bluuebunny/crossref_metadata_2025 huggingface dataset:
Flexible Transparent Reduced Graphene Oxide Sensor Coupled with Organic Dye Molecules for Rapid Dual‐Mode Ammonia Gas Detection
Authors: Duy Le Thai , Trung Tran Quang , Dang Vinh Quang , Hwang Byeong‐Ung , Siddiqui Saqib , Son Il‐Yung , Yoon Seung Kyun , Chung Dong June , Lee Nae‐Eung
Published: April 2016

Flexible chemical sensors utilizing chemically sensitive nanomaterials are of great interest for wearable sensing applications. However, obtaining high performance flexible chemical sensors with high sensitivity, fast response, transparency, stability, and workability at ambient conditions is still challenging. Herein, a newly designed flexible and transparent chemical sensor of reduced graphene oxide (R‐GO) coupled with organic dye molecules (bromophenol blue) is introduced. This device has promising properties such as high mechanical flexibility (>5000 bending cycles with a bending radius of 0.95 cm) and optical transparency (>60% in the visible region). Furthermore, stacking the water‐trapping dye layer on R‐GO enables a higher response as well as workability in a large relative humidity range (up to 80%), and dual‐mode detection capabilities of colorimetric and electrical sensing for NH3 gas (5–40 ppm). These advantageous attributes of the flexible and transparent R‐GO sensor coupled with organic dye molecules provide great potential for real‐time monitoring of toxic gas/vapor in future practical chemical sensing at room conditions in wearable electronics.
Combinatorial Study of Temperature‐Dependent Nanostructure and Electrical Conduction of Polymer Semiconductors: Even Bimodal Orientation Can Enhance 3D Charge Transport
Authors: Park Sangsik , Lee Moo Hyung , Ahn Kwang Seok , Choi Hyun Ho , Shin Jihye , Xu Jie , Mei Jianguo , Cho Kilwon , Bao Zhenan , Lee Dong Ryeol , Kang Moon Sung , Kim Do Hwan
Published: April 2016

Temperature‐dependent (80–350 K) charge transport in polymer semiconductor thin films is studied in parallel with in situ X‐ray structural characterization at equivalent temperatures. The study is conducted on a pair of isoindigo‐based polymers containing the same π‐conjugated backbone with different side chains: one with siloxane‐terminated side chains (PII2T‐Si) and the other with branched alkyl‐terminated side chains (PII2T‐Ref). The different chemical moiety in the side chain results in a completely different film morphology. PII2T‐Si films show domains of both edge‐on and face‐on orientations (bimodal orientation) while PII2T‐Ref films show domains of edge‐on orientation (unimodal orientation). Electrical transport properties of this pair of polymers are also distinctive, especially at high temperatures (>230 K). Smaller activation energy (E
A) and larger pre‐exponential factor (μ
0) in the mobility‐temperature Arrhenius relation are obtained for PII2T‐Si films when compared to those for PII2T‐Ref films. The results indicate that the more effective transport pathway is formed for PII2T‐Si films than for the other, despite the bimodally oriented film structure. The closer π–π packing distance, the longer coherence length of the molecular ordering, and the smaller disorder of the transport energy states for PII2T‐Si films altogether support the conduction to occur more effectively through a system with both edge‐on and face on orientations of the conjugated molecules. Reminding the 3D nature of conduction in polymer semiconductor, our results suggest that the engineering rules for advanced polymer semiconductors should not simply focus on obtaining films with conjugated backbone in edge‐on orientation only. Instead, the engineering should also encounter the contribution of the inevitable off‐directional transport process to attain effective transport from polymer thin films.
Designing Colloidal Molecules with Microfluidics
Authors: Shen Bingqing , Ricouvier Joshua , Malloggi Florent , Tabeling Patrick
Published: April 2016

The creation of new colloidal materials involves the design of functional building blocks. Here, a microfluidic method for designing building blocks one by one, at high throughput, with a broad range of shapes is introduced. The method exploits a coupling between hydrodynamic interactions and depletion forces that controls the configurational dynamics of droplet clusters traveling in microfluidic channels. Droplet clusters can be solidified in situ with UV. By varying the flow parameters, clusters are prescribed a given size, geometry, chemical and/or magnetic heterogeneities enabling local bonding. Compact structures (chains, triangles, diamonds, tetrahedrons,...) and noncompact structures, such as crosses and T, difficult to obtain with current techniques are produced. Size dispersions are small (2%) and throughputs are high (30 000 h−1). The work opens a new pathway, based on microfluidics, for designing colloidal building blocks with a potential to enable the creation of new materials.
High‐Performance Polymer Solar Cells Based on a Wide‐Bandgap Polymer Containing Pyrrolo[3,4‐f]benzotriazole‐5,7‐dione with a Power Conversion Efficiency of 8.63%
Authors: Lan Liuyuan , Chen Zhiming , Hu Qin , Ying Lei , Zhu Rui , Liu Feng , Russell Thomas P. , Huang Fei , Cao Yong
Published: April 2016

A novel donor–acceptor type conjugated polymer based on a building block of 4,8‐di(thien‐2‐yl)‐6‐octyl‐2‐octyl‐5H‐pyrrolo[3,4‐f]benzotriazole‐5,7(6H)‐dione (TZBI) as the acceptor unit and 4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)­benzo­[1,2‐b:4,5‐b′]dithiophene as the donor unit, named as PTZBIBDT, is developed and used as an electron‐donating material in bulk‐heterojunction polymer solar cells. The resulting copolymer exhibits a wide bandgap of 1.81 eV along with relatively deep highest occupied molecular orbital energy level of −5.34 eV. Based on the optimized processing conditions, including thermal annealing, and the use of a water/alcohol cathode interlayer, the single‐junction polymer solar cell based on PTZBIBDT:PC71BM ([6,6]‐phenyl‐C71‐butyric acid methyl ester) blend film affords a power conversion efficiency of 8.63% with an open‐circuit voltage of 0.87 V, a short circuit current of 13.50 mA cm−2, and a fill factor of 73.95%, which is among the highest values reported for wide‐bandgap polymers‐based single‐junction organic solar cells. The morphology studies on the PTZBIBDT:PC71BM blend film indicate that a fibrillar network can be formed and the extent of phase separation can be mani­pulated by thermal annealing. These results indicate that the TZBI unit is a very promising building block for the synthesis of wide‐bandgap polymers for high‐performance single‐junction and tandem (or multijunction) organic solar cells.
Molybdenum Disulfide/Nitrogen‐Doped Reduced Graphene Oxide Nanocomposite with Enlarged Interlayer Spacing for Electrocatalytic Hydrogen Evolution
Authors: Tang Yu‐Jia , Wang Yu , Wang Xiao‐Li , Li Shun‐Li , Huang Wei , Dong Long‐Zhang , Liu Chun‐Hui , Li Ya‐Fei , Lan Ya‐Qian
Published: April 2016

Facile design of low‐cost and highly active catalysts from earth‐abundant elements is favorable for the industrial application of water splitting. Here, a simple strategy to synthesize an ultrathin molybdenum disulfide/nitrogen‐doped reduced graphene oxide (MoS2/N‐RGO‐180) nanocomposite with the enlarged interlayer spacing of 9.5 Å by a one‐step hydrothermal method is reported. The synergistic effects between the layered MoS2 nanosheets and N‐doped RGO films contribute to the high activity for hydrogen evolution reaction (HER). MoS2/N‐RGO‐180 exhibits the excellent catalytic activity with a low onset potential of −5 mV versus reversible hydrogen elelctrode (RHE), a small Tafel slope of 41.3 mV dec−1, a high exchange current density of 7.4 × 10−4 A cm−2, and good stability over 5 000 cycles under acidic conditions. The HER performance of MoS2/N‐RGO‐180 nanocomposite is superior to the most reported MoS2‐based catalysts, especially its onset potential and exchange current density. In this work, a novel and simple method to the preparation of low‐cost MoS2‐based electrocatalysts with the extraordinary HER performance is presented.
Muropeptides in Pseudomonas aeruginosa and their Role as Elicitors of β‐Lactam‐Antibiotic Resistance
Authors: Lee Mijoon , Dhar Supurna , De Benedetti Stefania , Hesek Dusan , Boggess Bill , Blázquez Blas , Mathee Kalai , Mobashery Shahriar
Published: April 2016

Muropeptides are a group of bacterial natural products generated from the cell wall in the course of its turnover. These compounds are cell‐wall recycling intermediates and are also involved in signaling within the bacterium. However, the identity of these signaling molecules remains elusive. The identification and characterization of 20 muropeptides from Pseudomonas aeruginosa is described. The least abundant of these metabolites is present at 100 and the most abundant at 55,000 molecules per bacterium. Analysis of these muropeptides under conditions of induction of resistance to a β‐lactam antibiotic identified two signaling muropeptides (N‐acetylglucosamine‐1,6‐anhydro‐N‐acetylmuramyl pentapeptide and 1,6‐anhydro‐N‐acetylmuramyl pentapeptide). Authentic synthetic samples of these metabolites were shown to activate expression of β‐lactamase in the absence of any β‐lactam antibiotic, thus indicating that they serve as chemical signals in this complex biochemical pathway.
Von komplexen Naturstoffen zu synthetisch leicht zugänglichen Mimetika mithilfe von computergestütztem De‐novo‐Design
Authors: Friedrich Lukas , Rodrigues Tiago , Neuhaus Claudia S. , Schneider Petra , Schneider Gisbert
Published: April 2016

Diese Konzeptstudie präsentiert einen neuen Ansatz für den Entwurf Naturstoff‐inspirierter chemischer Verbindungen mit gewünschten pharmakologischen Eigenschaften. Wir stellen hier das computergestützte De‐novo‐Design von synthetisch zugänglichen Mimetika des strukturell komplexen, pflanzlichen Sesquiterpens (−)‐Englerin A vor. Wir synthetisierten leitstrukturähnliche Verbindungen ausgehend von käuflich verfügbaren Grundbausteinen und testeten diese auf ihre Aktivität gegen mehrere mit einem Computerprogramm vorhergesagte makromolekulare Targets. Sowohl die Designvorlage (−)‐Englerin A als auch deren niedermolekularen Mimetika zeigten nanomolare Bindungsaffinitäten und blockierten den Kalziumkanal TRPM8 (transient receptor potential melastatin 8) in einem zellbasiertem Assay. Die mit dem Computerverfahren erhaltene neuartige Leitstruktur besitzt keine ersichtliche Targetpromiskuität oder Frequent‐Hitter‐Eigenschaften.
Formation and Redox Interconversion of Niobium Methylidene and Methylidyne Complexes
Authors: Searles Keith , Smith Kyle T. , Kurogi Takashi , Chen Chun‐Hsing , Carroll Patrick J. , Mindiola Daniel J.
Published: April 2016

The niobium methylidene [{(Ar′O)2Nb}2(μ2‐Cl)2(μ2‐CH2)] (2) can be cleanly prepared via thermolysis or photolysis of [(Ar′O)2Nb(CH3)2Cl] (1) (OAr′=2,6‐bis(diphenylmethyl)‐4‐tert‐butylphenoxide). Reduction of 2 with two equivalents of KC8 results in formation of the first niobium methylidyne [K][{(Ar′O)2Nb}2(μ2‐CH)(μ2‐H)(μ2‐Cl)] (3) via a binuclear α‐hydrogen elimination. Oxidation of 3 with two equiv of ClCPh3 reforms 2. In addition to solid state X‐ray analysis, all these complexes were elucidated via multinuclear NMR experiments and isotopic labelling studies, including a crossover experiment, support the notion for a radical mechanism as well as a binuclear α‐hydrogen abstraction pathway being operative in the formation of 2 from 1.
Enantioselective Organocatalytic Construction of Spiroindane Derivatives by Intramolecular Friedel–Crafts‐Type 1,4‐Addition
Authors: Yoshida Keisuke , Itatsu Yukihiro , Fujino Yuta , Inoue Hiroki , Takao Ken‐ichi
Published: April 2016

The highly enantioselective organocatalytic construction of spiroindanes containing an all‐carbon quaternary stereocenter by intramolecular Friedel–Crafts‐type 1,4‐addition is described. The reaction was catalyzed by a cinchonidine‐based primary amine and accelerated by water and p‐bromophenol. A variety of spiro compounds containing quaternary stereocenters were obtained with excellent enantioselectivity (up to 95 % ee). The reaction was applied to the asymmetric formal synthesis of the spirocyclic natural products (−)‐cannabispirenones A and B.
Iridium‐Catalyzed Enantioselective Hydroalkynylation of Enamides for the Synthesis of Homopropargyl Amides
Authors: Bai Xiao‐Yan , Wang Zi‐Xuan , Li Bi‐Jie
Published: April 2016

Reported is an iridium‐catalyzed asymmetric hydroalkynylation of enamides with terminal alkynes. The reaction occurs regioselectively at the β‐position of an enamide to produce homopropargyl amides. Good to high enantioselectivity was observed with an iridium complex ligated by a chiral bis(phosphine) ligand. This method provides a straightforward route to synthesize chiral homopropargyl amides with a stereocenter β to the amide.
Selenium‐Enriched Nickel Selenide Nanosheets as a Robust Electrocatalyst for Hydrogen Generation
Authors: Wang Fengmei , Li Yuanchang , Shifa Tofik Ahmed , Liu Kaili , Wang Feng , Wang Zhenxing , Xu Peng , Wang Qisheng , He Jun
Published: April 2016

To address the urgent need for clean and sustainable energy, the rapid development of hydrogen‐based technologies has started to revolutionize the use of earth‐abundant noble‐metal‐free catalysts for the hydrogen evolution reaction (HER). Like the active sites of hydrogenases, the cation sites of pyrite‐type transition‐metal dichalcogenides have been suggested to be active in the HER. Herein, we synthesized electrodes based on a Se‐enriched NiSe2 nanosheet array and explored the relationship between the anion sites and the improved hydrogen evolution activity through theoretical and experimental studies. The free energy for atomic hydrogen adsorption is much lower on the Se sites (0.13 eV) than on the Ni sites (0.87 eV). Notably, this electrode benefits from remarkable kinetic properties, with a small overpotential of 117 mV at 10 mA cm−2, a low Tafel slope of 32 mV per decade, and excellent stability. Control experiments showed that the efficient conversion of H+ into H2 is due to the presence of an excess of selenium in the NiSe2 nanosheet surface.
Cu–S‐(propyl)‐2‐aminobenzothioate on magnetic nanoparticles: highly efficient and reusable catalyst for synthesis of polyhydroquinoline derivatives and oxidation of sulfides
Authors: Ghorbani‐Choghamarani Arash , Tahmasbi Bahman , Moradi Parisa , Havasi Nasrin
Published: April 2016

Cu–S‐(propyl)‐2‐aminobenzothioate supported on functionalized Fe3O4 magnetic nanoparticles is reported as a reusable and highly efficient nanocatalyst for the one‐pot synthesis of polyhydroquinoline derivatives and also for selective oxidation of sulfides to sulfoxides. The prepared nanoparticles were characterized using Fourier transform infrared spectroscopy, vibrating sample magnetometry, thermogravimetric analysis, transmission and scanning electron microscopies, energy‐dispersive X‐ray spectroscopy, X‐ray diffraction, inductively coupled plasma atomic emission spectroscopy and atomic absorption spectroscopy. The nanocatalyst was easily recovered using an external magnet and reused several times without significant loss of its catalytic efficiency. Copyright © 2016 John Wiley & Sons, Ltd.
SNF5 is Involved in Suppression of Hepatocellular Carcinoma Progression via TGF‐Beta 1 Signaling
Authors: Sun Hongmiao , Zhong Xinping , Wang Chunyu , Wang Shengli , Lin Lin , Zou Renlong , Wu Yi , Sun Ning , Sun Ge , Wen Tao , Chi Zhi‐Hong , Zhao Yue
Published: April 2016

SNF5 (SMARCB1/INI1/BAF47), a core subunit of SWI/SNF complex, has been reported to modulate cell proliferation and apoptosis. Genetic evidence has suggested that SNF5 participates in tumor suppression. However, the detailed biological function and underlying mechanisms of SNF5 in hepatocellular carcinoma (HCC) progression remain unclear. Here, SNF5 expression reduction in HCC tissues compared with the adjacent non‐cancerous tissues has been demonstrated. Importantly, the results showed that reduced SNF5 expression has a strong correlation with worse overall survival of HCC patients. The data demonstrated that knockdown of SNF5 significantly promoted cell growth and migration in Hep3B and HCCLM3 cell lines. Interestingly, it was found that SNF5 suppressed transforming growth factor‐β1 (TGF‐β1) expression, and SNF5 mRNA expression was negatively correlated with TGF‐β1 in HCC tissues. Furthermore, depletion of SNF5 attenuated the sensitivity of HCC cells to sorafenib. Thus, the data suggested that SNF5 may participate in HCC suppression, and reduced expression of SNF5 correlates with the poor differentiation and prognosis of HCC, indicating that SNF5 might be an important prognostic biomarker and promising therapeutic target for HCC. Anat Rec, 299:869–877, 2016. © 2016 Wiley Periodicals, Inc.
Nailfold Videocapillaroscopic Features and Other Clinical Risk Factors for Digital Ulcers in Systemic Sclerosis: A Multicenter, Prospective Cohort Study
Authors: Cutolo Maurizio , Herrick Ariane L. , Distler Oliver , Becker Mike O. , Beltran Emma , Carpentier Patrick , Ferri Clodoveo , Inanç Murat , Vlachoyiannopoulos Panayiotis , Chadha‐Boreham Harbajan , Cottreel Emmanuelle , Pfister Thomas , Rosenberg Daniel , Torres Juan V. , Smith Vanessa ,   on behalf of the CAP Study Investigators
Published: April 2016

Objective

To identify nailfold videocapillaroscopic features and other clinical risk factors for new digital ulcers (DUs) during a 6‐month period in patients with systemic sclerosis (SSc).

Methods

In this multicenter, prospective, observational cohort study, the videoCAPillaroscopy (CAP) study, we evaluated 623 patients with SSc from 59 centers (14 countries). Patients were stratified into 2 groups: a DU history group and a no DU history group. At enrollment, patients underwent detailed nailfold videocapillaroscopic evaluation and assessment of demographic characteristics, DU status, and clinical and SSc characteristics. Risk factors for developing new DUs were assessed using univariable and multivariable logistic regression (MLR) analyses.

Results

Of the 468 patients in the DU history group (mean ± SD age 54.0 ± 13.7 years), 79.5% were female, 59.8% had limited cutaneous SSc, and 22% developed a new DU during follow‐up. The strongest risk factors for new DUs identified by MLR in the DU history group included the mean number of capillaries per millimeter in the middle finger of the dominant hand, the number of DUs (categorized as 0, 1, 2, or ≥3), and the presence of critical digital ischemia. The receiver operating characteristic (ROC) of the area under the curve (AUC) of the final MLR model was 0.738 (95% confidence interval [95% CI] 0.681–0.795). Internal validation through bootstrap generated a ROC AUC of 0.633 (95% CI 0.510–0.756).

Conclusion

This international prospective study, which included detailed nailfold videocapillaroscopic evaluation and extensive clinical characterization of patients with SSc, identified the mean number of capillaries per millimeter in the middle finger of the dominant hand, the number of DUs at enrollment, and the presence of critical digital ischemia at enrollment as risk factors for the development of new DUs.
New Perspectives in Rheumatology: Avoiding Antimalarial Toxicity
Authors: Rosenbaum James T. , Mount George R. , Youssef Jameel , Lin Phoebe
Published: April 2016

This report inaugurates New Perspectives in Rheumatology, a series of authoritative articles that focus on recent scientific and clinical developments and their potential to reshape rheumatology practice. Anticipated topics include the implementation of new guidelines and emerging information from clinical and translational research.

Richard J. Bucala, MD, PhD

Editor‐in‐Chief

Robert Terkeltaub, MD

Co‐Editor and Review Article Editor
Epigenetic Reprogramming in Naive CD4+ T Cells Favoring T Cell Activation and Non‐Th1 Effector T Cell Immune Response as an Early Event in Lupus Flares
Authors: Coit Patrick , Dozmorov Mikhail G. , Merrill Joan T. , McCune W. Joseph , Maksimowicz‐McKinnon Kathleen , Wren Jonathan D. , Sawalha Amr H.
Published: April 2016

Objective

Systemic lupus erythematosus (SLE) is a relapsing autoimmune disease that affects multiple organ systems. T cells play an important role in the pathogenesis of lupus; however, early T cell events triggering disease flares are incompletely understood. This study was undertaken to examine DNA methylation in naive CD4+ T cells from lupus patients to determine if epigenetic remodeling in CD4+ T cells is an early event in lupus flares.

Methods

A total of 74 lupus patients with an SLE Disease Activity Index score of 0–18 were included. Naive CD4+ T cells were isolated from peripheral blood samples, and DNA was extracted for genome‐wide methylation assessment. RNA was also extracted from a subset of patients to determine the relationship between epigenetic changes and transcription activity using RNA sequencing and microRNA arrays.

Results

We demonstrated that naive CD4+ T cells in lupus undergo an epigenetic proinflammatory shift, implicating effector T cell responses in lupus flare. This epigenetic landscape change occurs without changes in expression of the corresponding genes, poises naive CD4+ T cells for Th2, Th17, and follicular helper T cell immune responses, and opposes inhibitory transforming growth factor β signaling. Bioinformatics analyses indicate that the epigenetic modulator EZH2 might play an important role in shifting the epigenetic landscape, with increased disease activity in lupus naive CD4+ T cells. Further, the expression of microRNA‐26a, which is sensitive to glucose availability and targets EZH2, was negatively correlated with disease activity in lupus patients.

Conclusion

An epigenetic landscape shift in naive CD4+ T cells that favors T cell activation and non‐Th1 immune responses predates transcription activity and correlates with lupus activity. A role for EZH2 dysregulation in triggering lupus flares warrants further investigation.
A Multicenter, Randomized, Double‐Blind, Placebo‐Controlled Study to Evaluate the Efficacy and Safety of Treatment With Sirukumab (CNTO 136) in Patients With Active Lupus Nephritis
Authors: Rovin Brad H. , van Vollenhoven Ronald F. , Aranow Cynthia , Wagner Carrie , Gordon Robert , Zhuang Yanli , Belkowski Stanley , Hsu Benjamin
Published: April 2016

Objective

To assess the efficacy and safety of sirukumab, an anti–interleukin‐6 monoclonal antibody, for the treatment of patients with active lupus nephritis (LN).

Methods

Patients with class III or class IV LN (as determined by renal biopsy within 14 months of randomization) who had persistent proteinuria (>0.5 gm/day) despite receiving immunosuppressive therapy and who were being treated with stable doses of a renin‐angiotensin system blocker were randomized (5:1) to receive treatment with sirukumab at a dose of 10 mg/kg intravenously (n = 21) or placebo (n = 4) every 4 weeks through week 24. The primary end point was the percent reduction in proteinuria (measured as the protein‐to‐creatinine [P:C] ratio in a 12‐hour urine collection) from baseline to week 24.

Results

Twenty‐five patients were enrolled, of whom 19 (76.0%) completed treatment through week 24 and 6 (24.0%) discontinued the study agent early, with 5 of the 6 discontinuing due to adverse events. At week 24, the median percent change in proteinuria from baseline to week 24 in sirukumab‐treated patients was 0.0% (95% confidence interval −61.8, 39.6). In contrast, the 4 placebo‐treated patients showed an increase in proteinuria (median percent reduction −43.3%) at week 24. Of note, a subset of 5 sirukumab‐treated patients had ≥50% improvement in their P:C ratio through week 28. In the sirukumab group, 47.6% of patients experienced ≥1 serious adverse event through week 40; most were infection‐related. No deaths or malignancies occurred. No serious adverse events were observed in the 4 placebo‐treated patients.

Conclusion

This proof‐of‐concept study did not demonstrate the anticipated efficacy nor did it demonstrate an acceptable safety profile for sirukumab treatment in this population of patients with active LN receiving concomitant immunosuppressive treatment.
Semiquantitative Imaging Biomarkers of Knee Osteoarthritis Progression: Data From the Foundation for the National Institutes of Health Osteoarthritis Biomarkers Consortium
Authors: Collins Jamie E. , Losina Elena , Nevitt Michael C. , Roemer Frank W. , Guermazi Ali , Lynch John A. , Katz Jeffrey N. , Kent Kwoh C. , Kraus Virginia B. , Hunter David J.
Published: April 2016

Objective

To determine the association between changes in semiquantitative magnetic resonance imaging (MRI) biomarkers over 24 months and radiographic and pain progression over 48 months in knees with mild‐to‐moderate osteoarthritis (OA).

Methods

We undertook a nested case–control study as part of the Foundation for the National Institutes of Health Biomarkers Consortium Project. We used multivariable logistic regression models to examine the association between change over 24 months in semiquantitative MRI markers and radiographic and pain progression in knee OA. MRIs were read according to the MRI OA Knee Score system. We focused on changes in cartilage, osteophytes, meniscus, bone marrow lesions, Hoffa‐synovitis, and effusion‐synovitis.

Results

The most parsimonious model included changes in cartilage thickness and surface area, effusion‐synovitis, Hoffa‐synovitis, and meniscal morphology (C statistic 0.740). Compared with no worsening, worsening in cartilage thickness in ≥3 subregions was associated with 2.8‐fold (95% confidence interval [95% CI] 1.3–5.9) greater odds of being a case, and worsening in cartilage surface area in ≥3 subregions was associated with 2.4‐fold (95% CI 1.3–4.4) greater odds of being a case. Worsening of meniscal morphology in any region was associated with 2.2‐fold (95% CI 1.3–3.8) greater odds of being a case. Worsening effusion‐synovitis and Hoffa‐synovitis were also associated with a greater odds of being a case (odds ratios 2.7 and 2.0, respectively).

Conclusion

Twenty‐four–month changes in cartilage thickness, cartilage surface area, effusion‐synovitis, Hoffa‐synovitis, and meniscal morphology were independently associated with OA progression, suggesting that these factors may serve as efficacy biomarkers in clinical trials of disease‐modifying interventions for knee OA.
Functional Interaction of the Ankylosing Spondylitis–Associated Endoplasmic Reticulum Aminopeptidase 2 With the HLA–B*27 Peptidome in Human Cells
Authors: Martín‐Esteban Adrian , Guasp Pablo , Barnea Eilon , Admon Arie , López de Castro José A.
Published: April 2016

Objective

To determine the influence of endoplasmic reticulum aminopeptidase 2 (ERAP‐2) expression on the HLA–B*27 peptidome in live cells.

Methods

Using immunoaffinity chromatography and acid extraction, HLA–B*27:05–bound peptides were isolated from 2 ERAP‐2–negative lymphoblastoid cell lines and 1 ERAP‐2–positive lymphoblastoid cell line expressing functionally indistinguishable ERAP‐1 variants. More than 2,000–4,000 B*27:05 ligands were identified from each cell line, and their relative abundance was established by quantitative tandem mass spectrometry and MaxQuant‐based peptide analyses. Pairwise comparisons were used to determine the structural features of peptides whose relative abundance was dependent on the presence of ERAP‐2. Synthetic peptide digestions were performed with recombinant ERAP‐1 and ERAP‐2. Peptide affinity was estimated with standard algorithms.

Results

The B*27:05 peptidome from ERAP‐2–positive cells showed 3–4% fewer peptides with N‐terminal basic residues than did the peptidome from ERAP‐2–negative cells. Among the shared peptides, those most abundant in the presence of ERAP‐2 included more nonamers, fewer decamers, and fewer N‐terminal basic residues than the peptides predominant in ERAP‐2–negative cells. These ERAP‐2–dependent changes did not alter the global affinity of the B*27:05 peptidome.

Conclusion

ERAP‐2 significantly influences the B*27:05‐bound peptidome by destroying some ligands and decreasing the abundance of many more ligands with N‐terminal basic residues, while increasing the abundance of nonamers. The former effects are best explained by direct ERAP‐2 trimming. The effects on peptide length might be attributed to ERAP‐2–induced activation of ERAP‐1 trimming. These data support the notion of a peptide‐mediated mechanism as the basis for the association of ERAP‐2 with ankylosing spondylitis. Analogous effects on other major histocompatibility complex class I peptidomes might explain the involvement of ERAP‐2 in HLA–B27–negative spondyloarthritis.
Associations of Circulating Cytokines and Chemokines With Cancer Mortality in Men With Rheumatoid Arthritis
Authors: England Bryant R. , Sokolove Jeremy , Robinson William H. , Thiele Geoffrey M. , Ganti Apar K. , Sayles Harlan , Michaud Kaleb , Caplan Liron , Davis Lisa A. , Cannon Grant W. , Sauer Brian , Singh Namrata , Blair Solow E. , Reimold Andreas M. , Kerr Gail S. , Schwab Pascale , Baker Josh F. , Mikuls Ted R.
Published: April 2016

Objective

To examine the potential of circulating cytokines and chemokines as biomarkers of cancer mortality risk in patients with rheumatoid arthritis (RA).

Methods

Male participants in the Veterans Affairs RA registry were followed up from the time of enrollment until death or December 2013. Cytokines and chemokines were measured in banked serum obtained at the time of enrollment, using a bead‐based multiplex assay, and a previously developed cytokine score was calculated. Vital status and cause of death were determined through the National Death Index. Associations of cytokines with cancer mortality were examined using multivariable competing‐risks regression.

Results

Among 1,190 men with RA, 60 cancer deaths (30 of which were attributable to lung cancer) occurred over 5,307 patient‐years of follow‐up. The patients had a mean age of 64.5 years, had established disease (median duration 8.7 years), were seropositive for rheumatoid factor (81%) or anti–cyclic citrullinated peptide antibody (77%), and frequently had a history of smoking (82% current or former). Seven of 17 analytes examined were individually associated with cancer mortality. The cytokine score was associated with overall cancer (subhazard ratio [SHR] 1.42, 95% confidence interval [95% CI] 1.08–1.85) and lung cancer (SHR 1.86, 95% CI 1.57–2.19) mortality in multivariable analyses. Those in the highest quartile of cytokine scores had a >2‐fold increased risk of overall cancer mortality (P = 0.039) and a 6‐fold increased risk of lung cancer mortality (P = 0.028) relative to the lowest quartile. A synergistic interaction between current smoking and high cytokine score was observed.

Conclusion

Serum cytokines and chemokines are associated with cancer and lung cancer mortality in men with RA, independent of multiple factors including age, smoking status, and prevalent cancer.
The molecular weight and concentration of dextran sulfate affect cell growth and antibody production in CHO cell cultures
Authors: Hyoung Park Jin , Sin Lim Myung , Rang Woo Ju , Won Kim Jong , Min Lee Gyun
Published: April 2016

To investigate the effect of dextran sulfate (DS), a widely used anti‐aggregation agent, on cell growth and monoclonal antibody (mAb) production including the quality attributes, DS with the three different MWs (4,000 Da, 15,000 Da, and 40,000 Da) at various concentrations (up to 1 g/L) was added to suspension cultures of two different recombinant CHO (rCHO) cell lines producing mAb, SM‐0.025 and CS13‐1.00. For both cell lines, the addition of DS, regardless of the MW and concentration of DS used, improved cell growth and viability in the decline phase of growth. However, it increased mAb production only in the CS13‐1.00 cells. Among the three different MWs, 40,000 Da DS was most effective in attenuating cell aggregation during the cultures of CS13‐1.00 cells, and showed the highest maximum mAb concentration. For SM‐0.025 cells, it significantly decreased specific mAb productivity, particularly at a high concentration of DS. Overall, DS addition did not negatively affect the quality attributes of mAbs (aggregation, charge variation, and glycosylation), though its efficacy on mAb quality depended on the MW and concentration of DS and cell lines. For both cell lines, the addition of DS did not affect N‐glycosylation of mAbs and decreased basic charge variants in mAbs. For CS13‐1.00 cells, the mAb monomer increased with the addition of 40,000 Da DS at 0.3–1.0 g/L. Taken together, to maximize the beneficial effect of DS addition on mAb production, the optimal MW and concentration of DS should be determined for each specific rCHO cell line. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:1113–1122, 2016
Continuous bind‐and‐elute protein A capture chromatography: Optimization under process scale column constraints and comparison to batch operation
Authors: Kaltenbrunner Oliver , Diaz Luis , Hu Xiaochun , Shearer Michael
Published: April 2016

Recently, continuous downstream processing has become a topic of discussion and analysis at conferences while no industrial applications of continuous downstream processing for biopharmaceutical manufacturing have been reported. There is significant potential to increase the productivity of a Protein A capture step by converting the operation to simulated moving bed (SMB) mode. In this mode, shorter columns are operated at higher process flow and corresponding short residence times. The ability to significantly shorten the product residence time during loading without appreciable capacity loss can dramatically increase productivity of the capture step and consequently reduce the amount of Protein A resin required in the process. Previous studies have not considered the physical limitations of how short columns can be packed and the flow rate limitations due to pressure drop of stacked columns. In this study, we are evaluating the process behavior of a continuous Protein A capture column cycling operation under the known pressure drop constraints of a compressible media. The results are compared to the same resin operated under traditional batch operating conditions. We analyze the optimum system design point for a range of feed concentrations, bed heights, and load residence times and determine achievable productivity for any feed concentration and any column bed height. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:938–948, 2016
Childhood brand nostalgia: A new conceptualization and scale development
Authors: Shields Alison B. , Johnson Jennifer Wiggins
Published: April 2016

This research seeks to expand the current understanding of nostalgia towards childhood as it relates to consumer brand relationships and provide a framework for better understanding the phenomenon as it appears in both academic and real‐world settings. In this paper, the authors use existing literature on nostalgia and consumer interviews to define childhood brand nostalgia as a positively valenced emotional attachment to a brand because of the brand's association with fond memories of the individual's non‐recent lived past. A scale to measure an individual's childhood brand nostalgia is developed and tested to ensure convergent, discriminant, and predictive validity. The scale is found to capture individual differences in nostalgic feelings towards a single brand, and individuals are found to have varying levels of nostalgic feelings for multiple brands across multiple product categories. This demonstrates the usefulness of this scale in determining a consumer's nostalgia towards a particular brand from their childhood. Copyright © 2016 John Wiley & Sons, Ltd.
Chemical Profile and Antioxidant Properties of Extracts and Essential Oils from Citrus × limon (L.) Burm. cv. Femminello Comune
Authors: Loizzo Monica Rosa , Tundis Rosa , Bonesi Marco , Sanzo Giuseppe Di , Verardi Alessandra , Lopresto Catia Giovanna , Pugliese Alessandro , Menichini Francesco , Balducchi Roberto , Calabrò Vincenza
Published: April 2016

Citrus × limon cv. Femminello Comune (Rutaceae) from Rocca Imperiale (Italy), one of the six Protected Geographical Indication (PGI) Italian lemon crops, has been recently received renewed interest. In this work, fresh and dried peels and leaves were extracted by hydrodistillation, supercritical fluid extraction (SFE), and Soxhlet apparatus. Chemical profile was assessed by gas chromatography (GC) and gas chromatography/mass spectrometry (GC/MS). Except for leaves extracts obtained by Soxhlet apparatus, the monoterpene hydrocarbons fraction dominated. Limonene, γ‐terpinene, and β‐pinene were the main identified compounds. The antioxidant activity was investigated using different in vitro assays namely 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH), ABTS, ferric reducing ability power (FRAP), and β‐carotene bleaching test. In DPPH test, the essential oil obtained by hydrodistillation of fresh peel exhibited the highest activity (IC50 of 1.17 mg/ml). Leaves extracted by SFE showed a good activity in both DPPH and β‐carotene bleaching test with IC50 values of 2.20 and 6.66 mg/ml, respectively. Monoterpene hydrocarbons fraction exhibited a positive Pearson's correlation coefficient with all antioxidant assays. Leaves, often considered waste material, should be considered from a different point because they represent a matrix of indisputable interest.
The effect of the glycolipoprotein extract (G‐90) from earthworm Eisenia foetida on the wound healing process in alloxan‐induced diabetic rats
Authors: Goodarzi Golnaz , Qujeq Durdi , Elmi Maryam M. , Feizi Farideh , Fathai Sadegh
Published: April 2016

Diabetes is now regarded as a major public health problem. The number of patients is estimated to increase to over 439 million cases by 2030. One of the major health clinical problems in patients with diabetes patients is impaired wound healing. Diabetic foot ulcer is a major complication of diabetes mellitus in 12 to 25% of patients, which increases the risk of damage in the limbs or amputation. The earthworm Eisenia foetida glycolipoprotein (as known G‐90) is a blend of macromolecules with some biological properties including mitogenicity, anticoagulation, fibrinolysis, bacteriostatic and antioxidatiaon. Given the biological properties of G‐90, this study was conducted to investigate the effect of extract obtained from the homogenate of Eisenia foetida (G‐90) on the wound healing process in alloxan‐induced diabetic rats. The results of the present study revealed that treatment by using G‐90 can speed up the wound healing process, which is exactly similar to the effect of D‐panthenol treatment in rats. These findings also demonstrated that G‐90 treatment decreases the risk of infection in the wound site compared with D‐panthenol treatment. In addition, histological analysis indicated that a better extracellular matrix formation with increased fibroblast proliferation, neovascularization, collagen synthesis and early epithelial layer formation was observed in G‐90 treated group. Therefore, the G‐90 could be considered as a new wound healing agent introducing promising therapeutic approaches in both human and veterinary medicine. Copyright © 2016 John Wiley & Sons, Ltd.
Nucleotide Binding Preference of the Monofunctional Platinum Anticancer‐Agent Phenanthriplatin
Authors: Riddell Imogen A. , Johnstone Timothy C. , Park Ga Young , Lippard Stephen J.
Published: April 2016

The monofunctional platinum anticancer agent phenanthriplatin generates covalent adducts with the purine bases guanine and adenine. Preferential nucleotide binding was investigated by using a polymerase stop assay and linear DNA amplification with a 163‐base pair DNA double helix. Similarly to cisplatin, phenanthriplatin forms the majority of adducts at guanosine residues, but significant differences in both the number and position of platination sites emerge when comparing results for the two complexes. Notably, the monofunctional complex generates a greater number of polymerase‐halting lesions at adenosine residues than does cisplatin. Studies with 9‐methyladenine reveal that, under abiological conditions, phenanthriplatin binds to the N1 or N7 position of 9‐methyladenine in approximately equimolar amounts. By contrast, comparable reactions with 9‐methylguanine afforded only the N7‐bound species. Both of the 9‐methyladenine linkage isomers (N1 and N7) exist as two diastereomeric species, arising from hindered rotation of the aromatic ligands about their respective platinum–nitrogen bonds. Eyring analysis of rate constants extracted from variable‐temperature NMR spectroscopic data revealed that the activation energies for ligand rotation in the N1‐bound platinum complex and the N7‐linkage isomers are comparable. Finally, a kinetic analysis indicated that phenanthriplatin reacts more rapidly, by a factor of eight, with 9‐methylguanine than with 9‐methyladenine, suggesting that the distribution of lesions formed on double‐stranded DNA is kinetically controlled. In addition, implications for the potent anticancer activity of phenanthriplatin are discussed herein.
Mild and Selective Catalytic Hydrogenation of the C=C Bond in α,β‐Unsaturated Carbonyl Compounds Using Supported Palladium Nanoparticles
Authors: Nagendiran Anuja , Pascanu Vlad , Bermejo Gómez Antonio , González Miera Greco , Tai Cheuk‐Wai , Verho Oscar , Martín‐Matute Belén , Bäckvall Jan‐E.
Published: April 2016

Chemoselective reduction of the C=C bond in a variety of α,β‐unsaturated carbonyl compounds using supported palladium nanoparticles is reported. Three different heterogeneous catalysts were compared using 1 atm of H2: 1) nano‐Pd on a metal–organic framework (MOF: Pd0‐MIL‐101‐NH2(Cr)), 2) nano‐Pd on a siliceous mesocellular foam (MCF: Pd0‐AmP‐MCF), and 3) commercially available palladium on carbon (Pd/C). Initial studies showed that the Pd@MOF and Pd@MCF nanocatalysts were superior in activity and selectivity compared to commercial Pd/C. Both Pd0‐MIL‐101‐NH2(Cr) and Pd0‐AmP‐MCF were capable of delivering the desired products in very short reaction times (10–90 min) with low loadings of Pd (0.5–1 mol %). Additionally, the two catalytic systems exhibited high recyclability and very low levels of metal leaching.
ChemInform Abstract: COMPARISON OF THE STRUCTURES OF TWO POLYANIONIC COMPOUNDS CADMIUM ARSENIC IODIDE (CD4AS2I3) AND CADMIUM PHOSPHORUS CHLORIDE (CD7P4CL6)
Authors: REBBAH A. , DESCHANVRES A.
Published: April 2016

Beide Verbindungen kristallisieren in der Raumgruppe Pa3 mit Z=8 für (I) bzw. Z =4 für (II).
ChemInform Abstract: CALCIUM THIOANTIMONATE (CA2SB2S5)‐A NEW ALKALINE EARTH THIOANTIMONATE(III) WITH THIOANTIMONATE (SB2S4) FOUR‐MEMBERED RINGS
Authors: CORDIER G. , SCHAEFER H. +
Published: April 2016

, kristallisiert in der Raumgruppe P21/c mit Z=4.
ChemInform Abstract: DIFFUSION VON SCHWEFEL IN EINER LEGIERUNG FE‐18%CR
Authors: DE RUGY H. , BARBOUTH N. , OUDAR J.
Published: April 2016

Die Aktivierungsenergie der Diffusion von S in Fe‐18%Cr wurde durch Messungen der S‐Konzentration in der erstarrten Schmelze nach 20 min bis 10 Tage langer Diffusion bei 850‐1200°C mit Hilfe einer 35 S‐Indikator‐Methode zu 44 kcal/mol bestimmt.
ChemInform Abstract: THE SYSTEM THALLIUM MONOBROMIDE/LEAD BROMIDE
Authors: KELLER H.‐L. , HAUEIS D. , NAUJOKAT W.
Published: April 2016

Das Phasendiagramm des Titelsystems ist im Bereich 200 bis 461°C wiedergegeben.
ChemInform Abstract: THE BEHAVIOR OF THE ZINC ELECTRODE IN ALKALINE SOLUTIONS. V. SUPERSATURATED ZINCATE SOLUTIONS
Authors: DIRKSE T. P.
Published: April 2016

Aus Lichtstreuungs‐, Dichte‐ und Viskositätsdaten von durch kathodi‐ sche Behandlung von Zn‐Elektroden in KOH‐Lösung hergestellten übersättigten Zinkatlösungen in Abhängigkeit von der Alterungszeit folgt, daß die gelösten Spezies in solchen Lösungen nicht völlig verschieden von denen in gesättigten oder ungesättigten Zinkatlösungen sind.
ChemInform Abstract: SODIUM THIOCHROMITE. A NEW MATERIAL FOR CATHODES IN SECONDARY LI BATTERIES
Authors: MOSHTEV R. V. , MANEV V. , NASSALEVKSA A. , PISTOIA G. , ICOVI M.
Published: April 2016

Durch elektrochemische Oxidation von NaCrS2 in Li‐Zellen entstehen Phasen des Typs NaxCrS2 ( x 2 0.1), die als Wirtsstrukturen für die Einlagerung von Li" . dienen können.
ChemInform Abstract: SYNTHESIS AND CRYSTAL CHEMISTRY OF LITHIUM THIOANTIMONATE (III) (LI3XSB6‐XS9) (X = 0.33)
Authors: OLIVIER‐FOURCADE J. , IZGHOUTI L. , PHILIPPOT E.
Published: April 2016

Die durch Erhitzen eines Li,S‐Sb2S3‐Gemischs für 48 h auf 480°C dargestellte neue Phase kristallisiert in der Raumgruppe Pl mit Z=1.
ChemInform Abstract: SYNTHESIS AND STRUCTURE OF BARIUM OXOMANGANATE (BA2MNO3)
Authors: SANDER K. , MUELLER‐BUSCHBAUM HK. +
Published: April 2016

Die Darstellung von Einkristallen der Titelverbindung gelingt durch Feststoffreaktion von BaCO3 und MnCO3 in H2‐Atmosphäre zum ersten Mal.
ChemInform Abstract: .SIGMA±PI. CONJUGATION IN BENZYL DERIVATIVES OF TIN AND MERCURY AS PROBED BY TIN‐119 AND MERCURY‐199 RESONANCE
Authors: KITCHING W. , DREW G. , ADCOCK W. , ABEYWICKREMA A. N.
Published: April 2016

Aus Benzylhalogeniden (I) entstehen die Hg‐Verbindungen (II) und (III) nach bekannten Verfahren in guten Ausbeuten.
ChemInform Abstract: EFFECTS OF THE ACIDITIES OF PHENOLS FROM SPECIFIC SUBSTITUENT‐SOLVENT INTERACTIONS. INHERENT SUBSTITUENT PARAMETERS FROM GAS‐PHASE ACIDITIES
Authors: FUJIO M. , MCIVER R. T. JUN. , TAFT R. W.
Published: April 2016

Mittels ICR‐Gleichgewichtskonstanten‐Methode werden, relativ zu Phenol, die Gasphasen‐Aciditäten von 38 m‐ und p‐substituierten Phenolen bestimmt.
ChemInform Abstract: CHIRAL 1,4‐BENZODIAZEPIN‐2‐ONE, TEMPLATE FOR ENANTIOSELECTIVE SYNTHESIS OF α‐AMINO ACIDS AND THEIR α‐DEUTERIO CONGENERS
Authors: DECORTE E. , TOSO R. , SEGA A. , SUNJIC V. , RUZIC‐TOROS Z. , KOJIC‐PRODIC B. , BRESCIANI‐PAHOR N. , NARDIN G. , RANDACCIO L.
Published: April 2016

Metallierung der Benzodiazepinone (I) mit Li‐N(iPr), und Alkylierung der erhaltenen Li‐Template mit dem Chlorester (II) liefert die Alkylierungsprodukte (III), die beim Behandeln mit D2O/D in DMSO H/D‐Austausch unter Bildung der Verbindungen (IV) eingehen.
ChemInform Abstract: METHANOLYSIS OF THE BENZYLIDENEANILINE DERIVATIVES ARC(MME3)=NAR′ (M = SI OR SN)
Authors: SECONI G. , PIRAZZINI G. , RICCI A. , FIORENZA M. , EABORN C.
Published: April 2016

Für die solvolytische Bildung der Benzylidenamine (II) aus den Titelverbindungen (I) werden Geschwindigkeitskonstanten von (0.55‐ 1. 12)‐ l0′5/s ermittelt, wobei ein Zusatz von Base oder Säure (ACOH) die Reaktion beschleunigt.
ChemInform Abstract: A NOTE ON STEREOCHEMICAL OBSERVATIONS OF THE DEPROTONATION OF ETHYL 2‐ALKENOATES
Authors: KREBS E.‐P.
Published: April 2016

Deprotonierung der (E)‐Alkylalkenoate (I) mit 1.2 Moläquiv. LDA in Gegenwart von 1.2 Moläquiv. THF/HMPT [für (Ic) 2.4 Moläquiv.] und anschließende Protonierung mit NH4Cl führen unter Umlagerung der Doppelbindung zu den isomeren Alkenylcarbon‐ säureestern (II) und (III).
ChemInform Abstract: AZIMINES. V. STUDIES ON THE STEREOISOMERISM AT THE N(2),N(3)‐BOND IN 2,3‐DIALKYL‐1‐PHTHALIMIDOAZIMINES
Authors: LEUENBERGER C. , HOESCH L. , DREIDING A. S.
Published: April 2016

Aus N‐Aminophthalimid und Bleitetr.acetat erzeugtes Phthalimidonitren (I) reagiert in situ mit dem Diazabicyclohepten (II) zu dem Azimin (III) und mit den isomeren 1,1′‐Dimethyl‐azoethanen (V) bzw. (VII) zu den Phthalimidoaziminen (VI) bzw. (VIII), wobei in beiden letzten Fällen die Nitrenaddition zu mindestens 95% stereospezifisch verläuft.
ChemInform Abstract: BASE CATALYZED REARRANGEMENTS INVOLVING YLIDE INTERMEDIATES. PART 9. THE REARRANGEMENT REACTIONS OF CYCLIC ALLYLIC AMMONIUM AND SULFONIUM YLIDES
Authors: MAGESWARAN S. , OLLIS W. D. , SUTHERLAND I. O.
Published: April 2016

Die allylischen Ammoniumylide (III) und (XII) sowie das Sulfoniumylid (XV) werden durch Behandlung der Salze (II) ‐ dargestellt durch Reduktion von (I) und anschließende Quatemierung ‐ , (XI) und (XIV) mit wäßrigem NaOH gebildet und meist als kristalline Substanzen isoliert, da ihre [3,2]‐sigmatropen Umlagerungen durch Spannungen in den dabei entstehenden bicyclischen Übergangszuständen verhindert werden.
ChemInform Abstract: A CATIONIC (3,4) SIGMATROPIC REARRANGEMENT
Authors: NISHIZAWA M. , NOYORI R.
Published: April 2016

Durch Erhitzen des Dibromketons (I) mit Fe2(CO)9 in wasserfreiem Benzol bildet sich das Heptadienon (II) neben geringen Mengen nicht‐identifizierterProdukte.