bluuebunny/crossref_metadata_2025 huggingface dataset:
Visible‐Light Photoredox Decarboxylative Couplings
Authors: Jin Yunhe , Fu Hua
Published: December 2016

Carboxylic acids and their derivatives are abundant and inexpensive organic and biomass‐derived platform molecules, and their conversion into high‐value products represents an important goal. Recently, visible‐light photoredox decarboxylative coupling reactions have become an important chemical transformation because of their wide substrate scope, mild reaction conditions, high efficiency, and practicability. This review summarizes recent advances in visible‐light photoredox decarboxylative coupling strategies, which include the formation of C−C and C−Y (Y=heteroatom) bonds.
Discovery of a PCAF Bromodomain Chemical Probe
Authors: Moustakim Moses , Clark Peter G. K. , Trulli Laura , Fuentes de Arriba Angel L. , Ehebauer Matthias T. , Chaikuad Apirat , Murphy Emma J. , Mendez‐Johnson Jacqui , Daniels Danette , Hou Chun‐Feng D. , Lin Yu‐Hui , Walker John R. , Hui Raymond , Yang Hongbing , Dorrell Lucy , Rogers Catherine M. , Monteiro Octovia P. , Fedorov Oleg , Huber Kilian V. M. , Knapp Stefan , Heer Jag , Dixon Darren J. , Brennan Paul E.
Published: December 2016

The p300/CBP‐associated factor (PCAF) and related GCN5 bromodomain‐containing lysine acetyl transferases are members of subfamily I of the bromodomain phylogenetic tree. Iterative cycles of rational inhibitor design and biophysical characterization led to the discovery of the triazolopthalazine‐based L‐45 (dubbed L‐Moses) as the first potent, selective, and cell‐active PCAF bromodomain (Brd) inhibitor. Synthesis from readily available (1R,2S)‐(−)‐norephedrine furnished L‐45 in enantiopure form. L‐45 was shown to disrupt PCAF‐Brd histone H3.3 interaction in cells using a nanoBRET assay, and a co‐crystal structure of L‐45 with the homologous Brd PfGCN5 from Plasmodium falciparum rationalizes the high selectivity for PCAF and GCN5 bromodomains. Compound L‐45 shows no observable cytotoxicity in peripheral blood mononuclear cells (PBMC), good cell‐permeability, and metabolic stability in human and mouse liver microsomes, supporting its potential for in vivo use.
Seed‐Mediated Growth of Colloidal Metal Nanocrystals
Authors: Xia Younan , Gilroy Kyle D. , Peng Hsin‐Chieh , Xia Xiaohu
Published: December 2016

Seed‐mediated growth is a powerful and versatile approach for the synthesis of colloidal metal nanocrystals. The vast allure of this approach mainly stems from the staggering degree of control one can achieve over the size, shape, composition, and structure of nanocrystals. These parameters not only control the properties of nanocrystals but also determine their relevance to, and performance in, various applications. The ingenuity and artistry inherent to seed‐mediated growth offer extensive promise, enhancing a number of existing applications and opening the door to new developments. This Review demonstrates how the diversity of metal nanocrystals can be expanded with endless opportunities by using seeds with well‐defined and controllable internal structures in conjunction with a proper combination of capping agent and reduction kinetics. New capabilities and future directions are also highlighted.
Benzo‐Fused Double [7]Carbohelicene: Synthesis, Structures, and Physicochemical Properties
Authors: Hu Yunbin , Wang Xiao‐Ye , Peng Pi‐Xian , Wang Xin‐Chang , Cao Xiao‐Yu , Feng Xinliang , Müllen Klaus , Narita Akimitsu
Published: December 2016

A benzo‐fused double [7]carbohelicene (D7H) was synthesized through a regioselective cyclodehydrogenation of a tetranaphthyl‐p‐terphenyl‐based precursor. The twisted (D7H‐1) and anti‐folded (D7H‐2) conformers of D7H were separated by recrystallization, and their double helicene structures with overlapping terminal benzene rings were unambiguously elucidated by X‐ray crystallography. A record‐high isomerization barrier (46.0 kcal mol−1) in double helicenes was estimated based on density functional theory (DFT) calculation, which resulted in the excellent conformational stability of D7H. The physicochemical properties of D7H‐1 and D7H‐2 were investigated by UV/Vis absorption spectroscopy and cyclic voltammetry, displaying the variation of electronic structure upon conformational changes. The optical resolution of the racemic D7H‐1 was carried out by chiral HPLC, offering enantiopure D7H‐1‐(P,P) and D7H‐1‐(M,M), which were further characterized by circular dichroism spectroscopy.
The influence ofin situsynthesized nanoparticles on microstructure and compression properties of polymer foams during supercritical carbon dioxide foaming
Authors: Yuan Huan , Xiong Yuanlu , Luo Guoqiang , Shen Qiang , Zhang Lianmeng
Published: December 2016

The influence ofin situsynthesized nanoparticles on the microstructure and compression properties of polymer foams during supercritical carbon dioxide foaming has been investigated. Thein situsynthesized Ag nanoparticles were chosen to be heterogeneous nucleating agent. For achieving our target, the influence of the nanoparticle size on the cell structure and the nucleation mechanism has been detailed discussed firstly. The results show that thein situsynthesized nanoparticles can be heterogeneous nucleation agent to improve the cell density of the PMMA‐based foams. The particle size is able to reduce to the critical size of heterogeneous nucleation agent and, then, can highly improve the cell density of the foams. The Ag nanoparticles with average size of 2.2 nm led to 85% increase in compressive strength of the foams. The improvement of strength of the polymer matrix and the microstructure of the foams can lead to the remarkable increase in the mechanical properties of the foams. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2017,134, 44629.
Design of green zinc‐based thermal stabilizers derived from tung oil fatty acid and study of thermal stabilization for PVC
Authors: Li Mei , Zhang Jinwen , Xin Junna , Huang Kun , Li Shouhai , Wang Mei , Xia Jianling
Published: December 2016

In this study, a new type of mixed calcium (Ca) and zinc (Zn) thermal stabilizers was prepared and evaluated for poly(vinyl chloride) (PVC) thermal stabilization. The mixed stabilizers were based on the Ca and Zn salts of polycarboxylic acid derived from eleostearic acid—the dominant fatty acid of tung oil fatty acids. Eleostearic acid was converted to a 21‐carbon diacid (C21DA) and a 22‐carbon triacid (C22TA), respectively, which were subsequently turned into calcium (Ca) and zinc (Zn) salts. Thermal stability of PVC compounds was examined by thermogravimetric analysis (TGA), discoloration test, Congo red test, and thermal decomposition kinetics. In comparison, commercial mixed Ca/Zn thermal stabilizers composed of stearate salts (CaSt2/ZnSt2), were employed as controls. Because the salts of C21DA, C22TA and stearate have different metal contents, thermal stabilization effects were compared on the basis of both equal salt weight and equal metal ion content. It was noted that under both cases the long‐term thermal stability of the PVC samples followed the order of C21DA‐Ca/C21DA‐Zn > C22TA‐Ca/C22TA‐Zn > CaSt2/ZnSt2. The results suggest that the mixed Ca/Zn salts based on tung oil‐derived polycarboxylic acids have higher metal ion contents and cycloaliphatic structures and can effectively improve the thermal stability of PVC. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44679.
Design of Block Copolymer Micellar Aggregates for Co‐Delivery of Enzyme and Anticancer Prodrug
Authors: Li Hongping , Chen Lulu , Shi Yuting , Yuan Binbin , Ma Yingxia , Wei Hua , Zhao Guanghui
Published: December 2016

Traditional enzyme–prodrug therapy (EPT) is a two‐step strategy, which has many serious deficiencies, so having a one‐step EPT treatment becomes a problem of immediate interest. This study aims to achieve an effective co‐delivery of horseradish peroxidase (HRP) as a kind of enzyme for prodrug activation and ethyl 3‐indoleacetate (EIA) as anticancer prodrug. A ternary block copolymer PEG‐PAsp(AED)‐CA consisting of poly(ethylene glycol) (PEG), reduction‐sensitive poly (N‐(2,2′‐dithiobis(ethylamine)) aspartamide) PAsp(AED), and cholic acid (CA) was synthesized and assembled into spherical micelles which encapsulated EIA in its hydrophobic core and HRP in a reduction‐sensitive interlayer. TEM photographs show that the polymer micelle is around 40 nm, and the cell survival rate test shows that the EIA/HRP polymer micelle is highly lethal to human lung adenocarcinoma cells. Thus, co‐delivery of EIA and HRP demonstrates great potential in cancer therapy, offering a structurally simple and highly tunable platform for the synchronous delivery of enzymes and prodrugs in EPT.
Cationic and Neutral Rotaxanes Having Different Functional Groups in the Axle Molecule and Their Coordination to PtII
Authors: Yu Gilbert , Suzaki Yuji , Osakada Kohtaro
Published: December 2016

Dibenzo[24]crown‐8 (DB24C8) forms rotaxanes with a linear molecule having a dialkylammonium group and a triazole group as well as with the acetylation product of a cationic axle molecule. The former cationic rotaxane is stabilized by multiple intermolecular hydrogen bonds between the NH2+ and oxyethylene groups. The neutral rotaxane contains the macrocycle in the vicinity of the terminal aryl group. The co‐conformation of both the cationic and neutral rotaxanes can be fixed by coordination of the triazole group of the axle molecule to PtCl2(dmso)2. A 1H NMR spectroscopic study on the thermodynamics of the Pt coordination revealed a larger association constant for the rotaxanes than for the corresponding axle molecules and a larger value for the neutral rotaxane than for the cationic rotaxane.
Metabolic engineering of Mannheimia succiniciproducens for succinic acid production based on elementary mode analysis with clustering
Authors: Kim Won Jun , Ahn Jung Ho , Kim Hyun Uk , Kim Tae Yong , Lee Sang Yup
Published: December 2016

Mannheimia succiniciproducens, a capnophilic gram‐negative rumen bacterium, has been employed for the efficient production of succinic acid. Although M. succiniciproducens metabolism was previously studied using a genome‐scale metabolic model, more metabolic characteristics are to be understood. To this end, elementary mode analysis accompanied with clustering (‘EMC’ analysis) is used to gain further insights on metabolic characteristics of M. succiniciproducens allowing efficient succinic acid production. Elementary modes (EMs) generated from the central carbon metabolic network of M. succiniciproducens are clustered to systematically analyze succinic acid production routes. Based on the results of EMC analysis, zwf gene is identified as a novel overexpression target for the improved succinic acid production. This gene is overexpressed in a previously constructed succinic acid‐overproducing M. succiniciproducens LPK7 strain. Heterologous NADPH‐dependent mdh is later intuitively selected for overexpression to synergistically improve succinic acid production by utilizing abundant NADPH pool mediated by the overexpressed zwf. The LPK7 strains co‐expressing mdh alone and both zwf and mdh genes are subjected to fed‐batch fermentation to better examine their succinic acid production performances. Strategies of EMC analysis will be useful for further metabolic engineering of M. succiniciproducens and other microorganisms to improve production of succinic acid and other chemicals of interest.
Increased Polysialylation of the Neural Cell Adhesion Molecule in a Transgenic Mouse Model of Sialuria
Authors: Kreuzmann Denise , Horstkorte Rüdiger , Kohla Guido , Kannicht Christoph , Bennmann Dorit , Thate Annett , Bork Kaya
Published: December 2016

Sialuria is a rare autosomal dominant disorder of mammalian metabolism, caused by defective feedback inhibition of the UDP‐N‐acetylglucosamine‐2‐epimerase N‐acetylmannosamine kinase (GNE), the key enzyme of sialic acid biosynthesis. Sialuria is characterized by overproduction of free sialic acid in the cell cytoplasm. Patients exhibit vastly increased urinary excretion of sialic acid and show differently pronounced developmental delays. The physiopathology of sialuria is not well understood. Here we established a transgenic mouse line that expresses GNE containing the sialuria mutation R263L, in order to investigate the influence of an altered sialic acid concentration on the organism. The transgenic mice that expressed the mutated RNA excreted up to 400 times more N‐acetylneuraminic acid than wild‐type mice. Additionally, we found higher sialic acid concentration in the brain cytoplasm. Analyzing the (poly)sialylation of neural cell adhesion molecule (NCAM) revealed increased polysialylation in brains of transgenic mice compared to wild‐type. However, we found only minor changes in membrane‐bound sialylation in various organs but, surprisingly, a significant increase in surface sialylation on leukocytes. Our results suggest that the intracellular sialic acid concentration regulates polysialylation on NCAM in vivo; this could play a role in the manifestation of the developmental delays in sialuria patients.
Reusable Electrochemical DNA Biosensor for the Detection of Waterborne Uranium
Authors: Jett Susan E. , Bonham Andrew J.
Published: December 2016

We have developed an electrochemical biosensor for the detection of uranium, in the uranyl ion form, at low levels in water. This biosensor could have both academic and environmental monitoring applications. Uranium contamination of water sources poses serious health consequences, and this biosensor may aid in the improvement of targeting and the efficiency of remediation of contaminated water sources by improving the speed of initial identification as well as monitoring during remediation efforts. Our design uses a modified uranyl‐binding aptamer that has been inserted into an oligonucleotide scaffold to create a reusable, conformation‐switching electrochemical DNA biosensor with an apparent dissociation constant of 15±5 μM and a limit of detection within an order of magnitude of the Environmental Protection Agency's maximum contamination level for uranium in drinking water.
Tuning the Intrinsic Photophysical Properties of Chlorophyll a
Authors: Wellman Sydney M. J. , Jockusch Rebecca A.
Published: December 2016

In nature, the finely tuned photophysical properties of chlorophyll a (Chla) are vital to the capture and transfer of sunlight during photosynthesis. In order to better understand how these properties are influenced by the molecular environment, we have examined the intrinsic spectroscopy of Chla in vacuo. Visible photodissociation action spectra (an indirect measure of absorption) of gaseous protonated Chla and Chla complexed with metal cations are reported. These show that spectral features within the Soret band (∼350–445 nm) have markedly different intensities depending on the identity of the cation. In contrast, fluorescence emission spectra of metalated Chla complexes show only small dependences on the identity of the metal ion, with emission maxima shifting from 661 to 654 nm. Remarkably, replacing the metal ion with a proton turns off the fluorescence of this key pigment. Density functional theory geometry‐optimized structures indicate that the most favorable site of protonation differs from that of metal cationization, and may help explain the surprising on/off behavior of Chla’s intrinsic fluorescence.
Dioxoiodane Compounds as Versatile Sources for Iodine(I) Chemistry
Authors: Muñiz Kilian , García Belén , Martínez Claudio , Piccinelli Alessandro
Published: December 2016

Invited for the cover of this issue is the group of Kilian Muñiz at the The Institute of Chemical Research of Catalonia (ICIQ). The image depicts an open gateway to a new universe of iodine(I) reagents, which display unique stability and reactivity. Read the full text of the article at 10.1002/chem.201603801.
TiO2‐Supported Re as a General and Chemoselective Heterogeneous Catalyst for Hydrogenation of Carboxylic Acids to Alcohols
Authors: Toyao Takashi , Siddiki S. M. A. Hakim , Touchy Abeda S. , Onodera Wataru , Kon Kenichi , Morita Yoshitsugu , Kamachi Takashi , Yoshizawa Kazunari , Shimizu Ken‐ichi
Published: December 2016

Invited for the cover of this issue are the group of Ken‐ichi Shimizu at Hokkaido University and the group of Kazunari Yoshizawa at Kyushu University. The image depicts the latest findings from Hokkaido dealing with selective hydrogenation of carboxylic acids having aromatic moieties to the corresponding alcohols over Re/TiO2. Read the full text of the article at 10.1002/chem.201604762.
Synthesis of Zero‐Valent Iron Nanoparticles Via Electrical Wire Explosion for Efficient Removal of Heavy Metals
Authors: Seyedi Seyed Mojtaba , Rabiee Hesamoddin , Shahabadi Seyed Mahdi Seyed , Borghei Seyed Mehdi
Published: December 2016

In this paper, electrical wire explosion (EWE) was used as a simple, clean, in situ method to synthesise nano zero‐valent iron (nZVI) particles in liquid mediums. The structural and physical properties of the synthesised nZVI particles were characterised by x‐ray diffraction, Brunauer–Emmett–Teller analysis, field emission scanning electron microscopy and transmission electron microscopy. The synthesised spherical nanoparticles, at a specific size of 10–50 nm, possessed large surface areas of approximately 13.27 m2/g, reinforcing the significant advantages of EWE, that is, less aggregation and in situ production of nanoparticles with enhanced removal efficacy, for groundwater treatment. After 1 h the adsorption capacity for Cr(VI), Ni(II), and Cd(II) (Q60 = Cions/Ciron(mg/g)) at pH 4 was approximately 143.4 (89.0%), 137.5 (79.0%), and 132.6 mg/g (72.0%), respectively. The effect of temperature was also examined at initial metal ions concentration of 70 mg/L, nZVI dosage of 0.2 g/L and pH 4. The results showed 45°C was the optimum temperature for adsorption of Cr(VI), Ni(II), and Cd(II) ions, and over a 60‐min period at this temperature adsorption capacity increased to 153.56 (95.3%), 158.91 (91.3%), and 163.90 mg/g (89.0%), respectively.
Lentiviral transduction and subsequent loading with nanoparticles do not affect cell viability and proliferation in hair‐follicle‐bulge‐derived stem cells in vitro
Authors: Schomann Timo , Mezzanotte Laura , Lourens Ierry‐Ann‐Lym M. , de Groot John C. M. J. , Frijns Johan H. M. , Huisman Margriet A.
Published: December 2016

The application of stem cells in the treatment of various degenerative diseases is highly promising. However, cell‐based therapy could be limited by the problem of low viability of grafted cells and uncertainty about their fate. The combination of molecular imaging and contrast‐enhanced MRI may give more insight into the survival and behavior of grafted stem cells. We explore hair‐follicle‐bulge‐derived stem cells (HFBSCs) as a potential candidate for autologous cell‐based therapy. HFBSCs are transduced with a lentiviral construct with genes coding for bioluminescent (Luc2) and fluorescent (copGFP) reporter proteins, and subsequently loaded with magnetic nanoparticles to enable MRI visualization. Thus, we investigate for the first time if lentiviral transduction and cellular loading with nanoparticles have a cytotoxic effect upon these stem cells. Transduction efficiency, proliferation rate, cell viability and reporter protein co‐expression during long‐term culture of transduced HFBSCs were studied using fluorescence and bioluminescence microscopy. In addition, the effect of TMSR50 nanoparticles on proliferation and viability was investigated using the MTS assay and bioluminescence microscopy. The amount of TMSR50‐loaded HFBSCs needed to reach signal threshold for MRI was assessed using an agarose phantom. Transduction with the Luc2‐copGFP construct did not influence senescence, proliferation, doubling time, and differentiation of the HFBSCs. CopGFP expression was visible immediately after transduction and persisted for at least 15 passages, concomitantly with Luc2 expression. Cellular loading with TMSR50 nanoparticles did not affect cell viability and proliferation. The results imply that combined MRI and bioluminescence imaging may enable in vivo localization and long‐term monitoring of grafted viable HFBSCs. Copyright © 2016 John Wiley & Sons, Ltd.
Total order in opportunistic networks
Authors: Costea Mihail , Ciobanu Radu‐Ioan , Marin Radu‐Corneliu , Dobre Ciprian , Mavromoustakis Constandinos X. , Mastorakis George , Xhafa Fatos
Published: December 2016

Opportunistic network applications are usually assumed to work only with unordered immutable messages, like photos, videos, or music files, while applications that depend on ordered or mutable messages, like chat or shared contents editing applications, are ignored. In this paper, we examine how total ordering can be achieved in an opportunistic network. By leveraging on existing dissemination and causal order algorithms, we propose a commutative replicated data type algorithm on the basis of Logoot for achieving total order without using tombstones in opportunistic networks where message delivery is not guaranteed by the routing layer. Our algorithm is designed to use the nature of the opportunistic network to reduce the metadata size compared to the original Logoot, and even to achieve in some cases higher hit rates compared to the dissemination algorithms when no order is enforced. Finally, we present the results of the experiments for the new algorithm by using an opportunistic network emulator, mobility traces, and Wikipedia pages.
Identifying and Understanding Strong Vibronic Interaction Effects Observed in the Asymmetry of Chiral Molecule Photoelectron Angular Distributions
Authors: Garcia Gustavo A. , Dossmann Héloïse , Nahon Laurent , Daly Steven , Powis Ivan
Published: December 2016

Electron–ion coincidence imaging is used to study chiral asymmetry in the angular distribution of electrons emitted from randomly‐oriented enantiomers of two molecules, methyloxirane and trifluoromethyloxirane, upon ionization by circularly polarized VUV synchrotron radiation. Vibrationally‐resolved photoelectron circular dichroism (PECD) measurements of the outermost orbital ionization reveal unanticipated large fluctuations in the magnitude of the forward–backward electron scattering asymmetry, including even a complete reversal of direction. Identification and assignment of the vibrational excitations is supported by Franck–Condon simulations of the photoelectron spectra. A previously proposed quasi‐diatomic model for PECD is developed and extended to treat polyatomic systems. The parametric dependence of the electronic dipole matrix elements on nuclear geometry is evaluated in the adiabatic approximation. It provokes vibrational level dependent shifts in amplitude and phase, to which the chiral photoelectron angular distributions are especially sensitive. It is shown that single quantum excitation of those vibrational modes, which experience only a relatively small displacement of the ion equilibrium geometry along the normal coordinate and which are then only weakly excited in the Franck–Condon limit, can be accompanied by big shifts in scattering phase; hence the observed big fluctuations in PECD asymmetry for such modes.
Functional Studies of Sodium Channels: From Target to Compound Identification
Authors: Bertrand Daniel , Biton Bruno , Licher Thomas , Chambard Jean‐Marie , Lanneau Christophe , Partiseti Michel , Lefevre Isabel A.
Published: December 2016

Over the last six decades, voltage‐gated sodium (Nav) channels have attracted a great deal of scientific and pharmaceutical interest, driving fundamental advances in both biology and technology. The structure and physiological function of these channels have been extensively studied; clinical and genetic data have uncovered their implication in diseases such as epilepsy, arrhythmias, and pain, bringing them into focus as current and future drug targets. While different techniques have been established to record the activity of Nav channels, proper determination of their properties still presents serious challenges, depending upon the experimental conditions and the desired subtype of channel to be characterized. The aim of this unit is to review the characteristics of Nav channels, their properties, the cells in which they can be studied, and the currently available techniques. Topics covered include the determination of Nav‐channel biophysical properties as well as the use of toxins to discriminate between subtypes using electrophysiological or optical methods. Perspectives on the development of high‐throughput screening assays with their advantages and limitations are also discussed to allow a better understanding of the challenges encountered in voltage‐gated sodium channel preclinical drug discovery. © 2016 by John Wiley & Sons, Inc.
Direct Conversion of Wheat Straw into Electricity with a Biomass Flow Fuel Cell Mediated by Two Redox Ion Pairs
Authors: Gong Jian , Liu Wei , Du Xu , Liu Congmin , Zhang Zhe , Sun Feifei , Yang Le , Xu Dong , Guo Hua , Deng Yulin
Published: December 2016

In this paper, a biomass flow fuel cell to directly convert wheat straw to electricity at low temperature (80–90 °C) and atmospheric pressure is presented. Two redox ion pairs, Fe3+/Fe2+ and VO2+/VO2+, acting as redox catalysts and charge carriers, were used in the anode and cathode flow tanks, respectively. The wheat straw was first oxidized by Fe3+ in the anode tank at approximately 100 °C. The reduced Fe2+ in the anode was used to construct a fuel cell with VO2+ in the cathode. The VO2+ ions were reduced to VO2+ and regenerated to VO2+ by oxygen oxidation. The wheat straw flow fuel cell showed a power output of 100 mW cm−2. Mediated with liquid Fe3+ carriers, the solid powder of wheat straw could be gradually degraded into low‐molecular‐weight organic molecules and even oxidized to CO2 at the anode without using noble‐metal catalysts. The overpotential for the electrodes of the flow fuel cell was examined and the energy cost was estimated.
Chemistry Future: Priorities and Opportunities from the Sustainability Perspective
Authors: Beller Matthias , Centi Gabriele , Sun Licheng
Published: December 2016

To celebrate the 10 year anniversary of ChemSusChem, we as the chairmen of the editorial board are writing this Essay to summarize important scientific contributions to our journal during the past decade in terms of sustainable science and technology. Bibliometric analysis of published papers show that biorefinery, solar energy conversion, energy‐storage materials, and carbon dioxide utilizations attracted most attention in this area. According to our own knowledge and understanding and from the sustainability point of view, we are also pointing out those research directions that we believe can play key roles in the future chemistry to meet the grand challenges in energy and environment. Hopefully, these perspective aspects will provide the readers with new angles to look at the chemistry in the coming decades and inspire the development of new technologies to make our society sustainable.
Synthesis of Concentrated Methylcyclohexane as Hydrogen Carrier through Photoelectrochemical Conversion of Toluene and Water
Authors: Kageshima Yosuke , Minegishi Tsutomu , Hisatomi Takashi , Takata Tsuyoshi , Kubota Jun , Domen Kazunari
Published: December 2016

A photoelectrochemical (PEC) cell consisting of a Pt‐loaded carbon black (Pt/C)‐based membrane electrode assembly (MEA) and a particulate SrTiO3 photoanode effected selective PEC conversion of toluene and water into methylcyclohexane (MCH) at concentrations up to >99 vol %. This cell exhibited 100 % faradaic efficiency (FE) and 18 % incident‐photon‐to‐current conversion efficiency (IPCE) at 320 nm without an external bias voltage in the PEC hydrogenation of pure toluene. It was also found that strong alkaline conditions are beneficial with the present MEA to suppress the competitive side reaction of hydrogen evolution, resulting in a high FE of 94 % even during MCH production from 1 vol % toluene in MCH. This study successfully demonstrated that the present PEC system is capable of producing concentrated MCH as a promising hydrogen carrier and that MCH production from toluene and water represents a means of artificial photosynthesis.
Consider program requirements, student needs when developing note‐taker program
Authors: Hope Joan
Published: December 2016

Abram Doane, J.D., M.H.A., M.A., coordinator for the Office for Academic Success at Salus University in Pennsylvania, recently launched a note‐taker program for the institution. We discussed the issues that arose and the practical solutions he put in place.
Consider the cost of attorney's fees when deciding whether to settle a case
Authors: Charmatz Marc
Published: December 2016

Most complaints brought under the Americans with Disabilities Act and Section 504 of the Rehabilitation Act get settled. Perhaps the number‐one reason for settlement of discrimination cases is the right of a plaintiff to recover attorney's fees. This article looks at the attorney's fees provisions under the ADA and Section 504.
Changing the practice: The synergy of the coalition
Authors: Meeks Lisa M. , Montgomery Tim , Moorehead Greg
Published: December 2016

Three years ago, three disability services providers connected with a simple idea — let's share what we know and in exchange learn from our peers as part of a formal network. This group has been infinitely more powerful than the sum of the individuals in it. Individually we are singular providers restricted to the autonomy and authority prescribed by our institutions, but together — as part of the coalition — we create a superior reservoir of education and grow our resources exponentially through the listserv, articles, books, research, and networking during the symposium. The Coalition for Disability Access in Health Science and Medical Education was formed — and thrives — under this idea of synergy.
Consider needs of deaf people in space design
Authors: Hope Joan
Published: December 2016

Deaf people exist in an environment built largely for and by hearing people. The DeafSpace Institute at Gallaudet University was founded to find ways to create spaces that meet the needs of deaf individuals. Its mission is “to serve as a center for the discovery, application and dissemination of knowledge about the essential ways deaf people inhabit space to enhance the quality of life for people of all abilities through design, research, education, and policy,” according to its website.
Assessing interacting impacts of artisanal and recreational fisheries in a small Marine Protected Area (Portofino, NW Mediterranean Sea)
Authors: Prato Giulia , Barrier Celine , Francour Patrice , Cappanera Valentina , Markantonatou Vasiliki , Guidetti Paolo , Mangialajo Luisa , Cattaneo‐Vietti Riccardo , Gascuel Didier
Published: December 2016

Marine Protected Areas (MPAs) have spread across the Mediterranean to protect its rich biodiversity and manage human activities for a more sustainable coastal development. Within MPAs, traditional artisanal fishing is competing for space and resources with increasing recreational fishing, likely leading to interacting ecological effects. Such effects are difficult to unravel, given the multispecies character of both fisheries and the complexity of the food webs upon which they both impact. To address these issues, we developed an Ecopath and EcoTroph trophic model for the Portofino MPA case study (NW Mediterranean), in particular to (1) identify keystone species and assess fishing impact on them; (2) analyze the interacting impact of artisanal and recreational fishing on ecosystem biomass and trophic structure; and (3) assess the impact of recreational fishing on artisanal fishing catches. Two high trophic level predator (HTLP) groups coupled important keystone roles with high sensitivity to fishing pressure and should thus be regarded as “sentinels” to be prioritized for the definition of management actions. Recreational fishing had the widest impact on the food web, strongly impacting HTLP. Simulation of different mortality scenarios for each fishery highlighted that the ecosystem is far from its carrying capacity for HTLP. Forbidding recreational fishing allowed a 24% increase in HTLP biomass and benefited artisanal fishing by increased availability of HTLP catches. Artisanal fishing alone could instead be maintained with a moderate impact on the food web. Overall, Ecopath and EcoTroph modeling is a valuable tool to advise MPA management, but it is essential to increase data availability and quality by developing long‐term monitoring programs on key species and on artisanal and recreational fishing.
A Quest for Atropisomerism in Cojoined Square‐Planar Metal Complexes: Synthesis and Structures of Sterically Congested Diplatinum Ethynediyl Adducts
Authors: Zhang Tianyi , Bhuvanesh Nattamai , Gladysz John A.
Published: December 2016

The reaction of trans‐[(C6F5)(p‐tol3P)2Pt(Cl)] and Me2PhP (4 equiv.) afforded trans‐[(C6F5)(Me2PhP)(p‐tol3P)Pt(Cl)] (2, 68 %), which is combined with HC≡CSiEt3 in HNEt2 in the presence of CuI (cat., –45 °C) to yield trans‐[(C6F5)(Me2PhP)(p‐tol3P)Pt(C≡CSiEt3)] (3, 62 %). The reaction of 2 and 3 in HNEt2 in the presence of nBu4NF/CuCl (cat., –45 °C) gave a series of PtC≡CPt complexes in which the two phosphine ligands have scrambled over all four positions. Preparative TLC afforded the target complex trans,trans‐[(C6F5)(p‐tol3P)(Me2PhP)Pt(C≡C)Pt(PPhMe2)(Pp‐tol3)(C6F5)] (4, 2.3 %) as well as trans,trans‐[(C6F5)(Me2PhP)2Pt(C≡C)Pt(PPhMe2)(Pp‐tol3)(C6F5)] (5, 5.6 %). The crystal structures of 2, 4, and 5 were determined. The last two show much congestion about the PtC≡CPt linkage, and various geometrical features have been analyzed. Low‐temperature 1H NMR spectra of 4 were recorded with the goal of observing separate signals for the Me2PhP groups. This would indicate a diastereotopic relationship and provide strong evidence for the first atropisomers based upon cojoined square‐planar complexes. However, no decoalescence was observed (CD2Cl2/–95 °C, CDFCl2/–100 °C). Together with other data, this suggests that interconversion of the putative atropisomers remains rapid on the NMR timescale at temperatures below –95 °C.
Layered Nitridomagnesogallates CaMg2GaN3 and CaMg2Ga2N4
Authors: Poesl Christine , Neudert Lukas , Schnick Wolfgang
Published: December 2016

The quaternary nitrides CaMg2GaN3 and CaMg2Ga2N4 were synthesized by means of solid‐state metathesis reactions. The crystal structures of both nitridomagnesogallates contain layers made up of either tetrahedral MN4 units (CaMg2Ga2N4) or both tetrahedral MN4 units and planar MN3 triangles (CaMg2GaN3) with mixed occupation of central atoms Mg and Ga. CaMg2GaN3 was obtained as a gray powder. Its crystal structure was determined on the basis of X‐ray powder diffraction data [P63/mmc (no. 194), a = 3.43093(8), c = 17.3989(5) Å, V = 177.368(9) Å3, Z = 2]. The compound is isotypic with CaMg2AlN3 and homeotypic with Ca2Mg5GeN6, ScAl3C3, and UAl3C3. The crystal structure of CaMg2Ga2N4 [P3m1(no. 164), a = 3.3859(3), c = 11.2378(11) Å, V = 111.57(2) Å3, Z = 1] was determined from single‐crystal X‐ray diffraction data and corroborated by Rietveld refinement. TEM investigations confirmed the metrics of both crystal structures and indicate the presence of both compounds as side products within one reaction batch. Structural similarities between CaMg2GaN3 and CaMg2Ga2N4 are discussed.
Preparation and evaluation of a novel sunflower oil‐based waterborne polyurethane nanoparticles for sustained delivery of hydrophobic drug
Authors: Omrani Ismail , Babanejad Niloofar , Shendi Hasan Kashef , Nabid Mohammad Reza
Published: December 2016

In the present study, a nanoparticulate system based on bio‐based waterborne polyurethane for the controlled delivery of raloxifene‐hydrochloride, as a model and drug with poor bioavailability, is described and considered to be an antiproliferative agent of mammary tissue. The main goal of this study was to investigate the effect of the encapsulation of raloxifene in bio‐based polyurethane, synthesized for the first time, as a polymer with anionic surface on the release profile as well as antiproliferative activity. Polyurethane was synthesized from bio‐based polyol, which was derived from sunflower oil. The structure of bio‐based polyurethane was characterized using1HNMR, FT‐IR, and TGA. Drug release studies showed controlled release of raloxifene from anionic nanoparticles that was mainly driven by diffusion‐based mechanism. Degradation of nanoparticles during the release of Ral was investigated applying SEM and caused mainly through the hydrolysis of polyurethane. MCF‐7 cell viability studies demonstrated that, raloxifene loaded nanoparticles promote the antiproliferative activity after 72 h of treatment. The bio‐based polyurethane has potential as a useful carrier for controlled release of hydrophobic drugs.

Practical applications: A novel carboxylic acid group containing polyol was prepared from sunflower oil and used in preparation of biodegradable waterborne polyurethane. The synthesized waterborne polyurethane was loaded by drug and its loading capacity was studied. Drug release studies showed controlled release of raloxifene from anionic nanoparticles that was mainly driven by diffusion‐based mechanism. Cell viability studies demonstrated that raloxifene loaded nanoparticles promote the antiproliferative activity.

A novel carboxylic acid group containing polyol was prepared from sunflower oil and used in preparation of biodegradable waterborne polyurethane. The synthesized waterborne polyurethane was loaded by drug and its loading capacity was studied. Drug release studies showed controlled release of raloxifene from anionic nanoparticles that was mainly driven by diffusion‐based mechanism. Cell viability studies demonstrated that raloxifene loaded nanoparticles promote the antiproliferative activity.
State of the art in rumen lipid protection technologies and emerging interfacial protein cross‐linking methods
Authors: Gadeyne Frederik , De Neve Nympha , Vlaeminck Bruno , Fievez Veerle
Published: December 2016

Polyunsaturated fatty acids given to ruminants are to a large extent hydrogenated to more saturated forms by microbial metabolism. Numerous protection technologies have been developed to overcome this hydrogenation process in order to increase the amount of unsaturated fatty acids bypassing the rumen and resulting in an effective transfer to the peripheral tissues. This review gives an overview of the current state of the art in rumen lipid bypass technologies, with the focus on both patent‐described protection mechanisms, possible advantages or drawbacks of the technologies, and protection results being described in recent scientific literature. Lipid bypass techniques which are dealt with include calcium salts, fatty acyl amides, aldehyde treatment, non‐enzymatic browning, lipid composite gels, and encapsulation within lipids. Further, the potential of a novel rumen lipid protection technology, based on interfacial cross‐linking of emulsions, is explored. Therefore, an overview is given on current knowledge of different types of enzymatically induced cross‐linking of protein at emulsion interfaces, both for existing food and possible ruminal bypass applications.

Practical applications: Both from a human and animal health care as well as from a resource‐saving and economic perspective, protection of PUFA from ruminal BH is of interest.

Protection, release, and absorption principle of a lipophilic rumen bypass product: As polyunsaturated fatty acids (P) are hydrogenated to more saturated fatty acids (S) upon ruminal passage (panel A), P sources administered to ruminants have to be protected against microbial turnover to transfer them to the peripheral tissues (panel B).
One‐Pot Preparation of Non‐Symmetric meso‐Aryl‐BODIPYs: Functional Derivatives with Unusual Reactivity
Authors: Cidarér Clemens , Hoffmann Martin , Oelmann Julian , Wolfram Benedikt , Bröring Martin
Published: December 2016

The formation of meso‐aryl‐BODIPYs (boron dipyrrins) through the acidic condensation of 3,4‐dialkylpyrroles with aromatic aldehydes, followed by 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) oxidation and BF2 complexation, has been reviewed. Surprisingly, it was found that the major products from these reactions were not the anticipated symmetric BODIPYs, but non‐symmetric derivatives carrying one benzyl substituent at the BODIPY α position. The best yields and simple purification conditions were be achieved if the oxidant was not employed in the one‐pot reaction sequence. Electron‐rich benzaldehydes provided the best results, whereas precursors with electron‐withdrawing substituents gave significant amounts of the symmetric BODIPYs as side‐products. This unexpected result can be rationalized mechanistically on the basis of two reaction pathways that diverge from a common intermediate at an early step in the condensation sequence. Preliminary reactivity investigations showed chlorination to give unexpected results, but a typical substitution and coupling chemistry.
Unsymmetrical Bipyrrole‐Derived β‐Tetraalkylporphycenes and C–H···Br–C Interaction Induced 2D Arrays of the 2:1 Supramolecular Sandwich Complex of Their cis‐/trans‐Dibromo Isomers
Authors: Pati Narendra N. , Kumar B. Sathish , Chandra Brijesh , Panda Pradeepta K.
Published: December 2016

Two novel stable β‐tetraethylporphycenes (TEPos), namely, trans‐TEPo (1T) and its unsymmetrical isomer cis‐TEPo (1C), were synthesized by reductive McMurry coupling of an unsymmetrical bipyrrole dialdehyde and were isolated through recrystallization. Both isomers showed interesting photophysical properties. Their corresponding dibromo derivatives obtained through bromination of a mixture of 1C and 1T, however, could not be separated in pure form. Interestingly, they were found to form an unprecedented 2:1 supramolecular sandwich complex through π–π stacking interactions, and in addition, only strong C–H···Br–C interactions among the oppositely oriented cis isomers led to the formation of 2D arrays in the solid state.
Cyclization of Malonate Derivatives with Iodine(III) Reagents
Authors: Malmedy Florence , Wirth Thomas
Published: December 2016

The cyclization of malonate derivatives by using hypervalent iodine(III) reagents is described. In this reaction, double bonds are dioxygenated to give five‐membered lactones in up to 70 % yield with diastereomeric ratios of up to 11:1.
The interplay between extrinsic and intrinsic controls in determining floodplain wetland characteristics in the South African drylands
Authors: Larkin Zacchary T. , Ralph Timothy J. , Tooth Stephen , McCarthy Terence S.
Published: December 2016

Controls on the characteristics of floodplain wetlands in drylands are diverse and may include extrinsic factors such as tectonic activity, lithology and climate, and intrinsic thresholds of channel change. Correct analysis of the interplay between these controls is important for assessing possible channel–floodplain responses to changing environmental conditions. Using analysis of aerial imagery, geological maps and field data, this paper investigates floodplain wetland characteristics in the Tshwane and Pienaars catchments, northern South Africa, and combines the findings with previous research to develop a new conceptual model highlighting the influence of variations in aridity on flow, sediment transport, and channel–floodplain morphology. The Tshwane–Pienaars floodplain wetlands have formed in response to a complex interplay between climatic, lithological, and intrinsic controls. In this semi‐arid setting, net aggradation (alluvium >7 m thick) in the wetlands is promoted by marked downstream declines in discharge and stream power that are related to transmission losses and declining downstream gradients. Consideration of the Tshwane–Pienaars wetlands in their broader catchment and regional context highlights the key influence of climate, and demonstrates how floodplain wetland characteristics vary along a subhumid to semi‐arid climatic gradient. Increasing aridity tends to be associated with a reduction in the ability of rivers to maintain through‐going channels and an increase in the propensity for channel breakdown and floodout formation. Understanding the interplay between climate, hydrology and geomorphology may help to anticipate and manage pathways of floodplain wetland development under future drier, more variable climates, both in South African and other drylands. Copyright © 2016 John Wiley & Sons, Ltd.
Coastal landscape as part of a global ocean: two shifts
Authors: Regnauld Hervé , Limido Patricia
Published: December 2016

Oceans and seas have long been considered as distinct areas, different from one another. At the end of the eighteenth century the idea began to appear (among romantic painters and poets) that they all formed a single space that would be a ‘global ocean’. Humboldt was the first scientist to take this idea seriously and to study oceans as a ‘whole’. He drew the first map (with isotherms) which could explain why oceans had to be understood as a global climatic machine. Since then the global behaviour of the ocean has become an undisputed scientific fact and many artists have produced paintings which ‘represent’ this state of knowledge. During the same period the coast lines were not considered as a global scientific object but as a discrete series of sites, all different from one another. Tourism was partly responsible for this division of coasts as each tourist place had to show it was unique and worth being visited. Many painters helped to highlight certain sites (Hudson River, Normandy, south coast of England). Then, at the end of the twentieth century some new equations dealing with sea level allowed the idea there was something like a global coastline, responding to a global climatic forcing. Few artists today tend to work with this global idea of local coasts but some of them, taking part in scientific cruises or fieldwork, do produce a new type of image for a global coastline.
Contribution of baseflow during dry spells in irregular channel cross section
Authors: Kim Tae Beom , Yang Jeong‐Seok
Published: December 2016

The discharge and water level of a gaining stream are known to be maintained during dry spells by baseflow, which is defined as discharge from underground storage. However, the effect of baseflow on a real river is not well known because direct measurements of baseflow in field are difficult to conduct. Therefore, this study attempts to clarify the contribution of baseflow to streamflow and the extent to which the water level is maintained even during dry spells. A digital filter technique is applied to the records of daily mean streamflow in order to estimate the amount of baseflow, and the lateral distribution method is applied to irregular cross sections at observational sites to obtain the stage–discharge rate curve. Through a comparison of the observed data and calculation results, the amount of baseflow is estimated across the channel, in addition to the maximum water level retained during dry spells in relation to the baseflow. Finally, based on the results of an energy conservation model, this study proposes that the source of the amount of baseflow estimated across a channel section may be different from that of the water level maintained during dry spells.
Differential effects of school experiences on active citizenship among German and Turkish‐origin students
Authors: Jugert Philipp , Eckstein Katharina , Noack Peter
Published: December 2016

While research suggests that schools can foster active citizenship among youth, studies have not tested whether ethnic minority youth may benefit differently from school experiences than ethnic majority youth. In this study of 219 students (138 German majority and 81 Turkish‐origin minority; Mage = 18.26; 55% females), we examined the association between different experiences at school and 4 indicators of youth active citizenship, controlling for various socio‐demographic characteristics. Although value of social studies was associated with three out of four active citizenship indicators among both ethnic groups, the effects of the other school‐related variables on active citizenship were moderated by ethnicity. Specifically, indicators of classroom climate, such as open classroom climate and classroom community, were only associated with greater active citizenship among Turkish‐minority youth, while participatory factors, such as engagement in school decisions, were only associated with active citizenship among native German youth.