.
An MTJ‐based non‐volatile flip‐flop for high‐performance SoC
Authors: Jung Youngdon , Kim Jisu , Ryu Kyungho , Kim Jung Pill , Kang Seung H. , Jung Seong‐Ook
Published: October 2012

The conventional magnetic tunneling junction (MTJ)‐based non‐volatile D flip‐flop (NVDFF) has a slow D‐Q delay and a tradeoff between its D‐Q delay and its sensing current. In addition, a sufficient write current cannot be obtained with the core device, since two MTJs exist in the write path and a write current degradation problem occurs due to the precharge transistors. The proposed MTJ‐based non‐volatile semidynamic flip‐flop (NVSDFF) has a semidynamic structure that ensures a fast D‐Q delay and separates the sensing circuit from the D‐Q signal path to reduce the sensing current without affecting the D‐Q delay. The proposed NVSDFF also provides a sufficient write current by merely using the core device, since only one MTJ exists in the write path. In addition, the head switch, which is added to remove the write current degradation problem, further reduces the sensing current. Thus, the proposed NVSDFF has a higher read disturbance margin than the previous NVDFF with an IO device. The HSPICE simulation results with the industry‐compatible 45 nm model parameter show that the D‐Q delay in the proposed NVSDFF is 50.5% of that of the previous NVDFF with an IO device, and the sensing current, 32.3%. In the proposed NVSDFF, the read disturbance margin is 15.9% larger than in the previous NVDFF with an IO device, and the area is 17.8% smaller. Copyright © 2012 John Wiley & Sons, Ltd.
Negative control of mast cell degranulation and the anaphylactic response by the phosphatase lipin1
Authors: Shin Jinwook , Zhang Ping , Wang Shang , Wu Jinhong , Guan Ziqiang , Zhong Xiao‐Ping
Published: October 2012

Mast cells play a critical role in the pathogenesis of allergic diseases; however, how mast cell function is regulated is still not well understood. Both phosphatidic acid (PA) and diacylglycerol (DAG) are important secondary messengers involved in mast cell activ‐ation. Lipin1 is a phosphatidate phosphatase that hydrolyzes PA to produce DAG, but the role of lipin1 in mast cell function has been thus far unknown. Here we show that lipin1 is an important and selective inhibitor of mast cell degranulation. Lipin1 deficiency enhanced FcεRI‐mediated β‐hexosaminidase and prostaglandin D2 release from mast cells in vitro and exacerbated the passive systemic anaphylaxis reaction in vivo. Lipin1 deficiency, however, did not exert obvious effects on IL‐6 or TNF‐α production following FcεRI engagement. FcεRI‐induced PKC and SNAP‐23 phosphorylation were augmented in the lipin1‐deficient mast cells. Moreover, inhibition of PKC activity reduced SNAP‐23 phosphorylation and mast cell degranulation in lipin1‐deficient mast cells. Together, our findings suggest that lipin1 may negatively control mast cell degranulation and the anaphylactic response through inhibiting the PKC‐SNAP‐23 pathway.
Structure and Magnetic Behavior of CuII MOFs Supported by 1,2,4‐Triazolyl‐Bifunctionalized Adamantane Scaffold
Authors: Senchyk Ganna A. , Lysenko Andrey B. , Rusanov Eduard B. , Chernega Alexander N. , Jezierska Julia , Domasevitch Konstantin V. , Ozarowski Andrew
Published: October 2012

New triazole‐based CuII metal–organic frameworks, [Cu(tr2ad)(SO4)]·3H2O (1), [Cu3(tr2ad)4(H2O)2(SO4)2]SO4·28H2O (2), [Cu3(tr2ad)4(H2O)4](SiF6)3·16H2O (3), constructed utilizing a rigid adamantane scaffold, tr2ad = 1,3‐bis(1,2,4‐triazol‐4‐yl)adamantane, were prepared hydrothermally, and their crystal structures were determined. The structure of 1 is built up from straight chains of corner‐sharing CuN4O2 octahedra supported by short μ2‐tr (tr = 1,2,4‐triazole) and μ2‐SO42– bridges. The tetradentate character of tr2ad results in the formation of layers. The 2D structures of 2 and 3 consist of discrete secondary building blocks [Cu3(μ2‐N1,N2‐tr)6] with triple [–N–N–] triazole links between the adjacent Cu centers [the Cu‐(tr)‐Cu separations are 3.806 and 3.756 Å for 2 and 3, respectively]. The distorted octahedral N4O2 environment of the peripheral Cu atoms is completed by water molecules and/or terminal sulfate anions. The linear magnetic clusters, which act as nodes, are joined together at average distances of 11.2 and 15.0–15.6 Å into square‐grid‐like networks that exploit the double‐bridging μ3‐ and μ4‐bis(triazole) modules. Uncoordinated counteranions and crystal water molecules fill the interlayer space and channels in the complexes and form extensive H‐bonding patterns. The exchange integrals J1 = 9.8 and J2 ≈ 0 cm–1 for the interaction J1(Ŝ1Ŝ2 + Ŝ2Ŝ3) + J2Ŝ1Ŝ3 were determined for 3 from magnetic susceptibility data and reproduced by a broken‐symmetry DFT calculation. The spin Hamiltonian parameters of 3 were found from high‐field electron paramagnetic resonance (EPR) spectra.
The reciprocal cycle of self‐concealment and trust in romantic relationships
Authors: Uysal Ahmet , Lin Helen Lee , Bush Amber L.
Published: October 2012

We propose that perceived partner concealment, self‐concealment from one's partner (i.e., keeping secrets from one's partner), and trust in one's partner form a reciprocal cycle in romantic relationships. In Study 1, participants in a romantic relationship (N = 94) completed a two‐time point survey within a span of 8 to 10 weeks. Results revealed that perceived partner concealment was associated with a loss of trust in partner, and low trust in partner was associated with an increase in self‐concealment from one's partner. Furthermore, the association between perceived partner concealment and self‐concealment from one's partner was mediated by trust. In Study 2, couples (N = 50) completed daily records for 14 consecutive days. Multilevel analyses indicated that on the days the individuals reported more self‐concealment, their partners reported lower trust in them. Moreover, on the days the partners reported lower trust, the partners also reported higher self‐concealment. These findings suggest that self‐concealment in romantic relationships can create a reciprocal cycle that involves loss of trust and more self‐concealment between partners, which would slowly deteriorate the relationship well‐being. Copyright © 2012 John Wiley & Sons, Ltd.
Leniency for out‐group offenders
Authors: Braun Judith , Gollwitzer Mario
Published: October 2012

The present research investigates leniency for out‐group offenders and differentiates it from the black sheep effect. The authors assume that leniency for out‐group offenders can be used by in‐group members to protect their group's image by displaying that they are not prejudiced. Thus, leniency should disappear when in‐group members have otherwise shown that they are not prejudiced (i.e., moral credentials). In two experiments, offenders' group membership and participants' opportunity to establish moral credentials were manipulated. Results showed that out‐group offenders received the lowest punishment severity ratings (Studies 1 and 2). However, this leniency effect vanished when participants had established moral credentials by either endorsing the participation of out‐group members in lobby groups (Study 1) or writing about a positive experience with an out‐group member (Study 2). These findings suggest that lenient punishments for out‐group offenders may sometimes reflect a relatively easy strategy to display the in‐group as being unprejudiced. Copyright © 2012 John Wiley & Sons, Ltd.
Time‐dependent changes of protein biomarker levels in the cerebrospinal fluid after blast traumatic brain injury
Authors: Ahmed Farid , Gyorgy Andrea , Kamnaksh Alaa , Ling Geoffrey , Tong Lawrence , Parks Steve , Agoston Denes
Published: October 2012

Time‐dependent changes of protein biomarkers in the cerebrospinal fluid (CSF) can be used to identify the pathological processes in traumatic brain injury (TBI) as well as to follow the progression of the disease. We obtained CSF from a large animal model (swine) of blast‐induced traumatic brain injury prior to and at 6, 24, 72 h, and 2 wk after a single exposure to blast overpressure, and determined changes in the CSF levels of neurofilament‐heavy chain, neuron‐specific enolase, brain‐specific creatine kinase, glial fibrillary acidic protein, calcium‐binding protein β (S100β), Claudin‐5, vascular endothelial growth factor, and von Willebrand factor using reverse phase protein microarray. We detected biphasic temporal patterns in the CSF concentrations of all tested protein markers except S100β. The CSF levels of all markers were significantly increased 6 h after the injury compared to preinjury levels. Values were then decreased at 24 h, prior to a second increase in all markers but S100β at 72 h. At 2 wk postinjury, the CSF concentrations of all biomarkers were decreased once again; brain‐specific creatine kinase, Claudin‐5, von Willebrand factor, and S100β levels were no longer significantly higher than their preinjury values while neurofilament‐heavy chain, neuron‐specific enolase, vascular endothelial growth factor, and glial fibrillary acidic protein levels remained significantly elevated compared to baseline. Our findings implicate neuronal and glial cell damage, compromised vascular permeability, and inflammation in blast‐induced traumatic brain injury, as well as demonstrate the value of determining the temporal pattern of biomarker changes that may be of diagnostic value.
Activation of rapid oestrogen signalling in aggressive human breast cancers
Authors: Poulard Coralie , Treilleux Isabelle , Lavergne Emilie , Bouchekioua‐Bouzaghou Katia , Goddard‐Léon Sophie , Chabaud Sylvie , Trédan Olivier , Corbo Laura , Le Romancer Muriel
Published: October 2012

Oestrogen receptors can mediate rapid activation of cytoplasmic signalling cascades by recruiting Src and PI3K. However, the involvement of this pathway in breast cancer remains poorly defined. We have previously shown that methylation of ERα is required for the formation of the ERα/Src/PI3K complex and that ERα is hypermethylated in a subset of breast cancers. Here, we used Proximity Ligation Assay to demonstrate that this complex is present in the cytoplasm of breast cancer cell lines as well as formalin‐fixed, paraffin‐embedded tumours. Of particular interest, the analysis of 175 breast tumours showed that overexpression of this complex in a subset of breast tumours correlates to the activation of the downstream effector Akt. Survival analysis revealed that high expression of this complex is an independent marker of poor prognosis and associated with reduced disease‐free survival. Our data introduces the new concept that the rapid oestrogen pathway is operative in vivo. It also provides a rationale for patient stratification defined by the activation of this pathway and the identification of target therapies.
Descriptive and predictive evaluation of high resolution Markov chain precipitation models
Authors: Sørup H. J. D. , Madsen H. , Arnbjerg‐Nielsen K.
Published: October 2012

A time series of tipping bucket recordings of very high temporal and volumetric resolution precipitation is modelled using Markov chain models. Both first and second‐order Markov models as well as seasonal and diurnal models are investigated and evaluated using likelihood based techniques. The first‐order Markov model seems to capture most of the properties of precipitation, but inclusion of seasonal and diurnal variation improves the model. Including a second‐order Markov Chain component does improve the descriptive capabilities of the model, but is very expensive in its parameter use. Continuous modelling of the Markov process proved attractive because of a marked decrease in the number of parameters. Inclusion of seasonality into the continuous Markov chain model proved difficult. Monte Carlo simulations with the models show that it is very difficult for all the model formulations to reproduce the time series on event level. Extreme events with short (10 min), medium (60 min) and long (12 h) durations were investigated because of their importance in urban hydrology. Both the descriptive likelihood based statistics and the predictive Monte Carlo simulation based statistics are valuable and necessary tools when evaluating model fit and performance. Copyright © 2012 John Wiley & Sons, Ltd.
A novel approach for bandwidth allocation among soft QoS traffic in wireless networks
Authors: Tan Liansheng , Zhu Zhongxun , Yuan Cao , Zhang Wei
Published: October 2012

The resource (bandwidth) allocation in a network is usually casted into a so‐called network utility maximization (NUM) problem, which solution strategy has successfully generated distributed algorithms for congestion controlling of elastic traffic in a wire‐lined network. However, for resource allocation of inelastic traffic including soft QoS (quality of service) traffic in a wireless network, this approach still faces challenges. First, it is hard for the wireless system to dynamically model the utility function of the users. Second, the utility function of soft QoS traffic is usually nonconcave, which brings the NUM optimization problem to be mathematically intractable. With deviation to the usual NUM theory, this paper proposes a novel optimization model and its algorithm to allocate bandwidth around the user's desired value to the soft QoS traffic in a wireless network. Our approach takes advantage of the basic feature of soft QoS traffic; that is, it demands a preferred amount of bandwidth but allows some flexibility during normal operation. Compared with the utility‐based approaches and solutions, our approach avoids the difficulty of finding the exact utility function expression for each user by using the preference bandwidth value. This facilitates the operation of real wireless networks. The proposed model and algorithm are verified by an example, which demonstrate better performance than the NUM approach.Copyright © 2012 John Wiley & Sons, Ltd.
Synthesis of aluminum methylcyclohexylphosphinate and its use as flame retardant for epoxy resin
Authors: Liu Jiyan , Chen Jia , Liu Xueqing , Sun Shan , Cai Shaojun
Published: October 2012

A novel aluminum phosphinate—aluminum methylcyclohexylphosphinate (Al(MHP))—was synthesized by reacting n‐butyl methylphosphonite with cyclohexene, followed by reacting with anhydrous AlCl3. The products were characterized with gas chromatography, Fourier transform infrared spectroscopy, hydrogen nuclear magnetic resonance, phosphorus nuclear magnetic resonance, X‐ray fluorescent spectroscopy, and thermogravimetric (TG) analyses. After blending with epoxy resin (EP), flame retardancy was estimated with the use of limited oxygen index (LOI) and UL‐94 test, and thermal stability was investigated using TG analysis. The morphologies and composition of the char obtained after being heated at 300 °C for 20 min followed by 500 °C for 3 min in the muffle furnace were characterized by scanning electron microscopy (SEM) with energy‐dispersive X‐ray (EDX) analysis. Results showed that Al(MHP) is an efficient flame retardant for EP, and Al(MHP)/EP can pass UL‐94V‐0 rating with an LOI of 28.8% by adding 15 wt.% of Al(MHP). TG results showed that the presence of Al(MHP) in EP increases the char yield and depresses the thermal decomposition. SEM‐EDX analysis showed that the char obtained at 300 °C is coherent and consists of P‐rich components; at higher temperature (500 °C), the char becomes tiny and loose and phosphorus element is released into gas. Compared with neat EP, composites have lower water absorption. Copyright © 2012 John Wiley & Sons, Ltd.
Analysis of an iterative penalty method for Navier–Stokes equations with nonlinear slip boundary conditions
Authors: Dai Xiaoxia , Tang Peipei , Wu Minghui
Published: October 2012

When we use penalty method to solve Navier–Stokes equations with nonlinear slip boundary conditions, the penalty parameter ϵ should be sufficiently small to yield an accurate approximation and the choice of ϵ depends on the mesh size h. However, the condition number of the associated stiffness matrix becomes large if ϵ is too small, which leads to the unstable computation. In this paper, we design an iterative penalty method for the problem and give some error estimates. In our algorithm, we can use a not very small penalty parameter ϵ independent of h to avoid the unstable computation. Numerical examples are given to show that the algorithm is very effective and powerful. Copyright © 2012 John Wiley & Sons, Ltd.
Simulating CO2 leakage into marine environments
Authors: Blackford Jerry
Published: October 2012

Jerry Blackford of the Plymouth Marine Laboratory leads the UK Research Council funded Quantifying and Monitoring Potential Ecosystem Impacts of Geological Carbon Storage (QICS) program, and is a founding member of the new UK CCS Research Centre leading the environment research team. Here he talks to Muriel Cozier about how the world's first experiment to simulate a CO2 leak from underground storage in a marine environment will go a long way toward improving our understanding of a series of complex interactions.
Cancer risk in long‐term users of vitamin K antagonists: A population‐based case–control study
Authors: Pottegård Anton , Friis Søren , Hallas Jesper
Published: October 2012

Some evidence suggests that long‐term use of vitamin K antagonists (VKAs) has a cancer chemopreventive effect. Such an effect would have considerable implications in terms of understanding tumor biology. To evaluate if long‐term VKA treatment influences the risk of developing cancer, we performed a matched case–control analysis. We used data from four Danish nationwide registers. Cases were all Danish individuals with a first‐time cancer diagnosis (except nonmelanoma skin cancer) between 2000 and 2009. For each case, eight controls, matched by birth year and gender, were selected from the source population by risk‐set sampling. Long‐term VKA use was defined as exposure to VKA for a period of 3 or more years. Conditional logistic regression was used to compute odds ratios (ORs) for cancer associated with long‐term VKA exposure, adjusting for potential confounders. Prespecified subanalyses were performed for selected cancer sites, subgroups and measures of exposure. A total of 238,196 cases and 1,713,176 controls were included. The adjusted OR for cancer associated with long‐term VKA exposure was 0.99 (95% CI: 0.95–1.02). Long‐term VKA use was associated with increased ORs for alcohol‐ or obesity‐related cancer sites, whereas we observed a decreased risk of prostate cancer (OR: 0.86; 95% CI: 0.78–0.95). Our study does not support a general chemopreventive effect of VKA drugs. However, in accordance with findings from previous studies, we found an inverse association between use of VKA and prostate cancer.
Lymphoma risk in livestock farmers: Results of the Epilymph study
Authors: Cocco Pierluigi , Satta Giannina , D'Andrea Ileana , Nonne Tinucia , Udas Giuseppe , Zucca Mariagrazia , Mannetje Andrea 't , Becker Nikolaus , Sanjosé Silvia de , Foretova Lenka , Staines Anthony , Maynadié Marc , Nieters Alexandra , Brennan Paul , Ennas Maria G. , Boffetta Paolo
Published: October 2012

We explored the risk of lymphoma and its most prevalent subtypes associated with occupational contact with livestock, and whether risk was modified by age at first contact, in 2,348 incident lymphoma cases and 2,462 controls who participated in the EPILYMPH case–control study. A detailed occupational history was collected in cases and controls, including working in a livestock farm, species of livestock, its approximate number and circumstances of contact. For each disease outcome, and each type of livestock, odds ratios (OR) and their 95% confidence intervals (95% CI) were calculated using unconditional logistic regression, adjusting for age, gender, education and center. Lymphoma risk (all subtypes combined) was not increased amongst those exposed to contact with any livestock (OR = 1.0, 95% CI 0.8–1.2). Overall, we did not observe an association between occupational contact with livestock and risk of lymphoma (all types) and B‐cell lymphoma. The risk of diffuse large B cell lyphoma (DLBCL) was significantly lower amongst subjects who started occupational contact with any species of livestock before or at age 12 (OR = 0.5, 95% CI 0.2–0.9), but not at older ages. A significant heterogeneity in risk of B cell lymphoma by age at first contact was detected for contact with cattle, poultry and swine. Early occupational contact with livestock might be associated with a decrease in risk of B cell lymphoma.
Potential effect of the risk of ovarian cancer algorithm (ROCA) on the mortality outcome of the Prostate, Lung, Colorectal and Ovarian (PLCO) trial
Authors: Pinsky Paul F. , Zhu Claire , Skates Steve J. , Black Amanda , Partridge Edward , Buys Saundra S. , Berg Christine D.
Published: October 2012

Recently, the Prostate, Lung, Colorectal and Ovarian (PLCO) Trial reported no mortality benefit for annual screening with CA‐125 and transvaginal ultrasound (TVU). Currently ongoing is the UK Collaborative Trial of Ovarian Cancer Screening (UKCTOCS), which utilizes the risk of ovarian cancer algorithm (ROCA), a statistical tool that considers current and past CA125 values to determine ovarian cancer risk. In contrast, PLCO used a single cutoff for CA125, based on current levels alone. We investigated whether having had used ROCA in PLCO could have, under optimal assumptions, resulted in a significant mortality benefit by applying ROCA to PLCO CA125 screening values. A best‐case scenario assumed that all cancers showing a positive screen result earlier with ROCA than under the PLCO protocol would have avoided mortality; under a stage‐shift scenario, such women were assigned survival equivalent to Stage I/II screen‐detected cases. Updated PLCO data show 132 intervention arm ovarian cancer deaths versus 119 in usual care (relative risk, RR = 1.11). Forty‐three ovarian cancer cases, 25 fatal, would have been detected earlier with ROCA, with a median (minimum) advance time for fatal cases of 344 (147) days. Best‐case and stage‐shift scenarios gave 25 and 19 deaths prevented with ROCA, for RRs of 0.90 (95% CI: 0.69–1.17) and 0.95 (95% CI: 0.74–1.23), respectively. Having utilized ROCA in PLCO would not have led to a significant mortality benefit of screening. However, ROCA could still show a significant effect in other screening trials, including UKCTOCS.
Improvement of the Performance of Liquid Crystal Displays by Doping with Supramolecule‐Protected Metal Nanoparticles
Authors: Shiraishi Yukihide , Kobayashi Shunsuke , Toshima Naoki
Published: October 2012

Metal nanoparticles are now creating a new class of materials that are different from either conventional bulk materials or atoms, giving one of the smallest building blocks of matter. Metal nanoparticles have various properties based on high surface area and quantum size effects. Here we focus on the application of metal nanoparticles to liquid crystal displays, which is providing a new field in science and technology. The doping of nanoparticles into liquid crystal materials induces the modification of almost all of the physical properties of the liquid crystal, causing a reduction in the response time of liquid crystal displays. These techniques may be an alternative approach for improving the properties of liquid crystals other than chemical synthesis.
Liquid‐Crystalline Catenanes and Rotaxanes
Authors: Sakuda Junji , Yasuda Takuma , Kato Takashi
Published: October 2012

Catenanes and rotaxanes are mechanically interlocked molecules. For further functionalization, the introduction of such molecules into ordered fluid states is of interest. The control of their dynamic properties in liquid‐crystalline order may lead to the development of new smart soft materials such as stimuli‐responsive materials and molecular machines. In this review, thermotropic and lyotropic liquid‐crystalline catenanes and rotaxanes are described. One approach to the induction of liquid crystallinity to [2]catenanes and [2]rotaxanes is the attachment of mesogenic moieties. Rigid‐rod polyrotaxanes that behave as mesogens also exhibit liquid‐crystalline properties.
Ionic Discotic Liquid Crystals
Authors: Chen Shuai , Eichhorn S. Holger
Published: October 2012

Ionic discotic liquid crystals are salts of discotic liquid crystals that may display lyotropic and thermotropic mesomorphism. Columnar structures of π‐π stacking ionic discotic liquid crystals function not only as anisotropic organic semiconductors, similar to their neutral analogues, but they may also efficiently conduct ions. This combination of electronic and ionic conduction is only one of several unique properties that these materials may display, but their systematic investigation has been limited because of their often complex synthesis, purification, and characterization. However, a comprehensive account of existing reports on ionic discotic liquid crystals is not straightforward, despite their relatively small number, because publications are scattered across different areas of research, such as liquid crystals, ionic liquids, and ionic self‐assembly. This review intends to provide a concise but comprehensive overview of the published work on ionic discotic liquid crystals and related compounds and is expected to stimulate further exploration. Highlighted in this review is the mesomorphism of ionic discotic liquid crystals and its dependence on structural changes, which is also the focus of most reported studies. Particular attention was given to the dependence of mesomorphism on the location and types of the charged groups as these are parameters unique to these compounds. Also described are electronic, optical, and other properties of these materials if reported.
Investigation of alginate–ϵ‐poly‐L‐lysine microcapsules for cell microencapsulation
Authors: Ma Ying , Zhang Ying , Liu Yang , Chen Li , Li Shen , Zhao Wei , Sun Guangwei , Li Na , Wang Yu , Guo Xin , Lv Guojun , Ma Xiaojun
Published: October 2012

Cell microencapsulation is a promising approach for cell implantation, cell‐based gene therapy, and large‐scale cell culture. The well‐studied α‐AP (alginate–α‐poly‐L‐lysine) microcapsules have been restricted to large‐scale cell‐culture and clinical applications because of high costs and cytotoxic effects in some cases. This study used ϵ‐poly‐L‐lysine (ϵ‐PLL), a high‐biocompatible and low‐cost food additives produced by fermentation, to prepare ϵ‐AP (alginate–ϵ‐PLL) microcapsules with various thickness membranes and swelling behaviors. ϵ‐AP microcapsules were permeable to BSA, a standard protein of culture medium. ϵ‐AP‐microencapsulated Chinese hamster ovary (CHO) cells proliferated with culture time; no obvious difference with α‐AP‐microencapsulated CHO cells during the early 19 days. Whereas ϵ‐AP‐microencapsulated CHO cells kept higher viability (OD = 0.646 ± 0.012) on the 22nd day and microcapsule strength (integrity rate of 88%) on the 24th day than that of α‐AP microcapsules (OD = 0.558 ± 0.025, integrity rate of 80%). ϵ‐AP (alginate‐ϵ‐PLL) microcapsules exhibited more superior properties and could lower the costs to broaden the applications of microencapsulation technology. © 2012 Wiley Periodicals, Inc. J Biomed Mater Res Part A, 2013.
Mechanisms of antiproliferative drug release from bioresorbable porous structures
Authors: Kraitzer Amir , Alperstein David , Kloog Yoel , Zilberman Meital
Published: October 2012

Restenosis (renarrowing of the blood vessel wall) and cancer are two different pathologies that have drawn extensive research attention over the years. Antiproliferative drugs such as paclitaxel inhibit cell proliferation and are therefore effective in the treatment of cancer as well as neointimal hyperplasia, which is known to be the main cause of restenosis. Antiproliferative drugs are highly hydrophobic and their release from porous biodegradable structures is therefore advantageous. The release profiles of four antiproliferative drugs from highly porous polymeric structures were studied in this study in light of the physical properties of both the host polymers and the drug molecules, and a qualitative model was developed. The chemical structure of the polymer chain directly affects the drug release profile through water uptake in the early stages or degradation and erosion in later stages. It also affects the release profile indirectly, through the polymer's 3D porous structure. However, this effect is minor. The drug volume and molecular area dominantly affect its diffusion rate from the 3D porous structure and the drug's solubility parameter compared with that of the host polymer has some effect on the drug release profile. This model can also be used to describe release mechanisms of other hydrophobic drugs from porous structures. © 2012 Wiley Periodicals, Inc. J Biomed Mater Res Part A, 2013.