bluuebunny/crossref_metadata_2025 huggingface dataset:
Iron‐Catalyzed Dioxygenation of Alkenes and Terminal Alkynes by using (Diacetoxyiodo)benzene as Oxidant
Authors: Srinivas B. T. V. , Rawat Vikas S. , Sreedhar Bojja
Published: November 2015

An iron‐catalyzed syn‐diacetoxylation of alkenes and 1,2‐oxyacetoxylation of terminal alkynes has been developed using (diacetoxyiodo)benzene as oxidant. A broad range of internal and terminal alkenes, including electron‐rich as well as electron‐deficient alkenes, gave the desired products in good to excellent yields with high diastereoselectivity (up to >99:1 dr). In addition the high catalytic activity of iron catalysis for the 1,2‐oxyacetoxylation of terminal alkynes is also reported. The roles of catalyst, oxidant and other reaction parameters were evaluated for activation of the unsaturated bond.

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Wafer‐Scale Coplanar Electrodes for 3D Conformal Organic Single‐Crystal Circuits
Authors: Zhao Xiaoli , Tong Yanhong , Tang Qingxin , Liu Yichun
Published: November 2015

Conformal organic single‐crystal circuit on 3D curved surfaces, which can provide sensory and scanning features for monitoring, biofeedback, and tracking of physiological function, presents one of the most promising technologies for high‐performance wearable and implantable electronics. However, the present organic single‐crystal circuits remain limited on rigid planar substrates, by the lack of fabrication techniques for mechanically elastic and flexible electrodes to conform to 3D curved surfaces. Here, a novel electrode design for the formation of a wafer‐scale coplanar electrode, together with only one individual flexible rubrene nanobelt, to achieve the 3D conformal single‐crystal transistors and circuits for the first time is proposed. Excellent electrical properties with device yield as high as 93.2%, field‐effect mobility up to 23.9 cm2 V−1 s−1, near‐zero threshold voltage, inverter gain over 23, and the extreme circuit stability with zero hysteresis are shown. The results open up the capability of organic single crystals for conformal circuits and reveal the strong potential of the new‐type electrode for future large‐scale wearable and implantable electronics.
Positive Effect of an Internal Depolarization Field in Ultrathin Epitaxial Ferroelectric Films
Authors: Liu Guangqing , Chen Jason , Lichtensteiger Céline , Triscone Jean‐Marc , Aguado‐Puente Pablo , Junquera Javier , Valanoor Nagarajan
Published: November 2015

The effect of intentionally introducing a large depolarization field in (001)‐oriented, epitaxial Pb(Zr0.2TiO0.8)O3 (PZT) ultrathin films grown on La0.67Sr0.33MnO3 (LSMO) buffered SrTiO3 (STO) substrates is investigated. Inserting between 3 and 10 unit cells of STO between two 3 nm thick PZT films significantly influences the out‐of‐plane (c) lattice constant as well as the virgin domain state. Piezoresponse force microscopy images reveal a nanoscale (180°) polydomain structure in these films. In comparison, a “reference” single layer PZT sample (6 nm thick without STO spacer) exhibits an elongated PZT c‐axis (0.416 nm) and is preferentially “down”‐polarized with large regions of monodomain contrast. It shows asymmetric switching loops (i.e., imprint) coupled with sluggish domain switching under external bias. It is shown that the insertion of STO drives a monodomain to 180° polydomain transition in the as‐grown state, which reduces the imprint by 80%. The insertion of the STO also profoundly improves dielectric leakage and hence the distribution of the applied electric field. Consequently, the critical pulse duration of the electric field required to initiate domain switching is reduced by two orders of magnitude relative to the reference sample. These results demonstrate the possibility of manipulating the depolarization field in such a way that it has positive effects on the ferroelectric behavior of ultrathin PZT films.
Mutant calreticulin‐expressing cells induce monocyte hyperreactivity through a paracrine mechanism
Authors: Garbati Michael R. , Welgan Catherine A. , Landefeld Sally H. , Newell Laura F. , Agarwal Anupriya , Dunlap Jennifer B. , Chourasia Tapan K. , Lee Hyunjung , Elferich Johannes , Traer Elie , Rattray Rogan , Cascio Michael J. , Press Richard D. , Bagby Grover C. , Tyner Jeffrey W. , Druker Brian J. , Dao Kim‐Hien T.
Published: November 2015

Mutations in the calreticulin gene (CALR) were recently identified in approximately 70–80% of patients with JAK2‐V617F‐negative essential thrombocytosis and primary myelofibrosis. All frameshift mutations generate a recurring novel C‐terminus. Here we provide evidence that mutant calreticulin does not accumulate efficiently in cells and is abnormally enriched in the nucleus and extracellular space compared to wildtype calreticulin. The main determinant of these findings is the loss of the calcium‐binding and KDEL domains. Expression of type I mutant CALR in Ba/F3 cells confers minimal IL‐3‐independent growth. Interestingly, expression of type I and type II mutant CALR in a nonhematopoietic cell line does not directly activate JAK/STAT signaling compared to wildtype CALR and JAK2‐V617F expression. These results led us to investigate paracrine mechanisms of JAK/STAT activation. Here we show that conditioned media from cells expressing type I mutant CALR exaggerate cytokine production from normal monocytes with or without treatment with a toll‐like receptor agonist. These effects are not dependent on the novel C‐terminus. These studies offer novel insights into the mechanism of JAK/STAT activation in patients with JAK2‐V617F‐negative essential thrombocytosis and primary myelofibrosis. Am. J. Hematol. 91:211–219, 2016. © 2015 Wiley Periodicals, Inc.
KIAA2022 nonsense mutation in a symptomatic female
Authors: Farach Laura S. , Northrup Hope
Published: November 2015

Mutations in the KIAA2022 gene have been implicated in non‐syndromic X‐linked intellectual disability. Thus far, all carrier females reported have been unaffected and genotype–phenotype correlations have not been described. Herein, we report a de novo KIAA2022 nonsense mutation in a 17‐year‐old female with short stature, microcephaly, severe intellectual disability, poor speech, epilepsy, and autistic behavior. X‐inactivation pattern is normal suggesting that the mutation is causing the phenotype. This report contests the current view that KIAA2022 mutations only affect males, which has implications for testing and genetic counseling. © 2015 Wiley Periodicals, Inc.
Ontogeny of 3D rib curvature and its importance for the understanding of human thorax development
Authors: García‐Martínez Daniel , Recheis Wolfgang , Bastir Markus
Published: November 2015

Objectives

Sagittal and axial rib orientation relative to the spine are two factors that modify rib cage morphology during ontogeny. Some studies suggest that these factors do not operate in the same way at the upper (ribs 1–5) and lower thorax (ribs 6–10) during postnatal growth, but it is unknown if the ontogenetic thoracic changes are produced by morphological changes of the ribs (intrinsic rib factors) or by external factors related to costal joints (extrinsic rib factors).

Material and methods

To clarify these questions, we applied 3D geometric morphometrics of landmarks and sliding semilandmarks (N = 20/rib) to 280 individual ribs (1–10) of Homo sapiens comprising the entire human ontogeny and growth simulations were carried out.

Results

PCA shows that intrinsic rib factors (rib torsion and axial rib curvature) are ontogenetic factors of variability that contribute to configuring the adult thorax shape. Moreover, growth simulations and regression slopes suggest that the upper thorax unit is comprised by ribs 1–7 and the lower unit at least by ribs 8–10.

Discussion

These results suggest anatomical constraints for ontogenetic rib variation, since ribs 1–7 (true ribs) are directly linked to the sternum. Moreover, these results are supported by functional anatomy because pulmonary kinematics would influence the upper unit and diaphragmatic kinematics would influence the lower one. Our findings are relevant not only to understanding how changes at individual ribs contribute to the adult thorax morphology, but also to the development and evolution of the modern human rib cage. Am J Phys Anthropol 159:423–431, 2016. © 2015 Wiley Periodicals, Inc.
Doxycycline inhibits TGF‐β1–induced extracellular matrix production in nasal polyp–derived fibroblasts
Authors: Shin Jae‐Min , Park Joo‐Hoo , Park Il‐Ho , Lee Heung‐Man
Published: November 2015

Background

Doxycycline has been shown to have antibacterial and anti‐inflammatory effects and suppresses collagen biosynthesis. The purpose of this study was to evaluate the effects of doxycycline on transforming growth factor (TGF)‐β1–induced myofibroblast differentiation and extracellular matrix production in nasal polyp–derived fibroblasts (NPDFs). We also determined the molecular mechanisms of action for doxycycline.

Methods

NPDFs were isolated from nasal polyps from 8 patients. Doxycycline was used to pretreat TGF‐β1–induced NPDFs. Cytotoxicity was evaluated using a 3‐(4,5‐dimethylthiazol‐2yl)‐2,5‐diphenyl‐tetrazolium bromide assay. Expression levels of α–smooth muscle actin (SMA) and fibronectin were measured using Western blot, reverse‐transcription polymerase chain reaction, and immunofluorescence staining. Total collagen production was analyzed with the Sircol collagen assay, while mitogen‐activated protein kinase (MAPK) and NF‐κB activation were determined using Western blot analysis. Luciferase assay was used to evaluate the transcriptional activity of NF‐κB.

Results

Although doxycycline (0 to 40 μg/mL) had no significant cytotoxic effects in TGF‐β1–induced NPDFs, it significantly reduced the expression levels of α‐SMA, fibronectin, and collagen in TGF‐β1–induced NPDFs in a dose‐dependent manner. Doxycycline also inhibited the TGF‐β1–induced activation of p38, c‐Jun NH2‐terminal kinase (JNK), and NF‐κB, and its inhibitory effects were similar to those of the specific inhibitors for each.

Conclusion

Doxycycline has an inhibitory effect on TGF‐β1–induced myofibroblast differentiation and extracellular matrix production via the p38 and JNK/NF‐κB signal pathways in NPDFs.
Activation of the motor cortex during phasic rapid eye movement sleep
Authors: De Carli Fabrizio , Proserpio Paola , Morrone Elisa , Sartori Ivana , Ferrara Michele , Gibbs Steve Alex , De Gennaro Luigi , Lo Russo Giorgio , Nobili Lino
Published: November 2015

When dreaming during rapid eye movement (REM) sleep, we can perform complex motor behaviors while remaining motionless. How the motor cortex behaves during this state remains unknown. Here, using intracerebral electrodes sampling the human motor cortex in pharmacoresistant epileptic patients, we report a pattern of electroencephalographic activation during REM sleep similar to that observed during the performance of a voluntary movement during wakefulness. This pattern is present during phasic REM sleep but not during tonic REM sleep, the latter resembling relaxed wakefulness. This finding may help clarify certain phenomenological aspects observed in REM sleep behavior disorder. Ann Neurol 2016;79:326–330
Poly(vinyl alcohol) modified by KE reactive dyes as a novel proton‐exchange membrane for potential fuel‐cell applications
Authors: Zhou Tianchi , He Xuemei , Xie Kongliang
Published: November 2015

A new type of proton‐exchange membrane based on poly(vinyl alcohol) (PVA) modified KE reactive dyes (KE‐4BD) was prepared and evaluated as H+‐conducting polymer electrolytes. The effects of the content of KE‐4BD on the membrane H+ conductivity and water uptake were studied with an alternating‐current impedance technique and the method of weighing, respectively. Fourier transform infrared and scanning electron microscopy were used for the chemical and structural characterization of these membranes. With all of these properties, the optimal mass ratio between PVA and KE‐4BD was 1:0.5, and the resulting membrane exhibited a high proton conductivity (0.109 S/cm) at room temperature; this afforded a power density of 83.9 mW/cm2 at 210.4 mA/cm2 and an open‐circuit voltage of 810.8 mV. The PVA/KE‐4BD membranes showed a high oxidative stability in Fenton's reagent (3% H2O2 v/v, 2 ppm FeSO4). Thermal analysis also showed that the membranes exhibited a significant improvement in thermal stability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43019.
China as a Global Force
Authors: Zhang Feng
Published: November 2015

Three foreign policy initiatives under President Xi Jinping over the past three years have considerably enhanced China's global influence: partnership diplomacy, the Silk Road economic diplomacy, and the new financial diplomacy. Partnership diplomacy seeks to forge a global network of partnership countries for China. The Silk Road economic diplomacy is the signature foreign policy proposal of Xi, and in some sense can be seen as the economic pillar of Xi's grand strategy for rejuvenating China on the world stage. Its stated objective is to promote common development between China and Eurasian countries, particularly in the field of infrastructure development. China has also been trying with very skillful and proactive diplomacy to create a new financial order to support the Silk Road project and China's economic diplomacy in general, including, but not limited to, the establishment of the much vaunted Asian Infrastructure Investment Bank.
Geophysical and Archaeological Characterization of a Modest Roman Villa: Methodological Considerations about Progressive Feedback Analyses in Sites with Low Geophysical Contrast
Authors: Pueyo Anchuela Óscar , Diarte Blasco Pilar , García Benito Carlos , Casas Sainz Antonio M. , Pocoví Juan Andrés
Published: November 2015

The low contrast in physical properties of archaeological elements compared to the host soil is a common drawback in geophysical surveys applied to subtle archaeological sites because those contrasts are usually what are being measured by most instruments. Furthermore, when archaeological elements and construction remains are placed within the same package of materials, differentiation of each can make the interpretation of geophysical data sometimes difficult. In this work we propose a dynamic, integrated approach for the characterization of an archaeological site with simple Roman construction materials in order to evaluate methodological considerations in the evaluation of this kind of sites. This approach includes: (i) a preliminary evaluation of construction material characteristics, according to the background provided by the historical and geographical context and from previous excavations, (ii) measurements of magnetic susceptibility of archaeological and natural materials in the site for direct modelling of the expected anomalies; (iii) a geophysical survey including magnetometry, multifrequency electromagnetic (EM) method and ground penetrating radar (GPR) (100, 250 and 500 MHz centre frequency antennas); (iv) geophysical data evaluation for planning subsequent systematic surveys; (v) dynamic interpretation of geophysical results through careful data evaluation of all previous steps. The final archaeological model from geophysical data has been successful due to the manner of data interpretation looking for orthogonal patterns of geophysical anomalies that were hypothesized to be subsurface walls. Modelling was then followed by archaeological excavations consisting of three trenches where the walls were exposed. The integration of geophysical data with excavations has permitted to evaluate significance of the different geophysical analysis and to identify their archaeological meaning. The proposed sequential methodology represents an innovative manner of analysis (i) in subtle sites where construction remains are scarce and the absence of well‐defined geophysical contrasts can limit the results of usual surveys and (ii) to increase the efficiency in the evaluation of more extensive survey areas. Copyright © 2015 John Wiley & Sons, Ltd.
Efficient Hole‐Transporting Materials with Triazole Core for High‐Efficiency Perovskite Solar Cells
Authors: Choi Hyeju , Jo Hyeonjun , Paek Sanghyun , Koh Kyungkuk , Ko Haye Min , Lee Jae Kwan , Ko Jaejung
Published: November 2015

Efficient hole‐transporting materials (HTMs), TAZ‐[MeOTPA]2 and TAZ‐[MeOTPATh]2 incorporating two electron‐rich diphenylamino side arms, through direct linkage or thiophen bridges, respectively, on the C3‐ and C5‐positions of a 4‐phenyl‐1,2,4‐triazole core were synthesized. These synthetic HTMs with donor–acceptor type molecular structures exhibited effective intramolecular charge transfer for improving the hole‐transporting properties. The structural modification of HTMs by thiophene bridging might increase intermolecular π–π stacking in the solid state and afford a better spectral response because of their increased π‐conjugation length. Perovskite‐based cells using TAZ‐[MeOTPA]2 and TAZ‐[MeOTPATh]2 as HTMs afforded high power conversion efficiencies of 10.9 % and 14.4 %, respectively, showing a photovoltaic performance comparable to that obtained using spiro‐OMeTAD. These synthetically simple and inexpensive HTMs hold promise for replacing the more expensive spiro‐OMeTAD in high‐efficiency perovskite solar cells.
Boundary Geometric Control of a Nonlinear Diffusion System with Time‐Dependent Spatial Domain
Authors: Maidi Ahmed , Corriou Jean‐Pierre
Published: November 2015

A Stefan problem represents a distributed parameter system with a time‐dependent spatial domain. This paper addresses the boundary control of the position of the moving liquid–solid interface in the case of nonlinear Stefan problem with Neumann actuation. The main idea consists in deriving an equivalent linear model by means of Cole‐Hopf tangent transformation, i.e. under a certain physical assumption, the original nonlinear Stefan problem is converted to a linear one. Then, the geometric control law is deduced directly from that developed, by the authors of the present paper, for the linear Stefan problem. Based on the fact that the Cole‐Hopf transformation is bijective, it is shown that the developed control law yields a stable closed‐loop system. The performance of the controller is evaluated through numerical simulation in the case of stainless steel melting characterized by a temperature‐dependent thermal conductivity, which is nonlinear. The objective is to control the position of the liquid–solid interface by manipulating a heat flux at the boundary.
Peptide nanospheres self‐assembled from a modified β‐annulus peptide of Sesbania mosaic virus
Authors: Matsuura Kazunori , Mizuguchi Yusaku , Kimizuka Nobuo
Published: November 2015

A novel β‐annulus peptide of Sesbania mosaic virus bearing an FKFE sequence at the C terminus was synthesized, and its self‐assembling behavior in water was investigated. Dynamic light scattering and transmission electron microscopy showed that the β‐annulus peptide bearing an FKFE sequence self‐assembled into approximately 30 nm nanospheres in water at pH 3.8, whereas the β‐annulus peptide without the FKFE sequence afforded only irregular aggregates. The peptide nanospheres possessed a definite critical aggregation concentration (CAC = 26 μM), above which the size of nanospheres were nearly unaffected by the peptide concentration. The formation of peptide nanospheres was significantly affected by pH; the peptide did not form any assemblies at pH 2.2, whereas larger aggregates were formed at pH 6.4–11.6. © 2015 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 106: 470–475, 2016.
Superparamagnetic iron oxide-enhanced MRI at 3 T for accurate axillary staging in breast cancer
Authors: Motomura K , Izumi T , Tateishi S , Tamaki Y , Ito Y , Horinouchi T , Nakanishi K
Published: November 2015

Background

The aim of this study was to evaluate whether MRI at 3 T with superparamagnetic iron oxide (SPIO) enhancement is an accurate and useful method for detecting metastases in sentinel nodes identified by CT-lymphography (CT-LG) in patients with breast cancer. The results were compared with those obtained using CT-LG alone and diagnosing metastasis according to size criteria.

Methods

Patients with clinically node-negative breast cancer were included. Sentinel nodes identified by CT-LG were evaluated prospectively using SPIO-enhanced MRI at 3 T. Sentinel node size was measured on CT-LG, and a node larger than 5 mm in short-axis diameter was considered metastatic. Sentinel nodes localized by CT-LG were removed, and imaging results and histopathological findings were compared.

Results

Sentinel nodes were identified successfully by CT-LG in 69 (99 per cent) of 70 patients. All 19 patients with a finding of metastasis in sentinel nodes at pathology were also shown to have metastases on MRI. Forty-eight of 50 patients with non-metastatic sentinel nodes diagnosed at pathology were classified as having non-metastatic nodes on MRI. On a patient-by-patient basis, the sensitivity, specificity and accuracy of MRI for the diagnosis of sentinel node metastases were 100, 96 and 97 per cent; respective values for CT-LG were 79, 56 and 62 per cent. The specificity and accuracy of MRI were superior to those of CT-LG (P < 0·001 and P = 0·002 respectively).

Conclusion

SPIO-enhanced MRI at 3 T is useful for accurate diagnosis of metastatic sentinel nodes, indicating that sentinel node biopsy may be avoided in patients with breast cancer who have non-metastatic sentinel nodes on imaging.
Effects of Selective Polymerization Conditions on Physical Properties of Nanometer‐Scale Silica/Polypyrrole Composites
Authors: Jung Yongju , Kim Seok , Spray Ryan L. , Yang Hye Jeong , Park Seong‐Hyo , Kim Seokhyeon , Lee Hochun
Published: November 2015

Nanometer‐scale (approximately 70 nm) silica/polypyrrole composites were synthesized using a selective polymerization based on an in situ‐generated strong oxidizing agent (NO
+ ions) on the silica surface. The effects of the concentrations of reactants (pyrrole monomer and NO2

− ions) and the presence of additional dopant anions (Cl− or ) on the polypyrrole (ppy) content and electric conductivity of the silica/ppy composites are examined. It was found that the ppy content in the silica/ppy composites increased with the reactant concentration in the range of 0.02–0.2 M. It is revealed that employing additional dopant anions could be a promising way to improve the electrical conductivity of the composites.
The Phormidolide Biosynthetic Gene Cluster: A trans‐AT PKS Pathway Encoding a Toxic Macrocyclic Polyketide
Authors: Bertin Matthew J. , Vulpanovici Alexandra , Monroe Emily A. , Korobeynikov Anton , Sherman David H. , Gerwick Lena , Gerwick William H.
Published: November 2015

Phormidolide is a polyketide produced by a cultured filamentous marine cyanobacterium and incorporates a 16‐membered macrolactone. Its complex structure is recognizably derived from a polyketide synthase pathway, but possesses unique and intriguing structural features that prompted interest in investigating its biosynthetic origin. Stable isotope incorporation experiments confirmed the polyketide nature of this compound. We further characterized the phormidolide gene cluster (phm) through genome sequencing followed by bioinformatic analysis. Two discrete trans‐type acyltransferase (trans‐AT) ORFs along with KS‐AT adaptor regions (ATd) within the polyketide synthase (PKS) megasynthases, suggest that the phormidolide gene cluster is a trans‐AT PKS. Insights gained from analysis of the mode of acetate incorporation and ensuing keto reduction prompted our reevaluation of the stereochemistry of phormidolide hydroxy groups located along the linear polyketide chain.
Unique Co‐Catalytic Behavior of Protic Ionic Liquids as Multifunctional Electrolytes for Water Splitting
Authors: Li Tianhao , Wang Xiaoyan , Yuan Weiyong , Li Chang Ming
Published: November 2015

Hydrogen production from water splitting holds great promise for solving today's energy crisis but it is challenging to have high efficiency and low cost. For the first time, a protic ionic liquid (PIL), diethylammonium formate (DEAF) was used as a multifunctional electrolyte in water splitting, demonstrating a unique role of co‐catalyst for the hydrogen evolution reaction (HER) with the highest current density (21 mA cm−2 at −0.5 V) and the most positive onset potential (−0.002 V) in comparison to aprotic ILs and commonly used inorganic salts. Moreover, the concentration of PIL and temperature of electrolyte solution were optimized. The possible mechanism for the multifunctionality and high performance for water splitting using this PIL was proposed using X‐ray photoelectron spectroscopy (XPS). The high performance for HER, simplicity and low cost for synthesis, and unique properties make DEAF highly promising as an electrolyte toward water splitting.
High‐Power‐Density Semiconductor–Air Batteries Based on P‐Type Germanium with Different Crystal Orientations
Authors: Ocon Joey D. , Abrenica Graniel Harne A. , Lee Jaeyoung
Published: November 2015

The quasi‐perpetual discharge behavior of Ge anodes in semiconductor–air batteries was first demonstrated in our previous studies, marked by high anode utilization and a flat discharge profile over long‐term discharge operation. In this Article, we show the crystal orientation dependence of the discharge behavior of p‐type Ge anodes. In general, p‐type Ge anodes at the low‐index crystal indices could operate in the milliampere‐scale current range and at high power densities, in stark contrast to the current‐limited operation of Si–air batteries.
Synthesis of Alkynylated Benzo[a]naphtho[2,3‐i]phenazine Derivatives
Authors: Hahn Sebastian , Biegger Philipp , Bender Markus , Rominger Frank , Bunz Uwe H. F.
Published: November 2015

Thermal condensation of 2,3‐diamino‐1,4‐(bistriisopropylsilylethynyl)benzene, ‐naphthalene,‐anthracene, and ‐benzothiadiazole substrates with 1,2‐naphthalenedione forms bent benzophenazine‐type heteroarenes in a one‐step reaction in good to excellent yields. The targets are investigated by UV/Vis spectroscopy, cyclic voltammetry, and single‐crystal X‐ray crystallography. The packing of the targets in the solid state follows either a herringbone or a brick wall motif. In the case of 8,13‐bis(triisopropylsilylethynyl)dibenzo[a,i]phenazine, polymorphs with either packing result.
Directly 2,12‐ and 2,8‐Linked ZnII Porphyrin Oligomers: Synthesis, Optical Properties, and Coherence Lengths
Authors: Jiang Hua‐Wei , Kim Taeyeon , Tanaka Takayuki , Kim Dongho , Osuka Atsuhiro
Published: November 2015

Directly 2,12‐ and 2,8‐linked ZnII porphyrin oligomers were prepared from 2,12‐ and 2,8‐diborylated ZnII porphyrin by a cross platinum‐induced coupling with a 2‐borylated ZnII porphyrin end unit followed by a triphenylphosphine (PPh3)‐mediated reductive elimination. Comparative studies on the steady‐state absorption and fluorescence spectra and the fluorescence lifetimes led to a conclusion that the exciton in the S1 state is delocalized over approximately four and two ZnII porphyrin units for 2,12‐ and 2,8‐linked ZnII porphyrin arrays, respectively.
Visible‐Light/Photoredox‐Mediated sp3 CH Functionalization and Coupling of Secondary Amines with Vinyl Azides in Flow Microreactors
Authors: Tiwari Dharmendra Kumar , Maurya Ram Awatar , Nanubolu Jagadeesh Babu
Published: November 2015

Structurally diverse imidazole derivatives were synthesized by a visible‐light/[Ru(bpy)3][(PF6)2]‐mediated coupling of vinyl azides and secondary amines in flow microreactors. This operationally simple and atom‐economical protocol allows the formation of three new CN bonds through the functionalization of sp3 CH bonds adjacent to the secondary nitrogen atom. In order to get mechanistic insight of the coupling reaction, several control experiments were carried out and discussed.
Three‐dimensional modelling and simulation of sequential co‐injection moulding with application to a toothbrush handle
Authors: Liu Qingsheng , Ouyang Jie , Li Wuming , Zhuang Xin , Jiang Chuntao
Published: November 2015

Sequential co‐injection moulding (SCIM) is a promising technique in industrial production. Because of the complex hydrodynamic effect of air on polymer melts in a moulding process, it is difficult to accurately design and control the process. Corresponding theoretical investigations are very limited, especially for the transient free surface flows in the filling stage. In this paper, a three‐dimensional (3‐D) unified model is proposed for simulating fluids flow in SCIM. The melted polymer and air in the cavity can be regarded as a continuous fluid. The evolution of the melt front interface and skin/core melt interface are captured simultaneously at any moment by the level set method; this method has been widely‐used in two‐phase flow for its ability to track interfaces. The finite volume method is combined with a domain extension technique to deal with 3‐D flows in an irregular cavity. The model is validated by simulating the SCIM process for a cavity with a block insert, and a distinct corner effect is observed. For a widely‐used plastic toothbrush made by SCIM, the evolutions of transient free surfaces in the filling stage are investigated. All numerical results are consistent with corresponding experimental results, and demonstrate the capability of the model with the domain extension technique to simulate multiphase flows in SCIM.
A new plant‐wide optimization method and its application to hydrometallurgy process
Authors: Yuan Qingyun , Wang Fuli , He Dakuo , Wang Hong , Liu Tan
Published: November 2015

This work aims to find an efficient and fast solution for the problem of plant‐wide optimization of a large‐scale industrial process. The process is composed of a series of unit processes with coupling relationships between them, which leads to the problem of optimizing a large number of design variables and constraints. Therefore, the solution to the optimization problem is time‐consuming and the global optimum is obtained with a low probability. To efficiently solve the problem, a new plant‐wide optimization method is developed that decomposes the complicated optimization problem into several easier solvable sub‐problems based on the coupling relationships between unit processes. Two metrics, constraints coupling and indices coupling, are defined in order to measure the extent of a coupling relationship between pairs of unit processes. Then, the global optimum is found by successively solving the sub‐problems. Finally, the hydrometallurgy process of a gold smelter is demonstrated to evaluate the performance of the proposed method.
Numerical investigation of the impact of thermophoresis on the capture efficiency of diesel particulate filters
Authors: Matte‐Deschênes Guillaume , Vidal David , Bertrand François , Hayes Robert E.
Published: November 2015

The present study investigates the impact of thermophoresis on soot capture in the clean cordierite porous wall of a diesel particulate filter (DPF). A three‐step numerical model was developed, consisting of: (1) numerically reconstructing a representative volume of the cordierite porous wall, (2) computing gas flow through the porous wall using the lattice Boltzmann method, and (3) predicting of the DPF capture efficiency based on the time‐dependent solution of a modified Langevin equation that takes thermophoresis into account. The validity of the approach was verified by carefully comparing the permeability predictions of a reconstructed cordierite porous wall to data from the literature. The impact of the magnitude and orientation of the thermophoretic force on the capture of soot particles of various sizes under different flow conditions was investigated. The thermophoretic force applied in or against the flow direction significantly affected the particle capture for the highest particle sizes and flow velocity investigated. Our results suggested that thermophoresis can potentially affect soot deposition uniformity in DPFs. Since the thermophoretic force mainly impacted soot capture efficiency in the presence of particle and flow inertia, a dimensionless criterion defined as the product of Stokes and Reynolds numbers is proposed to predict the onset of what can be called thermophoresis‐enhanced inertial impaction. While similar results have been reported by others using simple flow geometries, this is the first time, to our knowledge, that this phenomenon is reported for a complex cordierite porous wall.
Are Family Small‐ and Medium‐Sized Enterprises More Socially Responsible Than Nonfamily Small‐ and Medium‐Sized Enterprises?
Authors: Laguir Issam , Laguir Lamia , Elbaz Jamal
Published: November 2015

This paper explores whether Moroccan family small‐ and medium‐sized enterprises (SMEs) are more or less likely to be socially responsible than nonfamily firms of comparable size. Basing on 20 qualitative case studies, we collected qualitative data during semi‐structured interviews with SME managers in charge of corporate social responsibility (CSR) issues. We then performed a content analysis. Our study provides consistent support for the stewardship perspective and shows that family SMEs are more likely to be socially responsible than nonfamily SMEs. We therefore posit that familySMEs hold distinctive perspectives on socially responsible business behavior as a result of their involvement in both their business and their community. Copyright © 2015 John Wiley & Sons, Ltd and ERP Environment
Generation of a KOR‐Cre knockin mouse strain to study cells involved in kappa opioid signaling
Authors: Cai Xiaoyun , Huang Huizhen , Kuzirian Marissa S. , Snyder Lindsey M. , Matsushita Megumi , Lee Michael C. , Ferguson Carolyn , Homanics Gregg E. , Barth Alison L. , Ross Sarah E.
Published: November 2015

The kappa opioid receptor (KOR) has numerous important roles in the nervous system including the modulation of mood, reward, pain, and itch. In addition, KOR is expressed in many non‐neuronal tissues. However, the specific cell types that express KOR are poorly characterized. Here, we report the development of a KOR‐Cre knockin allele, which provides genetic access to cells that express KOR. In this mouse, Cre recombinase (Cre) replaces the initial coding sequence of the Opkr1 gene (encoding the kappa opioid receptor). We demonstrate that the KOR‐Cre allele mediates recombination by embryonic day 14.5 (E14.5). Within the brain, KOR‐Cre shows expression in numerous areas including the cerebral cortex, nucleus accumbens and striatum. In addition, this allele is expressed in epithelium and throughout many regions of the body including the heart, lung, and liver. Finally, we reveal that KOR‐Cre mediates recombination of a subset of bipolar and amacrine cells in the retina. Thus, the KOR‐Cre mouse line is a valuable new tool for conditional gene manipulation to enable the study of KOR. genesis 54:29–37, 2016. © 2015 Wiley Periodicals, Inc.
Specialists in ancient trees are more affected by climate than generalists
Authors: Gough Leonie A. , Sverdrup‐Thygeson Anne , Milberg Per , Pilskog Hanne E. , Jansson Nicklas , Jonsell Mats , Birkemoe Tone
Published: November 2015

Ancient trees are considered one of the most important habitats for biodiversity in Europe and North America. They support exceptional numbers of specialized species, including a range of rare and endangered wood‐living insects. In this study, we use a dataset of 105 sites spanning a climatic gradient along the oak range of Norway and Sweden to investigate the importance of temperature and precipitation on beetle species richness in ancient, hollow oak trees. We expected that increased summer temperature would positively influence all wood‐living beetle species whereas precipitation would be less important with a negligible or negative impact. Surprisingly, only oak‐specialist beetles with a northern distribution increased in species richness with temperature. Few specialist beetles and no generalist beetles responded to the rise of 4°C in summer as covered by our climatic gradient. The negative effect of precipitation affected more specialist species than did temperature, whereas the generalists remained unaffected. In summary, we suggest that increased summer temperature is likely to benefit a few specialist beetles within this dead wood community, but a larger number of specialists are likely to decline due to increased precipitation. In addition, generalist species will remain unaffected. To minimize adverse impacts of climate change on this important community, long‐term management plans for ancient trees are important.
Does origin always matter? Evaluating the influence of nonlocal seed provenances for ecological restoration purposes in a widespread and outcrossing plant species
Authors: Reiker Jutta , Schulz Benjamin , Wissemann Volker , Gemeinholzer Birgit
Published: November 2015

For restoration purposes, nature conservation generally enforces the use of local seed material based on the “local‐is‐best” (LIB) approach. However, in some cases recommendations to refrain from this approach have been made. Here we test if a common widespread species with no obvious signs of local adaptation may be a candidate species for abandoning LIB during restoration. Using 10 microsatellite markers we compared population genetic patterns of the generalist species Daucus carota in indigenous and formerly restored sites (nonlocal seed provenances). Gene diversity overall ranged between He = 0.67 and 0.86 and showed no significant differences between the two groups. Hierarchical AMOVA and principal component analysis revealed very high genetic population admixture and negligible differentiation between indigenous and restored sites (FCT = 0.002). Moreover, differentiation between groups was caused by only one outlier population, where inbreeding effects are presumed. We therefore conclude that the introduction of nonlocal seed provenances in the course of landscape restoration did not jeopardize regional species persistence by contributing to inbreeding or outbreeding depressions, or any measurable adverse population genetic effect. On the basis of these results, we see no obvious objections to the current practice to use the 10‐fold cheaper, nonlocal seed material of D. carota for restoration projects.
World Bank Partnerships and the Promise of Democratic Governance
Authors: Kramarz Teresa
Published: November 2015

The World Bank promotes public–private partnerships as vehicles for democratizing environmental governance. This article presents an overview of their constitution in the World Bank, including what the Bank as an organization identified as their promise, and investigates what its partnerships for biodiversity conservation achieved. The article focuses on the institutional design of partnerships’ governance structures, and assesses their democratic quality based on their potential to enable inclusion and empowerment of stakeholders. It examines nine global biodiversity partnerships between the World Bank and non‐state actors from 1992 to 2008 and analyses the extent to which they have fulfilled the principled expectations expressed by the Bank. I find that partnerships have been organized through institutional arrangements that fail to promote inclusiveness and empowerment, which are minimum normative inputs for democratic decision‐making in natural resource management. This suggests that World Bank partnerships are not sufficiently well poised to fulfil the democratic promise. Copyright © 2015 John Wiley & Sons, Ltd and ERP Environment
Interagency Aspects of Environmental Policy: The Case of Environmental Health
Authors: Negev Maya
Published: November 2015

National government agencies typically are fragmented into fields, such as health, environment, transportation, economy and agriculture. Yet, advancing environmental health (EH) policy requires collaboration across agencies. This paper maps instruments for interagency EH cooperation, explores EH policy dynamics in Israel and identifies implications for policy integration. Twenty‐six semi‐structured interviews were conducted with policy‐makers and other stakeholders, and two integration instruments were explored in depth: an interministerial committee and a parliamentary committee. The examination revealed that integration of EH considerations may occur in various policy‐making settings and is sensitive to other inhibiting and facilitating factors, e.g. power relations and political will. In this preliminary qualitative study, higher levels of integration in the policy process did not result in more integrated EH outputs. We conclude that integration of EH considerations can take many forms and levels of cooperation, but always requires attention to the local setting, specific inhibitors and evaluation of outcomes. Copyright © 2015 John Wiley & Sons, Ltd and ERP Environment
Cultivar discrimination and prediction of mixtures of Tunisian extra virgin olive oils by FTIR
Authors: Abdallah Marwa , Vergara‐Barberán María , Lerma‐García María Jesús , Herrero‐Martínez José Manuel , Simó‐Alfonso Ernesto F. , Guerfel Mokhtar
Published: November 2015

Fourier‐transform infrared spectroscopy, followed by multivariate treatment of the spectral data, was used to classify Tunisian extra virgin olive oils (EVOOs) according to their cultivar. Moreover, these data were also employed to establish the composition of binary mixtures of EVOOs from different cultivars. For this purpose, the spectra were divided in 20 regions, being the normalized peak areas within these regions used as predictors. Using linear discriminant analysis, an excellent resolution between EVOOs from different cultivar was obtained. Moreover, multiple linear regression models were used to predict the composition of binary mixtures of EVOOs, being in all cases capable of predicting the percentage of one of the oils with average validation errors below 6%. Thus, the FTIR method proposed in this work, followed by chemometric analysis, could be used in an industrial setting since no complicated laboratory facilities are required, which could save great deal of time and money.

Practical applications: EVOO quality can be affected by different parameters, such as cultivar and maturity index, among others, consequently, it is necessary to develop analytical methods able to verify EVOO quality, and also to control its origin since olive oil producers have to include in their manufactured products the cultivar (monovarietal oils) from which the oil was obtained. Currently, almost all the research related to Tunisian EVOOs has been mainly focused on the improvement and characterization of the two main cultivars (Chétoui and Chemlali). Thus, to diversify Tunisian olive oil resources and improve the quality of olive oil produced in Tunisia, research on additional cultivars needs to be conducted. Thus, the present methodology (including the application of chemometric techniques) could be used as an authentication tool for olive oil industry to assess cultivar of EVOO.

ATR‐FTIR data of Tunisian EVOOs are used to predict EVOO cultivar using LDA.
Relationships between plasma and erythrocyte fatty acids in the de novo lipogenesis pathway, and metabolic disorders in French elderly patients
Authors: Henry Olivier , Vaysse Carole , Lopez Carlos , Driss Fathi , Fonseca Isabelle , Simon Noëmie , Guillou Céline Le , Masselin‐Silvin Sylvie , David Jean‐Philippe , Combe Nicole , Mendy François
Published: November 2015

Undernutrition has been identified as a major contributing factor to morbidity and mortality in hospitalized aged patients. The lipid calorie undernutrition may lead to de novo lipogenesis (DNL); among the endogenous fatty acids, 16: 1(n‐9) and 18:1 (n‐7) have been previously associated with a higher risk of sudden cardiac arrest (SCA). The aim was to examine possible associations between the fatty acids in the DNL pathway present in both plasma and erythrocytes of 188 patients aged 84 ± 7 years (48 men and 140 women) entering the geriatric department for evaluation and rehabilitation, and their metabolic disorders. The 18:1(n‐7) content in plasma cholesteryl esters (CE) was significantly higher in men (1.67 vs. 1.58% in women; P < 0.05). An inverse relationship was found between 18:1 (n‐7) and the two precursors of essential fatty acids (EFA), that is linoleic acid [18:2 (n‐6); LA] and alpha‐linolenic acid [18:3 (n‐3); ALA]. Moreover, an inverse relationship was found between 16: 1(n‐9) and LA. Sixty‐four percent of men suffered from dysglycemia versus 46% of women (P < 0.05). These patients were characterized by significantly higher content (+37%) of 16:1(n‐7) which derives mostly from DNL. Prevalence of metabolic syndrome (MetS) was 30–40%, associated with a higher level of 18:0, regardless of sex.

Practical applications: Improving nutrition for the elderly patients is a key challenge for rehabilitation. The diet of our oldest old patients was low in total calories and low in fat; it might be partly responsible for the levels of fatty acids from DNL observed. Further study is needed to investigate whether it is possible to reduce both 18:1 (n‐7) and 16: 1(n‐9) levels. We propose to test the improvement of diet for our oldest old patients by increasing fat up to 70 g/d which is the lower limit of the recommended amounts.

Simplified summary of the main objective: to examine potential relationships between the fatty acids in the DNL pathway and metabolic disorders (dysglycemia and MetS), factors of the cardiovascular risk in the elderly patients by sex.
Shea butter solid nanoparticles for curcumin encapsulation: Influence of nanoparticles size on drug loading
Authors: Hajj Ali Hassan , Michaux Florentin , Bouelet Ntsama Isabelle Sandrine , Durand Pierrick , Jasniewski Jordane , Linder Michel
Published: November 2015

In the present work, shea butter solid lipid nanoparticles (SLN) were prepared by sonication using nonionic surfactants as stabilizers without organic solvent. The mixture design methodology enabled to control particles size from 50 nm to more than 1 μm according to the mixture composition. Then, curcumin, a natural polyphenol, has been encapsulated in nanoparticles with a wide range of diameters (50–230 nm) and the encapsulation efficiency has been related to the particles sizes. The bigger the nanoparticles, the lower the encapsulation efficiency. The lipid structure at non dispersed state and under SLN form has been studied by differential scanning calorimetry and X‐ray diffraction. From the obtained results, encapsulated curcumin did not affect the lipid properties at the SLN state unlike at non dispersed state. The localization of the curcumin in the outer shell of the lipid nanoparticles explained the evolution of the encapsulation efficiency according to the nanoparticles size.

Practical applications: Solid lipid nanoparticles (SLN) can be used for the delivery of both hydrophobic and hydrophilic drugs. Preparing such nanovectors with natural, non‐expensive materials and easily available (i.e., shea butter) will promote their potential use in several applications like oral, parenteral, dermal or ocular delivery. Controlling the particles size from the formulation composition and also the drug loading from SLN properties is of main importance to optimize the use of SLN as colloidal carrier.

Mixture design of experiments methodology allowed the control of shea butter solid lipid nanoparticles size upon system composition. The influence of SLN size on the encapsulation efficiency of curcumin was studied.