bluuebunny/crossref_metadata_2025 huggingface dataset:
Functional Discharge Readiness and Mobility Following Total Knee Arthroplasty for Osteoarthritis: A Comparison of Analgesic Techniques
Authors: Chan Ee‐Yuee , Teo Yee‐Hong , Assam Pryseley N. , Fransen Marlene
Published: April 2014

Objective

To determine if functional discharge readiness and mobility following total knee arthroplasty (TKA) for osteoarthritis is delayed after femoral nerve block (FNB) with or without patient‐controlled analgesia (PCA) opioid compared with PCA opioid alone.

Methods

We analyzed secondary outcomes from a randomized controlled trial with 200 patients undergoing unilateral TKA. Experimental group 1 received single‐injection FNB with intravenous PCA opioid, experimental group 2 received continuous FNB, and the control group received PCA opioid alone. FNB was administered using bupivacaine. Patients followed a structured TKA pathway. Discharge readiness outcomes included achievement of 90° knee flexion, independent walking, and stair climbing, and were assessed daily before discharge or day 6, whichever came first. Mobility outcomes included the Timed Up and Go (TUG) test, the 6‐Minute Walk Distance (6MWD), and self‐reported physical function, and were assessed at weeks 2 and 12. TUG was also assessed on days 3 to 6, postoperation.

Results

Both FNB groups (77%) were more likely to achieve 90° knee flexion compared with the control group (59%); odds ratio (OR) 2.3, 95% confidence interval (95% CI) 1.1, 4.8 for single‐injection FNB, and OR 2.3, 95% CI 1.1, 4.9 for continuous FNB. There were no significant differences in independent walking and stair‐climbing ability before discharge, TUG, 6MWD, or self‐reported physical function, between the FNB groups compared with the control group.

Conclusion

After TKA, FNB (single‐injection with PCA opioid or continuous) does not delay achievement of 90° knee flexion or other measures of functional discharge readiness and mobility compared with PCA opioid alone.
Oxygen‐Free Highly Conductive Graphene Papers
Authors: Šimek Petr , Sofer Zdeněk , Jankovský Ondřej , Sedmidubský David , Pumera Martin
Published: April 2014

Graphene papers have a potential to overcome the gap from nanoscale graphene to real macroscale applications of graphene. A unique process for preparation of highly conductive graphene thin paper by means of Ar+ ion irradiation of graphene oxide (GO) papers, with carbon/oxygen ratio reduced to 100:1, is presented. The composition of graphene paper in terms of carbon/oxygen ratio and in terms of types of individual oxygen‐containing groups is monitored throughout the process. Angle‐resolved high resolution X‐ray photoelectron spectroscopy helps to investigate the depth profile of carbon and oxygen within reduced GO paper. C/O ratios over 100 on the surface and 40 in bulk material are observed. In order to bring insight to the processes of oxygen removal from GO paper by low energy Ar+ ion bombardment, the gases released during the irradiation are analyzed by mass spectroscopy. It is proven that Ar+ ion beam can be applied as a technique for fabrication of highly reduced graphene papers with high conductivities. Such highly conductive graphene papers have great potential to be used in application for construction of microelectronic and sensor devices.
Controlled Synthesis of Organic Nanophotonic Materials with Specific Structures and Compositions
Authors: Cui Qiu Hong , Zhao Yong Sheng , Yao Jiannian
Published: April 2014

Organic nanomaterials have drawn great interest for their potential applications in high‐speed miniaturized photonic integration due to their high photoluminescence quantum efficiency, structural processability, ultrafast photoresponse, and excellent property engineering. Based on the rational design on morphological and componential levels, a series of organic nanomaterials have been controllably synthesized in recent years, and their excitonic/photonic behaviors has been fine‐tuned to steer the light flow for specific optical applications. This review presents a comprehensive summary of recent breakthroughs in the controlled synthesis of organic nanomaterials with specific structures and compositions, whose tunable photonic properties would provide a novel platform for multifunctional applications. First, we give a general overview of the tailored construction of novel nanostructures with various photonic properties. Then, we summarize the design and controllable synthesis of composite materials for the modulation of their functionalities. Subsequently, special emphasis is put on the fabrication of complex nanostructures towards wide applications in isolated photonic devices. We conclude with our personal viewpoints on the development directions in the novel design and controllable construction of organic nanomaterials for future applications in highly integrated photonic devices and chips.
New candidate loci identified by array‐CGH in a cohort of 100 children presenting with syndromic obesity
Authors: Vuillaume Marie‐Laure , Naudion Sophie , Banneau Guillaume , Diene Gwenaelle , Cartault Audrey , Cailley Dorothée , Bouron Julie , Toutain Jérôme , Bourrouillou Georges , Vigouroux Adeline , Bouneau Laurence , Nacka Fabienne , Kieffer Isabelle , Arveiler Benoit , Knoll‐Gellida Anja , Babin Patrick J. , Bieth Eric , Jouret Béatrice , Julia Sophie , Sarda Pierre , Geneviève David , Faivre Laurence , Lacombe Didier , Barat Pascal , Tauber Maithé , Delrue Marie‐Ange , Rooryck Caroline
Published: April 2014

Syndromic obesity is defined by the association of obesity with one or more feature(s) including developmental delay, dysmorphic traits, and/or congenital malformations. Over 25 syndromic forms of obesity have been identified. However, most cases remain of unknown etiology. The aim of this study was to identify new candidate loci associated with syndromic obesity to find new candidate genes and to better understand molecular mechanisms involved in this pathology. We performed oligonucleotide microarray‐based comparative genomic hybridization in a cohort of 100 children presenting with syndromic obesity of unknown etiology, after exhaustive clinical, biological, and molecular studies. Chromosomal copy number variations were detected in 42% of the children in our cohort, with 23% of patients with potentially pathogenic copy number variants. Our results support that chromosomal rearrangements are frequently associated with syndromic obesity with a variety of contributory genes having relevance to either obesity or developmental delay. A list of inherited or apparently de novo duplications and deletions including their enclosed genes and not previously linked to syndromic obesity was established. Proteins encoded by several of these genes are involved in lipid metabolism (ACOXL, MSMO1, MVD, and PDZK1) linked with nervous system function (BDH1 and LINGO2), neutral lipid storage (PLIN2), energy homeostasis and metabolic processes (CDH13, CNTNAP2, CPPED1, NDUFA4, PTGS2, and SOCS6). © 2014 Wiley Periodicals, Inc.
Microduplication 10q24.31 in a Spanish girl with scoliosis and myopathy: The critical role of LBX
Authors: Fernández‐Jaén Alberto , Suela Javier , Fernández‐Mayoralas Daniel Martín , Fernández‐Perrone Ana Laura , Wotton Karl R. , Dietrich Susanne , Castellanos Maria del Carmen , Cigudosa Juan C. , Calleja‐Pérez Beatriz , López‐Martín Sara
Published: April 2014

LBX1 plays a cardinal role in neuronal and muscular development in animal models. Its function in humans is unknown; it has been reported as a candidate gene for idiopathic scoliosis. Our goal is to document the first clinical case of a microduplication at 10q24.31 (chr10:102927883‐103053612, hg19), affecting exclusively LBX1. The patient, a 12‐year‐old girl, showed attention problems, dyspraxia, idiopathic congenital scoliosis, and marked hypotrophy of paravertebral muscles. Her paternal aunt had a severe and progressive myopathy with a genetic study that revealed the same duplication. We propose to consider genetic studies, particularly of LBX1, in patients with scoliosis and/or hypotrophy‐hypoplasia of paravertebral muscles of unknown etiology. © 2014 Wiley Periodicals, Inc.
Mutations in RARS cause hypomyelination
Authors: Wolf Nicole I. , Salomons Gajja S. , Rodenburg Richard J. , Pouwels Petra J. W. , Schieving Jolanda H. , Derks Terry G. J. , Fock Johanna M. , Rump Patrick , van Beek Daphne M. , van der Knaap Marjo S. , Waisfisz Quinten
Published: April 2014

Hypomyelinating disorders of the central nervous system are still a diagnostic challenge, as many patients remain without genetic diagnosis. Using magnetic resonance imaging (MRI) pattern recognition and whole exome sequencing, we could ascertain compound heterozygous mutations in RARS in 4 patients with hypomyelination. Clinical features included severe spasticity and nystagmus. RARS encodes the cytoplasmic arginyl‐tRNA synthetase, an enzyme essential for RNA translation. This protein is among the subunits of the multisynthetase complex, which emerges as a key player in myelination. Ann Neurol 2014;76:134–139
Linking MRI postprocessing with magnetic source imaging in MRI‐negative epilepsy
Authors: Wang Zhong I. , Alexopoulos Andreas V. , Jones Stephen E. , Najm Imad M. , Ristic Aleksandar , Wong Chong , Prayson Richard , Schneider Felix , Kakisaka Yosuke , Wang Shuang , Bingaman William , Gonzalez‐Martinez Jorge A. , Burgess Richard C.
Published: April 2014

Objective

MRI‐negative (MRI–) pharmacoresistant focal epilepsy (PFE) patients are most challenging for epilepsy surgical management. This study utilizes a voxel‐based MRI postprocessing technique, implemented using a morphometric analysis program (MAP), aiming to facilitate detection of subtle focal cortical dysplasia (FCD) in MRI– patients. Furthermore, the study examines the concordance between MAP‐identified regions and localization from magnetic source imaging (MSI).

Methods

Included in this retrospective study were 25 MRI– surgical patients. MAP was performed on T1‐weighted MRI, with comparison to a normal database. The pertinence of MAP+ areas was confirmed by MSI, surgical outcome and pathology. Analyses of MAP and MSI were performed blindly from patients' clinical information and independently from each other.

Results

The detection rate of subtle changes by MAP was 48% (12/25). Once MAP+ areas were resected, patients were more likely to be seizure‐free (p = 0.02). There were no false positives in the 25 age‐matched normal controls. Seven patients had a concordant MSI correlate. Patients in whom a concordant area was identified by both MAP and MSI had a significantly higher chance of achieving a seizure‐free outcome following complete resection of this area (p = 0.008). In the 9 resected MAP+ areas, pathology revealed FCD type IA in 7 and type IIB in 2.

Interpretation

MAP shows promise in identifying subtle FCD abnormalities and increasing the diagnostic yield of conventional MRI visual analysis in presurgical evaluation of PFE. Concordant MRI postprocessing and MSI analyses may lead to the noninvasive identification of a structurally and electrically abnormal subtle lesion that can be surgically targeted. Ann Neurol 2014;759–770
Durch Dithienylethen‐Einheiten modifizierte Rubyrine
Authors: Zhou Zhikuan , Chang Yi , Shimizu Soji , Mack John , Schütt Christian , Herges Rainer , Shen Zhen , Kobayashi Nagao
Published: April 2014

Zwei stabile, kernmodifizierte Rubyrine mit einer oder zwei Diethienylethen(DTE)‐Einheiten (1 und 2) wurden hergestellt. Das Rubyrin 1 mit einer “geschlossenen” DTE‐Einheit zeigt 26 π‐Aromatizität, während bei Einführung einer “offenen” DTE‐Einheit in den Makrocyclus 2 dieser sich als nichtaromatische Verbindung verhält.
Catalytic Asymmetric Synthesis of 8‐Oxabicyclooctanes by Intermolecular [5+2] Pyrylium Cycloadditions
Authors: Witten Michael R. , Jacobsen Eric N.
Published: April 2014

Highly enantioselective intermolecular [5+2] cycloadditions of pyrylium ion intermediates with electron‐rich alkenes are promoted by a dual catalyst system composed of an achiral thiourea and a chiral primary aminothiourea. The observed enantioselectivity is highly dependent on the substitution pattern of the 5π component, and the basis for this effect is analyzed using experimental and computational evidence. The resultant 8‐oxabicyclo[3.2.1]octane derivatives possess a scaffold common in natural products and medicinally active compounds and are also versatile chiral building blocks for further manipulations. Several stereoselective complexity‐generating transformations of the 8‐oxabicyclooctane products are presented.
Single‐Electron/Pericyclic Cascade for the Synthesis of Dienes
Authors: Campbell Natalie E. , Sammis Glenn M.
Published: April 2014

The highly efficient and diastereoselective synthesis of E dienes has been accomplished through radical cyclization of bromoallyl hydrazones. This methodology has been further extended to generate these products through a one‐pot condensation/radical cyclization/cycloreversion cascade from simple aldehyde starting materials in high yields (>75 %) and high diastereoselectivities (>95:5). Mechanistic investigations suggest that the cascade reaction proceeds through a cyclic diazene intermediate prior to the cycloreversion.
Core‐Modified Rubyrins Containing Dithienylethene Moieties
Authors: Zhou Zhikuan , Chang Yi , Shimizu Soji , Mack John , Schütt Christian , Herges Rainer , Shen Zhen , Kobayashi Nagao
Published: April 2014

Two stable core‐modified rubyrins bearing one and two dithienylethene (DTE) units (1 and 2) have been synthesized. With one “closed‐form” DTE unit, 1 shows aromaticity associated with its conjugated circuit of 26 π‐electrons. In contrast, rubyrin 2 containing one “open‐form” DTE unit has nonaromatic properties.
A novel polybenzoxazine containing styrylpyridine structure via the Knoevenagel reaction
Authors: Zhang Huachuan , Li Min , Deng Yuyuan , Zhang Chengxi , Ran Qichao , Gu Yi
Published: April 2014

In this article, a kind of styrylpyridine‐containing polybenzoxazine was obtained via the Knoevenagel reaction between benzaldehyde and methylpyridine groups. The benzoxazine monomer (MPBC) containing the benzaldehyde and methylpyridine groups was synthesized firstly and its structure was characterized by Fourier transform infrared (FTIR) spectra, 1H NMR and 13C NMR. With the aid of differential scanning calorimetry, FTIR, and photoluminescent tests, the interesting curing behaviors were probed. The results showed that the ring‐opening polymerization occurred at lower temperature, and the Knoevenagel reaction further took place at elevated temperature. The amine and phenol moieties were bonded together to form the styrylpyridine structure. Due to these special crosslinking structures, the corresponding polybenzoxazine exhibited excellent thermal stability, and had a special high char yield of 74.5%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40823.
Preparation and properties of polyethylene terephthalate/polyethylene/near infrared reflective pigment composites
Authors: Lai S. ‐M. , Hung K. ‐C. , Lai Wei‐Jen , Zeng Jiun‐Wei , Cheng K. ‐C.
Published: April 2014

Polyethylene terephthalate/high density polyethylene (PET/HDPE) composites containing a near infrared reflective (NIR, nickel antimony titanium yellow rutile) pigment was prepared using ethylene‐glycidyl methacrylate‐vinyl acetate (EGMA‐VA) as a compatibilizer to increase the infrared reflection of PET/HDPE and limit the thermal heat accumulation in light of environmental and energy conservation concerns. HDPE was premixed with NIR to form N‐HDPE masterbatch. A good interfacial bonding between PET matrix and HDPE dispersed phase with the help of compatibilizer was confirmed through Fourier transform‐infrared spectra, scanning electron microscopy, and torque rheometer. For PET/N‐HDPE composites, the major X‐ray diffraction peaks and melting behaviors remained unchanged, indicating the limited alternation of crystalline structure for the composite systems with or without compatibilizer. The observed increment in the crystallization temperature of PET for the investigated PET/N‐HDPE composites was mainly due to the nucleation role of both inorganic NIR and HDPE. Tensile strength and elongation at break for compatibilized cases at various N‐HDPE contents conferred higher values than those of the corresponding counterparts without compatibilizer. Yet, Young's modulus for compatibilized systems was about 40% lower than that for systems without compatibilizer, attributed to the rubbery nature of EGMA‐VA. With the inclusion of NIR into HDPE to form PET/N‐HDPE composites with or without EGMA‐VA compatibilizer, the values of reflectance increased to a great degree. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40830.
Subgrouping of Patients With Rheumatoid Arthritis Based on Pain, Fatigue, Inflammation, and Psychosocial Factors
Authors: Lee Yvonne C. , Frits Michelle L. , Iannaccone Christine K. , Weinblatt Michael E. , Shadick Nancy A. , Williams David A. , Cui Jing
Published: April 2014

Objective

Among patients with rheumatoid arthritis (RA), pain may be attributed to peripheral inflammation or other causes, such as central pain mechanisms. The aim of this study was to use self‐report measures and physical examination findings to identify clusters of RA patients who may have different causes of pain as well as different prognoses and treatment options.

Methods

Data from 169 RA patients with pain scores of >0 (on a 10‐point numeric rating scale) in the Brigham and Women's Hospital Rheumatoid Arthritis Sequential Study were analyzed. The patients completed questionnaires on pain, fatigue, and psychosocial factors. A hierarchical agglomerative clustering procedure with Ward's method was used to obtain subgroups. Multivariate analysis of variance was used to determine the contribution of each variable in a cluster. General linear regression models were used to examine differences in clinical characteristics across subgroups. Discriminant analyses were performed to determine coefficients for linear combinations of variables that assigned cluster membership to individual cases.

Results

Three clusters best fit these data. Cluster 1 consisted of 89 individuals with low levels of inflammation, pain, fatigue, and psychosocial distress. Cluster 2 consisted of 57 individuals with minimal inflammation but high levels of pain, fatigue, and psychosocial distress. Cluster 3 consisted of 23 individuals with active inflammatory disease, manifested by high swollen joint counts, high C‐reactive protein levels, and high levels of pain and fatigue.

Conclusion

Although most patients had low levels of inflammation, pain, and fatigue, 47.3% continued to report having moderate to high levels of pain and fatigue. Most of these patients had minimal signs of inflammation but high levels of fatigue, pain catastrophizing, and sleep disturbance, indicative of a chronic widespread pain syndrome.
Reversing Vascular Dysfunction in Rheumatoid Arthritis: Improved Augmentation Index but Not Endothelial Function With Peroxisome Proliferator–Activated Receptor γ Agonist Therapy
Authors: Ormseth Michelle J. , Oeser Annette M. , Cunningham Andrew , Bian Aihua , Shintani Ayumi , Solus Joseph , Tanner S. Bobo , Stein C. Michael
Published: April 2014

Objective

To examine the hypothesis that improving insulin sensitivity improves vascular function in rheumatoid arthritis (RA).

Methods

We performed a 20‐week, single center, randomized, double‐blind, placebo‐controlled crossover study. Patients with RA (n = 34) with moderate disease activity who were receiving stable disease‐modifying antirheumatic drug therapy were randomized to drug sequence, receiving either pioglitazone 45 mg/day or matching placebo for 8 weeks, followed by a 4‐week washout period and the alternative treatment for 8 weeks. We measured changes in vascular stiffness (augmentation index and aortic pulse wave velocity [PWV]), endothelial function (reactive hyperemia index), and blood pressure. High‐sensitivity C‐reactive protein levels and the homeostatic model assessment of insulin resistance were also measured. The treatment effect of pioglitazone on outcomes was analyzed using linear mixed‐effects models.

Results

Pioglitazone treatment resulted in a change in augmentation index of −4.7% units (95% confidence interval [95% CI] −7.9, −1.5) (P = 0.004) and in diastolic blood pressure of −3.0 mm Hg (95% CI −5.7, −0.2) (P = 0.03), but did not significantly change aortic PWV (P = 0.33) or reactive hyperemia index (P = 0.46). The improvements in augmentation index and diastolic blood pressure were not mediated by the effect of pioglitazone on insulin resistance or inflammation.

Conclusion

Our findings indicate that pioglitazone improves some indices of vascular function, including augmentation index and diastolic blood pressure, in patients with RA. This is not mediated by improved insulin sensitivity.
New Population‐Based Reference Values for Spinal Mobility Measures Based on the 2009–2010 National Health and Nutrition Examination Survey
Authors: Assassi Shervin , Weisman Michael H. , Lee MinJae , Savage Laurie , Diekman Laura , Graham Tiffany A. , Rahbar Mohammad H. , Schall Joan I. , Gensler Lianne S. , Deodhar Atul A. , Clegg Daniel O. , Colbert Robert A. , Reveille John D.
Published: April 2014

Objective

To report population‐based percentile reference values for selected spinal mobility measures in a nationally representative sample of 5,001 US adults ages 20–69 years who were examined in the 2009–2010 US National Health and Nutrition Examination Survey (NHANES).

Methods

Occiput‐to‐wall distance (OWD), thoracic expansion (TE), and anterior lumbar flexion (ALF; by modified Schober test) were measured by trained examiners in a standardized manner. TE was measured at the xiphisternal level, while the lower reference point for ALF was a line marked at the level of the superior margin of the lateral iliac crests. We report reference values based on the 95th percentile for the OWD and the 5th percentile for TE and ALF, as well as other summary statistics for these measures, in the study population.

Results

An OWD of >0 was present in 3.8% of the participants, while 8.8% of them had out‐of‐range values for TE based on the commonly used threshold of 2.5 cm. The 95th percentile of the OWD measurement was 0, while the 5th percentile for TE and ALF were 1.9 cm and 2 cm, respectively. The spinal measures were significantly associated with sex, age, ethnicity, height, and body mass index (BMI). Exclusion of individuals with severe obesity (BMI >35 kg/m2) changed the proposed reference values for TE and ALF to 2.2 cm and 1.9 cm, respectively.

Conclusion

We verified a reference value of 0 for the OWD in the general population. Using the reported population‐based percentile values, new reference values for TE and ALF can be derived.
A Reagent‐Free Oxidative Cyclization Approach to Indolizine Derivatives from α‐Picoline Derivatives and Nitroolefins
Authors: Gao Meng , Tian Jun , Lei Aiwen
Published: April 2014

A reagent‐free oxidative cyclization between α‐picoline derivatives and nitroolefins has been developed. This approach, in which the nitro group acts as an internal oxidant, provides an extremely simple, efficient, and atom‐economic way to construct heteroaromatic indolizine derivatives.
A cleavable silica‐binding affinity tag for rapid and inexpensive protein purification
Authors: Coyle Brandon L. , Baneyx François
Published: April 2014

We describe a new affinity purification tag called Car9 that confers proteins to which it is fused micromolar affinity for unmodified silica. When appended to the C‐terminus of GFPmut2 through a flexible linker, Car9 promotes efficient adsorption to silica gel and the fusion protein can be released from the particles by incubation with L‐lysine. Using a silica gel column and the lysine elution approach in fast protein liquid chromatography (FPLC) mode, Car9‐tagged versions of GFPmut2, mCherry and maltose binding protein (MBP) can be recovered from clarified lysates with a purity of 80–90%. Capitalizing on silica's ability to handle large pressure drops, we further show that it is possible to go from cell lysates to purified protein in less than 15 min using a fully disposable device. Finally, we demonstrate that the linker‐Car9 region is susceptible to proteolysis by E. coli OmpT and take advantage of this observation to excise the C‐terminal extension of GFPmut2‐Car9 by incubating purified fusion protein with cells that overproduce the outer membrane protease OmpT. The set of strategies described herein, should reduce the cost of affinity purification by at least 10‐fold, cut down purification times to minutes, and allow for the production of proteins with native (or nearly native) termini from their C‐terminally‐tagged versions. Biotechnol. Bioeng. 2014;111: 2019–2026. © 2014 Wiley Periodicals, Inc.
Derivatization of Antibody Fab Fragments: A Designer Enzyme for Native Protein Modification
Authors: Liebscher Sandra , Kornberger Petra , Fink Gerhard , Trost‐Gross Eva‐Maria , Höss Eva , Skerra Arne , Bordusa Frank
Published: April 2014

Bioconjugates, such as antibody–drug conjugates, have gained recent attention because of their increasing use in therapeutic and diagnostic applications. Commonly used conjugation reactions based upon chemoselective reagents exhibit a number of drawbacks: most of these reactions lack regio‐ and stereospecificity, thus resulting in loss of protein functionality due to random modifications. Enzymes provide an obvious solution to this problem, but the intrinsic (natural) substrate specificities of existing enzymes pose severe limitations to the kind of modifications that can be introduced. Here we describe the application of the novel trypsin variant trypsiligase for site‐specific modification of the C terminus of a Fab antibody fragment via a stable peptide bond. The suitability of this designed biocatalyst was demonstrated by coupling the Her2‐specific Fab to artificial functionalities of either therapeutic (PEG) or diagnostic (fluorescein) relevance. In both cases we obtained homogeneously modified Fab products bearing the artificial functionality exclusively at the desired position.
The Influence of the Precipitation/Ageing Temperature on a Cu/ZnO/ZrO2 Catalyst for Methanol Synthesis from H2 and CO2
Authors: Frei Elias , Schaadt Achim , Ludwig Thilo , Hillebrecht Harald , Krossing Ingo
Published: April 2014

For heterogeneous catalysts, the constitution of the precursor is an important parameter to adjust the properties of the active catalyst. Therefore, we examined the influence of the temperature during the precipitation process and during the ageing time in the mother liquor for a Cu/ZnO/ZrO2 catalyst system obtained through a coprecipitation route. The variation of the temperature affects the ratio and crystallinity of the precursor phases zincian malachite and aurichalcite, as detected by powder XRD (phase and line width) and FTIR spectroscopy (characteristic asymmetric CO stretching modes of the carbonate anions at $\tilde \nu $=1600–1100 cm−1). Therefore, the precatalyst surface area (As,BET) and pore distribution are adjustable (i.e., As,BET of 190 m2 g−1 was reached). The influence of the synthesis conditions on the catalysts activity for methanol production was analyzed and discussed up to the level of productivity/activity testing at 413/513 K and 40 bar total H2/CO2 pressure. The best catalyst showed a methanol productivity of 9.16 mmol gcat−1 h−1 (513 K, 40 bar, and gas hourly space velocity=8000) and is better than an industrial catalyst tested under the same conditions (8.34 mmol gcat−1 h−1). However, despite considerable differences in the precursor and precatalyst structure and morphology, their influence on the methanol productivity is only small. This demonstrates that the active catalyst is formed under reaction conditions.
Aqueous Sodium‐Ion Battery using a Na3V2(PO4)3 Electrode
Authors: Song Weixin , Ji Xiaobo , Zhu Yirong , Zhu Hanjun , Li Fangqian , Chen Jun , Lu Fang , Yao Yinpeng , Banks Craig. E.
Published: April 2014

The front cover artwork is provided by the group of Prof. Dr. Xiaobo Ji at Central South University (PR China). The image represents the electrochemical behaviors of NASICON Na3V2(PO4)3 utilized in Li+‐, Na+‐, and K+‐based aqueous electrolytes. Read the full text of the article at 10.1002/celc.201300248.
Gold‐Catalyzed Cascade Reactions of Furan‐ynes with External Nucleophiles Consisting of a 1,2‐Rearrangement: Straightforward Synthesis of Multi‐Substituted Benzo[b]furans
Authors: Sun Ning , Xie Xin , Liu Yuanhong
Published: April 2014

A gold‐catalyzed cycloisomerization of silyl‐protected 2‐(1‐alkynyl)‐2‐alken‐1‐(2‐furanyl)‐1‐ols with various nucleophiles including water, alcohol, aniline, sulfonamide, and electron‐rich arene has been developed. The method provides a highly efficient access to 5,7‐disubstituted or 2,5,7‐trisubstituted benzo[b]furans with a wide diversity of substituents under mild reaction conditions, which are not easily available by other methods. Remarkably, an interesting rearrangement of the alkyl group from C2 to the C3 position of the furan ring takes place during the cyclization process. The following gold‐assisted allylic substitution enables an elaboration of benzo[b]furans on its side chain of the C5 position with a wide range of functional groups.
Plasmon‐Enhanced Photocurrent Generation from Click‐Chemically Modified Graphene
Authors: Yenchalwar Sandeep G. , Reddy Devarapalli Rami , Deshmukh Ashvini B. , Shelke Manjusha V.
Published: April 2014

The visible‐light response of Au nanoparticles (AuNPs) assembled on rGO through different molecular bridges was investigated by transient photocurrent generation. We prepared rGO with two self‐assembled monolayers (SAMs), one linear and the other with aromatic triazoles through a click cycloaddition reaction. A fivefold photocurrent enhancement was observed for triazole linkers over the aminopropyltrimethoxysilane (APTMS) linker. Cyclic voltammetry (CV) and impedance measurements also suggest fast electron transfer on account of the low resistance offered by the click‐modified rGO surface whereby introduction of triazoles offers the efficient bridge between the donor AuNPs and acceptor rGO.
Silver‐Catalyzed Formal Insertion of Arynes into RfI Bonds
Authors: Zeng Yuwen , Hu Jinbo
Published: April 2014

An unprecedented silver‐catalyzed formal insertion of arynes into RfI (Rf=CF3, C2F5) bonds has been developed. This protocol provides easy access to various ortho‐perfluoroalkyl iodoarenes under mild conditions. In this insertion reaction, an ionic atom‐transfer reaction of RfI occurs, and a silver‐mediated metathesis process is involved in the efficient transfer of the electropositive iodine atom.
Spatial Variability of Soil Parameters of the van Genuchten Model at a Regional Scale
Authors: Wang Yunqiang , Shao Ming'an , Han Xiangwei , Liu Zhipeng
Published: April 2014

Spatial heterogeneity of soil water retention curves (SWRC) plays an important role in modelling the movement of water and solutes in soils. To characterize the spatial variability of SWRC parameters fitted by the van Genuchten (VG) equation, and then identify factors that closely correlated with the VG parameters, we collected undisturbed and disturbed soil samples from the upper 0–5 cm soil layer at 382 sampling sites across the entire Loess Plateau of China (~620 000 km2). We determined the SWRC and six other soil properties as well as nine environmental factors for each site. Results showed that the saturated water content (θs) and a curve‐shape parameter that is related to soil pore size distribution (n) were weakly spatially variable (coefficient of variation (CV) = 15%), and that the residual soil water content (θr) and a scaling parameter that is related to the inverse of the air entry pressure (α) were moderately (CV = 96%) and strongly variable (CV = 136%), respectively. Semivariograms of and log(α) were best‐fitted by an isotropic exponential model, while those of θs and log(n) were fitted by an isotropic spherical model. Fractal analysis indicated that log(α) demonstrated the most short‐range variation, while log(n) reflected the importance of long‐range variation. Bulk density and the contents of clay, silt, sand and soil organic carbon contributed greatly to the variations in the VG parameters (except α). However, the vegetation, topographic and climatic elements as well as land use also usually explained some of the variation. The VG parameters, at the regional scale, demonstrated different characteristics of spatial variation, which comprehensively reflected the combined effects of processes involving the soil, vegetation, topography and climate as well as effects of land use, which is often determined by human activity.
Mechanistic and Cytotoxicity Studies of Group IV β‐Diketonate Complexes
Authors: Lord Rianne M. , Mannion James J. , Hebden Andrew J. , Nako Adi E. , Crossley Benjamin D. , McMullon Max W. , Janeway Felix D. , Phillips Roger M. , McGowan Patrick C.
Published: April 2014

Group IV metal complexes have previously shown promise as novel anticancer agents. Here, we discuss the mechanistic and cytotoxic nature of a series of group IV β‐diketonate coordination complexes. Clear evidence that the ligands are exchangeable on the metal centre and that the β‐diketonate ligands can act as potential drug delivery vehicles of the group IV metal ions was obtained. When evaluated for the cytotoxicity against human colon adenocarcinoma (HT‐29) and human breast adenocarcinoma (MCF‐7) cell lines, a general trend of decreasing potency down the group IV metals was observed. The most promising results obtained were for the hafnium complexes, with the tris diphenyl β‐diketonate hafnium complex exhibiting IC50 values of 4.9±0.9 μM and 3.2±0.3 μM against HT‐29 and MCF‐7, respectively, which are comparable with the activity of cisplatin against the same cell lines. This tri β‐diketonate hafnium complex is the first to show potent in vitro cytotoxic activity. The results reported show that ligand design has a significant effect on the cytotoxic potential of the complexes, and that these group IV complexes warrant further evaluation as novel metal‐containing anticancer agents.
Recipes 2.0: building for today and tomorrow
Authors: Dooley Rion , Hanlon Matthew R.
Published: April 2014

The history of science gateway development has, in many ways, been a story of the ‘Haves’ vs. the ‘Have‐nots’. Large infrastructure projects led the way, building thick client portals to provide coherent interfaces to an incoherent environment. Contrast this with the way the modern Web is designed using light, front end components, and outsourcing much of the heavy lifting to a mash‐up of REST application programming interfaces, and it is easy to see why modern web applications can be prototyped and refined into stable products in the time it previously took thick client portals to do an initial release. This paper argues that a ‘build for today’ philosophy can lead to the rapid development of science gateways to serve the ‘Have‐nots’. With this philosophy in mind, we are presenting Gateway DNA, a set of responsive front end components built on top of the iPlant Agave application programming interfaces. This toolkit provides the boilerplate for rapid development of lightweight science gateways using only HTML, JavaScript, and CSS. Using Gateway DNA, developers can easily stand up new gateways or quickly add new functionality to existing ones. Copyright © 2014 John Wiley & Sons, Ltd.
Excited‐State Intramolecular Proton Transfer: Photoswitching in Salicylidene Methylamine Derivatives
Authors: Jankowska Joanna , Rode Michał F. , Sadlej Joanna , Sobolewski Andrzej L.
Published: April 2014

The effect of chemical substitutions on the photophysical properties of the salicylidene methylamine molecule (SMA) (J. Jankowska, M. F. Rode, J. Sadlej, A. L. Sobolewski, ChemPhysChem, 2012, 13, 4287–4294) is studied with the aid of ab initio electronic structure methods. It is shown that combining π‐electron‐donating and π‐electron‐withdrawing substituents results in an electron‐density push‐and‐pull effect on the energetic landscape of the ground and the lowest excited ππ* and nπ* singlet states of the system. The presented search for the most appropriate SMA derivatives with respect to their photoswitching functionality offers an efficient prescreening tool for finding chemical structures before real synthetic realization.
Construction of Hybrid Supercapacitor–Batteries with dual‐scale shelled architecture
Authors: Qian Zhongyu , Peng Tao , Wang Jun , Qu Liangti
Published: April 2014

Pseudocapacitors bridge the gap between supercapacitors and batteries. Controllable microstructures grown on substrates have achieved success with regard to energy storage. However, traditional designs have only focused on the surface of scaffolds, which results in high specific capacitance values for the electroactive material rather than the electrodes. Inspired by slurry‐casting, a dual‐scale shell‐structured NiCo2O4 on nickel foam was assembled by using a simple and flexible solution‐based strategy. First, NiCo2O4 nanosheets covering the Ni foam skeleton surface loosely (the sample is denoted as ′pasted′) is obtained by a solution‐grown and ′dip‐and‐dry′ process (in a cobalt–nickel hydroxide solution) followed by annealing. Secondly, the NiCo2O4 nanosheets are filled in the pores of the Ni scaffold (the obtained material is denoted as ′tailored′) through chemical bath deposition process followed by annealing. The capacitance per weight of electroactive materials is not outstanding (1029 F g−1 at 10 mA cm−2), but is competitive with regard to area (3.23 F cm−2 at 10 mA cm−2). However, features in the cycling performance imply that the electrode exhibits a hybrid supercapacitor–battery behavior and that thermodynamic hysteresis promotes the ’breaking’ and ’fusing’ behavior of the material. The overall design highlights a new pathway to step out from surface to space.
Hardware Design Optimization and Process Control for a Low Friction Coefficient Substrate and Film: A Case Study in the Semiconductor Industry
Authors: Fumagalli Francesco , Marelli Sara , Angilletta Domenico , Capellini Stefano , Sgroi Marcello
Published: April 2014

For semiconductor devices, the use of amorphous carbon films as a sacrificial hard mask material is commonplace in the integration for patterning of 90 nm and below technology node devices. These films have an intrinsically low friction coefficient. At the same time, for planarity reasons, double‐side polished (DSP) wafers have been progressively introduced. The combination of double side polished silicon wafers, together with their covering with amorphous carbon film, dramatically decreases the friction coefficient and incommodes their robotic handling. This issue may be faced by developing a tool designed for that specific purpose, and by optimizing the deposition conditions so as to obtain a reliable industrial high‐yield process.
Comparison of electronic volume and forward scatter principles of cell selection using flow cytometry for the evaluation of acrosome and plasma membrane integrity of bull spermatozoa
Authors: Standerholen Fride Berg , Myromslien Frøydis Deinboll , Kommisrud Elisabeth , Ropstad Erik , Waterhouse Karin Elisabeth
Published: April 2014

The objective of the study was to compare two different flow cytometers to reveal if there are differences between them and to find the most suitable protocol for analysis of spermatozoa. These two flow cytometers; Cell Lab Quanta™ and Coulter Epics XL, have different principles to calculate cell size, electric volume, and forward scatter (FS), respectively. Flow cytometry is a valuable tool to assess various spermatozoa quality traits simultaneously, such as plasma membrane and acrosome integrity. A double‐ and triple‐stain combination was performed to compare evaluation of these two parameters by both flow cytometers and to assess the need of a fluorescent probe to identify the spermatozoa. Propidium iodide was used to assess the proportion of dead spermatozoa, whereas Alexa Fluor® 488 conjugated peanut agglutinin (PNA‐ Alexa 488) was used to evaluate the percentage of acrosome intact and acrosome–reacted cells or degenerated cells. In the triple‐stain protocol, MitoTracker® Orange (MO) was included to test the capacity of this probe to discriminate spermatozoa from egg yolk and debris particles present in the semen sample. Cryopreserved semen from 13 Norwegian Red bulls was included in the study and the semen was evaluated immediately after thawing and after 3 hr incubation at 37°C. The results show that there is good agreement between the instruments. Nevertheless, a significant difference was found in percentages of acrosome intact live spermatozoa (% AIL) when including MO as a spermatozoa identification probe, compared to assessment without MO, with the Coulter Epics XL, while no significant difference was found when including the probe with the Cell Lab Quanta. In conclusion, the results show that cell size measurement based on electronic volume used by the Cell Lab Quanta flow cytometer is more accurate than FS used by the Coulter Epics XL flow cytometer in identification of spermatozoa. © 2014 International Society for Advancement of Cytometry
IRF4 at the crossroads of effector T‐cell fate decision
Authors: Huber Magdalena , Lohoff Michael
Published: April 2014

Interferon regulatory factor 4 (IRF4) is a transcription factor that is expressed in hematopoietic cells and plays pivotal roles in the immune response. Originally described as a lymphocyte‐specific nuclear factor, IRF4 promotes differentiation of naïve CD4+ T cells into T helper 2 (Th2), Th9, Th17, or T follicular helper (Tfh) cells and is required for the function of effector regulatory T (eTreg) cells. Moreover, IRF4 is essential for the sustained differentiation of cytotoxic effector CD8+ T cells, for CD8+ T‐cell memory formation, and for differentiation of naïve CD8+ T cells into IL‐9‐producing (Tc9) and IL‐17‐producing (Tc17) CD8+ T‐cell subsets. In this review, we focus on recent findings on the role of IRF4 during the development of CD4+ and CD8+ T‐cell subsets and the impact of IRF4 on T‐cell‐mediated immune responses in vivo.
iNKT‐cell help to B cells: A cooperative job between innate and adaptive immune responses
Authors: Dellabona Paolo , Abrignani Sergio , Casorati Giulia
Published: April 2014

T‐cell help to B lymphocytes is one of the most important events in adaptive immune responses in health and disease. It is generally delivered by cognate CD4+ T follicular helper (TFH) cells via both cell‐to‐cell contacts and soluble mediators, and it is essential for both the clonal expansion of antibody (Ab)‐secreting B cells and memory B‐cell formation. CD1d‐restricted invariant natural killer T (iNKT) cells are a subset of innate‐like T lymphocytes that rapidly respond to stimulation with specific lipid antigens (Ags) that are derived from infectious pathogens or stressed host cells. Activated iNKT cells produce a wide range of cytokines and upregulate costimulatory molecules that can promote activation of dendritic cells (DCs), natural killer (NK) cells, and T cells. A decade ago, we discovered that iNKT cells can help B cells to proliferate and to produce IgG Abs in vitro and in vivo. This adjuvant‐like function of Ag‐activated iNKT cells provides a flexible set of helper mechanisms that expand the current paradigm of T‐cell–B‐cell interaction and highlights the potential of iNKT‐cell targeting vaccine formulations.
A randomized controlled trial of an Internet‐based cognitive–behavioural intervention for non‐specific chronic pain: An effectiveness and cost‐effectiveness study
Authors: de Boer M.J. , Versteegen G.J. , Vermeulen K.M. , Sanderman R. , Struys M.M.R.F.
Published: April 2014

Background

Cognitive–behavioural treatment can nowadays be delivered through the Internet. This form of treatment can have various advantages with regard to availability and accessibility. Previous studies showed that Internet‐based treatment for chronic pain is effective compared to waiting‐list control groups.

Methods

We conducted a randomized controlled trial comparing an Internet‐based cognitive–behavioural intervention with e‐mail therapist contact to a face‐to‐face cognitive–behavioural group intervention. Of the 72 participants who were randomly assigned to an Internet or a group course, 50 participants completed the intervention. Participants were assessed at baseline (T0), immediately after the 7‐week course (T1) and at the booster session 2 months later (T2). Pain‐related catastrophizing was the primary outcome measure. Pain intensity, fatigue, pain‐related interference, locus of control, pain coping, global health‐related quality of life and medical expenses were secondary outcome variables.

Results

Significant improvement was found on catastrophizing, pain coping, locus of control and aspects of global health‐related quality of life in both the Internet and the group courses directly after the course and at the booster session. Pain intensity was improved in both courses at the booster session. At T2, improvement in catastrophizing, pain intensity, pain coping and some quality of life dimensions was significantly greater in completers of the Internet course than in the group course. Furthermore, the Internet course was cost‐effective compared to the group course.

Conclusions

We conclude that the Internet‐based cognitive–behavioural intervention was at least as effective as the face‐to‐face group intervention and, on some outcome measures appeared to be even more effective.
Investigation of Manganese–Iron Oxide Materials based on Manganese Ores as Oxygen Carriers for Chemical Looping with Oxygen Uncoupling (CLOU)
Authors: Mohammad Pour Nasim , Azimi Golnar , Leion Henrik , Rydén Magnus , Mattisson Tobias , Lyngfelt Anders
Published: April 2014

Oxygen carrier materials were synthesized using five different types of manganese ores with addition of iron oxide (Fe2O3), and they were investigated for their reactivity and properties in chemical looping with oxygen uncoupling (CLOU). Two different Mn/Fe molar ratios (1:2 and 2:1) were examined. The samples were manufactured by using a lab‐scale extrusion method followed by sintering at 950 °C for 4 h. To measure their reactivity, the materials were exposed to gaseous CH4 and syngas (50:50 CO/H2) as well as solid fuel (petroleum coke), in a batch fluidized‐bed reactor. With CH4, the materials based on ores from Brazil and Gabon with a Mn/Fe molar ratio 2:1 showed the best reactivity. For reduction using syngas, samples based on Eastern European and South African ores provided higher amounts of oxygen equivalent, up to 3–5 % of their mass. To investigate the ability of the samples to release gas‐phase oxygen, solid fuel experiments using 0.1 g of petroleum coke in a bed of 10 g oxygen carrier were performed at 950 °C with Brazilian, Gabon, and Eastern European ores. In these solid fuel tests samples with a Mn/Fe molar ratio of 1:2 showed higher uncoupling rates. Based on X‐ray diffraction analysis, the primary phase detected in all fresh particles was the oxidized form of MnyFe1−yOx, that is, bixbyite [(Mn,Fe)2O3]. All of the particles showed sufficiently high crushing strength (>2 N) and a reasonable attrition resistance (attrition index <6 wt % h−1). This suggests that the materials could be suitable for practical applications. It is concluded that the oxygen carriers made by manganese ores have the potential to be used as oxygen carriers for chemical‐looping combustion and chemical looping with oxygen uncoupling.