bluuebunny/crossref_metadata_2025 huggingface dataset:
Mesenchymal Stromal Cells in Animal Bleomycin Pulmonary Fibrosis Models: A Systematic Review
Authors: Srour Nadim , Thébaud Bernard
Published: October 2015

Idiopathic pulmonary fibrosis is an inexorably progressive lung disease with few available treatments. New therapeutic options are needed. Stem cells have generated much enthusiasm for the treatment of several conditions, including lung diseases. Human trials of mesenchymal stromal cell (MSC) therapy for pulmonary fibrosis are under way. To shed light on the potential usefulness of MSCs for human disease, we aimed to systematically review the preclinical literature to determine if MSCs are beneficial in animal bleomycin pulmonary fibrosis models. The MEDLINE and Embase databases were searched for original studies of stem cell therapy in animal bleomycin models of pulmonary fibrosis. Studies using embryonic stem cells or induced pluripotent stem cells were excluded. Seventeen studies were selected, all of which used MSCs in rodents. MSC therapy led to an improvement in bleomycin-induced lung collagen deposition in animal lungs and in the pulmonary fibrosis Ashcroft score in most studies. MSC therapy improved histopathology in almost all studies in which it was evaluated qualitatively. Furthermore, MSC therapy was found to improve 14-day survival in animals with bleomycin-induced pulmonary fibrosis. Bronchoalveolar lavage total and neutrophil counts, as well as transforming growth factor-β levels, were also reduced by MSCs. MSCs are beneficial in rodent bleomycin pulmonary fibrosis models. Since most studies examined the initial inflammatory phase rather than the chronic fibrotic phase, preclinical data offer better support for human trials of MSCs in acute exacerbations of pulmonary fibrosis rather than the chronic phase of the disease.

Significance

There has been increased interest in mesenchymal stromal cell therapy for lung diseases. A few small clinical trials are under way in idiopathic pulmonary fibrosis. Preclinical evidence was assessed in a systematic review, as is often done for clinical studies. The existing studies offer better support for efficacy in the initial inflammatory phase rather than the fibrotic phase that human trials are targeting.
Gluten-free food database: the nutritional quality and cost of packaged gluten-free foods
Authors: Missbach Benjamin , Schwingshackl Lukas , Billmann Alina , Mystek Aleksandra , Hickelsberger Melanie , Bauer Gregor , König Jürgen
Published: October 2015

Notwithstanding a growth in popularity and consumption of gluten-free (GF) food products, there is a lack of substantiated analysis of the nutritional quality compared with their gluten-containing counterparts. To put GF foods into proper perspective both for those who need it (patients with celiac disease) and for those who do not, we provide contemporary data about cost and nutritional quality of GF food products. The objective of this study is to develop a food composition database for seven discretionary food categories of packaged GF products. Nutrient composition, nutritional information and cost of foods from 63 GF and 126 gluten-containing counterparts were systematically obtained from 12 different Austrian supermarkets. The nutrition composition (macro and micronutrients) was analyzed by using two nutrient composition databases in a stepwise approximation process. A total of 63 packaged GF foods were included in the analysis representing a broad spectrum of different GF categories (flour/bake mix, bread and bakery products, pasta and cereal-based food, cereals, cookies and cakes, snacks and convenience food). Our results show that the protein content of GF products is >2 fold lower across 57% of all food categories. In 65% of all GF foods, low sodium content was observed (defined as <120 mg/100 g). Across all GF products, 19% can be classified as source high in fiber (defined as >6g/100 g). On average, GF foods were substantially higher in cost, ranging from +205% (cereals) to +267% (bread and bakery products) compared to similar gluten-containing products. In conclusion, our results indicate that for GF foods no predominant health benefits are indicated; in fact, some critical nutrients must be considered when being on a GF diet. For individuals with celiac disease, the GF database provides a helpful tool to identify the food composition of their medical diet. For healthy consumers, replacing gluten-containing products with GF foods is aligned with substantial cost differences but GF foods do not provide additional health benefits from a nutritional perspective.
Evaluation of nutritional and economic feed values of spent coffee grounds andArtemisia princepsresidues as a ruminant feed usingin vitroruminal fermentation
Authors: Seo Jakyeom , Jung Jae Keun , Seo Seongwon
Published: October 2015

Much research on animal feed has focused on finding alternative feed ingredients that can replace conventional ones (e.g., grains and beans) to reduce feed costs. The objective of this study was to evaluate the economic, as well as nutritional value of spent coffee grounds (SCG) and Japanese mugwort (Artemisia princeps) residues (APR) as alternative feed ingredients for ruminants. We also investigated whether pre-fermentation usingLactobacillusspp. was a feasible way to increase the feed value of these by-products. Chemical analyses and anin vitrostudy were conducted for SCG, APR, and their pre-fermented forms. All the experimental diets forin vitroruminal fermentation were formulated to contain a similar composition of crude protein, neutral detergent fiber and total digestible nutrients at 1x maintenance feed intake based on the dairy National Research Council (NRC). The control diet was composed of ryegrass, corn, soybean meal, whereas the treatments consisted of SCG, SCG fermented withLactobacillusspp. (FSCG), APR, and its fermented form (FAPR). The treatment diets replaced 100 g/kg dry matter (DM) of the feed ingredients in the control. Costs were lower for the all treatments, except FAPR, than that of the control. After 24-h incubation, the NDF digestibility of the diets containing SCG and its fermented form were significantly lower than those of the other diets (P< 0.01); pre-fermentation tended to increase NDF digestibility (P= 0.07), especially for APR. Supplementation of SCG significantly decreased total gas production (ml/g DM) after 24-h fermentation in comparison with the control (P< 0.05); however, there were no significant differences between the control and the SCG or the APR diets in total gas production, as expressed per Korean Won (KRW). Diets supplemented with SCG or FSCG tended to have a higher total volatile fatty acid (VFA) concentration, expressed as per KRW, compared with the control (P= 0.06). Conversely, the fermentation process of SCG and APR significantly decreased total gas production and VFA production as expressed per KRW (P< 0.05). Because of their nutrient composition and relatively lower cost, we concluded that SCG and APR could be used as alternative feed sources, replacing conventional feed ingredients. However, pre-fermentation of agricultural by-products, such as SCG and APR, may be inappropriate for improving their nutritive considering the increase in production costs.
Cheetahs (Acinonyx jubatus) running the gauntlet: an evaluation of translocations into free-range environments in Namibia
Authors: Weise Florian J. , Lemeris Joseph R. , Munro Stuart J. , Bowden Andrew , Venter Cicelia , van Vuuren Marlice , van Vuuren Rudie J.
Published: October 2015

Following dramatic range and population declines, the cheetah is Africa’s most endangered large felid. In Namibia, private land managers still trap cheetahs but increasingly consider moving animals instead of killing them. Across Africa, managers have translocated perceived conflict carnivores for decades, but rarely evaluated their actions. We analyse the outcomes of 15 cheetah translocations (for 23 adults and 10 dependent offspring) into free-range environments in Namibia. We released cheetahs at an average distance of 419.6 km ± 216.1 km SD (range: 71–816 km) after captive periods ranging from 1–1,184 days (350.6 days ± 439.0 days SD). An individual’s ability to survive the first year predominantly determined the overall translocation success of 40%. Post-release conflict and homing had less impact on success. Cheetah survival was lowest in the first three months after release. Human persecution (50% of deaths) and spotted hyaenas (29% of deaths) had the highest effect on survival. The degree of habituation to humans acquired during captivity significantly influenced chances of survival. Cheetahs surviving the initial post-release period (∼90 days) often settled into ranges and females reproduced successfully. However, all individuals exhibited extensive movements, frequently roaming >4,000 km2in the first six months after release (with a maximum of 19,743 km2in 112 days), resulting in low release site fidelity. Soft release and larger recipient area size did not improve site fidelity. Based on these outcomes, we evaluated which unfenced conservation areas in Namibia could potentially receive cheetahs. We found that there are currently few public and/or private reserves large enough to contain the movement profiles we observed in this study. This suggests that most translocations will result in cheetahs re-entering farmlands where they face a high risk of persecution. In conclusion, translocations into unconfined areas can successfully conserve individual cheetahs. Due to high mortality and unpredictable outcomes, however, conservation efforts need to focus on improving tolerance of cheetahs in commercial livestock and game farming areas in order to reduce the number of indiscriminately trapped animals.
Urban habitat complexity affects species richness but not environmental filtering of morphologically-diverse ants
Authors: Ossola Alessandro , Nash Michael A. , Christie Fiona J. , Hahs Amy K. , Livesley Stephen J.
Published: October 2015

Habitat complexity is a major determinant of structure and diversity of ant assemblages. Following the size-grain hypothesis, smaller ant species are likely to be advantaged in more complex habitats compared to larger species. Habitat complexity can act as an environmental filter based on species size and morphological traits, therefore affecting the overall structure and diversity of ant assemblages. In natural and semi-natural ecosystems, habitat complexity is principally regulated by ecological successions or disturbance such as fire and grazing. Urban ecosystems provide an opportunity to test relationships between habitat, ant assemblage structure and ant traits using novel combinations of habitat complexity generated and sustained by human management. We sampled ant assemblages in low-complexity and high-complexity parks, and high-complexity woodland remnants, hypothesizing that (i) ant abundance and species richness would be higher in high-complexity urban habitats, (ii) ant assemblages would differ between low- and high-complexity habitats and (iii) ants living in high-complexity habitats would be smaller than those living in low-complexity habitats. Contrary to our hypothesis, ant species richness was higher in low-complexity habitats compared to high-complexity habitats. Overall, ant assemblages were significantly different among the habitat complexity types investigated, although ant size and morphology remained the same. Habitat complexity appears to affect the structure of ant assemblages in urban ecosystems as previously observed in natural and semi-natural ecosystems. However, the habitat complexity filter does not seem to be linked to ant morphological traits related to body size.
Peptide Materials Obtained by Aggregation of Polyphenylalanine Conjugates as Gadolinium‐Based Magnetic Resonance Imaging Contrast Agents
Authors: Diaferia Carlo , Gianolio Eliana , Palladino Pasquale , Arena Francesca , Boffa Cinzia , Morelli Giancarlo , Accardo Antonella
Published: October 2015

Peptide materials based on the aggregation of polyphenylalanine conjugates containing gadolinium complexes and acting as potential contrast agents (CAs) in magnetic resonance imaging (MRI) are described. Monomers contain two (F2) or four (F4) phenylalanine residues for self‐assembly, a chelating agent, 1,4,7,10‐tetraazacyclododecane‐N,N,N,N‐tetraacetic acid (DOTA) or diethylenetriaminepentaacetic acid (DTPA), for achieving gadolinium coordination, and ethoxylic linkers at two (L2) or six (L6) poly(ethylene glycol) (PEG) units between the chelating group and the peptide region. Both DOTA and DTPA tetraphenylalanine derivatives, and their gadolinium complexes DOTA(Gd)‐L6‐F4 and DTPA(Gd)‐L6‐F4, are able to self‐aggregate at very low concentration. Structural characterization, obtained by circular dichroism and infrared measurements, confirms the amyloid type fibril formation in which an antiparallel peptide alignment is preferred. Amyloid type fibril formation is also observed, in solid state, by transmission electron microscopy images and X‐ray diffraction patterns. The relaxivity values of DOTA(Gd)‐L6‐F4 and DTPA(Gd)‐L6‐F4 and their ability to enhance the MRI cellular response on the J774A.1 mouse macrophages cell line indicate that these peptide materials are promising candidate as a new class of supramolecular gadolinium based MRI contrast agents.
Advanced Inorganic Nanoarchitectures from Oriented Self‐Assembly
Authors: Lu Chenguang , Tang Zhiyong
Published: October 2015

Complex and well‐defined nanostructures are promising for emerging properties with broad applications. Self‐assembly processes driven by diverse interactions generate varied nanostructures by using versatile nanocrystals as building blocks, while oriented attachment growth allows individual nanocrystals to be integrated and fused into highly anisotropic structures. By a combination of self‐assembly technique and oriented attachment growth, many advanced nanostructures can be made. Such approaches can be viewed as an architecture of the nanoscale counterparts in the microworld, named as nanoarchitectures.
Trifluorodiazoethane (CF3CHN2) in the Uncatalyzed Cyclopropanation of 3‐Arylmethylenebenzofuran‐2(3 H)‐ones
Authors: Zhu Chuan‐Le , Ma Jun‐An , Cahard Dominique
Published: October 2015

The uncatalyzed cyclopropanation of 2,2,2‐trifluorodiazoethane onto 3‐arylmethylenebenzofuran‐2(3 H)‐ones leads to highly functionalized trifluoromethylated spirocyclopropanes. A thermal activation mode not requiring the addition of a transition metal provided high product yields, whereas a salt effect benefited the diastereomeric ratios obtained. The products are readily elaborated to non‐spiro derivatives.
MiniAp‐4: A Venom‐Inspired Peptidomimetic for Brain Delivery
Authors: Oller‐Salvia Benjamí , Sánchez‐Navarro Macarena , Ciudad Sonia , Guiu Marc , Arranz‐Gibert Pol , Garcia Cristina , Gomis Roger R. , Cecchelli Roméo , García Jesús , Giralt Ernest , Teixidó Meritxell
Published: October 2015

Drug delivery across the blood–brain barrier (BBB) is a formidable challenge for therapies targeting the central nervous system. Although BBB shuttle peptides enhance transport into the brain non‐invasively, their application is partly limited by lability to proteases. The present study proposes the use of cyclic peptides derived from venoms as an affordable way to circumvent this drawback. Apamin, a neurotoxin from bee venom, was minimized by reducing its complexity, toxicity, and immunogenicity, while preserving brain targeting, active transport, and protease resistance. Among the analogues designed, the monocyclic lactam‐bridged peptidomimetic MiniAp‐4 was the most permeable. This molecule is capable of translocating proteins and nanoparticles in a human‐cell‐based BBB model. Furthermore, MiniAp‐4 can efficiently deliver a cargo across the BBB into the brain parenchyma of mice.
A Multifunctional Subphthalocyanine Nanosphere for Targeting, Labeling, and Killing of Antibiotic‐Resistant Bacteria
Authors: Roy Indranil , Shetty Dinesh , Hota Raghunandan , Baek Kangkyun , Kim Jeesu , Kim Chulhong , Kappert Sandro , Kim Kimoon
Published: October 2015

Developing a material that can combat antibiotic‐resistant bacteria, a major global health threat, is an urgent requirement. To tackle this challenge, we synthesized a multifunctional subphthalocyanine (SubPc) polymer nanosphere that has the ability to target, label, and photoinactivate antibiotic‐resistant bacteria in a single treatment with more than 99 % efficiency, even with a dose as low as 4.2 J cm−2 and a loading concentration of 10 nM. The positively charged nanosphere shell composed of covalently linked SubPc units can increase the local concentration of photosensitizers at therapeutic sites. The nanosphere shows superior performance compared to corresponding monomers presumably because of their enhanced water dispersibility, higher efficiency of singlet‐oxygen generation, and phototoxicity. In addition, this material is useful in fluorescence labeling of living cells and shows promise in photoacoustic imaging of bacteria in vivo.
Microhydration Effects on the Ultrafast Photodynamics of Cytosine: Evidences for a Possible Hydration‐Site Dependence
Authors: Ho Jr‐Wei , Yen Hung‐Chien , Shi Hui‐Qi , Cheng Li‐Hao , Weng Chih‐Nan , Chou Wei‐Kuang , Chiu Chih‐Chung , Cheng Po‐Yuan
Published: October 2015

Ultrafast excited‐state deactivation dynamics of small cytosine (Cy) and 1‐methylcytosine (1mCy) microhydrates, Cy⋅(H2O)1‐3 and 1mCy⋅(H2O)1,2, produced in a supersonic expansion have been studied by mass‐selected femtosecond pump–probe photoionization spectroscopy at about 267 nm excitation. The seeded supersonic expansion of Ar/H2O gas mixtures allowed an extensive structural relaxation of Cy and 1mCy microhydrates to low‐energy isomers. With the aid of electronic structure calculations, we assigned the observed ultrafast dynamics to the dominant microhydrate isomers of the amino‐keto tautomer of Cy and 1mCy. Excited‐state lifetimes of Cy⋅(H2O)1‐3 measured here are 0.2–0.5 ps. Comparisons of the Cy⋅H2O and 1mCy⋅H2O transients suggest that monohydration at the amino Watson–Crick site induces a substantially stronger effect than at the sugar‐edge site in accelerating excited‐state deactivation of Cy.
Controlled Synthesis of N‐Doped Carbon Nanospheres with Tailored Mesopores through Self‐Assembly of Colloidal Silica
Authors: Wang Gang , Sun Yuhan , Li Debao , Liang Hai‐Wei , Dong Renhao , Feng Xinliang , Müllen Klaus
Published: October 2015

Limited strategies have been established to prepare monodisperse mesoporous carbon nanospheres (MCNs) with tailored pore sizes. In this work, a method is reported to synthesize MCNs by combining polymerization of aniline with co‐assembly of colloidal silica nanoparticles. The controlled self‐assembly behavior of colloidal silica enables the formation of uniform composite nanospheres and convenient modulation over mesopores. After carbonization and removal of sacrificial templates, the resultant MCNs possess tunable mesopores (7–42 nm) and spherical diameters (90–300 nm), as well as high surface area (785–1117 m2 g−1), large pore volume (1.46–2.01 cm3 g−1) and abundant nitrogen moieties (5.54–8.73 at %). When serving as metal‐free electrocatalysts for the oxygen reduction reaction (ORR), MCNs with an optimum pore size of 22 nm, compared to those with 7 and 42 nm, exhibit the best ORR performance in alkaline medium.
Expanding the Ligand Framework Diversity of Carbodicarbenes and Direct Detection of Boron Activation in the Methylation of Amines with CO2
Authors: Chen Wen‐Ching , Shen Jiun‐Shian , Jurca Titel , Peng Chun‐Jung , Lin Yen‐Hsu , Wang Yi‐Ping , Shih Wei‐Chih , Yap Glenn P. A. , Ong Tiow‐Gan
Published: October 2015

A simple and convergent synthetic strategy used to increase the diversity of the carbodicarbene ligand framework through incorporation of unsymmetrical pendant groups is reported. Structural analysis and spectroscopic studies of ligands and their Rh complexes are reported. Reactivity studies reveal carbodicarbenes as competent organocatalysts for amine methylation using CO2 as a synthon. A unique BH‐activated boron–carbodicarbene complex was isolated as a reaction intermediate, providing mechanistic insight into the CO2 functionalization process.
Spontaneous Mirror‐Symmetry Breaking in Isotropic Liquid Phases of Photoisomerizable Achiral Molecules
Authors: Alaasar Mohamed , Prehm Marko , Cao Yu , Liu Feng , Tschierske Carsten
Published: October 2015

Spontaneous mirror‐symmetry breaking is of fundamental importance in science as it contributes to the development of chiral superstructures and new materials and has a major impact on the discussion around the emergence of uniform chirality in biological systems. Herein we report chirality synchronization, leading to spontaneous chiral conglomerate formation in isotropic liquids of achiral and photoisomerizable azobenzene‐based rod‐like molecules. The position of fluorine substituents at the aromatic core is found to have a significant effect on the stability and the temperature range of these chiral liquids. Moreover, these liquid conglomerates occur in a new phase sequence adjacent to a 3D tetragonal mesophase.
Fabrication of micro‐meltblown filtration media using parallel plate die design
Authors: Hassan Mohammad Abouelreesh , Khan Saad A. , Pourdeyhimi Behnam
Published: October 2015

Meltblown fibers are typically produced using a die technology based on the slot concept, an extension of the sheet die technology with a series of holes substituting the center rectangular slot of the sheet die. While this prevalent technology has met with considerable success, an economical, facile design would be desirable. In this study a new parallel plate die concept to fabricate micro‐meltblown fibers that offers simplicity, ease of use, and low cost was examined. The new die concept had parallel plates forming channels for polymer melt to flow through with a set of air holes surrounding them. This die design produced meltblown fibrous media with fibers in the range of 3–10 μm with pore size between 20 and 60 microns. The underlying mechanisms leading to such large fiber size formation and its implication in air filtration performance has been discussed. While conventional meltblown die generates fibers of smaller diameter and webs with higher filtration efficiency than the parallel plate geometry, design modifications could enhance the parallel plate meltblown die performance and make it a viable alternative. These die adaptations that include reducing air flow resistance, increasing the number of air nozzles around the polymer nozzles, recessing the polymer spinnerets above the die face, and having inclined air channels to increase the drag force on the fibers has been discussed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 42998.
Outcomes in emergency general surgery following the introduction of a consultant-led unit
Authors: Shakerian R , Thomson B N , Gorelik A , Hayes I P , Skandarajah A R
Published: October 2015

Background

Patients presenting with emergency surgical conditions place significant demands on healthcare services globally. The need to improve emergency surgical care has led to establishment of consultant-led emergency surgery units. The aim of this study was to determine the effect of a changed model of service on outcomes.

Methods

A retrospective observational study of all consecutive emergency general surgical admissions in 2009–2012 was performed. A 2-year time frame before and after the establishment of the emergency general surgery (EGS) service was used to determine the number of admissions and operations, emergency department and hospital length of stay, as well as complication rates.

Results

The study included 7233 acute admissions. The EGS service managed 4468 patients (61·6 per cent increase) and performed 1804 operations (41·0 per cent increase). The most common diagnoses during the EGS period included acute appendicitis (532, 11·9 per cent), biliary disease (361, 8·1 per cent) and abdominal pain (561, 12·6 per cent). Appendicectomy (536, 29·7 per cent), cholecystectomy (239, 13·2 per cent) and laparotomy (226, 12·5 per cent) were the most commonly performed procedures. In the EGS period, time in the emergency department was reduced (from 8·0 to 6·0 h; P < 0·001), as was length of hospital stay (from 3·0 to 2·0 days; P < 0·001). The number of complications was reduced by 46·8 per cent, from 172 (6·2 per cent) to 147 (3·3 per cent) (P < 0·001), with a 53 per cent reduction in the number of deaths in the EGS period, from 29 (16·9 per cent) to seven (8 per cent) (P = 0·039).

Conclusion

The establishment of a consultant-led emergency surgical service has been associated with improved provision of care, resulting in timely management and improved clinical outcomes.
Eupalitin induces apoptosis in prostate carcinoma cells through ROS generation and increase of caspase‐3 activity
Authors: Kaleem Sarjeel , Siddiqui Sahabjada , Siddiqui Hefazat Hussain , Badruddeen  , Hussain Arshad , Arshad Mohammad , Akhtar Juber , Rizvi Aleza
Published: October 2015

Prostate cancer is the second most common malignancy in the human reproductive system. Eupalitin is one of the O‐methylated flavonol‐exhibited enhanced cancer chemopreventive agents. The current study highlights the structural determination of eupalitin and aims to explore the antitumor activity of eupalitin in human prostate cancer cell (PC3) and its underlying mechanism. Eupalitin structure was determined by using FTIR, 1H NMR, and 13C NMR. PC3 cells were treated with increasing concentrations of eupalitin, followed by analysis of the cell viability with an MTT assay. The results demonstrated that eupalitin markedly inhibited the proliferation of PC3 cells in a concentration‐dependent manner. The results from fluorescent microscopic analysis of nuclear condensation and intracellular ROS generation determined that eupalitin significantly induced ROS level lead to nuclear apoptosis. Cell cycle analysis revealed that eupalitin‐induced cell cycle progression as a percentage of cells in G0/G1 phase decreased whereas S phase increased. Caspase‐3 immunofluorescence analysis confirms the efficacy of eupalitin‐inducing apoptotic pathway and cell death. Thus, our study is helpful in understanding the mechanism underlying these effects in prostate cancer and it may provide novel molecular targets for prostate cancer therapy.
Brief intervention in ED for risky drinking found promising for teens
Authors: Knopf Alison
Published: October 2015

Screening and brief intervention for risky drinking in teens in the emergency department (ED), done with a computer or a therapist, is effective in the short and long term, researchers have found.
Asymmetric Amination of Secondary Alcohols by using a Redox‐Neutral Two‐Enzyme Cascade
Authors: Chen Fei‐Fei , Liu You‐Yan , Zheng Gao‐Wei , Xu Jian‐He
Published: October 2015

Multienzyme cascade approaches for the synthesis of optically pure molecules from simple achiral compounds are desired. Herein, a cofactor self‐sufficient cascade protocol for the asymmetric amination of racemic secondary alcohols to the corresponding chiral amines was successfully constructed by employing an alcohol dehydrogenase and a newly developed amine dehydrogenase. The compatibility and the identical cofactor dependence of the two enzymes led to an ingenious in situ cofactor recycling system in the one‐pot synthesis. The artificial redox‐neutral cascade process allowed the transformation of racemic secondary alcohols into enantiopure amines with considerable conversions (up to 94 %) and >99 % enantiomeric excess at the expense of only ammonia; this method thus represents a concise and efficient route for the asymmetric synthesis of chiral amines.
Selective Formation of Hägg Iron Carbide with g‐C3N4 as a Sacrificial Support for Highly Active Fischer–Tropsch Synthesis
Authors: Park Hunmin , Youn Duck Hyun , Kim Jae Young , Kim Won Yong , Choi Yo Han , Lee Young Hye , Choi Sun Hee , Lee Jae Sung
Published: October 2015

The Fischer–Tropsch synthesis (FTS) is a feasible pathway to chemicals and fuels from underutilized resources like coal, natural gas, biomass, and shale gas, instead of the current petroleum‐based production. Owing to its high activity and low price, the iron‐based catalysts are widely used in FTS, yet catalysts with higher activity and better selectivity should be developed for widespread applications. Herein, we report a unique strategy to synthesize an efficient iron catalyst for FTS by applying a graphitic carbon nitride (g‐C3N4) as a sacrificial support. The iron catalyst on g‐C3N4 is effectively reduced to a state that is rapidly and selectively converted to highly crystalline and pure Hägg carbide (χ‐Fe5C2) phase during the FTS reaction. The obtained catalyst exhibits outstanding CO conversion, and high selectivity for C5+ products, outperforming most of the recently reported carbon‐based iron catalysts.
Biofunctionalization of Polyoxometalates with DNA Primers, Their Use in the Polymerase Chain Reaction (PCR) and Electrochemical Detection of PCR Products
Authors: Debela Ahmed M. , Ortiz Mayreli , Beni Valerio , Thorimbert Serge , Lesage Denis , Cole Richard B. , O'Sullivan Ciara K. , Hasenknopf Bernold
Published: October 2015

The bioconjugation of polyoxometalates (POMs), which are inorganic metal oxido clusters, to DNA strands to obtain functional labeled DNA primers and their potential use in electrochemical detection have been investigated. Activated monooxoacylated polyoxotungstates [SiW11O39{Sn(CH2)2CO}]8− and [P2W17O61{Sn(CH2)2CO}]6− have been used to link to a 5′‐NH2 terminated 21‐mer DNA forward primer through amide coupling. The functionalized primer was characterized by using a battery of techniques, including electrophoresis, mass spectrometry, as well as IR and Raman spectroscopy. The functionality of the POM‐labeled primers was demonstrated through hybridization with a surface‐immobilized probe. Finally, the labeled primers were successfully used in the polymerase chain reaction (PCR) and the PCR products were characterized by using electrophoresis.
CH Bond Activation by Early Transition Metal Carbide Cluster Anion MoC3−
Authors: Li Zi‐Yu , Hu Lianrui , Liu Qing‐Yu , Ning Chuan‐Gang , Chen Hui , He Sheng‐Gui , Yao Jiannian
Published: October 2015

Although early transition metal (ETM) carbides can activate CH bonds in condensed‐phase systems, the electronic‐level mechanism is unclear. Atomic clusters are ideal model systems for understanding the mechanisms of bond activation. For the first time, CH activation of a simple alkane (ethane) by an ETM carbide cluster anion (MoC3−) under thermal‐collision conditions has been identified by using high‐resolution mass spectrometry, photoelectron imaging spectroscopy, and high‐level quantum chemical calculations. Dehydrogenation and ethene elimination were observed in the reaction of MoC3− with C2H6. The CH activation follows a mechanism of oxidative addition that is much more favorable in the carbon‐stabilized low‐spin ground electronic state than in the high‐spin excited state. The reaction efficiency between the MoC3− anion and C2H6 is low (0.23±0.05) %. A comparison between the anionic and a highly efficient cationic reaction system (Pt++C2H6) was made. It turned out that the potential‐energy surfaces for the entrance channels of the anionic and cationic reaction systems can be very different.
Insight into the Mechanism of the Initial Reaction of an OH Radical with DNA/RNA Nucleobases: A Computational Investigation of Radiation Damage
Authors: Milhøj Birgitte O. , Sauer Stephan P. A.
Published: October 2015

Earlier theoretical investigations of the mechanism of radiation damage to DNA/RNA nucleobases have claimed OH radical addition as the dominating pathway based solely on energetics. In this study we supplement calculations of energies with the kinetics of all possible reactions with the OH radical through hydrogen abstraction and OH radical addition onto carbon sites, using DFT at the ωB97X‐D/6‐311++G(2df,2pd) level with the Eckart tunneling correction. The overall rate constants for the reaction with adenine, guanine, thymine, and uracil are found to be 2.17×10−12, 5.64×10−11, 2.01×10−11, and 5.03×10−12 cm3 molecules−1 s−1, respectively, which agree exceptionally well with experimental values. We conclude that abstraction of the amine group hydrogen atoms competes with addition onto C8 as the most important reaction pathway for the purine nucleobases, while for the pyrimidine nucleobases addition onto C5 and C6 competes with the abstraction of H1. Thymine shows favourability against abstraction of methyl hydrogens as the dominating pathway based on rate constants. These mechanistic conclusions are partly explained by an analysis of the electrostatic potential together with HOMO and LUMO orbitals of the nucleobases.
Azobenzene C‐Nucleosides for Photocontrolled Hybridization of DNA at Room Temperature
Authors: Goldau Thomas , Murayama Keiji , Brieke Clara , Asanuma Hiroyuki , Heckel Alexander
Published: October 2015

Herein, we report the reversible light‐regulated destabilization of DNA duplexes by using azobenzene C‐nucleoside photoswitches. The incorporation of two different azobenzene residues into DNA and their photoswitching properties are described. These new residues demonstrate a photoinduced destabilization effect comparable to the widely applied D‐threoninol‐linked azobenzene switch, which is currently the benchmark. The photoswitches presented herein show excellent photoswitching efficiencies in DNA duplexes – even at room temperature – which are superior to commonly used azobenzene‐based nucleic acid photoswitches. In addition, these photoswitching residues exhibit high thermal stability and excellent fatigue resistance, thus rendering them one of the most efficient candidates for the regulation of duplex stability with light.
Phase behaviour of sesame (Sesamum indicum L.) seed oil using supercritical CO2
Authors: Feihrmann Andresa Carla , Giufrida Willyan Machado , Saldaña Marleny D. A. , de Carvalho Lima Jéssica , Ferreira‐Pinto Leandro , Botelho José Rafael Santos , Cabral Vladimir Ferreira , de Carvalho Junior Raul Nunes , Corazza Marcos Lúcio , Cardozo‐Filho Lucio
Published: October 2015

New experimental data were measured for phase transition of the binary system CO2 + black sesame oil. A variable volume cell was employed using the static synthetic method in a temperature range of 303–333 K, pressures up to 20 MPa, and CO2 mass fractions between 0.12–0.39 g/g. For mass fractions > 0.39, phase transition data were not measured due to pressure limitations of the high‐pressure system used. Vapour‐liquid transitions (VLE) of bubble point (BP) were determined. Phase transition data of CO2 + black sesame oil were compared to reported data from the literature involving CO2 and similar oils. The trend of the phase transition behaviour between all systems compared was similar. Phase equilibrium data obtained experimentally were successfully modelled with the Peng‐Robinson equation of state (PR‐EoS) combined with the van der Waals mixing rule (PR‐vdW2) and Wong‐Sandler mixing rule (PR‐WS).
Detection of the Elusive Triazane Molecule (N3H5) in the Gas Phase
Authors: Förstel Marko , Maksyutenko Pavlo , Jones Brant M. , Sun Bing‐Jian , Chen Shih‐Hua , Chang Agnes H.‐H. , Kaiser Ralf I.
Published: October 2015

The front cover artwork is provided by the groups of Prof. R. I. Kaiser (University of Hawaii) and Prof. A. H.‐H. Chang (National Dong Hwa University). The image shows a triazane molcule as it sublimes from irradiated ammonia ices along with its ion profile after photoionization; ammonia has been detected on Kuiper Belt Objects with Pluto being the most prominent member (courtesy NASA). Read the full text of the article at 10.1002/cphc.201500560
Dispersion of Polymers in Metallic Gallium
Authors: Kumar Vijay Bhooshan , Gedanken Aharon , Avnir David , Porat Ze'ev
Published: October 2015

This work examines the concept of dispersing polymers in metals. Herein, this was mainly studied with molten gallium, in which 5‐18 wt % of various short‐chain polymers were incorporated and mixed. The nature of the solidified products was examined by using X‐ray diffraction, electron microscopy, UV/Vis, differential scanning calorimetry, and thermal gravimetric analyses. It was found that some polymers can be dispersed as small domains within molten metals to form a heterogeneous solid. The ability to dope Ga with large polymers opens a new avenue to electronic materials.
Study of Multiporphyrin Compounds as Colorimetric Sitting‐Atop Metal Complexes: Synthesis and Photophysical Studies
Authors: Costa Joana I. T. , Oliveira Elisabete , Santos Hugo M. , Tomé Augusto C. , Neves Maria G. P. M. S. , Lodeiro Carlos
Published: October 2015

Mono‐, di‐, tri‐, and hexaporphyrin derivatives were synthesized and their sensorial ability toward Na+, Li+, Ca2+, Cu2+, Ni2+, Co2+, Fe3+, Zn2+, Cd2+, Hg2+, Ag+, Cr3+, Pb2+, and Al3+ was explored by absorption and emission spectroscopy and 1H NMR spectroscopy. For all of the studied porphyrin derivatives the most significant spectral changes were observed upon addition of Zn2+, Cd2+, Cu2+, Co2+, Pb2+, Hg2+, and Fe3+, which resulted in a color change from red to green. When the remaining metal ions were tested, no significant changes were observed. The results reveal, as expected, the formation of mononuclear complexes for porphyrin 4, dinuclear complexes for diporphyrin 7, and trinuclear complexes for triporphyrins 9 and 10. In addition, complexes of type M6L were determined for hexaporphyrin 8. The NMR spectroscopy studies suggest that the interaction with the metals occurs with the formation of sitting‐atop complexes. This study also shows that the sensitivity increases with increasing number of coordination sites, with the most pronounced case observed for Hg2+. The lowest value of detectable concentration of 0.05 μm for Hg2+ was achieved for hexaporphyrin 8.
A Self‐Assembling Octahedral Aggregate of Poly(methyl methacrylate) Nanospheres on a Silver Substrate
Authors: Chen Shaoyun , Hu Chenglong , Zhang Weihong , Chen Jian
Published: October 2015

A large‐area, self‐assembling, octahedral aggregate composed of poly(methyl methacrylate) nanospheres (PMMA‐NS) was constructed by using a one‐step electrodeposition approach from an aqueous solution containing AgNO3 and PMMA‐NS as sacrificial electrolytes. The surface chain geometry of the product was revealed by Raman spectroscopy. The results revealed that the orientation of chains of the PMMA‐NS octahedron is different from that of the nonaggregated PMMA‐NS because of the interfacial interactions between the polymer chain and Ag metal. This can be explained by the crystal surface free energy of the octahedral Ag substrate, which gives rise to diverse conformations of the PMMA molecular chain at different surface regions of the silver substrate. In addition, the adsorptive properties of PMMA‐NS octahedra are such that the adsorbent–adsorbate system is cost‐effective, efficient and fast for the removal of dyes from contaminated wastewater.
Complex metacommunity structure for benthic invertebrates in a low‐diversity coastal system
Authors: Valanko Sebastian , Heino Jani , Westerbom Mats , Viitasalo Markku , Norkko Alf
Published: October 2015

The majority of studies in metacommunity ecology have focused on systems other than marine benthic ecosystems, thereby providing an impetus to broaden the focus of metacommunity research to comprise marine systems. These systems are more open than many other systems and may thus exhibit relatively less discrete patterns in community structure across space. Metacommunity structure of soft‐sediment benthic invertebrates was examined using a fine‐grained (285 sites) data set collected during one summer across a large spatial extent (1700 km2). We applied the elements of metacommunity structure (EMS) approach, allowing multiple hypothesis of variation in community structure to be tested. We demonstrated several patterns associated with environmental variation and associated processes that could simultaneously assemble species to occur at the sites. A quasi‐Clementsian pattern was observed frequently, suggesting interdependent ecological relationships among species or similar response to an underlying environmental gradient across sites. A quasi‐nested clumped species loss pattern was also observed, which suggests nested habitat specialization. Species richness declined with depth (from 0.5 to 44.8 m). We argue that sensitive species may survive in shallower water, which are more stable with regard to oxygen conditions and present greater habitat complexity, in contrast to deeper waters, which may experience periodic disturbance due to hypoxia. Future studies should better integrate disturbance in terms of temporal dynamics and dispersal rates in the EMS approach. We highlight that shallow water sites may act as sources of recruitment to deeper water sites that are relatively more prone to periodic disturbances due to hypoxia. However, these shallow sites are not currently monitored and should be better prioritized in future conservation strategies in marine systems.
Illegal tusk harvest and the decline of tusk size in the African elephant
Authors: Chiyo Patrick I. , Obanda Vincent , Korir David K.
Published: October 2015

Harvesting of wild populations can cause the evolution of morphological, behavioral, and life history traits that may compromise natural or sexual selection. Despite the vulnerability of large mammals to rapid population decline from harvesting, the evolutionary effects of harvesting on mega‐fauna have received limited attention. In elephants, illegal ivory harvesting disproportionately affects older age classes and males because they carry large tusks, but its' effects on tusk size for age or tusk size for stature are less understood. We tested whether severe historical elephant harvests eliminated large tuskers among survivors and whether elephants born thereafter had smaller tusks. Adjusting for the influence of shoulder height – a metric strongly correlated with body size and age and often used as a proxy for age – we compared tusk size for elephants sampled in 1966–1968, prior to severe ivory harvesting in the late 1970s and early 1980s, with tusk size of survivors and elephants born during population recovery in the mid‐1990s. In a regional population, tusk length declined by ˜21% in male and by ˜27% in female elephants born during population recovery, while tusk length declined by 22% in males and 37% in females among survivors. Tusk circumference at lip declined by 5% in males but not in females born during population recovery, whereas tusk circumference reduced by 8% in male and by 11% in female survivors. In a single subpopulation, mean tusk length at mean basal tusk circumference declined by 12.4% in males and 21% in females. Tusk size varied between elephant social groups. Tusk homogeneity within social groups and the often high genetic similarity within social groups suggest that tusk size may be heritable. Our findings support a hypothesis of selection of large tuskers by poachers as a driver of the decline in tusk size for age proxy and contemporary tusk evolution in African elephants.
Facile Preparation of 2,6‐Pyridinedicarb­oxylic Acid Protected Gold Nanoparticles with Sensitive Chromium‐Ion Sensing and Efficient Catalysis
Authors: Yang Xin , Fu Shanshan , Ren Guojuan , Chai Fang , Qu Fengyu
Published: October 2015

The detection of Cr3+ and Cr6+ ions is very important as they are dangerous pollutants and carcinogens. Herein, we describe the preparation of 2,6‐pyridinedicarboxylic acid functionalized gold nanoparticles (PDCA–AuNPs) and their application as colorimetric sensors for the detection of Cr3+ and Cr6+ ions in water samples. The PDCA–AuNPs could be induced to aggregate quickly in the presence of Cr3+ ions, and the aggregation can be observed through the colorimetric response and special localized surface plasmon resonance (LSPR) of the gold nanoparticles. A linear response to the concentration of Cr3+ ions was observed from 10 nM to 1 μM. The detection limit is as low as 2 nM, which is below the maximum recommended contamination level of the World Health Organization for the chromium content (0.962 μM) in drinking water. The highly specific interactions of Cr3+ ions with PDCA–AuNPs provided excellent selectivity towards the detection of Cr3+ ions over other metal ions (Pb2+, Mg2+, Zn2+, Ni2+, Cu2+, Co2+, Ca2+, Mn2+, Fe2+, Cd2+, Ba2+, Cr6+, Ag+, Fe3+, Al3+, and Hg2+). Additionally, Cr6+ ions can be determined through the detection of Cr3+ ions after reduction by ascorbic acid. This method can offer the additional advantage of the efficient detection of Cr3+ and Cr6+ ions over other ions in environmental lake water. Additionally, the PDCA–AuNPs can be used as an efficient catalyst for the reduction of 4‐nitrophenol (4‐NP) and K3[Fe(CN)6].
Anion‐Triggered Modulation of Structure and Magnetic Properties of Copper(I)–Dysprosium(III) Complexes Derived from 1‐Hydroxybenzotriazolate
Authors: Han Song‐De , Wang Qing‐Lun , Xu Jian , Bu Xian‐He
Published: October 2015

Solvothermal reaction of CuX (X = Cl, Br, I) and Dy(NO3)3·6H2O with a polydentate 1‐hydroxybenzotriazole (HL) ligand afforded three CuI–DyIII heterometallic complexes formulated as [Cu3Dy(L)6]n (1), [Cu5DyBr(L)7(H2O)2]n (2), and [Cu6DyI3(L)6]n (3). Although identical stoichiometric ratios of the reactants were used in the formation of 1–3, their structures display clear diversity, which is indicative of anion‐triggered structural modulation. Complex 1 shows a 2D layer with CuI chains as building units, which are further connected by DyIII to lead to the final structure. Complex 2 displays a double parallel DyIII–CuI chain bridged by L ligands. Complex 3 features a 2D sheet built from the alternating arrangement of Dy2 and CuI6I3 units. Magnetic analyses indicate that complex 3 exhibits single‐molecule magnet like behavior at low temperature.
Imidazolium Dicarboxylate Based Metal–Organic Frameworks Obtained by Solvo‐Ionothermal Reaction
Authors: Farger Pierre , Guillot Régis , Leroux Fabrice , Parizel Nathalie , Gallart Mathieu , Gilliot Pierre , Rogez Guillaume , Delahaye Emilie , Rabu Pierre
Published: October 2015

Solvo‐ionothermal reactions were run between cobalt acetate or zinc acetate and 1,3‐bis(carboxymethyl)imidazolium chloride ([(MimCO2H)2][Cl]). These reactions led to two isostructural metal–organic frameworks (MOFs). These two compounds, [(MimCO2)2]2Co and [(MimCO2)2]2Zn, were obtained as single crystals, and their structures were determined by single‐crystal X‐ray diffraction. These two analogs have a 2D framework consisting of the stacking of layers formed by interconnection of rings containing ligands and metal ions. The structural and thermal properties were analyzed by means of ancillary techniques encompassing FTIR, UV/Vis, NMR spectroscopy, and TGA/TDA measurements. In addition, magnetic and EPR spectroscopic measurements on [(MimCO2)2]2Co showed that the Co2+ ions are in a high‐spin configuration with a large magnetic anisotropy relying on a rather unusual distorted tetrahedral coordination. The investigation of the optical properties revealed the photoluminescence of [(MimCO2)2]2Zn.
Direct Access to Inversely Polarized Phosphaalkenes from Elemental Phosphorus or Polyphosphides
Authors: Cicač‐Hudi Mario , Bender Johannes , Schlindwein Simon Hugo , Bispinghoff Mark , Nieger Martin , Grützmacher Hansjörg , Gudat Dietrich
Published: October 2015

Phosphorus‐containing multiple‐bond systems have received great interest in various applications but often require elaborate syntheses and special precursors. In this paper, we describe simple methods for the synthesis of imidazoyl phosphinidenes and bis(imidazolyl)–P(I) halides from elemental phosphorus or the heptaphosphides Na3P7 and (Me3Si)3P7. The reactions of imidazolium salts with KOtBu and P4 afford mixtures of imidazoyl phosphinidenes and Pn compounds and, for N‐methylated imidazolium salts, also bis(imidazolyl)–P(I) halides. NMR spectroscopy studies revealed the formation of a bis(imidazoyl)‐substituted tetraphosphatriene and the bicyclic anion HP4– as transient intermediates and indicated the participation of tBuOH in the formation of imidazoyl phosphinidenes. Na3P7 and (Me3Si)3P7 can be obtained from P4 and Pred in excellent yields by a safe and simple method and are versatile precursors for the synthesis of imidazoyl phosphinidenes with varying steric demand.