bluuebunny/crossref_metadata_2025 huggingface dataset:
Magnetic Field Enhancement of Organic Light‐Emitting Diodes Based on Electron Donor–Acceptor Exciplex
Authors: Basel Tek , Sun Dali , Baniya Sangita , McLaughlin Ryan , Choi Hyeonho , Kwon Ohyun , Vardeny Z. Valy
Published: November 2015

Reverse intersystem crossing (RISC) from triplet to singlet states has been recently introduced to photophysics of organic chromophores. One type of RISC occurs in donor (D)–acceptor (A) composites that form an exciplex manifold in which the energy difference, ΔEST between the lowest singlet (S1) and triplet (T1) levels of the exciplex is small (<100 meV) thus allowing RISC at room temperature. This adds a delayed component to the photoluminescence emission that is widely known as thermally activated delayed fluorescence. Here, it is found that the electroluminescence in organic light‐emitting diodes (OLED) based on electron D–A exciplex is significantly enhanced (up to ≈40%) by applying magnetic field, due to the existence of an additional spin‐mixing channel between singlet and triplet states in the exciplex. The large magneto‐electroluminescence (MEL) in N,N,N′,N′‐tetrakis(4‐methoxyphenyl)benzidine: tris‐[3‐(3‐pyridyl)mesityl]borane [D–A] based OLEDs is demonstrated. These results are supported by magneto‐photoluminescence (MPL) measurements, and density functional theory calculations. Importantly, it is found that both MEL and MPL are thermally activated indicating the dominant role of the RISC process. The MEL(B) response using the Δg mechanism is analyzed, where the electron and hole g‐values are different from each other because they reside in different molecules.
Facile growth of 1‐D nanowire‐based WO3 thin films with enhanced photoelectrochemical performance
Authors: Ding Jin‐Rui , Kim Kyo‐Seon
Published: November 2015

A flame reactor embedded with a constant tungsten wire feeding system to prepare one‐dimensional (1‐D) nanostructured tungsten oxide thin film for photoelectrochemical (PEC) water splitting was developed. Photoactive vertically‐aligned nanowire‐based WO3 thin films could be obtained with a controlled thickness via a flame vapor deposition process followed by air‐annealing. The PEC performances of WO3 photoelectrodes for different thin film thicknesses were examined. The optimum thickness of WO3 thin film was found to be about 7.2 μm for PEC water splitting based on incident photon‐to‐current efficiency plots and I–V curves. The WO3 prepared with optimum thickness showed better PEC performance than those of recently reported nanostructured WO3 photoanodes. © 2015 American Institute of Chemical Engineers AIChE J, 62: 421–428, 2016
Fast pyrolysis of glucose‐based carbohydrates with added NaCl part 2: Validation and evaluation of the mechanistic model
Authors: Zhou Xiaowei , Mayes Heather B. , Broadbelt Linda J. , Nolte Michael W. , Shanks Brent H.
Published: November 2015

A mechanistic model considering the significant catalytic effects of Na+ on fast pyrolysis of glucose‐based carbohydrates was developed in Part 1 of this study. A computational framework based on continuous distribution kinetics and mass action kinetics was constructed to solve the mechanistic model. Agreement between model yields of various pyrolysis products with experimental data from fast pyrolysis of glucose‐based carbohydrates dosed with NaCl ranging from 0–0.34 mmol/g at 500 °C validated the model and demonstrated the robustness and extendibility of the mechanistic model. The model was able to capture the yields of major and minor products as well as their trends across NaCl concentrations. Modeling results showed that Na+ accelerated the rate of decomposition and reduced the time for complete thermoconversion of carbohydrates. The sharp reduction in the yield of levoglucosan (LVG) from fast pyrolysis of cellulose in the presence of NaCl was mainly caused by reduced decomposition of cellulose chains via end‐chain initiation and depropagation due to Na+ favoring competing dehydration reactions. Analysis of the contributions of reaction pathways showed that the decomposition of LVG made a minor contribution to its yield reduction and contributed less than 0.5% to the final yield of glycolaldehyde from fast pyrolysis of glucose‐based carbohydrates in the presence of NaCl. © 2015 American Institute of Chemical Engineers AIChE J, 62: 778–791, 2016
Osmotic power production from seawater brine by hollow fiber membrane modules: Net power output and optimum operating conditions
Authors: Zhang Sui , Chung Tai‐Shung
Published: November 2015

This study analyzes the net energy output and optimum operating conditions for osmotic power generation from seawater brine based on the currently available hollow fiber membranes in the module scale. Factors that are influential on membrane performances, such as external concentration polarization, internal concentration polarization, salt reverse diffusion, and dilution have been taken into account. Net power density is defined and applied to characterize the efficiency of the PRO system, in terms of power production minus pumping energy, pretreatment cost and energy consumption by pressure drop in the membranes. When using 1 M NaCl as the draw solution and 10 mM NaCl as the feed, it is found that up to 7 W m−2 net power density can be harvested by the PRO system depending on the water sources. Coupling with the existing RO plant is highly beneficial in terms of readily available high pressure source, high salinity and less or negligible pretreatment costs for the draw solution. Sources with higher salt concentrations are preferred. The optimum hydraulic pressure, module length, flow rate to membrane area ratio and feed to draw flow rate ratio have also been analyzed to maximize the net power output. In addition, implications on hollow fiber development are discussed. Fibers with high water permeability, lower structural parameter, good mechanical stability, better fouling resistance, and outer‐selective configurations are recommended for further studies. © 2015 American Institute of Chemical Engineers AIChE J, 62: 1216–1225, 2016
Understanding hydrotropism: A chemical engineering perspective
Authors: Gao Qian , Xiao Jie , Chen Xiao Dong
Published: November 2015

The mechanism of root hydrotropism has been a mystery for many years, due to the complexity of the interactions between the external environment and plants themselves. To gain an engineering perspective, the time‐dependent hydrotropism of a single root has been modeled, initially using a two‐dimensional model. Based on the water and nutrient distribution in rhizosphere as computed with the conservation equations, together with a basic reaction‐kinetics‐type growth model and an intuitive root bending model, it has been found that the root already possesses the property of hydrotropism. For the first time, hydrotropism could be tracked by a process engineering model, which is a new idea based on chemical engineering concept, suggesting an alternative mechanism of hydrotropism. The effects of different initial root widths, lengths, and other growth/transport coefficients on root hydrotropism have then been explored. © 2015 American Institute of Chemical Engineers AIChE J, 62: 1331–1346, 2016
Developmental patterns of bilateral asymmetry in ancestral puebloans
Authors: Waxenbaum Erin B. , Sirak Kendra A.
Published: November 2015

Objectives

Producing and maintaining a bilaterally symmetric phenotype throughout the lifespan is energetically demanding. Over the course of an individual's life, various intrinsic and external stressors impact the growth trajectory. These perturbations can compromise the allocation of energetic resources to processes that maintain developmental precision, potentially resulting in bilateral asymmetry (BA). Because different stressors are present during the lifespan, BA is a valuable tool for examining the unique factors impacting symmetrical growth and development. This study examines BA in paired long bones across a developmental skeletal series.

Methods

The humeri, radii, femora, and tibiae of 198 individuals from Ancestral Puebloan New Mexico (919–1670 CE) are analyzed to explore BA across development. Individuals are separated into five age categories, and by sex when possible, to explore patterns of BA.

Results

Significant BA is found in the bones of the upper limb when the interaction between bone and age is examined. Results suggest that BA in the humerus and radius becomes more right‐biased with age. These directional trends are not observed in the lower limbs. Division into age categories illuminates patterns of asymmetry associated with age‐related activities and physiological maturity, indicating that BA is differentially affected by varying environmental stressors across development.

Conclusions

Our findings support the hypothesis that BA in long bones is influenced by environmental stressors that impact an individual's ability to produce symmetric morphological traits over the lifespan. Right‐biased BA in the upper limb bones indicates that this variation from a symmetric ideal is strongly influenced by handedness resulting from habitual manual activities. Am. J. Hum. Biol. 28:421–430, 2016. © 2015 Wiley Periodicals, Inc.
Occupational exposures and chronic kidney disease: Possible associations with endotoxin and ultrafine particles
Authors: Sponholtz Todd R. , Sandler Dale P. , Parks Christine G. , Applebaum Katie M.
Published: November 2015

Background

Chronic kidney disease (CKD) carries a high public health burden yet there is limited research on occupational factors, which are examined in this retrospective case‐control study.

Methods

Newly diagnosed cases of CKD (n = 547) and controls (n = 508) from North Carolina provided detailed work histories in telephone interviews. Unconditional logistic regression was used to estimate odds ratios (ORs) and 95% confidence intervals (CIs).

Results

There was heterogeneity in the association of CKD and agricultural work, with crop production associated with increased risk and work with livestock associated with decreased risk. Work with cutting/cooling/lubricating oils was associated with a reduced risk. CKD risk was increased for working in dusty conditions.

Conclusions

CKD risk was reduced in subjects with occupational exposures previously reported to involve endotoxin exposure. Further, exposure to dusty conditions was consistently associated with increased risk of glomerulonephritis across industry, suggesting that research on CKD and ultrafine particulates is needed. Am. J. Ind. Med. 59:1–11, 2016. © 2015 Wiley Periodicals, Inc.
Reduced sinonasal levels of 1α‐hydroxylase are associated with worse quality of life in chronic rhinosinusitis with nasal polyps
Authors: Schlosser Rodney J. , Carroll William W. , Soler Zachary M. , Pasquini Whitney N. , Mulligan Jennifer K.
Published: November 2015

Background

Patients with chronic rhinosinusitis with nasal polyps (CRSwNP) have deficiencies in circulating and sinonasal levels of the inactive form of vitamin D3, 25‐hydroxycholecalciferol (25VD3). Moreover, CRSwNP patients have reduced epithelial cell–specific expression of 1α‐hydroxylase; the enzyme responsible for the conversion of 25VD3 to its metabolically active form, 1α,25‐dihydroxyvitamin D3 (1,25VD3). The objective of this work was to determine the impact of sinonasal 1α‐hydroxylase levels combined from all cellular sources on subjective disease severity and to identify variables influencing its expression.

Methods

Blood and sinus tissue explants were collected at the time of surgery from control, chronic rhinosinusitis without nasal polyps (CRSsNP), CRSwNP, and allergic fungal rhinosinusitis (AFRS) patients. 1α‐Hydroxylase was measured by immunostaining with flow cytometric analysis. Subjective disease severity was measured by the 22‐item Sino‐Nasal Outcomes Test (SNOT‐22). 1,25VD3 and 25VD3 were measured by enzyme‐linked immunosorbent assay (ELISA).

Results

Patients with CRSwNP or AFRS have reduced 1α‐hydroxylase and 1,25VD3 compared to controls or CRSsNP. Circulating 1,25VD3 levels were the same among all groups. No differences in sinonasal 1α‐hydroxylase or 1,25VD3 were found between CRSwNP and AFRS. Gender, age, race, atopy, and systemic 25VD3 had no impact on sinonasal 1α‐hydroxylase levels in any group. However, CRSwNP patients with asthma had higher 1α‐hydroxylase than those without asthma. Total 1α‐hydroxylase levels inversely correlated with SNOT‐22 in CRSwNP, but not CRSsNP.

Conclusion

Patients with CRSwNP and AFRS both have reduced sinonasal 1α‐hydroxylase and 1,25VD3 compared to controls or CRSsNP. Reductions in intracellular 1α‐hydroxylase combined from all sinonasal cell types were associated with more severe subjective disease severity in CRSwNP.
Mometasone furoate nasal spray in the treatment of nasal polyposis in Chinese patients: a double‐blind, randomized, placebo‐controlled trial
Authors: Zhou Bing , He Gang , Liang Jianping , Cheng Lei , Mehta Anish , Liu Shu , Yu Wenbo , Wang Zaiqi , Han Demin
Published: November 2015

Background

Although mometasone furoate nasal spray (MFNS) has demonstrated efficacy in nasal polyposis (NP) in Western populations, data in Asian populations is limited.

Methods

This randomized, double‐blind study evaluated MFNS 200 μg twice per day (BID) vs placebo in Chinese adults with bilateral nasal polyps (graded as 1, 2, or 3 by the investigator). A 14‐day placebo run‐in period was followed by a 16‐week treatment period with MFNS 200 μg BID vs placebo (1:1 ratio). The co‐primary endpoints were change from baseline in nasal congestion/obstruction averaged over the first 4 weeks of treatment and change from baseline in the total polyp size score (sum of scores from the left and right nasal fossa) at week 16. Secondary endpoints included other sinonasal symptoms scores and safety outcomes such as monitoring laboratory measurements, vital signs, and adverse events (AEs).

Results

There were 748 patients randomized, 375 received MFNS 200 μg BID and 373 received placebo. The between‐treatment difference in least squares (LS) mean change from baseline in nasal congestion/obstruction over 4 weeks of treatment was −0.14 (95% confidence interval [CI], −0.22 to −0.06) for MFNS vs placebo (p = 0.0007). The between‐treatment difference in LS mean change from baseline in total polyp size score at week 16 was −0.30 (95% CI, −0.45 to −0.15) for MFNS vs placebo (p < 0.0001). Serious AEs were rare (0.5% and 0.8% in MFNS and placebo groups, respectively) and considered not drug‐related. There were significantly more AEs of epistaxis with MFNS vs placebo (p = 0.009).

Conclusion

This study demonstrated that MFNS was effective and well tolerated in this population of adult, Chinese patients with NP.
The effects of house dust mite sublingual immunotherapy in patients with allergic rhinitis according to duration
Authors: Lin Zhibin , Liu Qihong , Li Tianying , Chen Dong , Chen Dehua , Xu Rui
Published: November 2015

Background

The safety and efficacy of sublingual immunotherapy (SLIT) have been demonstrated in the recent 2 decades. However, the data is still mixed regarding the efficacy of house dust mite (HDM) SLIT. The objective of this work was to evaluate the different clinical efficacy SLIT in patients with allergic rhinitis (AR) according to different durations of treatment.

Methods

A total of 500 subjects with HDM‐induced AR were randomized to receive SLIT with Dermatophagoides farinae (Der.f) drops or pharmacotherapy with oral antihistamines. Patients in the SLIT group were further divided into SLIT1, SLIT2, and SLIT3 subgroups. After SLIT completion, a yearly follow‐up visit was given to patients in the SLIT1 and SLIT2 subgroups. The total nasal symptom score (TNSS), the proportion of medication withdrawal, the visual analogue scale (VAS) score, and Rhinoconjunctivitis Quality of Life Questionnaire (RQLQ) scores were assessed at each monthly visit.

Results

Comparing with the baseline value, TNSS, VAS, and RQLQ were significantly improved in 3 SLIT subgroups after treatment (p < 0.05). In addition, patients in SLIT3 subgroup achieved the highest proportion of medication withdrawal compared to the SLIT1 and SLIT2 subgroups (p < 0.05). After 1‐year follow‐up, no significant differences were observed in TNSS, VAS scores, and the proportion of medication withdrawal of SLIT1 and SLIT2 subgroups (p > 0.05) with respect to the completion value. No severe systemic adverse events (AEs) were reported.

Conclusion

The randomized study suggested that 3‐year courses of SLIT in patients with AR was more efficacious than 1‐year or 2‐year courses. Furthermore, patients achieved 1‐year long‐term clinical benefits from HDM SLIT.
Anatomic variants of the paranasal sinuses in patients with recurrent acute rhinosinusitis
Authors: Loftus Patricia Anne , Lin Juan , Tabaee Abtin
Published: November 2015

Background

The incidence and potential disease impact of paranasal sinus anatomic variants in patients with recurrent acute rhinosinusitis (RARS) has important implications for management, including surgery, but is incompletely defined.

Methods

A retrospective review of 26 patients with RARS who had undergone computed tomography (CT) was performed. Patient demographics, RARS severity and comorbidities were reviewed. CT scans were reviewed for the incidence of anatomic variants in all patients. The pattern of inflammatory changes was explored in the subset of patients with acute rhinosinusitis at the time of CT. Potential correlation between the presence of anatomic variants and disease severity were investigated.

Results

In the patient cohort who met inclusion criteria, the most common variants included agger nasi cell (88.5%), concha bullosa (53.8%), infraorbital cell (50%), and deviated nasal septum with middle meatus obstruction (42%). In exploring correlations with RARS severity, type 2 frontal cells correlated with a greater number of years with RARS (0.0363). In the 23 patients who underwent CT at the time of an acute infection, no statistically significant correlation was found between severity or location of inflammatory changes and the presence of anatomic variants.

Conclusion

This study describes the incidence of anatomic variants in a cohort of patients with RARS. A correlation between the presence of anatomic variants and the pattern of inflammatory changes was not identified.
Subepithelial inflammatory load and basement membrane thickening in refractory chronic rhinosinusitis with nasal polyposis: a histopathological study
Authors: Bassiouni Ahmed , Ou Judy , Rajiv Sukanya , Cantero Daniel , Vreugde Sarah , Wormald Peter‐John
Published: November 2015

Background

A subgroup of chronic rhinosinusitis with nasal polyps (CRSwNP) patients is refractory to optimal surgical therapy and requires multiple revision sinus operations. Studies have shown that mucosal eosinophilia correlates with disease severity. We hypothesized that a high‐grade tissue inflammatory load is associated with these refractory patients.

Methods

A single‐surgeon, retrospective case‐control study comparing 20 CRSwNP patients requiring a second surgery during follow‐up (refractory group) vs a matched cohort of 20 CRSwNP patients without needing further revision surgery (control group). Hematoxylin and eosin (H&E)‐stained tissue harvested intraoperatively (×2 for the refractory group) were recalled for histopathological examination of subepithelial inflammation and basement membrane (BM) thickness.

Results

The refractory group had a significantly higher average eosinophil count (49 vs 18), relative eosinophilia (55% vs 32%) as well as total inflammatory cell count (86 vs 49) than the control group (p < 0.05). However within the refractory group, the eosinophil‐lymphocyte ratio was reduced from their first to their second (revision) surgeries whereas the total averaged inflammatory cell count remained unchanged. No significant difference in BM thickness was found between the groups.

Conclusion

These findings suggest that a higher inflammatory and eosinophilic load is associated with refractory disease and thus may be useful in predicting need for future revision surgery in CRSwNP.
The role for human nasal epithelial nuclear factor kappa B activation in histamine‐induced mucin 5 subtype B overproduction
Authors: Wang Weiwei , Shao Shengwen , Wang Sha
Published: November 2015

Background

Mucin 5 subtype B (MUC5B) is 1 of the major mucins secreted by airway epithelial cells. We sought to determine the effect of histamine on MUC5B expression in human nasal epithelial cells.

Methods

Human nasal epithelial cells from allergic rhinitis patients were cultured, and stimulated with 4 concentrations of histamine, or pretreated with a specific nuclear factor‐kappa B (NF‐κB) inhibitor (Bay11‐7082) before histamine stimulation. Immunocytochemistry and Western blotting were used to detect phosphorylated inhibitor of kappa B alpha (p‐IκBα), NF‐κBp65 and MUC5B protein. MUC5B content in supernatants was assayed by enzyme‐linked immunosorbent assay (ELISA).

Results

Histamine promoted IκBα phosphorylation and NF‐κBp65 nuclear translocation. A concentration‐dependent histamine‐induced increase of MUC5B protein was observed, and its content in supernatants was upregulated in a concentration‐dependent fashion, but these effects were attenuated by Bay11‐7082.

Conclusion

Histamine activated the IκBα/NF‐κB pathway by promoting IκBα phosphorylation and inducing NF‐κBp65 nuclear translocation, contributing to MUC5B overproduction and secretion.
Gender‐specific differences in chronic rhinosinusitis patients electing endoscopic sinus surgery
Authors: Lal Devyani , Rounds Alexis B. , Divekar Rohit
Published: November 2015

Background

The objective of this study was to investigate gender‐specific differences in chronic rhinosinusitis (CRS) patients electing endoscopic sinus surgery (ESS).

Methods

This study was a retrospective review of CRS patients electing ESS (2011–2013) at a tertiary‐care center.

Results

ESS was elected by 272 patients (mean age 54.6 years; 48.5% female). Mean Lund‐Mackay computed tomography (CT) score was 10.9; total 22‐item Sino‐Nasal Outcome Test (SNOT‐22) score was 41.8. Compared to men, women electing ESS had lower CT score (10.1 vs 11.7; p = 0.01) but higher total SNOT‐22 score (44.9 vs 39; p = 0.02). Women reported significantly worse postnasal drainage (p < 0.0001) and embarrassment (p = 0.0021). SNOT‐22 scores declined with advancing age (women, p = 0.003; men, p = 0.0005). Reduction in CT scores with age was seen only in males (p = 0.03). Stratifying by age, females aged 61 to 80 years had higher SNOT‐22 scores compared to male counterparts (p = 0.04), whereas CT scores were similar. More women underwent surgery for CRS without nasal polyps (CRSsNP) (54.9%) whereas more men underwent surgery for CRS with nasal polyps (CRSwNP) (57.4%), but this difference missed statistical significance (p = 0.052). Women with CRSwNP had higher SNOT‐22 scores than men (p = 0.02) for similar CT scores. Men electing ESS for CRSsNP had higher CT scores than women (p = 0.02). Women with CRSsNP aged 18 to 40 years reported higher SNOT‐22 scores than men (p = 0.003), even though CT scores were lower (p = 0.005).

Conclusion

Equivalent numbers of men and women underwent ESS for CRS. Overall, women electing ESS had higher total SNOT‐22 scores and lower Lund‐Mackay CT scores than men. Women reported more problems with postnasal drainage (CRS overall, CRSsNP, and CRSwNP), embarrassment (CRS overall and CRSwNP), and facial pain (CRSwNP). Gender differences in CRS are poorly understood and merit further study.
Longitudinal effect of eteplirsen versus historical control on ambulation in Duchenne muscular dystrophy
Authors: Mendell Jerry R. , Goemans Nathalie , Lowes Linda P. , Alfano Lindsay N. , Berry Katherine , Shao James , Kaye Edward M. , Mercuri Eugenio ,   for the Eteplirsen Study Group and Telethon Foundation DMD Italian Network
Published: November 2015

Objective

To continue evaluation of the long‐term efficacy and safety of eteplirsen, a phosphorodiamidate morpholino oligomer designed to skip DMD exon 51 in patients with Duchenne muscular dystrophy (DMD). Three‐year progression of eteplirsen‐treated patients was compared to matched historical controls (HC).

Methods

Ambulatory DMD patients who were ≥7 years old and amenable to exon 51 skipping were randomized to eteplirsen (30/50mg/kg) or placebo for 24 weeks. Thereafter, all received eteplirsen on an open‐label basis. The primary functional assessment in this study was the 6‐Minute Walk Test (6MWT). Respiratory muscle function was assessed by pulmonary function testing (PFT). Longitudinal natural history data were used for comparative analysis of 6MWT performance at baseline and months 12, 24, and 36. Patients were matched to the eteplirsen group based on age, corticosteroid use, and genotype.

Results

At 36 months, eteplirsen‐treated patients (n = 12) demonstrated a statistically significant advantage of 151m (p < 0.01) on 6MWT and experienced a lower incidence of loss of ambulation in comparison to matched HC (n = 13) amenable to exon 51 skipping. PFT results remained relatively stable in eteplirsen‐treated patients. Eteplirsen was well tolerated. Analysis of HC confirmed the previously observed change in disease trajectory at age 7 years, and more severe progression was observed in patients with mutations amenable to exon skipping than in those not amenable. The subset of patients amenable to exon 51 skipping showed a more severe disease course than those amenable to any exon skipping.

Interpretation

Over 3 years of follow‐up, eteplirsen‐treated patients showed a slower rate of decline in ambulation assessed by 6MWT compared to untreated matched HC. Ann Neurol 2016;79:257–271
Katalytische elektrophile C‐H‐Silylierung von Pyridinen ermöglicht durch vorübergehende Aufhebung der Aromatizität
Authors: Wübbolt Simon , Oestreich Martin
Published: November 2015

Eine C‐H‐Silylierung von Pyridinen wurde entwickelt, die scheinbar dem Mechanismus einer elektrophilen aromatischen Substitution (SEAr) folgt. Reaktionen von 2‐ und 3‐substituierten Pyridinen mit Hydrosilanen in Gegenwart eines Katalysators, welcher die Si‐H‐Bindung in ein Hydrid und ein Siliciumelektrophil spaltet, ergeben die entsprechenden 5‐silylierten Pyridine. Diese formale Silylierung einer aromatischen C‐H‐Bindung ist das Ergebnis einer dreistufigen Reaktionssequenz bestehend aus einer Pyridinhydrosilylierung, einer dehydrierenden C‐H‐Silylierung der Enaminzwischenstufe und einer Retro‐Hydrosilylierung des 1,4‐Dihydropyridins. Die Schlüsselzwischenstufen wurden 1H‐NMR‐spektroskopisch nachgewiesen und schrittweise einzeln hergestellt. Dieses komplexe Wechselspiel elektrophiler Silylierungen, Hydridübertragungen und Protonenabstraktionen wird durch einen einzigen Katalysator vermittelt.
Catalytic Electrophilic CH Silylation of Pyridines Enabled by Temporary Dearomatization
Authors: Wübbolt Simon , Oestreich Martin
Published: November 2015

A CH silylation of pyridines that seemingly proceeds through electrophilic aromatic substitution (SEAr) is reported. Reactions of 2‐ and 3‐substituted pyridines with hydrosilanes in the presence of a catalyst that splits the SiH bond into a hydride and a silicon electrophile yield the corresponding 5‐silylated pyridines. This formal silylation of an aromatic CH bond is the result of a three‐step sequence, consisting of a pyridine hydrosilylation, a dehydrogenative CH silylation of the intermediate enamine, and a 1,4‐dihydropyridine retro‐hydrosilylation. The key intermediates were detected by 1H NMR spectroscopy and prepared through the individual steps. This complex interplay of electrophilic silylation, hydride transfer, and proton abstraction is promoted by a single catalyst.
Preparation of 0.4Li2MnO3·0.6LiNi1/3Co1/3Mn1/3O2 with tunable morphologies via polyacrylonitrile as a template and applications in lithium‐ion batteries
Authors: Miao Xiaowei , Ni Huan , Sha Xuerong , Wang Ting , Fang Jianhui , Yang Gang
Published: November 2015

Samples of 0.4Li2MnO3·0.6LiNi1/3Co1/3Mn1/3O2 (LMO) with tunable morphologies were synthesized via polyacrylonitrile (PAN) as a template. The starting PAN/N,N‐dimethylformamide (DMF) ratios, including 1:9, 1:10, 1:12, and 1:14, were optimized for the fiber morphologies and electrochemical performance. Through electrospinning, metal salts were well dispersed in the PAN fibers. The crystal structure and morphologies of the PAN/LMO fibers were characterized by X‐ray diffraction, scanning electron microscopy, and thermal analysis. Along with the decrease in the concentration of PAN in the precursor, the diameters of the PAN/LMO fibers decreased. On the other hand, at the highest and lowest concentrations, 1:9 and 1:14, of PAN with DMF, micrometer PAN fibers were electrospun, whereas ratios of PAN to DMF of 1:10 and 1:12 resulted in the electrospinning of millimeter‐long fibers of PAN. In the interface of PAN and metal salts, LMOs were grown and accompanied the decomposition of PAN, and the crystal morphologies of LMO quite depended on the diameter and length of the PAN/LMO nanofibers. During heat treatment, the morphologies of the PAN fibers controlled the removal of small molecules and the crystal morphologies of LMOs. The charge/discharge results indicate that LMO with a tubular structure delivered a capacity of 262.3 mAh/g at a cutoff voltage of 2.5–4.8 V at a 0.1 C rate. Benefitting from a unique hollow and nanocrystalline architecture, it also exhibited good rate and cycling performances. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43022.
Specific heavy metal ion recovery with ion‐imprinted cryogels
Authors: Jalilzadeh Mitra , Uzun Lokman , Şenel Serap , Denizli Adil
Published: November 2015

In this study, the functional monomers, N‐methacryloyl‐l‐aspartic acid and N‐methacryloyl‐l‐cysteine were synthesized through a reaction between appropriate amino acids and methacryloyl chloride. Then, Pb(II) or Cd(II) ion‐imprinted 2‐hydroxyethyl methacrylate based cryogels were prepared by free radical polymerization method under partially frozen conditions. Following the characterization of matrices, adsorption of heavy metal ions was examined in batch mode from aqueous solution considering several parameters affecting the adsorption performance. The actual adsorption capacities were 44.5, 65.3, and 86.7 mg/g for Cd‐1, Cd‐2, and Cd‐3 cryogels meanwhile those were 41.9, 86.3, and 122.7 mg/g for Pb‐1, Pb‐2, and Pb‐3 cryogels, respectively at optimum pH: 5.5. By increasing temperature, adsorption capabilities of both cryogels were inhibited because of the electrostatic nature of coordinated covalent bonds and collapsing of coordination spheres. The adsorption process was very fast, the equilibrium adsorption was achieved in about 60 min, which was directly related to macroporous structure and interconnected flow‐channels of cryogels. Kinetics and adsorption isotherms were also studied. Langmuir isotherms and pseudo‐second order kinetic model were well suited to adsorption data, which also indicated that the process occurred without any diffusion restrictions or steric hindrances. Finally, the competitive adsorption studies were performed using multi‐ion containing synthetic wastewater to show whether the cryogels developed are suitable for specific heavy metal recycling or not. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43095.
Preparation, structure, and property of wood flour incorporated polypropylene composites prepared by a solid‐state mechanochemical method
Authors: Niu Zhihai , Chen Yinghong , Feng Jiabing
Published: November 2015

In this article, a solid‐state mechanochemical method based on a pan‐mill equipment was used to prepare 60 wt % loading of wood flour (WF) incorporated polypropylene (PP) wood–plastic composite (WPC) with good comprehensive performance. The particle size distribution, crystallization, microstructure, and properties of the prepared WPC were accordingly investigated. The results show that under co‐effects of the strong shear force field of pan milling and the compatibilization of PP grafted maleic anhydride (PP‐g‐MAH), the mixture of PP and WF is effectively pulverized and homogeneously mixed. Meanwhile, the WF particles are adequately activated by exposure of their characteristic functional groups, which is beneficial to the interfacial mechanochemical reaction. PP‐g‐MAH and PP prove to be in situ grafted onto WF particles surface during pan milling, thus resulting in the substantial enhancement in both the dispersion of the added WF fillers in PP matrix and the interfacial bonding. The mechanochemical effects of pan milling could also remarkably promote the heterogeneous nucleation effect of WF particles on PP crystallization and influence the dynamic mechanical behavior of composite. Compared with the unmilled and uncompatibilized composite, the milled and compatibilized WPC material possesses greatly enhanced mechanical performance and shows good application prospects. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43108.
A Novel Method of Urinary Sphincter Deficiency: Serial Histopathology Evaluation in a Rat Model of Urinary Incontinence
Authors: Khorramirouz Reza , Mozafarpour Sarah , Kameli Seyedeh Maryam , Ladi Seyedian Seyedeh Sanam , Oveisi Nasim , Rahimi Zahra , Alijani Maryam , Kajbafzadeh Abdol‐Mohammad
Published: November 2015

In this study, a novel technique of irreversible sphincter deficiency by pudendal nerve transection (PNT) using 40 female rats for studying the pathophysiology of stress urinary incontinence associated with childbirth was developed. Of the 40 rats, 10 served as controls and the remaining underwent bilateral PNT at the anastomotic lumbosacral trunk level. Urethral morphological changes following bilateral PNT were assessed with serial hematoxylin and eosin (H&E) and immunohistochemistry (IHC) staining methods at 50, 90, and 130 days post‐intervention. Leak point pressure (LPP) measurement was used to determine the effect of pudendal injury on urethral outlet resistance after the transection. H&E and IHC staining showed irreversible loss of striated muscle mass of the sphincter region and increase in collagen deposition compatible with muscle atrophy. LPP measurements also significantly decreased following bilateral PNT. In conclusion, a novel method of irreversible sphincter insufficiency was developed. This model effectively decreased urethral outlet resistance and caused irreversible striated muscle atrophy. It was suggested that this technique can be used to develop a permanent sphincter deficiency model for the preclinical testing of treatment modalities exclusively triggering the pudendal nerve. Anat Rec, 299:173–180, 2016. © 2015 Wiley Periodicals, Inc.
Anti‐Inflammatory and Neuroprotective Effects of Triptolide via the NF‐κB Signaling Pathway in a Rat MCAO Model
Authors: Bai Shi , Hu Zhiying , Yang Yang , Yin Yifei , Li Weiyun , Wu Lijuan , Fang Marong
Published: November 2015

Stroke is the leading cause of neurological disability in humans. Middle cerebral artery occlusion (MCAO) followed by reperfusion is widely accepted to mimic stroke in basic medical research. Triptolide is one of the major active components of the traditional Chinese herb Tripterygium wilfordii Hook F, and has been reported to have potent anti‐inflammatory and immunosuppressive properties. Since its preclinical effects on stroke were still unclear, we decided to study the effects of Triptolide on focal cerebral ischemia/reperfusion injury in this study. The results showed that Triptolide treatment significantly attenuates brain infarction volume, water content, neurological deficits, and neuronal cell death rate, which were increased in the MCAO model rats. Immunohistochemistry was used to analyze the expression of glial fibrillary acidic protein (GFAP), Cyclooxygenase‐2 (COX‐2), inducible nitric oxide (iNOS), and NF‐κB in the ischemic brains. The administration of Triptolide showed down‐regulation of the iNOS, COX‐2, GFAP, and NF‐κB expression in MCAO rats. It also increased the expression of bcl‐2, and suppressed levels of bax and caspase‐3 compared with the MCAO group. Our findings revealed that Triptolide exerts its neuroprotective effects against inflammation with the involvement of inhibition of NF‐κB activation. Anat Rec, 299:256–266, 2016. © 2015 Wiley Periodicals, Inc.
Evaluation of Novel Chalcone Oximes as Inhibitors of Tyrosinase and Melanin Formation in B16 Cells
Authors: Radhakrishnan Sini K. , Shimmon Ronald G. , Conn Costa , Baker Anthony T.
Published: November 2015

A series of hydroxy‐substituted chalcone oxime derivatives were synthesized. These compounds were then evaluated for their inhibitory activities on tyrosinase and melanogenesis in murine B16F10 melanoma cells. The structures of the synthesized compounds were confirmed by 1H NMR, 13C NMR, FTIR, and HRMS. Two of the compounds exhibited much higher tyrosinase inhibitory activities (IC50 values of 4.77 and 7.89 μM, respectively) than the positive control, kojic acid (IC50: 22.25 μM). Kinetic studies revealed them to act as competitive tyrosinase inhibitors with their Ki values of 5.25 and 8.33 μM, respectively. Both the compounds inhibited melanin production and tyrosinase activity in B16 cells. Docking results confirmed that the active inhibitors strongly interacted with the mushroom tyrosinase residues.
Tetramer formation of tumor suppressor protein p53: Structure, function, and applications
Authors: Kamada Rui , Toguchi Yu , Nomura Takao , Imagawa Toshiaki , Sakaguchi Kazuyasu
Published: November 2015

Tetramer formation of p53 is essential for its tumor suppressor function. p53 not only acts as a tumor suppressor protein by inducing cell cycle arrest and apoptosis in response to genotoxic stress, but it also regulates other cellular processes, including autophagy, stem cell self‐renewal, and reprogramming of differentiated cells into stem cells, immune system, and metastasis. More than 50% of human tumors have TP53 gene mutations, and most of them are missense mutations that presumably reduce tumor suppressor activity of p53. This review focuses on the role of the tetramerization (oligomerization), which is modulated by the protein concentration of p53, posttranslational modifications, and/or interactions with its binding proteins, in regulating the tumor suppressor function of p53. Functional control of p53 by stabilizing or inhibiting oligomer formation and its bio‐applications are also discussed. © 2015 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 106: 598–612, 2016.
Regioselectivities in Fe(III)‐catalyzed Cycloisomerization Reactions of γ‐Allenyl Alcohols
Authors: Kim Jae Hyung , Kim Seung Wook , Jung Min Seok , Ahn Kwang‐Hyun , Kang Eun Joo
Published: November 2015

Iron‐catalyzed intramolecular hydroalkoxylation reactions of allenes were performed to provide various tetrahydrofurans by regioselective 5‐exo cyclization pathway, as the Lewis acidic activation of Fe(III) salts toward unsaturated CC bonds, allenes and alkenes. Cyclohexyl substituted allenes especially isomerized to dienes at a rapid rate, which underwent a competing 6‐endo cyclization mode. The plausible mechanism was presented by experimental results of the reaction intermediates and computational study of Fe‐allene and Fe‐diene complexes.
Willingness to Pay for Green Products in Air Travel: Ready for Take‐Off?
Authors: Hinnen Gieri , Hille Stefanie Lena , Wittmer Andreas
Published: November 2015

We examine the willingness to pay (WTP) for green products in air travel. Green products in aviation are supplementary services, which are sold on top of the travel service (e.g. carbon offsets, organic on‐board food). We identify a set of potential green products in aviation and report the preferences for additional airline services of 811 Swiss air travellers using an adaptive choice‐based conjoint survey. We find that 20% of those passengers who are interested in purchasing supplementary services show a considerable WTP for green products. The green segment differs from the regular segment only in terms of behavioural features, not in terms of demographic or socio‐economic characteristics. Copyright © 2015 John Wiley & Sons, Ltd and ERP Environment
Titanium‐Microfiber‐Supported Binary‐Oxide Nanocomposite with a Large Highly Active Interface for the Gas‐Phase Selective Oxidation of Benzyl Alcohol
Authors: Zhao Guofeng , Fan Songyu , Tao Longgang , Chai Ruijuan , Zhang Qiaofei , Liu Ye , Lu Yong
Published: November 2015

Thin‐sheet sinter‐locked Ti‐microfiber‐supported binary‐oxide‐nanocomposite catalysts engineered on the micro‐ to macroscales were developed for the gas‐phase aerobic oxidation of benzyl alcohol to benzaldehyde. The catalysts demonstrated higher activity than single‐oxide and noble‐metal catalysts with good stability and regenerability. The catalysts were obtained by placing transient metal (e.g., Ni, Co, Cu, Mn) nitrates onto a Ti‐microfiber surface by impregnation, and the supported nitrates were subsequently in situ transformed into the binary‐oxide composites in the real reaction stream at 300 °C. Among them, CoO‐2.5–CuOx‐2.5/Ti‐fiber was found to be the best catalyst; it delivered 93.5 % conversion of benzyl alcohol (b.p. 210 °C) with 99.2 % selectivity to benzaldehyde at 230 °C. In situ induced formation of “CoO@Cu2O” ensembles (i.e., larger CoO nanoparticles partially covered with smaller Cu2O clusters and/or nanoparticles) was identified, which by nature resulted in a large Cu2O–CoO interface and led to a significant improvement in the low‐temperature activity.
Fabrication of Ruthenium Nanoparticles in Porous Organic Polymers: Towards Advanced Heterogeneous Catalytic Nanoreactors
Authors: Mondal John , Kundu Sudipta K. , Hung Ng Wilson Kwok , Singuru Ramana , Borah Parijat , Hirao Hajime , Zhao Yanli , Bhaumik Asim
Published: November 2015

A novel strategy has been adopted for the construction of a copolymer of benzene–benzylamine‐1 (BBA‐1), which is a porous organic polymer (POP) with a high BET surface area, through Friedel–Crafts alkylation of benzylamine and benzene by using formaldehyde dimethyl acetal as a cross‐linker and anhydrous FeCl3 as a promoter. Ruthenium nanoparticles (Ru NPs) were successfully distributed in the interior cavities of polymers through NaBH4, ethylene glycol, and hydrothermal reduction routes, which delivered Ru‐A, Ru‐B, and Ru‐C materials, respectively, and avoided aggregation of metal NPs. Homogeneous dispersion, the nanoconfinement effect of the polymer, and the oxidation state of Ru NPs were verified by employing TEM, energy‐dispersive X‐ray spectroscopy mapping, cross polarization magic‐angle spinning 13C NMR spectroscopy, and X‐ray photoelectron spectroscopy analytical tools. These three new Ru‐based POP materials exhibited excellent catalytic performance in the hydrogenation of nitroarenes at RT (with a reaction time of only ≈30 min), with high conversion, selectivity, stability, and recyclability for several catalytic cycles, compared with other traditional materials, such as Ru@C, Ru@SiO2, and Ru@TiO2, but no clear agglomeration or loss of catalytic activity was observed. The high catalytic performance of the ruthenium‐based POP materials is due to the synergetic effect of nanoconfinement and electron donation offered by the 3D POP network. DFT calculations showed that hydrogenation of nitrobenzene over the Ru (0001) catalyst surface through a direct reaction pathway is more favorable than that through an indirect reaction pathway.
A Redox‐Active Dinuclear Platinum Complex Exhibiting Multicolored Electrochromism and Luminescence
Authors: Yoshida Masaki , Yashiro Naoki , Shitama Hotaka , Kobayashi Atsushi , Kato Masako
Published: November 2015

A redox series of cyclometalated platinum complexes based on a dinuclear motif linked by acetamidato (aam) bridging ligands, [Pt2(μ‐aam)2(ppy)2] (ppy−=2‐phenylpyridinate ion), has been synthesized. The complexes in this series are easily oxidized and reduced by both electrochemical and chemical methods, and this is accompanied by multistep changes in their optical properties, that is, multiple color changes and luminescence. Isolation of the complexes and the structural determination of three oxidation states, +2, +2.33, and +3, have been achieved. The mixed‐valent complex, with an average oxidation state of +2.33, forms a trimer based on the dinuclear motif. The mixed‐valent complex has a characteristic color owing to intervalence transitions in the platinum chain. In contrast, the divalent complex exhibits strong red phosphorescence originating from a triplet metal‐metal‐to‐ligand charge transfer (3MMLCT) state. This study demonstrates the unique chromic behavior of a redox‐active and luminescent platinum complex.
Formation of MgxNbyOx+y through the Mechanochemical Reaction of MgH2 and Nb2O5, and Its Effect on the Hydrogen‐Storage Behavior of MgH2
Authors: Pukazhselvan D. , Perez José , Nasani Narendar , Bdikin Igor , Kovalevsky Andrei V. , Fagg Duncan Paul
Published: November 2015

The present study aims to understand the catalysis of the MgH2–Nb2O5 hydrogen storage system. To clarify the chemical interaction between MgH2 and Nb2O5, the mechanochemical reaction products of a composite mixture of MgH2+0.167 Nb2O5 was monitored at different time intervals (2, 5, 15, 30, and 45 min, as well as 1, 2, 5, 10, 15, 20, 25, and 30 h). The study confirms the formation of catalytically active Nb‐doped MgO nanoparticles (typically MgxNbyOx+y, with a crystallite size of 4–8 nm) by transforming reactants through an intermediate phase typified by Mgm−xNb2n−yO5n−(x+y). The initially formed MgxNbyOx+y product is shown to be Nb rich, with the concentration of Mg increasing upon increasing milling time. The nanoscale end‐product MgxNbyOx+y closely resembles the crystallographic features of MgO, but with at least a 1–4 % higher unit cell volume. Unlike MgO, which is known to passivate the surfaces in MgH2 system, the Nb‐dissolved MgO effectively mediates the Mg–H2 sorption reaction in the system. We believe that this observation will lead to new developments in the area of catalysis for metal–gas interactions.
Big Data and Adverse Drug Reaction Detection
Authors: Harpaz R , DuMochel W , Shah NH
Published: November 2015

Big Data holds the promise of fundamentally transforming the manner in which adverse drug reactions can be identified and evaluated. This commentary discusses new data sources that are envisioned to form a Big Data‐enabled pharmacovigilance system and the role of these data in powering the future of adverse drug reactions detection.
Fighting Fenton Chemistry: A Highly Active Iron(III) Tetracarbene Complex in Epoxidation Catalysis
Authors: Kück Jens W. , Anneser Markus R. , Hofmann Benjamin , Pöthig Alexander , Cokoja Mirza , Kühn Fritz E.
Published: November 2015

Organometallic Fe complexes with exceptionally high activities in homogeneous epoxidation catalysis are reported. The compounds display FeII and FeIII oxidation states and bear a tetracarbene ligand. The more active catalyst exhibits activities up to 183 000 turnovers per hour at room temperature and turnover numbers of up to 4300 at −30 °C. For the FeIII complex, a decreased Fenton‐type reactivity is observed compared with FeII catalysts reported previously as indicated by a substantially lower H2O2 decomposition and higher (initial) turnover frequencies. The dependence of the catalyst performance on the catalyst loading, substrate, water addition, and the oxidant is investigated. Under all applied conditions, the advantageous nature of the use of the FeIII complex is evident.
Possible High Efficiency Platform for Biosensors Based on Optimum Physical Chemistry of Carbon Nanotubes
Authors: Yousefi Amin Termeh , Tanaka Hirofumi , Bagheri Samira , Kadri Nahrizul Adib , Ikeda Shoichiro , Mahmood Mohamad Rusop , Miyake Mikio
Published: November 2015

Carbon nanotube (CNT)‐based electrochemical biosensors are used to determine the concentration of analytes by measuring mass, heat, or oxygen. CNTs, as an immobilizing platform of biomaterials, play an important role in enhancing the electron transfer mechanism of a biosensor. The large surface area and optimum aspect ratio (length to thickness) of CNTs maximize the amount of immobilized biomaterials on the surface. In this study, various aspect ratios of CNTs are reported, based on the alteration of growth mechanisms using CVD. The growth‐dependent and ‐independent parameters of the CNT arrays are studied as functions of the synthesis method.